JPH0441685B2 - - Google Patents

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a novel polymer and a method for producing the same, and more specifically, a novel polymer having an organosilicon group in its side chain and its production. It is about law.

(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 polymer of a styrene derivative in which a silyl group is bonded to a 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 polymer in which a silyl group is bonded to one or two kebenzyl groups.

(Structure of the Invention) The present invention relates to a linear polymer comprising polymerized units represented by the following structural formula () and having a molecular weight of 1,000 to 2,000,000.

(In the formula, R ₁ , R ₂ , R ₃ are hydrogen or from 1 to carbon number
Represents 10 alkyl, aryl, and aralkyl groups. 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) -CHn (SiR ₁ R ₂ R ₃ ) _n is ortho to the vinyl group, It can be in either meta or para position, but
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.

The molecular weight of the linear polymer in the present invention is 1000 to
2000000, but more preferably 10000 or more
2000000.

The linear polymer of the present invention can be obtained by polymerizing monomers represented by the structural formula ().

The above monomer is obtained by lithiation of the methyl group of vinyltoluene with a specific organic lithium compound, and then
It is manufactured by adding a chlorosilane compound into the system.

There are no particular restrictions on the polymerization method, 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, azonitrile such as azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylmaleronitrile), peroxide jitter
These include peroxides such as shari-butyl, dicumyl peroxide, and methyl ethyl ketone peroxide, and hydroxyperoxides such as cumene hydroperoxide and tertiary-hydroperoxy.

The polymer in the present invention can also be produced by polymerizing in the presence of an inert liquid. 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.

(Effect of the invention) Novel polymer obtained by the invention ()
is considered to be used as a flame retardant due to its flame retardant effect due to its silicon atoms, and it can also be used as a functional polymer by using the silicon atoms in the side chain, and can be used in oxygen permeable films, photoresists, and electron beam resists. Useful as a component of polymers. 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 are shown below, but these do not limit the present invention.

Example 1 5.0 g of 4-bis(trimethylsilyl)methylstyrene, 20 ml of xylene and 0.05 g of azobisisobutyronitrile were placed in a 50 ml ampoule.
After thorough mixing and dissolution, the inside of the ampoule tube was purged with nitrogen and the tube was sealed. This was immersed in a water bath at 80°C for 24 hours. After cooling, the sealed tube was broken and the contents were poured into hexane, the precipitate was filtered out, thoroughly washed with hexane, dried under vacuum, and the weight was determined to be 4.9.
It was hot at g.

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: 69.05 (68.62) H: 10.01 (9.98) Si: 20.94 (21.40) Infrared absorption spectrum; 3060, 3000, 2950,
2830, 1610, 1510, 1410, 1250, 1200, 1030,
Since the absorption derived from the C=C2 double bond in the 770 and 690 cm ^-1 monomers disappeared, it was confirmed that it had become a polymer. 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 1,100,000.

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 the obtained product was 4.8 g, and its elemental analysis values and main peaks in the infrared absorption spectrum were as follows.

Elemental analysis values (theoretical values are shown in parentheses) C: 72.41 (72.75) H: 11.62 (11.05) Si: 15.97 (16.20) Infrared absorption spectrum; 3060, 3030, 2950,
2800, 1610, 1510, 1410, 1250, 1180, 1030,
770, 690 cm ^-1 Moreover, when the molecular weight was measured in the same manner as in Example 1, the molecular weight was 900,000.

Example 3 The reaction and operation were carried out in the same manner as in Example 1 except that 4-triethylsilylmethylstyrene was used instead of 4-bis(trimethylsilyl)methylstyrene. The yield of the product obtained is
It weighs 4.8g, 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: 76.75 (77.51) H: 11.05 (10.41) Si: 12.20 (12.08) Infrared absorption spectrum; 3060, 3030, 2950,
2800, 1610, 1510, 1410, 1250, 1180, 1030,
770, 700 cm ^-1 Moreover, when the molecular weight was measured in the same manner as in Example 1, the molecular weight was 1,200,000.

Example 4 The reaction and operation were carried out in the same manner as in Example 1 except that 4-dimethylphenylsilylmethylstyrene was used instead of 4-bis(trimethylsilyl)methylstyrene. The yield of the obtained product was 4.5 g, and its elemental analysis values and main peaks in the infrared absorption spectrum were as follows.

Elemental analysis values (theoretical values are shown in parentheses) C: 80.69 (80.89) H: 8.29 (7.99) Si: 11.02 (11.13) Infrared absorption spectrum; 3060, 3000, 2950,
2830, 1610, 1520, 1410, 1220, 1160, 770,
740, 700 cm ^-1 Moreover, when the molecular weight was measured in the same manner as in Example 1, the molecular weight was 850,000.

Example 5 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 produce 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 measured by gas chromatography, in which air was added to one side of the film and passed through to the other side, the selective permeability of oxygen (oxygen fraction after passing/initial oxygen fraction) was 3.5. .

Claims (1)

[Claims] 1. A linear polymer consisting of polymerized units represented by the following structural formula () and having a molecular weight of 1,000 to 2,000,000. [In the formula, R ₁ , R ₂ , and R ₃ represent hydrogen or an alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group. n and m are a combination of 1 or 2 such that the sum is 3, except when R ₁ , R ₂ , and R ₃ are all methyl groups and n = 2 and m = 1] 2 Structure The compound according to claim 1, wherein in formula (), n=1 and m=2. 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 () It consists of a polymerized unit represented by the following structural formula (), which is characterized by polymerizing a monomer represented by
A method for producing linear polymers 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 to carbon number
Represents 10 alkyl groups, aryl groups, and aralkyl groups. n and m are a combination of 1 or 2 whose sum is 3. However, this excludes the case where R ₁ , R ₂ , and R ₃ are all methyl groups, and n=2 and m=1. )