WO2000037517A1 - Copolymere olefine/styrene/diene reticule, procede de production dudit copolymere et ses utilisations - Google Patents
Copolymere olefine/styrene/diene reticule, procede de production dudit copolymere et ses utilisations Download PDFInfo
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- WO2000037517A1 WO2000037517A1 PCT/JP1999/007239 JP9907239W WO0037517A1 WO 2000037517 A1 WO2000037517 A1 WO 2000037517A1 JP 9907239 W JP9907239 W JP 9907239W WO 0037517 A1 WO0037517 A1 WO 0037517A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/08—Copolymers of styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/08—Copolymers of styrene
- C08J2325/10—Copolymers of styrene with conjugated dienes
Definitions
- the present invention provides a method for producing an olefin-styrene-gen-based cross-copolymer or a cross-copolymer having excellent mechanical properties, high heat resistance, excellent processability, and excellent economical efficiency.
- the present invention relates to a cross-copolymer or a cross-copolymer, and an excellent method for producing an oxygen-based cross-copolymer or a cross-copolymer. And regarding these uses.
- the above copolymers do not have a styrene chain structure, they have low compatibility with styrene-based polymers, and are not suitable for use as alloys and compatibilizers with styrene-based polymers. Have. In addition, mechanical properties such as initial elastic modulus and high-temperature properties (heat resistance) are insufficient.
- JP-A-9 one 3 0 9 9 2 5 discloses, in Japanese Patent Laid-1 1- 1 3 0 8 0 8 No., styrene content each 1-5 5 mol 0/0, 1-9 9 moles 0 / o indicates that the ethylene-styrene alternating structure and the styrene chain structure have isotactic stereoregularity, the head has a styrene chain structure, and the alternating degree of the copolymer (A in the present specification) (No.) is 70 or less.
- Ethylene monoolefin copolymer obtained by copolymerizing ethylene with 1-hexene, 1-octene, etc. so-called LLDPE
- LLDPE Low Density Polyethylene
- printability and paintability are low, and special treatment such as corona treatment is required for printing and painting.
- aromatic vinyl compound polymers such as polystyrene and polar polymers
- other expensive compatibilizers are used. There was a need.
- the surface hardness is low and there is a problem that it is easily damaged.
- the methyl group of the paramethylstyrene unit of the copolymer is activated, for example, lithiation is performed, and the polymerization is started at that point.
- the methyl group must be chemically activated after recovery and purification, and a long-term reaction is required to complete this step, which is not practical.
- Another problem is that paramethylstyrene is more expensive than styrene.
- the grafted copolymer thus obtained generally has a force having a graft chain branched one by one from the polymer main chain, and when this is used as a composition or a compatibilizer, the polymer microstructure The strength of the interface is not sufficient.
- a general known radical graft formulation is used to obtain an orefin-based copolymer or an orefine-styrene-based copolymer during polymerization or molding.
- a method for obtaining a graft copolymer is known.
- this method is disadvantageous in terms of cost, and the obtained graft copolymer is generally inhomogeneous, and generally has problems such as partial gelation and insolubility, and impairment of moldability.
- the grafted copolymer thus obtained generally has a graft chain branched one by one from the polymer main chain, and when this is used as a composition or a compatibilizer, The strength of the polymer microstructure interface is not sufficient.
- the described coordination polymerization catalyst has a low copolymerization ability with respect to diene (divinylbenzene), so that a large amount of gen must be charged into the polymerization solution in the coordination polymerization step. A large amount of unreacted Jen remains. If such a coordination polymerization solution is used as it is in the next step, the degree of crosslinking of the resulting polymer will be significantly increased due to the residual jen, which will cause gelation and remarkably poor processability. Therefore, it is not possible to proceed to the next graft copolymerization step without separating and purifying the polymer from the coordination polymerization solution. Separating and purifying the polymer from the polymerization liquor is very laborious and will result in significant cost savings.
- diene divinylbenzene
- Japanese Patent Application Laid-Open No. 1-118510 discloses that a vinylbenzene copolymer is synthesized by coordination polymerization using a Ziegler-Natta catalyst, and then a polystyrene chain is graphed from anion polymerization. A technique for converting the same (the same meaning as the cross-copolymerization in the present invention) is disclosed.
- the Ziegler-Natta catalyst is used in the coordination polymerization step, the gen content in the obtained copolymer is highly non-uniform, and therefore the copolymer obtained by the grafting is also difficult. It is non-uniform, causing gelation and poor workability.
- the concept of the olefin vinylbenzene copolymer in the present technology does not include an aromatic vinyl compound (styrene).
- the described Ziegler-Natta catalyst has a low copolymerization ability with respect to gen (divinylbenzene), so that a large amount of gen must be charged to the polymerization solution in the coordination polymerization step. Will leave a large amount of unreacted gen. If such a coordination polymerization solution is used as it is in the next step, the degree of cross-linking of the resulting polymer will be significantly increased due to the residual jen, which will cause gelation and remarkably poor processability. Therefore, it is not possible to proceed to the next graft copolymerization step without separating and purifying the polymer from the coordination polymerization solution.
- gen divinylbenzene
- Polymers from Polymerization Liquids-Separation and purification can be very time-consuming and can lead to significant cost increases.
- a single-site coordination polymerization catalyst homogeneous coordination polymerization catalyst
- a similar problem occurs because the copolymerization ability for gen (divinylbenzene) is generally insufficient.
- Polystyrene resin composition> an aromatic vinyl compound resin, for example, a styrene resin or a rubber-reinforced styrene resin is a material having excellent shape stability and rigidity, but has a drawback of poor mechanical properties, particularly toughness.
- HIPS rubber-reinforced styrene resins
- an elastic rubber phase is discontinuously dispersed in a hard resin
- the mechanical strength tensile strength, rigidity
- heat resistance heat resistance
- moldability surface gloss
- the resin is thermally degraded during molding due to the double bond of butadiene and isoprene in the rubber-like body.
- the composition of the hydrogenated styrene-butadiene block copolymer and the styrene-based resin has a problem that the rigidity of the resin composition is significantly reduced.
- WO9881000 publication discloses a composition with an aromatic vinyl compound-based resin using an ethylene-styrene pseudo-random copolymer obtained using a geometrically constrained catalyst (CGCT catalyst). Is described. However, the pseudo-random copolymer does not contain the chain structure of the aromatic vinyl compound unit, and the content of the aromatic vinyl compound unit is limited to 50 mol% or less at the maximum. The physical properties of the composition are limited due to its low compatibility with
- polyolefins such as polyethylene and polypropylene have been representative of general-purpose plastics, and have been used in large quantities in household goods.
- polyethylene and polypropylene have excellent mechanical strength, moldability, heat resistance, chemical resistance, etc., and are widely used as general-purpose resins for films and containers. I have.
- improvements in polyolefin polymerization technology have made it possible to obtain high-performance polyolefins, and attempts have been made to use them in fields where engineering plastics have been used in the past.
- the impact resistance is not enough, it is difficult to use it for automotive parts such as bumpers and instrument panels, and housing parts for home appliances such as refrigerators and washing machines.
- WO98 / 10015 and JP-A-10-61094 disclose a polyolefin using an ethylene-styrene pseudo-random copolymer obtained using a geometrically constrained catalyst (CGCT catalyst).
- CGCT catalyst geometrically constrained catalyst
- a composition with an epoxy resin is described.
- a composition of polypropylene and an ethylene-styrene copolymer is effective in improving impact resistance, but there is room for improvement in the balance between mechanical properties (flexural strength and flexural modulus). .
- a polymer composition that balances the different properties of the high rigidity and glass transition temperature of aromatic vinyl compound polymers, the flexibility and low glass transition point of the olefin polymer, and the high solvent resistance derived from the crystal structure. Is desired.
- a composition comprising a blend of an aromatic vinyl compound polymer and an olefin polymer has not been able to obtain the expected physical properties due to poor compatibility between these resins. For this reason, various compatibilizers have been studied.
- a compatibilizer for example, a hydrogenated block copolymer (SEBS, SEPS, etc.) obtained by hydrogenating a block copolymer of an aromatic vinyl compound and a gen compound has been used.
- SEBS hydrogenated block copolymer
- SEPS hydrogenated block copolymer
- J. Polym. Sci., Polym. Letters, 19, '79 (1981), JP-A-56-83338, U.S. Pat. , Specification of Japanese Patent Application Laid-Open No. 025-25) Because these resins are obtained through a hydrogenation process that is expensive to manufacture, , Very expensive. In addition, the mechanical properties (breaking strength, tensile modulus, elongation) of the resulting compatibilized composition are not sufficient.
- USP 546,018,188 describes an ethylene-styrene pseudorandom obtained using a geometrically constrained catalyst (CG CT catalyst) as a compatibilizer between an aromatic vinyl compound polymer and an olefin polymer.
- CG CT catalyst geometrically constrained catalyst
- Compositions using copolymers are described.
- the pseudo-random copolymer does not contain the chain structure of the aromatic vinyl compound unit, and the content of the aromatic vinyl compound unit is limited to 50 mol% or less at the maximum. Due to the low compatibility with the coalescence, the performance as a compatibilizer and the physical properties of the composition are limited.
- JP-A No. 1 1 - 1 3 0 8 0 8 No. styrene content each 1-5 5 mol Publication 0/0 from 1 to 9 9 mole 0/0 has stereoregularity of ⁇ i Sotakutei click on E Ji Ren one styrene alternating structure and styrene chain structures, also, the high molecular weight ethylene one styrene copolymer polymer having a styrene chain structure is described .
- High-temperature resins such as ethylene-propylene-copolymer (EPDM) and other resins such as elastomers, elastomers, ethylene-propylene copolymers (EPR), and ethylene-propylene copolymers, and ethylene-propylene copolymers.
- EPDM ethylene-propylene-copolymer
- EPR ethylene-propylene copolymers
- a method of crosslinking with a crosslinking agent such as peroxide or sulfur to improve characteristics such as compression set is known.
- the crosslinked products of these resin and the resin were low in polarity, and were insufficient in compatibility with other resins, paintability, and the like.
- WO 96Z0776 S1, WO 99Z10395, and US Pat. No. 5,869,591 mainly disclose pseudo-random ethylene-aromatic vinyl compounds.
- the crosslinked product of the copolymer is disclosed in JP-A-11-293045, JP-A-11-293406, JP-A-11-293072.
- the bridge body is disclosed in Japanese Unexamined Patent Publications Nos. Hei 7-2782831 and Hei 10-282842, and a random copolymer of ethylene and ethylene-refined aromatic vinyl compound is disclosed in Japanese Patent Application Laid-Open Nos.
- Hei 7-27 830, Hei 8-13414, Hei 8-225156, Hei 10-1682 No. 42 discloses ethylene-a one-year-old olefin-aromatic vinyl compound-non-conjugated gen-random copolymer, and Japanese Patent Application Laid-Open Nos. 10-26-325 and 10-26. Nos. 4,313, and W098 / 3,540 describe crosslinked products of ethylene-aromatic vinyl compound-non-conjugated polyene, respectively.
- the crosslinked products using these ethylene-aromatic vinyl compound (styrene) copolymers were particularly low in tensile modulus, heat resistance, and cold resistance, and had the drawback that sufficient mechanical strength could not be obtained.
- terpolymers and quaternary copolymers may have insufficient reproducibility due to complicated polymerization behavior.Complex brands are required for industrial production, and Not a target.
- ethylene-aromatic vinyl compound (styrene) copolymer itself has low crosslinkability, a large amount of a crosslinking agent, a crosslinking accelerator, a crosslinking accelerator and Z or A cross-linking agent must be used, which is disadvantageous in terms of cost. Further, these additives have a disadvantage that an unpleasant odor remains in the product.
- non-conjugated polyenes and non-conjugated gens are copolymerized in a one-stage polymerization to introduce a bridge point into an ethylene-aromatic vinyl compound (styrene) copolymer. A large amount of gen must be copolymerized, and the resulting copolymer itself crosslinks during polymerization, insolubilizing or gelling, causing deterioration in physical properties and workability.
- Foams obtained by foaming thermoplastic resin are excellent in lightness, heat insulation, sound insulation, vibration absorption, cushioning, gas permeability, etc., packaging materials for food containers, cushioning materials, heat insulation materials, etc. Has been used as. Specific application fields include food packaging materials, packaging materials for equipment, building materials, civil engineering construction materials, and the like.
- thermoplastic resins used as the base for these foamed materials include ethylene, propylene and other olefin-based resins, styrene-based resins, urethane-based resins, and vinyl chloride-based resins. Fats and the like can be given.
- Polyolefin, polypropylene and other olefin-based resins generally have a high degree of crystallinity, and abrupt changes in viscosity occur as the crystal melts, so molding is not always easy, and cross-linking was performed to improve the melting properties. . The balance of mechanical properties and heat resistance of the obtained foam was also insufficient.
- Urethane-based resin foams have features such as excellent compression recovery properties, but urethane bonds are easily hydrolyzed and have problems with chemical stability, and they are expensive to produce industrially. Had disadvantages.
- polyvinyl chloride-based materials are generated due to concerns about the generation of chlorine and chlorine-based compounds during incineration and decomposition, and the effect of plasticizers contained on living bodies. There is a growing need to substitute other materials for ash.
- JP-A-9-109925 describes a crosslinked product of an ethylene-aromatic vinyl compound-1 (gen) copolymer (composition) and a foamed product thereof.
- Examples are cross-linked products of an ethylene-styrene copolymer such as a pseudo-random copolymer, and the cross-linked structure is obtained by bonding a gen moiety in a polymer main chain with a cross-linking agent. It is a network structure.
- foams mainly composed of an ethylene-styrene copolymer have a characteristic that they have excellent flexibility due to the styrene composition. ⁇ They have the disadvantage that their flexibility is lost at low temperatures and their heat resistance is low. I have. For this reason, the ability to form a composition with a resin such as LLDPE or crosslink to improve low-temperature characteristics and heat resistance. However, it does not sufficiently improve the temperature dependence of the soft touch. Furthermore, foams mainly composed of ethylene styrene copolymer are excellent as flexible foams due to low initial elastic modulus, but they are not suitable for use in foams that have a certain degree of rigidity and flexibility. Not appropriate.
- the present invention relates to the above-mentioned conventional ethylene-styrene copolymer and ethylene.
- the present invention provides, as applications of the cross-copolymer of the present invention, various kinds of resin compositions containing the cross-copolymer which have solved the problems of the above-mentioned conventional various resin compositions and processed products and have been improved. And products.
- Cross-copolymer of the present invention the styrene content to zero. 0 3 mol% or more 9 6 mol% or less, Jen content to zero. 0 0 0 1 mole 0/0 or 3 moles 0/0 or less, the balance being Orefu I (Cross-copolymerized olefin-styrene-copolymer) in which a vinyl compound polymer is cross-copolymerized (cross-copolymerized) with the copolymer of olefin-styrene-copolymer Polymer or olefin-styrene-gene-based cross-copolymer), and the cross-copolymerized cross chain is other than a syndiotactic aromatic vinyl compound polymer (syndiotactic polystyrene) It is a cross copolymer.
- cross copolymer of the present invention is a copolymer that can be obtained by the following production method, that is, a coordination polymerization step and a cross-forming step.
- the present invention is a cross copolymer preferably composed of the structure shown in FIG. 1 or mainly containing the structure shown in FIG.
- the copolymer mainly has a structure in which the main-chain olefin-styrene-copolymer and the vinyl compound polymer are cross-linked (cross-linked) at one or more points in the main chain. is there.
- a cross-coupling structure can be called a star structure.
- Segregated starch copolymer Polymer preprints, 1998, March.
- the vinyl compound polymer cross-linked to the 1-gen copolymer is referred to as a cross chain.
- a graft copolymer known to those skilled in the art is a copolymer mainly having a polymer chain branched from one or more points of a main chain.
- a structure in which the polymer main chain and other polymer chains cross-link (cross-link) (It can also be said to be a star structure) is considered that when used as a composition or compatibilizer, it generally provides superior strength at the polymer microstructure interface and provides high mechanical properties as compared to a graphitized structure.
- cross-link cross-link
- the present invention has excellent workability in which the MFR measured at 200 ° C. and a load of 5 kg is 0.05 g / 10 minutes or more, preferably 0.2 g / 10 minutes or more. It is a olefin-styrene-gen-based cross copolymer.
- the present invention is a cross copolymer, wherein the cross-copolymerized cross chain has substantially no stereoregularity. That is, the present invention is an olefin-styrene-gen-based cross-copolymer characterized by having a racemic diad fraction or a method diad fraction of less than 0.85, preferably 0.75 or less.
- the olefin is ethylene, or an olefin-styrene-gen-based cross-copolymer in which two or more types of olefins containing ethylene are used.
- the present invention is more preferably an olefin-styrene-gen-based cross copolymer having an aromatic vinyl compound polymer as a cross chain.
- Orefi down one styrenic one diene type cross-copolymer of the present invention the styrene content to zero. 0 3 mole 0/0 to 9 6 mole 0/0 or less, Jen content to zero. 0 0 0 1 mole 0/0 or more It is a cross-copolymer obtained by using an olefin-styrene-gen copolymer having 3 mol% or less and the balance being olefin.
- a method for producing an olefin-styrene-gen-based cross-copolymer or cross-copolymer having excellent mechanical properties, high heat resistance, excellent processability, and excellent economical efficiency A styrene-one-gen-based cross-copolymer or cross-copolymer is provided. Also, an excellent method for producing an ore-gene-based cross-copolymer or a cross-copolymer is provided. These cross copolymers and cross copolymers are extremely useful in a wide range of applications.
- FIG. 1 is a conceptual diagram showing a structure mainly contained in a cross-linked copolymer of the present invention.
- FIG. 2 Conceptual diagram showing the structure of a conventional grafted copolymer.
- Figure 3 Example 14 1H-NMR spectrum of 14A obtained in the coordination polymerization step
- Fig. 4 Example 14; 1 H-NMR spectrum of 14-B obtained in the cross-linking step.
- Fig. 5 Example 14: Acetone insoluble fraction obtained by solvent fractionation. NM R spectrum.
- Example 14 14-A viscoelastic spectrum obtained in the coordination polymerization step.
- Figure 7 Example 14, viscoelastic spectrum of 14-B obtained in the crossing step.
- Figure 8 Example 7, viscoelastic spectrum of 7-A obtained in the coordination polymerization step.
- FIG. 11 is a TEM photograph of 14B obtained in Example 14.
- a cross-copolymerization product is a cross-copolymer which can be directly obtained by the following production method, that is, a coordination polymerization step and a cross-forming step. It is a composition containing.
- the present invention is a cross copolymer that can be obtained by the following production method.
- the present cross copolymer production method can produce a cross copolymer having uniformity, good processability, and excellent physical properties with efficiency and economy suitable for industrialization.
- the olefin-styrene-gen copolymer used in the present invention can be obtained by copolymerizing styrene monomer, ore monomer, and gen monomer in the presence of a single-site coordination polymerization catalyst.
- Examples of the olefin used in the coordination polymerization step of the present invention include ethylene, a monoolefin having 3 to 20 carbon atoms, that is, propylene, 1-butene, 1-hexene, 4-methyl-11-pentene, 1—Octene and cyclic olefins, ie cyclopentene and norbornene.
- ethylene a monoolefin having 3 to 20 carbon atoms
- propylene 1-butene, 1-hexene, 4-methyl-11-pentene, 1—Octene and cyclic olefins, ie cyclopentene and norbornene.
- ethylene is used. More preferably, ethylene is used.
- a mixture of ethylene and "one-olefin is used, and particularly preferably, ethylene is used.
- the styrene used in the coordination polymerization step of the present invention is preferably used alone.
- Other aromatic vinyl compounds such as p-chlorostyrene, p-tert-butyl styrene, "monomethylstyrene, vinylnaphthalene, p-methylstyrene, It may be used as a mixture with vinylnaphthalene, vinylanthracene and the like.
- a gen capable of coordination polymerization is used as the gen used in the coordination polymerization step of the present invention.
- a gen in which a plurality of double bonds (vinyl groups) are bonded via a C6 to C30 hydrocarbon group containing one or more aromatic vinyl ring structures.
- the remaining double bond is a polymer capable of anionic, radial or cationic polymerization.
- most preferably ol And various kinds of divinylbenzene and mixtures thereof are suitably used.
- the amount of gen used in the coordination polymerization step is, in a molar ratio, 1/100 or less 1/500 or more, preferably 1/400 or less, of the amount of styrene used. It is preferably at least 20000, particularly preferably at most 1Z100, and at least 1Z100,000. If the coordination polymerization step is carried out at a Gen concentration higher than this, a large amount of the crosslinked structure of the polymer will be formed during polymerization, causing gelation, etc., and the processability of the cross copolymer finally obtained through the crossing step And physical properties deteriorate.
- the coordination polymerization step is carried out at a higher gen concentration, the residual gen concentration in the coordination polymerization liquid will increase, and this polymerization liquid is used as it is in the cross-forming step (such as anion polymerization). In such a case, a large number of cross-linked structures are generated, and the resulting cross-copolymer similarly has poor processability and physical properties.
- the copolymer of olefin and styrene obtained in the coordination polymerization step has a styrene content of 0.03 mol% or more and 96 mol% or less, and a gen content of 0.001 mol% or more and 3 mol% or less.
- styrene content 0.0 3 mole 0/0 over 2 5 mole 0/0 or less
- styrene content is 0.0 to 3 mol% or more 1 5 mole 0/0 or less, particularly preferably 3 mol 0/0 or 1 5 mole 0/0 following Jen content 0.0 0 1 mole 0/0 or 0.5 mol 0/0 or less, the balance being Orefi down
- An olefin-styrene-gen copolymer is used.
- the single-site coordination polymerization catalyst used in the coordination polymerization step includes a polymerization catalyst composed of a soluble transition metal catalyst and a co-catalyst, such as a soluble Zieg 1 ar-Natta catalyst, methylaluminoxane, and a boron compound.
- Activated metal catalysts so-called meta-metallic catalysts, half-metallic metal-catalysts, CGCT catalysts, etc.).
- polymerization catalysts described in the following documents and patents can be used. You.
- JP-A-3-163688, JP-A-7-53618, and EP-A-416815 are examples of the CGCT catalyst.
- the force which is preferably used for obtaining a cross-copolymer or a cross-copolymer of the present invention is obtained by using an orylene-styrene-copolymer having a uniform composition in which the polymer is uniformly contained in the polymer. It is difficult to obtain a copolymer having a uniform composition using a Zieg 1 ar-Natta catalyst, and a single-site coordination polymerization catalyst is preferably used.
- a single-site coordination polymerization catalyst is a polymerization catalyst composed of a soluble transition metal catalyst and a cocatalyst, and a transition metal compound catalyst (a so-called metallocene catalyst or half metal catalyst) activated with methylaluminoxane, boron compound, or the like. It is a polymerization catalyst composed of an oral catalyst and a CGCT catalyst.
- the most preferably used coordination polymerization catalyst is a polymerization catalyst comprising a transition metal compound represented by the following general formula (1) and a cocatalyst.
- the addition property of the cross-copolymer is deteriorated. Also, if a large amount of unpolymerized gene remains in the polymerization solution obtained in the coordination polymerization step, the degree of cross-linking of the cross chain will be significantly increased during the subsequent anion polymerization, and the resulting cross
- the copolymerized copolymer or the cross-copolymer is insoluble, gelled, or deteriorates processability.
- a polymerization catalyst composed of a transition metal compound represented by the following general formula (1) and a co-catalyst a copolymer of olefin and styrene having an extremely high activity and uniform composition suitable for industrialization is used. It is possible to produce polymers. Also, it is possible to provide a high transparency of the copolymer in particular 1 mole% or more 2 0 mole 0/0 copolymers of the following styrene content.
- the styrene content of 1 mole 0/0 to 9 6 mol% or less of the composition excellent in mechanical properties, Orefi down one styrene one diene copolymer having a styrene chain structure of Tsu Dotiru to the steric regularity of Aisotakuteiku heavy Coalescence can be given.
- a and B are unsubstituted or substituted cyclopentaphenanthryl groups, unsubstituted or substituted benzoindenyl groups, unsubstituted or substituted cyclopentapentaenyl groups, unsubstituted or substituted It is a group selected from an indenyl group or an unsubstituted or substituted fluorenyl group.
- Y has a bond with A and B, and also includes hydrogen or a hydrocarbon group having 1 to 15 carbon atoms (which may include 1 to 3 nitrogen atoms, oxygen, sulfur, phosphorus, and silicon atoms).
- a methylene group, a silylene group, an ethylene group, a germylene group, and a boron residue having The substituent is They may be different or the same.
- Y may have a cyclic structure such as a cyclohexylidene group or a cyclopentylidene group.
- X represents hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkyl aryl group having 8 to 12 carbon atoms, or a hydrocarbon having 1 to 4 carbon atoms.
- M is zirconium, hafnium, or titanium.
- At least one of A and B is selected from an unsubstituted or substituted cyclopentaphenanthryl group, an unsubstituted or substituted benzoindenyl group, or an unsubstituted or substituted indenyl group.
- the polymerization catalyst comprises a transition metal compound of the above general formula (1), which is a selected group, and a co-catalyst.
- the unsubstituted or substituted cyclopentaphenanthryl group can be represented by the following formulas 7 to 8.
- R 1 to R 8 are each hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an alkyl group having 7 to 20 carbon atoms.
- aryl group, a halogen atom, OS i R 3 groups, an S i R 3 group or a PR 2 group R is a hydrocarbon group of 1 to 1 0 carbon atoms none.
- R 1 and R 2 may be the same or different, and adjacent R l and R 2 groups may be 5
- R3s, R4s, and R5s may be the same or different from each other, and adjacent R3, R4, and R5 groups are united to form a 5- to 8-membered aromatic or aliphatic ring. May be formed. (However, this does not apply to the case of becoming an unsubstituted cyclopentaphenanthrene group.)
- R 6, R 7, and R 8 may be the same or different.
- unsubstituted cyclopentaphenanthryl group examples include a 3-cyclopenta [c] phenanthryl group and a 1-cyclopenta [1] phenanthryl group.
- the unsubstituted or substituted benzoindenyl group can be represented by the following formulas 9 to 11. ⁇
- benzoindenyl groups 4,5-benzo-1-indenyl, (also known as benzo (e) indenyl), 5,6-benzo-11-indenyl, 6,7-benzodienyl
- 1-indenyl is a substituted benzoindenyl group
- An unsubstituted or substituted cyclopentagenenyl group, an unsubstituted or substituted indenyl group, and an unsubstituted or substituted fluorenyl group can be represented by Figs. 1 2
- the unsubstituted indenyl group is 1-indenyl
- the substituted indenyl group is 4-alkyl-111-indenyl, 4-aryl-1-indenyl, 4,5-dialkyl-11-indenyl, 4,6 —Dialkyl-1-1indenyl, 5,6—dialkyl-1-1indenyl, 4,5—diaryl-1-1indenyl, 5-aryl-1—indenyl, 4-ary-5 Alkyl 1 1 indenyl, 2,6-dialkyl 1 4 — aryl 1 1 indenyl, 5, 6 — diaryl 1 1 1 indenyl, 4, 5, 6 — triaryl 1 1 Monoindenyl and the like.
- the unsubstituted cyclopentagenenyl group is cyclopentagenenyl
- the substituted cycle pentagenenyl group is 4-aryl-11-cyclopentagenenyl
- 4,5-diaryl-11-cyclopentagenenyl 5-Alkyl-4-aryl-1-cyclopentagenenyl
- 4-Alkyl-5-aryl-1-cyclopentenyl 4,5-Dialkyl-1-cyclopentagenenyl
- 5-Tri Alkylsilyl-14-alkyl-11-cyclopentagenenyl, 4,5-dialkylsilyl-1-cyclopentagenenyl and the like can be mentioned.
- Examples of the unsubstituted fluorenyl group include 91-fluorenyl group, and examples of the substituted fluorenyl group include 7-methyl-9-fluorenyl group and benzo-19-fluorenyl group.
- both A and B are unsubstituted or substituted cyclopentaphenanthryl groups, unsubstituted or substituted benzoindenyl groups, or unsubstituted or substituted indenyl groups, they are the same or different. You may.
- at least one of A and B may be an unsubstituted or substituted cyclopentaphenanthryl group or an unsubstituted or substituted benzoindenyl group. Particularly preferred.
- a and B are unsubstituted or substituted benzoindenyl groups.
- Y has a bond with A and B, and as a substituent, hydrogen or a hydrocarbon group having 1 to 15 carbon atoms (1 to 3 nitrogen, oxygen, sulfur, , Phosphorus, and silicon atoms), a methylene group, a silylene group, an ethylene group, a germylene group, and a boron residue.
- the substituents may be different or the same.
- Y may have a cyclic structure such as a cyclohexylidene group and a cyclopentylidene group.
- Y is a substituted methylene group which has a bond with A and B and is substituted by hydrogen or a hydrocarbon group having 1 to 15 carbon atoms.
- hydrocarbon substituent include an alkyl group, an aryl group, a cycloalkyl group, and a cycloaryl group. The substituents may be different or the same.
- Y is, - CH 2 -, one CM e 2 -, one CE t 2 -, one CP h 2 one, xylidine to cyclohexylene, cyclopentylidene, or the like.
- Me represents a methyl group
- Et represents an ethyl group
- Ph represents a phenyl group.
- X represents hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkyl aryl group having 8 to 12 carbon atoms, or a hydrocarbon having 1 to 4 carbon atoms.
- Halogen is chlorine, bromine, etc.
- alkyl group is methyl group, ethyl group, etc.
- aryl group is phenyl group
- alkylaryl group is benzyl group
- silyl group is silyl group.
- M is zirconium, hafnium, and still titanium. Particularly preferred Jill:? Ni is c
- a transition metal catalyst component include a substituted methylene bridged structure specifically exemplified in EP-0 872 492 A2 and Japanese Patent Application Laid-Open No. 11-108808. In addition to the above transition metal compounds, the following compounds may be mentioned.
- the titanium and hafnium complexes exemplified as zirconium complexes are the same as above. Are preferably used. Further, a mixture of a racemic body and a meso body may be used. Preferably, racemic or pseudo-racemic is used. In these cases, D-form or L-form may be used.
- a co-catalyst used in the production method of the present invention a co-catalyst conventionally used in combination with a transition metal catalyst component can be used.
- a co-catalyst aluminoxane (or alumoxane) is used.
- a boron compound is suitably used.
- the co-catalyst used at that time is preferably an aluminoxane (or alumoxane) represented by the following general formulas (4) and (5).
- R is an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or hydrogen, and m is an integer of 2 to 100.
- Each R may be the same or different.
- R is an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or hydrogen
- N is an integer of 2 to 100.
- R may be the same or different from each other, and is preferably an aluminoxane, preferably, methylalumoxane, ethylalumoki Power of using sun and triisobutylalumoxane Particularly preferably, methylalumoxane is used. If necessary, a mixture of these different types of alumoxanes may be used.
- alumoxanes may be used in combination with alkylaluminum, for example, trimethylaluminum, triethylaluminum, alkylaluminum containing triisobutylaluminum dihalogen, for example, dimethylaluminum dimethyl chloride.
- alkylaluminum is effective for removing a polymerization inhibitor such as a polymerization inhibitor in styrene, styrene, water in a solvent, and other substances that inhibit polymerization, and detoxifying the polymerization reaction.
- a polymerization inhibitor such as a polymerization inhibitor in styrene, styrene, water in a solvent, and other substances that inhibit polymerization, and detoxifying the polymerization reaction.
- a boron compound known as a co-catalyst together with the above-described transition metal catalyst component for example, a boron compound specifically exemplified as a co-catalyst in EP 0 728 492 A2 Can be used.
- boron compounds and the above-mentioned organic aluminum compounds may be used at the same time.
- the monomers exemplified above, the transition metal catalyst component which is a metal complex, and the cocatalyst are brought into contact with each other. Any known method can be used.
- a mixed alkane solvent, cyclohexane, toluene, or ethylbenzene is used.
- the polymerization form may be either solution polymerization or slurry polymerization. If necessary, known methods such as batch polymerization, continuous polymerization, preliminary polymerization, and multistage polymerization can be used.
- the pipe-shaped polymerization can includes various known mixers such as a dynamic or static mixer and a static mixer which also serves as heat removal, and a cooler equipped with a heat removal thin tube. It may have various known coolers. Also, a batch type prepolymerization can may be provided. Further, a method such as gas phase polymerization can be used.
- the polymerization temperature is suitably from 178 ° C to 200 ° C.
- a polymerization temperature lower than 178 ° C is industrially disadvantageous, and a temperature higher than 200 ° C is not appropriate because decomposition of the metal complex occurs. Further industrially, it is preferably 0 ° (: to 160 ° C., particularly preferably 30 ° (: to 160 ° C.).
- the pressure during the polymerization is suitably from 0.1 to 100 atm, preferably from 1 to 30 atm, and particularly preferably from 1 to 10 atm, industrially.
- the ratio of the aluminum of the complex to the metal of the complex is from 0.1 to 100, preferably from 10 to 100,000. Used in the ratio of If it is less than 0.1, the metal complex cannot be activated effectively, and if it exceeds 1000, it is economically disadvantageous.
- a force s preferably 0.1 to 10 in the ratio of boron atom / complex metal atom in the ratio of 0.01 to L 00, preferably 0.1 to 10; Preferably used in 1.
- the metal complex cannot be activated effectively, and if it exceeds 100, it is economically disadvantageous.
- the metal complex and co-catalyst can be mixed and prepared outside the polymerization tank, or mixed in the tank during polymerization.
- the copolymer of olefin-styrene-gen used in the present invention>', the copolymer of olefin-styrene-gen used in the present invention has the above-mentioned coordination weight.
- the synthesizing step it is synthesized from each monomer of styrene, orange and gen using the above-mentioned coordination polymerization catalyst, preferably a single-site coordination polymerization catalyst.
- the copolymer of olefin and styrene obtained in the coordination polymerization step of the present invention is preferably an ethylene-styrene-gen copolymer or ethylene-styrene-gen.
- the copolymer of olefin-styrene-gen obtained in the coordination polymerization step of the present invention may have a cross-linked structure with the contained gen monomer, but the gel content is 10 wt. Below, it is necessary to be preferably 0.1% by weight or less.
- the ethylene-styrene-gen copolymer obtained in the coordination polymerization process is a styrene unit of the head-to-doel attributed to the peak observed at 40 to 45 ppm by 13 C-NMR measurement based on TMS. It is preferable to have a chain structure of 42.3 to 43.1 ppm, 43.7 to 44.5 ppm, 40.4 to 41.0 ppm, 43.0 to 4 3. It preferably has a chain structure of styrene unit attributable to the peak observed at 6 ppm.
- the copolymer suitably used in the present invention is an ethylene-styrene-gen copolymer obtained by using a metallocene catalyst capable of producing isotactic polystyrene by homopolymerization of styrene. It is an ethylene-styrene-diene copolymer obtained using a meta-mouth catalyst capable of producing polyethylene by homopolymerization of ethylene.
- the obtained ethylene-styrene-gen copolymer can have, in its main chain, both an ethylene-different structure, a styrene chain structure of a head till, and a structure in which ethylene unit and styrene unit are bonded.
- the ethylene-styrene-gene copolymer obtained in the coordination polymerization step has a steric structure of a phenyl group having an alternating structure of styrene and ethylene represented by the following general formula (3) contained in the structure. Regularity is greater than 0.5, preferably greater than 0.75, particularly preferably greater than 0.95, in isotactic diat fraction (or method diat fraction) m. is there.
- the isotactic diad fraction m of the alternating copolymerized structure of ethylene and styrene is defined as the peak area A r derived from the r-structure of the methylene carbon peak appearing at around 25 ppm and the peak area Am derived from the m-structure.
- the peak appearance position may shift slightly depending on the measurement conditions and solvent. For example, when TMS is used as a solvent, using double-mouthed form as the solvent, the peak derived from the r structure has a peak near 25.4 to 25.5 ppm, and the peak derived from the m structure has a peak of 2 ppm. Appears around 5.2 to 25.3 ppm.
- the m-structure represents a meso-diadite structure
- the r-structure represents a racemic diad structure.
- the r-structure belongs to the alternating copolymer structure of ethylene and styrene. Is substantially not observed.
- the ethylene-styrene-gen copolymer obtained in the coordination polymerization step is divided into the copolymer and the alternate structure of styrene and ethylene represented by the general formula (3) contained in the structure.
- the alternating structure index ⁇ (represented by the following equation (1)) indicating a combination is smaller than 70, larger than 0.01, preferably smaller than 30 and larger than 0.1. It is preferred that they are united.
- a 3 is the sum of the areas of three types of peaks a, b, and c derived from the ethylene-styrene alternating structure represented by the following general formula (3,) and obtained by 13 C-NMR measurement. It is.
- A2 is the sum of the areas of the peaks derived from main chain methylene and main chain methine carbon observed in the range of 0 to 50 ppm by 13 C-NMR based on TMS.
- Ph represents a phenyl group
- X represents the number of repeating units, and represents an integer of 2 or more.
- Gen content is 3 mol 0/0 or less, preferably in 1 mole 0/0 less ethylene one styrene diene copolymer, having heads one til the styrene chain, isotactic in ⁇ or ethylene one styrene alternating structure Having a stereoregularity of less than 70 and / or having an alternating structure index value of less than 70 is effective because it is an elastomer copolymer having high transparency and high mechanical strength such as breaking strength.
- a copolymer having such characteristics can be suitably used in the present invention.
- a copolymer having a high degree of isotactic stereoregularity in an ethylene-styrene alternating structure and having an alternating structure index smaller than 70 is preferable as the copolymer of the present invention.
- Particularly preferred as the copolymer of the present invention is a copolymer having a styrene chain of one till, having an isotactic stereoregularity in an ethylene-styrene alternating structure, and having an alternating structure index ⁇ value of less than 70. .
- the preferred ethylene-styrene-gen copolymer of the present invention has an alternating structure of ethylene and styrene having high stereoregularity, an ethylene chain of various lengths, a heterogeneous bond of styrene, and a heterogeneous bond of styrene at the same time. It is characterized by having various structures such as styrene chains.
- the ratio of the alternating structure is determined by the value obtained from the above equation in accordance with the polymerization catalyst used, the polymerization conditions, and the styrene content in the copolymer. Various changes can be made within a range of less than 70.
- Alternating index values less than 70 mean that while being a crystalline polymer, it provides significant mechanical strength, solvent resistance, toughness, and transparency, as well as partially crystalline polymers. Or to become a non-crystalline polymer.
- the copolymer used in the present invention can be obtained by controlling the degree of crystallinity by controlling the styrene content or by an appropriate method. It is possible to provide various properties such as non-crystalline and partially crystalline polymer.
- the copolymer used in the present invention is compared with a conventional ethylene-styrene copolymer or an ethylene-styrene-gen copolymer having no stereoregularity and not having a styrene chain of a header.
- a conventional ethylene-styrene copolymer or an ethylene-styrene-gen copolymer having no stereoregularity and not having a styrene chain of a header In the range of each styrene content and various degrees of crystallinity, the performance such as initial tensile modulus, hardness, rupture strength, solvent resistance, transparency, etc. is improved, and new low crystalline resin, thermoplastic elastomer It exhibits physical properties characteristic of a transparent soft resin.
- the ethylene-styrene-styrene copolymer as a typical and preferred example of the copolymer of olefin-styrene-gene used in the present invention has been described.
- the copolymer of ethylene-styrene-gene used in the present invention is, of course, described. Coalescence is not limited to this.
- the weight-average molecular weight of the copolymer of olefin and styrene used in the present invention is 10,000 or more, preferably 30,000 or more, particularly preferably 60,000 or more, and 100,000 or less, preferably 500,000 or less. Less than 10,000.
- the molecular weight distribution (M w / M n) is 6 or less, preferably 4 or less, particularly preferably 3 or less.
- the weight average molecular weight refers to a molecular weight in terms of polystyrene obtained by using GPC and standard polystyrene. The same applies to the following description.
- the weight-average molecular weight of the olefin-styrene-gen copolymer used in the present invention is required within the above range by a known method using a chain transfer agent such as hydrogen, or by changing the polymerization temperature. It can be adjusted accordingly.
- anionic polymerization radical polymerization, or cationic polymerization can be employed depending on the type of the vinyl compound monomer to be polymerized in the cross-copolymerization step.
- the conversion of one kind of vinyl compound monomer to be polymerized in the cross-forming step is preferably 20% or more, particularly preferably 506 or more, and most preferably 70% or more.
- the length (molecular weight) of the cross-chain portion is a force that can be estimated from the molecular weight of the homopolymer that has not been cross-linked. Its length is expressed as a weight average molecular weight ', preferably 50,000 or more and 500,000 or less. , Particularly preferably 50,000 or more and 500,000 or less, most preferably It is 10,000 or more and 150,000 or less.
- the molecular weight distribution (MwZMn) is preferably 6 or less, particularly preferably 4 or less, and most preferably 3 or less.
- the cross-forming step of the present invention is preferably performed subsequent to the coordination polymerization step, using the polymerization solution obtained in the above-described coordination polymerization step. Then, the copolymer obtained in the above coordination polymerization step is recovered from the polymerization solution, dissolved in a new solvent, and the monomers used in the cross-linking step are added, and the anion, radical, or cation is added.
- the cross-copolymerization step may be performed in the presence of a polymerization initiator. Furthermore, the copolymer obtained in the above coordination polymerization step is recovered from the polymerization solution, and cross-copolymerized by suspension polymerization or emulsion polymerization in the monomer and Z or a solvent used in the cross-forming step. It is also possible.
- Radical polymerization initiators described in 1987 are suitably used.Radical polymerization can also be performed by thermal polymerization without using an initiator.
- any vinyl compound monomer capable of radical polymerization can be used.
- Preferred vinyl compound monomers include styrene, ⁇ -methylstyrene, ⁇ -tert-butylstyrene, and ⁇ - Aromatic vinyl compounds such as styrene, monomethylstyrene, vinylnaphthalene, and vinylanthracene; butane compounds such as butadiene, isoprene, and chloroprene; and vinylcyclohexene, vinylcyclohexane, and methylacrylate Polar monomers such as methacrylates such as acrylates and methyl methacrylate, acrylonitrile, and maleic anhydride; and mixtures thereof, preferably aromatic vinyl compounds or aromatics Vinyl compounds and their radical polymerizable A mixture of monomers, and most preferably an aromatic vinyl compound is used.
- Particularly preferably known in the art such as slurry polymerization, bulk polymerization, solution polymerization and emulsion polymerization
- any known method such as batch polymerization, plug flow continuous polymerization, continuous polymerization using a loop reactor, multistage continuous polymerization, batch polymerization, or prepolymerization can be used.
- the polymerization temperature is suitably from 0 ° C to 300 ° C. If the polymerization temperature is lower than 0 ° C, the polymerization rate is low, which is industrially disadvantageous. If the temperature is higher than 300 ° C, depolymerization or the like occurs, and the molecular weight of the polymer decreases, which is not appropriate. More preferably, it is 50 ° C to 300 ° C industrially.
- the pressure at the time of polymerization is suitably from 0.1 to 100 atm, preferably from 1 to 30 atm, and particularly preferably from 1 to 10 atm.
- Particularly suitable as the cross-forming step of the present invention is an anion polymerization step using an anion polymerization initiator and a monomer capable of anion polymerization.
- Anion polymerization is based on the fact that the conversion rate of the vinyl compound monomer species is extremely high, that a polymer having a relatively high molecular weight can be obtained even at a low monomer concentration, and that polymerization is sufficiently fast even under low monomer concentration conditions. It is very preferred for the present invention because of its speed.
- the vinyl compound monomer conversion rate is high, monomers capable of anion polymerization are consumed, and it is possible to substantially eliminate the monomer from remaining in the polymerization solution.
- any vinyl compound monomer capable of anion polymerization can be used.
- Vinyl compound monomers capable of anion polymerization are described, for example, in “Anionic Polymer Polymerization”, Marcel Dekker, Inc., 1996, Henry L. Hsieh and Roderic P. Quirk.
- aromatic vinyl compounds such as styrene, p-methylstyrene, p-tert-butylstyrene, p-chlorostyrene, high-methylstyrene, vinylnaphthalene and vinylanthracene; gen compounds such as butadiene and isoprene; Acrylates such as methyl acrylate, methacrylates such as methyl methacrylate, and mixtures thereof are used.
- an aromatic vinyl compound or a mixture of an aromatic vinyl compound and an anion-polymerizable monomer most preferably, an aromatic vinyl compound is used.
- a monomer for example, styrene
- a new monomer compound of the same kind in a lump or continuously or stepwise. May be dispensed.
- the ratio of the structure having a cross chain is significantly increased, and the mechanical properties of a composition containing the same can be further improved.
- the monomer polymerized in the anion polymerization step of the present invention is different from the monomer used in the coordination polymerization step, for example, when the monomer is different from styrene, a copolymer is separated and recovered from the polymerization solution, and this polymer is used as a solvent. It is preferable to redissolve in water and to add a new monomer to be polymerized by anionic polymerization for polymerization. Further, anion polymerization may be performed by adding a new monomer to the polymerization solution obtained in the coordination polymerization step at a time or in a stepwise manner. In this case, the cross chain has a random or block or tapered block copolymer structure of the monomer remaining in the coordination polymerization step and the newly added monomer.
- the cross chains and homopolymers (meaning non-cross-linked polymer chains) polymerized in the anion polymerization step of the present invention may have a cross structure due to a small amount of remaining gen monomer.
- the anion polymerization step (cross-forming step) of the present invention is performed subsequent to the above-mentioned coordination polymerization step.
- the copolymer obtained in the coordination polymerization step is subjected to any polymer recovery method such as a crumb forming method, a steam stripping method, a direct devolatilization method using a devolatilization tank, a devolatilization extruder, or the like. It may be used to separate and purify it from the polymerization solution and use it in the anion polymerization step. However, it is economically preferable to use the polymer after the coordination polymerization in the next anion polymerization step after or without releasing the residual orifice from the polymerization solution.
- the coordination polymerization solution containing the polymer can be used in the cross-forming step without separating the polymer from the coordination polymerization solution.
- the monomer to be polymerized in the anion polymerization step is styrene
- a styrene monomer may be added if necessary, but the residual residue not polymerized in the coordination polymerization step
- the monomer may be used as it is. If necessary, the above-mentioned vinyl compound monomer capable of anion polymerization may be added.
- the solvent is Anion polymerization step
- the solvent is particularly preferred force s of hexane and benzene to a chain does not cause inconvenience such as movement mixed Al force down solvents Ya consequent opening during Anion polymerization
- the polymerization temperature is 1 5 0 ° C
- Other solvents such as toluene and ethylbenzene can be used as long as they are as follows.
- any known method such as batch polymerization, continuous polymerization, batch polymerization, slurry polymerization, and prepolymerization can be used.
- the pressure during the polymerization is suitably from 0.1 to 100 atm, preferably from 1 to 30 atm, and particularly preferably from 1 to 10 atm, industrially.
- a known anion polymerization initiator can be used.
- anionic polymerization initiators are described, for example, in “Anionic Polymer Polymers”, Marcel Dekker, Inc., 1996, Henry L. Hsieh and Roderic P. Quirk. ing.
- an alkyllithium compound such as a lithium salt such as biphenyl, naphthalene or pyrene is used, and particularly preferably a sodium salt, particularly preferably sec-butyllithium or n (normal) monobutyllithium.
- a multifunctional initiator a dilithium compound or a trilithium compound may be used.
- a known radical polymerization terminal coupling agent may be used if necessary.
- the amount of the initiator is at least the equivalent of the oxygen atom contained therein, particularly preferably at least 2 equivalents. It is preferable to use In the coordination polymerization step, when a boron compound is used as a co-catalyst of the polymerization catalyst, the amount thereof is sufficiently smaller than the oxygen atom equivalent in methylalumoxane, so that the amount of the initiator can be reduced. It is possible.
- the length of the cross chain and the molecular weight of the uncrosslinked homopolymer can be arbitrarily changed by appropriately adjusting the amount of the initiator. You.
- the length (molecular weight) of the cross-chain portion can be estimated from the molecular weight of the uncrosslinked homopolymer, but the length is preferably 500 to 500,000 as a weight average molecular weight, and particularly preferably. Is from 5,000 to 500,000, and most preferably from 10,000 to 150,000.
- the molecular weight distribution (MwZMn) is preferably 6 or less, particularly preferably 4 or less, and most preferably 3 or less.
- the ratio (cross-copolymerization ratio) of the cross-copolymerized copolymer of the olefin-styrene-one copolymer or the olefin-gene copolymer used is determined by the ratio of the original olefin-styrene-one copolymer. It is 1% by weight or more, preferably 10% by weight or more, particularly preferably 30% by weight or more and 100% by weight or less of the gen copolymer.
- the olefin-styrene-gen-based cross-copolymer or cross-copolymer of the present invention itself has high mechanical properties (rupture strength, tensile modulus), high-temperature properties, and high transparency due to its composition. Furthermore, the main chain component and composition, cross ratio, cross density, cross chain component and composition, cross chain molecular weight, ratio of uncrossed polymer (homopolymer), etc. can be changed arbitrarily. It has the feature that its high temperature characteristics, hardness, optical characteristics, etc. can be adjusted in a wide range.
- the gel content is very low, so it has good processability.
- the cross chain does not contain a syndiotactic aromatic vinyl compound polymer (syndiotactic polystyrene) structure, high processing temperatures are required. (More than about 270 ° C).
- the olefin-styrene-gen-based cross copolymer or cross copolymer of the present invention may be used alone, or may be used as a composition with another polymer.
- syndiotactic resin which has low compatibility with other resins, especially aromatic vinyl compound resin of atactic, and is difficult to process.
- Cross-chains composed of high-molecular aromatic vinyl compound polymers are not suitable.
- it has no stereoregularity, that is, a cross-copolymer having a cross-chain of 0.85 or less, preferably 0.75 or less in racemic or meso-diadite fraction.
- a coalesced or cross-copolymer is preferred.
- a polymer of the same type as the cross chain to be generated is generated, and the obtained polymer is a copolymer obtained by coordination polymerization,
- a cross-copolymer having a cross-chain and a composition having any composition of “a polymer of the same type as the cross chain that has not been cross-linked” are obtained.
- This composition is described herein as a cross-copolymer.
- the amount of Ru contained "Polymer one cross chain and same type that were not crossing” the whole 9 0 by weight 0/0 or less, preferably 5 0 wt% or less, particularly preferably 3 0 wt% It is as follows.
- the amount of the “polymer of the same type as the cross chains not cross-linked” can be changed.
- Such “polymers of the same type as the cross chains that have not been cross-linked” can be removed by solvent separation or the like, but can be used as they are without separation.
- the amount of the “olefin-styrene-styrene copolymer” having no cross chain is not more than 99% by weight, preferably not more than 50% by weight, particularly preferably not more than 30% by weight of the whole.
- olefin-styrene-gene copolymer refers to the copolymer of olefin-styrene-gen obtained in the above coordination polymerization process.
- the cross copolymer acts as a compatibilizer, the cross copolymer is well compatibilized and exhibits good physical properties.
- the styrene content based on the whole (the styrene content in the used olefin-styrene-copolymer and the styrene content in the cross-chain, the styrene content in the polystyrene) total) of 1 mol% or more 9 9 molar 0/0 or less, preferably 8 0 mol% 5 mol% or more or less.
- the styrene content relative to the whole is 1 mole 0/0 to 9 9 mole 0/0 or less, the preferred properly 5 mole % or more 8 0 mole 0/0 less is c
- ethylene-styrene-gen-based cross-copolymers obtained by cross-polymerizing polystyrene by anion polymerization or radical polymerization with ethylene-styrene-gen-copolymer include ethylene-styrene-gen-copolymer and polystyrene cross-copolymer Chemically modified Tylene-styrene-gen copolymer and polystyrene are included. Since the polystyrene cross-copolymerized ethylene-styrene-copolymer acts as a compatibilizer between the ethylene-styrene-copolymer and polystyrene, the cross-copolymer has good compatibility.
- This cross-copolymer can have high mechanical properties (initial modulus, hardness, breaking strength, elongation) and heat resistance.
- This cross-copolymer exhibits a wide range of properties from elastomer to plastic depending on its composition. In addition, it has high transparency by preparing the composition of the copolymer, cross copolymer and polystyrene obtained by coordination polymerization, and copolymerizing the cross chain with a polar monomer having an appropriate refractive index. You can also.
- Ethylene-styrene-gen-based cross-copolymers whose cross chains are composed of a copolymer of styrene and methacrylate, especially methyl methacrylate (MMA), have particularly high transparency. Depending on its composition, It can cover a wide range of physical properties up to the lastomer.
- This copolymer is, for example, an ethylene-styrene-divinylbenzene copolymer and an unreacted styrene monomer.
- the cross copolymer is an ethylene-styrene-divinylbenzene copolymer, a styrene-MMA copolymer, a cross-linked ethylene-styrene-divinylbenzene copolymer, and an uncrossed styrene-MMA copolymer in any proportion. And obtained as a composition containing
- cross-copolymers of the present invention produced by the cross-linking process using anion polymerization, those having an anion-polymerizable genite such as butadiene or isoprene as the cross chain have good cross-linking properties.
- a crosslinked product having a high degree of crosslinking can be easily formed by using a very small amount of a crosslinking agent or a crosslinking assistant.
- a good crosslinkable polymer has been obtained by copolymerizing a crosslinkable gen monomer when polymerizing in one step using a coordination polymerization catalyst or the like. However, it was generally difficult to obtain a high gen content copolymer by this method.
- the coordination polymerization step in the production method of the present invention, only a very small amount of gen is used.
- an arbitrary amount of crosslinkable gen can be added and copolymerized. Can be arbitrarily controlled. Zhen content of the case, with respect to the total polymer 0. 0 1 molar 0/0 or more, 8 0 mole 0/0 or less, preferably 0. 5 mol 0/0 to 3 0 mol 0/0 or less.
- the copolymerization form of GenUnit in the cross chain may be any block structure such as diblock or triblock, a tapered block structure, or a random structure.
- the cross-copolymer of the present invention can have a feature that the temperature dependence of the elastic modulus is small by adjusting the composition. That, resulting et from measured boss was viscoelasticity spectrum at 1 Hertz 'is E', and the 2 X 1 0 7 P a more 2 X 1 0 9 P a or less at 0 ° C, and in 1 0 0 ° C 5 X 10 6 Pa or more 1 X 10 It is in the range of 8 Pa or less.
- the ratio of E 'at 0 ° C: E' at 100 ° C is in the range of 1: 1 to 100: 1, preferably in the range of 1: 1 to 10: 1. .
- E 'sharply decreases at approximately 1 1 0 ° C or more, equal to or less than 1 3 0 ° C in approximately 1 0 6 P a.
- the cross copolymer of the present invention can have the characteristics of moderate elongation, flexibility, good processability, and low temperature dependence of elastic modulus.
- the cross-copolymer or cross-copolymer of the present invention has high safety because it contains essentially no chlorine, and has a low environmental load even when incinerated or landfilled during waste disposal. Has advantages.
- the cross-copolymer or cross-copolymer of the present invention may contain a softening agent, a heat stabilizer, an antistatic agent, a weathering agent, an anti-aging agent, and a filling material as necessary without impairing the object of the present invention.
- Additives such as coloring agents, coloring agents, lubricants, anti-fog agents, and foaming agents can be added.
- cross-copolymer or cross-copolymer of the present invention can be suitably used as the following films, sheets, tubes and containers, and can be used as flooring materials, building materials, wall materials, wallpaper, automobile interior materials, Useful as seal materials such as packing, and synthetic leather
- the cross copolymer of the present invention has high tensile modulus, hardness, breaking strength, and appropriate elongation, and thus is useful as various packaging, packaging films, containers, and sheet tubes.
- the cloth copolymer having a transparency of 1 mm or less in sheet X having a transparency of 50% or less, preferably 30% or less, particularly preferably 10% or less, has a good dynamic property. It is particularly useful as a transparent film because of its physical properties (breaking strength, elongation, tensile modulus, permanent elongation). Depending on its composition, such a film can be used as a single-layer or multi-layer stretch packaging film having excellent elasticity and good recovery properties and excellent strength. By optimizing the composition, physical properties close to soft PVC, especially tensile elasticity Since it is possible to have an efficiency and a cutting property, it can be easily adapted to an automatic packaging machine for a soft PVC stretch film which has been widely used in the past.
- the viscoelastic spectrum is at least 80 ° C, preferably at least 90 ° C, particularly preferably at least 100 ° C.
- the viscoelastic spectrum is at least 80 ° C, preferably at least 90 ° C, particularly preferably at least 100 ° C.
- In above has a peak of tan S or 1 0 0 ° C or higher temperatures, as those E 'has a 1 0 7 or more values, because of its high heat resistance, which can be used in microwave ovens It is mainly useful as a film for food packaging.
- this film also has a shrink property, it is useful as a shrink wrapping film.
- those having a tensile modulus of preferably higher than 50 MPa, particularly preferably higher than 100 MPa can be used as films and sheets for packages. Examples of such sheets include blisters, PTP (presss t ro ro u g h c k a g e), packing sheets, heat seal films, and the like.
- the thickness of the film, sheet, or tube is not limited, but is usually not more than 3 mm and not less than 10 microns. In particular, it is preferable that the film has a thickness of 1 mm or less, 10 ⁇ m or more, preferably 200 ⁇ m or less and 10 ⁇ m or more.
- the film and sheet can be formed by any molding method and manufacturing method known to those skilled in the art. In addition, this film may be blended with other polymers, elastomers, rubber, etc., if necessary, or may be multilayered with other films, for example, ethylene-vinyl acetate resin / polyolefin resin. can do.
- stabilizers if necessary, stabilizers, antiaging agents, lightfastness improvers, UV absorbers, plasticizers, softeners, lubricants, processing aids, colorants, antistatic agents, antifoggants, antiblocking Agents, nucleating agents, foaming agents and the like can be added. These can be used alone or in combination of two or more.
- an arbitrary amount of a olefin-styrene copolymer having an arbitrary styrene content can be added to the composition to form a composition.
- a styrene copolymer having an arbitrary styrene content
- a styrene copolymer may be added.
- the olefin may be the same as or different from the olefin used in the copolymer.
- composition with an ethylene-styrene copolymer having a len content of 1 to 50 mol 0 / o, preferably 1 to 25 mol 0 / o has a controlled balance of mechanical strength, heat resistance and cold resistance. It can be used as an elastomer of initial elastic modulus, hardness, heat resistance, and transparency suitable for the application.For example, stretch packaging film, shrink packaging film, sheets, tubes, various packaging materials, containers Useful as
- the cross copolymer of the present invention or the composition thereof has high mechanical properties.
- it since it has high flexibility and high initial elastic modulus, high temperature properties (heat resistance) and hardness, which the conventional ethylene-styrene random or pseudo-random copolymer itself could not have, it replaces soft or hard vinyl chloride resin. Very useful.
- cross copolymer is a concept that includes pure “cross copolymer”.
- the aromatic vinyl compound monomer used in the aromatic vinyl compound-based polymer include styrene and various substituted styrenes such as p-methylstyrene, m-methylstyrene, 0-methylstyrene, and 0-tert-butylstyrene.
- M-t-butylstyrene M-t-butylstyrene, p-t-butylstyrene, -methylstyrene and the like, and also compounds such as divinylbenzene having a plurality of vinyl groups in one molecule. Further, a copolymer between these aromatic vinyl compounds is also used.
- the stereoregularity between the aromatic groups of the aromatic vinyl compound may be any of atactic, isotactic, and syndiotactic.
- Monomers that can be copolymerized with the aromatic vinyl compound include butadiene, iraprene, other conjugated gens, atarilic acid, methacrylic acid, and amide derivatives. Examples include ester derivatives, maleic anhydride and derivatives thereof.
- the copolymerization mode may be any of block copolymerization, tapered block copolymerization, random copolymerization, and alternating copolymerization.
- a polymer obtained by graft polymerization of the above aromatic vinyl compound to the polymer comprising the above monomer and containing an aromatic vinyl compound in an amount of 10% by weight or more, preferably 30% by weight or more may be used. Absent.
- the above-mentioned aromatic vinyl compound-based polymer needs to have a weight average molecular weight in terms of styrene of 30,000 or more, preferably 50,000 or more, in order to exhibit the performance as a practical resin.
- aromatic vinyl compound resins examples include isotactic polystyrene (i-PS), syndiotactic polystyrene (s-PS), atactic polystyrene (a-PS), and rubber-reinforced polystyrene (HIPS).
- i-PS isotactic polystyrene
- s-PS syndiotactic polystyrene
- a-PS atactic polystyrene
- HIPS rubber-reinforced polystyrene
- ABS Acrylonitrile-butadiene-styrene copolymer
- AS resin styrene-acrylonitrile copolymer
- SBS styrene-one block Z-tapered copolymers
- SEBS hydrogenated styrene-one block Z-tapered copolymers
- SBR Hydrogenated styrene-copolymer (such as hydrogenated SBR), styrene-maleic acid copolymer, Ren one imide of maleic acid copolymers can be mentioned up.
- the concept also includes petroleum resin.
- low-density polyethylene LDPE
- high-density polyethylene HDPE
- linear low-density polyethylene LLDPE
- isotactic polypropylene i-I PP
- syndiotactic polypropylene s-PP
- atactic polypropylene A-PP
- propylene-ethylene block copolymer propylene-ethylene random copolymer
- ethylene-propylene-gen copolymer EPDM
- ethylene-vinyl acetate copolymer polyisobutene
- polybutene poly
- examples thereof include a cyclic olefin polymer such as norbornene and a cyclic olefin copolymer such as an ethylene-norbornene copolymer.
- An olefin resin copolymerized with a gen such as ⁇ -gen may be used:
- a gen such as ⁇ -gen
- the above-mentioned olefin-based polymers have been developed in order to exhibit the performance as a practical resin.
- the weight average molecular weight in terms of styrene must be 10,000 or more, preferably 30,000 or more.
- Polyamides such as nylon, polyimides, polyesters such as polyethylene terephthalate, polyvinyl alcohol, SBS (styrene-butadiene block copolymer), SEBS (hydrogenated styrene butadiene block copolymer) Styrene (styrene-isoprene block copolymer), SEPS (hydrogenated styrene-isoprene block copolymer), SBR (styrene-butadiene block copolymer), hydrogenated SBR, etc.
- Block copolymers which do not fall under the category of the aromatic vinyl compound-based resin, natural rubber, silicone resin, and silicone rubber.
- a known filler can be used.
- Preferable examples are calcium carbonate, talc, clay, calcium silicate, magnesium carbonate, magnesium hydroxide, my power, barium sulfate, titanium oxide, aluminum hydroxide, silica, carbon black, wood powder, Wood pulp and the like can be exemplified.
- a conductive filler made of glass fiber, known graphite, carbon fiber, or the like can be used.
- Mineral oil-based softeners such as raffinic, naphthenic, aroma-based process oils, liquid paraffin, castor oil, linseed oil, oreffinic waxes, mineral waxes, various known esters, etc. Is used.
- the cross copolymer of the present invention can be used as a composition with another resin.
- These compositions include a composition of an aromatic vinyl compound-based polymer and a cross-copolymer, a composition of an orefin-based resin and a cross-copolymer, and a composition of an aromatic vinyl compound-based polymer and an orefin-based resin.
- the composition include a cross-copolymer as a solubilizer. Further, it can be suitably used as a composition with a filler or a plasticizer.
- a known suitable blend method can be used.
- single screw and twin screw extruders nomber mixers Melt mixing can be performed using a plastic mill, a co-kneader, or a heating port.
- melt mixing it is also possible to uniformly mix the respective raw materials using a Henschel mixer, a ribbon blender, a super mixer, a tumbler, or the like.
- the melting and mixing temperature is not particularly limited, and is generally 5 ', 100 to 300 ° (: preferably, 150 to 250 ° C).
- known molding methods such as vacuum molding, injection molding, blow molding, and extrusion molding can be used.
- composition of the cross copolymer and the aromatic vinyl compound polymer of the present invention has a composition of 1 to 99% by weight of the cross copolymer and 99 to 1% by weight of the aromatic vinyl compound resin.
- the composition can have a wide range of physical properties, from high toughness plastics to flexible elastomers, depending on the composition.
- composition of the cross-copolymerization product 1-5 0% by weight and an aromatic vinyl compound type resin 9 9-5 0% by weight as the toughness is high plastic, cross-copolymerization product 5 0-9 9 wt 0/0 and aroma
- a composition of 50 to 1% by weight of a vinyl group resin is useful as an elastomer having a wide range of mechanical properties, especially a high tensile modulus.
- an arbitrary amount of polystyrene may be added in an arbitrary amount to form a composition.
- the composition with 50 to 99% by weight of polystyrene has a higher initial modulus, hardness and heat resistance, and is useful as an impact-resistant resin.
- a cross-copolymer of polystyrene cross-copolymerized ethylene-styrene-co-copolymer can be made into a new styrene resin having impact resistance by forming a composition with polystyrene.
- the present composition is characterized by having excellent surface gloss.
- a composition with various styrene resins can be used to balance physical properties.
- a new styrene resin with excellent impact resistance or transparency can be obtained.
- a composition with a styrene-methacrylic acid ester copolymer for example, a styrene-methyl methacrylate copolymer, has high transparency, and depending on the composition, a wide range from a transparent plastic to a transparent elastomer. Cover physical properties Rukoto can.
- the composition may contain the above-mentioned "Other resins, elastomers, rubbers", plasticizers, fillers and stabilizers, anti-aging agents, light resistance improvers, ultraviolet absorbers, softeners, lubricants , Processing aids, coloring agents, antistatic agents, antifogging agents, antiblocking agents, crystal nucleating agents, foaming agents, and the like.
- composition of the cross-copolymerization product and Orefi emissions based polymer of the present invention has a composition of 1 to 50% by weight of the polymer and 99 to 50% by weight of the olefin resin.
- This composition can control the balance of mechanical strength possessed by the polyolefin, and is suitable for general-purpose applications such as films and containers, and also for automobile parts such as bumpers and instrument panels, refrigerators and washing machines. It can be used for housing parts of home appliances. In addition, it is possible to improve the printability and colorability of the polyolefin resin.
- a composition with polypropylene has improved impact resistance and is well balanced with various mechanical properties, such as flexural strength and flexural modulus.
- various mechanical properties such as flexural strength and flexural modulus.
- the surface hardness is less reduced, that is, the surface is less scratched.
- the composition may contain, as necessary, the above-mentioned "Other resins, elastomers, rubbers", plasticizers, fillers and stabilizers, antioxidants, light resistance improvers, ultraviolet absorbers, softeners, Lubricants, processing aids, coloring agents, antistatic agents, antifogging agents, antiblocking agents, crystal nucleating agents, foaming agents and the like can be used.
- Aromatic vinyl compound polymer, olefin polymer, cross-copolymer composition >
- the cross-copolymer of the present invention can be suitably used as a compatibilizer or a composition of an aromatic vinyl compound-based resin and an olefin-based resin.
- Compatibilizer when used as a composition, 1-9 8 weight percent of the weight of the overall cross-copolymerization product, the total Orefi down resin and an aromatic vinyl compound 'based resin 9 9-2 wt 0/0 ( However O, Le off fin-based resin, an aromatic vinyl compound type resin is a composition of 1 weight 0/0 or more) Used.
- the cross-copolymer is 1 to 50% by weight of the total weight, and the total of the olefin resin and the aromatic vinyl compound resin is 99 to 50% by weight (however, the olefin resin, each 1 wt% or more group vinyl compound resin), most preferably 1 to 3 0 wt by weight of the overall cross-copolymerization product 0 /.
- the total amount of the olefin resin and the aromatic vinyl compound resin is 99 to 70% by weight (however, the olefin resin and the aromatic vinyl compound resin are each used in a composition of 10% by weight 96 or more).
- the composition may contain the above-mentioned "Other resins, elastomers, rubbers", plasticizers, fillers and stabilizers, anti-aging agents, light resistance improvers, ultraviolet absorbers, softeners, lubricants , Processing aids, coloring agents, antistatic agents, antifogging agents, antiblocking agents, nucleating agents, foaming agents, and the like.
- the composition comprises 90 to 1% by weight of a filler, 10 to 99% by weight of a cross-copolymer, preferably 75 to 25% by weight of a filler, and 25 to 75% by weight of a cross-copolymer. It has the following composition.
- a filler is effective in imparting flame retardancy, improving surface hardness and elastic modulus, imparting static electricity, and improving heat resistance, and is useful as a building material, a floor material, and a wall material.
- the composition may contain, as necessary, the above-mentioned “Other resins, elastomers, rubbers”, plasticizers and stabilizers, antioxidants, light resistance improvers, ultraviolet absorbers, softeners, lubricants, and processing.
- Auxiliary agents, coloring agents, antistatic agents, antifogging agents, antiblocking agents, nucleating agents, foaming agents and the like can be used.
- the composition comprises 50 to 1% by weight of a plasticizer, 50 to 99% by weight of a cross-copolymer, preferably 30 to 1% by weight of a plasticizer, and 70 to 9.9% by weight of a cross-copolymer. It has the following composition.
- these softeners and plasticizers may be added during processing in an extruder or kneading machine, or may be added to the copolymer in advance during the production of the copolymer of olefin and styrene. You can leave it.
- the composition may contain, as necessary, the above-mentioned fillers and stabilizers, antioxidants, lightfastness improvers, ultraviolet absorbers, softeners, lubricants, processing aids, Coloring agents, antistatic agents, antifogging agents, antiblocking agents, crystal nucleating agents, foaming agents and the like can be used.
- a filler composition having well-balanced physical properties and workability can be obtained by adding a plasticizer.
- a resin composition comprising 30 to 98% by weight of the cross-copolymer, 70 to 2% by weight in total of the plasticizer and the filler is preferable.
- plasticizer and filler are each 1% by weight or more.
- a cross-copolymer of the present invention preferably an ethylene-styrene-divinylbenzene-based cross-copolymer, or a polymer having a radical-crosslinkable monomer (for example, butadiene, isoprene, etc.) unit in the cross chain;
- a cross-copolymer consisting of an ethylene-styrene-divinylbenzene-based cross-copolymer having a (block, random, tapered random) copolymer of these monomers and styrene as a cross chain is known. It is possible to crosslink by the method described above. These can be elastomers with further improved high temperature mechanical properties such as breaking strength, tensile modulus and compression set properties.
- thermoplastic resin examples include an olefin-based resin, an aromatic vinyl compound-based resin, “other resins, elastomers, and rubbers”. In this case, it is preferable to crosslink a composition comprising 1 to 100% by weight, preferably 30 to 100% by weight of the cross copolymer.
- Examples of the rubber include natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, chloroprene rubber, acrylonitrile-butadiene rubber, and the like.
- cross-copolymer of the present invention is blended with another resin such as a crystalline resin, and is subjected to dynamic vulcanization (dynamically heat treatment) in the presence of an organic peroxide-phenol resin crosslinking agent. It is possible to crosslink).
- Examples of the crystalline resin that is used herein include a homopolymer of a one-year-old olefin having 2 to 20 carbon atoms, or a copolymer thereof.
- crystalline Orefui down resin an ethylene homopolymer, propylene alone polymer or a propylene content of 5 0 mole 0/0 or more propylene scratch.
- One year old refin copolymers are particularly preferred.
- the above-mentioned crystalline resin can be used alone or in combination.
- blends of the cross-copolymers of the present invention having different styrene contents and compositions can be used. These may be reacted with the main component in addition to the dynamic vulcanization reaction, or may be used as a mere blend material after the reaction is completed.
- the crosslinked product of the cross copolymer of the present invention (including the dynamically vulcanized product) is superior to known crosslinked products of ethylene-styrene copolymer in mechanical properties such as tensile modulus and breaking strength. Also, heat resistance and mechanical properties at high temperatures are improved. Also, compared to the conventional crosslinked polyolefin-based elastomer, it has the feature of being superior in printability, mechanical strength and compatibility with various resins.
- the crosslinked cross-copolymer of the present invention includes, in addition to a crosslinking agent, a crosslinking accelerator, a crosslinking accelerator, a co-crosslinking agent, a dispersant, a softener, an anti-adhesive agent, an anti-scorch agent, a filler, and a pigment.
- a foaming agent and the like can be added.
- crosslinking agent examples include a peroxide crosslinking agent and a sulfur crosslinking agent, and these can be used alone or in combination of two or more.
- Peroxide crosslinking agents include t-butyl peroxide, di (t-butyl) peroxide, t-butyl butoxydiisopropyl carbonate, t-butyl, cumyl peroxide, t-butyl butoxybenzoate, dik Milperoxa And benzoyl peroxide and the like.
- the amount of the crosslinking agent is not particularly limited, but is preferably from 0.01 to 10 parts by weight based on 100 parts by weight of the resin composition. If the added amount of the crosslinking agent is small, crosslinking becomes insufficient, and if the added amount is excessive, unreacted crosslinking agent remains, resulting in deterioration of physical properties and the like.
- crosslinking accelerator examples include guanidine derivatives, thioureas, xanthates, dithioammonium salts, aldehyde ammonium compounds, thiuramusulfides, thiazole derivatives, sulfenamide compounds, and the like. Can be.
- the amount of these crosslinking accelerators is not particularly limited, but is preferably 10 parts by weight or less based on 100 parts by weight of the resin composition. Excessive addition results in various deteriorations in physical properties.
- co-crosslinking agent examples include divinylbenzene, sulfur, p-quinondioxime, p, p-dibenzoylquinondioxime, dinitrosobenzene, N-methyl-N'-4-dinitrazoaniline, ethylene glycol dime Tactylate, trimethylolpropane dimethacrylate, maleic anhydride, and the like.
- the amount of the co-crosslinking agent is not particularly limited, but is preferably 20 parts by weight or less.
- Examples of the resin that can be blended into the crosslinked product of the present invention include the aromatic vinyl compound-based resin and the olefin-based resin, but are not particularly limited to thermoplastic resins, thermosetting resins, and the like.
- a non-mixer a Brabender, a lab plastic mill, a 21-roll, a roll, a single-screw extruder, a twin-screw extruder, etc.
- a system either a batch system or a continuous system is possible.
- a hensile mixer a super mixer, a tumbler, or the like.
- Kneading and cross-linking can be performed independently or simultaneously (dynamic cross-linking or dynamic vulcanization).
- the temperature range of these kneading and crosslinking processes is not particularly limited, but is preferably 50 to 350 ° C, more preferably 100 ° (: to 280 ° C).
- the method for forming the crosslinked body of the present invention is not particularly limited, and examples thereof include extrusion molding, injection molding, calendar molding, compression molding, blow molding, foam molding, and transfer molding.
- crosslinked cross-copolymer of the present invention is not particularly limited, and examples thereof include exterior parts for automobiles, interior parts for automobiles, parts for home electric appliances, foam materials, packaging containers, gaskets, seal materials, and the like. be able to.
- the molded article of the present invention can be subjected to secondary processing as needed.
- secondary processing include machining, bonding, printing, painting, surface treatment, and application of an anti-fogging agent.
- the cross copolymer of the present invention can be suitably used as a foam (foam material).
- a method for producing the foam a known production method can be used.
- the cross-copolymer of the present invention and a blowing agent, a crosslinking agent and other additives, if necessary, are heated and melted, and the mixture is heated and compressed while being extruded, and then the pressure is reduced.
- Foaming and foaming The foaming agent and, if necessary, the radical crosslinking agent may be added either before or after the polymer is heated or melted.
- the blending can be performed by a known method, for example, an extruder, a mixer, a blender or the like.
- Crosslinking may be carried out by radiation (electron beam, gamma ray, etc.) in addition to the above-mentioned method by adding a crosslinking agent.
- the foam material composed of the cross-copolymer can be prepared in a wide range of physical properties according to the intended use. is there.
- a foam material covering a wide range of physical properties from a relatively hard foam material such as polystyrene to a flexible foam material made of polyurethane or polyolefin.
- the foam material is obtained by adding the above-mentioned aromatic vinyl compound-based resin, olefin-based resin, “other resin, elastomer, rubber” to the cross-copolymer.
- Etc. can be made from blended ones. Examples include foam materials made of blends with LLDPE and polystyrene resins. In this case, the cross-copolymer is 1 to 100% by weight, preferably 30 to 100% by weight. / 0 containing the resin composition foam used.
- the method for producing the foam of the present invention is not particularly limited, and examples thereof include known techniques such as a method of adding a foaming agent such as an inorganic or organic chemical foaming agent and a physical foaming agent.
- a foaming agent such as an inorganic or organic chemical foaming agent
- a physical foaming agent such as an inorganic or organic chemical foaming agent.
- foams are described in, for example, "Plastic Foam Handbook" (published by Nikkan Kogyo Shimbun, published in 1973).
- inorganic blowing agent examples include sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, ammonium nitrite, azide compound, sodium borohydride, metal powder and the like.
- Organic foaming agents include azodiphenol amide, azobisformamide, azobisisoptyronitrile, barium azodicarboxylate, N, ⁇ 'nitronitropentapentamethylenetetramine, ⁇ , ⁇ , and monophenylamine.
- Examples of the physical foaming agent include hydrocarbons such as pentane, butane, and hexane; halogenated hydrocarbons such as methyl chloride and methylene chloride; gases such as nitrogen and air; trichlorofluoromethane; and dichlorodifluoro. Rometan, Triclo mouth Trifluorene And fluorinated hydrocarbons such as chlorodifluoroethane and nitrofluorofluorocarbon.
- microcapsule type foaming agents can also be exemplified.
- the state of the cells present in the foam of the present invention such as closed cells, open cells, and a mixed state thereof.
- the shape of the cells is not particularly limited, such as spherical, dodecahedral, and amorphous. .
- the foam of the present invention can be crosslinked by a chemical method such as electron beam, radiation, peroxide or the like, if necessary. At that time, a crosslinking auxiliary agent, a co-crosslinking agent or the like may be used.
- oxide crosslinking agents examples include 1,1-bis- (t-butyloxy) -13,3,5—trimethylcyclohexane, dicumyloxide, t—butylcumyloxide, n— Butyl-4,4-monobis (t-butylvaloxy) node, a, a 'Bis (t-butylvinyloxy) -1-m-diisopropylbenzene, 2,5-dimethyl-1,2,5-di (T-butylperoxy) hexane, benzoyl peroxide, m-toluoyl peroxide, t-hexyloxy 2 -ethylhexane, t -butylbutyloxy 2 -ethylhexane , T-butyrno ,.
- Examples thereof include 1-hydroxyisobutyrate, 1-cyclohexyl-1-methyl-resyl-peroxy-12-ethyl-hexanoate and the like.
- the amount of the crosslinking agent to be added is not particularly limited, but is preferably 0.001 to 30% by weight.
- Crosslinking aids include divinylbenzene, diarylbenzene, divinylnaphthalene, polyethylene dimethacrylate, trimethylolprono, trimethacrylate, 1,2,4-triaryltrimethyl.
- Illustrative examples include a reate, a 1,9-nonanediol dimethacrylate, a polyene compound, and the like.
- the nucleating agents applicable to the present invention include talc, calcium carbonate, and magnesium carbonate.
- organic nucleating agents such as phosphates, phenols, amines, etc.
- thermoplastic resin examples include an olefin resin, an aromatic vinyl compound resin, and a rubber.
- Examples of the rubber include natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, chloroprene rubber, acrylonitrile-butadiene rubber, and the like.
- a dispersant a softener, an anti-tackiness agent, a filler, a pigment, and the like can be added to the foam of the present invention.
- the molding method of the obtained foam sheet, film, etc. such as extrusion molding, injection molding, blow molding, and the like, and sheet film, etc. can be formed into containers, etc. by thermoforming, compression molding, etc. It is possible. In addition, embossing, printing, and the like can be performed.
- the present cross copolymer is characterized by having excellent printability.
- the foam of the present invention can be used as a container for building materials such as flooring materials, wall materials, and wallpaper, interior and exterior parts for automobiles, electric material parts, gaskets, cushioning materials, foods, and the like.
- the cross-copolymer composition, cross-linked product, and foam of the present invention are useful as films, sheets, tubes, containers, and the like, similarly to the cross-copolymer.
- it can be suitably used as a building material, a wall material, a wallpaper, and a floor material.
- building materials such as a building material, a wall material, a wallpaper, and a floor material.
- they When used in these applications, they have high mechanical strength and elongation, and they can arbitrarily change mechanical properties such as elastic modulus from the area similar to polyolefin to the area of soft, hard, and hard.
- High heat resistance, hardness is the basis of its usefulness .
- the fact that the filler can be filled at a high content while maintaining the physical properties to a certain extent means that, in these applications, it can be particularly flame-retardant, and is of great value.
- the olefin-styrene cross-copolymer of the present invention can be produced according to the above-mentioned method for producing an olefin-styrene cross-copolymer.
- the amount of diene used in the coordination polymerization step is at a concentration in the solvent of the polymerization solution, 0.5% by volume or less, preferably 0.1 vol 0/0 or less, most preferably 0. 0 5 vol 0/0 below 0. 0 0 0 5 vol% or more. If the coordination polymerization step is carried out at a gen concentration higher than this, many crosslinked structures of the polymer will be formed during the polymerization, causing gelation, etc., or the cross-copolymerized polymer finally obtained through the cross-forming step It is not preferable because processability and physical properties deteriorate.
- the coordination polymerization step Orefi down one diene copolymer obtained in Gen content to zero. 0 0 0 1 mole 0/0 than the 3 mol 0/0 or less, the balance is Orefi down, Zhen content 0.
- the coordination polymerization catalyst used in the coordination polymerization step in the production of the ore- gen-based cross-copolymer the single-site co-ordination polymerization catalyst used in the above-mentioned method for the production of the ore- fin-styrene- gen-based cross-copolymer is used Can be done.
- a polymerization catalyst comprising a soluble transition metal catalyst represented by the above general formula (1) and the following general formula (2) and a cocatalyst is used.
- a polymerization catalyst comprising a soluble transition metal catalyst represented by the above general formula (1) and a cocatalyst is used.
- C p is an unsubstituted or substituted cyclopentaphenanthryl group, an unsubstituted or substituted benzoindenyl group, an unsubstituted or substituted cyclopentagenenyl group, an unsubstituted or substituted indenyl group, or unsubstituted Or a group selected from substituted fluorenyl groups.
- Y ' has a bond to Cp and Z, and also has a hydrogen or a methylene group, a silylene group, an ethylene group, an germylene group, or a boron residue having a hydrocarbon group having 1 to 15 carbon atoms. It is.
- the substituents may be different or the same.
- Y and may have a cyclic structure.
- ⁇ is a ligand containing nitrogen, oxygen or y ⁇ , a ligand coordinating to M ′ with nitrogen, oxygen or y ⁇ ⁇ and having a bond with Y ', and further having hydrogen and a substituent having 1 to 15 carbon atoms. It is.
- M ' is zirconium, hafnium, or titanium.
- X and are hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkyl aryl group having 8 to 12 carbon atoms, and a carbon atom having 14 to 14 carbon atoms.
- ⁇ is an integer of 1 or 2.
- the orrefengen-based cross-copolymer has good low-temperature properties and good compatibility with various resins, although its mechanical properties are inferior to the corresponding orefin-styrene-gen-based cross-copolymer. Therefore, the use of the above-mentioned olefin-styrene-gen-based cross-copolymer, that is, cross-copolymer and aromatic vinyl compound
- the present invention is useful as a composition with an organic polymer, a composition of an olefin polymer, or a composition with an aromatic vinyl compound polymer or an olefin polymer. Further, the filler composition, the plasticizer composition, the crosslinked product, and the foam can be suitably used. Syndiotactic Polystyrene Cross Copolymerization Method for the Production of Tylene-Styrene-Gene Cross Copolymer>
- the present invention further comprises a coordination polymerization step using a polymerization catalyst comprising the transition metal compound represented by the general formula (1) and the co-catalyst, to obtain a copolymer of an olefin-styrene-one-gen copolymer, preferably an ethylene-styrene copolymer.
- a styrene-one copolymer or an ethylene-one copolymer, preferably an ethylene- ⁇ -olefin-gen copolymer is synthesized, and syndiotacticity is obtained with or without styrene monomer.
- Syndiotactic polystyrene cross-copolymerized olefin-styrene-gen-cross cross-copolymer or syndoxy characterized in that the cross-forming step is carried out by coordination polymerization using a catalyst for polystyrene polymerization.
- This is a method for producing an otact polystyrene cross-copolymerized orange-gen cross copolymer.
- the transition metal compound preferably used in the method for producing a syndiotactic polystyrene cross-copolymerized polyethylene cross-copolymer or a syndiotactic polystyrene cross-copolymerized oxygen cross-copolymer is preferred.
- the general formula (1) it is particularly preferable that at least one of ⁇ and ⁇ is an unsubstituted or substituted cyclopentaphenanthryl group or an unsubstituted or substituted benzylindenyl group.
- a polymerization catalyst comprising the transition metal compound represented by the general formula (1) and a co-catalyst in the coordination polymerization step, it is possible to commercialize the olefin-styrene-gen copolymer or the olefin-gen copolymer. It can be produced with suitable significantly higher activity.
- a sufficient amount of gen for cross-linking can be copolymerized in the main chain, so that the residual gen concentration in the resulting polymerization solution is extremely low, and Can be used in the crossing process You. Therefore, it is very economical as a manufacturing method. Since the residual gen concentration in the polymerization solution is low, the obtained cross copolymer has a very low degree of crosslinking and a low gel component, and can have good mechanical properties and workability.
- the amount of gen used is preferably 1/300 or less (molar ratio) of the amount of styrene used, and more preferably 1Z500 or less.
- the kind of monomer such as olefin and gen used is the same as described above.
- ethylene or a mixture of ethylene and a carbon having up to 3 to 8 carbon atoms is used as the olefin, and divinylbenzene is used as the gen.
- the polymerization method of the coordination polymerization step or the cross-forming step (coordination polymerization) of the present invention the same ones as those in the coordination polymerization step are used.
- a known catalyst can be used as the catalyst for syndiotactic polystyrene polymerization used in the cross-forming step of the present invention.
- a known catalyst can be used.
- a polymerization catalyst comprising a transition metal compound represented by the following general formula and a cocatalyst is used.
- L is a cyclopentagenenyl group, an alkyl group, an alkyl aryl group, having 1 to 30 carbon atoms, two adjacent carbons of which may have a 4- to 8-membered ring. It is a substituted cyclopentagenenyl group having an arylalkyl group as a substituent.
- the substituent of the cyclopentagenenyl group may contain 1 to 3 silicon, boron, nitrogen, and / or nitrogen atoms, if necessary.
- L include a cyclopentagenenyl group, a pentamethylcyclopentagenenyl group, an indenyl group, a 2-methylindenyl group, a 1,2,3-trimethylindenyl group, and a 4-phenyl-1-indenyl group.
- X includes a halogen such as chlorine and fluorine, an alkoxy group such as a methoxy 'group, hydrogen, a dialkylamide group such as a dimethylamide group, and a benzyl group.
- M is titanium, zirconium, Hafnium, preferably titanium.
- syndiotactic structure in the syndiotactic polystyrene cross-copolymerized olefin-styrene-gencloth copolymer or the syndiotactic polystyrene cross-copolymerized olefin-gen cross copolymer obtained by the present invention.
- the weight-average molecular weight is 1000 to 500,000, preferably 10,000 to 300,000, and the molecular weight distribution is 5 or less, preferably 3 or less, 1 . 2 or more.
- the olefin-styrene-gen copolymer or the olefin-gene copolymer used can be obtained in the same manner by using the transition metal compound represented by the general formula (1) and the cocatalyst.
- the composition and molecular weight of the used olefin-styrene-gen copolymer are the same as those of the above-mentioned olefin-styrene-gen copolymer.
- the copolymers obtained in each of the examples and comparative examples were analyzed by the following means.
- 13C-NMR spectrum was measured using T-MS with a heavy solvent or heavy 1,1,2,2-tetrachloroethane solvent using heavy-mouthed form solvent or heavy 1,1,2,2-tetrachloroethane solvent using ⁇ -500 manufactured by JEOL Ltd. .
- the measurement based on TMS is as follows. First, the shift value of the center peak of the triplet 13 C-N 'MR peak of heavy 1,1,2,2-tetrachloroethane was determined based on TMS. 'The shift value of the triplet center peak of heavy 1, 1, 2, 2, 2—tetrachloroethane is 73.89 pD m Met.
- the copolymer was dissolved in 1,1,2,2-tetrachloroethane and the 13C-NMR was measured.
- the peak shift value was calculated for the 1,1,2,2-tetrachloroethane. The calculation was performed assuming that the triplet center peak was 7 3.89 ppm. The measurement was performed by dissolving 3% by weight / volume of the polymer in these solvents.
- the 13 C-NMR spectrum measurement for quantifying the peak area was performed by the proton gate decoupling method with NOE eliminated, and the pulse width was 45. Using a pulse, the repetition time was 5 seconds as a standard.
- the measurement was carried out under the same conditions except that the repetition time was changed to 1.5 seconds.
- the peak area quantitative value of the copolymer coincided with the case of the repetition time of 5 seconds within the measurement error range.
- the styrene content in the copolymer was determined by 1 H-NMR, and the equipment used was “-500” manufactured by JEOL Ltd. and “AC-250” manufactured by BRUCKER. Using heavy 1,1,2,2-tetrachloroethane and TMS, the peak derived from phenyl group proton (6.5 to 7.5 ppm) and the proton peak derived from alkyl group (0 to 0 ppm) were used. (8 to 3 ppm).
- the gen (divinylbenzene) content in the copolymer was determined by 1 H-NMR.
- a weight average molecular weight in terms of standard polystyrene was determined using GPC (gel permeation chromatography).
- the copolymer soluble in THF at room temperature was measured using HLC-820, manufactured by Tosoh Corporation, using THF as a solvent.
- the copolymer insoluble in THF at room temperature was measured at 145 ° C using ortho-dichlorobenzene as a solvent and an HLC-8121 device manufactured by Tosoh Corporation.
- the DSC measurement was performed using a DSC 200 manufactured by Seiko Denshi Co., Ltd. at a heating rate of 10 ° C./min under a stream of N 2 .
- the film-shaped sample is compliant with JIS K-6251, the film is pressed into a No. 1 type test piece shape, and a Shimadzu AGS-100 D-type tensile tester is used to pull the sample at a speed of 50%. It was measured at 0 mm / min.
- the strain recovery value in the bow I tension test was measured by the following method.
- the elastic recovery was determined as follows.
- the hardness was determined according to the JIS K-7215 plastic durometer-hardness test method for the type A and D durometers.
- Vicat softening point>' Prepare a 4 mm thick sheet by the hot press method and test 1 O mm X 1 O mm The specimen was cut. Measured in accordance with JIS K-7206 using Toyo Seiki HDT & VSPT tester S3-FH, load was 320 g, initial temperature was 40 ° C, and heating condition was 50 ° CZ hr.
- Transparency was measured by forming a sheet to a thickness of 1 mm by the hot press method (temperature 200 ° C, time 4 minutes, pressure 50 kg / cm 2 G), and according to JISK-7105 plastic optical property test method, Nippon Denshoku Total light transmittance and haze were measured using a turbidity meter NDH2000 manufactured by Kogyosha.
- a 1/4 inch bar was molded, a notch was inserted, and the temperature was determined at 23 ° C according to the JIS K-7110 hardness test method for hard plastics.
- 1 ⁇ 4 inch bars were molded and determined at 23 ° C according to the bending test method of JIS K-7203 hard plastic.
- Tables 1 and 2 show comparative production examples and analysis results of the ethylene-styrene copolymer used as comparative examples.
- the divinylbenzene used in the following polymerization has a purity of 80% manufactured by Aldrich.
- the amount of divinylbenzene becomes 1Z160 of the amount of styrene in a molar ratio. If 1 m1 is used for 800 ml of styrene, it will be 1/1270.
- SE 8 is a mixture of 5 batches polymerized under the same conditions
- Polymerization was carried out using an autoclave with a capacity of 10 L, a stirrer and a heating and cooling jacket.
- Polymerization was carried out under the conditions shown in Table 1 using the same apparatus and procedure as in Example 1. Ethylene was purged when the consumption of ethylene reached approximately 80 L (polymerization time: 30 minutes) under standard conditions. A part (about 800 ml) of the polymerization solution was taken out, and 25 g of a styrene-ethylene-ethylene copolymer (polymer 1-2-A) was recovered by a methanol precipitation method.
- Polymerization was performed using a polymerization vessel with a capacity of 150 L, a stirrer and a heating and cooling jacket. 69 L of dehydrated cyclohexane, 3 L of dehydrated styrene, and 7.5 ml of divinylbenzene were charged, and heated and stirred at an inner temperature of 50 ° C. Triisobutyl aluminum 84 mmo 1, methylalumoxane ( PMA 0-3) manufactured by Tohoku Sozo Co., Ltd. was added by 84 mm 01 based on A1.
- the catalyst rac—dimethylmethylenebis (4,5-benzene) was removed from the catalyst tank installed on the polymerization vessel.
- (11-Indenyl) 84 ml of zirconium dichloride and about 100 ml of a toluene solution of 2 mm 01 of triisobutylaluminum were added to the polymerization vessel. Heating started immediately, and cooling water was introduced into the jacket. The internal temperature was increased to a maximum of 55 ° C, and thereafter maintained at about 50 ° C, and polymerization was carried out for 50 minutes while maintaining the pressure at 1.0 MPa.
- the gas phase of the polymerization reactor was purged several times with nitrogen.
- the temperature inside the polymerization vessel was heated until it reached about 70 ° C., and 3 L of styrene was added.
- the n-butyllithium hexane solution was converted to butyllithium from a tank placed on the polymerization canister, and 210 mm01 was added.Anion polymerization was started, and the mixture was stirred at 70 ° C for 30 minutes.
- the polymer was recovered by the crumb forming method as described above. Including a dispersant (pull mouth nick: trade name) that stirred the polymerization solution vigorously It was thrown into heated water at 97 ° C over 1 hour.
- Example 10 butadiene was added in the cross-forming step, and in Example 16, isoprene was added to perform polymerization. The addition of these gens was performed after the ethylene was released and before the addition of butyllithium.
- Example 15 rac-dimethylmethylenebis (4,5-benzo-11-indenyl) zirconium dichloride was replaced by rac-dimethylmethylene (4,5-benzo-11-indenyl). ) (1-indenyl) zirconium dichloride was used.
- Table 3 summarizes the polymerization conditions of each example. Table 3 Polymerization conditions
- MAO P PMAO
- MAO solvent T toluene C; cyclohexane-notyllithium ⁇ ; ⁇ -butyllithium s; sec-butyllithium Bd; butadiene IP; isoprene
- Table 4 shows the analysis results of the polymers obtained in the examples and comparative examples.
- polymer A in each example refers to the copolymer obtained in the coordination polymerization step
- polymer B refers to the copolymer obtained in the crossing step (anion polymerization step). Show.
- 1A described in ⁇ of the polymer indicates the polymer recovered by extracting a part of the polymerization solution obtained in the K-position merging step, and 1B indicates the polymer obtained in the cross-forming step.
- B is the weight of the polymer obtained in the crossing step.
- the glass transition point corresponding to the styrene homopolymer overlaps with the melting point beak and is not clear.
- 1A described in ⁇ of the polymer is a polymer '3 ⁇ 4: a part of which is extracted from the polymerization solution obtained in the coordination polymerization step and recovered, and
- One B value is the weight of the polymer obtained in the crossing step.
- Butadiene is also contained at 1.5moI%, (calculated from 1H-NMR spectrum)
- the glass transition point corresponding to the styrene homopolymer overlaps with the 3 ⁇ 4 point beak and is not clear.
- the styrene-ethylene-ethylene copolymer preferably used in the present invention is a structure represented by the following general formula, which is a typical structure derived from styrene and ethylene, in an arbitrary ratio. It is a copolymer that can be included. In addition to the following structures, it has a structure derived from a small amount of genunitt.
- Ph represents a phenyl group
- X represents the number of repeating units, and represents an integer of 2 or more.
- Ethylene unit or a structure consisting of an ethylene unit and two head units of styrene unit.
- the above peaks may have slight shifts, microstructures of peaks, or peak shoulders.
- Table 5 shows the S and m values obtained in the examples. In addition, it shows the gen content determined by 1 H-NMR. . Table 5 Results of analysis of styrene-ethylene-ethylene copolymer Example St content Divinylbenzene content ⁇ value m value
- Example II-A 8.3 0.04 ⁇ 0.036> 0.95
- Example 2 2-A 9.7 0 .05 ⁇ 0.004 6> 0.95
- Example 3 3-A 9.6 0.10 ⁇ 0.06 7> 0.95
- Example 4 4 -A 1 2.2 0 .05 ⁇ 0.04 9> 0.95
- Example 5 5-A1 1.0 0.08 ⁇ 0 .06 8> 0.95
- Example 7 7 -A 1 2.80.05 ⁇ 0.04 7> 0.95
- Example 1 3 1 3—A 1 0.3 About 0.17> 0.95
- Solvent fractionation of the polymers obtained in the crossing step of each of the examples and comparative examples was performed.
- solvent separation was performed in the following procedure. 1 to 2 g of the cross-linked copolymer was precisely weighed and dissolved in a small amount of heated and an appropriate amount of toluene.
- the cross-copolymer of this example can be substantially dissolved in hot toluene at about 100 ° C.
- the toluene solution was slowly added dropwise to a vigorously stirred 100-fold solution of cold acetone, and the acetone-insoluble matter was filtered and vacuum-dried (80, until the weight change disappeared).
- Polymer C of each of Examples and Comparative Examples which was an insoluble fraction was obtained.
- Table 4 shows the analysis results of polymer A obtained in the coordination polymerization step and polymer B obtained in the cross-forming step (anion polymerization step).
- FIG. 3 shows the aromatic proton region of the polymer 14-A obtained in Example 14, and
- FIG. 4 shows the aromatic proton region of the 1H-NMR spectrum of the polymer 14-B.
- polymer A a peak derived from the styrene unit of the ethylene-styrene-gen copolymer obtained by coordination polymerization is observed.
- polymer B another peak derived from the styrene unit of the atactic polystyrene chain is observed. Observed clearly.
- the molecular weight and the molecular weight distribution of the polymer B obtained in the cross-linking step are increased as compared with the polymer A obtained in the coordination polymerization step.
- a GPC peak having a narrow molecular weight distribution (1.0 to 1.3) is also observed. This indicates the presence of polystyrene homopolymer due to anion-riving polymerization.
- Table 6 summarizes the results of solvent fractionation and the results of analysis of the acetone-insoluble fraction (polymer-41 (, 7_C, 13-C, 14-C)).
- Atactic take PS homopoly observed in polymer B obtained in the crossing process The sharp GPC peak of the polymer disappears in Polymer C, and Polymer C, which is an acetone-insoluble fraction obtained by solvent fractionation, is a fraction substantially free of styrene homopolymer.
- the polymer A-B (Polymer 4-B, 7-B, 13-B, 14-B) obtained in the cross-linking process contains a maximum of 15 to 25% by weight of acetone-soluble fraction. (Atactic polystyrene)
- the glass transition point corresponding to the styrene homopolymer overlaps with the melting point peak and is not clear
- FIG. 5 shows the aromatic proton region of the 1 H—NMR spectrum of polymer 14 C obtained in Example 14.
- polymer A the force of observing only the protons derived from the styrene unit of the random copolymer obtained by coordination polymerization
- polymer C similarly to polymer B, the peak derived from the styrene unit in the polystyrene chain are clearly observed.
- polymer C has an increased molecular weight and molecular weight distribution compared to the corresponding polymer A.
- the styrene content of polymer C was measured by 1 H—NMR.
- the styrene content is lower than that of polymer B (corresponding to the amount of atactic polystyrene homopolymer removed by solvent fractionation), and is also higher than that of the corresponding polymer A. This increase in styrene content corresponds to the amount of polystyrene in the cross-linked polymer chain.
- B obtained in the cross-forming step of each Example is a composition containing a copolymer of styrene-ethylene-divinylbenzene copolymer with polystyrene and a polystyrene homopolymer (cross-copolymer). It can be seen that it is. In contrast, in Comparative Examples 1 and 2, in which divinylbenzene was not used in the coordination polymerization step, no significant increase in the molecular weight of polymer B was observed compared to polymer A.
- polymer B Although the styrene content of polymer B increased, the styrene content of polymer C in the acetone-insoluble fraction after solvent fractionation was almost the same as polymer A, and polymer B obtained in the cross-linking step was It is considered to be a mixture of styrene-ethylene copolymer and atactic polystyrene.
- the composition of cross-copolymer 7-B was determined from the mass balance (Masbara, Isis) calculated from the average molecular weight and the insoluble content of acetate.
- Tables 7, 8, and 9 show the physical property test results of the polymers obtained in each of the examples and comparative examples.
- Example 7 Polymer type 1 B 2-B 2-A 3-B 4-B 5-B 6- B 7-B 8— B Elongation at break (%) 540 42 7 540 453 400 292 550 3 00 4 5 7 Yield point strength (MPa) Yield point is yield point, yield point is yield point, yield point is yield point , Yield point, Yield point, Yield point, Yield point is not observed Observed Not observed Not observed Not observed Not observed Not observed Not observed Not observed Not observed Not observed Not observed Not observed Not observed Not observed Not measured 0 34. 5 42. 0 25. 0 39. 4 3 5. 0 3 9.3 Tensile modulus 4 1. 7 1 66 27. 0 1 4 1 1 88 440 98. 4 24 1 34. 4 (P a)
- Example 1 4 Polymer type 9-1 B 1 0-B 11-B 12-B 13-A 13-B 14-A 14-B Elongation at break 3 20 400 300 4 1 0 577 440 6 1 7 3 1 3
- Yield point strength Yield point, Yield point, Yield point, Yield point, 1 large, 1 S, 1 large, s, n Yield, 1 ?,
- Blend 1 50% by weight of ethylene-styrene copolymer (SE-1) and 50% by weight of polystyrene (GP-1) were kneaded with a brabender Comparative Example 6
- Blend 2 Ethylene-styrene copolymer ( Kneading 50% by weight of SE-2) and 50% by weight of polystyrene (GP-1) with Brabender.
- the polymer B (cross-copolymer) obtained in the cross-linking step has a lower initial elastic modulus and a lower elastic modulus than the polymer A (ethylene-styrene-diene copolymer) obtained in the coordination polymerization step. It can be seen that the 0%, 300% modulus, Shore hardness, and pit softening point (heat resistance) are remarkably improved. In Examples 4 and 7 in which the amount of divinyl benzene used was optimized, the mechanical strength (rupture strength) was further improved, and the elongation showed a value of 300% or more.
- the polymer C (aceton-insoluble fraction) was hot-pressed (180 ° (:, 50 kg / cm 2)) to form a 0.1-0.2 mm thick film.
- the test piece was cut in the shape of a No. 1 test piece and subjected to a tensile test in the same manner, and the results were compared with the polymer A obtained in the coordination polymerization step, the copolymer obtained in the cross-forming step, and the polymer. (Table 10)
- the mechanical strength cannot be simply compared due to the difference in the measurement method (test piece thickness and shape) from those of Polymers A and B, but the polymer A obtained in the coordination polymerization step and Comparative Examples It shows that the material has a higher tensile modulus and a higher elongation of more than 200%. Due to the film, the vicat softening point could not be measured, but the polymer 41 (:, 7-C has a high Tg (90-100 ° C) due to the cross-chain polystyrene structure) It is clear that the heat resistance has been improved.
- Example 14 has relatively good transparency
- Polymer B obtained in Comparative Examples 1 and 2 has remarkably low breaking strength and elongation. .
- a mixture of an ethylene-styrene copolymer and polystyrene also has a remarkably low breaking strength and elongation.
- the cross-copolymer (composition containing a cross-copolymerized styrene-ethylene-gen copolymer and polystyrene homopolymer) obtained in the present invention has good processability (MFR, load 5 kg, 200 ° C).
- MFR processability
- the MFR measured at C is greater than or equal to 0.2 g / l 0 min.). This is because the coordination polymerization catalyst used in the present invention can copolymerize gen with high efficiency, and cross-linking proceeds sufficiently at a very low gen usage level.
- the concentration of residual gen in the coordination polymerization solution is sufficiently low, crosslinking of the copolymer in the genite during coordination polymerization is suppressed to an extremely low level, and generation of gel components is suppressed. It is thought to be. Furthermore, in the subsequent anion polymerization step, the generation of the gel component and the crosslinked structure by the anion polymerization is suppressed due to the low Z amount of the zene. That is, since the formation of the gel component in the coordination polymerization step and the anion polymerization step is suppressed to an extremely low level, good moldability can be obtained.
- the gel content of the polymer B obtained in the crossing step was measured. That is, a purified 1.0 g polymer (molded product having a diameter of about l mm and a length of about 3 mm) was wrapped in a 100-mesh stainless steel net bag and weighed precisely. After extracting this in boiling xylene for about 5 hours, the net bag was recovered and dried at 90 ° C. in a vacuum for 10 hours or more. After cooling sufficiently, the net bag was precisely weighed, and the amount of the polymer gel was calculated by the following equation.
- FIG. 6 shows the viscoelastic spectrum of 14-A obtained in Example 14 and FIG. 7 shows the viscoelastic spectrum of 14B obtained in Example 14.
- FIG. 8 shows the viscoelastic spectrum of 7-A obtained in Example 7, and
- FIG. 9 shows the viscoelastic spectrum of 7-B obtained in Example 7.
- E, in particular 7- B has the feature that but takes an almost constant value, E 'is at 5 X 1 0 7 below P a higher 5 X 1 0 8 P a at 0 ° C, and located 1 X 1 0 7 P a higher 1 X 1 0 8 P a following range in at 1 0 0, a polymer is small change in E 'with temperature.
- FIG. 10 shows a viscoelastic spectrum of an ethylene-styrene copolymer having substantially the same styrene content.
- FIG. 11 shows a TEM photograph of 14-B obtained in Example 14. A microstructure of less than 0.05 micron is observed, and the polystyrene homopolymer is well dispersed. Power.
- the cross copolymer of the present invention was pelletized by the following method.
- the obtained pellets were used for forming the following films and producing various compositions.
- the dried crumb-shaped polymer is a 30 mm twin-screw extruder made by Ikegai Iron and Steel P At CM30, the strand is drawn under the conditions of a die temperature of 160 ° C and a screw rotation speed of 200 rpm, and after cooling with water, pelletized with a fan cutter (FC110) made by Hoshi Plastics. Shape.
- Table 12 shows the molding conditions of each film.
- Table 13 shows the evaluation results of the obtained films.
- Table 12 shows the molding conditions of each film.
- Table 13 shows the evaluation results of the obtained films.
- the cross-copolymer film has higher mechanical strength (rupture strength and tensile modulus) than the conventional ethylene-styrene copolymer film and the olefin-based elastomer film. Have. Further, the cross-copolymer is moderately elastic and has good acupressure recovery.
- the acupressure recovery property and the superacupressure recovery property of the stretch film were obtained as follows.
- the acupressure recovery of the film is as follows: after stretching the film by 10% in the width direction, pushing the 12.5 mm diameter rod into the 45 mm diameter film surface and returning instantaneously.
- the depth (mm) was determined as the super shiatsu restorability, and the critical depth to return within 1 minute was determined as the shiatsu restorability. Five tests were performed, and the average was shown.
- the thickness is 1 mm and the layer composition ratio is EV AZP—1 (P—3) / EVA (25% / 50% / 2) 5%).
- Table 14 shows the evaluation results of this film.
- compositions, crosslinked products and foams shown in Tables 15 to 25 are as follows.
- the cross-copolymers, olefin-based resins, and aromatic vinyl compound-based resins (polystyrene) are shown in parts by weight.
- the mixture was melt-kneaded at a mixing ratio of 16 with a 30 mm twin screw extruder at 200 to obtain a resin composition.
- a resin composition was obtained by melt-kneading in the same manner as in Tables 15 and 16 except that an ethylene-styrene copolymer and SEBS were used instead of the cross copolymer.
- SEBS ethylene-styrene copolymer
- only a polyethylene Z polystyrene and a polypropylene Z polystyrene were kneaded to obtain a resin composition.
- Table 15 shows polystyrene (GP-1) and polypropylene (J105), and Table 16 shows polystyrene (GP-1) and polyethylene (M850) obtained in this example.
- the mechanical properties of a composition obtained by adding a certain amount of the cross-copolymer, the ethylene-styrene copolymer obtained in Reference Example, and SEBS as a compatibilizer are shown.
- the resulting composition has remarkably improved elongation and strength at break, and exhibits an excellent compatibilizing effect. Also, it has a feature that the hardness is not reduced by the addition of the cross copolymer. On the other hand, addition of the ethylene-styrene copolymer is not sufficient in both elongation and strength at break. In the case of SEBS, which has been conventionally used as a compatibilizer, the elongation is excellent, but the strength at break is lower than that of the cross copolymer. Further, in the case of these ethylene-styrene copolymers and SEBS, the surface hardness is also reduced, and the composition is less damaged.
- the cross-copolymer obtained in the present invention gives excellent physical properties as a compatibilizer and composition of a polystyrene resin and a polyolefin resin.
- Denkastyrol GP-1 manufactured by Denki Kagaku Kogyo Co., Ltd.
- Polypropylene Grand Polypro "J-105" (Grand Bollima One)
- Polyethylene M850 (Keyo Polyethylene)
- Cross-copolymer composition composition with polyolefin resin>
- the cross-copolymer and the olefin-based polymer (polypropylene) were melt-kneaded at a cylinder temperature of 200 ° C with a 30 mm twin-screw extruder at the compounding ratio shown in Table 17, and the chlorinated copolymer and the olefin were mixed.
- a resin composition was obtained.
- the cross copolymer instead, EPR and ethylene-styrene copolymer were similarly melt-kneaded at the compounding ratio shown in Table 17.
- Various physical properties of the obtained composition were measured and compared with the results of polypropylene alone.
- Table 17 shows the physical properties of the composition of the polypropylene and the cross-copolymer.
- the composition has high mechanical properties (flexural strength and flexural modulus), hardness, heat resistance (bicut softening point) and impact strength, and excellent The result is an impact propylene composition.
- the impact resistance is excellent, the flexural modulus is lowered and the heat resistance (the vicat softening point) is also lowered.
- heat resistance Vicat softening point
- hardness decrease.
- the cross-copolymer obtained in the present invention gives excellent physical properties when it is used as a composition with a polyolefin-based resin such as polypropylene.
- a polyolefin-based resin such as polypropylene.
- J-105 manufactured by Grand Volima
- EPR used were Tuffma-P-280 (manufactured by Mitsui Chemicals).
- Tuffma-P-280 manufactured by Mitsui Chemicals
- the cross-copolymer and various aromatic vinyl compound polymers were melt-kneaded at a mixing ratio of Table 18 in a 30 mm ⁇ twin screw extruder at 200 ° C to obtain an aromatic vinyl compound resin composition. Obtained.
- a sheet with a thickness of 1 mm was created by press molding (180 ° C / 3 min) and punched into the shape of a No. 2 dumbbell. It was determined according to the test method. The test was performed at a tensile speed of 2 mm Z min. Others were determined by the above method.
- Cross copolymer obtained by the process of the present invention 5 0 wt% or less as described above, preferably is good Ku compatibilized with 3 0 wt 0/0 following polystyrene homopolymers one composition It has good physical properties.
- the physical properties of the composition obtained by newly adding polystyrene to the cross copolymer are shown.
- Table 18 a composition composed of 50 parts / 50 parts of a cross-copolymer and polystyrene has properties as a thermoplastic resin having high impact resistance, although transparency is lost.
- the present production cross-copolymerization product obtained by the process tension high similarity to (up to 3 0 wt 0/0 approximately containing organic polystyrene homopolymer) modulus and heat resistance It has physical properties close to that of an elastomer having the same hardness, elongation and elongation.
- Tables 19, 20 and 21 summarize the physical properties of the composition of the cross copolymer of the present invention and various fillers. It can be seen that when calcium carbonate is used as a filler, both high elongation and tensile modulus are satisfied. Also, it has high hardness and vicat softening point (heat resistance), and has sufficient physical properties as a practical filler composition. On the other hand, when an ethylene-styrene copolymer is used, the breaking strength is high, but the elongation and tensile modulus are low, giving a brittle impression. Also, it has low hardness and low surface damage. Vicat softening point (heat resistance) 'is also insufficient.
- the cross-copolymer filler composition has high tensile modulus, hardness, and vicat softening point (heat resistance), although the mechanical properties vary. I understand that there is.
- Tensile breaking strength Pa 39 39 35 7 33 Elongation at break% 457 550 300 763 723
- Table 23 summarizes the physical properties of the composition of the cross copolymer of the present invention and a paraffinic or naphthenic plasticizer. Compared with the ester plasticizer, the decrease in physical properties is smaller than that of the ester plasticizer, and the glass transition point is also reduced to 140 ° C or less.
- Ethylene-styrene copolymer SE 5100 Ester plasticizer 2 0 2 0 2 0 2 0 2 0 2 0
- the plasticizers used were PL-100 (ester type, manufactured by Mitsubishi Gas Chemical), NM-280 (naphthene type, manufactured by Idemitsu Kosan), and PW-90 (paraffin type, manufactured by Idemitsu Kosan). is there.
- Dynamic cross-linking was carried out at a kneading temperature of 160 ° C and a kneading time of 9 minutes using a laboratory plastic mixer unit (R60 type, manufactured by Toyo Seiki Co., Ltd.) with the formulation shown in Table 24.
- a sheet having a thickness of 1 mm was formed from the obtained resin composition under pressing conditions (200 ° C., 4 minutes, 50 kg / cm 2 before), and various physical properties were evaluated.
- the abbreviations in the table are shown below.
- Polystyrene; Denkastyrol GP-1 manufactured by Denki Kagaku Kogyo
- Crosslinking agent Peroxide; Perkimil D-40 (manufactured by NOF Corporation, pure content: 40%), Crosslinking aid: divinylbenzene (purity: 96%)
- the dynamic crosslinked product of the cross-copolymer of the present invention has less elongation, but has excellent mechanical strength (rupture strength, tensile modulus) and high hardness, compared to the dynamically crosslinked product of ethylene-styrene copolymer. High heat resistance (Vicat softening point). (Table 24) By changing the composition of the cross-copolymer itself, the various physical properties of the dynamically cross-linked cross-copolymer can be adjusted to be similar to those of the conventional dynamically cross-linked ethylene-styrene copolymer.
- the chemical foaming agent was kneaded under the conditions shown in Table 25 at a kneading temperature of 150 ° C and a kneading time of 1 minute using a Labo Plastomill mixer unit (R60 type) manufactured by Toyo Seiki Co., Ltd.
- the obtained resin composition was subjected to sheet press molding at a press temperature of 150 ° C with a thickness of 0.5 mm, and further subjected to a foaming treatment at 230 ° C to obtain a sample for evaluation. did.
- the abbreviations in the table are shown below.
- Blowing agent VINIHOLE AC # 3 M (azodicarbonamide) (manufactured by Eiwa Chemical Co., Ltd.)
- cross-copolymer foam of the present invention has relatively low elongation, it has excellent mechanical strength (rupture strength, tensile elastic modulus), high hardness, and high heat resistance (Vicat softening point) ( Table 25).
- Polyolefin foams and ethylene-styrene copolymer foams are characterized by high elongation, low breaking strength, tensile modulus and hardness, and can be said to be very flexible foams.
- aromatic vinyl compound (polystyrene) foams are characterized by very low elongation, high tensile modulus, and hardness, and are the opposite poles of off-line foams.
- the foam of the cross-copolymer of the present invention exhibits physical properties between an orefin-based foam and a polystyrene-based foam, and the composition of the cross-copolymer itself is changed so that the It can be arbitrarily changed from a flexible area close to the foam to an area close to the polystyrene foam.
- the physical properties can be arbitrarily changed by foaming after forming a composition with an aromatic vinyl compound resin, a olefin resin, and another resin or an elastomer.
- a cross-linking step was performed by radical polymerization to synthesize a cross-copolymer.
- Example R 1 Example R 2 Example R 3 Example R 4 Example R 5 Reference Example Polymer Liquid Reference Example 1 Reference Example 2 Reference Example 2 Reference Example 2 Reference Example 2
- Table 28 shows the analysis results of the obtained polymers. Styrene content and methyl methacrylate content were determined by 1 H-NMR.
- the styrene content in the entire polymer that is, the styrene content in the ethylene-styrene-gen copolymer obtained in the copolymerization step, and the amount of styrene in the radical polymerization (cross-forming step) »)).
- Table 29 summarizes the physical properties of the cross copolymers obtained in Examples R1 to R5 and the copolymers obtained in Reference Examples 1 and 2.
- the cross-linking step was carried out by radical polymerization, and the polystyrene was cross-linked.
- the polymer of Example R1 was compared with the polymer before cross-linking (the ethylene-styrene-gen copolymer obtained in the coordination polymerization step). It shows high tensile modulus, hardness, and vicat softening point, and has moderate elongation, indicating the characteristics of a cross-copolymer.
- a styrene monomer and a methyl methacrylate monomer (MMA) are used in the cross-forming step.
- the resulting copolymer has a similarly high tensile modulus, hardness, Vicat softening point and moderate elongation.
- copolymers having a styrene-MMA copolymer as a cross chain have transparency.
- the copolymer obtained in Example R 4 has excellent transparency.
- Dimethylsilanediyl tramethylcyclopentagenenyl t-butylamide titanium dichloride (
- Polymerization was carried out using a 10 L capacity autoclave equipped with a stirrer and a heating and cooling jacket.
- the obtained polymer solution was discharged into a vessel containing a small amount of butanol in advance, and then poured into a large amount of a vigorously stirred methanol solution little by little to recover the polymer.
- the polymer was air dried at room temperature for 24 hours and then dried at 80 in vacuum until no change in weight was observed. 380 g of polymer (polymer R 1 —B) were obtained.
- Polymerization was carried out in the same manner as in Example 1 under the conditions shown in Table 30. After the coordination polymerization, 18 g of an ethylene-octene-diene copolymer (polymer R 2 -A) obtained by extracting a part of the polymerization solution was obtained. The copolymer (polymer R) obtained after the completion of the anion polymerization was obtained. 2—B) was 234 g.
- Table 31 shows the analysis results of the obtained polymers.
- 1A described in ⁇ of the polymer indicates a polymer that is obtained by extracting a part of the polymerization solution obtained in the coordination polymerization step, and 1B indicates the copolymer obtained in the cross-forming step. Is shown.
- the value of B is the overlap of the copolymer obtained in the crossing step.
- FIG. 12 shows a GPC curve of a polymer R4-B obtained by the cross-forming step (anion polymerization).
- the curve consists of a number of complex overlapping peaks.
- the peak shapes of the RI detector (indicating the distribution of the whole polymer) and the UV detector (indicating the distribution of styrene unit in the polymer) are almost the same, It is considered that the copolymer fraction also contains polystyrene chains.
- Table 32 shows the physical properties of the obtained polymer.
- the obtained polystyrene cross-copolymerized ethylene-1-octene-gene cross-copolymer has reduced elongation and improved strength at break as compared with the ethylene-1-octene-one co-polymer obtained in the coordination polymerization step. However, the tensile modulus and hardness are improved.
- ethylene was 100 L under the standard condition.
- the ethylene was released, and the internal temperature was heated to 70 ° C.
- a small amount of the polymerization solution was withdrawn, and a polymer (polymer RA) was obtained by coordination polymerization by meta-precipitation. Nitrogen was bubbled while being careful not to foam the polymerization solution, and residual ethylene was removed from the polymerization vessel and the polymerization solution as much as possible.
- methylalumoxane was added with a syringe of 300 mm 01, and 100 ml of a toluene solution containing 300 "mo 1 of cyclopentazinyl titrate was added. . That Thereafter, the temperature was maintained at 70 ° C for 2 hours.
- the obtained polymer solution was discharged into a vessel containing a small amount of butanol in advance, and then poured little by little into a large amount of vigorously stirred methanol solution to recover the polymer. .
- the polymer was air-dried at room temperature for 24 hours, and then dried at 80 ° C. under vacuum until no change in weight was observed. 364 g of polymer (Polymer R-B) was obtained.
- Table 33 shows the polymerization conditions
- Table 34 shows the analysis values of the obtained polymer.
- Polymer R—B had a melting point of 25 ° C. derived from syndiotactic polystyrene and exhibited a heat of fusion of about 10 J 7 g.
- a dumbbell was punched out from a sheet obtained by press-molding the obtained cross copolymer at a press temperature of 300 ° C. and 50 atm for 4 minutes. When the mechanical properties were measured, the elongation was 330%, the breaking strength was 19.0 MPa, the 100% modulus was 14. OMPa, and the tensile modulus was 56.0 MPa.
- Catalyst A rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride M AOP; P MAO solvent T; toluene
- One of the polymers described in (1) is the coordination polymerization step, and — B is the value of the copolymer obtained in the cross-linking step.
- T R— A is the coordination polymerization solution. Partly obtained by meta prayer,
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Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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EP99961335A EP1170313B1 (en) | 1998-12-22 | 1999-12-22 | Cross-copolymerized olefin/styrene/diene copolymer, process for the production of the same and uses thereof |
DE69942460T DE69942460D1 (de) | 1998-12-22 | 1999-12-22 | Cross-kopolymerisierte olefin/styrol/dien kopolymere, ihre herstellungsverfahren und verwendung |
US09/831,380 US6559234B1 (en) | 1998-12-22 | 1999-12-22 | Cross-copolymerized olefin/styrene/diene copolymer, process for the production of the same and uses thereof |
JP2000589585A JP4398591B2 (ja) | 1998-12-22 | 1999-12-22 | クロス共重合化オレフィン−スチレン−ジエン共重合体、その製造方法及びその用途 |
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JP36536298 | 1998-12-22 | ||
JP10/365362 | 1998-12-22 | ||
JP11/258618 | 1999-09-13 | ||
JP25861899 | 1999-09-13 |
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PCT/JP1999/007239 WO2000037517A1 (fr) | 1998-12-22 | 1999-12-22 | Copolymere olefine/styrene/diene reticule, procede de production dudit copolymere et ses utilisations |
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US (1) | US6559234B1 (ja) |
EP (1) | EP1170313B1 (ja) |
JP (4) | JP4398591B2 (ja) |
CN (1) | CN1331706A (ja) |
DE (1) | DE69942460D1 (ja) |
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Also Published As
Publication number | Publication date |
---|---|
US6559234B1 (en) | 2003-05-06 |
EP1170313A1 (en) | 2002-01-09 |
JP2009299068A (ja) | 2009-12-24 |
JP4783324B2 (ja) | 2011-09-28 |
DE69942460D1 (de) | 2010-07-15 |
EP1170313B1 (en) | 2010-06-02 |
JP2007217706A (ja) | 2007-08-30 |
JP4398591B2 (ja) | 2010-01-13 |
EP1170313A4 (en) | 2002-10-29 |
JP4691182B2 (ja) | 2011-06-01 |
CN1331706A (zh) | 2002-01-16 |
JP2009299067A (ja) | 2009-12-24 |
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