KR100204178B1 - Process of production of graft copolymers - Google Patents

Abstract

Styrene monomer and hydrocarbon group-containing styrene monomer having an unsaturated bond

(A) transition metal compounds and

(C) hybridization in the presence of a catalyst having a main component of a compound which reacts with an electrical transition metal compound to form an ionic complex, and subsequently graft polymerizes the ethylenically unsaturated monomer to the obtained styrenic interpolymer. It is a method for producing a styrenic graft copolymer.

Description

Process for preparing graft interpolymer

The present invention relates to a method for preparing a graft interpolymer. Specifically, styrene-based grafts having excellent impact resistance and heat resistance and graft polymerization of ethylene-based monomers to styrene-based copolymers, particularly styrene-based copolymers having a syndiotactic structure, have good compatibility with other resins. The present invention relates to a method for efficiently preparing a copolymer.

Conventionally, styrene-based polymers produced by radical polymerization methods are molded into various shapes by various molding methods, and are widely used in household electric appliances, office equipment, household goods, packaging containers, toys, furniture, synthetic paper, and other industrial materials. The three-dimensional structure has an atactic structure, which has the drawback of poor heat resistance and chemical resistance.

The present inventors have solved the drawbacks of the styrene polymer of the atactic structure, and succeeded in the development of a highly syndiotactic styrene polymer, and a styrene-based copolymer obtained by hybridizing the styrene monomer and other components. (Japanese Patent Laid-Open No. 62-104818, No. 62-187708, No. 63-241009),

These polymers are excellent in heat resistance, chemical resistance and electrical properties and are expected to be applied in various fields. However, the polymer, in particular syndiotactic polystyrene, lacks usability with other resins and hardly adheres to metals and the like.

In addition, there is a problem that the impact resistance is not sufficient. By the way, the olefin polymerization by cationic transition metal complex has been reported from the edge.

For example, (1) Natta et al. Reported the polymerization of ethylene using titanocene dichloride / triethylaluminum as a catalyst (J. Polymer Sci., 26, 120 (1964)). Breslow et al. Also report polymerization of ethylene on titanocene dichloride / dimethylaluminum chloride catalysts (J. Am. Chem. Soc., 79, 5072 (1957)). In addition, Dyachkovskii et al suggest that the polymerization activity of ethylene by titanocene dichloride / dimethylaluminum chloride catalyst is a titanocene monomethyl cation (J. Polymer Sci., 16, 2333 (1967)). However, the ethylene activity in these methods is very low.

(2) Jordan et al. Synthesize and isolate biscyclopentadienyl zirconium methyl (tetrahydrofuran) tetraphenylboric acid by reaction of zirconocene dimethyl and silver tetraphenylborate. (J. Am. Chem. Soc., 108, 7410 (1986)). Moreover, they synthesize | combine and isolate biscyclopentadienyl zirconium benzyl (tetrahydrofuran) tetra phenyl boric acid by reaction of a zirconocene benzyl and ferrocenium tetraphenyl borate (J. Am. Chem. Soc., 109). , 4111 (1987). However, even in these catalysts, it was confirmed that ethylene was slightly polymerized, but the polymerization activity was very low.

(3) Turner et al. Used a boron complex containing specific amines such as triethylammonium tetraphenylborate, triethylammonium tetratolylborate and triethylammonium tetra (pentafluorophenyl) borate as a methyllocene compound. The polymerization method of -olefin is proposed (Japanese Patent Laid-Open No. 1-502036). However, the application of catalyst systems such as (1)-(3) is limited to homopolymerization and hybrid polymerization of α-olefins, and therefore does not develop into styrene-based monomas.

However, Japanese Patent Laid-Open No. 3-7705 discloses a copolymer of an olefin and a syndiotactic polystyrene or a copolymer of an olefin, an unsaturated carboxylic acid ester and a syndiotactic polystyrene. In the case where the amount of monoma is low, the copolymer has a high crystallinity, but when the amount of monoma for the polymerization is increased, an amorphous polymer is formed, which sufficiently improves the mechanical, thermal and chemical properties of syndiotactic polystyrene. Can't be saved.

Therefore, there is a limitation in the monomer for hybrid polymerization that can be hybridized, and there is a disadvantage that a material that utilizes the characteristics of syndiotactic polystyrene due to complexing with other thermoplastic resins or fillers cannot be obtained extensively.

In addition, although it is conceivable to use a resin compatibilizer as the third component, it is not preferable because the molding temperature of syndiotactic polystyrene is high, which is not suitable, and there is a possibility that it may cause performance degradation due to the addition of the third component. .

Synthetic polystyrene and various materials, particularly polymer materials and metals, are laminated to produce respective characteristics, and thus, attempts to develop a wider range of applications are made. For example, multilayering of syndiotactic polystyrene is considered, but since it does not have interfacial adhesion, the interface is peeled off and it is not practical.

In addition, the above-described interpolymers are excellent in interfacial adhesion. However, when the monomeric content for interpolymerization increases, amorphous polymers are generated, resulting in a significant decrease in performance. As a result, a laminate material having excellent physical properties cannot be obtained.

Therefore, the inventors of the present invention have conducted intensive studies to solve the drawbacks of the syndiotactic polystyrene and to develop a styrene-based polymer having excellent compatibility with other resins or adhesion with metals and excellent impact resistance.

In the process, it has been found that graft polymerization of ethylenically unsaturated monomers to certain styrene-based interpolymers has properties suitable for this purpose.

Therefore, the present inventors have continued to study and succeed in developing a method of efficiently proceeding the graft polymerization to produce a styrene-based graft copolymer having excellent properties at any graft rate and high productivity. In addition, it was found that the graft interpolymer obtained thereby was effective for various uses.

In other words, the present invention comprises a styrene monomer and a hydrogen carbonate-containing styrene monomer having an unsaturated bond with (A) the transition metal compound and (B) the transition metal compound to form an ionic complex as a main component. It is to provide a method for producing a styrenic graft interpolymer using a catalyst.

1-7 show strands obtained in Example 17 or Comparative Examples 1-3, respectively.

Electron micrograph of the cut plane (X1000).

8-14 show compositions obtained in Example 18 or Comparative Examples 4-6, respectively.

Electron micrograph of cut surface (X100)

The method of the present invention is a process for producing a styrene copolymer by hybridizing a styrene monomer and a hydrocarbon group-containing styrene monomer having an unsaturated bond (step 1) and graft polymerization of ethylenically unsaturated monomer on the styrene copolymer. It became the process (process 2) to make.

Styrene-based monomas used in Step 1 are various, but the following general formula [1]:

···[One]

[Wherein, R ¹ represents a substituent containing at least ^one of a hydrogen atom, a halogen atom or a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom atom, a phosphorus atom, a selenium atom, a silicon atom and a tin atom, and m is 1- The integer of 3 is shown. However, when m is plural, each R <^1> may be same or different. It is styrene-type monoma-I represented by].

This styrene-based monoma-I is specifically styrene; p-methylstyrene; o-methylstyrene; m-methylstyrene; 2,4-dimethylstyrene; 2,5-dimethylstyrene; 3,4-dimethylstyrene; 3,5-dimethylstyrene; alkyl styrene such as pt-butylstyrene, p-chlorostyrene: m-chlorostyrene: o-chlorostyrene: p-bromostyrene: m-bromostyrene: o-bromostyrene: p-fluoro styrene: m-fluor Styrene: o-fluorostyrene: halogenated styrene, such as o-methyl-p-fluorostyrene, 4-vinyl biphenyl: vinyl biphenyls, such as 3-vinyl biphenyl and 2-vinyl biphenyl, 1- (4-vinyl Phenyl) -naphthalene: 2- (4-vinylphenyl) -naphthalene: 1- (3-vinylphenyl) -naphthalene: 2- (3-vinylphenyl) -naphthalene: 1- (2-vinylphenyl) -naphthalene: 2 Vinylphenylnaphthalenes such as-(2-vinylphenyl) naphthalene, 1- (4-vinylphenyl) -anthracene: 2- (4-vinylphenyl) -anthracene: p- (4-vinylphenyl) -anthracene: 1- (3-vinylphenyl) -anthracene: 2- (3-vinylphenyl) -anthracene: 9- (3-vinylphenyl) -anthracene: 1- (2-vinylphenyl) -anthracene: 2- (2-vinylphenyl) -Anthracene: vinylphenyl anthracenes such as 9- (2-vinylphenyl) -anthracene, and 1- (4-vinylphenyl) -phenanthrene: 2- (4 -Vinylphenyl) -phenanthrene: 3- (4-vinylphenyl) -phenanthrene: 4- (4-vinylphenyl) -phenanthrene: 9- (4-vinylphenyl) -phenanthrene: 1- (3-vinyl Phenyl) -phenanthrene: 2- (3-vinylphenyl) -phenanthrene: 3- (3-vinylphenyl) -phenanthrene: 4- (3-vinylphenyl) -phenanthrene: 9- (3-vinylphenyl) Phenanthrene: 1- (2-vinylphenyl) -phenanthrene: 2- (2-vinylphenel) -phenanthrene: 3- (2-vinylphenyl) -phenanthrene: 4- (2-vinylphenyl) -phenan Tren: vinylphenylphenanthrenes such as 9- (2-vinylphenyl) -phenanthrene, 1- (4-vinylphenyl) -pyrene: 2- (4-vinylphenyl) -pyrene: 1- (3-vinylphenyl ) -Pyrene: 2- (3-vinylphenyl) -pyrene: 1- (2-vinylphenyl) -pyrene: vinylphenylpyrenes such as 2- (2-vinylphenyl) -pyrene and 4-vinyl-p-ter Phenyl: 4-vinyl-m-terphenyl: 4-vinyl-o-terphenyl: 3-vinyl-m-terphenyl: 3-vinyl-m-terphenyl: 3-vinyl-o-terphenyl: 2-vinyl -p-terphenyl: 2-vinyl-m-terphenyl: vinyl-phenyl such as 2-vinyl-o-terphenyl, vinyl-phenyl-terminated such as 4- (4-vinylphenyl) -p-terphenyl Neils, 4-vinyl-4'-methylphenyl: 4-vinyl-3'-methylbiphenyl: 4-vinyl-2'-methylbiphenyl: 2-methyl-4-vinylphenyl: 3-methyl-4-vinylphenyl Vinyl alkyl biphenyls such as 4-vinyl-4′-fluorobiphenyl: 4-vinyl-3′-fluorobiphenyl: 4-vinyl-2′-fluorobiphenyl: 4-vinyl-2-fluorobiphenyl 4-vinyl-3-fluorobiphenyl 4-vinyl-4'-chlorobiphenyl 4-vinyl-3'-chlorobiphenyl 4-vinyl-2'-chlorobiphenyl 4-vinyl-2- Chlorobiphenyl: 4-vinyl-3-fluorobiphenyl: 4-vinyl-4'-bromobiphenyl: 4-vinyl-3'-bromobiphenyl: 4-vinyl-2'-bromobiphenyl: 4-vinyl 2-bromobiphenyl: halogenated vinyl biphenyls, such as 4-vinyl-3-bromobiphenyl, trialkyl silyl vinyl biphenyls, such as 4-vinyl-4'-trimethylsilyl biphenyl, 4-vinyl-4 '-Trimethylstannyl biphenyl: trialkylstannyl vinyl biphenyls such as 4-vinyl-4'-tributylstannyl biphenyl and 4-vinyl-4'-trimethylsilinyl biphenyl Trialkylsilylmethylvinylbiphenyls such as 4-vinyl-4'-trimethylstannylmethylbiphenyl and the like: trialkylstannylmethylvinylbiphenyls such as 4-vinyl-4'-tributylstannylmethylbiphenyl , p-chloroethyl styrene: m-chloroethyl styrene: halogen-substituted alkyl styrene such as o-chloroethyl styrene, p-trimethylsilyl styrene: m-trimethylsilyl styrene: o-trimethylsilyl styrene: p-triethyl silyl styrene: m-triethylsilyl styrene: o-triethyl silyl styrene: alkyl silyl styrenes such as p-dimethyl-t-butylsilyl styrene, p-dimethylphenyl silyl styrene: p-methyldiphenyl silyl styrene: p-triphenylsilyl Phenyl group-containing silyl styrene, such as styrene, p-dimethyl chloro silyl styrene: p-methylcyclo silyl styrene: p- tricholosilyl styrene: p- trichloro silyl styrene: p-dimethyl bromosilyl styrene: p-dimethyl Halogen-containing silyl styrenes such as iodine silyl styrene, p- (p-t Methyl-silyl), and the silyl group-containing silyl styrenes, or a mixture of two or more of them, such as dimethylsilyl styrene.

The hydrocarbon group-containing styrene monomer having an unsaturated bond is various, but is generally of the following general formula [2]:

···[2]

[Wherein, R ₂ represents a hydrocarbon group having an unsaturated bond and n represents an integer of 1 or 2; And R ¹ and n are the same as described above.].

R ² in the formula is preferably a hydrocarbon group having an unsaturated bond, particularly a hydrocarbon group having an unsaturated bond having ² to 10 carbon atoms. For example, a vinyl group, an allyl group, a metalyl group, a homoallyl group, a pentenyl group, a deshenyl group, etc. are shown.

Specific examples of the styrene-based mono-II include p-divinylbenzene: m-divinylbenzene: monovinyl p-allylstyrene having methylene skeleton and? -Olefin skeleton in the same molecule, in addition to trivinylbenzene: m-alkylstyrene : Metallyl styrene: Homoallyl styrene: Butenyl styrene: Pentenyl styrene: Desenyl styrene etc. Or what mixed 2 or more types of these is mentioned.

In this case, when a monomer of an olefin skeleton is used, the reaction is suppressed even if the hybridization ratio is relatively increased, and therefore, it is suitable for a hybrid polymer having many graft starting points.

In step 1 of the method of the present invention, the styrene-based monomer having an unsaturated bond with the hydrocarbon group-containing styrene-based monomer, in particular, the styrene-based monomer and the styrene-based mono-II, but the hybridization of the catalyst (A) It is a catalyst mainly comprising a contact product of a metal compound and (B) an organic aluminum compound and a condensing agent.

Here, there are various (A) transition metal compounds, but the following general formulas [4], [5], [6] or [7]

M ¹ R ³ _a R ⁴ _b R ⁵ _c R ⁶ _{4- (a + b + c)} ... [4]

M ² R ⁷ _d R ⁸ _e R ⁹ _{3- (d + e)} ... [5]

O = M ³ R ¹⁰ _f R ¹¹ _2-f [6] or

O = M ⁴ R ¹² _g R ¹³ _h R ¹⁴ _{3- (g + h)} ... [7]

[Wherein, R ³ to R ¹⁴ are each hydrogen atom: halogen atom: alkyl group of 1-20 carbon atoms: alkoxy group of 1-20 carbon atoms: allyl group of 6-20 carbon atoms: allylalkyl group of 7-20 carbon atoms, 6- 20 allyloxy group: C1-C20 acyloxy group: acetylacetonyl group: cyclopenta dienyl group: substituted cyclopentadienyl group or indenyl group. A, b and c are each an integer of 0 or more satisfying 0 ≤ a + b + c ≤ 4, d and e are each an integer of 0 or more satisfying 0 ≤ d + e ≤ 3, and f is 0 ≤ f ≤ An integer of 0 or more satisfying 2, g and h each represent an integer of 0 or more satisfying 0 ≦ g + h ≦ 3. And M ¹ and M ² represent titanium: zirconium: hafnium or vanadium, and M ² and M ⁴ represent vanadium.

Among these transition metal compounds, those in which M ¹ in the general formula [4] is titanium or zirconium are preferably used.

Herein, the halogen atoms in the formula represented by R ³ to R ¹⁴ are chlorine, bromine, iodine or fluorine atoms.

Moreover, the cyclopentadienyl group by which the substituted cyclopentadienyl group substituted 1 or more of C1-C6 alkyl groups specifically, methylcyclopentadienyl group: 1,2-dimethylcyclopentadienyl group: pentamethylcyclopentadienyl group, etc. to be.

In the above formula, R ³ to R ¹⁴ each represent a hydrogen atom and an alkyl group having 1 to 20 carbon atoms (specifically, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, amyl group, isoamyl group and octyl group). , 2-ethylhexyl group), an alkoxy group having 1 to 20 carbon atoms (specifically methoxy group, ethoxy group, propoxy group, butoxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, etc.), carbon number 6-20 allyl groups (specifically, phenyl groups, naphthyl groups), arylalkyl groups (specifically, benzyl groups, phenethyl groups, 9-anthrylmethyl groups, etc.) having 7 to 20 carbon atoms, and acyloxy groups having 1-20 carbon atoms ( Specifically, an acetyloxy group, a stearoyloxy group, etc.) may be sufficient. These R ³ -R ¹⁴ may be the same or different as long as the above conditions are provided.

As such, specific examples of the titanium compound among the transition metal compounds represented by the general formulas [4] to [7] include tetramethoxytitanium: tetraethoxytitanium: tetra-n-butoxytitanium: tetraisopropoxytitanium: cyclo Pentadienyl trimethyl titanium: Titanium tetrachloride: Titanium trichloride: dimethoxy titanium dichloride: methoxy titanium trichloride: trimethoxy titanium chloride: cyclopentadienyl triethyl titanium: cyclopentadienyl tripropyl titanium: cyclopentadienyl Tributyl titanium: methylcyclopentadienyltrimethyl titanium: methylcyclopentadienyltribenzyl titanium: 1,2-dimethylcyclopentadienyltrimethyl titanium: tetra methylcyclopentadienyltrimethyl titanium: pentamethylcyclopentadienyltrimethyl titanium Pentamethylcyclopentadienyl triethyl titanium: Pentamethylcyclopentadienyl tripropyl titanium: Pentamethylcyclopentadiene Tributyl titanium: pentamethylcyclopentadienyl titanium triphenyl: pentamethylcyclopentadienyltribenzyl titanium: cyclopentadienylmethyl titanium dichloride: cyclopentadienylethyl titanium dichloride: pentamethylcyclopentadienylethyl titanium Dichloride: Cyclopentadienyl dimethyl titanium monochloride: Cyclopentadienyl diethyl titanium monochloride: Cyclopentadienyl titanium trimethoxide: Cyclopentadienyl titanium triethoxide: Cyclopentadienyl titanium tripropoxide : Cyclopentadienyl titanium tripropoxide: Cyclopentadienyl titanium triphenoxide: Pentamethylcyclopentadienyl titanium trimethoxide: Pentanmethylcyclopentadienyl titanium triepoxide: Pentamethylcyclopentadienyl titanium tree Bromine: pentamethylcyclopentadienyl titanium triphenoxide: cyclopentadienyl titanium trichlora De: pentamethylcyclopentadienyl titanium trichloride: cyclopentadienylmethoxytitanium dichloride: cyclopentadienyldimethoxytitanium chloride: pentamethylcyclopentadienylmethoxytitanium dichloride: cyclotadienyltribenzyl titanium: cyclo Pentadienyldimethylmethoxytitanium: methylcyclopentadienyldimethylmethoxytitanium: pentamethylcyclopentadienylmethyldiethoxytitanium: indenyl titanium trichloride: indenyl titanium trimethoxide: indenyl titanium triethoxide Indenyl trimethyl titanium: Indenyl tribenzyl titanium etc. are mentioned.

Moreover, bis (cyclopentadienyl) dimethyl titanium: bis (cyclopentadienyl) diphenyl titanium: bis (cyclopentadienyl) diphenyl titanium: bis (cyclopentadienyl) as a biscyclopentadienyl substituent in a titanium compound ) Diethyl titanium: bis (cyclopentadienyl) dibenzyl titanium: bis (methylcyclopentadienyl) dimethyl titanium: bis (pentamethylcyclopentadienyl) dimethyl titanium: bis (methyldicyclopentadienyl) dibenzyl Titanium: bis (pentamethylcyclopentadienyl) dibenzyl titanium: bis (pentamethylcyclopentadienyl) chloromethyltitanium; Bis (pentamethyl cyclopentadienyl) hydride methyl titanium etc. are mentioned.

Moreover, the titanium compound containing crosslinked ligands, such as ethylene bis (indenyl) dimethyl titanium: ethylene bis (tetrahydro indenyl) dimethyl titanium: dimethyl silane bis (cyclopentadienyl) dimethyl titanium, is also mentioned.

These transition metal compounds may also be complexed with Lewis bases.

Among the titanium compounds, in the catalyst system combined with the catalyst component (B), when it is necessary to increase the molecular weight of the styrene polymer, a titanium compound having an alkoxide and a substituted? Electron ligand is preferable.

In addition, when reducing the molecular weight, a titanium compound having a π-electron ligand and a halogen ligand is preferable.

Specific examples of the zirconium compound among the transition metal compounds represented by the general formulas [4] to [7] include cyclopentadienyl zirconium trimethoxide: pentamethylcyclopenta dienyl zirconium trimethoxide: cyclopentadienyl Tribenzyl zirconium: pentamethylcyclopentadienyl tribenzyl zirconium: bisdenyl zirconium dichloride: zirconium dibenzyl dichloride: zirconium tetrabenzyl: tributoxy zirconium chloride: triisopropoxy zirconium chloride and the like.

Specific examples of the hafnium compound include cyclopentadienyl hafnium trimethoxide: pentamethylcyclopentadienylharnium trimethoxide: cyclopentadienyltribenzyl hafnium: pentamethylcyclopentadienyltribenzyl hafnium and bisdenyl Hafnium dichloride: Hafnium dibenzyldichloride: Hafnium tetrabenzyl: Tributoxy hafnium chloride: Triisopropoxy hafnium chloride, etc. are mentioned.

Specific examples of the vanadium compound include vanadium trichloride: vanadium trichloride: vanadium triacetylacetite: vanadium tetrachloride: vanadium tributoxide: vanadil dichloride: vanadil bisacetylacetate: vanadil triacetylacetonite, and the like. Can be mentioned.

On the other hand, (B) component of a catalyst is a catalyst product of an organoaluminum compound and a condensing agent.

Here, as an organoaluminum compound, it is a general formula

AlR ¹⁵ ₃

[In formula, R <^15> represents a C1-C8 alkyl group.] The organoaluminum compound shown, specifically, trialkyl aluminum, such as trimethyl aluminum, triethyl aluminum, and triiso butyl aluminum, is mentioned, Especially, trimethyl Aluminum is preferred.

In addition, the condensing agent may typically include water, and in addition, various condensation reactions of the trialkylaluminum, such as copper sulfate pentahydrate, adsorbed water to inorganic or organic substances, and the like can be given.

Representative examples of the catalyst product of the organoaluminum compound, which is the component (B) of the catalyst used in the present invention, and a condensing agent include a contact product of trialkyl aluminum represented by the general formula AlR ¹⁵ ₃ with water. General formula below [8]

···[8]

[In formula, q is a polymerization degree of 0-50 and R <^16> represents the C1-C8 alkyl group.] The chain alkyl aluminoxane represented by following or general formula [9]

[9]

And cyclic alkylalumine oxane (repeating unit 2-50) having a repeating unit represented by [wherein, R ¹⁶ is the same as the former].

Generally, the contact product of aluminum and water, such as trialkylaluminum, is a mixture of unreacted trialkylaluminum and various condensation products together with the above-described linear alkylaluminoxane or cyclic alkylaluminoxane, or they are complicated. These are mixed molecules, and these are various products depending on the contact conditions of trialkylaluminum and water as a condensing agent.

There is no restriction | limiting in particular in reaction of alkyl aluminum and a condensation agent at this time, What is necessary is just to react according to the method of pride.

For example, ① a method of dissolving an organoaluminum compound in an organic solvent and contacting it with water.

(2) A method of adding an original organoaluminum compound at the time of polymerization and then adding water.

③ There is a method of reacting the crystallized water contained in the metal salt or the like or the adsorbed water into the organic material with the organoaluminum compound.

In addition, although this reaction advances even without a solvent, it is preferable to carry out in a solvent, As a suitable solvent, Aliphatic hydrocarbons, such as hexane, heptane, decane, or aromatic hydrocarbons, such as benzene and toluene xylene, are mentioned.

The water may contain up to 20% of sulfur compounds such as ammonia hydrogen and amine hydrogen sulfide such as ethylamine and phosphorus compounds such as phosphite ester.

In the present invention, the catalyst product (for example, alkylaluminoxane) of the organoaluminum compound used as the component (B) of the catalyst and the condensing agent is a solid residue after the above-mentioned contact reaction and a hydrous compound is used. It is effective to filter and heat-treat the filtrate at 30-200 ° C., preferably at 40-150 ° C., for 20 minutes-8 hours, preferably 30 minutes-5 hours, while distilling off the solvent under normal or reduced pressure.

In this heat treatment, a temperature may be selected according to various situations, but is usually in the above range.

Generally, it is ineffective below 30 ° C., and above 200 ° C. is undesirable due to thermal decomposition of the alkylaluminoxane itself.

The reaction product under the heat treatment conditions is obtained as a colorless solid or in solution.

The product thus obtained can be dissolved or diluted in a hydrocarbon solvent as necessary to be used as a catalyst solution.

A suitable example of the contact product of the organoaluminum compound and the condensing agent used as component (B) of such a catalyst, in particular alkylaluminoxane, is an aluminum-methyl group (Al-CH ₃ ) bond observed in the proton nuclear magnetic resonance spectrum. The high magnetic field component in the methyl proton signal region is 50% or less.

In other words, when the above-mentioned contact product was observed at room temperature and its proton nuclear magnetic resonance ( ¹ H-NMR) spectrum in a toluene solvent, the methyl proton signal by Al-CH ₃ was 1.0-0.5 based on tetramethylsilane (TMS). It is seen in the range of ppm.

Since the proton signal (O ppm) of the TMS be in the methyl proton observation area by the _{Al-CH 3, Al-CH} 3 and is measured based on the methyl proton signal of toluene 2.35ppm, based on the methyl proton signal due to the magnetic field component (I.e., -0.1-0.5 ppm) and other disturbance components (i.e. 1.0--0.1 ppm), the high magnetic field component is not more than 50% of the total, preferably 45-5% of the catalyst (B It can be used as a component.

The catalyst used in the method of the present invention contains the above-mentioned components (A) and (B) as main components, and other catalyst components (D) can be added, and catalytic activity (D) is added as the catalyst component (D) is added. Can be significantly improved.

This catalyst component (D) is represented by the following general formula [10]:

R ¹⁷ _k AlY _3-k [10]

[Wherein, R ¹⁷ represents a hydrocarbon group such as an alkyl group having 1 to 18 carbon atoms, preferably 1-12, an alkenyl group, an aryl group, an aralkyl group or an alkoxy group, and Y represents a hydrogen atom or a halogen atom. K is in a range of 1 ≦ K ≦ 3.].

The organoaluminum compound which is this (D) component specifically, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, diethyl 1 type, or 2 or more types of aluminum ethoxide etc. are mentioned.

Moreover, general formula [11] in the range which does not impair stereoregularity.

W-R ^18- (P) _r -R ¹⁹ -W '

[In formula, R <^18> , R <^19> is a C6-C40 substituted aromatic hydrocarbon which has a substituent containing a hetero atom, such as a C1-C20 hydrocarbon group, a C7-C30 substituted aromatic hydrocarbon group, or oxygen, nitrogen, and sulfur. Group, p is a hydrocarbon group of 1-20 carbon atoms,

or

R ²⁰ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. W, W 'represents a hydroxyl group, an aldehyde group and a carboxyl group, and r represents an integer of 0 or 1-5. The organic compound having at least two hydroxyl groups or an aldehyde group and a carboxyl group represented by

Specific examples of the organic compound represented by the general formula [11] include 2,2'-dihydroxy-3,3'-di-t-butyl-5,5'-dimethyldiphenylsulfide: 2,2 '-Dihydroxy-3,3'-di-t-butyl-5,5'-dimethyldiphenyl ether and the like can be given.

In the method of the present invention, a catalyst containing (A) and (B) as a main component is used, and the proportion of each of these components is based on the type of each component and the styrene-based monomers, particularly styrene-based monomers -I, II. Depending on the type and other conditions and not determined uniformly, the ratio of the aluminum in the component (B) to the transition metal (for example, titanium) in the component (A), i.e., aluminum / transition metal (molar ratio) is 1 -10 ⁶ , preferably 10-10 ⁴ .

In addition, in the hybrid polymerization of styrene monomer and hydrocarbon group-containing styrene monomer having an unsaturated bond, the use ratio thereof is not particularly limited and may be appropriately selected according to various situations.

In general, the following graft polymerization step (step 2) may be determined according to the desired number of graft initiation points or the amount of graft, and in the case of increasing the number of graft initiation points or the amount of grafts, a hydrocarbon-containing styrene monomer having an unsaturated bond ( Styrene Monomer II, etc.) may be increased.

In the hybridization of styrene-based mono-I and styrene-based mono-II, the ratio of styrene-based mono-II to the total amount of styrene-based mono-I, II is usually 1 X 10 ^-10 -50 mol%, preferably 1 X 10 ^-8 -20 mol%, and more preferably 1 X 10 ^-6 -15 mol%.

The ratio of the use of the raw material monoma and the catalyst may be appropriately determined, but in general, the ratio of styrene monoma-I and II to aluminum in the contact product of component (B) of the catalyst, that is, styrene monoma-I and II / aluminum ( molar ratio) is 1-10 ^6, preferably 10 ² - 10 ⁴ a.

The catalyst used in the step (1) of the process of the present invention is a (A) transition metal compound and (C) transition, in addition to (A) a transition metal compound and (B) a catalyst composed mainly of a contact product of an organic aluminum and a condensing agent. The catalyst which has a compound which makes a ionic complex react with a metal compound and forms an ionic complex as a main component, or the catalyst which has the said (A) component, (C) component, and (D) component as a main component is used.

What is necessary is just to select suitably the transition metal compound which is (A) component from the above. Preferably, transition metal compounds represented by the general formulas [4], [5], [6], and [7] may be used. More preferably, in general formula [4], R <^3> -R <^6> is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a hydrogen atom, a C1-C12 alkyl group, and a C1-C12 alkoxy Group, a C6-C20 aryl group, a C6-C20 allyloxy group, a C6-C20 arylalkyl group, or a halogen atom, At least 1 of R <^3> -R <^6> is a cyclopentadienyl group and a substituted cyclopentadie Preferred are titanium compounds having a nil group, an indenyl group, and a substituted indenyl group.

Although the organoaluminum compound which is (D) component should just be selected suitably from the above-mentioned, Preferably, what is represented by General formula [10] is used.

The component (C) is not particularly limited as long as it is a compound which reacts with the transition metal compound of component (A) to form an ionic complex. However, the cation and the plurality of groups are preferably VB, VIB, VIIB, VIIB groups. And coordination complex compounds of anions bonded with an element selected from Group VIII, Group IB, Group IIB, Group IIIA, Group IVA, and Group VA.

About this (C) component, the coordination complex compound represented by following formula [12] or [13] can be used.

([L ¹ -H] ^{U +} ) _V ([M ⁵ X ¹ X ² ... X ^S ] ^(st)- ) _i ... 12

Or ([L ² ] ^{U +} ) _V ([M ⁶ X ¹ X ² ... X ^S ] ^(st)- ) _i ... [13]

[L, L²M⁷, R²¹, R²², R⁸Or R²³ ₃C is. L in formula [12], [13]^OneSilver Lewis base, M⁵And M⁶Are elements selected from Group VB, Group VIB, Group VIII, Group IB, Group IIB, Group IIIA, IVA or Group VA, respectively: M⁷Silver metal selected from Groups IB, IIB and VIII of the stock price table, M⁸Silver, metal selected from group VIII of the stock price table^One-X^SRepresents a hydrogen atom, a dialkyl amino group, an alkoxy group, an allyloxy group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, a substituted alkyl group, an organic metaroid group or a halogen atom, respectively , R²¹And R²²Is a cyclodienyl group, a substituted cyclopentadienyl group, an indenyl group, or a fluorenyl group, respectively.²³Represents a hydrocarbon group. t is M⁵, M⁶The valence of is an integer from 1-7, S is an integer from 2-8, u is [L^One-H], [L²] Is an integer 1-7, V is an integer greater than or equal to 1, and I = u x v / (s-t).]

Specific examples of the tooth base represented by L ¹ include ethers such as dimethyl ether, diethyl ether and tetrahydrofuran, thioethers such as tetrahydrothiophene, esters such as ethyl benzoate, acetonitrile and benzo Nitriles such as nitrile, trimethylamine, triethylamine, tributylamine, N, N-dimethyl aniline, amines such as 2,2'-bipyridine and phenanthroline, triethylphosphine, triphenylphosphine Phosphines, ethylene, butadiene, 1-pentene, isoprene, pentadiene, 1-hexene and derivatives thereof with cyclic unsaturated hydrocarbons, benzene, toluene, xylene, cyclopentatriene, cyclooctadiene, cyclo Octatriene, cyclooctatetraene, derivatives thereof, etc. are mentioned.

Specific examples of M ⁵ and M ⁶ include B, Al, Si, P, As, Sb, and the like, and specific examples of M ⁷ include Li, Na, Ag, and Cu, and specific examples of M ⁸ include Fe, Co, and Ni. Can be mentioned.

Specific examples of X ¹ -X ^S include dimethylamino group, diethylamino group as dialkyl amine group, methoxy group, ethoxy group as alkoxy group, n-butoxy group, phenoxy group as allyloxy group, 2,6-dimethyl phenoxy group, Naphthyloxy group, alkyl group having 1-20 carbon atoms, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, n-octyl group, 2-ethylhexyl group, aryl group having 6-20 carbon atoms, alkyl As aryl group or arylalkyl group, phenyl group, p-tolyl group, benzyl group, pentafluorophenyl group, 3,5-di (trifluoromethyl) phenyl group, 4-t-butylphenyl group, 2,6-dimethylphenyl group, 3,5- Dimethylphenyl group, 2,4-dimethylphenyl group, 1,2-dimethylphenyl group, F, Cl, Br, I as halogen, 5 methyl antimony group, trimethylsilyl group, trimethyl germanyl group, diphenyl arsine group as organic metaroid group And dicyclohexyl antimony group and diphenyl boron group.

Specific examples of the substituted cyclopentadienyl group of R ²¹ and R ²² include a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group.

Among the compounds of the above formulas [12] and [13], specifically, the following may be used.

For example, as the compound of formula [12], tetraphenylborate triethylammonium, tetraphenylborate tripropylammonium, tetraphenylborate tri (n-butyl) ammonium, tetra (o, p-dimethylphenyl) borate tri (n- Butyl) ammonium, tetraphenylborate trimethylammonium, tetra (p-trifluoromethyl) borate tri (n-butyl) ammonium, tetraphenylborate triphenylphosphonium, tetraphenylborate tri (methylphenyl) phosphonium, tetraphenylborate tri ( Dimethylphenyl) phosphonium, tetra (pentafluorophenyl) boric acid, isopropylammonium, tetraphenylborate dicyclohexyl ammonium, tetra (pentafluorophenyl) boric acid triethylammonium, tetra (pentafluorophenyl) boric acid tri (n-butyl) Ammonium, hexafluorobisic acid triethylammonium, tetra (pentafluorophenyl) boric acid dimethylanilinium, tetra (pentafluorophenyl) borate diethylanilinium, tetra (pentafluorophenyl) Boric acid di-n-butylanilinium, tetra (pentafluorophenyl) borate methyldiphenylammonium, tetra (pentafluorophenyl) borate p-bromo-N, N'-dimethylanilinium, and the like.

On the other hand, as the compound of formula [13], tetraphenylborate ferrocene, tetra (pentafluorophenyl) borate ferrocene, tetra (pentafluorophenyl) borate decamethylferrocene, tetra (pentafluorophenyl) borate acetylferrocene and tetra ( Pentafluorophenyl) boric acid propyl ferrocene, tetra (pentafluorophenyl) boric acid cyano ferrocenium, tetraphenyl boric acid, tetra (pentafluorophenyl) boric acid, tetraphenyl borate trityl, tetra (pentafluorophenyl) triborate , Hexafluorobisic acid, silver hexafluoroantimonic acid, silver tetrafluoroborate and the like.

The catalyst used in the method of the present invention is composed of the above-mentioned components (A) and (B) as the main component, (A) component, (B) component and (D) component as main components, and the above (A) There exist some which have a component and (C) component as a main component, and others have the said (A) component, (C) component, and (D) component as a main component.

In this case, the addition ratio of (A) component and (C) component does not have a restriction | limiting in particular, The molar ratio of (A) component: (C) component is 1: 0.01-1: 100, especially 1: 1: 1-1: 10 It is desirable to.

The components (A) and (C) may be contacted in advance to separate and clean the contact product, or may be contacted in the polymerization system.

In addition, the usage-amount of (D) component is 0-100 mol normally with respect to 1 mol of (A) components.

When the component (D) is used, polymerization activity can be achieved, but when the amount is too large, the effect corresponding to the amount of addition is not obtained.

In addition, you may use (D) component in contact with (A) component, (C) component, or the contact product of (A) component and (C) component. This contact may be carried out in advance, or may be sequentially added and brought into contact with the polymerization system.

In addition, the polymerization temperature, polymerization time, polymerization method and the like of step 1 may be appropriately selected, but in general, the polymerization temperature is 0-120 ° C, preferably 10-80 ° C, and the polymerization time is selected at 1 second-10 hours. good.

The polymerization method may be any of a block, a solution, and suspension polymerization.

Examples of solvents that can be used in solution polymerization include aliphatic hydrocarbons such as pentane, hexane and heptane, alicyclic hydrocarbons such as cyclohexane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene. have.

Among these, aliphatic hydrocarbons and aromatic hydrocarbons are preferable.

In this case, the monoma / solvent (volume ratio) can be arbitrarily selected.

The amount of the component (C) is a raw material monoma / coordination complex compound (molar ratio) 1 - is preferably 10 ⁷ to 10 ^9, in particular 100.

In the method of this invention, after manufacturing a styrenic interpolymer by the said process 1, it carries out the process (step 2) which graft-polymerizes ethylenically unsaturated monomer.

Here, as the styrenic interpolymer obtained in Step 1, the structure thereof is not particularly limited.

However, as described above, as a hydrocarbon group-containing styrene monomer having an unsaturated bond, a monomer containing a styrene skeleton and an α-olefin skeleton in the same molecule was used, and a hybrid polymer was prepared using the catalyst of the production method of the present invention. In this case, even if the hybridization ratio of monoma is relatively high, crosslinking reaction can be suppressed and a straight chain hybrid polymer can be obtained effectively.

As a result of examining the cause, it was found that the hybrid polymerization was not present in the monostyrene styrene skeleton, but was hybridized with the α-olefin skeleton to remain a double bond of the styrene skeleton.

Interpolymers having such a structure have not been known in the past.

The ethylenically unsaturated monomers usable here are of the general formula [3]

[3]

[Wherein, Q ¹ , Q ² , Q ³ and Q ₄ each contain one or more of hydrogen, halogen or carbon, oxygen, nitrogen, sulfur, phosphorus, silane, silicon and tin atoms And substituents, and these Q ¹ to Q ⁴ may be the same or different.] As long as the formula is represented, various monomers may be mentioned as long as the monomer is capable of hybridizing with the repeating unit of the styrene-based interpolymer. .

Suitable examples include (1) acrylic acid, methacrylic acid, derivatives thereof, (2) acrylamide, methacrylamide, derivatives thereof, (3) vinyl acetate, derivatives thereof, (4) cinnamic acid, crotonic acid, Derivatives, (5) acrylonitrile, methacrylonitrile, derivatives thereof, (6) maleic acid, fumaric acid, maleic anhydride, derivatives thereof, (7) maleimide, derivatives thereof, (8) itaconic acid, ita anhydride Cholic acid, derivatives thereof, (9) acrolein, (10) vinyl ketones, (11) dienes, (12) styrene, derivatives thereof, (13) α-olefins or (14) cyclic olefins have.

Here, as the derivative of (meth) acrylic acid in the compound of (1), allyl acrylate: isopropyl acrylate: ethyl acrylate: 2,3-epoxypropyl acrylate: 2-chloroethyl acrylate: acrylic acid chloride: cyclododecyl acrylate: diacrylate Bromopropyl: 6,8-dimethyl-1-oxy-5-chromenyl methyl acrylate: 1,2,2,2-tetrachloroethyl acrylate: tetrahydrofurfuryl acrylate: hydroxyethyl acrylate: hydroxypropyl acrylate: η ^6- (2-phenylethyl acrylate) Tricarbonyl chrome: butyl acrylate: 2-propynyl acrylate: benzyl acrylate: 2- (1-aziridine) ethyl methacrylate: p-acetyl phenyl: methacrylate Acid 2-acetosylethyl: Methacrylic acid 1- (9-Anthyl) ethyl: Methacrylic acid Ethyl: Methacrylic acid 2,3-Ethiothiopropyl: Methacrylic acid 2,3-Epoxypropyl: Methacrylic acid Octa Decyl: methacrylate octafluoropentyl: Methacrylic acid p-chlorophenyl: Methacrylic acid chloromethyl: Methacrylic acid 2- (diethylamino) ethyl: Methacrylic acid cyclohexyl: Methacrylic acid 2,6-di-t-butylphenyl: Methacrylic acid p -Dimethylaminobenzyl: Methacrylic acid 2- (N, N'-dimethylcarbamoyloxyethyl): Methacrylic acid 2,6-dimethylphenyl: Methacrylic acid 1,2,2,2-tetrachloroethyl: Meta Trifluoroethyl methacrylate: 2,2,4-trimethyl-3-one-1-pentyl methacrylate: p-nitrophenol methacrylate: 2-pyridine methacrylic acid: phenyl methacrylate: ferrocene ethyl methacrylate : Methacrylic acid t-butyl: Methacrylic acid fluoride: Methacrylic acid Benzyl: Methacrylic acid p-methylphenyl: Methacrylic acid 3,4-methylenedioxybenzyl: Methacrylic acid 2-mercapto benzothiazole: Methacrylic Acid (-)-3-mentyl and the like.

As a derivative of the (meth) acrylamide which is the compound of said (2), N-methyl acrylamide: N-ethyl acrylamide: N-isopropyl acrylamide: N- (eta)-butyl acrylamide: N-sec- butyl acryl Amides: N-isobutylacrylamide: Nt-butylacrylamide: N- (1,1-dimethylpropyl) acrylamide: N-cyclohexylacrylamide: N- (1,1-dimethylbutyl) acrylamide: N- (1-ethyl-1-methylpropyl) acrylamide: Nn-heptylacrylamide: N- (1,1-dimethylpentyl) acrylamide: N- (1-ethyl-1-methylbutyl) acrylamide: N- ( 1-ethyl-1,2-dimethylpropyl) acrylamide: N- (1,1-diethylpropyl) acrylamide: Nn-octylacrylamide: N- (1,1,3,3-tetramethylbutyl) acryl Amides: N- (1,2,3,3-tetramethylbutyl) acrylamide: N- (1-ethyl-1,3-dimethylbutyl) acrylamide: N- (1,1-diethylbutyl) acrylamide : N- (1-ethyl-1-methylpentyl) acrylamide: N- (1-propyl-1,3-dimethylpart Tyl) acrylamide: N- (1,1-diethylpentyl) acrylamide: N- (1-butyl-1,3-dimethylbutyl) acrylamide: N-dodecylacrylamide: N- (1-methylound Acylamide: N- (1,1-dibutylpentyl) acrylamide: N- (1-methyltridecyl) acrylamide: N- (1-methylpentadecyl) acrylamide: N- (1-methylhepta Decyl) acrylamide: N- (1-adamantyl) acrylamide: N- (7,7-dimethylbicyclo [3,2,0] hepto-6-yl) acrylamide: N-allylacrylamide: N -(1,1-dimethylpropyl) acrylamide: N-benzylacrylamide: N-phenylacrylamide: N- (2-methylphenyl) acrylamide: N- (4-methylphenyl) acrylamide: N- (1-naph Tyl) acrylamide: N- (2-naphthyl) acrylamide: N-methyl methacrylamide: N-ethyl methacrylamide: Nn-butyl methacrylamide: Nt-butyl methacrylamide: Nn-octyl methacrylamide : Nn-dodecyl methacrylamide: N-cyclohexyl methacrylamide: N- (7,7-dimeth Bicyclo [3,2,0] hepto-6-yl) methacrylamide: N-allyl methacrylamide: N- (1,1-dimethylpropenyl) methacrylamide: N-benzylmethacrylamide: N- [1- (4-Chlorophenyl)] ethyl methacrylamide: N-phenyl methacrylamide: N- (2-methylphenyl) methacrylamide, N- (3-methylphenyl) methacrylate: N- (4-methylphenyl ) Methacrylamide: N, N-bis (2-cyanoethyl) acrylamide: N- (4-cyano-2,2,6,6-tetramethyl-4-piperidine) acrylamide: N- (2-cyanoethyl) methacrylamide: N- (1,1-dimethyl-2-cyanoethyl) acrylamide: N- (hydroxymethyl) acrylamide: N- (methoxymethyl) acrylamide: N -(Hydroxymethyl) acrylamide: N- (methoxymethyl) acrylamide: N- (ethoxymenyl) acrylamide: N- (n-propoxymethyl) acrylamide: N- (isopropoxymethyl) acryl Amide: N- (n-butoxymethyl) acrylamide: N, N'-methylenebisacrylamide: 1,2-bisacrylamide De ethane: 1,3-bisacrylamide propane: 1,4-bisacrylamide butane: 1,5-bisacrylamide pentane: 1,6-bisacrylamide hexane: 1,7-bisacrylamide heptane: 1, 8-bisacrylamide octane: 1,9-bisacrylamide nonane: 1,10-bisacrylamide decane: 1,12-bisacrylamide decane: 1,1,1-trimethylamine-2- (N-phenyl- N-acryloyl) propaneimide: 1,1-dimethyl-1- (2-hydroxy) propylamine-N-phenyl-N-methacryloylglycineimide: N- (2-dimethylaminoethyl) Acrylamide: N- (2-diethylaminoethyl) acrylamide: N- (2-monoglinoethyl) acrylamide: N- (3-dimethylaminopropyl) acrylamide: N- (3-diethylaminopropyl ) Acrylamide: N- (3-propylaminopropyl) acrylamide: N- [3-bis (2-hydroxyethyl) aminopropyl] acrylamide: N- (1,1-dimethyl-2-dimethylaminoethyl) Acrylamide: N- (2,2-dimethyl-3-dimethylami Propyl) acrylamide: N- (2,2-dimethyl-3-diethylaminopropyl) acrylamide: N- (2,2-dimethyl-dibutylaminopropyl) acrylamide: N- (1,1-dimethyl- 3-dimethylaminopropyl) acrylamide: N-acryloylglycinamide: N- (2,4-dinitrophenylhydrazono) methyleneacrylamide: 2-acrylamidepropane sulfonic acid: 2-acrylamide-n-butane sulfonic acid : 2-acrylamide-n-hexane sulfonic acid: 2-acrylamide-n-octane sulfonic acid: 2-acrylamide-n-dodecane sulfonic acid: 2-acrylamide-n- tetradecane sulfonic acid: 2-acrylamide-2- Methylpropane sulfonic acid: 2-acrylamide-2-phenylpropane sulfonic acid: 2-acrylamide-2,4,4-trimethylpentane sulfonic acid: 2-acrylamide-2-methylphenylethane sulfonic acid: 2-acrylamide-2- (4 -Chlorophenyl) propane sulfonic acid: 2-acrylamide-2-carboxymethylpropane sulfonic acid: 2-acrylamide-2- (2-pyridyl) propane sulfonic acid: 2-acrylic Mid-1-methylpropane sulfonic acid: 3-acrylamide-3-methylbutane sulfonic acid: 2-ketacrylamide-n-decane sulfonic acid: 2-methacrylamide-n-tetradecane sulfonic acid: 4-methacrylimidebenzene sulfonic acid Sodium: N- (2,3-dimethylphenyl) methacrylamide: N- (2-hydroxyphenyl) methacrylamide: N- (2-methoxyphenyl) methacrylamide: N- (4-methoxyphenyl ) Methacrylamide: N- (3-ethoxyphenyl) methacrylamide: N- (4-ethoxyphenyl) methacrylamide: N- (3chlorophenyl) methacrylamide: N- (4-chlorophenyl) Methacrylamide: N- (4-bromophenyl) methacrylamide: N- (2,5-dichlorophenyl) methacrylamide: N- (2,3,6-trichlorophenyl) methacrylamide: N- (4-nitrophenyl) methacrylamide: N, N-dimethylacrylamide: N, N-diethylacrylamide: N, N-dibutylacrylamide: N, N-diisobutylacrylamide: N, N- Dicyclohexylacrylamide: N, N-bis (4-methylpentyl) acrylic Amides: N, N-diphenylacrylamide: N, N-bis (5-methylhexyl) diacrylamide: N, N-dibenzylacrylamide: N, N-bis (2-ethylhexyl) acrylamide: N -Methyl-N-phenylacrylamide: N-acryloylpyrrolidine: N-acryloylpiperidine: N-acryloylmorpholine: N-acryloylthiamorpholine: N, N-dimethylmethacrylamide N, N-diethyl methacrylamide N, N-diphenyl methacrylamide N-methyl-N-phenyl methacrylamide N-methacryloylpiperidine N- (2-hydroxyethyl) Acrylamide: N- (2-hydroxypropyl) acrylamide: N- (1,1-dimethyl-2-hydroxyethyl) acrylamide: N- (1-ethyl-2-hydroxyethyl) acrylamide: N -(1,1-dimethyl-3-hydroxybutyl) acrylamide: N- (2-chloroethyl) acrylamide: N- (1-methyl-2-chloroethyl) acrylamide: N- (2,2, 2-trichloro-1-hydroxyethyl) acrylamide: N- (2,2,2-trichloro-1-methoxyethyl) acrylic De: N- (1,2,2,2-tetrachloroethyl) acrylamide: N- (2,2,3-trichloro-2-hydroxypropyl) acrylamide: N- (2-chlorocyclohexyl) Acrylamide: N- (2,2-dichlorofluoroethyl) acrylamide: N- (2,2,2-trifluoroethyl) acrylamide: N- (3,3,3-trifluoropropyl) acryl Amides: N- (3,3-difluorobutyl) acrylamides: N, N-bis (2,2-difluoroethyl) acrylamides: N, N-bis (2,2,2-fluoroethyl ) Acrylamide: ethyl-2-acrylamide acetate: acryloyl dicyanidiamide: methacryloyl dicyanidiamide: N- (1-naphthyl) methacrylamide: N- (2-naphthyl) methacrylamide N-formylacrylamide N-acetylacrylamide N- (2-oxopropyl) acrylamide N- (1-methyl-2-oxopropyl) acrylamide N- (1-isobutyl-2- Oxopropyl) acrylamide: N- (1-benzyl-2-oxopropyl) acrylamide: N- (1,1-methyl-3-oxobutyl ) Acrylamide and the like.

Moreover, vinyl acetate which is a compound of (3), and its derivative are vinyl acetate, vinyl thio acetate, (alpha)-(1-cyclohexenyl) vinyl acetate, etc. Examples of the derivatives of cinnamic acid and crotonic acid as compounds of (4) include ethyl cinnamic acid, phenyl cinnamic acid, cinnamic acid t-butyl, crotonaldehyde, methyl crotonate, ethyl α-cyanocrotonate, and α-ethoxycroton Methyl acid and the like.

Among the compounds of (5), derivatives of (meth) acrylonitrile include vinylidene cyanide, α-methoxy acrylonitrile, α-phenyl acrylonitrile, α-acetoxy acrylonitrile and the like.

Among the compounds of (6), there may be mentioned derivatives of maleic acid, fumaric acid or maleic anhydride or maleic acid, esters of fumaric acid, and substituents of maleic acid, fumaric acid and maleic anhydride. For example, diethyl fumarate and fumaric acid Phenyl, fumaronitrile, methylfumaric acid, methyl ethyl fumarate, methylmaleic anhydride, dimethylmaleic anhydride, phenylmaleic anhydride, diphenylmaleic anhydride, chloromaleic anhydride, dichloromaleic anhydride, fluoric anhydride, Difluoromaleic anhydride,

Bromomaleic anhydride, dibromomaleic anhydride, methylmaleic acid, dimethyl maleic acid, phenylmaleic acid, chloro maleic acid, dichloro maleic acid, fluoro maleic acid, difluoro maleic acid, bromo maleic acid, dimethyl maleic acid Diethyl maleate, diethyl methyl maleate, dipropyl maleate, diisopropyl maleate, dibutyl maleate, diisobutyl maleate, dipentyl maleate, diisopentyl maleate, dihexyl maleate, Diheptyl maleate, dipentyl maleate, bis (2-ethylhexyl maleate), dinonyl maleate, dihexadecyl maleate, dipropargyl maleic acid, bis [2- (2-chloroethoxy maleic acid) Ethyl], dibenzyl maleate, methyl allyl maleate, methyl-2-butenyl maleate, methyl-3-butenyl maleate, allyl-3-methylthiopropyl maleate, allyl-3-ethylthio maleate Flofil, allyl-3-ethylthiopropyl maleate, allyl-3-phenylthiopropyl maleate, methyl-p-chlorophenyl maleate, butyl-p maleate -Chlorophenyl, maleic acid benzyl-p-chlorophenyl, maleic acid diphenyl, maleic acid di-m-cresyl, maleic acid di-p-cresyl, maleic acid-m-heptyl, nonyl maleic acid, decyl maleic acid , Dodecyl maleate, octadecyl maleate, fluoroalkyl maleate, and the like.

Among the compounds of (7), derivatives of maleimide include N-butyl maleimide, N-phenyl maleimide, N- (2-methylphenyl) maleimide, N-cyclohexyl maleimide, N- (2,6-dimitel ) Maleimide, N- (2,6-diethyl) maleimide, N- (α-naphthyl) maleimide and the like.

Among the compounds of (8), itaconic acid or derivatives of itaconic anhydride include diethyl itaconic acid, di-n-octyl itaconic acid, cis-glutaconic acid, diethyl cis-glutaconate, trans-glutaconic acid, trans Diethyl glutaconate and the like.

Acrolein of the compound of (9) is acrolein. Methacrolein, α-chloro acrolein, β-cyano acrolein and the like.

(10) Vinyl ketones of this compound include methyl vinyl ketone, phenyl vinyl ketone, ethyl vinyl ketone, n-propyl vinyl ketone, cyclohexyl vinyl ketone, isobutyl vinyl ketone and the like.

As dienes of the compound of (11), 1,3-butadiene: isoprene: 1-ethoxy-1,3-buradiene: chloroferene: 1-methoxy-1,3-cyclohexadiene: 1- Acetoxy-1,3-butadiene: 2-acetoxy-3-methyl-1,3-butadiene: 1-chloro 1,3-butadiene: 1- (4-pyridyl) -1,3-butadiene: munic acid : Diethyl muconate etc. are mentioned.

As the styrene of the compound of (12) or a derivative thereof, for example, the styrene monoma-I represented by the general formula [1] may be covered, but p-dimethylamino styrene: styrene sulfonate: p-nitro styrene: p-hydroxy styrene: p-vinylbenzoic acid 2,3-epoxy propyl: p-vinyl benzoic acid chloride: p-vinyl benzoic acid phenyl: p-vinyl benzoic acid methyl: p-vinyl benzoic acid 3-methoxy phenyl: p-isopropenyl phenol: p-cyano styrene: oxygen atoms such as p-acetoxy styrene. The styrene derivative or alpha-methylstyrene containing hetero atoms, such as a nitrogen atom, may be sufficient.

(Alpha) -olefins of the compound of (13) include ethylene: propylene: 1-butene: 1-octene: 4-methylpentene-1, 3-methylbutene-1 and the like.

Examples of the cyclic olefins of the compound of (14) include monocyclic olefins such as cyclobutene and cyclopentene: cyclohexene, and substituted monocyclic olefins such as 3-methyl cyclopentene: 3-methyl cyclohexene and norbornene. 1,2-dihydroxy-dicyclopentadiene: 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene Olefin, 5-methyl norbornene: 5-ethyl norbornene: 5-propyl norbornene: 5,6-dimethyl norbornene 1-methylnorbornene: 7-methyl norbornene: 5,5,6 -Trimethyl norbornene: 5-phenyl norbornene: 5-benzyl norbornene: 5-ethylene norbornene: 5-vinylnorbornene: 2-methyl-1,4,5,8-dimethano-1, 2,3,4,4a, 5,8, .8a-octohydronaphthalene: 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a Octohydronaphthalene: 2,3-dimethyl-1,4,5,8-dimethino-1,2,3,4,4a, 5,8,8a-ucto hydronaphthalene: 5-chloronorbornene: 5 , 5-dichloronorbornene: 5- Luoronorbornene: 5,5,6-trifluoro-6-trifluoromethyl norbornene: 5-chloromethyl norbornene: 5-methoxynorbornene: 5-dimethylamino norbornene and the like Substituted polycyclic olefins; and the like.

Although selection of these monomas is suitably selected according to the purpose of use of the graft copolymer obtained, in order to improve adhesiveness etc., it is preferable to have polar groups, such as unsaturated carboxylic acid or its derivative (s).

Moreover, maleimide or its derivative is used for the improvement of heat resistance. In cyclic olefins such as norbornene, ethylenically unsaturated monomers having a high glass transition temperature of the polymer are preferable.

In the method of the present invention, in the graft polymerization of step 2, the styrene-based mono-I, II or the catalyst of this reaction is removed as necessary for the styrenic interpolymer obtained in step 1, and then the methylene unsaturated monoma is added thereto. React

Here, the graft polymerization usually proceeds by shining a polymerization initiator or light.

In this graft polymerization, the styrene-based interpolymer may be previously activated by illuminating a polymerization initiator or light, and then ethylenically unsaturated monomer may be added.

In addition, after adding or adding ethylenic fluoride monomer to a styrenic interpolymer, you may add a polymerization initiator or shine.

As a polymerization initiator, there exist various things generally used conventionally, For example, an anionic polymerization initiator, a cationic polymerization initiator, or a radical polymerization initiator is mentioned.

In addition, polymerization can be initiated by heat, light (ultraviolet light, visible light, infrared light), electron beam, radiation, or the like.

In addition, when grafting α-olefins such as ethylene and propylene, styrenes, and cyclic olefins, by using a catalyst having a transition metal and an organic metal as a main component, not only the graft ratio but also the amount of graft can be increased.

Anionic polymerization initiators include alkali metals (Cs, Rb, K, Na, Li), alkali metal alkyls (n-butyl-Li, octyl-K, dibenzyl-Ba), alkali metal aromatic complexes (Na-naphthalene), alkalis Metal amides (KNH _2, Lin (C ₂ H ₅ ) ₂ ), and the like.

Cationic polymerization initiators include protonic acid, carbanium ion salts, halogens and the like. These protonic acids include hydrogen halides (HC1, HI, etc.), oxo acids (sulfuric acid, methanesulfonic acid, etc.), super acids and their derivatives (HC1O ₄ , CF ₃ SO ₃ H, ClSO ₃ H, CH ₃ COC1O _4, etc.), Metal oxides (silica alumina, CrO ₃ , NoO _3, etc.) and other solid acids (poly (styrenesulfonic acid)), Nafion-H, sulfuric acid-aluminum sulfate complex, and the like.

In addition, carboxylic banyum the ionic salt is triphenylmethyl salt _{^{(Pb 3 C + Base -)}} , Trojan required salt _{^{(C 7 H 7 + Base -}} ) ( where, Base ^- is _{^{SbC1 6 -, SnC1 5 -,}} PF 6 , C1O ₄ ^-. shows the like) and the like. Halogen includes I ₂ and IBr.

Also, metal halides (A1Cl ₃ , SnC1 ₄ , SnBr ₄ , TiC1 ₄ , FeC1 ₃ , BF ₃ , BCl _3, etc.) or organometallic compounds (RA1C1 ₂ , R ₂ A1C1, R ₃ A1, R ₂ Zn) (here , R represents an alkyl group such as methyl group, ethyl group or the like.

The radical polymerization initiators include peroxides, azo compounds and other compounds.

Here, the peroxides include acetyl peroxide, cumyl peroxide, t-butyl peroxide, propionyl peroxide, benzoyl peroxide, 2-chloro benzoyl peroxide, 3-chloro benzoyl peroxide, 4-chloro benzoyl peroxide, 2,4-dichloro benzoyl peroxide, 4-bromomethyl benzoyl peroxide, lauroyl peroxide, potassium peroxide, diisopropyl percarbonate, tetrahydrohydro peroxide, 1-phenyl-2-methylpropyl-1-hydro peroxide, pertriphenyl acetate t-butyl, t -Butyl hydroperoxide and t-butyl formate, t-butyl peracetate, t-butyl perbenzoate, t-butyl perphenyl acetate, t-butyl perphenyl acetate, per-methoxy butyl acetate, per-N- (3-toluyl) carbamic acid t-butyl and the like.

Specific examples of the azo compound include 2,2'-azobispropane: 2,2-dichloro-2,2-azobis propane: 1,1'-azo (methylethyl) diacetate: 2,2'-azobis ( 2-amidinopropane) hydrochloride: 2,2'-azobis (2-amidinopropane) nitrate: 2,2-azobis isobutane: 2,2'-azobisiso butyronitrile: 2,2'- Azobis isobutyronitrile and SnC1 ₄ (1 / 21.5), methyl 2'-azobis-2-methylpropionate: 2,2'-dichloro-2,2'-azobisbutane;2,2'-Azobis-2-methylbutyronitrile:2,2'-Azobisisobutyrate dimethyl: 2,2'-Azobisisobutyrate dimethyl / SnC1 ₄ (1 / 19.53): 1,1'- Azobis (1-methylbutyronitrile-3-sodium sulfonate): 2- (4-methylphenylazo) -2-methylmalonodinitrile: 4,4'-azobis-4-cyanovaleroic acid: 3, 5-dihydroxymethyl phenylazo-2-methyl malonodinitrile: 2- (4-bromophenyl azo) -2-allyl malonodinitrile: 2,2'-azobis-2-methyl valeronitrile: 4 , 4'-azobis-4-cyano valenoic acid dimethyl: 2,2'-azobis-2,4-dimethyl valeronitrile: 1,1'-azobiscyclohexane nitrile: 2,2'-azobis 2-propyl butyronitrile: 1,1-azobis-1-chlorokenyl ethane: 1,1'-azobis-1-cyclohexane carbonitrile: 1,1'-azobis-cycloheptane nitrile: 1, 1'-azobis-1-phenylethane: 1,1'-azobiscumene: 4-nitrophenylazobenzylcyanoacetic acid methyl: phenylazo diphenylmethane: phenyl azo Triphenyl methane: 4-nitrophenyl azotriphenylmethane: 1,1'-azobis-1,2-diphenyl ethane: poly (bisphenol A-4,4'-azobis-4-cyano pentanoate) Poly (tetra ethylene glycol-2,2-azobis isobutylate).

Moreover, as a compound other than that, 1, 4-bis (penta methylene) -2- tetracene: 1, 4- dimethoxy carbonyl- 1, 4- diphenyl- 2-tetracene: benzenesulfonyl azide, etc. There is this.

In the case of grafting α-olefins such as ethylene and propylene, styrenes, and cyclic olefins in a catalyst mainly composed of a transition metal and an organic metal, the transition metal compounds may be represented by the general formulas [4,] [5], In addition to [6] and [7], chromium compounds, nickel compounds and neodynium compounds may be used.

As the organometallic compound, the aluminoxanes of the general formulas [8] and [9] and the organoaluminum compounds of the general formula [10] can be used.

In the method of the present invention, the graft polymerization process (step 2) proceeds to the polymerization reaction by selecting appropriate conditions using the raw materials, initiators, and the like as described above.

As reaction conditions of the styrenic interpolymer obtained in Step 1 and the initiator, the reaction temperature may be -100-200 ° C, preferably -80-120 ° C, and the reaction time may be appropriately selected from 1 second to 10 hours.

In addition, after reacting an initiator such as alkyl lithium with the styrenic interpolymer obtained in Step 1, the graft efficiency can be improved by washing the unreacted residual initiator.

In the case where the graft chain is formed as an unreacted styrene monomer and a hybrid polymerization chain, after the synthesis of the graft precursor (step 1), an ethylenically unsaturated monoma is added with the graft initiator as it is to perform the graft reaction. Do it.

Here, when the catalyst used in step 1 can be used in the graft polymerization step of step 2, it is very efficient to use α-olefins such as ethylene and propylene, dienes such as butadiene and isoprene as ethylenically unsaturated monomers. Graft interpolymers can be prepared.

The ratio of styrene-based monoma-II and the initiator used in step 1 is usually the latter / former = 1 x 10 ^-7-10 (molar ratio). There is no particular restriction on the graft polymerization, and it may be selected according to various situations.

The ratio of styrenic mono-II and graftable ethylenically unsaturated monomer used in step 1 is set to the former / the latter = 0.01-500 (molar ratio), preferably 0.1-300 (molar ratio).

Moreover, polymerization temperature is -100 degreeC-200 degreeC, Preferably it is -80 degreeC-120 degreeC, and superposition | polymerization time is suitably selected from 5 second-24 hours.

As a polymerization method of the said process 2, any of a block, a solution, and suspension polymerization is possible.

As a solvent that can be used in solution polymerization, aliphatic hydrocarbons such as pentane, hexane and heptane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene or halogens such as oxygen, nitrogen and sulfur A polymerization solvent containing an atom can be used.

Herein, the solvent used may be the same as or different from that used in Step 1 above.

In addition, a washing process may be performed to remove the remaining unreacted monomer and catalyst and to improve the graft efficiency.

The graft interpolymer obtained in the method of the present invention has a three-dimensional main chain structure of a repeating unit derived from a syndiotactic structure (specifically, styrene-based monoma-I) and a repeating unit derived from styrene-based monoma-II. Hybrid syndiotactic structure), preferably a styrene-based interpolymer having a highly syndiotactic structure.

In addition, although the molecular weight of this main chain is variously obtained according to polymerization conditions etc., in general, the weight average molecular weight is 1,000 by gel permeation chromatography (GPC) [1,2,4-trichlorobenzene, 135 degreeC polystyrene conversion] measurement. -3,000,000, preferably 5,000-2,500,000.

As a highly syndiotactic structure, the stereochemical structure has a highly syndiotactic structure, that is, a stereo structure in which a phenyl group or a substituted phenyl group, which is a chain to the main chain formed from a carbon-carbon bond, is located opposite to each other. The taxity is measured by nuclear magnetic resonance ( ¹³ C-NMR method) using carbon isotopes.

Tacticity as measured by ¹³ C-NMR can be expressed as abundance of a plurality of consecutive units, for example, two diamonds, three triads, and five pentads. The styrenic interpolymer having the highly syndiotactic structure referred to in the invention is in the chain of styrene repeating units, usually at least 75%, preferably at least 85%, or at least 30% of racemic diamond in racemic diamond. As mentioned above, it shows preferably having 50% or more of syndiotacticity.

In addition, the steric structure of the graft chain of the graft polymer is not particularly limited, and it is possible to obtain an atactic, isotactic or syndiotactic structure depending on the type of the polymerization initiator or the like.

The graft interpolymer of the present invention thus obtained has various molecular weights, but preferably the graft component in the graft interpolymer is 0.005-99% by weight, and 1,2,4-trichlorobenzene The reduced viscosity at a concentration of 0.06 g / dl measured at 135 ° C. is 0.01-20 dl / g. If the reduced viscosity is too small, the physical properties of the polymer are not sufficient, and if the reduction viscosity is too large, the moldability deteriorates.

This graft interpolymer is especially a styrene derived from a hydrocarbon group-containing styrene monomer (styrene monomer-II) having an unsaturated bond with a styrene unit derived from a styrene monomer (such as styrene monomer-I) constituting the main chain. The unit has a syndiotactic structure (preferably a hybrid syndiotactic structure), in which an ethylenically unsaturated monoma (preferably monoma having a polar group) is grafted.

Here, the content of the graft monomer in the graft interpolymer is not necessarily the same depending on the kind of monoma used, the ratio of the graft starting point, etc., but is usually 0.005-90% by weight, preferably 0.01-70% by weight.

The styrenic interpolymers of the present invention are particularly improved in compatibility, adhesiveness, and wet temperature while retaining the heat resistance, chemical resistance, and the like of syndiotactic polystyrene.

Therefore, the styrenic hybrid polymer of the present invention is easily compounded with other resins, glass fibers, talc, fillers, ceramics, metals, and the like, and enables the application of syndiotactic styrene resins to composite materials.

In addition, the styrenic interpolymers of the present invention are effectively used as modifiers, compatibilizers and the like of various resins.

Next, the present invention will be described in more detail with reference to Examples.

In addition, this invention does not have any limitation in the following Example.

Example 1

(1) Preparation of methyl aluminoxane

200 ml of toluene, 17.7 g (71 mmol) of copper sulfate pentahydrate (CuSO ₄ · 5H ₂ O), and 24 ml (250 mmol) of trimethylaluminum were added to a 500 ml glass vessel substituted with argon, and the reaction was carried out at 40 ° C. for 8 hours. I was. Thereafter, toluene was distilled off under reduced pressure from the solution obtained by removing the solid component to obtain 6.7 g of a catalyst product. The molecular weight measured by this freezing point drop method was 610.

Further, based on Japanese Patent Application Laid-Open No. 62-325391, a proton nuclear magnetic resonance spectrum in a high magnetic field component by ¹ H-NMR measurement, i.e., toluene solution at room temperature, was measured (Al-CH ₃ ) -based methyl proton. The signal is seen in the range of 1.0 to 0.5 ppm on the basis of tetramethylsilane. Although the proton signal of tetramethylsilane is 0ppm, Al-CH, because the _third engagement observation area by the methyl proton based on, the Al-CH ₃ methyl proton signal 2.35 of toluene at standard tetramethylsilane the proton signal based on a combination When measured on the basis of ppm and divided into high magnetic components (ie, -0.1 to -0.5 ppm), the high magnetic components were 43% of the total.

(2) Preparation of p-methylstyrene-divinylbenzene interpolymer

Subsequently, after replacing the reaction vessel with an inner volume of 0.5 L with a stirrer, it was heated to 70 ° C., and 50 ml of toluene sufficiently dried therein and a divinylbenzene-containing monomer (divinylbenzene (m-, p-mixture) 66.1 weight %, 33.9% by weight of ethyl styrene (m-, p-mixture)) 3.0 ml of the mixture was added, and 1.5 mM of methylaluminoxane and 1.5 mM of triisobutylaluminum (TIBA) obtained in the above (1) were added. Stir for minutes. Subsequently, 0.003 mM of pentamethylcyclodienyl titanium trimethoxide was added and reacted for 2 hours. Then, 1/10 was taken out in the state which stirred and made the whole uniform, methanol was inject | poured and reaction was stopped.

Next, a mixed solution of hydrochloric acid and methanol was added to decompose the catalyst component.

Furthermore, when the obtained styrene type interpolymer was wash | cleaned at 50 degreeC with methyl ethyl ketone (containing 2 weight% of p-t- butylcatechol) for 2 hours, 99% was an insoluble matter.

The styrenic interpolymer insoluble in this methyl ethyl ketone was dissolved in chloroform to obtain a chloroform solution of the styrene interpolymer from a soluble component. The weight average molecular weight of the styrenic interpolymer soluble in this chloroform was 658,000, and the number average molecular weight was 180,000.

In addition, it is proved from the results of infrared absorption spectrum (IR) and nuclear magnetic resonance spectrum (NMR) that the styrene-based interpolymer is a thermally reactive styrene-based interpolymer having a syndiotactic structure.

(a) Measurement by IR

The peak of the double bond remaining in the polymerization site of divinylbenzene in the IR spectrum of the styrene-based copolymer was confirmed according to 1630 cm ^-1 .

(b) Measurement by NMR

As a result of measuring the ¹³ C-NMR spectrum of the styrenic cyclic polymer, the aromatic ring C ₁ carbon signal was observed at 145.1 ppm, 114.9 ppm, and 142.3 ppm. From this signal, it was confirmed that the steric structure of the styrene-based interpolymer was a syndiotactic structure.

(3) Graft reaction of methyl methacrylate (MMA)

The former p-methylstyrene-divinylbenzene interpolymer was washed three times with 200 ml of toluene and the unreacted catalyst was removed. Then, toluene was added and the total amount was 300 ml. Thereafter, 4 mM of n-butyllithium (n-BuLi) was added thereto and reacted at room temperature for 8 hours.

After completion of the reaction, the mixture was washed three times with 200 ml of toluene to remove unreacted n-BuLi.

Then, toluene was added and the total amount was 300 ml.

Thereafter, the reaction system was quenched at -78 ° C (dry ice + methanol), 20 ml of MMA was added dropwise, and the reaction was carried out for 8 hours.

After completion of the reaction, methanol was injected to stop the reaction. The yield of the MMA graft styrenic interpolymer obtained here was 4.2 g.

The (C = 0) peak of MMA was found at 1730 cm <^-1> in the IR spectrum of the said styrene type interpolymer. Moreover, it was confirmed that the peak of the double bond of divinylbenzene disappeared at 1630 cm <-1>.

In the 1,2,4-trichlorobenzene solution of this interpolymer, the reduced viscosity at 0.05 g / kPa measured at 135 ° C was 1.98 g / kPa. In addition, ¹³ C-NMR of the dipolymer was measured at 135 ° C. in 1,2,4-trichlorobenzene, and a signal was observed at 145.4 ppm. From this, the styrene chain was found to be syndiotactic. Moreover, the thictitiser by ¹³ C-NMR was 95% in racemic diamond. In addition, the ratio of p-methylstyrene and MMA determined from NMR was 1: 2.75 (weight ratio).

Example 2

A grafted styrene-divinylbenzene interpolymer of MMA was obtained in the same manner as in Example 1 (2) and (3) except that styrene was used instead of p-methylstyrene during the polymerization of the styrenic copolymer. The yield of the obtained styrenic interpolymer was 5.8 g.

The (C = 0) peak of MMA was found at 1730 cm <-1> in the IR spectrum of the said styrene type interpolymer.

In the 1,2,4-trichlorobenzene solution of this interpolymer, the reduced viscosity at 0.05 g / kPa measured at 135 ° C was 1.98 g / kPa.

Moreover, the thictitiser by ¹³ C-NMR was 95% in racemic diamond.

In addition, the ratio of styrene and MMA determined by NMR was 1: 2.82 (weight ratio).

Example 3

The acrylonitrile-grafted styrene-divinylbenzene interpolymer was obtained like Example 2 except having used acrylonitrile instead of MMA at the time of grafting. The yield of the obtained styrenic interpolymer was 25.2 g.

The peak of acrylonitrile was confirmed by 2240 cm <^-1> in the IR spectrum of said styrene polymer.

The reduced viscosity at a concentration of 0.05 g / dl at 135 ° C in the 1,2,4-trichlorobenzene solution of this interpolymer was 1.94 g / dl.

Moreover, the thictitiser by ¹³ C-NMR was 95% in racemic diamond.

In addition, the ratio of styrene and MMA determined by NMR was 1: 15.8 (weight ratio).

Example 4

The graft styrene-divinylbenzene interpolymer of isoprene was obtained in the same manner as in Example 2 except that isoprene was used in place of MMA and reacted at 50 ° C. The yield of the obtained styrenic interpolymer was 12.3 g.

840㎝ of the IR spectrum of the styrene-based polymer of ^-1, 1380㎝ ^-1, confirmed the peak of isoprene in 2960㎝ ^-1.

The reduced viscosity of the copolymer at a concentration of 0.05 g / dl, measured at 135 ° C in a 1,2,4-trichlorobenzene solution was 1.87 dl / g.

Moreover, the thictitiser by ¹³ C-NMR was 95% in racemic diamond.

In addition, the ratio of styrene and MMA determined by NMR was 1: 7.20 (weight ratio).

Example 5

In the same manner as in Example 2, butadiene was used instead of MMA and reacted at 50 ° C in grafting to obtain grafted styrene-divinylbenzene interpolymers of isoprene. The yield of the obtained styrenic interpolymer was 8.4 g.

The peak of butadiene was confirmed at 960 cm <^-1> in the IR spectrum of the said styrene polymer.

The reduced viscosity of the copolymer at a concentration of 0.05 g / dl, measured at 135 ° C, in the 1,2,4-trichlorobenzene solution was 1.89 dl / g.

Moreover, the thictitiser by ¹³ C-NMR was 95% in racemic diamond.

In addition, the ratio of styrene and MMA determined by NMR was 1: 4.60 (weight ratio).

Example 6

The grafted styrene-divinyl of MMA in the same manner as in Example 2 except that tetraethoxytitanium (TET) was used instead of pentamethylcyclopentadiethyltitanium trimethoxide as a catalyst in the polymerization of the styrene-based copolymer. A benzene interpolymer was obtained. The yield of the obtained styrenic interpolymer was 3.5 g.

The (C = 0) peak of MMA was confirmed at 1730 cm <^-1> in the IR spectrum of the said styrene polymer.

In the 1,2,4-trichlorobenzene solution of this interpolymer, the reduced viscosity at a concentration of 0.05 g / dl measured at 135 ° C was 2.00 dl / g.

Moreover, the thictitiser by ¹³ C-NMR was 95% in racemic diamond.

In addition, the ratio of styrene and MMA determined by NMR was 1: 2.18 (weight ratio).

Example 7

A grafted styrene-divinylbenzene interpolymer of MMA was obtained in the same manner as in Example 2 except that the polymerization solvent was changed from toluene to hexane. The yield of the obtained styrenic interpolymer was 5.6 g.

The (C = 0) peak of MMA was found at 1730 cm <^-1> in the IR spectrum of the said styrene polymer.

The reduced viscosity at a concentration of 0.05 g / dl at 135 ° C. in the 1,2,4-trichlorobenzene solution of this interpolymer was 2.0 dl / g.

Moreover, the thictitiser by ¹³ C-NMR was 95% in racemic diamond.

In addition, the ratio of styrene and MMA determined by NMR was 1: 4.09 (weight ratio).

Example 8

A grafted styrene-divinylbenzene interpolymer of MMA was obtained in the same manner as in Example 2 except that the polymerization solvent was changed from toluene to heptane. The yield of the obtained styrenic interpolymer was 8.1 g.

The (C = 0) peak of MMA was found at 1730 cm <^-1> in the IR spectrum of the said styrene polymer.

The reduced viscosity at a concentration of 0.05 g / dl at 135 ° C in the 1,2,4-trichlorobenzene solution of this interpolymer was 2.05 dl / g.

Moreover, the thictitiser by ¹³ C-NMR was 95% in racemic diamond.

In addition, the ratio of styrene and MMA determined by NMR was 1: 6.36 (weight ratio).

Example 9

A grafted styrene-divinylbenzene interpolymer of MMA was obtained in the same manner as in Example 2 except that azobisisobutyronitrile (AIBN) was used instead of n-BuLi as a catalyst during grafting. The yield of the obtained styrenic interpolymer was 3.1 g.

The (C = 0) peak of MMA was found at 1730 cm <^-1> in the IR spectrum of the said styrene polymer.

The reduced viscosity at 0.05 g / kPa measured at 135 ° C in the 1,2,4-trichlorobenzene solution of this interpolymer was 2.07 dl / g.

Moreover, the thictitiser by ¹³ C-NMR was 95% in racemic diamond.

In addition, the ratio of styrene and MMA determined by NMR was 1: 1.82 (weight ratio).

Example 10

In an argon atmosphere, 70 ml of toluene, 60 ml of styrene, and 2 ml of p-divinyl styrene were added to a 200 ml reaction vessel at room temperature, and 10 mmol of the methylaluminoxane prepared in Example 1 (1) was added thereto, followed by raising to 50 캜. . Furthermore, 0.1 mmol of tetraethoxy titanium was added and hybridization reaction was carried out for 1 hour.

Subsequently, the reaction product corresponding to 5 ml from the hybrid polymerization system was divided in an argon atmosphere, placed in a pressure-resistant glass reaction vessel, washed with 100 ml of hexane, decantation of the hybrid polymerization powder three times, and finally 200 ml of hexane. Input.

2 mmol of diethylaluminum monochloride was added thereto, and ethyl was continuously added at 2.4 kg / cm 2 G at 70 ° C. for 3 hours. The pressure was released and the obtained interpolymer was put in methanol, washed and dried to obtain 2.85 g of the interpolymer. In order to prove that the obtained interpolymer is a graft interpolymer of ethylene having syndiotactic polystyrene as a main chain, the following analysis was carried out.

First, IR and ¹³ C-NMR of the graft precursor were measured. As IR, absorption of the vinyl group of the divinylbenzene residue was recognized at ₁₆₃₀ cm ^{−1, and} an absorbance ratio of 1605 cm ⁻¹ of the styrene residue unit (D ₁₆₃₀ / D ₁₆₀₅ ) was 0.26.

In addition, a sharp peak attributable to aromatic ring quaternary carbon was recognized at 145.2 ppm by ¹³ C-NMR, and the styrene chain was found to have a syndiotactic structure. In addition, when the IR measurement of the copolymer after graft was performed, absorption derived from the methyl chain was recognized in 720 cm ^{-1 to} 730 cm ^-1 , and the absorption strength of the vinyl group derived from the divinylbenzene residue was lowered. The decrease in D ₁₆₃₀ / D ₁₆₀₅ to 0.16 proved that graft interpolymers were being produced.

IR was measured by changing the mixing ratio of high density polyethylene and syndiotactic polystyrene to obtain the hybrid polymerization composition, and a calibration acid was prepared from the absorbance ratios of 720 cm ^-1 and 1605 cm ^-1 .

The weight ratio of styrene and ethylene obtained from this was 1: 1.03. Moreover, the reduced viscosity in the 1,2,4-trichlorobenzene solution of this copolymer at a density | concentration of 0.05 g / dl measured at 135 degreeC was 1.66 dl / g.

Example 11

(1) Preparation of tetra (pentafluorophenyl) borate trin-butylammonium

Pentafluorophenyllithium prepared from bromopentafluorobenzene (152 mmol) and butyllithium (152 mmol) was reacted with 45 mmol boron trichloride in hexane to give tri (pentafluorophenyl) boron as a white solid. 41 mmol of tri (pentafluorophenyl) boron and 41 mmol of pentafluorophenyllithium were reacted to isolate lithium tetra (pentafluorophenyl) boron as a white solid. Subsequently, 16 mmol of lithium tetra (pentafluorophenyl) boron and 16 mmol of trin-butylamine hydrochloride were reacted in water to obtain 12.8 mmol of tetra (pentafluorophenyl) borontrin-butylammonium as a white solid. .

(2) Preparation of Styrene-Divinylbenzene Ethylene Interpolymer

20 ml of styrene and 1.2 ml of divinylbenzene (compound described in Example 1) were added to a 100 ml stainless reaction vessel dried in an argon atmosphere, and 0.03 mmol of triisobutylaluminum (TIBA) was added at 70 ° C. Hold for 30 minutes.

Further, 0.5 µmol of tetrapentafluorophenyl) borontrin-butylammonium prepared in the above (1) and 0.5 µmol of pentamethylcyclopentadiethyltrimethyltitanium were added, and hybrid polymerization was started under stirring. After reacting for 2 hours, 30 ml of dry toluene was added to make a slurry, and a small amount was sampled, and IR and ¹³ C-NMR were measured. In IR, absorption of the vinyl group of the divinylbenzene residue was recognized at 1630 cm <-1>, and the absorbance ratio (D ₁₆₃₀ / D ₁₆₀₅ ) with 1505 cm <-1> of a styrene residue unit was 0.31.

In addition, a sharp peak by aromatic ring quaternary carbon was recognized at 145.2 ppm by 13 C-NMR measurement, and the styrene chain was found to have a syndiotactic structure.

In addition, ethylene was continuously introduced at 9 kg / cm 2 G for 10 hours to the reaction system at 70 ° C. in order to continue the graft reaction. Then, the pressure was released, the copolymer was added to methanol, washed, and dried to obtain 4.86 g of the copolymer.

IR measurement of this copolymer showed that the absorption of methylene chain was recognized at 720cm ^-1 and 730cm ^-1 , and the absorption strength of vinyl group by divinylbenzene residue was lowered and D ₁₆₃₀ / D ₁₆₀₅ decreased to 0.18. It has been found that graft interpolymers are produced from these compounds. IR was measured by changing the mixing ratio of high-density polyethylene and syndiotactic polystyrene to determine the hybrid polymerization composition, and a calibration curve was prepared from the absorbance ratios of 720 cm ^-1 and 1605 cm ^-1 .

From this, the weight ratio of styrene and ethylene was 1: 0.07.

In addition, the reduced viscosity of the copolymer at a concentration of 0.05 g / dl, measured at 135 ° C in the 1,2,4-trichlorobene solution was 1.34 dl / g.

Example 12

Subsequently, after replacing the reaction vessel with an internal volume of 0.5 L with nitrogen, it was heated to 70 ° C. and sufficiently dried to 50 ml of toluene, a monomer containing divinylbenzene (66.1% by weight of divinylbenzene (m-, p-mixture), 0.1 ml of ethyl styrene (m-, p-mixture) 33.9 wt%) was added, and 1.5 mmol of methylaluminoxane and 1.5 mmol of triisobutylaluminum (TIBA) obtained in Example 1 (2) were added. And stirred for 30 minutes. Then, 0.003 mmol of pentamethylcyclopentadienyl titanium trimethoxide was added and reacted for 2 hours.

After completion of the reaction, a large amount of hexane was added and the interfacial technique was followed to wash the interpolymer. Thereafter, the exclusive volume was 100 ml, and 3.0 mmol of a hexane solution of n-butyllithium was added at 50 ° C to react for 2 hours. After the reaction, unreacted n-butyllithium was washed out by decantation.

The resulting copolymer was cooled to -78 ° C, 30 ml of glycidyl methacrylate was added with 100 ml of hexane, and graft hybrid polymerization was carried out for 12 hours.

After completion of the reaction, the reaction mixture was poured into a large amount of methanol, washed and dried to obtain 17.8 g of a graft interpolymer. When the obtained graft copolymer was extracted with methyl ethyl ketone as the extraction solvent, 93% was an insoluble portion. Moreover, the reduced viscosity in 0.05 g / kPa of the insoluble part measured at 135 degreeC in the 1,2, 4- trichlorobenzene solution was 1.47 dl / g.

In addition, after using a differential scanning calorimeter (Seiko Electronics Co., Ltd. product, DSC-200) to raise the temperature of 5.7 mg of the copolymer of the copolymer at 50 to 310 ° C at a rate of 20 ° C / min, at 310 to 30 ° C The temperature was lowered at a rate of 20 ° C./min. In addition, the endothermic pattern at the time of raising the temperature at a rate of 20 ° C / min again at 30 to 315 ° C was observed.

As a result, it was confirmed that the graft interpolymer had a dissolution temperature at 263 ° C. In addition, syndiotacticity was 95% or more in racemic pentaad by measurement of ¹³ C-NMR.

The composition of the graft interpolymer was found to be 55% by weight of styrene units and 45% by weight of glycidyl methacrylate by measurement of ¹ H-NMR.

Example 13

A graft interpolymer was synthesized in the same manner as in Example 12 except that the amount of glycidyl methacrylate added was 2 ml.

After completion of the reaction, the resultant was poured into a large amount of methanol and washed and dried to obtain 6.73 g of a graft interpolymer.

When the obtained graft interpolymer was extracted with methyl ethyl ketone as the extraction solvent, 97% was an insoluble portion.

Moreover, the reduced viscosity of 0.05 g / kPa of the insoluble part measured at 135 degreeC in the 1,2, 4- trichlorobenzene solution was 1.53 dl / g.

In addition, after using a differential scanning calorimeter (Seiko Electronics Co., Ltd. product, DSC-200) to raise the temperature of 5.7 mg of the copolymer of the copolymer at 50 to 310 ° C at a rate of 20 ° C / min, at 310 to 30 ° C The temperature was lowered at a rate of 20 ° C./min. In addition, the endothermic pattern at the time of raising the temperature at a rate of 20 ° C / min again at 30 to 315 ° C was observed.

As a result, it was confirmed that the graft interpolymer had a dissolution temperature at 263 ° C. In addition, syndiotacticity was 95% or more in racemic pentaad by measurement of ¹³ C-NMR.

The composition of the graft interpolymer was found to be 92% by weight of styrene units and 8% by weight of glycidyl methacrylate by measurement of ¹ H-NMR.

Example 14

Graft polymerization was performed for 4 hours at 70 ° C using 2 g of maleic anhydride and 2.1 g of styrene instead of glycidyl methacrylate and 50 mg of benzoyl peroxide as a radical polymerization initiator instead of n-butyllithium. A graft interpolymer was synthesized as in Example 12. After completion of the reaction, the resultant was poured into a large amount of methanol, washed and dried to obtain 6.0 g of a graft interpolymer.

When the obtained graft copolymer was extracted with methyl ethyl ketone as the extraction solvent, 98% was an insoluble portion.

In addition, the reduced viscosity of the insoluble portion at a concentration of 0.05 g / dl, measured at 135 ° C in the 1,2,4-trichlorobenzene solution was 1.37 dl / g.

In addition, after using a differential scanning calorimeter (Seiko Electronics Co., Ltd. product, DSC-200) to raise the temperature of 5.7 mg of the copolymer of the copolymer at 50 to 310 ° C at a rate of 20 ° C / min, at 310 to 30 ° C The temperature was lowered at a rate of 20 ° C./min. In addition, the endothermic pattern at the time of raising the temperature at a rate of 20 ° C / min again at 30 to 315 ° C was observed.

As a result, it was confirmed that the graft interpolymer had a dissolution temperature at 263 ° C. In addition, syndiotacticity was 93% or more in racemic pentaad by measurement of ¹³ C-NMR.

The composition of the graft interpolymer was found to be 97% by weight of styrene units and 3% by weight of maleic anhydride by measurement of ¹ H-NMR.

Example 15

The reaction vessel with a volume of 0.5 liter stirrer was replaced with nitrogen, and then heated to 70 ° C., to which a mixture of 300 ml of sufficiently dried toluene, 200 ml of styrene, and 30 mmol of p- (4-pentenyl) styrene was added. 12 mmol of the aluminoxane and 12 mmol of TIBA obtained in Example 1 (2) were added thereto, followed by stirring for 30 minutes.

Subsequently, 15 mol of pentamethylcyclopentadiethyltitanium trimethoxide was added, and the reaction was carried out for 2 hours.

After completion of the reaction, the mixture was poured into a large amount of methanol, washed, and dried to obtain 10.5 g of the interpolymer. Methyl ethyl ketone was extracted as a extraction solvent in the obtained interpolymer as a solvent, and 98% was an insoluble part.

Moreover, the reduced viscosity in 0.05 g / Pa of insoluble parts measured at 135 degreeC in the 1,2, 4- trichlorobenzene solution was 2.0 g / Pa.

In addition, after using a differential scanning calorimeter (Seiko Electronics Co., Ltd. product, DSC-200) to raise the temperature of 5.7 mg of the copolymer of the copolymer at 50 to 310 ° C at a rate of 20 ° C / min, at 310 to 30 ° C The temperature was lowered at a rate of 20 ° C./min. In addition, the endothermic pattern at the time of raising the temperature at a rate of 20 ° C / min again at 30 to 315 ° C was observed.

As a result, it was confirmed that the graft interpolymer had a dissolution temperature at 245 ° C. In addition, syndiotacticity was 92% or more by racemipentaad by measurement of ¹³ C-NMR.

In IR, a stretching wave of carbon-carbon double bonds by styrene units was recognized at 1630 cm ^-1 , and the hybridization reaction with styrene was mainly carried out by olefin units of p- (4-pentenyl) styrene.

5 g of the interpolymer was dispersed in 100 ml of toluene under argon atmosphere, and graft interpolymer was synthesized as in Example 12 using 10 ml of glycidyl methacrylate.

After completion of the reaction, the resultant was put in a large amount of methanol and washed and dried to obtain 6.5 g of a graft interpolymer. Soxhlet extraction of the obtained graft copolymer using methyl ethyl ketone as an extraction solvent showed 96% of the insoluble portion. In addition, the reduced viscosity of the insoluble portion at a concentration of 0.05 g / dl at 135 ° C in the 1,2,4-trichlorobenzene solution was 2.10 dl / g.

In addition, after using a differential scanning calorimeter (Seiko Electronics Co., Ltd. product, DSC-200) to raise the temperature of 5.7 mg of the copolymer of the copolymer at 50 to 310 ° C at a rate of 20 ° C / min, at 310 to 30 ° C The temperature was lowered at a rate of 20 ° C./min. In addition, the endothermic pattern at the time of raising the temperature at a rate of 20 ° C / min again at 30 to 315 ° C was observed.

As a result, it was confirmed that the graft interpolymer had a dissolution temperature at 244 ° C. In addition, syndiotacticity was 91% or more by racemic pentaad by measurement of ¹³ C-NMR.

The composition of the graft interpolymer was found to be 80% by weight of styrene units and 20% by weight of glycidyl methacrylate by measurement of ¹ H-NMR. As IR, the absorption line of 1630 cm <^-1> was lost, and it confirmed that it was a graft body.

Example 16-1

(1) Preparation of Styrene-Divinylbenzene Interpolymer (Graft Precursor)

Substituting the reaction vessel with a stirrer with a volume of 4.0 L with nitrogen and heating it to 70 DEG C, 250 ml of toluene dried sufficiently, 1000 ml of styrene and divinylbenzene-containing monomer (divinylbenzene (m-, p-mixture) 66.1% by weight, 33.9% by weight of ethyl styrene (m-, p-mixture)) 0.1 ml of a mixture was added, and 8.5 mmol of methylaluminoxane and triisobutylaluminum (TIBA) obtained in Example 1 (2) were added. 8.5 mmol was added and stirred for 30 minutes. Then, 0.043 mmol of pentamethylcyclopentadienyl titanium trimethoxide was added, and reaction was performed for 5 hours.

After completion of the reaction, methanol was added to terminate the reaction, and the polymer was washed with methanol acetate to decompose the catalyst component.

The obtained interpolymer was washed with methyl ethyl ketone (containing 2 wt% of p-t-butyl catechol) at 50 ° C for 4 hours, and 97% was an insoluble portion. This insoluble portion was dissolved in chloroform to obtain a chloroform solution of a styrenic interpolymer from the soluble component. The weight average molecular weight of the styrenic interpolymer soluble in this chloroform was 724,000, and the number average molecular weight was 243,000.

As a result of using a differential scanning calorimeter (Seiko Electronics Co., Ltd., DSC-11), it was confirmed that the graft copolymer had a dissolution temperature at 268 ° C and a glass transition temperature at 98 ° C. In addition, the aromatic ring C ₁ carbon signal was recognized at 145.2 ppm by ¹³ C-NMR measurement, and it was confirmed that the syndiotactic structure was present. In IR, absorption of the vinyl group of the divinylbenzene residue at 1630 cm <^-1> was recognized.

(2) graft reaction of n-phenylmaleide (n-PMI)

The styrene-divinylbenzene interpolymer obtained in (1) was washed with toluene, thoroughly washed with methanol and dried under reduced pressure at 40 ° C., and 140 g was put into a reaction vessel with an internal volume of 1 L of stirrer and replaced with nitrogen. Subsequently, 420 ml of sufficiently dry toluene was added, and the mixture was heated to 50 ° C. and the system was slowly stirred.

After 1 hour, a solution of 45.9 g of nPMI dissolved in 200 ml of sufficiently dried THF and a solution of 2.13 g of azobisisobutyronitrile (AIBN), a dried 30 ml THF radical initiator, were added, and the temperature in the system was 70%. The reaction was carried out for 5 hours after raising to ℃.

Methanol was added to stop the reaction, and the mixture was sufficiently washed with acetone (solvent of nPMI) and N, N-dimethylformamide (solvent of polynPMI).

After completion of the reaction, the resultant was poured into a large amount of methanol, washed, and dried to obtain 163 g of a graft copolymer.

The obtained interpolymer was insoluble in 90% of this washing treatment. In addition, the reduced viscosity of the insoluble portion in the 1,2,4-trichlorobenzene solution at a concentration of 0.05 g / dl at 135 ° C was 1.30 dl / g.

In addition, after using a differential scanning calorimeter (Seiko Electronics Co., Ltd. product, DSC-200) to raise the temperature of 5.7 mg of the copolymer of the copolymer at 50 to 310 ° C at a rate of 20 ° C / min, at 310 to 30 ° C The temperature was lowered at a rate of 20 ° C./min. In addition, the endothermic pattern at the time of raising the temperature at a rate of 20 ° C / min again at 30 to 315 ° C was observed.

As a result, ¹³ C-NMR of the graft interpolymer was measured, and an aromatic signal with a syndiotactic structure was observed at 145.4 ppm. In addition, syndiotactose was more than 94% of racemic pentaad by ¹³ C-NMR.

Measurement of ¹ H-NMR showed that the nPMI of the graft interpolymer was 8% by weight.

Roneun IR is not the absorption of 1630㎝ ^-1 peak due to the double bond of divinylbenzene, it was confirmed that the new (C = 0) of the peak shown in nPMI 1710㎝ ^-1.

Examples 16-2 to 16-14

The same reaction as in Example 16-1 was carried out except for the conditions shown in Table 1. In the graft reaction, when the monomer was α-methylstyrene, the precursor was added to 600 mL of n-heptane, cooled to -78 ° C, and stirred slowly, and a methylene chloride solution of triethyloxonium boron tetrafluoride (1 mol / L) and 5 ml of sufficiently dried α-methylstyrene were added and reacted for 6 hours.

In the graft reaction, when the monomer is norbornene, the precursor was added to 420 ml of toluene, heated to 50 ° C., and stirred slowly. A toluene solution of norbornene (6.7 mol / l) was added and reacted for 6 hours.

In Examples 16-1, 16-10, and 16-14, the obtained styrenic graft polymer was pelletized using a twin screw mixer having a cylinder temperature of 300 ° C, injection molded at 300 ° C to obtain a test plate, and then again at 230 ° C. Heated for 10 minutes.

The heat deflection temperature (HDT: JIS-K 7270) and the flexural modulus (JIS-K 7203) were measured using this test plate.

The obtained results are shown in the first table. Here, the thermal deformation temperature of syndiotactic polystyrene is 100.3 ° C. and the flexural modulus is 39.500 kg / cm 2 based on the physical properties.

Synthesis of Precursors Styrene (ml) Styrene derivative (ml) MIP ^{* 1} (%) Tm ^{* 2} (℃) Mw ^{* 3} Example 16-1 Example 16-2 Example 16-3 Example 16-4 Example 16-5 Example 16-6 Example 16-7 Example 16-8 Example 16-9 Example 16-10 Example 16-11 Example 16-12 Example 16-13 Example 16-14 100010001000100010001000100010001000100010001000100010001000 DVB ^{* 4} 6.2DVB 3.7DVB 2.5DVB 6.2DVB 6.2DVB 6.2DVB 6.2DVB 6.24PST ^{* 5} 8.3DVB 6.2DVB 6.24PST 8.3DVB 6.24PST 8.3 9798989797979797949797949794 268269269268268268268263263268268263268263 724 × 10 ³ 857 × 10 ³ 911 × 10 ³ 724 × 10 ³ 724 × 10 ³ 724 × 10 ³ 724 × 10 ³ 724 × 10 ³ 638 × 10 ³ 724 × 10 ³ 724 × 10 ³ 638 × 10 ³ 724 × 10 ³ 638 × 10 ³ * 1: insoluble part in methyl ethyl ketone * 2: melting point * 3: weight average molecular weight (standard polystyrene conversion) * 4: divinylbenzene * 5: 4-pentenyl styrene

Grafting Reaction Precursor usage (g) Graft Monomer (g) Initiator (mmol) Example 16-1 Example 16-2 Example 16-3 Example 16-4 Example 16-5 Example 16-6 Example 16-7 Example 16-8 Example 16-9 Example 16-10 Example 16-11 Example 16-12 Example 16-13 Example 16-14 1401401401401401401401401408080808080 nPMI 45.9 n PMI 27.5 n PMI 18.3 n PMI 114.8 n PMI 45.9 o MPMI ^{* 12} 49.6 n CMI ^{* 6} 47.2 n PMI 11.4 n PMI 50.0 α-methylstyrene 45.6α-methylstyrene 45.6α-methylstyrene 45.6 norbornene 37.0 norbornene 37.0 AIBN ^{* 7} 13AIBN 13AIBN 13AIBN 13ACN * 8 16AIBN 13AIBN 13AIBN 13AIBN 13THF ^{* 9} 5BFD ^{* 10} 5TBF 5 ^{* 11 * 11} * 6: N-cyclohexyl maleimide * 7: azobisisobutyronitrile * 8: azobiscyclohexanecarbonitrile * 9: triethyl oxonium boron tetrafluoride * 10: boron trifluoride diethyl etherite * 11 : Nickel acetylacetonite 0.03 mmol and methylaluminoxane 3 mmol were used. * 12: N- (o-methylphenyl) maleimide

Graft Interpolymer Quantity (g) Reduced viscosity ^{* 13} (㎗ / g) Tm (℃) Tactical (%) Example 16-1 Example 16-2 Example 16-3 Example 16-4 Example 16-5 Example 16-6 Example 16-7 Example 16-8 Example 16-9 Example 16-10 Example 16-11 Example 16-12 Example 16-13 Example 16-14 163159159200161163162150171107105112109111 3.032.221.923.972.722.122.071.984.211.991.981.912.102.21 265266267258263261264264257252254251261259 9493958992919094909293909190 * 13: It measured at 135 degreeC using the density | concentration 0.5g / dl and 1,2, 4- trichlorobenzene as a solvent.

Graft Interpolymer Graft (% by weight) Heat deflection temperature (℃) Flexural modulus (㎏ / ㎠) Example 16-1 Example 16-2 Example 16-3 Example 16-4 Example 16-5 Example 16-6 Example 16-7 Example 16-8 Example 16-9 Example 16-10 Example 16-11 Example 16-12 Example 16-13 Example 16-14 14.111.89.730.313.014.113.57.118.225.023.828.535.727.8 129.8 -------- 126.3 --- 121.8 43800 -------- 42500 --- 43500

Example 17 and Comparative Examples 1-3

Using the styrenic graft interpolymers obtained in Examples 12 and 14, the resins in the ratios shown in the second table were prepared at 300 ° C. using a small molding machine (Model CS-183, manufactured by Custom Sciemtific Instrument). Mix for 5 minutes, then extrude to form strands.

The electron micrograph (x100) of the cut surface of the obtained strand is shown to FIG. 1 thru | or FIG.

Resin and composition ratio drawing GMA-SPS ^{* 1} MAn-SPS ^{* 2} SPS Nylon 6.6 ^{* 3} PET ^{* 4} Example 17-1 0.2 - 0.4 0.4 - One Example 17-2 0.2 - 0.4 - 0.4 2 Example 17-3 - 0.2 0.4 0.4 - 3 Example 17-4 - 0.5 0.5 - - 4 Comparative Example 1 - - 0.5 0.5 - 5 Comparative Example 2 - - 1.0 - - 6 Comparative Example 3 - - 0.5 - 0.5 7 * 1 Obtained in Example 12 * 2 Obtained in Example 14 * 3 Ubegosan Co., Ltd. product 2020B * 4 Mitsubishi Rayon Co., Ltd., MA-560-R

Example 18 and Comparative Examples 4-6

The styrenic graft interpolymers obtained in Examples 16-4, 16-7 and 16-14 were used for the evaluation according to Example 17, except that the styrene graft interpolymers were mixed in the proportions shown in Table 3.

The obtained results are shown in Tables 3 and 8 to 14.

In Examples 18-1, 18-2 and Comparative Example 5, the heat deformation temperature and the elastic modulus of the test plate injection molded according to Example 16-1 were measured.

The obtained result is shown in a 4th table | surface.

Resin and composition ratio (wt%) Styrene Graft Copolymer nPMI-SPS ^{* 1} nCMI-SPS ^{* 2} Norbornen SPS ^{* 3} Example 18-1 1.6 - - Example 18-2 1.0 - - Example 18-3 - 1.0 - Example 18-4 - - 1.6 Example 18-5 - - 1.0 Comparative Example 4 - - - Comparative Example 5 - - - Comparative Example 6 - - - * 1 obtained in Example 16-4 * 2 obtained in Example 16-7 * 3 obtained in Example 16-1

Resin and composition ratio (wt%) drawing Etc SPS PolynPMI ^{* 4} Polynorbornene ^{* 5} Example 18-1 0.4 - - 8 Example 18-2 1.0 - - 9 Example 18-3 1.0 - - 10 Example 18-4 0.4 - - 11 Example 18-5 1.0 - - 12 Comparative Example 4 1.8 0.2 - 13 Comparative Example 5 1.6 0.4 - 14 Comparative Example 6 1.8 - 0.2 ^{* 6} * 4: The homopolymer of n-phenylmaleimide is shown. This was synthesized as described in Macromolecular Vol. 23, p 4508 to 4513 (published in 1990). * 5: A homopolymer of norbornene. After nitrogen-substituted the reaction vessel with a 0.5 liter stirrer, the solution was dried with 150 ml of dry toluene, 0.08 mmol of nickel acetylacetonate, 16 mmol of methyl aluminoxane, and 186 ml (6.7 mol) of toluene solution of norbornene. It is obtained by putting into a reactor and reacting at 50 degreeC for 4 hours. (Yield 75%) * 6: Molding not possible

Heat deflection temperature (℃) Flexural modulus (㎏ / ㎠) Example 18-1 115.5 48600 Example 18-5 114.9 46900 Comparative Example 5 102.8 40800

Example 19

20% by weight of the styrenic graft copolymer obtained in Examples 12 and 14, 70% by weight of the resin mixture consisting of 80% by weight of syndiotactic polystyrene (SPS) and 30% by weight of 30 mm cut glass fiber, respectively Melting and mixing at ° C to obtain a glass fiber reinforced resin composition.

The cross section of this composition was observed to find that the resin and the glass fiber were sufficiently bonded.

Example 20

40 mg of styrene-based graft interpolymer (45% by weight of glycidyl methacrylate unit) obtained in Example 12 was sandwiched between two sheets of aluminum sheet (50 µm thick and 15 mm wide), and the surface of 15 mm x 15 mm It heated at 300 degreeC for 2 minutes so that it might become this adhesive surface, and then pressed (10 kg / cm <2>) for 1 minute, and obtained the multilayer material.

It was 30.5 kg / (15mm * 15mm) when the test board of the obtained multilayer material was pulled at 20 mm / min, and the shear peeling strength was measured.

Moreover, when copper and a glass plate were used instead of aluminum, it was 28.0 kg / (15mm * 15mm), and 35.0kg / (15mm * 15mm), respectively.

In this case, no adhesion was achieved with SPS or a styrene-divinylbenzene interpolymer.

Example 21

A multilayer material was obtained in the same manner as in Example 19 except that the styrenic graft interpolymer (8% by weight of glycidyl methacrylate unit) obtained in Example 13 was used.

It was 29.0 kg / (15mm * 15mm) when the test board of the obtained multilayer material was pulled at 20 mm / min, and the shear peeling strength was measured.

Moreover, when copper and a glass plate were used instead of aluminum, they were 26.0 kg / (15 mm * 15 mm) and 31.0 kg / (15 mm * 15 mm), respectively.

Example 22

The sheet of 50 mm x 50 mm x 0.5 mm was obtained by press molding at 300 degreeC from the resin composition obtained in Example 17 or Comparative Examples 1-3 with the composition shown in Table 5.

The obtained sheet was pressed at a temperature and a pressure of 0.5 kg / cm 2 shown in Table 5 for 5 minutes to obtain a multilayer material.

Resin composition Adhesive Lamination Temperature (℃) Stacking state Example 17-1 Example 17-2 Example 17-3 Example 17-4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Aluminum Copper Nylon 6.6 Copper Copper 6.6 300300300240300300240 Good Good Good Good Good Resin Layer Crack Resin Layer Cracking

Styrene-based interpolymers according to the production method of the present invention are significantly improved compatibility, adhesion, wettability while retaining the heat resistance, chemical resistance and the like of syndiotactic polystyrene.

Therefore, the styrenic interpolymer according to the production method of the present invention can be easily compounded with glass fibers, talc metals, etc., and enables the development of the syndiotactic structure of the styrene-based resin into a composite material.

In addition, the styrenic interpolymers according to the production method of the present invention are effectively used as modifiers, compatibilizers and the like of various resins.

Claims (4)

Styrene monomer and hydrocarbon group-containing styrene monomer having an unsaturated bond (A) transition metal compounds and (C) hybridization in the presence of a catalyst having a main component of a compound which reacts with an electric transition metal compound to form an ionic complex, and subsequently graft polymerizes the ethylenically unsaturated monomer to the obtained styrenic interpolymer. Method for producing a styrenic graft copolymer. The method of claim 1, A method for producing a styrenic graft interpolymer wherein the styrenic interpolymer has a syndiotactic structure. The method of claim 1, Styrene monomers are of the general formula [1] ···[One] [Wherein, R ¹ represents a substituent containing at least ^one of a hydrogen atom, a halogen atom or a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom and a tin atom, and m is 1- The integer of 3 is shown. However, when m is plural, each R <^1> may be same or different.] The styrene-type monomer-I represented by [], and the hydrocarbon group containing styrene-type monomer which have an unsaturated bond are general formula [2]. ···[2] [Wherein, R ² represents a hydrocarbon group having an unsaturated bond and n represents an integer of 1 or 2; R ¹ and m are the same as described above.] Is a styrene monomer-II, and an ethylenically unsaturated monomer is represented by the general formula [3]. [3] [Wherein, Q ¹ , Q ² , Q ³ , and Q ⁴ each represent one or more of hydrogen, halogen, or carbon, oxygen, nitrogen, sulfur, phosphorus, selenium, silicon, and tin; And the substituents thereof contained, and these Q ¹ to Q ⁴ may be the same or different.] The method for producing a styrene-based graft copolymer. The method of claim 1, Ethylenically unsaturated monomers include (1) acrylic acid, methacrylic acid, derivatives thereof, (2) acrylamide, methacrylamide, derivatives thereof, (3) vinyl acetate, derivatives thereof, (4) cinnamic acid, crotonic acid , Derivatives thereof, (5) acrylonitrile, methacryl nitrile, derivatives thereof, (6) maleic acid, fumaric acid, maleic anhydride, derivatives thereof, (7) maleimide, derivatives thereof, (8) itaconic acid , Itaconic anhydride, derivatives thereof, (9) acrolein, (10) vinyl ketones, (11) dienes, (12) styrene, derivatives thereof, (13) α-olefins or (14) cyclic olefins. Method for producing a styrenic graft copolymer.