JPH10152560A - Method for producing organopolysiloxane - Google Patents

Abstract

(57) [Summary] (Solution) SOLUTION: Unsaturated compounds such as allyl glycidyl ether and 1-vinyl-3,4-epoxycyclohexane are added to SiH of organohydrogenpolysiloxane represented by average composition formula (2). Of the organohydrogenpolysiloxane described above, and c moles of unreacted SiH
A method for producing an organopolysiloxane represented by an average compositional formula (1), wherein c is added with another kind of the above unsaturated compound in an amount of c mol. (R represents a C _1-6 alkyl group or a phenyl group;
≦ a ≦ 20, 1 ≦ b ≦ 10, 1 ≦ c ≦ 10. X and Y are mutually different organic groups, such as 3-glycidoxypropyl group, 2- (3 ′, 4′-epoxycyclohexyl) ethyl group, etc. [Effect] Introduced into an organic resin as a silicone resin modifier. By doing, depending on the type of the functional group, heat resistance,
An organopolysiloxane that can impart properties such as weather resistance, moldability, water repellency, and adhesion can be easily synthesized at a high yield.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing a novel organopolysiloxane containing an organic functional group, which is used as a modifier for an organic resin in the fields of paints, molding materials, medical materials and various coating materials. About.

[0002]

2. Description of the Related Art Conventionally, organopolysiloxanes containing organic functional groups have been
It is 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 release, molding processability, and thermal shock resistance to organic resins. Is what you do.

As such organopolysiloxanes having an organic functional group, compounds having an alcoholic hydroxyl group at both terminals of dimethylpolysiloxane (Japanese Patent Publication No. 54-8718) and dimethylpolysiloxane at both terminals have been known. Having a functional group (see JP-A-58-217)
Nos. 515 and 59-123502), and methylpolysiloxane having a functional group in a side chain (Japanese Patent Publication No. 61-189).
Nos. 68 and 61-28880), methylphenylpolysiloxanes containing alcoholic hydroxyl groups at the side chains and at both ends have been proposed, and all of these organopolysiloxanes have a functional group within one molecule. And polysiloxanes containing different functional groups in one molecule have not been proposed.

[0004] The above-mentioned organopolysiloxanes in which the functional groups are all the same in one molecule have characteristics corresponding to the functional groups, but are more compatible with the organic resin than such organopolysiloxanes. There is a demand for an advantageous method for producing an organopolysiloxane which is expensive and more effectively used as a resin modifier or the like.

[0005]

Means and Action for Solving the Problems The present inventors have
As a result of intensive studies to meet the above demand, allyl glycidyl ether, 1- to 1-SiH of organohydrogenpolysiloxane represented by the following average composition formula (2)
Two kinds of unsaturated compounds selected from vinyl-3,4-epoxycyclohexane, allyl alcohol, allyl glycol, allyl acrylate and allyl methacrylate are successively subjected to an addition reaction, that is, one of the above unsaturated compounds is B mol is added to the SiH group of the organohydrogenpolysiloxane of the following formula (2), and then c mol of the other unsaturated compound is added to cmol of the unreacted SiH of the organohydrogenpolysiloxane. By doing so, it has been found that an organopolysiloxane represented by the following average composition formula (1) can be obtained.

[0006]

Embedded image (Where R represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, a, b, and c are each a positive number and 1 ≦ a ≦ 20,
1 ≦ b ≦ 10 and 1 ≦ c ≦ 10. X and Y are mutually different organic groups, a 3-glycidoxypropyl group, 2-
(3 ′, 4′-epoxycyclohexyl) ethyl group, 3
-Hydroxypropyl group, 3- (2'-hydroxyethoxy) propyl group, 3-acryloxypropyl group, 3-
Selected from methacryloxypropyl groups. )

[0007] The organopolysiloxane of the above formula (1) has two different functional groups in one molecule, and the present inventors consider that these organopolysiloxanes are composed of an organic resin such as an epoxy resin, High compatibility with acrylic resin, etc., depending on the type of the functional group, can be given properties such as heat resistance, weather resistance, moldability, water repellency, adhesion, for example, epoxy group and alcoholic Polysiloxane containing hydroxyl group, (meth) acryloxy group and alcoholic hydroxyl group can be measured to improve adhesion at interface, improve strength by using various crosslinking points, and modify by grafting with various organic resins. I learned. In particular, since this organopolysiloxane has two types of functional groups, it is possible to use a different crosslinking method or separate polymerization and crosslinking by utilizing the difference in reactivity. The inventors have found that they have excellent properties as a filler, and have accomplished the present invention.

Accordingly, the present invention provides a method for producing the organopolysiloxane of the formula (1), wherein the compound of the formula (2) and the unsaturated compound are successively hydrosilylated.

Hereinafter, the present invention will be described in more detail.
The target organopolysiloxane in the production method according to the present invention is represented by the following average composition formula (1).

[0010]

Embedded image (However, X and Y are mutually different organic groups, and are 3-glycidoxypropyl group, 2- (3 ′, 4′-epoxycyclohexyl) ethyl group, 3-hydroxypropyl group,
It is selected from a (2'-hydroxyethoxy) propyl group, a 3-acryloxypropyl group, and a 3-methacryloxypropyl group. R represents an alkyl group having 1 to 6 carbon atoms or a phenyl group. a, b and c are each positive numbers and 1 ≦ a ≦ 2
0, 1 ≦ b ≦ 10, 1 ≦ c ≦ 10. )

Here, R is an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group or a propyl group or a phenyl group as described above, and particularly preferably, a methyl group and a phenyl group are industrially preferred. These are preferably used 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. Further, a, b, and c are within the above ranges. If the length of the siloxane is too long (a, b, and c exceed the above upper limit), the viscosity becomes too high, and the handleability is deteriorated. It is not preferable because the compatibility with the organic resin also decreases.

The compound of the above formula (1) can be easily synthesized in a high yield and easily by introducing different organic groups X and Y by a partial hydrosilylation reaction according to the following production method.

That is, first, allyl glycidyl ether, 1-vinyl-3,4-epoxycyclohexane, allyl alcohol, allyl glycol, allyl acrylate, methacryl, are added to SiH of an organohydrogenpolysiloxane represented by the following average composition formula (2). One mole of an unsaturated compound selected from allyl acid is added by b mole. This gives a corresponding addition product represented by the average composition formula (2 ′).

[0014]

Embedded image

The compound of the formula (2 ') can be separately prepared by a hydrolysis or equilibration reaction in advance.

Next, to the compound in which the SiH group of the formula (2 ') still remains, another one of the above unsaturated compounds is added in a molar amount of c. Thereby, the organopolysiloxane of the above formula (1) is obtained.

The organohydrogenpolysiloxane of the formula (2) can be easily prepared by equilibrating tetramethylcyclotetrasiloxane with various cyclic polysiloxanes and disiloxanes as terminal groups with sulfuric acid or sulfonic acids. Can be manufactured. This equation (2)
Examples of the organohydrogenpolysiloxane include, but are not limited to, the following. In the following formula, Me is a methyl group, Ph
Represents a phenyl group (the same applies hereinafter).

[0018]

Embedded image

The above-mentioned sequential hydrosilylation reaction is preferably carried out in the presence of a platinum catalyst. As described above, the above-mentioned organohydrogenpolysiloxane is first partially reacted with an alkene containing a functional group (the above unsaturated compound) in the presence of a platinum catalyst. ), And after confirming that all of the functional group-containing alkene has been consumed, a different functional group-containing alkene is hydrosilylated.

In this case, the platinum catalyst may be any of those used for a known hydrosilylation reaction. However, industrially, chloroplatinic acid is preferable, and the platinum catalyst is heated at a temperature of 60 to 120 ° C. for 2 to 8 hours. , The addition reaction can be completed. The amount of the platinum catalyst added is a catalytic amount, which is usually 2 to 400 parts by weight of the organohydrogenpolysiloxane.
It is about ppm.

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 adjusting the viscosity and reaction temperature of the system. Can be done with Also,
When adding an alcoholic hydroxyl group-containing alkene,
Alcohol solvents such as ethanol, isopropyl alcohol, butanol, and isobutanol can be used. If potassium acetate is added to this system in an amount of 0.001 to 0.5% by weight based on the amount of the organohydrogenpolysiloxane, the addition reaction can be quickly performed. Can be completed.

Further, an organohydrogenpolysiloxane of the formula (2 ') is separately prepared by an acid equilibration reaction or a decomposition reaction, and an addition reaction is carried out in the same manner as described above to obtain an organopolysiloxane of the formula (1). In this case, X is a 3-acryloxypropyl group or 3-
A methacryloxypropyl group is preferred.

[0023]

According to the production method of the present invention, a compound containing a different kind of functional group in one molecule, having high compatibility with an organic resin, and being introduced into an organic resin as a silicone resin modifier, According to the type of the functional group, an organopolysiloxane capable of imparting properties such as heat resistance, weather resistance, moldability, water repellency, and adhesion can be easily synthesized at a high yield.

[0024]

The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Example 1 A flask was charged with 40 g of toluene.
9.6 g of allyl methacrylate and 0.1 g of a 2% ethanol solution of chloroplatinic acid were charged, and 100 g of hydrogenpolysiloxane represented by the following average composition formula was added at 80 ° C.
The mixture was added dropwise over a period of time, and after completion of the addition, the mixture was aged at 80 ° C. for 1 hour. After confirming that the absorption of the allyl group of the allyl methacrylate (1650 cm ^-1 ) has disappeared with an infrared spectrophotometer,
The reaction mixture was cooled to room temperature.

[0026]

Embedded image

Next, another flask was charged with 60 g of toluene, 61.8 g of allyl glycol, and 0.2 g of a 2% ethanol solution of chloroplatinic acid, and the reaction mixture (addition of the hydrogen polysiloxane and allyl methacrylate at 80 ° C.) was added. Of the product in toluene over 2 hours,
After completion of the dropwise addition, the mixture was aged at 80 ° C. for 2 hours.
It was confirmed that i-H absorption (2160 cm ^-1 ) had disappeared.

Toluene, unreacted raw materials, and the like were distilled off under reduced pressure and filtered to obtain 161.8 g of a corresponding addition product.
Isolated. This product was confirmed to have the following average composition formula from the following physical properties. The yield was 96%.

[0029]

Embedded image Viscosity: 715 cs (25 ° C.) Refractive index: 1.4894 (25 ° C.) H ¹ -NMR (δ, acetone δ = 2.0 standard [the same applies hereinafter]): 0.07 (38.1H) 1.50 ( 12H)
1.54 (12H) 3.47 (33.2H) 5.43
(0.7H) 6.00 (0.7H) 7.31 (20H) Infrared absorption spectrum: Fig. 1

Example 2 An addition reaction was carried out in the same manner as in Example 1 except that 50 g of toluene, 16.1 g of allyl glycidyl ether, and 0.1 g of a 2% ethanol solution of chloroplatinic acid were initially charged in a flask. Two steps were performed to obtain 161.6 g (98% yield) of the corresponding addition product. This was confirmed to have the following average composition formula from the following physical properties.

[0031]

Embedded image Viscosity: 1530 cs (25 ° C.) Refractive index: 1.4960 (25 ° C.) H ¹ -NMR (δ): 0.07 (36H) 0.48 (1
2H) 1.55 (12H) 2.43 (1.3H) 2.6
0 (1.3H) 3.42 (34.7H) 7.35 (20
H) Infrared absorption spectrum: Fig. 2

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of an organopolysiloxane according to the present invention.

FIG. 2 is an infrared absorption spectrum of the organopolysiloxane according to the present invention.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Kenichi Isobe 2-3-1 Isobe, Annaka-shi, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology Laboratory

Claims (2)

[Claims] 1. Average composition formula (2) (However, R represents an alkyl group having 1 to 6 carbon atoms or a phenyl group. A, b, and c are each positive numbers and 1 ≦ a ≦ 20,
1 ≦ b ≦ 10 and 1 ≦ c ≦ 10. )) To the SiH of the organohydrogenpolysiloxane represented by the formula (1), one kind of unsaturated compound selected from allyl glycidyl ether, 1-vinyl-3,4-epoxycyclohexane, allyl alcohol, allyl glycol, allyl acrylate and allyl methacrylate. b mole, and then c mole of unreacted SiH of the organohydrogenpolysiloxane.
The average compositional formula (1) is characterized in that one mole of the above unsaturated compound is added to the above compound in an amount of c mol. (However, X and Y are mutually different organic groups, and are 3-glycidoxypropyl group, 2- (3 ′, 4′-epoxycyclohexyl) ethyl group, 3-hydroxypropyl group,
It is selected from a (2'-hydroxyethoxy) propyl group, a 3-acryloxypropyl group, and a 3-methacryloxypropyl group. R, a, b, and c have the same meaning as described above. )
A method for producing an organopolysiloxane represented by the formula: 2. An average composition formula (2 ′) (However, X is a 3-glycidoxypropyl group, 2-
(3 ′, 4′-epoxycyclohexyl) ethyl group, 3
-Hydroxypropyl group, 3- (2'-hydroxyethoxy) propyl group, 3-acryloxypropyl group, 3-
Selected from methacryloxypropyl groups. R is carbon number 1
And represents an alkyl group or a phenyl group. a, b and c are positive numbers, respectively, 1 ≦ a ≦ 20, 1 ≦ b ≦ 10, 1 ≦ c
≦ 10. Allyl glycidyl ether is added to the organohydrogenpolysiloxane represented by
One of unsaturated compounds selected from -vinyl-3,4-epoxycyclohexane, allyl alcohol, allyl glycol, allyl acrylate, allyl methacrylate and different from X of the organohydrogenpolysiloxane of the above formula (2 ') Average composition formula (1) characterized by adding a compound forming a functional group. (However, X and Y are mutually different organic groups, and are 3-glycidoxypropyl group, 2- (3 ′, 4′-epoxycyclohexyl) ethyl group, 3-hydroxypropyl group,
It is selected from a (2'-hydroxyethoxy) propyl group, a 3-acryloxypropyl group, and a 3-methacryloxypropyl group. R, a, b, and c have the same meaning as described above. )
A method for producing an organopolysiloxane represented by the formula: