Linear polar-nonpolar diblock copolymers and their uses

Abstract

Linear diblock copolymers of the general structure "polymer A-linkage-polymer B" (wherein polymer A is a non-polar polymer that is essentially a copolymer of propylene and ethylene, where propylene represents 51 to 99% by weight of polymer A, and polymer B is a polar polymer), as well as uses of said diblock copolymers to tailor polymer bulk and interfacial properties in end uses, and polymer A-linkage, which are useful intermediate materials for the preparation of diblock copolymers.

Description

[Technical Field]

[0001] The present invention relates to a polymer structure useful as an intermediate for forming linear diblock copolymers of the general structure "polymer A-linkage-polymer B" (wherein polymer A is a nonpolar polymer that is essentially a copolymer of propylene and ethylene, and polymer B is a polar polymer), as well as such diblock copolymers, and also to the use of such diblock copolymers for modifying polymer bulk and interfacial properties in end applications. [Background technology]

[0002] The plastics manufacturing industry produces a wide range of articles derived from various different polymers, which may be thermoplastic or thermosetting polymer materials. When producing articles with desired performance characteristics, it is fairly common for the industry to rely on mixtures of different polymers in bulk, or to layer or laminate one polymer species on a second polymer species, possibly with a tie-layer between the two thin layers, or to fill or reinforce the bulk polymer with fillers or particulate matter, which may be minerals or other polymer materials. In all these activities, a key challenge for the industry is to manipulate interfacial and surface effects to mitigate, and where possible, avoid, the detrimental or inferior performance resulting from the combination of different polymer materials in the end application. For example, a combination of tensile strength and impact resistance may be required, a combination of flexibility and surface integrity, and / or a combination of stiffness and lamination ability, and printability and paintability may be required. These challenges for the industry become even more apparent when attempting to manipulate systems in which combinations of polar and nonpolar materials exist, through their combined surface or bulk interactions. A significant portion of the plastics industry involves the melt processing of polymer mixtures, and in many cases, obtaining a homogeneous mixture of these materials is impossible or extremely difficult. Homogeneity is necessary to enable the processing of the formulation into a finished product and to provide uniform properties in the finished product. This is especially true for mixtures of polymer materials processed in molten form by, for example, extrusion (including film molding), injection molding, rotational molding, blow molding, or thermoforming, where a homogeneous mixture of polymers in the molten state is required for smooth processing and the production of articles with uniform contents. Homogeneity means that an article has a substantially uniform polymer content throughout its body, and includes both the miscibility of the polymers and the dispersibility of one polymer within another.

[0003] The incompatibility of different polymers can also present challenges for the reuse of polymer materials. Reuse is often carried out by melting and mixing plastic materials for reuse, and currently, it is often necessary to pre-separate different types of plastics in order to obtain a relatively uniform recovered material that is attractive for reuse in the industry. Improving the compatibility of polymers, such as high-density polyethylene and polystyrene, means that more polymer waste and polymer species can be reused in the same method / reactor, eliminating the need to separate polymers and improving the value and usefulness of the reused polymers. Plastic films can be laminated to other surfaces, for example, requiring an adhesive or sealable surface to achieve good integrity. Furthermore, or in other ways, plastic films are printable or paintable, while simultaneously needing sufficient strength and possibly barrier properties, particularly for use in the packaging industry. Additives have been proposed to improve the compatibility and / or surface properties of polymer systems. However, many additives are expensive and, furthermore, do not provide the desired degree of compatibility with the polymer material, nor do they produce the desired surface effects while retaining other desirable properties of the polymer. There is a need to provide alternative polymer auxiliaries that can meet such field performance requirements.

[0004] In WO2017 / 046009, we discussed the structure. [ka] This document describes polymer additives having (wherein R and R 1 C1-C1 may be the same or different, and each independently represents an alkyl group or an aryl group, and X may be hydrogen, or branched or linear C1-C1. 20 The substituents may be alkyl groups, and the aromatic ring substituent bonded to polymer B is meta-configured or para-configured to the aromatic ring substituent bonded to polymer A. Polymer A is a nonpolar polymer (or copolymer) formed by a metallocene-catalyzed reaction, and polymer B is a polymer formed by a radical-catalyzed reaction of a polar monomer (which may be together with a nonpolar polymer to form a copolymer segment).

[0005] Polymer A is a nonpolar polymer containing chains of ethylene structural units formed by a metallocene catalytic reaction, while polymer B is derived from a polar monomer. Polymer A may be a copolymer of ethylene and one or more alkene monomers in an amount of 1 to 50 mol%, preferably 2 to 4 mol%. Polymer A may be an ethylene-propylene copolymer. We also, firstly, formula [ka] The present invention describes the production of such diblock copolymers, including the formation of intermediate polymer materials (wherein polymer A is derived from at least 50 mol% ethylene).

[0006] While these polymers are useful in many applications, there are other applications where they are not suitable due to their stiffness, high melt viscosity, and resulting high processing temperatures. We have found that these challenges can be overcome in specific applications, such as adhesion to polyolefin substrates and applications requiring lower processing temperatures, by increasing the propylene content of polymer A to over 50 mol%, preferably over 60 mol%. We also found that the use of these polymers as polymer additives can impart low-temperature strength to materials made from polymers containing these additives. [Overview of the Initiative]

[0007] Accordingly, the present invention addresses the above-mentioned problems by providing an improved linear diblock copolymer intended for development in industrial applications where handling interfacial and surface interactions is of paramount importance, particularly in systems combining or closely spaced polar and nonpolar materials. The present invention also provides intermediates useful for the production of such diblock copolymers. In the first embodiment, the present invention relates to a diblock copolymer having the following general structure: [ka] (wherein R and R 1 (These may be the same or different, and each independently represents an alkyl group or an aryl group; X may be hydrogen, or a branched or linear C1-C20 alkyl group; and the aromatic ring substituent bonded to polymer B is meta-configured or para-configured to the aromatic ring substituent bonded to polymer A.) a) Polymer A is a polymer containing repeating units derived from propylene and ethylene, wherein the propylene content is 51-99% based on the total average molecular weight of polymer A, and the remainder up to 100% is derived from ethylene, and b) The present invention relates to a diblock copolymer characterized in that polymer B is a chain of structural units derived from one or more α,β-unsaturated monomers selected from the group consisting of styrene, substituted styrene, acrylate, methacrylate, vinyl ester, fumarate ester, maleic anhydride and their derivatives, and diene compounds.

[0008] In another aspect, the present invention relates to a polymer composition containing the diblock copolymer of the present invention. In a further aspect, the present invention is a substrate having an outer surface, and a layer of the polymer composition adjacent to the outer surface of the substrate, wherein the polymer composition contains the diblock copolymer of the present invention, an article comprising the layer. [[ID=X]] In a further aspect, the present invention relates to the use of the diblock copolymer of the present invention as a performance promoting additive to a polymer composition, wherein the additive is present in an amount of 0.1 to 20% by mass based on the total mass of the polymer composition.

[0009] In a further aspect, the present invention is a method for preparing the diblock copolymer according to the first embodiment described above, a) In a first step, propylene and ethylene are polymerized in the presence of a metallocene catalyst system to form a polymer A, wherein the polymer A has a propylene content of 51 to 99% based on the number average molecular weight of the polymer A, and the balance up to 100% is derived from ethylene, a chain consisting of propylene structural units and ethylene structural units, and the reaction is carried out in the presence of a linking molecule of formula II in a reactor,

Chemical formula

Chemical formula

[0010] In a further embodiment, the present invention relates to a method for producing the diblock copolymer described in the first embodiment, the method comprising the steps of: supplying and adding a terminally unsaturated polymer material corresponding to formula III to a reactor; further introducing one or more α,β-unsaturated monomers selected from the group consisting of styrene, substituted styrene, acrylate, methacrylate, vinyl ester, fumarate ester, maleic anhydride and their derivatives, and diene compounds; and in a subsequent polymerization reaction, reacting the α,β-unsaturated monomers at their terminal unsaturations to form and add polymer B (wherein R, R1, and X are as previously defined). In a further embodiment, the present invention relates to a terminally unsaturated polymer material suitable as a starting material for forming the diblock copolymer described in the first embodiment, wherein the terminally unsaturated material has a structure of formula III, polymer A is a polymer essentially composed of repeating units derived from propylene and ethylene, and the propylene content is 51 to 99% based on the total average molecular weight of polymer A, with the remainder up to 100% derived from ethylene.

[0011] In a further embodiment, the present invention relates to the use of a diblock copolymer of the general structure of formula I as an additive to polymer materials (wherein R and R 1 The present invention relates to the use of polymers characterized in that the elements may be the same or different, each independently representing an alkyl group or an aryl group, X may be hydrogen, or a branched or linear C1-C20 alkyl group, the aromatic ring substituent bonded to polymer B may be meta-configured or para-configured to the aromatic ring substituent bonded to polymer A), polymer A is a nonpolar polymer formed by metallocene catalytic polymerization of propylene with ethylene, the propylene content is 51-99% based on the total average molecular weight of polymer A, with the remainder up to 100% derived from ethylene, and polymer B is a polymer formed by a radical catalytic reaction of polar monomers. [Brief explanation of the drawing]

[0012] [Figure 1] The PP / PE-t-DIB 1HNM spectrum is shown. [Modes for carrying out the invention]

[0013] As described above, in one embodiment, the present invention relates to a diblock copolymer that can be represented as a "polymer A-linkage-polymer B" with an essentially linear structure, and more specifically, to a structure that can be represented by the following structural formula. [ka] (In the formula, R and R1 may be the same or different, and each independently represents an alkyl group or an aryl group; X may be hydrogen, or a C1-C20 alkyl group which may be branched or linear; and the aromatic ring substituent bonded to polymer B may be meta-configured or para-configured to the aromatic ring substituent bonded to polymer A and to intermediates for the formation of such diblock copolymers.)

[0014] The diblock copolymer of the present invention is characterized by a selected configuration of polymer A and polymer B, where the properties of polymer A (which is generally considered to be a nonpolar form of diblock copolymer) and polymer B (which is conversely considered to be a polar form of diblock copolymer) are defined in consideration of the properties of two or more materials used together with the diblock copolymer to form a specific formulation, and the usage of a specific end application. In Formulas I and III, the polymer A of the present invention represented above is a polymer chain containing repeating structural units derived from propylene monomers and ethylene monomers, and preferably these are the only units in polymer A. The chain is rich in structural units derived from propylene, and the content derived from propylene is 51 - 99% based on the number average molecular weight of polymer A, and the remaining up to 100% is derived from ethylene. In a preferred embodiment, the content derived from propylene is from 55%, more preferably from 60%, independently, up to 97%, more preferably up to 95%, and the remaining up to 100% is derived from ethylene. In a highly preferred embodiment of the present invention, polymer A is derived from propylene monomers and ethylene monomers, the propylene content is 55 - 95%, and the ethylene content is 45 - 5%. The number average molecular weight of polymer A is selected considering the intended use. Typically, the number average molecular weight of polymer A has a lower limit of 500 g / mol -1 to an upper limit of 20,000 g / mol -1 ranging. The lower limit is preferably at least 1000 g / mol -1 , more preferably at least 2000 g / mol -1 , and on the other hand, the upper limit is preferably at most 15,000 g / mol -1 , more preferably at most 10,000 g / mol -1 . The number average molecular weight can be measured by GPC referring to polystyrene standards in the range of 500 - 25,000 g / mol -1 . A highly preferred example of polymer A for the present invention is a polymer structure derived from propylene monomers and ethylene monomers, with a propylene content of 55 - 95% of the number average molecular weight, an ethylene content of 45 - 5% of the number average molecular weight, and a number average molecular weight of 500 - 20,000 g / mol -1 .

[0015] The composition of polymer A in this invention can be best measured by NMR. The presence of peaks other than those originating from polyethylene-DIB and polypropylene-DIB indicates that the polymer is a copolymer rather than a mixture of the two materials. The NMR will show two peaks for the copolymer: one if it is an ethylene molecule attached to the DIB, and another if it is a propylene molecule attached to the PIB. The amount of propylene in polymer A can also be measured by NMR spectroscopy.

[0016] Polymer B of the present invention, represented in Formula I, is a chain of structural units derived from one or more α,β-unsaturated monomers selected from the group consisting of styrene, substituted styrene, acrylic acid esters and methacrylic acid esters, diene compounds, vinyl esters, fumarate esters, itaconic acid esters and maleic anhydride and their derivatives, and diene compounds, as well as two or more combinations thereof. The number-average molecular weight of polymer B is variable and selected considering the intended end use, and typically polymer B has a lower limit of 1000 gmol. -1 ~Upper limit 100,000 gmol -1 It will have a number-average molecular weight within the range of [specify range]. The lower limit is preferably at least 1500 gmol. -1 , more preferably at least 2000 gmol -1 , more preferably at least 5000 gmol -1 On the other hand, the upper limit is preferably at most 70,000 gmol. -1 , more preferably up to 40,000 gmol -1In one preferred embodiment, polymer B consists of a single polymerization chain or copolymer chain derived from one or more acrylate monomers or methacrylate monomers, wherein alkyl acrylates and especially methyl acrylates are preferred to obtain polymer B having a number average molecular weight in the range of 1200 to 2500. In particular, the (meth)acrylate monomers or monomers(s) selected for polymer B include one or more (meth)acrylate compounds having C4-C22 alkyl substituents, which may be branched or linear alkyl. In an example of a preferred material used in the present invention, polymer B consists of a single polymerization chain or copolymer chain derived from one or more such monomers. Examples of such monomers are 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, t-butyl (meth)acrylate, dodecyl (meth)acrylate, decyl (meth)acrylate, and C12-C15 chain length monomers. In another preferred embodiment, polymer B consists of a single polymerization chain or copolymer chain derived from one or more vinyl ester monomers. Examples include vinyl acetate, vinyl 2-ethylhexanoate, vinyl octanoate, vinyl benzoate, vinyl decanoate, vinyl neodecanoate, vinyl pivalate, vinyl propionate, vinyl stearate, and vinyl valerate. In yet another preferred embodiment, polymer B may contain chains of structural units derived from one or more diene compounds. These dienes may be non-hydrogenated dienes, hydrogenated dienes, or partially hydrogenated dienes. More preferably, the second block of the copolymer consists of a single polymerization chain or copolymer chain derived from isoprene, piperylene, or butadiene, or a mixture thereof. In yet another preferred embodiment, polymer B contains chains of styrene structural units derived from styrene or its derivatives, such as alpha-methylstyrene and para-alkylstyrene, such as para-methyl and butylstyrene.

[0017] With respect to Formula I above, the particularly preferred diblock copolymer of the present invention is a polymer structure in which polymer A is derived from propylene monomer and ethylene monomer, the propylene content is 55-95% of the total average molecular weight, the ethylene content is 45-5% of the total average molecular weight, and the number average molecular weight is 500-20,000 gmol. -1 The polymer B is a chain of structural units derived from one or more α,β-unsaturated monomers selected from the group consisting of acrylates, methacrylates, vinyl esters, fumarates, and maleic anhydride compounds, and the amount is 1,000 to 100,000 gmol. -1 Preferably 1,000 to 10,000 gmol -1 It is a diblock copolymer having a number-average molecular weight within the range of [specify range].

[0018] As described above, polymers A and B are linked together by a "linkage compound." The linkage compound is derived from the substance of formula II. [ka] (In the formula, R and R1 may be the same or different, and each independently represents an alkyl group or an aryl group, and X may be hydrogen, or a branched or linear C1-C) 20 (The alkyl group may also be an alkyl group, and the aromatic ring substituent is arranged in a meta-substituted or para-substituted configuration.) Preferably, R group and R 1 Each group independently represents an alkyl group having 1 to 4 carbon atoms, more preferably R and R 1 The compounds are the same, and most preferably both are methyl. Preferably, the aromatic ring substituent is in a meta-substituted configuration. An example of a preferred substance for use as a linkage compound is 1,3-di-(isopropenyl)benzene.

[0019] The diblock copolymer of the present invention can be prepared by a conventional procedure, which can be summarized as comprising a first step of reacting and polymerizing propylene monomer and ethylene monomer together in the presence of a linkage. This provides an “intermediate product” of the present invention containing a linkage having polymer A, which in a subsequent second step is contacted with selected α,β-unsaturated monomers under reaction conditions to polymerize these α,β-unsaturated monomers, thereby obtaining the added polymer B. The “intermediate product” described above consists of general formula III.

[0020] [ka] (In the formula, polymers A, R, R 1 (and X includes the preferred embodiments described above, as already stated.) For convenience in subsequently preparing a variety of diblock copolymers in which the properties and composition of polymer B may vary, the intermediate product may be recovered and isolated from the first reaction before the second polymerization step.

[0021] These intermediate products of the present invention can be readily converted to the diblock copolymer of the present invention by the method described in WO2017046009. More specifically, the diblock copolymer of the present invention is a) In the first step, propylene and ethylene are polymerized in the presence of a metallocene catalyst system to form polymer A, wherein polymer A is a chain composed of propylene structural units and ethylene structural units, the reaction is carried out in a reactor in the presence of a linkage product of formula II, and during the reaction, the linkage product is introduced to the ends of polymer A, forming the terminally unsaturated (double bond) intermediate of the present invention of formula III. b) In any second step, recover the intermediate of formula III from the reaction mixture of the first step, and c) In a subsequent step, the polymer B can be prepared by reacting the intermediate of formula III with a polar monomer at its terminal double bond in a subsequent polymerization reaction (wherein R, R1, and X are as previously defined).

[0022] Step a) may be carried out under hydrogen pressure to control the properties of polymer A. In this specification, the word “end” as used in reference to a polymerization chain (or block) simply refers to the end of the polymerization chain (or block) and does not imply any further mechanical requirement that the end of the chain (or block) in question is the end where the polymerization reaction has ended. References to “end” should be interpreted similarly. The subsequent polymerization reaction or third step may be an anionically initiated reaction or a free radical initiated reaction, but radical polymerization is preferred. This method for producing diblock copolymers is described in the patent publications EP2684940, WO2017046009 and WO2019063836. The production of polymer B by radical polymerization has broader applications than production by anionic polymerization because it is easier to control and provides a material that is easier to purify. Radical polymerization also has broader applications within the range of monomers that can be polymerized and it is easier to control the molecular weight within a selected range compared to anionic polymerization methods. Therefore, the embodiment of the method in step c) is preferably carried out in the presence of a radical source. As is known in the art, such a radical source may be a chemical initiator species or an external physical energy input, such as UV light or other radiation sources. Preferably, the radical source is a chemical initiator species, such as a peroxide initiator, an azo initiator or other such species.

[0023] Therefore, by producing polymer B using radical polymerization, the structure of the final diblock copolymer can be more easily adapted to the application in which the diblock copolymer is designed. Thus, the selection of the chemical properties, structure, and physical characteristics of the combination of polymers A and B can be adapted according to the specific intended use of the diblock copolymer, with respect to other materials in which the diblock copolymer is used in a particular end application, and while ensuring the desired compatibility of the materials in which the diblock copolymer is used. It is important that polymer A terminally bonds to polymer B, thereby generally giving a linear molecule, while leaving polymer A available for interaction with the bulk polymer system in which polymer A may be intended to unfold. This is somewhat analogous to surfactants, which have lipophilic / oleophobic properties in the same molecular structure and combine lipophilic and oleophobic substances in a stable system. Therefore, it is important that the linkage between polymer A and polymer B is located at the end of the polymerization chain of polymer A.

[0024] To achieve this terminal configuration of the linkage between polymer A and polymer B, it is essential that the method by which the copolymer is prepared is specific to the terminal functionalization of polymer A. Selecting a metallocene-catalyzed reaction in the first step of the preparation method appears to favorably promote such terminal functionalization. Similarly, it is important that the terminal functionalization formed on polymer A is sufficiently reactive to enable the formation of polymer B under practical radical polymerization conditions from an industrial perspective, while at the same time not being so highly reactive that undesirable side reactions occur to a considerable extent. A suitable metallocene catalyst for the production of polymer A contains a transition metal, particularly a metal of Group IV of the periodic table, e.g., Ti, Zr, or Hf, and one or more ligands, e.g., cyclopentadienyl ("Cp"), substituted cyclopentadienyls (including indenyl, fluorenyl, and their derivatives), and the above-mentioned crosslinking variants. Further ligands may be integrated or bonded to the metal by heteroatoms, e.g., N, O, S, or P, and may include crosslinking to the above-mentioned Cp-type ligands. Such catalysts are usually synthesized and stored as metal dichloride / dialkyl (e.g., dibenzyl) or monoalkyl-monochroide species ("pre-catalyst"). These are activated in solution by the addition of a co-catalyst, usually methylaluminoxane (MAO), but alternatively, non-coordinating / weakly coordinating anions can be used, such as a combination of a boron-coordinating species, e.g., Ph3C+B(C6F5)4-, and a trialkylaluminum species, e.g., i-(C4H9)3Al. Examples of such catalysts include Cp2MCl2, Cp<*>2MCl2, EBIMCl2, Flu(Ph2Me)CpMCl2, and Cp(Me)4(Me2Si)NtBuMCl2 (wherein M represents a transition metal). Preferred catalysts are those in which M represents zirconium. An example catalyst is Cp2ZrCl2 used with a co-catalyst.

[0025] The diblock copolymers of the present invention are highly suitable for end applications where their unique polar-nonpolar dichotomy can be utilized as a means of adjusting polymer interface properties and polymer bulk properties relative to the system in which they exist. In fact, the copolymers of the present invention can function as compatibilizers, solubilizers, adhesives, or dispersants. The high propylene content of polymer A in the present invention provides a material in which polymer A has a lower degree of crystallinity and a lower glass transition temperature compared to polymer A being 100% ethylene or 100% propylene. In other words, this makes it possible to produce the diblock copolymer of the present invention in which polymer A may be amorphous, having, if any, one or more of the following: lower viscosity, lower melting point, lower Tg, lower crystallinity temperature, or lower degree of crystallinity.

[0026] These properties can offer manufacturing advantages and provide block copolymers that are more suitable for specific applications than conventional block copolymers, such as WO2017046009. For example, lower viscosity of the intermediate makes it easier to manufacture diblock copolymers, requiring less energy, and enabling better mixing and improved processing. Lower melting points of the intermediate can further reduce foaming in the reactor. Benefits in end-use applications include improved low-temperature strength in molded articles due to a lower glass transition temperature, which also provides more flexible molded articles. The lower degree of crystallinity allows for longer open times and lower temperature requirements in adhesive applications, as well as improved adhesion to polyolefin substrates and improved compatibility with both bulk polyethylene and polypropylene materials.

[0027] The following are examples of possible uses for the diblock copolymer of the present invention. - Additives for polypropylene, including PP-based waxes. Additives can be designed to adjust the hardness, viscosity, impact properties, and surface or interfacial properties of polypropylene. Surface adjustment can also result in improved properties, such as surface adhesion, anti-adhesion, friction, and surface tension of coatings. - A viscosity modifier for polymers that provides strength, viscosity, etc., for all polymer processing methods used in the manufacture of molded articles, films, and fibers. - Additives for improving the dispersibility of various commonly used polymer additives (e.g., plasticizers, rheology modifiers, lubricants, mold release agents, antioxidants, UV protection agents, fillers, foaming agents, recycled materials, etc.), and for improving biodegradability, friction, conductivity, tribology, and electromagnetic interaction by dispersing particles that cause such interactions. - Additives for molten, particularly (but not limited to) solvent-free polymer mixtures. This includes polyolefin-polar polymer mixtures, such as polystyrene, polyamide, EVOH, PET, ABS, TPU, etc. - Additives for processing mixed polymers: • All molding applications (including, but not limited to, injection, rotary, compression, pressurized, slush molding, blow molding, and thermoforming). • All extrusion applications (including, but not limited to, pipes and tubes, co-extrusion, film forming, coating, lamination, blown films, tie layers, calendering, welding, etc.). • For all casting purposes. - Additives for mixed polymer formulations: • Hot melt adhesive (HMA). PO-based. EVA-based. • Pressure-sensitive adhesive (PSA). SBC type. Acrylic type. • Water-based adhesive (WBA). Acrylic type. - Additives for heavy oil fractions, including bitumen modifiers. - An additive used to control the foaming of polymers. - Preventive additives, such as those used to control viscosity and dispersibility in rust-preventive formulations. - Additives for polymer composite materials (including reinforcing materials, nanocomposite materials, and biocomposite materials). - Additives for building materials, such as panel boards, to adjust viscosity and dispersibility and control wax coatings. - Additives for carbon-based composite materials, such as composite materials filled with carbon black, graphene, or carbon nanotubes (CNTs). - Additives for "smart" material composites, such as polymer composites containing materials that interact with electromagnetic radiation. - Additives for bio-composite materials, such as wood-plastic composites. - Additives for dispersing other additives and colorants in polymers. - Additives for polymerization in solution. - An additive for adjusting the viscosity of vegetable oils. - Water-based polymer systems, such as water-based formulations, such as adhesives (foaming or otherwise), additives for coatings and paints. - Polymer additives for crystal transformation: • Crystallization of ethylene polymers and ethylene copolymers containing (natural or synthetic) waxes. • Crystallographic transformation of ethylene polymers and ethylene copolymers. • Crystallographic transformation of polar polymers, such as crystallographic transformation in polyamides.

[0028] The polarity / nonpolarity balance of the diblock copolymer of the present invention can enable the diblock copolymer to function in a manner similar to the hydrophilicity / hydrophobicity balance of a common surfactant, which can provide a stable polymer-in-polymer composite material mixture with superior integrity, and / or a polymer-in-polymer dispersion with improved definition and improved overall physical performance characteristics. In this example, the diblock copolymer functions as a compatibilizer for nonpolar and polar polymer systems, but can be present in an amount of 0.1 to 20% by mass based on the total mass of all present components, including the diblock copolymer. When such a composite material and / or dispersion is prepared, the diblock copolymer may be pre-mixed with either the polar or nonpolar polymer component, or it may be introduced as a separate flow when combining the polar and nonpolar polymer components of the composite material.

[0029] The polarity / nonpolarity balance of the copolymer allows the diblock copolymer of the present invention to function as an agglomeration promoter, facilitating and promoting surface contact agglomeration from one surface to a second, different surface having a different polarity. An example in this case is contact coating or contact painting of a polymer to a surface of different polarity, which may be an organic polymer surface or an inorganic surface. In this example, the diblock copolymer of the present invention can be formulated and present on either or both of the materials constituting the first surface and / or the second surface. The polarity / nonpolarity balance of diblock copolymers can also function as wetting agents to modulate the surface properties of polymer composite materials, in which case the diblock copolymer may be used in bulk or as a surface coating. For example, diblock copolymers can be used to impart anti-condensation properties to the surface to which they are applied, or to composite materials and mixtures containing diblock copolymers. When packaging food, an undesirable characteristic is the presence of condensed water droplets within the package. The presence of diblock copolymers can modulate the surface properties of composite polymer mixtures and their films in a way that reduces water droplets, as they promote the formation of aqueous films, facilitate evaporation, or reduce droplet formation.

[0030] The polarity / nonpolarity balance of the diblock copolymer of the present invention can function in a manner that facilitates the dispersion of particulate matter, such as fillers, in the polymer matrix. Fillers are small-sized particulate matter, and examples include natural animal or plant fibers, mineral fibers, glass, metals, and the like. The polarity / non-polarity balance of the diblock copolymer of the present invention allows the diblock copolymer to function in a manner similar to waxes, which are commonly used as lubricants in plastic injection molding, extrusion, or pultrusion operations. The diblock copolymer of the present invention can also be used as a “tie layer” or adhesive to facilitate adhesion of one surface to a second surface, in which case the diblock copolymer is arranged as a separate layer adjacent to the first and second surfaces. The present invention will be explained by referring to the following example which demonstrates the preparation of an intermediate suitable for the production of a diblock copolymer for use as a polymer additive. [Examples]

[0031] Preparation of the polypropylene-polyethylene diisopropenylbenzene intermediate "PP / PE-t-DIB" A 2L stainless steel high-pressure reactor equipped with a heating jacket was dried overnight under vacuum at 125°C. Then, a comonomer solution (total volume 1L) consisting of 1,3-diisopropenylbenzene (350ml, 1.84mol - compound I) and toluene (650ml, 3.29mol) was added while the reactor was initially heated to 60°C. After filling the reactor with an alkene mixture consisting of propylene and ethylene in a molar ratio of 70:30 (100kPa), hydrogen (100kPa) was added. Once the alkene uptake stabilized, metallocene rac-dichloroethylene bis(indenyl)zirconium(IV) (2.6x10) was added. -5 A toluene solution consisting of (mol) methylaluminoxane (MAO) (30 ml) and toluene (20 ml) was injected. The reaction temperature was maintained at 60°C. The reaction was stopped after 120 minutes, and the polymer product was precipitated by pouring it into cold methanol (2 L) while stirring for 1 hour.

[0032] The product was recovered by filtration, washed with methanol, dried, and washed again with tetrahydrofuran (200 ml). The polymer product, 1,3-diisopropenylbenzene-terminated polypropylene-polyethylene (also known as PP / PE-t-DIB), was dried by heating at 70°C under vacuum for 24 hours to obtain a yield of 15.6 g. This corresponds to a productivity of 12,500 kg polymer / mol[Zr].h. To confirm that the desired terminal functionalization structure can be obtained, the PP / PE-t-DIB can be characterized by nuclear magnetic resonance spectroscopy. For example, NMR spectra can be recorded with the Bruker DPX400 and DPX500 spectrometers. <1> H and <13> The 13C NMR spectrum is referenced internally using solvent resonance for tetramethylsilane. The specified NMR assignment (including polymer samples) is used if necessary. <1> H- <1> H(COSY), <13> C- <1> H(HMQC) and <13> C- <1> This can be confirmed by correlation experiments involving H(HMBC).

[0033] especially, <1> ¹H NMR spectroscopy can be used to confirm the end insertion of compound I. Figure 1 shows a typical PP / PE-t-DIB prepared by the above method, where polymer A is polypropylene-polyethylene and 1,3-diisopropenylbenzene ("1,3-DIB"). <1> The 1H NMR spectrum is shown. See Figure 1 on page 1 of the drawings: PP / PE-t-DIB 1HNM spectrum. Example 2 The method of Example 1 was repeated in two runs using a mixture of 30% ethylene and 70% propylene, and compared to a similar reaction using 100% ethylene and 100% propylene.

[0034] The obtained materials were analyzed to determine their crystallinity, melting point, and the glass transition temperature and propylene content of the two operations according to the present invention. The results were as follows: [Table 1]

Claims

1. A diblock copolymer with the following structure, 【Chemistry 1】 (In the formula, R and R 1 (These may be the same or different, and each independently represents an alkyl group or an aryl group; X is hydrogen, or a branched or linear C1-C20 alkyl group; the aromatic ring substituent bonded to polymer B is meta-configured or para-configured with respect to the aromatic ring substituent bonded to polymer A.) a) Polymer A is a polymer essentially composed of repeating units derived from propylene and ethylene, wherein the propylene content is 55-95% based on the total average molecular weight of polymer A, the ethylene content is 45-5%, and the number average molecular weight of polymer A is 500-20,000 gmol-1, and b) A diblock copolymer characterized in that polymer B is a chain of structural units derived from one or more α,β-unsaturated monomers selected from the group consisting of styrene, substituted styrene, acrylate, methacrylate, vinyl ester, fumarate ester, maleic anhydride and their derivatives, and diene compounds.

2. The diblock copolymer according to claim 1, wherein polymer B is a chain of structural units derived from acrylates, methacrylates, vinyl esters, fumarate esters, maleic anhydride, and derivatives thereof, or combinations of two or more thereof.

3. A polymer composition containing the diblock copolymer described in claim 1.

4. A substrate having an outer surface, and An article comprising a layer of polymer composition adjacent to the outer surface of a substrate, wherein the polymer composition contains the diblock copolymer described in claim 1.

5. Use of the diblock copolymer according to claim 1 as an additive to a polymer composition, wherein the additive is present in an amount of 0.1 to 20% by mass based on the total mass of the polymer composition containing the additive.

6. A method for preparing the diblock copolymer according to claim 1, a) In the first step, propylene and ethylene are polymerized in the presence of a metallocene catalyst to form polymer A, the propylene content is 55-95% based on the total average molecular weight of polymer A, the ethylene content is 45-5%, the number average molecular weight of polymer A is 500-20,000 gmol-1, and the reaction is carried out in a reactor in the presence of the linkage molecule of formula II. 【Chemistry 2】 During the reaction, linkage molecules are introduced to the ends of polymer A, forming the terminal unsaturated intermediate of formula III. 【Transformation 3】 b) In an optional second step, recover intermediate III from the reaction mixture of the first step, and c) A method characterized in that, in the third step, intermediate III is reacted with a polar monomer at its terminal double bond in a subsequent polymerization reaction to form polymer B (wherein R, R1, and X are as previously defined).

7. A method for producing the diblock copolymer described in claim 1, comprising the steps of: supplying and adding a terminally unsaturated polymer material corresponding to formula III to a reactor; further introducing one or more α,β-unsaturated monomers selected from the group consisting of styrene, substituted styrene, acrylate, methacrylate, vinyl ester, fumarate ester, maleic anhydride and their derivatives, and diene compounds to the reactor; and in a subsequent polymerization reaction, reacting the α,β-unsaturated monomers at their terminal unsaturations to form and add polymer B (wherein R, R1, and X are as previously defined).

8. The use of diblock copolymers having the following structure as additives to polymer materials, 【Chemistry 4】 (In the formula, R and R 1 (These may be the same or different, and each independently represents an alkyl group or an aryl group; X is hydrogen, or a branched or linear C1-C20 alkyl group; and the aromatic ring substituent bonded to polymer B is meta-configured or para-configured to the aromatic ring substituent bonded to polymer A.) The invention is characterized in that polymer A is a nonpolar polymer formed by metallocene catalytic polymerization of propylene with ethylene, the propylene content is 55 to 95% based on the total average molecular weight of polymer A, the ethylene content is 45 to 5%, the number average molecular weight of polymer A is 500 to 20,000 gmol-1, and polymer B is a polymer formed by radical catalytic reaction of polar monomers.

9. The polymer of the following formula III. 【Transformation 5】 (In the formula, R and R 1 (These may be the same or different, and each independently represents an alkyl or aryl group; X is hydrogen, or a branched or linear C1-C20 alkyl group; the aromatic ring substituent corresponds to a meta or para configuration; furthermore, polymer A is essentially composed of repeating units derived from propylene and ethylene, the propylene content is 55-95% based on the total average molecular weight of polymer A, the ethylene content is 45-5%, and the number average molecular weight of polymer A is 500-20,000 gmol-1)

10. Use of the polymer according to claim 9 for preparing the diblock copolymer according to claim 1 or 2.

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