JP2950812B1 - Liquid solvent-free silicone resin and its manufacturing method - Google Patents

Abstract

Abstract: PROBLEM TO BE SOLVED: To provide a liquid solventless silicone resin and a method for producing the same. SOLUTION The present invention relates to a liquid solventless silicone resin and a method for producing the same, the resin comprising a poly (organocyclosiloxane) (A), an organic cyclosiloxane (B) having an unsaturated hydrocarbon group, and diphenyldihydroxysilane. It is obtained by mixing (C) at a constant ratio and then proceeding with an equilibrium condensation polymerization reaction in the presence of an anionic polymerization catalyst. The liquid solvent-free silicone resin of the present invention is colorless and transparent, and is stable on storage. It can be reinforced by employing various reinforcing agents.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid solvent-free silicone resin and a method for producing the same, wherein the resin comprises a poly (triorganic) siloxane (A), an unsaturated hydrocarbon-containing organocyclosiloxane (B), It is obtained by mixing diphenyldihydroxysilane (C) at a fixed ratio and then proceeding with an equilibrium condensation polymerization reaction in the presence of an anionic polymerization catalyst. The liquid solventless silicone resin of the present invention is colorless and transparent, In addition, it is stable and can be reinforced by using various reinforcing agents.

[0002]

2. Description of the Related Art As is well known, a silicone resin is produced by subjecting a polyfunctional organic chlorosilane or an organic alkoxysilane to a hydrolysis-condensation polymerization reaction, and in a heating or in the presence of a catalyst, a three-dimensional network structure is formed by a further change. An insoluble and insoluble thermosetting product is obtained, and the cured silicone resin has good insulation properties, is stable over a wide temperature, humidity and frequency range, and has better anti-oxidation, arc resistance, It has properties such as radiation resistance, climate resistance, waterproofing, saltproofing, and moldproofing. For this reason, various products such as insulating varnishes, paints, molding materials and the like are produced using silicon resin as a base material, and are widely applied in various industrial sectors.

[0003] Most silicone resins form a three-dimensional network structure by condensation-curing crosslinking. Such a resin contains a large amount of silanol, and can be used as a molding material after adding an inorganic filler such as glass fiber or quartz powder. It could release air bubbles to produce a transparent product.

[0004] Dimethyldichlorosilane (dimethy)
l dichloro silane, (CH_Three)_TwoS
iCl_Two), Diphenyldichlorosilane (diphen)
yldichloro silane, (C₆H_Five)_Two
SiCl_Two), Phenyltrichlorosilane (pheny)
l trichlorosilane, (C₆H _Five)
_TwoSiCl_Three) And vinylmethyldichlorosilane (CH
_Two= CH-Si CH_TwoCl_Two) As raw material and hydrolysis
After the condensation reaction, the silanol content of the resin produced is extremely low.
Heats polymerized silicone resin containing vinyl groups
And a peroxide as an initiator to form a vinyl group double bond.
Open a three-dimensional network structure
Products that do not release low molecular weight materials when pressed
However, the shrinkage ratio during resin curing is relatively large,
Cracking phenomenon was easy to occur.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a kind of liquid solventless silicone resin and a method for producing the same. The liquid solventless silicone resin of the present invention has the above-mentioned disadvantages of the conventional silicone resin. Even if a polymerization-type curing method or a molding and curing method is adopted, the resin composition has relatively good strength, a small shrinkage rate, and does not generate a crack.

[0006]

According to the first aspect of the present invention, there is provided a material represented by the following A to C: In the dimethylpolysiloxane represented by Chemical Formula 1, in Chemical Formula 1, R ¹ is a methyl group or a vinyl group;
² , R ³ , R ⁴ , and R ⁵ are an organic group such as a methyl group, a vinyl group, or a phenyl group; m and n are from 0 to 1000; In the vinylmethylcyclosiloxane represented by Chemical Formula 2, in Chemical Formula 2, R ⁶ and R ⁷ are a methyl group, a vinyl group, or a phenyl group, and R ⁶ is a methyl group or a phenyl group. R ⁷ is a vinyl group, p is 3, 4 or 5, C.I. The diphenyldihydroxysilane represented by the above chemical structural formula 3
This is a method for producing a liquid solventless silicone resin in which the above are mixed at a fixed ratio and the reaction is allowed to proceed at 140 to 180 ° C. in the presence of an anion polymerization catalyst to obtain a liquid solventless silicone resin.

[0007] The invention according to claim 2 is the above-mentioned reaction,
The method is a method for producing a liquid solventless silicone resin according to claim 1, wherein the process is carried out at 160 ° C.

According to a third aspect of the present invention, the molar ratio of the materials represented by A, B, and C is set to 1-5: 1: 5-1. Liquid non-solvent silicone resin.

According to a fourth aspect of the present invention, the anionic polymerization catalyst is selected from the group consisting of KOH, LiOH or an alkali metal hydroxide which can be substituted for the same, or a reaction product of these with cyclosiloxane. The method for producing a liquid solvent-free silicone resin according to claim 1, wherein potassium silicate (sodium silicate), sodium silicate (lithium silicate), or lithium silicate (lithium silicate) is used. I have.

According to a fifth aspect of the present invention, the weight of the anionic polymerization catalyst is 0.005 to 0.04% of the total weight of the materials represented by A, B, and C (the weight of the alkali metal hydroxide). ). The method for producing a liquid solvent-free silicone resin according to claim 1, wherein

The invention according to claim 6 employs a reduced-compression polymerization reaction system in the above reaction, and the degree of vacuum is 0.01 MPa to 0.0 MPa.
The method according to claim 1, wherein the pressure is 95 MPa.

According to the present invention, a liquid solventless silicone resin is obtained by the above-described method.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The liquid solvent-free silicone resin of the present invention has the following A to C, namely: Dimethyl polysiloxane represented by the above chemical structural formula 1
In e), in Chemical Formula 1, R ¹ is a methyl group or a vinyl group, and R ² , R ³ , R ⁴ , and R ⁵ are the same or different organic groups of a methyl group, a vinyl group, or a phenyl group, preferably A methyl group, m and n being from 0 to 1000, B. In the vinylmethylcyclosiloxane represented by Chemical Formula 2, in Chemical Formula 2, R ⁶ and R ⁷ are a methyl group, a vinyl group, or a phenyl group, and preferably, R ⁶ is a methyl group or A phenyl group, R ⁷ is a vinyl group,
p is 3, 4 or 5, of which p is most preferably 4. The diphenyldihydroxysilane represented by the above chemical structural formula 3
ilan)). The above-mentioned A, B, and C are each a well-known organic silicon common raw material, all of which are provided as commercial products. These are reacted at a fixed ratio in the presence of an anionic polymerization catalyst to obtain the liquid non-aqueous solution of the present invention. Obtain solvent silicone resin. The thus obtained liquid solventless silicone resin of the present invention is not described in the past literature and is not well known.

In the present invention, after dividing the materials represented by A, B, and C into predetermined ratios, the dose of each group is calculated to be 1 to 1.5: 1: 5 to 1 by mole calculation. Ratio. Then, under the presence of the anionic polymerization catalyst, the material undergoes an equilibrium polycondensation reaction, that is, under the presence of the anion polymerization catalyst, the material undergoes the condensation polymerization reaction, and at the same time, the Si—O—Si chain After the molecular rearrangement basic structure is completed, the equilibrium step is reached, thus completing the equilibrium polycondensation reaction.

The anionic polymerization catalyst used for the condensation polymerization is an alkali metal hydroxide such as KHO, NaOH, LiHO and a reaction product thereof with cyclosiloxane, such as potassium silicate, sodium silicate, lithium silicate. (Lithium silane), in which
Preferably, it is potassium silicate, and its dose is 0.005 to 0.04% by weight (calculated by KOH), preferably 0.01 to 0.02% by weight of the silicone resin. The temperature is 140-180 ° C, preferably 1
The reaction is carried out under vacuum, the degree of vacuum is from 0.01 MPa to 0.095 MPa, and the reaction time is generally in the range of from 1 to 3 hours.

The liquid solvent-free silicone resin of the present invention can be reinforced by employing various reinforcing agents. When selecting a reinforcing agent, it is necessary to consider the matching between the refractive index and the liquid solvent-free silicone resin. As a commonly used reinforcing agent, gas-phase white carbon (white-car) is used.
bon), precipitation method white carbon, and MQ resin (silicon resin containing a vinyl group), and preferably, hydrophobic gas phase method white carbon tos employing surface treatment.
are and the amount of the reinforcing agent to be added are 50 to 120%, preferably 80 to 100% of the weight of the liquid solventless silicone resin.

[0017]

EXAMPLE 1 250 equipped with stirrer, thermometer, oil-water separator and cooler
59.2 grams of viscosity 50 in a 3 ml three-necked flask.
0 cp of trimethylsilane
lane edge-sealed polydimethylsiloxane (poly)
dimethyl siloxane), 34.4 grams of 1.3.5.7-tetravinyl-1.3.5.7-
Tetramethyl-cyclotetrasiloxane (1.3.5.
7-tetra vinyl-1.3.5.7-tet
ra methyl-cyclotetra silo
xane), 21.6 grams of diphenyldihydroxysilane
an) and 2.3 grams of potassium diphenylhydroxysilane catalyst (KHO having a content in potassium silicate of 1).
%), Add the above, expand sales and gradually increase to 150-160 ° C
Until the pressure is reduced, and the escaped water in the reaction derivative is removed in a timely manner. After 1-2 hours, when the material becomes transparent, it indicates that there is no water and other low molecular weight substances have evaporated, so if the reaction is stopped, a colorless and sticky transparent silicone resin is obtained. Can be

Example 2 In 10 grams of the colorless, viscous and transparent silicone resin obtained as described above, 5 grams of a hydrogen-containing silicone oil containing phenyl groups, 10 grams of a hydrophobic gas phase method and a trace platinum catalyst were used. And knead to make uniform
Press in the mold at 0 ° C. for 5 minutes to obtain a mold product. The obtained molded product does not cause yellowing or cracking even when heated at 200 ° C. for 4 hours, and has good hardness, strength and transparency.

[0019]

According to the present invention, there is provided a kind of liquid solvent-free silicone resin and a method for producing the same. The liquid solvent-free silicone resin of the present invention solves the above-mentioned disadvantages of the conventional silicone resin, and can be cured by polymerization. Regardless of the method used or the method of molding and curing, it has a relatively good strength, a small shrinkage rate, and no cracks.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C08G 77/08 C08G 77/06

Claims (6)

(57) [Claims] 1. The following materials A to C: Dimethyl polysiloxane represented by the following chemical structural formula 1
In e), In the above chemical formula 1, R ¹ is a methyl group or a vinyl group;
² , R ³ , R ⁴ , and R ⁵ are an organic group such as a methyl group, a vinyl group, or a phenyl group; m and n are from 0 to 1000; Vinyl methyl cyclosiloxane represented by the following chemical structural formula 2
In the formula, In the above chemical structural formula 2, R ⁶ and R ⁷ are a methyl group, a vinyl group or a phenyl group, R ⁶ is a methyl group or a phenyl group, R ⁷ is a vinyl group, and p is 3, 4 or 5 C. A diphenyldihydroxysilane represented by the following chemical structural formula 3
silane), embedded image A method for producing a liquid solventless silicone resin, in which the above are mixed at a fixed ratio and the reaction is allowed to proceed at 140 to 180 ° C in the presence of an anionic polymerization catalyst to obtain a liquid solventless silicone resin. 2. The method for producing a liquid solventless silicone resin according to claim 1, wherein the reaction is allowed to proceed at 150 to 160 ° C. 3. The liquid solventless silicon according to claim 1, wherein the molar ratio of the materials represented by A, B, and C is 1-5: 1: 5-1. Resin manufacturing method. 4. An anion polymerization catalyst comprising KOH, Li
OH or its alternative alkali metal hydroxide, or one of them, or potassium silicate (pot, a reaction product of cyclosiloxane with them)
assiumsilane, sodium silicate (sod)
ium silane, lithium silicate (lithiu)
The method for producing a liquid solvent-free silicone resin according to claim 1, wherein the silicone resin is m silane or an alternative thereto. 5. The weight of the anionic polymerization catalyst is 0.005 to 0.005 of the total weight of the materials represented by A, B and C.
The method for producing a liquid solvent-free silicone resin according to claim 1, wherein the content is 0.04% (by an alkali metal hydroxide weight meter). 6. A reduced-compression polymerization reaction system is adopted in the above reaction,
The method according to claim 1, wherein the degree of vacuum is 0.01 MPa to 0.095 MPa.