Hydrogenated block copolymers as compatibilizers

Abstract

This invention provides a hydrogenated block copolymer as a compatibilizer. [Solution] Structure (EB-EB') n A hydrogenated block copolymer represented by X is disclosed, where X is a residue of a coupling agent and n is an integer between 2 and 20. Each block EB and block EB' independently consists essentially of ethylene ("E") units and butylene ("B") units. Block EB has a butylene ("B") unit content of 10–30% by weight, and block EB' has a butylene ("B") unit content of at least 70% by weight. The hydrogenated block copolymer has a number-average molecular weight (Mn) of 150–400 kg / mol, a melting temperature (Tm) of <110°C, and a dissolution temperature (Ts) of <70°C. The hydrogenated block copolymer can be used as a compatibilizer for polyolefin blends exhibiting improved mechanical properties and processability.

Description

[Technical Field]

[0001] This disclosure relates to hydrogenated block copolymers, methods for preparing them, and their uses as compatibilizers. [Background technology]

[0002] Thermoplastic polymers such as polyethylene (PE) and isotactic polypropylene (iPP) are among the most widely produced polyolefins and account for the majority of global plastic production and plastic waste flows. Mixed PE / iPP waste presents recycling challenges due to their mismatch, which results in poor interfacial adhesion and inferior mechanical properties. While melt blending is a potential recycling strategy, phase separation between PE and iPP limits its effectiveness.

[0003] Current compatibilizers, such as hydrogenated polybutadiene-derived block copolymers, can improve toughness, but often require high melting or dissolution temperatures (e.g., Tm > 100°C) for processing. This increases energy consumption and processing complexity, potentially creating barriers to industrial implementation. Alternative approaches, including graft copolymers or multiblock copolymers, can also improve compatibility between polyolefins, but may require relatively high loadings (e.g., >10 wt%) to achieve comparable improvements in mechanical properties.

[0004] Therefore, there is still a need for a compatibilizer that can effectively mix two or more polyolefins while improving processability and enabling processing at lower temperatures. [Overview of the Initiative]

[0005] In the first aspect, the present disclosure relates to the structure (EB-EB') nThe present invention relates to a hydrogenated block copolymer represented by X, where X is a coupling agent residue and n is an integer between 2 and 20. Each block EB and EB' independently consists of ethylene units and butylene units. Block EB contains 1 to 10 ethyl branches per 100 backbone carbon atoms, derived from hydrogenated 1,2-addition units of butadiene. Block EB has a butylene unit content of 10 to 30% by weight, and block EB' has a butylene unit content of at least 70% by weight. The hydrogenated block copolymer has a number-average molecular weight (Mn) of 150 to 400 kg / mol, a melting temperature (Tm) of <110°C, and a dissolution temperature (Ts) of <70°C.

[0006] In the second embodiment, the hydrogenated block copolymer has the structure (EB-EB') n The hydrogenated block copolymer has X, n=2, and is a hydrogenated triblock copolymer having the structure EB-EB'-EB.

[0007] In the third embodiment, the hydrogenated triblock copolymer has a weight ratio of block EB to block EB' in the range of 5:1 to 1:1.

[0008] In the fourth embodiment, each block EB and EB' of the hydrogenated block copolymer is derived from a polybutadiene block before hydrogenation, and after hydrogenation, each block EB and EB' independently has a hydrogenation level of more than 90%. [Modes for carrying out the invention]

[0009] The following terms will be used throughout this specification.

[0010] "Consists of" refers to a composition that includes only the components specifically listed, excluding other components that substantially affect the technical solution or specific function of the present invention. However, the presence of small amounts of other components that do not substantially affect the technical effect of the present invention, such as trace amounts of stabilizers, process residues, or solvents used during preparation, is not excluded.

[0011] "At least one of the groups [A, B, and C, etc.]" or "any of the groups [A, B, and C, etc.]" means a single member from a group, two or more members from a group, or a combination of members from a group. For example, "At least one of A, B, and C" includes, for example, A only, B only, or C only, as well as A and B, A and C, B and C; or A, B and C, or any other combination of A, B and C. In another example, "At least one of A and B" means A only, B only, and A and B.

[0012] The enumeration of embodiments presented as "A, B, or C" should be interpreted as including only embodiment A, only embodiment B, only embodiment C, "A or B", "A or C", "B or C", or "A, B, or C".

[0013] "Any of A, B, or C" refers to one choice from A, B, or C.

[0014] "Any of A, B, and C" refers to one or more options from A, B, and C.

[0015] The "vinyl aromatic unit content" or VAC of a block copolymer refers to the weight percentage of polymerized vinyl aromatic monomers, such as styrene, in the block copolymer, calculated by dividing the sum of the molecular weights of all vinyl aromatic units by the total molecular weight of the block copolymer. VAC is determined by proton nuclear magnetic resonance ( 1 (H NMR) and 13 This can be determined using 13C NMR. VAC is sometimes used interchangeably with PSC, i.e., polystyrene content.

[0016] "Butylene unit content" refers to the content of butylene units ("B") in the hydrogenated block copolymer, in units of wt%. Butylene units are obtained / formed by polymerization of 1,3-butadiene monomers via 1,2-addition followed by hydrogenation. 1,3-butadiene monomers can also polymerize via 1,4-addition, which upon hydrogenation yields ethylene units ("E"). Both butylene units and ethylene units may be part of the hydrogenated block copolymer, which may also contain vinyl aromatic units and / or ethylene-propylene units in any order. The butylene unit content is 1 H NMR and 13 C NMR.

[0017] "Coupling efficiency (CE)" refers to the value obtained by dividing the weight of coupled polymer molecules by the total weight of both coupled polymer molecules and uncoupled polymer molecules, expressed as a percentage (%). CE can be used to determine the diblock content in the entire block copolymer. For example, if the coupling efficiency is 80%, the polymer contains 20 wt% of diblocks and 80 wt% of triblocks and multi-arm blocks.

[0018] "Molecular weight" or number average molecular weight (Mn) refers to the number average molecular weight of a polymer block or block copolymer in kg / mol. The Mn value can be measured using gel permeation chromatography (GPC), also referred to as size exclusion chromatography (SEC), using polybutadiene calibration standards. The chromatograph may use a refractive index detector, an ultraviolet detector, or a combination thereof, and is calibrated using commercially available polybutadiene molecular weight standards. The molecular weight determined in this way is the polybutadiene equivalent molecular weight.

[0019] (In the present specification, the molecular weight value determined by GPC corresponds to the peak molecular weight (Mp), which is defined as the molecular weight corresponding to the apex of the polymer peak in the chromatogram. In the case of block copolymers prepared by sequential polymerization, the molecular weight of individual blocks can be estimated from GPC analysis by monitoring the shift of the chromatographic peak after formation of the additional block. For example, the molecular weight of block "B'" can be estimated as Mp(B-B')-Mp(B). In embodiments, GPC can be calibrated using polybutadiene standards to provide polybutadiene equivalent molecular weights, or using polystyrene standards according to, for example, ASTM D5296 to provide styrene equivalent molecular weights (Ms).

[0020] "Hydrogenation level" refers to the level (percentage) of saturation of double bonds (e.g., olefins, aromatics, etc.) in the block copolymer, 1 which can be measured by 1H NMR.

[0021] "Residual unsaturation" or RU refers to the level of unsaturation, i.e., the carbon-carbon double bonds per gram of the block copolymer. RU 1 can be measured using 1H NMR or ozonolysis titration.

[0022] "Unit" refers to a structural building block derived from one or more polymerized monomers, representing a repeating entity that forms part of a polymer or copolymer chain. Unlike "monomer", which is an individual molecule prior to polymerization, a "unit" is the converted version of the monomer after undergoing the polymerization process.

[0023] "Compatibilizer" refers to a macromolecular species (or polymer) that exhibits interfacial activity in a polymer blend. Typically, the chains of a compatibilizer have a block structure, where one block is miscible with one component of the blend and another block is miscible with the other component. The compatibilizer may be reactive and form chemical links with the polymers, or non-reactive and remain miscible without forming chemical bonds.

[0024] "Polydispersity index" or PDI refers to the weight-average molecular weight (M w ) and the number-average molecular weight (M n ), sometimes also referred to as the molecular weight distribution. PDI is used to indicate the distribution of polymer chain molecular weights in a given polymer. PDI can be calculated over the entire GPC, or over a fraction of the GPC such as the peak between two extreme apparent molecular weight values.

[0025] "Dissolution temperature" or Ts refers to the temperature at which a polymer sample becomes clear in a non-polar solvent such as cyclohexane. Ts is determined by first dissolving the polymer in cyclohexane at 40 to 80°C, cooling the solution to 25°C, and then gradually reheating it with stirring. Ts is recorded as the temperature at which the polymer sample becomes clear when slowly heated at a rate of 1°C / min under stirring.

[0026] The present disclosure relates to a hydrogenated block copolymer containing block EB having a low butylene (B) unit content and block EB' having a high butylene (B') unit content for use as a compatibilizer for blending two or more different polyolefins. The resulting polyolefin blends exhibit improved mechanical properties and processability suitable for a wide range of applications.

[0027] (Hydrogenated Block Copolymer): The polymer of the present invention is produced by hydrogenation of a polybutadiene block copolymer having blocks of 1,2 and 1,4 repeating units in different ratios. The hydrogenated block copolymer is a sequential or coupling block copolymer comprising block EB (low 1,2RU ratio) and block EB' (high 1,2RU ratio), where block EB and block EB' independently consist of ethylene (E) units and butylene (B) units after hydrogenation. In this case, the butylene (B) units are produced by hydrogenation of 1,2-polybutadiene repeating units, sometimes called vinyl. The ethylene (E) units are produced by hydrogenation of 1,4-polybutadiene repeating units, with two ethylene repeating units produced by hydrogenation of one 1,4-butadiene repeating unit.

[0028] In this embodiment, the hydrogenated block copolymer has the structure (EB-EB') n The molecule has X, where X is a residue of the coupling agent, and n is an integer between 2 and 20, or between 2 and 10, or between 2 and 4.

[0029] In this embodiment, the hydrogenated block copolymer has the structure (EB-EB') n It contains X, where n=2, and forms a hydrogenated triblock copolymer (EB-EB'-EB).

[0030] In the embodiment, the hydrogenated block copolymer further comprises a block "S" composed of vinyl aromatic units, with a structure (S-EB-EB') n The molecule has X, where X is a residue of the coupling agent, and n is an integer between 2 and 20, or between 2 and 10, or between 2 and 4.

[0031] In the embodiment, the vinyl aromatic unit is derived from polymerized vinyl aromatic monomers selected from the group consisting of styrene, para-methylstyrene, para-ethylstyrene, para-n-propylstyrene, para-iso-propylstyrene, para-n-butylstyrene, para-sec-butylstyrene, para-iso-butylstyrene, para-t-butylstyrene, isomers of para-decylstyrene, isomers of para-dodecylstyrene, ortho-substituted styrene, meta-substituted styrene, alpha-methylstyrene, 1,1-diphenylethylene, and mixtures thereof.

[0032] In the embodiment, if the hydrogenated block copolymer contains block "S", it has a vinyl aromatic unit content (VAC) of <20, <15, >2, 2-20, 3-15, or 5-20% by weight of the total weight of the hydrogenated block copolymer.

[0033] In the embodiment, each block "S", if present, is measured by GPC using a polystyrene calibration standard according to ASTM D5296 to have a molecular weight (M) of <50, or >2, or 2-50, or 3-30, or 5-15, or 4-12 kg / mol. p ) has.

[0034] In this embodiment, each block "S", if present, has a hydrogenation level of <30%, <20%, <10%, or <5%.

[0035] In this embodiment, each block EB and EB' before hydrogenation is a polymer block of polybutadiene derived from 1,3-butadiene monomer. After hydrogenation, each block EB and EB' independently has a hydrogenation level of >90%, >92%, >95%, >98%, >99%, or up to 100%.

[0036] In the embodiment, the 1,3-butadiene monomer is incorporated into each block EB by 1,4 addition in an amount of at least 75, or <94, or <88, or 75-88, or 77-86, or 80-86, or 80-88% by weight relative to the total weight of the polymerized 1,3-butadiene monomer in the block EB, with the remainder being by 1,2 addition.

[0037] In the embodiment, block EB has a butylene ("B") unit content of 6 to 30, or 8 to 28, or 10 to 30, or 10 to 26, or 12 to 25, or 14 to 23, or 14 to 20, or 12 to 20, or 14 to 25, or >6, or >12, or <25% by weight of block EB.

[0038] In the embodiment, each block EB, measured before hydrogenation by 1H NMR, contains 1 to 10 ethyl branches per 100 backbone carbon atoms, or 1.5 to 9, or 2.0 to 8.8, or 3.5 to 7.5, or >1.5, or <8, derived from the hydrogenated 1,2-addition unit of 1,3-butadiene.

[0039] In the embodiment, each block EB' has a butylene ("B") unit content of at least 70, or >75, or <90, or 70-90, or 75-85, or 70-85, or 75-90% by weight of the total weight of block EB'.

[0040] In the embodiment, the 1,3-butadiene monomer is incorporated into block EB' by 1,2 addition in an amount of at least 70, or >75, or <90, or 70-90, or 75-85, or 70-85, or 75-90% by weight relative to the total weight of the polymerized 1,3-butadiene monomer in block EB', with the remainder being by 1,4 addition.

[0041] In the embodiment, the hydrogenated block copolymer has a melting temperature (Tm) of <110°C, or <100°C, or <95°C, or <90°C, or <80°C, or >10°C, or 10-100°C, or 20-95°C, or 30-60°C, or 30-50°C, or 10-50°C, or 30-90°C, as measured by differential scanning calorimetry (DSC) according to ASTM D3418.

[0042] In the embodiment, the hydrogenated block copolymer is measured by differential scanning calorimetry (DSC) according to ASTM D3418 to have a crystallization temperature (T) of <150°C, or <130°C, or <100°C, or >10°C, or 10-150°C, or 15-130°C, or 20-110°C, or 30-80°C. c ) has.

[0043] In the embodiment, the hydrogenated block copolymer is measured by differential scanning calorimetry (DSC) according to ASTM D3418 to have a crystallinity (X) in the range of 2-25%, or 4-20%, or 5-15%, or 2-15%, or 5-25%, or <40%, or <30%, or <25%, or >2%. c ) has.

[0044] In this embodiment, block EB' is an amorphous polymer block.

[0045] In the embodiment, the hydrogenated block copolymer has a weight ratio of block EB to block EB' in the range of 5:1 to 1:1, or 4:1 to 1:1, or 1.5:1.

[0046] In this embodiment, each block EB has a number-average molecular weight (Mn) of >60, >70, <95, 50-120, 55-110, 60-100, 65-95, 50-95, or 65-120 kg / mol.

[0047] In the embodiment, each block EB' has a number-average molecular weight (Mn) of >95, or <130, or 70-150, or 80-140, or 90-130, or 70-120, or 90-130 kg / mol. For polymers produced by coupling, this block is defined as twice the molecular weight of the B' segment before coupling.

[0048] In the embodiment, the hydrogenated block copolymer has a number average molecular weight (Mn) of >120, or >150, or >200, or >220, or <400, or 120-400, or 150-400, or 200-400, or 210-380, or 220-350, or 230-320, or 200-320, or 240-400 kg / mol.

[0049] In the embodiment, the hydrogenated block copolymer has a polydispersity index (PDI) of >1.2 or <2.5.

[0050] (Preparation of hydrogenated block copolymers): Hydrogenated block copolymers can be prepared by sequentially or successively polymerizing monomers in solution, i.e., in a solvent, in the presence of an initiator / catalyst, by stepwise adding monomers and initiators, then coupling the resulting block copolymer with a coupling agent, and finally by a hydrogenation step.

[0051] In embodiments, hydrogenated block copolymers are prepared by first polymerizing 1,3-butadiene monomer in a mixture of polar and nonpolar solvents in the presence of an initiator for 30 minutes to 10 hours at a suitable temperature and time, e.g., 20 to 80°C, to form a first block EB. The volume ratio of polar solvent to nonpolar solvent used for polymerization of the first block EB may be in the range of 1.0:1500 to 1.5:1200, or 1.3:1200 to 1.5:1000. Then, an excess of polar solvent is added to this reaction mixture (i.e., living polymer solution), followed by the addition of further 1,3-butadiene monomer, and the polymerization reaction is continued for a further 2 to 10 hours to form a second block EB'. Finally, a coupling agent (if necessary) is added to couple the diblock copolymers to form a triblock copolymer. The coupling reaction can be carried out at a temperature of 10 to 30°C for 5 to 15 hours.

[0052] In the embodiment, after stepwise polymerization, the triblock copolymer is hydrogenated in the presence of a hydrogenation catalyst at a temperature of <350°C, <250°C, <100°C, or >50°C and a hydrogen pressure of <1000 psig, or 500-900 psig, or >450 psig. The hydrogenation reaction can be carried out in a single solvent, which may be polar or nonpolar.

[0053] Examples of polar solvents include tetrahydrofuran (THF), triethylamine (TEA), 1,4-dioxane, pyridine, tetramethylethylenediamine, diethyl ether, and glycyrm ether (e.g., dimethoxyethane, diglym (bis(2-methoxyethyl) ether, etc.)).

[0054] Examples of nonpolar solvents include cyclohexane, n-hexane, n-heptane, n-octane, n-pentane, and isopentane.

[0055] In embodiments, modifiers are used during polymerization to control the vinyl content in the polymer to a desired level. The modifiers help improve the efficiency of monomer incorporation during polymerization (e.g., 1,2-addition or 1,4-addition). Examples of modifiers include dimethyl ether, diethyl ether, ethyl methyl ether, ethyl propyl ether, diethoxypropane, 1,2-diethoxyethane, 1,2-dimethoxyethane, and ortho-dimethoxybenzene. The amount of modifier used depends on the type of modifier, for example, 0.5 to 20, 1 to 15, or 1 to 10% by weight relative to the total weight of the monomers being polymerized.

[0056] Examples of catalysts / initiators for polymerization include organic monoalkali metal compounds "RM", where R is an alkyl, cycloalkyl, or aryl radical containing 4 to 8 carbon atoms, such as an n-butyl radical, and M is an alkali metal, such as an alkyllithium compound, s-butyllithium, n-butyllithium, t-butyllithium, amyllithium, or a di-sec-butyllithium adduct of m-diisopropenylbenzene. In embodiments, the initiator / catalyst is used in an amount of 0.002 to 5, or 0.005 to 4.5, or 0.01 to 4, or 0.015 to 3.8, or 0.02 to 3.5% by weight relative to the total weight of the monomers to be polymerized.

[0057] Examples of coupling agents include di- or multi-vinylalene compounds; di- or multi-epoxides; di- or multi-isocyanates; di- or multi-alkoxysilanes; di- or multi-imines; di- or multi-aldehydes; di- or multi-ketones; alkoxytin compounds; di- or multi-halides, e.g., silicon halides and halosilanes; mono-, di- or polyanhydrides; di- or multi-esters, e.g., esters of monoalcohols and polycarboxylic acids; diesters which are esters of monohydric alcohols and dicarboxylic acids; diesters which are esters of monobasic acids and polyalcohols, e.g., glycerol; divinylbenzene; dichloroethane; dibromobutane; esters of carboxylic acids; and mixtures thereof.

[0058] In the embodiment, the coupling agent is a silane compound, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltributoxysilane, vinylethoxydimethoxysilane, vinylethoxydipropoxysilane, propenylethoxydimethoxysilane, propenylethoxydipropoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), methyltrimethoxysilane (MTMS), dichlorodimethylsilane, or mixtures thereof.

[0059] In the embodiment, the coupling agent is used in an amount of 1 to 15, 2 to 14, 3 to 12, or 5 to 10% by weight relative to the total weight of the monomers to be polymerized.

[0060] Examples of hydrogenation catalysts include transition metals, such as nickel, cobalt, rhodium, ruthenium, palladium, platinum, other Group VIIIb (Groups 8-10) metals, or mixtures thereof. Hydrogenation catalysts can be heterogeneous, supported heterogeneous, or homogeneous. In embodiments, hydrogenation catalysts are prepared by combining a Group VIIIb metal carboxylate or alkoxide with an alkyl or hydride of a metal selected from Groups IA, II-A, and III-B of the periodic table. In embodiments, hydrogenation catalysts are formed from Group 8-10 metal compounds, such as palladium, nickel, cobalt, or aluminum alkyl. In embodiments, hydrogenation catalysts are formed by reacting a Group VIII metal carboxylate with another metal alkyl, such as Lialkyl containing n-butyllithium and sec-butyllithium, or metal hydrides such as lithium hydride and aluminum lithium hydride.

[0061] Examples of aluminum alkyl compounds include those with formula R n AlX 3-n Examples of organoaluminum compounds include the following, where R is C1~C 10 Or a C2-C8 hydrocarbon group, where X is hydrogen or R2, and R2 is a C1-C2 hydrocarbon group different from R. 10The hydrocarbon group is n, where n is 1, 2, or 3. In embodiments, the aluminum alkyl compound is a trialkylaluminum compound. In embodiments, the aluminum alkyl compound has an aluminum-to-cobalt molar ratio of 1:1 to 20:1, or 1:1 to 5:1, or 1:1 to 2:1.

[0062] Examples of nickel or cobalt compounds that may be soluble include nickel carboxylates, such as nickel octanoate, nickel stearate, nickel decanoate, nickel acetylacetanoate, nickel naphthenate, and nickel octate; and cobalt carboxylates, such as cobalt stearate, cobalt octanoate, and cobalt versatate. In embodiments, the hydrogenation catalyst is a Wilkinson catalyst (e.g., chloride tris(triphenylphosphine)-rhodium(I)).

[0063] (Properties of Hydrogenated Block Copolymers): Hydrogenated block copolymers exhibit improved processability compared to conventional hydrogenated polybutadiene-derived compatibilizers. In particular, the microstructure of EB blocks and EB' blocks, including the butylene unit content and branching level derived from the 1,2-addition of 1,3-butadiene, reduces the crystallinity of the polymer and lowers the temperature required for dissolution in nonpolar solvents. Lower dissolution temperatures facilitate processing steps such as hydrogenation at low temperatures, solution handling, and characterization.

[0064] In the embodiment, the hydrogenated block copolymer has a dissolution temperature (Ts) in cyclohexane of <70°C, or <65°C, <60°C, or <50°C, or <45°C, or <40°C, or >2°C, or 2 to 60°C, or 5 to 50°C, or 2 to 50°C, or 5 to 40°C.

[0065] The dissolution temperature (Ts) may decrease with increasing branching content or butylene unit content in the EB block, which reduces crystallinity and improves solubility in nonpolar solvents such as cyclohexane. In certain embodiments, the hydrogenated block copolymer dissolves at temperatures close to ambient temperature.

[0066] (End-use): Hydrogenated block copolymers can be used in many applications, particularly for compatibilizing blends of different polyolefins, including recycled materials.

[0067] In embodiments, the polyolefin blend composition comprises, based on the total weight of the polyolefin blend composition, 90 to 99.5% by weight of polyethylene (PE) and isotactic polypropylene (iPP); 0.5 to 10% by weight of hydrogenated block copolymer; and up to 10% by weight of additives. The polyolefin may be virgin, post-consumer recycled (PCR) material, post-industrial recycled (PIR) material, or a mixture thereof. In embodiments, the blend has a PE to iPP weight ratio in the range of 1:10 to 10:1, or 1:8 to 8:1, or 1:5 to 5:1, or 1:3 to 3:1.

[0068] In the embodiment, the polyolefin blend composition contains 0.5 to 10, 1 to 10, 1 to 8, or 0.5 to 5% by weight of hydrogenated block copolymer based on the total weight of the polyolefin blend composition, with the remainder being a combination of PE and iPP in a weight ratio of 1:10 to 10:1.

[0069] Examples of PE used in polyolefin blend compositions include low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), high-density polyethylene (HDPE), medium-density polyethylene (MDPE), high-molecular-weight polyethylene (HMWPE), ultra-high-molecular-weight polyethylene (UHMWPE), and mixtures thereof. In this embodiment, the PE is HDPE.

[0070] In addition to iPP, or instead of iPP, other polypropylenes (PPs) can be used in polyolefin blend compositions. In embodiments, PP is a heterogeneous polymer composition comprising a propylene homopolymer matrix or a random copolymer matrix in which propylene copolymer components are dispersed. This polypropylene copolymer contains one or more comonomers selected from ethylene or higher alpha-olefins. In embodiments, the random copolymer matrix comprises a propylene monomer and at least one comonomer selected from the group consisting of ethylene, C4-C8 alpha-olefins, such as 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene and mixtures thereof. In embodiments, PP is a blend of polypropylene and a random copolymer of ethylene and / or butene, or a crystalline random copolymer of ethylene and propylene combined with a rubbery ethylene-propylene copolymer. Polypropylene copolymers can also be used, which include copolymers with propylene copolymerizable comonomers such as ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, or one or more conjugated or unconjugated dienes. In embodiments, PP is a polypropylene homopolymer.

[0071] In embodiments, the polyolefin blend composition further comprises at least one additive selected from activators, curing agents, stabilizers, thickeners, binders, slip agents, mold release agents, antimicrobial agents, surfactants, antioxidants, ozone degradation inhibitors, color change pH indicators, plasticizers, tackifiers, film-forming additives, dyes, pigments, UV stabilizers, UV absorbers, catalysts, fillers, other resins, flame retardants, viscosity modifiers, wetting agents, deaeration agents, toughness improvers, adhesion promoters, heat stabilizers, lubricants, flow modifiers, drip inhibitors, antistatic agents, processing aids, stress-relieving additives, foaming agents, foaming nucleating agents, weld line strength enhancers, and mixtures thereof.

[0072] In the embodiment, if the additive is added, it is in an amount of up to 10, or 0.5 to 10, or 1 to 8, or 1 to 5, or >1, or <7% by weight of the total weight of the polyolefin blend composition.

[0073] (Preparation of Polyolefin Blend Compositions): Polyolefin blend compositions can be prepared by mixing all components in any order or simultaneously before forming an article, using standard methods and equipment, such as dry blending and compounding. Articles can be manufactured by injection blow molding, injection molding, extrusion blow molding, co-extrusion, cast film extrusion, blow film extrusion, injection stretch blow molding, rotational molding, thermoforming, thermal fusion, foam blow molding, pultrusion, calendering, additive manufacturing, or any other known manufacturing method.

[0074] In the embodiment, the polyolefin blend composition is prepared by compounding the components in an extruder at a temperature of 150-250°C or 160-220°C for 2-60 minutes. Then, the resulting polyolefin blend composition is used to prepare a sample specimen by molding at a temperature of 160-240°C.

[0075] Examples of articles made from polyolefin blend compositions include bottles, containers, fuel tanks, drums, furniture, signage, wheels, toys, and gardening products. Polyolefin blend compositions can also be used in many other applications, such as piping, packaging, automobiles, films, geomembranes, roofs, pond liners, caps and closures, as well as core layers of multilayer polyolefin sheets or films, containers, household goods, and insulation layers for power cables.

[0076] (Properties of Polyolefin Blend Compositions): Polyolefin blend compositions containing hydrogenated block copolymers exhibit improved mechanical properties, processability, and better thermal properties compared to blends that do not contain hydrogenated block copolymers.

[0077] In embodiments, the polyolefin blend composition comprises 90-99.5% by weight of a blend of polyethylene (PE) and isotactic polypropylene (iPP); 0.5-10% by weight of a hydrogenated block copolymer; and up to 10% by weight of an additive, having at least one of the following:

[0078] Young's modulus measured according to ASTM D638, >1 or <10, or 1 to 10, or 1 to 5, or 1 to 3 GPa.

[0079] Yield stress measured according to ASTM D638: >22, <60, 20-60, 22-55, 24-50, or 20-40 MPa.

[0080] Fracture strain measured according to ASTM D638: >150%, <1000%, 150-1000%, 180-900%, or 200-850%.

[0081] Breaking stress measured according to ASTM D638: >20, <60, 20-60, 22-55, 24-50, or 20-45 MPa.

[0082] (Analytical method): The number-average molecular weight (Mn) of hydrogenated block copolymers can be measured by gel permeation chromatography (GPC) using a polybutadiene standard to provide the polybutadiene equivalent molecular weight.

[0083] The butylene unit content in EB and EB' blocks is due to protons ( 1 H)NMR and / or carbon ( 13This can be determined using nuclear magnetic resonance (NMR) spectroscopy, such as ¹¹¹ NMR. Butylene units correspond to structural units formed from the 1,2-addition of 1,3-butadiene followed by hydrogenation, generating ethyl side branches along the polymer backbone. The butylene unit content can be calculated by integrating the signal corresponding to the ethyl branching group against the signal corresponding to the polymer backbone. The reported value can be expressed as a weight percentage of butylene units relative to the total weight of the polymer block.

[0084] The number of ethyl branches in the EB block is 1 1H NMR or 13 This can be determined using nuclear magnetic resonance spectroscopy, such as 13C NMR. In hydrogenated polybutadiene-derived polymers, ethyl branching occurs from the 1,2-addition of 1,3-butadiene followed by hydrogenation. These branchings produce characteristic methyl and methylene signals that can be distinguished from the signal of the main polymer backbone. The number of ethyl branchings can be quantified by integrating the signal corresponding to the terminal methyl group of the ethyl branch with respect to the signal corresponding to the backbone methylene carbon or proton. From these integrals, the number of ethyl branchings per 100 backbone carbon atoms can be calculated. In certain embodiments, the EB block contains 1 to 10 ethyl branchings per 100 backbone carbon atoms.

[0085] The hydrogenation level of a block copolymer is assessed by evaluating the decrease or absence of the olefinic proton signal relative to the saturated skeleton signal. 1 This can be determined by 1H NMR spectroscopy. In certain embodiments, the hydrogenation level corresponds to the percentage of unsaturated carbon-carbon bonds converted to saturated bonds during hydrogenation.

[0086] The melting temperature (Tm) of a hydrogenated block copolymer can be determined by differential scanning calorimetry (DSC) according to ASTM D3418. In certain embodiments, the polymer sample is heated to a temperature above the melt transition temperature, cooled to a temperature below the crystallization temperature, and then reheated at a controlled heating rate. The melting temperature can be recorded as the peak temperature of the endothermic melt observed during the heating cycle.

[0087] The dissolution temperature (Ts) of hydrogenated block copolymers can be determined using a cyclohexane dissolution test. In this test, the polymer sample is first dissolved in cyclohexane at a temperature high enough to obtain a homogeneous solution. The solution is then cooled to approximately 25°C and subsequently reheated with stirring at a controlled rate of approximately 1°C / min. The dissolution temperature (Ts) is recorded as the temperature at which the polymer solution becomes visually clear during the reheating step.

[0088] (Examples): The following examples are intended to be non-limiting.

[0089] The components used in the examples include the following:

[0090] HDPE-1 has a manganese content of 22 kg / mol, a PDI of 3.8, an MFI of 4.4 g / 10 min at 190°C / 2.16 kg, and a viscosity of 0.952 g / cm³. 3 This is polyethylene manufactured by Dow Chemical, with a density of 131°C and a melting point of 131°C.

[0091] PP-1 has a manganese content of 162 kg / mol, a PDI of 2.2, an MFI of 1.8 g / 10 min at 230°C / 2.16 kg, and a yield of 0.905 g / cm³. 3 This is polypropylene manufactured by TotalEnergies, with a density of 162°C and a melting point of 162°C.

[0092] (Example 1 - Preparation of Hydrogenated Block Copolymer). 1,3-butadiene monomer was polymerized in a mixture of THF and cyclohexane solvent (volume ratio 1.8:1000) using a sec-butyllithium (Li) catalyst at 40°C for 8 hours to obtain the first block EB. Then, excess THF was added to the living polymer solution to a molar concentration of [THF]:[Li]=200:1, followed by the addition of further 1,3-butadiene monomer, and the reaction was continued for another 8 hours to form the second block EB'. After the monomer was completely converted to polymer, dichlorodimethylsilane was added in a weight ratio of dichlorodimethylsilane to Li of 1:2 to couple the living diblock copolymer at 20°C for 10 hours to obtain a triblock copolymer. The hydrogenation of triblock copolymers was carried out in toluene using a chloride tris(triphenylphosphine)-rhodium(I) catalyst in combination with triphenylphosphine, with hydrogen gas (500 psi pressure) at 100°C for 12 hours to produce hydrogenated triblock copolymers having the structure EB-EB'-EB. Various hydrogenated triblock copolymers were prepared, and their details are shown in Tables 1 and 2. Some examples show EB blocks outside the preferred range, and these are included to demonstrate the influence of EB block microstructure on polymer properties.

[0093] Table 1 [Table 1]

[0094] Table 2 [Table 2]

[0095] (Examples 2-3 - Preparation of Polyolefin Blend Compositions). The components of the composition were compounded at 190°C for 12 minutes using a twin-screw microcompounder. The resulting material was then formed into a 0.5 mm thick film sample at 180°C and cooled to ambient temperature (25°C). The compositional details are shown in Tables 3 and 4, and the properties are shown in Tables 5 and 6.

[0096] Table 3 Table 3

[0097] Table 4 Table 4

[0098] Table 5 Table 5

[0099] Table 6 Table 6

Claims

1. Structure (EB-EB') ｎ A hydrogenated block copolymer represented by X, During the ceremony, X is a residue of the coupling agent, n is an integer between 2 and 20. Each block EB and EB' independently consists of ethylene units and butylene units. Here Block EB contains 1 to 10 ethyl branches derived from the hydrogenation 1,2-addition unit of butadiene per 100 carbon atoms in the backbone. Block EB has a butylene unit content of 10 to 30% by weight. Block EB' has a butylene unit content of at least 70% by weight, The aforementioned hydrogenated block copolymer The number-average molecular weight (Mn) of 150–400 kg / mol was measured by gel permeation chromatography (GPC) calibrated with a polybutadiene standard. According to ASTM D3418, the melting temperature (Tm) is <110°C, and < Dissolution temperature (Ts) at 70°C A hydrogenated block copolymer having the following properties.

2. The hydrogenated block copolymer according to claim 1, wherein block EB has a butylene ("B") unit content of 12 to 20% by weight.

3. The hydrogenated block copolymer according to claim 1 or 2, wherein n = 2.

4. The hydrogenated block copolymer according to claim 1 or 2, wherein the weight ratio of block EB to block EB' is in the range of 5:1 to 1:

1.

5. The hydrogenated block copolymer according to claim 1 or 2, wherein each block EB and EB' before hydrogenation is a polymer block of polybutadiene, and after hydrogenation, each block EB and EB' independently has a hydrogenation level of >90%.

6. The hydrogenated block copolymer according to claim 1 or 2, wherein block EB' has a butylene ("B") unit content of 70 to 90% by weight.

7. The aforementioned hydrogenated block copolymer has the structure (S-EB-EB') ｎ The hydrogenated block copolymer according to claim 1 or 2, further comprising a block "S" composed of vinyl aromatic units such that X is present.

8. The hydrogenated block copolymer according to claim 7, wherein the vinyl aromatic unit is derived from a polymerized vinyl aromatic monomer selected from the group consisting of styrene, para-methylstyrene, para-ethylstyrene, para-n-propylstyrene, para-iso-propylstyrene, para-n-butylstyrene, para-sec-butylstyrene, para-iso-butylstyrene, para-t-butylstyrene, isomers of para-decylstyrene, isomers of para-dodecylstyrene, ortho-substituted styrene, meta-substituted styrene, alpha-methylstyrene, 1,1-diphenylethylene, and mixtures thereof.

9. <Melting temperature (Tm) of 100°C, <Crystallization temperature of 150°C (T ｃ ), and Crystallinity of 2-25% (X ｃ ) A hydrogenated block copolymer according to claim 1 or 2, having at least one of the above.

10. A hydrogenated block copolymer according to claim 1 or 2, having a number-average molecular weight (Mn) of 200 to 400 kg / mol.

11. A hydrogenated block copolymer according to claim 1 or 2, having a dissolution temperature (Ts) of 2 to 50°C.

12. The hydrogenated block copolymer according to claim 1 or 2, wherein block EB' is an amorphous polymer block.

13. Each block EB has a number-average molecular weight (Mn) of >60 kg / mol, Each block EB' has a number-average molecular weight (Mn) of >95 kg / mol. The hydrogenated block copolymer according to claim 1 or 2.

14. A polyolefin blend composition, wherein based on the total weight of the polyolefin blend composition, (a) A blend of polyethylene and isotactic polypropylene in a weight of 90-99.5% (b) 0.5 to 10% by weight of the hydrogenated block copolymer according to claim 1, and (c) Additives up to 10% by weight A polyolefin blend composition containing the following:

15. The polyolefin blend composition according to claim 14, wherein the blend has a weight ratio of polyethylene to isotactic polypropylene in the range of 1:10 to 10:1.

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