JPH06329802A - Organopolysiloxane and method for producing the same - Google Patents

Abstract

(57) [Summary] [Structure] Average composition formula (1) or (2) (However, X is an acryloxypropyl group or methacryloxypropyl group, Y is an organic group selected from a carboxyethyl group, a carboxypropyl group and a carboxydecyl group,
R ¹ represents an alkyl group having 1 to 6 carbon atoms or a phenyl group. a, b, c are integers, 0 ≦ a ≦ 100, 1 ≦ b ≦ 2
0 and 1 ≦ c ≦ 20. ) An organopolysiloxane represented by [Effect] The organopolysiloxane containing both a (meth) acrylic group and a carboxyl group in one molecule of the present invention has high compatibility with an organic resin, and the (meth) acrylic group can be combined with other radically polymerizable monomers. By copolymerization, properties such as lubricity, releasability and water solubility can be imparted to the resin while being introduced into the resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel organopolysiloxane preferably used as a modifier of an organic resin in the fields of paints, molding materials, medical materials, various coating materials and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Organopolysiloxanes containing organic functional groups have hitherto been known.
Widely used as a resin modifier in the fields of paints, molding materials, medical materials, various coating materials, etc., and imparts properties such as heat resistance, weather resistance, mold releasability, moldability, and thermal shock resistance to organic resins. To do.

As the organopolysiloxane having such an organic functional group, a compound having an alcoholic hydroxyl group at both ends of dimethylpolysiloxane (Japanese Patent Publication No. 54-8718) and both ends of dimethylpolysiloxane have hitherto been used. A compound having a functional group in (JP-A-58-217)
515 and 59-123502), a methylpolysiloxane having a functional group in its side chain (Japanese Patent Publication No. 61-189).
No. 68, No. 61-288880), a methylphenyl polysiloxane having an alcoholic hydroxyl group at the side chain and both ends is proposed. Recently, organopolysiloxanes containing different functional groups such as (meth) acryl group, epoxy group, alcoholic hydroxyl group in one molecule (Japanese Patent Laid-Open Nos. 2-294962 and 294963) are also proposed.

However, heretofore, an organopolysiloxane containing both functional groups of a (meth) acrylic group and a carboxyl group has not been known.

[0005]

Means and Actions for Solving the Problems The inventors of the present invention have made earnest studies on organic organopolysiloxanes that are more effectively used as resin modifiers and the like, and as a result, are represented by the following average composition formula (3). The organopolysiloxane represented by the following average composition formula (1) is obtained by adding c moles of an unsaturated compound selected from acrylic acid, methacrylic acid, and undecylenic acid to the SiH group of the organohydrogenpolysiloxane. Similarly, by adding 2 mol of an unsaturated compound selected from acrylic acid, methacrylic acid and undecylenic acid to the SiH group of the organohydrogenpolysiloxane represented by the following average composition formula (4), the following average composition formula (2) It was found that the organopolysiloxane represented by

[0006]

[Chemical 7] (However, X is an acryloxypropyl group or methacryloxypropyl group, Y is an organic group selected from a carboxyethyl group, a carboxypropyl group and a carboxydecyl group,
R ¹ represents an alkyl group having 1 to 6 carbon atoms or a phenyl group. a, b, c are integers, 0 ≦ a ≦ 100, 1 ≦ b ≦ 2
0 and 1 ≦ c ≦ 20. )

In this case, the average composition formulas (3), (4)
In order to prevent a dehydrogenation reaction when an unsaturated compound selected from acrylic acid, methacrylic acid, and undecylenic acid is added to the organohydrogenpolysiloxane, the active hydrogen of the carboxyl group of these unsaturated compounds is converted to an alkyl group or a silyl group. Organo containing both a (meth) acrylic group and a carboxyl group in one molecule represented by the average composition formulas (1) and (2) is obtained by adding a substituted unsaturated compound and then hydrolyzing or desilylating. It has been found that polysiloxanes are obtained more advantageously.

Further, the organopolysiloxanes of the above average composition formulas (1) and (2) are prepared by combining the polysiloxane represented by the following average composition formula (5) or (8) and the compound represented by the average composition formula (6). Method of equilibration, polysiloxane of average composition formula (5) or (8) and average composition formula (7)
It was found that it can also be obtained by the method of hydrolyzing and equilibrating the compound with.

[0009]

[Chemical 8] (However, X, Y, R ¹ , a, and c have the same meanings as described above, R ² represents a methyl group or an ethyl group, and d is an integer of 3
≦ d ≦ 10. )

Since the organopolysiloxanes of the average composition formulas (1) and (2) have functional groups of both (meth) acrylic group and carboxyl group in one molecule, they are organic resins such as epoxy resin and acrylic resin. It has high compatibility with, such as heat resistance, weather resistance, molding processability,
It has been found that properties such as adhesiveness, lubricity, and water solubility can be imparted, strength can be improved by utilizing different crosslinking points, and modification can be achieved by grafting with various organic resins.
In particular, since this organopolysiloxane has two kinds of functional groups, it is possible to use different crosslinking methods or separate polymerization and crosslinking due to the difference in reactivity, so that the resin modification It has excellent properties as a qualitative agent, and by containing a carboxyl group, it is possible to impart excellent lubricity, releasability, water solubility, etc. It was found to be effective in forming. It was also found that a functional group-containing siloxane-grafted acrylic polymer, which has been difficult to synthesize until now, can be obtained by radically copolymerizing an acrylic group or a methacrylic group alone or with another polymerizable monomer. did. Further, it has been found that the compatibility of the organopolysiloxane with a diphenylsiloxane unit or a methylphenylsiloxane unit significantly improves the compatibility with an organic resin, and the present invention has been completed.

The present invention will be described in more detail below. The organopolysiloxane according to the present invention is represented by the following average composition formula (1) or (2).

[0012]

[Chemical 9] (However, X is an acryloxypropyl group or methacryloxypropyl group, Y is an organic group selected from a carboxyethyl group, a carboxypropyl group and a carboxydecyl group,
R ¹ represents an alkyl group having 1 to 6 carbon atoms or a phenyl group. a, b, c are integers, 0 ≦ a ≦ 100, 1 ≦ b ≦ 2
0 and 1 ≦ c ≦ 20. )

Here, X is a 2-acryloxypropyl group, a 3-acryloxypropyl group, a 2-methacryloxypropyl group or a 3-methacryloxypropyl group, and R
^As mentioned above, ¹ is an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group or a phenyl group, but a methyl group and a phenyl group are particularly preferable industrially.
It is desirable to use these in combination. For example, by introducing a diphenylsiloxane unit or a methylphenylsiloxane unit into a siloxane having a dimethylsiloxane unit as a main chain, the reactivity and compatibility with an organic resin can be further improved. In this case, the introduction amount of the phenyl group is R ¹
The content is preferably 5 to 50 mol%, and if it is more than this, the compatibility with the organic resin may decrease.
Further, a, b, and c are in the above ranges, and if the length of siloxane is too long (a, b, and c exceed the above upper limit), the viscosity becomes too high and the handleability deteriorates. It is not preferable because the compatibility with the organic resin is also reduced.

The above-mentioned organopolysiloxanes (1) and (2) are selected from organohydrogenpolysiloxanes represented by the following average composition formulas (3) and (4) and acrylic acid, methacrylic acid, and undecylenic acid, respectively. It can be easily produced in high yield by hydrosilylation reaction with a saturated compound.

[0015]

[Chemical 10]

The organohydrogenpolysiloxanes of the formulas (3) and (4) are tetramethylcyclotetrasiloxane or tetraalkyldisiloxane, functional group X-containing dialkoxysilanes and their hydrolysates, and various cyclic polysiloxanes and disiloxanes. It can be easily prepared by subjecting siloxane or the like to equilibration reaction with sulfuric acid or sulfonic acids. Specific examples include the following, but of course the present invention is not limited thereto. In the formula below, Me
Represents a methyl group, Ph represents a phenyl group, X ′ represents a 3-acryloxypropyl group or a 3-methacryloxypropyl group (the same applies hereinafter).

[0017]

[Chemical 11]

[0018]

[Chemical 12]

[0019]

[Chemical 13]

The above hydrosilylation reaction is preferably carried out in the presence of a platinum catalyst. In this case, as the platinum catalyst, any of those known in the hydrosilylation reaction can be used, but chloroplatinic acid is industrially preferable. The amount of platinum catalyst added is a catalytic amount, usually about 2 to 400 ppm of the organohydrogenpolysiloxane.

The conditions for the above hydrosilylation reaction are appropriately selected, but it is possible to employ the conditions of reacting at a temperature of 60 to 120 ° C. for 2 to 8 hours.

The reaction is carried out in the presence of an aromatic hydrocarbon solvent such as benzene, toluene and xylene, and an aliphatic hydrocarbon solvent such as hexane, heptane and octane, in order to control the viscosity of the system and the reaction temperature. Can be done at.

When carrying out the hydrosilylation reaction, unsaturated compounds (acrylic acid, methacrylic acid) to be reacted with the compounds of the above formulas (3) and (4) in order to prevent a dehydrogenation reaction which may occur during the hydrosilylation reaction. , Undecylenic acid), a method of adding an unsaturated compound in which active hydrogen of a carboxyl group is substituted with an alkyl group or a silyl group is effective. Specifically, it is preferable to use those silylated with a silylating agent such as acrylic acid, methacrylic acid, methyl ester of undecylenic acid, ethyl ester, butyl ester and hexamethyldisilazane, and these unsaturated compounds are used. When used, the compounds of the formulas (1) and (2) can be obtained in the same manner by hydrolyzing and desilylating after completion of the addition and removing the protecting group.

The compound of the above formula (1) or (2) is obtained by equilibrating the compound represented by the following average composition formula (5) or (8) with the compound of the formula (5), or the compound of the formula (7). It can also be produced by hydrolysis and equilibration.

[0025]

[Chemical 14] (However, X, Y, R ¹ , a, and c have the same meanings as described above, R ² represents a methyl group or an ethyl group, and d is an integer of 3
≦ d ≦ 10. )

That is, whether the equilibrium reaction of the carboxyl group-containing polysiloxane represented by the formula (5) or (8) and the compound represented by the formula (6) is carried out preferably in the presence of an acid, particularly concentrated sulfuric acid or trifluoromethanesulfonic acid. The compound of formula (7) and water are preferably equilibrated in the presence of an acid, especially concentrated sulfuric acid or trifluoromethanesulfonic acid. The carboxyl group-containing polysiloxanes of the formulas (5) and (8) are hydrogen polysiloxane, acrylic acid,
It can be obtained by adding methacrylic acid, undecylenic acid or an ester thereof or a silylated product, and post-treating if necessary. Alternatively, it can be obtained by converting a cyano group into a carboxyl group by heating the compound of the following formula, disiloxane, cyclic polysiloxane and the like in an equilibrium reaction with sulfuric acid, sulfonic acid and the like, and then heating under acidic condition.

[0027]

[Chemical 15] (R ¹ and R ² have the same meanings as above.)

The compound of formula (8) can also be obtained by equilibrating a compound of the following formula with cyclic polysiloxane or the like.

[0029]

[Chemical 16]

Specific examples of the carboxyl group-containing polysiloxanes represented by the formulas (5) and (8) include the following, but of course the invention is not limited thereto.

[0031]

[Chemical 17]

[0032]

[Chemical 18]

Concentrated sulfuric acid or trifluoromethanesulfonic acid is preferably used as a catalyst for equilibrating the above compounds, and equilibration occurs when these catalysts are added in an amount of 0.5 to 20% by weight of the whole raw material. . in this case,
It may be heated if necessary, but in the case of heating it is about 60-
Equilibration is complete in 2 to 20 hours at a temperature of 80 ° C. If the amount of the catalyst (acid) added is less than 0.5%, the equilibrium reaction is remarkably slow, and if it exceeds 20%, the (meth) acrylic group may decompose.

After the equilibration, the compound of the formula (1) or (2) can be recovered by washing with water according to a conventional method.

The organopolysiloxane of the present invention is used as a modifier for organic resins in the fields of paints, molding materials, medical materials and various coating materials.

[0036]

INDUSTRIAL APPLICABILITY The organopolysiloxane containing both a (meth) acrylic group and a carboxyl group in one molecule of the present invention has a high compatibility with an organic resin, and a (meth) acrylic group is used as another radical-polymerizable monomer. By copolymerizing with the body,
While being introduced into the resin, the carboxyl group can impart properties such as lubricity, releasability, and water solubility.
Further, according to the production method of the present invention, such an organopolysiloxane can be easily synthesized in a high yield.

[0037]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.

[Example 1] 40 g of toluene in a flask,
Charge CH ₂ ═CHC ₈ H ₁₆ COOSiMe ₃ 51.2 g and 0.1 g of a 2% ethanol solution of chloroplatinic acid at 80 ° C.
Then, 83.8 g of hydrogen polysiloxane represented by the following average composition formula is added dropwise over 2 hours, and after completion of the addition, 80 ° C.
Aged for 2 hours. After confirming that the absorption of Si-H (2160 cm ^-1 ) disappeared with an infrared spectrophotometer,
The reaction mixture was cooled to room temperature. Next, 2.2 g of 0.05 N hydrochloric acid was added dropwise, and the mixture was stirred at room temperature for 2 hours. After washing with water, toluene was distilled off under reduced pressure, and 114.6 g of the corresponding addition product was isolated by filtration. From the physical properties shown below, this product was confirmed to have the following average composition formula. The yield was 95%.

[0039]

[Chemical 19]

[Example 2] The following raw materials were placed in a flask, and after stirring, 0.2 g of trifluoromethanesulfonic acid was added.
Slowly insert. Then, the mixture is aged at 60 ° C. for 5 hours and cooled to room temperature. Add 0.1 g of water and stir for 1 hour. Sodium hydrogen carbonate 3.0 g, anhydrous sodium sulfate 3.0 g
Was added and stirred for 3 hours, then filtered to give the corresponding product 9
4.3 g was isolated. From the physical properties shown below, it was confirmed that the product had the following average composition formula. The yield is 9
It was 6%.

[0041]

[Chemical 20]

[Example 3] CH ₂ = CHC ₈ H was added to the flask.
₁₆ COOH 36.8 g and 0.1 g of a 2% ethanol solution of chloroplatinic acid were charged, and 108.6 g of hydrogen polysiloxane represented by the following average composition formula was added dropwise at 80 ° C. in 2 hours. Aged for hours. After confirming the disappearance of Si-H absorption (2160 cm ^-1 ) with an infrared spectrophotometer, the mixture was cooled to room temperature. 136.7 g of the corresponding addition product were isolated by filtration.
From the physical properties shown below, this product was confirmed to have the following average composition formula. The yield was 94%.

[0043]

[Chemical 21]

Example 4 CH ₂ = CHC ₈ H was added to the flask.
₁₆ COOH 27.6 g and 0.1 g of a 2% ethanol solution of chloroplatinic acid were charged, and 109.6 g of hydrogen polysiloxane represented by the following average composition formula was added dropwise at 80 ° C. in 2 hours. Aged for hours. After confirming the disappearance of Si-H absorption (2160 cm ^-1 ) with an infrared spectrophotometer, the mixture was cooled to room temperature.

[0045]

[Chemical formula 22] After adding 0.1 g of water and stirring for 1 hour, 3.0 g of sodium hydrogen carbonate and 3.0 g of anhydrous sodium sulfate were added. Three
After stirring for a period of time, 139.2 g of the corresponding product was isolated by filtration. From the physical properties shown below, this product was confirmed to have the following average composition formula. The yield was 95%.

[0046]

[Chemical formula 23]

Example 5 40 g of toluene in a flask,
Charge CH ₂ ═CHC ₈ H ₁₆ COOSiMe ₃ 76.8 g, and 0.1 g of a 2% ethanol solution of chloroplatinic acid at 80 ° C.
Then, 85.8 g of hydrogen polysiloxane represented by the following average composition formula was added dropwise over 2 hours, and after completion of the addition, 80 ° C.
Aged for 2 hours. After confirming that the absorption of Si-H (2160 cm ^-1 ) disappeared with an infrared spectrophotometer,
The reaction mixture was cooled to room temperature. Next, 3.3 g of 0.05 N hydrochloric acid was added dropwise, and the mixture was stirred at room temperature for 2 hours. After washing with water, toluene was distilled off under reduced pressure, and 132.5 g of the corresponding addition product was isolated by filtration. From the physical properties shown below, this product was confirmed to have the following average composition formula. The yield was 94%.

[0048]

[Chemical formula 24]

Example 6 CH ₂ = CHC ₈ H ₁₆ COOH
36.8 g, 0.1 g of a 2% ethanol solution of chloroplatinic acid
Then, 83.8 g of hydrogen polysiloxane represented by the following average composition formula was added dropwise at 80 ° C. over 2 hours, and after completion of the addition, the mixture was aged at 80 ° C. for 2 hours. S with infrared spectrophotometer
After confirming that i-H absorption (2160 cm ⁻¹ ) had disappeared, the mixture was cooled to room temperature. 114.6 g of the corresponding addition product were isolated by filtration. From the physical properties shown below, this product was confirmed to have the following average composition formula. The yield was 95%.

[0050]

[Chemical 25]

[Brief description of drawings]

1 is an infrared absorption spectrum of the product of Example 1. FIG.

2 is an infrared absorption spectrum of the product of Example 2. FIG.

FIG. 3 is an infrared absorption spectrum of the product of Example 3.

FIG. 4 is an infrared absorption spectrum of the product of Example 4.

5 is an infrared absorption spectrum of the product of Example 5. FIG.

FIG. 6 is an infrared absorption spectrum of the product of Example 6.

Claims (8)

[Claims] 1. An average composition formula (1): (However, X is an acryloxypropyl group or methacryloxypropyl group, Y is an organic group selected from a carboxyethyl group, a carboxypropyl group and a carboxydecyl group,
R ¹ represents an alkyl group having 1 to 6 carbon atoms or a phenyl group. a, b, c are integers, 0 ≦ a ≦ 100, 1 ≦ b ≦ 2
0 and 1 ≦ c ≦ 20. ) An organopolysiloxane represented by 2. An average composition formula (2): (However, X, Y, R ¹ , a, and b have the same meanings as those in claim 1.) 3. An average composition formula (3): (However, X, R ¹ , a, b and c have the same meanings as in claim 1.) SiH of the organohydrogenpolysiloxane represented by the formula (1) is selected from acrylic acid, methacrylic acid and undecylenic acid. The method for producing an organopolysiloxane according to claim 1, wherein one or more kinds of unsaturated compounds are added by c mol. 4. An unsaturated compound in which the active hydrogen of the carboxyl group of acrylic acid, methacrylic acid or undecylenic acid is substituted with an alkyl group or a silyl group on SiH of the organohydrogenpolysiloxane represented by the average composition formula (3). The method for producing an organopolysiloxane according to claim 1, wherein at least one of them is added in a cmol amount, and then hydrolysis or desilylation is performed. 5. Average composition formulas (5) and (6), or (5) and (7) (However, X, Y, R ¹ , a and c have the same meanings as in claim 1. R ² represents a methyl group or an ethyl group. D is an integer and 3 ≦ d ≦ 10. The method for producing an organopolysiloxane according to claim 1, wherein the compound represented by the formula (1) is equilibrated, or water is added to carry out hydrolysis and equilibration. 6. An average composition formula (4): (However, X, R ¹ , a and b have the same meanings as in claim 1.) SiH of the organohydrogenpolysiloxane represented by (1) is unsaturated selected from acrylic acid, methacrylic acid and undecylenic acid. The method for producing an organopolysiloxane according to claim 2, wherein 2 moles of one or more compounds are added. 7. An organohydrogenpolysiloxane having an average compositional formula (4), SiH, acrylic acid,
The active hydrogen of the carboxyl group of methacrylic acid or undecylenic acid is added to 2 moles of one or more unsaturated compounds in which an alkyl group or a silyl group is substituted, followed by hydrolysis or desilylation. 2. The method for producing an organopolysiloxane as described in 2. 8. Average composition formulas (8) and (6), or (8) and (7) (However, X, Y, R ¹ and a are the same as those in claim 1,
R ² and d have the same meanings as described in claim 5. )
The method for producing an organopolysiloxane according to claim 2, wherein the compound represented by (1) is equilibrated, or water is added to effect hydrolysis and equilibration.