Two-component block copolymer

Abstract

Two-component block copolymers made from conjugated dienes and monovinyl aromatic monomers by batch organolithium-initiated polymerization exhibit advantageous performance in the production of crosslinked microcellular rubber compounds and pressure-sensitive hot-melt adhesives. The two-component block copolymers are partially coupled with a coupling agent that connects the internal monovinyl aromatic blocks. Their uncoupled low molecular weight fractions have a higher monovinyl aromatic repeat unit content than their coupled high molecular weight fractions. Crosslinked microcellular rubber products made from the two-component block copolymers exhibit lower density, smaller and more uniform cell size, higher softness, and higher resilience than prior art block copolymers. Rubber compounding of compounds containing the two-component block copolymers proceeds at slightly lower torque and slightly lower temperature than prior art block copolymers. Pressure-sensitive hot-melt adhesives formulated with the two-component block copolymers are well suited for labels and exhibit higher tack and a higher softening temperature than those made from prior art block copolymers.

Description

[Technical Field]

[0001] The present invention relates to bicomponent block copolymers of conjugated dienes and monovinyl aromatic monomers, and more specifically to microcellular crosslinked rubber compounds and hot-melt pressure-sensitive adhesives containing the bicomponent block copolymers. The novel bicomponent block copolymers of the present invention can be used to produce microcellular crosslinked rubber compounds with uniformly sized closed cells, no bubble blister defects, improved softness, and higher resilience. Hot-melt pressure-sensitive adhesives based on the novel bicomponent block copolymers exhibit improved tack and use temperature. [Background technology]

[0002] Microcellular rubber compounds are widely used in manufacturing various products such as shoe soles, sandals, cushion pads, floats, soundproof sheets, vibration damping materials, shock absorbing protectors, sealing applications, etc. Moreover, these materials are highly accepted in the market due to their lightweight and cost-effective properties.

[0003] When these compounds are foamed, closed cells are formed by the expansion of chemical or physical blowing agents under the influence of heat, or by a combination of heat and vacuum at temperatures and pressures typical for vulcanization compounding. Crosslinking of microcellular rubber compounds adds improved, long-lasting mechanical performance. Rubber elasticity during foaming is enhanced in most processes by partial crosslinking prior to or simultaneously with the foaming stage, which is important for maintaining a closed-cell structure. During the time that elapses between the end of foaming and optimal crosslinking, foam rubber compounds tend to shrink. Block copolymers of conjugated dienes and monovinyl aromatic monomers have been used in crosslinked microcellular rubber compositions to avoid this shrinkage defect.

[0004] Patent Document 1 is (BS) n , or (BS) n B or (SB) mThe present invention discloses a non-crosslinked elastic foam based on a block copolymer having a block configuration of the form: wherein B represents substantially 1-3 butadiene polymer, S represents substantially styrene polymer, n is an integer ranging from 2 to 10, and m is an integer ranging from 1 to 10. The composition also includes a polystyrene homopolymer. Nevertheless, this composition is disadvantageous because it contains environmentally harmful chlorohydrofluorocarbons as a blowing agent and exhibits very large cell sizes of 0.6 to 1.1 mm.

[0005] Patent Document 2 discloses a compound represented by the general formula (AE): n A, (AE) n or ((AE) n ) m Disclosed is a crosslinked rubber foam composition comprising a block copolymer of monovinyl aromatic and conjugated diene monomers having X, wherein n is in the range of 1 to 4, m is in the range of 2 to 8, A represents a monovinyl aromatic polymer block, E represents a conjugated diene polymer block and / or a selectively hydrogenated product thereof, and X represents a coupling agent residue. The composition may also contain other rubbers, such as natural rubber, diene-type synthetic rubber, and non-diene synthetic rubber.

[0006] Patent Document 3 discloses a crosslinked rubber foam composition containing a block copolymer containing a vinyl aromatic monomer unit and a conjugated diene monomer unit, and / or a block copolymer containing a vinyl aromatic monomer unit, a conjugated diene monomer unit, and an alkylene monomer unit. The composition also contains an olefin-based copolymer (such as polyethylene, ethylene-1-butene copolymer, ethylene-octene copolymer, etc.), and optionally an ethylene-based copolymer having an unsaturated group, such as EPDM. Among the various arrangement structures disclosed for the block copolymer, a preferred block configuration has end blocks rich in vinyl aromatic repeating units and an elastomeric repeating unit midblock.

[0007] Patent Document 4 discloses a rubber vulcanized foam compound containing a block copolymer having a molecular architecture consisting of polystyrene end blocks and an elastomeric midblock. The elastomeric midblock is butadiene, isoprene, ethylene, butylene, or propylene-based. The compound further incorporates a styrene-butadiene random copolymer with a high and / or average bound styrene content, as well as an ethylene-propylene copolymer (EPR) or an ethylene-propylene-diene terpolymer (EPDM).

[0008] The compositions disclosed in Patent Documents 2 to 4 include block copolymers with end blocks rich in vinyl aromatic repeat units surrounding a midblock rich in conjugated diene repeat units (or their hydrogenated products). Therefore, all of them have the disadvantage of requiring high compounding temperatures. This is because the vinyl aromatic repeat unit-rich end blocks of the block copolymers disclosed therein form an intermolecular physical network that softens sufficiently to flow only above 120°C. This high operating compounding temperature can cause premature decomposition of chemical blowing agents and / or premature initiation of crosslinking. This is particularly limiting when compounding is performed in a batch mixer such as a Banbury mixer.

[0009] Patent Document 5 discloses a crosslinked microcellular rubber foam composition containing a tapered diblock copolymer of a conjugated diene and a vinyl aromatic monomer. The tapered diblock copolymer disclosed therein is produced by a batch anionic solution polymerization process. The composition also contains a random copolymer of a conjugated diene and a vinyl aromatic monomer obtained by either anionic solution polymerization or free-radical emulsion polymerization.

[0010] Patent Document 6 discloses a crosslinked microcellular rubber foam composition containing a tapered diblock copolymer of a conjugated diene and a monovinyl aromatic monomer. The tapered diblock copolymer disclosed therein is produced by a batch anionic polymerization process. The composition also contains an ethylene / vinyl acetate copolymer.

[0011] The main advantages of the compositions disclosed in Patent Documents 5 and 6 are their sufficient processability in batch mixer equipment and minimal shrinkage of the foamed compounds. Nevertheless, crosslinked microcellular rubber compounds containing block copolymers of the type disclosed therein suffer from the disadvantages of non-uniform cell size, bubble bulging defects, low softness and low elasticity.

[0012] Patent Document 7 discloses the formulation of a vulcanized microporous rubber compound based on a block copolymer of styrene and butadiene. A small amount of resin with a styrene content of 40-80% is included to add hardness to the formulation. The formulation is taught to be advantageous for forming microporous or microcellular sandal soles. However, this patent document lacks a description of the molecular structure of the block copolymer and information on its composition range.

[0013] U.S. Patent Nos. 5,629,999, 5,729,963, 5,729,973, and 5,729,973 show various polymer foam compositions in which the polymers used have a preferred tan delta value (ratio of loss modulus to storage modulus, also known as dissipation factor) in the molten state of slightly below 1 for proper closed-cell foaming.

[0014] Microcellular crosslinked rubber compounds containing tapered block copolymers of butadiene and styrene produced by anionic solution polymerization in a continuous reactor process are known to have a good balance between shrinkage and surface aesthetics and to be easily processable in batch compounding equipment. Nevertheless, they still impart hardness and low elasticity to the microcellular crosslinked rubber compounds. Furthermore, continuous anionic polymerization processes lack the flexibility of batch processes to switch polymerization recipes to obtain different rubber grades without incurring production costs that result in off-grade transitions.

[0015] As described above, there is a need for block copolymers of conjugated dienes and vinyl aromatic repeating units that can be fully compounded with additional ingredients to produce microcellular crosslinked rubber compounds without problems of premature blistering or premature crosslinking. There is also a need for compositions based on block copolymers of crosslinked dienes and vinyl aromatic repeating units that provide crosslinked microcellular rubber compounds without problems of shrinkage during manufacturing. There is also a further need for crosslinked rubber foam compounds containing block copolymers of conjugated dienes and vinyl aromatic repeating units that can be molded into articles having excellent surface appearance, no bubble blister defects, improved softness, and high resilience. There is also a further need for a batch polymerization process for producing block copolymers of conjugated dienes and vinyl aromatic repeating units with excellent foaming properties. [Prior art documents] [Patent documents]

[0016] [Patent Document 1] British Patent No. 1,249,220 [Patent Document 2] European Patent Application Publication No. 0,323,653 [Patent Document 3] European Patent No. 2,546,291 [Patent Document 4] International Publication No. 2008 / 083451 [Patent Document 5] British Patent No. 1,111,250 [Patent Document 6] U.S. Patent No. 4,003,860 [Patent Document 7] Brazilian Patent Application Publication No. 0601080-6 [Patent Document 8] European Patent No. 0674578 [Patent Document 9] U.S. Patent No. 8,772,414 [Patent Document 10] US Patent Application Publication No. 2015 / 0259491 Summary of the Invention

[0017] The present invention provides novel bicomponent block copolymers prepared from monovinyl aromatic monomers and conjugated diene monomers by alkyllithium-initiated solution polymerization. As used in the specification and claims of the present invention, the term "bicomponent block copolymer" refers to a polymer blend containing two types of block copolymer molecules that differ from each other in molecular weight, block configuration, and monovinyl aromatic repeat unit content.

[0018] Each type of block copolymer molecule in a bicomponent block copolymer can be distinguished as a peak in the molecular weight distribution of the entire bicomponent block copolymer. The fraction with the highest molecular weight peak in the molecular weight distribution corresponds to coupled block copolymer molecules. In these coupled block copolymer molecules, the coupling agent residue is covalently bonded only to two or more internal monovinyl aromatic homopolymer blocks. The remainder of each coupled block copolymer molecule is composed of polymer blocks made of monovinyl aromatic repeat units interspersed with conjugated diene or polymer blocks incorporating only conjugated diene repeat units. Adjacent to the coupled block copolymer peak in the molecular weight distribution of the bicomponent block copolymer, an additional peak or several peaks can be distinguished in the lower molecular weight range, grouping non-coupled block copolymer molecules. These non-coupled block copolymer molecules have a single monovinyl aromatic homopolymer endblock per molecule, and the remainder of each non-coupled block copolymer molecule is constructed by polymer blocks containing conjugated diene repeat units interspersed with monovinyl aromatic diene repeat units or containing only conjugated diene repeat units. The average monovinyl aromatic repeat unit content of the coupled block copolymer molecules is lower than that of the uncoupled block copolymer molecules. Furthermore, the average molecular weight of the individual monovinyl aromatic homopolymer interior blocks in the coupled block copolymer molecules is lower than the average molecular weight of the monovinyl aromatic homopolymer end blocks found in the uncoupled block copolymer molecules. Furthermore, the average molecular weight of the outer blocks containing conjugated diene repeat units in the coupled block copolymer is approximately the same as the molecular weight of the blocks containing conjugated diene repeat units found in the uncoupled block copolymer.

[0019] The present invention also provides a process for obtaining novel two-component block copolymers in a batch polymerization reactor. The present invention also provides a composition for preparing crosslinked microcellular rubber compounds which comprises, among other typical ingredients of this class of compounds, a novel two-component block copolymer.

[0020] The compositions of the present invention allow the compounding stage of crosslinked microcellular rubber production to be achieved at low temperatures in an internal batch mixer, such as a Banbury mixer, which is beneficial in avoiding premature expansion of the chemical blowing agent and avoiding the problem of premature crosslinking. The compounding stage also proceeds at lower torque than prior art block copolymers of the same Mooney viscosity, so incorporating two-component block copolymers into this type of compounding is beneficial because it provides energy savings in the compounding process. The compositions of the present invention also offer the advantage that the shrinkage of the microcellular compound during the crosslinking stage is negligible. Molded articles made with the compositions of the present invention exhibit excellent surface appearance, no bubble bulging, high softness, and high resilience.

[0021] The present invention also provides hot melt pressure sensitive adhesive formulations that contain, among other typical components of this class of adhesives, novel two-component block copolymers that have been unexpectedly found to provide improved tack and service temperature range. [Brief explanation of the drawings]

[0022] [Figure 1] 1 shows a schematic diagram of a two-component block copolymer consisting of about 38 wt. % of a coupled block copolymer C of formula [D-(D / A)-A1]4-X (left side) and about 62 wt. % of an uncoupled block copolymer U of formula D-(D / A)-A2 (right side). [Figure 2] Shown is a schematic diagram of a two-component block copolymer consisting of about 34 wt. % of coupled block copolymer C of formula [D-(D / A)-A1]4-X (left side) and about 66 wt. % of uncoupled block copolymer U of formula D-(D / A)-A2 (top right tetrad) and D-(D / A)-A1 (bottom right). [Figure 3] 1 shows a schematic diagram of a two-component block copolymer consisting of about 38 wt. % of coupled block copolymer C of formula [B-(B / A)-A1]4-X (left side) and about 62 wt. % of uncoupled block copolymer U of formula B-(B / A)-A2 (right side). [Figure 4] Figure 1 shows a schematic diagram of a two-component block copolymer consisting of about 34 wt% of coupled block copolymer C of formula [B-(B / A)-A1]4-X (left side) and about 66 wt% of uncoupled block copolymer U of formula B-(B / A)-A2 (top right tetrad) and B-(B / A)-A1 (bottom right), where At is about 39 wt%. [Figure 5] 1 shows a schematic diagram of a two-component block copolymer consisting of about 38 wt. % of coupled block copolymer C of formula [(B / A)-A1]4-X (left side) and about 62 wt. % of uncoupled block copolymer U of formula (B / A)-A2 (right side). [Figure 6] Shown is a schematic diagram of a two-component block copolymer consisting of about 34 wt. % of coupled block copolymer C of formula [(B / A)-A1]4-X (left side) and about 66 wt. % of uncoupled block copolymer U of formula (B / A)-A2 (top right tetrad) and (B / A)-A1 (bottom right). [Figure 7] 1 shows a schematic diagram of a two-component block copolymer consisting of about 38 wt. % of coupled block copolymer C of formula [B-A1]4-X (left side) and about 62 wt. % of uncoupled block copolymer U of formula B-A2 (right side). [Figure 8] Shown is a schematic diagram of a two-component block copolymer consisting of about 34 wt. % of coupled block copolymer C of formula [B-A1]4-X (left side) and about 66 wt. % of uncoupled block copolymer U of formulas B-A2 (top right tetrad) and B-A1 (bottom right). [Figure 9] 1 shows the molecular weight distributions of the dicomponent block copolymers of Examples 4 and 13 compared to the state-of-the-art block copolymers of Comparative Example C-2 and Buna® BL30-4548. DETAILED DESCRIPTION OF THE INVENTION

[0023] In Figures 1 through 8, black bars indicate the sequence of monovinyl aromatic repeat units, gray bars indicate the sequence of conjugated diene repeat units, and X is the residue of a tetrafunctional coupling agent. In Figures 1 through 6, black lines in the sequence of conjugated diene repeat units represent different configurations in which monovinyl aromatic repeat units are copolymerized with conjugated diene repeat units. These positions and spacings do not indicate the specific location of individual monovinyl aromatic repeat units, but rather indicate the concentration trends of monovinyl aromatic repeat units scattered along the block that also contains conjugated diene repeat units. Thus, a slight gradient followed by a steep concentration profile, characteristic of tapered copolymerization, is shown in Figures 1 and 2. Randomization involving only a portion of the conjugated diene repeat units is shown in Figures 3 and 4. Fully randomized configurations involving all conjugated diene repeat units are shown in Figures 5 and 6.

[0024] DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS The present invention provides novel bicomponent block copolymers comprising two types of block copolymer molecules, C and U, made from monovinyl aromatic monomers and conjugated diene monomers.

[0025] In one embodiment, the dicomponent block copolymer of the present invention has a molecular weight distribution with at least two distinguishable fractions, each of which has a peak in the molecular weight distribution, obtained by a three-column gel permeation chromatography technique using a differential refractive index detector and relying on a universal calibration molecular weight curve referenced to polystyrene standards (GPC-RI). Adjacent fractions are separated from each other by minima in the molecular weight distribution curve. Block copolymer C is constituted by the fraction with the highest molecular weight peak in the molecular weight distribution, and block copolymer U constitutes the remainder of the molecular weight distribution.

[0026] In one embodiment, the diblock copolymer of the present invention has an amount of block copolymer C, as quantified by the integral of the fraction having the highest molecular weight peak relative to the entire diblock copolymer molecular weight distribution obtained by GPC-RI, of 20% to 80%, more preferably 30% to 60%, and most preferably 35% to 45%. Additionally, the diblock copolymer of the present invention has an amount of block copolymer U, as quantified by the integral of the remaining portion of the molecular weight distribution obtained by GPC-RI, of 80% to 20%, more preferably 70% to 40%, and most preferably 65% ​​to 55%. In one embodiment, the diblock copolymer of the present invention has a total monovinyl aromatic repeat unit content of 20% to 50% by weight, % A t as determined by proton NMR analysis.

[0027] The binary block copolymers of the present invention have a characteristic monovinyl aromatic repeat unit blockiness degree, which is determined by proton NMR analysis. The monovinyl aromatic repeat unit blockiness degree is quantified as the mole percent of monovinyl aromatic repeat units that are not covalently bonded to conjugated diene repeat units in the block copolymer, based on the total monovinyl aromatic repeat units. In one embodiment, the binary block copolymers of the present invention have a monovinyl aromatic repeat unit blockiness degree of 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 monovinyl aromatic repeat units.

[0028] A distinguishing feature of the binary block copolymers of the present invention is that the monovinyl aromatic repeat unit content of block copolymer U is higher than the monovinyl aromatic repeat unit content of block copolymer C. The monovinyl aromatic repeat unit weight percent content, %A, of block copolymer U is U , the monovinyl aromatic repeat unit weight percent content of block copolymer C, %AC , and the monovinyl aromatic repeat unit weight percent composition difference, %CD, between block copolymer fractions U and C is calculated as follows:

[0029]

number

[0030] where %C uv represents the percentage amount of the fraction having the highest molecular weight peak, which corresponds to block copolymer C relative to the total molecular weight distribution of the two-component block copolymer of the present invention obtained by GPC technique (GPC-UV) using a three-column set, a UV absorbance detector at a wavelength of 261 nm, and relying on a universal calibration molecular weight curve referenced to polystyrene standards; %A t is the total monovinyl aromatic content of the entire binary block copolymer of the present invention on a weight basis as determined by proton NMR analysis; %C ri is the percentage amount of the fraction having the highest molecular weight peak, which corresponds to block copolymer C relative to the total molecular weight distribution of the binary block copolymer of the present invention obtained by gel permeation chromatography technique (GPC-RI) using a three-column set, employing a differential refractive index detector, and relying on a universal calibration molecular weight curve referenced to polystyrene standards.

[0031] In one embodiment, the bicomponent block copolymers of the present invention exhibit a monovinyl aromatic repeat unit weight percent composition difference, %CD, between block copolymer fractions U and C of at least 10 wt%, preferably at least 15 wt%, and most preferably at least 20 wt%.

[0032] Tan delta, defined as the ratio of loss modulus to storage modulus, is well known in the art as a highly appropriate indicator of the balance between the flowability and melt strength of various polymeric materials, and therefore their foaming ability. Without being limited to a particular theory, polymeric materials with tan delta values ​​less than 1.0 have sufficient melt strength to maintain a closed-cell structure during expansion of the blowing agent, which helps narrow the cell size distribution and improve the aesthetics of the foam surface. Conversely, polymeric materials with tan delta values ​​greater than 1.0 under processing conditions tend to experience cell membrane rupture and cell coalescence during foaming, potentially widening the cell size distribution to the point where blistered surface defects can occur in the foamed product.

[0033] After extensive investigation, it was determined that prior art copolymers obtained by batch alkyllithium solution copolymerization of monovinyl aromatic monomers and conjugated diene monomers did not yield adequate tan delta profiles, and their viscoelastic behavior was found to be related to poor foaming performance. Several conventional block copolymer structures were tested (tapered linear block copolymers, partially coupled tapered block copolymers, various levels of monovinyl aromatic repeat unit blockiness, various levels of monovinyl aromatic content, various molecular weights, oil-extended block copolymers, and even mixtures of tapered linear block copolymers with different monovinyl aromatic repeat unit contents), all of which exhibited tan delta profiles slightly above 1.0 over a fairly wide oscillatory shear frequency range. When formulated into crosslinked microcellular foam compositions, these prior art alternatives produced molded articles lacking clean surface aesthetics due to apparent cell expansion defects. Nevertheless, it has been surprisingly found that the diblock copolymers of the present invention have characteristic viscoelastic behavior that is advantageous for foaming purposes, since they exhibit only a tan delta value of less than 1.00 over a wide range of shear rates and processing temperatures during crosslinking. Correspondingly, crosslinked microcellular compositions based on the diblock copolymers have been found to have very uniform cell sizes, and their molded articles have excellent surface aesthetics without bubble blister defects.

[0034] In one embodiment, the diblock copolymers of the present invention exhibit a maximum tan delta value of 0.74 to 0.95, more preferably 0.74 to 0.88, and most preferably 0.74 to 0.81, when subjected to dynamic oscillatory shear testing at 100°C and 13.95% strain, covering an oscillation frequency range of 0.25 rad / s to 200 rad / s. Typically, when subjected to dynamic oscillatory shear testing, the diblock copolymers of the present invention have a tan delta value of less than 1.00 when subjected to dynamic oscillatory shear testing at 100°C and 13.95% strain, covering an oscillation frequency range of 0.25 to 200 rad / s. At higher temperatures, the diblock copolymers of the present invention have also been found to have tan delta values ​​of less than 1.00, less than 0.95, less than 0.90, or less than 0.85 when subjected to dynamic oscillatory shear testing at 140°C and 13.95% strain, covering an oscillation frequency range of 0.25 to 200 rad / s.

[0035] In one embodiment, the two-component block copolymer of the present invention has a Mooney viscosity (ML1+4, 100° C.) of 25-90, preferably 30-60, and more preferably 35-55. In one embodiment, the diblock copolymers of the present invention have a complex shear kinematic viscosity of 50,000 Pa·s to 360,000 Pa·s when evaluated at 13.95% strain, a vibration frequency of 0.99 rad / s, and a temperature of 100° C. In one embodiment, the diblock copolymers of the present invention have a complex kinematic viscosity of 3,000 Pa·s to 12,000 Pa·s when evaluated at 100 rad / s and 100° C.

[0036] Alkyllithium-initiated batch copolymerization of conjugated diene monomers and monovinyl aromatic monomers, either in bulk or in nonpolar hydrocarbon solvent solution, in the absence of polar modifier compounds or randomizers, produces what are known as tapered or step-wise diblock copolymers of the D-(D / A)-A type, where D is a polymer block rich in conjugated diene repeat units, (D / A) is a polymer block whose composition gradually changes from being more rich in conjugated diene repeat units toward the end adjacent to the D block to being substantially rich in monovinyl aromatic repeat units toward the opposite end, and A is a polymer block formed exclusively from monovinyl aromatic repeat units. The preparation and application of such tapered or stepped diblock copolymers of conjugated diene monomers and monovinyl aromatic monomers is well known to those skilled in the art and is defined and described in H.L.H. Sie, R.P. Quirk, Anionic Polymerization: Principles and Practical Applications, Marcel Dekker, Inc., pp. 239-251 and 448-454.

[0037] In a preferred embodiment, the bicomponent block copolymer of the present invention comprises a block copolymer C and a block copolymer U, wherein: The block copolymer C has the general formula: [D-(D / A)-A1] n -X; The block copolymer U has the general formula: D-(D / A)-A2; or D-(D / A)-A2 and D-(D / A)-A1, where D is a polymer block formed from at least one conjugated diene monomer and at least one monovinyl aromatic monomer, wherein the conjugated diene repeat units are in molar excess over the monovinyl aromatic repeat units along the entire length of the polymer block; (D / A) is a polymer block formed from at least one conjugated diene monomer and at least one monovinyl aromatic monomer, the polymer block end opposite A1 or A2 being composed primarily of conjugated diene repeat units and gradually varying in composition along its length until it is composed essentially of monovinyl aromatic repeat units toward the end adjacent A1 or A2; A1 and A2 are polymer blocks formed exclusively from monovinyl aromatic monomers; Polymer block A2 has a higher molecular weight than polymer block A1; X is the residue of a coupling agent; n is an integer with a value between 2 and 30; Formula [D-(D / A)-A1] n -X coupled block copolymer molecules account for about 20 to about 80 weight percent of the molecular weight distribution of the two-component block copolymer as measured by GPC-RI; the uncoupled block copolymer molecules of formula D-(D / A)-A2 account for about 20 to about 80 weight percent of the molecular weight distribution of the two-component block copolymer as measured by GPC-RI; The uncoupled block copolymer molecules of formula D-(D / A)-A1 account for about 0 to about 20 weight percent of the molecular weight distribution of the binary block copolymer as measured by GPC-RI.

[0038] In another embodiment, the bicomponent block copolymer of the present invention comprises a block copolymer C and a block copolymer U, wherein: The block copolymer C has the general formula: [B-(B / A)-A1] n -X; The block copolymer U has the general formula: B-(B / A)-A2; or B-(B / A)-A2 and B-(B / A)-A1, where: B is a polymer block formed exclusively from one or more conjugated diene monomers; (B / A) is a polymer block formed from at least one conjugated diene monomer and at least one monovinyl aromatic monomer, wherein the conjugated diene and monovinyl aromatic repeat units are randomly arranged along the polymer block; A1 and A2 are polymer blocks formed only from monovinyl aromatic monomers, and polymer block A2 has a higher molecular weight than polymer block A1; X is the residue of a coupling agent; n is an integer having a value between 2 and 30; Formula [B-(B / A)-A1] n -X coupled block copolymer molecules account for about 20 to about 80 weight percent of the molecular weight distribution of the two-component block copolymer as measured by GPC-RI; the uncoupled block copolymer molecules of formula B-(B / A)-A2 account for about 20 to about 80 weight percent of the molecular weight distribution of the two-component block copolymer as measured by GPC-RI; The uncoupled block copolymer molecules of formula B-(B / A)-A1 account for about 0 to about 20 weight percent of the molecular weight distribution of the binary block copolymer as measured by GPC-RI.

[0039] In another embodiment, the bicomponent block copolymer of the present invention comprises a block copolymer C and a block copolymer U, wherein: Block copolymer C has the general formula [B-A1] n -X: and The block copolymer U has the general formula B-A2; or B-A2 and B-A1, where: B is a polymer block formed exclusively from one or more conjugated diene monomers; A1 and A2 are polymer blocks formed exclusively from monovinyl aromatic monomers; Polymer block A2 has a higher molecular weight than polymer block A1; X is the residue of a coupling agent; n is an integer with a value between 2 and 30; Formula [B-A1] n -X coupled block copolymer molecules account for about 20 to about 80 weight percent of the molecular weight distribution of the two-component block copolymer as measured by GPC-RI; the uncoupled block copolymer molecules of formula B-A2 account for about 20 to about 80 weight percent of the molecular weight distribution of the two-component block copolymer as measured by GPC-RI; The uncoupled block copolymer molecules of formula B-A1 account for about 0 to about 20 weight percent of the molecular weight distribution of the binary block copolymer as measured by GPC-RI.

[0040] In another embodiment, the bicomponent block copolymer of the present invention comprises a block copolymer C and a block copolymer U, wherein: The block copolymer C has the general formula: [(B / A)-A1] n -X; The block copolymer U has the general formula: (B / A)-A2; or (B / A)-A2 and (B / A)-A1, where: (B / A) is a polymer block formed from at least one conjugated diene monomer and at least one monovinyl aromatic monomer, wherein the conjugated diene and monovinyl aromatic repeat units are randomly arranged along the polymer block; A1 and A2 are polymer blocks formed only from monovinyl aromatic monomers, and polymer block A2 has a higher molecular weight than polymer block A1; X is the residue of a coupling agent; n is an integer with a value between 2 and 30; Formula [(B / A)-A1] n -X coupled block copolymer molecules account for about 20 to about 80 weight percent of the molecular weight distribution of the two-component block copolymer as measured by GPC-RI; the uncoupled block copolymer molecules of formula (B / A)-A2 account for about 20 to about 80 weight percent of the molecular weight distribution of the two-component block copolymer as measured by GPC-RI; The uncoupled block copolymer molecules of formula (B / A)-A1 account for about 0 to about 20% by weight of the molecular weight distribution of the binary block copolymer as measured by GPC-RI.

[0041] Another aspect of the present invention provides a method for making novel bicomponent block copolymers in a batch reactor, which comprises reacting at least one conjugated diene monomer and one monovinyl aromatic monomer under anionic polymerization conditions and forming a bicomponent block copolymer comprising two types of block copolymer molecules C and U.

[0042] A preferred embodiment of the present invention is a process 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 a reactor in any order; A monofunctional organolithium initiator compound is added to the reactor and the monomer mixture is anionically polymerized to complete conversion to form a compound of formula D-(D / A)-A1 (-) forming a block copolymer anion of A limited amount of coupling agent is added to the reactor to form the copolymer anion D-(D / A)-A1 (-) By coupling only a portion of the uncoupled block copolymer anion D-(D / A)-A1 (-) and the formula [D-(D / A)-A1] n - forming a mixture of coupled block copolymer molecules of X; A monovinyl aromatic monomer is added to the reactor and this monomer is anionically polymerized to form the remaining block copolymer anion D-(D / A)-A1 (-) Add to this the equation D-(D / A)-A2 (-) and a chain-extended tapered block copolymer anion of the formula [D-(D / A)-A1]n forming a mixture of coupled block copolymer molecules of -X; and Add the proton donor compound or electrophilic monofunctional additive to the reactor and the remaining block copolymer anion D-(D / A)-A2 (-) in an amount sufficient to stop

[0043] In this way, a bicomponent block copolymer comprising two types of block copolymer molecules C and U is produced in situ in a batch reactor, wherein: C is of the general formula [D-(D / A)-A1] n -X block copolymer; U is a block copolymer of the general formula D-(D / A)-A2; D is a polymer block formed from a conjugated diene monomer and a monovinyl aromatic monomer, with the conjugated diene repeat unit having the highest molar amount; (D / A) is a polymer block whose composition gradually changes from being richer in conjugated diene repeat units toward the end adjacent to the D block to being substantially richer in monovinyl aromatic repeat units toward the opposite end; A1 and A2 are polymer blocks containing only monovinyl aromatic repeating units; Polymer block A2 has a higher molecular weight than polymer block A1; X is the residue of a coupling agent.

[0044] n is an integer ranging from 2 to about 30 depending on the coupling agent used; Block copolymer C has a higher molecular weight and a lower monovinyl aromatic repeat unit content than block copolymer U.

[0045] An additional embodiment of the present invention is a process for producing novel dicomponent block copolymers in a batch reactor by: 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 anionically polymerizing the monomer mixture to full conversion to form a dicomponent block copolymer of the formula D-(D / A)-A1. (-) adding a coupling agent to the reactor to form a block copolymer anion D-(D / A)-A1 (-) By coupling only a part of the block copolymer anion D-(D / A)-A1 (-) and the formula [D-(D / A)-A1] n -X; adding a limited amount of a proton donor compound or an electrophilic monofunctional compound to the reactor to terminate only a portion of the block copolymer anions to form a mixture of coupled tapered block copolymer molecules of the formula D-(D / A)-A1 (-) a block copolymer anion of the formula [D-(D / A)-A1] n and forming a mixture of coupled block copolymer molecules of -X and block copolymer D-(D / A)-A1; and forming the remaining block copolymer anion D-(D / A)-A1 by adding a monovinyl aromatic monomer to the reactor and anionically polymerizing this monomer. (-) Add to this the equation D-(D / A)-A2 (-) a chain-extended block copolymer anion of the formula [D-(D / A)-A1] n forming a mixture of coupled block copolymer molecules of formula D-(D / A)-A1 and block copolymer molecules of formula D-(D / A)-A1; adding a proton donor compound or an electrophilic monofunctional compound, or a mixture thereof, to the reactor to form a mixture of coupled block copolymer molecules of formula D-(D / A)-A2 (-) in an amount sufficient to stop

[0046] In this way, a bicomponent block copolymer containing two block copolymer molecules, C and U, is produced in situ in a batch reactor, where C has the general formula [D-(D / A)-A1] n and U is a block copolymer of the general formula D-(D / A)-A2 and D-(D / A)-A1, where D is a polymer block formed from a conjugated diene monomer and a monovinyl aromatic monomer and has the highest molar amount of conjugated diene repeat units, (D / A) is a polymer block that gradually changes in composition from being more enriched in conjugated diene repeat units toward the end adjacent to the D block until it is substantially enriched in monovinyl aromatic repeat units toward the opposite end, A1 and A2 are polymer blocks containing only monovinyl aromatic repeat units, polymer block A2 has a higher molecular weight than polymer block A1, X is the residue of a coupling agent, and n is an integer ranging from 2 to about 30 depending on the coupling agent used, and block copolymer C has a higher molecular weight and a lower monovinyl aromatic repeat unit content than block copolymer U.

[0047] Another embodiment of the present invention is a process for producing novel binary block copolymers, comprising adding a hydrocarbon solvent, a randomizer or polar modifier, and at least one conjugated diene monomer to a reactor in any order; adding a monofunctional organolithium initiator compound to the reactor and anionically polymerizing the conjugated diene monomer to a conversion level of about 80% to about 95%; and (-) a monovinyl aromatic monomer is added to the reactor, which initially randomly copolymerizes with the remaining conjugated butadiene monomer to form a block copolymer anion B-(B / A) until the conjugated diene is completely converted; (-) and then incorporating only the monovinyl aromatic monomer into the block copolymer anion until the monovinyl aromatic monomer is completely converted to form a block copolymer anion of formula B-(B / A)-A1 (-) a limited amount of coupling agent is added to the reactor to form a copolymer anion B-(B / A)-A1(-) By coupling only a part of the block copolymer anion B-(B / A)-A1 (-) and the formula [B-(B / A)-A1] n and forming a mixture of coupled block copolymer molecules of B-(B / A)-A1 by adding a monovinyl aromatic monomer to the reactor and anionically polymerizing the monomer; (-) Add to the equation B-(B / A)-A2 (-) and a monovinyl aromatic chain-extended block copolymer anion of the formula [B-(B / A)-A1] n a proton donor compound or an electrophilic monofunctional additive to the reactor to form a mixture of coupled block copolymer molecules B-(B / A)-A2; and (-) in an amount sufficient to stop

[0048] In this way, a bicomponent block copolymer containing two block copolymer molecules C and U is produced in situ in a batch reactor, where C has the general formula [B-(B / A)-A1] n -X block copolymer; U is a block copolymer of the general formula B-(B / A)-A2, where B is a polymer block containing only conjugated diene repeat units, (B / A) is a polymer block containing monovinyl aromatic and conjugated diene repeat units randomly arranged along the polymer block, A1 and A2 are polymer blocks containing only monovinyl aromatic repeat units, polymer block A2 has a higher molecular weight than polymer block A1, X is the residue of a coupling agent, and n is an integer ranging from 2 to about 30 depending on the coupling agent used, and block copolymer C has a higher molecular weight and a lower monovinyl aromatic repeat unit content than block copolymer U.

[0049] Another embodiment of the present invention is a process for producing novel binary block copolymers, comprising adding a hydrocarbon solvent, a randomizer or polar modifier, and at least one conjugated diene monomer to a reactor in any order; adding a monofunctional organolithium initiator compound to the reactor and anionically polymerizing the conjugated diene monomer to a conversion level of about 80% to about 95%; and (-) a monovinyl aromatic monomer is added to the reactor, which initially randomly copolymerizes with the remaining conjugated butadiene monomer to form a block copolymer anion B-(B / A) until the conjugated diene is completely converted; (-) and then adding only the monovinyl aromatic monomer to the block copolymer anion until the monovinyl aromatic monomer is completely converted to form a block copolymer anion of formula B-(B / A)-A1 (-) a limited amount of coupling agent is added to the reactor to form a copolymer anion B-(B / A)-A1 (-) By coupling only a part of the block copolymer anion B-(B / A)-A1 (-) and the formula [B-(B / A)-A1] n -X; adding a limited amount of a proton donor compound or an electrophilic monofunctional compound to the reactor to terminate only a portion of the block copolymer anions to form a mixture of coupled block copolymer molecules of the formula B-(B / A)-A1 (-) a block copolymer anion of the formula [B-(B / A)-A1] n -X and a mixture of block copolymers of the formula B-(B / A)-A1; adding a monovinyl aromatic monomer to the reactor and anionically polymerizing the monomer to form an anionic block copolymer B-(B / A)-A1 (-) Add to the equation B-(B / A)-A2 (-) a chain-extended block copolymer anion of the formula [B-(B / A)-A1] nforming a mixture of coupled block copolymer molecules of formula B-(B / A)-A1 and block copolymer molecules of formula B-(B / A)-A1; adding a proton donor compound or an electrophilic monofunctional compound to the reactor and dissolving all remaining block copolymer anions B-(B / A)-A2 (-) in an amount sufficient to stop

[0050] In this way, a bicomponent block copolymer containing two block copolymer molecules, C and U, is produced in situ in a batch reactor, where C has the general formula [B-(B / A)-A1] n and U is a block copolymer of the general formula: B-(B / A)-A2 and B-(B / A)-A1, where B is a polymer block containing only conjugated diene repeat units, (B / A) is a polymer block containing monovinyl aromatic and conjugated diene repeat units randomly arranged along the polymer block, A1 and A2 are polymer blocks containing only monovinyl aromatic repeat units, polymer block A2 has a higher molecular weight than polymer block A1, X is a residue of a coupling agent, and n is an integer ranging from 2 to about 30 depending on the coupling agent used, and block copolymer C has a higher molecular weight and a lower monovinyl aromatic repeat unit content than block copolymer U.

[0051] Another embodiment of the present invention is a process for preparing novel binary block copolymers, comprising adding a hydrocarbon solvent, a randomizer or polar modifier, at least one monovinyl aromatic monomer, and at least one conjugated diene monomer to a reactor in any order; adding a monofunctional organolithium initiator compound to the reactor; and anionically copolymerizing the monovinyl aromatic monomer and the conjugated diene monomer to complete conversion to produce a diblock copolymer of the formula (B / A): (-) by adding a monovinyl aromatic monomer to the reactor and anionically polymerizing the monomer to form a random copolymer anion (B / A) (-) Add to this the formula (B / A)-A1 (-)a limited amount of coupling agent is added to the reactor to form a block copolymer anion (B / A)-A1 (-) By coupling only a part of the block copolymer anion (B / A)-A1 (-) and the formula [(B / A)-A1] n and forming a mixture of coupled block copolymer molecules of (B / A)-X by adding a monovinyl aromatic monomer to the reactor and anionically polymerizing the monomer to form a block copolymer anion (B / A)-A1. (-) Add to this the formula (B / A)-A2 (-) and a chain-extended block copolymer anion of the formula [(B / A)-A1] n forming a mixture of coupled block copolymer molecules of (B / A)-X; adding a proton donor compound or an electrophilic monofunctional additive to the reactor and all remaining block copolymer anions (B / A)-A2 (-) in an amount sufficient to stop

[0052] In this way, a bicomponent block copolymer containing two block copolymer molecules, C and U, is produced in situ in a batch reactor, where C has the general formula [(B / A)-A1] n -X block copolymer, U is a block copolymer of the general formula: (B / A)-A2, (B / A) is a polymer block containing randomized monovinyl aromatic and conjugated diene repeat units, A1 and A2 are polymer blocks containing only monovinyl aromatic repeat units, polymer block A2 has a higher molecular weight than polymer block A1, X is a residue of a coupling agent, n is an integer ranging from 2 to about 30 depending on the coupling agent used, and block copolymer C has a higher molecular weight and a lower monovinyl aromatic repeat unit content than block copolymer U.

[0053] Another embodiment of the present invention is a process for preparing novel binary block copolymers, comprising adding a hydrocarbon solvent, a randomizer or polar modifier, at least one monovinyl aromatic monomer, and at least one conjugated diene monomer to a reactor in any order; adding a monofunctional organolithium initiator compound to the reactor; and anionically copolymerizing the monovinyl aromatic monomer and the conjugated diene monomer to full conversion to produce a diblock copolymer of the formula (B / A): (-) by adding a monovinyl aromatic monomer to the reactor and anionically polymerizing the monomer to form a random copolymer anion (B / A) (-) Add to this the formula (B / A)-A1 (-) a limited amount of coupling agent is added to the reactor to form a block copolymer anion (B / A)-A1 (-) By coupling only a part of the block copolymer anion (B / A)-A1 (-) and the formula [(B / A)-A1] n adding a limited amount of a proton donor compound or an electrophilic monofunctional compound to the reactor to terminate only a portion of the block copolymer anions to form a mixture of coupled block copolymer molecules of formula (B / A)-A1 (-) a block copolymer anion of the formula [(B / A)-A1] n -X and a mixture of block copolymers of formula (B / A)-A1; adding a monovinyl aromatic monomer to the reactor and anionically polymerizing the monomer to produce a mixture of block copolymers of formula (B / A)-A1; (-) Add to this the formula (B / A)-A2 (-) a chain-extended block copolymer anion of the formula [(B / A)-A1] n forming a mixture of coupled block copolymer molecules of formula (B / A)-X and block copolymer molecules of formula (B / A)-A1; adding a proton donor compound or an electrophilic monofunctional additive, or a mixture thereof, to the reactor to form a mixture of all remaining block copolymer anions (B / A)-A2 (-)in an amount sufficient to stop

[0054] In this way, a bicomponent block copolymer containing two block copolymer molecules, C and U, is produced in situ in a batch reactor, where C has the general formula [(B / A)-A1] n and U is a block copolymer of the general formula (B / A)-A2 and (B / A)-A1, (B / A) is a random copolymer block containing monovinyl aromatic and conjugated diene repeat units, A1 and A2 are polymer blocks containing only monovinyl aromatic repeat units, polymer block A2 has a higher molecular weight than polymer block A1, X is a residue of a coupling agent, and n is an integer ranging from 2 to about 30 depending on the coupling agent used, and block copolymer C has a higher molecular weight and a lower monovinyl aromatic repeat unit content than block copolymer U.

[0055] Another embodiment of the present invention is a process for producing novel binary block copolymers, comprising adding a hydrocarbon solvent, a randomizer or polar modifier, and at least one conjugated diene monomer to a reactor in any order; adding a monofunctional organolithium initiator compound to the reactor and anionically polymerizing the conjugated diene monomer until complete conversion to produce a diblock copolymer of formula B (-) adding a monovinyl aromatic monomer to the reactor and anionically polymerizing the monomer to form a polymer anion B; (-) Add to equation B-A1 (-) a limited amount of coupling agent is added to the reactor to form a block copolymer anion B-A1 (-) By coupling only a part of the block copolymer anion B-A1 (-) and formula [B-A1] n forming a mixture of coupled block copolymer molecules of B-A1-X; and forming an anionic block copolymer B-A1 by adding a monovinyl aromatic monomer to the reactor and anionically polymerizing the monomer. (-)Add to equation B-A2 (-) and a chain-extended block copolymer anion of formula [B-A1] n a proton donor compound or an electrophilic monofunctional compound in the reactor to generate a mixture of coupled block copolymer molecules B-A2; (-) in an amount sufficient to stop

[0056] In this way, a bicomponent block copolymer containing two types of block copolymer molecules C and U is produced in situ in a batch reactor, where C is represented by the general formula [B-A1] n -X block copolymer, U is a block copolymer of the general formula B-A2, B is a polymer block containing only conjugated diene repeat units, A1 and A2 are polymer blocks rich in monovinyl aromatic repeat units, polymer block A2 has a higher molecular weight than polymer block A1, X is a residue of a coupling agent, n is an integer ranging from 2 to about 30 depending on the coupling agent used, and block copolymer C has a higher molecular weight and a lower monovinyl aromatic repeat unit content than block copolymer U.

[0057] Another embodiment of the present invention is a process for producing novel binary block copolymers, comprising adding a hydrocarbon solvent, a randomizer or polar modifier, and at least one conjugated diene monomer to a reactor in any order; adding a monofunctional organolithium initiator compound to the reactor and anionically polymerizing the conjugated diene monomer until complete conversion to produce a diblock copolymer of formula B (-) adding a monovinyl aromatic monomer to the reactor and anionically polymerizing the monomer to form a polymer anion B; (-) Add to equation B-A1 (-) a limited amount of coupling agent is added to the reactor to form a block copolymer anion B-A1 (-) By coupling only a part of the block copolymer anion B-A1 (-)and formula [B-A1] n -X; adding a limited amount of a proton donor compound or an electrophilic monofunctional compound to the reactor to terminate only a portion of the block copolymer anions to form a mixture of coupled block copolymer molecules of formula B-A1 (-) Block copolymer anion of formula [B-A1] n -X coupled block copolymer molecules and a mixture of block copolymers of formula B-A1; adding a monovinyl aromatic monomer to the reactor and anionically polymerizing the monomer to produce a mixture of block copolymer anions of formula B-A1 (-) Add to equation B-A2 (-) A chain-extended block copolymer anion of formula [B-A1] n forming a mixture of coupled block copolymer molecules of formula B-A1 and block copolymer molecules of formula B-A2; adding a proton donor compound or an electrophilic monofunctional additive, or a mixture thereof, to the reactor to form a mixture of coupled block copolymer molecules of formula B-A2; (-) in an amount sufficient to stop

[0058] In this way, a bicomponent block copolymer containing two types of block copolymer molecules C and U is produced in situ in a batch reactor, where C is represented by the general formula [B-A1] n -X block copolymer; U is a block copolymer of the general formula B-A2 and B-A1, B is a polymer block containing only conjugated diene repeat units, A1 and A2 are polymer blocks rich in monovinyl aromatic repeat units, polymer block A2 has a higher molecular weight than polymer block A1, X is a residue of a coupling agent, n is an integer ranging from 2 to about 30 depending on the coupling agent used, and block copolymer C has a higher molecular weight and a lower monovinyl aromatic repeat unit content than block copolymer U.

[0059] In some embodiments of the method for obtaining the binary block copolymer of the present invention, a proton donor and / or a monofunctional electrophilic terminator is added to partially deactivate the block copolymer anion before the block copolymerization of the last monovinyl aromatic monomer. Such a terminator can be added to the reactor before the last monovinyl aromatic monomer is added or simultaneously with the last monovinyl aromatic monomer. Examples of such a terminator include water, polymerization inhibitors such as tert-butylcatechol, phenolic antioxidants, alcohols, organic acids, inorganic acids, chlorotrimethylsilane, etc.

[0060] Block copolymerization is typically carried out under an inert atmosphere in an inert hydrocarbon solvent using highly purified reagents to prevent premature termination of the polymerization reaction. Suitable solvents for practicing 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, and the like, or mixtures thereof. Cyclohexane is the preferred solvent for the present invention.

[0061] In some embodiments, random copolymerization of monovinyl aromatic monomers and conjugated diene monomers is promoted using a randomizer, also known as a polar modifier, to form (B / A) random polymer blocks and accelerate the addition of monovinyl aromatic monomers to polymer anions terminated with conjugated dienyllithium units. The randomizer also induces 1,2- and 3,4-addition of anionically polymerized conjugated dienes. Nevertheless, 1,2- and 3,4-vinyl-added conjugated diene repeat units are more reactive to crosslinking / vulcanization reactions. Therefore, an optimal amount of polar modifier compound must be selected to balance the copolymerization rate in the process for producing the two-component block copolymer of the present invention and the crosslinking rate of the microcellular rubber compound of the present invention. The acceleration of block polymerization rate and enrichment of 1,2- and 3,4-vinyl addition during conjugated diene polymerization vary depending on the polar modifier selected, and this behavior is well known to those skilled in the art. Polar modifiers that can be used to prepare the binary block copolymers of the present invention include ethers, tertiary amines, aminoethers, and Lewis bases such as Group IA alkali metal alkoxides, and combinations thereof. Specific examples of 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, tetramethylene oxide (tetrahydrofuran), 1,2-dimethoxyethane, bis-tetrahydrofuran, ditetrahydrofurylpropane (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, combinations thereof, and the like.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 the like, 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, polyfunctional, and oligomeric alkyl and cyclic metal alkoxides, such as sodium tert-butoxide, sodium tert-butoxide amylate, sodium mentholate, potassium tert-butoxide, potassium tert-amylate, potassium mentholate, potassium 3,7-dimethyl-3-octanolate, and the like, and mixtures thereof. The polar modifier can be charged directly to the reactor or can be dissolved in a solvent beforehand for use in the process. The concentration of the polar modifier in the reaction system of the present invention is 5 to 5000 parts per 1 million parts by weight of the solvent, more preferably 10 to 1000 parts per 1 million parts by weight of the solvent, and most preferably 20 to 100 parts per 1 million parts by weight of the solvent.

[0062] Conjugated diene monomers suitable for use in preparing the binary 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.

[0063] Monovinyl aromatic monomers suitable for use in preparing the binary block copolymers of the present invention include, but are not limited to, styrene, 3-methylstyrene, α-methylstyrene, p-methylstyrene, α,4-dimethylstyrene, t-butylstyrene, o-chlorostyrene, 2-butenylnaphthalene, 4-t-butoxystyrene, 3-isopropenylbiphenyl, 4-vinylpyridine, 2-vinylpyridine, isopropenylnaphthalene, 4-n-propylstyrene, and combinations thereof.

[0064] The two-component block copolymers of the present invention are prepared by anionic polymerization by contacting anionically polymerizable monomers with a monofunctional organolithium compound as an initiator. A preferred class of these compounds can be represented by the formula RLi, where R is a hydrocarbon radical selected from the group consisting of aliphatic, alicyclic, and aromatic radicals containing 1 to 20 carbon atoms, although higher molecular weight initiators can also be used. Many anionic polymerization initiators are well known and commercially available. Monofunctional organolithium compounds such as butyllithium are commonly used initiators. Specific examples of these initiators include cycloalkyllithium compounds such as methyllithium, ethyllithium, tert-butyllithium, sec-butyllithium, n-butyllithium, n-decyllithium, isopropyllithium, eicosyllithium, and cyclohexyllithium, and aryllithium compounds such as phenyllithium, naphthyllithium, p-toluyllithium, and 1,1-diphenylhexyllithium. Monofunctional organolithium compounds substituted with protected polar functional groups can also be used as initiators for anionic polymerization.

[0065] In embodiments relating to the process for producing the binary block copolymer of the present invention, the amount of monofunctional organolithium initiator varies depending on the desired viscosity of the binary block copolymer and the purity level of the solvent and monomers used in the process. Preferably, the amount of monofunctional organolithium initiator in the process for producing the binary block copolymer of the present invention is from about 2 millimoles to about 30 millimoles per kilogram of the total conjugated diene monomers plus monovinyl aromatic monomers charged to the reactor, more preferably from about 12 millimoles to about 26 millimoles per kilogram of the total conjugated diene monomers plus monovinyl aromatic monomers charged to the reactor, and most preferably from about 16 millimoles to about 22 millimoles per kilogram of the total conjugated diene monomers plus monovinyl aromatic monomers charged to the reactor.

[0066] Anionic polymerizations are typically carried out at temperatures ranging from -100°C to 150°C, preferably 25°C to 120°C. Typically, 50-90% by weight of the reaction solvent is used to control viscosity in the reaction zone, preferably 70-85%. Typical residence times for anionic polymerizations vary from 0.1 to 5 hours, preferably 0.2 to 1 hour, depending on reaction temperature, monomer concentration, and initiator level.

[0067] In an embodiment of the method provided by the present invention, anionically polymerized block copolymer anions undergo partial coupling. Partial coupling means that a portion of all living anionically polymerized polymer chain ends are coupled with a coupling agent. Reaction of the living anionically polymerized block copolymer chain ends with a suitable coupling agent results in a coupled block copolymer that does not have an anionically active center for further polymerization. The coupling agent desirably couples 2 to 30 anionically polymerized polymer chains, although coupling agents capable of coupling more chains can also be used. Suitable coupling agents for use in the partial coupling step include, but are not limited to, epoxidized soybean oil, silicon halides, functionalized silicon compounds such as silane compounds, and functionalized oligomeric compounds such as those described in U.S. Pat. No. 7,517,934, the entire disclosure of which is incorporated herein by reference. Silicon tetrachloride, methyl silicon trichloride, and dimethyl silicon dichloride are examples of suitable coupling agents, with silicon tetrachloride being particularly well suited for this application. Partial coupling is achieved by controlling the stoichiometric ratio of coupling agent to living polymer. Partial coupling results in block copolymer blends with desired properties.

[0068] Next, upon completion of the polymerization reaction, the entire reaction mixture is treated to terminate the block copolymer anions and recover the two-component block copolymer of the present invention. This termination is achieved by feeding a proton donor compound, such as water, alcohol, or an organic or inorganic acid, to the reactor. The amount of terminating agent added must be at least the stoichiometric amount corresponding to the amount of block copolymer anions remaining in the reactor.

[0069] A further step in all embodiments of the method for producing the bicomponent block copolymer of the present invention is the desirability of adding an antioxidant system while the bicomponent block copolymer is still in hydrocarbon solution. The antioxidant system protects the bicomponent block copolymer from degradation in subsequent processing steps, separating it from the solvent, and extending the shelf life of the final product. A wide variety of antioxidant systems are known in the art, and any system can be used without limiting the scope of the present invention. A preferred antioxidant system consists of a synergistic blend of hindered phenol 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(octyl mercapto)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, 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 the like, and mixtures thereof.Examples of suitable phosphite antioxidants include, but are not limited to, tris(nonylphenyl)phosphite, tris(2,4-ditert-butylphenyl)phosphite, butylidenebis[2-tert-butyl-5-methyl-p-phenylene]-P,P,P',P'-tetratridecylbis(phosphine), 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 2,4-bis(1,1-dimethylpropyl)phenyl, and 4-(1,1-dimethylpropyl)phenyl phosphite. Examples of suitable antioxidants include a mixture of octadecyloxyphenyltriesters, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 2-(1,1-dimethylethyl)-6-methyl-4-[3-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]propyl]phenol, and mixtures thereof. The preferred amount of antioxidant system used is 0.1 to 1.5 parts per 100 parts by weight of the binary block copolymer of the present invention.

[0070] An additional step in all embodiments of the method for producing the diblock copolymer of the present invention is to isolate the diblock copolymer from the solvent by any finishing process known in the art, such as roll milling, vacuum-assisted devolatilization, precipitation and drying, steam stripping followed by dehydration and drying.

[0071] An optional step in all embodiments of the method for producing the binary block copolymer of the present invention is the inclusion of an extender oil in the binary block copolymer. The oil can be added while the binary block copolymer is still in solution in a hydrocarbon solvent or at any stage of the subsequent finishing process. Suitable oils for oil extension include, but are not limited to, mineral oil, paraffinic oil, naphthenic oil, relatively naphthenic-rich oil, relatively aromatic-rich oil, aromatic oil, highly aromatic oil, very highly aromatic oil, and the like, or mixtures thereof. The preferred oil content is 0 to 12 parts per 100 parts by weight of the binary block copolymer, more preferably 0 to 10 parts per 100 parts by weight of the binary block copolymer, and most preferably 0 to 8 parts per 100 parts by weight of the binary block copolymer.

[0072] Another aspect of the present invention provides a composition for producing a crosslinked microcellular rubber compound, the composition comprising: Two-component block copolymers; a blowing agent or mixture of blowing agents; and A crosslinking agent or mixture of crosslinking agents.

[0073] Optionally, the composition contains 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, ground crosslinked microcellular rubber compounds, fillers, plasticizers, blowing agent activators, crosslinking agent activators, crosslinking accelerators, vulcanization retarders, antioxidants, antiozonants, UV stabilizers, light stabilizers, fragrances or odorants, termite repellents, antibacterial agents, metal deactivators, dyes, pigments, mold release agents, and the like, or mixtures thereof.

[0074] A preferred embodiment of the present invention is a composition for producing a crosslinked microcellular compound comprising: (1) A two-component block copolymer comprising two types of block copolymer molecules C and U, C is of the general formula [D-(D / A)-A1] n -X block copolymer, and U is a block copolymer of the general formula D-(D / A)-A2 or D-(D / A)-A2 and D-(D / A)-A1, D is a polymer block formed from at least one conjugated diene monomer and at least one monovinyl aromatic monomer, wherein the conjugated diene repeat units are in molar excess over the monovinyl aromatic repeat units along the entire length of the polymer block; (D / A) is a polymer block formed from at least one conjugated diene monomer and at least one monovinyl aromatic monomer, the polymer block end opposite A1 or A2 being composed primarily of conjugated diene repeat units and gradually varying in composition along its length until it is composed essentially of monovinyl aromatic repeat units toward the end adjacent A1 or A2; A1 and A2 are polymer blocks formed only from monovinyl aromatic monomers, and polymer block A2 has a higher molecular weight than polymer block A1; X is a residue of a coupling agent, n is an integer between 2 and 30; a two-component block copolymer, wherein the amount of the two-component block copolymer is 50 to 100 parts by weight per 100 parts by weight of the polymer raw materials contained in the formulation for producing the crosslinked microcellular rubber compound; (2) a blowing agent, or a mixture of chemical blowing agents, in an amount of 1 to 10 parts by weight per 100 parts by weight of polymeric ingredients included in the formulation for producing a crosslinked microcellular rubber compound; and (3) A crosslinking agent, or mixture of crosslinking agents, in an amount of 0.5 to 5 parts by weight per 100 parts by weight of polymeric raw materials included in a formulation for producing a crosslinked microcellular rubber compound.

[0075] The composition may include one or more optional additives such as: 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, such polymers preferably comprising 0 to about 50 parts per 100 parts by weight of polymeric ingredients in the formulation for producing the crosslinked microcellular rubber compound; a filler or a mixture of fillers or a rubber vulcanization compound powder, preferably in an amount of 0 to about 200 parts per 100 parts by weight of the polymeric raw materials included in the formulation for producing the crosslinked microcellular rubber compound; a plasticizer or mixture of plasticizers in an amount of 0 to 40 parts by weight per 100 parts by weight of polymeric raw materials included in the formulation for producing the crosslinked microcellular rubber compound; an antioxidant or mixture of antioxidants in an amount preferably of 0 to 2 parts by weight per 100 parts by weight of polymeric raw materials included in the formulation for producing the crosslinked microcellular rubber compound; a mixture of blowing agent activators or chemical blowing agent accelerators in an amount preferably of 0 to about 5 parts per 100 parts by weight of polymeric ingredients included in the formulation for producing the crosslinked microcellular rubber compound; a crosslinker activator or a mixture of crosslinker activators in an amount preferably of 0 to 5 parts per 100 parts by weight of polymeric raw materials included in the formulation for producing a crosslinked microcellular rubber compound; a crosslinking accelerator or mixture of crosslinking accelerators, preferably in an amount of 0 to 5 parts by weight per 100 parts by weight of the polymeric raw materials included in the formulation for producing the crosslinked microcellular rubber compound; and Other additives such as vulcanization retarders, antiozonants, UV stabilizers, light stabilizers, fragrances or odorants, termite repellents, antibacterial agents, metal deactivators, dyes, pigments, mold release agents, and the like and mixtures thereof.

[0076] Another embodiment of the present invention is a composition for producing a crosslinked microcellular compound comprising: (1) A two-component block copolymer comprising two types of block copolymer molecules C and U, wherein the block copolymer C has the general formula [B-(B / A)-A1] n -X, wherein the block copolymer U has the general formula B-(B / A)-A2 or B-(B / A)-A2 and B-(B / A)-A1, wherein B is a polymer block formed exclusively from one or more conjugated diene monomers, (B / A) is a polymer block formed from at least one conjugated diene monomer and at least one monovinyl aromatic monomer, the conjugated diene and monovinyl aromatic repeat units being randomly arranged along the polymer block, A1 and A2 are polymer blocks formed exclusively from monovinyl aromatic monomers, the polymer block A2 has a higher molecular weight than the polymer block A1, X is a residue of a coupling agent, n is an integer having a value of 2 to 30, and the amount of the bicomponent block copolymer is 50 to 100 parts by weight per 100 parts by weight of the polymer ingredients included in the formulation for producing a crosslinked microcellular rubber compound; (2) a blowing agent, or a mixture of chemical blowing agents, preferably in an amount of 1 to 10 parts by weight per 100 parts by weight of the polymeric ingredients included in the formulation for producing the crosslinked microcellular rubber compound; and (3) A crosslinking agent, or mixture of crosslinking agents, preferably in an amount of 0.5 to 5 parts per 100 parts by weight of polymeric raw materials included in the formulation for producing the crosslinked microcellular rubber compound.

[0077] The composition may include one or more optional additives such as: 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, such polymers preferably comprising 0 to about 50 parts per 100 parts by weight of polymeric ingredients in the formulation for producing the crosslinked microcellular rubber compound; a filler or a mixture of fillers or a rubber vulcanization compound powder, preferably in an amount of 0 to about 200 parts per 100 parts by weight of the polymeric raw materials included in the formulation for producing the crosslinked microcellular rubber compound; a plasticizer or mixture of plasticizers in an amount of 0 to 40 parts by weight per 100 parts by weight of polymeric raw materials included in the formulation for producing the crosslinked microcellular rubber compound; an antioxidant or mixture of antioxidants in an amount preferably of 0 to 2 parts by weight per 100 parts by weight of polymeric raw materials included in the formulation for producing the crosslinked microcellular rubber compound; a mixture of blowing agent activators or chemical blowing agent accelerators in an amount preferably of 0 to about 5 parts per 100 parts by weight of polymeric ingredients included in the formulation for producing the crosslinked microcellular rubber compound; a crosslinker activator or a mixture of crosslinker activators in an amount preferably of 0 to 5 parts per 100 parts by weight of polymeric raw materials included in the formulation for producing a crosslinked microcellular rubber compound; a crosslinking accelerator or mixture of crosslinking accelerators, preferably in an amount of 0 to 5 parts by weight per 100 parts by weight of the polymeric raw materials included in the formulation for producing the crosslinked microcellular rubber compound; and Other additives such as vulcanization retarders, antiozonants, UV stabilizers, light stabilizers, fragrances or odorants, termite repellents, antibacterial agents, metal deactivators, dyes, pigments, mold release agents, and the like and mixtures thereof.

[0078] Another embodiment of the present invention is a composition for producing a crosslinked microcellular compound comprising: (1) A two-component block copolymer comprising two types of block copolymer molecules C and U, wherein the block copolymer C has the general formula [B-A1] n-X, wherein the block copolymer U has the general formula B-A2 or B-A2 and B-A1, where B is a polymer block formed from one or more conjugated diene monomers, A1 and A2 are polymer blocks formed from monovinyl aromatic monomers, the polymer block A2 has a higher molecular weight than the polymer block A1, X is a residue of a coupling agent, and n is an integer having a value of 2 to 30, and preferably the amount of the bicomponent block copolymer is 50 to 100 parts by weight per 100 parts by weight of polymer raw materials in a formulation for producing a crosslinked microcellular rubber compound; (2) a blowing agent, or mixture of chemical blowing agents, preferably in an amount of 1 to 10 parts by weight per 100 parts by weight of the polymeric ingredients in the formulation; and (3) A crosslinking agent, or mixture of crosslinking agents, in an amount preferably between 0.5 and 5 parts per 100 parts by weight of polymeric raw materials in said formulation.

[0079] Other polymers may be added to the formulation, 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, and any mixtures thereof, with such polymers preferably comprising from 0 to about 50 parts per 100 parts by weight of the polymeric ingredients in the formulation to produce the crosslinked microcellular rubber compound.

[0080] Optional additives to the polymeric ingredients in the formulation for producing the crosslinked microcellular rubber compound include: a filler or a mixture of fillers or a rubber vulcanization compound powder, preferably in an amount of 0 to about 200 parts per 100 parts by weight; a plasticizer or mixture of plasticizers in an amount preferably of 0 to 40 parts per 100 parts by weight; an antioxidant or mixture of antioxidants in an amount preferably of 0 to 2 parts per 100 parts by weight; a mixture of blowing agent activators and / or chemical blowing agent accelerators in an amount preferably of 0 to about 5 parts per 100 parts by weight; a crosslinker activator or a mixture of crosslinker activators in an amount preferably of 0 to 5 parts per 100 parts by weight; a crosslinking accelerator or mixture of crosslinking accelerators in an amount of preferably 0 to 5 parts per 100 parts by weight; and Other additives such as vulcanization retarders, antiozonants, UV stabilizers, light stabilizers, fragrances or odorants, termite repellents, antibacterial agents, metal deactivators, dyes, pigments, mold release agents, and the like and mixtures thereof.

[0081] Another embodiment of the present invention is a composition for producing a crosslinked microcellular compound, comprising a bicomponent block copolymer, a blowing agent, and a crosslinking agent. The bicomponent block copolymer comprises block copolymer molecules C and U, where: The block copolymer C has the general formula [(B / A)-A1] n -X, and the block copolymer U has the general formula (B / A)-A2 or (B / A)-A2 and (B / A)-A1; (B / A) is a polymer block formed from at least one conjugated diene monomer and at least one monovinyl aromatic monomer, preferably wherein the conjugated diene and monovinyl aromatic repeat units are randomly arranged along the polymer block; A1 and A2 are polymer blocks formed only from monovinyl aromatic monomers, and polymer block A2 has a higher molecular weight than polymer block A1; X is the residue of a coupling agent; n is an integer having a value of 2 to 30, and preferably the amount of the two-component block copolymer is 50 to 100 parts by weight per 100 parts by weight of the polymeric raw materials contained in the formulation for producing the crosslinked microcellular rubber compound. A blowing agent is preferably added in an amount of 1 to 10 parts by weight per 100 parts by weight, and a crosslinking agent is preferably added in an amount of 0.5 to 5 parts by weight per 100 parts by weight.

[0082] Optionally, the ingredients in the formulation include the following per 100 parts of polymeric ingredients in the formulation to produce a crosslinked microcellular rubber compound: 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, preferably in an amount of 0 to about 50; a filler, a mixture of fillers, or a rubber vulcanization compound powder, preferably in an amount of 0 to about 200 parts; a plasticizer or mixture of plasticizers, preferably in an amount of 0 to 40 parts; an antioxidant or a mixture of antioxidants, preferably in an amount of 0 to 2 parts; a mixture of blowing agent activators or chemical blowing agent accelerators, preferably in an amount of 0 to about 5 parts; a crosslinker activator or a mixture of crosslinker activators in an amount preferably of 0 to 5 parts per 100 parts by weight; a crosslinking accelerator or mixture of crosslinking accelerators, preferably in an amount of 0 to 5 parts; and Other additives such as vulcanization retarders, antiozonants, UV stabilizers, light stabilizers, fragrances or odorants, termite repellents, antibacterial agents, metal deactivators, dyes, pigments, mold release agents, and the like and mixtures thereof.

[0083] Fillers suitable for use in the crosslinked microcellular rubber foam composition of the present invention include, but are not limited to, carbon black, silica, calcium silicate, aluminum silicate, magnesium silicate, sodium silicate, potassium silicate, chalk, dolomite, kaolin clay, calcined clay, hard clay, activated clay, halloysite, sericite, wollastonite, bentonite, light calcium carbonate, ground calcium carbonate, magnesium carbonate, talc, diatomaceous earth, titanium oxide, zinc oxide, calcium oxide, aluminum hydroxide, magnesium hydroxide, gypsum, mica, barium sulfate, calcium sulfate, alumina trihydrate, natural fibers, synthetic fibers, and combinations thereof.

[0084] Plasticizers suitable for use in the crosslinked microcellular rubber foam compositions of the present invention include, but are not limited to, mineral oils such as paraffinic oils, naphthenic oils, relatively naphthenic oils, relatively aromatic oils, aromatic oils, highly aromatic oils, and very highly aromatic oils; paraffins such as unbranched paraffins, isoparaffins, ceresin, isoceresin, paraffin wax, and other mineral waxes; petroleum distillation residues such as montan wax, ozokerite, asphaltenes, bitumen, and pitch; fatty acids such as stearic acid or palmitic acid; metal salts of fatty acids such as zinc soaps of unsaturated fatty acids, zinc soaps of saturated fatty acids, calcium soaps of unsaturated fatty acids, zinc stearate, and calcium stearate; Included are organic acid monoesters such as alkyl or alkoxyalkyl oleates and stearates; organic acid diesters such as dialkyl, dialkoxyalkyl, and alkylaryl phthalates, terephthalates, sebacates, adipates, and glutarates; coumarone and indene resins; trialkyl, trialkoxyalkyl, alkyl diaryl, and triaryl phosphates; polyhydric alcohol 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, factice, and combinations thereof.

[0085] Antioxidants suitable for use in the crosslinked microcellular rubber foam compositions of the present invention include, but are not limited to, hindered phenols such as 2,6-di-t-butyl-p-cresol (BHT), 2,4-dimethyl-6-t-butylphenol, 2,4-dimethyl-6-(α-methyl-cyclohexyl)-phenol, 4-methoxymethyl-2,6-di-t-butyl-phenol, butylated reaction products of p-cresol with dicyclopentadiene, alkylated phenols, styrenated and alkylated phenols, styrenated phenol (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-methylphenylacrylate; bisphenols such as 2,2'-methylene-bis -(4-methyl-6-t-butyl-phenol) (BPH), 2,2'-methylene-bis(4-methyl-6-cyclohexyl-phenol) (CPH), 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol) (IBPH), 2,2'-dicyclopentyl-bis(4-methyl-6-t-butyl-phenol) (DBPH), 2,2'-methylene-bis(4-ethyl-6-t-butyl-phenol), 4,4'-thio-bis(3-methyl benzimidazole derivatives such as 2-mercaptobenzimidazole (MBI), 4-methyl-2-mercaptobenzimidazole and 5-methyl-2-mercaptobenzimidazole (MMBI), zinc-2-mercaptobenzimidazole (ZMBI), zinc-4-methyl-2-mercaptobenzimidazole and zinc-5-methyl-2-mercaptobenzimidazole (ZMMBI).

[0086] Suitable blowing agents for use in the crosslinked microcellular rubber foam composition of the present invention include, but are not limited to, organic chemical blowing agents such as azodicarbonamide (ADC), N,N'-dinitrosopentamethylenetetramine (DNPT), benzenesulfohydrazide (BSH), benzene-1,3-disulfohydrazide, 4,4'-oxybis(benzenesulfonylhydrazide), p-toluenesulfonic acid hydrazide, toluenesulfonylsemicarbazide, 5-phenyltetrazole, trihydrazine triazine; inorganic chemical blowing agents such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, potassium bicarbonate, potassium carbonate; physical blowing agents such as high pressure nitrogen or supercritical carbon dioxide, and combinations thereof.

[0087] Chemical blowing agent activators suitable for use in the crosslinked microcellular rubber foam compositions of the present invention include, but are not limited to, zinc oxide, zinc benzenesulfinate, zinc stearate, zinc 2-ethylhexanoate, zinc carbonate, zinc ditolylsulfonate, calcium carbonate, calcium oxide, magnesium oxide, silica, urea, stearic acid, adipic acid, triethanolamine, diphenylamine derivatives, and combinations thereof.

[0088] Suitable crosslinking agents for use in the crosslinked microcellular 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-azepinone) (CLD), 2-morpholino-dithio-benzothiazole (MBSS), dipentamethylenethiuram tetrasulfide (DPTT), N-oxydiethylenedithiocarbamyl-N'-oxydiethylenesulfonamide (OTOS), and tetramethylthiuram disulfide (TMTD); and organic peroxides such as dicumyl peroxide, t-butyl perbenzoate, t-butylsimyl peroxide, di-t-butyl peroxide. Examples of the peroxysilane include butyl peroxide, lauroyl peroxide, 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane, α,α'-bis(t-butylperoxy)-1,3-diisopropylbenzene, α,α'-bis(t-butylperoxy)-1,4-diisopropylbenzene, n-butyl-4,4-bis(t-butylperoxy)valerate, t-butylperoxyisopropyl carbonate, 1,4-bis-(t-butylperoxyisopropyl)-benzene, di-t-amyl peroxide, t-butylperoxybenzoate, t-amylperoxybenzoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, and the like, or mixtures thereof.

[0089] Suitable crosslinking accelerators for use in the crosslinked microcellular rubber foam compositions of the present invention include, but are not limited to, mercapto accelerators such as 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS), zinc-2-mercaptobenzothiazole (ZMBT); sulfonamide accelerators such as N-cyclohexyl-2-benzothiazylsulfenamide (CBS), N-tert-butyl-2-benzothiazylsulfenamide (TBBS), and 2-benzothiazyl-N-sulfene morpholide (MBS); thiuram accelerators such as tetramethylthiuram disulfide (TMTD), tetramethylthiuram monosulfide (TMTM), and tetraethylthiuram disulfide. sulfide (TETD); dithiocarbamate accelerators such as zinc dimethyldithiocarbamate (ZDMC), zinc diethyldithiocarbamate (ZDEC), and zinc dibutyldithiocarbamate (ZDBC); dithiocarbamyl sulfenamide accelerators such as N-oxydiethylenedithiocarbamyl, N'-oxydiethylenesulfonamide (OTOS); guanidine accelerators such as diphenylguanidine (DPG), di-o-tolylguanidine (DOTG), and o-tolylbiguanidine (OTBG), triazine accelerators, xanthate accelerators, aldehyde-amine accelerators, amine accelerators, thiurea accelerators, dithiophosphate accelerators, and mixtures thereof.

[0090] Crosslinker activators suitable for use in the crosslinked microcellular rubber foam compositions of the present invention include, but are not limited to, zinc oxide, magnesium oxide, Ca(OH), stearic acid, zinc stearate, zinc laurate, dibutylaminooleate, 1,3-diphenylguanidine phthalate, monoethanolamine, diethanolamine, triethanolamine, dibutylamine, dibenzylamine, and mixtures thereof.

[0091] Another aspect of the present invention provides a composition for making a hot melt pressure sensitive adhesive comprising: Two-component block copolymers; tackifying resin; and extender oils or plasticizers; and Antioxidant.

[0092] Optionally, the hot melt pressure-sensitive adhesive composition comprises other additives, such as fillers, waxes, photoinitiators, crosslinking agents, crosslinking coagents, crosslinking retarders, adhesion promoters or coupling agents, UV stabilizers, light stabilizers, ozone stabilizers, epoxy resins, asphalt, reinforcing resins, fragrances or odorants, termite repellents, biocides, antifungal agents, antibacterial agents, metal deactivators, dyes, pigments, colorants, flame retardants, blowing agents, blowing agent activators, or refractive index modifiers.

[0093] A preferred embodiment of the present invention is a hot melt pressure sensitive adhesive composition comprising: (a) a two-component block copolymer having a molecular weight distribution that is wholly or partially resolved to show at least two peaks, the copolymer comprising about 20% by weight to about 50% by weight of C and U; C is contained in the higher molecular weight peak in the molecular weight distribution of the bicomponent block copolymer and comprises coupled block copolymer molecules of the formula: [D-(D / A)-A1] n -X; or [B-(B / A)-A1] n -X; or [(B / A)-A1] n -X; or [B-A1] n -X, or mixtures thereof, and U is included in the remaining low molecular weight peak or peaks of the molecular weight distribution of the dicomponent block copolymer and includes uncoupled block copolymer molecules of the formula: D-(D / A)-A2 or D-(D / A)-A2 and D-(D / A)-A1; or B-(B / A)-A2 or B-(B / A)-A2 and B-(B / A)-A1; or (B / A)-A2 or (B / A)-A2 and (B / A)-A1; or B-A2 or B-A2 and B-A1, or a mixture thereof, B is a polymer block formed solely from conjugated diene monomers, (B / A) is a random polymer block formed from at least one conjugated diene monomer and at least one monovinyl aromatic monomer; D is a polymer block formed from at least one conjugated diene monomer and at least one monovinyl aromatic monomer, wherein the conjugated diene repeat units are in molar excess over the monovinyl aromatic repeat units along the entire length of the polymer block; (D / A) is a polymer block formed from at least one conjugated diene monomer and at least one monovinyl aromatic monomer, wherein the end of the polymer block opposite A1 or A2 is composed primarily of conjugated diene repeat units, and the composition of the polymer block gradually changes along the length of the block until the end adjacent A1 or A2 is composed essentially of monovinyl aromatic repeat units; A1 and A2 are polymer blocks formed only from monovinyl aromatic monomers, and polymer block A2 has a larger molecular weight than polymer block A1. X is the residue of a coupling agent; n is an integer with a value between 2 and 30; (b) about 30% to about 70% by weight of a tackifying resin; (c) about 10% to about 30% by weight of an extender oil or plasticizer; (d) about 0.05 wt. % to about 3.0 wt. % of an antioxidant; (e) Optionally, other additives, such as: fillers, waxes, photoinitiators, crosslinking agents, crosslinking coagents, crosslinking retarders, adhesion promoters or coupling agents, UV stabilizers, light stabilizers, ozone stabilizers, epoxy resins, asphalt, reinforcing resins, fragrances or odorants, termite repellents, biocides, antifungal agents, antibacterial agents, metal deactivators, dyes, pigments, colorants, flame retardants, blowing agents, blowing agent activators, or refractive index modifiers.

[0094] Tackifying resins suitable for use in formulating the hot melt pressure sensitive adhesives of the present invention include, but are not limited to: rosin esters such as Sylvalite® RE100L, Sylvalite® RE115, Sylvalite® RE85L, Foral® 85, Foral® 105, Pentalyn® H, and Permalyn® 3100; styrenated terpenes such as Sylvares® ZT5100, Sylvares® ZT105LT ... ) ZT115LT; polyterpene resins such as Sylvares® TR1100 and Sylvares® TR7115; terpene phenols such as Sylvares® TP2040 and Sylvares® TP115; aliphatic hydrocarbon resins such as Piccotac® 1100, Piccotac® 115, and Wingtack® 95; hydrogenated hydrocarbon resins such as Regalrez® 1094, Eastotac® H100, and Eastotac® H130. Sylvalite® and Sylvares®; terpene-phenolic resins; synthetic C5 resins; alkylaryl resins; phenol-formaldehyde resins; and mixtures thereof. Tackifying resins are commercially available from Kraton Corporation. Foral®, Pentalyn®, Permalyn™, Piccotac®, Regalrez™, and Eastotac® tackifiers are commercially available from Eastman Chemical Company. Wingtack® tackifier is commercially available from Total Cray Valley.

[0095] Extender oils suitable for use in formulating the hot melt pressure sensitive adhesives of the present invention include, but are not limited to: mineral oils; naphthenic oils; paraffinic oils; aromatic oils; vegetable oils; animal oils, and the like, and mixtures thereof.

[0096] Plasticizers suitable for use in formulating the hot melt pressure sensitive adhesives of the present invention include, but are not limited to: olefin oligomers; epoxidized oils; phthalate esters such as dioctyl phthalate, diisoundecyl phthalate, diisononyl phthalate; dialkyl esters of aliphatic dicarboxylic acids; polybutene or polyisobutylene having a molecular weight of less than 3000, and the like, and mixtures thereof.

[0097] Suitable antioxidants for use in formulating the hot-melt pressure-sensitive adhesives of the present invention include, but are not limited to, phenolic antioxidants such as Irganox® 1010, Irganox® 1076, Irganox® 565, Irganox® 1520, Irganox® 1098, Anox® 20, or Ultranox® 276; phosphite antioxidants such as Alkanox® TNPP, Alkanox® 240, Ultranox® 626, or Weston® 618F; thioester antioxidants such as Naugard® DSTDP; and mixtures thereof, such as Ultranox® 877A. Irganox® antioxidants are commercially available from BASF. Anox™, Ultranox®, Alkanox™, Weston® and Naugard® antioxidants are commercially available from Addivant.

[0098] Example The following examples are intended to illustrate the features of the present invention and are not intended to limit its scope. Comparative examples using conventional techniques are included for reference. The bicomponent block copolymers and conventional copolymers synthesized in the following examples and comparative examples were characterized by the following techniques: proton nuclear magnetic resonance (NMR) using a 300 MHz Bruker, Model Fourier 300 spectrometer. 1H-NMR or proton NMR) to quantify the total styrene repeat unit content and block styrene content. The total styrene repeat unit content of a block copolymer is measured as set forth in International Standard ISO 21561-1. In the following examples, the total styrene repeat unit content is reported as weight percent based on the total weight of the block copolymer. The measurement of block styrene content takes into account the amount of styrene repeat units incorporated as homopolymer blocks, i.e., styrene repeat units that form part of a given block copolymer without a covalent bond to a conjugated diene monomer. Block styrene content is measured by proton NMR as reported in U.S. Pat. No. 9,771,473. In the following examples, the block styrene content is reported as weight percent based on the entire block copolymer. In these examples, the only monovinyl aromatic monomer used is styrene, so the total monovinyl aromatic repeat unit content (%A) is reported as a percentage. t ) quantitatively corresponds to the total styrene content measured in the examples. Similarly, the monovinyl aromatic repeat unit blockiness in these examples is calculated from the quotient of the block styrene content to the total styrene content and is reported as a mole percent on a monovinyl aromatic repeat unit basis.

[0099] Gel permeation chromatography (GPC) was performed using a Waters Alliance e2695 HPLC with a three-column set covering a molecular weight range of 1,000 to 4,000,000 g / mol, referenced to narrow MWD polystyrene standards, in series with a differential refractive index detector and a diode array detector. The GPC-RI modality used the differential refractive index detector signal and a universal molecular weight vs. elution time calibration curve constructed from narrow MWD polystyrene standards to determine the molecular weight distribution, weight average molecular weight (M), and other parameters of the different block copolymers analyzed. w ), and the polydispersity index of the molecular weight distribution (ratio of weight average molecular weight to number average molecular weight, M w / M nWhenever multiple peaks appeared in the molecular weight distribution, the amount of coupled block copolymer (%C) was measured by integrating the peak with the highest molecular weight using GPC-RI. ri ) was quantified, which was reported as a percentage of the overall GPC-RI molecular weight distribution of the analyzed block copolymer. In the GPC-UV modality, the signal of a diode array detector at a wavelength of 261 nm, which responds only to the amount of monovinyl aromatic repeat units in the block copolymer, was used together with a universal calibration molecular weight curve referenced to narrow MWD polystyrene standards to determine the monovinyl aromatic repeat unit-weighted coupled block copolymer content (%C uv ) was measured. Whenever multiple peaks appeared in the molecular weight distribution, %C uv is obtained by integration of the highest molecular weight peak of the monovinyl aromatic repeat unit weighted molecular weight distribution and is reported as a percentage of the total GPC-UV monovinyl aromatic repeat unit weighted molecular weight distribution.

[0100] Next, the %A obtained from proton NMR t (i.e., total styrene repeat content), %C obtained from GPC-RI ri , and %C obtained from GPC-UV uv The monovinyl aromatic repeat unit weight percent content of the block copolymer uncoupled fraction, %A U and use these to determine the monovinyl aromatic repeat unit weight percent content of the block copolymer coupling fraction, %A C Finally, these are used to calculate the compositional difference in monovinyl aromatic repeat units between the uncoupled and coupled fractions of the block copolymer, %CD, as follows:

[0101]

number

[0102] The viscoelastic properties of the block copolymers prepared in the examples were evaluated using an Alpha Technologies RPA2000 instrument. Oscillatory shear measurements were performed at temperatures of 100°C or 140°C with a maximum strain of 13.95%. Complex dynamic shear viscosity (η*) is reported at oscillation frequencies of 0.99 and 100 rad / s, while tan delta is reported at several oscillation frequencies covering the frequency range of 0.25 to 200 rad / s. Mooney viscosity (ML1+4) was measured at 100°C using a Monsanto Mooney MV2000 instrument according to ASTM D1646.

[0103] Example 1: Synthesis of a two-component block copolymer; a prototype prepared using silicon tetrachloride as a coupling agent. 0.896 kg of cyclohexane, 0.042 kg of styrene, and 0.105 kg of butadiene were charged to a 2-liter reactor under a nitrogen atmosphere with stirring. The initial reactor charge was heated to a temperature of 74.0°C, and then 2.845 mmol of n-butyllithium was fed to the reactor. Polymerization of the initial monomer charge reached a peak temperature of 110.8°C. After waiting 1 minute, 0.188 mmol of silicon tetrachloride coupling agent was fed to the reactor. After waiting 5 minutes, 0.028 kg of styrene was fed to the reactor. During this charge, the reactor temperature temporarily dropped to 91.6°C. As a result of the heat of polymerization of the second styrene charge, the reaction reached a peak temperature of 94.7°C. After waiting for 1 minute, 1.782 mmol of monofunctional alcohol was fed into the reactor to terminate the polymer anion. The specific formulation and polymerization process conditions for this binary block copolymer synthesis example are shown in Table 1. Next, 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 roll milling. The weight average molecular weight (M w) was 169.8 kg / mol. The molecular weight distribution showed a polydispersity index of 1.26. The molecular weight distribution of the block copolymer showed two peaks, the low molecular weight peak corresponding to the uncoupled linear tapered block copolymer of formula D-(D / A)-A2, and the high molecular weight peak corresponding to the coupled tapered styrene-butadiene block copolymer [D-(D / A)-A1]. n=2~4 The coupled tapered block copolymer content (%C ri ) was 27.4% of the total block copolymer molecular weight distribution as determined by GPC-RI. The monovinyl aromatic repeat unit weighted coupling level (%C) by GPC-UV was uv ) was 22.0%. The total styrene repeat unit content of the two-component block copolymer was 40.0 wt %, while the block styrene content was 31.8 wt %. Therefore, the monovinyl aromatic repeat unit blockiness in the two-component block copolymer was 79.5 mol %. As can be seen from calculations using the coupling levels measured by GPC-RI and GPC-UV and the total styrene content measured by proton NMR, the monovinyl aromatic repeat unit content (%A) of the coupled tapered block copolymer fraction was 79.5 mol %. C ) was 32.2 wt %, while the uncoupled tapered block copolymer fraction (%A U ) was 42.9 wt%. The compositional difference (%CD) of monovinyl aromatic repeat units between the uncoupled and coupled tapered block copolymer fractions was 10.7%. Specific GPC and NMR characteristics of this diblock copolymer are shown in Table 2. The complex dynamic shear viscosity of the diblock copolymer at 0.99 rad / s was 76198 Pa·s, which decreased to 4744 Pa·s when evaluated at an oscillation frequency of 100 rad / s. The tan delta of the diblock copolymer exhibited predominantly elastic behavior (tan delta less than 1.00) over the entire frequency range from 0.25 to 200 rad / s, reaching a maximum value of 0.81 (tan delta) at 2.51 rad / s. max The detailed rheological properties of this two-component block copolymer are shown in Table 3.

[0104] Embodiments of the invention The term "dual-component block copolymer (DCBC)" as used herein refers to a polymer blend containing two types of block copolymer molecules differing in molecular weight, block sequence, and monovinyl aromatic repeat unit content. A bimodal molecular weight distribution, such as that shown in Comparative Example C-2 in Figure 9, does not by itself satisfy the necessary properties for a DCBC. Various other properties are also required for the DCBC of the present invention. Aspects to consider for a DCBC include: a high monovinyl aromatic repeat unit content in the uncoupled fraction; a coupling agent connecting the internal monovinyl aromatic homopolymer blocks; a specific coupling range; a specific total monovinyl aromatic repeat unit content range; a defined conjugated diene block structure; a Mooney viscosity range; a complex viscosity range; and a tan delta profile. However, not all of these aspects are required to define a dual-component block copolymer according to the present invention. Some embodiments of methods for making DCBC are provided below. The claims submitted for a patent relating to this invention are incorporated herein by reference to ensure explicit literal support for the claims.

[0105] 1. A method for producing a bicomponent block copolymer, comprising: charging a batch reactor with a solvent such as cyclohexane, a monovinyl aromatic monomer such as styrene, and a conjugated diene monomer such as butadiene to provide an initial content (in alternative embodiments, with or without a randomizer or polar modifier); [In an alternative embodiment, the conjugated diene alone is initially charged without the monovinyl aromatic monomer and allowed to convert fully or partially.] mixing and heating the initial contents; adding n-butyllithium or a similar lithium initiator to the reactor; polymerizing the initial contents to form a polymeric anion; adding a coupling agent, such as silicon tetrachloride or methyl silicon trichloride, to the reactor to partially couple the polymeric anion, and waiting preferably less than 10 minutes, more preferably less than about 1 minute; [In another embodiment, the polymer anion is partially terminated at this stage.] adding additional monovinyl aromatic monomer, such as styrene, to the reactor; [The same or different monovinyl aromatic monomers can be used] terminating the polymer anion by adding a terminating agent, such as a monofunctional alcohol, to the reactor; adding an antioxidant, preferably a phenolic antioxidant and / or a phosphite antioxidant, to the reactor; and recovering the block copolymer by any method known in the art, such as steam stripping-dehydration-drying, direct desolventization, vacuum-assisted desolventization, etc. A method comprising: 2. Weight average molecular weight (M w 2. The method of embodiment 1, wherein the ρ is in the range of 70 to 500, preferably 120 to 230, more preferably 150 to 180 kg / mol, and one example is 169.8 kg / mol.

[0106] 3. The method of Example 1 or 2, wherein the bicomponent block copolymer has a molecular weight distribution with two peaks and a polydispersity index of 1.00 to 1.90, preferably 1.10 to 1.40, more preferably 1.20 to 1.33, and in a particular example a value of 1.26.

[0107] 4. One of the two peaks is called the low molecular weight peak and the other peak is called the high molecular weight peak, where the low molecular weight peak corresponds to a non-coupled linear tapered block copolymer with the formula D-(D / A)-A2, and the high molecular weight peak corresponds to [D-(D / A)-A1] n=2~4 The method of embodiment 3, wherein the coupled taper has a formula of —Si, preferably a styrene-butadiene block copolymer.

[0108] 5. The content of coupled tapered block copolymer in the total block copolymer molecular weight distribution (%C) determined by GPC-RI ri 5. The method of embodiment 4, wherein the % % of the total mass of the polymer is 20 to 80%, preferably 25 to 50%, more preferably 30 to 45%, typically 35 to 42%, and in a particular example, 38.6%.

[0109] 6. The method of embodiment 1 or 5, wherein the compositional difference of monovinyl aromatic repeat units between the uncoupled and coupled fractions of the bicomponent block copolymer, %CD, is 10-35%, preferably 15-30%, more preferably 17-28%, typically 20-26%, and in a particular example 25.6%.

[0110] 7. The method of embodiment 1, 5 or 6, wherein the monovinyl aromatic repeat unit blockiness is 76 to 88 mol %, preferably 78 to 86 mol %, more preferably 80 to 83 mol %, and in a particular example 82.3 mol %.

[0111] 8. Total monovinyl aromatic repeat unit content of the binary block copolymer, %A t is 20 to 50 wt. %, preferably 30 to 50 wt. %, more preferably 38 to 48 wt. %, and in a particular example 40.1 wt. %.

[0112] 9. Total monovinyl aromatic repeat unit content (%A) of the coupled tapered block copolymer fraction C 9. The method of embodiment 1, 7 or 8, wherein the amount of the hydroxybenzoate is 5 to 35 wt %, preferably 15 to 30 wt %, more preferably 20 to 25 wt %, and in a particular example 24.8 wt %.

[0113] 10. The method of embodiment 1, 7, 8, or 9, wherein the bicomponent block copolymer has a complex dynamic shear viscosity at 0.99 rad / s of 50,000 to 360,000 Pa·s, preferably 60,000 to 90,000 Pa·s, more preferably 70,000 to 82,000, and in a particular example 76,198 Pa·s.

[0114] 11. The method of embodiment 10, wherein the bicomponent block copolymer has a complex dynamic shear viscosity at an oscillation frequency of 100 rad / s of between 3,000 and 12,000 Pa·s, preferably between 4,200 and 5,200 Pa·s, more preferably between 4,500 and 4,900 Pa·s, and in a particular example, 4,744 Pa·s.

[0115] 12. The method of any one of embodiments 1-11, wherein the coupling agent is silicon tetrachloride. 13. The method of any one of embodiments 1-11, wherein the coupling agent is silicon methyl trichloride.

[0116] 14. The method of embodiment 1 or 2, wherein the bicomponent block copolymer has a trimodal molecular weight distribution. 15. Weight average molecular weight (M w 15. The method of embodiment 14, wherein the saturation temperature is in the range of 70 to 500, preferably 140 to 190, more preferably 150 to 180 kg / mol, and in one example is 159.6 kg / mol.

[0117] 16. The method of embodiment 15, wherein the bicomponent block copolymer has a polydispersity index of 1.00 to 1.90, preferably 1.10 to 1.40, more preferably 1.15 to 1.30, with a particular example having a value of 1.22.

[0118] Example 2: Synthesis of a two-component block copolymer; a prototype prepared using methyl silicon trichloride as a coupling agent. The same procedure as in Example 1 was used to prepare a two-component block copolymer, except that 0.230 mmol of methyl silicon trichloride was used as the coupling agent instead of silicon tetrachloride. The specific formulation and polymerization process conditions for this two-component block copolymer synthesis example are shown in Table 1. Next, 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 roll milling. The weight average molecular weight (Mw ) was 171.8 kg / mol. The molecular weight distribution showed a polydispersity index of 1.19. The molecular weight distribution of the block copolymer showed two peaks, the low molecular weight peak corresponding to the uncoupled linear tapered block copolymer of formula D-(D / A)-A2, and the high molecular weight peak corresponding to the coupled tapered styrene-butadiene block copolymer [D-(D / A)-A1]. n=2~3 The coupled tapered block copolymer content (%C ri The monovinyl aromatic repeat unit blockiness, determined by GPC-RI, was 25.5% of the total block copolymer molecular weight distribution. The total styrene repeat content of the diblock copolymer was 40.2 wt%, while the styrene block content was 32.1 wt%. Therefore, the monovinyl aromatic repeat unit blockiness was 79.9 mol%. Specific GPC and NMR properties of this diblock copolymer are shown in Table 2. The complex dynamic shear viscosity of the diblock copolymer at 0.99 rad / s was 72,962 Pa·s, which decreased to 4,833 Pa·s when evaluated at an oscillation frequency of 100 rad / s. The tan delta of the diblock copolymer exhibited predominantly elastic behavior (tan delta less than 1.00) over the entire frequency range from 0.25 to 200 rad / s, reaching a maximum value of 0.86 at 0.99 rad / s. Detailed rheological properties of this diblock copolymer are shown in Table 3.

[0119] Examples 3-12: Synthesis of two-component block copolymers; prototypes covering different levels of viscosity, coupling, and composition. 71.50 ± 0.14 kg of cyclohexane, approximately 1.58 or approximately 2.56 kg of styrene, and 6.64 ± 0.02 kg of butadiene were charged to a 189-liter reactor under a nitrogen atmosphere with stirring. 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 fed to the reactor. Polymerization of the initial monomer charge reached a peak temperature of approximately 99.7 to approximately 104.8 °C. After a one-minute wait, approximately 13.88 to approximately 31.42 mmol of silicon tetrachloride coupling agent was fed to the reactor. After a five-minute wait, approximately 2.78 or approximately 1.82 kg of styrene was fed to the reactor. During the final monomer charge, the reactor temperature decreased to approximately 98.1±2.4°C. As a result of the heat of polymerization reaction of the second styrene charge, the reaction temperature increased to approximately 102.0±1.5°C. After waiting for 1 minute, 143.3±23.3 mmol of monofunctional alcohol was fed into the reactor to terminate the polymer anion. The specific formulation and polymerization process conditions for each binary block copolymer synthesis example are shown in Table 1. Next, 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 steam stripping and oven drying. The weight average molecular weight (M w ) varied from 147.4 to 225.5 kg / mol. The molecular weight distributions showed polydispersity indices of 1.24 to 1.40. The molecular weight distributions of the block copolymers showed two peaks, the low molecular weight peak corresponding to the uncoupled linear tapered block copolymer of formula D-(D / A)-A2, and the high molecular weight peak corresponding to the coupled tapered styrene-butadiene block copolymer [D-(D / A)-A1]. n=2~4 The coupled tapered block copolymer content (%C ri ) varied from 23.0 to 38.6% of the total block copolymer molecular weight distribution as determined by GPC-RI. The monovinyl aromatic weighted coupling level (%C) by GPC-UV uvThe vinyl aromatic repeat content (%A) of the coupled tapered block copolymer fractions ranged from about 14.6 to about 24.6%. The total styrene repeat unit content of the diblock copolymers ranged from 39.9 to 40.8% by weight, while the styrene block content ranged from 30.5% to 35.6% by weight. Thus, the monovinyl aromatic repeat unit blockiness in the diblock copolymers varied from 76.5 mol % to 87.5 mol %. As evident from calculations using the coupling levels measured by GPC-RI and GPC-UV and the total styrene content measured by proton NMR, the vinyl aromatic repeat content (%A) of the coupled tapered block copolymer fractions was significantly higher than that of the diblock copolymers. C ) was about 24.8 to about 32.6 wt.%, while the uncoupled tapered block copolymer fraction (%A U The compositional difference (%CD) of monovinyl aromatic repeat units between the uncoupled and coupled tapered block copolymer fractions ranged from about 43.6 to about 50.5 wt%. The %CD ranged from about 11.1 wt% to 25.6 wt%. The molecular weight distribution of Inventive Example 4 is shown in Figure 9. Specific GPC and NMR characteristics of these two-component block copolymers are listed in Table 2. The complex dynamic shear viscosity of the block copolymers at 0.99 rad / s varied from 52,210 to 142,236 Pa·s, decreasing to values ​​of 3,571 to 6,241 Pa·s when evaluated at an oscillation frequency of 100 rad / s. The Mooney viscosity (ML1+4, 100°C) of the block copolymers ranged from 28.6 to 66.0. The tan delta of the two-component block copolymers exhibited predominantly elastic behavior (tan delta less than 1.00) over the entire frequency range from 0.25 to 200 rad / s, with maxima ranging from 0.75 to 0.93 at various frequencies. The detailed rheological properties of these two-component block copolymers are shown in Table 3.

[0120] Example 13: Synthesis of a two-component block copolymer; a prototype in which the block copolymer anion was partially deactivated prior to monovinyl aromatic chain extension. The recipe used in Example 4 was scaled up 272.7 times for an industrial reactor. Nevertheless, some of the block copolymer anion that remained active after coupling was deactivated before carrying out the second styrene charge polymerization. The weight average molecular weight (M w ) was 159.6 kg / mol. The molecular weight distribution showed a polydispersity index of 1.22. The molecular weight distribution of the block copolymer showed three peaks, the low molecular weight peak corresponding to the uncoupled linear tapered block copolymer of formula D-(D / A)-A1, which is the product of partial deactivation of the block copolymer anion prior to polymerization of the second styrene charge, and the high molecular weight peak corresponding to the coupled tapered styrene-butadiene block copolymer [D-(D / A)-A1]. n=2~4 The peak in the middle of the molecular weight range corresponded to the uncoupled linear tapered block copolymer of formula D-(D / A)-A2 produced after the second styrene charge polymerization. The molecular weight distribution by GPC-RI of the two-component block copolymer produced in Example 13 is shown in Figure 9. The coupled tapered block copolymer content (%C ri ) was 37.4% of the total block copolymer molecular weight distribution as determined by GPC-RI. The monovinyl aromatic weighted coupling level (%C) by GPC-UV was uv ) was 24.8%. The uncoupled linear tapered block copolymer D-(D / A)-A1 accounted for 15.6% of the total block copolymer molecular weight distribution as determined by GPC-RI. The total styrene repeat unit content of the two-component block copolymer was 39.8 wt%, while the block styrene content was 34.2 wt%. Thus, the monovinyl aromatic repeat unit blockiness was 86.0 mol%. As can be seen from calculations using the coupling levels measured by GPC-RI and GPC-UV and the total styrene content measured by NMR, the vinyl aromatic repeat unit content (%A) of the coupled tapered block copolymer fraction was 86.0 mol%. CThe monovinyl aromatic repeat unit (%CD) composition difference (%CD) between the uncoupled and coupled tapered block copolymer fractions was 26.4 wt%, compared with 47.7 wt% for the uncoupled tapered block copolymer fraction corresponding to the two lower molecular weight peaks. The monovinyl aromatic repeat unit (%CD) composition difference (%CD) between the uncoupled and coupled tapered block copolymer fractions was 21.3%. Specific GPC and NMR properties of these diblock copolymers are shown in Table 2. The complex dynamic shear viscosity of the block copolymer at 0.99 rad / s was 71,321 Pa·s, but decreased to 4,709 Pa·s when evaluated at an oscillation frequency of 100 rad / s. The Mooney viscosity (ML1+4, 100°C) of the block copolymer was 39.0. The tan delta of the diblock copolymer exhibited predominantly elastic behavior (tan delta less than 1.00) over the entire frequency range from 0.25 to 200 rad / s, reaching a maximum value of 0.85 at 2.51 rad / s. Detailed rheological properties of this diblock copolymer are shown in Table 3.

[0121] Comparative example C-1: Synthesis of a linear tapered block copolymer; low viscosity prototype. 71.56 g of cyclohexane-4, 4.32 g of styrene, and 6.64 kg of butadiene were charged to a 189-liter reactor under a nitrogen atmosphere with stirring. The reactor charge temperature was adjusted to 50.5°C, and then 286.6 mmol of n-butyllithium was fed to the reactor. Polymerization of the initial monomer charge reached a peak temperature of 106.3°C. After waiting 1 minute, 347.4 mmol of monofunctional alcohol was fed to the reactor to terminate the polymer anion. The specific formulation and polymerization process conditions for this non-coupled tapered block copolymer synthesis example are shown in Table 1. Next, 0.5 phr of a phenolic antioxidant and 0.6 phr of a phosphite antioxidant were added to the rubber solution. The non-coupled tapered block copolymer was recovered by steam stripping and oven drying. The weight average molecular weight (M) of the synthesized non-coupled tapered block copolymer was 0.5 phr. w) was 93.2 kg / mol. The molecular weight distribution showed a polydispersity index of 1.03, with a single narrow peak corresponding to the uncoupled linear tapered block copolymer of the formula D-(D / A)-A. The total styrene repeat unit content of the uncoupled tapered block copolymer was 40.5 wt%, while the styrene block content was 30.0 wt%. Therefore, the monovinyl aromatic repeat unit blockiness was 73.9 mol%. Specific GPC and NMR properties of this uncoupled tapered block copolymer are shown in Table 2. The complex dynamic shear viscosity of the uncoupled tapered block copolymer at 0.99 rad / s was 49951 Pa·s, which decreased to 4927 Pa·s when evaluated at an oscillation frequency of 100 rad / s. The Mooney viscosity (ML1+4, 100°C) of the uncoupled tapered block copolymer was 32.4. The tan delta of the two-component block copolymer showed predominantly viscous behavior (tan delta greater than 1.00) in the frequency range of 0.84 to 25 rad / s, with a maximum tan delta of 1.36 at 5.0 rad / s. The detailed rheological properties of this non-coupled tapered block copolymer are shown in Table 3.

[0122] Comparative example C-2: Synthesis of a coupled tapered block copolymer; medium viscosity prototype. 71.41 kg of cyclohexane, 4.36 kg of styrene, and 6.63 kg of butadiene were charged to a 189-liter reactor under a nitrogen atmosphere with stirring. The initial reactor charge was heated to a temperature of 51.5°C, and then 285.5 mmol of n-butyllithium was fed to the reactor. The polymerization reached a peak temperature of 108.6°C. After a one-minute wait, 19.9 mmol of silicon tetrachloride coupling agent was fed to the reactor. After a five-minute wait, 178.1 mmol of monofunctional alcohol was fed to the reactor to terminate the block copolymer anion. The specific formulation and polymerization process conditions for this partially coupled tapered block copolymer synthesis example are shown in Table 1. Next, 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 w ) was 160.1 kg / mol. The molecular weight distribution showed a polydispersity index of 1.39. The molecular weight distribution of the block copolymer showed two peaks, the low molecular weight peak corresponding to the uncoupled linear tapered block copolymer of the formula D-(D / A)-A, and the high molecular weight peak corresponding to the formula [D-(D / A)-A] n=2~4 The coupled tapered block copolymer content (%C ri ) accounted for 34.5% of the total molecular weight distribution of the partially coupled tapered block copolymer as determined by GPC-RI. The weighted coupling level of the monovinyl aromatic repeat unit (%C) obtained by GPC-UV was uvThe coupling level (ML) was 35.5%, which was in excellent agreement with the coupling level obtained by GPC-RI, as a result of the same monovinyl aromatic repeat unit content in the uncoupled and coupled fractions. The total styrene repeat unit content of the partially coupled tapered block copolymer was 42.2 wt %, while its block styrene content was 31.6 wt %. Therefore, the monovinyl aromatic repeat unit blockiness was 74.7 mol %. Specific GPC and NMR properties of this partially coupled tapered block copolymer are shown in Table 2. The complex dynamic shear viscosity of the partially coupled tapered block copolymer at 0.99 rad / s was 75,924 Pa·s, which decreased to 6,128 Pa·s when evaluated at an oscillation frequency of 100 rad / s. The Mooney viscosity (ML1+4, 100°C) of the partially coupled tapered block copolymer was 40.6. The tan delta of the binary block copolymer exhibited predominantly viscous behavior (tan delta greater than 1.00) in the frequency range of 0.84 to 25 rad / s, with a maximum tan delta of 1.27 at 5.0 rad / s. The detailed rheological properties of this partially coupled tapered block copolymer are shown in Table 3. The molecular weight distribution of Comparative Example C-2 is shown in Figure 9.

[0123] Comparative example C-3: Synthesis of linear tapered block copolymers with high viscosity levels in a pilot plant reactor. The same procedure as in Comparative Example C-1 was carried out, but the dosage of n-butyllithium was reduced to 264.4 mmol to increase the molecular weight. The specific formulation and polymerization process conditions for each non-coupled tapered block copolymer synthesis example are shown in Table 1. The weight average molecular weight (M w) was 107.8 kg / mol. The molecular weight distribution showed a polydispersity index of 1.03, with a single narrow peak corresponding to the uncoupled linear tapered block copolymer of the formula D-(D / A)-A. The total styrene repeat unit content of the uncoupled tapered block copolymer was 38.9 wt%, while the block styrene content was 28.8%. Therefore, the monovinyl aromatic repeat unit blockiness was 74.0 mol%. Specific GPC and NMR properties of this uncoupled tapered block copolymer are shown in Table 2. The complex dynamic shear viscosity of the uncoupled tapered block copolymer at 0.99 rad / s was 96,249 Pa·s, which decreased to 6,269 Pa·s when evaluated at an oscillation frequency of 100 rad / s. The Mooney viscosity (ML1+4, 100°C) of the uncoupled tapered block copolymer was 53.1. The tan delta of the two-component block copolymer showed predominantly viscous behavior (tan delta greater than 1.00) in the frequency range of 0.25 to 5 rad / s, with a maximum tan delta of 1.17 at 0.99 rad / s. The detailed rheological properties of this non-coupled tapered block copolymer are shown in Table 3.

[0124] [Table 1]

[0125] [Table 2]

[0126] [Table 3]

[0127] It should be noted that the batch synthesis process carried out in Inventive Examples 1-13 produces bicomponent block copolymers having at least two distinguishable fractions, each differing in molecular weight and monovinyl aromatic repeat unit content, with the lower molecular weight fraction having a higher monovinyl aromatic repeat unit content than the fraction exhibiting a higher molecular weight.

[0128] It should also be noted that all of the binary block copolymers prepared in Inventive Examples 1-13, whether linear or coupled, have a higher degree of monovinyl aromatic repeat unit blockiness than the prior art tapered block copolymers prepared in Comparative Examples 1-3. This is the result of the monovinyl aromatic block chain extension performed on the remaining polymer anion after the coupling step.

[0129] The polydispersity index of all the binary block copolymers prepared in Inventive Examples 1-13, reaching a maximum of 1.40, is within the range of typical low values ​​expected for organolithium-initiated batch polymerization processes followed by coupling. These low levels of polydispersity are not obtainable by alternative prior art organolithium-initiated continuous polymerization processes typically used to produce block copolymers intended for the production of crosslinked microcellular rubbery articles. A comparison of the molecular weight distributions of the binary block copolymers prepared in Inventive Examples 4 and 13 and Comparative Example 2, prepared in a batch reactor, and the commercial reference Buna® BL30-4548 (manufactured by ARLANXEO), a typical block copolymer prepared by a prior art process in a continuous polymerization reactor, which has a unimodal but very broad molecular weight distribution, is shown in Figure 9.

[0130] All of the two-component block copolymers prepared in Examples 1-13, regardless of their complex dynamic shear viscosity and Mooney viscosity levels or the type of coupling agent used, exhibit tan delta values ​​less than 1.0 across the entire frequency range evaluated. Inventive Examples 1 and 11 show that a monovinyl aromatic repeat unit composition difference (%CD) of as little as 11% between the uncoupled and coupled fractions of the two-component block copolymers is still sufficient to promote this tan delta behavior. In contrast, the prior art linear tapered block copolymers prepared in Comparative Example 1 at a low viscosity level and Comparative Example 3 at a high viscosity level exhibit predominantly viscous behavior across a fairly broad portion of the evaluated frequency spectrum, as evidenced by tan delta values ​​greater than 1.0. Similarly, the partially coupled tapered block copolymer of Comparative Example 2, made according to the prior art and having a homogeneous monovinyl aromatic repeat unit content between the coupled and uncoupled fractions and a moderate viscosity level, also exhibits tan delta values ​​greater than 1.0 across a broad portion of the evaluated frequency spectrum. As previously mentioned, it is well known in the art that polymeric materials with predominantly elastic behavior, i.e., with tan delta values ​​less than 1.0, are more suitable for foaming applications due to their higher melt strength during expansion of the blowing agent. From a comparison of these tan delta profiles, it can be concluded that the two-component block copolymers according to the present invention are more suitable for foaming purposes than prior art linear tapered block copolymers or homogeneous composition partially coupled tapered block copolymers.

[0131] Inventive Example 13 and Figure 9 demonstrate that a bicomponent block copolymer can have a trimodal molecular weight distribution. Specifically, in Inventive Example 13, the uncoupled block copolymer fraction U is composed of tapered linear block copolymer molecules of formula D-(D / A)-A1, which account for approximately 15.6% of the molecular weight distribution, and tapered linear block copolymer molecules of formula D-(D / A)-A2, which account for approximately 47.0 wt% of the molecular weight distribution. Here, the monovinyl aromatic block A2 has a higher molecular weight than the monovinyl aromatic block A1. Despite this trimodal molecular weight distribution, the bicomponent block copolymer prepared in Inventive Example 13 exhibits a tan delta value of only less than 1.0 over the entire frequency range evaluated.

[0132] Example 14: Synthesis of a two-component block copolymer with a high monovinyl aromatic repeat unit content. Approximately 65.98 kg of cyclohexane, approximately 1.88 kg of styrene, and approximately 5.75 kg of butadiene were charged to a 189-liter reactor under a nitrogen atmosphere with stirring. The reactor temperature was set to 55.7°C, and then 322.9 mmol of n-butyllithium was fed to the reactor. The polymerization of the first monomer charge reached a peak temperature of 98.8°C. Next, 31.42 mmol of silicon tetrachloride coupling agent was fed to the reactor. After a three-minute wait, approximately 3.08 kg of styrene was fed to the reactor. As a result of the heat of polymerization of the second styrene charge, the reaction temperature rose to approximately 101.2°C. After a one-minute wait, all polymer anions were terminated by the addition of a monofunctional alcohol. The formulation and polymerization process conditions are shown in Table 4. Next, 0.5 phr of a phenolic antioxidant and 0.6 phr of a phosphite antioxidant were added to the rubber solution. Samples of the two-component block copolymer were recovered by roll milling at 125°C and characterized. The weight average molecular weight (M w ) is 181.0 kg / mol, and the polydispersity M w / M nThe molecular weight distribution by GPC-RI showed three peaks: a low molecular weight peak at 11.0% corresponding to the uncoupled linear tapered block copolymer of formula D-(D / A)-A1; a medium molecular weight peak at 51.6% corresponding to the uncoupled linear tapered block copolymer of formula D-(D / A)-A2; and a coupled tapered styrene-butadiene block copolymer [D-(D / A)-A1]. n=2~4 -Si indicates a high molecular weight peak of 37.4% (%C ri The total styrene repeat unit content of the diblock copolymer was 47.8 wt %, while the styrene block content was 39.9%. Therefore, the monovinyl aromatic repeat unit blockiness of the diblock copolymer was 83.4 mol %. Specific GPC and NMR characteristics of the diblock copolymer are shown in Table 5. The complex dynamic shear viscosity of the diblock copolymer at 0.99 rad / s was 105,345 Pa·s, which decreased to 5,649 Pa·s when evaluated at an oscillation frequency of 100 rad / s. The Mooney viscosity (ML1+4, 100°C) was 48. The tan delta of the diblock copolymer exhibited predominantly elastic behavior (tan delta less than 1.00) over the entire frequency range from 0.25 to 200 rad / s, and showed a maximum value of 0.76 at a frequency of 2.51 rad / s when evaluated at 100°C and 13.95% strain. The same oscillatory shear test at a temperature of 140°C showed a maximum tan delta value of 0.70 at a frequency of 25.12 rad / s. The rheological properties of this binary block copolymer are shown in Table 6.

[0133] Example 15. Synthesis of a two-component block copolymer with a high monovinyl aromatic repeat unit content and high molecular weight. Approximately 48.02 kg of cyclohexane, approximately 1.40 kg of styrene, and approximately 4.19 kg of butadiene were charged to a 189-liter reactor under a nitrogen atmosphere with stirring. The reactor temperature was set to 54.1°C, and then 219.7 mmol of n-butyllithium was fed to the reactor. The polymerization of the first monomer charge reached a peak temperature of 96.8°C. Next, 18.33 mmol of silicon tetrachloride coupling agent was fed to the reactor. After a three-minute wait, approximately 2.35 kg of styrene was fed to the reactor. As a result of the heat of polymerization of the second styrene charge, the reaction temperature rose to approximately 99.0°C. After a one-minute wait, a monofunctional alcohol was fed to the reactor to terminate all polymer anions. The formulation and polymerization process conditions are shown in Table 4. Next, 0.5 phr of a phenolic antioxidant and 0.6 phr of a phosphite antioxidant were added to the rubber solution. Samples of the two-component block copolymer were recovered by roll milling at 125°C and characterized. The weight average molecular weight (M w ) is 233.7 kg / mol, and the polydispersity M w / M n The molecular weight distribution by GPC-RI showed three peaks: a low molecular weight peak at 4.0% corresponding to the uncoupled linear tapered block copolymer of formula D-(D / A)-A1; a medium molecular weight peak at 54.3% corresponding to the uncoupled linear tapered block copolymer of formula D-(D / A)-A2; and a coupled tapered styrene-butadiene block copolymer [D-(D / A)-A1]. n=2~4 -Si indicates a high molecular weight peak of 41.7% (%C riThe total styrene repeat unit content of the diblock copolymer was 48.4 wt %, while the styrene block content was 39.7%. Therefore, the monovinyl aromatic repeat unit blockiness of the diblock copolymer was 82.0 mol %. GPC and NMR characteristics of the diblock copolymer are shown in Table 5. The complex dynamic shear viscosity of the diblock copolymer at 0.99 rad / s was 155,221 Pa·s, which decreased to 6,467 Pa·s when evaluated at an oscillation frequency of 100 rad / s. The Mooney viscosity (ML1+4, 100°C) was 66. The tan delta of the diblock copolymer exhibited predominantly elastic behavior (tan delta less than 1.00) over the entire frequency range from 0.25 to 200 rad / s, and showed a maximum value of 0.68 at a frequency of 0.50 rad / s when evaluated at 100°C and 13.95% strain. The same oscillatory shear test at a temperature of 140°C showed a maximum tan delta value of 0.62 at 2.51 rad / s. The rheological properties of this binary block copolymer are shown in Table 6.

[0134] Example 16. Diblock copolymer containing paraffinic oil. The rubber solution prepared in Inventive Example 15 was blended with 4 ppm of PRIMOL™ 352 paraffinic oil from ExxonMobil. A sample of the oil-extended diblock copolymer was recovered by roll milling at 125°C and characterized. The complex dynamic shear viscosity of the diblock copolymer at 0.99 rad / s was 101,760 Pa·s, decreasing to 4,968 Pa·s when measured at an oscillation frequency of 100 rad / s. The Mooney viscosity (ML1+4, 100°C) was 50. The tan delta of the diblock copolymer exhibited predominantly elastic behavior (tan delta less than 1.00) over the entire frequency range from 0.25 to 200 rad / s, and showed a maximum value of 0.72 at a frequency of 0.99 rad / s when evaluated at 100°C and 13.95% strain. The same oscillatory shear test at a temperature of 140°C showed a maximum tan delta value of 0.65 at 5.00 rad / s. The rheological properties of this binary block copolymer are shown in Table 6.

[0135] Invention Example 17. Synthesis of a two-component block copolymer with high vinyl aromatic repeat unit content and low coupling degree. The monomer loading, reaction sequence, and reaction temperature were the same as in Inventive Example 15, except that 174.5 mmol of n-butyllithium and 6.55 mmol of silicon tetrachloride were added. The detailed recipe and reaction temperature are shown in Table 4. A sample of the rubber solution was taken from the batch, and the two-component block copolymer was separated from the solvent by roll milling at 125°C. The weight average molecular weight (M w ) is 190.5 kg / mol, and the polydispersity M w / M n The molecular weight distribution by GPC-RI showed two peaks: a low molecular weight peak at 80.0%, corresponding to the uncoupled linear tapered block copolymer of formula D-(D / A)-A2, and a coupled tapered styrene-butadiene block copolymer [D-(D / A)-A1]. n=2~4 -Si indicates a high molecular weight peak of 20.0% (%C ri The total styrene repeat unit content of the diblock copolymer was 48.7 wt %, while the styrene block content was 39.6%. Therefore, the monovinyl aromatic repeat unit blockiness of the diblock copolymer was 81.3 mol %. The results of GPC and NMR characterization of the diblock copolymer are shown in Table 5. The complex dynamic shear viscosity of the diblock copolymer at 0.99 rad / s was 248,560 Pa·s, which decreased to 8,761 Pa·s when evaluated at an oscillation frequency of 100 rad / s. The Mooney viscosity (ML1+4, 100°C) was 83. The tan delta of the diblock copolymer exhibited predominantly elastic behavior (tan delta less than 1.00) over the entire frequency range from 0.25 to 200 rad / s, and showed a maximum value of 0.69 at a frequency of 0.25 rad / s when evaluated at 100°C and 13.95% strain. The same oscillatory shear test at a temperature of 140°C showed a maximum tan delta value of 0.70 at 0.25 rad / s. The rheological properties of this binary block copolymer are shown in Table 6.

[0136] Example 18. Diblock copolymer containing naphthenic oil. The rubber solution prepared in Inventive Example 15 was blended with 9 ppb of NYFLEX® 223 naphthenic oil from NYNAS. A sample of the oil-extended diblock copolymer was recovered by roll milling at 125°C and characterized. The complex dynamic shear viscosity of the diblock copolymer at 0.99 rad / s was 124,840 Pa·s, decreasing to 6,594 Pa·s when measured at an oscillation frequency of 100 rad / s. The Mooney viscosity (ML1+4, 100°C) was 49. The tan delta of the diblock copolymer exhibited predominantly elastic behavior (tan delta less than 1.00) over the entire frequency range from 0.25 to 200 rad / s, and showed a maximum value of 0.87 at a frequency of 0.99 rad / s when evaluated at 100°C and 13.95% strain. The same oscillatory shear test at a temperature of 140°C showed a maximum tan delta value of 0.80 at 0.84 rad / s. The rheological properties of this binary block copolymer are shown in Table 6.

[0137] [Table 4]

[0138] [Table 5]

[0139] [Table 6]

[0140] Inventive Examples 14-18 demonstrate that the rheological properties of oil-free diblock copolymers, such as Inventive Example 14, can be matched with oil-extended diblock copolymers, such as Inventive Examples 16 and 18, with only an appropriate amount of molecular weight increase depending on the oil content. Regardless of oil type or coupling level, the oil-extended diblock copolymers remain primarily elastic, as evidenced by tan delta values ​​less than 1.0 across the full oscillatory shear frequency spectrum tested. These Inventive Examples also demonstrate that the predominantly elastic behavior of the diblock copolymers prevails even at temperatures as high as 140°C.

[0141] Hypothetical Example The structures of the two-component block copolymers of the present invention are shown in Figures 1 to 8. Figure 1 shows a schematic diagram of a two-component block copolymer consisting of about 38 wt% of a coupled block copolymer C of formula [D-(D / A)-A1]4-X (left side) and about 62 wt% of an uncoupled block copolymer U of formula D-(D / A)-A2 (right side). t The monovinyl aromatic repeat unit weight percent content %A of block copolymer C is about 41% by weight. The monovinyl aromatic repeat unit blockiness is about 87.5 mol%. C is about 21 wt.%. The monovinyl aromatic repeat unit weight percent content %A of the block copolymer U U is about 52 wt %. Thus, the compositional difference in monovinyl aromatic repeat unit weight percent, %CD, between block copolymer fractions U and C is about 31 wt %.

[0142] FIG. 2 shows a schematic diagram of a two-component block copolymer consisting of about 34% by weight of coupled block copolymer C of formula [D-(D / A)-A1]4-X (left side) and about 66% by weight of uncoupled block copolymer U of formula D-(D / A)-A2 (four molecules on the top right, corresponding to about 57% by weight) and D-(D / A)-A1 (bottom right, corresponding to about 9% by weight). tThe monovinyl aromatic repeat unit blockiness is about 86.5 mol %. C is about 21% by weight, A U is about 48% by weight. Therefore, %CD is about 27% by weight.

[0143] FIG. 3 shows a schematic diagram of a two-component block copolymer consisting of about 38% by weight of a coupled block copolymer C of formula [B-(B / A)-A1]4-X (left side) and about 62% by weight of an uncoupled block copolymer U of formula B-(B / A)-A2 (right side). t The monovinyl aromatic repeat unit blockiness is about 87.5 mol %. C is about 21% by weight, A U is about 52% by weight. Therefore, %CD is about 31% by weight.

[0144] FIG. 4 shows a schematic diagram of a two-component block copolymer consisting of about 34% by weight of coupled block copolymer C of formula [B-(B / A)-A1]4-X (left side) and about 66% by weight of uncoupled block copolymer U of formulas B-(B / A)-A2 (four molecules on the top right, corresponding to about 57% by weight) and B-(B / A)-A1 (lower right, corresponding to about 9% by weight). t The monovinyl aromatic repeat unit blockiness is about 86.5 mol %. C is about 21% by weight, A U is about 48% by weight. Therefore, %CD is about 27% by weight.

[0145] FIG. 5 shows a schematic diagram of a two-component block copolymer consisting of about 38% by weight of coupled block copolymer C of formula [(B / A)-A1]4-X (left side) and about 62% by weight of uncoupled block copolymer U of formula (B / A)-A2 (right side). t The monovinyl aromatic repeat unit blockiness is about 87.5 mol %. C is about 21% by weight, A U is about 52% by weight. Therefore, %CD is about 31% by weight.

[0146] Figure 6 shows a schematic diagram of a two-component block copolymer consisting of about 34 wt% of coupled block copolymer C of formula [(B / A)-A1]4-X (left side) and about 66 wt% of uncoupled block copolymer U of formula (B / A)-A2 (four molecules on the top right, corresponding to about 57 wt%) and (B / A)-A1 (bottom right, corresponding to about 9 wt%). t The monovinyl aromatic repeat unit blockiness is about 86.5 mol %. C is about 21% by weight, A U is about 48% by weight. Therefore, %CD is about 27% by weight.

[0147] Figure 7 shows a schematic diagram of a two-component block copolymer consisting of about 38% by weight of coupled block copolymer C of formula [B-A1]4-X (left side) and about 62% by weight of uncoupled block copolymer U of formula B-A2 (right side). t The monovinyl aromatic repeat unit blockiness is about 100 mol %. C is about 21% by weight, A U is about 52% by weight. Therefore, %CD is about 31% by weight.

[0148] Figure 8 shows a schematic diagram of a two-component block copolymer consisting of about 34 wt% of coupled block copolymer C of formula [B-A1]4-X (left side) and about 66 wt% of uncoupled block copolymer U of formulas B-A2 (four molecules on the top right, corresponding to about 57 wt%) and B-A1 (bottom right, corresponding to about 9 wt%). t The monovinyl aromatic repeat unit blockiness is about 100 mol %. C is about 21% by weight, A U is about 48% by weight. Therefore, %CD is about 27% by weight.

[0149] In Figures 1-8, black bars indicate the sequence of monovinyl aromatic repeat units, gray bars indicate the sequence of conjugated diene repeat units, and X is the residue of a tetrafunctional coupling agent. In Figures 1-6, black lines in the sequence of conjugated diene repeat units represent different configurations in which monovinyl aromatic repeat units are copolymerized with conjugated diene repeat units. Their position and spacing indicate the concentration trend of monovinyl aromatic repeat units scattered along the block that also contains conjugated diene repeat units, rather than the specific location of individual monovinyl aromatic repeat units. Thus, a slight gradient followed by a steep concentration profile, characteristic of tapered copolymerization, is shown in Figures 1 and 2. Randomization involving only a portion of the conjugated diene repeat units is shown in Figures 3 and 4. Fully randomized configurations involving all conjugated diene repeat units are shown in Figures 5 and 6.

[0150] End Use Examples The following inventive examples demonstrate the formulation of rubber compounds containing a bicomponent block copolymer, a chemical blowing agent, and a crosslinking agent. The compounds are pre-crosslinked in a sealed, heated compression mold, followed by a sudden depressurization and mold opening, allowing the microcellular rubber to expand. The crosslinking stage of the microcellular rubber probe is then completed in a forced convection oven. The comparative examples use the same formulation and method for obtaining crosslinked microcellular rubber probes, but employ the prior art block copolymers prepared in Comparative Examples 1-3, as well as a commercially available block copolymer reference (Buna® BL30-4548) that exhibits a unimodal and very broad molecular weight distribution.

[0151] The crosslinked microcellular rubber probes were visually inspected to check the surface appearance and were measured before and after the crosslinking step to check the volumetric shrinkage. In addition, the probes were analyzed for the following aspects: Density was measured using a MUVER brand electronic density meter, model 5085-2, according to the ISO 2781 standard. Number-average cell size and cell size standard deviation were measured by epifluorescence microscopy using a Carl Zeiss AXIOTECH 100HD microscope and digital image analysis. Hardness was measured using a Bareiss brand Shore A durometer in accordance with DIN 53505 and ISO 868 standards, mounted in a MUVER 5019 holder. Resilience was measured using a Zwick 5109 rebound resilience tester.

[0152] Example 19: A rubber compound was prepared by compounding 100 phr of the diblock copolymer prepared in Inventive Example 3, 6 phr of azodicarbonamide (Celogen™ AZ-130, manufactured by CelChem, LLC) as a blowing agent, and 1.1 phr of dicumyl peroxide as a crosslinker on a roll mill. The rubber compound was compression molded, overfilling the mold by 3% to ensure a tight mold seal. The mold was heated to 92.8 kgf / cm on a heating plate at 150°C. 2 The mold was then cooled to 120°C while still under pressure. The mold clamping pressure was then released, and the compression press plate was opened. The foam immediately expanded, as evidenced by the upper mold plaque lifting. 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 conditioned at 23°C for 24 hours. The crosslinked microcellular foam rubber probe thus prepared had a smooth surface without bubble bulging defects. The volumetric shrinkage of the pre-crosslinked probe compared to the fully crosslinked probe was 3.9%. The crosslinked microcellular rubber probe had a crosslinking coefficient of 0.446 g / cm. 3The crosslinked microcellular rubber probe had a density of 1.0 μm, a number average cell size of 6.74 μm, a standard deviation of cell size of 2.09 μm, a Shore A hardness of 28.0, and a modulus of 37.9%. In Table 7, the formulation and evaluation results of the crosslinked microcellular rubber probe are compared with the remaining inventive and comparative examples.

[0153] Example 20: A rubber compound containing the two-component block copolymer prepared in Inventive Example 4 and a crosslinked microcellular rubber probe were prepared as in Inventive Example 19. The crosslinked microcellular rubber probe thus prepared had a smooth surface without bubble blister defects. The volume shrinkage of the pre-crosslinked probe compared to the fully crosslinked probe was 3.9%. The crosslinked microcellular probe had a viscosity of 0.464 g / cm. 3 The crosslinked microcellular rubber probe had a density of 1.02 μm, a number average cell size of 8.08 μm, a standard deviation of cell size of 2.40 μm, a Shore A hardness of 38, and a modulus of 37.9%. In Table 7, the formulation and evaluation results of the crosslinked microcellular rubber probe are compared with the remaining inventive and comparative examples.

[0154] Example 21: A rubber compound containing the two-component block copolymer prepared in Inventive Example 5 and a crosslinked microcellular rubber probe were prepared as in Example 19. The crosslinked microcellular rubber probe thus prepared had a smooth surface without blister defects. The volume shrinkage of the pre-crosslinked probe compared to the fully crosslinked probe was 4.0%. The density of the crosslinked microcellular probe was 0.662 g / cm. 3 , Shore A hardness 38.0, and elasticity 37.0%. In Table 7, the formulation and evaluation results of the crosslinked microcellular rubber probe are compared with the remaining invention examples and comparative examples.

[0155] Comparative example C-4: A rubber compound containing the prior art non-coupled tapered block copolymer prepared in Comparative Example C-1 and a crosslinked microcellular rubber probe were prepared as in Inventive Example 19. The crosslinked microcellular foam rubber probe thus prepared had an irregular surface with bubble bulging defects. The volume shrinkage by comparing the volume of the pre-crosslinked probe with the volume of the fully crosslinked probe was 3.9%. The crosslinked microcellular rubber probe had a viscosity of 0.526 g / cm. 3 The crosslinked microcellular rubber probe had a density of 1.0 μm, a number average cell size of 13.1 μm, a standard deviation of cell size of 8.79 μm, a Shore A hardness of 55.0, and a modulus of 28.2%. In Table 7, the formulation and evaluation results of the crosslinked microcellular rubber probe are compared with the remaining inventive and comparative examples.

[0156] Comparative example C-5: A rubber compound containing the prior art coupled tapered block copolymer prepared in Comparative Example C-2 and a crosslinked microcellular rubber probe were prepared as in Inventive Example 19. The crosslinked microcellular rubber probe thus prepared had an irregular surface with bubble blister defects. The volume shrinkage by comparing the volume of the pre-crosslinked probe with the volume of the fully crosslinked probe was 4.0%. The crosslinked microcellular rubber probe had a viscosity of 0.790 g / cm. 3 The crosslinked microcellular rubber probe had a density of 1.0 μm, a number average cell size of 9.50 μm, a cell size standard deviation of 3.38 μm, a Shore A hardness of 76.0, and a modulus of 31.0%. In Table 7, the formulation and evaluation results of the crosslinked microcellular rubber probe are compared with the remaining inventive and comparative examples.

[0157] Comparative example C-6: A rubber compound containing the prior art non-coupled tapered block copolymer prepared in Comparative Example C-3 and a crosslinked microcellular rubber probe were prepared as in Inventive Example 19. The crosslinked microcellular rubber probe thus prepared had an irregular surface with bubble blister defects. The volume shrinkage by comparing the volume of the pre-crosslinked probe with the volume of the fully crosslinked probe was 3.9%. The crosslinked microcellular rubber probe had a viscosity of 0.694 g / cm. 3 The crosslinked microcellular rubber probe had a density of 1.00 μm, a number average cell size of 6.40 μm, a standard deviation of cell size of 2.00 μm, a Shore A hardness of 53, and a modulus of 32.8%. In Table 7, the formulation and evaluation results of the crosslinked microcellular rubber probe are compared with the remaining inventive and comparative examples.

[0158] Comparative example C-7: Instead of the bicomponent block copolymer, a rubber compound containing the conventional block copolymer Buna® BL30-4548 (a block copolymer with a unimodal and very broad molecular weight distribution, as shown in Figure 9, and a commercially available reference for microcellular rubber applications) and a crosslinked microcellular rubber probe were prepared as in Example 19. The compression molding, mold cooling, decompression, and mold opening conditions were exactly the same as those in Example 19. However, when the load pressure on the hot mold was released and the press plates were opened, the rubber compound expanded only to a very limited extent, and no lifting of the plaque on the mold top was discernible. The crosslinked rubber probe thus prepared had a smooth surface without bubble bulging defects. The volume shrinkage, calculated by comparing the volume of the pre-crosslinked probe with that of the fully crosslinked probe, was 0%. The crosslinked rubber probe had a very high viscosity of 1.042 g / cm. 3 The density of the rubber compound was 1.03 μm, confirming the poor foaming performance of this rubber compound. Optical microscopy analysis revealed a very low cell count, with an average cell size of 14.25 μm and a standard deviation of 5.04 μm. The cross-linked rubber probe had a Shore A hardness of 43 and a modulus of elasticity of 37.5%. Table 7 compares the formulation and evaluation results of the cross-linked rubber probe with the remaining invention examples and comparative examples.

[0159] In Inventive Example 19 and Comparative Example C-4, the block copolymers used in the compounding had very similar Mooney viscosity values, 32.0 and 32.4, respectively, and very similar complex shear viscosities at 100°C, as evident from Table 3 (see Inventive Example 3 and Comparative Example C-1). It should be noted that the use of the two-component block copolymer of the present invention in the rubber compound compound of Inventive Example 19 produced crosslinked microcellular rubber probes with smoother surfaces, lower densities, smaller and more uniformly sized cells, lower hardness, and higher modulus than when compounded using the prior art non-coupled tapered block copolymer in Comparative Example C-4. Low volume shrinkage was obtained for both Inventive Example 19 and Comparative Example C-4.

[0160] In Inventive Example 20 and Comparative Example C-5, the block copolymers used in the compounding had very similar Mooney viscosity values, 39.2 and 40.6, respectively, and very similar complex shear viscosities at 100°C, as evident from Table 3 (see Inventive Example 4 and Comparative Example C-2). It should be noted that the use of the two-component block copolymer of the present invention in the rubber compound formulation of Inventive Example 20 produced crosslinked microcellular rubber probes with smoother surfaces, lower densities, smaller and more uniformly sized cells, much lower hardness, and higher modulus than when compounded using the prior art coupled tapered block copolymer in Comparative Example C-5. Low volume shrinkage was obtained for both Inventive Example 20 and Comparative Example C-5.

[0161] The block copolymers used in the compounding of Inventive Example 21 and Comparative Example C-6 had very similar complex shear viscosity profiles at 100°C (see Inventive Example 3 and Comparative Example C-1), as evidenced in Table 3. Note that the use of the two-component block copolymer of the present invention in the rubber compound formulation of Inventive Example 21 was performed to produce crosslinked microcellular rubber probes with smoother surfaces, lower densities, lower hardness, and higher moduli than when compounded using the prior art non-coupled tapered block copolymer in Comparative Example C-6. Low volume shrinkage was obtained for both Inventive Example 21 and Comparative Example C-6.

[0162] [Table 7]

[0163] Example 22: A foamable rubber compound was prepared by compounding 100 phr of the diblock copolymer of Example 13, 6 phr of azodicarbonamide, and 1.1 phr of dicumyl peroxide on a roll mill. The foamable rubber compound was compression molded, overfilling the mold with 3% rubber compound to ensure a tight seal. The mold was heated to 92.8 kgf / cm on a heating plate at 170°C. 2 The mold was then clamped at a clamping pressure of 0.05 for 3 minutes. The pressure load on the mold was then released, and the compression press plate was opened. The bubbles immediately expanded, which was confirmed by the upper mold plaque lifting. The mold and crosslinked microcellular rubber probe were then quenched in water at 23°C. The crosslinked microcellular rubber probe was removed from the mold and dried on absorbent paper. The crosslinked microcellular rubber probe was then conditioned for 7 days in a controlled atmosphere room at 23°C and 50% relative humidity. The crosslinked microcellular rubber probe thus prepared had a smooth surface without bubble bulging defects. Its density was 0.624 g / cm. 3The crosslinked microcellular rubber compound showed 0% shrinkage after conditioning for 7 days in a controlled atmosphere room. The formulation and properties of the crosslinked microcellular rubber compound are summarized in Table 8.

[0164] Comparative Example 7: A foamable rubber compound containing Buna® BL30-4548 instead of the two-component block copolymer and a crosslinked microcellular rubber probe were prepared as in Inventive Example 22. The compression molding conditions were exactly the same as in Inventive Example 22, but when the load pressure on the hot mold was released and the compression press plate was opened, the expansion of the rubber compound foam occurred to a very limited extent, and no lifting of the plaque on the top of the mold was recognized. The crosslinked microcellular foam rubber probe thus prepared had a smooth surface without bubble bulging defects. 0.986 g / cm 3 The density of 1000 MPa indicated the low foaming performance of this compound. The formulation and properties of the crosslinked microcellular rubber compound are summarized in Table 8.

[0165] [Table 8]

[0166] Overall, in all cases where the diblock copolymers of the present invention were used to produce crosslinked microcellular rubber probes, a smooth surface appearance was obtained, whereas when the tapered block copolymers of the prior art were used, both uncoupled and coupled, the resulting microcellular rubber probes had surface blister defects. Improved foaming performance was also demonstrated when the diblock copolymers of the present invention were used, as evidenced by lower probe density and more uniformly sized cells than when using the prior art alternatives. Furthermore, when the diblock copolymers of the present invention were included, higher softness (lower Shore A hardness) and higher modulus were obtained in the crosslinked rubber compounds. Under the same pre-crosslinking / molding, vacuum, and crosslinking conditions, formulations containing the diblock copolymers enabled the production of crosslinked microcellular rubber probes, whereas this was not possible when using the commercially available reference Buna® BL30-4548 microcellular foam.

[0167] In the following examples, compounding evaluations were performed in a laboratory internal mixer. The compounds contained either the binary block copolymer of the present invention or a prior art tapered block copolymer. Torque and temperature readings were collected to evaluate compounding performance. Compounding evaluations were performed on an Intelli-Torque Plasti-Corder equipped with a Brabender brand CAM blade and a Prep-Mixer measuring head with a net chamber volume of 420 ml. The standard compound used also contained emulsion SBR, filler, plasticizer, antioxidant, chemical blowing agent, blowing agent activator, crosslinker, crosslinking accelerator, and crosslinker activator.

[0168] Example 23: Compounding evaluation was performed in a laboratory internal mixer. The initial charge included 80 phr of the diblock copolymer prepared in Example 3 and 20 phr of Emulprene 1502 (a cold emulsion styrene-butadiene random copolymer with 23.5% styrene repeat unit content, manufactured by Dynasol Group). Mixing was initiated with the chamber temperature stabilized at 45°C. After 1 minute of mixing, 2.5 phr of naphthenic oil and 1.7 phr of paraffin wax were added. After 4 minutes of mixing, 70 phr of hard clay, 35 phr of aluminum silicate, 4.5 phr of azodicarbonamide (Celogen™ AZ-130), and 1.0 phr of Wingstay® L (OMNOVA Solutions Inc.) antioxidant were added. After 8 minutes of mixing, 3.0 phr of sulfur, 3.5 phr of stearic acid, and 3.5 phr of zinc oxide were added. At 10 minutes of mixing time, 1 phr of diphenylguanidine (DPG) and 2.3 phr of 2-benzothiazyl-N-sulfene morpholide (MBS) were added. At a total mixing time of 12 minutes, the torque reading was 106.2 N m and the internal temperature of the mixing chamber was 87°C. The formulation evaluation results are shown in Table 9.

[0169] Example 24: A compounding evaluation was performed similar to that of Inventive Example 23 using the binary block copolymer of Inventive Example 4. With a total mixing time of 12 minutes, the torque reading was 110.2 N m and the internal temperature of the mixing chamber was 87°C. The compounding evaluation results are shown in Table 9.

[0170] Example 25: The binary block copolymer of Inventive Example 13 was used in a compounding evaluation similar to Inventive Example 23. With a total mixing time of 12 minutes, the torque reading was 110.0 N·m and the internal temperature of the mixing chamber was 87°C. The compounding evaluation results are shown in Table 9.

[0171] Example 26: A compounding evaluation was performed similar to that of Inventive Example 23 using the binary block copolymer of Inventive Example 5. With a total mixing time of 12 minutes, the torque reading was 115.6 N·m and the internal temperature of the mixing chamber was 88°C. The compounding evaluation results are shown in Table 9.

[0172] Comparative example C-9: A compounding evaluation was performed similar to Inventive Example 23 using the tapered linear block copolymer of Comparative Example 1. With a total mixing time of 12 minutes, the torque reading was 109.9 N·m and the internal temperature of the mixing chamber was 88°C. The compounding evaluation results are shown in Table 9.

[0173] Comparative example C-10: A compounding evaluation was performed similar to Inventive Example 23 using the tapered coupled block copolymer of Comparative Example 2. With a total mixing time of 12 minutes, the torque reading was 112.2 N·m and the internal temperature of the mixing chamber was 87°C. The compounding evaluation results are shown in Table 9.

[0174] Comparative example C-l1: A compounding evaluation was performed similar to Inventive Example 23 using the tapered block copolymer of Comparative Example 3. With a total mixing time of 12 minutes, the torque reading was 119.6 N·m and the internal temperature of the mixing chamber was 90°C. The compounding evaluation results are shown in Table 9.

[0175] Comparative example C-12: A blending evaluation was performed using Buna® BL30-4548 as in Inventive Example 23. The total blending time was 12 minutes, the torque reading was 114.3 N m, and the internal temperature of the mixing chamber was 90°C. The blending evaluation results are shown in Table 9.

[0176] In Inventive Example 23 and Comparative Example 9, the block copolymers used in the compounding had very similar Mooney viscosity values, 32.0 and 32.4, respectively, and very similar complex shear viscosity profiles at 100°C (see Inventive Example 3 and Comparative Example 1), as seen in Table 3. Note that when the compound contained the binary block copolymer, slightly lower torque and lower chamber temperature were obtained at the end of the compounding cycle than when it contained the prior art non-coupled tapered block copolymer.

[0177] In Inventive Examples 24 and 25, and Comparative Example 10, the block copolymers used in the compounding had very similar Mooney viscosity values ​​of 39.2, 39.0, and 40.6, respectively, and very similar complex shear viscosity profiles at 100°C (see Inventive Example 4, Inventive Example 13, and Comparative Example 2), as seen in Table 3. Again, it should be noted that when the compound contained the binary block copolymer, a slightly lower torque and lower chamber temperature were obtained at the end of the compounding cycle than when the compound contained the prior art non-coupled tapered block copolymer.

[0178] In Inventive Example 26 and Comparative Example 11, the block copolymers used in the compounding had very similar complex shear viscosity profiles at 100°C, higher than the previous examples (see Inventive Example 3 and Comparative Example 1), as seen in Table 3. Again, it is noted that when the compound contained the two-component block copolymer, a slightly lower torque and lower chamber temperature were obtained at the end of the compounding cycle than when it contained the prior art non-coupled tapered block copolymer.

[0179] Furthermore, when comparing the compounding of Inventive Examples 23-26 with that of the compounding containing the prior art commercial reference Buna® BL30-4548 in Comparative Example 12, it is noted that the inventive two-component block copolymers result in lower temperatures at the end of the compounding cycle and, in most cases, slightly lower final torque.

[0180] The slightly lower torque when compounding formulations containing the inventive two-component block copolymers represents an advantage because it reduces the power consumption required to carry out the compounding operation. The slightly lower final internal chamber temperature when compounding formulations containing the inventive two-component block copolymers represents an advantage because it better avoids the problems of premature crosslinking and premature blistering during the mixing operation. This is particularly advantageous when using crosslinking systems and / or blowing agent systems with low activation temperatures.

[0181] [Table 9]

[0182] The following examples demonstrate the formulation and performance of hot-melt pressure-sensitive adhesives containing the binary block copolymers of the present invention or prior art block copolymers. The formulations employed were customized for labeling purposes. The adhesive properties were evaluated using the following test methods: Brookfield viscosity at 150, 160, and 177°C according to ASTM D1084 / D2556; ring and ball softening point temperature was obtained according to ASTM D36; loop tack test at 23°C was performed according to PSTC-16; rolling ball tack was evaluated at 23°C as standardized in PSTC-6; peel strength at an angle of 180° and 23°C according to PSTC-1; and shear strength at 23°C according to ASTM D3654.

[0183] Example 27: A hot melt pressure sensitive adhesive for labeling was prepared using the following formulation: 100 parts by weight of a two-component block copolymer (M 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 at 100°C ML1+4 = 40.7, Tan delta at 100°C and 13.95% strain covering vibration frequencies from 0.25 to 200 rad / s max =0.81), 178 parts by weight of hydrogenated gum rosin tackifier Foral® 85 from Eastman Chemical Company, 50 parts by weight of naphthenic oil Nyflex® 223 from NYNAS, and 4 parts by weight of antioxidant Irganox® 1010 from BASF. Compounding was carried out in a 500 ml cylindrical metal vessel equipped with a controlled heating mantle and an adjustable stirring speed with a three-blade propeller. The tackifier, naphthenic oil, and antioxidant were first heated to 135°C under a nitrogen atmosphere and gently stirred to melt the ingredients. After melting, the stirring speed was set to 300 RPM, and the temperature was increased to 155°C over 30 minutes. Next, the diblock copolymer was gradually added, and the stirring speed was increased to 750 RPM. The temperature was then controlled at 170±5°C for the next 2 hours, during which time stirring was carried out at 750 RPM to ensure the compound was homogenized. The adhesive has a Brookfield viscosity of 66,300 mP·s (cP) at 150°C, 46,380 mP·s (cP) at 160°C, and 19,680 mP·s (cP) at 177°C; a ring and ball softening point temperature of 90.9°C; and a stiffness of 1.000 N·m (8.853 lbf) at 23°C. f -in) loop tack, 7.1mm (0.28in) rolling ball tack at 23°C; 1.83kg (4.04lb) at 180° angle and 23°C f ) peel strength; and shear strength of 9.58 minutes at 23°C under a 1000g load. The adhesive formulation and performance are shown in Table 10.

[0184] Comparative example C-13: A hot melt pressure-sensitive adhesive for labeling was prepared as in Inventive Example 27, except that the binary block copolymer was replaced with Solprene® 1205 from Dynasol Group. Solprene® 1205 is a tapered styrene-butadiene block copolymer with a total styrene content of 25 wt%, a block styrene content of 17.5 wt%, a Mooney viscosity ML of 1+4, and a 100°C value of 47, making it an established standard in hot melt pressure-sensitive adhesive formulations. This adhesive has Brookfield viscosities of 14,000 mP·s (cP) at 150°C, 10,750 mP·s (cP) at 160°C, and 7,050 mP·s (cP) at 177°C; a ring and ball softening point temperature of 69.95°C; and a shear strength of 0.690 N·m (6.132 lbf) at 23°C. f 11mm (0.44in) loop tack at 23°C; 1.486kg (3.275lb) rolling ball tack at 180° angle and 23°C f ) peel strength; and shear strength of 1.55 minutes at 23°C under a 1000g load. The adhesive recipe and properties are shown in Table 10.

[0185] Comparative example C-14: A hot melt pressure-sensitive adhesive for labeling was prepared as in Inventive Example 27, except that the diblock copolymer was replaced with Calprene® 540 from the Dynasol Group. 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, and is also sold for use in formulating hot melt pressure-sensitive adhesives. This adhesive has Brookfield viscosities of 13260 mP·s (cP) at 150°C, 9300 mP·s (cP) at 160°C, and 5470 mP·s (cP) at 177°C; a ring and ball softening point temperature of 85.3°C; and a shear strength of 0.570 N·m (5.05 lbf) at 23°C. f 25mm (0.98in) loop tack at 23°C; 1.86kg (4.09lb) at 180° angle and 23°C f) peel strength; and shear strength of 1.55 minutes at 23°C under a 1000 g load. The recipe and properties of this adhesive are shown in Table 10.

[0186] [Table 10]

[0187] Performance evaluation of hot-melt pressure-sensitive adhesive formulations for labeling shows that the two-component block copolymers provide excellent adhesion. This may be related to the higher wettability and adhesive ability of the terminal conjugated diene-rich block of the coupling fraction. On the other hand, the higher softening point temperature of adhesives formulated with the two-component block copolymers may be advantageous for extending the adhesive's service temperature range, making them useful for labeling goods exposed to high temperatures during transportation. The Brookfield viscosity of the hot-melt adhesives according to the present invention is at the upper end of their processing utility, but can nevertheless be easily reduced by appropriate adjustment of molecular parameters such as molecular weight, coupling level, and / or functionality of the coupling agent used.

[0188] End-use application In summary, in one embodiment, the present invention provides a dicomponent 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-A1]nX, or a mixture thereof, and 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 block formed solely from conjugated diene monomers, (B / A) is a random polymer block formed from at least one conjugated diene monomer and at least one monovinyl aromatic monomer, and D is a random polymer block formed from at least one conjugated diene monomer and at least one monovinyl aromatic monomer. A polymer block formed from monovinyl aromatic monomers, wherein the conjugated diene repeat units are in molar excess over the monovinyl aromatic repeat units along the entire length of the polymer block; (D / A) is a polymer block formed from at least one conjugated diene monomer and at least one monovinyl aromatic monomer, wherein the end of the polymer block opposite A1 or A2 is composed primarily of conjugated diene repeat units, and the composition of the polymer block gradually changes along the length of the block until it is composed essentially of monovinyl aromatic repeat units at the end adjacent A1 or A2; A1 and A2 are polymer blocks formed exclusively from monovinyl aromatic monomers, and polymer block A2 has a higher molecular weight than polymer block A1; X is a residue of a coupling agent; and n is an integer having a value of 2 to 30.

[0189] Preferably, the molecular weight distribution of the dicomponent block copolymer exhibits at least two peaks that are partially or completely separated; and / or block copolymer C constitutes the highest molecular weight peak fraction in the molecular weight distribution, and block copolymer U constitutes the remainder 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 repeat unit content of the dicomponent block copolymer is about 20 to about 50 wt %; and / or the monovinyl aromatic repeat unit content of block copolymer U is at least 10 wt % higher than the monovinyl aromatic repeat unit content of block copolymer C.

[0190] The primary anticipated end use of the bicomponent block copolymers of the present invention is to produce crosslinked microcellular rubber products as described herein. However, the bicomponent block copolymers of the present invention may also be useful in asphalt reinforcement, adhesives, sealants, coatings, insulation, and plastic compositions. End use uses for the block copolymers are described in U.S. Patent Application No. 2017 / 0210841, filed January 26, 2017 as U.S. Patent Application No. 15 / 417,193, and published July 27, 2017, which is incorporated by reference. One use is a bitumen composition that can include bitumen; one or more additives selected from the group consisting of plasticizers, fillers, crosslinking agents, flow resins, tackifying resins, processing aids, antiozonants, and antioxidants; and the bicomponent block copolymer composition described and claimed herein. Here, the bituminous composition comprises from about 0.5 to about 25 weight percent, preferably from about 0.5 to about 8 weight percent for road paving applications, and from 3 to about 25 weight percent for roofing, shingle, and waterproofing membrane applications. The bitumen composition can also be emulsified in water using an emulsifier.

[0191] One application is an adhesive composition that can include the two-component block copolymer composition described and claimed herein and at least one additive selected from the group consisting of tackifying resins; plasticizers; solvents; coupling agents; crosslinking agents; photoinitiators; and antioxidants. The adhesive composition comprises from about 0.5 to about 50 weight percent of the two-component block copolymer composition. Another application is a sealant composition that can include the two-component block copolymer composition described and claimed herein and at least one additive selected from the group consisting of tackifying resins; plasticizers; fillers; coupling agents; processing aids; and antioxidants. The sealant composition comprises from about 0.5 to about 50 weight percent of the two-component block copolymer composition. Another suitable application of the present 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 the two-component block copolymer, for the specific purpose of improving gloss while minimizing compromise in impact strength. This can include a mixture of a polymer composition with the two-component block copolymer composition described and claimed herein.

[0192] Various modifications of the techniques, procedures, materials, and equipment will be apparent to those skilled in the art from the above described invention. 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 two-component block copolymer comprising C and U, C is: [D-(D / A)-A １ ] ｎ -X; [B-(B / A)-A １ ] ｎ -X; [(B / A)-A １ ] ｎ -X; or [B-A １ ] ｎ -X Including, U is: D-(D / A)-A ２ or D-(D / A)-A ２ and D-(D / A)-A １ ; B-(B / A)-A ２ or B-(B / A)-A ２ and B-(B / A)-A １ ; (B / A)-A ２ or (B / A)-A ２ and (B / A)-A １ or B-A ２ or B-A ２ and B-A １ Including, The two-component block copolymer is [D-(D / A)-A １ ] ｎ -X and [D-(D / A)-A ２ or D-(D / A)-A ２ and D-(D / A)-A １ or [B-(B / A)-A １ ] ｎ -X and [B-(B / A)-A ２ or B-(B / A)-A ２ and B-(B / A)-A １ or [(B / A)-A １ ] ｎ -X and [(B / A)-A ２ or (B / A)-A ２ and (B / A)-A １ or [B-A １ ] ｎ -X and [B-A ２ or B-A ２ and B-A １ and B is a polymer block formed solely from conjugated diene monomers, (B / A) is a random polymer block formed from at least one conjugated diene monomer and at least one monovinyl aromatic monomer; D is a polymer block formed from at least one conjugated diene monomer and at least one monovinyl aromatic monomer, wherein the conjugated diene repeat units are in molar excess over the monovinyl aromatic repeat units along the entire length of the polymer block; (D / A) is a polymer block formed from at least one conjugated diene monomer and at least one monovinyl aromatic monomer, and A １ or A ２ The polymer block end opposite to A is mainly composed of conjugated diene repeat units, and the composition of the polymer block is １ or A ２ gradually varies along the length of the block until it consists essentially of monovinyl aromatic repeat units at the end adjacent A １ and A ２ is a polymer block formed solely from monovinyl aromatic monomers, and polymer block A ２ is polymer block A １ It has a larger molecular weight than X is a residue of a coupling agent; n is an integer having a value from 2 to 30; The molecular weight distribution of the bicomponent block copolymer exhibits at least two peaks that are partially or completely separated; Block copolymer C constitutes the highest molecular weight peak fraction of the molecular weight distribution, and block copolymer U constitutes the remainder of the molecular weight distribution; Block copolymer C accounts for about 20 to about 80% of the molecular weight distribution; The total monovinyl aromatic repeat unit content of the bicomponent block copolymer is from about 20 to about 50 weight percent; the monovinyl aromatic repeat unit content of block copolymer U is at least 10 wt. % higher than the monovinyl aromatic repeat unit content of block copolymer C; Optionally, further comprising an extender oil; Two-component block copolymer.

2. C is: [D-(D / A)-A １ ] ｎ -X, U is: D-(D / A)-A ２ or D-(D / A)-A ２ and D-(D / A)-A １ Including, Formula D-(D / A)-A ２ and the uncoupled block copolymer molecules comprise from about 20 to about 80 weight percent of the molecular weight distribution of the dicomponent block copolymer; Formula D-(D / A)-A １ and the uncoupled block copolymer molecules comprise from about 0 to about 20 weight percent of the molecular weight distribution of the dicomponent block copolymer; the monovinyl aromatic repeat unit blockiness of the two-component block copolymer is greater than or equal to about 76 mole percent, based on the total monovinyl aromatic repeat units; Optionally, the diblock copolymer further comprises 0 to about 12 wt. % of an extender oil. The two-component block copolymer of claim 1 .

3. C is: [B-(B / A)-A １ ] ｎ -X, U is: B-(B / A)-A ２ or B-(B / A)-A ２ and B-(B / A)-A １ Including, Formula B-(B / A)-A ２ and the uncoupled block copolymer molecules comprise from about 20 to about 80 weight percent of the molecular weight distribution of the dicomponent block copolymer; Formula B-(B / A)-A １ and the uncoupled block copolymer molecules comprise from about 0 to about 20 weight percent of the molecular weight distribution of the dicomponent block copolymer; Optionally, the diblock copolymer further comprises 0 to about 12 wt. % of an extender oil. The two-component block copolymer of claim 1 .

4. C is: [(B / A)-A １ ] ｎ -X, U is: (B / A)-A ２ or (B / A)-A ２ and (B / A)-A １ Including, Formula (B / A)-A ２ and the uncoupled block copolymer molecules comprise from about 20 to about 80 weight percent of the molecular weight distribution of the dicomponent block copolymer; Formula (B / A)-A １ and the uncoupled block copolymer molecules comprise from about 0 to about 20 weight percent of the molecular weight distribution of the dicomponent block copolymer; Optionally, the diblock copolymer further comprises 0 to about 12 wt. % of an extender oil. The two-component block copolymer of claim 1 .

5. C is: [B-A １ ] ｎ -X, U is: B-A ２ or B-A ２ and B-A １ Including, Formula B-A ２ and the uncoupled block copolymer molecules comprise from about 20 to about 80 weight percent of the molecular weight distribution of the dicomponent block copolymer; Formula B-A １ and the uncoupled block copolymer molecules comprise from about 0 to about 20 weight percent of the molecular weight distribution of the dicomponent block copolymer; the monovinyl aromatic repeat unit blockiness of the two-component block copolymer is greater than or equal to about 90 mole percent, based on the total monovinyl aromatic repeat units; Optionally, the diblock copolymer further comprises 0 to about 12 wt. % of an extender oil. The two-component block copolymer of claim 1 .

6. 3. The binary block copolymer of claim 2, wherein the monovinyl aromatic repeat unit blockiness of the binary block copolymer is at least about 80 mole percent based on total monovinyl aromatic repeat units.

7. 6. The binary block copolymer according to claim 1, wherein U has a monovinyl aromatic repeat unit content at least 20% by weight higher than C.

8. n is an integer from 2 to 4, and the polydispersity ratio M of the two-component block copolymer ｗ / M ｎ is less than 1.50; or n is an integer from 2 to 30, and the polydispersity ratio M of the two-component block copolymer ｗ / M ｎ is less than 1.90, The two-component block copolymer according to any one of claims 1 to 5.

9. In dynamic oscillatory shear testing, the material exhibited only tan delta values ​​of less than 0.95 when the oscillatory frequency was varied from 0.25 to 200 rad / s at 100°C and 13.95% strain; Optionally, in a dynamic oscillatory shear test, the polymer exhibits only tan delta values ​​of less than 0.95 when the oscillatory frequency is varied from 0.25 to 200 rad / s at 140°C and 13.95% strain. The two-component block copolymer according to any one of claims 1 to 5.

10. In dynamic oscillatory shear testing, the material exhibited only tan delta values ​​less than 0.90 when the oscillatory frequency was varied from 0.25 to 200 rad / s at 100°C and 13.95% strain; Optionally, in a dynamic oscillatory shear test, the polymer exhibits only tan delta values ​​of less than 0.90 when the oscillatory frequency is varied from 0.25 to 200 rad / s at 140°C and 13.95% strain. The two-component block copolymer according to any one of claims 1 to 5.

11. In dynamic oscillatory shear testing, the material exhibited only tan delta values ​​of less than 0.85 when the oscillatory frequency was varied from 0.25 to 200 rad / s at 100°C and 13.95% strain; Optionally, in a dynamic oscillatory shear test, the polymer exhibits only tan delta values ​​of less than 0.85 when the oscillatory frequency is varied from 0.25 to 200 rad / s at 140°C and 13.95% strain. The two-component block copolymer according to any one of claims 1 to 5.

12. The two-component block copolymer has a Mooney viscosity (ML1+4, 100°C) of about 25 to about 90; the complex dynamic shear viscosity of the dicomponent block copolymer is from about 50,000 Pa s to about 360,000 Pa s when evaluated at a frequency of 0.99 rad / s, a temperature of 100° C., and a strain of 13.95%; The complex dynamic shear viscosity of the bicomponent block copolymer is from about 3,000 Pa·s to about 12,000 Pa·s when evaluated at a frequency of 100 rad / s, a temperature of 100° C., and a strain of 13.95%. The two-component block copolymer according to any one of claims 1 to 5.

13. A two-component block copolymer comprising C and U, C is a coupled block copolymer comprising repeat units derived from a conjugated diene monomer and a monovinyl aromatic monomer, C having only a plurality of monovinyl aromatic interior blocks as interior blocks and only a conjugated diene-rich remainder; each monovinyl aromatic interior block of C is bonded at one end to a coupling agent residue and at the other end to a single conjugated diene-rich remainder; C has a single coupling agent residue per molecule, said coupling agent residue being attached only to the monovinyl aromatic interior block; U is an uncoupled block copolymer comprising repeat units derived from a conjugated diene monomer and a monovinyl aromatic monomer, U having only a single monovinyl aromatic endblock and a single conjugated diene-rich remainder; U has a lower molecular weight than C; U has a higher content of monovinyl aromatic repeat units than C; U has a higher monovinyl aromatic block content than C; The remaining U and C conjugated diene-rich fractions are of equal molecular weight, (a) the molecular weight distribution of the two-component block copolymer exhibits at least two peaks; (b) Block copolymer C constitutes the highest peak fraction of the molecular weight distribution, and block copolymer U constitutes the remainder of the molecular weight distribution; (c) block copolymer C accounts for about 20 to about 80% of the molecular weight distribution; (d) the total monovinyl aromatic repeat unit content of the bicomponent block copolymer is from about 20 to about 50 weight percent; (e) the monovinyl aromatic repeat unit content of block copolymer U is at least 10 wt. % higher than the monovinyl aromatic repeat unit content of block copolymer C; (f) the monovinyl aromatic repeat unit blockiness of the binary block copolymer is greater than or equal to about 77 mole percent, based on total monovinyl aromatic repeat units; (g) the binary block copolymer has a Mooney viscosity (ML1+4, 100°C) of about 25 to about 70; (h) the complex dynamic shear viscosity of the bicomponent block copolymer is greater than about 50,000 Pa s and less than about 150,000 Pa s when evaluated at a frequency of 0.99 rad / s, a temperature of 100° C., and a strain of 13.95%; (i) the complex dynamic shear viscosity of the bicomponent block copolymer is greater than about 3,000 Pa s and less than about 7,000 Pa s when evaluated at a frequency of 100 rad / s, a temperature of 100° C., and a strain of 13.95%; (j) In dynamic oscillatory shear testing of the bicomponent block copolymer, the copolymer exhibits a tan delta value of less than 0.95 at a temperature of 100°C and a strain of 13.95% over an oscillatory frequency range of 0.25 to 200 rad / s. Two-component block copolymer.

14. The block copolymer C has the general formula: [D-(D / A)-A １ ] ｎ -X, The block copolymer U has the general formula: D-(D / A)-A ２ or D-(D / A)-A ２ and D-(D / A)-A １ and (a) D is a polymer block formed from at least one conjugated diene monomer and at least one monovinyl aromatic monomer, wherein the conjugated diene repeat units are in molar excess over the monovinyl aromatic repeat units along the entire length of the polymer block; (b) (D / A) is a polymer block formed from at least one conjugated diene monomer and at least one monovinyl aromatic monomer, and A １ or A ２ The polymer block end opposite to A is mainly composed of conjugated diene repeat units, and its composition is １ or A ２ gradually varies along the length of the block until it consists essentially of monovinyl aromatic repeat units at the end adjacent (c) A １ and A ２ is a polymer block formed solely from monovinyl aromatic monomers, (d) Polymer Block A ２ is polymer block A １ It has a larger molecular weight than (e) X is a residue of a coupling agent and n is an integer having a value from 2 to 30; (f) Formula [D-(D / A)-A １ ] ｎ -X coupled block copolymer molecules account for about 20 to about 80 weight percent of the molecular weight distribution of the dicomponent block copolymer; (g) Formula D-(D / A)-A ２ and the uncoupled block copolymer molecules comprise from about 20 to about 80 weight percent of the molecular weight distribution of the dicomponent block copolymer; (h) Formula D-(D / A)-A １ and the uncoupled block copolymer molecules comprise from about 0 to about 20 weight percent of the molecular weight distribution of the dicomponent block copolymer. The two-component block copolymer of claim 13.

15. 3. A method for producing the two-component block copolymer of claim 2, comprising: charging an aliphatic hydrocarbon solvent, a conjugated diene monomer, and a monovinyl aromatic monomer into a batch reactor; charging an organolithium initiator to a batch reactor; completely copolymerizing the monomers to form a polymeric anion; charging a limited amount of coupling agent into a batch reactor to couple only a portion of the polymer anions; charging additional and / or different monovinyl aromatic monomers to the batch reactor; completely block copolymerizing the monovinyl aromatic monomer; dosing a proton donor or electrophilic monofunctional compound to deactivate any remaining polymer anions in the batch reactor; and Recovering the two-component block copolymer A method comprising:

16. 4. A method for producing the two-component block copolymer of claim 3, comprising: charging an aliphatic hydrocarbon solvent, a randomizer, and a conjugated diene monomer into a batch reactor; charging an organolithium initiator to a batch reactor; polymerizing the conjugated diene monomer fed to a batch reactor to a conversion level of about 80% to about 95%; charging a monovinylaromatic monomer to a batch reactor; completely copolymerizing the remaining conjugated diene monomer with the monovinyl aromatic monomer fed to the reactor to form a polymeric anion; adding a limited amount of coupling agent to partially couple the polymer anions; charging additional and / or different monovinyl aromatic monomers to the batch reactor; completely block copolymerizing the monovinyl aromatic monomer; introducing a proton donor or electrophilic monofunctional compound to deactivate any remaining polymer anions; and Recovering the two-component block copolymer A method comprising:

17. 5. A method for producing the two-component block copolymer of claim 4, comprising: charging an aliphatic hydrocarbon solvent, a randomizer, a conjugated diene monomer, and a monovinyl aromatic monomer into a batch reactor; charging an organolithium initiator to a batch reactor; completely copolymerizing the conjugated diene monomer and the monovinyl aromatic monomer; charging additional and / or different monovinyl aromatic monomers to the batch reactor; completely block copolymerizing the monovinyl aromatic monomer fed to the batch reactor to form a polymeric anion; introducing a limited amount of coupling agent to couple only a portion of the polymer anions; charging additional and / or different monovinyl aromatic monomers to the batch reactor; completely block copolymerizing the monovinyl aromatic monomer; adding a proton donor or an electrophilic monofunctional compound to completely deactivate the remaining polymer anions; and Recovering the two-component block copolymer A method comprising:

18. 6. A method for producing the two-component block copolymer of claim 5, comprising: charging an aliphatic hydrocarbon solvent, a randomizer, and a conjugated diene monomer into a batch reactor; charging an organolithium initiator to a batch reactor; completely polymerizing the conjugated diene monomer; charging a monovinylaromatic monomer to a batch reactor; completely block copolymerizing the monovinyl aromatic monomer fed to the batch reactor to form a polymeric anion; adding a limited amount of coupling agent to partially couple the polymer anions; charging additional and / or different monovinyl aromatic monomers to the batch reactor; completely block copolymerizing the monovinyl aromatic monomer; adding a proton donor or an electrophilic monofunctional compound to completely inactivate the polymer anions remaining in the batch reactor; and Recovering the two-component block copolymer A method comprising:

19. charging a limited amount of a proton donor or electrophilic monofunctional compound to deactivate only a portion of the polymer anions in the batch reactor prior to charging additional and / or different monovinyl aromatic monomers; or Concurrently with the step of dosing the additional and / or different monovinyl aromatic monomer, dosing a limited amount of a proton donor or electrophilic monofunctional compound to deactivate only a portion of the polymer anions in the batch reactor. The method of any one of claims 15 to 18, further comprising:

20. 1. A composition for a crosslinked microcellular rubber article, comprising: The two-component block copolymer according to any one of claims 1 to 5; Foaming agent; and crosslinking agent A composition comprising:

21. 21. The composition of claim 20, 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, ground crosslinked microcellular rubber compounds, fillers, plasticizers, blowing agent activators, crosslinker activators, crosslinking accelerators, vulcanization retarders, antioxidants, antiozonants, UV stabilizers, light stabilizers, fragrances or odorants, termite repellents, biocides, antifungal agents, antibacterial agents, antimicrobial agents, metal deactivators, dyes, pigments, mold release agents, and the like, or mixtures thereof.

22. 1. A composition for a hot melt pressure sensitive adhesive, comprising: The two-component block copolymer according to any one of claims 1 to 5; Tackifying resin; extender oil; and antioxidant A composition comprising:

23. 23. The composition of claim 22, further comprising at least one additive selected from the group consisting of fillers, waxes, photoinitiators, crosslinking agents, crosslinking coagents, crosslinking retarders, adhesion promoters or coupling agents, UV stabilizers, light stabilizers, ozone stabilizers, epoxy resins, asphalt, reinforcing resins, fragrances or odorants, termite repellents, biocides, antifungal agents, antibacterial agents, metal deactivators, dyes, pigments, colorants, flame retardants, blowing agents, blowing agent activators, refractive index modifiers, and the like, or mixtures thereof.

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