JPH0564962B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for producing a silicon-containing polymer. [Prior Art] Silicone (organopolysiloxane) is currently 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 method. There are few practical examples of silicon-containing polymers other than silicone, for example, It has been known. () is, as shown in the formula below,
Manufactured in a solvent such as xylene. The same applies to (). () is insoluble and infusible, while () is soluble in solvents and thermoplastic.
() is obtained by thermally decomposing () under high temperature and pressure, and is soluble in solvents and thermoplastic.
(), () and () are used as ceramic binders, and () and () are used as precursors of ceramics (SiC), especially ceramic (SiC) fibers (Nippon Carbon Co., Ltd., trade name “Nicalon”). () is a polymer of vinyl silane, and its copolymer with ethylene is used in large quantities as water-crosslinkable polyethylene for covering electric wires. Related to the present invention There are almost no examples of polymers such as TiCl ₄
Or allylsilane _{( CH2} =CH- _CH2-
There are only examples of polymerization of SiH ₃ ) and copolymerization of allylsilane with ethylene or propylene (Journal of Polymer Science, Vol. 31, No.
122, 181 (1958), Italian Patent 606018). However, in these catalyst systems, silyl groups (-
Due to the influence of SinH _2o+1 ), the polymerization of silicon-containing monomers is poor and the polymer yield is low. Furthermore, copolymerization with α-olefin is difficult. Further, there is a problem that crosslinking between molecular chains is likely to occur during the polymerization or post-treatment process due to the interaction between the silyl groups (-SinH _2o+1 ) and the catalyst. On the other hand, the present inventors have found that when the polymer of the silicon compound according to the present invention using the above-mentioned catalyst system is fired at high temperature, the conversion yield to ceramics (SiC) is high, and it is very promising as a prepolymer for ceramics. have already proposed (for example, Japanese Patent Application No. 62-015929 (Japanese Patent Publication No. 1-239010), Patent Application No. 62-031514).
(Unexamined Japanese Patent Publication No. 1-239011)). The silyl groups in this polymer have excellent reactivity, C=C, C=0, NH, O-H,

[Problem to be solved by the invention]

An object of the present invention is to provide a novel method for producing highly useful silicon-containing polymers as described above. [Means and effects for solving the problem] As a result of intensive studies to achieve the above-mentioned problem, the present inventors have found that by copolymerizing a silicon compound and an α-olefin in the presence of a specific catalyst, The present inventors have found that the object of the present invention can be achieved and have completed the present invention. That is, the present invention provides a composition (A) in which a titanium compound is supported on a composition containing magnesium halide, and a composition having the general formula AIR ¹ _o
X _3-o (where R ¹ is an alkyl group having 1 to 12 carbon atoms,
is a halogen atom, and n is 1≦n≦3). (However, m is 0 or a positive integer from 1 to 20, n
is 1, 2 or 3, R ² is hydrogen, an alkyl group, an aryl group or a halogen, R ³ is an alkylene group or a phenylene group, and R ² and R ³ are
It may contain functional groups such as COOH, NH ₂ , CI, and OH. ) and a silicon compound represented by α-
This is a method for producing a silicon-containing polymer, characterized by copolymerizing it with an olefin, and furthermore, it is a method for producing a silicon-containing polymer as described above, which is carried out in the presence of an electron-donating compound. The present invention will be explained in detail below. The silicon compound used for polymerization in the present invention has the general formula where m is 0 or 1 to
A positive integer of 20, n being 1, 2 or 3. ^R2
is hydrogen, an alkyl group, an aryl group, or a halogen, such as H, CH ₃ , C ₂ H ₅ , i-
C ₃ H ₇ , Ф (Ф represents a phenyl group. The same applies hereinafter),
Examples include ФCH ₃ , CH ₂ Ф, F, Cl, Br, etc.
The smaller the number of carbon atoms, the more preferable it is, and hydrogen is most preferable. R ³ is an alkylene group or a phenylene group, such as CH ₂ , Ф (Ф represents a phenylene group; the same applies hereinafter), CH ₂ Ф, and the like. Note that R ₂ and R ³ may contain a functional group such as COOH, NH ₂ , Cl, or OH. 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. HSiCl ₃ +ClH ₂ C−(CH ₂ ) _o −CH=CH ₂ −HCl ――――→ 600℃ Cl ₃ Si(CH ₂ ) _o+1 −CH=CH ₂ LiAlH ₄ ―――――――― ――――――――――――――→ H ₃ Si (CH ₂ ) _o+1 CH=CH ₂ HSiCl ₃ +H ₃ C (CH ₂ ) _o −CH=CH ₂ BCl ₃ , 300℃ ― ――――――――――→ −H ₂ Cl ₃ Si (CH ₂ ) _o+1 CH＝CH ₂ LiAlH ₄ ―――――――――――――――――――― ―→ H ₃ Si(CH ₂ ) _o+1 CH=CH ₂ SiH ₄ +CH ₂ =CH(CH ₂ ) _o CH=CH ₂ Pt, 200℃ ―――――――――――――― ――――――――→ H ₃ Si (CH ₂ ) _o+2 CH=CH ₂ SiH ₄ +CH≡CHPt, 200℃ ――――――――→ H ₃ SiCH=CH ₂ SiH ₄ +ClH ₂ C −(CH ₂ ) _o −CH=CH ₂ −HCl ――――――――――――――――――――→ H ₃ Si(CH ₂ ) _o+1 CH=CH ₂ SiH ₄ +H ₃ C (CH ₂ ) _o CH=CH ₂ −H ₂ ――――――――――――――――――――――→ H ₃ Si (CH ₂ ) _o+1 CH=CH ₂ Among these, SiH ₄ is used as a raw material. In particular, is a hydrosilylation reaction that uses transition metals as catalysts, and is easily targeted.
₃ SiH units (for example, Japanese Patent Application No. 1988-88871
238590), 62-89888 (JP-A-1-238591), 62
-307492 (JP-A-1-287090)) can be obtained. However, SiH ₄ is
In recent years, demand for polysilicon and amorphous silicon has expanded, and silicon has become manufactured cheaply and in large quantities, and it is a new silicon raw material that is expected to continue to grow in this trend. The same can be said for Si ₂ H ₆ and Si ₃ H ₈ . Two or more of these silicon compounds can also be used simultaneously. Further, as separately proposed by the present inventors, the silicon compound used in the present invention can also be radically polymerized. (Patent application No. 62-97417 (Unexamined Japanese Patent Publication No. 1997-236206), No. 62-98698
(Unexamined Japanese Patent Publication No. 1-236212)). On the other hand, in the present invention, the α-olefin used for copolymerization with a silicon compound has the general formula (However, R ⁴ and R ⁵ are hydrogen, alkyl group, halogen, aryl group, alkenyl group, alkoxy group, nitro group, cyano group, carboalkoxy group, or acetoxy group, and COOH, NH ₂ , CI,
It may contain a functional group such as OH. ), and specific examples include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-
These include pentene-1, butadiene, isoprene, and styrene. Next, the copolymerization method in the present invention will be explained. The present invention is a catalyst in which a titanium compound is supported on a composition containing magnesium halide as a catalyst (catalyst
It is characterized by the use of component (A). Magnesium halide in the present invention is
Contains halogen and magnesium in the molecule.
Examples include magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride, and magnesium oxyhalide, and among these, magnesium chloride is most preferred. There are no particular limitations on the method for producing these magnesium halides, such as Mg(OR ⁶ ) (OR ⁷ ), Mg(OR)X (where R ⁶ and R ⁷ are an alkyl group, an aryl group, or a derivative thereof, A method of halogenating a magnesium compound such as (X is a halogen atom) can also be adopted. On the other hand, a titanium compound is a trivalent or tetravalent titanium compound, and typical examples include titanium trichloride, titanium tetrachloride, titanium tetraodoride, titanium tetraiodide, methoxytitanium trichloride, dimethoxytitanium dichloride, and triethoxytitanium. Examples include titanium chloride. Among them, chlorine-containing titanium compounds such as titanium tetrachloride are preferred. The method of supporting a titanium compound on magnesium halide is not particularly limited in the present invention, and is already known (Ger. 2000586,
Ger. 1939074, Japanese Patent Publication No. 43-13050, Polymer Journal, 12 , 603 (1980), etc.), for example, the following method can be suitably employed. A method of co-pulverizing magnesium halide and titanium compound using a pole mill, etc. A method of injecting and supporting magnesium halide powder into a solution of benzene, toluene, heptane, hexane, etc. containing a titanium compound. In the present invention, the magnesium halide and titanium compound are essential components, but it is also possible to include a third component such as the following electron-donating compounds and halogenated hydrocarbons such as carbon tetrachloride and chloroform. It is preferable in terms of polymer yield and polymer physical properties. According to the method, the desired catalyst can be easily obtained by allowing these third components to coexist in the system. The electron-donating compound is an electron-donating compound having O, N, P, S, or Si, and includes, for example, ester, ether, ketone, aldehyde, amine, amide, nitrile, thioester, and thioether. Examples of esters include organic acid esters and inorganic acid esters such as carbonic acid, sulfuric acid, phosphoric acid, phosphorous acid, and silicic acid. Examples of organic acid esters include methyl formate,
Saturated or unsaturated aliphatic organic acid esters such as n-butyl formate, allyl acetate, methyl acrylate, methyl chloroacetate, methyl benzoate, n- or i-propyl benzoate, cyclohexyl benzoate, p-oxybenzoic acid Methyl, cyclohexyl p-oxybenzoate, methyl anisate, methyl p-ethoxybenzoate, ethyl p-toluate,
Examples include aromatic carboxylic acid esters such as ethyl p-toluate, phenyl p-toluate, ethyl p-aminobenzoate, and dimethyl terephthalate, and alicyclic organic acid esters such as methyl cyclohexanecarboxylate. Typical examples of inorganic acid esters include trimethylphosphite, triphenylphosphite, diethylbenzylphosphonate, dipropyl sulfate, isoamyl sulfite, and alkoxysilanes and alkylalkoxysilanes such as ethyl silicate and methyl silicate. . Ethers include diethyl ether, dibutyl ether, diphenyl ether, etc., ketones include methyl ethyl ketone, aldehydes include acetaldehyde, benzaldehyde, etc., and amines include n-propylamine,
Examples of the nitrile include aniline, pentanedinitrile and the like, amides such as propanamide, and thioethers such as allylbenzyl sulfite. These electron-donating compounds can be used alone or in combination of two or more, and organic acid esters and ethers having an aromatic group or a group derived therefrom are particularly preferred. In the above catalyst components, the content of magnesium halide is 50wt% or more, preferably
It is 70wt% or more. Further, the amount of Ti supported is 10 wt% or less, preferably 5 wt% or less, and more preferably in the range of 0.5 to 2 wt%. Next, the organoaluminum compound (catalyst (B) component) used during polymerization in the present invention will be explained. The organoaluminum compound used as component (B) has the general formula AIR ¹ _o X _3-o (where R ¹ is a carbon number of 1 to 12
an alkyl group, X is a halogen atom, n is 1≦n≦
3), such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-iso-butylaluminum, tri-n-hexylaluminum, diethylaluminum monochloride, di-iso-butylaluminum Monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminium monobromide, diethylaluminum monoiodide, diethylaluminum monofluoride, etc. are used singly or in combination of two or more. In addition to the above-mentioned components (A) and (B), electron-donating compounds such as those used in the catalyst (A) component, especially methyl benzoate, ethyl benzoate,
Methyl p-toluate, ethyl p-toluate,
Organic acid esters such as methyl anisate and ethyl anisate can also be used. The proportions used of (A), (B) and electron-donating compounds can vary within a wide range. Generally, the number of moles of titanium atoms in component (A) is 1 to 1 mole of component (B).
Preferably it is in the range of 500 moles. On the other hand, for the electron-donating compound, 5 mol or less per 1 mol of the organoaluminum compound used as component (B),
Preferably it is 0.01 to 1.5 mol. For the polymerization reaction, methods and conditions commonly used in conventional techniques can be employed. The polymerization temperature at that time is in the range of 20 to 100°C, preferably 40 to 90°C, and the polymerization pressure is usually in the range of 1 to 100 kg/cm ² abs, preferably 1 to 50 kg/cm ² abs. In general, aliphatic, alicyclic, aromatic hydrocarbons or mixtures thereof can be used as a solvent in the polymerization reaction, such as propane, butane, pentane, hexane, heptane, cyclohexane, benzene, etc., and mixtures thereof. used. The polymerization can also be carried out by a bulk polymerization method using the liquid monomer itself as a solvent or by a so-called gas phase polymerization method in which a gaseous monomer and a catalyst are brought into contact with each other under substantially no solvent. The molecular weight of the polymer produced in the method of the present invention varies depending on the reaction mode, catalyst system, and polymerization conditions, but can be controlled by adding hydrogen, alkyl halides, dialkyl zinc, etc. as necessary. . In the present invention, the structure of the polymer is not particularly limited, and the repeating units, molecular weight and its distribution, degree of crosslinking, etc. are determined by the type of monomer,
It can vary depending on the polymerization mode. The most typical polymer structures include, for example, (However, m is 0 or a positive integer from 1 to 20, n
is 1, 2 or 3, R ² is hydrogen, an alkyl group, an aryl group or a halogen, R ³ is an alkylene group or a phenylene group, and R ² and R ³ are
It may contain functional groups such as COOH, NH ₂ , CI, and OH. Furthermore, R ⁴ and R ⁵ are hydrogen, an alkyl group, a halogen, an aryl group, an alkenyl group, an alkoxy group, a nitro group, a cyano group, a carbalkoxy group, or an acetoxy group, and COOH,
It may contain functional groups such as NH ₂ , 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 1,000,000,
Preferably, it is about 200 to 1,000,000 in terms of moldability of the polymer and solubility in solvents. The composition ratio of the monomers is 0.00001 to 100000 parts by weight of α-olefin to 1 part by weight of the silicon compound;
The amount is preferably 0.001 to 1000 parts by weight, and can be arbitrarily selected depending on the intended use of the copolymer. In the present invention, silicon compounds and α-olefins are essential components, and two or more of each of these can be used, and other polymerizable monomers such as norbornene can also be used simultaneously. The silicon-containing polymer in the present invention can be easily obtained from inexpensive monomers as described above. For example, polymers made from the conventional alkylchlorosilane described above and having the following repeating structural units, for example, In comparison, 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 can be produced at a lower cost than before. 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 SiH ₃ groups present in the silicon-containing polymer of the present invention are relatively stable and are not easily oxidized even in air at room temperature, and are only oxidized at high temperatures of about 100 to 200°C. Only. Since the silicon-containing polymer according to the present invention is soluble in solvents and thermoplastic, it has great industrial utility and can be expected to have many uses. Examples include prepolymers for ceramics (SiC), binders for ceramics, surface treatment agents, water repellents, raw materials for IPN, semiconductors, and photoresists. The functions of these polymers are the high reactivity of Si-H bonds and
This utilizes the electrical conductivity and photodegradability of Si-Si bonds. In particular, the function suitably utilized in the present invention lies in the reactivity of silyl groups (-SinH _2o+1 ),
For example, by incorporating some of the silicon compounds in the form of copolymerization into polymers such as polyethylene, polypropylene, polybutene, and polystyrene, it can impart crosslinking properties, foaming properties, and reactivity with other monomers or polymers. such as being able to
It is possible to incorporate interesting functionality into conventional polymers. In other words, the present invention greatly contributes to the creation of novel, highly functional materials that have never existed before. [Example] The present invention will be explained below using Examples. Example 1 (1) Preparation of solid catalyst component A vibratory mill equipped with a crushing pot having an internal volume of 600 ml and containing 80 steel balls with a diameter of 12 mm was prepared. To this pot were added 20 g of commercially available MgCl ₂ , 2 ml of methyl paratoluate, 2 ml of CCl ₄ and 1 ml of ethyl silicate, and the mixture was ground at room temperature for 20 hours. Next, add 10g of this crushed material to a 200ml flask.
50 ml of TiCl ₄ and 100 ml of n-heptane were added, and the reaction was carried out at 80° C. for 2 hours in a nitrogen atmosphere. Further, washing by decantation was repeated eight times using 100 ml of n-heptane at room temperature to obtain a solid catalyst component slurry (component (A) of the present invention). When we sampled a portion of this and evaporated n-heptane and analyzed it, we found that the external catalyst component was
It contained 1.5wt% Ti and 20wt% Mg. (2) Polymerization 74ml of vinylsilane in a 500ml autoclave
g, 14 g of propylene, 214 ml of n-heptane,
As a catalyst, 2.0 g of the above slurry catalyst as a solid component, 7 ml of triisobutylaluminum,
0.7 ml of methyl p-toluate was added, and reaction was carried out at 70°C for 3 hours (reaction pressure: 3 kg/cm ² G). After the reaction was completed, unreacted vinylsilane and propylene were purged, the contents were taken out, and filtered to obtain 38 g of a white powdery polymer. From elemental analysis values, the composition ratio of vinylsilane in the polymer was 78% by weight. Example 2 An experiment was conducted in the same manner as in Example 1, except that 10 g of vinylsilane and 102 g of propylene were used as monomers for polymerization. The yield of polymer was 85g. From the elemental analysis values, the composition ratio of vinylsilane in the polymer was 1.2% by weight. Example 3 An experiment was carried out in the same manner as in Example 1, except that 7 g of allylsilane and 97 g of propylene were used as monomers for polymerization. The yield of polymer was 69g. From the elemental analysis values, the composition ratio of acrylic silane in the polymer is
It was 3.1% by weight. Example 4 An experiment was carried out in the same manner as in Example 1, except that 13 g of vinylsilane and 109 g of ethylene were used as monomers for polymerization, and methyl p-toluate was not used. The yield of the polymer was 88g, and the composition ratio of vinylsilane in the polymer was 1.9% by weight based on elemental analysis.
It was hot. Comparative Example 1 An experiment was carried out in the same manner as in Example 1, except that 2 g of TiCl ₃ type catalyst (manufactured by Toho Titanium Co., Ltd.) and 7 ml of triisobutylaluminum were used as catalysts. The yield of the polymer was 11 g, and elemental analysis showed that the composition ratio of vinylsilane in the polymer was 37% by weight. [Effects of the Invention] The present invention provides a novel method for producing an industrially useful silicon-containing polymer. For more information,
The main features of the present invention are inexpensive monomers and an economical polymerization method, and various functions (applications) can be expected from the specific physical properties and reactivity of the obtained polymer, especially the silyl group. For example, prepolymers especially for ceramics (SiC), modifiers for various polymers,
Raw materials for IPN, surface treatment agents, etc. In particular, the reactivity of silyl groups can be used to impart functions such as crosslinkability, foamability, and reactivity with other monomers or polymers to conventional polymers such as polyethylene, polypropylene, polybutadiene, and polystyrene. This will greatly contribute to the creation of new highly functional materials.

Claims (1)

[Claims] 1. A composition containing a magnesium halide supporting a titanium compound (A), and a composition having the general formula AIR ¹ _o
In the presence of a catalyst consisting of an ^{organoaluminum} compound (B) represented _by formula (However, m is 0 or a positive integer from 1 to 20, n
is 1, 2 or 3, R ² is hydrogen, an alkyl group, an aryl group or a halogen, R ³ is an alkylene group or a phenylene group, and R ² and R ³ are
It may contain functional groups such as COOH, NH ₂ , CI, and OH. ) and a silicon compound represented by α-
A method for producing a silicon-containing polymer, which comprises copolymerizing a silicon-containing polymer with an olefin. 2. The method according to claim 1, which is carried out in the presence of an electron-donating compound.