KR20090111341A - Cage-cleavable siloxane resin having functional group and method for production thereof - Google Patents

Abstract

Disclosed is a cage-cleavable siloxane resin having a vinyl, alkyl, phenyl, (meth)acryloyl or aryl group or an oxirane ring, which is compatible with other resin and is controlled in molecular weight distribution and molecular structure. Also disclosed is a method for producing the cage-cleavable siloxane resin in high yield. A cage-cleavable siloxane compound can be produced by hydrolyzing at least one silicon compound represented by the general formula (1) in a non-polar solvent, a polar solvent or a mixture thereof in the presence of a basic catalyst and also partially condensing the compound, re-condensing the resulting polycondensation product in a non-polar solvent in the presence of a basic catalyst, and equilibrating the re-condensed product with a disiloxane compound. R1SiX3 (1) wherein R1 represents a vinyl, alkyl, phenyl, (meth)acryloyl or aryl group or a group having an oxirane ring; X represents a hydroxylable group selected from an alkoxy group, a halogen atom and a hydroxyl group.

Description

Cage-CLEAVABLE SILOXANE RESIN HAVING FUNCTIONAL GROUP AND METHOD FOR PRODUCTION THEREOF}

The present invention relates to a cage cleavage type siloxane resin and a method for producing the same. Specifically, a silicon atom is selected from a vinyl group, an alkyl group, a phenyl group, a (meth) acryl group, an allyl group, or an oxirane ring. Cage cleavage type siloxane resin having two or more organic functional groups, at least two of which have a reactive organic functional group containing an unsaturated double bond selected from a vinyl group, a (meth) acryl group or an allyl group, and a method for producing the same .

Since polyphenylsiloxane is excellent in heat resistance, electrical insulation, etc., it is used other than a coating material, a sealing material, an interlayer insulation film. As an example of the method for producing this polyphenylsiloxane, phenyltrichlorosilane is hydrolyzed in an organic solvent to form phenyltrihydroxysilane, and the hydrolyzate is heated using an alkaline transition and condensation catalyst in a solvent free of water and dehydrated. A method of obtaining a cage-type octaphenylsiloxane by condensation polymerization (Patent Literature 1), the cage-type octaphenylsiloxane is separated, and heat-polymerized again using an alkaline transition and a condensation catalyst to lower the intrinsic viscosity of the phenylsiloxane prepolymer. The method of obtaining (patent document 2), and also the method of heat-polymerizing it using an alkaline transition and a polycondensation catalyst (nonpatent literature 1), etc. are known.

In addition, as a synthesis method of a cage cleavage siloxane resin in which part of the siloxane resin forming the cage form is broken and a part of the cage is cleaved, a synthesis method of siloxane having a cyclohexyl group has been reported by Feher, FJ (Non In addition, the manufacturing method of the cage cleavage type | mold siloxane resin which has a phenyl group and a vinyl group, for example is reported (refer patent document 3).

Moreover, in the said patent document 3, the silicon compound which the triorgano silyl group which has a reactive functional group couple | bonded with all or one part of SiO of the molecular chain terminal of cage-type polyphenylsilsesquioxane which does not contain a silanol group is alkaline in an organic solvent. A method for producing a phenylsiloxane polymer having a reactive functional group by heating and equilibrating in the presence of a transition and condensation catalyst is described.

[Patent Document 1] Japanese Patent Publication No. 40-1598900

[Patent Document 2] Japanese Patent Application Laid-open No. 50-139900

[Patent Document 3] Japanese Patent Application Laid-Open No. 10-251407

[Non-Patent Document 1] J. Polymer Sci. Part C No. 1, pp. 83-97 (1963)

[Non-Patent Document 2] J. Am. Chem. Soc. 111, 1741-8 (1989)

The conventional method of synthesizing cage cleaved siloxane resins as described above requires a long reaction time, does not yield the desired product in high yield, and obtains sufficient physical properties such as elastic modulus and thermal expansion coefficient because the number of reactive functional groups having curability is small. I do not lose. On the other hand, cage-type siloxanes having only one type of curable reactive functional group on all silicon atoms have high crystallinity because of their good symmetry in molecular structure. Therefore, compatibility with other resin is not good, and it is difficult to produce various molded objects which mixed with other resin and modified physical property.

SUMMARY OF THE INVENTION An object of the present invention is to solve a conventional drawback and to use a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group, or an oxirane ring having compatibility with other resins and having controlled molecular weight distribution and molecular structure. Eggplant is to provide a cage cleavage type siloxane resin. In addition, the present invention provides a method for producing such a cage cleavage type siloxane resin in high yield.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors discovered that this could be solved by specific reaction conditions, and came to complete this invention.

That is, this invention is the following general formula (2)

[Wherein R ¹ is a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, and at least two of (m + n) R ^{1 's} have a vinyl having an unsaturated double bond A reactive organic functional group selected from the group, the (meth) acryloyl group or the allyl group, and R ² represents a methyl group. m is an integer of 1-4, n is an integer of 8-16, and the sum of m and n is 10-20.] It is a cage cleavage type siloxane resin represented by.

Moreover, this invention is following General formula (1)

[Wherein R ¹ is a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, and X represents a hydrolyzable group selected from an alkoxy group, a halogen atom or a hydroxyl group.] One or two or more of the silicon compounds represented by the above is hydrolyzed in the presence of a basic catalyst or in a solvent in which one or both of the polar solvents are combined, and at the same time partially condensed, and the resulting polycondensate is also nonpolar. A cage cleavage type siloxane resin obtained by equilibrating a disiloxane compound to the recondensate obtained by recondensing in the presence of a solvent and a basic catalyst.

Moreover, this invention is following General formula (1)

[Wherein R ¹ is a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, and X represents a hydrolyzable group selected from an alkoxy group, a halogen atom or a hydroxyl group.] One or two or more of the silicon compounds represented by the above is hydrolyzed in the presence of a basic catalyst or in a solvent in which one or both of the polar solvents are combined, and at the same time partially condensed, and the resulting polycondensate is also nonpolar. A method for producing a cage cleaved siloxane resin, wherein the disiloxane compound is equilibrated with the recondensate obtained by recondensing in the presence of a solvent and a basic catalyst.

Examples of the structural formula of the cage cleavage type siloxane resin in the present invention are shown in the following formulas (4) to (10). Here, structural formula (4) is the case of m = 2 and n = 8 in general formula (2), and (5) is m = 3, n = 9, (6) is m = 2, n = 10 similarly below (7) is m = 3, n = 11, (8) is m = 2, n = 12, (9) is m = 3, n = 13, and (10) is m = 2 and n = 14. Moreover, the cage cleavage type siloxane resin of this invention may take m and n numbers other than these, but it is not limited to this. In addition, R <^1> and R <^2> in structural formula (4)-(10) are the same as that of the general formula (2).

In the cage cleavage type siloxane resin production method of the present invention, first, a silicon compound represented by the general formula (1) is hydrolyzed in a solvent in which one or both of a nonpolar solvent and a polar solvent are combined in the presence of a basic catalyst. Is done. In general formula (1), R <^1> is an organic group chosen from the group which has a vinyl group, a phenyl group, an alkyl group, a (meth) acryloyl group, an allyl group, or an oxirane ring, and group which has an unsaturated double bond in order to provide curability. Include.

In General formula (1), X is a hydrolysable group, Specifically, Although an alkoxy group, a halogen atom, or a hydroxyl group is mentioned, It is preferable that it is an alkoxyl group. As an alkoxy group, a methoxy group, an ethoxy group, n- and i-propoxy group, n-, i-, and t-butoxy group etc. are mentioned. It is preferable that it is a methoxy group with high reactivity among these.

About the silicon compound represented by General formula (1), when a specific example of a preferable compound is shown, phenyl trimethoxysilane, phenyl triethoxysilane, methyl trimethoxysilane, methyl triethoxysilane, ethyltrimethoxysilane , Ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, octyltrimeth Methoxysilane, octyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3 -Acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclo Hexylethyl) trimethoxysilane, allyltrimeth Sisilran, it is in the allyl triethoxysilane, p- styryl triethoxysilane, p- styryl trimethoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane, and the and the like silane. Among them, phenyltrimethoxysilane, methyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and vinyltrimethoxysilane, which are easily available, are available. More preferred.

As a basic catalyst used for the said hydrolysis reaction, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyl trimethylammonium hydroxide besides alkali metal hydroxides, such as potassium hydroxide, sodium hydroxide, and cesium hydroxide, are mentioned. Ammonium hydroxide salts, such as a lock seed and the benzyl triethylammonium hydroxide, are illustrated. Among them, tetramethylammonium hydroxide is preferably used in view of high catalytic activity. Basic catalysts are usually used as an aqueous solution.

About hydrolysis reaction conditions, 0-60 degreeC is preferable and 20-40 degreeC of reaction temperature is more preferable. If reaction temperature is lower than 0 degreeC, reaction rate will become slow and a hydrolysable group will remain in an unreacted state, resulting in a large consumption of reaction time. On the other hand, if it is higher than 60 DEG C, the reaction rate is too fast, so that a complicated condensation reaction proceeds, and as a result, the high molecular weight of the hydrolysis product is promoted. Moreover, 2 hours or more of reaction time is preferable. If the reaction time is less than 2 hours, the hydrolysis reaction does not proceed sufficiently and the hydrolyzable groups remain in an unreacted state.

The presence of water is essential for the hydrolysis reaction, which may be supplied from an aqueous solution of a basic catalyst or may be added as separate water. The amount of water is more than an amount sufficient to hydrolyze the hydrolyzable group, preferably 1.0 to 1.5 times the theoretical amount. In the case of hydrolysis, one or both of a nonpolar solvent and a polar solvent may be used. Preferably, both are used, or only polar solvent is used. As a polar solvent, alcohol, such as methanol, ethanol, 2-propanol, or another polar solvent can be used. Preferably, it is C1-C6 lower alcohols which are soluble in water, and it is more preferable to use 2-propanol. If only the non-polar solvent is used, the reaction system is not uniform and the polymer is easily precipitated during the reaction.

After completion of the hydrolysis reaction, the reaction solution is neutralized with a weakly acidic solution to approximate neutrality or acidity, and then water or a water-containing reaction solvent are separated. Separation of water or a water-containing reaction solvent may be carried out by washing the solution with brine or the like to sufficiently remove moisture and other impurities, and then drying the solution with a drying agent such as anhydrous magnesium sulfate. When a polar solvent is used, means, such as evaporation under reduced pressure, can be employ | adopted, after removing a polar solvent, a nonpolar solvent is added, a polycondensate is melt | dissolved, and washing and drying are performed as mentioned above. As for the weakly acidic solution, sulfuric acid dilute solution, hydrochloric acid dilute solution, citric acid solution, acetic acid, aqueous ammonia chloride solution, malic acid solution, phosphoric acid solution, oxalic acid solution and the like are used. If the nonpolar solvent is separated by means of evaporation or the like, the hydrolysis reaction product can be recovered. However, if the nonpolar solvent can be used as the nonpolar solvent used in the next reaction, it is not necessary to separate it.

In the hydrolysis reaction of the present invention, the condensation reaction of the hydrolyzate occurs with the hydrolysis. The polycondensate with the condensation reaction of the hydrolyzate is usually a colorless viscous liquid having a number average molecular weight of 500 to 7000. The polycondensate is a resin (or oligomer) having a number average molecular weight of 500 to 3000, depending on the reaction conditions, and most, preferably almost all, of the hydrolyzable group X represented by the general formula (1) are substituted with OH groups Most of the OH groups, preferably 95% or more, are condensed.

As for the structure of the polycondensate, as the plural types of cage type, ladder type, and random type siloxane, the ratio of the complete cage type to the compound having the cage type is small, and the incomplete cage type in which part of the cage is opened. The structure is the master. This polycondensate is also heated in the presence of a nonpolar solvent and a basic catalyst to selectively prepare a recondensate (siloxane of cage-like structure) by condensing siloxane bonds (called recondensation).

When obtaining a recondensate, water or a water containing reaction solvent is isolate | separated, and a recondensation reaction is performed in presence of a nonpolar solvent and a basic catalyst. About reaction conditions of recondensation reaction, the range of reaction temperature is preferable 90-200 degreeC, and 100-140 degreeC is more preferable. If the reaction temperature is too low, sufficient driving force is not obtained to cause the recondensation reaction and the reaction does not proceed. If the reaction temperature is too high, the reactive organic functional group may cause a self-polymerization reaction. Therefore, it is necessary to suppress the reaction temperature or add a polymerization inhibitor or the like. The reaction time is preferably 2 to 12 hours. The amount of the nonpolar solvent is preferably used in an amount sufficient to dissolve the hydrolysis reaction product, and the amount of the basic catalyst is in the range of 0.1 to 5 wt% based on the recondensate. More preferably, it is the range of 0.5-2.Owt%.

As a nonpolar solvent, what is necessary is just to have little or no solubility with water, and a hydrocarbon type solvent is preferable. Examples of the hydrocarbon solvent include nonpolar solvents having a low boiling point such as toluene, benzene, and xylene, and among them, toluene is preferable. On the other hand, as a basic catalyst, the basic catalyst used for a hydrolysis reaction can be used, Alkali metal hydroxides, such as potassium hydroxide, sodium hydroxide, and cesium hydroxide, or tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutyl Ammonium hydroxide salts, such as ammonium hydroxide, benzyl trimethylammonium hydroxide, benzyl triethylammonium hydroxide, etc. are mentioned, The catalyst which is soluble in nonpolar solvents, such as tetraalkylammonium, is preferable. In addition, when using a nonpolar solvent when hydrolyzing the silicon compound of General formula (1) in presence of a basic catalyst, the thing similar to what was illustrated above can be used. The nonpolar solvents used in the hydrolysis reaction and the nonpolar solvents used for obtaining the recondensate may be the same or different ones. In order to simplify the synthesis procedure and the like, the same ones are preferably used. .

The hydrolysis product used for recondensation is preferably water washed, dehydrated and concentrated, but can be used without performing water washing and dehydration. In this reaction, although water may be present, it is not necessary to actively add, and it is better to stay at the moisture level coming from the basic catalyst solution. In addition, when the hydrolysis of the polycondensate is not sufficiently performed, water more than the theoretical amount necessary for hydrolyzing the remaining hydrolyzable group is required. After the recondensation reaction, the catalyst is washed with water to remove and concentrate to obtain a recondensate.

Subsequently, the cage cleavage type siloxane resin can be obtained by adding a disiloxane compound to the recondensate obtained above. About this disiloxane compound, it can be represented by following General formula (3) specifically. Moreover, about the reaction at the time of adding a disiloxane compound to recondensate, nonpolar solvents, such as toluene, benzene, and xylene, and basics, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide, are mentioned. It is preferable to carry out in the presence of a catalyst.

(Wherein R ¹ is one or two groups selected from a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, and R ² represents a methyl group.)

The addition reaction under the base catalyst between the recondensate described above and the disiloxane compound represented by the general formula (3) is an equilibrium reaction, and cleavage of the recondensate composed of silicon atom units (T units) having 3/2 oxygen atoms bonded thereto. Alternatively, the former (the cleavage of the recondensate) needs to be performed as preferentially as it is a competitive reaction of high molecular weight by the recondensate alone. In addition, since the reaction in the present invention is basically an equilibrium reaction, the number-average molecular weight Mn, the yield, and the production rate of the cage cleaved siloxane having a reactive functional group at the terminal of the target are reaction temperature, reaction time, ratio of addition amount of both raw materials, Since it determines by itself based on alkali catalyst amount etc., it is preferable to carry out on condition described below.

That is, it is preferable that the recondensate obtained above adds the disiloxane compound represented by General formula (3) in presence of a nonpolar solvent and a basic catalyst. About reaction conditions, the range of 90-200 degreeC is preferable and, as for reaction temperature, 100-140 degreeC is more preferable. However, as for the low boiling point of the disiloxane compound represented by the general formula (3), the reaction temperature may be higher than the boiling point and may evaporate out of the reaction system. Under basic conditions, the siloxane bonds that form the cage of the recondensate are in the equilibrium state of cleavage and bond. If a disiloxane compound is present, a portion of the cage is stable with cleavage because the cleaved portion reacts with the disiloxane compound. The cage cleavage type siloxane resin is obtained. The cage cleavage siloxane here refers to a siloxane molecular structure in which at least one of the siloxane bonds forming the cage structure is broken to form an incomplete cage structure. Moreover, as for reaction time, 1-5 hours are preferable.

When using a nonpolar solvent in the equilibrium reaction of a recondensate and a disiloxane compound, the usage amount of a nonpolar solvent is good enough to melt | dissolve a recondensate. On the other hand, the reaction ratio between the recondensate and the disiloxane compound is 0.5 to 4.0 moles of the disiloxane compound per 1 mole of the structural unit represented by [R ¹ SiO _1.5 ] ₁₀ corresponding to 10 T units of the recondensate. Preferably, it is hydrolyzed and added so that it may become 1.0-2.0 mol. If the disiloxane compound is less than this range, the reaction does not proceed. On the contrary, if the disiloxane compound is too large, the unreacted substance may adversely affect the physical properties of the product. In addition, in the case of using a highly volatile disiloxane compound such as hexamethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, and the like, the amount of volatilized during the reaction is also considered. Even if you set a large amount of addition, it does not interfere. In addition, as an example of the nonpolar solvent used here, the same thing as what is used when obtaining a recondensate can be illustrated, It may be the same as what is used when obtaining a recondensate, and another thing may be used.

In addition, when using a basic catalyst in the equilibrium reaction of a recondensate and a disiloxane compound, about basic usage amount of a basic catalyst, a basic catalyst is 0.05 with respect to 1 mol of structural units of the recondensate represented by [R ¹ SiO _1.5 ] ₁₀ . It is good to add so that it may become -0.15 mol, Preferably it is 0.06-0.1 mol.

When the specific example of a preferable compound is shown about the disiloxane compound represented by General formula (3), 1, 3- diphenyl- 1, 1, 3, 3- tetramethyl disiloxane, hexamethyl disiloxane, and hexaethyl disiloxane are shown. , Hexaphenyldisiloxane, pentamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetravinyldimethyldisiloxane, 1,3-diethyl-1,1,3 , 3-tetramethyldisiloxane, 1,3-din-propyl-1,1,3,3-tetramethyldisiloxane, 1,3-dibutyl-1,1,3,3-tetramethyldisiloxane, 1,3-dipentyl-1,1,3,3-tetramethyldisiloxane, 1,3-dioctyl-1,1,3,3-tetramethyldisiloxane, 1,3-dimethacryloxymethyl- 1,1,3,3-tetramethyldisiloxane, 1,3-di (3-methacryloxypropyl) -1,1,3,3-tetramethyldisiloxane, 1,3-diacryloxymethyl-1 , 1,3,3-tetramethyldisiloxane, 1,3-di (3-acryloxypropyl) -1,1,3,3-tetramethyldisiloxane, 1,3-di (3-glycidoxypropyl ) -1,1,3,3-tetramethyldisiloxane, bis [2- (3,4-epoxy Chlohexyl) ethyl] -tetramethyldisiloxane, 1,3-diallyl-1,1,3,3-tetramethyldisiloxane, 1,2-dip-styryl-1,1,3,3-tetra Methyl disiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, and the like.

Cage cleavage type siloxane resin obtained by this invention is structural formula (4)-(10) whose m of General formula (2) is 1-4, n is 8-16, and the sum of m and n is 10-20. It is often obtained as a mixture of compounds represented by these. In addition, the number average molecular weight Mn of the cage cleavage type siloxane resin obtained is the range of 600-10000 normally.

Effect of the Invention

By using the cage cleavage siloxane resin production method of the present invention, a structure-controlled cage cleavage siloxane resin having a low molecular weight dispersion degree can be produced in high yield. The resulting cage cleaved siloxane resin has low molecular symmetry, low viscosity, and compatible compatibility with siloxane oligomers having reactive functional groups, and therefore can be widely used as a raw material for curable resin compositions. Moreover, since it is a siloxane of the structure similar to a cage structure, the molded object obtained by hardening | curing the curable resin composition containing the cage cleavage type | mold siloxane resin of this invention has the same strength, transparency, heat resistance, and dimensional stability as an inorganic glass, The same high toughness and good workability are imparted, and are applied to optical applications such as lenses, optical disks, optical fibers and flat panel display substrates, and window materials such as various transportation machines and houses. It can also be used for various transparent members that require light weight, high impact strength, and the like, and both benefits and impacts are large.

1 is a GPC chart of a recondensate wherein R ¹ is CH ₂ = CH-.

FIG. 2 is a GPC chart of a cage cleaved siloxane resin mixture in which R ¹ is CH ₂ ═CH— and R ² is CH ₃ −.

3 is an MS spectrum of a cage cleaved siloxane resin mixture in which R ¹ is CH ₂ = CH— and R ² is CH ₃ −.

4 is a GPC chart of the recondensate wherein R ¹ is (CH _3- : CH ₂ = CH- = 5: 5).

5 is a GPC chart of a cage cleaved siloxane resin in which R ¹ is (CH _3- : CH ₂ = CH- = 5: 7) and R ² is CH _3- .

6 is a GPC chart of a cage cleaved siloxane resin mixture in which R ¹ is (CH _3- : CH 2 = CH- = 2: 10) and R ² is CH _3- .

7 is a GPC chart of a cage cleavage type siloxane resin mixture when R ¹ and R ² are as shown in the figure.

8 is a cage cleaved siloxane resin mixture with R ¹ = (CH ₂ = C (CH ₃ ) -COO- (CH ₂ ) _3- : CH ₂ = CH- = 2: 10), R ² = CH _3- GPC chart.

Hereinafter, the present invention will be described in more detail based on Examples.

<Example 1>

Into a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 150 ml of toluene and 85 ml of 2-propanol (IPA) were added as a solvent, and 37.2 g of a 5% aqueous tetramethylammonium hydroxide solution (TMAH aqueous solution) as a basic catalyst. Put it. 25 ml of toluene and 50.3 g of trimethoxyvinylsilane (KBM1OO3 manufactured by Shin-Etsu Chemical Co., Ltd.) were added to the dropping funnel, and the toluene solution of trimethoxyvinylsilane was added dropwise at room temperature for 3 hours while stirring the reaction vessel. After completion of the dropwise addition of trimethoxyvinylsilane, the mixture was stirred at room temperature for 2 hours. After stirring for 1 hour, stirring was stopped and left standing for 1 day. The reaction solution was neutralized with 23.0 g of 10% aqueous citric acid solution, washed with saturated brine, and dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to give 20.6 g of a polycondensate in a yield of 77%. This polycondensate was a white solid that was insoluble in various organic solvents. Moreover, as a result of measuring GPC of a polycondensate, the number average molecular weight was Mn1188 and molecular weight dispersion degree (Mw / Mn) was 2.03.

Next, 15.0 g of the polycondensate obtained above, 380 ml of toluene and 1.72 g of a 5% aqueous TMAH solution were added to a reaction vessel equipped with a stirrer, Dean-Stark, cooling tube, and thermometer, and the water was distilled off at 120 ° C. While toluene was heated to reflux to carry out a recondensation reaction. After toluene reflux, the mixture was stirred for 3 hours, and then returned to room temperature to terminate the reaction. The reaction solution was neutralized with 23.0 g of 10% citric acid, washed with saturated brine, and dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 14.5 g of a recondensate. The resulting recondensate was a white solid, poorly soluble in various solvents. The result of measuring GPC of this recondensate is shown in FIG. [R ¹ SiO _1.5] of the re-condensation product, which is represented by _n, n is 13 or more cage-siloxane, a ladder (ladder) type siloxane, and a peak including a random siloxane-type 1 [number average molecular weight Mn1979 (Mw / Mn2.03 )] And peak 2 (number average molecular weight Mn747 (Mw / Mn1.02)) containing cage-type siloxane whose n is 12 or less were obtained.

Subsequently, 14.5 g of the recondensate obtained above, 300 ml of toluene, 3.0 g of a 5% TMAH aqueous solution, and 1,3-divinyl-1,1,3, were added to a reaction vessel equipped with a stirrer, a Dean Stark, and a cooling tube. 9.76 g of 3-tetramethyldisiloxane (TMDVDS: LS-7250, manufactured by Shin-Etsu Chemical Co., Ltd.) was added thereto, and toluene was heated to reflux at 120 ° C. to carry out equilibration reaction. After toluene reflux, the mixture was stirred for 3 hours and then returned to room temperature to terminate the reaction. The reaction solution was neutralized with 3.24 g of 10% citric acid, washed with saturated brine, and dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 16.9 g of the desired cage cleavage siloxane (mixture) in a yield of 88%. The obtained cage cleavage type siloxane resin was a colorless viscous liquid soluble in various organic solvents.

The result of measuring GPC of this cage cleavage type siloxane resin is shown in FIG. The number average molecular weight of the cage cleaved siloxane resin was obtained as MnlO49 (peak 3: Mw / Mn1.17). Peak 1 (Mn1979) of the recondensate shifted to the low molecular side and peak 2 (Mn747) shifted to the polymer side by the equilibrium reaction of the disiloxane compound (peak 3). The number average molecular weight of the shifted peak was almost identical to the value in which one molecule of the disiloxane compound was added to the number average molecular weight of peak 2 of the recondensate. Also as to peak 1, [R ¹ SiO _1.5] the great compound more than n 13 of _n, the equilibration reaction is coupled is repeated with the cutting of a siloxane bond in the heating of n is made small, this and the disiloxane compound is that the reaction I think. From this result, it turns out that cage cleavage type | mold siloxane resin was obtained by cut | disconnecting a part of siloxane bond which forms the cage of a polycondensate, and reacting with a disiloxane compound.

Furthermore, when 1H-NMR of the cage cleavage type siloxane resin obtained above was measured, the 5.8-6.2 ppm multiplet peak by 6.2-5.7 ppm vinyl group, and the peak integral ratio by 0.17 ppm methyl group, It was methyl group 6 with respect to vinyl group 15.4.

Moreover, the result of having performed mass spectrometry by the obtained cage cleavage type | mold siloxane resin by the liquid chromatography atmospheric pressure ionization analyzer (LC / APCI-MS) is shown in FIG. In addition, Table 1 summarizes the main peaks detected by mass spectrometry and the numerical values corresponding to m and n in the general formula (2). The peak m / z to be detected is the molecular weight of the cage cleavage type siloxane resin represented by the following general formula (2) (wherein m is 1 to 4, n is 8 to 16, and the sum of m and n is 10 to 20). Ammonium ion is added value. From the mass spectrometry results, it can be seen that the cage cleavage siloxane resin was obtained by cleaving a part of the siloxane bonds forming the cage of the polycondensate and reacting with the disiloxane compound.

<Example 2>

As in Example 1, in a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 384 ml of toluene, 40.0 g of 5% TMAH aqueous solution, 192 ml of 2-propanol (IPA), 43.6 g of trimethoxyvinylsilane, trimethoxy A solution of 47.4 g of methylsilane and 128 ml of IPA was added dropwise for 3 hours, and then stirred at room temperature (20-25 ° C.) for 3 hours. This reaction solution was allowed to stand for 1 day. The reaction solution was neutralized with 10% aqueous citric acid solution, washed with saturated brine, and dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 46.6 g of a polycondensate having a methyl group and a vinyl group in a yield of 80%. As a result of measuring the GPC of this polycondensate, the number average molecular weight was Mn1447 (Mw / Mn31.5).

Next, 15.0 g of the polycondensate obtained above, 380 ml of toluene and 1.72 g of a 5% aqueous TMAH solution were added to a reaction vessel equipped with a stirrer, a Dean Stark, a cooling tube, and a thermometer, and the toluene was heated to reflux at 120 ° C. while the water was distilled off. To carry out a recondensation reaction. After toluene reflux, the mixture was stirred for 3 hours, and then returned to room temperature to terminate the reaction. The reaction solution was neutralized with 23.0 g of 10% citric acid, washed with saturated brine, and dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 14.5 g of a recondensate. As a result, a colorless transparent liquid was obtained. The result of measuring GPC of this recondensate is shown in FIG. Peak 4 [number average molecular weight Mn1676 (Mw / Mn1.27)] and n containing cage type siloxane, ladder type siloxane, and random type siloxane in which n is 13 or more among the recondensates represented by [R ¹ SiO _1.5 ] _n ; The peak 5 (number average molecular weight Mn645 (Mw / Mn1.02)) containing this 12 or less cage type siloxane was obtained. However, R ^{1 in the} recondensate [R ¹ SiO _1.5 ] _n includes _one having only a vinyl group, one having only a methyl group, and one having two kinds of vinyl groups and methyl groups.

10 g of the recondensate obtained above, 342 ml of toluene, 3.0 g of a 5% TMAH aqueous solution and 9.6 g of TMDVDS were placed in a reaction vessel equipped with a stirrer, a Dean Stark and a cooling tube, and toluene was heated to reflux at 120 ° C. while distilling off water. Hydrolysis addition reaction was performed. After stirring for 3 hours while refluxing toluene, the reaction was returned to room temperature to complete the reaction. The reaction solution was neutralized with 1.2 g of 10% citric acid, washed with distilled water, and dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 11.4 g of the desired cage cleavage type siloxane resin in a yield of 86%. The obtained cage cleavage type siloxane resin was a colorless viscous liquid soluble in various organic solvents. The result of measuring GPC of this cage cleavage type siloxane resin is shown in FIG. The number average molecular weight of the cage cleaved siloxane was obtained as Mn928 (peak 6: Mw / Mn1.16).

<Example 3>

7.95 g of the recondensate obtained in the same manner as in Example 1, 1.41 g of hexamethyldisiloxane, 0.47 g of a 5% TMAH aqueous solution, and 50 ml of toluene were placed in a reaction vessel equipped with a stirrer, Dean Stark and a cooling tube, at 80 ° C. After stirring for 3 hours, the temperature was raised to 100 ° C, increased for 1.5 hours, and further heated to 130 ° C and stirred for 1.5 hours. The reaction solution was returned to room temperature, neutralized with citric acid and 3.24 g of 10% citric acid, washed with saturated brine, and dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 9.45 g of the desired cage cleavage type siloxane resin in a yield of 94%. The obtained cage cleavage siloxane was a colorless viscous liquid soluble in various organic solvents. The result of measuring GPC of this cage cleavage type siloxane resin is shown in FIG. The number average molecular weight of the cage cleaved siloxane resin was obtained as Mn939 (Peak 7: Mw / Mn1.12).

<Example 4>

5.00 g of recondensate obtained in the same manner as in Example 1, 1,3-di (3-glycidoxypropyl) -1,1,3,3-tetramethyldisiloxane (LS of Shin-Etsu Chemical Co., Ltd.) -7970) 2.28 g, 5% TMAH aqueous solution, 1.14 g and 63 ml of toluene were placed in a reaction vessel equipped with a stirrer, Dean Stark, and a cooling tube, and toluene was heated to reflux at reflux to remove water at 120 ° C. A condensation reaction was performed. After toluene reflux for 5 hours, the reaction mixture was returned to room temperature to complete the reaction. The reaction solution was washed with saturated brine and dehydrated with anhydrous magnesium sulfate. The reaction mixture of the desired cage cleavage type siloxane resin, the recondensate, and 1,3-bis (glycidoxypropyl) -1,1,3,3-tetramethyldisiloxane by filtration-separating anhydrous magnesium sulfate and concentrating. 6.48 g was obtained in 89% yield. In GPC, the peak (peak 9: Mn357) of the disiloxane which is a raw material, and the peak (peak 8: Mn1242) containing cage cleavage type siloxane and a recondensate were confirmed. The obtained reaction mixture was a transparent viscous liquid soluble in various organic solvents. The result of measuring GPC of this reaction mixture is shown in FIG.

<Example 5>

4.00 g of the recondensate obtained in the same manner as in Example 1, 2.27 g of 1,3-di (3-methacryloxypropyl) -1,1,3,3-tetramethyldisiloxane, 1.07 g of a 5% aqueous TMAH solution, and 60 ml of toluene was placed in a reaction vessel equipped with a stirrer, Dean Stark and a cooling tube, and toluene was heated to reflux while distilling off water at 120 ° C to conduct a recondensation reaction. After toluene reflux for 5 hours, the reaction mixture was returned to room temperature to complete the reaction. The reaction solution was washed with saturated brine and dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to react the desired cage cleavage siloxane resin with the recondensate and 1,3-di (3-methacryloxypropyl) -1,1,3,3-tetramethyldisiloxane. 5.51 g of the mixture was obtained in a yield of 91%. In GPC, the peak (peak 11: Mn422) of the disiloxane which is a raw material, and the peak (peak 10: Mn1122) containing cage cleavage type | mold siloxane resin and the recondensate were confirmed. The reaction mixture containing the obtained cage cleavage type siloxane resin was a transparent viscous liquid soluble in various organic solvents. The result of measuring GPC of this reaction mixture is shown in FIG.

In Examples 1 to 5 described above, the amounts added at the time of equilibrating the disiloxane compound to the recondensate are summarized in Table 2 below.

In addition, in Table 3 below, the results of GPC calculation of the cage cleavage type siloxane resin obtained in Examples 1 to 5 are collectively shown. By equilibration of the disiloxane compound, peak 1 (Mn1979) of the recondensate was shifted to the low molecular side, and peak 2 (Mn747) was shifted to the polymer side. The number average molecular weight of the shifted peak was almost identical to the value in which one molecule of the disiloxane compound was added to the number average molecular weight of peak 2 of the recondensate. Also as to peak 1, [R ¹ SiO _1.5] as a large compound more than n 13 of _n, the coupling is repeated with the cutting of a siloxane bond in the heating of the equilibrated reaction n is made small, which in the disiloxane compound that additional I think. These results show that the cage cleavage type siloxane resins obtained in Examples 1 to 5 were obtained by cleaving a part of the siloxane bonds forming the cage of the polycondensate and reacting with the disiloxane compound.

In addition, the compatibility of the cage cleavage type siloxane obtained in the said Examples 1-5 with other siloxane resins (11)-(14) was confirmed. The results are shown in Table 4. From these results, cage-type siloxanes, which are recondensates, have high crystallinity and little compatibility with other siloxane resins, but in cage cleavage siloxane resins that cleave some siloxane bonds in a cage-like structure by equilibration reactions, other siloxanes. It can be seen that the compatibility with the resin is greatly improved. In addition, the symbol in Table 4 shows "(circle): compatibility, x: no compatibility". Moreover, the siloxane resins (11), (12), (13), and (14) which confirmed compatibility are compounds represented by the general formula shown below.

Table 5 below shows peaks 3, 6, 7, 8, and 10 except for the disiloxane compound as a raw material in the GPC chart of the cage cleavage type siloxane resin obtained in Examples 1 to 5, respectively. Recalculate by dividing by, and use the formula (2)

However, the result which puts together the number average molecular weight and the area ratio of the molecular weight range which correspond to (m is 1-4, n is 8-16, and the sum of m and n is 10-20) is shown.

Claims (10)

General formula (2)

[Wherein R ¹ is a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, and at least two of (m + n) R ^{1 's} have a vinyl having an unsaturated double bond A reactive organic functional group selected from the group, the (meth) acryloyl group or the allyl group, and R ² represents a methyl group. m is an integer from 1 to 4, n is an integer from 8 to 16, and the sum of m and n is 10 to 20.] Cage cleavage type siloxane resin, characterized in that represented by. The method of claim 1, Cage cleavage type siloxane resin, characterized in that the number average molecular weight Mn is in the range of 600 to 10000, and the proportion of the peak having the largest area in the GPC chart is 50% or more. The method of claim 1, Cage cleavage type siloxane resin whose number average molecular weight Mn is the range of 900-2000, and molecular weight dispersion degree (Mw / Mn) is 1.0-3.5. General formula (1)

[Wherein R ¹ is a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, and X represents a hydrolyzable group selected from an alkoxy group, a halogen atom or a hydroxyl group.] One or two or more of the silicon compounds represented by the above is hydrolyzed in the presence of a basic catalyst or in a solvent in which one or both of the polar solvents are combined, and at the same time partially condensed, and the resulting polycondensate is also nonpolar. The cage cleavage type siloxane resin obtained by equilibrating a disiloxane compound with the recondensate obtained by recondensing in presence of a solvent and a basic catalyst. The method of claim 4, wherein The disiloxane compound is represented by the following general formula (3)

[Wherein R ¹ is a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, and R ² represents a methyl group.] Cage cleavage type siloxane resin, characterized in that represented by. The method of claim 4, wherein Cage cleavage type siloxane resin whose number average molecular weight Mn is the range of 600-10000, and molecular weight dispersion degree (Mw / Mn) is 1.0-3.5. General formula (1)

[Wherein R ¹ is a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, and X represents a hydrolyzable group selected from an alkoxy group, a halogen atom or a hydroxyl group.] One or two or more of the silicon compounds represented by the above is hydrolyzed in the presence of a basic catalyst or in a solvent in which one or both of the polar solvents are combined, and at the same time partially condensed, and the resulting polycondensate is also nonpolar. A method for producing a cage cleavage type siloxane resin, wherein the disiloxane compound is equilibrated with the recondensate obtained by recondensing in the presence of a solvent and a basic catalyst. The method of claim 7, wherein Cage cleavage type siloxane resin is following general formula (2)

[Wherein R ¹ is a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, and at least two of (m + n) R ^{1 's} have a vinyl having an unsaturated double bond A reactive organic functional group selected from the group having a group, a (meth) acryloyl group or an allyl group, and R ² represents a methyl group. m is an integer from 1 to 4, n is an integer from 8 to 16, and the sum of m and n is 10 to 20.] Method for producing a cage cleavage type siloxane resin, characterized in that. The method of claim 7, wherein While the amount of the basic catalyst used is in the range of 0.05 to 0.15 moles with respect to 1 mole of the structural unit represented by [R ¹ SiO _1.5 ] ₁₀ in the recondensate, the disiloxane compound is represented by the general formula (3) [Wherein R ¹ is a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, and R ² represents a methyl group.] Method for producing a cage cleavage type siloxane resin, characterized in that represented by. The method of claim 7, wherein The number average molecular weight Mn of the cage cleavage type siloxane resin obtained is 600-10000, and molecular weight dispersion degree (Mw / Mn) is 1.0-3.5, The manufacturing method of cage cleavage type siloxane resin.

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