JPH0521140B2 - - Google Patents

Description

[Detailed description of the invention]

"Industrial Application Field" The present invention relates to a novel silicon-containing polymer. More specifically, the present invention relates to silicon-containing polymers that have high performance properties such as heat resistance, coating properties, and transparency and are useful as electronic materials. "Prior Art" Silica, polyimide, and the like have been used as heat-resistant insulating materials in the field of electronic materials, but these materials are not necessarily satisfactory in terms of processability and performance. Therefore, the present inventors focused on polymers containing siloxane bonds that have heat-resistant insulating properties, as seen in heat-resistant insulating oils mainly composed of polysiloxane, and silica (SiO ₂ ). Regarding the properties of these polymers, the former is oily or has a low melting point and is difficult to use as a solid heat-resistant insulating material, while the latter requires chemical vapor deposition (CVD) to form insulating films.
This method uses a gas reaction and has low productivity. Therefore, we focused on ladder polymers containing siloxane bonds as a way to solve these problems. Ladder polymers are known to be one method for improving the solubility, heat resistance, etc. of polymers. However, as a ladder polymer containing siloxane bonds, the general formula All-siloxane ladder polymers such as
In addition, there are problems such as the tendency for cracks to occur in the coating film, so it has not been put into practical use yet. Also general formula A siloxane-containing ladder polymer has also been published (US Pat. No. 3,485,857), but it has problems with coating properties such as a low molecular weight and easy cracking of the coating. ``Problems to be Solved by the Invention'' The purpose of the present invention is to improve the drawbacks of these silicon-containing ladder polymers, and to develop a new silicon-containing ladder polymer that is soluble in solvents and has excellent heat-resistant insulation and coating properties. The purpose of this invention is to provide polymers. "Means for Solving the Problems" The present invention consists of a unit represented by the following general formula () and the unit expressed by the following general formula () A repeating polymer chain represented by the following general formula () containing is the unit expressed by the following general formula () The weight average molecular weight measured by gel permeation chromatography is in the range of 3.0 × 10 ³ to 6.5 × 10 ⁵ (in each of the above formulas,
R ¹ is a hydrocarbon group or a fluorine-substituted hydrocarbon group,
R ² is hydrogen or trialkylsiloxy group, R ³ and R ⁴
are hydrocarbon groups or fluorine-substituted hydrocarbon groups which may be the same or different from each other, R ⁵ and R ⁶ are hydrogen or hydrocarbon residues of a vinyl polymerization initiator, and (r+
s):t is (5-100):1, p is 1-5 and (r
+s+t):p is in the range of (5 to 100):1)
The present invention provides a silicon-containing step ladder polymer and a method for producing the same. The number of carbon atoms in R ¹ is preferably 1 to 10. R ¹
is more preferably an alkyl group having 1 to 4 carbon atoms, a fluorine-substituted alkyl group, or a phenyl group. If the number of carbon atoms in R ¹ becomes large, the heat resistance of the silicone-containing step ladder polymer of the present invention will decrease, and steric hindrance will appear in the synthesis reaction of the polymer, which is not preferable. However, aromatic hydrocarbons such as phenyl groups have little tendency to reduce heat resistance. When R ² is a trialkylsilyl group, the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The larger the number of carbon atoms, the lower the rate of the trialkylsilylation reaction of the silanol group (Si-OH) in the silicon-containing Steps Prader polymer synthesis reaction according to the present invention, and the lower the heat resistance, which is not preferable. The number of carbon atoms in R ³ and R ⁴ is preferably 1 to 10. R ³ and R ⁴ more preferably have 1 to 1 carbon atoms.
4, a fluorine-substituted alkyl group, or a phenyl group. If the number of carbon atoms in R ³ and R ⁴ becomes large, the heat resistance of the silicon-containing step ladder polymer of the present invention will decrease, and steric hindrance will appear in the synthesis reaction of the polymer, which is not preferable. However, aromatic hydrocarbons such as phenyl groups have little tendency to reduce heat resistance. If the ratio of unit ()/unit () is less than 5, the heat resistance of the silicon-containing step ladder polymer of the present invention is undesirably low. This ratio is 100
If it exceeds this amount, the adhesive function of the step ladder polymer of the present invention will deteriorate, which is not preferable. If the total amount of the unit () and the unit () (mole ratio) is less than 5, the heat resistance of the silicon-containing Stepladder polymer of the present invention will be poor, while if it is larger than 100, the molar ratio of the unit () will be lower than 5. is difficult to synthesize. Preferably, the unit chain of the ladder structure composed of the unit () and the unit selected from the unit () is composed of 5 to 100 of the units () and (). If the number is less than 5, the heat resistance of the silicon-containing step ladder polymer of the present invention will be poor, while if the number is more than 100, it will be difficult to synthesize. In the step ladder polymer of the present invention, it is preferable that the unit chain is polymerized by bonding with units () or chains of five or less units. It is preferable that the chain of units () be as short as possible. When it exceeds 5, the heat resistance of the step ladder polymer of the present invention decreases, which is not preferable. The molecular weight of the Steps Prader polymer of the present invention is
The weight average molecular weight is 3.0× ¹⁰³ to 6.5 as measured by GPC (gel permeation chromatography) method.
It is preferably ×10 ⁵ . This molecular weight is 3.0×
If it is smaller than 10 ³ , cracks will easily form in the film of the Steps Prader polymer of the present invention, while if it is larger than 6.5×10 ⁵ , the coating properties will be poor and the workability will be poor, which is not preferable. The molecular weight distribution (weight average molecular weight/number average molecular weight) of the Steps Prader polymer of the present invention is 2.5
It is preferable that it is above. This is because if it is smaller than 2.5, the coating properties of the step ladder polymer of the present invention will be low, and cracks will easily occur in the film. The silicon-containing Stepprader polymer of the present invention exhibits an infrared absorption spectrum unique to the 1,5-disylpyran ring chain at a wave number of 960 cm ^-1 . Further, the infrared absorption spectrum unique to the siloxane bond of the unit () exists in the wave number region of 1020 to 1090 cm ^-1 . The absorbance ratio of wave number 1080 to wave number 960 cm ^-1 (A1080/A960) is preferably 0.05 to 0.3. If the absorbance ratio is less than 0.05, the polymerization by units () is insufficient, while if it is more than 0.3, the fraction of the ladder structure becomes small, which is not preferable because the heat resistance of the step ladder polymer of the present invention decreases. The silicon-containing step ladder polymer of the present invention typically has the following structure. A-Z [-B-Z-] _o A' Here, A has the following structure. Here, R ⁵ and R ⁶ are hydrogen or a hydrocarbon residue of a vinyl polymerization initiator, and when one is hydrogen, one is the hydrocarbon residue; r≧1, s≧1, r
+s+t=4~99, t is an integer and t/(r+s)=
It is 0.01-0.2. A′ has the following structure. Here, R ⁵ , R ⁶ , r, t and s have the same meanings as above. B has the following structure. Here, R ⁵ , R ⁶ , r, t and s have the same meanings as above. Z has the following structure. Here, p is an integer from 1 to 5. Said n is about 0-1300. The above example is a typical example, but in rare cases, B may be substituted for Z, especially when it is a short chain with a degree of polymerization of 6 or less. Also, there are cases where two B's connected are connected to another B via the Z mentioned above. The name "Step" ladder polymer of the present invention has a ladder structure formed by repeating the above units (), in which the unit chains A, A' and B are -O
This originates from the fact that they are connected using -SiR ³ R ⁴ -O- or -O- as a step. In order to produce the silicon-containing Steps Prader polymer of the present invention, first, the general formula CH ₂ =CHSiR ¹ X ₂ (where R ¹ represents the same meaning as above, and A vinyl silane derivative represented by a dialkylamino group, chlorine, bromine, iodine, an alkoxy group having 7 or less carbon atoms, or a thioalkoxy group having 7 or less carbon atoms, is subjected to vinyl polymerization using a catalyst. According to the general formula A polyvinylsilane prepolymer represented by (where R ¹ and X have the same meanings as above,
R ⁵ and R ⁶ represent hydrogen or a hydrocarbon residue of the vinyl polymerization initiator, and m represents an integer of 5 to 100. )
Manufacture. For the vinyl polymerization of the vinyl silane derivative CH ₂ =CHSiR ¹ X ₂ , radical polymerization, ionic polymerization, etc. are selected depending on the type of substituent X. For example, when X is a dialkylamino group, anionic polymerization using an organometallic catalyst such as alkyl lithium or alkylaluminum is possible, and when X is an alkoxy group, halogen group, or thioalkoxy group, azobisisomerization is possible. Radical polymerization is possible using radical polymerization catalysts such as azonitrile such as butyronitrile, peroxides such as benzoyl peroxide and lauroyl peroxide, and other dicarbonate catalysts. The anionic polymerization of the vinylsilane derivative in which X is a dialkylamino group is performed, for example, in an aliphatic hydrocarbon such as n-hexane, n-heptane, or n-octane, or an aromatic hydrocarbon such as benzene, toluene, or xylene. n-hexane solution of butyl lithium and n-hexane solution of butyl lithium
- Addition of the required amount of catalyst, such as a hexane solution, and carried out at relatively low temperatures. This polymerization temperature is usually -
A temperature of 10 to 90°C, preferably -5 to 50°C is employed. The radical polymerization of the vinylsilane derivative in which X is a halogen group, an alkoxy group, or a thioalkoxy group is carried out using the radical polymerization catalyst in a hydrocarbon solvent such as toluene or xylene or without a solvent, usually at 50 to 200°C, preferably. It can be carried out at temperatures of 80-150°C. Many documents already exist regarding these vinyl polymerization methods themselves, and the vinyl polymerization in the present invention can be performed by any known method and is not particularly limited to the above-mentioned method. Next, this vinyl polymer (prepolymer) is made into a step ladder polymer. One of the methods is that when X in the vinyl polymer () is the alkylamino group, chlorine, bromine or iodine, these Xs are previously converted to R ⁷ COO
- (wherein R ⁷ represents an alkyl group having 4 or less carbon atoms), substituted with an acyloxy group,
The prepolymer is then subjected to intramolecular hydrolytic condensation with a stoichiometric (relative to Si) amount of water and the general formula R ³ R ⁴ Si as the prepolymer and step agent.
(OCOR ⁷ ) ₂ (wherein R ³ , R ⁴ and R ⁷ represent the same as mentioned above). When the functional group X of the prepolymer is a dialkylamino group, the acyloxylation of the prepolymer () is carried out by adding to the polymer in an inert aromatic hydrocarbon solvent such as benzene, toluene, or xylene.
An organic acid represented by the general formula R ⁷ COOH (where R ⁷ represents the same as above) is added and reacted. In this case, the reaction temperature can be -5 to 70°C, preferably 10 to 50°C. The amount of the acid can be 3 to 5 times, preferably 4 to 4.5 times by mole, the amount of Si in the prepolymer. When the functional group X of the prepolymer is a halogen group, the polymer has the general formula (R ⁷ CO) ₂ O (wherein R ⁷ represents the same as above.) Adding the acid anhydride represented by
The acyloxylation reaction is carried out while distilling off the generated organic acid halide. The reaction temperature in this case is
A temperature of 20 to 150°C, preferably 40 to 120°C can be employed. The amount of the acid anhydride is 1.5 to 2.5 times by mole, preferably 2 to 2.3 times the Si of the prepolymer.
Molar times can be adopted. For the purpose of preferentially forming the desired ladder structure (a repeating structure of units ()), acyloxylated prepolymers are used in inert aromatic hydrocarbon solvents such as benzene, toluene, and xylene at a relatively low temperature. The hydrolytic condensation is carried out at a polymer concentration, for example from 1 to 30% by weight, preferably from 3 to 15% by weight. In order to obtain the step ladder polymer of the present invention, the hydrolytic condensation reaction is carried out by (1) converting the acyloxylated prepolymer into a step agent R ³ R ⁴ Si
(OCOR ⁷ ) ₂ , or (2) after performing intramolecular hydrolytic condensation of the prepolymer, a step agent R ³ R ⁴ Si (OCOR ⁷ ) is added to carry out the hydrolytic condensation reaction. It is carried out in any of the following ways. In either method, the hydrolytic condensation reaction can be carried out by adding water in an amount of 1 to 100 moles relative to the Si involved in the reaction. In order to make this reaction more mild and preferentially form the desired ladder structure, the amount of water added is preferably from equimolar to 10 mol, preferably from equimolar to 3 mol, relative to Si. This water is preferably gradually added dropwise to react in the presence or absence of a suitable catalyst. Examples of suitable catalysts include inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as acetic acid, and bases such as sodium hydroxide and amines.
This hydrolysis condensation reaction is carried out under relatively mild conditions.
For example, the temperature is -5 to 80°C, preferably 20 to 60°C. Another method for converting the vinyl polymer (prepolymer) into a step ladder polymer is when X in the vinyl polymer (prepolymer) is the alkoxy group or thioalkoxy group,
R ³ R ⁴ SiY ² (where R ³ and R ⁴ represent the same as above, Y is an acyloxy group having 2 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 carbon atom This is a method in which the vinyl polymer is reacted with an acid anhydride represented by the general formula (R ⁷ CO) ₂ O in the presence of a compound represented by (representing a thioalkoxy group of -4). In this case, the reaction temperature can be 30 to 170°C, preferably 50 to 130°C, more preferably 50 to 90°C under a reduced pressure of 50 to 200 mmHg. The amount of the acid anhydride is 1 to 3 times the mole of Si in the vinyl polymer and the stepping agent (if Y is an alkoxy group or a thioalkoxy group), preferably
1.2 to 2 moles can be used. During this reaction, it is preferable to carry out the reaction while distilling off the acetate ester produced. In this reaction, a portion of is formed. After this reaction, water may be added to perform hydrolysis or hydrolytic condensation and hydrolysis, but the purpose is an auxiliary reaction or purpose to stabilize the polymer by removing the acyl groups remaining in the resulting polymer. It has a meaning as a reaction for completing the ladder structure and stabilizing it. In this case, the reaction temperature for hydrolysis or hydrolytic condensation can be relatively mild, for example, from -5 to 80°C, preferably from 20 to 60°C. The amount of water added is preferably equal to or less than the mole of Si in the vinyl polymer. If the amount of water is too large, crosslinking of the polymer may occur, which is not preferable. In any of the methods for converting the prepolymer into a Steps Prader polymer, the hydrolytic condensation reaction employed in those methods is carried out at a relatively low temperature as described above, but it is possible to further advance the reaction and make it into a polymer. For the purpose, the generated reaction solution is heated to 50-150℃.
Preferably, it may be heated to 70 to 120°C and aged for 0.5 to 5 hours. The silicon-containing Stepladder polymer thus synthesized contains a small amount of silanol groups (Si--OH) due to the steric structure of the polymer and the reaction conditions. Therefore, when concentrating the polymer solution or storing it for a long time,
Crosslinking between polymer chains may occur, resulting in a gelation phenomenon. In order to suppress this phenomenon and stabilize the produced polymer, hexaalkylsilazane represented by the general formula R ⁸ ₃ Si-NH-SiR ⁸ ₃ or the general formula
Trialkylaciloxysilane represented by R ⁸ ₃ Si-OCOR ⁹ (where R ⁸ represents an alkyl group having 1 to 10 carbon atoms, and R ⁹ represents an alkyl group having 1 to 4 carbon atoms), etc. It is also possible to add a silylating agent to the reaction. Through this reaction, the hydroxyl group of the silanol group is replaced with a trialkylsiloxy group, thereby stabilizing the polymer. This silylation reaction itself is a well-known method for reactions of general polysiloxanes or organosilicon compounds, and any known method can be applied to the present invention, and the present invention is not limited to any particular method. . On the other hand, one of the uses of the silicon-containing step ladder polymer according to the present invention is as an insulating varnish for electronic materials, and in this case, an adhesive function is required.
Some presence of silanol groups (SiOH) is desirable. In this case, the conditions for the stabilization reaction are adjusted according to the purpose, and the silanol group content of the produced polymer is determined as the value of the molar ratio of [OH]:[Si].
It is preferable to control it to 0.0005 to 0.25. The polymer according to the present invention includes aliphatic hydrocarbons such as n-hexane and n-heptane, aromatic hydrocarbons such as benzene and toluene, propyl acetate,
It is soluble in many solvents including esters such as ethyl acetate, and the solvent can be selected depending on the purpose of use. "Effects of the Invention" Next, the properties and uses of the polymer of the present invention will be described. As mentioned above, this polymer is easily soluble in solvents and has good coating properties. In addition, the coating film can be heat cured at a temperature of 150 to 200°C without cracking, the thermal decomposition starting temperature is 300°C, and the weight loss is less than 15% when heated to 490°C. Show your gender. Furthermore, this polymer is colorless. These properties have many advantages in terms of workability (productivity) and performance over polyimide resins, which are typical heat-resistant insulating polymers that are commonly used. Due to these advantages, the polymer according to the present invention can be widely used as a chemical material for electrical and electronic devices such as liquid crystal alignment films for liquid crystal display cells, insulating protective films for color filters, and wire coating agents. "Examples" The present invention will be explained in detail below using Examples. Example 1 (1) Synthesis of prepolymer: 50 g of methyl vinylbis(dimethylamino)silane and 80 ml of n-hexane were placed in a 300 ml three-necked flask purged with nitrogen, and 11 mmol of n-butyllithium was added at room temperature in a nitrogen stream. It was added in the form of an n-hexane solution and polymerization was carried out with stirring. 40℃
After carrying out the polymerization reaction at a temperature of 3 hours, the reaction solution was dropped into methanol to precipitate the polymer.
This polymer was repeatedly washed and filtered with methanol 3 to 4 times, and then dried in vacuum. The obtained polymer weighed 23.3 g, and the average degree of polymerization was 12.5 as determined by molecular weight measurement using GPC (gel permeation chromatography) method. (2) Synthesis of Steps Prader Polymer 300ml in a 500ml three-necked flask purged with nitrogen
20 g of the prepolymer obtained in (1) was added to toluene and dissolved. After dissolution, 30 ml of glacial acetic acid was added dropwise at room temperature while stirring in a nitrogen stream to react. After reacting for 1 hour, 1.5 of dimethyl diacetoxysilane
After stirring was continued for 15 minutes, 2.5 ml of water was added dropwise over 10 minutes, and the reaction was continued at room temperature for 1 hour with stirring. After the reaction, transfer the resulting solution to a separating funnel and add 200ml of diethyl ether.
Water was added and washed by shaking to separate the aqueous layer.
After repeating this water washing operation three times, the organic layer was separated, anhydrous potassium carbonate was added thereto, and the mixture was dried overnight. After removing the potassium carbonate, the solution was transferred to a flask and heated with hot water to distill off the ether. 75~
The solution was heated to 80°C and the toluene was distilled off under reduced pressure to concentrate the solution. Concentrate to approximately 10% polymer solution. A portion of this solution was collected and subjected to infrared absorption spectrum analysis and molecular weight measurement by GPC method.
Infrared absorption spectrum analysis was performed after applying the solution to a KBr plate and drying it at 70°C. As shown in Figure 1, the obtained absorption spectra show the characteristic absorption spectrum of the siloxane bonds constituting the ladder structure (the repeating structure of units ()) at 960 cm ^-1 , and the characteristic absorption spectra of the siloxane bonds constituting the step bonds (units ()) at 960 cm -1. The absorption spectra due to bonding are shown at 1020 and 1080 cm ^-1 . The absorbance ratio of this spectrum is
The value of A1080/A960 was 0.1. Furthermore, the results of molecular weight measurement showed that the weight average molecular weight was 1.7×10 ⁴ , and a step ladder polymer consisting of a hydrolyzed condensate of 15 prepolymers was produced. Furthermore, as a result of infrared absorption spectrum measurement, silanol groups (Si-
Although the presence of OH) was observed, this amount was
KELLUM et al.'s method (Anal.Chem.391623 (1967))
According to analysis, the [OH]/[Si] ratio was 0.1. Example 2 (1) Prepolymer synthesis Polymerization was carried out in the same manner as in Example 1, except that the amount of n-butyllithium catalyst used was changed to 10 mmol and 23 mmol, to obtain two types of polymers with different degrees of polymerization. From GPC measurements, the average degree of polymerization was 13.9 and 13.9, respectively.
It was 6.6. (2) Synthesis of Steps Prader Polymer 15g of the prepolymer with a degree of polymerization of 13.9 obtained in (1)
A RADA polymer was synthesized in the same manner as in Example 1, except that 5 g of a polymer with a polymerization degree of 6.6 was used and the amount of diethyldiacetoxysilane was 2.0 g. From the measurement results, the weight average molecular weight is 2.5×10 ⁴ ,
The absorbance ratio of infrared absorption spectrum A1080/A960 is
It was 0.12. Comparative Example 1 (1) Synthesis of prepolymer Polymerization was carried out under the same conditions as in Example 1. The average degree of polymerization of the obtained prepolymer was 11.8. (2) Synthesis of ladder polymer 15 g of the prepolymer obtained in (1) was dissolved in 230 ml of toluene, and a reaction was carried out using the same equipment and conditions as in Example 1. After 22 ml of glacial acetic acid was added dropwise and reacted for 1 hour, 1.7 ml of water was added dropwise to react. After the dropwise addition, stirring was continued for 1 hour to continue the reaction. Washing with water, drying and concentration were performed in the same manner as in Example 1. The analysis results show that the weight average molecular weight is 1.4× ¹⁰³ , and the absorbance ratio in the infrared absorption spectrum is
A1080/A960 was 0.08. Also [OH]/
[Si] ratio was 0.28. Comparative Example 2 (1) Synthesis of prepolymer 15.0 g of methylvinyl diethoxysilane was placed in a nitrogen-substituted flask, 0.05 g of azobisisobutyronitrile was added as a radical polymerization initiator, and the mixture was heated in an oil bath at 140~ Polymerization was carried out at 150°C in a nitrogen stream for 6 hours. After the polymerization was completed, unreacted monomers were removed by vacuum distillation to obtain 13.4 g of polymer. The average degree of polymerization was 11.2. (2) Synthesis of Steps Prader Polymer Add 150 ml of toluene and 0.5 g of dimethyl diethoxysilane to 10.0 g of the prepolymer obtained in (1).
The mixture was transferred to a three-necked flask with a capacity of 300 ml, and 1.2 ml of IN-hydrochloric acid aqueous solution was added thereto, followed by reaction at 50° C. for 3 hours with stirring. After the reaction solution was washed with water and separated three times, the toluene layer was separated and dried over anhydrous potassium carbonate. The toluene solution is concentrated under reduced pressure at 70°C to remove toluene. Analysis of the produced liquid showed that the weight average molecular weight by GPC method was 2300, the infrared absorption spectrum was unchanged compared to the prepolymer, and no absorption spectrum at 960 cm ^-1 was observed. Example 3 A step ladder polymer was synthesized under the same conditions as in Example 1. The obtained polymer had a weight average molecular weight of 1.6×10 ⁴ and an [OH]/[Si] ratio of 0.12. The polymer solution was concentrated by distilling off toluene.
% by weight solution, 0.8 g of hexamethyldisilazane (hereinafter abbreviated as HMD) was added to 100 ml of this solution, and the mixture was reacted at 90° C. for 1 hour with stirring. After the reaction, toluene was distilled off under reduced pressure at 80℃ and the solution was
It was concentrated to % by weight. The obtained Stetsprader polymer had a weight average molecular weight of 2.9×10 ⁴ , and the analysis results showed that the [OH]/[Si] ratio was 0.002. Example 4 (1) Synthesis of prepolymer 70 g of vinyl methyl diethoxysilane and 0.7 g of azobisisobutyronitrile were placed in a 200 ml three-necked flask purged with nitrogen at 130°C in a nitrogen stream.
The polymerization reaction was carried out for 10 hours under stirring. After the reaction was completed, unreacted monomers were distilled off under reduced pressure.
59.1g of polymer was obtained. The molecular weight of the obtained polymer was 4300 as determined by GPC measurement. (2) Synthesis of ladder polymer 50 g of the above prepolymer and 2.1 g of dimethyl diethoxysilane were dissolved in 800 ml of purified toluene, filled in a 23-necked flask equipped with a distiller and purged with nitrogen, and 50 g of acetic anhydride was added. 80℃ in nitrogen stream
Make it react. After 20 minutes had passed from the start of the reaction, the pressure in the reaction tank was reduced to 120 mmHg through a distiller, and the reaction was continued for 3 hours while distilling off the produced ethyl acetate. After the reaction was completed, the reaction vessel was cooled to 30°C, and then 4 ml of distilled water was added dropwise to react, and the reaction was continued for 1 hour. After the reaction is completed, the reaction solution is transferred to a separatory funnel and washed with water to separate the organic layer. After repeating this water washing operation three times, the organic layer is dehydrated and dried with anhydrous potassium carbonate. The dried organic layer was transferred to a distillation vessel, toluene was distilled off under reduced pressure at a temperature of 70°C, and the mixture was concentrated to a 7% polymer solution. The molecular weight of the obtained polymer was measured by GPC method, and the weight average molecular weight was 3.5×10 ⁴ , and the molecular weight distribution was 5.7.
It was hot. The infrared absorption spectrum of this polymer confirmed an absorption at 960 cm ^-1 indicating a ladder structure. Example 5 3.0 g of trimethyl monoacetoxysilane was added to 200 ml of a 10% by weight toluene solution of Steps Prader polymer obtained in the same manner as in Example 1.
After reacting at ℃ for 1 hour, the mixture was transferred to a separatory funnel, washed with water, and separated three times. The toluene layer was dehydrated and dried over anhydrous potassium carbonate, and the toluene was distilled off and concentrated under reduced pressure at 70°C to obtain a 14% by weight polymer solution. As a result of the analysis, the amount of silanol residues was [OH]/
The [Si] ratio was 0.008. Example 6 A 15% by weight solution of the polymer obtained in Examples 1 and 3 and Comparative Examples 1 and 2 was spin-coated onto a silicon wafer (rotation speed: 1000 rpm) and heated at 170°C for 30 minutes. and the electrical properties were investigated. Additionally, the heat resistance of the polymer itself was measured. The results are shown in the table below.

[Table] From these results, it was confirmed that the silicone-containing step ladder polymer according to the present invention has desirable properties as a heat-resistant insulating film. Example 7 A similar reaction was carried out in Example 1 except that methyl vinyl bis(dimethylamino)silane was replaced with 70 g of phenyl vinyl bis(dimethylamino)silane. As a result of analyzing the obtained Stets Prader polymer, an infrared absorption spectrum at 960 cm ^-1 was confirmed, and the absorbance ratio to the absorption at 1080 cm ^-1 was A1080/
The value of A960 is 0.15 and the weight average molecular weight is 2.1×10 ⁴
The molecular weight distribution was 3.7. In addition, the silanol group (SiOH) has a molar ratio of [OH]/[Si] of 0.12.
It was hot. Example 8 A similar reaction was carried out in Example 1 except that methylvinyl bis(dimethylamino)silane was replaced with 65 g of trifluoropropyl vinyl bis(dimethylamino)silane. As a result of analyzing the obtained Steps Prader polymer, an infrared absorption spectrum at 960 cm ^-1 was confirmed, and the absorbance ratio of the infrared absorption spectrum was A1080/
A960 was 0.10, the weight average molecular weight was 1.8×10 ⁴ , and the amount of silanol groups was 0.15 in the molar ratio of [OH]/[Si]. Example 9 A reaction was carried out in the same manner as in Example 1, except that 1.7 g of methyl phenyl diacetoxysilane was used in place of dimethyl diacetoxysilane in the stepladderization reaction of Example 1. As a result of analyzing the obtained Steps ladder polymer, the infrared absorption spectrum shows a ladder structure.
Absorption at 960 cm ^-1 was confirmed. As a result of molecular weight measurement by GPC, the weight average molecular weight was 2.0×10 ⁴ molecular weight distribution was 2.7. Further, the silanol group content was 0.14 in terms of [OH]/[Si] ratio.

[Brief explanation of the drawing]

FIG. 1 is an infrared absorption spectrum of the silicon-containing step ladder polymer according to the present invention obtained in Example 1.

Claims (1)

[Claims] 1. A unit represented by the following general formula () and the unit expressed by the following general formula () A repeating polymer chain represented by the following general formula () containing is the unit expressed by the following general formula () The weight average molecular weight measured by gel permeation chromatography is in the range of 3.0 × 10 ³ to 6.5 × 10 ⁵ (in each of the above formulas,
R ¹ is a hydrocarbon group or a fluorine-substituted hydrocarbon group,
R ² is hydrogen or trialkylsiloxy group, R ³ and R ⁴
are hydrocarbon groups or fluorine-substituted hydrocarbon groups which may be the same or different from each other, R ⁵ and R ⁶ are hydrogen or hydrocarbon residues of a vinyl polymerization initiator, and (r+
s):t is (5-100):1, p is 1-5 and (r
+s+t):p is in the range of (5 to 100):1)
A silicon-containing stepladder polymer characterized by: 2 The infrared absorption spectrum unique to the siloxane bond of the unit () exists in the wave number region of 1020 to 1090 cm ^-1 , and a ring structure that can be formed by repeating the repeating unit (), that is, a molecule of 1,3-disylpropylene 1,5- formed by endosiloxy condensation
Shows the infrared absorption spectrum of the disylpyran ring with a unique wave number of 960 cm ^-1 , and the absorption wave number of 1080 cm ^-1 .
^Absorbance ratio (A1080/
A960) is from 0.05 to 0.3. 3 The number of carbon atoms in R ¹ is 1 to 10;
R ² is a trialkylsilyl group composed of hydrogen or alkyl having 1 to 10 carbon atoms;
3. The polymer according to claim 1, wherein ^R3 and ^R4 have 1 to 10 carbon atoms. 4 R ¹ is an alkyl group having 1 to 4 carbon atoms, a fluorine-substituted alkyl group, or a phenyl group; R ² is a trialkylsilyl group composed of hydrogen or an alkyl having 1 to 4 carbon atoms;
4. The polymer according to claim 3, wherein ^R3 and ^R4 are an alkyl group having 1 to 4 carbon atoms, a fluorine-substituted alkyl group, or a phenyl group. 5 Claims characterized in that R ¹ is a methyl group, trifluoropropyl group, or phenyl group; R ² is hydrogen or a trimethylsilyl group; R ³ and R ⁴ are a methyl group or a phenyl group Polymer according to item 4. 6. The polymer according to claim 1, wherein the hydrocarbon residue of the vinyl polymerization initiator has 2 to 18 carbon atoms. 7 General formula A polyvinylsilane prepolymer ^represented by (where R ¹ is a hydrocarbon group or a fluorine-substituted hydrocarbon group, and R ⁵ and R ⁶ are hydrogen or a hydrocarbon residue of a vinyl polymerization initiator, ^and m represents an ^integer from 5 to ¹⁰⁰ . 4 or less alkyl group), and then intramolecular hydrolytic condensation of the prepolymer with a stoichiometric amount (relative to Si) of water, and the general formula of the prepolymer and step agent. R ³ R ⁴ Si(OCOR ⁷ ) ₂ (where R ³ and R ⁴
is a hydrocarbon group or a fluorine-substituted hydrocarbon group,
R ³ and R ⁴ may be the same group or different groups, and R ⁷ is an alkyl group having 1 to 4 carbon atoms. ) A method for producing a silicon-containing Stepladder polymer, the method comprising carrying out hydrolytic condensation with the polymer. 8 The number of carbon atoms in R ¹ is 1 to 10;
8. The method according to claim 7, wherein ^R3 and ^R4 have 1 to 10 carbon atoms; and the vinyl polymerization initiator residue has 2 to 18 carbon atoms. 9 R ¹ is an alkyl group having 1 to 4 carbon atoms,
A fluorine-substituted alkyl group having 1 to 4 carbon atoms or a phenyl group; R ³ and R ⁴ are an alkyl group having 1 to 4 carbon atoms, a fluorine-substituted alkyl group, or a phenyl group; The method described in Scope Item 8. 10. The method according to claim 9, wherein the R ¹ is a methyl group, a trifluoropropyl group, or a phenyl group; and R ³ and R ⁴ are a methyl group or a phenyl group. 11. The method according to any one of claims 7 to 10, wherein R ⁷ is a methyl group. 12 The X ¹ is a dialkylamino group, and the acyloxylation is performed on the prepolymer in an inert aromatic hydrocarbon solvent with the general formula R ⁷ COOH (wherein
R ⁷ represents the same as above. ) Claims 7 to 1 are characterized in that the method is carried out by adding and reacting an organic acid represented by
The method described in any of Item 1. 13 The reaction is carried out at -5 to 70°C, preferably 10 to 50°C.
13. The method according to claim 12, characterized in that the method is carried out by: 14 Adjust the amount of the acid added to the amount of the prepolymer.
Claim 1 characterized in that the amount is 3 to 5 times, preferably 4 to 4.5 times by mole relative to Si.
2 or 13. 15 said X ¹ is chlorine, bromine or iodine,
The acyloxylation is carried out in an inert hydrocarbon solvent by adding an acid anhydride represented by the general formula (R ⁷ CO) ₂ O (where R ⁷ is the same as above) to the prepolymer. The method according to claim 7, characterized in that it is carried out by reacting. 16 The reaction is carried out at 20-150°C, preferably 40-120°C.
Claim 1 characterized in that
The method described in Section 5. 17 The amount of the acid anhydride to be added is 1.5 to 2.5 times the mole of Si in the prepolymer, preferably 2
17. The method according to claim 15 or 16, characterized in that the amount is increased by ~2.3 moles. 18 Hydrolytic condensation of the acyloxylated prepolymer in an inert aromatic hydrocarbon solvent,
The concentration of the acyloxylated prepolymer is 1 to 1.
Claims 7 to 17 characterized in that it is carried out in a concentration of 30% by weight, preferably 3 to 15% by weight.
The method described in any of the paragraphs. 19 For the hydrolytic condensation, water is added in an amount of 1 to 100 mol, preferably 1 to 10 mol, and more preferably 3 mol to the Si involved in the reaction. A method according to any one of claims 7 to 18, characterized in that: 20. The method according to claim 19, characterized in that the hydrolysis is carried out in the presence of an acid or a base. 21 The hydrolytic condensation is preferably carried out at -5 to 80°C.
The method according to any one of claims 7 to 20, characterized in that the method is carried out at a temperature of 20 to 60°C. 22. The polymer according to any one of claims 7 to ^{21, characterized in that the acyloxylated prepolymer is hydrolyzed in the coexistence of the step agent R3R4Si(OCOR7 ) 2} _. A method for producing an element-containing Steps Prader polymer. 23 After performing intramolecular hydrolytic condensation of the acyloxylated prepolymer, the step agent
22. The method for producing a silicon-containing step ladder polymer according to any one of claims 7 to 21, characterized in that R ³ R ⁴ Si (OCOR ⁷ ) is added and hydrolysis condensation is carried out. 24 After the hydrolytic condensation reaction, the reaction product liquid is heated to 50 to 150 °C, preferably 70 to 120 °C for 0.5 to 5
The method according to any one of claims 7 to 23, characterized in that heating is performed for a period of time. 25 After performing the hydrolytic condensation, the resulting polymer contains hexaalkyl represented by the general formula R ⁸ ₂ Si-NH-SiR ⁸ ₃ (where R ⁸ is an alkyl group having 1 to 10 carbon atoms). Silazane or general formula R ⁸ ₃ Si−
OCOR ⁹ (herein, R ⁸ has the same meaning as above, and R ⁹ is an alkyl group having 1 to 4 carbon atoms.) A patent characterized in that a trialkylaciloxysilane represented by the formula OCOR 9 is subjected to an addition reaction. A method according to any one of claims 7 to 24. 26 General formula A polyvinylsilane ^prepolymer represented ^by
R ⁵ and R ⁶ are hydrogen or a hydrocarbon residue of the vinyl polymerization initiator, and m represents an integer of 5 to 100. ) with the general formula R ³ R ⁴ SiY ₂ (where R ³
and R ⁴ is a hydrocarbon group or a fluorine-substituted hydrocarbon group, R ³ and R ⁴ may be the same group or different groups, Y is an acyloxy group having 2 to 5 carbon atoms, It is an alkoxy group having 1 to 4 carbon atoms or a thioalkoxy group having 1 to 4 carbon atoms. ) is reacted with an acid anhydride represented by the general formula (R ⁷ CO) ₂ O (where R ⁷ is an alkyl group having 1 to 4 carbon atoms). A method for producing a silicon-containing Stepsprader polymer. 27 R ¹ has 1 to 10 carbon atoms; R ³ and R ⁴ have 1 to 10 carbon atoms; and the vinyl polymerization initiator residue has 2 to 18 carbon atoms. 27. The method of claim 26, characterized in: 28 R ¹ represents an alkyl group having 1 to 4 carbon atoms, a fluorine-substituted alkyl group, or a phenyl group; R ³ and R ⁴ represent an alkyl group having 1 to 4 carbon atoms, a fluorine-substituted alkyl group, or a phenyl group 28. A method according to claim 27, characterized in that: 29 Claim 28, wherein R ¹ is a methyl group, trifluoropropyl group, or phenyl group; R ³ and R ⁴ are a methyl group or phenyl group; and Y is an ethoxy group. The method described in. 30. The method according to any one of claims 26 to 29, wherein the R ⁷ is a methyl group. 31 The reaction is carried out at 30-170°C, preferably 50-130°C.
℃, more preferably 50 to 200 mmHg under reduced pressure
Claim 2 characterized in that the process is carried out at 90°C.
The method according to any one of Items 6 to 30. 32 The above Y is the above acyloquine group, and the amount of the acid anhydride is 1 to 1 with respect to Si of the vinyl polymer.
Claim 2, characterized in that the reaction is carried out at a ratio of 3 moles, preferably 1.2 to 2 times.
The method according to any one of Items 6 to 31. 33 The Y is the alkoxy group or the thioalkoxy group, and the reaction is carried out in an amount of the acid anhydride of 1 to 3 times, preferably 1.2 to 2 times, the amount of Si in the vinyl polymer and the step agent. Claims 26 to 3 are characterized in that:
The method described in any of Item 1. 34. The method according to any one of claims 26 to 33, characterized in that water is added after the reaction to perform hydrolysis or hydrolytic condensation and hydrolysis. 35 The reaction temperature when adding the water and performing hydrolysis or hydrolytic condensation and hydrolysis is -5 to 80°C.
35. A process according to claim 34, characterized in that it is carried out at a temperature of preferably 20 to 60<0>C. 36 Adjust the amount of water to be added to the Si of the vinyl polymer.
36. The method according to claim 34 or 35, characterized in that the amount is equal to or less than equimolar. 37 After the hydrolytic condensation reaction, the reaction product liquid is heated to 50 to 150°C, preferably 70 to 120°C by 0.5 to 5
37. A method according to claim 34, 35 or 36, characterized in that heating is performed for a period of time. 38 After the above-mentioned hydrolysis or hydrolytic condensation and hydrolysis, the resulting polymer has the general formula R ⁸ ₃ Si-
Hexaalkylsilazane represented by NH-SiR ⁸ ₃ (here R ⁸ represents an alkyl group having 1 to 10 carbon atoms) or the general formula R ⁸ ₃ Si-OCOR ⁹ (here R ⁸
has the same meaning as above, and R ⁹ is an alkyl group having 1 to 4 carbon atoms. ) Claims 34 to 37 are characterized in that a trialkylaciloxysilane represented by:
The method described in any of the paragraphs.