Two-component block copolymer

Abstract

Disclosed is a dual component block copolymer prepared from a conjugated diene and a monovinyl aromatic monomer in a batch organolithium initiated polymerization that exhibits advantageous properties in the production of crosslinked microcellular rubber compounds and pressure sensitive hot melt adhesives. The dual component block copolymer is partially coupled with a coupling agent moiety that links the internal monovinyl aromatic block. The uncoupled low molecular weight portion of the dual component block copolymer has a higher content of monovinyl aromatic repeat units than the coupled high molecular weight portion. Crosslinked microcellular rubber articles prepared from the dual component block copolymer have lower viscosity, smaller or more homogeneous cell size, higher softness and higher resilience than crosslinked microcellular rubber articles prepared from prior art block copolymers. Rubber compounding formulations containing the dual component block copolymer are performed at slightly lower torque and at slightly lower temperature than formulations containing prior art block copolymers. Pressure sensitive hot melt adhesives formulated with the dual component block copolymer are well suited for labels and have higher tack and higher softening temperature than adhesives made from prior art block copolymers.

Description

[0001] This application is a divisional application of the application filed on December 10, 2019, with international application number PCT / IB2019 / 001434, Chinese application number 201980004574.7, and entitled "Bibliopolymer".

[0002] Cross-references to related applications

[0003] This application claims priority to U.S. Patent Application No. 16 / 595,913, filed October 8, 2019, and U.S. Provisional Application No. 62 / 782,668, filed December 20, 2018, each of which is incorporated herein by reference. Background Technology 1. Technical Field

[0005] This invention relates to bicomponent block copolymers of conjugated dienes and monovinyl aromatic monomers, and more specifically to microporous crosslinked rubber compounds comprising bicomponent block copolymers and hot-melt pressure-sensitive adhesives. The novel bicomponent block copolymers of this invention can be used to produce microporous crosslinked rubber compounds with closed cells of uniform size, free from foaming defects, and exhibiting improved softness and high resilience. Hot-melt pressure-sensitive adhesives based on the novel bicomponent block copolymers show improved tack and operating temperature.

[0006] 2. Existing Technology Description

[0007] Microporous rubber compounds have been widely used in the manufacture of various products, such as shoe soles, slippers, cushioning pads, flotation products, sound insulation panels, vibration damping materials, shock absorbers, and sealing applications. Moreover, these materials have gained widespread market acceptance due to their lightweight and cost-effectiveness.

[0008] In the foaming of these compounds, closed-cell structures are formed under the influence of heat, or a combination of heating and decompression at typical temperatures and pressures used for vulcanization compounding, through the expansion of chemical or physical foaming agents. Crosslinking of microporous rubber compounds increases improved and durable mechanical properties. The elasticity of the rubber during foaming is important in maintaining the closed-cell structure; in most processes, partial crosslinking before or during the foaming stage enhances the rubber's elasticity. During the time elapsed between the end of expansion and achieving optimal crosslinking, foamed rubber compounds tend to shrink. Block copolymers of conjugated dienes and monovinyl aromatic monomers have been used in crosslinked microporous rubber compositions to avoid this shrinkage defect.

[0009] GB 1,249,220 discloses uncrosslinked elastic foams based on block copolymers, with a block configuration of (BS). n Or (BS) n B or (SB)m Where B essentially represents a 1,3-butadiene polymer, S essentially represents a styrene polymer, n is an integer from 2 to 10, and m is an integer from 1 to 10. The composition may also include a polystyrene homopolymer. However, this composition has disadvantages because it contains chlorofluorocarbons as a blowing agent, which is harmful to the environment, and exhibits a relatively large pore size of 0.6 to 1.1 mm.

[0010] EP 0,323,653 A1 discloses a crosslinked rubber foam composition comprising a component having the general formula (AE). n A, (AE) n Or (AE) n ) m X is a block copolymer of a monovinyl aromatic polymer and a conjugated diene monomer, wherein n is 1-4, m is 2-8, A represents a monovinyl aromatic polymer block, E represents a conjugated diene polymer block and / or its selectively hydrogenated product, and X represents a coupling agent residue. The composition also includes other rubbers, such as natural rubber, diene-type synthetic rubber, and non-diene synthetic rubber.

[0011] EP 2,546,291 discloses crosslinked rubber foam compositions comprising block copolymers containing vinyl aromatic monomer units and conjugated diene monomer units, and / or block copolymers containing vinyl aromatic monomer units, conjugated diene monomer units, and alkylene monomer units. The compositions also include olefin-based copolymers (such as polyethylene, ethylene-1-butene copolymers, ethylene-octene copolymers, etc.), and optionally ethylene-based copolymers having unsaturated groups, such as EPDM. Among the various sequence structures disclosed for block copolymers, preferred block configurations have terminal blocks rich in vinyl aromatic repeating units and intermediate blocks of elastomeric repeating units.

[0012] WO 2008 / 083451 A1 discloses a foaming compound for rubber vulcanization comprising a block copolymer having a molecular configuration consisting of polystyrene end blocks and an elastomeric intermediate block; the elastomeric intermediate block is based on butadiene, isoprene, ethylene, butene, or propylene. The compound also incorporates a styrene-butadiene random copolymer having a high and / or average bound styrene content, and an ethylene-propylene copolymer (EPR) or an ethylene-propylene-diene terpolymer (EPDM).

[0013] The compositions disclosed in EP 0,323,653 A1, EP 2,546,291, and WO 2008 / 083451 A1 comprise block copolymers (or hydrogenated products thereof) in which terminal blocks rich in vinyl aromatic repeating units surround intermediate blocks rich in conjugated diene repeating units. Therefore, they all suffer from the disadvantage of requiring very high mixing temperatures. This is because the terminal blocks of the block copolymers disclosed therein form an intermolecular physical network that softens sufficiently to flow only above 120°C. Such high operating mixing temperatures can lead to premature decomposition and / or premature crosslinking of the chemical blowing agent. This is particularly limiting when mixing in batch internal mixers (e.g., Banbury mixers).

[0014] GB 1,111,250 discloses a crosslinked microporous rubber foam composition comprising a graded diblock copolymer of a conjugated diene and a vinyl aromatic monomer. The disclosed graded diblock copolymer is produced in a batch anionic solution polymerization process. The composition also includes a random copolymer of a conjugated diene and a vinyl aromatic monomer obtained by anionic solution polymerization or by free radical emulsion polymerization.

[0015] US 4,003,860 discloses a crosslinked microporous rubber foam composition comprising a graded diblock copolymer of a conjugated diene and a monovinyl aromatic monomer. The disclosed graded diblock copolymer is produced in a batch anionic solution polymerization process. The composition also includes an ethylene / vinyl acetate copolymer.

[0016] The main advantage of the compositions disclosed in GB 1,111,250 and US 4,003,860 is their adequate processability in batch internal mixer equipment and minimized shrinkage of the foaming compound. However, crosslinked microporous rubber compounds, including such block copolymers disclosed herein, have disadvantages such as inhomogeneous pore size, appearance foaming defects, low softness, and low resilience.

[0017] BRPI 0601080-6A discloses a formulation of a vulcanized microporous rubber compound comprising a block copolymer of styrene and butadiene as the main component. This includes a small amount of resin with a styrene content of 40% to 80% to increase the hardness of the formulation. This formulation is known to be advantageous for molding microporous or micro-honeycomb sandal soles. However, this patent lacks a description of the molecular configuration of the block copolymer and information regarding its compositional range.

[0018] EP 0674578 B1, US 8,772,414 B2 and US 2015 / 0259491 A1 show various polymeric foaming compositions in which, for proper closed-cell foaming, the polymer used preferably has a Tanδ value (the ratio of loss modulus to storage modulus, also known as the dissipation factor) slightly less than 1 in the molten state.

[0019] Microporous crosslinked rubber compounds comprising graded block copolymers of butadiene and styrene, prepared by anionic solution polymerization in a continuous reactor, are known to have a good balance between shrinkage and surface aesthetics, and sufficient processability in batch mixing equipment. However, they still impart hardness and low resilience to the microporous crosslinked rubber compounds. Moreover, continuous anionic polymerization processes lack the flexibility of batch processes, which allow switching polymerization formulations to obtain different rubber grades without incurring unqualified transition production.

[0020] As described above, there is a need for block copolymers of conjugated dienes and vinyl aromatic repeating units that can be readily mixed with other components to produce microporous crosslinked rubber compounds without premature blow molding or premature crosslinking. There is also a need for compositions based on block copolymers of conjugated dienes and vinyl aromatic repeating units that prevent shrinkage issues during the production of crosslinked microporous rubber compounds. Furthermore, there is a need for crosslinked rubber foam compounds comprising block copolymers of conjugated dienes and vinyl aromatic repeating units, which can be molded into articles with excellent surface appearance, no foaming defects, improved softness, and high resilience. A batch polymerization process is also needed to produce block copolymers of conjugated dienes and vinyl aromatic repeating units with excellent foaming properties. Summary of the Invention

[0021] This invention provides novel bicomponent block copolymers prepared by solution polymerization of monovinyl aromatic and conjugated diene monomers initiated by alkyllithium. As used in the specification and claims of this invention, the term "bicomponent block copolymer" or "bicomponent block copolymers" refers to a polymer blend comprising two block copolymer molecules that differ from each other in molecular weight, block arrangement, and the content of monovinyl aromatic repeating units.

[0022] Each block copolymer molecule in a bicomponent block copolymer can be distinguished by a peak in the molecular weight distribution of the entire bicomponent block copolymer. The portion of the peak with the highest molecular weight in its molecular weight distribution corresponds to a coupled block copolymer molecule. In these coupled block copolymer molecules, the coupling agent residues are covalently bonded to only two or more internal monovinyl aromatic homopolymer blocks. The remainder of each coupled block copolymer molecule comprises polymer blocks consisting of conjugated dienes and scattered monovinyl aromatic repeating units, or polymer blocks incorporating only conjugated diene repeating units. In the lower molecular weight range, adjacent to the coupled block copolymer peaks in the molecular weight distribution of the bicomponent block copolymer, another peak, or peaks, can be distinguished, representing the polymerization of uncoupled block copolymer molecules. Each molecule of these uncoupled block copolymers has a single monovinyl aromatic homopolymer terminal block, and the remainder of each uncoupled block copolymer molecule consists of polymer blocks containing, or containing only, conjugated diene repeating units in which monovinyl aromatic diene repeating units are dispersed. The average monovinyl aromatic repeating unit content in coupled block copolymer molecules is lower than that in uncoupled block copolymer molecules. Furthermore, the average molecular weight of the individual monovinyl aromatic homopolymer intrapolymer blocks in coupled block copolymer molecules is lower than the average molecular weight of the monovinyl aromatic homopolymer terminal blocks present in uncoupled block copolymer molecules. Similarly, the average molecular weight of the peripheral blocks containing conjugated diene repeating units in coupled block copolymers is substantially the same as the molecular weight of the blocks containing conjugated diene repeating units present in uncoupled block copolymers.

[0023] The present invention also provides a method for obtaining novel bicomponent block copolymers in a batch polymerization reactor.

[0024] The present invention also provides compositions for producing crosslinked microporous rubber compounds, including novel two-component block copolymers, and other typical components for such compounds.

[0025] The compositions of this invention enable the mixing stage of crosslinked microporous rubber production to be completed at reduced temperatures in an internal batch mixer (e.g., Banbury), which helps avoid the problems of premature expansion and premature crosslinking of chemical foaming agents. The mixing stage is also carried out with lower torque compared to prior art block copolymers with the same Mooney viscosity, thus the incorporation of bicomponent block copolymers into such formulations is beneficial because energy can be saved during the mixing process. The compositions of this invention also offer the advantage of negligible shrinkage of the microporous compounds during the crosslinking stage. Molded articles produced with the compositions of this invention exhibit excellent surface appearance, are bubble-free, and possess high softness and resilience.

[0026] The present invention also provides hot-melt pressure-sensitive adhesive formulations comprising a novel two-component block copolymer, as well as other typical components for such adhesives. Surprisingly, hot-melt pressure-sensitive adhesives comprising this novel two-component block copolymer exhibit improved tack and operating temperature range. Attached Figure Description

[0027] Figure 1 A schematic diagram of a bicomponent block copolymer is shown, consisting of approximately 38% by weight of a coupled block copolymer C of the formula [D-(D / A)-A1]4-X (left side) and approximately 62% by weight of an uncoupled block copolymer U of the formula D-(D / A)-A2 (right side).

[0028] Figure 2 A schematic diagram is shown of a bicomponent block copolymer consisting of approximately 34 wt% of a coupled block copolymer C of the formula [D-(D / A)-A1]4-X (left side) and approximately 66 wt% of uncoupled block copolymers U of the formulas D-(D / A)-A2 (upper right 4 molecules) and D-(D / A)-A1 (lower right).

[0029] Figure 3 A schematic diagram of a bicomponent block copolymer is shown, consisting of approximately 38% by weight of a coupled block copolymer C of the formula [B-(B / A)-A1]4-X (left side) and approximately 62% by weight of an uncoupled block copolymer U of the formula B-(B / A)-A2 (right side).

[0030] Figure 4 A schematic diagram is shown of a bicomponent block copolymer consisting of approximately 34 wt% of a coupled block copolymer C of formula [B-(B / A)-A1]4-X (left side) and approximately 66 wt% of uncoupled block copolymers U of formulas B-(B / A)-A2 (top right 4 molecules) and B-(B / A)-A1 (bottom right). A t It is approximately 39% by weight.

[0031] Figure 5 A schematic diagram of a bicomponent block copolymer is shown, consisting of approximately 38% by weight of a coupled block copolymer C of the formula [B-(B / A)-A1]4-X (left side) and approximately 62% by weight of an uncoupled block copolymer U of the formula B-(B / A)-A2 (right side).

[0032] Figure 6 A schematic diagram of a bicomponent block copolymer is shown, consisting of approximately 34 wt% of a coupled block copolymer C of the formula [B-(B / A)-A1]4-X (left side) and approximately 66 wt% of uncoupled block copolymers U of the formulas B-(B / A)-A2 (upper right 4 molecules) and (B / A)-A1 (lower right).

[0033] Figure 7 A schematic diagram of a bicomponent block copolymer is shown, consisting of approximately 38% by weight of a coupled block copolymer C of formula [B-A1]4-X (left side) and approximately 62% by weight of an uncoupled block copolymer U of formula B-A2 (right side).

[0034] Figure 8 A schematic diagram is shown of a bicomponent block copolymer consisting of approximately 34% by weight of a coupled block copolymer C of formula [B-A1]4-X (left side) and approximately 66% by weight of uncoupled block copolymers U of formulas B-A2 (upper right 4 molecules) and B-A1 (lower right).

[0035] exist Figures 1 to 8 In the diagram, black bars represent the sequence of monovinyl aromatic repeating units, gray bars represent the sequence of conjugated diene repeating units, and X represents the residues of a tetrafunctional coupling agent. Figures 1 to 6 In the sequence of conjugated diene repeating units, the black lines represent different arrangements where monovinyl aromatic repeating units copolymerize with conjugated diene repeating units; their positions and spacing are not specific locations of individual monovinyl aromatic repeating units, but rather show a concentration trend of monovinyl aromatic repeating units dispersed along blocks that also contain conjugated diene repeating units. Therefore, in Figure 1 and Figure 2 The data shows the characteristics of graded copolymerization: a slight gradient followed by a steep gradient concentration curve; Figure 3 and Figure 4 The randomization of only a portion of the conjugated diene repeating units was described; Figure 5 and Figure 6 The diagram shows a completely random arrangement of all conjugated diene repeating units.

[0036] Figure 9 The prior art block copolymers of Comparative Example C-2 and Comparative Example C-2 are shown. Compared to BL 30-4548, the molecular weight distribution of the bicomponent block copolymers in Examples 4 and 13. Detailed Implementation

[0037] This invention provides a novel bicomponent block copolymer made from monovinyl aromatic and conjugated diene monomers, comprising two types of block copolymer molecules, C and U.

[0038] In one embodiment, the bicomponent block copolymer of the present invention has a molecular weight distribution with two distinguishable fractions, each fraction having a peak in the molecular distribution, which can be obtained by gel permeation chromatography using a 3-column array, a differential refractive index detector, and relying on a universally calibrated molecular weight profile (GPC-RI) involving polystyrene standards. Adjacent fractions are demarcated from each other at local minima in the molecular weight distribution profile. Block copolymer C consists of the fraction with the highest molecular weight peak in the molecular weight distribution, while block copolymer U constitutes the remaining fraction of the molecular weight distribution.

[0039] In one embodiment, the bicomponent block copolymer of the present invention has a certain amount of block copolymer C, which is quantified by integrating the portion having the highest molecular weight peak relative to the entire molecular weight distribution of the bicomponent block copolymer obtained by GPC-RI, and is 20% to 80%, more preferably 30% to 60%, and most preferably 35% to 45%. Additionally, the bicomponent block copolymer of the present invention has a certain amount of block copolymer U, which is quantified by integrating the remaining molecular weight distribution relative to the entire molecular weight distribution of the bicomponent block copolymer obtained by GPC-RI, and is 80% to 20%, more preferably 70% to 40%, and most preferably 65% ​​to 55%. In one embodiment, the total monovinyl aromatic repeating unit content %A of the bicomponent block copolymer of the present invention is determined by proton NMR analysis. t It ranges from 20% to 50% by weight.

[0040] The bicomponent block copolymer of the present invention has a characteristic monovinyl aromatic repeating unit blockiness, as determined by proton NMR analysis. The blockiness of the monovinyl aromatic repeating unit is quantified as the molar percentage of monovinyl aromatic repeating units in the block copolymer that are not covalently bonded to conjugated diene repeating units, based on the total number of monovinyl aromatic repeating units. In one embodiment, the blockiness of the monovinyl aromatic repeating unit in the bicomponent block copolymer of the present invention is about 76 mol% to about 100 mol%, more preferably about 81 mol% to about 100 mol%, and most preferably about 85 mol% to about 100 mol%, based on the total number of monovinyl aromatic repeating units.

[0041] A significant feature of the bicomponent block copolymers of the present invention is that the content of monovinyl aromatic repeating units in block copolymer U is higher than that in block copolymer C. The weight percentage (%) of monovinyl aromatic repeating units in block copolymer U is shown in Figure A. U The weight percentage (%) of monovinyl aromatic repeating units in block copolymer C C The difference in weight percentage composition (%CD) between the U and C portions of the block copolymer is calculated as follows:

[0042]

[0043]

[0044] %CD = %A U -%A C Among them, %C uv It is the percentage of the peak with the highest molecular weight (which corresponds to block copolymer C) relative to the entire molecular weight distribution of the diblock copolymer of the present invention obtained by GPC technology using a 3-column array, employing an ultraviolet absorption detector at a wavelength of 261 nm, and relying on a universally calibrated molecular weight profile (GPC-UV) involving polystyrene standards.

[0045] %A t The total monovinyl aromatic compound content, by weight, of all bicomponent block copolymers of the present invention, obtained by proton NMR analysis; and

[0046] %C ri It is the percentage of the peak with the highest molecular weight (corresponding to block copolymer C) relative to the overall molecular weight distribution of the bicomponent copolymer of the present invention obtained by using a 3-column gel permeation chromatography technique with a differential refractive index detector and relying on a universally calibrated molecular weight profile (GPC-RI) involving polystyrene standards.

[0047] In one embodiment, the bicomponent block copolymer of the present invention has a weight percentage composition difference %CD of monovinyl aromatic repeating units between the U and C portions of the block copolymer, which is at least 10% by weight, preferably at least 15% by weight, and most preferably at least 20% by weight.

[0048] Tanδ, defined as the ratio of loss modulus to storage modulus, is well-known in the art as a highly suitable indicator of the balance between flowability and melt strength, and therefore also a highly suitable indicator of the foaming capacity of various polymer materials. Without being limited by any particular theory, polymer materials with a Tanδ value below 1.0 can possess sufficient melt strength to maintain a closed-cell structure during the expansion of the blowing agent, which will benefit from a narrower pore size distribution, thereby improving the aesthetics of the foam surface. Conversely, under processing conditions, polymer materials with a Tanδ value above 1.0 are therefore prone to cell membrane rupture and cell coalescence during foaming, which may lead to a wider pore size distribution, even to the point of causing surface defects such as bulging during foaming.

[0049] Extensive research has confirmed that prior art copolymers obtained through intermittent alkyllithium solution copolymerization of monovinyl aromatic compounds and conjugated diene monomers fail to achieve suitable Tanδ distributions, and their viscoelastic behavior has been found to be associated with poor foaming properties. Several prior art block copolymer structures have been tested (gradually variable linear block copolymers, partially coupled gradually variable block copolymers, various levels of monovinyl aromatic repeating units, various levels of monovinyl aromatic content, various molecular weights, oil-extended block copolymers, and even mixtures of gradually variable linear block copolymers with different monovinyl aromatic repeating unit contents), and all of these block copolymer structures result in Tanδ distributions slightly above 1.0 over a fairly wide range of oscillating shear frequencies. These prior art alternatives, when formulated into crosslinked microporous foam compositions, produce molded articles lacking a neat surface aesthetic due to significant foaming defects. However, it was unexpectedly discovered that the bicomponent block copolymers of the present invention exhibit characteristic viscoelastic behavior, which makes them advantageous for foaming purposes, as they exhibit Tanδ values ​​of only less than 1.00 over a wide range of shear rates and processing temperatures prior to any crosslinking. Accordingly, crosslinked microporous compositions based on bicomponent block copolymers have been found to have very uniform cell sizes, and their molded articles exhibit excellent surface aesthetics without foaming defects.

[0050] In one embodiment, when a dynamic oscillatory shear test is performed at 100°C and 13.95% strain, with an oscillation frequency sweep from 0.25 rad / s to 200 rad / s, the bicomponent block copolymer of the present invention exhibits a maximum Tanδ value of 0.74 to 0.95, more preferably 0.74 to 0.88, and most preferably 0.74 to 0.81. Typically, for dynamic oscillatory shear tests at 100°C and 13.95% strain, the Tanδ value of the bicomponent block copolymer of the present invention is less than 1.00 when the oscillation frequency varies from 0.25 to 200 rad / s. Similarly, at higher temperatures, at 140°C and 13.95% strain, the Tanδ value of the bicomponent block copolymer of the present invention is less than 1.00, 0.95, 0.90, or 0.85 when the oscillation frequency varies from 0.25 to 200 rad / s.

[0051] In one embodiment, the Mooney viscosity (ML 100°C 1+4) of the bicomponent block copolymer of the present invention is 25 to 90, preferably 30 to 60, and more preferably 35 to 55.

[0052] In one embodiment, the composite shear dynamic viscosity of the bicomponent block copolymer of the present invention, evaluated at 13.95% strain, an oscillation frequency of 0.99 rad / s, and a temperature of 100°C, is from 50,000 Pa⁻² to 360,000 Pa⁻². In another embodiment, the composite dynamic viscosity of the bicomponent block copolymer of the present invention, evaluated at 100 rad / s and 100°C, is from 3,000 Pa⁻² to 12,000 Pa⁻².

[0053] In the absence of polar modifiers or atactic agents, intermittent copolymerization of conjugated dienes and monovinyl aromatic monomers initiated by alkyllithium in bulk or nonpolar hydrocarbon solvent solutions produces D-(D / A)-A type diblock copolymers, referred to as graded or hierarchical copolymers, where D is a polymer block rich in conjugated diene repeating units; (D / A) is a polymer block that is increasingly rich in conjugated diene repeating units toward its end adjacent to the D block, and its composition gradually changes until it becomes substantially rich in monovinyl aromatic repeating units toward its opposite end; and A is a polymer block consisting only of monovinyl aromatic repeating units. The production and application of such graded or hierarchical diblock copolymers of conjugated dienes and monovinyl aromatic monomers are well known to those skilled in the art and described in HLHsie, RPQuirk, Anionic Polymerization: Principles and Practical Applications, Marcel Dekker, Inc., pp. 239-251 and 448-454.

[0054] In a preferred embodiment, the bicomponent block copolymer of the present invention comprises block copolymer C and block copolymer U, wherein

[0055] The general formula for block copolymer C is:

[0056] [D-(D / A)-A1] n -X; and

[0057] The general formula for block copolymer U is:

[0058] D-(D / A)-A2; or

[0059] D-(D / A)-A2 and D-(D / A)-A1, where

[0060] D is a polymer block made of at least one conjugated diene monomer and at least one monovinyl aromatic monomer, wherein the molar amount of the conjugated diene repeating unit is greater than the molar amount of the monovinyl aromatic repeating unit over the entire length of the polymer block.

[0061] (D / A) is a polymer block made of at least one conjugated diene monomer and at least one monovinyl aromatic monomer, wherein the polymer block end opposite to A1 or A2 is mainly composed of conjugated diene repeating units, and its composition gradually changes along its length until it becomes substantially composed of monovinyl aromatic repeating units toward its end adjacent to A1 or A2.

[0062] A1 and A2 are polymer blocks made solely of monovinyl aromatic monomers;

[0063] The molecular weight of polymer block A2 is greater than that of polymer block A1;

[0064] X is a residue of the coupling agent;

[0065] n is an integer with a value between 2 and 30;

[0066] Determined by GPC-RI, the formula [D-(D / A)-A1] n -X-coupled block copolymer molecules account for approximately 20 to approximately 80% by weight of the molecular weight distribution of the two-component block copolymer;

[0067] As determined by GPC-RI, the uncoupled block copolymer molecules of formula D-(D / A)-A2 account for approximately 20 to approximately 80% by weight of the molecular weight distribution of the bicomponent block copolymer; and

[0068] As determined by GPC-RI, the uncoupled block copolymer molecules of formula D-(D / A)-A1 account for approximately 0 to approximately 20% by weight of the molecular weight distribution of the bicomponent block copolymer.

[0069] In another embodiment, the bicomponent block copolymer of the present invention comprises block copolymer C and block copolymer U, wherein

[0070] The general formula for block copolymer C is:

[0071] [B-(B / A)-A1] n -X; and

[0072] The general formula for block copolymer U is:

[0073] B-(B / A)-A2; or

[0074] B-(B / A)-A2 and B-(B / A)-A1, where:

[0075] B is a polymer block made solely of one or more conjugated diene monomers;

[0076] (B / A) is a polymer block made of at least one conjugated diene monomer and at least one monovinyl aromatic monomer, wherein the conjugated diene repeating unit and the monovinyl aromatic repeating unit are randomly arranged along the entire length of the polymer block;

[0077] A1 and A2 are polymer blocks made solely of monovinyl aromatic monomers, wherein the molecular weight of polymer block A2 is greater than that of polymer block A1.

[0078] X is a residue of the coupling agent;

[0079] n is an integer with a value between 2 and 30;

[0080] Determined by GPC-RI, the formula [B-(B / A)-A1] n -X-coupled block copolymer molecules account for approximately 20 to approximately 80% by weight of the molecular weight distribution of the two-component block copolymer;

[0081] As determined by GPC-RI, the uncoupled block copolymer molecules of formula B-(B / A)-A2 account for approximately 20 to approximately 80% by weight of the molecular weight distribution of the bicomponent block copolymer; and

[0082] As determined by GPC-RI, the uncoupled block copolymer molecules of formula B-(B / A)-A1 account for approximately 0 to approximately 20% by weight of the molecular weight distribution of the bicomponent block copolymer.

[0083] In another embodiment, the bicomponent block copolymer of the present invention comprises block copolymer C and block copolymer U, wherein:

[0084] The general formula for block copolymer C is:

[0085] [B-A1] n -X; and

[0086] The general formula for block copolymer U is:

[0087] B-A2; or

[0088] B-A2 and B-A1, where:

[0089] B is a polymer block made solely of one or more conjugated diene monomers;

[0090] A1 and A2 are polymer blocks made solely of monovinyl aromatic monomers;

[0091] The molecular weight of polymer block A2 is greater than that of polymer block A1;

[0092] X is a residue of the coupling agent;

[0093] n is an integer with a value between 2 and 30;

[0094] Determined by GPC-RI, formula [B-A1] n -X-coupled block copolymer molecules account for approximately 20 to approximately 80% by weight of the molecular weight distribution of the two-component block copolymer;

[0095] As determined by GPC-RI, the coupled block copolymer molecules of formula B-A2 account for approximately 20 to approximately 80% by weight of the molecular weight distribution of the two-component block copolymer; and

[0096] As determined by GPC-RI, the molecules of the coupled block copolymer of formula B-A1 account for approximately 0 to approximately 20% by weight of the molecular weight distribution of the two-component block copolymer.

[0097] In another embodiment, the bicomponent block copolymer of the present invention comprises block copolymer C and block copolymer U, wherein:

[0098] The general formula for block copolymer C is:

[0099] [(B / A)-A1] n -X; and

[0100] The general formula for block copolymer U is:

[0101] (B / A)-A2; or

[0102] (B / A)-A2 and (B / A)-A1, where:

[0103] (B / A) is a polymer block made of at least one conjugated diene monomer and at least one monovinyl aromatic monomer, wherein the conjugated diene repeating unit and the monovinyl aromatic repeating unit are randomly arranged along the polymer block;

[0104] A1 and A2 are polymer blocks made solely of monovinyl aromatic monomers, wherein the molecular weight of polymer block A2 is greater than that of polymer block A1.

[0105] X is a residue of the coupling agent;

[0106] n is an integer with a value between 2 and 30;

[0107] Determined by GPC-RI, formula [(B / A)-A1] n -X-coupled block copolymer molecules account for approximately 20 to approximately 80% by weight of the molecular weight distribution of the two-component block copolymer;

[0108] As determined by GPC-RI, the uncoupled block copolymer molecules of formula (B / A)-A2 account for approximately 20 to approximately 80% by weight of the molecular weight distribution of the bicomponent block copolymer; and

[0109] As determined by GPC-RI, the uncoupled block copolymer molecules of formula (B / A)-A1 account for approximately 0 to approximately 20% by weight of the molecular weight distribution of the bicomponent block copolymer.

[0110] Another aspect of the present invention provides a method for preparing novel bicomponent block copolymers in a batch reactor, the method comprising: reacting at least one conjugated diene monomer with a monovinyl aromatic monomer under anionic polymerization conditions; and forming a bicomponent block copolymer comprising two types of block copolymer molecules, C and U.

[0111] A preferred embodiment of the present invention is a method for producing novel bicomponent block copolymers in a batch reactor, comprising:

[0112] The hydrocarbon solvent, at least one monovinyl aromatic monomer, and at least one conjugated diene monomer are added to the reactor in any order;

[0113] A monofunctional organolithium initiator compound is added to the reactor and the monomer mixture is anionicly polymerized to complete conversion to form the formula D-(D / A)-Al. (-) Block copolymer anions;

[0114] A limited amount of coupling agent is added to the reactor to couple only a portion of the copolymer anionic D-(D / A)-A1. (-) This results in the formation of uncoupled block copolymer anions D-(D / A)-Al. (-) With the formula [D-(D / A)-A1] n A mixture of -X-coupled block copolymer molecules;

[0115] A monovinyl aromatic monomer is added to the reactor and anionicly polymerized, then added to the remaining block copolymer anionic D-(D / A)-A1. (-) Thus, the formula D-(D / A)-A2 is formed. (-) Chain-extended graded block copolymers with anionic and [D-(D / A)-A1] formula n A mixture of -X-coupled block copolymer molecules; and

[0116] Add a sufficient amount of proton donor compound or electrophilic monofunctional additive to the reactor to terminate the reaction of all remaining block copolymer anionic D-(D / A)-A2. (-) .

[0117] In this manner, a bicomponent block copolymer comprising two types of block copolymer molecules, C and U, is produced in situ in a batch reactor, wherein:

[0118] C is the general formula [D-(D / A)-A1] n -X block copolymers;

[0119] U is a block copolymer of the general formula D-(D / A)-A2;

[0120] D is a polymer block composed of conjugated diene and monovinyl aromatic monomer, wherein the repeating unit of conjugated diene accounts for the majority of the molar amount;

[0121] (D / A) is a polymer block that is more rich in conjugated diene repeating units toward the end adjacent to the D block and gradually changes its composition until it becomes substantially rich in monovinyl aromatic repeating units toward the opposite end.

[0122] A1 and A2 are polymer blocks containing only monovinyl aromatic monomers;

[0123] The molecular weight of polymer block A2 is greater than that of polymer block A1;

[0124] X is a residue of the coupling agent;

[0125] n is an integer from 2 to approximately 30, depending on the coupling agent used; and

[0126] Block copolymer C has a higher molecular weight and a lower content of monovinyl aromatic repeating units than block copolymer U.

[0127] Another embodiment of the present invention is a method for producing novel bicomponent block copolymers in a batch reactor, comprising: adding a hydrocarbon solvent, at least one monovinyl aromatic monomer, and at least one conjugated diene monomer to the reactor in any order; adding a monofunctional organolithium initiator compound to the reactor and anionicly polymerizing the monomer mixture to complete conversion to form D-(D / A)-Al. (-) The block copolymer anion; adding a coupling agent to the reactor to couple only a portion of the copolymer anion D-(D / A)-A1. (-) This results in the formation of block copolymer anions D-(D / A)-Al. (-) With the formula [D-(D / A)-A1] n A mixture of graded block copolymer molecules coupled with -X; a limited amount of proton donor compound or electrophilic monofunctional compound is added to the reactor to terminate only part of the block copolymer anion, thereby producing the formula D-(D / A)-A1. (-) Block copolymer anionic, formula [D-(D / A)-A1] n A mixture of -X-coupled block copolymer molecules and block copolymer D-(D / A)-A1; a monovinyl aromatic monomer is added to the reactor and anionicly polymerized, then added to the remaining block copolymer anionic D-(D / A)-A1. (-) Thus, the formula D-(D / A)-A2 is formed.(-) Chain-extended graded block copolymers, anionic, formula [D-(D / A)-A1] n A mixture of -X-coupled block copolymer molecules and D-(D / A)-A1 block copolymer molecules; a sufficient amount of a proton donor compound or an electrophilic monofunctional compound or a mixture of both is added to the reactor to terminate all remaining block copolymer anionic D-(D / A)-A2. (-) .

[0128] In this manner, bicomponent block copolymers comprising two types of block copolymer molecules, C and U, are produced in situ in a batch reactor: where C is of the general formula [D-(D / A)-A1]. n -X block copolymers, U being block copolymers of the general formulas D-(D / A)-A2 and D-(D / A)-A1; wherein D is a polymer block made of a conjugated diene and a monovinyl aromatic monomer, wherein the conjugated diene repeating unit constitutes the majority of the molar amount; wherein (D / A) is a polymer block that is more rich in conjugated diene repeating units toward its end adjacent to the D block and gradually changes its composition until it is substantially more rich in monovinyl aromatic repeating units toward its opposite end; wherein A1 and A2 are polymer blocks containing only monovinyl aromatic repeating units; wherein the molecular weight of polymer block A2 is greater than that of polymer block A1; wherein X is a residue of a coupling agent; wherein n is an integer from 2 to about 30 depending on the coupling agent used; and wherein block copolymer C has a higher molecular weight and a lower content of monovinyl aromatic repeating units than block copolymer U.

[0129] Another embodiment of the present invention is a method for producing novel bicomponent block copolymers, comprising: adding a hydrocarbon solvent, a randomizer or polar modifier, and at least one conjugated diene monomer in any order to a reactor; adding a monofunctional organolithium initiator compound to the reactor and anionicly polymerizing the conjugated diene monomer to achieve a conversion of about 80% to about 95%, thereby forming a copolymer of formula B. (-) The polymer anion; a monovinyl aromatic monomer is added to the reactor, which initially randomly copolymerizes with the remaining conjugated butadiene monomer to generate a block copolymer anion B-(B / A). (-) Continue until the conjugated diene is completely converted, then only monovinyl aromatic monomers are incorporated into the block copolymer anion until the monovinyl aromatic monomers are completely converted, thereby forming the formula B-(B / A)-A1. (-) The polymer anion; a limited amount of coupling agent is added to the reactor to couple only a portion of the copolymer anion B-(B / A)-A1. (-) This results in the formation of block copolymer anions B-(B / A)-Al. (-)With the formula [B-(B / A)-A1] n A mixture of -X-coupled block copolymer molecules; a monovinyl aromatic monomer is added to the reactor and anionicly polymerized, which is then added to the block copolymer anionic B-(B / A)-A1. (-) Thus, the formula B-(B / A)-A2 is formed. (-) Monovinyl aromatic chain-extended block copolymers with anionic [B-(B / A)-A1] n A mixture of -X-coupled block copolymer molecules; a sufficient amount of proton donor compound or electrophilic monofunctional additive is added to the reactor to terminate the reaction with all remaining block copolymer anions B-(B / A)-A2. (-) .

[0130] In this manner, a bicomponent block copolymer comprising two types of block copolymer molecules, C and U, is produced in situ in a batch reactor: where C is of the general formula [B-(B / A)-A1]. n -X block copolymer, U is a block copolymer of the general formula B-(B / A)-A2; wherein B is a polymer block containing only conjugated diene repeating units; wherein (B / A) is a polymer block containing monovinyl aromatic and conjugated diene repeating units randomly arranged along the polymer block; wherein A1 and A2 are polymer blocks containing only monovinyl aromatic repeating units; wherein the molecular weight of polymer block A2 is greater than the molecular weight of polymer block A1; wherein X is a residue of a coupling agent; wherein n is an integer from 2 to about 30 depending on the coupling agent used; and wherein block copolymer C has a higher molecular weight and a lower content of monovinyl aromatic repeating units than block copolymer U.

[0131] Another embodiment of the present invention is a method for producing novel bicomponent block copolymers, comprising: adding a hydrocarbon solvent, a random agent or a polar modifier, and at least one conjugated diene monomer in any order to a reactor; adding a monofunctional organolithium initiator compound to the reactor and anionicly polymerizing the conjugated diene monomer to achieve a conversion of about 80% to about 95%, thereby forming a copolymer of formula B. (-) The polymer anion; a monovinyl aromatic monomer is added to the reactor, which initially randomly copolymerizes with the remaining conjugated butadiene monomer to generate a block copolymer anion B-(B / A). (-) Continue until the conjugated diene is completely converted, then add only monovinyl aromatic monomers to the block copolymer anion until the monovinyl aromatic monomers are completely converted, thereby forming formula B-(B / A)-A1. (-) The polymer anion; a limited amount of coupling agent is added to the reactor to couple only a portion of the copolymer anion B-(B / A)-A1. (-)This results in the formation of block copolymer anions B-(B / A)-Al. (-) With the formula [B-(B / A)-A1] n A mixture of -X coupled block copolymer molecules; the addition of a limited amount of a proton donor compound or an electrophilic monofunctional compound to the reactor to terminate only part of the block copolymer anion, thereby producing a product having the formula B-(B / A)-A1. (-) Block copolymer anionic, having the formula [B-(B / A)-A1] n A mixture of -X-coupled block copolymer molecules and block copolymers of formula B-(B / A)-A1; a monovinyl aromatic monomer is added to a reactor and anionicly polymerized, and then added to the block copolymer anionic B-(B / A)-A1. (-) Thus, the formula B-(B / A)-A2 is formed. (-) Chain-extended block copolymers, anionic, formula [B-(B / A)-A1] n A mixture of -X-coupled block copolymer molecules and block copolymer molecules of formula B-(B / A)-A1; a sufficient amount of proton donor compound or electrophilic monofunctional additive is added to the reactor to terminate the reaction of all remaining block copolymer anionic B-(B / A)-A2. (-) .

[0132] In this manner, a bicomponent block copolymer comprising two types of block copolymer molecules, C and U, is produced in situ in a batch reactor: where C is of the general formula [B-(B / A)-A1]. n -X block copolymers, U being block copolymers of the general formulas B-(B / A)-A2 and B-(B / A)-A1; wherein B is a polymer block containing only conjugated diene repeating units; wherein (B / A) is a polymer block containing monovinyl aromatic and conjugated diene repeating units randomly arranged along the polymer block; wherein A1 and A2 are polymer blocks containing only monovinyl aromatic repeating units; wherein the molecular weight of polymer block A2 is greater than that of polymer block A1; wherein X is a residue of a coupling agent; wherein n is an integer from 2 to about 30 depending on the coupling agent used; and wherein block copolymer C has a higher molecular weight and a lower content of monovinyl aromatic repeating units than block copolymer U.

[0133] Another embodiment of the present invention is a method for producing novel bicomponent block copolymers, comprising: adding a hydrocarbon solvent, a random agent or a polar modifier, at least one monovinyl aromatic monomer and at least one conjugated diene monomer in any order to a reactor; adding a monofunctional organolithium initiator compound to the reactor to anionicly copolymerize the monovinyl aromatic and conjugated diene monomers to complete conversion, forming the (B / A) formula. (-)The random copolymer anion; a monovinyl aromatic monomer is added to the reactor and anionicly polymerized, and then added to the random copolymer anion (B / A). (-) Thus, the formula (B / A)-A1 is formed. (-) The block copolymer anion; a limited amount of coupling agent is added to the reactor to couple only a portion of the copolymer anion B-(B / A)-A1. (-) This results in the formation of block copolymer anions B-(B / A)-Al. (-) With the formula [B-(B / A)-A1] n A mixture of -X-coupled block copolymer molecules; a monovinyl aromatic monomer is added to the reactor and anionicly polymerized, which is then added to the block copolymer anionic (B / A)-A1. (-) Thus, the formula (B / A)-A2 is formed. (-) The chain-extended block copolymer anionic with formula [(B / A)-A1] n A mixture of -X-coupled block copolymer molecules; a sufficient amount of proton donor compound or electrophilic monofunctional additive is added to the reactor to terminate the reaction with all remaining block copolymer anions (B / A)-A2. (-) .

[0134] In this manner, a bicomponent block copolymer comprising two types of block copolymer molecules, C and U, is produced in situ in a batch reactor: where C is of the general formula [(B / A)-A1]. n -X block copolymer, U is a block copolymer of the general formula (B / A)-A2; wherein (B / A) is a polymer block containing random monovinyl aromatic and conjugated diene repeating units; wherein A1 and A2 are polymer blocks containing only monovinyl aromatic repeating units; wherein the molecular weight of polymer block A2 is greater than that of polymer block A1; wherein X is a residue of a coupling agent; wherein n is an integer from 2 to about 30 depending on the coupling agent used; and wherein block copolymer C has a higher molecular weight and a lower content of monovinyl aromatic repeating units than block copolymer U.

[0135] Another embodiment of the present invention is a method for producing novel bicomponent block copolymers, comprising: adding a hydrocarbon solvent, a random agent or a polar modifier, at least one monovinyl aromatic monomer and at least one conjugated diene monomer in any order to a reactor; adding a monofunctional organolithium initiator compound to the reactor to anionicly copolymerize the monovinyl aromatic and conjugated diene monomers to complete conversion, to form formula (B / A). (-) The random copolymer anion; a monovinyl aromatic monomer is added to the reactor and anionicly polymerized, and then added to the random copolymer anion (B / A). (-)Thus, the formula (B / A)-A1 is formed. (-) The block copolymer anion; a limited amount of coupling agent is added to the reactor to couple only a portion of the copolymer anion (B / A)-A1. (-) This results in the formation of block copolymer anions (B / A)-Al. (-) With the formula [(B / A)-A1] n A mixture of -X coupled block copolymer molecules; the addition of a limited amount of a proton donor compound or an electrophilic monofunctional compound to the reactor to terminate only part of the block copolymer anion, thereby producing a product having the formula (B / A)-A1. (-) Block copolymer anionic, having the formula [(B / A)-A1] n A mixture of -X-coupled block copolymer molecules and block copolymers of formula (B / A)-A1; a monovinyl aromatic monomer is added to the reactor and anionicly polymerized, and then added to the block copolymer anionic (B / A)-A1. (-) Thus, the formula (B / A)-A2 is formed. (-) Chain-extended block copolymers, anionic, formula [(B / A)-A1] n A mixture of -X-coupled block copolymer molecules and block copolymer molecules of formula (B / A)-A1; a sufficient amount of a proton donor compound or an electrophilic monofunctional compound or a mixture of both is added to the reactor to terminate all remaining block copolymer anionic (B / A)-A2. (-) .

[0136] In this manner, a bicomponent block copolymer comprising two types of block copolymer molecules, C and U, is produced in situ in a batch reactor: where C is of the general formula [(B / A)-A1]. n -X block copolymer, U is a block copolymer having the general formula (B / A)-A2 and (B / A)-A1; wherein (B / A) is a random copolymer block containing monovinyl aromatic and conjugated diene repeating units; wherein A1 and A2 are polymer blocks containing only monovinyl aromatic repeating units; wherein the molecular weight of polymer block A2 is greater than that of polymer block A1; wherein X is a residue of a coupling agent; wherein n is an integer from 2 to about 30 depending on the coupling agent used; and wherein block copolymer C has a higher molecular weight and a lower content of monovinyl aromatic repeating units than block copolymer U.

[0137] Another embodiment of the present invention is a method for producing novel bicomponent block copolymers, comprising: adding a hydrocarbon solvent, a random agent or a polar modifier, and at least one conjugated diene monomer in any order to a reactor; adding a monofunctional organolithium initiator compound to the reactor and anionicly polymerizing the conjugated diene monomer to complete conversion, to form a copolymer of formula B.(-) The polymer anion; a monovinyl aromatic monomer is added to the reactor and the monomer is anionicly polymerized, and then added to the polymer anion B. (-) Thus, formula B-A1 is formed. (-) The block copolymer anion; a limited amount of coupling agent is added to the reactor to couple only a portion of the copolymer anion B-A1. (-) This results in the formation of block copolymer anionic B-A1. (-) With equation [B-A1] n A mixture of -X-coupled block copolymer molecules; a monovinyl aromatic monomer is added to the reactor and anionicly polymerized, then added to the block copolymer anionic B-A1. (-) Thus, formula B-A2 is formed. (-) The chain-extended block copolymer anionic with formula [B-A1] n A mixture of -X-coupled block copolymer molecules; a sufficient amount of proton donor compound or electrophilic monofunctional additive is added to the reactor to terminate the reaction with all remaining block copolymer anionic B-A2. (-) .

[0138] In this manner, bicomponent block copolymers comprising two types of block copolymer molecules, C and U, are produced in situ in a batch reactor: where C is of the general formula [B-A1]. n -X block copolymer, U is a block copolymer of general formula B-A2; wherein B is a polymer block containing only conjugated diene repeating units; wherein A1 and A2 are polymer blocks rich in monovinyl aromatic repeating units; wherein the molecular weight of polymer block A2 is greater than that of polymer block A1; wherein X is a residue of a coupling agent; wherein n is an integer from 2 to about 30 depending on the coupling agent used; and wherein block copolymer C has a higher molecular weight and a lower content of monovinyl aromatic repeating units than block copolymer U.

[0139] Another embodiment of the present invention is a method for producing novel bicomponent block copolymers, comprising: adding a hydrocarbon solvent, a random agent or a polar modifier, and at least one conjugated diene monomer in any order to a reactor; adding a monofunctional organolithium initiator compound to the reactor and anionicly polymerizing the conjugated diene monomer to complete conversion, to form a copolymer of formula B. (-) The polymer anion; a monovinyl aromatic monomer is added to the reactor and the monomer is anionicly polymerized, and then added to the polymer anion B. (-) Thus, formula B-A1 is formed. (-) The block copolymer anion; a limited amount of coupling agent is added to the reactor to couple only a portion of the copolymer anion B-A1. (-) This results in the formation of block copolymer anionic B-A1.(-) With equation [B-A1] n A mixture of -X coupled block copolymer molecules; the addition of a limited amount of a proton donor compound or an electrophilic monofunctional compound to the reactor to terminate only part of the block copolymer anion, thereby producing a product having the formula B-A1 (-) The block copolymer anionic, having the formula [B-A1] n A mixture of -X-coupled block copolymer molecules and block copolymers of formula B-A1; a monovinyl aromatic monomer is added to the reactor and anionicly polymerized, and then added to the remaining block copolymer anionic B-A1. (-) Thus, formula B-A2 is formed. (-) Chain-extended block copolymers, anionic, formula [B-A1] n A mixture of -X-coupled block copolymer molecules and block copolymer molecules of formula B-A1; a sufficient amount of a proton donor compound or an electrophilic monofunctional compound or a mixture of both is added to the reactor to terminate all remaining block copolymer anionic B-A2. (-) .

[0140] In this manner, bicomponent block copolymers comprising two types of block copolymer molecules, C and U, are produced in situ in a batch reactor: where C is of the general formula [B-A1]. n -X block copolymer, U is a block copolymer having the general formula B-A2 and B-A1; wherein B is a polymer block containing only conjugated diene repeating units; wherein A1 and A2 are polymer blocks rich in monovinyl aromatic repeating units; wherein the molecular weight of polymer block A2 is greater than that of polymer block A1; wherein X is a residue of a coupling agent; wherein n is an integer from 2 to about 30 depending on the coupling agent used; and wherein block copolymer C has a higher molecular weight and a lower content of monovinyl aromatic repeating units than block copolymer U.

[0141] In some embodiments of the method for obtaining the bicomponent block copolymer of the present invention, a proton donor and / or a monofunctional electrophilic terminator are added prior to the block copolymerization of the last feed of the monovinyl aromatic monomer to deactivate the anionic portion of the block copolymer. This terminator may be added to the reactor before or simultaneously with the last feed of the monovinyl aromatic monomer. Examples of such terminators include water, polymerization inhibitors such as tert-butylcatechol, phenolic antioxidants, alcohols, organic acids, inorganic acids, trimethylsilane, etc.

[0142] Block copolymerization is typically carried out under an inert atmosphere in an inert hydrocarbon solvent with highly purified reagents to prevent premature termination of the polymerization reaction. Suitable solvents for carrying out the present invention include, but are not limited to, pentane, hexane, heptane, octane, decane, cyclopentane, cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, benzene, naphthalene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, n-propylbenzene, isopropylbenzene, n-butylbenzene, etc., or mixtures thereof. Cyclohexane is a preferred solvent of the present invention.

[0143] In some embodiments, a random agent, also known as a polar modifier, is employed to promote the random copolymerization of monovinyl aromatic and conjugated diene monomers to form (B / A) random polymer blocks, and to promote the addition of monovinyl aromatic monomers to polymer anions terminated with conjugated diene lithium units. The random agent also induces 1,2- and 3,4-additions to the anionicly polymerized conjugated dienes. However, the repeating units of the conjugated dienes with 1,2-vinyl and 3,4-vinyl additions are more reactive to the crosslinking / vulcanization reaction. Therefore, an optimal amount of polar modifier compound should be selected to achieve a balance between the copolymerization rate in the process of preparing the bicomponent block copolymer of the present invention and the crosslinking kinetics of the microporous rubber compound of the present invention. The acceleration of block polymerization kinetics and the enrichment of 1,2-vinyl and 3,4-vinyl additions during conjugated diene polymerization vary with the selected polar modifier, a behavior well known to those skilled in the art. Polar modifiers that can be used to produce the bicomponent block copolymers of the present invention include Lewis bases, such as ethers, tertiary amines, amino ethers, and Group IA alkali metal alkoxides, and combinations thereof. Specific examples of these suitable ether polar modifiers include, but are not limited to, monofunctional, polyfunctional, and oligomeric alkyl and cyclic ethers, such as dimethyl ether, diethyl ether, ethyl methyl ether, ethyl propyl ether, di-n-propyl ether, methyl tert-butyl ether, tetrahydrofuran, 1,2-dimethoxyethane, bis(tetrahydrofuran), ditetrahydrofuranpropane (DTHFP), and ethyl tetrahydrofurfuryl ether. Specific examples of suitable tertiary amine polar modifiers include, but are not limited to, monofunctional, polyfunctional, or oligomeric alkyl and cyclic tertiary amines, such as dimethylethylamine, trimethylamine, triethylamine, N,N,N',N'-tetramethylethylenediamine (TMEDA), N,N,N',N'”,N”-pentamethyldiethylenetriamine, 1,3,5-trimethylhexahydro-1,3,5-triazine, and combinations thereof, etc. Specific examples of suitable amino ether polar modifiers include, but are not limited to, tetrahydrofurfuryl-N,N-dimethylamine, bis(2-(dimethylamino)ethyl) ether, 2,2-dimorpholinoethyl ether, and mixtures thereof. Specific examples of suitable Group IA alkali metal alkoxides (lithium, sodium, potassium, rubidium, and cesium salts) include, but are not limited to, monofunctional, multifunctional, and oligomeric alkyl and cyclic metal alkoxides, such as sodium tert-butoxide, sodium tert-amyloxide, sodium menthol, potassium tert-butoxide, potassium tert-amyloxide, potassium menthol, potassium 3,7-dimethyl-3-octanol, and mixtures thereof. The polar modifier can be directly loaded into the reactor or pre-dissolved in the solvent used in the process. In the reaction system of the present invention, the concentration of the polar modifier is 5 to 5000 parts per million parts of solvent, more preferably 10 to 1000 parts per million parts of solvent, and most preferably 20 to 100 parts per million parts of solvent.

[0144] Suitable conjugated diene monomers for preparing the bicomponent block copolymers of the present invention include, but are not limited to, 1,3-butadiene, isoprene, 1,3-pentadiene, methylpentadiene, phenylbutadiene, 2,3-dimethyl-1,3-butadiene, 2,4-hexadiene, 1,3-hexadiene, 1,3-cyclohexadiene, 3,4-dimethyl-1,3-hexadiene, 1,3-octadiene, 4,5-diethyl-1,3-octadiene, and combinations thereof.

[0145] Suitable monovinyl aromatic monomers for preparing the bicomponent block copolymers of the present invention include, but are not limited to, styrene, 3-methylstyrene, α-methylstyrene, p-methylstyrene, α,4-dimethylstyrene, tert-butylstyrene, o-chlorostyrene, 2-butenylnaphthalene, 4-tert-butoxystyrene, 3-isopropenylbiphenyl, 4-vinylpyridine, 2-vinylpyridine, isopropenylnaphthalene, 4-n-propylstyrene, and combinations thereof.

[0146] The bicomponent block copolymers of the present invention are prepared by anionic polymerization of anionic polymerizable monomers with a monofunctional organolithium compound as an initiator. Preferred classes of these compounds can be represented by the formula RLi, where R is a hydrocarbon group selected from aliphatic, alicyclic, and aromatic groups containing 1 to 20 carbon atoms, although initiators with higher molecular weights can be used. Many anionic polymerization initiators are well known and commercially available. Monofunctional organolithium compounds, such as butyllithium, are examples of commonly used initiators. Specific examples of these initiators include methyllithium, ethyllithium, tert-butyllithium, sec-butyllithium, n-butyllithium, n-decyllithium, isopropyllithium, eicosyllithium, cycloalkyllithium compounds such as cyclohexyllithium, and aryllithium compounds such as phenyllithium, naphthiumlithium, p-tolyllithium, 1,1-diphenylhexyllithium, etc. Monofunctional organolithium compounds substituted with protected polar functional groups can also be used as initiators for anionic polymerization.

[0147] In embodiments relating to the method for preparing the bicomponent block copolymer of the present invention, the amount of the monofunctional organolithium initiator varies depending on the desired viscosity of the bicomponent block copolymer and the purity levels of the solvents and monomers used in the method for its preparation. Preferably, in the preparation of the bicomponent block copolymer of the present invention, the amount of the monofunctional organolithium initiator is about 2 mmol to about 30 mmol per kilogram of all conjugated diene monomers plus monovinyl aromatic monomers loaded into the reactor, more preferably about 12 mmol to about 26 mmol per kilogram of all conjugated diene monomers plus monovinyl aromatic monomers loaded into the reactor, and most preferably about 16 mmol to about 22 mmol per kilogram of all conjugated diene monomers plus monovinyl aromatic monomers loaded into the reactor.

[0148] Anionic polymerization is typically carried out in a temperature range of -100°C to 150°C, preferably between 25°C and 120°C. 50 to 90% by weight of the reaction solvent is typically used to control the viscosity within the reaction zone, preferably 70 to 85%. Typical residence time in anionic polymerization varies from 0.1 to 5 hours, preferably 0.2 to 1 hour, depending on the reaction temperature, monomer concentration, and initiator level.

[0149] In embodiments of the method provided by this invention, the anionicly polymerized block copolymer anions undergo partial coupling. Partial coupling refers to the coupling of a portion of the ends of all the anionicly polymerized polymer chains with a coupling agent. The reaction of the ends of the anionicly polymerized block copolymer chains with a suitable coupling agent results in the coupled block copolymer having no anionic active centers for further polymerization. Ideally, the coupling agent couples between 2 to 30 anionicly polymerized polymer chains, although coupling agents capable of coupling a greater number of chains can also be used. Suitable coupling agents for the partial coupling step include, but are not limited to, epoxidized soybean oil, silicon halides, functionalized silicon compounds such as silane compounds, and functionalized oligomers such as those listed in U.S. Patent No. 7,517,934, which is incorporated herein by reference in its entirety. Silicon tetrachloride, methylsilicon trichloride, and dimethylsilicon dichloride are specific examples of suitable coupling agents, with silicon tetrachloride being particularly suitable for this application. Partial coupling is achieved by controlling the stoichiometric ratio of the coupling agent to the active polymer. Partial coupling provides the desired properties for block copolymer blends.

[0150] After the polymerization reaction is complete, the entire reaction mixture is treated to terminate the block copolymer anions and recover the bicomponent block copolymer of the present invention. This termination reaction is accomplished by adding a proton donor compound, such as water, alcohol, or organic or inorganic acid, to the reactor. The amount of terminating agent to be added should be at least a stoichiometric amount corresponding to the amount of block copolymer anions remaining in the reactor.

[0151] An additional step in all embodiments of the method for preparing the bicomponent block copolymer of the present invention is the addition of an antioxidant system while the bicomponent block copolymer is still in a hydrocarbon solution. The antioxidant system prevents the bicomponent block copolymer from degrading in subsequent processing steps, thereby isolating it from the solvent and extending the shelf life of the final product. Various antioxidant systems are well known in the art, and any system can be used without limiting the scope of the invention. A preferred antioxidant system consists of a synergistic blend of hindered phenolic and phosphite antioxidants. Examples of suitable hindered phenolic antioxidants include, but are not limited to, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,4-bis(octylmercapto)-6-(4-hydroxy-3,5-di-tert-butylaniline)-1,3,5-triazine, and 2,4-bis(octylthiomethyl) 6-Methylphenol, 2,4-bis(dodecylthiomethyl)-6-methylphenol, 2-(1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl)-4,6-di-tert-pentylphenyl acrylate, α-tocopherol, and mixtures thereof. Examples of suitable phosphite-type antioxidants include, but are not limited to, tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, butylidene bis[2-tert-butyl-5-methyl-p-phenylene]-P,P,P'. P'-tetra-tetraylbis(phosphine), 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, mixed phosphorous acid 2,4-bis(1,1-dimethylpropyl)phenyltriester and 4-(1,1-dimethylpropyl)phenyltriester, 3,9-bis(octadecoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(isodecoxy)-2 ,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 2-(1,1-dimethylethyl)-6-methyl-4-[3-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphacyclohepten-6-yl]oxy]propyl]phenol, and mixtures thereof. The preferred dosage of the antioxidant system is 0.1 to 1.5 parts per 100 parts by weight of the bicomponent block copolymer of the present invention.

[0152] Another step in all embodiments of the method for preparing the bicomponent block copolymer of the present invention is to separate the bicomponent block copolymer from the solvent by any post-processing technique known in the art, such as roller milling, vacuum-assisted evaporation, precipitation and drying, stripping followed by dehydration and drying, etc.

[0153] An optional step in all embodiments of the method for preparing the bicomponent block copolymer of the present invention is to incorporate an incremental oil into the bicomponent block copolymer. The oil can be added while the bicomponent block copolymer is still in a hydrocarbon solvent solution or at any stage of its post-processing. Suitable oils for oiling include, but are not limited to: mineral oil, paraffin oil, naphthenic oil, relative naphthenic oil, relative aromatic oil, aromatic oil, highly aromatic oil, very highly aromatic oil, etc., or mixtures thereof. The oil content is preferably 0 to 12 parts per 100 parts by weight of the bicomponent block copolymer, more preferably 0 to 10 parts per 100 parts by weight of the bicomponent block copolymer, and most preferably 0 to 8 parts per 100 parts by weight of the bicomponent block copolymer.

[0154] Another aspect of the present invention provides a composition for generating a crosslinked microporous rubber compound, comprising:

[0155] Bicomponent block copolymer;

[0156] Foaming agents, or mixtures of multiple foaming agents; and

[0157] Crosslinking agent or a mixture of multiple crosslinking agents.

[0158] Optionally, the composition comprises other additives, such as styrene-butadiene random copolymers, styrene-isoprene-butadiene random copolymers, natural rubber, polybutadiene, polyisoprene rubber, ethylene / α-olefin / non-conjugated diene terpolymers, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, finely ground cross-linked microporous rubber compounds, fillers, plasticizers, foaming activators, cross-linking activators, cross-linking accelerators, vulcanization inhibitors, antioxidants, anti-ozone agents, ultraviolet stabilizers, light stabilizers, fragrances or flavorings, termite repellents, antimicrobial agents, metal passivators, dyes, pigments, release agents, etc., or mixtures thereof.

[0159] A preferred embodiment of the present invention is a composition for producing a cross-linked microporous compound, comprising:

[0160] (1) A two-component block copolymer, comprising: two types of block copolymer molecules C and U, wherein:

[0161] C represents the general formula [D-(D / A)-A1] n -X block copolymers, where U is a block copolymer of the general formula D-(D / A)-A2 or D-(D / A)-A2 and D-(D / A)-A1.

[0162] D is a polymer block composed of at least one conjugated diene monomer and at least one monovinyl aromatic monomer, wherein the conjugated diene repeating unit has a higher molar content than the monovinyl aromatic repeating unit throughout the polymer block.

[0163] (D / A) is a polymer block made of at least one conjugated diene monomer and at least one monovinyl aromatic monomer, wherein the polymer block end opposite to A1 or A2 is mainly composed of conjugated diene repeating units, and its composition gradually changes along its length until it becomes substantially composed of monovinyl aromatic repeating units toward its end adjacent to A1 or A2.

[0164] A1 and A2 are polymer blocks made solely of monovinyl aromatic monomers, wherein the molecular weight of polymer block A2 is greater than that of polymer block A1.

[0165] X is a residue of the coupling agent;

[0166] n is an integer with a value between 2 and 30; and

[0167] The amount of the two-component block copolymer is 50 to 100 parts per 100 parts by weight of polymer raw material contained in the formulation, in order to produce a cross-linked microporous rubber compound.

[0168] (2) A mixture of foaming agents or chemical foaming agents, used in an amount of 1 to 10 parts per 100 parts by weight of polymeric raw material contained in the formulation, to produce a cross-linked microporous rubber compound; and

[0169] (3) A crosslinking agent or a mixture of crosslinking agents, used in an amount of 0.5 to 5 parts per hundred parts by weight of polymeric raw material contained in the formulation, to produce a crosslinked microporous rubber compound.

[0170] The composition may contain one or more optional additives, such as:

[0171] Other polymers, including styrene-butadiene random copolymers, styrene-isoprene-butadiene random copolymers, natural rubber, polybutadiene, polyisoprene rubber, ethylene / α-olefin / non-conjugated diene terpolymers, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, or any mixtures thereof, wherein such polymers preferably comprise 0 to about 50 parts per hundred parts by weight of polymer feedstock in the formulation to produce a crosslinked microporous rubber compound;

[0172] A mixture of filler or filler or rubber vulcanizing compound powder, preferably 0 to about 200 parts per hundred parts by weight of polymer raw material contained in the formulation, to produce a cross-linked microporous rubber compound.

[0173] Plasticizer or mixture of plasticizers, in amounts of 0 to 40 parts per hundred parts by weight of polymer raw material contained in the formulation, to produce a cross-linked microporous rubber compound;

[0174] Antioxidant or mixture of antioxidants, preferably in an amount of 0 to 2 parts per 100 parts by weight of polymeric raw material contained in the formulation, to produce a cross-linked microporous rubber compound;

[0175] A mixture of foaming agent activator or chemical foaming agent accelerator, used in an amount of 0 to 5 parts per 100 parts by weight of polymer raw material contained in the formulation, to produce a cross-linked microporous rubber compound.

[0176] The crosslinking agent activator or mixture of crosslinking agents activators is preferably 0 to 5 parts per 100 parts by weight of polymer raw material contained in the formulation, to produce a crosslinked microporous rubber compound.

[0177] A crosslinking accelerator or mixture of crosslinking accelerators, preferably in an amount of 0 to 5 parts per 100 parts by weight of polymerizing raw material contained in the formulation, to produce a crosslinked microporous rubber compound; and

[0178] Other additives, such as sulfurization inhibitors, anti-ozone agents, UV stabilizers, light stabilizers, fragrances or flavorings, termite inhibitors, antimicrobial agents, metal passivators, dyes, pigments, release agents, and mixtures thereof.

[0179] Another preferred embodiment of the present invention is a composition for preparing cross-linked microporous compounds, comprising:

[0180] (1) A two-component block copolymer comprising two types of block copolymer molecules, C and U, wherein the general formula of block copolymer C is [B-(B / A)-A1]. n -X, and the general formula of the block copolymer U is B-(B / A)-A2, or B-(B / A)-A2 and B-(B / A)-A1, wherein B is a copolymer block made only of one or more conjugated dienes, wherein (B / A) is a polymer block made of at least one conjugated diene monomer and at least one monovinyl aromatic monomer, wherein the conjugated diene and monovinyl aromatic repeating units are randomly arranged along the polymer block, wherein A1 and A2 are polymer blocks made only of monovinyl aromatic monomers, wherein the molecular weight of polymer block A2 is greater than the molecular weight of polymer block A1, wherein X is a residue of the coupling agent, wherein n is an integer value from 2 to 30, wherein the amount of the two-component block copolymer is 50 to 100 parts per 100 parts by weight of polymeric raw material contained in the formulation to produce a crosslinked microporous rubber compound;

[0181] (2) A mixture of foaming agents or chemical foaming agents, preferably in an amount of 1 to 10 parts per 100 parts by weight of polymeric raw material contained in the formulation, to produce a cross-linked microporous rubber compound; and

[0182] (3) A crosslinking agent or a mixture of crosslinking agents, preferably 0.5 to 5 parts per 100 parts by weight of polymer raw material contained in the formulation, to produce a crosslinked microporous rubber compound.

[0183] The composition may contain one or more optional additives, such as:

[0184] Other polymers, including styrene-butadiene random copolymers, styrene-isoprene-butadiene random copolymers, natural rubber, polybutadiene, polyisoprene rubber, ethylene / α-olefin / non-conjugated diene terpolymers, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, or any mixtures thereof, wherein such polymers are preferably contained in 0 to 50 parts per 100 parts by weight of polymer feedstock in the formulation to produce a crosslinked microporous rubber compound;

[0185] A mixture of filler or filler or rubber vulcanizing compound powder, preferably 0 to 200 parts per hundred parts by weight of polymer raw material contained in the formulation, to produce a cross-linked microporous rubber compound.

[0186] Plasticizer or mixture of plasticizers, in an amount of 0 to 40 parts per 100 parts by weight of polymeric raw material contained in the formulation, to produce a cross-linked microporous rubber compound.

[0187] Antioxidant or mixture of antioxidants, preferably in an amount of 0 to 2 parts per 100 parts by weight of polymeric raw material contained in the formulation, to produce a cross-linked microporous rubber compound.

[0188] A mixture of foaming agent activator or chemical foaming agent accelerator, preferably 0 to 5 parts per 100 parts by weight of polymer raw material contained in the formulation, to produce a cross-linked microporous rubber compound.

[0189] The crosslinking agent activator or mixture of crosslinking agents activators is preferably 0 to 5 parts per 100 parts by weight of polymer raw material contained in the formulation, to produce a crosslinked microporous rubber compound.

[0190] A crosslinking agent accelerator or a mixture of crosslinking agents accelerators, preferably in an amount of 0 to 5 parts per 100 parts by weight of polymerizing raw material contained in the formulation, to produce a crosslinked microporous rubber compound; and

[0191] Other additives, such as sulfurization inhibitors, anti-ozone agents, UV stabilizers, light stabilizers, fragrances or flavorings, termite inhibitors, antimicrobial agents, metal passivators, dyes, pigments, release agents, and mixtures thereof.

[0192] Another preferred embodiment of the present invention is a composition for preparing cross-linked microporous compounds, comprising:

[0193] (1) A two-component block copolymer comprising two types of block copolymer molecules, C and U, wherein the general formula of block copolymer C is [B-A1]. n -X, and the general formula of the block copolymer U is B-A2, or B-A2 and B-A1; B is a polymer block made of one or more conjugated diene monomers; A1 and A2 are polymer blocks made of only monovinyl aromatic monomers; the molecular weight of polymer block A2 is greater than the molecular weight of polymer block A1; X is a residue of the coupling agent; and n is an integer from 2 to 30, preferably the amount of the two-component block copolymer is 50 to 100 parts per 100 parts by weight of polymeric raw material in the formulation, to produce a crosslinked microporous rubber compound;

[0194] (2) A mixture of foaming agents or chemical foaming agents, preferably in an amount of 0 to 10 parts per 100 parts by weight of polymer raw material in the formulation; and

[0195] (3) A crosslinking agent or a mixture of crosslinking agents, preferably in an amount of 0.5 to 5 parts per 100 parts by weight of polymer raw material in the formulation.

[0196] Other polymers may be added to the formulation, such as: styrene-butadiene random copolymer, styrene-isoprene-butadiene random copolymer, natural rubber, polybutadiene, polyisoprene rubber, ethylene / α-olefin / non-conjugated diene terpolymer, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, and any mixture thereof, wherein such polymer is preferably contained in 0 to about 50 parts per 100 parts by weight of polymer raw material in the formulation to produce a crosslinked microporous rubber compound.

[0197] Additives that may be added to the polymer raw materials in the formulation to produce cross-linked microporous rubber compounds include:

[0198] The filler or mixture of fillers or compound powder for rubber vulcanization, preferably in an amount of 0 to about 200 parts per 100 parts by weight;

[0199] Plasticizer or mixture of plasticizers, preferably in an amount of 0 to 40 parts per 100 parts by weight;

[0200] Antioxidant or mixture of antioxidants, preferably in an amount of 0 to 2 parts per 100 parts by weight;

[0201] A mixture of foaming agent activator and / or chemical foaming agent accelerator, preferably in an amount of 0 to about 5 parts per 100 parts by weight;

[0202] The crosslinking agent activator or a mixture of crosslinking agents activators is preferably 0 to 5 parts per 100 parts by weight;

[0203] A crosslinking accelerator or a mixture of crosslinking accelerators, preferably in an amount of 0 to 5 parts per 100 parts by weight; and

[0204] Other additives, such as vulcanization inhibitors, anti-ozone agents, UV stabilizers, light stabilizers, fragrances or flavorings, termite inhibitors, antimicrobial agents, metal passivators, dyes, pigments, release agents, and mixtures thereof.

[0205] Another preferred embodiment of the present invention is a composition for preparing crosslinked microporous compounds, comprising: a two-component block copolymer; a foaming agent; and a crosslinking agent. The two-component block copolymer comprises block copolymers C and U, wherein:

[0206] The general formula for block copolymer C is [(B / A)-A1]. n -X, and the general formula of the block copolymer U is (B / A)-A2, or (B / A)-A2 and (B / A)-A1;

[0207] (B / A) is a polymer block made of at least one conjugated diene monomer and at least one monovinyl aromatic monomer, preferably wherein the conjugated diene repeating unit and the monovinyl aromatic repeating unit are randomly arranged along the polymer block;

[0208] A1 and A2 are polymer blocks made solely of monovinyl aromatic monomers, wherein the molecular weight of polymer block A2 is greater than that of polymer block A1.

[0209] X is a residue of the coupling agent; and

[0210] n is an integer from 2 to 30, and preferably the amount of the bicomponent block copolymer is 50 to 100 parts per 100 parts by weight of the polymeric raw material contained in the formulation, to produce a crosslinked microporous rubber compound. The amount of foaming agent added is preferably 1 to 10 parts per 100 parts by weight, and the amount of crosslinking agent added is preferably 0.5 to 5 parts per 100 parts by weight.

[0211] To generate cross-linked microporous rubber compounds, the optional components in the formulation, relative to 100 parts by weight of polymer raw material, include:

[0212] Other polymers, such as: styrene-butadiene random copolymers, styrene-isoprene-butadiene random copolymers, natural rubber, polybutadiene, polyisoprene rubber, ethylene / α-olefin / non-conjugated diene terpolymers, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, and any mixtures thereof, preferably in amounts from 0 to 50 parts.

[0213] The filler or mixture of fillers or compound powder for rubber vulcanization is preferably 0 to about 200 parts;

[0214] The amount of plasticizer or mixture of plasticizers is preferably 0 to 40 parts;

[0215] Antioxidant or mixture of antioxidants, preferably in an amount of 0 to 2 parts;

[0216] A mixture of foaming agent activator or chemical foaming agent accelerator, preferably in an amount of 0 to about 5 parts;

[0217] The crosslinking agent activator or a mixture of crosslinking agents activators is preferably 0 to 5 parts per 100 parts by weight;

[0218] A crosslinking accelerator or a mixture of crosslinking accelerators, preferably in an amount of 0 to 5 parts; and

[0219] Other additives, such as vulcanization retarders; anti-ozone agents; UV stabilizers; light stabilizers; fragrances or flavorings; termite repellents; bactericides; antifungal agents; antimicrobial agents; antibacterial agents; metal passivators; dyes; pigments; release agents, etc., and mixtures thereof.

[0220] Suitable fillers in the crosslinked microporous rubber foam compositions used in this invention include, but are not limited to, carbon black, silica, calcium silicate, aluminum silicate, magnesium silicate, sodium silicate, potassium silicate, chalk, dolomite, kaolin, calcined clay, hard clay, activated clay, halloysite, sericite, wollastonite, bentonite, light calcium carbonate, heavy calcium carbonate, magnesium carbonate, talc, diatomaceous earth, titanium dioxide, zinc oxide, calcium oxide, aluminum hydroxide, magnesium hydroxide, gypsum, mica, barium sulfate, calcium sulfate, alumina trihydrate, natural fibers, synthetic fibers, and combinations thereof.

[0221] Plasticizers suitable for use in the crosslinked microporous rubber foam compositions of the present invention include, but are not limited to, mineral oils (e.g., paraffin oils), naphthenic oils, relative naphthenic oils, relative aromatic oils, aromatic oils, highly aromatic oils, and extremely aromatic oils; alkanes, such as unbranched alkanes, isoalkanes, ceresin waxes, isoceresin waxes, paraffin waxes, and other mineral waxes; petroleum distillation residues, such as lignite wax, ceresin waxes, asphaltenes, tar, and bitumen; fatty acids, such as stearic acid or palmitic acid; and fatty acid metal salts, such as zinc soaps of unsaturated fatty acids, zinc soaps of saturated fatty acids, calcium soaps of unsaturated fatty acids, zinc stearate, and stearic acid. Calcium; monoesters of organic acids, such as alkyl or alkoxyalkyl oleates and stearates; diesters of organic acids, such as dialkyl, dialkoxyalkyl and alkylaryl phthalates, terephthalates, sebates, adipates and glutarates; coumarones and indene resins; trialkyl, trialkoxyalkyl, alkyl diaryl and triaryl phosphates; polyol esters of fatty acids, such as pentaerythritol tetrastearate; castor oil, linseed oil, rapeseed oil, coconut oil, palm oil, soybean oil, epoxidized soybean oil, tall oil, pine tar, beeswax, carnauba wax, lanolin, oleogloss and combinations thereof.

[0222] Antioxidants suitable for use in the crosslinked microporous rubber foam compositions of the present invention include, but are not limited to, hindered phenols, such as 2,6-di-tert-butyl-p-cresol (BHT), 2,4-dimethyl-6-tert-butylphenol, 2,4-dimethyl-6-(α-methyl-cyclohexyl)-phenol, 4-methoxymethyl-2,6-di-tert-butylphenol, the butylation product of p-cresol with dicyclopentadiene, alkylated phenols, stylated and alkylated phenols, stylated phenols (SPH), pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 2-(1,1-dimethylethyl)-6-[3-(1,1-dimethylethyl)-2-hydroxy-5-methylphenyl]methyl]-4-methylphenyl acrylate; bisphenols, such as 2,2'-methylenebis-(4-methyl) 2,2'-Methylenebis(4-methyl-6-cyclohexylphenol) (BPH), 2,2'-isobutylenebis(4,6-dimethylphenol) (IBPH), 2,2'-dicyclopentylbis(4-methyl-6-tert-butylphenol) (DBPH), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol); benzimidazole derivatives, such as 2-mercaptobenzimidazole (MBI), 4-methyl-2-mercaptobenzimidazole and 5-methyl-2-mercaptobenzimidazole (MMBI), zinc salt of 2-mercaptobenzimidazole (ZMBI), zinc salt of 4-methyl-2-mercaptobenzimidazole and 5-methyl-2-mercaptobenzimidazole (ZMMBI).

[0223] The foaming agents suitable for use in the crosslinked microporous rubber foam compositions of the present invention include, but are not limited to: organic chemical foaming agents, such as azodicarbonamide (ADC), N,N'-dinitrospentamethylenetetramine (DNPT), benzenesulfonyl hydrazine (BSH), benzene-1,3-disulfonyl hydrazine, 4,4'-oxobis(benzenesulfonyl hydrazine), p-toluenesulfonyl hydrazine, toluenesulfonamide, 5-phenyltetrazole, trihydrazine; inorganic chemical foaming agents, such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, potassium bicarbonate, potassium carbonate; and physical foaming agents, such as high-pressure nitrogen or supercritical carbon dioxide, and combinations thereof.

[0224] Chemical foaming agents and activators suitable for use in the crosslinked microporous rubber foam compositions of the present invention include, but are not limited to: zinc oxide, zinc benzenesulfonate, zinc stearate, zinc 2-ethylhexanoate, zinc carbonate, zinc xylenesulfonate, calcium carbonate, calcium oxide, magnesium oxide, silicon dioxide, urea, stearic acid, adipic acid, triethanolamine, diphenylamine derivatives, and combinations thereof.

[0225] The crosslinking agents suitable for the crosslinked microporous rubber foam compositions of the present invention include, but are not limited to, sulfur; sulfur donors, such as dithiodimorpholine (DTDM), caprolactam disulfide, N,N'-dithiobis(hexahydro-2H-azaphenone) (CLD), 2-morpholinodithiobenzothiazole (MBSS), tetrasulfide bis(pentylthiuram) (DPTT), N-oxodiethylenedithiocarbamoyl-N'-oxodiethylenesulfonamide (OTOS), and tetramethylthiuram disulfide (TMTD); and organic peroxides, such as dicumyl peroxide, tert-butyl peroxide, etc. Tert-butylcumyl oxide, di-tert-butyl peroxide, lauroyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, α,α'-bis(tert-butylperoxy)-1,3-diisopropylbenzene, α,α'-bis(tert-butylperoxy)-1,4-diisopropylbenzene, n-butyl-4,4-bis(tert-butylperoxy)valerate, tert-butylperoxyisopropyl carbonate, 1,4-bis(tert-butylperoxyisopropyl)benzene, di-tert-pentyl peroxide, tert-butyl peroxybenzoate, tert-pentyl peroxybenzoate, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, etc., or mixtures thereof.

[0226] The crosslinking accelerators suitable for use in the crosslinked microporous rubber foam compositions of the present invention include, but are not limited to, thiol accelerators, such as 2-mercaptobenzothiazole (MBT), dibenzothiazole disulfide (MBTS), and zinc 2-mercaptobenzothiazole (ZMBT); sulfonamide accelerators, such as N-cyclohexyl-2-benzothiazole sulfinamide (CBS), N-tert-butyl-2-benzothiazole sulfinamide (TBBS), and 2-benzothiazole-N-sulfoxide morpholine (MBS); and thiuram accelerators, such as tetramethylthiuram disulfide (TMTD), tetramethylthiuram monosulfide (TMTM), and tetraethylthiuram disulfide. (TETD); dithiocarbamate accelerators, such as zinc dimethyl dithiocarbamate (ZDMC), zinc diethyl dithiocarbamate (ZDEC), and zinc dibutyl dithiocarbamate (ZDBC); dithiocarbamylsulfenamide accelerators, such as N-oxydiethylenedithiocarbamate-N'-oxydiethylenesulfenamide (OTOS); guanidine accelerators, such as diphenylguanidine (DPG), di-o-tolylguanidine (DOTG), and o-tolyl biguanide (OTBG); triazine accelerators; xanthate ester accelerators; aldehyde-amine accelerators; amine accelerators; thiourea accelerators; dithiophosphate accelerators; and mixtures thereof.

[0227] The crosslinking agents and activators in the crosslinked microporous rubber foam compositions applicable to the present invention include, but are not limited to, zinc oxide, magnesium oxide, Ca(OH)2, stearic acid, zinc stearate, zinc laurate, dibutylamino oleate, diphenylguanidine 1,3-phthalate, monoethanolamine, diethanolamine, triethanolamine, dibutylamine, dibenzylamine, and mixtures thereof.

[0228] Another aspect of the present invention provides a composition for producing a hot melt pressure-sensitive adhesive, comprising:

[0229] Bicomponent block copolymer;

[0230] Tackifying resins; and

[0231] Increasing oil or plasticizer; and

[0232] Antioxidants.

[0233] Optionally, the hot melt pressure-sensitive adhesive composition contains other additives such as: fillers, waxes, photoinitiators, crosslinking agents, crosslinking aids, crosslinking inhibitors, tackifiers or coupling agents, UV stabilizers, light stabilizers, ozone stabilizers, epoxy resins, bitumen, reinforcing resins, fragrances or flavorings, termites, biocides, antifungals, antimicrobials, metal passivators, dyes, pigments, colorants, flame retardants, foaming agents, foaming agent activators or refractive index modifiers.

[0234] A preferred embodiment of the present invention comprises a hot melt pressure-sensitive adhesive composition including the following:

[0235] (a) about 20% by weight to about 50% by weight of a bicomponent block copolymer having a molecular weight distribution showing at least two fully or partially resolved peaks and containing C and U, wherein

[0236] C is encompassed by the peaks with higher molecular weights in the molecular weight distribution of the bicomponent block copolymer, and includes coupled block copolymer molecules of the following formula:

[0237] [D-(D / A)-A1] n -X; or

[0238] [B-(B / A)-A1] n -X; or

[0239] [(B / A)-A1] n -X; or

[0240] [B-A1] n -X, or a mixture of the above, and wherein

[0241] U is encompassed by one or more of the remaining low molecular weight peaks in the molecular weight distribution of the bicomponent block copolymer, and includes uncoupled block copolymer molecules of the following formula:

[0242] D-(D / A)-A2 or D-(D / A)-A2 and D-(D / A)-A1; or

[0243] B-(B / A)-A2 or B-(B / A)-A2 and B-(B / A)-A1; or

[0244] (B / A)-A2 or (B / A)-A2 and (B / A)-A1; or

[0245] B-A2 or B-A2 and B-A1, or a mixture of the above, wherein

[0246] B is a polymer block made solely of conjugated diene monomers, in which

[0247] (B / A) is a random polymer block composed of at least one conjugated diene monomer and at least one monovinyl aromatic monomer, wherein

[0248] D is a polymer block composed of at least one conjugated diene monomer and at least one monovinyl aromatic monomer, wherein the conjugated diene repeating unit has a higher molar content than the monovinyl aromatic repeating unit along the entire length of the polymer block.

[0249] (D / A) is a polymer block made of at least one conjugated diene monomer and at least one monovinyl aromatic monomer, wherein the polymer block end opposite to A1 or A2 is mainly composed of conjugated diene repeating units, wherein the composition of the polymer block gradually changes along the block length until it becomes that the end adjacent to A1 or A2 is basically composed of monovinyl aromatic repeating units.

[0250] A1 and A2 are polymer blocks made solely of monovinyl aromatic monomers, wherein the molecular weight of polymer block A2 is greater than that of polymer block A1.

[0251] X is a residue of the coupling agent, and in which

[0252] n is an integer with a value between 2 and 30;

[0253] (b) about 30% by weight to about 70% by weight of tackifier resin;

[0254] (c) From about 10% by weight to about 30% by weight of incremental oil or plasticizer;

[0255] (d) About 0.05% by weight to about 3.0% by weight of antioxidants;

[0256] (e) Optional other additives, such as: fillers, waxes, photoinitiators, crosslinking agents, crosslinking aids, crosslinking inhibitors, tackifiers or coupling agents, UV stabilizers, light stabilizers, ozone stabilizers, epoxy resins, bitumen, reinforcing resins, fragrances or flavorings, termites, biocides, antifungals, antimicrobials, metal passivators, dyes, pigments, colorants, flame retardants, foaming agents, foaming agent activators or refractive index modifiers.

[0257] The tackifying resins suitable for the hot melt pressure-sensitive adhesive formulations of the present invention include, but are not limited to: rosin esters, such as... RE100L RE115、 RE85L, 85. 105. H and 3100; Styrated terpenes, such as ZT5100 ZT105LT and ZT115LT; Polyterpene resin, such as TR1100 and TR7115; Terpene phenolic plastics, such as... TP2040 and TP115; aliphatic hydrocarbon resins, such as 1100 115 and 95; hydrogenated hydrocarbon resins, such as 1094 H100 and H130. and Terpene phenol resins; synthetic C5 resins; alkyl-aryl resins; phenolic resins; and mixtures thereof. Tackifier resins are available from Kraton. and The tackifier is available from Eastman Chemical Company. The tackifier is available from Total Cray Valley.

[0258] The incremental oils used in the hot melt pressure-sensitive adhesive formulations applicable to the present invention include, but are not limited to: mineral oil; naphthenic oil; paraffin oil; aromatic oil; vegetable oil; animal oil, etc., and mixtures thereof.

[0259] Plasticizers suitable for use in the hot melt pressure-sensitive adhesive formulations of the present invention include, but are not limited to: olefin oligomers; epoxidized oils; phthalates, such as dioctyl phthalate, diisodecyl phthalate, diisononyl phthalate; aliphatic dicarboxylic acid dialkyl esters; polybutene or polyisobutylene with a molecular weight of less than 3000, etc., and mixtures thereof.

[0260] Antioxidants suitable for use in the hot melt pressure-sensitive adhesive formulations of the present invention include, but are not limited to, phenolic antioxidants, such as... 1010 1076、 565、 1520 1098 20 or 276; Phosphite antioxidants, such as: TNPP, 240. 626 or 618F; Thioester antioxidants, such as DSTDP; and their mixtures, such as 877A. Antioxidants are available from BASF; and Antioxidants are available from Addivant.

[0261] Example

[0262] The following examples are provided to illustrate the features of the invention and are not intended to limit its scope. Comparative examples used in the prior art are included for reference. The bicomponent block copolymers synthesized in the following examples and comparative examples, as well as prior art copolymers, were characterized by proton nuclear magnetic resonance (¹H-NMR or proton NMR) using a 300 MHz Bruker Fourier 300 spectrometer to quantify the total styrene repeating unit content and the block styrene content. The total styrene repeating unit content in the block copolymer was measured as shown in International Standard ISO 21561-1. In the following examples, the total styrene repeating unit content is reported as a weight percentage of the total weight of the block copolymer. The measurement of the block styrene content indicates the number of styrene repeating units introduced as homopolymer blocks; that is, the number of styrene repeating units that form part of a given block copolymer and are not covalently linked to the conjugated diene monomer. The block styrene content was measured by proton NMR as reported in US 9,771,473 B2. In the following examples, the block styrene content is reported as a weight percentage of the total weight of the block copolymer. Since styrene is the only monovinyl aromatic monomer used in these embodiments, the total content (%A) of monovinyl aromatic repeating units is... t The quantity corresponds to the total styrene content measured in the examples. Similarly, in these examples, the blockiness of the monovinyl aromatic repeating unit is calculated based on the quotient of the block styrene and the quotient of the total styrene content, and is reported as a molar percentage in terms of the monovinyl aromatic repeating unit.

[0263] Gel permeation chromatography (GPC) was performed using a tandem differential refractive index detector and a diode array detector on a Waters Alliance e2695 HPLC system connected to a three-column array to cover a molecular weight measurement range from 1,000 to 4,000,000 g / mol and to include narrow MWD polystyrene standards. In GPC-RI mode, the molecular weight distribution and weight-average molecular weight (Mb) of the different block copolymers analyzed were measured using the signal from the differential refractive index detector and a universal calibration curve of molecular weight versus elution time constructed from narrow MWD polystyrene standards. w ), and the polydispersity index of molecular weight distribution (the ratio of weight-average molecular weight to number-average molecular weight, M w / M n GPC-RI is also used to quantify the amount (%C) of coupling block copolymers by integrating the peak with the highest molecular weight. riThe percentage of the total GPC-RI molecular weight distribution of the analyzed block copolymer when multiple peaks appear in the molecular weight distribution is reported. In GPC-UV mode, the signal of the diode array detector at a wavelength of 261 nm responds only to the number of monovinyl aromatic repeating units in the block copolymer, and the monovinyl aromatic repeating unit-weighted coupling block copolymer content (%C) is measured using a universal molecular weight calibration curve involving narrow MWD polystyrene standards. uv ); %C is obtained by integrating the highest molecular weight peak in the weighted molecular weight distribution of monovinyl aromatic repeating units. uv It is reported as the percentage of the weighted molecular weight distribution of the entire GPC-UV monovinyl aromatic repeating unit when multiple peaks appear in the molecular weight.

[0264] Then, %A was obtained using proton NMR. t (i.e., total styrene content), %C obtained from GPC-RI ri %C obtained from GPC-UV uv Used to calculate the weight percentage (%A) of monovinyl aromatic repeating units in the uncoupled portion of the block copolymer. U And used to calculate the weight percentage (%) of monovinyl aromatic repeating units in the coupling portion of block copolymers. C Finally, these were used to calculate the compositional difference %CD between the uncoupled and coupled portions of the block copolymer, as shown below:

[0265]

[0266]

[0267] %CD = %A U -%A C

[0268] The viscoelastic properties of the block copolymers prepared in the examples were evaluated using an RPA2000 instrument from Alpha Technologies. Oscillatory shear measurements were performed at 13.95% of maximum strain at temperatures of 100°C or 140°C. Composite dynamic shear viscosity (η*) was reported at oscillation frequencies of 0.99 and 100 rad / s, while Tanδ was reported at several oscillation frequencies ranging from 0.25 to 200 rad / s. Mooney viscosity (ML 1+4) was determined at 100°C using a Monsanto Mooney MV 2000 instrument in accordance with ASTM D1646.

[0269] Embodiment 1 of the present invention:

[0270] Synthesis of a two-component block copolymer; preparation of a prototype using silicon tetrachloride as a coupling agent. Under a nitrogen atmosphere and with stirring, 0.896 kg of cyclohexane, 0.042 kg of styrene, and 0.105 kg of butadiene were added to a 2-liter reactor. The initial reactor feed was heated to 74.0 °C, and then 2.845 mmol of n-butyllithium was added to the reactor. The polymerization of the first monomer feed reached a peak temperature of 110.8 °C. After a 1-minute wait, 0.188 mmol of silicon tetrachloride coupling agent was added to the reactor. After a 5-minute wait, 0.028 kg of styrene was added to the reactor; during this feed, the reactor temperature temporarily dropped to 91.6 °C. Due to the heat of polymerization of the second styrene feed, the reaction reached a peak temperature of 94.7 °C. After a 1-minute wait, 1.782 mmol of a monofunctional alcohol was added to the reactor to terminate the polymer anionization. Table 1 shows the specific formulation and polymerization conditions of this two-component block copolymer synthesis example. Then, 0.5 phr of phenolic antioxidant and 0.6 phr of phosphite antioxidant were added to the rubber solution. The block copolymer was recovered by roller milling. The weight-average molecular weight (M) of the synthesized bicomponent block copolymer was... w The molecular weight was 169.8 kg / mol. The molecular weight distribution exhibited a polydispersity index of 1.26. The molecular weight distribution of the block copolymers showed two peaks: a low molecular weight peak corresponding to the uncoupled linear graded block copolymer of formula D-(D / A)-A2, and a peak corresponding to the coupled graded styrene-butadiene block copolymer [D-(D / A)-A1]. n＝2-4 -Si high molecular weight peak. The content (%C) of the coupled graded block copolymer was determined by GPC-RI. ri This represents 27.4% of the total molecular weight distribution of the block copolymer. The weighted coupling level (%C) of the monovinyl aromatic repeating units, as measured by GPC-UV, is... uv The content of monovinyl aromatic repeating units in the bicomponent block copolymer was 22.0%. The total styrene repeating unit content was 40.0% by weight, while the block styrene content was 31.8% by weight. Therefore, the blockiness of the monovinyl aromatic repeating units in the bicomponent block copolymer was 79.5 mol%. The content of monovinyl aromatic repeating units in the coupled graded block copolymer moiety (%A) was revealed by calculations using coupling levels determined by GPC-RI and GPC-UV and total styrene content determined by proton NMR. C The content was 32.2 wt%, while the content (%A) in the uncoupled graded block copolymer portion was... UThe content of the monovinyl aromatic repeating unit was 42.9 wt%. The component difference (%CD) between the uncoupled and coupled graded block copolymer portions was 10.7%. Specific GPC and NMR characterizations of this bicomponent block copolymer are described in Table 2. The composite dynamic shear viscosity of the bicomponent block copolymer was 76198 Pa⁻² at an oscillation frequency of 0.99 rad / s, decreasing to 4744 Pa⁻² when evaluated at an oscillation frequency of 100 rad / s. The Tanδ of the bicomponent block copolymer revealed its predominantly elastic behavior (Tanδ < 1.00) across the entire frequency sweep from 0.25 to 200 rad / s, with a maximum of 0.81 (Tanδ < 1.00) at 2.51 rad / s. max Details of the rheological characteristics of this bicomponent block copolymer are shown in Table 3.

[0271] Embodiments of the present invention

[0272] As used in the specification and claims of this invention, the term "bicomponent block copolymer" or "bicomponent block copolymers" (DCBC) refers to a polymer blend comprising two block copolymer molecules that differ from each other in molecular weight, block arrangement, and the content of monovinyl aromatic repeating units. For example... Figure 9 The molecular weight distribution with two peaks shown in Comparative Example C-2 does not alone satisfy the properties required for DCBC. According to the present invention, DCBC also requires various other properties. Aspects to be considered for DCBC include: a high content of monovinyl aromatic repeating units in the uncoupled portion; coupling agents connecting the internal monovinyl aromatic homopolymer blocks; a defined coupling range; a defined range of total monovinyl aromatic repeating unit content; a defined conjugated diene block structure; a Mooney viscosity range; a composite viscosity range; and a Tanδ distribution, although all of these aspects are not required to define a bicomponent block copolymer according to the present invention. Some embodiments of methods for preparing DCBC are provided below. The claims filed with respect to the invention are incorporated herein by reference to ensure clear textual support for the claims within this specification.

[0273] 1. A method for preparing a bicomponent block copolymer, comprising the following steps:

[0274] Solvents such as cyclohexane, monovinyl aromatic monomers such as styrene, and conjugated diene monomers such as butadiene are added to the batch reactor to provide the initial contents [for alternative embodiments, random agents or polar modifiers may be added or not];

[0275] [In an alternative embodiment, only the conjugated diene monomer is initially added without the addition of the monovinyl aromatic monomer, and all or part of it is converted.]

[0276] Mix and heat the initial contents;

[0277] Add n-butyllithium or a similar lithium initiator to the reactor;

[0278] The initial contents polymerize to form polymeric anions;

[0279] The polymer anions are partially coupled by adding a coupling agent such as silicon tetrachloride or methylsilyl trichloride to the reactor, preferably waiting for less than 10 minutes, more preferably less than about 1 minute;

[0280] [In another embodiment, the polymerization of the anion is partially terminated at this stage.]

[0281] Add additional monovinyl aromatic monomers, such as styrene, to the reactor;

[0282] [The same or different monovinyl aromatic monomers can be used]

[0283] A terminator, such as a monofunctional alcohol, is added to the reactor to terminate the polymerization of anions.

[0284] Preferably, antioxidants, such as phenolic antioxidants and / or phosphite antioxidants, are added to the reactor; and

[0285] Block copolymers can be recovered using any method known in the art, such as steam stripping-dehydration-drying, direct solvent removal, vacuum-assisted solvent removal, etc.

[0286] 2. According to the method of Embodiment 1, the weight-average molecular weight (M) of the synthesized bicomponent block copolymer is... w The concentration is 70 kg / mol to 500 kg / mol, preferably 120 kg / mol to 230 kg / mol, more preferably 150 kg / mol to 180 kg / mol, and one example is 169.8 kg / mol.

[0287] 3. According to the method of embodiment 1 or 2, the molecular weight distribution of the two-component block copolymer has two peaks and a polydispersity index between 1.00 and 1.90, preferably between 1.10 and 1.40, more preferably between 1.20 and 1.33, and the polydispersity index value of a particular example is 1.26.

[0288] 4. According to the method of embodiment 3, one of the two peaks is called the lower molecular weight peak, and the other peak is called the higher molecular weight peak, wherein the lower molecular weight peak corresponds to the uncoupled linear graded block copolymer of formula D-(D / A)-A2, and the higher molecular weight peak corresponds to formula [D-(D / A)-A1]. n＝2-4 -Si coupled graded block copolymers, preferably styrene-butadiene.

[0289] 5. According to the method of Embodiment 4, the content (%C) of coupled graded block copolymers in the total block copolymer molecular weight distribution determined by GPC-RI. ri The content is between 20% and 80%, preferably between 25% and 50%, more preferably between 30% and 45%, typically between 35% and 42%, and in a specific instance 38.6%.

[0290] 6. According to the method of embodiment 1 or 5, wherein the component difference %CD of the monovinyl aromatic repeating unit between the uncoupled and coupled portions of the bicomponent block copolymer is between 10% and 35%, preferably between 15% and 30%, more preferably between 17% and 28%, typically between 20% and 26%, and in a particular example 25.6%.

[0291] 7. According to the method of embodiment 1, 5 or 6, wherein the blockiness of the monovinyl aromatic repeating unit is between 76 mol% and 88 mol%, preferably between 78 mol% and 86 mol%, more preferably between 80 mol% and 83 mol%, and a specific example is 82.3 mol%.

[0292] 8. According to the method of embodiment 1, 5, 6 or 7, the total content %A of the monovinyl aromatic repeating units of the bicomponent block copolymer. t Between 20% and 50% by weight, preferably between 30% and 50% by weight, more preferably between 38% and 48% by weight, and in a specific example 40.1% by weight.

[0293] 9. According to the method of embodiment 1, 7 or 8, the total content (%A) of the monovinyl aromatic repeating units in the coupled graded block copolymer portion C The content is between 5% by weight and 35% by weight, preferably between 15% by weight and 30% by weight, more preferably between 20% by weight and 25% by weight, and in a specific example it is 24.8% by weight.

[0294] 10. The method according to embodiment 1, 7, 8 or 9, wherein the composite dynamic shear viscosity of the bicomponent block copolymer at 0.99 rad / s is between 50,000 Pa-s and 360,000 Pa-s, preferably between 60,000 Pa-s and 90,000 Pa-s, more preferably between 70,000 Pa-s and 82,000 Pa-s, with one example being 76,198 Pa-s.

[0295] 11. The method according to embodiment 10, wherein the composite dynamic shear viscosity of the bicomponent block copolymer at an oscillation frequency of 100 rad / s is between 3,000 Pa-s and 12,000 Pa-s, preferably between 4,200 Pa-s and 5,200 Pa-s, more preferably between 4,500 Pa-s and 4,900 Pa-s, and in one example 4,744 Pa-s.

[0296] 12. The method according to any one of embodiments 1 to 11, wherein the coupling agent is silicon tetrachloride.

[0297] 13. The method according to any one of embodiments 1 to 11, wherein the coupling agent is methyltrichlorosilane.

[0298] 14. The method according to embodiment 1 or 2, wherein the bicomponent block copolymer has a molecular weight distribution with three peaks.

[0299] 15. According to the method of embodiment 14, the weight-average molecular weight (M) of the synthesized bicomponent block copolymer is... w The concentration is 70 kg / mol to 500 kg / mol, preferably 140 kg / mol to 190 kg / mol, more preferably 150 kg / mol to 180 kg / mol, and one example is 159.6 kg / mol.

[0300] 16. The method according to embodiment 15, wherein the polydispersity index of the bicomponent block copolymer is between 1.00 and 1.90, preferably between 1.10 and 1.40, more preferably between 1.15 and 1.30, and the polydispersity index value of a particular example is 1.22.

[0301] Embodiment 2 of the present invention:

[0302] Synthesis of a two-component block copolymer; preparation of a prototype using methyltrichloride as a coupling agent. The two-component block copolymer was prepared using the same method as in Example 1, but with 0.230 mmol of methyltrichloride used instead of silicon tetrachloride as the coupling agent. Table 1 shows the specific formulation and polymerization conditions for this two-component block copolymer synthesis example. Then, 0.5 phr of a phenolic antioxidant and 0.6 phr of a phosphite antioxidant were added to the rubber solution. The block copolymer was recovered by roller milling. The weight-average molecular weight (M) of the synthesized two-component block copolymer was... w The molecular weight was 171.8 kg / mol. The molecular weight distribution exhibited a polydispersity index of 1.19. The molecular weight distribution of the block copolymers showed two peaks: a low molecular weight peak corresponding to the uncoupled linear graded block copolymer of formula D-(D / A)-A2, and a peak corresponding to the coupled graded styrene-butadiene block copolymer [D-(D / A)-A1]. n＝2-3-Si-CH3 high molecular weight peak. The content (%C) of the coupled graded block copolymer was determined by GPC-RI. ri The styrene repeating units comprise 25.5% of the total molecular weight distribution of the block copolymer. The total styrene repeating unit content of the bicomponent block copolymer is 40.2% by weight, while the styrene block content is 32.1% by weight. Therefore, the blockiness of the monovinyl aromatic repeating units is 79.9 mol%. Specific GPC and NMR characterizations of this bicomponent block copolymer are described in Table 2. The composite dynamic shear viscosity of the bicomponent block copolymer is 72962 Pa⁻² at an oscillation frequency of 0.99 rad / s, decreasing to 4833 Pa⁻² when evaluated at an oscillation frequency of 100 rad / s. The Tanδ of the bicomponent block copolymer reveals predominantly elastic behavior (Tanδ < 1.00) across the entire frequency sweep from 0.25 rad / s to 200 rad / s, with a maximum value of 0.86 at 0.99 rad / s. Details of the rheological characteristics of this bicomponent block copolymer are shown in Table 3.

[0303] Embodiments 3 to 12 of the present invention

[0304] Synthesis of a two-component block copolymer; scanning viscosity, coupling, and compositional differences of the prototype: Under a nitrogen atmosphere and with stirring, 71.50 ± 0.14 kg of cyclohexane, approximately 1.58 kg or approximately 2.56 kg of styrene, and 6.64 ± 0.02 kg of butadiene were added to a 189 L reactor. The initial reactor temperature was set to approximately 56.0 to approximately 66.0 °C, and then approximately 273.0 to approximately 321.0 mmol of n-butyllithium was added to the reactor. The polymerization of the first monomer feed reached a peak temperature of approximately 99.7 to approximately 104.8 °C. After waiting for 1 minute, approximately 13.88 to approximately 31.42 mmol of silicon tetrachloride coupling agent was added to the reactor. After waiting for 5 minutes, approximately 2.78 or approximately 1.82 kg of styrene was added to the reactor. During the final monomer loading, the reactor temperature dropped to approximately 98.1 ± 2.4 °C. Due to the heat of reaction from the second styrene charging polymerization, the reaction temperature rose to approximately 102.0 ± 1.5 °C. After waiting for 1 minute, 143.3 ± 23.3 mmol of a monofunctional alcohol was added to the reactor to terminate the polymer anionization. Table 1 shows the specific formulations and polymerization process conditions for each bicomponent block copolymer synthesis example. Then, 0.5 phr of a phenolic antioxidant and 0.6 phr of a phosphite antioxidant were added to the rubber solution. The block copolymers were recovered by steam stripping and oven drying. The weight-average molecular weight (M) of the synthesized block copolymers was... wThe molecular weights ranged from 147.4 to 225.5 kg / mol. The molecular weight distribution exhibited a polydispersity index of 1.24 to 1.40. The molecular weight distribution of the block copolymers showed two peaks: a low molecular weight peak corresponding to the uncoupled linear graded block copolymer of formula D-(D / A)-A2, and a peak corresponding to the coupled graded styrene-butadiene block copolymer [D-(D / A)-A1]. n＝2-4 -Si high molecular weight peak. The content (%C) of coupled graded block copolymers in the entire block copolymer molecular weight distribution was determined by GPC-RI. ri The weighted coupling levels (%C) of monovinyl aromatic compounds ranged from 23.0% to 38.6% as obtained by GPC-UV. uv The content of styrene repeating units in the bicomponent block copolymer was approximately 14.6% to approximately 24.6%. The total styrene repeating unit content was 39.9% to 40.8% by weight, while the styrene block content was 30.5% to 35.6% by weight. Therefore, the blockiness of the monovinyl aromatic repeating units in the bicomponent block copolymer was 76.5 mol% to 87.5 mol%. The content of vinyl aromatic repeating units in the coupled graded block copolymer moiety (%A) was revealed by calculations using coupling levels determined by GPC-RI and GPC-UV and total styrene content determined by proton NMR. C The content (%A) was from about 24.8% to about 32.6% by weight, while the content (%A) in the uncoupled graded block copolymer portion was... U The percentage of monovinyl aromatic repeating units was from about 43.6% to about 50.5% by weight. The component difference (%CD) between the uncoupled and coupled graded block copolymer portions was from about 11.1% to 25.6% by weight. The molecular weight distribution of Example 4 of the present invention is as follows: Figure 9 As shown in Table 2, specific GPC and NMR characterizations of these bicomponent block copolymers are described. The composite dynamic shear viscosity of the block copolymers at 0.99 rad / s ranges from 52,210 to 142,236 Pa⁻², decreasing to 3,571 to 6,241 Pa⁻² when evaluated at an oscillating frequency of 100 rad / s. The Mooney viscosity (ML100℃1+4) of the block copolymers ranges from 28.6 to 66.0. The Tanδ of the bicomponent block copolymers reveals predominantly elastic behavior (Tanδ < 1.00) across the entire frequency sweep from 0.25 to 200 rad / s, showing maximum values ​​ranging from 0.75 to 0.93 at different frequencies. Details of the rheological characteristics of these bicomponent block copolymers are shown in Table 3.

[0305] Embodiment 13 of the present invention:

[0306] Synthesis of a two-component block copolymer; Prototype: The block copolymer anionic fraction was deactivated before the monovinyl aromatic chain extension. The formulation used in Example 4 was scaled up by 272.7 times, reaching the level of an industrial reactor. However, a portion of the block copolymer anionic fraction that remained active after coupling was deactivated before the second styrene-feed polymerization. The weight-average molecular weight (M) of the two-component block copolymer is... w The molecular weight was 159.6 kg / mol. The polydispersity index of the molecular weight distribution was 1.22. The molecular weight distribution of the block copolymer exhibited three peaks: a low molecular weight peak, corresponding to the uncoupled linear graded block copolymer of formula D-(D / A)-A1 produced by partial anionic inactivation of the block copolymer before the second styrene-feed polymerization; and a high molecular weight peak, corresponding to the coupled graded styrene-butadiene block copolymer [D-(D / A)-A1]. n＝2-4 -Si; and a medium molecular weight peak, which corresponds to the uncoupled linear graded block copolymer of formula D-(D / A)-A2 obtained after the second styrene-feed polymerization. Figure 9 The molecular weight distribution of the bicomponent block copolymer produced in Example 13, obtained by GPC-RI, is shown. The percentage of coupled graded block copolymers (%C) in the overall block copolymer molecular weight distribution was determined by GPC-RI. ri ) accounted for 37.4%. The weighted coupling level (%C) of monovinyl aromatic repeating units, as measured by GPC-UV. uv The percentage of uncoupled graded block copolymer D-(D / A)-A1 was 24.8%, as determined by GPC-RI. The total styrene repeating unit content of the bicomponent block copolymer was 39.8% by weight, while the block styrene content was 34.2% by weight. Therefore, the blockiness of the monovinyl aromatic repeating unit was 86.0 mol%. The content of vinyl aromatic repeating units in the coupled graded block copolymer fraction (%A) was revealed by calculations using coupling levels determined by GPC-RI and GPC-UV and total styrene content determined by NMR. CThe content of the monovinyl aromatic repeating unit was 26.4% by weight, while the content in the uncoupled graded block copolymer portion was 47.7% by weight. The component difference (%CD) between the uncoupled and coupled graded block copolymer portions was 21.3%. Specific GPC and NMR characterizations of this bicomponent block copolymer are described in Table 2. The composite dynamic shear viscosity of the block copolymer at an oscillation frequency of 0.99 rad / s was 71321 Pa⁻², decreasing to 4709 Pa⁻² when evaluated at an oscillation frequency of 100 rad / s. The Mooney viscosity (ML100℃1+4) of the block copolymer was 39.0. The Tanδ of the bicomponent block copolymer revealed predominantly elastic behavior (Tanδ < 1.00) across the entire frequency scan from 0.25 to 200 rad / s, showing a maximum of 0.85 at 2.51 rad / s. Details of the rheological characteristics of this bicomponent block copolymer are shown in Table 3.

[0307] Comparative Example C-1

[0308] Synthesis of a linear graded block copolymer; a prototype with a low viscosity level was prepared by adding 71.56 kg of cyclohexane, 4.32 kg of styrene, and 6.64 kg of butadiene to a 189 L reactor under nitrogen atmosphere and stirring. The reactor feed temperature was adjusted to 50.5 °C, and then 286.6 mmol of n-butyllithium was added to the reactor. The polymerization of the first monomer feed reached a peak temperature of 106.3 °C. After waiting for 1 minute, 347.4 mmol of a monofunctional alcohol was added to the reactor to terminate the polymer anion. Table 1 shows the specific formulation and polymerization process conditions of this example of synthesizing an uncoupled graded block copolymer. Then, 0.5 phr of phenolic antioxidant and 0.6 phr of phosphite antioxidant were added to the rubber solution. The uncoupled graded block copolymer was recovered by steam stripping and oven drying. The weight-average molecular weight (M) of the synthesized uncoupled graded bicomponent block copolymer was... wThe molecular weight was 93.2 kg / mol. The molecular weight distribution exhibited a polydispersity index of 1.03, with a single narrow peak corresponding to the uncoupled linear graded block copolymer of formula D-(D / A)-A. The total styrene repeating unit content of the uncoupled graded block copolymer was 40.5 wt%, while the styrene block content was 30.0 wt%. Therefore, the blockiness of the monovinyl aromatic repeating unit was 73.9 mol%. Specific GPC and NMR characterizations of this uncoupled graded block copolymer are described in Table 2. The composite dynamic shear viscosity of the uncoupled graded block copolymer was 49951 Pa⁻² at an oscillation frequency of 0.99 rad / s, decreasing to 4927 Pa⁻² when evaluated at an oscillation frequency of 100 rad / s. The Mooney viscosity (ML100℃ 1+4) of the uncoupled graded block copolymer was 32.4. The Tanδ values ​​of the bicomponent block copolymer revealed predominantly viscous behavior (Tanδ > 1.00) in the frequency range of 0.84 to 25 rad / s, with a maximum Tanδ of 1.36 at 5.0 rad / s. Details of the rheological characteristics of this uncoupled graded block copolymer are shown in Table 3.

[0309] Comparative Example C-2

[0310] Synthesis of a partially coupled graded block copolymer; a prototype with a medium viscosity level. 71.41 kg of cyclohexane, 4.36 kg of styrene, and 6.63 kg of butadiene were added to a 189 L reactor under a nitrogen atmosphere and with stirring. The initial reactor feed was heated to 51.5 °C, and then 285.5 mmol of n-butyllithium was added to the reactor. Polymerization reached a peak temperature of 108.6 °C. After waiting 1 minute, 19.9 mmol of silicon tetrachloride coupling agent was added to the reactor. After waiting 5 minutes, 178.1 mmol of a monofunctional alcohol was added to the reactor to terminate the block copolymer anion. Table 1 shows the specific formulation and polymerization process conditions of this partially coupled graded block copolymer synthesis example. Then, 0.5 phr of a phenolic antioxidant and 0.6 phr of a phosphite antioxidant were added to the rubber solution. The block copolymer was recovered by steam stripping and oven drying. The weight-average molecular weight (M) of the block copolymer was... w The molecular weight was 160.1 kg / mol. The polydispersity index of the molecular weight distribution was 1.39. The molecular weight distribution of the block copolymer showed two peaks: a low molecular weight peak corresponding to the uncoupled linear graded block copolymer of formula D-(D / A)-A, and a peak corresponding to formula [D-(D / A)-A]. n＝2-4 -Si-coupled graded styrene-butadiene block copolymer high molecular weight peak. The content (%C) of the coupled graded block copolymer was determined by GPC-RI. riThis represents 34.5% of the total molecular weight distribution of the partially coupled graded block copolymers. The weighted coupling level (%C) of the monovinyl aromatic repeating units was obtained by GPC-UV. uv The styrene content was 35.5%, which closely matched the coupling level obtained by GPC-RI, due to the same content of monovinyl aromatic repeating units in both the uncoupled and coupled portions. The total styrene repeating unit content of the partially coupled graded block copolymer was 42.2 wt%, while its block styrene content was 31.6 wt%. Therefore, the blockiness of the monovinyl aromatic repeating units was 74.7 mol%. Specific GPC and NMR characterizations of this partially coupled graded block copolymer are described in Table 2. The composite dynamic shear viscosity of the partially coupled graded block copolymer was 75924 Pa⁻² at an oscillation frequency of 0.99 rad / s, decreasing to 6128 Pa⁻² when evaluated at an oscillation frequency of 100 rad / s. The Mooney viscosity (ML100℃1+4) of the partially coupled graded block copolymer was 40.6. The Tanδ values ​​of the bicomponent block copolymers revealed predominantly viscous behavior (Tanδ > 1.00) in the frequency range of 0.84 to 25 rad / s, with a maximum Tanδ of 1.27 at 5.0 rad / s. Details of the rheological characteristics of this partially coupled, graded bicomponent block copolymer are shown in Table 3. The molecular weight distribution of Comparative Example C-2 is as follows... Figure 9 As shown.

[0311] Comparative example C-3:

[0312] Linear graded block copolymers with high viscosity levels were synthesized in a pilot-scale reactor. The same procedures as in Comparative Example C-1 were performed, but the dosage of n-butyllithium was reduced to 264.4 mmol to increase the molecular weight. Table 1 shows the specific formulations and polymerization conditions for each uncoupled graded block copolymer synthesis example. The weight-average molecular weight (Mi) of the uncoupled graded block copolymers is also shown. wThe molecular weight was 107.8 kg / mol. The molecular weight distribution exhibited a polydispersity index of 1.03, with a single narrow peak corresponding to the uncoupled linear graded block copolymer of formula D-(D / A)-A. The total styrene repeating unit content of this uncoupled graded block copolymer was 38.9 wt%, while the block styrene content was 28.8 wt%. Therefore, the blockiness of the monovinyl aromatic repeating unit was 74.0 mol%. Specific GPC and NMR characterizations of this uncoupled graded block copolymer are described in Table 2. The composite dynamic shear viscosity of the uncoupled graded block copolymer was 96249 Pa⁻² at an oscillation frequency of 0.99 rad / s, decreasing to 6269 Pa⁻² when evaluated at an oscillation frequency of 100 rad / s. The Mooney viscosity (ML100℃ 1+4) of the uncoupled graded block copolymer was 53.1. The Tanδ values ​​of the bicomponent block copolymer revealed predominantly viscous behavior (Tanδ > 1.00) in the frequency range of 0.25 to 5 rad / s, with a maximum Tanδ of 1.17 at 0.99 rad / s. Details of the rheological characteristics of this uncoupled, graded bicomponent block copolymer are shown in Table 3.

[0313]

[0314]

[0315]

[0316] It can be seen that the intermittent synthesis method carried out in Examples 1 to 13 of the invention provides a bicomponent block copolymer, each having at least two distinguishable portions with different molecular weights and monovinyl aromatic repeating unit contents, wherein the portion with the lower molecular weight has a higher monovinyl aromatic repeating unit content than the portion with the higher molecular weight.

[0317] It can also be seen that, compared with the linear or coupled prior art graded block copolymers prepared in Comparative Examples 1 to 3, all the bicomponent block copolymers prepared in Examples 1 to 13 of the Invention have a higher degree of monovinyl aromatic repeating unit blockiness. This is due to the monovinyl aromatic block chain extension of the remaining polymer anions after the coupling step.

[0318] The polydispersity index of all the bicomponent block copolymers prepared in Examples 1 to 13 of this invention reached a maximum of 1.40, which is within the typical low range expected for organolithium-initiated batch polymerization followed by coupling. It is worth noting that these low levels of polydispersity cannot be obtained by alternative prior art organolithium-initiated continuous polymerization methods, which are typically used to produce block copolymers intended for the manufacture of crosslinked microporous rubber articles. Figure 9The paper presents the bicomponent block copolymers of Examples 4, 13 and Comparative Example 2 of the present invention prepared in a batch reactor, as well as a commercial reference. Comparison of molecular weight distribution of BL 30-4548 (from ARLANXEO) BL 30-4548 is a unimodal but very broad molecular weight distribution, and it is a typical block copolymer prepared in a continuous polymerization reactor using existing technology.

[0319] All the bicomponent block copolymers prepared in Examples 1 to 13 of the present invention exhibited Tanδ values ​​below 1.0 across the entire evaluated frequency range, independent of their composite dynamic shear viscosity and Mooney viscosity levels, and also independent of the type of coupling agent used. An examination of Examples 1 and 11 of the invention reveals that a component difference (%CD) of as low as 11% between the uncoupled and coupled portions of the bicomponent block copolymers was sufficient to promote this Tanδ behavior. In contrast, the prior art linear graded block copolymers with low viscosity levels prepared in Comparative Example 1 and high viscosity levels prepared in Comparative Example 3, as revealed by Tanδ values ​​greater than 1.0, primarily exhibited viscous behavior across a fairly broad evaluated spectrum. Similarly, the partially coupled graded block copolymer of Comparative Example 2, prepared according to the prior art, with a uniform content of monovinyl aromatic repeating units between the coupled and uncoupled portions and a moderate viscosity level, also exhibited Tanδ values ​​above 1.0 across a fairly broad evaluated spectrum. As previously mentioned, it is well known in the art that polymeric materials primarily exhibiting elastic behavior (i.e., Tanδ values ​​below 1.0) are more suitable for foaming applications due to their higher melt strength during the expansion of the blowing agent. By comparing these Tanδ curves, it can be concluded that the bicomponent block copolymers according to the present invention are more suitable for foaming than prior art linear graded block copolymers or homogeneous partially coupled graded block copolymers.

[0320] In embodiment 13 and Figure 9 The invention demonstrates that bicomponent block copolymers can have three molecular weight distributions. Specifically, in Example 13, the uncoupled block copolymer portion U consists of approximately 15.6% linear block copolymer molecules of formula D-(D / A)-A1 and approximately 47.0% linear block copolymer molecules of formula D-(D / A)-A2, wherein the monovinyl aromatic block A2 has a larger molecular weight than the monovinyl aromatic block A1. Despite having this three molecular weight distribution, the bicomponent block copolymer prepared in Example 13 exhibits a Tanδ value below 1.0 across the entire evaluated frequency range.

[0321] Embodiment 14 of the present invention:

[0322] Synthesis of a bicomponent block copolymer with a high content of monovinyl aromatic repeating units. Approximately 65.98 kg of cyclohexane, approximately 1.88 kg of styrene, and approximately 5.75 kg of butadiene were added to a 189 L reactor under a nitrogen atmosphere and with stirring. The reactor temperature was set to 55.7 °C, and then 322.9 mmol of n-butyllithium was added to the reactor. The polymerization of the first monomer feed reached a peak temperature of 98.8 °C. 31.42 mmol of silicon tetrachloride coupling agent was added to the reactor. After waiting 3 minutes, approximately 3.08 kg of styrene was added to the reactor. Due to the heat of reaction of the polymerization of the second styrene feed, the reaction temperature rose to approximately 101.2 °C. After waiting 1 minute, all polymer anions were terminated by adding a monofunctional alcohol. The formulation and polymerization process conditions are shown in Table 4. Then, 0.5 phr of a phenolic antioxidant and 0.6 phr of a phosphite antioxidant were added to the rubber solution. The bicomponent block copolymer samples were recovered and characterized by roller milling at 125 °C. The weight-average molecular weight (Mi) of the bicomponent block copolymer was determined. w The polydispersity M is 181.0 kg / mol. w / M n The value was 1.23; the molecular weight distribution measured by GPC-RI showed three peaks: a low molecular weight peak of 11.0%, corresponding to the uncoupled linear grade-changing block copolymer of formula D-(D / A)-A1; a medium molecular weight peak of 51.6%, belonging to the uncoupled linear grade-changing block copolymer of formula D-(D / A)-A2; and a high molecular weight peak of 37.4% (%C). ri This describes a coupled, graded styrene-butadiene block copolymer [D-(D / A)-A1]. n＝2-4-Si. The total styrene repeating unit content of the bicomponent block copolymer is 47.8 wt%, while the styrene block content is 39.9%. Therefore, the blockiness of the monovinyl aromatic repeating unit of the bicomponent block copolymer is 83.4 mol%. Specific GPC and NMR characterizations of the bicomponent block copolymer are described in Table 5. The composite dynamic shear viscosity of the bicomponent block copolymer is 105345 Pa⁻² at an oscillation frequency of 0.99 rad / s, decreasing to 5649 Pa⁻² when evaluated at an oscillation frequency of 100 rad / s. The Mooney viscosity (ML100℃1+4) is 48. The Tanδ of the bicomponent block copolymer reveals predominantly elastic behavior (Tanδ < 1.00) across the entire frequency sweep from 0.25 to 200 rad / s, showing a maximum of 0.76 at a frequency of 2.51 rad / s at 100℃ and 13.95% strain. The same oscillatory shear test, but performed at 140°C, revealed a maximum Tanδ value of 0.70 at a frequency of 25.12 rad / s. The rheological characteristics of this bicomponent block copolymer are shown in Table 6.

[0323] Embodiment 15 of the present invention.

[0324] Synthesis of a bicomponent block copolymer with high content of monovinyl aromatic repeating units and high molecular weight. Approximately 48.02 kg of cyclohexane, approximately 1.40 kg of styrene, and approximately 4.19 kg of butadiene were added to a 189 L reactor under a nitrogen atmosphere and with stirring. The reactor temperature was set to 54.1 °C, and then 219.7 mmol of n-butyllithium was added to the reactor. The polymerization of the first monomer feed reached a peak temperature of 96.8 °C. Then, 18.33 mmol of silicon tetrachloride coupling agent was added to the reactor. After waiting 3 minutes, approximately 2.35 kg of styrene was fed into the reactor. Due to the heat of reaction of the polymerization of the second styrene feed, the reaction temperature rose to approximately 99.0 °C. After waiting 1 minute, a monofunctional alcohol was added to the reactor to terminate all polymer anions. The formulation and polymerization process conditions are shown in Table 4. Then, 0.5 phr of a phenolic antioxidant and 0.6 phr of a phosphite antioxidant were added to the rubber solution. A sample of the bicomponent block copolymer was recovered by roller milling at 125 °C and characterized. The weight-average molecular weight (M) of the bicomponent block copolymer was determined. w The concentration was 233.7 kg / mol, and the polydispersity M was... w / M n The value was 1.17; the molecular weight distribution measured by GPC-RI showed three peaks: a low molecular weight peak of 4.0%, corresponding to the uncoupled linear grade-changing block copolymer of formula D-(D / A)-A1; a medium molecular weight peak of 54.3%, belonging to the uncoupled linear grade-changing block copolymer of formula D-(D / A)-A2; and a high molecular weight peak of 41.7% (%C).ri This describes a coupled, graded styrene-butadiene block copolymer [D-(D / A)-A1]. n＝2-4 -Si. The total styrene repeating unit content of the bicomponent block copolymer is 48.4 wt%, while the styrene block content is 39.7%. Therefore, the blockiness of the monovinyl aromatic repeating unit of the bicomponent block copolymer is 82.0 mol%. The GPC and NMR characterization of the bicomponent block copolymer is described in Table 5. The composite dynamic shear viscosity of the bicomponent block copolymer is 155221 Pa-s at an oscillation frequency of 0.99 rad / s, decreasing to 6467 Pa-s when evaluated at an oscillation frequency of 100 rad / s. The Mooney viscosity (ML100℃1+4) is 66. The Tanδ of the bicomponent block copolymer reveals predominantly elastic behavior (Tanδ < 1.00) across the entire frequency sweep from 0.25 to 200 rad / s, showing a maximum value of 0.68 at a frequency of 0.50 rad / s when evaluated at 100℃ and 13.95% strain. The same oscillatory shear test, but performed at 140°C, showed a maximum Tanδ value of 0.62 at 2.51 rad / s. The rheological characteristics of this bicomponent block copolymer are shown in Table 6.

[0325] Embodiment 16 of the present invention.

[0326] A two-component block copolymer containing paraffin oil. The rubber solution prepared in Example 15 of this invention uses 4 phr of paraffin oil from ExxonMobil. 352 was prepared. The oil-extended bicomponent block copolymer samples were recovered and characterized by roller milling at 125 °C. The composite dynamic shear viscosity of the bicomponent block copolymer was 101760 Pa⁻² at an oscillation frequency of 0.99 rad / s, decreasing to 4968 Pa⁻² when measured at an oscillation frequency of 100 rad / s. The Mooney viscosity (ML100 °C 1+4) was 50. The Tanδ of the bicomponent block copolymer revealed predominantly elastic behavior (Tanδ < 1.00) across the entire frequency sweep from 0.25 to 200 rad / s, showing a maximum value of 0.72 at 0.99 rad / s when evaluated at 100 °C and 13.95% strain. The same oscillating shear test, performed at 140 °C, showed a maximum Tanδ value of 0.65 at 5.00 rad / s. The rheological characteristics of this bicomponent block copolymer are shown in Table 6.

[0327] Embodiment 17 of the present invention.

[0328] Synthesis of a bicomponent block copolymer with a high content of monovinyl aromatic repeating units and low coupling. The monomer loading, reaction sequence, and reaction temperature were performed as in Example 15 of the invention, but with the addition of 174.5 mmol of n-butyllithium and 6.55 mmol of silicon tetrachloride. Detailed formulations and reaction temperatures are shown in Table 4. Samples of the rubber solution were taken from this batch, and the bicomponent block copolymer was separated from the solvent by roller milling at 125°C. The weight-average molecular weight (M2) of this bicomponent block copolymer was determined. w The concentration is 190.5 kg / mol, and the polydispersity M is... w / M n The value was 1.18; the molecular weight distribution measured by GPC-RI showed two peaks: a low molecular weight peak of 80.0%, corresponding to the uncoupled linear graded block copolymer of formula D-(D / A)-A2; and a high molecular weight peak of 20.0% (%C). ri This describes a coupled, graded styrene-butadiene block copolymer [D-(D / A)-A1]. n＝2-4 The total styrene repeating unit content of the bicomponent block copolymer is 48.7 wt%, while the styrene block content is 39.6%. Therefore, the blockiness of the monovinyl aromatic repeating unit of the bicomponent block copolymer is 81.3 mol%. The results of GPC and NMR characterization of the bicomponent block copolymer are described in Table 5. The composite dynamic shear viscosity of the bicomponent block copolymer is 248560 Pa⁻² at an oscillation frequency of 0.99 rad / s, decreasing to 8761 Pa⁻² when evaluated at an oscillation frequency of 100 rad / s. The Mooney viscosity (ML100℃ 1+4) is 83. The Tanδ of the bicomponent block copolymer reveals predominantly elastic behavior (Tanδ < 1.00) across the entire frequency sweep from 0.25 to 200 rad / s, showing a maximum value of 0.69 at a frequency of 0.25 rad / s when evaluated at 100℃ and 13.95% strain. The same oscillatory shear test, but performed at 140°C, showed a maximum Tanδ value of 0.70 at 0.25 rad / s. The rheological characteristics of this bicomponent block copolymer are shown in Table 6.

[0329] Embodiment 18 of the present invention.

[0330] A two-component block copolymer containing naphthenic oil. The rubber solution prepared in Example 15 of this invention uses 9 phr of naphthenic oil from NYNAS. 223 Preparation. The oil-extended bicomponent block copolymer samples were recovered and characterized by roller milling at 125 °C. The composite dynamic shear viscosity of the bicomponent block copolymer was 124840 Pa⁻² at an oscillation frequency of 0.99 rad / s, decreasing to 6594 Pa⁻² when measured at an oscillation frequency of 100 rad / s. The Mooney viscosity (ML100 °C 1+4) was 49. The Tanδ of the bicomponent block copolymer revealed predominantly elastic behavior (Tanδ < 1.00) across the entire frequency sweep from 0.25 to 200 rad / s, showing a maximum value of 0.87 at 0.99 rad / s when evaluated at 100 °C and 13.95% strain. The same oscillatory shear test, performed at 140 °C, showed a maximum Tanδ value of 0.80 at 0.84 rad / s. The rheological characteristics of this bicomponent block copolymer are shown in Table 6.

[0331] Table 4. Formulations and block copolymerization conditions for Examples 14 to 18 of the Invention

[0332]

[0333] Table 5. GPC and NMR characterization of the bicomponent block copolymers of Examples 14 to 17 of the Invention.

[0334]

[0335] Table 6 shows the rheological characteristics of the bicomponent block copolymers of Examples 14 to 18 of the Invention.

[0336]

[0337] Examples 14 to 18 of this invention demonstrate that the rheological properties of oil-free bicomponent block copolymers (e.g., Example 14) can be matched with those of oil-extended bicomponent block copolymers (e.g., the oil-extended bicomponent block copolymers of Examples 16 and 18), simply by appropriately increasing the molecular weight according to the oil content. Regardless of the type of oil or the level of coupling, the oil-extended bicomponent block copolymers primarily retain elastic behavior, as revealed by the measured Tanδ values ​​being below 1.0 across the entire oscillatory shear spectrum. These examples also demonstrate that even at temperatures up to 140°C, the bicomponent block copolymers still exhibit predominantly elastic behavior.

[0338] Assumed Implementation

[0339] The structure of the bicomponent block copolymer of the present invention is as follows: Figure 1-8 As shown in the image.

[0340] Figure 1A schematic diagram is shown of a bicomponent block copolymer consisting of approximately 38 wt% of a coupled block copolymer C of formula [D-(D / A)-A1]4-X (left side) and approximately 62 wt% of an uncoupled block copolymer U of formula D-(D / A)-A2 (right side). The total content A of the monovinyl aromatic repeating units is also shown. t It is approximately 41% by weight. The blockiness of the monovinyl aromatic repeating unit is approximately 87.5 mol%. (The percentage by weight of monovinyl aromatic repeating units in block copolymer C is %A.) C It is approximately 21% by weight. (%A) Weight percentage of monovinyl aromatic repeating units in block copolymer U. U It is approximately 52% by weight; therefore, the weight percentage composition difference %CD between the monovinyl aromatic repeating units of the block copolymer components U and C is approximately 31% by weight.

[0341] Figure 2 A schematic diagram is shown of a bicomponent block copolymer consisting of approximately 34 wt% of a coupled block copolymer C of the formula [D-(D / A)-A1]4-X (left side) and approximately 66 wt% of uncoupled block copolymers U of the formulas D-(D / A)-A2 (top right 4 molecules, equivalent to approximately 57 wt%) and D-(D / A)-A1 (bottom right, equivalent to approximately 9 wt%). A t It is approximately 39% by weight. The blockiness of the monovinyl aromatic repeating unit is approximately 86.5 mol%. A C Approximately 21% by weight, A U It is approximately 48% by weight. Therefore, %CD is approximately 27% by weight.

[0342] Figure 3 A schematic diagram is shown of a bicomponent block copolymer consisting of approximately 38 wt% of a coupled block copolymer C of formula [B-(B / A)-A1]4-X (left side) and approximately 62 wt% of an uncoupled block copolymer U of formula B-(B / A)-A2 (right side). A t It is approximately 41% by weight. The blockiness of the monovinyl aromatic repeating unit is approximately 87.5 mol%. A C Approximately 21% by weight, A U It is approximately 52% by weight; therefore, %CD is approximately 31% by weight.

[0343] Figure 4 A schematic diagram is shown of a bicomponent block copolymer consisting of approximately 34 wt% of a coupled block copolymer C of formula [B-(B / A)-A1]4-X (left side) and approximately 66 wt% of uncoupled block copolymers U of formulas B-(B / A)-A2 (top right 4 molecules, equivalent to approximately 57 wt%) and B-(B / A)-A1 (bottom right, equivalent to approximately 9 wt%). A tIt is approximately 39% by weight. The blockiness of the monovinyl aromatic repeating unit is approximately 86.5 mol%. A C Approximately 21% by weight, A U It is approximately 48% by weight; therefore, %CD is approximately 27% by weight.

[0344] Figure 5 A schematic diagram is shown of a bicomponent block copolymer consisting of approximately 38 wt% of a coupled block copolymer C of formula [(B / A)-A1]4-X (left side) and approximately 62 wt% of an uncoupled block copolymer U of formula (B / A)-A2 (right side). A t It is approximately 41% by weight. The blockiness of the monovinyl aromatic repeating unit is approximately 87.5 mol%. A C Approximately 21% by weight, A U It is approximately 52% by weight; therefore, %CD is approximately 31% by weight.

[0345] Figure 6 A schematic diagram is shown of a bicomponent block copolymer consisting of approximately 34 wt% of a coupled block copolymer C of formula [(B / A)-A1]4-X (left side) and approximately 66 wt% of uncoupled block copolymers U of formula (B / A)-A2 (upper right 4 molecules, equivalent to approximately 57 wt%) and (B / A)-A1 (lower right, equivalent to approximately 9 wt%). A t It is approximately 39% by weight. The blockiness of the monovinyl aromatic repeating unit is approximately 86.5 mol%. A C Approximately 21% by weight, A U It is approximately 48% by weight; therefore, %CD is approximately 27% by weight.

[0346] Figure 7 A schematic diagram is shown of a bicomponent block copolymer consisting of approximately 38% by weight of a coupled block copolymer C of formula [B-A1]4-X (left side) and approximately 62% by weight of an uncoupled block copolymer U of formula B-A2 (right side). A t It is approximately 41% by weight. The blockiness of the monovinyl aromatic repeating unit is approximately 100 mol%. A C Approximately 21% by weight, A U It is approximately 52% by weight; therefore, %CD is approximately 31% by weight.

[0347] Figure 8 A schematic diagram is shown of a bicomponent block copolymer consisting of approximately 34 wt% of a coupled block copolymer C of formula [B-A1]4-X (left side) and approximately 66 wt% of uncoupled block copolymers U of formulas B-A2 (top right 4 molecules, equivalent to approximately 57 wt%) and B-A1 (bottom right, equivalent to approximately 9 wt%). A t It is approximately 39% by weight. The blockiness of the monovinyl aromatic repeating unit is approximately 100 mol%. AC For approximately 21% by weight, A U It is approximately 48% by weight; therefore, %CD is approximately 27% by weight.

[0348] exist Figures 1 to 8 In the diagram, black bars represent the sequence of monovinyl aromatic repeating units, gray bars represent the sequence of conjugated diene repeating units, and X represents the residues of a tetrafunctional coupling agent. Figures 1 to 6 In the sequence of conjugated diene repeating units, the black lines represent different arrangements where monovinyl aromatic repeating units copolymerize with conjugated diene repeating units; their positions and spacing are not specific locations of individual monovinyl aromatic repeating units, but rather show a concentration trend of monovinyl aromatic repeating units dispersed along blocks that also contain conjugated diene repeating units. Therefore, in Figure 1 and Figure 2 The data shows the characteristics of graded copolymerization: a slight gradient followed by a steep gradient concentration curve; Figure 3 and Figure 4 The randomization of only a portion of the conjugated diene repeating units was described. Figure 5 and Figure 6 The diagram shows the complete random arrangement of all conjugated diene repeating units.

[0349] Examples for final application

[0350] The following embodiments of the invention show formulations of rubber mixtures comprising a two-component block copolymer, a chemical foaming agent, and a crosslinking agent. The compound is pre-crosslinked in a sealed and heated compression mold, followed by sudden decompression and mold opening to allow for microporous rubber expansion; the crosslinking stage of the microporous rubber probe is then completed in a forced convection oven. In comparative examples, the same formulation and method are used to obtain crosslinked microporous rubber probes, but using prior art block copolymers prepared in Comparative Examples 1 to 3, and a commercial block copolymer reference exhibiting a unimodal and very broad molecular weight distribution (…). BL 30-4548).

[0351] The cross-linked microporous rubber probe was visually inspected to assess its surface appearance, and measurements were taken before and after the cross-linking stage to determine the volume shrinkage rate. In addition, the probe was analyzed in the following aspects:

[0352] Density was measured using a MUVER electronic densitometer, model 5085-2, according to the ISO 2781 standard method. Number-average cell size and standard deviation of cell size were measured using epifluorescence microscopy with a Carl Zeiss AXIOTECH 100HD microscope and digital image analysis. Hardness was measured using a Bareiss Shore A hardness tester conforming to DIN 53505 and ISO 868 standards, mounted on a MUVER 5019 holder. Resilience was measured using a Zwick 5109 resilience tester.

[0353] Embodiment 19 of the present invention:

[0354] A rubber compound was prepared by mixing a 100 phr bicomponent block copolymer prepared in Example 3 of the invention, 6 phr azodicarbonamide (Celogen AZ-130, purchased from CelChem, LLC) as a foaming agent, and 1.1 phr dicumyl peroxide as a crosslinking agent in a roller mill. The rubber compound was molded, with an excess of 3% to ensure a seal in the mold. At 92.8 kgf / cm²... 2 Under clamping pressure, the mold was clamped with a heating plate at 150°C for 3 minutes. Afterward, the mold was cooled to 120°C while maintaining pressure. Then, the clamping pressure on the mold was released, and the compression plate was opened. Foam expansion then occurred, which could be seen by lifting the upper mold plate. The pre-crosslinked foam probe was quenched in water at 23°C. Crosslinking was completed by placing the pre-crosslinked foam probe in a forced convection oven at 100°C for 6 hours. The rubber foam probe was then treated at 23°C for 24 hours. The crosslinked microporous foam rubber probe prepared in this way has a smooth surface and no foaming defects. By comparing the volumes of the pre-crosslinked and fully crosslinked probes, the volume shrinkage rate was 3.9%. The density of the crosslinked microporous rubber probe was 0.446 g / cm³. 3 The number-average pore size was 6.74 micrometers, the standard deviation of the pore size was 2.09 micrometers, the Shore A hardness was 28.0, and the resilience was 37.9%. The formulation and evaluation results of the cross-linked microporous rubber probe were compared with the remaining examples and comparative examples of the present invention in Table 7.

[0355] Embodiment 20 of the present invention:

[0356] The rubber compound and crosslinked microporous rubber probe were prepared as in Example 19 of the invention, but comprising the two-component block copolymer prepared in Example 4 of the invention. The crosslinked microporous foam rubber probe prepared in this manner has a smooth surface and is free of foaming defects. By comparing the volumes of pre-crosslinked and fully crosslinked probes, the volume shrinkage rate was 3.9%. The density of the crosslinked microporous rubber probe was 0.464 g / cm³. 3The number-average pore size was 8.08 micrometers, the standard deviation of the pore size was 2.40 micrometers, the Shore A hardness was 38, and the resilience was 37.9%. The formulation and evaluation results of the cross-linked microporous rubber probe were compared with the remaining examples and comparative examples of the present invention in Table 7.

[0357] Embodiment 21 of the present invention:

[0358] The rubber compound and crosslinked microporous rubber probe were prepared as in Example 19 of the invention, but comprising the two-component block copolymer prepared in Example 5 of the invention. The crosslinked microporous foam rubber probe prepared in this manner has a smooth surface and is free of foaming defects. The volume shrinkage rate was 4.0% when comparing the volumes of the pre-crosslinked and fully crosslinked probes. The density of the crosslinked microporous probe was 0.662 g / cm³. 3 The Shore A hardness is 38.0, and the resilience is 37.0%. The formulation and evaluation results of the cross-linked microporous rubber probe were compared with the remaining examples and comparative examples of the present invention in Table 7.

[0359] Comparative example C-4:

[0360] The rubber compound and crosslinked microporous rubber probe were prepared as in Example 19 of the invention, but included the prior art uncoupled graded block copolymer prepared in Comparative Example C-1. The crosslinked microporous foam rubber probe prepared in this manner has an irregular surface and exhibits foaming defects. By comparing the volumes of pre-crosslinked and fully crosslinked probes, the volume shrinkage rate was 3.9%. The density of the crosslinked microporous rubber probe was 0.526 g / cm³. 3 The number-average pore size was 13.1 micrometers, the standard deviation of the pore size was 8.79 micrometers, the Shore A hardness was 55.0, and the resilience was 28.2%. The formulation and evaluation results of the cross-linked microporous rubber probe were compared with the remaining examples and comparative examples of the present invention in Table 7.

[0361] Comparative example C-5:

[0362] The rubber compound and coupled microporous rubber probe were prepared as in Example 19 of the invention, but included the prior art crosslinked graded block copolymer prepared in Comparative Example C-2. The crosslinked microporous foam rubber probe prepared in this manner has an irregular surface and exhibits foaming defects. By comparing the volumes of pre-crosslinked and fully crosslinked probes, the volume shrinkage rate was 4.0%. The density of the crosslinked microporous rubber probe was 0.790 g / cm³. 3 The number-average pore size was 9.50 micrometers, the standard deviation of the pore size was 3.38 micrometers, the Shore A hardness was 76.0, and the resilience was 31.0%. The formulation and evaluation results of the cross-linked microporous rubber probe were compared with the remaining examples and comparative examples of the present invention in Table 7.

[0363] Comparative example C-6:

[0364] The rubber compound and crosslinked microporous rubber probe were prepared as in Example 19 of the invention, but included the prior art uncoupled graded block copolymer prepared in Comparative Example C-3. The crosslinked microporous foam rubber probe prepared in this manner has an irregular surface and exhibits foaming defects. By comparing the volumes of pre-crosslinked and fully crosslinked probes, the volume shrinkage rate was 3.9%. The density of the crosslinked microporous rubber probe was 0.694 g / cm³. 3 The number-average pore size was 6.40 micrometers, the standard deviation of the pore size was 2.00 micrometers, the Shore A hardness was 53, and the resilience was 32.8%. The formulation and evaluation results of the cross-linked microporous rubber probe were compared with the remaining examples and comparative examples of the present invention in Table 7.

[0365] Comparative example C-7:

[0366] An attempt was made to prepare the rubber compound and crosslinked microporous rubber probe as described in Example 19, but incorporating prior art block copolymers. BL 30-4548 ( Figure 9 The block copolymer shown is a unimodal block copolymer with a very broad molecular weight distribution (a commercial reference for microporous rubber applications), rather than a two-component block copolymer. Although the molding, mold cooling, decompression, and mold opening conditions fully comply with those specified in Example 19 of the invention, the expansion of the rubber mixture is very limited when the load pressure on the hot mold is released and the pressure plate is opened, as no lifting of the upper plate of the mold was observed. The crosslinked microporous foam rubber probe prepared in this manner has a smooth surface and is free of bubbling defects. The volume shrinkage rate is 0% when comparing the volumes of pre-crosslinked and fully crosslinked probes. The crosslinked rubber probe has a high density of 1.042 g / cm³. 3 This demonstrates that the rubber compound has poor foaming properties. Optical microscopy analysis showed a very low cell count, with a number-average cell size of 14.25 micrometers and a standard deviation of 5.04 micrometers. The cross-linked rubber probe had a Shore A hardness of 43 and a resilience of 37.5%. The formulation and evaluation results of the cross-linked microporous rubber probe were compared with the remaining examples and comparative examples of the present invention in Table 7.

[0367] In Inventive Example 19 and Comparative Example C-4, the block copolymers used in the formulations have very similar Mooney viscosity values ​​of 32.0 and 32.4, respectively, and very similar composite shear viscosity profiles at 100°C, as shown in Table 3 (see Inventive Example 3 and Comparative Example C-1). It should be noted that the crosslinked microporous rubber probes produced using the bicomponent block copolymer of the present invention in the formulation of rubber compounds in Inventive Example 19, compared to those formulated using a prior art uncoupled graded block copolymer in Comparative Example C-4, have a smoother surface, lower density, smaller and more uniform pore size, lower hardness, and higher resilience. Both Inventive Example 19 and Comparative Example C-4 achieve lower volume shrinkage rates.

[0368] In Examples 20 and C-5 of the present invention, the block copolymers used in the formulations had very similar Mooney viscosity values ​​of 39.2 and 40.6, respectively, and very similar composite shear viscosity profiles at 100°C, as shown in Table 3 (see Examples 4 and C-2 of the present invention). It should be noted that the crosslinked microporous rubber probes produced using the bicomponent block copolymer of the present invention in the formulation of rubber compounds in Example 20 of the present invention, compared to those produced using a prior art coupled graded block copolymer in Comparative Example C-5, have a smoother surface, lower density, smaller and more uniform pore size, lower hardness, and higher resilience. Both Examples 20 and C-5 achieved lower volume shrinkage rates.

[0369] In Example 21 and Comparative Example C-6 of the present invention, the block copolymers used in the formulations exhibited very similar composite shear viscosity profiles at 100°C, as can be seen from Table 3 (see Example 3 and Comparative Example C-1 of the present invention). It should be noted that, compared to the formulation using a prior art uncoupled graded block copolymer in Comparative Example C-6, the crosslinked microporous rubber probe produced in Example 21 of the present invention using the two-component block copolymer of the present invention in the formulation of the rubber compound exhibits a smoother surface, lower density, lower hardness, and higher resilience. Both Example 21 of the present invention and Comparative Example C-6 achieved lower volume shrinkage rates.

[0370]

[0371] Invention Embodiment 22:

[0372] A foamable rubber compound was prepared by mixing a 100 phr bicomponent block copolymer, 6 phr azodicarbonamide, and 1.1 phr dicumyl peroxide of Example 13 in a roller mill. The foamable rubber compound was compressed and molded, with an excess of 3% rubber compound added to ensure mold sealing. The mold was heated to 170°C at a clamping pressure of 92.8 kgf / cm².2 The mold is clamped for 3 minutes. Then the pressure load on the mold is released, and the pressure plate is opened. Foam expansion occurs immediately, which can be seen from the lifting of the upper mold plate. The mold and the cross-linked microporous rubber probe are then rapidly cooled in water at 23°C. The cross-linked microporous rubber probe is removed from the mold and dried with absorbent paper. The cross-linked microporous rubber probe is then conditioned for 7 days in a controlled atmosphere chamber at 23°C and 50% relative humidity. The cross-linked microporous foam rubber probe prepared in this way has a smooth surface and no foaming defects. Its density is 0.624 g / cm³. 3 The shrinkage rate was 0% after being placed in a controlled atmosphere room for 7 days. Table 8 summarizes the formulation and properties of the cross-linked microporous rubber compound.

[0373] Comparative Example 7:

[0374] The foamable rubber compound and cross-linked microporous rubber probe are prepared as in Embodiment 22 of the invention, but containing... BL 30-4548, instead of a two-component block copolymer. Although the compression molding conditions were exactly the same as in Example 22 of the invention, the expansion of the rubber compound foam was very limited when the load pressure on the hot mold was released and the pressure plate was opened, as no lifting of the upper plate of the mold was observed. The cross-linked microporous foam rubber probe prepared in this way has a smooth surface and no foaming defects. Its density is 0.986 g / cm³. 3 This indicates that the compound has low foaming properties. Table 8 summarizes the formulations and properties of the crosslinked microporous rubber compounds.

[0375] Table 8 Formulations and properties of cross-linked microporous rubber compounds

[0376]

[0377] In general, the surface finish obtained in each case of using the bicomponent block copolymer of the present invention to produce crosslinked microporous rubber probes is smoother, whereas the microporous rubber probes produced when using uncoupled or coupled graded block copolymers of the prior art exhibit foaming defects on the surface. When using the bicomponent block copolymer of the present invention, lower probe density and more uniform cell size also demonstrate better foaming performance compared to using prior art alternatives. Furthermore, when incorporating the bicomponent block copolymer of the present invention, higher softness (lower Shore A hardness) and higher resilience are obtained in the crosslinked rubber compound. It is noteworthy that, under the same pre-crosslinking / molding, decompression, and crosslinking conditions, formulations containing the bicomponent block copolymer can produce crosslinked microporous rubber probes, whereas when using commercial references… Microporous foaming is not possible with BL 30-4548.

[0378] In the following examples, mixing evaluation was performed in a laboratory internal mixer. The formulation contained the bicomponent block copolymer of the present invention or a prior art graded block copolymer. Torque and temperature readings were collected to evaluate mixing performance. Mixing evaluation was performed in a Brapender Intelli-Torque Plasti-Corder equipped with a Prep-Mixer measuring head, CAM blades, and a 420 ml clean chamber. The standard formulation used also included emulsion SBR, fillers, plasticizers, antioxidants, chemical foaming agents, foaming agent activators, crosslinking agents, crosslinking promoters, and crosslinking agent activators.

[0379] Invention Embodiment 23:

[0380] The mixing was evaluated in a laboratory internal mixer. The initial feed consisted of 80 phr of the bicomponent block copolymer prepared in Example 3 and 20 phr of Emulprene 1502 (a cold emulsion styrene-butadiene random copolymer from Dynasol Group with 23.5% styrene repeating units), and mixing was initiated at a stable room temperature of 45°C. At 1 minute of mixing, 2.5 phr of naphthenic oil and 1.7 phr of paraffin were added. At 4 minutes of mixing, 70 phr of hard clay, 35 phr of aluminosilicate, and 4.5 phr of azodicarbonamide were added. AZ-130) and 1.0 phr Antioxidant L (from OMNOVASolutions Inc.). At a mixing time of 8 minutes, 3.0 phr of sulfur, 3.5 phr of stearic acid, and 3.5 phr of zinc oxide were added. At a mixing time of 10 minutes, 1 phr of diphenylguanidine (DPG) and 2.3 phr of 2-benzothiazolyl-N-sulfoxide morpholine (MBS) were added. At a total mixing time of 12 minutes, the torque reading was 106.2 Nm, and the internal temperature of the mixing chamber was 87°C. The compounding evaluation results are listed in Table 9.

[0381] Invention Embodiment 24:

[0382] The mixing evaluation was performed as in Example 23 of this invention, but using the bicomponent block copolymer of Example 4 of this invention. At a total mixing time of 12 minutes, the torque reading was 110.2 Nm, and the internal temperature of the mixing chamber was 87°C. The mixing evaluation results are listed in Table 9.

[0383] Invention Embodiment 25:

[0384] The mixing evaluation was performed as in Example 23 of this invention, but using the bicomponent block copolymer of Example 13 of this invention. At a total mixing time of 12 minutes, the torque reading was 110.0 Nm, and the internal temperature of the mixing chamber was 87°C. The mixing evaluation results are listed in Table 9.

[0385] Invention Embodiment 26:

[0386] The mixing evaluation was performed as in Example 23 of this invention, but using the bicomponent block copolymer of Example 5 of this invention. At a total mixing time of 12 minutes, the torque reading was 115.6 Nm, and the internal temperature of the mixing chamber was 88°C. The mixing evaluation results are listed in Table 9.

[0387] Comparative example C-9:

[0388] The mixing evaluation was performed as in Example 23 of this invention, but using the graded linear block copolymer of Comparative Example 1. At a total mixing time of 12 minutes, the torque reading was 109.9 Nm, and the internal temperature of the mixing chamber was 88°C. The mixing evaluation results are listed in Table 9.

[0389] Comparative Example C-10:

[0390] The mixing evaluation was performed as in Example 23 of this invention, but using the graded coupling block copolymer of Comparative Example 2. At a total mixing time of 12 minutes, the torque reading was 112.2 Nm, and the internal temperature of the mixing chamber was 87°C. The mixing evaluation results are listed in Table 9.

[0391] Comparative example C-11:

[0392] The mixing evaluation was performed as in Example 23 of this invention, but using the graded block copolymer of Comparative Example 3. At a total mixing time of 12 minutes, the torque reading was 119.6 Nm, and the internal temperature of the mixing chamber was 90°C. The mixing evaluation results are listed in Table 9.

[0393] Comparative example C-12:

[0394] Perform the mixing evaluation as in Embodiment 23 of the present invention, but using BL 30-4548. At a total mixing time of 12 minutes, the torque reading was 114.3 Nm, and the internal temperature of the mixing chamber was 90°C. The mixing evaluation results are listed in Table 9.

[0395] In Examples 23 and 9 of the present invention, the block copolymers used in the formulations had very similar Mooney viscosity values ​​of 32.0 and 32.4 at 100°C, and very similar composite shear viscosity profiles, as can be seen from Table 3 (see Examples 3 and 1 of the present invention). It can be observed that at the end of the mixing cycle, when the formulation contains a bicomponent block copolymer, a slightly lower torque and a lower chamber temperature are obtained compared to when it contains a prior art uncoupled graded block copolymer.

[0396] In Examples 24, 25, and Comparative Example 10 of the present invention, the block copolymers used in the formulations had very similar Mooney viscosity values ​​at 100°C, namely 39.2, 39.0, and 40.6, respectively, and very similar composite shear viscosity profiles, as can be seen from Table 3. (See Examples 4, 13, and Comparative Example 2 of the present invention). Similarly, it can be found that at the end of the mixing cycle, when the formulation contains a two-component block copolymer, a slightly lower torque and a lower chamber temperature are obtained compared to when it contains a prior art uncoupled graded block copolymer.

[0397] In Examples 26 and 11 of the present invention, the block copolymers used in the formulations had very similar composite shear viscosity profiles at 100°C, which were higher than those in the previous examples, as can be seen in Table 3 (see Examples 3 and 1 of the present invention). Similarly, it can be found that at the end of the mixing cycle, when the formulation contained a two-component block copolymer, a slightly lower torque and a lower chamber temperature were obtained compared to when it contained a prior art uncoupled graded block copolymer.

[0398] Furthermore, when comparing the mixing of formulations in Comparative Examples 23 to 26 with that in Comparative Example 12, prior art commercial references are included. When the formulations of BL 30-4548 are compounded, it can be found that the bicomponent block copolymers of the present invention are compounded to a slightly lower temperature at the end of the compounding cycle and, in most cases, exhibit a slightly lower final torque.

[0399] A slightly lower torque is advantageous when compounding formulations containing the bicomponent block copolymers of the present invention, as the compounding operation requires less power. A lower final internal chamber temperature is also advantageous when compounding formulations containing the bicomponent block copolymers of the present invention, as it better avoids problems of premature crosslinking and premature foaming during the mixing process. This is particularly advantageous when using crosslinking systems and / or foaming agent systems with low activation temperatures.

[0400]

[0401] The following examples illustrate the formulation and properties of hot-melt pressure-sensitive adhesives comprising the two-component block copolymers of the present invention or prior art block copolymers. The formulations used are tailored for label bonding purposes. The adhesive properties were evaluated using the following test methods: Brinell viscosity at 150°C, 160°C, and 177°C was obtained according to ASTM D1084 / D2556; the ring and ball softening point temperature was obtained according to ASTM D36; a ring fast-tack test was performed at 23°C according to PSTC-16; and rolling ball tack was evaluated at 23°C according to PSTC-6. Peel strength at 180° angle and 23°C was determined according to PSTC-1; and shear strength at 23°C was determined according to ASTM D3654.

[0402] Invention Embodiment 27:

[0403] A hot-melt pressure-sensitive adhesive for labels was prepared using the following formulation: 100 parts by weight of a two-component block copolymer (M) having properties similar to those of Example 13 of the Invention. w =174.0 kg / mol, uncoupled block copolymer D-(D / A)-A1 content = 15.16%, uncoupled block copolymer D-(D / A)-A2 content = 46.01%, coupled block copolymer [D-(D / A)-A1] n＝2-4 -Si content = 38.83%, %A t =40.08, blockiness =83.06%, Mooney viscosity ML100℃1+4 =40.7, Tanδmax =0.81 during oscillation frequency sweep from 0.25 to 200 rad / s at 100℃ and 13.95% strain, 178 parts by weight of hydrogenated rosin tackifier from Eastman Chemical Company. 85 and 50 parts by weight of NYNAS naphthenic oil 223 and 4 parts by weight of antioxidants purchased from BASF 1010. The formulation was carried out in a 500 mL cylindrical metal container equipped with a controlled heating hood and a three-bladed propeller with adjustable stirring speed. First, the tackifier, naphthenic oil, and antioxidant were heated at 135°C under a nitrogen atmosphere and slowly stirred to melt the components. After melting, the stirring speed was set to 300 RPM, and the temperature was raised to 155°C over 30 minutes. The two-component block copolymer was then gradually added, and the stirring speed was increased to 750 RPM. The temperature was then maintained at 170 ± 5°C for the next 2 hours while stirring at 750 RPM to ensure homogenization of the formulation. The binder exhibited a Brinell viscosity of 66300 cP at 150°C, 46380 cP at 160°C, and 19680 cP at 177°C; a ring and ball softening point of 90.9°C; and a ring fast tack of 8.853 lb at 23°C.f -in, with a rolling ball tack of 0.28in at 23°C; and a peel strength of 4.04lb at a 180° angle and 23°C. f The shear strength at 23°C under a 1000g load is 9.58 minutes. The formulation and properties of the adhesive are shown in Table 10.

[0404] Comparative example C-13:

[0405] Prepare a hot melt pressure-sensitive adhesive for labels as described in Embodiment 27 of the invention, but using Dynasol Group's... 1205 replaces the two-component block copolymer. 1205 is a graded styrene-butadiene block copolymer with a total styrene content of 25% by weight and a block styrene content of 17.5% by weight. Its Mooney viscosity (ML100°C 1+4) is 47, which is a recognized benchmark for hot-melt pressure-sensitive adhesive formulations. The adhesive's Brinell viscosity is 14000 cP at 150°C, 10750 cP at 160°C, and 7050 cP at 177°C; its ring and ball softening point is 69.95°C; and its ring fast tack at 23°C is 6.132 lb. f -in; rolling ball tack at 23°C is 0.44in; peel strength at 180° angle and 23°C is 3.275lb. f The shear strength at 23°C under a 1000g load is 1.55 minutes. The formulation and properties of this adhesive are listed in Table 10.

[0406] Comparative example C-14:

[0407] Prepare a hot melt pressure-sensitive adhesive for labels as described in Embodiment 27 of the invention, but using Dynasol Group's... Calprene 540 replaces the two-component block copolymer. Calprene 540 is a linear styrene-butadiene-styrene triblock copolymer with a total styrene content of 40% by weight and a block styrene content of 38% by weight. It is also the formulation for commercially available hot melt pressure-sensitive adhesives. This adhesive exhibits a Brinell viscosity of 13260 cP at 150°C, 9300 cP at 160°C, and 5470 cP at 177°C; a ring and ball softening point of 85.3°C; and a ring fast tack of 5.05 lb at 23°C. f -in; rolling ball tack at 23°C is 0.98in; peel strength at 180° angle and 23°C is 4.09lb. f The shear strength of the adhesive at 23°C under a 1000g load is 713.5 minutes. The evaluation of the adhesive is shown in Table 10.

[0408] Table 10 Formulation and Performance Evaluation of Hot Melt Pressure Sensitive Adhesives

[0409]

[0410] Performance evaluation of hot-melt pressure-sensitive adhesive formulations for labels indicates that the two-component block copolymer exhibits excellent tack, which may be related to the high wettability and adhesion of the terminally conjugated diene-rich blocks in its coupling portion. On the other hand, the higher softening point temperature of the adhesive formulated with the two-component block copolymer can benefit from a wider operating temperature range, as it can be used for labels on goods exposed to high temperatures during transport. The Brinell viscosity of the hot-melt adhesive according to the invention is at its upper limit for practical processing; however, its viscosity can be easily reduced by appropriately adjusting molecular parameters, such as molecular weight, coupling level, and / or the functionality of the coupling agent used.

[0411] Terminal Applications

[0412] In summary, in one embodiment, the present invention provides a bicomponent block copolymer comprising C and U, wherein C comprises: [D-(D / A)-A1]nX; [B-(B / A)-A1]nX; [(B / A)-A1]nX; or [(B / A)-A1]nX, or a mixture thereof, and wherein U comprises: D-(D / A)-A2, or D-(D / A)-A2 and D-(D / A)-A1; B-(B / A)-A2, or B-(B / A)-A2 and B-(B / A)-A1; (B / A)-A2, or (B / A)-A2 and (B / A)-A1; or B-A2, or B-A2 and B-A1, or a mixture thereof, wherein B is a polymer made solely of conjugated dienes. A polymer block (B / A) is a random polymer block made of at least one conjugated diene monomer and at least one monovinyl aromatic monomer; D is a polymer block made of at least one conjugated diene monomer and at least one monovinyl aromatic monomer, wherein the molecular weight of the conjugated diene repeating unit is greater than the molecular weight of the monovinyl aromatic repeating unit over the entire length of the polymer block; (D / A) is a polymer block made of at least one conjugated diene monomer and at least one monovinyl aromatic monomer, wherein the polymer block end opposite to A1 or A2 is mainly composed of conjugated diene repeating units, wherein the composition of the polymer block gradually changes along the entire block length until it is substantially composed of monovinyl aromatic repeating units at the end adjacent to A1 or A2. A1 and A2 are polymer blocks made only of monovinyl aromatic monomers, wherein the molecular weight of polymer block A2 is greater than the molecular weight of polymer block A1, X is a coupling agent residue, and n is an integer from 2 to 30.

[0413] Preferably, the molecular weight distribution of the bicomponent block copolymer exhibits at least two partially or fully distinguishable peaks; and / or block copolymer C comprises the portion of the molecular weight distribution with the highest molecular weight peak, while block copolymer U constitutes the remaining portion of the molecular weight distribution; and / or block copolymer C accounts for about 20% to about 80% of the molecular weight distribution. Optionally, the total monovinyl aromatic repeating unit content of the bicomponent block copolymer is about 20% to about 50% by weight; and / or the monovinyl aromatic repeating unit content in block copolymer U is at least 10% by weight higher than the monovinyl aromatic repeating unit content in block copolymer C.

[0414] The primary intended end use of the two-component block copolymers of the present invention is for the manufacture of the crosslinked microporous rubber articles described herein. However, the two-component block copolymers of the present invention can also be used in bitumen reinforcement, adhesives, sealants, coatings, insulation materials, and plastic compositions. The end use of the block copolymers is described in U.S. Patent Application Serial No. 15 / 417,193, filed January 26, 2107, and in U.S. Patent Publication No. 017 / 0210841A1, published July 27, 2017, which is incorporated herein by reference. One application is bitumen compositions, which may include bitumen; one or more additives selected from the group consisting of: plasticizers; fillers; crosslinking agents; flow resins; tackifying resins; processing aids; anti-ozone agents; and antioxidants; and the two-component block copolymer compositions described and claimed herein, wherein the bitumen composition comprises about 0.5 wt% to about 25 wt%, preferably about 0.5 wt% to about 8 wt%, for paving applications, and 3 wt% to about 25 wt% for roofing, wall paneling, and waterproofing membrane applications. Asphalt compositions can also be emulsified in water with an emulsifier.

[0415] One application is an adhesive composition that may comprise at least one additive selected from the group consisting of: tackifying resins; plasticizers; solvents; coupling agents; crosslinking agents; photoinitiators; and antioxidants; and another application is a two-component block copolymer composition as described and claimed herein, wherein the adhesive composition comprises about 0.5% to about 50% by weight of a two-component block copolymer composition. Another application is a sealant composition that may comprise at least one additive selected from the group consisting of: tackifying resins; plasticizers; fillers; coupling agents; processing aids; and antioxidants; and a two-component block copolymer composition as described and claimed herein, wherein the sealant composition comprises about 0.5% to about 50% by weight of a two-component block copolymer composition. Another suitable application of the invention is the production of high-impact styrene resins, such as HIPS and ABS, obtained by bulk polymerization of styrene or bulk copolymerization of styrene and acrylonitrile, in the presence of two-component block copolymers, for the specific purpose of improving gloss with minimal impact strength trade-offs. This may include mixtures of polymer compositions described and claimed herein and two-component block copolymer compositions.

[0416] While the invention has been described above, various modifications to the technology, procedures, materials, and apparatus will be apparent to those skilled in the art. All such variations within the scope and spirit of the invention are intended to be included within the scope of the appended claims.

Claims

1. A bicomponent block copolymer composition comprising C and U, wherein C is a coupled block copolymer comprising repeating units from a conjugated diene monomer, block A1, and residues of a coupling agent, wherein block A1 is made solely of a monovinyl aromatic monomer, wherein block A1 is bonded to the coupling agent, and wherein C has an externally terminal portion rich in conjugated diene monomers. U is an uncoupled block copolymer comprising repeating units from a conjugated diene monomer and a terminal block A2 made solely of a monovinyl aromatic monomer, wherein the molecular weight of polymer block A2 is greater than that of polymer block A1. Compared to C, U has a lower molecular weight and a higher content of monovinyl aromatic repeating units, and among which C accounts for 20% to 80% of the molecular weight distribution.

2. A bicomponent block copolymer composition comprising C and U, wherein C is a coupled block copolymer comprising repeating units from a conjugated diene monomer and a monovinyl aromatic monomer, wherein C contains only monovinyl aromatic endblocks and only conjugated diene-rich terminal portions. U is a non-coupled block copolymer comprising repeating units from a conjugated diene monomer and a monovinyl aromatic monomer, wherein U has only a single monovinyl aromatic terminal block and a single conjugated diene-rich terminal moiety, wherein U has a molecular weight lower than C, in which U has a higher content of monovinyl aromatic repeating units than C, wherein U has a higher content of monovinyl aromatic blocks than C, wherein U and C have terminal portions rich in conjugated dienes of the same molecular weight, wherein C accounts for 20% to 80% of the molecular weight distribution.

3. A bicomponent block copolymer composition comprising C and U, wherein C includes: [D-(D / A)-A1] n -X; [B-(B / A)-A1] n -X; [(B / A)-A1] n -X; or [B-A1] n -X, or a mixture of the above, and wherein U includes: D-(D / A)-A2 or D-(D / A)-A2 and D-(D / A)-A1; B-(B / A)-A2 or B-(B / A)-A2 and B-(B / A)-A1; (B / A)-A2 or (B / A)-A2 and (B / A)-A1; or B-A2 or B-A2 and B-A1, or a mixture of the above, wherein B is a polymer block made solely of conjugated diene monomers, in which (B / A) is a random polymer block composed of at least one conjugated diene monomer and at least one monovinyl aromatic monomer, wherein D is a polymer block composed of at least one conjugated diene monomer and at least one monovinyl aromatic monomer, wherein the conjugated diene repeating unit has a higher molar content than the monovinyl aromatic repeating unit along the entire length of the polymer block. (D / A) is a polymer block made of at least one conjugated diene monomer and at least one monovinyl aromatic monomer, wherein the polymer block end opposite A1 or A2 is mainly composed of conjugated diene repeating units, wherein the composition of the polymer block gradually changes along the block length until it becomes substantially composed of monovinyl aromatic repeating units at the end adjacent to A1 or A2. A1 and A2 are polymer blocks made solely of monovinyl aromatic monomers, wherein the molecular weight of polymer block A2 is greater than that of polymer block A1. C accounts for 20% to 80% of the molecular weight distribution, of which X is a residue of the coupling agent, and in which n is an integer with a value between 2 and 30.

4. The bicomponent block copolymer composition according to any one of claims 1-3, wherein... The bicomponent block copolymer composition has a molecular weight distribution exhibiting at least two peaks, wherein C constitutes the portion of the molecular weight distribution having the highest molecular weight peak, and wherein U constitutes the remaining portion of the molecular weight distribution.

5. The bicomponent block copolymer composition according to claim 1 or 2, wherein... C has each internal monovinyl aromatic block bonded at one end to a coupling agent residue and at the other end to a single conjugated diene-rich terminal portion, wherein Each molecule of C has a single coupling agent residue, wherein the coupling agent residue is bonded only to a monovinyl aromatic endoplast, wherein U consists of only a single monovinyl aromatic terminal block and a single conjugated diene-rich terminal moiety, and in which The conjugated diene-rich terminal portion includes conjugated diene monomer repeating units dispersed with monovinyl aromatic monomer repeating units, or contains only conjugated diene monomer repeating units.

6. The bicomponent block copolymer composition according to claim 5, wherein... The total content of monovinyl aromatic repeating units in the bicomponent block copolymer composition is 20% to 50% by weight.

7. The bicomponent block copolymer composition according to claim 6, wherein... The content of monovinyl aromatic repeating units in U is at least 10% higher by weight than the content of monovinyl aromatic repeating units in C.

8. The bicomponent block copolymer composition according to claim 7, wherein... The block degree of the monovinyl aromatic repeating units in the two-component block copolymer composition is at least 76 mol%, based on the total monovinyl aromatic repeating units.

9. The bicomponent block copolymer composition according to claim 8, wherein... The content of monovinyl aromatic repeating units in U is at least 20% higher by weight than the content of monovinyl aromatic repeating units in C.

10. The bicomponent block copolymer composition according to claim 3, wherein... n is an integer from 2 to 4, and the polydispersity ratio M of the bicomponent block copolymer is... w / M n Less than 1.50; or n is an integer from 2 to 30, and the polydispersity ratio M of the bicomponent block copolymer is... w / M n Less than 1.

90.

11. The bicomponent block copolymer composition according to claim 3, wherein... When the oscillation frequency varied from 0.25 rad / s to 200 rad / s at a temperature of 100°C and a strain of 13.95%, the dynamic oscillatory shear test of the bicomponent block copolymer composition showed a Tanδ value of less than 0.

95. Optionally, the dynamic oscillating shear test exhibits a Tanδ value of less than 0.95 when the oscillation frequency varies from 0.25 rad / s to 200 rad / s at a temperature of 140 °C and a strain of 13.95%.

12. The bicomponent block copolymer composition according to claim 3, wherein... The Mooney viscosity ML1+4 of the two-component block copolymer composition is from 25 to 90 at 100°C; and The composite dynamic shear viscosity of the bicomponent block copolymer composition, evaluated at 100°C, 13.95% strain, and 0.99 rad / s, is between 50,000 Pa⁻¹ and 360,000 Pa⁻¹; and The composite dynamic shear viscosity of the bicomponent block copolymer composition, evaluated at 100°C, 13.95% strain, and 100 rad / s, is between 3,000 Pa-s and 12,000 Pa-s.

13. The bicomponent block copolymer composition according to any one of claims 1-3, wherein The molecular weight distribution of the two-component block copolymer composition exhibits at least two peaks; C constitutes the portion of the molecular weight distribution that has the highest molecular weight peak, and U constitutes the remaining portion of the molecular weight distribution; The total content of monovinyl aromatic repeating units in the bicomponent block copolymer composition is from 20% to 50% by weight; The content of monovinyl aromatic repeating units in U is at least 10% by weight higher than the content of monovinyl aromatic repeating units in block copolymer C; The degree of blockiness of the monovinyl aromatic repeating units in the two-component block copolymer composition is equal to or greater than 77 mol%, based on the total number of monovinyl aromatic repeating units; The Mooney viscosity ML1+4 of the two-component block copolymer composition is from 25 to 70 at 100°C; and At a temperature of 100°C and a strain of 13.95%, the dynamic oscillatory shear test of the bicomponent block copolymer showed a Tanδ value of less than 0.95 when scanning oscillation frequencies from 0.25 rad / s to 200 rad / s.

14. The bicomponent block copolymer composition according to claim 3, wherein... C includes: [D-(D / A)-A1] n -X, and among them U includes: D-(D / A)-A2 or D-(D / A)-A2 and D-(D / A)-A1, where The uncoupled block copolymer molecules of formula D-(D / A)-A2 account for 20% to 80% by weight of the molecular weight distribution of the bicomponent block copolymer. The uncoupled block copolymer molecules of formula D-(D / A)-A1 account for 0% to 20% by weight of the molecular weight distribution of the bicomponent block copolymer. The monovinyl aromatic repeating unit block fraction of the bicomponent block copolymer is equal to or greater than 76 mol%, based on the total monovinyl aromatic repeating units, and The bicomponent block copolymer optionally further comprises 0% to 12% by weight of incremental oil.

15. The bicomponent block copolymer composition according to claim 3, wherein... C includes: [B-(B / A)-A1] n -X, and among them U includes: B-(B / A)-A2 or B-(B / A)-A2 and B-(B / A)-A1, where: The uncoupled block copolymer molecules of formula B-(B / A)-A2 account for 20% to 80% by weight of the molecular weight distribution of the bicomponent block copolymer. The uncoupled block copolymer molecules of formula B-(B / A)-A1 account for 0% to 20% by weight of the molecular weight distribution of the bicomponent block copolymer, and The bicomponent block copolymer optionally further comprises 0% to 12% by weight of incremental oil.

16. The bicomponent block copolymer composition according to claim 3, wherein... C includes: [(B / A)-A1] n -X, and among them U include: (B / A)-A2 or (B / A)-A2 and (B / A)-A1, where: The uncoupled block copolymer molecules of formula (B / A)-A2 account for 20% to 80% by weight of the molecular weight distribution of the bicomponent block copolymer. The uncoupled block copolymer molecules of formula (B / A)-A1 account for 0% to 20% by weight of the molecular weight distribution of the bicomponent block copolymer, and The bicomponent block copolymer optionally further comprises 0% to 12% by weight of incremental oil.

17. The bicomponent block copolymer composition according to claim 3, wherein... C includes: [B-A1] n -X, and among them U include: B-A2 or B-A2 and B-A1, where The uncoupled block copolymer molecules of formula B-A2 account for 20% to 80% by weight of the molecular weight distribution of the bicomponent block copolymer. The uncoupled block copolymer molecules of formula B-A1 account for 0% to 20% by weight of the molecular weight distribution of the bicomponent block copolymer. The degree of blockiness of the monovinyl aromatic repeating units in the bicomponent block copolymer is equal to or greater than 90 mol%, based on the total number of monovinyl aromatic repeating units, and The bicomponent block copolymer optionally further comprises 0% to 12% by weight of incremental oil.

18. A bicomponent block copolymer composition comprising C and U, wherein C has the general formula: [D-(D / A)-A1] n -X And U has a general formula: D-(D / A)-A2; or D-(D / A)-A2 and D-(D / A)-A1, in: (a)D is a polymer block made of at least one conjugated diene monomer and at least one monovinyl aromatic monomer, wherein the conjugated diene repeating unit has a higher molar content than the monovinyl aromatic repeating unit along the entire length of the polymer block; (b) (D / A) is a polymer block made of at least one conjugated diene monomer and at least one monovinyl aromatic monomer, wherein the polymer block end opposite to A1 or A2 is mainly composed of conjugated diene repeating units, and the polymer block gradually changes its composition until it becomes substantially composed of monovinyl aromatic repeating units at the end adjacent to A1 or A2. (c)A1 and A2 are polymer blocks made solely of monovinyl aromatic monomers; (d) The molecular weight of polymer block A2 is greater than that of polymer block A1; (e)X is a residue of the coupling agent, and n is an integer from 2 to 30; and (f) Equation [D-(D / A)-A1] n -X-coupled block copolymer molecules account for 20% to 80% of the molecular weight distribution of the two-component block copolymer; (g) The uncoupled block copolymer molecules of formula D-(D / A)-A2 account for 20% to 80% by weight of the molecular weight distribution of the two-component block copolymer; (h) The uncoupled block copolymer molecules of formula D-(D / A)-A1 account for 0% to 20% by weight of the molecular weight distribution of the two-component block copolymer.

19. A method for preparing a bicomponent block copolymer, comprising the following steps: In the presence of an organolithium initiator and a hydrocarbon solvent, conjugated diene monomers and monovinyl aromatic monomers are copolymerized to produce polymer anions; Partial polymer anion deactivation is achieved through reaction with coupling agents, proton donor compounds, electrophilic terminators, or mixtures thereof. Use the remaining polymer anions to copolymerize more and / or different monovinyl aromatic monomer blocks; Polymer anions are deactivated by reaction with proton donor compounds, electrophilic monofunctional compounds, or mixtures thereof; Recycle bicomponent block copolymers.

20. The method of claim 19, further comprising the following steps: Aliphatic hydrocarbon solvent, conjugated diene monomer, and monovinyl aromatic monomer are added to the reactor; An organolithium initiator is added to the reactor; The monomers are allowed to fully copolymerize and form polymeric anions; A limited amount of coupling agent is added to the reactor to couple only a portion of the polymeric anions; Add more and / or different monovinyl aromatic monomers to the reactor; Allows for the complete block copolymerization of the monovinyl aromatic monomers; Adding a proton donor or an electrophilic monofunctional compound to deactivate all remaining polymeric anions in the reactor; and Recycled two-component block copolymer compositions.

21. A method for preparing a bicomponent block copolymer, comprising the following steps: Conjugated diene monomers are polymerized in the presence of an organolithium initiator, a hydrocarbon solvent, and a random agent to produce polymeric anions; Monovinyl aromatic monomer block copolymerization is achieved by reacting with the above-mentioned polymer anions; Partial polymer anion deactivation is achieved through reaction with coupling agents, proton donor compounds, electrophilic terminators, or mixtures thereof. Use the remaining polymer anions to copolymerize more and / or different monovinyl aromatic monomer blocks; The polymer anion is completely deactivated by reaction with a proton donor compound, an electrophilic monofunctional compound, or a mixture of the above; and Recycle bicomponent block copolymers.

22. The method of claim 21, further comprising the following steps: Add aliphatic hydrocarbon solvent, random agent, and conjugated diene monomer to the reactor; An organolithium initiator is added to the reactor; The conjugated diene monomers added to the reactor are allowed to polymerize to a conversion level of 80 to 95%; A monovinyl aromatic monomer is added to the reactor; The remaining conjugated diene monomer and the monovinyl aromatic monomer added to the reactor are allowed to completely copolymerize, wherein a polymeric anion is formed; A limited amount of coupling agent is added to partially couple the polymeric anion; Add more and / or different monovinyl aromatic monomers to the reactor; Allows for the complete block copolymerization of the monovinyl aromatic monomers; Add a proton donor or an electrophilic monofunctional compound to deactivate all remaining polymeric anions; as well as Recycled two-component block copolymer compositions.

23. A method for preparing a bicomponent block copolymer, comprising the following steps: In the presence of an organolithium initiator, a random agent and a hydrocarbon solvent, conjugated diene monomers and monovinyl aromatic monomers are copolymerized to produce polymeric anions; The above-mentioned polymer anions are used to copolymerize more and / or different monovinyl aromatic monomer blocks; Partial polymer anion deactivation is achieved through reaction with coupling agents, proton donor compounds, electrophilic terminators, or mixtures thereof. Use the remaining polymer anions to copolymerize more and / or different monovinyl aromatic monomer blocks; Polymer anions are deactivated by reaction with proton donor compounds, electrophilic monofunctional compounds, or mixtures thereof; and Recycle bicomponent block copolymers.

24. The method of claim 23, further comprising the following steps: Add aliphatic hydrocarbon solvent, random agent, conjugated diene monomer and monovinyl aromatic monomer to the reactor; An organolithium initiator is added to the reactor; The conjugated diene monomer and the monovinyl aromatic monomer are allowed to be fully copolymerized; Add more and / or different monovinyl aromatic monomers to the reactor; The addition of monovinyl aromatic monomers to the reactor allows for complete block copolymerization, in which polymeric anions are formed; A limited amount of coupling agent is added to couple only a portion of the polymeric anions; Add more and / or different monovinyl aromatic monomers to the reactor; Allows for the complete block copolymerization of the monovinyl aromatic monomers; Adding a proton donor or an electrophilic monofunctional compound to completely deactivate any remaining polymeric anions; and Recycled two-component block copolymer compositions.

25. A method for preparing a bicomponent block copolymer, comprising the following steps: Conjugated diene monomers are polymerized in the presence of an organolithium initiator, a hydrocarbon solvent, and a random agent until complete monomer conversion is achieved to produce polymer anions. More and / or different monovinyl aromatic monomer block copolymers can be copolymerized by reacting with the above polymer anions; Partial polymer anion deactivation is achieved through reaction with coupling agents, proton donor compounds, electrophilic terminators, or mixtures thereof. Use the remaining polymer anions to copolymerize more and / or different monovinyl aromatic monomer blocks; Polymer anions are deactivated by reaction with proton donor compounds, electrophilic monofunctional compounds, or mixtures thereof; and Recycle bicomponent block copolymers.

26. The method of claim 25, further comprising the following steps: Add aliphatic hydrocarbon solvent, random agent and conjugated diene monomer to the reactor; An organolithium initiator is added to the reactor; Allow the conjugated diene monomer to fully polymerize; A monovinyl aromatic monomer is added to the reactor; The addition of monovinyl aromatic monomers to the reactor allows for complete block copolymerization, in which polymeric anions are formed; A limited amount of coupling agent is added to partially couple the polymeric anion; Add more and / or different monovinyl aromatic monomers to the reactor; Allows for the complete block copolymerization of the monovinyl aromatic monomers; Adding a proton donor or an electrophilic monofunctional compound to completely deactivate any remaining polymeric anions in the reactor; and Recycled two-component block copolymer compositions.

27. A method for preparing a two-component block copolymer composition, comprising the following steps: Add aliphatic hydrocarbon solvent, conjugated diene monomer, and monovinyl aromatic monomer to the reactor; An organolithium initiator is added to the reactor; The monomers are allowed to fully copolymerize and form polymeric anions; A limited amount of coupling agent is added to the reactor to couple only a portion of the polymeric anions; Add more and / or different monovinyl aromatic monomers to the reactor; Allows for the complete block copolymerization of the monovinyl aromatic monomers; Add a proton donor or an electrophilic monofunctional compound to deactivate any remaining polymeric anions in the reactor; as well as Recycled two-component block copolymer compositions.

28. A method for preparing a two-component block copolymer composition, comprising the following steps: Add aliphatic hydrocarbon solvent, random agent, and conjugated diene monomer to the reactor; An organolithium initiator is added to the reactor; The conjugated diene monomers added to the reactor are allowed to polymerize to a conversion level of 80 to 95%; A monovinyl aromatic monomer is added to the reactor; The remaining conjugated diene monomer and the monovinyl aromatic monomer added to the reactor are allowed to fully copolymerize, wherein polymeric anions are formed; A limited amount of coupling agent is added to partially couple the polymeric anion; Add more and / or different monovinyl aromatic monomers to the reactor; Allows for the complete block copolymerization of the monovinyl aromatic monomers; Add a proton donor or an electrophilic monofunctional compound to deactivate all remaining polymeric anions; as well as Recycled two-component block copolymer compositions.

29. A method for preparing a two-component block copolymer composition, comprising the following steps: Add aliphatic hydrocarbon solvent, atactic agent, conjugated diene monomer and monovinyl aromatic monomer to the reactor; An organolithium initiator is added to the reactor; The conjugated diene monomer and the monovinyl aromatic monomer are allowed to fully copolymerize; Add more and / or different monovinyl aromatic monomers to the reactor; The addition of monovinyl aromatic monomers to the reactor allows for complete block copolymerization, in which polymeric anions are formed; A limited amount of coupling agent is added to couple only a portion of the polymeric anions; Add more and / or different monovinyl aromatic monomers to the reactor; Allows for the complete block copolymerization of the monovinyl aromatic monomers; Adding a proton donor or an electrophilic monofunctional compound to completely deactivate any remaining polymeric anions; and Recycled two-component block copolymer compositions.

30. A method for preparing a two-component block copolymer composition, comprising the following steps: Add aliphatic hydrocarbon solvent, random agent, and conjugated diene monomer to the reactor; An organolithium initiator is added to the reactor; Allow the conjugated diene monomer to fully polymerize; A monovinyl aromatic monomer is added to the reactor; The addition of monovinyl aromatic monomers to the reactor allows for complete block copolymerization, in which polymeric anions are formed; A limited amount of coupling agent is added to partially couple the polymeric anion; Add more and / or different monovinyl aromatic monomers to the reactor; Allows for the complete block copolymerization of the monovinyl aromatic monomers; Adding a proton donor or an electrophilic monofunctional compound to completely deactivate any remaining polymeric anions in the reactor; and Recycled two-component block copolymer compositions.

31. The method according to any one of claims 27 to 30, further comprising the following steps: By adding a limited amount of a proton donor or an electrophilic monofunctional compound, only a portion of the polymeric anion in the reactor is deactivated before the step of adding more and / or different monovinyl aromatic monomers; or A limited amount of proton donor or electrophilic monofunctional compound is added, thereby simultaneously with the step of adding more and / or different monovinyl aromatic monomers, deactivating only a portion of the polymeric anions in the reactor.

32. A composition for cross-linking microporous rubber articles, comprising: The two-component block copolymer composition according to any one of claims 1 to 3 and 14 to 18; and the foaming agent.

33. The composition of claim 32, further comprising at least one additive selected from the group consisting of: styrene-butadiene random copolymers; styrene-isoprene-butadiene random copolymers; natural rubber; polybutadiene; polyisoprene rubber; ethylene / α-olefin / non-conjugated diene terpolymers; ethylene-propylene copolymers; ethylene-vinyl acetate copolymers; milled crosslinked microporous rubber compounds; fillers; plasticizers; foaming agent activators; crosslinking agents; crosslinking agent activators; crosslinking accelerators; vulcanization retarders; antioxidants; antiozone agents; ultraviolet stabilizers; light stabilizers; fragrances or flavorings; termite repellents; microbial agents; antifungal agents; antimicrobial agents; antibacterial agents; metal passivators; dyes; pigments; release agents; or mixtures thereof.

34. A composition for use in hot melt pressure-sensitive adhesives, comprising: The bicomponent block copolymer composition according to any one of claims 1 to 3 and 14 to 18; And tackifying resin.

35. The composition of claim 34, further comprising at least one additive selected from the group consisting of: antioxidants; extender oils; fillers; waxes; photoinitiators; crosslinking agents; crosslinking aids; crosslinking delay agents; tackifiers or coupling agents; UV stabilizers; light stabilizers; ozone stabilizers; epoxy resins; tar; reinforcing resins; fragrances or flavorings; termite repellents; microbial agents; antifungal agents; antibacterial agents; metal passivators; dyes, pigments or colorants; flame retardants; foaming agents; foaming agent activators; refractive index modifiers; or mixtures thereof.

36. An adhesive composition comprising 0.5% to 50% by weight of a two-component block copolymer composition according to any one of claims 1-3 and 14-18.

37. A sealant composition comprising 0.5% to 50% by weight of a two-component block copolymer composition according to any one of claims 1-3 and 14-18.

38. An asphalt composition for paving, roll roofing, roofing wall panels and waterproof membranes, comprising 0.5% by weight to about 25% by weight of a two-component block copolymer composition according to any one of claims 1-3 and 14-18; Asphalt; and Optionally present, at least one additive selected from the group consisting of: plasticizers; fillers; crosslinking agents; flow resins; tackifying resins; processing aids; antioxidants; and ozone deodorizers.

39. A high-impact styrene resin comprising a two-component block copolymer composition according to any one of claims 1-3 and 14-18.

40. An ABS resin prepared by bulk polymerization of styrene, acrylonitrile, and optionally other copolyyl copolymerizable monomers in the presence of a two-component block copolymer composition according to any one of claims 1-3 and 14-18.

41. The bicomponent block copolymer composition according to claim 1, wherein... The molecular weight distribution of the bicomponent block copolymer exhibits at least two peaks, wherein Block copolymer C constitutes the portion of the molecular weight distribution with the highest molecular weight peak, and block copolymer U constitutes the remaining portion of the molecular weight distribution, wherein... The block copolymer has C accounting for 20% to 80% of its molecular weight distribution; The total content of monovinyl aromatic repeating units in the two-component block copolymer composition is 20% to 50% by weight; The content of monovinyl aromatic repeating units in block copolymer U is at least 10% by weight higher than the content of monovinyl aromatic repeating units in block copolymer C; The degree of blockiness of the monovinyl aromatic repeating units in the two-component block copolymer composition is equal to or greater than 77 mol%, based on the total number of monovinyl aromatic repeating units; The Mooney viscosity (ML100℃ 1+4) of the two-component block copolymer composition is 25 to 70; and The composite dynamic shear viscosity of the bicomponent block copolymer composition evaluated at 100°C, 13.95% strain, and 0.99 rad / s is greater than 50,000 Pa-s and less than 150,000 Pa-s. The composite dynamic shear viscosity of the bicomponent block copolymer composition, evaluated at 100°C, 13.95% strain, and 100 rad / s, is greater than 3,000 Pa⁻¹ and less than 7,000 Pa⁻¹; and When the bicomponent block copolymer was subjected to a dynamic oscillatory shear test at a temperature of 100°C and a strain of 13.95%, and the oscillation frequency ranged from 0.25 rad / s to 200 rad / s, the Tanδ value was less than 0.95.

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