Method for preparing low-silanol polyorganosiloxanes

Abstract

Provide a process for preparing a polyorganosiloxane in which the polar Si-O-C bonds and silanol groups are minimized, thus ensuring that the polyorganosiloxane has dielectric properties suitable for radio frequency applications. 【Solution】Formula (I) [O 3-a / 2 R a SiY(SiR a O 3-a / 2 ) b c (R 1 SiO 3 / 2 ) d (R 2 2SiO 2 / 2 ) e (R 3 3SiO 1 / 2 ) f (SiO 4 / 2 ) g [O 3-h / 2 R 4 h Si(SiR 5 2) i SiR 4 j O 3-j / 2 k Provide a process for preparing a polyorganosiloxane of formula (I).​​

Claims

1. A process for preparing a polyorganosiloxane of formula (I), [O ３－ａ／２ R ａ SiY(SiR ａ O ３－ａ／２ ) ｂ ] ｃ (R １ SiO ３／２ ) ｄ (R ２ ２ SiO ２／２ ) ｅ (R ３ ３ SiO １／２ ) ｆ (SiO ４／２ ) ｇ [O ３－ｈ／２ R ４ ｈ Si (SiR ５ ２ ) ｉ SiR ４ ｊ O ３－ｊ／２ ] ｋ (I) [In the formula, the group R may be the same or different, and may be a hydrogen group or an unsaturated hydrocarbon group, which is a monovalent Si-C bonded unsubstituted or heteroatom-substituted organic hydrocarbon group having 1 to 18 carbon atoms.] Y is a divalent to dodecavalent organic unsubstituted or heteroatom-substituted organic group having a chemical bond, an oxygen atom, or 1 to 24 carbon atoms bonded to a silicon atom by a Si-C bond. group R １ , R ２ and R ３ These are, independently of each other, a hydrogen group, or a saturated or unsaturated Si-C bonded C1-C18 hydrocarbon group which may be substituted by a heteroatom or unsubstituted, or a C1-C12 hydrocarbon group which may be bonded via an oxygen atom and contain a heteroatom, or a silanol group, and group R １ , R ２ and R ３ In either case, their definitions can be adopted independently of each other, and therefore, two or more groups R bonded to the same silicon atom １ , R ２ and / or R ３ This may be a different group from the defined group. group R ４ These are, independently of each other, any one of the following: a hydrogen group, a silanol group, or a monovalent Si-C bonded or Si-O-C bonded unsubstituted or heteroatom-substituted organic hydrocarbon group having 1 to 18 carbon atoms, which may be an unsaturated hydrocarbon group. group R ５ These are, independently of each other, a monovalent Si-C bonded unsubstituted or heteroatom-substituted organic hydrocarbon group having 1 to 18 carbon atoms, which may be a hydrogen group or an unsaturated hydrocarbon group, or a group of the following formula (II): [O ３－ａ／２ R ａ SiY(SiR ａ O ３－ａ／２ ) ｂ ] ｃ (R １ SiO ３／２ ) ｄ (R ２ ２ SiO ２／２ ) ｅ (R ３ ３ SiO １／２ ) ｆ (SiO ４／２ ) ｇ (-I), [In the formula, all bases Y, R, R １ , R ２ , R ３ , R ４ and R ５ With 100 mol% as the base, at least 0.1 mol% must be an olefinic or acetylene unsaturated group. All bases Y, R, R １ , R ２ , R ３ , R ４ and R ５ With 100% by weight, the total maximum of 3% by weight consists of Si-O-C bonding groups and silanol groups. Also, all base Y, R, R １ , R ２ , R ３ , R ４ and R ５ Assuming that is 100% by weight, the total maximum of 0.5% by weight is silanol groups. a is 0, 1, or 2, and the subscripts a on both sides of base Y can adopt their definitions independently of each other; therefore, independently of each other, different subscripts a can have different values ​​within a given range. b is a number having a value between 1 and 11, preferably 1. c has values ​​between 0 and 0.

9. d has a value between 0 and 0.

8. e has a value between 0 and 0.

5. f has values ​​between 0.01 and 0.

6. g has a value between 0 and 0.

6. h and j are 0, 1, or 2, independently of each other. i is an integer with values ​​between 0 and 50. k has values ​​between 0 and 0.

9. c + d + e + f + g + k = 1, where at least one value c, d, or k is > 0, and e + g is ≤ 0.

6. In the formulas, the bases R and R in formulas (I) and (II) １ , R ２ , R ３ , R ４ and R ５ Furthermore, the subscripts a, b, c, d, e, f, g, h, and i may have the same definition independently of each other, and these definitions may be adopted independently of each other within the range of values ​​specified. In the first step, the silane of formula (III) ( ６ ｌ ()) ７ ４－ｌ (?).、 [In the formula, R ７ It is a hydrolyzable group, l is an integer with a value of 0, 1, or 2. If l = 1, R ６ is based on R １ And when l = 2, R ６ is based on R ２ That is the case. and / or di, oligo, or polysilane of formula (IV) R ７ ３－ｈ R ４ ｈ Si(SiR ５ ２ ) ｉ SiR ４ ｊ R ７ ３－ｊ (IV) [In the formula, the above R ７ It is a hydrolyzable group, R ４ , R ５ , h, i, and j have the same definitions as above. and / or organyl crosslinked silicone of formula (V) R ７ ３－ａ R ａ SiY(SiR ａ R ７ ３－ａ ) ｂ (V) [In the formula, R ７ R, Y, a, and b have the definitions already described. Mix with water and hydrolyzable group R ７ If at least one of the components is not a halogen group, the reaction is carried out in the presence of a non-aqueous miscible aprotic solvent using one or more catalytic amounts of acids that promote the hydrolysis and condensation of the components of formulas (III), (IV), and (V). After the reaction has occurred, reduce both the water and the remaining amount of acid in the organic phase to less than 10,000 ppm each. In the second step, the reaction product from the first step is dissolved in an inert organic solvent, without water, in the presence of an auxiliary base, according to formula (VI). R ３ ３ SiR ８ (VI) [In the formula, R ３ R has the same definition as above, ８ [It is a halogen atom.] A process involving reacting it with halosilane.

2. Group R, R １ , R ２ , R ３ , R ４ and R ５ The process according to claim 1, wherein the group is selected from a methyl group, a phenyl group, a vinyl group, an acryloyloxy group, and a methacryloyloxy group, and an acrylic acid ester or methacrylic acid ester of an unbranched or branched alcohol having 1 to 15 carbon atoms.

3. The process according to claim 1 or 2, wherein the aprotic solvent is an aromatic hydrocarbon.

4. The process according to any one of claims 1 to 3, wherein the auxiliary base is used in at least equimolar amounts relative to the halosilane.

5. The process according to any one of claims 1 to 4, wherein the auxiliary base is selected from basic metal salts and nitrogen compounds.

6. The process according to any one of claims 1 to 5, wherein in the third step, the polyorganosiloxane of formula (I) is bonded to a metal substrate.

7. The process according to claim 6, wherein in the fourth step, the polyorganosiloxane of formula (I) is crosslinked.

8. A metal-clad laminate that can be manufactured by the method described in claim 6 or 7.

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