JPH0441687B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a novel copolymer and a method for producing the same, and more particularly, it relates to a copolymer of a styrene derivative having organosilicon in the side chain and a method for producing the same. . (Prior Art) A large number of styrene derivatives have been developed and synthesized in the past, and their polymerizability is utilized to widely utilize them in the synthesis of functional polymers and the like. As styrene derivatives having silicon atoms, para-trimethylsilylstyrene, para-trimethylsilylmethylstyrene, dimethylphenylsilylstyrene, etc. are known. Although many polymers of these compounds are known, a copolymer of a styrene derivative in which a silyl group is bonded to 2-kebenzyl group has not been known so far. As a result of repeated consideration based on this background,
The present inventors have now synthesized a novel styrene derivative copolymer in which a silyl group is bonded to one or two kebenzyl groups. (Structure of the Invention) The copolymer according to the present invention has a molecular weight of 1000 and is composed of polymerized units represented by the structural formula () and the structural formula ().
to 2,000,000 linear copolymers. [In the formula, R ₁ , R ₂ , R ₃ are hydrogen or from 1 carbon number
represents an alkyl group, aryl group, or aralkyl group of 10, and n and m are 1 or 2 such that the sum is 3.
A combination of However, this excludes the case where R ₁ , R ₂ , and R ₃ are all methyl groups, and n=2 and m=1. Y
and Z is hydrogen, a hydrocarbon group (1 to 10 carbon atoms),
Halogenated hydrocarbon group (1 to 10 carbon atoms), halogen, cyano group, hydroxyl group, COOR ₄ (R ₄ is hydrogen or a hydrocarbon group with 1 to 10 carbon atoms), COR ₅ (R ₅ is 1 to 10 carbon atoms) ), OCOR ₆ (R ₆ is a hydrocarbon group having 1 to 10 carbon atoms), or CONHR ₇ (R ₇ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms). ] -CHn(SiR ₁ R ₂ R ₃ ) _n may be at any position of ortho, meta, or para to the vinyl group,
Para is more preferred. Also, the sum of n and m is 3
It is a combination of 1 or 2 such that n=
1, m=2 is more preferable because the effect of the silyl group on flame retardation etc. becomes more pronounced. R ₁ , R ₂ ,
R ₃ is hydrogen or an alkyl group having 1 to 10 carbon atoms,
Although it represents an aryl group or an aralkyl group, it is preferably a methyl group, an ethyl group, or a phenyl group in view of the reactivity of the silyl group. In the structural formula (), Y is hydrogen or a methyl group, Z is a phenyl group, a cyano group,
Chloromethylphenyl group, halogen or
COOR ₄ , COR ₅ , OCOR ₆ , CONHR ₇ (R ₄ , R ₅ ,
R ₆ R ₇ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms)
Electron-withdrawing groups such as are preferred. Of course, copolymers containing multiple types of polymer units () are also included in the present invention. The molar fractions of the polymerized units () and () are each 10 mol% or more and 98 mol% or less. Furthermore, preferably the moiety represented by the structural formula () is 20 mol%
The content is not less than 80 mol%. In addition, within the range that hardly changes the properties of the copolymer, the polymer unit ()
A small amount of a third component other than () and () may be included in the copolymer. The molecular weight of the copolymer in the present invention is 1000 to 1000.
2000000, but more preferably 10000 or more
2000000. The copolymer of the present invention can be obtained by copolymerizing a monomer represented by the structural formula () and a monomer represented by the structural formula (). [In the formula, R ₁ , R ₂ , R ₃ are hydrogen or from 1 carbon number
10 represents an alkyl group, aryl group, or aralkyl group, and n and m are 1 or 2 such that the sum of the solubility is 3.
A combination of However, this excludes the case where R ₁ , R ₂ , and R ₃ are all methyl groups, and n=2 and m=1. Y
and Z is hydrogen, a hydrocarbon group (1 to 10 carbon atoms),
Halogenated hydrocarbon group (1 to 10 carbon atoms), halogen, cyano group, hydroxyl group, COOR ₄ (R ₄ is hydrogen or a hydrocarbon group with 1 to 10 carbon atoms), COR ₅ (R ₅ is 1 to 10 carbon atoms) ), OCOR ₆ (R ₆ is a hydrocarbon group having 1 to 10 carbon atoms), or CONHR ₇ (R ₇ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms). ] The monomer represented by the structural formula () is produced by a method in which the methyl group of vinyltoluene is previously lithiated with a specific organolithium compound, and then a chlorosilane compound is added to the system. Examples of monomers represented by structural formula () are:
Hydrocarbon compounds such as styrene, methylstyrene, diphenylethylene, ethylstyrene, dimethylstyrene, vinylnaphthalene, hinylphenanthrene, vinylmesitylene, 3,4,6-trimethylstyrene; chlorstyrene, methoxystyrene, bromustyrene, cyano Styrene derivatives such as styrene, fluorostyrene, dichlorostyrene, chloromethylstyrene, trifluorostyrene, trifluoromethylstyrene; acrylonitrile derivatives such as acrylonitrile, methacrylonitrile, α-acetoxyacrylonitrile; acrylic acid, methacrylic acid; acrylic acid Acrylic acid esters such as methyl, lauryl acrylate, chloromethyl acrylate, and ethyl acetoxyacrylate;
Methacrylic acid esters such as cyclohexyl methacrylate; diethyl maleate, diethyl fumarate; vinyl ketones such as methyl vinyl ketone and ethyl isopropenyl ketone; vinylidene compounds such as vinylidene chloride, vinylidene bromide, and vinylidene cyanide; acrylamide, metallylamide, N-
Examples include acrylamide derivatives such as phenylacrylamide; fatty acid vinyl derivatives such as vinyl acetate, vinyl butyrate, and vinyl caprate. Among these, Y and Z are hydrogen, cyano group, chloro group, methyl group, phenyl group, chloromethylphenyl group, COOH, COOMe, COOC ₆ H ₁₁ ,
More preferred are COMe, OCMe or _CONH2 . The copolymer of the present invention has the structural formulas () and ()
There are no particular restrictions on the polymerization method used for production using the monomers represented by the formula, and polymerization by heating is sufficient, but it is often preferable to use a polymerization initiator. The polymerization initiators used include acyl peroxides such as benzoyl peroxide and lauroyl peroxide, azobisisobutyronitrile,
Azonitriles such as 2,2'-azobis(2,4-dimethylmaleronitrile), peroxides such as ditertiary butyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, tertiary hydroperoxide, etc. Hydroperoxides. The polymer in the present invention can also be produced by polymerizing in the presence of an inert liquid. Examples of inert liquids include aliphatic hydrocarbons such as normal pentane, normal hexane, normal heptane, and normal octane, alcohols such as methanol, ethanol, and isopropyl alcohol, acetone, methyl ethyl ketone,
Ketones such as diethyl ketone, diethyl ether, methyl ethyl ether, dibutyl ether,
Ethers such as dioxane and tetrahydrofuran, aromatic hydrocarbons such as benzene, toluene and xylene, esters such as ethyl formate, ethyl acetate and butyl acetate, amides such as dimethylformamide and dimethylacetamide, chloroform and methylene chloride. , aliphatic halides such as dichloroethane, aromatic halides such as chlorobenzene, and polar liquids such as dimethyl sulfoxide can also be used. Note that these liquids can be used alone or as a mixture of two or more liquids. There is no limit to the reaction temperature, but it is preferably about 20°C to 120°C, more preferably 60°C to 100°C.
That's about it. (Effects of the Invention) The copolymer of the present invention can be used as a flame retardant due to its flame retardant effect due to its silicon atoms, and
It becomes a functional polymer by using silicon atoms in the side chain.
It is useful for use in oxygen permeable films and as a component of polymers for photoresists and electron beam resists.
Furthermore, by incorporating this polymer, adhesion with silicone oil, glass fiber, etc., which are silicon compounds, becomes very good, and it is also useful as a modifier for composite materials using silicon compounds. (Example) Examples of the present invention will be shown below, but these are not intended to limit the present invention. Example 1 A mixture of 8.0 g of 4-bis(trimethylsilyl)methylstyrene, 2.0 g of styrene, and 0.1 g of azobisisobutyronitrile was poured into a 30 ml ampoule tube, the inside of the ampoule tube was purged with nitrogen, and the tube was sealed. . After immersing this in an aqueous solution at 80°C for 24 hours, the sealed tube was broken and the solidified contents were taken out.
After washing with methanol and vacuum drying, the weight was measured to be 9.7 g (yield 97%). The elemental analysis values and main peaks in the infrared absorption spectrum of this product are as follows. Elemental analysis values (theoretical values are shown in parentheses) C: 73.47 (73.35) H: 9.58 (9.53) Si: 16.95 (17.12) Infrared absorption spectrum (cm ^-1 ) 3060, 2950, 2830, 1610, 1510, 1410, 1250,
1200, 1030, 770, and 690 cm ^-1 Infrared absorption spectrum, the peaks due to carbon-carbon double bonds completely disappeared, elemental analysis values, and yield showed that the obtained solid was 4-
It was concluded that it was a copolymer of bis(trimethylsilyl)methylstyrene and styrene. The molecular weight of this product was measured by gel permeation chromatography using polystyrene as a calibration curve, and the molecular weight was found to be
It was 1200000. Example 2 The reaction and operation were carried out in the same manner as in Example 1, except that 4-bis(triethylsilyl)methylstyrene was used instead of 4-bis(trimethylsilyl)methylstyrene. The yield of solid obtained is
9.8g (98%), and its elemental analysis values and main peaks in the infrared absorption spectrum are as follows. Elemental analysis values (theoretical values are shown in parentheses) C: 76.42 (76.65) H: 10.74 (10.39) Si: 12.84 (12.96) Infrared absorption spectrum (cm ^-1 ) 3060, 2950, 2800, 1610, 1510, 1410 ,1250,
1330, 770, 690 cm ^-1 Moreover, when the molecular weight was measured in the same manner as in Example 1, the molecular weight was 1,100,000. Examples 3 to 12 Copolymerization of the monomer represented by the structural formula () and the monomer represented by the structural formula () was performed using the same method as in Example 1, and the obtained copolymer was subjected to elemental analysis. and infrared absorption spectra were measured.
The results are shown in Table 1. According to these results, the obtained copolymer is
All of them were included in claim 1.

【table】

[Table] Example 13 After dissolving 1 g of the polymer synthesized in Example 1 in 20 ml of tetrahydrofuran, this solution was applied to a clean glass surface to make a polymer film. After removing the solvent tetrahydrofuran by drying at 20° C. for 24 hours, the polymer film was peeled off by immersing the glass in water, and the film was vacuum-dried for 48 hours. When air was added to one side of this film and measured by gas chromatography, the oxygen permselectivity (oxygen fraction after passing/initial oxygen fraction) was 3.1. .

Claims (1)

[Claims] 1 Consisting of polymerized units represented by the following structural formulas () and (), the molar fraction of the polymerized units () and () is 10 mol% or more and 98 mol% or less, respectively, and the molecular weight is 1000 or more. 2000000 linear copolymer. [In the formula, R ₁ , R ₂ , R ₃ are hydrogen or from 1 carbon number
represents an alkyl group, aryl group, or aralkyl group of 10, and n and m are 1 or 2 such that the sum is 3.
A combination of However, this excludes the case where R ₁ , R ₂ , and R ₃ are all methyl groups, and n=2 and m=1. Y
and Z is hydrogen, carbon hydrogen group (1 to 10 carbon atoms),
Halogenated hydrocarbon group (1 to 10 carbon atoms), halogen, cyano group, hydroxyl group, COOR ₄ (R ₄ is hydrogen or a hydrocarbon group with 1 to 10 carbon atoms), COR ₅ (R ₅ is 1 to 10 carbon atoms) ), OCOR ₆ (R ₆ is a hydrocarbon group having 1 to 10 carbon atoms), or CONHR ₇ (R ₇ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms). 2. The compound according to claim 1, wherein n=1 and m=2 in the structural formula (). 3 In the structural formula (), R ₁ , R ₂ , R ₃ are methyl groups,
The compound according to claim 1 or 2, which is either an ethyl group or a phenyl group. 4 Structural formula below () The monomer shown by and the following structural formula () Consisting of polymerized units represented by the following structural formulas () and () characterized by copolymerizing monomers represented by the following, the molar fraction of the polymerized units () and () is 10 mol% or more and 98 mol, respectively. % or less, and a method for producing a linear copolymer with a molecular weight of 1,000 to 2,000,000. [In the formula, R ₁ , R ₂ , R ₃ are hydrogen or from 1 carbon number
represents an alkyl group, aryl group, or aralkyl group of 10, and n and m are 1 or 2 such that the sum is 3.
A combination of However, this excludes the case where R ₁ , R ₂ , and R ₃ are all methyl groups, and n=2 and m=1. Y
and Z is hydrogen, a hydrocarbon group (1 to 10 carbon atoms),
Halogenated hydrocarbon group (1 to 10 carbon atoms), halogen, cyano group, hydroxyl group, COOR ₄ (R ₄ is hydrogen or a hydrocarbon group with 1 to 10 carbon atoms), COR ₅ (R ₅ is 1 to 10 carbon atoms) ), OCOR ₆ (R ₆ is a hydrocarbon group having 1 to 10 carbon atoms), or CONHR ₇ (R ₇ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms). ]