JPH01278532A - Silicon-containing polymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject polymer having a narrow molecular weight distribution and terminal reactive silicon-hydrogen bonds by reacting a silicon compound having direct bonds of silicon atom to hydrogen atom with a diene compound. CONSTITUTION:The objective polymer, obtained by mixing (A) preferably 100pts. wt. compound, expressed by formula I (R<1>-R<4> are 1-8C alkyl, etc.; R<5> is alkylene, etc.; n is 0-9) and having silicon-hydrogen bonds and alkyl groups linked to the silicon atom (e.g., methylphenysilane) with (B) preferably 40-160 pts.wt. diene compound (e.g., 1,3-butadiene), further adding (C) preferably 0.001-7 pts.wt. hydrosilylation catalyst (e.g., chloroplatinic acid) and carrying out reaction at, e.g., 20-200 deg.C, and expressed by formula II (R<6> is bifunctional organic group; m is 3-15).

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention relates to a silicon-containing polymer and a method for producing the same. More specifically, the molecular weight distribution is narrow, and the silicon-terminated
The present invention relates to a silicon-containing polymer having hydrogen bonds and a method for producing the same.

[Prior Art] In the field of polymer composites, there is a demand for silicon-containing polymers having reactive silicon-hydrogen bonds at their terminals.

As such a silicon-containing polymer, a method has been proposed for producing it by, for example, a hydrolylation reaction between a diaryl diester compound and a dihydrosilane compound (Bull et al.
, Chem, Soc, Japan, vol. 34, 1
(page 8).

[Problems to be solved by the invention] However, conventionally known silicon-containing polymers have a wide molecular weight distribution, and the characteristics of polymer composite materials using them are poor.
For example, it is extremely difficult to predict fluidity and moldability at the design stage, making it difficult to handle.

[Means for Solving the Problems] In order to solve the problem described in item 1, the present invention has a structure represented by the following general formula (I), and has a number average molecular weight in terms of polystyrene of 500 to 50,000. , molecular weight distribution or 1
．． 02 to 1.25.

R+ R3 (wherein R1-R4 may be the same or different and represent an alkyl group or aryl group having 1 to 8 carbon atoms, and R5 represents an alkylene group, imino group, alkylimino group, arylene group or oxygen atom) , R6 represents a divalent organic group,
n is a number from 0 to 9, and m is a number from 3 to 15. However, the silicon atom directly bonded to R6- and the silicon atom at the end of the polymer each have 1 or more carbon atoms.
~8 alkyl groups shall be bonded. ) The silicon-containing polymer having the structure represented by the general formula (I) of the present invention has a polystyrene equivalent number average molecular weight (M stone) of 500 to 50.
000, preferably from 2,000 to 10,000, and the molecular weight distribution (polystyrene equivalent weight average molecular weight (Mw)/Mite) is from 1.02 to 1.25, preferably from 1.05 to 1.15.

Here, if the number average molecular weight is less than 500, the viscosity of the polymer will be low and moldability will be poor, and if it exceeds 50,000, the flow characteristics of the polymer will be poor. In addition, the molecular weight distribution is 1.2
If it exceeds 5, the flow characteristics and moldability of the polymer will deteriorate.

Among R1-R4 in the structure represented by general formula (I) constituting the polymer of the present invention, the alkyl group includes a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group,
Examples of the aryl group include an octyl group, a phenyl group, a xylyl group, and a tolyl group. However, in general formula (I), the silicon atom directly bonded to R6- and the silicon atom at the end of the polymer each have one or more alkyl groups, preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably is assumed to have a methyl group bonded to it.

Among R5 in the structure represented by general formula (I), alkylene groups include those having 2 to 6 carbon atoms such as ethylene group, propylene group, hexamethylene group, and alkylimino groups include methylimino group, ethylimino group, propyl Those having 1 to 6 carbon atoms such as imino group and butylimino group, arylene group include phenylene group, tolylene group,
Examples include those having 6 to 8 carbon atoms such as a xylylene group, and preferred examples include a phenylene group and an oxygen atom.

In addition, 2 of R6 in the structure represented by general formula (I)
Examples of the valent organic group include alkylene groups having 4 to 10 carbon atoms such as tetramethylene group, hexamethylene group, octamethylene group, decamethylene group, and the following general formula (III).
Examples include groups represented by the following.

General formula (III) (CH2 sho , preferably a number from 2 to 5. Here, R7 represents a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group. However, it may be linear or branched, and the alkylene group may further include a phenyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a methoxy group, an oxy group,
It may be added with a substituent such as a chlorine atom.

Among R6, preferred are tetramethylene group, 2-methyltetramethylene group, heptamethylene group, octamethylene group, cycloheptyl group, cycloheptyl group, formula % formula % (where plq and R7 are as above) The same applies to the following.).

Next, as a method for producing the polymer of the present invention, a method may be mentioned in which (a) a compound represented by the following general formula (II) and (b) a diene compound are reacted in the presence of a hydrosilylation catalyst. .

(In the formula, R1-R5 and n are the same as in general formula (I). However, when n=0, at least one of R1 and R2 is an alkyl group having 1 to 8 carbon atoms, and n≧ In the case of 1, one or more alkyl groups having 1 to 8 carbon atoms are bonded to the silicon atoms at both ends.) (a) A compound represented by the above general formula (II) (hereinafter,
It will be referred to as "compound (a)." ) is a silicon compound having two silicon-hydrogen bonds in which a hydrogen atom is directly bonded to a silicon atom. Here, the two silicon-hydrogen bonds may be on the same silicon atom or on different silicon atoms. Is there a silicon-hydrogen bond in a silicon compound?
If the number is more than 1, crosslinking occurs between the polymers, and a linear silicon-containing polymer cannot be obtained. Moreover, a polymer cannot be obtained from a silicon compound having one silicon-hydrogen bond.

Furthermore, compound (a) must have at least one alkyl group, preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group, bonded to a silicon atom having a silicon-hydrogen bond.

If an alkyl group is not bonded to a silicon atom having a silicon-hydrogen bond, the reactivity with the diene compound (b) described later will be significantly high, making it difficult to control the reaction and obtaining a polymer with a small molecular weight distribution. I can't do anything anymore.

Specific examples of compound (a) include methylphenylsilane, dimethylsilane, 1,1. ．． 3.3-tetramethyldisiloxane, 1,1,3,3,5゜5-hexamethyltrisiloxane, 1,1,3゜3.5,5,7.7-octamethyltitranoxane, Examples include 1,4-bis(dimethylsilyl)benzene, 1,2-bis(dimethylsilyl)ethane, and bis(dimethylsilyl)amine, preferably methylphenylsilane, 1,1°3.
Examples include 3-tetramethyldisiloxane and 1,4-bis(dimethylsilyl)benzene.

These compounds (a) can be used alone or in combination of two or more.

Moreover, the molecular weight of compound (a) is preferably 11,000 molecule ff or less in order to facilitate the polymerization reaction.

(b) The diene compound (hereinafter referred to as "compound (b)") is a compound having two carbon-carbon double bonds in one molecule.

Examples of the compound (b) include hydrocarbon diene compounds such as pentadiene, hexadiene, and octadiene, and diene compounds represented by the following general formula (IV).

General formula (IV) CpH2,-1-X-C1H2,-1(IV) (X, p
and q are the same as in general formula (III) above. ) Among these, the hydrocarbon diene compound may be cyclic, linear, or branched, and the hydrocarbon diene compound may further include a phenyl group, a methoxycarbonyl group, an aethoxycarbonyl group, a methoxy group, It may be added with a substituent such as a xy group or a chlorine atom.

Among compounds (b), 1,3-butadiene, 2-methyl-1,3-butadiene, 1,4-hebutadiene, 1
, 3-cyclopentadiene, 1,3-cyclohexadiene, diallyl ether, diallylbutylamine, diallylamine, 1,4-diallylpiperazine and the like are preferred.

In the present invention, generally 40 to 160 parts by weight, preferably 80 to 120 parts by weight of compound (b) are reacted with 100 parts by weight of compound (a). At this time, it is necessary that compound (a) and compound (b) be reacted in the presence of a hydrosilylation catalyst.

Here, the hydrosilylation catalyst is a compound that has the effect of promoting the addition reaction between an unsaturated compound and a hydrosilane, and includes, for example, Group (I) transition metal complexes such as chloroplatinic acid and rhodium chloride phosphine complexes. I can do it. The amount of these hydrosilylation catalysts used is 10
The amount is usually 0.001 to 7 parts by weight, preferably 0.03 to 3 parts by weight.

In addition, in the reaction, the above compound (a), compound (b'
) and a hydrosilylation catalyst, an organic solvent can be added as necessary.

Examples of such organic solvents include chloroform, methylene chloride, dichloromethane, carbon tetrachloride, halogenated hydrocarbons such as ethyl chloride, n-hexadi, n-pentane, heptane, 2-methylbutane, 2-methylpentane, 2,2
-Aliphatic hydrocarbons such as dimethylbutane, toluene,
Examples include aromatic hydrocarbons such as xylene, alcohols such as methanol and ethanol, ketones such as methyl ethyl ketone, and ethers such as diethyl ether.

The amount of the organic solvent used does not need to be particularly limited as long as the concentration of the reaction system is low and the reaction rate is not too slow, but it is usually 2 parts by weight per 100 parts by weight of compound (a).
000 parts by weight or less, preferably 500 to 1000 parts by weight
Parts by weight.

These organic solvents can be used alone or in combination of two or more.

Further, in the present invention, the reaction temperature between compound (a) and compound (b) is usually 20 to 200°C.

Note that the reaction system in the present invention is usually purged with an inert gas such as argon to maintain the water content at about 1100 pp or less.

[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

In the examples, parts and percentages are based on weight unless otherwise specified. In addition, various 4 (standards) in Examples are as follows.

The weight average molecular weight and number average molecular weight in terms of polystyrene were measured by gel permeation chromatography (GPC) under the following conditions.

A sample was prepared by dissolving 1 g of the silicon-containing polymer in 100 cc of tetrahydrofuran. Moreover, the standard polystyrene manufactured by Pressure Chemical Company, USA was used.

Equipment: Made by Waters, USA, high-temperature high-speed gel permeation chromatogram (Model 150-CALC/GPC) Column: Made by Toyo Soda ■, TSK gelG4000
, Measurement temperature: 40°C Flow rate: Icc/min For elemental analysis, CHN-Coder M manufactured by Yanagimoto Seisakusho
A new model 260-50 infrared absorption analyzer manufactured by Hitachi was used for infrared absorption analysis.

Example 40 parts of 1,1,3,3-tetramethyldisiloxane, 33 parts of 1,7-octadiene,
390 parts of n-hexane and 0.1 part of dichloroplatinic acid were added, the mixture was sealed, and the mixture was reacted at 100°C for 13 days. Next, 0.7 g of the polymer of the present invention was isolated by reducing the pressure of the reaction system to remove n-hexane and low-boiling compounds.

0.5 g of the obtained polymer of the present invention was added to 10 m of n-hexane.
1 dissolved in ethyl ether 5 under nitrogen atmosphere.
The polymer of the present invention was purified by adding the solution dropwise into 0 ml of water with stirring and treating the resulting white precipitate with neutral alumina.

Next, the polystyrene equivalent weight average molecular weight and number average molecular weight of the polymer of the present invention were measured, and the molecular weight distribution (M
w/M n ) was calculated. The results are shown in Table 1.

Further, the results of elemental analysis are shown in Table 2.

Furthermore, infrared absorption analysis was performed, and the results are shown in FIG.

15 Examples 2 to 6 In the same manner as in Example 1, except that the compound (a), compound (b), organic solvent, their usage amounts and reaction times were as shown in Table 1, The reaction and the resulting polymer were purified.

Next, the polystyrene equivalent weight average molecular weight and number average molecular weight of the obtained polymer were measured, and the molecular weight distribution was calculated. The results are shown in Table 1. Further, the results of elemental analysis are shown in Table 2.

Furthermore, infrared absorption analysis was performed, and the results are shown in FIGS. 2 to 6.

Blank space below: 161 [Effects of the Invention] Since the polymer of the present invention has a silicon-hydrogen bond at the terminal, it can be used in combination with other polymeric compounds, for example, by reacting with polybutadiene to improve the water resistance of polybutadiene. It is suitable as a regulation.

Furthermore, since it has a specific molecular weight distribution, it is advantageous in the production and design of polymer compound materials.

Furthermore, the method for producing the polymer of the present invention can be carried out using silicon.

[Brief explanation of the drawing]

1 to 6 show the results of infrared absorption analysis in Examples 1 to 6. Patent applicant: Japan Synthetic Rubber Co., Ltd.

Claims (2)

[Claims] (1) A silicon-containing polymer having a structure represented by the following general formula (I), a polystyrene equivalent number average molecular weight of 500 to 50,000, and a molecular weight distribution of 1.02 to 1.25. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 to R^4 may be the same or different and represent an alkyl group or aryl group having 1 to 8 carbon atoms, and R^
5 represents an alkylene group, imino group, alkylimino group, arylene group, or oxygen atom, R^6 represents a divalent organic group, n is a number from 0 to 9, and m is a number from 3 to 15. be. However, one or more alkyl groups having 1 to 8 carbon atoms are bonded to the silicon atom directly bonded to -R^6- and the terminal silicon atom of the polymer, respectively. ) (2) A method for producing a silicon-containing polymer, which comprises reacting (a) a compound represented by the following general formula (II) and (b) a diene compound in the presence of a hydrosilylation catalyst. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, R^1 to R^5 and n are the same as in general formula (I). However, if n = 0, R^1 and R^
At least one of 2 is an alkyl group having 1 to 8 carbon atoms, and when n≧1, one or more alkyl groups having 1 to 8 carbon atoms are bonded to the silicon atoms at both ends, respectively. )