KR100455842B1 - Styrenic Copolymers and Process for Producing the Same - Google Patents

Abstract

The α-olefin / styrene monomer / diene / syndiotactic polystyrene (sPS) random copolymer according to the present invention is a terpolymerizable metal of α-olefin / styrene monomer / diene to α-olefin, styrene monomer and diene compound. Injecting a Rosene catalyst (A) and a cocatalyst to prepare an α-olefin / styrene-based monomer / diene terpolymer, and remove the α-olefin in the same reactor or to another reactor to remove the α-olefin, and syndiotactic styrene The polymerizable metallocene catalyst (B) and the cocatalyst are injected to produce the polymerization.

Description

Styrenic Copolymers and Process for Producing Them {Styrenic Copolymers and Process for Producing the Same}

Field of invention

The present invention relates to a process for preparing α-olefins / styrene-based monomers / dienes / sPS random copolymers. More specifically, the present invention is excellent in heat resistance, impact resistance and compatibility by using a plurality of metallocene catalyst, stable physical properties because there is no gelation, easy to control the content of styrene, ethylene and sPS and have high productivity The present invention relates to a method for producing an α-olefin / styrene-based monomer / diene / sPS random copolymer in which an α-olefin / styrene-based monomer / diene-based monomer and sPS are bonded to each other.

Background of the Invention

Generally, olefinic or styrene-based polymers are prepared by radical polymerization, ion polymerization or coordination polymerization by Ziegler-Natta Catalysts. By radical polymerization or ionic polymerization, an atactic polymer is obtained. In the case of coordination polymerization using a Ziegler-Natta catalyst, an isotactic polymer is mainly obtained. Synthetic polymers having a syndiotactic structure were known in theory, but the actual production was possible after the metallocene catalyst was applied.

Metallocene catalysts capable of producing polyolefins having improved physical properties or polystyrene having stereoregularity include metal compounds, which are compounds of transition metals of Group 4 of the periodic table, one or two cycloalkanedienyl groups, and derivatives thereof. It has a structure combined with a ligand consisting of. The Group 4 transition metals on the periodic table include titanium (Ti), zirconium (Zr) and hafnium (Hf), and cycloalkanedinyl groups include cyclopentadienyl, indenyl and fluorenyl groups and derivatives thereof.

This type of catalyst is used together with a cocatalyst. A Ziegler-Natta catalyst, which is a conventionally used catalyst, consists of a main catalyst of a halogenated titanium compound, which is a transition metal compound, and a cocatalyst of alkylaluminum. Examples of titanium halide compounds include titanium tetrachloride, and examples of alkylaluminum include trimethylaluminum and triethylaluminum. Meanwhile, recently developed metallocene catalysts use alkylaluminum oxane, which is a reaction product of water and an alkylaluminum compound, as cocatalysts, so that stereoregular polystyrenes (syndiotactic polystyrenes and isoforms) have not been produced until now. Tactile polystyrene) and polyolefins with improved physical properties. In particular, syndiotactic polystyrene (hereinafter referred to as "sPS") is a structure in which the phenyl groups in the polymer backbone are alternately positioned, and unlike the conventional amorphous general purpose atactic polystyrene, the melting point as a polymer having a crystalline structure ( Tm) has been of interest because of its excellent heat resistance and mechanical properties at about 270 ° C.

European Patent Publication No. 210 615 A2 (1987) discloses sPS having stereoregularity and cyclopentadienyl titanium trichloride and alkyl-substituted cyclopentadienyl titanium trichloride, i.e., pentamethylcyclopentadienyl titanium trichloride, for preparing the same Is starting. These catalysts are known to have good catalyst activity, molecular weight and syndiotactic index.

Japanese Patent Laid-Open Nos. 63-191811 and 3-250007 disclose metallocene catalysts having a sulfur bridge bond, and Japanese Patent Laid-Open Nos. 3-258812, 4-275313 and 5-105712 are alkyl bridges. Metallocene catalysts having a bond are disclosed. However, these catalysts have a disadvantage of difficulty in commercialization due to low production yield.

U.S. Patent No. 4,544,762 discloses an alpha-olefin system having a higher stereoregularity and a method of preparing a polymer more highly active than a Ziegler-Natta catalyst using a transition metal catalyst such as a metallocene catalyst and a reaction product of alkylaluminum and a metal hydrate. And a styrene polymer production method.

Japanese Patent Laid-Open Nos. 62-104818 and 62-187708 disclose metallocene catalysts for producing sPS. This metallocene catalyst has a structure in which a group IVB transition metal is used as a center metal and a cyclopentadienyl group derivative is used as a ligand. Alkyl aluminum oxane, which is a reaction product of alkyl aluminum and a metal hydrate, is used as a promoter.

U. S. Patent No. 5,026, 798 also discloses a process for polymers having high stereoregularity and high molecular weight using metallocene catalysts.

Applicant discloses a novel alkyl bridge bimetallic metallocene (ABBM), silyl bridge bimetallic metal for producing sPS having excellent stereoregularity, high melting temperature and good molecular weight distribution in US Patent Application No. 6,284,700. Rosene (SBBM) and alkyl-silyl bridging bimetallic metallocenes (A-SBBM) catalysts are disclosed.

The sPS disclosed as described above is excellent in heat resistance, but the impact resistance and compatibility with general-purpose resins such as polyolefins have been limited, thereby limiting application development.

On the other hand, copolymerization between aromatic vinyl compounds such as ethylene and styrene has been carried out for the past decade. First, a method using a heterogeneous Ziegler-Natta catalyst was attempted (Polymer Bulletin 20, 237-241, 1988). However, with traditional non-uniform Ziegler-Natta catalyst systems, the catalyst activity is extremely low, the styrene content in the resulting copolymer is low, the homogeneity of the copolymer is poor and almost all of it is obtained as a mixture of homopolymers. In addition, an ethylene / styrene copolymer prepared using a homogeneous Ziegler-Natta catalyst system composed of a transition metal compound and an organoaluminum compound and a method of manufacturing the same are known.

Japanese Patent Laid-Open Nos. 3-163088 and 7-53618 disclose a pseudo-random ethylene / styrene copolymer in which a common styrene chain is not present using a Constrained Geometry Catalyst. In this case, the general styrene chain means a head-to-tail bond chain of styrene. However, the phenyl group present in the alternating structure of the pseudorandom ethylene / styrene copolymer has no stereoregularity, and exhibits the characteristics of an amorphous resin having no crystallinity below a specific styrene content. Therefore, the production method using a large amount of organoaluminum adopted in the above technique is not an efficient production method because it generates a large amount of sPS in addition to the ethylene / styrene copolymer under mild reaction conditions.

Japanese Patent Laid-Open No. 6-49132 and Polymer Preprints (Japan 42, 2292, 1993) disclose the preparation of styrene / ethylene copolymers of similar structure, which are named pseudorandom copolymers because they do not exist in general. Prepared using a bridged Cp-type Zr complex and promoter. However, according to the Polymer Preprints, the phenyl group did not have any stereoregularity in the ethylene / styrene alternating structure in the pseudorandom copolymer.

On the other hand, styrene / ethylene alternating copolymers can be prepared using titanium complexes with phenol substituents, see Japanese Patent Application Laid-Open No. 3-250007 and Stud. Surf. Sci. Catal. 517 (1990). These copolymers do not contain any structure other than ethylene / styrene alternating arrangements, ie ethylene chains, styrene chains (including the head-head or tail-tail bonds of styrene), and the alternating degree is at least 70 or higher. More specifically, it has a value of 90 or more. That is, the copolymer is an almost perfect alternating copolymer with a very high degree of alternating degree. On the other hand, since the content of ethylene and styrene is fixed at about 50% to 50%, there is a disadvantage that the composition of the copolymer cannot be changed. Moreover, the phenyl group has isotactic stereoregularity with an isotactic diad index of 0.92. In addition, the copolymer has a molecular weight of 20,000 or less, which is inadequate in terms of physical properties, has a very low catalytic activity, and in copolymerization, a large amount of homopolymer such as sPS is produced.

Macromol. Chem., 191, 2387 (1990) disclose a method for preparing a styrene / ethylene copolymer using CpTiCl ₃ as a transition metal compound and methyl aluminoxane as a promoter. However, small amounts of pseudorandom copolymers without styrene chains are produced at certain catalyst / cocatalyst ratios, with very low catalytic activity. In addition, in this document, the content about the stereoregularity of a phenyl group is not reported.

Eur. Polym. In J., 31, 79 (1995), ethylene / styrene copolymerization was carried out under various conditions using an alkylate of the same catalyst (CpTiBz ₃ ), resulting in a mixture of homopolymers of polyethylene and sPS rather than copolymers. Could get Macromolecules, 29, 1158 (1996) disclose the results of ethylene / styrene copolymerization using CpTiCl ₃ and boron type cocatalysts. As a result, copolymers having a high level of alternating structure and sPS, polyethylene, etc. A mixture could be obtained. However, this document does not mention the stereoregularity of the phenyl group.

U. S. Patent No. 5,883, 213 discloses ethylene / styrene copolymerization results using bridged Cp-type Zr complexes and methylaluminoxane cocatalysts, wherein the bridged Cp-type Zr complexes used as catalysts generally contain isotactic polypropylene. It has a C2 symmetric structure known to produce. The copolymer can vary in styrene content from 1 to 55 mole percent and is known to exhibit an isotactic diad index of 0.95 or greater. However, this copolymer has a low alternating index of less than 60% even at high styrene content of 50 mol% or more.

The method disclosed in European Patent Publication No. 416,815 A2 has a low yield of polymer per unit metal, uses a large amount of organoaluminum compound, requires extreme conditions of high temperature and high pressure, and is industrially limited. Has no stereoregularity of copolymerized styrene and has amorphous properties above a certain styrene concentration. In addition, since the pseudo-random structure is not suitable for the production of alternating copolymer (alternating copolymer).

Conventional sPS is limited in the development of the use due to the impact resistance and inferior compatibility, the ethylene / aromatic vinyl copolymer has a disadvantage in that the heat resistance is weak, and the compatibility with polyolefins. However, attempts to remedy this drawback include the method disclosed in Japanese Patent Application Laid-open No. 5-247147, which uses a Ziegler-Natta catalyst and grafts the macroma of ethylene / propylene / butenylstyrene terpolymer onto sPS. One copolymer was prepared. This graft copolymer has excellent heat resistance, elongation and compatibility.

The method disclosed in Japanese Patent Laid-Open No. 11-124420 produced a terpolymer macroma of ethylene / styrene / divinylbenzene and a copolymer grafted to sPS. However, it is impossible to prevent the physical property degradation due to gelation with divinylbenzene in the manufacturing process, and the economic activity is insufficient due to the very low activity.

In PCT No. 01-19881, a terpolymer of low pressure ethylene / styrene / divinylbenzene was prepared, and a cross copolymer was prepared by supplying 10 times more high-pressure ethylene than the initial stage in the next step. This copolymer has the advantage of a simple manufacturing method and high activity, but has a disadvantage in that heat resistance is inferior to polyethylene level.

The present inventors solve the disadvantages of the prior art, excellent heat resistance, impact resistance and compatibility, there is no gelation is easy to form, easy to control the content of styrene, ethylene and sPS, α-olefin / styrene having high productivity A method for producing a monomer / diene / sPS random copolymer was developed.

It is an object of the present invention to provide a method for preparing α-olefin / styrene-based monomer / diene / sPS random copolymer.

Another object of the present invention is to provide a method for producing an α-olefin / styrene-based monomer / diene / sPS random copolymer, which is excellent in molding while maintaining excellent heat resistance and no gelation, while significantly improving impact resistance.

Still another object of the present invention is to provide a method for producing an α-olefin / styrene-based monomer / diene / sPS random copolymer having excellent compatibility with a polyolefin or polystyrene resin.

Still another object of the present invention is to provide a method for preparing α-olefin / styrene-based monomer / diene / sPS random copolymer, in which the content of styrene, ethylene and sPS is easily controlled.

Both the above and other objects of the present invention can be achieved by the present invention described below. Hereinafter, the content of the present invention will be described in detail.

1 is a process chart showing a method of preparing an α-olefin / styrene-based monomer / diene / sPS random copolymer according to the present invention.

Figure 2 is an electron micrograph of the copolymer prepared in Example 1.

3a and 3b are polarization micrographs of the copolymer prepared in Example 1.

Figure 4 is an electron micrograph of the copolymer prepared in Comparative Example 2.

The α-olefin / styrene-based monomer / diene / syndiotactic polystyrene (sPS) random copolymer of the present invention is prepared by combining α-olefin, styrene, diene monomer and sPS with each other using a plurality of metallocene catalysts. The method for producing the styrene-based copolymer is as shown in the process chart disclosed in FIG.

1 is a first method of preparing a terpolymer of? -Olefin / styrene monomer / diene by adding a terpolymer co-polymerizable metallocene catalyst (A) and a cocatalyst to? -Olefin, styrene monomer, and diene compound. After the step reaction and the removal of the α-olefin consisting of a second stage reaction to supply the sPS polymerizable metallocene catalyst (B) and the co-catalyst finally to prepare the α-olefin / styrene monomer / diene / sps random copolymer do.

Hereinafter, a method of preparing the α-olefin / styrene-based monomer / diene / sPS random copolymer of the present invention will be described in more detail.

The method of FIG. 1 consists of a two step process. In the first step, the α-olefin, styrene monomer, diene compound, terpolymer copolymerization metallocene catalyst (A) and a cocatalyst were supplied to the first reactor to prepare a terpolymer of α-olefin / styrene monomer / diene. In the second step, the product and the unreacted mixture from which the α-olefin has been degassed are transferred to the second reactor, followed by supplying an sPS polymerizable metallocene catalyst (B) and a promoter to continue polymerization. In this method, the second reactor may be polymerized continuously in one reactor in the same manner as the first reactor, or another reactor may be used.

Examples of the α-olefins used in the present invention include ethylene, propylene, 1-butene, 1-hexene, 1-octene, and the like, and ethylene and propylene are preferable.

The styrenic monomers used in the present invention are represented by the following structural formula (I):

Wherein J ¹ is a hydrogen atom; Halogen atom; Or a substituent including at least one carbon atom, oxygen atom, silicon atom, phosphorus atom, sulfur atom, serenium or tin atom, and when m or 2, m may each independently have a different substituent.

Examples of the styrene monomer having the above formula (I) include alkyl styrene, halogenated styrene, halogen-substituted alkyl styrene, alkoxy styrene, vinyl biphenyl, vinylphenylnaphthalene, vinylphenylanthracene, vinylphenylpyrene, trialkylsilylvinyl biphenyl, tri Alkyl stenibiphenyl, alkyl silyl styrene, carboxymethyl styrene, alkyl ester styrene, vinylbenzene sulfonic acid ester, vinyl benzyl dialkoxy phosphide, etc. are mentioned.

Alkyl styrene includes styrene, methyl styrene, ethyl styrene, butyl styrene, para-methyl styrene, para-t-butyl styrene, dimethyl styrene, and the like. Halogenated styrene includes chloro styrene, bromostyrene, and fluoro styrene. Examples of the halogen-substituted alkyl styrene include chloromethyl styrene, bromomethyl styrene and fluoromethyl styrene. Examples of the alkoxy styrene include methoxy styrene, ethoxy styrene and butoxy styrene. Vinyl biphenyl, 3-vinyl biphenyl, 2-vinyl biphenyl, and the like, and as vinyl phenyl naphthalene, 1- (4-vinyl biphenyl naphthalene), 2- (4-vinyl biphenyl naphthalene), 1- (3 -Vinylbiphenylnaphthalene), 2- (3-vinylbiphenylnaphthalene), 1- (2-vinylbiphenylnaphthalene), and the like, and examples of vinylphenyl anthracene include 1- (4-vinylphenyl) anthracene and 2- ( 4-vinylphenyl) anthracene, 9- (4-vinylphenyl) anthracene, 1- (3- Vinylphenyl) anthracene, 9- (3-vinylphenyl) anthracene, 1- (2-vinylphenyl) anthracene, and the like. As vinylphenylpyrene, 1- (4-vinylphenyl) pyrene and 2- (4-vinylphenyl) ) Pyrene, 1- (3-vinylphenyl) pyrene, 2- (3-vinylphenyl) pyrene, 1- (2-vinylphenyl) pyrene, 2- (2-vinylphenyl) pyrene and the like, and trialkylsilylvinyl Examples of biphenyl include 4-vinyl-4-trimethylsilylbiphenyl, and alkyl silyl styrene includes p-trimethylsilyl styrene, m-trimethylsilyl styrene, o-trimethylsilyl styrene, p-triethyl silyl styrene, and m-. Triethylsilyl styrene, o-triethylsilyl styrene, and the like.

The dienes used in the present invention include all compounds capable of coordination polymerization, and include 1,4-hexadiene, 1,5-hexadiene, ethylidene norbornene, dicyclopentadiene, nobornadiene, 4- Vinyl-1-cyclohexene, 3-vinyl-1-cyclohexene, 2-vinyl-1-cyclohexene, 1-vinyl-1-cyclohexene, o-divinylbenzene, p-divicylbenzene, m-divinylbenzene is preferred. It is more preferable to use dienes in which a plurality of double bonds (vinyl groups) are bonded via a hydrocarbon group having 6 to 30 carbon atoms containing a single or a plurality of aromatic vinyl ring structures, and various divinyls of ortho, para, and meta Most preferably, benzene and mixtures thereof are used.

In the present invention, a plurality of metallocene catalysts are used. That is, by using together the terpolymer co-polymerizing metallocene catalyst (A) and the syndiotactic styrene-based polymerizable metallocene catalyst (B) of α-olefin / styrene monomer / diene, α-olefin / styrene monomer / diene Α-olefin / styrene-based monomer / diene / sPS random copolymer in which a terpolymer of and sPS is bonded is prepared. In this case, the metallocene catalysts (A, B) are used in sequence by dividing into two stages.

The terpolymer co-polymerizable metallocene catalyst (A) used in the present invention is not limited as long as it is a reactive catalyst between α-olefin and an aromatic vinyl compound, and the sPS polymerizable metallocene catalyst (B) is syndiotactic Any catalyst can be used as long as it can produce a styrenic polymer. Among the previously disclosed catalysts, single site coordination polymerization catalysts suitable for coordination polymerization are metallocene catalysts, half metallocene catalysts, constrained geometry catalysts (CGC), and Ziegler- Natta catalysts can be used.

Ternary co-polymerizable metallocene catalyst (A) usable in the present invention is U.S. Patent No. 5,324,800, Japanese Patent Application Laid-Open No. 4-300904, Japanese Patent Application Laid-Open No. 7-536l8, Japanese Patent Application Laid-Open No. 6-49132, Japanese Patent Application Laid-Open No. 3-l63088 No. 9-309925, No. 6-184179, Polymer preprints, Japan, 42, 2292 (1993), Macromol. Chem., Rapid Commun., 17, 745 (1966), EP 0872492A2 and the like. In addition, CGC catalysts disclosed in Japanese Patent Laid-Open Nos. 11-124420, 7-53618, 3-163088, EP-A-416815, and Japanese Patent Laid-Open No. 1-118510, Stud. Surf. Sci. Ziegler-Natta catalysts disclosed in Catal., 517 (1990), and the like can also be used.

The sPS polymerizable metallocene catalyst (B) of the present invention is not limited as long as it can produce a syndiotactic styrene-based polymer as described above, but it is preferable to use the catalyst disclosed in the US Patent Application No. 6,284,700 of the applicants. desirable. The catalysts disclosed in this patent application are novel alkyl bridge bimetallic metallocenes (ABBM), silyl bridge bimetallic metallocenes (SBBM) and alkyl-silyl bridge bimetallic metallocenes (A-SBBM) It is possible to produce syndiotactic polystyrene having excellent catalyst stereoregularity, high melting temperature and good molecular weight distribution.

Representative examples of the sPS polymerizable metallocene catalyst (B) usable in the present invention are represented by the following structural formulas (II) to (VI):

In the formulas (II) to (VI), M, M ', M "and M'" are each independently a transition metal of Group 4, 5 and 6 of the periodic table, preferably titanium of transition group 4, Zirconium or hafnium; Cp, Cp ', Cp "and Cp'" are each independently a cyclopentadienyl group, indenyl group, fluorenyl group or derivatives thereof which generate? 5 bonds with transition metals M, M ', M "and M'". As, they are represented by the following structural formulas (a), (b), (c) or (d);

(In the structural formulas (a), (b), (c) and (d), r ¹ to r ¹⁶ each independently represent a hydrogen atom; a C _1-20 alkyl group, a cycloalkyl group or an alkoxy group; C _1-20 aryl Group, an alkylaryl group or an arylalkyl group; f is one of integers of 4 to 8)

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ and X ¹² are each independently a hydrogen atom; Hydroxide groups; Halogen atom; C _1-20 alkyl, cycloalkyl or alkoxy groups; C _6-40 aryl group, alkylaryl group or arylalkyl group; Or formula -YR ⁵ Y'R 'one is represented by a (the formula -YR ⁵ Y'R' and Y and Y 'are independently an oxygen atom, a sulfur atom, -Nr ¹⁷ and -Pr respectively at ^18, r ⁵ may each independently be represented by the formula R ', R'-O-R'",-(R" -O-R '")-or R'"-N (r ¹⁹ ) -R "" Wherein R ′, R ″, R ′ ″ and R ″ ″ are each independently C _6-30 straight alkyl or branched alkyl group; C _3-30 cycloalkyl group or substituted cycloalkyl group; or C _6-40 aryl group, alkylaryl group or aryl alkyl group; r ^17, r ¹⁸ and r ¹⁹ is a hydrogen atom, an alkyl group of C _1~10, a cycloalkyl group or an alkoxy group; an aryl group of C _6~30, alkylaryl group or aryl alkyl group, R 'is independently a hydrogen atom; C _1-10 straight alkyl or branched alkyl group; C _3-20 cycloalkyl group or substituted cycloalkyl group; C _6-20 aryl group, alkylaryl group or arylalkyl group ); G, G 'and G "is a transition as to connect the metals and other transition metals can be represented by the formula -YR ⁵ Y'-, each independently (Y and Y in the formula -YR ⁵ Y'-' each are independently Is an oxygen atom, a sulfur atom, -Nr ¹⁷ or -Pr ¹⁸ , and R ⁵ is each independently of the formula R ', R'-O-R'",-(R" -O-R '")-or R'" -N (r ¹⁹ ) -R "" (wherein R ', R ", R'" and R "" are each independently a C _6-30 straight alkyl group or a branched alkyl group; C _3-30 Cycloalkyl group or substituted cycloalkyl group; or C _6-40 aryl group, alkylaryl group or arylalkyl group); Y, Y ', Y "and Y'" are each independently an oxygen atom, a sulfur atom, -Nr ¹⁷ or -Pr ¹⁸ and (wherein r ¹⁷ and r ¹⁸ is a hydrogen atom, an alkyl group, a cycloalkyl group or an alkoxy group of C _1~10; being an aryl group, an alkylaryl group or an arylalkyl group of C _6~30); Q is nitrogen r ²⁰ represents the atoms in the or -Cr ^20, A hydrogen atom; being an aryl group, an alkylaryl group or an arylalkyl group of C _6~30);; alkyl group, a cycloalkyl group or an alkoxy group of C _1~10 and Z is a carbon atom, a silicon atom, germanium or an ethylene group.

In the present invention, metallocene catalysts (A, B) are used to polymerize the copolymer with the cocatalyst. An organic metal compound may be used as a cocatalyst, or a mixture of non-coordinated Lewis acid and alkyl aluminum may be used together. Organometallic compounds usable in the present invention include alkylaluminum oxane or organoaluminum compounds. Representative examples of the alkyl aluminum oxane include methylaluminium oxane and modified methylaluminium oxane. Examples of the organoaluminum compound include aluminum oxane having a unit represented by the following formula (VII), and these include a chain-shaped aluminum oxane represented by the following formula (VII) and a cyclic aluminum oxane represented by the following formula (VII). have:

In the formulas (iii), (iii) and (iii), R 'is a C _1-6 alkyl group, and q is an integer of 0-100.

Alkyl aluminum in the alkyl aluminum or non-coordinating Lewis acid used as a promoter in the present invention is trimethyl aluminum, triethyl aluminum, diethyl aluminum chloride, dimethyl aluminum chloride, triisobutyl aluminum, diisobutyl aluminum chloride. , Tri (n-butyl) aluminum, tri (n-propyl) aluminum and triisopropylaluminum; non-coordinated Lewis acids include N, N-dimethyl aniline tetrakis (pentafluorophenyl) borate, triphenyl carbeni Um tetrakis (pentafluorophenyl) borate, ferrocerium tetrakis (pentafluorophenyl) borate, tris (pentafluorophenyl) borate.

In the present invention, the ratio of the use of the terpolymer copolymerizable metallocene catalyst (A) and the sPS polymerizable metallocene catalyst (B), that is, the molar ratio of the Group 4 transition metal (eg, titanium, zirconium, hafnium) in the catalyst component is The range in which the syndiotactic styrene-based component does not exceed 50 weight% among the amount of polymers polymerized by a catalyst is preferable, and 40 weight% or less is more preferable. If the syndiotactic styrene-based component exceeds 50% by weight, such properties as the toughness and remarkably low impact resistance of the pure syndiotactic styrene-based resin are exhibited.

In the present invention, in using an organometallic compound which is a cocatalyst with a plurality of metallocene catalysts (A, B), a Group 4 transition metal in the components of aluminum and the metallocene catalyst (A + B) among the components of the organometallic compound The ratio of to, that is, the molar ratio of aluminum to transition metal is preferably in the range of 0.1: 1 to 100,000: 1, and more preferably in the range of 1: 1 to 10,000: 1. The ratio between the molar ratio (α) of the transition metal in the aluminum and the metallocene catalyst (A) in the organometallic compound and the molar ratio (β) of the transition metal in the aluminum and metallocene catalyst (B) in the organometallic compound, i.e., α / The β ratio is preferably in the range of 0.1 to 100, more preferably in the range of 0.5 to 50, and most preferably in the range of 1 to 30.

When using alkyl aluminum as a promoter in this invention, the molar ratio of the transition metal in the component of an alkyl aluminum: metallocene catalyst (A + B) is preferably in the range of 1: 1-100,000: 1, and is 50: 1-1. The range of 10,000: 1 is more preferable, and the range of 100: 1-1,000: 1 is the most preferable. When the non-coordinated Lewis acid is used as the cocatalyst component, the molar ratio of the non-coordinated Lewis acid: transition metal in the component of the metallocene catalyst (A + B) is preferably in the range of 0.1: 1 to 20: 1, most preferably. It is 1 below.

The plurality of metallocene catalysts and cocatalysts may be mixed and prepared outside the polymerization reactor, or mixed in the polymerization reactor at the time of polymerization. In addition, in the preparation of the copolymer of the present invention, additives, adjuvants, and the like, which are commonly used in polymers, may be included within the range of not impairing the effects of the present invention, and most preferably, antioxidants, lubricants, and plasticizers. plasticizers, ultraviolet absorbers, stabilizers, pigments, dyes and sulfates, asbestos, staining agents, talc, silica, ceramics, inorganic fillers such as ceramics, and / or blowing agents. Can be.

Although the polymerization temperature for copolymerizing a styrene system using the catalyst system of this invention does not have a restriction | limiting in particular, 0-180 degreeC is preferable and 30-100 degreeC is more preferable. In the present invention, the polymerization time is not particularly limited.

The monomer which can be polymerized using the catalyst system of the present invention is an α-olefin monomer in addition to a styrene aromatic derivative, and the α-olefin monomer may copolymerize two or more kinds of monomers.

The polymerization method usable in the present invention is not particularly limited, and bulk polymerization, solution polymerization and the like which are generally used are possible. When using a solvent, you may use aliphatic hydrocarbons, such as pentane, hexane, heptane, cyclic aliphatic hydrocarbons, such as cyclohexane, and aromatic hydrocarbon solvents, such as benzene, toluene, xylene, ethylbenzene. In addition, the shape of the polymerization reactor is not particularly limited, but in general, a stirred tank reactor, a plug-flow reactor capable of mixing and kneading is preferable, and a product The flow of is preferably batch or continuous.

The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

The specifications of the plurality of metallocene catalysts (A) and (B) used in the following Examples and Comparative Examples are as follows.

(A) Terpolymer Copolymerizable Metallocene Catalysts of α-olefins / Styrene Monomers / Dienes

In Example 1 and Comparative Example 2, (t-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichlorido (A ₁ ) was used, and in example 2 rac-ethylene Bis (indenyl) zirconium dichloride (A ₂ ) was used.

(B) syndiotactic styrene-based polymerizable metallocene catalyst

Cp * Ti [OC ₆ H ₄ C (CH ₃ ) ₂ C ₆ H ₄ O] ₃ TiCp * (Cp * means pentamethylcyclopentadienyl group) disclosed in U.S. Patent Application No. 6,284,700 It was.

In Examples 1 and 2 (manufacturing method of FIG. 1), α-olefin / styrene-based monomer / diene / sPS random copolymers were prepared using a plurality of metallocene catalysts (A and B). In Comparative Example 1, sPS was polymerized using only the sPS polymerizable metallocene catalyst (B), and in Comparative Example 2, α-olefin / styrene-based monomer / was used using only the terpolymer co-polymerizable metallocene catalyst (A ₁ ). The terpolymer of the diene was polymerized, and in Comparative Example 3-5, the sPS and the terpolymer were mixed in different amounts.

Example 1

400 ml of toluene purified, 200 ml of purified styrene, 0.5 ml of purified divinylbenzene (Aldrich, 80% by weight), 10 mmol of triisobutylaluminum (based on aluminum) were added to a 2-liter high pressure reactor, and the temperature was raised to 70 ° C. I was. Injects 6 mmol of MAO (based on aluminum) and 10 μmol of (t-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride (A ₁ ) under a nitrogen atmosphere. At the same time, 8 atm of ethylene was injected to initiate polymerization. After 90 minutes, the ethylene gas was evacuated to sufficiently remove ethylene in the system, and then 10 mmol of Cp * Ti [OC ₆ H ₄ C (CH ₃ ) ₂ C ₆ H ₄ O based on 1 mmol of aluminum (Aluminum) and titanium. ₃ TiCp * (B) was injected and stirred for 30 minutes. Hydrochloric acid / methanol mixed solution was added to stop the reaction and washed, and the resulting polymer was recovered. It dried over 150 hours under reduced pressure 150 degreeC, and obtained 86 g of polymers.

The content of styrene, ethylene and divinylbenzene in the polymer was measured by 1 H-NMR analysis, and the content of polystyrene having a syndiotactic structure was measured by 13 C-NMR analysis. The weight average molecular weight of the polymer in terms of polystyrene and the number average molecular weight were obtained, and the melting point of the polymer was measured with a differential scanning calorimeter, and measured at a molding temperature of 300 ° C. in a mold according to ASTM D-256. Was prepared and the Izod impact strength was measured using a 1/8 "notched specimen, and the results are shown in Table 1. Each of the specimens formed by the ASTM D-256 at a magnification of 5,000 times was scanned electron microscope. The fracture surface was observed, and the shape thereof is shown in FIG. 2, and the melting / crystallization was performed at a magnification of 100 times with a polarization microscope while the temperature rising rate was 60 ° C./min and the cooling rate was 20 ° C./min from room temperature to 300 ° C. The behavior was continuously observed to show the state at 275 ° C. of the temperature rising process in FIG. 3A and the state at 240 ° C. of the cooling process in FIG. 3B, respectively.

Example 2

rac-ethylene bis (indenyl) zirconium dichloride (A ₂ ) was injected instead of (t-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride catalyst (A ₁ ) Except that was carried out in the same manner as in Example 1. 116 g of polymer were obtained, and the other physical properties are shown in Table 1.

Comparative Example 1

400 mL of purified toluene, 200 mL of purified styrene, and 10 mmol of triisobutylaluminum (based on aluminum) were added to a 2L high pressure reactor, and the mixture was heated to 70 ° C. In a nitrogen atmosphere, 1 mmol of MAO (based on aluminum) and 10 μmol of Cp * Ti [OC ₆ H ₄ C (CH ₃ ) ₂ C ₆ H ₄ O] ₃ TiCp * (B) were injected for 30 minutes Stirred. Post-treatment was carried out in the same manner as in Example 1 to obtain 99 g of a polymer, and the other physical properties were measured in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2

400 ml of toluene purified, 200 ml of purified styrene, 0.5 ml of purified divinylbenzene (Aldrich, 80% by weight), 10 mmol of triisobutylaluminum (based on aluminum) were added to a 2-liter high pressure reactor, and the temperature was raised to 70 ° C. I was. Injects 6 mmol of MAO (based on aluminum) and 10 μmol of (t-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride (A ₁ ) under a nitrogen atmosphere. At the same time, 8 atmospheres of ethylene were injected and polymerized, and after 90 minutes, ethylene gas was discharged to sufficiently remove ethylene in the system. Post-treatment was performed in the same manner as in Example 1 to obtain 50 g of a polymer, and the other physical properties were measured in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 3-5

Three batches of the syndiotactic polystyrene obtained in Comparative Example 1 and the α-olefin / styrene monomer / diene obtained in Comparative Example 2 in a batch type mixer (total internal volume: 60 ml) of Haake, Germany 0.1 weight% of coalescence and styrene antioxidant (primary and secondary) were added, and it knead | mixed for 7 minutes at 50 rpm at the temperature of 280 degreeC. At this time, the contents of the sPS and terpolymer were different as shown in Table 1, and the other physical properties were measured in the same manner as in Example 1 and the results are shown in Table 1.

In FIG. 4, the fractured surface of the specimen molded in Comparative Example 4 was measured with an electron microscope at a magnification of 5,000 times.

Example Comparative Example One 2 One 2 3 4 5 Ingredient (% by weight) Styrene 69.5 26.5 sPS 61.8 90/10 (terpolymer / sPS) 80/20 60/40 Ethylene 30.3 72.8 38.0 Divinylbenzene 0.2 0.7 0.2 sPS 7.2 5.4 - Molecular Weight Mw 354,400 - 236,000 - - - - Mn 19,000 - 10,200 - - - - Melting Point (℃) 264 118/263 271 - - - - Impact Strength (Kgfcm / cm) 84.2 31.9 2.1 - 15.6 14.6 8.5

From the results of FIGS. 2, 3A and 3B, the α-olefin / styrene-based monomer / diene / sPS random copolymer of the present invention prepared using a plurality of metallocene catalysts (A, B) is phase separated during melting and cooling. It can be seen that the phenomenon does not appear, thereby confirming that it is a homopolymer. On the other hand, according to Figure 4 phase separation phenomenon was observed in the specimen of the melt melt mixed terpolymer and sPS.

In addition, the α-olefin / styrene-based monomer / diene / sPS random copolymer of the present invention from the results of Table 1 compared to the melt mixture of sPS and sPS and α-olefin / styrene-based monomer / diene terpolymer as a single polymer It can be seen that it shows excellent impact strength. Therefore, it can be seen that the copolymer prepared according to the present invention is a novel homopolymer having both the properties of sPS having excellent heat resistance and the properties of α-olefin / styrene-based monomer / diene terpolymer having excellent impact resistance.

The present invention uses a ternary co-polymerizable metallocene catalyst (A) and a syndiotactic styrene-based polymerizable metallocene catalyst (B) of α-olefin / styrene-based monomer / diene in sequence to maintain heat resistance and impact resistance. Α-olefin / styrene-based monomer / diene / sPS randomly improved, no gelling, excellent molding, good compatibility with polyolefin or polystyrene resin, and easy control of the content of styrene, ethylene and sPS It has the effect of providing the manufacturing method of a copolymer.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (6)

The α-olefin / styrene-based monomer / diene terpolymer is prepared by injecting the α-olefin / styrene-based monomer / diene ternary copolymerizable metallocene catalyst (A) and a promoter into the α-olefin, styrene-based monomer and diene compound. To manufacture; And To remove the α-olefin in the same reactor or to another reactor, and continue polymerization by injecting syndiotactic styrene-based polymerizable metallocene catalyst (B) and a promoter; Process for producing α-olefin / styrene monomer / diene / sps random copolymer, characterized in that consisting of steps. According to claim 1, wherein the α-olefin is ethylene, propylene, 1-butene, 1-hexene, 1-octene, the diene compound is a compound capable of coordination polymerization 1,4-hexadiene, 1,5-hexa Diene, ethylidene-norbornene, dicyclopentadiene, norbornadiene, 4-vinyl-1-cyclohexene, 3-vinyl-1-cyclohexene, 2-vinyl-1-cyclohexene, 1- Of the α-olefin / styrene-based monomer / diene / sPS random copolymer, characterized in that it is selected from the group consisting of vinyl-1-cyclohexene, o-divinylbenzene, p-divizylbenzene and m-divinylbenzene. Manufacturing method. The method of claim 1, wherein the promoter is an organometallic compound or a mixture of non-coordinated Lewis acid and alkylaluminum, characterized in that the α-olefin / styrene monomer / diene / sps random copolymer Manufacturing method. The use ratio of the terpolymer co-polymerizable metallocene catalyst (A) and the syndiotactic styrene-based polymerizable metallocene catalyst (B) of the α-olefin / styrene-based monomer / diene, that is, in the catalyst component. The molar ratio of Group 4 transition metals (e.g., titanium, zirconium and hafnium) of α-olefin is characterized in that the syndiotactic styrene-based component is produced in a range of not more than 50 wt% in the amount of polymer produced by each catalyst. / Styrene-based monomer / diene / sPS random copolymer production method. 4. The method of claim 3, wherein the ratio of aluminum in the organometallic compound as the cocatalyst to the Group 4 transition metal in the component of the metallocene catalyst sum (A + B), that is, the molar ratio of aluminum: transition metal is 0.1: A molar ratio (α) of the transition metal in the terpolymer co-polymerizable metallocene catalyst (A) of aluminum and the α-olefin / styrene-based monomer / diene in the organometallic compound, and the organometallic compound. Α-olefin / styrene, wherein the ratio between the molar ratio β of the transition metal in the heavy aluminum and the syndiotactic styrene-based polymerizable metallocene catalyst (B), i.e., is in the range of 0.1 to 100. Method of producing a monomer / diene / sPS random copolymer. The molar ratio of the transition metal in the component of the alkylaluminum: metallocene catalyst sum (A + B), which is the promoter, is in the range of 1: 1 to 100,000: 1, and the non-coordinating Lewis acid is the promoter. : The molar ratio of the transition metal in the component of the metallocene catalyst mixture (A + B) is in the range of 0.1: 1 to 20: 1, and the method for producing α-olefin / styrene-based monomer / diene / sPS random copolymer .