JPH08109266A - Production of polydiarylsilmethylene - Google Patents

Abstract

PURPOSE: To produce a polydiarylsilmethylene having a desired structure under sufficiently controlled conditions without producing by-products. CONSTITUTION: A polydiarylsilmethylene is produced by subjecting a monomer component contg. at least one 1,1,3,3-tetraaryl-1,3-disilacyclobutane represented by the formula: (Ar2 SiCH2 )2 (wherein Ar is an arom. group optionally substd. by an org. or inorg. group or groups) to ring-opening polymn. in the presence of a catalyst selected from among a gold compd., a silver compd., metallic copper, a copper alloy, and a copper compd.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a silicon carbide polymer having carbon-silicon as a main chain skeleton.

[0002]

2. Description of the Related Art The synthesis of polysilmethylene having carbon-silicon as the main chain is known to be a method of condensation polymerization by dehalogenation of dichlorosilane and dichloromethylene, and ring-opening polymerization of disilacyclobutane. In condensation polymerization, not only silicon-carbon bonds are necessarily formed, but also carbon-carbon and silicon-silicon bonds are formed, and a polymer in which these bond units are randomly connected is formed. On the other hand, in ring-opening polymerization, the ring strain energy of the cyclic compound to be a monomer, and the steric effect due to the substituents of silicon atom and carbon atom,
Since the electronic effect governs the reactivity, the cyclic compounds that can be used for ring-opening polymerization are limited.

Although some cyclic compounds having a high strain energy are easily opened to give a polymer by simply heating, polymerization of the cyclic compound is generally carried out under the polymerization conditions such as the kind of catalyst used and the reaction temperature. It is known to be greatly affected by.

1,1,3,3-tetramethyl-1,3-
Disilacyclobutane gives a polymer having a molecular weight of hundreds of thousands or more when heated to 100 ° C. or higher, and 1,3-dimethyl-1,3-diphenylsilacyclobutane gives 190
It has been reported that the same polymerization occurs when heated above ℃ (N. Nametkin, V. Vdovin, V. Zavyalov, Akad. Nau
k SSSR, 162 (4), 824 (1965)).

It has been revealed that the above-mentioned disilacyclobutane compound easily undergoes ring-opening polymerization with an alkali metal salt which is a general anionic polymerization catalyst to produce an amorphous polymer (NS Nametkin, VM Vdovin, Buletin of the
Academy of Sciences of the USSR, Chemical Series
1092 (1974)), and platinum, rhodium, nickel, palladium and other hydrosilylation catalysts, as well as silver, copper,
It is known that halides such as mercury, indium and bismuth also cause ring-opening polymerization (VA Poletaev, V.
M. Vdovin, NS Nametkin, Akad. Nauk SSSR, 208
(5), 1112 (1973)).

1,1,3,3-tetraphenyl-1,3
-Disilacyclobutane is reported to give a crystalline polymer by ring-opening polymerization only after heating it to 180 ° C or more for a long time (N. Nametkin, V. Vdovin, V. Zavyalov, A.
kad. Nauk SSSR, 162 (4), 824 (1965)). Also, 1,
A mixture of 1,3,3-tetramethyl-1,3-disilacyclobutane and 1,1,3,3-tetraphenyl-1,3-disilacyclobutane is heated and the composition ratio of each monomer (molar ratio ) Is a copolymer of 9/1 and has a glass transition temperature of −
It is reported that a polymer having a temperature of 80 ° C. was obtained (N. Nametkin,
V. Vdovin, AS Zelenaya, Akad. Nauk SSSR (1966)
170 (5) 1088.).

Polysilmethylene having silicon as a main chain constituent atom to which a phenyl group having a substituent is bonded is 1,1,
Unless the ring-opening polymerization of 3,3-tetraaryl-1,3-disilacyclobutane is performed, it is extremely difficult to generate a polymer by condensation polymerization or a polymer reaction. Polysilmethylene having an aryl group in which a silicon atom has a substituent is important from the viewpoint of improving physical properties and high functionality, but a method for producing such a polymer is not known. It cannot be said that a polymerization method capable of controlling the molecular weight and the molecular weight distribution of polydiarylsilmethylene has been sufficiently disclosed. Further, in order to improve the demerit that occurs because polydiphenylsilmethylene is a crystalline polymer having a melting point of about 350 ° C. and a decomposition point of about 370 ° C., a copolymer giving a higher glass transition temperature and its production. Development of methods is desired.

[0008]

Generally, in polymerization,
Controlling the concentration of the polymerization initiating species is controlling the molecular weight and molecular weight distribution of the produced polymer, which is extremely important in designing the polymer material. From the viewpoint of structural control, the non-catalytic thermal polymerization in which the polymerization initiation species, the concentration of the initiation species and the initiation mechanism are not specified is not a preferable method.

It is an object of the present invention to provide a method for producing polydiarylsilmethylene of the desired structure under well controlled conditions. Another object of the present invention is to provide a method for producing a polydiarylsilmethylene by polymerizing polysilmethylene having an aromatic group such as a phenyl group with or without a substituent, and copolymerizing the same.

[0010]

The present invention has achieved the above object by using a specific transition metal catalyst. That is, the present invention provides the following general formula (I) (Ar ₂ SiCH ₂ ) ₂ (I) (wherein Ar may be different from each other, and an aromatic group with or without an organic or inorganic substituent) Wherein the organic substituent contains or does not contain a heteroatom), and a monomer containing one or more kinds of 1,1,3,3-tetraaryl-1,3-disilacyclobutane is represented by gold. A method for producing polydiarylsilmethylene, which comprises subjecting ring-opening polymerization to the presence of a catalyst selected from the group consisting of a compound, a silver compound, metallic copper, a copper alloy and a copper compound.

In the present invention, Ar is an aromatic group having or not having an organic or inorganic substituent, and the organic substituent has or does not contain a hetero atom. Representative examples thereof include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a biphenyl group and a naphthyl group. Examples of the aromatic group having an inorganic or organic substituent containing a hetero atom include a fluorophenyl group, a chlorophenyl group and a bromophenyl group such as fluorine,
Those containing halogen such as chlorine and bromine, nitrophenyl groups, nitrosophenyl groups, aminophenyl groups, aryl groups represented by substituted aminophenyl groups, etc., in which a nitrogen atom is directly bonded to an aromatic nucleus, cyanophenyl groups, An aryl group in which a carbon atom is directly bonded to an aromatic nucleus represented by a substituted oxycarbonylphenyl group, an aryl group in which an oxygen atom is directly bonded to an aromatic nucleus represented by a methoxyphenyl group, a phenoxyphenyl group, a trimethylsiloxyphenyl group, etc. , An aryl group in which a silicon atom is directly bonded to an aromatic nucleus represented by a trimethylsilylphenyl group, a trimethoxysilylphenyl group, a pentamethyldisilanylphenyl group, and the like. Representative examples of organic substituents include 1 to 1 carbon atoms with or without heteroatoms.
It is an aliphatic group of 2. Examples thereof include saturated aliphatic hydrocarbon groups represented by methyl group, ethyl group, isopropyl group, hexyl group, dodecyl group, etc .; represented by vinyl group, ethynyl group, allyl group, hexenyl group, hexynyl group, etc. Unsaturated aliphatic hydrocarbon group; a halogen-substituted aliphatic group represented by chloromethyl group, trifluoromethyl group, etc., methoxymethyl group, methyloxycarbonylmethyl group, 2-oxopropyl group, etc. Oxygen aliphatic group; Nitrogen-containing aliphatic group represented by N, N-dimethylaminomethyl group, aminomethyl group, etc., Silicon-containing aliphatic group represented by trimethylsilylmethyl group, trimethoxysilylmethyl group, etc. You can

1,1,3,3-tetraaryl-1,3
Examples of the disilacyclobutane compound include tetraphenyldisilacyclobutane, tetratolyldisilacyclobutane, tetraxylyldisilacyclobutane, tetra (ethylphenyl) disilacyclobutane, tetra (hexylphenyl) disilacyclobutane, tetra (dodecylphenyl) Disilacyclobutane, tetra (anisyl) disilacyclobutane, tetra (trimethylsilylphenyl) disilacyclobutane, tetra (fluorophenyl) disilacyclobutane, tetra (chlorophenyl) disilacyclobutane, tetra (trifluoromethylphenyl) disilacyclobutane, tetra (Cyanophenyl) disilacyclobutane, tetra (chloronaphthyl) disilacyclobutane,
1,3-diphenyl-1,3-di (fluorophenyl)
-1,3-disilacyclobutane, diphenyldi (chlorophenyl) disilacyclobutane, diphenyldi (trifluoromethylphenyl) disilacyclobutane, diphenyldi (p-tolyl) disilacyclobutane, diphenyldianisyldisilacyclobutane, di ( Examples thereof include p-tolyl) di (anisyl) disilacyclobutane and diphenyldi (1-naphthyl) disilacyclobutane.

As the catalyst that can be used in the present invention, as the gold compound, monovalent and trivalent gold chloride, gold bromide, gold iodide, gold cyanide, chloroauric acid, bromoauric acid, Cyanodiauric acid and salts of these acids, monovalent organic gold compounds and their complex compounds, monovalent gold compounds having a sulfur-containing ligand and their complex compounds, and monovalent and trivalent gold oxides As a silver compound, monovalent halides, oxides, carbonates, nitrates, sulfates, and carboxylates; and as copper, copper alloys and their compounds, copper plates, copper metal, copper powder, and copper wires. , Copper filaments and other metallic copper, copper alloys typified by bronze, brass, white copper, cuprous chloride, cuprous bromide, cuprous oxide, trimethylsilylmethyl copper ((Me ₃ SiCH ₂ Cu)), etc. Monovalent copper compound, cupric chloride, bromide Cupric, cupric oxide, copper nitrate, copper sulfate, cupric acetate, copper naphthenate, copper oleate (I
Examples thereof include divalent copper compounds such as I), copper (II) acetylacetonate, bisethylenediamine copper (II) chloride, and tetraammine copper (II) sulfate, and copper complex compounds.

The types of these metals and substituents are 1,
It is appropriately selected in consideration of the type of 1,3,3-tetraaryl-1,3-disilacyclobutane, the solvent, the polymerization temperature, etc., and in the case of the copolymerization described later, it affects the copolymerizability of each monomer. We must consider that it is one of the factors. It is needless to say that the polymerization catalyst needs to be selected from compounds having high thermal stability, especially in a system that requires polymerization at high temperature.

The ring-opening polymerization mechanism of 1,1,3,3-tetraaryl-1,3-disilacyclobutane of the present invention is not clear at present, but it is presumed to be like ionic polymerization using these metals as counterions. To be done.

The catalyst of the present invention is selected from the above-mentioned series of compound groups according to the reactivity of 1,1,3,3-tetraaryl-1,3-disilacyclobutane, the reaction temperature, etc. be able to. Generally, the amount of catalyst added is one of the factors that control the molecular weight and molecular weight distribution of the polymer.
Therefore, when a polymer having a large molecular weight is to be produced, the addition concentration is low, and when a polymer having a small molecular weight is to be obtained, the addition amount is high. Although it depends on the target molecular weight, the amount of the added catalyst can be used in an amount of 1/10000 (molar ratio) to 1/5 (same) with respect to the monomer, and 1/10000 to 1/5.
0 (molar ratio) is more preferable in consideration of polymerization conditions and the like.

Polymerization may be carried out by adding a catalyst to a single monomer or a mixture of monomers, or by adding a monomer or a monomer solution by dispersing the catalyst in a suitable solvent. 1,
1,3,3-Tetraaryl-1,3-disilacyclobutane dissolves in aromatic hydrocarbons and their derivatives, and halogen-containing hydrocarbons, regardless of any substituents. As the polymerization solvent of the present invention, an aprotic solvent is preferable, and one having a high boiling point and a low vapor pressure is preferable because the polymerization temperature is relatively high. Polydiaryl silmethylenes generally have poor solubility, and in particular, polydiphenyl silmethylene has extremely poor solubility and shows solubility only in limited solvents such as diphenyl ether and diphenyl sulfone at high temperatures. Solution homogeneous polymerization can be obtained by dissolving a monomer at a temperature equal to or higher than the melting point of diphenylsulfone, adding a catalyst and keeping the temperature constant for a desired time, and then separating and purifying a solvent and a polymer. From the viewpoint of ease of polymer separation, solvent heterogeneous polymerization in which the produced polymer precipitates when reaching a certain molecular weight is preferable. Further, a bulk polymerization method in which a catalyst is added to the monomer is also mentioned as a preferable method from the viewpoint of inhibiting the catalytic action by the solvent.

The polymerization temperature is not particularly limited as long as it is below the decomposition temperature of the polymer and above the melting or melting temperature of the monomer. For example, in the case of polydiphenylsilmethylene, 3
It is preferably less than 70 ° C and 150 ° C or more.

According to the invention, the specific 1,1,3,3-tetraaryl-forming polysilmethylene polymers
1,3-disilacyclobutane having at least one kind of 1,1,3,3-tetraaryl-1,3-disilacyclobutane having a different structure from random, block, alternating copolymer, etc. 1,3,3-tetraaryl-1,3
Anything that can be copolymerized with disilacyclobutane can be used as the monomer for copolymerization. Particularly 1,3-diaryl-1,3-dialkyl-1,3-disilacyclobutane, 1,1,3,3-tetraalkyl-1,3-disilacyclobutane, 1,3-diaryl-1,3- Dialkoxy-1,3-disilacyclobutane, 1,3-dialkyl-1,3-dialkoxy-1,3-disilacyclobutane, 1,1,3,3-tetraalkoxy-1,3-disilacyclobutane Needless to say, silacyclobutane compounds having similar reactivity to these can also be preferably used.

For example, 1,3-disilacyclobutane compounds include 1,1,3,3-tetramethyl-1,3-disilacyclobutane and 1,1,3,3-tetraethyl-
1,3-disilacyclobutane, 1,1,3,3-tetrapropyl-1,3-disilacyclobutane, 1,1,3
3-tetramethoxydi-1,3-silacyclobutane,
1,1,3,3-tetraethoxy-1,3-disilacyclobutane, 1,1,3,3-tetrapropoxy-1,3
-Disilacyclobutane, 1,1,3,3-tetraphenoxy-1,3-disilacyclobutane, 1,1,3,3-
Tetraxylenoxy-1,3-disilacyclobutane,
1,1,3,3-tetrachloro-1,3-disilacyclobutane, 1,1,3,3-tetrabromo-1,3-disilacyclobutane, 1,3-diphenyl-1,3-dimethyl-1 , 3-disilacyclobutane, 1,3-diphenyl-1,3-diethyl-1,3-disilacyclobutane,
1,3-diphenyl-1,3-dibutyl-1,3-disilacyclobutane, 1,3-diphenyl-1,3-dimethoxy-1,3-disilacyclobutane, 1,3-diphenyl-1,3- Diethoxy-1,3-disilacyclobutane, 1,3-diphenyl-1,3-dichloro-1,3-
Disilacyclobutane, 1,3-dimethyl-1,3-diethyl-1,3-disilacyclobutane, 1,3-dimethyl-1,3-dihexyl-1,3-disilacyclobutane,
1,3-dimethyl-1,3-dichloro-1,3-disilacyclobutane, 1,3-dimethyl-1,3-dibromo-
1,3-disilacyclobutane etc. can be mentioned.

The silacyclobutane compound is 1,1
-Dimethyl silacyclobutane, 1,1-diethyl silacyclobutane, 1,1-dibutyl silacyclobutane, 1,
1-diphenylsilacyclobutane, 1,1-ditolylsilacyclobutane, 1,1-dimethoxysilacyclobutane, 1,1-diethoxysilacyclobutane, 1,1-diphenoxysilacyclobutane, 1,1-dichlorosilacyclobutane, 1 , 1-dibromosilacyclobutane, 1-
Methyl-1-ethylsilacyclobutane, 1-methyl-1
-Phenylsilacyclobutane, 1-ethyl-1-phenylsilacyclobutane, 1-methyl-1-chlorosilacyclobutane, 1-phenyl-1-chlorosilacyclobutane and the like can be mentioned.

As the copolymerization method, the above-mentioned 1,1,
It goes without saying that the polymerization can be carried out by the same method as the homopolymerization of 3,3-tetraaryl-1,3-disilacyclobutane, and the copolymerization amount can be changed according to the purpose.
The polydiarylsilmethylene produced by the present invention is represented by the following formula:-(Ar ₂ SiCH ₂ ) _n- (wherein Ar has an organic or inorganic substituent independently in each unit. Or an aromatic group which does not have it, and the organic substituent contains or does not contain a hetero atom.) The value of n may be 2 or more, and 10 or more is preferable in view of crystallinity and moldability.

Poly (diphenylsilmethylene) and the like are considered to have the same basic structure regardless of whether they are produced by thermal polymerization or by catalytic polymerization as described in this specification. Very little is known about molecular weight and molecular weight distribution. These polymers have low solubilities in solvents such as toluene and tetrahydrofuran at room temperature, and their molecular weight cannot be determined by a usual method such as GPC and vapor pressure drop of a solution. By measuring the thermal behavior of the polymer using DSC (polymer crystallization temperature or melting point), the difference in the degree of polymerization of the polymer can be qualitatively known, but the true degree of polymerization cannot be known. Although it is possible to obtain knowledge about the molecular weight and the molecular weight distribution by measuring the melt viscosity of a polymer, analysis by this method has not been performed so far.

In the vicinity of the melting point, polydiphenylsilmethylene undergoes thermal deterioration due to elimination of the phenyl group bonded to the silicon atom, and this deterioration also occurs during polymerization at high temperatures. This deterioration is suppressed by adding phthalocyanine or its derivative (hereinafter collectively referred to as "phthalocyanines") to the polymerization system. The phthalocyanines used in the present invention are preferably those which do not decompose at the polymerization temperature and have no sublimation property, and those in which phthalocyanines are coordinated with a metal can also be used without any problem. The phthalocyanines that can be added should be appropriately selected depending on the resin structure and temperature, but it is known that an aromatic group bonded to silicon easily causes bond cleavage with an acid, etc. Those having no or extremely weak properties are preferable. Various substituents have been introduced to improve the solubility of phthalocyanine, but sulfonic acid residues, carboxylic acid residues and the like are not preferred. Even the central metal of phthalocyanine can be used without any problem except for metals having an oxidizing property such as manganese, iron and cobalt.
The addition amount of the phthalocyanines in the present invention,
The content is 0.01 to 20% by weight, preferably 0.1-10% by weight, based on 1,1,3,3-tetraaryl-1,3-disilacyclobutane. The phthalocyanine-based stabilizer used in the above has an effect as a stabilizer even during the molding process, and therefore it is not necessary to remove it from the polydiphenylsilmethylene.

[0025]

INDUSTRIAL APPLICABILITY The present invention provides a 1,1,3,3-tetraaryl-1,3-disilacyclobutane compound whose molecular weight and molecular weight distribution are qualitatively adjusted by a controlled method. Methylene can be produced without by-products.

Further, by copolymerization, various polysilmethylenes having different substituents can be obtained. in addition,
A poly (silmethylene)-(silpropene) copolymer can also be provided with an optional composition depending on the purpose.

The method of the present invention provides a method for producing a polymer having a silicon-carbon skeleton, which is expected to have specific physical properties, and can be widely used in industry.

[0028]

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

¹ H-NMR, ¹³ C-NMR, ²⁹ Si-N in the description of characterization of products in the following examples.
MR is proton nuclear magnetic resonance spectrum, carbon 1
3 shows a nuclear magnetic resonance spectrum and a silicon 29 nuclear magnetic resonance spectrum. CDCl ₃ represents deuterated chloroform,
Of the display of proton nuclear magnetic resonance spectrum data,
S, d, t, and m shown in () respectively represent a singlet, a doublet, a triplet, and a multiplet, br is broad, st is high intensity, and wk
Represents intensity, and 1H, 2H, 3H, etc. mean spectral intensities corresponding to one, two, and three protons, respectively.
All chemical shifts of ¹ H-NMR spectrum are CD
The resonance position of residual CHCl ₃ in the Cl ₃ solvent was set to 7.24 pp.
This is the value when m is set. ^{In the 13} C-NMR spectrum, it is the value when the chemical shift of carbon of CDCl ₃ is 77.0 ppm. The chemical shift of the ²⁹ Si-NMR spectrum is determined by the external standard tetramethylsilane (CDCl
It is the value when the chemical shift of silicon of ₃ solutions) is 0 ppm. GC-MS is a gas chromatograph mass spectrometry,
GPC stands for gel permeation chromatograph.
Polymer analysis by DSC (Differential Scanning Calorimeter): 1st temperature rise: 25 ° C to 400 ° C (10 ° C / min), temperature fall: 40
0 ° C to 100 ° C (5 ° C / min), Second temperature rise: 100 ° C to
The temperature program was 400 ° C. (10 ° C./min), and the endothermic peak of the second temperature increase was taken as the melting point.

Reference Example 1 (1,1,3,3-tetra (p-tolyl) -1,3-disilacyclobutane ([(p-
Synthesis of tol) ₂ SiCH ₂ ] ₂ ) Chloromethyldi (p-tolyl) chlorosilane was obtained from chloromethyltrichlorosilane and p-tolylmagnesium chloride by a conventional method. This chloromethyldi (p-tolyl) chlorosilane (107 g) was added dropwise to 12 g of magnesium flakes and 120 mL of tetrahydrofuran over 2 hours. After completion of the dropwise addition, the mixture was heated under reflux for 5 hours, 400 mL of toluene was added, and after cooling, 200 mL of water was added. The organic layer was washed with water three more times, the organic layer was dried over magnesium sulfate, and then the solvent was removed by a rotary evaporator. The obtained solid was dissolved in hot hexane, filtered, and cooled to obtain tetra (p-tolyl) disilacyclobutane crystals in a yield of about 70%.

Tetra (p-tolyl) disilacyclobuta
Melting point: 145 ° C .;¹H-NMR (CDCl₃, Δ ＝,
ppm): 1.08 (s, 2H), 2.38 (s, 6H),
7.19 (d, 4H), 7.5 (d, 4H);¹³C-N
MR (CDCl₃, Δ =, ppm): 0.93, 21.4
5,128.6,134.1,134.3,139.
1; ²⁹Si-NMR (CDCl₃): Δ = −6.25 ppm
 .

Reference Example 2 (1,1,3,3-tetra (m-tolyl) -1,3-disilacyclobutane ([(m-
Synthesis of tol) ₂ SiCH ₂ ] ₂ ) Chloromethyldi (m-tolyl) chlorosilane was obtained by a conventional method from chloromethyltrichlorosilane and m-tolylmagnesium chloride. This chloromethyldi (m-tolyl) chlorosilane (105 g) was added dropwise to 12 g of magnesium shavings and 120 mL of tetrahydrofuran over 2 hours. After completion of dropping, the mixture was heated under reflux for 5 hours, 220 mL of hexane and 80 mL of toluene were added, and after cooling, 200 mL of water was added. The organic layer washed with water three times was dried over magnesium sulfate, and then the solvent was removed by a rotary evaporator. The obtained solid was dissolved in hot hexane, filtered and then cooled to obtain tetra (m-tolyl) disilacyclobutane crystals in a yield of about 70%.

Tetra (m-tolyl) disilacyclobutane: melting point 106 ° C .; ¹ H-NMR (CDCl ₃ , δ =,
ppm): 1.10 (s, 4H), 2.32 (s, 12)
H), 7.1-7.3 (m, 8H), 7.4-7.5.
(M, 8H); ¹³ C-NMR (CDCl ₃ , δ =, pp
m): 0.90, 21.34, 127.6, 130.0,
131.3, 134.9, 137.0, 137.3; ²⁹
_{Si-NMR (CDCl 3):} δ = -6.01ppm.

(Example 1) 1,1,3,3- in the presence of (copper (II) acetylacetonate (Cu (acac) ₂ ))
Tetraphenyl-1,3-disilacyclobutane ((Ph
Polymerization of ₂ SiCH ₂ ) ₂ ) Tetraphenyldisilacyclobutane ((Ph ₂ SiCH
₂ ) ₂ ) 1 g and 0.8 g toluene 0.78 mg Cu (a
cac) _{2 in a} glass ampoule, degassed,
I sealed it. 6 in an oil bath keeping this sealed tube at 150 ° C
Heated for hours. The sealed tube was opened, the content was heated under reflux with 100 mL of toluene, cooled, and filtered. This is 100 ℃
After drying for 15 hours, 0.82 g of polymer was obtained.

Document description (N. Nametkin, V. Vdovin, V. Z
It was confirmed to be polydiphenylsilmethylene by comparison with the infrared absorption spectrum of avyalov, Akad. Nauk SSSR, 162 (4), 824 (1965)). Figure 1 shows the infrared absorption spectrum (KB) of polydiphenylsilmethylene obtained by thermal polymerization.
r tablet, transmission spectrum). The broad absorption around 3450 cm ^-1 is due to the water content in KBr. FIG. 2 is an infrared absorption spectrum (KBr tablet, transmission spectrum) of the polydiphenylsylmethylene obtained in this example. 34
The wide absorption around 60 cm ^-1 is due to the water content in KBr. The melting point of the polydiphenylmethylene obtained in this example was observed at 350 ° C. by DCS analysis.

Example 2 Polymerization of (Ph ₂ SiCH ₂ ) _{2 in} the Presence of Cuprous Chloride (CuCl) Tetraphenyldisilacyclobutane ((Ph ₂ SiCH
₂ ) ₂ ) 0.5 g was put into a glass ampoule together with 1 mg of CuCl, deaerated and then sealed. Shake the sealed tube vigorously to mix the contents, and then 60 in an oil bath maintained at 153 ° C.
Heated for minutes. 7 minutes after the start of heating, the contents gelled,
It became solid after 30 minutes. Open the sealed tube and fill the contents with 10
The mixture was heated to reflux with mL of toluene, cooled and collected by filtration, and the obtained white solid was dried at 120 ° C. for 6 hours to obtain 0.45 g of a polymer.

As in Example 1, it was confirmed from the results of infrared absorption spectrum and DSC analysis that it was polydiphenylsilmethylene.

Example 3 (Polymerization of [(p-tol) ₂ SiCH ₂ ] _{2 in} the Presence of Cu (acac) ₂ ) Tetra (p-tolyl) disilacyclobutane ([(p-to
l) ₂ SiCH ₂ ] ₂ ) 0.2 g was added with 0.1 mg of Cu (aca
c) It was put together with _{2 in a} glass ampoule, deaerated, and then sealed. 1.5 in an oil bath keeping this sealed tube at 160 ° C
Heated for hours. The sealed tube was opened, the contents were dissolved in hot diphenyl ether, and then this solution was added dropwise to methanol. The generated white precipitate was washed with methanol three times, filtered, and dried at 95 ° C. to obtain 0.16 g of a polymer.

¹ H-NMR (CDCl ₃ , δ =, ppm):
-1.3 to -0.5 (br, 2H), 2.12 (br,
8.9H), 6.45-6.70 (m, 12.2H);
¹³ C-NMR (CDCl ₃ , δ =, ppm): 21.2.
27.2, 135.2, 135.4, 137.5; ²⁹ S
_{i-NMR (CDCl 3):} δ = -9.89ppm.

Example 4 (Polymerization of [(m-tol) ₂ SiCH ₂ ] _{2 in} the Presence of Cu (acac) ₂ ) Tetra (m-tolyl) disilacyclobutane ([(m-to
l) ₂ SiCH ₂ ] ₂ ) (0.2 g) was placed in a glass ampoule together with 0.3 mg of copper (II) acetylacetonate and 1 mL of toluene, deaerated and then sealed. This sealed tube is 150
It heated for 8 hours in the oil bath maintained at ℃. After the heating was started, the solution became cloudy and a large amount of precipitate was formed 2 hours later. 8
After a while, stop heating, dissolve the contents in hot chloroform,
Next, this solution was added dropwise to methanol. The resulting white precipitate was collected by filtration and dried to obtain 0.15 g of a polymer.

¹ H-NMR (CDCl ₃ , δ =, ppm):
-1.0 (br, 1.6H), 1.95 (s, 6H),
6.39 (br-s, 3.8H), 6.84 (br-
s, 4.8H); ¹³ C-NMR (CDCl ₃ , δ =, pp
m): 21.0, 126.3, 128.9, 132.6,
135.2, 135.8, 138.3; ²⁹ Si-NMR
(CDCl ₃ ): δ = −9.78 ppm.

(Example 5) ((Ph ₂ in the presence of copper powder)
Polymerization of SiCH ₂ ) ₂ ) Tetraphenyldisilacyclobutane ((Ph ₂ SiCH
₂ ) ₂ ) 0.2 g was put into a glass ampoule together with 1 mg of copper powder, deaerated, and then sealed. When this sealed tube was heated in an oil bath maintained at 150 ° C. for 15 hours, the entire contents became a white solid. The sealed tube was opened, the contents were washed with hot chloroform, and dried to obtain 0.18 mg of a polymer.

As in Example 1, it was confirmed from the results of infrared absorption spectrum and DSC analysis that it was polydiphenylsilmethylene.

Example 6 Polymerization of (Ph ₂ SiCH ₂ ) _{2 in} the Presence of Chloroauric Acid (HAuCl ₄ ) Tetraphenyldisilacyclobutane ((Ph ₂ SiCH
₂ ) ₂ ) 0.2 g was put into a glass ampoule together with 1 mg of HAuCl ₄ , deaerated and then sealed. This sealed tube is 150 ℃
When heated for 15 hours in an oil bath kept at, the entire contents became solid. The sealed tube was opened, the contents were washed with hot chloroform, and dried to obtain 0.18 mg of polymer.

As in Example 1, it was confirmed from the results of infrared absorption spectrum and DSC analysis that it was polydiphenylsilmethylene.

[0046] (Example 7) (Cu (acac) in the ₂ presence _{[(p-tol) 2 SiCH} 2] 2 and (Ph ₂ SiCH _{2) 2}
Copolymerization of 0.5 g of tetraphenyldisilacyclobutane and 0.5 g of tetra (p-tolyl) disilacyclobutane were placed in a glass ampoule together with 1 mg of copper (II) acetylacetonate, degassed and then sealed. The sealed tube was heated for 3 hours in an oil bath maintained at 160 ° C. The sealed tube was opened, the contents were dissolved in hot chloroform, and this solution was then added dropwise to methanol. The white precipitate formed was collected by filtration and
It was dried at 0 ° C. to obtain 0.95 g of a copolymer.

¹ H-NMR (CDCl ₃ , δ =, ppm):
-1.2 to -0.2 (br, 2H), 2.09 (br,
3.3H), 6.46~7.05 (m, 11H ); 29 S
i-NMR (CDCl ₃ , δ =, ppm): -9.51,-
9.56, -9.67, -9.91, -10.02.

[0048] (Example 8) (Cu (acac) in the ₂ presence _{[(m-tol) 2 SiCH} 2] 2 and (Ph ₂ SiCH _{2) 2}
Copolymerization of tetraphenyldisilacyclobutane 0.5 g and tetra (m-tolyl) disilacyclobutane 0.5 g were put in a glass ampoule together with 1 mg of copper (II) acetylacetonate, degassed and then sealed. The sealed tube was heated in an oil bath maintained at 150 ° C for 7 hours. The sealed tube was opened, the contents were dissolved in hot chloroform, and this solution was then added dropwise to methanol. The white precipitate formed was collected by filtration and dried to obtain 0.4 g of a copolymer.

¹ H-NMR (CDCl ₃ , δ =, ppm):
-1.3 to -0.6 (br, 1H), 1.95 (br,
1.5H), 6.39 to 7.04 (m, 4.8H); ²⁹
Si-NMR (CDCl ₃ , δ =, ppm): -9.65,
-9.84.

Example 9 [(m-tol) ₂ SiCH ₂ ] ₂ and [(p-tol) ₂ SiC in the presence of Cu (acac) ₂
Copolymerization of H ₂ ] ₂ 0.5 g of tetra (p-tolyl) disilacyclobutane and tetra (m-tolyl) disilacyclobutane were put in a glass ampoule together with 1 mg of copper (II) acetylacetonate and deaerated. I sealed it later. The sealed tube was heated in an oil bath maintained at 150 ° C for 7 hours. The sealed tube was opened, the contents were dissolved in hot chloroform, and this solution was then added dropwise to methanol. The resulting white precipitate was collected by filtration and dried to obtain 0.16 g of a copolymer.

¹ H-NMR (CDCl ₃ , δ =, ppm):
-1.3 to -0.5 (br, 1H), 1.9 to 2.3
(Br, 3.9H), 6.4 to 7.0 (m, 5.2)
H); ²⁹ Si-NMR (CDCl ₃ , δ =, ppm):-
9.65, -9.92-10.03, -10.11.

(Example 10) ([(p-tol) ₂ SiCH ₂ ] ₂ / [(m-tol) ₂ Si in the presence of Cu (acac) ₂
CH ₂ ] ₂ / (Ph ₂ SiCH ₂ ) ₂ Copolymerization) Tetraphenyldisilacyclobutane 0.3 g, tetra (p-tolyl) disilacyclobutane 0.35 g and tetra (m-tolyl) disilacyclobutane 0.35 g And 1 mg
It was put in a glass ampoule together with copper (II) acetylacetonate, degassed, and then sealed. The sealed tube was heated in an oil bath maintained at 150 ° C for 7 hours. The sealed tube was opened, the contents were dissolved in hot chloroform, and this solution was then added dropwise to methanol. The white precipitate thus formed was collected by filtration and dried to obtain 0.34 g of a copolymer.

¹ H-NMR (CDCl ₃ , δ =, ppm):
-1.3 to -0.6 (br, 1H), 1.95 and 2.09 (br, 2.5H), 6.3 to 7.2 (m,
5.5 H); ²⁹ Si-NMR (CDCl ₃ , δ =, pp
m): -10.0, -9.86, -9.65.

(Example 11) (Copolymerization of (Ph ₂ SiCH ₂ ) ₂ and tetramethyldisilacyclobutane ((Me ₂ SiCH ₂ ) ₂ ) in the presence of Cu (acac) ₂ ) Tetraphenyldisilacyclobutane 0 .2 g and 0.2 g of tetramethyldisilacyclobutane were put in a glass ampoule together with 1 mg of copper (II) acetylacetonate, deaerated and then sealed. The sealed tube was heated in an oil bath maintained at 150 ° C for 15 minutes. Open the sealed tube and fill the contents with 20
It was dissolved in mL of chloroform and then added dropwise to 200 mL of methanol. The white precipitate thus formed was collected by filtration and dried at 150 ° C. to obtain 0.28 g of a copolymer.

¹ H-NMR (CDCl ₃ , δ =, ppm):
-0.8 to 0.0 (br-m, 1.5H), 0.08
(S, 1.7H), 6.6 to 7.4 (br, 1H); ²⁹
Si-NMR (CDCl ₃ , δ =, ppm): -0.1
0.4 (st: 0.19, wk: -0.10, 0.0
6, 0.34), -8.0 (wk).

Example 12 (P in the presence of CuCl
h ₂ SiCH ₂ ) ₂ and dimethyldiphenyldisilacyclobutane (copolymerization of (MePhSiCH ₂ ) ₂ )) Tetraphenyldisilacyclobutane 0.2 g and trans-dimethyldiphenyldisilacyclobutane 0.2 g
It was put in a glass ampoule together with mg of cuprous chloride, deaerated, and then sealed. The sealed tube was heated in an oil bath maintained at 150 ° C for 120 minutes. Open the sealed tube, dissolve the contents in 10 mL of chloroform, then add 100 mL of methanol.
Dropped into mL. The white precipitate formed was collected by filtration,
After drying at 0 ° C., 0.32 g of a copolymer was obtained.

¹ H-NMR (CDCl ₃ , δ =, ppm):
-0.8 to 0 (m, 7H), 6.7 to 7.5 (m, 1)
7.8H); ²⁹ Si-NMR (CDCl ₃ , δ =, pp
m): -4.2 to -5.5 (br), -0.8 to -10.
0 (br).

Example 13 (Polymerization of tetraphenyldisilacyclobutane with different monomer / catalyst ratio) 0.52 g of tetraphenyldisilacyclobutane was added to 0.5 wt.
It was placed in a glass ampoule together with 69 mg of copper bisacetylacetonate and 0.5 ml of o-xylene, deaerated and then sealed. Seal the tube in an oil bath for 150
Heated at ℃ 14 hours. The contents gelled 10 minutes after the start of heating and became solid after 30 minutes. The sealed tube was opened, the content was heated with 100 g of toluene, cooled and filtered, and the obtained white solid was dried at 100 ° C. for 6 hours to obtain 0.47 g of a polymer (sample # 1). Similarly, 0.60 g of monomer, 3.94 mg of copper catalyst, 0.5 ml of o
-0.58 g of polymer (Sample # 2) was obtained from the reaction with xylene, 0.49 g of monomer, 32.0 mg
From the reaction with the copper catalyst of Example 1 and 0.5 ml of o-xylene, 0.35 g of a polymer (Sample # 3) was obtained. The thermal behavior of the obtained polymer sample was analyzed using DSC. The temperature rising / falling temperature / temperature rising program is the same as that described in the first embodiment. The results are shown in the table below.

(Table 1) Sample 1st temperature rising / falling temperature 2nd temperature rising Endothermic peak Exothermic peak Endothermic peak # 1 351 ° C 320 ° C 349 ° C # 2 349 ° C 315 ° C 347 ° C # 3 340 ° C 287 ° C 305,319, 325 ° C

Example 14 (In the presence of phthalocyanine, copper (II) acetylacetonate (Cu (aca
c) ₂ ) 1,1,3,3-tetraphenyl-in the presence of
1,3-disilacyclobutane _{((Ph 2 SiCH 2) 2} ) of polymerization) tetraphenyl-disilacyclobutane ((Ph ₂ SiCH _2)
2 ) 1 g and 0.8 g toluene 0.78 mg Cu (ac
It was put in a glass ampoule together with ac) ₂ and 0.02 g of phthalocyanine, deaerated, and then sealed. This sealed tube 15
Heated for 6 hours in an oil bath maintained at 0 ° C. The sealed tube was opened, the content was heated under reflux with 100 mL of toluene, cooled, and filtered. This is dried at 100 ° C for 15 hours and 0.32
g of polymer was obtained. As in Example 1, it was confirmed from the results of infrared absorption spectrum and DSC analysis that it was polydiphenylsilmethylene.

(Comparative Example 1) (By thermal reaction (Ph ₂ Si
Polymerization test of CH ₂ ) ₂ ) Tetraphenyldisilacyclobutane was placed in a glass ampoule, deaerated, and then sealed. When this sealed tube was heated in an oil bath maintained at 150 ° C. for 15 hours, the contents remained liquid and did not change. Crystallized on cooling. From the ¹ H-NMR spectrum of this sample, it was confirmed to be tetraphenyldisilacyclobutane. No decrease in melting point was observed in the blending test, and the starting material, tetraphenyldisilacyclobutane, was quantitatively recovered.

(Comparative Example 2) ((Ph
₂ SiCH _{2) 2} Place the polymerization test) tetraphenyl disilacyclobutane 0.5g of glass ampoule together with bis (triphenylphosphine) platinum (II) dichloride 5 mg, was degassed and sealed.
When this sealed tube was heated in an oil bath maintained at 150 ° C. for 24 hours, the content was colored slightly yellow but remained unchanged as a liquid. Crystallize on cooling and this sample
It was confirmed from the ¹ H-NMR spectrum that the starting material was tetraphenyldisilacyclobutane. Tetraphenyldisilacyclobutane was recovered almost quantitatively.

Comparative Example 3 (Polymerization test of (Ph ₂ SiCH ₂ ) _{2 in} the presence of rhodium complex) 0.5 g of tetraphenyldisilacyclobutane was added together with 5 mg of tris (triphenylphosphine) rhodium (I) chloride. It was put in a glass ampoule, deaerated, and then sealed. When this sealed tube was heated in an oil bath maintained at 150 ° C. for 24 hours, the content turned a little brown, but remained unchanged as a liquid. It crystallized on cooling, and it was confirmed from the ¹ H-NMR spectrum that this sample was tetraphenyldisilacyclobutane as a raw material. Tetraphenyldisilacyclobutane was recovered almost quantitatively.

(Comparative Example 4) (Heating experiment of potassium silanolate and (Ph ₂ SiCH ₂ ) ₂ ) 0.5 g of tetraphenyldisilacyclobutane was added to 2 mL of benzene and 5 mg of potassium trimethylsilanolate (K).
It was put in a glass ampoule together with OSi (CH ₃ ) ₃ ), deaerated, and then sealed. When this sealed tube was heated for 42 hours in an oil bath maintained at 150 ° C., the content remained liquid and did not change. When this sample was analyzed by GPC (toluene elution, polystyrene reduced molecular weight), it was found to be a mixture of unreacted tetraphenyldisilacyclobutane (16%) and a compound having a molecular weight of 1000 or less (84%). They were all soluble in toluene and were not high molecular weight poly (diphenylsilmethylene).

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum of polydiphenylsilmethylene obtained by thermal polymerization.

FIG. 2 is an infrared absorption spectrum of polydiphenylsilmethylene obtained in Example 1.

Claims (4)

[Claims] 1. The following general formula (I) (Ar ₂ SiCH ₂ ) ₂ (I) (wherein Ar may be different from each other and is an aromatic group with or without an organic or inorganic substituent). And the organic substituent contains or does not contain a heteroatom), and a gold compound is used as a monomer containing one or more kinds of 1,1,3,3-tetraaryl-1,3-disilacyclobutane. A method for producing polydiarylsilmethylene, which comprises performing ring-opening polymerization in the presence of a catalyst selected from the group consisting of a silver compound, copper metal, a copper alloy and a copper compound. 2. The method according to claim 1, wherein
1,3,3-tetraaryl-1,3-disilacyclobutane, silacyclobutane compound and 4 on the silicon atom
Polydiarylsilmethylene copolymer characterized by copolymerizing with a silicon-containing four-membered ring compound selected from 1,3-disilacyclobutane compounds in which at least one of the four substituents is other than an aryl group Manufacturing method. 3. The catalyst is a monovalent or trivalent gold compound,
A monovalent silver compound, a copper metal, an alloy of copper and a monovalent or divalent copper compound are selected.
The method for producing the polydiarylsilmethylene according to 1. 4. The method for producing polydiarylsilmethylene according to claim 1, wherein the polymerization is carried out in the presence of phthalocyanine or a derivative thereof.