JPH0485311A - Syndiotactic alkylstyrene polymer and resin composition containing same - Google Patents

Abstract

PURPOSE:To obtain an alkylstyrene polymer desirable for molding in a low- temperature mold by selecting a polymer comprising specified alkylstyrene repeating units and being chiefly syndiotactic in its stereoregularity. CONSTITUTION:A polymer comprising repeating units [I] of formula I and repeating units [II] of formula II [wherein R<2> is H or a substituent containing at least one kind of halogen, carbon, oxygen, nitrogen, sulfur, phosphorus, selenium, silicon and tin; q is 1-5; when q is two or greater, R<2> groups may be the same or different foam each other provided that the case in which repeating unit II is identical with repeating unit [I] is excluded], containing 0.1-100mol% repeating units [I] and 0-99.9mol% repeating units [II] and being chiefly syndiotactic in its stereoregularity.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention mainly relates to an alkylstyrenic polymer having a syndiotactic structure and a resin composition containing the polymer.

[Prior art and problems to be solved by the invention] Styrenic polymers conventionally produced by radical polymerization methods, etc. are molded into various shapes by various molding methods, and are used in household electrical appliances, office equipment, and home appliances. supplies, packaging containers, toys,
Furniture 2 Although it is widely used as synthetic paper and other industrial materials, it has a disadvantage in that its three-dimensional structure has an crunchy structure and is inferior in heat resistance and chemical resistance.

The group of the present inventors has succeeded in developing a styrene polymer mainly having a syndiotactic structure in order to overcome the drawbacks of the styrenic polymer having an active structure, and published JP-A-62 The invention was disclosed in JP-A-104818 and JP-A-62-187708. These polymers have excellent heat resistance, chemical resistance, and electrical properties, but when performing low-temperature mold molding, it is preferable to lower the glass transition temperature from the viewpoint of energy efficiency.

Copolymerization is generally used as a method to satisfy this requirement, but in the case of styrenic polymers, which are crystalline polymers and mainly have a syndiotactic structure, the above-mentioned copolymerization method is used. However, the main drawback is that the crystallinity of the styrenic polymer having a syndiotactic structure is inhibited.

Therefore, the present inventors solved the drawbacks of the above-mentioned conventional technology,
We have conducted extensive research to develop a technology that can lower the glass transition temperature of styrenic polymers with a syndiotactic structure without inhibiting their crystallinity.

[Means for Solving the Problems] As a result, it has been found that the above problems can be effectively achieved by using a specific alkylstyrene polymer. The present invention was completed based on this knowledge.

That is, the present invention General formula [I] (R').

(In the formula, R' represents a linear or branched alkyl group having 5 to 20 carbon atoms, and p represents an integer of 1 to 5.

However, when P is plural, each R' may be the same or different. ] Repeating unit CI) and general formula (I[) (R”)Q represented by represents a substituent containing one or more of atoms, silicon atoms, and tin atoms, and q represents an integer of 1 to 5.However, when q is plural, each R2 may be the same or different. .

) having a repeating unit (■) represented by A polymer containing 0 to 99.9 mol % of [), whose stereoregularity provides an alkyl styrene polymer mainly having a syndiotactic structure, and which contains 1 to 99 mol % of the alkyl styrene polymer by weight. % and general formula (II[) (R').

[In the formula, R3 represents a hydrogen atom, 2 halogen atoms, or a substituent containing one or more of carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, selenium atom, silicon atom, and tin atom, and r is Indicates an integer from 1 to 5. However, when r is plural, each R3 may be the same or different.

] A styrenic polymer having a repeating unit CII [) whose stereoregularity mainly has a syndiotactic structure (excluding cases where it is the same as the alkylstyrene polymer described above)99- Styrenic polymer having a syndiotactic structure consisting of 1% by weight (excluding cases where it is the same as the alkylstyrene polymer) 99~
1% by weight of the resin composition.

The alkylstyrene polymer in the present invention has the repeating unit [II] represented by the general formula (1) and the repeating unit CII represented by the general formula (II) as described above. The combination of repeating units CI) and (II) constitutes a polymer comprising one, two or more types of repeating units. Furthermore, since the above repeating units [I] and (If) do not necessarily represent only one type of repeating unit, but also represent two or more types of repeating units, the polymer of the present invention may be a homopolymer or a binary copolymer. In addition to polymers, it also includes multi-component copolymers such as ternary copolymers and quaternary copolymers. Therefore, in the present specification, the alkylstyrene polymer includes copolymers even if it is simply referred to as a polymer, unless it is necessary to specifically explain it separately from a copolymer.

The alkylstyrene polymer of the present invention having the above repeating unit can be produced by various methods, for example, the general formula [bi] (R')p [wherein R' and p are the same as above] It is. ] and the general formula [■゛] (R2)q [wherein R2 and q are the same as above. ] is produced by copolymerizing a styrenic monomer using (a) a transition metal component and (b) a contact product (reaction product) of an organoaluminum compound and a condensing agent as catalyst components. .

Here, in the styrenic monomer represented by the general formula [■°] giving the repeating unit CI), R1 has 5 carbon atoms.
~20 straight-chain or branched alkyl groups, such as n-pentyl L 5ec-pentyl groups.

Neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, etc., and p is an integer of 1 to 5. In addition,
When p represents a plurality, each R1 may be the same or different.

Specific examples of such alkylstyrene monomers include p-n-pentylstyrene, p-5ec pentylstyrene, p-neopentylstyrene, p-n-heptylstyrene, p-n-octylstyrene, p-n-nonylstyrene. , pn-decylstyrene, pn-undecylstyrene, pn-dodecylstyrene, pn-)
Lidecyl Stire7. p-n-tetradecylstyrene, p
-n-pentadecylstyrene, pn-hexadecylstyrene, pn-heptadecylstyrene,
Examples include pn-octadecylstyrene, pn-nonadecylstyrene, pn-eicosylstyrene, mn-hexyl-pn-nonylstyrene, and the like.

Furthermore, the general formula [■
In the styrenic monomer represented by ゛], R2 is
Hydrogen atom, halogen atom or carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom.

Indicates a substituent containing at least one of a selenium atom, a silicon atom, and a tin atom.

Here, examples of the halogen atom include chlorine, fluorine, bromine, and iodine. Further, specific examples of substituents containing carbon atoms include alkyl groups having 1 to 20 carbon atoms such as methyl group, ethyl group, isopropyl group, and tertiary-butyl group; hydrogen atom, halogen atom or carbon atom on benzene ring; Oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, selenium atoms.

An aryl group having 6 to 30 carbon atoms and having a substituent containing a silicon atom or a tin atom; a chloroethyl group.

Examples include halogen-substituted alkyl groups having 1 to 20 carbon atoms such as bromoethyl group.

Also, as an aryl group with 6 to 30 carbon atoms having a substituent on the benzene ring containing a hydrogen atom, a halogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom, or a tin atom, etc. For example, benzene ring, naphthalene ring.

Phenanthrene ring, anthracene ring, indene ring.

Azulene ring, heptalene ring, biphenylene ring.

aS-indacene ring S-indacene ring, acenaphthylene ring, phenalene ring, fluoranthene ring.

Acephenanthrene ring, naphthacene ring, preiazone ring, picene ring, perylene ring, pentacene ring.

Rubisene ring, corocene ring, vilanthrene ring, opalene ring and their alkyl substituents (methyl group).

ethyl group, isopropyl group, tert-butyl group, etc.), halogen substituents, alkyl groups (chloroethyl group, bromoethyl group, etc.), substituents containing oxygen atoms (methoxy group, ethoxy group, isopropoxy group, methoxycarbonyl group, acetyloxy groups), substituents containing silicon atoms (
trimethylsilyl group, etc.), substituents containing a tin atom (trimethylstannyl group, tributylstannyl group, triphenylstannyl group, etc.), substituents containing a nitrogen atom (dimethylamino group, diazo group, nitro group, cyano group, etc.) )
, a substituent containing a sulfur atom (sulfone group).

Sulfonic acid methyl ester group, phenylthio group.

methylthio group, mercapto group), substituents containing a selenium atom (methylseleno group, phenylselenoxyl group, etc.), substituents containing a phosphorus atom (phosphoric acid methyl ester group, sulfite ester group, dimethylphosphino group, phenylphosphinyl group, etc.) substituted at any position.

In addition, as substituents containing an oxygen atom, methoxy group, ethoxy group, isopropoxy group, methquin carbonyl group,
Examples include an acetyloxy group, and examples of the substituent containing a silicon atom include a trimethylsilyl group. Examples of substituents containing a tin atom include trimethylstannyl group,
Examples include tributylstannyl group and triphenylstannyl group. Further, examples of substituents containing a nitrogen atom include a dimethylamino group, a diazo group, a nitro group, and a cyano group, and examples of substituents containing a sulfur atom include a sulfone group, a sulfonic acid methyl ester group, a phenylthio group,
Examples include methylthio group and mercapto group. Also,
Examples of substituents containing a selenium atom include a methylseleno group and a phenylselenoxyl group, and examples of substituents containing a phosphorus atom include a phosphoric acid methyl ester group, a sulfite ester group, a dimethylphosphino group, and a phenyl phosphorus group. Examples include finyl group.

In addition, in the styrene monomer represented by the general formula [■“], q is an integer from 1 to 5, and when q is a plurality of qs, the nine R2s may be the same or different. It may be.

Such styrenic monomers include styrene, p
- Alkyl such as methylstyrene, O-methylstyrene m-methylstyrene; 2,4-dimethylstyrene; 2,5-dimethylstyrene; 3,4-dimethylstyrene; 3,5-dimethylstyrene; p-tert-butylstyrene Styrene, p-chlorostyrene, m-chlorostyrene, 0-chlorostyrene, p-bromostyrene, m
- Halogenated styrenes such as bromostyrene, 0-furomostyrene, P-fluorostyrene, m-fluorostyrene, 0-fluorostyrene, 0-methyl-p-fluorostyrene, 4-vinylbiphenyl.

Vinylbiphenyls such as 3-vinylbiphenyl and 2-vinylphenyl, 1-(4-vinylphenyl)-naphthalene, 2-(4-vinylphenyl)-naphthalene, 1
-(3-vinylphenyl)-naphthalene, 2-(3-vinylphenyl)-naphthalene, 1-(2-vinylphenyl)-naphthalene 2-(2-vinylphenyl)-naphthalene, etc. vinylphenylnaphthalene flN, 1- (
4-vinylphenyl)-anthracene, 2-(4-vinylphenyl)-anthracene, 9-(4-vinylphenyl)-anthracene, 1-(3-vinylphenyl)-anthracene, 2-(3-vinylphenyl)- Anthracene, 9-(3-vinylphenyl)-anthracene, 1-
(2-vinylphenyl) to anthracene, 2-(2-vinylphenyl)-anthracene, vinylphenylanthracenes such as 9-(2-vinylphenyl)-anthracene, 1-(4-vinylphenyl)-phenanthrene2
-(4-vinylphenyl)-phenanthrene.

3-(4-vinylphenyl)-phenanthrene 4- (
4-vinylphenyl)-phenanthrene.

9-(4-vinylphenyl)-phenanthrene 2l-
(3-vinylphenyl)-phenanthrene 2- (3-
vinylphenyl)-phenanthrene.

3-(3-vinylphenyl)-phenanthrene.

4-(3-vinylphenyl)-phenanthrene.

9-(3-vinylphenyl)-phenanthrene.

1-(2-vinylphenyl)-phenanthrene.

2-(2-vinylphenyl)-phenanthrene.

3-(2-vinylphenyl)-phenanthrene.

4-(2-vinylphenyl)-phenanthrene.

Vinylphenylphenanthrenes such as 9-<2-vinylphenyl)-phenanthrene, 1-(4-vinylphenyl)-pyrene, 2-(4-vinylphenyl)-pyrene, 1-(3-vinylphenyl)-pyrene, 2-(3-vinylphenyl)-pyrene.

Vinylphenylpyrenes such as 1-(2-vinylphenyl)-pyrene and 2-(2-vinylphenyl)-pyrene,
4-vinyl-p-terphenyl, 4-vinyl-m-terphenyl, 4-vinyl-〇terphenyl, 3-vinyl-p-terphenyl
-terphenyl.

3-vinyl-m-terphenyl, 3-vinyl-〇terphenyl, 2-vinyl-p-terphenyl.

2-vinyl-m-9-phenyl Vinylterphenyls such as 2-vinyl-゛-terphenyl, vinylphenylterphenyls such as 4(4-vinylphenyl)-p-terphenyl, 4-vinyl 4゛-methyl biphenyl, 4-
Vinyl-3'-methylbiphenyl, 4-vinyl-2'-
Vinylalkylbiphenyls such as methylbiphenyl, 2-methyl-4-vinylbiphenyl, 3-methyl-4-vinylbiphenyl, 4-vinyl-4'-fluorobiphenyl, 4-vinyl-3''-fluorobiphenyl, 4-vinyl-2 '-Fluorobiphenyl.

4-vinyl-2-fluorobiphenyl 4-vinyl-3
-fluorobiphenyl, 4-vinyl-41-chlorobiphenyl, 4-vinyl-3+-chlorobiphenyl, 4-vinyl-2'-chlorobiphenyl, 4-vinyl-2-chlorobiphenyl, 4-vinyl-3-chlorobiphenyl, 4
-vinyl-4'-bromobiphenyl, 4-vinyl-3'
- Halogenated vinylbiphenyls such as bromobiphenyl, 4-vinyl-2°-bromobiphenyl, 4-vinyl-2-bromobiphenyl, 4-vinyl-3-bromobiphenyl, 4-vinyl-4′-methoxybiphenyl 4-
Vinyl-3°-methoxybiphenyl, 4-vinyl-2′-methoxybiphenyl.

4-vinyl-2-methoxybiphenyl 4-vinyl-3
-Methoxybiphenyl, 4-vinyl-4-ethoxybiphenyl, 4-vinyl-3'-ethoxybiphenyl, 4-
Vinyl-2'-ethoxybiphenyl, 4-vinyl-2-
Ethoxybiphenyl.

Alkoxyvinylbiphenyls such as 4-vinyl-3-ethoxybiphenyl, 4-vinyl-4methoxycarbonylbiphenyl, alkoxycarbonylvinylbiphenyls such as 4-vinyl-4'ethoxycarbonylbiphenyl, 4-vinyl 4-methoxymethyl Alkoxyalkylvinylbiphenyls such as biphenyl, 4-vinyl-4
Trialkylsilylvinylbiphenyls such as trimethylsilylbiphenyl, 4-vinyl-4+-trimethylstannylbiphenyl, trialkylstannylbiphenyls such as 4-vinyl 4'-tributylstannylbiphenyl, 4vinyl-4''-trimethylsilyl Trialkylsilylmethylvinylbiphenyls such as methylbiphenyl, 4-vinyl-4'-trimethylstannylmethylbiphenyl, trialkylstannylmethylvinylbiphenyls such as 4-vinyl-4'-triethylstannylmethylbiphenyl, pchloroethyl Styrene, halogen-substituted alkylstyrenes such as m-chloroethylstyrene and 0-chloroethylstyrene, and P-methoxystyrene.

m-methoxystyrene, 0-methoxystyrene.

Alkoxystyrene such as p-ethoxystyrene, m-ethoxystyrene 0-ethoxystyrene, alkoxycarbonylstyrene such as p-methoxycarbonylstyrene and m-methoxycarbonylstyrene, acetyloxystyrene, ethanoyloxystyrene, acyloxy such as hendiyloxystyrene Styrene, alkyl ether styrenes such as p-vinylhensylpropyl ether, trialkylsilylstyrenes such as p-t-limethylsilylstyrene, trimethylstyrenes such as p-1-limethylscunnylstyrene, and p-tributylstannylstyrene. Examples include triarylstannylstyrenes such as alkylstannylstyrene and p-triphenylstannylstyrene, and vinylstyrenes such as ethyl vinylhenzenesulfonate vinylhensyldimethoxyphosphide and P-vinylstyrene.

The styrenic copolymer of the present invention has the above-described repeating units, and furthermore, its stereoregularity mainly has a syndiotactic structure. Here, the syndiotactic structure in a styrenic polymer means that the stereochemical structure is mainly a syndiotactic structure, that is, a phenyl group or substituted phenyl group that is a side chain is formed from a main chain formed from carbon-carbon bonds. It means that it has a three-dimensional structure that is located in the opposite direction alternately, and its toughness is determined by the nuclear magnetic resonance method ("C") using isotopic carbon.
-NMR method).

``Toughness measured by C-NMR method is
The presence ratio of a plurality of consecutive structural units, for example, can be indicated by a diad F for two units, a triand for three units, and a pentad for five units; "has" means
The degree of syndiotacticity varies slightly depending on the type of substituent and the chain of each repeating unit, and in the chain of styrenic repeating units, it is usually 75% or more for racemic diats, preferably 85% or more, or racemic pens. It refers to a substance having syndiotacticity of 30% or more, preferably 50% or more in Tad.

Furthermore, in the alkylstyrene polymer of the present invention,
Not only between the bonded repeating units [■] but also between the repeating units H] and [I[) form a syndiotactic structure (co-syndiotactic structure). In addition, this copolymer also contains a repeating unit (I
), (IF) in various forms including block copolymerization, random copolymerization, and alternating copolymerization.

Note that the alkylstyrene-based polymer mainly having a syndiotactic structure as used in the present invention does not necessarily have to be a single copolymer. As long as the syndiotacticity is within the above range, it may be a mixture with a styrene polymer having an isotactic or atactic structure, or it may be incorporated into a polymer chain. Further, the alkylstyrene polymer of the present invention may be a mixture of substances having different molecular weights, and the degree of polymerization is at least 5 or more, preferably 1.
Refers to 0 or more. In terms of weight average molecular weight, it is preferably from s,ooo to 800,000. If the degree of polymerization is less than 5, bleeding occurs and the composition lacks long-term stability. Note that there is no particular restriction on the molecular weight distribution.

Furthermore, there are various types of transition metal compounds used in the transition metal component (a) which is a catalyst component, but in particular, those having the general formula %() M 3 RI I , RI 2.2 I.

]1 ... [Vl) or M' R13g R"), R" [:l-f94h1
... [■] [In the formula, R4 to RI5 are each independently a hydrogen atom.

Halogen atom, alkyl group having 1 to 20 carbon atoms, 1 to 20 carbon atoms
20 alkoxy group, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and an acyloxy group having 1 to 20 carbon atoms.

Represents an acetylacetonyl group, a cyclopentagenyl group, a substituted cyclopentagenyl group or an indenyl group. Furthermore, a, b, and c represent integers greater than or equal to 0 that satisfy O≦a+b+C≦4, and d and e represent 0 that satisfies 0≦d+e≦3.
f is an integer greater than or equal to 0 that satisfies 0≦f≦2, and g and h are integers greater than or equal to 0 that satisfy 0≦g+h≦3. Furthermore, Ml, M2 represent titanium zirconium, hafnium or vanadium, M3. M' represents vanadium. ] is preferably used. Above - general formula (IV), (V), (V
Among the transition metal compounds represented by [) or [■],
In particular, it is preferable to use a titanium compound or a zirconium compound represented by the general formula (IV).

The above general formula [IV), [V), (Vl) or [
Among those represented by R4 to RIS in [2]], specific examples of the halogen atoms include chlorine, fluorine, bromine, and iodine. Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, amyl group, isoamyl group, octyl group, 2-ethylhexyl group, etc. can be mentioned.

Further, specific examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, amyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, etc. can. Further, specific examples of the aryl group having 6 to 20 carbon atoms include phenyl group and naphthyl group.

Next, specific examples of the arylalkyl group having 7 to 20 carbon atoms include a Hensyl group, a phenethyl group, and a 9-anthrylmethyl group.

Further, specific examples of the acyloxy group having 1 to 20 carbon atoms include an acetyloxy group and a stearoyloxy group. Further, as the substituted cyclopentadienyl group, for example, a cyclopentadienyl group substituted with one or more alkyl groups having 1 to 6 carbon atoms, specifically,
Examples include methylcyclopentadienyl group and pentamethylcyclopentadienyl group. These R4
~RI5 may be the same or different as long as the above conditions are met.

Such the general formula (TV), (V),
Among the transition metal compounds represented by (■) or [■], specific examples of titanium compounds include tetramethoxytitanium, tetraethoxytitanium, tetra-n-butoxytitanium, tetraisopropoxytitanium, cyclohentacyenyltrimethyltitanium, Cyclopentadienyltriethyltitanium, cyclopentadienyltripropyltitanium, cyclopentadienyltributyltitanium, methylcyclopentagenyltrimethyltitanium, 1,2-dimethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltrimethyltitanium, Pentamethylcyclopentagenyl triethyl titanium, Pentamethylcyclopentagenyl triprobyl titanium, Pentamethylcyclopentagenyl tributyl titanium, Cyclopentajenylmethyltitanium dichloride Pentamethylcyclopentagenylmethyltitanium dichloride, Pentamethylcyclopentagenyl titanium ethyl titanium dichloride, pentamethylcyclopentadienyl dimethyl titanium monochloride,
Cyclopentadienyl diethyl titanium monochloride, cyclopentadienyl titanium trimethoxide, cyclopentajenyl titanium triethoxide, cyclopentajenyl titanium tripropoxide, cyclopentajenyl titanium triphenoxide, pentamethylcyclopentadienyl titanium Trimethoxide, pentamethylcyclopentadienyl titanium triethoxide, pentamethylcyclopentadienyl titanium tributoxide, pentamethylcyclopentagenyl titanium tributoxide, pentamethylcyclopentadienyl titanium triphenoxide, cyclopentagenyl Titanium trichloride, pentamethylcyclopentagenyl titanium trichloride, cyclopentajenylmethoxytitanium dichloride, cyclopentajenylmethoxytitanium chloride, pentamethylcyclopentagenylmethoxytitanium dichloride, cyclopentajenyltribenzyltitanium, pentamethylcyclo Examples include pentagenylmethyljethoxytitanium indenyltitanium trichloride, indenyltitanium trimethoxide, indenyltitanium triethoxide, indenyltrimethyltitanium, and indenyltribenzyltitanium.

Among these titanium compounds, compounds that do not contain halogen atoms are preferred, and in particular, four-coordination titanium compounds in which at least one ligand is an unsaturated π-electron system ligand as described above are preferred. .

In addition, the general formula (IV), [V], C■; or (
Among the transition metal compounds represented by Examples include pentagenyltribenzylzirconium, bisindenylzirconium dichloride, zirconium dibenzyldichloride, zirconiumtetrabenzyl, tributoxyzirconium chloride, triisopropoxyzirconium chloride, and the like.

Further, similar specific examples of hafnium compounds include cyclopentadienyl hafnium trimethoxide, pentamethylcyclopentadienyl hafnium trimethoxide, cyclopentadienyl tribenzyl hafnium, pentamethylcyclopentadienyl tribezyl hafnium,
Bisindenyl hafnium dichloride, hafnium dibenzyl dichloride. Examples include hafnium tetrabenzyl, driftoxyhafnium chloride, triisopropoxyhafnium chloride, and the like.

Furthermore, similar specific examples of vanadium compounds include vanadium trichloride, vanadyl trichloride, vanadium triacetylacetonate vanadium tetrachloride, vanadium tributoxide vanadyl dichloride,
Examples include vanadyl bisacetylacetonate and vanadyl triacetylacetonate.

On the other hand, the contact product of Φ) organoaluminium, which is another component of the catalyst, and the condensing agent is disclosed in, for example, JP-A No. 62-18770.
This is the same type as that described in Publication No. 8, and the details are as follows.

That is, this contact product is obtained by bringing various organoaluminiums into contact with a condensing agent.

Here, the organoaluminum compound usually has the general formula: A I R''3 [wherein R1b represents an alkyl group having 1 to 20 carbon atoms].

] Organoaluminum represented by these, specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, etc., are mentioned, and among them, trimethylaluminum is the most preferable.

On the other hand, the condensing agent typically includes water,
In addition, any substance with which trialkylaluminum undergoes a condensation reaction, such as copper sulfate pentahydrate.

Examples include various types of water adsorbed on inorganic and organic substances.

A typical example of the contact product of the organoaluminium, which is the component (b) of the catalyst used in the present invention, and the condensing agent is the contact product of the trialkylaluminum represented by the general formula Affi Rlth+ and water. , specifically, the general formula [wherein RI6 is the same as above, n indicates the degree of polymerization, and is a number from 2 to 50. ] Chain alkylaluminoxane or general formula +A! -0-h [In the formula, R111 and n are the same as above. ] Examples include cyclic alkylaluminoxane having a repeating unit represented by the following. Among such alkylaluminoxanes, those in which RIb is a methyl group, ie, methylaluminoxane, are particularly preferred.

Generally, the product of contact between an organoaluminum compound such as trialkylaluminum and water is a mixture of unreacted trialkylaluminum, various condensation products, as well as the above-mentioned linear alkylaluminoxane and cyclic alkylaluminoxane, and furthermore, a mixture of unreacted trialkylaluminum and various condensation products. are molecules that are complexly associated, and these produce various products depending on the contact conditions between trialkylaluminium and water.

There is no particular limitation on the method of contacting the organoaluminum compound with water at this time, and the reaction may be carried out according to a known method. For example, ■ a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, ■ a method in which an organoaluminum compound is initially added during polymerization and water is added later, and ■ a method in which metal salts, etc. There is a method of reacting contained crystal water or water adsorbed on inorganic or organic substances with an organoaluminum compound. Note that the above water may contain up to about 20% of amines such as ammonia and ethylamine, sulfur compounds such as hydrogen sulfide, and phosphorus compounds such as phosphorous esters. Although the above catalytic reaction proceeds without a solvent, it is preferable to carry out it in a solvent. Preferably, suitable solvents include aliphatic hydrocarbons such as hexane, heptane, and decalin, benzene, toluene, and xylene. Examples include aromatic hydrocarbons.

In the present invention, the contact product of the organoaluminum and the condensing agent used as component (b) of the catalyst (for example, alkylaluminoxane) is obtained after the above-mentioned contact reaction, and when a water-containing compound is used, the solid residue is separated by filtration, The filtrate is heated at a temperature of 30 to 200°C, preferably 40 to 200°C, under normal pressure or reduced pressure.
at a temperature of 150°C for 20 minutes to 8 hours, preferably 30
Preferably, the material is heat-treated while distilling off the solvent for a period of minutes to 5 hours.

In this heat treatment, the temperature may be determined as appropriate depending on various circumstances, but it is usually carried out within the above range. Generally, the effect does not appear at temperatures below 30°C, and 2
If the temperature exceeds 00°C, thermal decomposition of the alkylaluminoxane itself occurs, which is not preferable.

Depending on the heat treatment conditions, the reaction product can be obtained in the form of a colorless solid or a solution. The product thus obtained can be used as a catalyst solution by dissolving or diluting it with a hydrocarbon solvent, if necessary.

A preferred example of a contact product of an organoaluminum and a condensing agent used as such a catalyst component, in particular an alkylaluminoxane, is based on the aluminum-methyl group (An CH3) bond observed in proton nuclear magnetic resonance spectroscopy. The high magnetic field component in the methyl proton signal region is 50% or less. In other words, when observing the proton nuclear magnetic resonance ('HNMR) spectrum of the above contact product in toluene solvent at room temperature, AI! C
Methyl proton signal based on H3 is 1.0 to -0.5 ppm based on tetramethylsilane (TMS)
found in the range of TMS proton signal (Opp
m) is A1. Since it is in the methyl proton observation region based on CH3, the methyl proton signal based on Af-CH3 was measured based on the methyl proton signal of toluene in the 7MS standard of 2.35 ppm, and the high magnetic field component (i.e. -〇, 1~ -0.5 ppm) and other magnetic field components (i.e., 0.1 to -0.1 ppm), the high magnetic field component accounts for less than 50% of the total, preferably 4
5 to 5% can be suitably used as the (b) component of the catalyst.

The catalyst used here has the above-mentioned components (a) and (b) as its main components, but in addition to the above, another catalyst component (C) can be added as desired, thereby increasing the catalyst component. By adding (C), the catalyst activity can be significantly improved.

The second catalyst component (C) has the general formula AIR" [where RI7 is a hydrogen atom, a halogen atom, or a carbon number 1
~8 alkyl group is shown. ] This shows an organoaluminum compound represented by:

Specifically, the organoaluminum compounds include triisobutylaluminum, isobutylaluminum hydride, trimethylaluminum, triethylaluminum,
Examples include diethylaluminum chloride.

The alkylstyrene polymer of the present invention is produced using the above catalyst, and any polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, etc. may be used. As the solvent, aliphatic hydrocarbons such as pentane, hexane, and heptane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as benzene, toluene, and xylene are used. Although the monomer/solvent ratio is arbitrary, from the viewpoint of productivity it is preferable to polymerize with a high concentration of styrenic monomer.

The polymerization conditions are not particularly limited, and can be carried out in the same manner as conventional methods, for example, polymerization conditions of 0 to 12
0°C1 Preferably at a temperature of 10-80°C for 5 minutes to 24
It can be carried out for an hour, preferably one hour or more. Also,
Although there are no particular restrictions on the polymerization pressure, it is effective to carry out the polymerization in the presence of hydrogen in order to control the molecular weight.

Further, after the polymerization is completed, the catalyst can be deactivated with alcohol or the like as in the conventional method.

Furthermore, when using this catalyst, (a
) component, (b) component, (C) component, the ratio with these solvents, and further (a) component, (b) component, (C) component.
) The order in which the component solvents and monomers are charged differs depending on their combination and is difficult to unambiguously define, but usually aluminum in catalyst component (b) and catalyst component (a)
The molar ratio of the transition metal therein, that is, the aluminum/transition metal (molar ratio) is 20/1 to 10,000/1, preferably 100/1 to 1,000/1.

Further, the molar ratio between the monomer and aluminum in the catalyst component (b), that is, the monomer/aluminum (molar ratio), is 10,000/1 to 0.01/1, preferably 200/1.
1 to 0.5/1.

Furthermore, aluminum in the catalyst component (C) and the catalyst component (
The molar ratio with aluminum in b) is [catalyst component (C)
aluminum in catalyst component (b)]/[aluminum in catalyst component (b)] (molar ratio) is 100/1 to 0/1, preferably 10/1 to 0/1.

The alkyl styrene polymer obtained in the above manner has high syndiotacticity as described above, but after polymerization, it is decalcified with a cleaning solution containing hydrochloric acid, etc., if necessary, and then washed. By removing the soluble content, it is possible to obtain a highly purified alkylstyrene polymer with extremely high syndiotoughness.

The alkylstyrene polymer of the present invention contains 0.1 to 100 mol% of the repeating unit (1) and 0 to 99.9 mol% of the repeating unit (II),
Preferably, it contains 2 mol% or more of the repeating unit (1), particularly preferably 8 to 100 mol% of the repeating unit [I], and 0 to 92 mol% of the repeating unit (IN).

Such alkylstyrene polymers have better thermal properties than styrene-lower alkylstyrene copolymers.

The present invention relates to the above alkylstyrene polymer in an amount of 1 to 99% by weight and the general formula (III) (R'').

[In the formula, R3 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 r represents an integer from 1 to 5. However, when r is plural, each R3 may be the same or different.

] A styrenic polymer having a repeating unit (I[[) whose stereoregularity mainly has a syndiotactic structure (excluding cases where it is the same as that of an alkylstyrene polymer)99- A resin composition comprising 1% by weight is also provided.

Here, regarding R3, examples of the halogen atom include chlorine, fluorine, bromine, and iodine. Further, specific examples of substituents containing carbon atoms include alkyl groups having 1 to 20 carbon atoms such as methyl group, ethyl group, isopropyl group, and tertiary-butyl group; hydrogen atom, halogen atom or carbon atom on benzene ring; Aryl group with 6 to 30 carbon atoms having a substituent containing oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, selenium atom, silicon atom or tin atom; halogen with 1 to 20 carbon atoms such as chloroethyl group and bromoethyl group Examples include substituted alkyl groups.

Also, as an aryl group with 6 to 30 carbon atoms having a substituent on the benzene ring containing a hydrogen atom, a halogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom, or a tin atom, etc. For example, Hensen ring, naphthalene ring.

Phenanthrene ring, anthracene ring, indene ring.

azulene ring, hebutalene ring, biphenylene ring aS-indacene ring, S-indacene ring, acenaphthylene ring, phenalene ring, fluoranthene ring.

Acephenanthrene ring, naphthacene ring, preiazone ring, picene ring, perylene ring, pentacene ring.

Rubisene ring, corocene ring, vilanthrene ring, ohalene ring and their alkyl substituents (methyl group).

ethyl group, isopropyl group, tert-butyl group, etc.), halogen substituents, alkyl groups (chloroethyl group, bromoethyl group, etc.), substituents containing oxygen atoms (methoxy group, ethoxy group, isopropoxy group, methoxycarbonyl group, acetyloxy groups), substituents containing silicon atoms (
trimethylsilyl group, etc.), substituents containing a tin atom (trimethylstannyl group, tributylstannyl group, triphenylstannyl group, etc.), substituents containing a nitrogen atom (dimethylamino group, diazo group, nitro group, cyano group, etc.) )
, substituents containing a sulfur atom (sulfonic acid methyl ester group, phenylthio group.

methylthio group, mercapto group, etc.), substituents containing a selenium atom (methylseleno group, phenylselenoxyl group, etc.), substituents containing a phosphorus atom (phosphoric acid methyl ester group, sulfite ester group, dimethylphosphino group, phenyl This includes those substituted with a phosphinyl group (such as a phosphinyl group) at any position.

In addition, as substituents containing an oxygen atom, methoxy group, ethoxy group, isopropoxy group, methoxycarbonyl group,
Examples include an acetyloxy group, and examples of the substituent containing a silicon atom include a trimethylsilyl group. Examples of substituents containing a tin atom include trimethylstannyl group,
Examples include tributylstannyl group and triphenylstannyl group. Further, examples of substituents containing a nitrogen atom include a dimethylamino group, a diazo group, a nitro group, and a cyano group, and examples of substituents containing a sulfur atom include a sulfone group, a sulfonic acid methyl ester group, a phenylthio group,
Examples include methylthio group and mercapto group. Also,
Examples of substituents containing a selenium atom include a methylseleno group and a phenylselenoxyl group, and examples of substituents containing a phosphorus atom include a phosphoric acid methyl ester group, a sulfite ester group, a dimethylphosphino group, and a phenyl phosphorus group. Examples include finyl group.

Furthermore, in the repeating unit represented by general formula (1), r is an integer from 1 to 5, and when r is a plurality of numbers, r R3's may be the same or different. It's okay.

The styrenic polymer consisting of the repeating unit (1) having such a substituent may be a mixture of substances having different molecular weights, and the degree of polymerization is at least 5 or more, preferably 1.
Refers to 0 or more. In terms of weight average molecular weight, it is preferably 8,000 to soo or ooo. In addition,
There are no particular restrictions on the molecular weight distribution.

Specific examples of the above-mentioned styrene polymers include polystyrene and poly(p-methylstyrene).

Poly(m-methylstyrene), poly(2,4-dimethylstyrene), poly(2,5-dimethylstyrene), poly(3,4-dimethylstyrene), poly(35-dimethylstyrene), poly(p- tert-butylstyrene)
Poly(alkylstyrene), poly(p-chlorostyrene), poly(m-chlorostyrene), poly(0-chlorostyrene), poly(p-bromostyrene), poly(
m-bromostyrene), poly(0-bromostyrene),
Poly(P-fluorostyrene), poly(m-fluorostyrene), poly(0-fluorostyrene), poly(0-fluorostyrene)
Poly(halogenated styrene) such as methyl-p-fluorostyrene), poly(4-vinylbiphenyl), poly(
3-vinylbiphenyl), poly(vinylbiphenyl) such as poly(2-vinylbiphenyl), poly(1-(4
-vinylphenyl)-naphthalene), poly(2-(4-
(vinylphenyl)-naphthalene).

Poly(1-(3-vinylphenyl)-naphthalene).

Poly(2-(3-vinylphenyl)-naphthalene) Poly(1-(2-vinylphenyl)-naphthalene).

Poly(vinylphenylnaphthalenes) such as poly(2-(2-vinylphenyl)-naphthalene), BoIJ(1-
(4-vinylphenyl)-anthracene).

poly(2-(4-vinylphenyl)-anthracene),
poly(9-(4-vinylphenyl)-anthracene),
poly(1-(3-vinylphenyl)-anthracene),
poly(2-(3-vinylphenyl)-anthracene),
poly(9-(3-vinylphenyl)-anthracene),
poly(vinylphenylanthracenes) such as poly(1-(2-vinylphenyl)-anthracene), poly(2-(2-vinylphenyl)-anthracene), HoIJ(9-(2-vinylphenyl)-anthracene), Po IJ (
1-(4-vinylphenyl)-phenanthrene), poly(2-(4-vinylphenyl)-phenanthrene), poly(3-(4-vinylphenyl)-phenanthrene),
Poly(4-(4-vinylphenyl)-phenanthrene)
, poly(9-(4-vinylphenyl)-phenanthrene), poly(1-(3-vinylphenyl)-phenanthrene), Bo+J(2-(3-vinylphenyl)-phenanthrene), poly(3-(3-vinylphenyl)-phenanthrene), -vinylphenyl)phenanthrene), poly(4-(3-vinylphenyl)-phenanthrene), poly(9-(3-vinylphenyl)-phenanthrene), poly(1-(2-vinylphenyl)-phenanthrene).

Vol 7 (2-(2-vinylphenyl)-phenanthrene), poly(3-(2-vinylphenyl)-phenanthrene), poly(4-(2-vinylphenyl)-phenanthrene), poly(9-(2- Poly(vinylphenylphenanthrenes) such as vinylphenyl)-phenanthrene), poly(1-(4-vinylphenyl)-pyrene), poly(2-(4-vinylphenyl)-pyrene), poly(1
(3-vinylphenyl)-pyrene), poly(2(3-vinylphenyl)-pyrene), poly(1-(2-vinylphenyl)-pyrene), poly(2-(2-vinylphenyl)-pyrene) poly(vinylphenylpyrenes) such as
Poly(4-vinyl-p-terphenyl), poly(4-vinyl-m-terphenyl), poly(4-vinyl-〇-terphenyl), poly(3-vinyl-p-terphenyl)
.

Poly(3-vinyl-m-terphenyl), poly(3-vinyl-0-terphenyl), poly(2-hinyl-p-terphenyl), poly(2-vinyl-m-terphenyl)
, poly(2-vinyl-〇-terphenyl) and other poly(
poly(vinylphenylterphenyls) such as poly(4-(4-vinylphenyl)-p-terphenyl), poly(4-vinyl-4'-methylbiphenyl), poly(4-vinyl-4'-methylbiphenyl), 3゛~methylbiphenyl), poly(4-vinyl-2''-methylbiphenyl)
, poly(2-methyl-4-vinylphenyl), poly(3
poly(vinylalkylbiphenyls) such as -methyl-4-vinylbiphenyl), poly(4-vinyl-4'-fluorobiphenyl).

Poly(4-vinyl-3'-fluorobiphenyl).

Poly(4-vinyl-2′-fluorobiphenyl)poly(
4-vinyl-2-fluorobiphenyl).

Poly(4-vinyl-3-fluorobiphenyl).

Poly(4-vinyl-4′-chlorobiphenyl)poly(4
~vinyl-3+-chlorobiphenyl)poly(4-vinyl-2′-chlorobiphenyl).

PoIJ (4-vinyl-2-chlorobiphenyl), poly(
4-vinyl-3-chlorobiphenyl), poly(4-vinyl-4'-bromobiphenyl), poly(4-vinyl-3
'-bromobiphenyl), poly(4-vinyl-2'-bromobiphenyl), poly(4-vinyl-2-bromobiphenyl), poly(4-vinyl-3-bromobiphenyl)
poly(halogenated vinylbiphenyls), poly(
4-vinyl-4゛-methoxybiphenyl), poly(4-
Vinyl-3'-methoxybiphenyl), poly(4-vinyl-2'-methoxybiphenyl).

poly(4-vinyl-2-methoxybiphenyl)poly(4
-vinyl-3-methoxybiphenyl).

Poly(4-vinyl-4′-ethoxybiphenyl)poly(
4-vinyl-3''-ethoxybiphenyl)poly(4-vinyl-2''-ethoxybiphenyl).

Poly(4-vinyl-2-ethoxybiphenyl).

Poly(alkoxyvinylbiphenyls) such as poly(4-vinyl-3-ethoxybiphenyl), poly(4-vinyl-4'-methoxycarbonylbiphenyl), poly(4-vinyl-4'-methoxycarbonylbiphenyl)
- poly(alkoxycarbonylvinylbiphenyls) such as -vinyl-4'-ethoxycarponylbiphenyl),
Poly(4-vinyl-4'-methoxymethylbiphenyl)
Poly(alkoxyalkyl vinylbiphenyls) such as
, poly(trialkylsilylvinylbiphenyls) such as poly(4-vinyl-4'-trimethylsilylbiphenyl), poly(4-vinyl-4'-)IJmethylstannylbiphenyl), poly(4-vinyl-4'- - poly(trialkylstannylbinylbiphenyls) such as tributylstannylbiphenyl), poly(4-vinyl-4"
- poly(trialkylsilylmethylvinylbiphenyls) such as trimethylsilylmethylbiphenyl), poly(
4-vinyl-4I-trimethylstannylmethylbiphenyl), poly(trialkylstannylmethylvinylbiphenyls) such as poly(4-vinyl-4I-triethylstannylmethylbiphenyl), poly(p-chloroethylstyrene), PoIJ (m-chloroethylstyrene)
, poly(halogen-substituted alkylstyrene) such as poly(0-chloroethylstyrene), poly(p-methoxystyrene), poly(m-methoxystyrene), poly(O-methoxystyrene), poly(P-ethoxystyrene) , poly(alkoxystyrenes) such as poly(m-ethoxystyrene), poly(0-ethoxystyrene), poly(P
-methoxycarbonylstyrene), poly(alkoxycarbonylstyrenes) such as poly(m-methoxycarbonylstyrene), poly(acetyloxystyrene), poly(ethanoyloxystyrene), poly(hendiyloxystyrene), etc. acyloxystyrenes)
, poly(alkyl ether styrenes) such as poly(p-vinylbenzylprobyl ether), poly(trialkylsilylstyrenes) such as poly(p-trimethylsilylstyrene), poly(p-1 trimethylscinnylstyrene) ), poly(triarylstanylstyrenes) such as poly(p-)butylstannylstyrene),
Poly(triarylstannylstyrenes) such as J(p-)'J phenylscunnylstyrene), poly(ethyl vinylhenzenesulfonate), poly(vinylhensyldimethoxyphosphide), poly(p-vinyl Examples include poly(vinylstyrenes) such as styrene).

By mixing the alkylstyrenic polymer of the present invention with a styrenic polymer having a mainly syndiotactic structure which is a crystalline polymer, a styrenic polymer having a mainly syndiotactic structure which is a crystalline polymer can be obtained. It is possible to lower the melting point and/or glass transition temperature without reducing the crystallinity of the material. This thermal behavior can be specifically observed by differential scanning calorimetry (DSC).

The blending ratio can be arbitrarily selected within the range of 1 to 99% by weight of the styrene polymer having a syndiotactic structure and 99 to 1% by weight of the alkylstyrene polymer having a syndiotactic structure. Among them, the former is preferably selected in the range of 2 to 90% by weight, the latter in the range of 10 to 98% by weight, particularly preferably the former in the range of 5 to 60% by weight, and the latter in the range of 40 to 95% by weight.

[Examples] Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Example 1 (1) Methylaluminoxane 2001 Ifl of toluene and copper sulfate pentahydrate (CuS04.5
H20) 17.7 g (7 1 mmol) and trimethylaluminum 24d (250 mmol) were added,
The reaction was carried out at 0°C for 8 hours. After that, solid components are removed,
Toluene was further distilled off under reduced pressure from the resulting solution to obtain 6.7 g of a contact product. The molecular weight of this product measured by freezing point depression method was 610. Also, the high magnetic field component by 'H-NMR measurement, that is,
In its proton nuclear magnetic resonance spectrum in toluene solvent at room temperature, the methyl proton signal based on the (A f - C H 3) bond is similar to that of tetramethylsilane (T
MS) standard is found in the range of 1.0 to -0.5 ppm. TMS proton signal (Oppm) is A1
Because it is in the methyl proton observation region based on -CH3,
The methyl proton signal based on this 142-CH3 was measured based on the 2.35 pp- methyl proton signal of toluene in the 7MS standard, and the high-field component (i.e.,
−〇． 1 to -0. 5 ppm) and other magnetic field components (i.e., 1.0 to -0.1 ppm), the high field component was 43% of the total.

(2) Production of 4-n-octylstyrene 1.70 g of granular metallic magnesium (
One drop of 1,2-dibromoethane was added dropwise to a solution of 0.07 mol) in diethyl ether (100 m) and heated to initiate the Grignard reagent production reaction. The temperature of the liquid was raised to reflux, and then -n-octyl bromide 12.11
11 (0.07 mol) of diethyl ether was slowly added dropwise over 30 minutes. After the dropwise addition was completed, the mixture was left under reflux for 1 hour. The reaction solution was cooled to room temperature, and p-bromostyrene 6,55d (0.05 mol) and nickel arsenide chloride (1,3-diphenylphosphinopropane) were added at room temperature.
It was added dropwise to a solution of 0.16 g (0.3 mmol) of the complex in diethyl ether (loo+te). After the dropwise addition was completed, the mixture was refluxed for 4 hours.

The reaction solution was poured into 500 d of ice water, and the pH was adjusted to be slightly acidic. Extraction with hexane, washing, drying. After solvent distillation and purification by silica gel column chromatography, 4-n-octylstyrene 12. 1 g
(yield 80%).

'H-NMR (solvent: deuterated chloroform, 90M);
δ 0.89 (3H, t, CH3), 6 1.0
0 to 1.8 0 (1 2 H, m, methylene [other than benzyl position]), δ 2.60 (2H, t, methylene [benzyl position]), 6 5.18 (2H, dd
, HC=C-[trans]), 6 5.70 (2H
, dd.

HC=C-Ccis]), 6 6.70 (IH, dd
.

C=CH- (α position]), 6 7.1 1 (2H,
dd.

meta position of vinyl group), 6 7.32 (2H, dd.

(3) Production of 4-n octyl styrene polymer having a syndiotactic structure In a dry reaction vessel under an argon atmosphere, 10 d of toluene was added to the methyl styrene obtained in (1) above at 70°C. Add 8×10-” moles of aluminoxane (2.6 moles/1-toluene solution [per aluminum atom]) and heat at 70°.
C, pentamethylcyclopentadienyl titanium trimethoxide (Cp”) was added to the reaction solution as the catalyst component (a).
Ti (OMe)+) 4XIO-5 mol (0.01 mol/l-toluene solution) 4-n-octylstyrene 19. 0 g (8.75XIO-''mol) was added and the reaction was allowed to proceed for 4 hours.

After that, the reaction product was added to a methanol-hydrochloric acid mixed solution to stop the reaction, and after deashing and filtration, it was further added with methanol for 3
Washed twice. After drying under reduced pressure, 4.0 g of polymer was obtained. When this molecular weight was measured by GPC (gel permeation chromatography), the weight average molecular weight (Mw) in terms of polystyrene was 220,00.
0, and the number average molecular weight (Mn) was 100,000.

Note that the measurement conditions for GPC were as follows.

Equipment: Waters ALS/'GPC244 type column:
TSK GH8P+TSK GMH6+Hitachi GL-A120+Hitachi CL-A130 Temperature: room temperature Injection amount: 500uf Concentration=lO ■15-related solvent: Chloroform flow rate: 1.4I11/min Example 2 4-n~octylstyrene 15.2g as a monomer (
7,00 x 10-” moles) and 1.82 g (8
, 75×10 −3 mol) was used in the same manner as in Example 1, and a polymer was obtained in a yield of 2.7 g.

The Mw of this polymer according to c and pc (measurement conditions are the same as in Example 1) is 85,000. Mn was 35,000.

IH-NMR (400M cell; solvent chloroform.

4n- determined from tetramethylsilane (Oppa+ standard)
The molar ratio of octyl styrene part/styrene part is 66/34
Met.

Example 3 8.5 g of 4-n-octylstyrene (4
, 38x I O-” mol) and 4.6 g of styrene (4,
A polymer was obtained in a yield of 2.75 g by the same procedure as in Example 1, except that 38×10-"mol) was used. The Mw of this polymer was determined by GPC (measurement conditions were the same as in Example 1).
is 64,000. Mn was 13.000.

The molar ratio of 4-n-octylstyrene moiety/styrene moiety determined from 'H-NMR (measurement conditions are the same as in Example 2) is:
It was 48152.

Example 4 7.6 g of 4-n-octylstyrene (3
,5X10-"mol) and 5.5g styrene (5,25X
A polymer was obtained in a yield of 1.04 g by the same procedure as in Example 1 except that G
Mw by PC (measurement conditions are the same as in Example 1) is 74
000, and Mn was 28.000.

The molar ratio of 4-n-octylstyrene moiety/styrene moiety determined from 'H-NMR (measurement conditions are the same as in Example 2) is:
It was 24/76.

Example 5 5.7 g (2
, 63
A polymer was obtained in a yield of 1.57 g by the same procedure as in Example 1 except that 3xlO-2 mol) was used. The Mw of this polymer by GPC (measurement conditions are the same as in Example 1) is:
52,000, and Mn was 14.000.

The molar ratio of 4-n-octylstyrene moiety/styrene moiety determined from 'H-NMR (measurement conditions are the same as in Example 2) is:
It was 23/77.

Example 6 3.8 g (1
,75
A polymer was obtained in a yield of 0.61 g by the same operation as in Example 1, except that OX10-''mol) was used.The Mw of this polymer was determined by GPC (measurement conditions were the same as in Example 1). ,
72,000. Mn was 34,000.

The molar ratio of 4-n-octylstyrene moiety/styrene moiety determined from 'H-NMR (measurement conditions are the same as in Example 2) is:
It was 12/88.

Further, this polymer was determined to have -70'C to 300'C by DSC (differential scanning calorimetry).

20℃/min, temperature increase (first heating), ■30
0"C, held for 5 minutes, ■300"C to -70"C.

7°C/min, temperature decrease (first cooling), -70
°C, held for 5 minutes, -70'C to 300'C.

When measured under the measurement conditions of temperature increase (second heating) at 20°C/min, the glass transition point (Tg) observed during second heating was 54.7°C, and
There was no melting point (Tm).

Example 7 1.9 g of 4-n-octylstyrene (0
, 88xlO pmol) and 8.19 g of styrene (7,8
A polymer was obtained in a yield of 1.31 g by the same procedure as in Example 1, except that 8×10-" mol) was used. The Mw of this polymer was determined by CPC (measurement conditions were the same as in Example 1). , 180,000, and Mn was 74,000.

The molar ratio of 4-n-octylstyrene moiety/styrene moiety determined from 'H-NMR (measurement conditions are the same as in Example 2) is:
It was 8/92.

Furthermore, when DSC (differential scanning calorimetry) was performed on this polymer (measurement conditions were the same as in Example 6),
The glass transition point (T
g) is 73.7°C, and the melting point (Tm) is
It didn't exist.

Example 8 0.95 g of 4-n-octyl styrene as 7-mer (
0.44× 10-” moles) and 8.65 g of styrene <8
．． A polymer was obtained in a yield of 2.98 g by the same procedure as in Example 1 except that 31xlO-2 mol) was used. Mw of this polymer by GPC (measurement conditions are the same as in Example 1)
is 350,000. Mn was 180.000.

The molar ratio of 4-n-octyl styrene moieties/styrene moieties determined from 'H-NMR (measurement conditions were the same #l as in Example 2) was 6/94.

Furthermore, when DSC (differential scanning calorimetry) was performed on this polymer (measurement conditions were the same as in Example 6),
The glass transition point (T
g) is 82.4°C, and the melting point (Tm) is
223.5°C, and the heat of fusion at that time is 13.4
(J/g).

Comparative Example 1 4-n-octylstyrene was mixed with azoisobutyronitrile (
AIBN) was used for radical polymerization, and the Mw by GPC (measurement conditions were the same as in Example 1) was 14,000, M
A polymer in which n was 37,000 was obtained.

13C-NMR (100 MHz: solvent chloroform, tetramethylsilane Opp+m standard) of the polymers or copolymers obtained in Examples 1 to 8 and Comparative Example 1 is shown in FIG. The polymer obtained in Example 1 does not have a peak broadening as in Comparative Example 1, which indicates that the polymer is a copolymer whose main chain mainly has a syndiotactic structure.

<Attribution of peaks> Around 40-41ρp+w Main chain methine Around 44-45 ppm Main chain methylene Example 9 Toluene 10M1, as catalyst component (b), triisobutylaluminum (TIBA) 4X10-3 mol (2 mol/! ~ toluene solution ) and methylaluminoxane 8X
The same procedure as in Example 1 was performed except that 10-3 mol (2,6 mol/2-toluene solution) was used, and a polymer was obtained in a yield of 8.55 g.

This polymer had an Mw of 180,000 and an Mn of 84.000 by GPC (measurement conditions were the same as in Example 1).

Further, '3C-NMR revealed that this main chain mainly had a syndiotactic structure.

Example 10 Toluene 10d, triisobutylaluminum (TIBA) 4X10-'' mol (2 mol/i, -toluene solution) as catalyst component (b) and methylaluminoxane 8X
The same procedure as in Example 7 was carried out except that 10-3 mol (2.6 mol/!-toluene solution) was used, and a polymer was obtained in a yield of 2.44 g.

This polymer had an Mw of 160,000 and an Mn of 76,000 by GPC (measurement conditions were the same as in Example 1).

The molar ratio of 4-n-octylstyrene moiety/styrene moiety determined from IH-NMR (measurement conditions are the same as in Example 2) is:
It was 9/91.

Furthermore, C-NMR revealed that this main chain mainly had a syndiotactic structure.

Table 1 shows the formulations used in Examples 1 to 10 above and the properties of the resulting polymers.

(Left below) Next, the thermal properties of a composition of the polymer or copolymer obtained in the above example and syndiotactic polystyrene will be compared with that of syndiotactic polystyrene alone.

Reference example 1 Synthesis internal volume of syndiotactic polystyrene 500 d
8 mmol of the contact product obtained in Example 1 (1) of heptane 200-9 as aluminum atoms, 0.08 mmol of titanium tetraethoxide and 50 styrene were added to a reaction vessel, and the mixture was heated at 50°C. Time polymerization was performed. After the reaction was completed, the product was washed with a hydrochloric acid-methanol mixture to decompose and remove the catalyst component, and dried to obtain 3.0 g of a polymer.

This polymer had an Mw of 200,000 and an Mn of 84.000 by GPC (measurement conditions were the same as in Example 1).

Furthermore, when DSC (differential scanning calorimetry) was performed on this polymer (measurement conditions were the same as in Example 6),
The glass transition point (T
g) is 98.5°C, and the melting point (Tm) is
267.8°C, and the heat of fusion at that time is 19.8 (
J/g).

Example 11 Polymer 15■ obtained in Example 1 (3) and polymer 285■ obtained in Reference Example 1 were heated and dissolved in 50 d of 1.2.4 trichlorohenzene (TCB) until completely dissolved. After that, it was added dropwise to 50011 dl of methanol to cause reprecipitation. A composition was prepared by filtering and drying this.

Furthermore, when DSC (differential scanning calorimetry) was performed on this composition (measurement conditions were the same as in Example 6),
The glass transition point (T
g) is 92.8°C, and the melting point (Tm) is
266.2°C, and the heat of fusion at that time is 19.5
(J/g).

Example 12 30 cm of the polymer obtained in Example 1 (3) and 270 cm of the polymer obtained in Reference Example 1 were heated and dissolved in 50 af of 1.2.4 trichlorobenzene (TCB), and after completely dissolving. ,
It was added dropwise to methanol 500 and reprecipitated. A composition was prepared by filtering and drying this.

Furthermore, when DSC (differential scanning calorimetry) was performed on this composition (measurement conditions were the same as in Example 6),
The glass transition point (T
g) is 90.3°C, and the melting point (Tm) is 2
65.5°C, and the heat of fusion at that time is 18.9 (
J/g).

Example 13 60 μ of the polymer obtained in Example 1 (3) and 240 μ of the polymer obtained in Reference Example 1 were heated and dissolved in 50 d of 1.2.4-trichlorobenzene (TCB) until completely dissolved. rear,
The mixture was added dropwise to 500 m of methanol for reprecipitation. A composition was prepared by filtering and drying this.

Furthermore, when DSC (differential scanning calorimetry) was performed on this composition (measurement conditions were the same as in Example 6),
The glass transition point (T
g) is 86.0°C, and the melting point (Tm) is
264.0°C, and the heat of fusion at that time is 16.9
(J/g).

Example 14 15 mg of the polymer obtained in Example 7 and 285 μg of the polymer obtained in Reference Example 1 were heated and dissolved in 1.2.4-1-lichlorohenzene (TCB) 50-, and after completely dissolving, It was added dropwise to 500 g of methanol to cause reprecipitation. A composition was prepared by filtering and drying this.

Furthermore, when DSC (differential scanning calorimetry) was performed on this composition (measurement conditions were the same as in Example 6),
The glass transition point (T
g) is 96.8°C, and the melting point (Tm) is
The temperature is 266.4℃, and the heat of fusion at that time is 19.3 (
J/g).

Example 15 30 cm of the polymer obtained in Example 7 and 270 mg of the polymer obtained in Reference Example 1 were mixed with 50 ai of 1.2.4-trichlorobenzene (TCB). After heating and dissolving it completely,
It was added dropwise to 500 d of methanol to cause reprecipitation. A composition was prepared by filtering and drying this.

Furthermore, when DSC (differential scanning calorimetry) was performed on this composition (measurement conditions were the same as in Example 6),
The glass transition point (T
g) is 94.5°C, and the melting point (Tm) is
267.4°C, and the heat of fusion at that time is 19.6
(J/g).

Example 16 60 μ of the polymer obtained in Example 7 and 240 μ of the polymer obtained in Reference Example 1 were mixed with 1,2,4-trichlorobenzene (
TCB) 50id was heated and dissolved, and after complete dissolution, it was added dropwise to methanol 500d to reprecipitate. Filter this
The composition was prepared by drying.

Furthermore, when DSC (differential scanning calorimetry) was performed on this composition (measurement conditions were the same as in Example 6),
The glass transition point (T
g) is 93.5°C, and the melting point (Tm) is
267.1°C, and the heat of fusion at that time is 17.0
(J/g).

Thermal properties of the compositions prepared in Examples 11 to 16 and the polymer produced in Reference Example 1 are shown in Table 2.

In Table 2, 1 indicates the polymer obtained in Example 1, ■ indicates the polymer obtained in Example 7, and ■ indicates the syndiotactic polystyrene obtained in Reference Example 1. shows.

Note that the heat of fusion was used as an index showing the degree of crystallinity.

(Left below) [Effects of the Invention] The alkylstyrenic polymer mainly having a syndiotactic structure of the present invention can be added to a styrenic polymer mainly having a syndiotactic structure, which is a crystalline polymer, to form crystals. The glass transition temperature can be lowered without reducing the crystallinity of a styrenic polymer, which is a styrene-based polymer mainly having a syndiotactic structure.

Thereby, it is possible to improve energy efficiency during low-temperature mold molding of a styrenic polymer, which is a crystalline polymer, and mainly has a syndiotactic structure.

Therefore, the styrenic polymer composition of the present invention is suitable for producing various molded products by low-temperature molding.

[Brief explanation of drawings]

Figures 1 (a) to (i) show the 13C-N of the polymers or copolymers obtained in Examples 1 to 8 and Comparative Example 1, respectively.
This is an MR spectrum. 41J

Claims (2)

[Claims] (1) General formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼... [I] [In the formula, R^1 represents a straight or branched alkyl group having 5 to 20 carbon atoms, and p is 1 to 5 indicates an integer. However, when p is plural, each R^1 may be the same or different. ] Repeating unit [I] and general formula ▲ Numerical formula, chemical formula, table, etc.▼... [II] [In the formula, R^2 is a hydrogen atom, a halogen atom, a carbon atom, an oxygen atom, It represents a substituent containing at least one of a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom, and a tin atom, and q represents an integer of 1 to 5. However, when q is plural, each R^2 may be the same or different. ] has a repeating unit [II] (excluding cases where it is the same as the repeating unit [I]), and the repeating unit [I] is 0.1 to 100 mol%, and the repeating unit [I] is 0.1 to 100 mol%. II] is an alkylstyrenic polymer containing 0 to 99.9 mol % of 0 to 99.9 mol %, the stereoregularity of which mainly has a syndiotactic structure. (2) 1 to 99% by weight of an alkylstyrene polymer mainly having a syndiotactic structure as claimed in claim 1 and a general formula ▲ Numerical formula, chemical formula, table, etc. ▼... [III] [In the formula, R^3 represents a hydrogen atom, a halogen atom, or a substituent containing one or more of carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, selenium atom, silicon atom, and tin atom, and r is an integer of 1 to 5. shows. However, when r is plural, each R^3 may be the same or different. ] A styrenic polymer having a repeating unit [III] represented by [III] whose stereoregularity mainly has a syndiotactic structure (excluding cases where it is the same as the above alkylstyrene polymer) 99-1 A resin composition consisting of % by weight.