JPH0725843B2 - Silicon-containing polymer compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) (However, when n is 1 and m is a positive integer of 5 to 20, or n is 2 or 3 and m is a positive integer of 0 or 1 to 20,
R ¹ is hydrogen, an alkyl group, an aryl group or halogen, and when n is 1 and m is 0 or a positive integer of 1 to 4, R ^{1 is}
Is an alkyl group, an aryl group or halogen. R ² is an alkylene group or a phenylene group, and R ¹ and R ²
May contain functional groups such as COOH, NH ₂ , Cl and OH. ) Relating to a silicon-containing polymer compound containing a repeating unit represented by (However, when n is 1 and m is a positive integer of 5 to 20, or n is 2 or 3 and m is a positive integer of 0 or 1 to 20,
R ¹ is hydrogen, an alkyl group, an aryl group or halogen, and when n is 1 and m is 0 or a positive integer of 1 to 4, R ^{1 is}
Is an alkyl group, an aryl group or halogen. R ² is an alkylene group or a phenylene group, and R ¹ and R ²
May contain functional groups such as COOH, NH ₂ , Cl and OH. ) And a silicon-containing polymer compound containing a repeating structural unit represented by

(Prior Art) Silicones (organopolysiloxanes) are currently the majority of industrial applications of polymers containing silicon.

The raw material used for this is alkylchlorosilanes, especially dimethyldichlorosilane, produced by the reaction of metallic silicon and halogenated hydrocarbons, the so-called direct method.
Except for silicone, there are few practical examples of silicon-containing polymers. It has been known. The polymer (a) is produced in a solvent such as xylene as shown in the following formula.

The same applies to the polymer (b). Polymer (a) is insoluble and infusible, while polymer (b) is solvent soluble and thermoplastic.

The polymer (c) is obtained by thermally decomposing the polymer (a) under high temperature and high pressure, and is soluble in a solvent and thermoplastic. Polymers (a), (b) and (c) are used for ceramics binders, and polymers (b) and (c) are used for ceramics (SiC) precursors, especially for ceramics (SiC) fibers. (Nippon Carbon Co., Ltd., product name "Nicalon").

However, for example, the production of the above-mentioned polymers (a), (b) and (c) using conventional alkylchlorosilanes as a raw material is carried out in a chloro system, and there is a concern that the equipment may be corroded and sodium may be generated. The process is also very complicated, such as using metal. The polymer (d) is a vinylsilane polymer, and a copolymer with ethylene is used as a water-crosslinkable polyethylene in a large amount for coating electric wires.

Alkenyl silanes are rarely used in polymers, and allylsilane (C
Only the polymerizing agent (coordinating anionic polymerization) of H ₂ = CH-CH ₂ -SiH ₃ ) is seen (Journal of Polymer Science, Vol31, No.12).
2,181 (1958), Italian patent 606018).

(Problems to be Solved by the Invention) An object of the present invention is to provide a novel silicon-containing polymer compound excellent in functionality and a method for producing the same, which does not use a metal such as sodium and has no fear of corrosion due to chlorine. Is to provide.

(Means for Solving the Problems) As a result of intensive studies for solving the above problems, the present inventors have found that the problems of the present invention can be solved by using a specific silicon compound, and finally the present invention The invention was completed.

Hereinafter, the present invention will be described in detail.

The present invention has the general formula (However, when n is 1 and m is a positive integer of 5 to 20, or n is 2 or 3 and m is a positive integer of 0 or 1 to 20,
R ¹ is hydrogen, an alkyl group, an aryl group or halogen, and when n is 1 and m is 0 or a positive integer of 1 to 4, R ^{1 is}
Is an alkyl group, an aryl group or halogen. R ² is an alkylene group or a phenylene group, and R ¹ and R ²
May contain functional groups such as COOH, NH ₂ , Cl and OH. The present invention provides a silicon-containing polymer compound comprising a repeating structural unit represented by the formula (1) or a silicon-containing polymer compound containing the repeating structural unit.

In particular, And a silicon-containing polymer compound composed of repeating structural units such as the above, or a silicon-containing polymer compound containing these repeating structural units. These repeating structural units are 2
It is also possible to include more than one species.

Next, a method for producing a silicon-containing polymer compound according to the present invention will be described.

The silicon-containing polymer compound according to the present invention has the general formula It can be obtained by homopolymerization of the silicon-containing α-olefin represented by or copolymerization of the silicon-containing α-olefin and α-olefin.

The silicon-containing α-olefin can be produced by various methods, for example, a method of reducing chlorosilane with LiAlH ₄ or the like can be adopted, but the present inventors have already proposed separately (Japanese Patent Application Nos. 62-88871 and 62-8671). -89888 and 62-307492), a method of using SiH ₄ , Si ₂ H ₆ or Si ₃ H ₈ as a raw material is the most preferable and economical method. In particular Is.

The reaction can be carried out using heat, light, radical initiators or transition metal catalysts.

The same applies to Si ₂ H ₆ and Si ₃ H ₈ .

SiH ₄ , Si ₂ H ₆ , and Si ₃ H ₈ used as raw materials have been mass-produced as semiconductor gas with the recent remarkable development of the semiconductor industry, and have recently become industrially available at low cost. Is.

On the other hand, as the α-olefin used in the copolymer,
For example, ethylene, propylene, butene-1, isobutylene, butadiene, isoprene, styrene, vinyl chloride, vinylidene chloride, vinyl fluoride, ethylene tetrafluoride, vinyl ether, acrylic ester, methyl methacrylate, vinyl acetate, acrylonitrile, nitro. Examples include ethylene.

The method for polymerizing the silicon-containing α-olefin is not particularly limited, and various methods such as coordination anion polymerization, radical polymerization and ionic polymerization can be adopted. That is, Ziegler-Natta type catalysts (catalysts composed of transition metal salts such as titanium halides, alkoxy titanium, vanadium halides, magnesium oxyhalides, zirconium halides and alkylated aluminum, and these transition metal salts are halogenated. A catalyst composed of alkylaluminum supported on a carrier having magnesium, magnesium oxide, magnesium oxyhalide, silica, alumina, etc. as a main component), a catalyst in which CrO ₃ is supported on SiO ₂ -Al ₂ O ₃ , MOO ₃ is attached to γ-Al ₂ O ₃ , LiAlH ₄ , NaH,
Catalyst reduced with H ₂ , CO, Cp ₂ Zr (CH ₃ ) ₂ or Cp ₂ Ti
Polymerization using a catalyst composed of Cl ₂ (where Cp is cyclopentadienyl) and an alkylaluminoxane (for example, JP-A-58-19309); metal oxides (CrO ₃ , SiO ₂ , Al ₂ O ₃₎
Etc.), hydrogen acid (H ₂ SO ₄ , H ₃ PO ₄ , HClO ₄ , HCl, etc.), Lewis acid (BF ₃ , AlCl ₃ , FeCl ₃ , SnCl _4, etc.) Cationic polymerization method; alkyl metal (Li , Na, K, etc.), alkyl alkali (C ₂ H ₅ Na, sodium naphthalene, (C ₂ H ₅ ).
₃ Al, C ₄ H ₉ Li, C ₆ H ₅ Li, etc.), hydroxide (NaOH, KOH, etc.) catalyst for anionic polymerization; heat, light, radiation, electricity or hydrogen peroxide, ammonium persulfate, peroxide Examples include radical polymerization using a catalyst such as benzoyl oxide, cumene peroxide, cyclohexane peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, methyl ethyl ketone peroxide, and azobisisobutyronitrile. .

The mode of polymerization is not particularly limited and may be either gas phase or liquid phase, and bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like can be adopted. The reaction temperature and the reaction pressure vary depending on the polymerization mode and the reaction monomer, but the reaction temperature is 0 to 400.
C., preferably 20 to 200.degree. C., and the reaction pressure is preferably high pressure in equilibrium, and is normal pressure to 1000 atmospheric pressure. It is also possible to carry out the polymerization using a solvent such as benzene, toluene, xylene, pentane, dimethylformamide, chloroform and water. In addition, various additives such as a molecular weight modifier may be used.

Further, in the case of the copolymerization of silicon-containing α-olefin and α-olefin, there is no particular limitation on the monomer composition and the polymerization mode, and various modes such as random, alternating, block and graft can be adopted.

The silicon-containing polymer in the present invention can be easily obtained from the inexpensive monomer as described above. Using the above-mentioned conventional alkylchlorosilane as a raw material, for example, a polymer having the following repeating structural unit, In comparison with the above, the production of the silicon-containing polymer compound in the present invention can be carried out in a non-chlorine system, there is no fear of corrosion, and the process becomes extremely simple. From the above, it seems that the silicon-containing polymer compound according to the present invention can be manufactured at a lower cost in the future.

Further, the silicon-containing polymer compound of the present invention is not only easy to manufacture, but also controls its processability (flowability of melt, solvent solubility), monomer composition of polymer, molecular weight, stereoregularity. It can be easily changed. Furthermore, the silyl groups present in the silicon-containing polymer of the present invention are relatively stable and do not easily oxidize at room temperature even in air, and the silyl group content is about 100%.
It only oxidizes at temperatures as high as ~ 200 ° C.

Since the silicon-containing polymer compound according to the present invention is soluble in a solution and is thermoplastic, it has great industrial utility and can be expected to have many uses. For example, ceramics (SiC)
Prepolymers, binders for ceramics, surface treatment agents, water repellents, IPN raw materials, semiconductors, photoresists, etc. The function of these polymer compounds is to utilize the high reactivity of the Si—H bond and the conductivity and photodegradability of the Si—Si bond. Particularly, the function preferably used in the present invention lies in the reactivity of silyl groups, and for example, in a polymer such as polystyrene, polyvinyl chloride, polymethacrylic acid, a silicon-containing repeating structural unit partially related to the present invention. It is possible to incorporate interesting functions into conventional polymers, such as being able to impart crosslinkability, foamability, reactivity with other monomers or polymers, by incorporating in the form of copolymers. That is, the present invention greatly contributes to the creation of a new high-performance material that has never existed before.

Examples Hereinafter, the present invention will be described with reference to Examples.

Example 1 (1) Synthesis of Polymerizable Monomer SiH ₄ and 1,7-octadiene were reacted using Pt (PΦ ₃ ) ₄ as a catalyst to obtain CH ₂ ═CHCH _{2 6} SiH ₃ .

(2) Preparation of catalyst component A vibration mill equipped with a grinding pot having an inner volume of 600 ml containing 80 steel balls having a diameter of 12 mm was prepared.

To this pot, add 20 g of commercially available MgCl ₂ , 2 ml of methyl paratoluate, 2 ml of CCl ₄ and 1 ml of ethyl silicate, and add 20 ml at room temperature.
Crushed for hours. Then add 10 of this crushed material to a 200 ml flask.
g, TiCl ₄ (50 ml) and n-heptane (100 ml) were added, and the reaction was carried out at 80 ° C. for 2 hours under a nitrogen atmosphere. At room temperature, n-
Using 100 ml of heptane, washing by decantation was repeated 8 times to obtain a solid catalyst component slurry.
A part of this was sampled, and n-heptane was evaporated and analyzed. As a result, the catalyst component was found to be 1.5 wt% Ti, and about 20 wt%.
% Mg.

(3) Polymerization To a 500 ml autoclave, 80 g of CH ₂ ═CHCH _{2 6} SiH ₃ as a monomer, 240 ml of n-heptane, 2.0 g of the above-mentioned slurry catalyst as a solid component as a catalyst, and 8 ml of triisobutylaluminum were added to 70 ° C. And reacted for 3 hours. After the reaction was completed, unreacted monomers were purged to take out the contents, and the contents were put into methanol and then filtered to obtain 69 g of a white solid polymer. The polymer yield was 86%.

The following results were obtained for the obtained polymer.

The number average molecular weight of about 90000 (although in terms of polystyrene) Elemental analysis wt% Found C 67.13 H 12.92 Si 67.27 theory C 67.52 H 12.75 Si 67.52 IR ( KBr) 2150cm -1 (νSi-H), 920cm -1 (δSi-H ) NMR (100MHz) 0.80ppm (- CH 2 SiH 3), 1.00~1.60ppm (-C H =, - CH 2 -), including LiOC ₂ H ₅ and 3.50ppm (-Si H ₃₎ the polymer 0.5g When it was decomposed with a C ₂ H ₅ OH solution and the amount of hydrogen gas generated was quantified, it was 229 Nml (theoretical value 23
6 Nml).

The polymer structure obtained as a result of the above is It was found to consist of repeating structural units.

Example 2 SiH ₄ and isoprene were used as catalysts and platinum was added to activated carbon at 0.5 w.
React using a t% supported Got

As a monomer in a 500 ml autoclave An experiment was conducted in the same manner as in Example 1 except that 80 g was used. 72 g of the obtained white solid polymer (polymer yield 90%)
Met.

The following results were obtained for the obtained polymer.

Number average molecular weight Approximately 120000 (converted to polystyrene) Elemental analysis wt% Measured value C 59.83 H 12.33 Si 27.91 Theoretical value C 59.91 H 12.07 Si 28.02 IR (KBr) 2150cm ^-1 (νSi-H), 920cm ^-1 (δSi-H ) NMR (100MHz) 0.80~0.90ppm (- CH 3, - CH 2 SiH 3), 1.00~1.60ppm (- CH =, - CH 2 -), LiOC the 3.50ppm (-S iH ₃₎ the above compound 0.5g _It was decomposed with a C ₂ H ₅ OH solution containing ₂ H ₅ and the amount of hydrogen gas generated was quantified.
335 Nml).

The structure of the polymer obtained above is It was found to consist of repeating structural units.

Example 3 Si ₂ H ₆ and acetylene were used as catalysts and platinum was added to activated carbon at 0.6.
CH ₂ = CH-Si ₂ H ₅ was obtained by carrying out the reaction using the one supported by wt%.

In a 100 ml autoclave, the above monomers (CH ₂ = CH
-Si ₂ H ₅ ) 17 g, benzoyl peroxide as a polymerization initiator
1.0 g was charged and reacted at 80 ° C. for 8 hours.

After the reaction was completed, the autoclave was opened and the viscous product 15
g (yield 88%) was obtained. The viscosity of this product is 2.5 cp at 20 ° C
Met.

The following results were obtained for the obtained polymer.

Number average molecular weight Approximately 3000 (however converted to polystyrene) Elemental analysis wt% Measured value C 26.81 H 10.31 Si 62.69 Theoretical value C 26.91 H 10.16 Si 62.93 IR (KBr) 2150cm ^-1 (νSi-H), 920cm ^-1 (δSi-H ) NMR (100MHz) 0.90~1.40ppm (- CH 2, - CH =), 3.30~3.60ppm (- Si 2 H 5), decomposing the compound 0.5g in C ₂ H ₅ OH solution containing LiOC ₂ H ₅ Then, when the amount of hydrogen gas generated was quantified, it was 609 Nml (theoretical value
627 Nml).

The structure of the polymer obtained above is It was found to consist of repeating structural units.

Example 4 As a monomer in a 500 ml autoclave 70 g, propylene 27 g, n-heptane 240 ml, TiCl ₃ type catalyst (manufactured by Toho Tintan Co., Ltd.) 2 g and triisobutylaluminum 7 ml were added, and the reaction was carried out at 70 ° C. for 3 hours. After the reaction was completed, the content of the unreacted monomer was purged, the content was taken out, put into methanol, and filtered to obtain 68 g of a white solid polymer.

The following results were obtained for the obtained polymer.

Number average molecular weight Approx. 20000 (converted to polystyrene) Elemental analysis wt% Measured value C 75.98 H 13.64 Si 10.08 Theoretical value C 76.25 H 13.53 Si 10.22 IR (KBr) 2150cm ^-1 (νSi-H), 920cm ^-1 (δSi-H ) NMR (100MHz) 0.80~0.90ppm (- CH 2 -SiH 3, -C H 3), 1.00~1.60ppm (- CH 2 -, - CH =), 3.50ppm (-S iH 3) the polymer 0.5g Was decomposed with a C ₂ H ₅ OH solution containing LiOC ₂ H ₅ and the amount of hydrogen gas generated was quantified and found to be 119 Nml.

The polymer obtained as a result of the above It was a copolymer of propylene and propylene, and the composition ratio of the former monomer was 62 wt%.

(Effect of the Invention) The present invention is a silyl group such _{(-SiH 3, -Si 2 H 5} , -Si 3 H 7) provides industrial containing useful novel silicon-containing polymer compound and their preparation It is a thing. Specifically, the silicon-containing polymer compound according to the present invention can be produced by an economical polymerization method using an inexpensive monomer, and the obtained polymer, especially the specific physical properties and reactivity of the cysyl group, Various functions (uses) can be expected. Examples include ceramics (SiC) prepolymers, modifiers of various polymers, IPN raw materials, and surface treatment agents. In particular, by utilizing the reactivity of silyl groups, it is possible to crosslink, foam, and react with other monomers or polymers to conventional polymers such as polystyrene, polyvinyl chloride, polybutadiene, and polymethylmethacrylate. It is possible to add functions and contributes greatly to the creation of new highly functional materials.

As described above, the industrial meaning of the method for producing a silicon-containing polymer of the present invention is extremely large.

Claims (4)

[Claims] 1. A general formula (However, when n is 1 and m is a positive integer of 5 to 20, or n is 2 or 3 and m is a positive integer of 0 or 1 to 20,
R ¹ is hydrogen, an alkyl group, an aryl group or halogen, and when n is 1 and m is 0 or a positive integer of 1 to 4, R ^{1 is}
Is an alkyl group, an aryl group or halogen. R ² is an alkylene group or a phenylene group, and R ¹ and R ²
May contain functional groups such as COOH, NH ₂ , Cl and OH. ) A silicon-containing polymer compound comprising a repeating structural unit represented by: 2. General formula (However, when n is 1 and m is a positive integer of 5 to 20, or n is 2 or 3 and m is a positive integer of 0 or 1 to 20,
R ¹ is hydrogen, an alkyl group, an aryl group or halogen, and when n is 1 and m is 0 or a positive integer of 1 to 4, R ^{1 is}
Is an alkyl group, an aryl group or halogen. R ² is an alkylene group or a phenylene group, and R ¹ and R ²
May contain functional groups such as COOH, NH ₂ , Cl and OH. ) A silicon compound represented by
Radical polymerization or cation polymerization is carried out, The manufacturing method of the silicon-containing polymer compound of Claim 1 characterized by the above-mentioned. 3. A general formula in a polymer chain (However, when n is 1 and m is a positive integer of 5 to 20, or n is 2 or 3 and m is a positive integer of 0 or 1 to 20,
R ¹ is hydrogen, an alkyl group, an aryl group or halogen, and when n is 1 and m is 0 or a positive integer of 1 to 4, R ^{1 is}
Is an alkyl group, an aryl group or halogen. R ² is an alkylene group or a phenylene group, and R ¹ and R ²
May contain functional groups such as COOH, NH ₂ , Cl and OH. ) A silicon-containing polymer compound containing a repeating structural unit represented by: 4. A general formula (However, when n is 1 and m is a positive integer of 5 to 20, or n is 2 or 3 and m is a positive integer of 0 or 1 to 20,
R ¹ is hydrogen, an alkyl group, an aryl group or halogen, and when n is 1 and m is 0 or a positive integer of 1 to 4, R ^{1 is}
Is an alkyl group, an aryl group or halogen. R ² is an alkylene group or a phenylene group, and R ¹ and R ²
May contain functional groups such as COOH, NH ₂ , Cl and OH. 4. The method for producing a silicon-containing polymer compound according to claim 3, wherein the silicon compound represented by the formula (4) is copolymerized with an α-olefin.