JPH0488004A - Styrene-based polymer, production thereof and gas separation membrane composed of the same polymer - Google Patents

Abstract

PURPOSE:To obtain the subject polymer, having high syndiotactivity and excellent in heat and chemical resistance and electrical characteristics with gas separation ability by polymerizing a silicon-containing styrene-based monomer using a specific catalyst. CONSTITUTION:A silicon-containing styrene-based monomer expressed by formula I (R<1> to R<3> are substituent group containing any one or more of H, C, Si, O and halogen) is polymerized by using a contact product of a transition metallic component (preferably a titanium or zirconium compound) and an organoaluminum compound (preferably trimethylaluminum) with a condensing agent as a catalyst component to afford the objective polymer which is a polymer having recurring units expressed by formula II, 5-100000 polymerization degree and the stereoregularity thereof mainly of a syndiotactic structure.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silicon-containing styrenic polymer, a method for producing the same, and a gas separation membrane made of the polymer.

More specifically, the present invention relates to a silicon-containing styrenic polymer mainly having a syndiotactic structure suitable for gas separation membranes such as oxygen enrichment membranes, bifunctional polymer precursors for resist materials, etc. The present invention relates to a production method and a gas separation membrane using the polymer.

[Prior art and problems to be solved by the invention] Silicon-containing styrenic polymers have been subjected to radical polymerization (for example, Poly
mer Journal, Vol, 17 No, 11.
ppH59-1172 (1985)), or Ziegler-Natsuta polymerization (e.g. Bull, Chem, Soc.
, Jpn, Vol. 32.534 (1960)).

or anionic polymerization (e.g. Makromol, Ch
em.

Vol, 183. No. 5.1181-90)), and most of them give an actic structure, but the isotactic structure is synthesized by the above-mentioned Bull, Chem, Soc, Jpn, Vo.
1, 32.534 (1960) reported that it was produced using a titanium tetrachloride=triethylaluminum catalyst.

Regarding silicon-containing styrenic copolymers, J.
Vac, Sci, Technol, B, Vol.
4. No.], 422 (1986) J, EIectr.
ochem, Soc,, Vol, I30. No.9
．． Examples of synthesis of copolymers by radical polymerization have been reported in 1962 (1983) and other publications.

However, there are still no examples of production of silicon-containing styrenic polymers or silicon-containing styrenic copolymers, which mainly have a syndiotactic structure.

Furthermore, in recent years, many gas separation membranes using organic polymers have been proposed. If oxygen in the air can be separated and concentrated at low cost using gas separation membranes, it is expected to make a significant contribution to the fields of combustion iron manufacturing, ceramics, waste treatment, and medicine.

In addition, basic characteristics required for an oxygen selectively permeable membrane are: 1) a high permeability coefficient;

11) have high permselectivity, and 1ii) are thermodynamically stable (Kagaku Kogyo, January 1987 issue, p. 56).

Conventionally, organopolysiloxanes have been put into practical use as oxygen permeable membranes, but these have poor membrane strength or heat resistance, and improvements have been desired.

Therefore, in order to strengthen the membrane strength, a copolymer of organopolysiloxane and polycarbonate (Japanese Unexamined Patent Publication No. 51-121
/1.85 Publication), a crosslinked copolymer of a mixture of a polyfunctional polymer and a terminally functional polymer and an α,ω-functional polyalkylmethylsiloxane (Japanese Unexamined Patent Publication No. 60-71006), Polymethylpentene, polyphenylene oxide, fumaric acid ester polymers, etc. were developed, but they had problems in their use in fields where heat resistance was required due to poor oxygen permeability due to lack of quality or crystallization. .

The applicant has so far succeeded in developing a styrenic polymer mainly having a syndiotactic structure.
Japanese Unexamined Patent Publication No. 62-104818 No. 62-187708
It was disclosed in the issue of the bulletin. These polymers are one-sided thermal,
Although it had excellent chemical resistance and electrical properties, the present inventors conducted extensive studies in order to further improve these properties and obtain a styrenic polymer that has gas separation ability.

The present invention aims to provide a silicon-containing styrenic polymer or copolymer having a syndiotactic structure as a crystalline polymer having excellent heat resistance, chemical resistance, and electrical properties and gas separation ability. This is the purpose.

[Means to solve the problem]

The present inventors have obtained a silicon-containing styrenic polymer or copolymer having a syndiotactic structure by polymerizing a silicon-containing styrene derivative or copolymerizing a silicon-containing styrene derivative and styrene. We found that this membrane satisfies all of the above conditions required for an oxygen selective permeation membrane, and in particular has excellent thermodynamic stability (heat resistance) derived from its crystallinity.Based on this knowledge, we developed this book. The invention was completed.

That is, the present invention provides general 2(1) SiR'R2R'' [wherein R2Rz and R3 are each independently a hydrogen atom,
Indicates a substituent containing one or more of carbon atoms, silicon atoms, oxygen atoms, and halogen atoms. ] Polymerization degree of 5 to 100.
000 polymer and whose stereoregularity is mainly a syndiotactic structure, a repeating unit represented by the general formula (1) [1
] and general formula (II) [wherein R4 is any one or more of 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, and a tin atom m represents an integer of 1 to 5. However, when m is plural, each R4 may be the same or different. ] is a repeating unit (I
T) (excluding the case where it is the same as the repeating unit CI)), and the repeating unit (1) is (1
, a silicon-containing styrenic copolymer containing 1 mol% or more of which has a stereoregularity mainly having a syndiotactic structure, and (a) a transition metal component and To) an organoaluminum compound as a catalyst component. Provided is a method for producing a silicon-containing styrenic polymer or copolymer, which comprises polymerizing a monomer corresponding to the above repeating unit using a contact product with a condensing agent. The present invention provides a gas separation membrane made of a polymer or copolymer.

The silicon-containing styrenic polymer of the present invention has the general formula (1
), and the silicon-containing group in the general formula (1) is a nuclear substituent. Here, R1, R2 and R3 may be any of various substituents as long as they contain one or more of hydrogen atom, carbon atom, silicon atom, oxygen atom and halogen atom, and each is the same or It's okay to be different. Examples of the halogen atoms contained in R', R2, and R3 include chlorine, fluorine, 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 terjalibdel group, or aryl groups having 6 to 20 carbon atoms such as phenyl group. There is. Specific examples of substituents containing carbon atoms and oxygen atoms include:
There are alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, and isopropoxy. Specific examples of substituents containing carbon atoms and silicon atoms include alkylsilyl groups having 1 to 20 carbon atoms such as trimethylsilyl groups, and silyl groups including aryl groups having 6 to 20 carbon atoms such as phenyldimethylsilyl groups. There is.

Specific examples of the silicon-containing styrenic polymer having a repeating unit represented by the general formula 1.1) include, for example:
Poly(p-trimethylsilylstyrene), poly(m-1
-dimethylsilylstyrene) poly(o-trimethylsilylstyrene), poly(P)-ethylsilylstyrene), poly(In-triethylsilylstyrene),
Poly (o-1-ethylsilylstyrene), Poly (
Al: torsilylstyrene polymers such as p-dimethyltertbutylsilylstyrene), poly(p-dimethylphenylsilylstyrene), poly(p-methyldiphenylsilylstyrene), poly<p-1-rephenylsilyl phenyl group-containing silylstyrene polymers such as styrene), poly<p-dimethylhydrosilylstyrene), poly(p-methyldihydrosilylstyrene), poly(p-
Nohydro group-containing silylstyrene polymers such as Halogen-containing silylstyrene polymers such as dimethylbromosilylstyrene), poly(p-dimethyliodosilylstyrene), poly(p-dimethylmethoxysilylstyrene), poly(p-methyldimethoxysilylstyrene), poly(p-dimethyldimethoxysilylstyrene), Alkoxy group-containing silylstyrene polymers such as 1-rimethoxysilylstyrene), poly(p-(p-4
Examples include silyl group-containing silylstyrene polymers such as dimethylsilylstyrene) and dimethylsilylstyrene.

The silicon-containing styrenic polymer of the present invention having such a substituent (silicon-containing styrenic polymer having a repeating unit represented by the above general formula (T)) has a degree of polymerization of 5 or more,
Usually 5-100,000, preferably 50-100,000
00, more preferably 100 to 50,000. If the degree of polymerization is less than 5, there will be a problem that the strength of the molded product will decrease, and if it exceeds 100,000, there will be a problem of a decrease in solubility and meltability. In addition,
There are no particular restrictions on the molecular weight distribution.

The silicon-containing styrenic polymer of the present invention further has stereoregularity mainly having 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 alternately opposite directions, and its toughness is determined by nuclear magnetic resonance method (13C-NMR method) using carbon isotope.

'Toughness measured by C-NMR method is
The presence ratio of a plurality of consecutive structural units can be expressed by, for example, a diad in the case of two units, a triat in the case of three units, and a pentad in the case of five units. "Have" means
The degree of syndiotacticity of the type of substituent varies slightly depending on the chain of each repeating unit, but in the chain of styrenic repeating units, it is usually 75% or more, preferably 85% or more in racemic diams, or racemic. It refers to a substance having a syndioctality of 30% or more, preferably 50% or more in terms of pentads.

According to the present invention, the silicon-containing styrenic polymer having repeating units represented by the general formula (I) contains (a) a transition metal component and (b) an organoaluminum compound and a condensing agent as catalyst components. Efficient production by polymerizing a silicon-containing styrenic monomer represented by the general formula (SiR'R2R3C, where B1.Bz and R3 are the same as above) using a contact product. I can do it.

Here, R1゜RZ, R3 in the general formula (B)
is the same as that shown in the description of general formula (1) above.

Specific examples of the silicon-containing styrenic monomer represented by the general formula [VI] include p-trimethylsilylstyrene, m-1-limethylsilylstyrene, O-trimethylsilylstyrene, p-triethylsilylstyrene, m
-triethylsilylstyrene, o-1-ethylsilylstyrene.

Alkylsilylstyrenes such as p-dimethyltert-butylsilylstyrene, p-dimethylphenylsilylstyrene, p-methyldiphenylsilylstyrene, p
-Phenyl group-containing silylstyrenes such as -1-rephenyldilylstyrene, p-dimethylbromosilylstyrene,
Hydro group-containing silylstyrenes such as p-methyldihydrosilylstyrene and p-trihydrosilylstyrene, P
Dimethylchlorosilylstyrene, p-methyldichlorosilylstyrene + pl'l crylosilylstyrene, p
- halogen-containing silylstyrenes such as dimethylbromosilylstyrene and p~dimethyliodosilylstyrene;
Alkoxy group-containing silylstyrenes such as p-dimethylmethoxysilylstyrene, p-methyldimethoxysilylstyrene + P-Frimethoxysilylstyrene, p-(p
-trimethylsilyl) dimethylsilylstyrene and other silyl group-containing silylstyrenes.

In addition, there are various types of transition metal compounds used in the transition metal component (a), which is a catalyst component, but in particular, the general formula % formula % () (in the formula, R5-R16 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms.

Alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, arylalkyl group having 7 to 20 carbon atoms, acyloxy group having 1 to 20 carbon atoms, acetylacetonyl group, cyclopentadienyl group, substituted cyclopenta Represents a jenyl group or an indenyl group. Also, a, b, c are O≦a +
b indicates an integer greater than or equal to 0 that satisfies 10≦4; d and e indicate integers greater than or equal to 0 that satisfy 0≦d+e≦3;
Indicates an integer greater than or equal to 0 that satisfies 0≦f≦2, and g and h are 0
Indicates an integer greater than or equal to 0 that satisfies ≦g+h≦3. Furthermore, M
+, M2 represents titanium zirconium, hafnium or vanadium; M3. M' represents vanadium. ] is preferably used. The above general formula (
Among the transition metal compounds represented by formula (III), (IV), (V) or (Vl), especially those of formula (III)
It is preferable to use a titanium compound or a zirconium compound represented by:

Among those represented by R5 to RI6 in the above general formula [I[1], (IV), EV) or [), specific examples of the halogen atom include chlorine, fluorine, bromine, and iodine. Examples of the alkyl group having 1 to 2 carbon atoms include methyl, 2-ethyl, propyl, isopropyl, n-butyl, isobutyl, amyl, isoamyl, octyl, and 2-ethylhegycyl. 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, 2-hexyloxy group, octyloxy group, 12-ethylhexyloxy group, etc. . Further, specific examples of the aryl group having 6 to 20 carbon atoms include phenyl group 1 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 methylcyclobentacyenyl group and pentamethylcyclopentadienyl group. These R5
-R16 may be the same or different as long as the above conditions are met.

Such, said - Noshiro (III), (IV),
Among the transition metal compounds represented by (V) or [■], specific examples of titanium compounds include tetrametallic titanium, tetraethoxytitanium, tetraisopropoxytitanium, tetraisopropoxytitanium, and cyclopentagenyl titanium. tributyl titanium cyclopentagenyl I/riethyl titanium, cyclopenxienyl triprobyl titanium, cyclopentagenyl tributyl titanium, methylcyclopentagenyl 1-limethyltitanium, ],,]2-dimethylcyclopentagenyl 1-li Methyl titanium pentamethylcyclopencdienyltrimethyltitanium, pentamethylcyclopentadienyltriethyltitanium, pankmethylcyclopentadienyl 1-lipropyl titanium, pentamethylcyclopentadienyl l-IJ butyl titanium, cyclopentadienyl methyl Titanium cyclolide Pentamethylcyclopentadienylmethyltitanium dichloride Pentamethylcyclopentajenyl ethyltitanium dichloride Pentamethylcyclopentajenylmethyltitanium dichloride Cyclopentajenyl diethyl titanium monochloride Cyclopentadienyl titanium 1-rimethoxide, cyclopenta Genyl titanium triethoxide, cyclopentadienyl titanium triethoxide, cyclopentadienyl titanium triphenoxide, pentamethyl cyclopentadienyl titanium trimethoxide, pentamethyl cyclopentadienyl titanium I. Methylcyclopentadienyl titanium tripropoxide, Bentamethylcyclopentadienylditane tributoxide, Pentamethylcyclopentadienyl titanium triphenoxide, Cyclopentadienyl titanium I-lichloride, Pentamethylcyclopentadienyl titanium trichloride, Cyclopentadienyl methoxytitanium dichloride, cyclopentajenyl methoxytitanium chloride, pentamethylcyclopentajenyl methoxytitanium dichloride cyclopentajenyl trihenzyl titanium, pentamethylcyclopentajenyl methyljethoxytitanium indenyl titanium trichloride, inde Nyl titanium trimethoxide Examples include indenyl titanium triethoxide, indenyl trimethyl titanium, and indenyl trihensyl titanium.

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

Also, the above - Noshiro [111), CIV), EV
) or (Vl), specific examples of zirconium compounds include cyclopentagenyl zirconium trimethoxide
Copenk dienyldyl: lium trimethoxide doconium, pentamethylcyclopentagenyl trihenyl zirconium bisindenylsilconium dichloride zirconium dihenyl dichloride zirconium tetrabenzyl, 1-ributoxyzirconium chloride l-liisopropoxyzirconium chloride Examples include.

Similarly, specific examples of hafnium compounds include cyclopentadienyl hafnium trimethoxide, pentamethylcyclopentadienyl hafnium trimethoxide, cyclopentadienyl trihensyl hafnium, and pentamethylcyclopentacyenyl trihedyl hafnium. ,
Examples include bisindenyl hafnium dichloride, hafnium dihensyl dichloride, hafnium tetrahensyl tributoxy hafnium chloride, and triisopropoxy hafnium chloride.

Further, similar specific examples of vanadium compounds include vanadium trichloride 2 vanadyl trichloride, vanadium triacetylacetonate vanadium 1, tetrachloride, vanadium tributoxide, vanadyl dichloride, vanadyl bisacetylacetonate, vanadyl trichloride, Examples include acetylacetoner-1.

On the other hand, the contact product of (b) organoaluminium, which is another component of the catalyst, and the condensing agent is disclosed in, for example, JP-A-6218770.
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 contacting various organic aluminums with a condensing agent.

Here, the organoaluminum compound is usually -Noshiro, /lR173 (wherein, R17 represents an alkyl group having 1 to 20 carbon atoms.

] Organic aluminum represented by these, specifically trimethylaluminum and triethylaluminum.

Examples include 1-realgyl aluminum such as triisobutylaluminum, and trimethylaluminum is the most preferred.

On the other hand, the condensing agent typically includes water,
In addition, there may be mentioned any other substances with which trialgyl aluminum undergoes a condensation reaction, such as copper sulfate pentahydrate inorganic substances and water adsorbed to organic substances.

A typical example of the contact product of the organoaluminum, 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 -Noshiro A ff R'' and water. There are, but specifically,
- Noshiro C In the formula, R17 is the same as above, and n indicates the number of repeating units and is a number from 2 to 50. ] or a linear alkylaluminoxane represented by the general formula % [wherein RI7 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 RI7 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 complexly associated molecules, and these produce various products depending on the conditions of contact between realkylaluminum 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 a 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 crystallization water contained in organic materials and water adsorbed on inorganic or organic materials with organoaluminum compounds. 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-mentioned contact 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, aromatic hydrocarbons such as xylene, etc. Examples include group 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 preferable example of the contact product of the organic alumina 1 used as the catalyst (b) component and the condensing agent, particularly an alkylaluminoxane, is a product observed in a propionic nuclear magnetic resonance spectrum ('11-NMR). The high magnetic field component in the aluminum-methyl group (methylproion signal region based on the A°C-CF(3) bond) is 50% or less. Proton nuclear magnetic resonance ('H-NMR) spec 1
When observing HEL, the methyl proton signal based on A f -CH3 is seen in the range of 1.0 to -0.5 ppm based on tetramethylsilane (TMS). TM
Since the S proton signal (Oppm) is in the methyl proton observation region based on ΔE-CH3, this ANC1
]3, the methyl proton signal of toluene in TMS standard 2.35pp
The high magnetic field component (i.e. 0.1 to -0.5
ppm) and other magnetic field components (i.e. 1.0 to −0.1
．． When divided into (ppm) and
) can be suitably used as a component.

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

This catalyst component (C) is, for example, -Noshiro % formula %: [In the formula, RI8 is a hydrogen atom, a halogen atom, or a carbon number 1
~8 alkyl group is shown. ] This shows an organoaluminum compound represented by:

Specific examples of the organoaluminum compound include triisobutylaluminum, isobutylaluminum hydride, trimethylaluminum 1.riedylaluminum, diethylaluminum chloride, and the like.

The silicon-containing styrenic polymer of the present invention is produced using the above catalyst, and any polymerization method such as bulk polymerization, solution polymerization, or suspension polymerization may be used. As the solvent, aliphatic hydrocarbons such as penkune, hexylene, heptane, etc., alicyclic hydrocarbons such as cyclohegysan, aromatic hydrocarbons such as henzhen, toluene, xylene, etc. 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 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.

In addition, after the polymerization is completed, the catalyst can be deactivated with alcohol as in the conventional method, and the obtained polymer can be purified by washing with alcohol and deashing using acid or alkali. can.

Furthermore, when using this catalyst, (a
) component, (b) component, and (C) component, the ratio of these components to the solvent, and further (a) component, (b) component, and (C) component.

The order in which the solvent and monomers are charged varies depending on their combination, and is difficult to define unambiguously, but it is usually determined by the molar ratio of aluminum in the catalyst component (b) to the transition metal in the catalyst component (a), i.e. Aluminum/transition metal (molar ratio) from 20/1 to 10,000/1, preferably 10
0/1 to 1,000/1.

Further, the molar ratio between the monomer and the catalyst component (aluminum in bJ, that is, the monomer/aluminum (molar ratio) is 10,000/1 to 0.01/], preferably 200/
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 silicon-containing styrenic polymer obtained in the above manner has high syndiotacticity as described above, but after polymerization, it may be deashed with a washing solution containing hydrochloric acid or the like as necessary. By washing to remove soluble components, a highly purified silicon-containing styrenic polymer with extremely high syndiotoughness can be obtained.

Next, the silicon-containing styrenic copolymer in the present invention is
Repeating unit [■] represented by the above-format C1) and -format (II) [wherein R4 is 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, It represents a substituent containing at least one of a silicon atom and a tin atom, and m represents an integer of 1 to 5. However, when m is plural, each R4 may be the same or different. ] It has a repeating unit (II) represented by.

Here, the repeating unit CI) is the same as above. Moreover, R4 of the repeating unit [11) is a hydrogen atom, a halogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom,
Indicates a substituent containing at least one of a phosphorus atom, 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 couscious butyl group; hydrogen atom, halogen atom or carbon atom on benzene ring; Oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, selenium atoms.

Examples thereof include an aryl group having 6 to 30 carbon atoms and a substituent containing a silicon atom or a tin atom; and a halogen-substituted alkyl group having 1 to 20 carbon atoms, such as a chloroethyl group and a 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 1 Phenalene ring, fluoranthene ring, acephenanthrene ring, naphthacene ring, preiazone ring, picene ring, perylene ring, pentacene ring, rubicene ring, corocene ring, pyrantrene ring, ohalene ring and these alkyl substituents (methyl group, ethyl group, isopropyl group, tert-butyl group), halogen substituent alkyl group (chloroethyl group, promoedyl group, etc.), substituents containing an oxygen atom (methoxy group, ethoxy group, isopropoxy group, methoxycarbonyl group, acetyloxy group, etc.), substituents containing silicon atoms (trimethylsilyl group, etc.), substituents containing tin atoms (trimethylstannyl group, tributylstannyl L, IJ phenylstannyl group, etc.) , substituents containing a nitrogen atom (dimethylamino group, diazo group, nitro group, cyano group, etc.), substituents containing a sulfur atom (sulfone group).

sulfonic acid methyl ester group, phenylthio group, methylthio group, mercapto group, etc.), substituents containing selenium atoms (
Includes methylseleno group, phenylselenoxyl group, etc., which are substituted with a substituent containing a phosphorus atom (phosphoric acid methyl ester group, anitrous acid ester group, dimethylphosphino group, phenylbosphinyl group, etc.) at any position. It will be done.

In addition, as substituents containing an oxygen atom, methoxy group, ethoxy group, isopropoxy group, methoxysulfonyl 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 the substituent containing a nitrogen atom include a dimethylamino group, a diazo group, a nitro group, and a cyano group, and examples of the substituent containing a sulfur atom include a sulfone group and a sulfonic acid methyl ester group.

Examples include phenylthio group, methylthio group, and mercapto group. In addition, examples of substituents containing a selenium atom include methylseleno group and phenylselenoxyl group, and examples of substituents containing a phosphorus atom include a phosphoric acid methyl ester group, a sulfite ester group, a dimethylphosphine group, and a phenyl selenium group. Examples include phosphinyl group.

Also, a repeating unit expressed in -form (II) [■]
, m is an integer from 1 to 5, and when m is a plurality of numbers, the m R4s may be the same or different.

The silicon-containing styrenic copolymer of the present invention uses (a) a transition metal component and (b) a contact product of an organoaluminum compound and a condensing agent as catalyst components, and has the following formula: Inside, R+, R2 and R3 are the same as above. ] and the silicon-containing styrene monomer represented by [■′
[In the formula, R4 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, m represents an integer of 1 to 5. However, when m is plural, each R4 may be the same or different.

] It can be efficiently produced by polymerizing a styrenic monomer represented by the following formula.

Here, the silicon-containing styrene monomer represented by the - format [VI] is the same as that described in connection with the method for producing a silicon-containing styrenic polymer of the present invention. Also, − format (
Specific examples of styrenic monomers represented by [■'] include styrene, p-methylstyrene, 0-methylstyrene, m-methylstyrene; 24-dimethylstyrene; 25
-dimethylstyrene 13,4-dimethylstyrene; 35
-Dimethylstyrene; alkylstyrene such as p-tert-butylstyrene, p-chlorostyrene, 5m-chlorostyrene, 0-chlorostyrene, p-bromostyrene, m-promostyrene, 0-bromostyrene, p-fluorostyrene m-fluoro Styrene, halogenated styrenes such as 0-fluorostyrene, 0-methyl-p-fluorostyrene, vinylbiphenyl such as 4-vinylbiphenyl, 3-vinylbiphenyl, 2-vinylbiphenyl 1L1-(4-vinylphenyl)-naphthalene, 2- (
4-vinylphenyl)naphthalene, 1-(3-vinylphenyl)-naphthalene 2-(3-vinylphenyl)-
Naphthalene l-(2-vinylphenyl)-naphthalene Vinylphenylnaphthalenes such as 2-(2-vinylphenyl)-naphthalene, 1-(4-vinylphenyl)-
Anthracene, 2-(4-vinylphenyl)-anthracene, 9-(4-vinylphenyl)-anthracene, 1
-(3-vinylphenyl)-anthracef, 2-(3-
Vinylphenyl)anthracene, 9-(3-vinylphenyl)anthracene, 1-(2-vinylphenyl)-
Anne 1~Lasen, 2-(2-vinylphenyl)-An 1
-Rase7. 9 Vinylphenylanthracenes such as (2-vinylphenyl)-andhracene, 1-(4
-vinylphenyl)-phenanthrene.

1-(4-vinylphenyl)-phenanthrene.

3-(4-vinylphenyl)-phenanthrene.

1-(4-vinylphenyl)-phenanthrene 9-(4
-vinylphenyl)-phenanthrene 1-(3-vinylphenyl)-phenanthrene.

2-(3-vinylphenyl)-phenanthrene 3-(3
-vinylphenyl)-phenanthrene 4-(3-vinylphenyl)-phenanthrene 9-(3-vinylphenyl)-phenanthrene 1(2-vinylphenyl)-phenanthrene 27 (2-vinylphenyl)-phenanthrene 3- (2-vinyl phenyl)-phenanthrene 4-
(2-vinylphenyl)-phenanthrene9- (2-
vinylphenylphenanthrenes such as vinylphenyl)-phenanthrene, l(4vinylphenyl)-pyrene, 2-(4-vinylphenyl)-pyrene, 1=(3-vinylphenyl)pyrene, 2-(3-vinylphenyl)-
Pyrene ■-(2-vinylphenyl)-pyrene, 1-(2
vinylphenylpyrenes such as vinylphenyl)-pyrene, 4-vinyl-p-terphenyl, 4-vinyl-m-terphenyl, 4-vinyl-0-terphenyl, 3-vinyl-p-terphenyl 3-vinyl-m-cuphenyl ,3
-Vinylterphenyls such as vinyl-〇terphenyl, 2-vinyl-p-terphenyl 2-vinyl-m-terphenyl, 2-vinyl-0terphenyl, 4(4-vinylphenyl)-p-cuphenyl, etc. vinyl phenylterphenyls, 4-vinyl 4°-methylbiphenyl
4-vinyl-3-methylbiphenyl 4-vinyl-2'
-Methylbiphenyl 2-methyl-4-hinyl phenyl 3-methyl-4-vinylphenyl and other vinylalkyl biphenyl, 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
-chlorobiphenyl 4-vinyl-4bromobiphenyl, 4-vinyl-3'-bromobiphenyl 4-vinyl-
2'-bromobiphenyl 4-hieru-2-bromobiphenyl, halogenated vinylbiphenyls such as 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-4ethoxybiphenyl 4-vinyl-3-ethoxybiphenyl 4-vinyl-2'-ethoxybiphenyl 4-vinyl-2-ethoxybiphenyl Alconitoxyvinylbiphenyl such as 4-vinyl-3-ethoxybiphenyl Alkoxycarponylvinylbiphenyls such as methoxycarbonylbiphenyl, 4-vinyl 4′-ethoxycarbonylbiphenyl, alkoxyalkylvinylbiphenyls such as 4-vinyl-4-methoxymethylbiphenyl, 4-vinyl 4′-trimethylsilylhyphenyl, etc. tri-4-trimethylscunnylbiphenyl 4vinyl-4'
-Trialgyl stannyl vinylbiphenyls such as -1-butyl scunnylbiphenyl, 4-vinyl-4'-
Trialkylsilylmethylvinylbiphenyls such as snow/limethylsilylmethylbiphenyl, 4-vinyl-4'
Trialkylscunnylmethylvinylbiphenyl ILp such as l-limethylstannylmethylhyphenyl, 4-vinyl-4triethylstannylmethylbiphenyl
Chloroethylstyrene, m-chloroethylstyrene 0
- Halogen-substituted alkylstyrene such as chloroethylstyrene, p-methoxystyrene, m-methoxystyrene, 0-methoxystyrene, p-ethoxystyrene, m-
Alkoxycarbonylstyrene such as 0-ethoxystyrene, 1-cystyrene, p-methoxycarbonylstyrene, m-methoxycarbonylstyrene, acetyloxystyrene, acyloxystyrene such as ethanoyloxystyrene, hendiyloxystyrene, p- Alkyl ether styrenes such as vinylhensylpropyl ether, trialkylsilylstyrenes such as p-trimethylsilylstyrene, p-
Trialkylscunnylstyrene such as trimedylscunnylstyrene, p-)butylscunnylstyrene, p-triphenylscunnylstyrene, ethyl vinylhenzenesulfonate, vinylhensyldimethoxyphosphide, p-vinylstyrene Examples include vinylstyrenes such as.

Further, the catalyst 7 polymerization method and polymerization conditions used in producing the silicon-containing styrenic copolymer of the present invention are the same as those described in connection with the production of the above polymer.

In the present invention, the -1 diary repeating unit [I] and [H
] are different types, and their various combinations constitute copolymers consisting of two or more types of structural repeating units. In any case, it is necessary that the repeating unit [I] be contained in the copolymer in an amount of 0.1 mol % or more.

If the proportion of the repeating unit [■] is 0.1 mol %, there is a problem that the oxygen permeability coefficient becomes small.

In addition, the above repeating units [1) and [■] do not necessarily represent only one type of repeating unit, but also represent two or more types of repeating units, so the copolymer of the present invention can include not only a binary copolymer but also two or more types of repeating units. It also includes multicomponent copolymers such as terpolymer and quaternary copolymer.

The silicon-containing styrenic copolymer of the present invention has the above-described repeating units, and furthermore, its stereoregularity mainly has a syndiotactic structure.

In the silicon-containing styrenic polymer of the present invention, not only the bonded repeating units [■] but also the repeating units (1) and (II) have a syndiotactic structure (co-syndiotactic structure). structure). In addition, the repeating unit (1), (I
t) block copolymerization.

There are various forms of random copolymerization or alternating copolymerization.

Note that the silicon-containing styrenic copolymer 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 (75% or more for racemic diand, 30% or more for racemic penhood), it may not be incorporated into a mixture or polymer chain with a styrene copolymer having an isotactic or active structure. It may be something that has been Also,
The silicon-containing styrenic copolymer 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, usually 5 to 100,000, preferably 50 to 10
0,000, more preferably 100 to 50,000. In terms of weight average molecular weight, preferably 8.000
~400.00. Note that the molecular weight distribution is not particularly limited.

Next, the gas separation membrane of the present invention is a silicon-containing styrenic polymer having a repeating unit represented by the above-mentioned form CI) or a repeating unit represented by the above-mentioned form (1) and a general formula (n). It is made of a silicon-containing styrenic copolymer having repeating units.

The gas separation membrane of the present invention has a high oxygen permeability coefficient,
In particular, the oxygen permeability coefficient is I x 10-9 (c + N (STP
) ・cm / +:ffl ・sec-cmllg
) or more, and the separation coefficient with nitrogen [oxygen permeability coefficient/nitrogen permeability coefficient] is 2.0 or more.

Here, the permeability coefficient is the amount of gas permeated through a unit thickness (1 cm2) per unit permeation area (1 cml), per unit time (1 second), per unit pressure difference (1 cm mercury column), and per unit permeation area (1 cm2) of the membrane. Condition (STP) (converted to 0°C, 1 atm)).

The silicon-containing styrenic polymer or copolymer mainly having a syndiotactic structure of the present invention is a crystalline polymer and has excellent heat resistance. Normally, a crystalline polymer has a smaller permeability coefficient than an amorphous state due to the shrinkage of the molecular gap or the suppression of molecular movement, but in the silicon-containing styrenic polymer or copolymer of the present invention, In other words, it can be used in a crystalline state.

The gas separation membrane of the present invention is mainly composed of a silicon-containing styrenic polymer or copolymer having a syndiotactic structure, but may also be made of a thermoplastic resin depending on moldability, stretchability, and other desired properties. Rubber, inorganic filler, antioxidant, nucleating agent, plasticizer.

The compatibilizer 2 may also contain a colorant, an antistatic agent, and the like.

The shape of the gas separation membrane of the present invention may be appropriately selected depending on the intended use, but it is generally in the form of a film or sheet. To obtain a film-like product, the following operations are usually performed. That is, first, the above-mentioned silicon-containing styrenic polymer or copolymer, or a mixture thereof with an appropriate amount of other components, is used as a molding material, and this is usually first subjected to extrusion molding, calendar molding, blow molding, or blow stretch molding. In some cases, it is further molded by injection molding or the like to obtain a preformed object for stretching (film sheet, tube, parison). In this molding, the heated and melted molding material may be molded in a softened state without being heated and melted in various molding machines. Here, the melting temperature of the forming abrasive is usually from the melting start temperature to the decomposition start temperature + 30°C.
However, if the temperature is too high, problems such as decomposition of the molding abrasive material occur, which is not preferable.

The thickness of the preformed body to be formed here may be selected arbitrarily, but is generally 5 mm or less, preferably 3 mm or less.
It may be appropriately selected within the range of mm to 0.002 mm. If the thickness exceeds 5 mm, the tension required for stretching is large and it is difficult to stretch. The crystallinity of the preform (film) is
It is 30% or less, preferably 20% or less, and more preferably 10% or less.

In addition, when producing a preform with as low a degree of crystallinity as possible, especially when molding a thick sheet, it is effective to rapidly cool the heated and melted molding material described in section 2 above during molding. In the rapid cooling, the refrigerant temperature is set below the glass transition temperature, preferably at least 20° C. lower than the glass transition temperature. If the refrigerant temperature is too high, cooling will be slow, and some crystallization will occur, making stretching difficult.

The preform is generally stretched uniaxially or biaxially at a temperature between the glass transition temperature and the melting point of the paste. Here, the stretching temperature is low temperature crystallization temperature + 50°C
The temperature below is preferable, and if the temperature is higher than that, it is difficult to obtain a film with a low degree of crystallinity.

Regarding the stretching ratio, in the case of -axis stretching, it should be stretched at a stretching ratio of 2 or more times in the stretching direction, preferably 3 to 10 times. In the case of biaxial stretching, the stretching should be carried out in each direction at a stretching ratio of 1.5 times or more, preferably 2 times or more. If the stretching ratio is too small, the physical properties of the resulting film will not be sufficiently improved. In addition, in the case of biaxial stretching, stretching may be performed simultaneously or sequentially in any order.

In addition, in the present invention, especially when performing biaxial stretching, a biaxially stretched molded product (biaxially stretched film) can also be obtained by direct inflation molding without using the above-mentioned molding material as a preform. I can do it. In inflation molding, the stretching temperature may be 10°C below the melting point. In stretch flow molding, the preform before stretching may be either a hot parison or a cold parison.

Further, in this inflation molding or stretch blow molding, -axis stretching is also possible if the blow-up ratio is made small. The film thus obtained has a thickness of 0.1 to 100 μm, preferably 1 to 50 μm.
Therefore, it is excellent as a gas separation membrane.

After the stretching treatment, further heat setting can be performed. This heat fixing may be carried out by subjecting the material such as a film to a tensioned state at a temperature range of not less than the glass transition temperature and not more than the melting point.

This heat treatment further improves the heat resistance, one-dimensional stability, chemical resistance, and gas permeability of materials such as films.

In addition, as a method for forming a thin film from the silicon-containing styrenic polymer or copolymer of the present invention, a method in which the styrenic polymer dissolved in a solvent is obtained by completely evaporating the solvent, or a method in which the styrenic polymer is dissolved in a solvent and obtained by completely evaporating the solvent, There is a method of developing it on a liquid and evaporating the solvent. As the former solvent, halogenated hydrocarbon solvents such as chloroform-2-dichloromethane, or aromatic solvents such as benzene, toluene, xylene, and 1.2.4-1-lichlorohenzene are suitable; as the latter solvent, Is the same thing as the former used?
In this case, a developing solution such as water must be selected that has a specific gravity lower than that of the developing solution used.

In this way, a cast film with a thickness of about 0.1 to 200 μm can be obtained.

〔Example〕

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

Examples] (1) Preparation of methylaluminoxane 200 mR of toluene and copper sulfate pentahydrate (CuSO-・51(20
) 1.7.7 g (71 mmol) and trimethylaluminum 24 m, l! (250 mmol) was added,
The reaction was carried out at 40°C for 8 hours. Thereafter, solid components were removed, and 1-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 was 610 as measured by the freezing point depression method.

In addition, in the high-field component determined by H-NMR measurement, that is, in the proton nuclear magnetic resonance spectrum in toluene solvent at room temperature, the methyl proton observation region based on the (Aff-CH3) bond is lamethylsilane (T
MS) standard is found in the range of 1.0 to -0.5 ppm. TMS proton signal (Oppm) is Af
Since it is in the methyl proton observation region based on f-CHff, the methyl proton signal that reveals this A ff -CH3 was measured based on the 2.35 ppm methyl proton signal of l-luene in the TMS standard, and the high-field component (i.e. , -0.1 to 0.5 ppm) and other magnetic field components (i.e., 1.0 = 0.1 rllll1 m), the liquid high magnetic field component accounted for 43% of the total.

(2) Mlta synthesis method of 4-trimethylsilylstyrene can be performed using known methods, such as Polymer Journa
Vol.], 7 No., 11. pp1159(19
85).

Under a stream of inert gas and stirring, 6.08 g (0.25 mol) of granular metallic magnesium was added to tetrahydrofuran (
One drop of 1,2-dibromoethane is added dropwise to the 150mu) solution and heated to initiate the Grignard reagent production reaction. The temperature of the solution was kept at ambient temperature until reflux, and then a solution of 22.7 mn (0,189 mol) of 4-chlorostyrene in tetrahydrofuran (39 mR) was slowly added dropwise over 30 minutes. After the addition is complete, the mixture is left under reflux for 1 hour. The reaction solution was brought to O''C in an ice-water bath, and 30 ml (0,236 mol) of trimethylsilyl chloride was mixed with tetrahydrofuran (
30 ml) solution was slowly added dropwise over 30 minutes.

After finishing dropping, leave in ice water bath for 1 hour. 5 of the reaction solution
Pour into ice water and adjust pl+ to make it slightly acidic. Extract with hexanoate, wash, dry, evaporate the solvent,
After distillation, 35.5 g of 4-trimethylsilylstyrene (
A yield of 95% and a boiling point of 55-57° C2 (specific gravity 0.89) were obtained.

H-NMR (solvent deuterium chloroborum, 22.5 MHz)
60.26 (9H, s, SiMez) δ 5.22
(1, H, d d, HC=C-C) Lance])65.
75 (IH, dd, J (C=C-[cis]) δ6.7
1 (] H, d d, C=H (, -Cα position]) 67
．． 36 (2f (, dd, meta position of vinyl group) 67
．． 50 (2H, dd, or-1-position of vinyl group) (3
) Production of poly(4-trimethylsilylstyrene) having a syndiotactic structure In a dry reaction vessel under an argon atmosphere, 10 mN of toluene and 1.0-' mol of triisobutylaluminum (TIBA) as catalyst component (b) were added at room temperature. (
2 mol/ff-toluene? Methylaluminoxane obtained in (1) above 4 x 101 2.6 mol/1. -Toluene solution) was added to this reaction solution at room temperature as the catalyst component (a).
e):+) 2 X 10-6 mol (0.01 mol/β
-totosyrun solution) and 15.4 g (8.75 x lO-'' mol) of 4-trimethylsilylstyrene were added and reacted for 15 hours.

Thereafter, the reaction product was added to a methanol-hydrochloric acid mixed solution to stop the reaction, and after deashing and filtration, the mixture was further washed three times with methanol. Drying under reduced pressure yielded 13.5 g of polymer. When this molecular weight was measured by GPC (gel permeation chromatography), the weight average molecule i (MW) in terms of polystyrene was 2.70
0,000 tear, number average molecular ft (Mn) is 1,2
It was 00,000. The measurement conditions for GPC (gel permeation chromatography) were as follows.

Equipment: Waters ALS/GPC Column: TSK GH8P+TSK GMH6+Hitachi G
L-A120 + Hitachi GI---A Temperature: Room temperature Solvent: Chloroform, Injection ft: 500μC Flow rate:
1.4 m27 minutes, concentration: 10 mg 15 mE Furthermore, regarding the polymer, DSC (differential scanning calorimetry)
030°C ~ 320°C Cl2O "07 minutes, temperature increase (first heating), ■ Hold at 325°C for 15 minutes, ■ 320°C ~ 30°C 7°C/min, (Firth 1-cooling), ■ 30 'C.

Hold for 5 minutes, ■30'C~320°Cl2O°C/min.

The crystallization temperature (Tc) at cooling down measured during first cooling was 263.3°C, which was the same as the glass transition temperature observed during second heating. (Tg) is
The temperature was 135.0°C, and the melting point (Tm) was 306.8°C.

In addition, when the first heating was measured on the rapidly cooled sample after the operation (2), the glass transition point (T
g) is 1.23.8°C, which is the low temperature crystallization temperature (T
cc) is 173.4°C1 Melting point (Tm) is 305.
It was 4°C.

FIG. 1 shows 13CNMR of the polymer obtained in Example 1 (
100MHz: 1.2.4-) Lichlorohensen (T
CB) / heavy benzene - 8/2 (volume percent) mixed solvent 130.6 ppm standard of single heavy benzene, 130°C)
The measurement results are shown below.

In addition, FIG. 2 shows HNMR of the polymer obtained in Example 1.
(270MHz: TCB/C8 Nolan D 1 8
-0.3 2 7ppm base. 130'c) measurement results are shown.

From FIGS. 1 and 2, it can be seen that this polymer mainly has a syndioctic structure.

Furthermore, from the half-value width of the peak of poly(4-trimethylsilylstyrene) shown in FIG. 1 (Example 1), this polymer has a syndiotacticity of 95% or more for racemic diacids and 80% or more for racemic diamonds. I understand.

Comparative Example 1 Radical polymerization of 4-trimethylsilylstyrene was performed using azoisobutyronitrile (AIBN). When this polymer was measured by DSC [measurement conditions: same as in Example 1], it was found that the polymer did not exhibit a melting point and was a non-quality polymer.

Figure 1 shows 13CNMR of the polymer obtained in Comparative Example 1.
(100MHz: TCB/heavybenzene-8/2 (volume percent) mixed solvent 1,30.
6 ppm standard, 130°C) are shown.

In addition, FIG. 2 shows the H-NM of the polymer obtained in Comparative Example 1.
R (2 7 0MHz+ TCB/C8 Nolan D 1
8 -0.3 2 7ppm group m. 130°C) are shown.

From FIGS. 1 and 2, it can be seen that this polymer has an active structure.

Next, referring to FIG. 1 and Part 2, it will be explained that the polymer obtained in Example 1 has a gingiotactic structure.

In FIG. 1, the upper row shows Example 1, and the lower row shows Comparative Example 1. Example 1-4 1, 0 9
ppm, 4 4. The peaks at 13 ppm are based on methine and methylene carbons, respectively, and 14
5, 8 2ppm, 1 3 6. 7 7ppm
The peaks are based on CI and C/l of the side chain Hensen's ring, respectively.

Comparing the upper part of Figure 1 with the actinic structure obtained in Comparative Example 1 shown in the lower part, the peak is very sharp, indicating that the main chains are stereoregularly arranged. There is.

In addition, in the upper row of FIG. 2, Example 1. Comparative example 1 is shown in the lower row.
Each case is shown. Main chain methine of Example 1,
The chemical shift values based on the carbon of methylene are shifted to the higher magnetic field side than the chemical shift value of Comparative Example 1.

Also, Bull, Chem, Soc, Jpn, Vo
According to I, 32.534 (1960), the melting point of isotactic poly(4-trimethylsilylstyrene) is 284"C, and the melting point of the polymer obtained in Example 1 is 306.8° C, it can be seen that the polymer obtained in Example 1 is a polymer whose three-dimensional structure (conformation) is highly stereoregular based on the isotactic structure.

From the above, it was confirmed that the polymer obtained in Example 1 had a syndiotactic structure.

Comparative Example 2 In a dry reaction vessel under an argon atmosphere, 200 mj of hebutane was added at 50°C! , triisobutylaluminum (TIBA) 2 X 1 o as the catalyst component (b)
-'moJl/ (2mo)shi/p, -i nol/-1=
7? Yong? I'j, ) and 2X10 3 mol (2,
Bentamethylcyclopentadienyl titanium trimethoxide (Cp”Ti (OMe)a) was added to the reaction solution as the catalyst component (a).
) 8×10 −5 mol (0.01 mol/!-toluene solution) and 50 mR of styrene were added and reacted for 2 hours.

Post-treatment was carried out in the same manner as in Example 1 to obtain 38.6 g of polymer.

Mw measured by GPC under the same measurement conditions as Example 1
was 300,000 and Mn was 140,000.

Dynamic viscoelastic behavior Here, the syndiotactic polyester obtained in Example 1
The heat resistance properties of (4-trimethylsilylstyrene) are compared with the syndiotactic polystyrene obtained in Comparative Example 2 based on dynamic viscoelastic behavior (temperature change in storage modulus).

The measuring strip is equipped with two viscoelastic analyzers (Rheometrics).
R3A H) Frequency: IHz Sample production under nitrogen flow Melt under pressure at 100 kg/cJ at 320°C for Example 1 and 300°C for Comparative Example 2 for 1 hour using a hot press molding machine and slowly cool. A film-like sample was prepared by this method.

FIG. 3 shows Example 1. The measurement results of the polymer obtained in Comparative Example 2 are shown.

From FIG. 3, syndiotactic poly(4-trimethylsilylstyrene) obtained in Example 1 is a crystalline polymer with higher heat resistance (comparing Tg and Tm) and lower elastic modulus than syndiotactic polystyrene. It can be seen that it is.

Gas separation properties Syndiotactic poly(4-trimethylsilylstyrene) obtained in Example 1 was dissolved in chloroform, the solution was spread on a glass plate, and after evaporation, a cast film was produced by drying under reduced pressure. .

The oxygen permeability coefficient (PO2) and nitrogen permeability coefficient (PH2) of this film were measured by a pressure method at room temperature with a differential pressure of 0.5 kg/cm, and found that P 02 = 1. OOX l O-9 P8□-4,56X10-” (separation coefficient α-2,19)
Met.

Example 2 Except that the reaction temperature was 70"C and the reaction time was 4 hours,
Example 1 was followed.

The yield of polymer was 15.4 g.

Mw measured by GPC under the same measurement conditions as Example 1
There were 210,000 Te and Mn was 38,000 Te.

In addition, T determined by DSC under the same measurement conditions as in Example 1
c, Tg, Tm are respectively 264.3°C114,1
°C, 298.4 °C.

Furthermore, the Tg of the cooled sample is 122.2°C, Tcc is 190.9°C, and Tm is 299.7°C.
Met.

Example 3 15.4 g of 4-1-limethylsilylstyrene (8,7
5xlO-2 mol), triisobutylaluminilla 1. (TIBA)4XIO-'mol(
2 mol/l-toluene solution) and (1) of Example 1 above
Add 4 x 10-' mol of methylaluminoxane obtained in (2.6 mol/1-1-luene solution), and at room temperature,
This reaction solution was added with pentamethylcyclopentadienyl titanium trimethoxide (Cp"Ti) as the catalyst component (a).
(OMe)s]2×10-6 mol (0.01 mol/!-
A toluene solution) was added thereto, and the mixture was reacted for 15 hours.

Post-treatment was carried out in the same manner as in Example 1, and a polymer was obtained in a yield of 12.9 g.

Mw determined by GPC under the same measurement conditions as Example 1 was 3,250,000, and Mn was 690,000.
Met.

In addition, Tc, Tg, and Tm determined by DSC under the same measurement conditions as in Example 1 were 266.0'C and 109, respectively.
,9°C,303,2°C.

Example 4 15.4 g of 4-trimethylsilylstyrene (8,75 g
x 10-2 mol), as catalyst component (b) - methylaluminoxane 8 obtained in (1) of Example 1 above
10-' mol (2,6 mol/ff1-1-luene solution) was added to this reaction solution at room temperature, and pentamethyl Schiff 1 copentadienyl titanium trimethoxy l'(Cp"Ti ( ○Mel+) 4 X 1
0-' mol (0.01 mol/1-1-toluene solution) was added and reacted for 15 hours.

Post-treatment was carried out in the same manner as in Example 1, and a polymer was obtained with a yield of 0.62 g.

Mw measured by GPC under the same measurement conditions as Example 1
is 2,570,000 and Mn is 480,00
It was 0.

Further, when measured using DSC under the same measurement conditions as in Example 1, Tc was not present, and Tg and Tm were each 122
．． The temperatures were 3°C, 295, and 6°C.

Example 5 Preparation of styrene/4-trimedelsilylstyrene copolymer with syndiotactic structure 10 mj of toluene was added to a dry reaction vessel at 7°C under an argon atmosphere.
! , as the catalyst component (b), triisobutylaluminum (TIBA)/1X10-'' mol (2 mol/I!-toluene solution) and 4×10-3 solution of methylaluminoxane obtained in (1) of Example 1 above. ) was added to this reaction solution at 70°C, and pentamethylcyclopentadienyl titanium trimethoxide (Cp”Ti (OMe), 12×10
-5 mol (0.01 mol/p toluene solution) and 4-
Trimethylsilylstyrene 0.77g (4, 38X10
-3 moles) and 8.66 g of styrene (8.31X10-2
mol) was added and reacted for 4 hours.

After that, the reaction product was added to a methanol-hydrochloric acid mixed solution to stop the reaction. After deashing and filtration, it was further washed three times with methanol. After drying under reduced pressure, 8.1 g of polymer was obtained. When this molecular weight was measured by GPC (gel permeation chromatography) in the same manner as in Example 1, the weight average molecular weight (Mw) in terms of polystyrene was as follows.
220,000, and the number average molecular weight (Mn) is 1.
It was 10,000. In addition, the trimethylstyrene moiety was 5 mol% from the area ratio of around 145 ppm and around 146 ppm in t,-NMR.
The measurement conditions for C are the same as in Example 1.

Furthermore, when this polymer was measured by DSC under the same conditions as in Example 1, the glass transition point (Tg) observed during second heating was 98.4°C, and the melting point (Tm ) is 2]. The temperature was 9.3°C.

Example 6 4-trimethylsilylstyrene 1.5 as 1,000 units
Example 5 was followed except that 4 g (8.76 x 10-3 moles) and 8.21 g (7.88 x 1.0-2 moles) of styrene were used.

The yield of copolymer was 9.7 g.

Mw measured by GPC under the same measurement conditions as Example 5
was 250,000 and Mn was 120,000. In addition, the trimethylsilylstyrene part is 10 mol%
Met.

Further, Tg determined by DSC under the same measurement conditions as in Example 5 was 104.3°C, and Tm was not confirmed.

Example 7 4-trimethylsilylstyrene 7.7 as a monomer
2g (4,38X10-2 mol) and 4.56g styrene
Example 5 was followed except that (C38xlO-2 mol) was used.

The yield of copolymer was 10.5 g.

Mw measured by GPC under the same measurement conditions as Example 5
was 140,000, and Mn was 46,000.

Further, the trimethylsilylstyrene moiety was 46 mol%.

Further, Tg determined by DSC under the same measurement conditions as in Example 5 was 108.3°C, and Tm was not confirmed.

Example 8 The reaction temperature was room temperature, the reaction time was 15 hours, and TIBA
4xlO-'mol Methylaluminoxane 4X10-
' Example 7 was followed except that 10-6 mol was used.

The yield of copolymer was 3.9 g. Mw measured by GPC under the same measurement conditions as Example 5 was 2.70
00. 000, and Mn was 870,000.

Further, the trimethylsilylstyrene moiety was 45 mol%.

Further, the Tg determined by DSC under the same measurement conditions as in Example 5 was 112.3°C, and the Tm was not confirmed.

Next, it will be explained that the copolymer obtained in Example 7 has a syndiotactic structure.

Example 7. +3(, -NMR(1 0 0
MHz: TCB/heavy benzene-8/2 (volume percent) 130.6 ppm standard for single benzene, 130
"C) is shown in FIG. 4. In Example 1, as shown in FIGS. 1 and 2, the main chain is mainly poly(4-trimethylsilylstyrene) having a syndiotactic structure, and in Comparative Example 2,
For example, as shown in Japanese Patent Application Laid-Open No. 62104818, the main chain is mainly polystyrene having a syndiotactic structure. The copolymer obtained in Example 7 is a copolymer of 4-trimethylsilylstyrene and styrene as shown in FIG.
Since it does not have a peak broadening like Comparative Example 1,
It can be seen that the main chain is mainly a random copolymer with a syndiotactic structure.

<Attribution of peaks> 4 0, 9 - 4 1. 4 ppm main chain methylene 44, 0-45. Oppm main chain methine gas separation characteristics The styrene/4-trimethylsilylstyrene copolymer having a syndiotactic structure obtained in Example 7 was dissolved in chloroform, the dissolved bone was spread on a glass plate,
After evaporation, a cast film was produced by drying under reduced pressure.

The oxygen permeability coefficient (Po.) and nitrogen permeability coefficient (p.□) of this film were determined by pressure method, differential pressure 0.5 kg/cd.

When measured at room temperature, P 02 = 1. 2 0 X 1 0 -9PN□-3
．． 45×10-' (separation coefficient α-3.48).

[Effects of the Invention] The silicon-containing styrenic polymer and copolymer of the present invention have high syndioecticity, excellent heat resistance, chemical resistance, and electrical properties, and have gas separation ability. .

Moreover, according to the method of the present invention, silicon-containing styrenic polymers and copolymers with high syndiotacticity can be efficiently produced.

Therefore, the present invention can be effectively utilized as a heat-resistant polymer for gas separation membranes such as oxygen enrichment membranes, resist materials, etc., and also as a functional polymer precursor.

[Brief explanation of drawings]

Figure 1 shows the polymers obtained in Example 1 and Comparative Example 1.
C-NMR spectrum, Figure 2 is the 'H-NMR spectrum of the polymers obtained in Example 1 and Comparative Example 1, Figure 3 is
The figure is a temperature change diagram of the storage modulus of the polymers obtained in Example 1 and Comparative Example 2, and FIG. Example 1. 2 is an IfCNMR spectrum diagram of the polymer or copolymer obtained in Comparative Example 1 and Comparative Example 2. FIG. ■ (PPM) Figure] 45 (PPM)

Claims (6)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. Indicates a substituent containing one or more of the following. ] Polymerization degree of 5 to 100, having a repeating unit represented by
A silicon-containing styrenic polymer which is a polymer of 0.000 and whose stereoregularity is mainly a syndiotactic structure. (2) As catalyst components, (a) a transition metal component and (b)
Using the contact product of an organoaluminum compound and a condensing agent, there are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1, R^2 and R^3 are each independently a hydrogen atom or a carbon atom. , represents a substituent containing at least one of a silicon atom, an oxygen atom, and a halogen atom. ] The method for producing a silicon-containing styrenic polymer according to claim 1, characterized in that a silicon-containing styrenic monomer represented by the following is polymerized. (3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. Indicates a substituent containing at least one of an atom and a halogen atom. ] Repeating unit [I] and general formula ▲ Numerical formula, chemical formula, table, etc. ▼... [II] (In the formula, R^4 is a hydrogen atom, a halogen atom, or a carbon atom, an oxygen atom, a nitrogen atom represents a substituent containing one or more of atom, sulfur atom, phosphorus atom, selenium atom, silicon atom, and tin atom, and m represents an integer of 1 to 5.However, when m is plural, each R^ 4 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 A silicon-containing styrenic copolymer containing 0.1 mol% or more, the stereoregularity of which is mainly a syndiotactic structure. (4) As catalyst components, (a) a transition metal component and (b)
Using the contact product of an organoaluminum compound and a condensing agent, the general formula ▲ has mathematical formulas, chemical formulas, tables, etc. ▼... [I'] [In the formula, R^1, R^2 and R^3 are Indicates a substituent independently containing one or more of a hydrogen atom, a carbon atom, a silicon atom, an oxygen atom, and a halogen atom. ] Silicon-containing styrenic monomers represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. 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 m represents an integer of 1 to 5. However, when m is plural, each R^4 may be the same or different. 4. The method for producing a silicon-containing styrenic copolymer according to claim 3, characterized in that a styrenic monomer represented by formula [I'] is copolymerized. (5) A gas separation membrane comprising the polymer according to claim 1 or the copolymer according to claim 3. (6) Oxygen permeability coefficient is 1 x 10^-^9 (cm^3 (S
TP)・cm/cm^2・sec/cmHg) or more, and the separation coefficient with nitrogen (oxygen permeability coefficient/nitrogen permeability coefficient)
The gas separation membrane according to claim 5, wherein is 2 or more.