JPS63183930A - Curable organopolysiloxane - Google Patents

Abstract

PURPOSE:To obtain a novel organopolysiloxane, having a specific structure, readily curable into a silicone rubber by adding an organic peroxide and heating and used as an useful material or reactive diluent. CONSTITUTION:A curable organopolysiloxane expressed by the formula (R<1> is H or methyl; R<2> is monofunctional hydrocarbon group; n is 0-1,000, a and b are 1, 2 or 3). The organopolysiloxane is obtained by, e.g. adding a solution of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and chloroplatinic acid in isopropyl alcohol, adding and reacting methyldichlorosilane therewith, adding and reacting triethylamine and alpha-acryloxymethyldimethylsilanol with the resultant product.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is directed to a novel curable organopolysiloxane that has not yet been published in any literature, particularly a curable organopolysiloxane that is useful as a main raw material for ultraviolet curable silicone rubber compositions. It concerns polysiloxane.

(Structure of the Invention) The curable organopolysiloxane of the present invention is represented by the general formula, in which R1 is a hydrogen atom or a methyl group, R2,
R3 is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a cycloalkyl group such as a cyclohexyl group, an alkenyl group such as a vinyl group or an allyl group, an aryl group such as a phenyl group or a tolyl group, or any of these groups. The same or different unsubstituted or substituted group selected from chloromethyl group, trifluoropropyl group, cyanoethyl group, etc. in which some or all of the hydrogen atoms bonded to the carbon atoms of are substituted with halogen atoms, cyano groups, etc. In the hydrogenated hydrogen group, n is an integer from O to 1,000, and a and b are 1.2 or 3, and examples include those of the following formula.

CH, CH.

10-C-CH=CH.

CH, CH.

The curable organopolysiloxane represented by the above general formula (1) is, for example, α represented by the general formula (where R2, R3, and n are the same as above),
An organosiloxane represented by the general formula is synthesized by an addition reaction of ω-divinylorganopolysiloxane and a chlorosilane represented by (where m is O~2) in the presence of a platinum catalyst, and then a general It can be obtained by adding acryloxymethylsilanol represented by the formula % formula % (R1 is the same as above) and reacting in the presence of a dehydrochlorination agent, specifically, the above formula (2
) to the α,ω-divinylorganopolysiloxane represented by formula (3) in an equimolar amount relative to the vinyl group, and then heated at 70 to 80°C in the presence of a platinum-based catalyst, such as chloroplatinic acid. After heating to cause an addition reaction.

Acryloxymethylsilanol represented by the formula (5) in an equimolar amount to the amount of chlorine may be added to this, and then the reaction may be carried out in the presence of a dehydrochlorination agent such as triethylamine.

The α,ω-divinylorganopolysiloxane used for the knee is represented by the formula %, and examples of the chlorosilane include dimethylchlorosilane ((CH,)2H8iCI2), methyldichlorosilane (CH,H81CQ, ), trichlorosilane (H5iCρS), etc. Examples of the acryloxymethylsilanol include those represented by the formula %, and the various curable organopolysiloxanes described above can be obtained from these.

The curable organoborisiloxane of the present invention thus obtained is a novel compound that has not been published in any literature, but it can be easily cured into silicone rubber by adding an organic peroxide and heating. However, when combined with a photoinitiator, it becomes an ultraviolet curable silicone rubber, and even when used alone, it becomes an electron beam curable silicone rubber, making it useful as a silicone rubber material. However, this low molecular weight material can be used as a reactive diluent. It is also considered useful.

Next, examples of the present invention will be given, and the viscosity in the examples is 25°C.
This shows the measured values at .

Example 1 15.8 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and an isopropyl alcohol solution of chloroplatinic acid (platinum 0.05 g (2% by weight) was added,
After stirring at 50-60°C.

23 g of methyldichlorosilane was added dropwise to this, and since the reaction was exothermic, it was cooled with ice and allowed to react at 50 to 60°C.
After the completion of the dropwise addition, the mixture was aged at 80°C for 2 hours, and then a mixture of 60g of triethylamine, 64g of α-acryloxymethyldimethylsilanol, and 100g of toluene was added dropwise to react. When the salt was separated in a furnace and stripped at 80°C and 74 m HH, 80g of a pale yellow liquid was obtained with physical properties of a viscosity of 18cS, a refractive index (at 25°C) of 1.4504, and a specific gravity (at 25°C) of 0.983. was obtained, but from the results of infrared absorption spectrum analysis (see Figure 1),
It was confirmed that it is expressed by the following formula.

Example 2 500 g of α,ω-divinyldimethylpolysiloxane (vinyl value 0.018 mol/100g) with a viscosity of 400 cS was placed in a 1ρ reaction flask equipped with a thermometer and a stirring device, and the mixture was heated at 120°C under a nitrogen gas flow. After heating for 2 hours to dehydrate, and cooling, 0.1 g of isopropyl alcohol solution of chloroplatinic acid (platinum content: 2% by weight) and 10 g of methyldichlorosilane were added to the sieve, heated at 50°C for 1 hour, and then heated at 80''C for 3 hours. After reacting for a time, nitrogen gas was passed through the solution at the same temperature to remove unreacted methyldichlorosilane from the system.

Next, add 36.4 g and 3.5 g of triethylamine.
- After adding 0.1 g of di-t-butyl-4-hydroxytoluene, 36.1 g of α-acryloxymethyldimethylsilanol was added dropwise over 30 minutes, and after reacting at 60°C for 2 hours, the generated salt was separated into a furnace. When the excess triethylamine was removed under reduced pressure by stripping under the conditions of 100℃/2■Hg, the viscosity was 588cS and the refractive index was 1.4.
080, 485 g of liquid with a specific gravity of 0.978 was obtained.
It was confirmed from infrared absorption spectrum analysis (see Figure 2) that this product was expressed by a linear formula.

Example 3 500 g of α,ω-divinyldimethylpolysiloxane (vinyl value 0.012 mol/100g) with a viscosity of 1,000cS was placed in an IQ reaction flask equipped with a thermometer and a stirring device, and heated at 120°C under a nitrogen gas stream. After cooling, 0.1 g of an isopropyl alcohol solution of chloroplatinic acid (platinum content: 2% by weight) and 1 gram of trichlorosilane were heated for 2 hours to dehydrate.
Add 0.8 g.

After reacting at 50'C for 1 hour and further at 80°C for 3 hours, unreacted totichlorosilane was removed from the system by flowing nitrogen gas into the solution at the same temperature.

Next, 36.4 g of triethylamine and 3.5 g of triethylamine were added to the knee.
- After adding 0.1 g of di-t-butyl-4-hydroxytoluene, 28.9 g of α-acryloxymethyldimethylsilanol was added dropwise over 30 minutes, and the resulting salt was reacted at 60°C for 2 hours. Separate and heat at 100℃72 me
When the excess triethylamine was removed under reduced pressure by stripping under Hg conditions, the viscosity was 1,230C3,
460 g of a liquid with a refractive index of 1.4069 and a specific gravity of 0.978 was obtained, which was confirmed by infrared absorption spectrum analysis (see FIG. 3) to be represented by the following formula.

Example 4 α,ω-divinyldimethyldiphenylpolysiloxane (vinyl value 0.018 mol/10
0 g, phenyl group content 30 mol%) was added, heated at 120'C for 2 hours under a nitrogen gas stream to dehydrate, and after cooling, an isopropyl alcohol solution of chloroplatinic acid (
0.1 g of platinum (2% by weight) and 4. methyldichlorosilane.
Add 6g.

After reacting at 50'C for 1 hour and further at 80°C for 3 hours, unreacted methyldichlorosilane was removed from the system by flowing nitrogen gas into the solution at the same temperature.

Next, 8 g of triethylamine and 0.1 g of 3,5-di-1-butyl-4-hydroxytoluene were added to this, and then α-acryloxymethyldimethylsilanol 11.
5 g was added dropwise over 30 minutes, and after reacting at 60°C for 2 hours, the produced salt was separated in a furnace and stripped at 100°C at 72 wa Hg to remove excess triethylamine under reduced pressure. 4,400cS, refractive index 1.
508, 196 g of liquid with a specific gravity of 1.081 was obtained,
This product was confirmed by infrared absorption spectrum analysis (see Figure 4) to be represented by the following formula.

Example 5 A 0.5Q reaction flask equipped with a thermometer and a stirring device had a viscosity of 5.0OOcS and an average compositional formula of CH.

■ -S L -CH=C)I.

CH.

Add 200 g of the polysiloxane shown below, heat it under a nitrogen gas stream at 120°C for 2 hours to dehydrate it, and after cooling, add 0.1 g of an isopropyl alcohol solution of chloroplatinic acid (platinum amount: 2% by weight) and trichlorosilane. Add 3.6g, 5
After reacting at 0''C for 1 hour and further at 80°C for 3 hours, unreacted trichlorosilane was removed from the system by flowing nitrogen gas into the solution at the same temperature.

Next, 8 g of triethylamine and 3,5-di-t
After adding 0.1 g of -butyl-4-hydroxytoluene, 8 g of α-acryloxymethyldimethylsilanol was added dropwise over 30 minutes, and after reacting at 60°C for 2 hours, the formed salt was measured and LOO°C/ When the excess triethylamine was removed under reduced pressure by stripping under the conditions of 2 nwmHg, the viscosity was 5,300 cS and the refractive index was 1.3.
91, 195 g of a pale yellow transparent liquid with a specific gravity of 1.220 was obtained, which was confirmed by infrared absorption spectrum analysis (see Figure 5) to be a substance represented by the following formula. .

Example 6 The methyldichlorosilane in Example 1 was changed to 8.3 g of dimethylchlorosilane, and the amount of toluene amine added was 18.2 g.
g, and treated in the same manner as in Example 1, except that 23.0 g of γ-methacryloxypropyldimethylsilanol was used instead of α-acryloxymethyldimethylsilanol, resulting in a viscosity of 480 cS and a refractive index of 1.4063. Specific gravity 0.
488 g of a pale yellow transparent liquid having physical properties of 974 was obtained, which was confirmed to be represented by the following formula from the results of infrared absorption spectrum analysis (see Figure 6).

[Brief explanation of the drawing]

The figures show infrared absorption spectra of the organopolysiloxanes of the present invention. Figure 1 is Example 1, Figure 2 is Example 2, Figure 3 is Example 3, and Figure 4 is Example 4. ．． FIG. 5 shows the infrared absorption spectrum of the organopolysiloxane obtained in Example 5, and FIG. 6 shows the infrared absorption spectrum of the organopolysiloxane obtained in Example 6. Procedural amendment (voluntary) April 25, 1988 1. Indication of the case 1988 Patent Application No. 15413 2. Name of the invention Curable organopolysiloxane 3. Person making the amendment Relationship to the case Name of the patent applicant (206) Shin-Etsu Chemical Co., Ltd. 4, agent °・(, /l, dn1 ■) Correct the chemical formula from lines 1 to 3 of page 9 of specification 8. 2) Delete "α-" on page 12, line 1 of the specification. 3) Correct the chemical formula with the chemical formula on page 16, lines 1 to 9 of the specification. 4) "Example 1" on page 20, lines 12 and 17 of the specification
is corrected to "Example 2". 5) Correct the chemical formula on page 21, lines 5 to 13 of the specification. that's all

Claims (1)

[Claims] 1. General formula (where R^1 is a hydrogen atom or a methyl group, R^2, R
^3 is the same or different unsubstituted or substituted monovalent hydrocarbon group, n is an integer of 0 to 1,000, and a and b are 1, 2, or 3). A curable organopolysiloxane.