JP4761139B2 - Efficient production method of siloxane polymer - Google Patents

Description

  The present invention relates to an efficient method for producing polysilsesquioxane or a copolymer of silsesquioxane and siloxane.

  Siloxane polymers such as polysiloxanes, polysilsesquioxanes, and their copolymers are heat resistant in the form of oils, rubbers, resins, etc. using their excellent physical and chemical properties. It is widely used as a high-performance and high-functional material related to weather resistance, impact resistance, sealing, encapsulation, insulation, lubrication, peeling, gas barrier, sealing, coating, etc., and is an extremely important polymer in the industry. . Among these, for example, in the production of polysilsesquioxane, conventionally, a method in which trichlorosilane or trialkoxysilane is used as a raw material, they are hydrolyzed using a catalyst such as an acid or a base, and further thermally polycondensation is performed. Was common. However, conventional polycondensation by normal heating may require heating at a high temperature for a long time, and development of a more efficient production method has been demanded. In terms of the structure of the polymer, there is a possibility that a completely condensed structure having no hydroxy group and an incompletely condensed structure having a remaining hydroxy group may be mixed on silicon, and it is important to control these structures. Furthermore, in the case of polysilsesquioxane, since there are many types of structures such as network type, cage type, ladder type, etc., the control of structure selectivity is also an important issue. It was said.

On the other hand, recently, chemical reactions using microwaves as a new heating method have been reported (Non-patent Documents 1 and 2). However, the scope of its use is still limited, and in the production of polysilsesquioxane and the like according to the present invention, the action and effect of microwave irradiation on the molecular weight of the resulting polymer is not known at all. It was. In early studies of chemical reactions using microwaves, there were many cases of using microwave ovens that could not control temperature as microwave irradiation devices, but in microwave irradiation without temperature control, reactions were controlled. However, this method has a large problem in terms of reproducibility and safety, and is not an industrially advantageous method.
"Microwave thermal catalyst that changes chemistry" Shozo Yanagida, Takeko Matsumura, Doujin Chemical (2004) “Acceleration of reaction by microwave irradiation” Tokuyama Hidetoshi, Nakamura Masaharu, Journal of Synthetic Organic Chemistry, Vol. 63, pp. 523-538 (2005)

  The present invention has been made in view of the circumstances as described above, and an object of the present invention is to provide a polysilsesquioxane whose structure is controlled by efficiently proceeding while controlling the reaction in the condensation polymerization process. Another object of the present invention is to provide a method for producing a copolymer of silsesquioxane and siloxane more efficiently.

  As a result of intensive studies to solve the above problems, the inventors of the present invention accelerated the reaction by controlling the temperature and irradiating microwaves in the condensation polymerization process. It has been found that the structure selectivity can be improved. Specifically, trialkoxysilane or a mixture of trialkoxysilane and dialkoxysilane is hydrolyzed in an aqueous solution in the presence of a catalyst, and then subjected to condensation polymerization by irradiating microwaves while controlling the temperature. The present invention has been completed by finding that it can proceed safely and efficiently, and that a structure-controlled polysilsesquioxane or a copolymer of silsesquioxane and siloxane can be efficiently produced. .

In the production of the polysilsesquioxane according to the present invention, the starting trialkoxysilanes are specifically represented by the following general formula (I):
R ¹ Si (OR ² ) ₃ (I)
(Wherein R ¹ represents a monovalent group selected from an alkyl group, an aryl group, an aralkyl group, a monovalent heterocyclic group, and a hydrogen atom, and R ² represents an alkyl group.)
The polysilsesquioxane obtained is represented by the following general formula (II)
(R ¹ SiO _3/2 ) _n (II)
(In the formula, R ¹ is the same as that in the above general formula (I), n is an integer of 2 to 50000, and when there is a terminal group, a hydroxy group, (This is an alkoxy group derived from a solvent.)
It is represented by

In the production of the copolymer of silsesquioxane and siloxane by the method of the present invention, the raw materials are trialkoxysilanes represented by the above general formula (I) and the following general formula (III)
R ³ R ⁴ Si (OR ⁵ ) ₂ (III)
(Wherein R ³ and R ⁴ represent the same or different monovalent groups selected from an alkyl group, an aryl group, an aralkyl group, a monovalent heterocyclic group, and a hydrogen atom, and R ² represents an alkyl group. .)
The resulting copolymer of silsesquioxane and siloxane is a mixture of dialkoxysilanes represented by the following general formula (IV):
(R ¹ SiO _3/2 ) _p (R ³ R ⁴ SiO) _q (IV)
Wherein R ¹ , R ³ and R ⁴ are the same as those in the general formula (I) and the general formula (III), p and q are integers of 1 to 50000, When there is a terminal group, it is a hydroxy group or an alkoxy group derived from a raw material or a solvent.)
It is represented by

That is, the method of the present invention comprises a trialkoxysilane represented by the general formula (I) or a trialkoxysilane represented by the general formula (I) and a dialkoxysilane represented by the general formula (III). Reaction of a mixture of alkoxysilanes using microwaves in the presence of a catalyst selected from hydrochloric acid, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and at a temperature of 20 to 250 ° C. By making the polysilsesquioxane represented by the general formula (II) or the silsesquioxane and siloxane copolymer represented by the general formula (IV), respectively, by a method of efficiently producing is there.

  The method of the present invention controls the temperature of the polysilsesquioxane represented by the general formula (II) or the copolymer of silsesquioxane and siloxane represented by the general formula (IV). It is also a method of increasing the molecular weight of the siloxane-based polymer by irradiating with microwaves. A catalyst can also be used in this high molecular weight method.

  By using the method of the present invention, there is an advantage that a high-molecular-weight siloxane-based polymer can be obtained in a short time compared to conventional normal heating. In addition, the siloxane-based polymer obtained by the method of the present invention has a feature that a specific structure can be selectively obtained in comparison with normal heating in terms of the polymer structure such as the ratio of residual hydroxy groups and the skeleton structure. .

Hereinafter, the present invention will be described in detail.
The method of the present invention includes a trialkoxysilane represented by the general formula (I) as a raw material, or a trialkoxysilane represented by the general formula (I) and a dialkoxysilane represented by the general formula (III). A method for producing polysilsesquioxane or a copolymer of silsesquioxane and siloxane using a mixture of alkoxysilanes, wherein the polycondensation process is carried out after hydrolysis in a water-containing liquid in the presence of a catalyst. And irradiating with microwaves while controlling the temperature.

In the present invention, the substituent R ¹ in the trialkoxysilanes represented by the general formula (I) is, as described above, an alkyl group, an aryl group, an aralkyl group, a monovalent heterocyclic group, and a hydrogen atom. The monovalent group to be selected is shown, but for those other than a hydrogen atom, more specifically, an alkyl group having preferably 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms, preferably 6 carbon atoms. -20, more preferably 6-10 aryl groups, preferably 7-20 carbon atoms, more preferably 7-10 aralkyl groups, or heteroatoms such as nitrogen, oxygen, sulfur, selenium, silicon, boron, etc. A monovalent heterocyclic ring having at least one member selected from the above, preferably a 3 to 10 membered ring, more preferably a 5 to 8 membered ring. Specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, neopentyl group, hexyl group, octyl group, decyl group, phenyl group, naphthyl group, anthryl group, benzyl group, phenethyl group, pyridyl group. Group, furyl group, thienyl group and the like, and a part of hydrogen atoms of these groups may be substituted with a group such as an alkyl group, an alkoxy group or a halogen atom which does not participate in the reaction. The substituent R ² is an alkyl group, and more specifically, an alkyl group having preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. Accordingly, examples of trialkoxysilanes represented by the above general formula (I) having those substituents include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, propyltriethoxysilane, and hexyltrimethoxysilane. , Isopropyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, naphthyltrimethoxysilane, anthryltrimethoxysilane, benzyltrimethoxysilane, phenethyltrimethoxy Examples thereof include silane, pyridyltrimethoxysilane, furyltriethoxysilane, thienyltrimethoxysilane, trimethoxysilane, and triethoxysilane.

In the present invention, R ³ and R ⁴ in the dialkoxysilanes represented by the general formula (III) are, as described above, an alkyl group, an aryl group, an aralkyl group, a monovalent heterocyclic group, and hydrogen. Although it shows the same or different monovalent groups selected from atoms, those other than hydrogen atoms are more specifically alkyl groups having preferably 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms. An aryl group having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, more preferably 7 to 10 carbon atoms, or a hetero atom such as nitrogen, oxygen or sulfur And a monovalent heterocyclic ring having at least one selected from selenium, silicon, boron and the like, preferably a 3- to 10-membered ring, more preferably a 5- to 8-membered ring. Specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, neopentyl group, hexyl group, octyl group, decyl group, phenyl group, naphthyl group, anthryl group, benzyl group, phenethyl group, pyridyl group. Group, furyl group, thienyl group and the like, and a part of hydrogen atoms of these groups may be substituted with a group such as an alkyl group, an alkoxy group or a halogen atom which does not participate in the reaction. The substituent R ⁵ is an alkyl group, and more specifically, an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. Accordingly, for example, dialkoxysilanes represented by the general formula (III) having those substituents are exemplified by dimethyldiethoxysilane, diethyldiethoxysilane, isopropylmethyldimethoxysilane, dibutyldimethoxysilane, hexylmethyldimethoxysilane, Decylmethyldiethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane, methylnaphthyldimethoxysilane, anthrylmethyldimethoxysilane, benzylmethyldiethoxysilane, methylpyridyldimethoxysilane, difuryldiethoxysilane, methylthienyldimethoxysilane, methyl Examples include dimethoxysilane and phenyldimethoxysilane.

  In addition, as the catalyst used in the reaction of the present invention, various catalysts conventionally used in the production of siloxane-based polymers can be used, but acids or bases are preferably used. Specific examples thereof include hydrochloric acid, sulfuric acid, hydrobromic acid, acetic acid, benzoic acid and the like as acids, and sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium carbonate as bases. Potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonia, triethylamine, triethanolamine, pyridine and the like. These catalysts can be used in combination of two or more, or a salt produced by mixing an acid and a base. The molar ratio of these catalysts to the raw material silanes can be arbitrarily selected as appropriate, but is usually in the range of 0.0000001 to 0.5.

  In the present invention, after the raw material is hydrolyzed in an aqueous solution, the temperature is controlled and microwave irradiation is performed to advance the condensation polymerization reaction. The temperature is 0 ° C. or higher, preferably 20 to It is performed at a temperature of 250 ° C, more preferably 30 to 150 ° C. Further, in the present invention, it is sufficient if there is more water than the catalyst amount necessary for hydrolysis, and it can be carried out regardless of the presence or absence of a solvent, but when using a solvent, methanol, ethanol, 2-propanol, Butanol, alcohols such as ethylene glycol, tetrahydrofuran, diethyl ether, dibutyl ether, diphenyl ether, diglyme, ethers such as polyethylene glycol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, nitriles such as acetonitrile and benzonitrile, dimethylformamide, Various solvents such as amides such as N-methylpyrrolidone, sulfoxides such as dimethyl sulfoxide, hydrocarbons such as benzene, toluene and xylene, water and the like can be used, and two or more kinds can be used in combination.

  In the present invention, various commercially available devices equipped with a contact-type or non-contact-type temperature sensor can be used for microwave irradiation. Furthermore, in the present invention, the degree of microwave irradiation output, whether the type of cavity is multimode or single mode, whether the irradiation mode is continuous or intermittent, etc. are arbitrarily determined according to the scale and type of reaction, etc. be able to.

  Since the reaction of the present invention usually proceeds almost quantitatively, no special purification operation is required after the reaction. However, when purification is performed, it can be easily carried out by commonly used means such as reprecipitation and chromatography. Can be reached.

According to the method of the present invention, the trialkoxysilanes represented by the general formula (I) can be converted from the general formula (R ¹ SiO _3/2 ) _n (II)
The polysilsesquioxane represented by this is produced. In the formula, R ¹ represents the same as those in the general formula (I), n is an integer of 2 to 50,000. Moreover, when there is a terminal group, it is a hydroxy group or an alkoxy group derived from a raw material or a solvent.
Further, according to the method of the present invention, a mixture of the trialkoxysilanes represented by the general formula (I) and the dialkoxysilanes represented by the general formula (III) can be obtained from the general formula (R ¹ SiO _{3 / 2} ) _p (R ³ R ⁴ SiO) _q (IV)
A copolymer of silsesquioxane and siloxane represented by In the formula, R ¹ , R ³ , and R ⁴ are the same as those in general formula (I) and general formula (III), and p and q are integers of 1 to 50000. When there is a terminal group, it is a group such as a hydroxy group or an alkoxy group derived from a raw material or a solvent.

  Furthermore, the siloxane-based polymer represented by the general formula (II) or the general formula (IV) can be efficiently made to have a high molecular weight by irradiating microwaves while controlling the temperature. This reaction proceeds regardless of the presence or absence of a solvent or a catalyst, but when a solvent is used, the solvents exemplified above can be used. Moreover, when using a catalyst, the acid and base catalyst etc. which were illustrated above can be used. The molar ratio of the catalyst to the repeating structural unit of the raw material polymer can be arbitrarily selected as appropriate, but is usually in the range of 0.0000001 to 0.5.

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples.

Example 1
After adding 0.35 ml of 6N hydrochloric acid solution and 0.25 ml of water to a mixed solution of 4.0 ml (20 mmol) of methyltriethoxysilane and 3 ml of ethanol, the mixture was stirred at 0 ° C. for 10 minutes and at room temperature for 10 minutes. Using a microwave irradiation apparatus equipped with a mold temperature sensor (Milestone, MICROSynth, multimode cavity), the reaction was carried out with stirring at 80 ° C. for 20 minutes to obtain polymethylsilsesquioxane. As a result of measuring the molecular weight of the produced polymer by GPC, it was Mw = 4,500 and Mw / Mn = 3.0 (polystyrene standard).

(Examples 2 to 8)
Table 1 shows the results obtained by carrying out the reaction in the same manner as in Example 1 except that the solvent ethanol is changed, and measuring the molecular weight of the produced polymethylsilsesquioxane by GPC in the same manner as in Example 1.

(Examples 9 to 13)
Polyphenylsilsesquioxane was obtained in the same manner as in Example 1 except that 3.6 ml (20 mmol) of phenyltrimethoxysilane was used instead of 4.0 ml (20 mmol) of methyltriethoxysilane. Table 2 shows the results obtained by measuring the molecular weight of polyphenylsilsesquioxane obtained by using various solvents by GPC in the same manner as in Example 1.

(Examples 14 to 17)
The reaction was conducted in the same manner as in Example 9 except that 0.022 g (0.21 mmol) of sodium carbonate and 0.55 ml of water were used instead of 0.35 ml of 6N hydrochloric acid solution and 0.25 ml of water. I got Sun. Table 3 shows the results of measuring the molecular weight of polyphenylsilsesquioxane obtained by using various catalysts (0.21 mmol) by GPC in the same manner as in Example 1.

(Example 18)
To a mixed solution of 2.8 ml (15 mmol) of phenyltrimethoxysilane, 0.85 ml (5 mmol) of dimethyldiethoxysilane and 3 ml of ethanol, a mixture of 0.029 g (0.21 mmol) of potassium carbonate and 0.55 ml of water was added. After stirring at 10 ° C. for 10 minutes and at room temperature for 10 minutes, the reaction was conducted with stirring at 80 ° C. for 20 minutes using a microwave irradiation apparatus to obtain a copolymer of phenylsilsesquioxane and dimethylsiloxane. The molecular weight (measured by GPC) and NMR spectrum data of the produced polymer are as follows. From the results of NMR and elemental analysis, the ratio of phenylsilsesquioxane: dimethylsiloxane was estimated to be about 3: 1.

Mw = 6,410, Mw / Mn = 3.0 (polystyrene standard)
¹ H-NMR (C ₆ D ₆ ) d (ppm) −0.4 to 1.2 (br m, CH ₃ ), 6.6 to 8.3 (br m, C ₆ H ₅ )
²⁹ Si-NMR (C ₆ D ₆ ) d (ppm) −82 to −69 (br m, PhSi (O—) ₃ ), −22 to −10 (br m, Me ₂ Si (O—) ₂ )
Elemental analysis
[(PhSiO _1.5 ) ₃ (Me ₂ SiO)] _n (= (C ₂₀ H ₂₁ O _5.5 Si ₄ ) _n )
Calculated value: C 52.03, H 4.58
Measurements: C 52.00, H 4.67

(Example 19)
Copolymerization of phenylsilsesquioxane and methylphenylsiloxane was carried out in the same manner as in Example 18 except that 0.90 ml (5 mmol) of methylphenyldimethoxysilane was used instead of 0.85 ml (5 mmol) of dimethyldiethoxysilane. A polymer was obtained. The molecular weight (measured by GPC) and NMR spectrum data of the produced polymer are as follows. From the results of NMR and elemental analysis, the ratio of phenylsilsesquioxane: methylphenylsiloxane was estimated to be about 3: 1. .

Mw = 2,860, Mw / Mn = 1.9 (polystyrene standard)
¹ H-NMR (C ₆ D ₆ ) d (ppm) 0.2 to 1.3 (br m, CH ₃ ), 6.8 to 8.3 (br m, C ₆ H ₅ )
²⁹ Si-NMR (C ₆ D ₆ ) d (ppm) −82 to −68 (brm, PhSi (O—) ₃ ), −33 to −23 (brm, MePhSi (O—) ₂ )
Elemental analysis
[(PhSiO _1.5 ) ₃ (MePhSiO)] _n (= (C ₂₅ H ₂₃ O _5.5 Si ₄ ) _n )
Calculated values: C 57.33, H 4.43
Measurements: C 57.27, H 4.66

( Reference Example 1 )
As a result of heating 100 mg of polyphenylsilsesquioxane (0.77 mmol per repeating structural unit) at 180 ° C. for 40 minutes using a microwave irradiation apparatus (CEM, Discover, single mode cavity), the molecular weight of the polymer (GPC Measured value) increased from Mw = 4,790 (Mw / Mn = 2.3) to Mw = 10,390 (Mw / Mn = 3.3).

( Reference Examples 2-12 )
In the presence of a catalyst and / or solvent, a polyphenylsilsesquioxane or a phenylsilsesquioxane / methylphenylsiloxane copolymer is heated and reacted in the same manner as in Example 20 at a temperature of 140 to 180 ° C. Table 4 shows the results obtained by measuring the molecular weight of these by GPC.

Comparative Example 1

(Comparative Example 1)
As a result of carrying out the reaction in the same manner as in Example 1 except that an oil bath was used instead of the microwave irradiation apparatus, the molecular weight of the obtained polymethylsilsesquioxane was Mw = 1,980. The molecular weight, Mw, was less than 4,500. This indicates that the microwave reaction proceeds more efficiently than the normal heating reaction in the oil bath .

Comparative Example 2

(Comparative Example 2)
The reaction was carried out in the same manner as in Example 16 except that an oil bath was used instead of the microwave irradiation apparatus. The molecular weight of the obtained polyphenylsilsesquioxane was measured by GPC. As shown in FIG. Was Mw = 3,540, which was smaller than Mw = 6,610 of Example 16. Furthermore, although the GPC peak was divided into two components, a high molecular weight side and a low molecular weight, in Comparative Example 2, the ratio of high molecular weight side: low molecular weight side was 77:23. In Example 16, it was 89:11, and it was found that microwave heating has the effect of decreasing the low molecular weight component and increasing the high molecular weight component.

Furthermore, when the structure of the produced polysilsesquioxane was compared by ²⁹ Si-NMR, a large difference was found between Example 16 and Comparative Example 2 as shown in FIG. That is, in Comparative Example 2, a T ² structure (−72 to −70 ppm) having a residual hydroxy group was observed in addition to a T ³ structure (−82 to −76 ppm) having a completely condensed structure in which all hydroxy groups were reacted. In Example 16, only the T ³ structure (−82 to −76 ppm) having a completely condensed structure was obtained. Further, even in a region of T ³ structure, between Examples and Comparative Examples, the difference of the signal pattern is seen, a strong signal that is believed to be derived from the specific skeletal structure in the embodiment is observed.

The above results show that the reaction by microwave heating proceeds more efficiently than the normal heating reaction by oil bath, and is also unique in terms of the ratio of residual hydroxy groups in the polymer and the distribution of the skeleton structure. It shows that it has a certain selectivity .

Comparative Examples 3-9

(Comparative Examples 3 to 9)
In other representative examples, as in Comparative Examples 1 and 2, the reaction was carried out in an oil bath, and the results of measuring the molecular weight of the produced polymer by GPC are shown in Table 5 together with the results of the corresponding examples. .

  In any of the comparative examples, the molecular weight of the polymer was smaller than the value of the corresponding example, and it was shown that the reaction is generally accelerated by using microwaves regardless of the raw materials used.

  Polysilsesquioxane obtained by the method of the present invention, or a copolymer of polysilsesquioxane and siloxane is used in the form of oil, rubber, resin, etc. by utilizing their excellent physical and chemical properties. Therefore, it is widely used as various functional materials such as heat resistance, weather resistance, impact resistance, sealing, encapsulation, insulation, lubrication, peeling, gas barrier, seal, coating and the like.

The figure which shows the molecular weight curve by GPC of the polyphenylsilsesquioxane produced | generated in Example 16 and Comparative Example 2 up and down, respectively. It shows the ^{29 Si-NMR} spectrum of polysilsesquioxane produced in Example 16 and Comparative Example 2, above and below, respectively.

Claims (2)

The following general formula (I)
R ¹ Si (OR ² ) ₃ (I)
(In the formula, R ¹ represents a monovalent group selected from an alkyl group, an aryl group, an aralkyl group, a monovalent heterocyclic group, and a hydrogen atom, and R ² represents an alkyl group.)
In the presence of a catalyst selected from hydrochloric acid, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate, the temperature is controlled at 20 to 250 ° C. The following general formula (II), characterized by irradiation
(R ¹ SiO _3/2 ) _n (II)
(In the formula, R ¹ is the same as that in the general formula (I), n is an integer of 2 to 50000, and when there is a terminal group, a hydroxy group, (This is an alkoxy group derived from a solvent.)
The manufacturing method of the siloxane type polymer represented by these. Formula (I)
R ¹ Si (OR ² ) ₃ (I)
(In the formula, R ¹ represents a monovalent group selected from an alkyl group, an aryl group, an aralkyl group, a monovalent heterocyclic group, and a hydrogen atom, and R ² represents an alkyl group.)
And a trialkoxysilane represented by the following general formula (III)
R ³ R ⁴ Si (OR ⁵ ) ₂ (III)
(In the formula, R ³ and R ⁴ represent the same or different monovalent groups selected from an alkyl group, an aryl group, an aralkyl group, a monovalent heterocyclic group, and a hydrogen atom, and R ² represents an alkyl group. .)
In the presence of a catalyst selected from hydrochloric acid, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate, a mixture of dialkoxysilanes represented by The following general formula (IV), characterized by irradiation with waves
(R ¹ SiO _3/2 ) _p (R ³ R ⁴ SiO) _q (IV)
Wherein R ¹ , R ³ and R ⁴ are the same as those in the general formula (I) and the general formula (III), p and q are integers of 1 to 50000, When there is a terminal group, it is a hydroxy group or an alkoxy group derived from a raw material or a solvent.)
The manufacturing method of the siloxane type polymer represented by these.

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