JPH01242593A - Production of silicon-containing polymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing silicon-containing polymers. For details, - Formula (1) (where m is 0 or a positive integer from l to 20, n is l
, 2 or 3.1 is hydrogen, an alkyl group, an aryl group or a halogen, R8 is an alkylene group or a phenylene group, and R1 and R2 are COOH, NHz, C1, O
(which may contain a functional group such as H) is anionically polymerized, or the silicon compound and an unsaturated hydrocarbon having at least one carbon-carbon double bond in the molecule, especially The present invention relates to a method for producing a silicon-containing polymer containing a 5i-H bond in the molecule by anionic copolymerization with an α-olefin.

BACKGROUND OF THE INVENTION At present, silicones (organopolysiloxanes) are the most commonly used industrially for polymers containing Si. The raw materials used for this are alkylchlorosilanes, in particular dimethyldichlorosilane, which are produced by the reaction of metallic silicon with halogenated hydrocarbons, the so-called direct process. There are few practical examples of silicon-containing polymers other than silicone, and for example, (■) (■) (III) (IV) are known. (I is produced in a solvent such as xylene as shown in the formula below.

The same applies to (II). (I) is insoluble and infusible, but (
I[) is solvent soluble and thermoplastic.

(III) is obtained by thermally decomposing (1) under high temperature and high pressure, and is soluble in solvents and thermoplastic.

(1), (II) and (I[[) are used for ceramic binders, and (II) and (III)
is a precursor of ceramics (SiC), especially used for ceramic (SiC) fibers (Nippon Carbon Co., Ltd., product name "Nicalon"), (rV) is a polymer of vinylsilane, and is a copolymer with ethylene. is used in large quantities as a water-crosslinkable polyethylene for covering electric wires.

However, there are almost no examples of CHg-bow R1 (R”)a 5inHxa*t polymers, and there are only a few Ziegler (
allylsilane (CHg・CI) using a Ziegler-type catalyst.
-C)I□-3i)I2) Polymerization examples are only seen (Journal Op Polymer Science (Jou
rnal of Polymer 5cienc
e)+Vol 31+N(i122+181(195
B), Italian Patent No. 60601B) The above-mentioned silicon compounds have recently become easy to manufacture industrially, as will be described later.

However, in these catalyst systems, -M has a silyl group 19
Due to the influence of (-3inHt-, +), the polymerization of 7-mer is poor and the polymer yield is low, and silyl groups (-5in)
There is a problem that cross-linking between molecular chains is likely to occur during the polymerization or post-treatment process due to the interaction between the (its-+) and the catalyst.

The present inventors have already discovered and proposed that CHg"'CR'(R")+a 5inHta-+ polymerizes in the presence of a radical initiator (Japanese Patent Application No. 62-097417, No. 62-098).
698).

However, in these radical polymerizations, the molecular weight! It has the disadvantage that IIIJ is difficult and it is difficult to produce a polymer with a desired molecular weight.

The present inventors have discovered that the polymer of the silicon compound according to the present invention using a Ziegler type catalyst has a high conversion yield into ceramics (SiC) when fired at high temperatures, and is very promising as a prepolymer for ceramics. It has already been proposed that
929, 62-031514) In addition, the silyl group g (-5 inHzn**) in the polymer has excellent reactivity, c, c% C-0, N-H, 0-H.

Coating agents, because they can react with various bonds such as
It has a wide range of applications for functional polymers such as compatibilizers and crosslinking agents.

SUMMARY OF THE INVENTION An object of the present invention is to overcome the various drawbacks of these Ziegler-type catalyst polymerizations and radical polymerizations, and to provide a highly useful method for producing silicon-containing polymers as described above.

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors conducted anionic polymerization of a specific silicon compound or anionic copolymerization of a specific silicon compound and a specific unsaturated hydrocarbon. The inventors have discovered that the objects of the present invention can be achieved by doing so, and have finally completed the present invention.

That is, the present invention provides - formula (I) (where m is 0 or a positive integer from 1 to 20, n is 1
．． 2 or 3, RI is hydrogen, an alkyl group, an aryl group or a halogen, R1 is an alkylene group or a phenylene group, lil and RZ are (:0O)I%NHz,
A method for producing a silicon-containing polymer, which is characterized by anionically polymerizing a silicon compound represented by (which may contain a functional group such as CI or OR), and further comprising the steps of: This is a method for producing a silicon-containing polymer, which comprises anionically copolymerizing at least one carbon and an unsaturated hydrocarbon having a carbon double bond.

The silicon compound used for polymerization in the present invention is represented by the general formula (1), where m is O or a positive integer from 1 to 20, n is 1, 2, or 3, and R1 is hydrogen, alkyl group, aryl group or halogen, e.g.
H, CHi, CJs, 1-CsTo, Φ (Φ represents a phenyl group, the same applies hereinafter), ΦCH3, CH! Φ, F
, CI, Br, etc., hydrogen, phenyl group,
Rz is preferably an alkenyl group or the like, and is an alkylene group or a phenylene group, such as CHi, Φ (Φ represents a phenylene group, the same applies hereinafter), Ca1. Φ etc. In addition, the above 1 and R2 are C00H1NH,,C
It may contain functional groups such as I and OR.

These silyl group-containing monomers, i.e., silicon compounds, related to the present invention can be produced by various methods, and are not particularly limited in the present invention. Can be adopted.

600℃ 1AIH4 ChSi(CL) p−+−CH−CHz−−−−−→
H3Si(CHz)n, +CHCHit ■-H.

LiAI)I4Clco5i(CHx) p. , CH, CH□H3Si(
C) 1), =+CH=CIIz ■Pt, 200
°C 51Hn +C)I! =CH(CHri, CLCIh
-1----→H3Si (CHz), 1-tcH=cH
z■5rHa + CIHtC−CCHt> p −
C) l=cL −−1→H3Si(CHz)p−+C
H=CH2 ■ Of these, ■, ■, ■, ■ are 5i) I4
In particular, ■ and ■ are hydrosilylation reactions using group II metals as a catalyst, and it is easy to obtain the desired 5iHs.
α-olefins containing groups can be obtained.

Lid (Sin) is a new silicon raw material that has grown in demand for use in polysilicon and amorphous silicon in recent years, and has become manufactured cheaply and in large quantities, and this trend is expected to further advance in the future. It is.

The same can be said for SiJ*, Si, and H.

Two or more of these silicon compounds can also be used simultaneously.

On the other hand, the unsaturated hydrocarbon of the present invention is a compound having at least one carbon-carbon double bond in the molecule, and these are -NH! , -OH, -CI.

-CN, -COOR, -Co(lfl, -CON
It may also contain functional groups such as Hz, especially α-olefins.

These unsaturated hydrocarbons themselves have anionic polymerization ability. Specifically, CHg=CH-CH
=Cl1z, CL・CCHs−CCHz, CHzI
ICCI-CHgCHt.

CL-CHCOOR, CHI-C(CH3)COOI?
, CHg=CH-C0-CH3, CH, .CHCN%
C)1. −, CI(NO□, CHz=C(CN)COO
CHzCH3, CHx-CHCONHt.

Two or more types of these can be used simultaneously.

The present invention is characterized in that the silicon compound described above is anionically polymerized or anionically copolymerized with an unsaturated hydrocarbon. Anionic polymerization is carried out using a catalyst (initiator), organic alkaline earth metals such as dialkyl strontium, diaryl strontium, dialkyl calcium, diaryl calcium, alkyl potassium, aryl potassium, alkyl sodium, aryl sodium, alkyl lithium, aryl Organic alkali metals such as lithium, alkali amides, Grignard reagents, alkali metal ketyls, alkali metal alkoxides, pyridine, tertiary amines, water, ethers, and the like are commonly used as catalysts. Also these 2[! Sometimes more than one type are used at the same time.

The polymerization mode is also not particularly limited, and may be either gas phase or liquid phase, and methods such as bulk polymerization and solution polymerization can be adopted.The reaction temperature and reaction pressure vary depending on the polymerization mode and reaction monomer, but the reaction temperature is -150℃. to 100°C, preferably -100 to 50°C. The reaction pressure is normal pressure to 1000 atm. In solution polymerization, a solution of benzene, toluene, xylene, hexane, diethyl ether, THF, glymes, liquid ammonia, DMSO, or the like is used for polymerization.

Anionic polymerization has a variety of excellent features not found in Ziegler-type catalyst polymerization and radical polymerization because the growing terminal is a carbon anion that is difficult to chain transfer. It is possible to synthesize polymers with the desired molecular weight. (2) Since it is a living polymerization, various new block copolymers can be synthesized by combining it with various silicon-containing monomers or α-olefin necks. ■
A functional group can be introduced into the terminal by reacting carbon dioxide, ethylene oxide, etc. with the growing terminal.

In the present invention, the structure of the polymer is not particularly limited, and the repeating unit, molecular weight and its distribution, degree of crosslinking, etc. can be changed depending on the type of monomer and the polymerization mode. The most typical polymer structure is, for example, (where m is O or a positive integer from 1 to 20, n is 1
．． 2 or 3, ill is hydrogen, alkyl group, aryl group or halogen, R1 is alkylene group or phenylene group, RI and R1 are coon, NHZ, CI
, OH, and other functional groups may be included. Further, R3 and R4 are hydrogen, an alkyl group, a halogen, an alkylene group, an alkenyl group, an alkoxy group, a nitro group, a cyano group,
A carbalkoxy group or an acetoxy group, and Co
), which may contain functional groups such as ol, NHx, CI, and OH.

There is no limit to the stereoregularity of the polymer, and there is no particular limit to the molecular weight, but it is usually 100 to 10,000,000,
Polymers having various stereoregularities can be synthesized by selecting reaction conditions, preferably from about 200 to 1,000,000, which is desirable from the viewpoint of polymer moldability and solubility in solvents. Furthermore, by selecting the amount of initiator, it is possible to synthesize a polymer of any desired molecular weight.

In copolymerization, the monomer composition ratio is 0.00001 to 1 part by weight of unsaturated hydrocarbon to 1 part by weight of silicon compound.
00.000 parts by weight, preferably o, ool to 1,0
00 parts by weight, and can be arbitrarily selected depending on the intended use of the copolymer.

The silicon-containing polymer in the present invention can be easily obtained from inexpensive monomers as described above. Polymers made from the conventional alkylchlorosilane described above and having, for example, the following repeating structural units (1)
Compared to (II), the production of the silicon-containing polymer in the present invention can be carried out in a non-chlorine system, there is no fear of corrosion, and the process is extremely simple.

From the above, it is believed that the polymer according to the present invention will be able to be manufactured at even lower cost in the future.

Furthermore, the silicon-containing polymer of the present invention is not only easy to manufacture, but also has good processability (melt flowability, solvent solubility), copolymer type (random, block, alternating, or graft), and copolymer type (random, block, alternating, or graft). It can be easily changed by controlling the monomer composition, molecular weight, and stereoregularity of the polymer. Furthermore, the stag group present in the silicon-containing polymer of the present invention is relatively stable and is not easily oxidized even in air at room temperature, and is only oxidized at a high temperature of about 100 to 200°C. do not have.

Since the silicon-containing polymer according to the present invention is soluble in solvents and thermoplastic, it has great industrial applicability and can be expected to have many uses.For example, prepolymers for ceramics (5iC), binders for ceramics, surface These include processing agents, water repellents, raw materials for IPN, semiconductors, and photoresists. The functions of these polymers utilize the high reactivity of 5i-H bonds and the electrical conductivity and photodegradability of 5i-3i bonds. Particularly, the function suitably utilized in the present invention lies in the reactivity of the silyl group (SiHz). It is possible to incorporate interesting functions into conventional polymers, such as the ability to impart cross-linking properties, foaming properties, and reactivity with other monomers or polymers. That is, the present invention greatly contributes to the creation of new highly functional materials that have not existed before.

Example Hereinafter, the present invention will be explained by examples.

Example 1 50 m of dehydrated and purified τHF and separately prepared T)IF of sodium naphthalene were added to a volume of 7.9 d (0,
Vinylsilane (COx-CI-3in
3) After adding 50 g and reacting at room temperature for 3 hours, the reaction solution was poured into 400 d of methanol and filtered to obtain 11 g of white powder.

According to GPC analysis, the molecular weight was 7000.

Mw/Ms bite was 1.1.

2120C1-', 92 in the infrared absorption spectrum
Strong absorption based on -5ins was observed at 0C1''.

When 1 g of product was decomposed using EtOH-Li solution, 1232 d of hydrogen gas (20° C.) was evolved. As a result of the value of 0 or more, which almost coincided with the theoretical quantity 1239d, it was identified that this had the structure.

Elemental analysis (unit %) Theoretical value C41,31N 10.4OSt 48.30
Analysis value C41,08H10,62 Example 2 In Example 1, allylsilane was used instead of vinylsilane in tllF solution 10a of 5081 sodium naphthalene.
Polymerization was performed in the same manner except for using +f (0.4 mol/1). As a result, 8 g of white powder was obtained.

According to GPC analysis, the molecular weight was 4000.

Mw/MW was 1.2.

2120C1m-', 9 in the infrared absorption spectrum
A strong absorption based on -5 iHz was observed at 20 cl'. When 1g of product is decomposed using EtOH-Li solution, 990jll! Hydrogen gas (20"C) was generated. This was more than 0, which was almost the same as the theoretical amount of 998 d, so it was identified as having the structure of .

Elemental analysis (unit %) Theoretical value C49,92H11,17St 38.91 Analytical value C50,03N 11.24 Example 3 After adding 50 g of vinylsilane in Example 1, it was reacted at room temperature for 3 hours, and then 20 g of styrene was added and further The reaction was allowed to proceed for 2 hours. The same post-treatment as in Example 1 was carried out to obtain white powder 2.
6g was obtained.

According to GPC analysis, the molecular weight is 65,000, M, /
The composition value of the vinylsilane determined by zero elemental analysis was 23% by weight, which was M, -1,1.

Example 4 The same procedure as in Example 1 was carried out except that 13 g of vinyldisilane (H*C-Cl-3ilhSilLd) was used instead of vinylsilane, and all other conditions were the same. As a result, 2.3 g of white powder was obtained.

According to GPC analysis, the molecular weight is 6000, and Mw/M
It was s −1,1.

2120 cm-', 92 in the infrared absorption spectrum
Strong absorption based on -SiH3 was observed at 0ell. When 1 g of the product was decomposed using an EtOH-Li solution, hydrogen gas (20°C) of 1358Id was generated. This was almost in agreement with the theoretical amount of 13611d. If the result is 0 or more, this can be identified as having the structure.

Elemental analysis (unit %) Theoretical value C27,22H9,14St 63.65 Analytical value C27,92H9,03 Effects of the invention The present invention originates from the discovery that α-olefin containing a silyl group undergoes anionic polymerization. According to the present invention, it is possible to produce a novel industrially useful silicon-containing polymer. Specifically, the main features of the present invention are an inexpensive polymer and an economical polymerization method, and the resulting polymer, especially the specific physical properties and reactivity of the silyl group, has various functions (
For example, especially ceramics (Si
C) prepolymers, modifiers for various polymers, raw materials for IPN, surface treatment agents, etc. In particular, by utilizing the reactivity of silyl groups, conventional polymers such as polystyrene, polybutadiene, and polymethyl methacrylate can be crosslinked.
It can provide functions such as foaming properties and reactivity with other monomers or polymers, making it a great contribution to the creation of new highly functional materials.

As described above, the method for producing a silicon-containing polymer of the present invention has extremely great industrial significance.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1 General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, m is 0 or a positive integer from 1 to 20, and n is 1
, 2 or 3, R^1 is hydrogen, an alkyl group, an aryl group, or a halogen, R^2 is an alkylene group or a phenylene group, and R^1 and R^2 are COOH, NH_
2. It may contain functional groups such as Cl and OH. ) A method for producing a silicon-containing polymer, which comprises anionically polymerizing a silicon compound represented by: 2. A method for producing a silicon-containing polymer, which comprises anionically copolymerizing the silicon compound according to claim 1 and an unsaturated hydrocarbon having at least one carbon-carbon double bond in the molecule. 3. The method according to claim 2, wherein the unsaturated hydrocarbon is a compound having a carbon-carbon double bond at its terminal.