阅读说明：本技术 氢化硅烷化可固化的有机硅树脂 (Hydrosilylation curable silicone resins ) 是由 S·斯威尔 古川晴彦 须藤通孝 西岛一裕 杉江敦司 于 2018-04-18 设计创作，主要内容包括：一种氢化硅烷化可固化的聚硅氧烷,其包含式(I)的单元和式(II)的单元中的至少一者,其中Ar为C<Sub>6</Sub>-C<Sub>20</Sub>芳基,R1为C<Sub>2</Sub>-C<Sub>20</Sub>烯基,并且R<Sup>2</Sup>、R<Sup>3</Sup>、R<Sup>4</Sup>和R<Sup>5</Sup>独立地为C<Sub>1</Sub>-C<Sub>20</Sub>烃基。<Image he="402" wi="700" file="DDA0002240625840000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(A hydrosilylation-curable polysiloxane comprising at least one of a unit of formula (I) and a unit of formula (II) wherein Ar is C 6 ‑C 20 Aryl, R1 is C 2 ‑C 20 Alkenyl, and R 2 、R 3 、R 4 And R 5 Independently is C 1 ‑C 20 A hydrocarbyl group.)

1. A hydrosilylation-curable polysiloxane comprising at least one of a unit of formula (I) and a unit of formula (II)

Wherein Ar is C₆-C₂₀Aryl radical, R¹Is C₂-C₂₀Alkenyl, and R²、R³、R⁴And R⁵Independently is C₁-C₂₀A hydrocarbyl group.

2. The polysiloxane of claim 1, wherein R²、R³、R⁴And R⁵Independently represent C₁-C₄An alkyl group.

3. The polysiloxane of claim 2, wherein R¹Is C₂-C₈An alkenyl group.

4. The polysiloxane of claim 3, comprising units of formula (I), and wherein less than 25 mole% of R in the hydrosilylation-curable polysiloxane¹The radical is derived from a unit of formula (II).

5. The polysiloxane of claim 4, wherein [ R ] in formula (I) or formula (II)²R³SiO_2/2]The unit is of 10 to 500 [ R ]²R³SiO_2/2]A portion of the polysiloxane chain of the unit.

6. The polysiloxane of claim 5, wherein the polysiloxane comprises [ ArSiO ] from 20 to 60 mol%_3/2]Units and 40 to 80 mol% of [ R%²R³SiO_2/2]And (4) units.

7. According to claim 6The polysiloxane of (a), wherein the polysiloxane further comprises 0.5 to 4.5 mol% of [ R%¹SiO_3/2]And (4) units.

8. The polysiloxane of claim 7, wherein R²、R³、R⁴And R⁵Independently represents a methyl or ethyl group.

9. The polysiloxane of claim 8, wherein [ R ] in formula (I)²R³SiO_2/2]The unit is of 30 to 200 [ R ]²R³SiO_2/2]A portion of the polysiloxane chain of the unit.

10. The polysiloxane of claim 9, wherein R²、R³、R⁴And R⁵Is methyl, R¹Is vinyl and Ar is phenyl.

Disclosure of Invention

The present invention provides a hydrosilylation-curable polysiloxane comprising at least one of a unit of formula (I) and a unit of formula (II)

Wherein Ar is C₆-C₂₀Aryl radical, R¹Is C₂-C₂₀Alkenyl, and R²、R³、R⁴And R⁵Independently is C₁-C₂₀A hydrocarbyl group.

Detailed Description

Unless otherwise indicated, percentages are weight percentages (wt%) and temperatures are in units of ° c. Unless otherwise indicated, the operations were performed at room temperature. Alkyl groups are saturated hydrocarbon groups which may be straight-chain or branched. Preferably, the alkyl group has one to six carbon atoms, preferably one or two. An alkenyl group is a hydrocarbyl group that may be straight-chain or branched and has at least one aliphatic carbon-carbon double bond, preferably one aliphatic carbon-carbon double bond. Preferably, the alkenyl group does not have an aromatic ring. Preferably, the alkyl and alkenyl groups are unsubstituted. The aryl group is derived from an aromatic compound which may be mononuclear or polynuclear. The aryl group may be substituted with an alkyl or alkoxy group. Preferably, the aryl group is unsubstituted. Preferably, the aryl group is a hydrocarbyl group.

As used herein, molecular weight M unless otherwise indicated_n、M_wAnd M_zHas conventional meaning and is determined by gel permeation chromatography. Molecular weights are reported herein in g/mole.

Preferably, -OSi (R) in formula (I) or (II)²)(R³) A unit is a unit having 10 to 500, preferably at least 20, preferably at least 30, preferably at least 35, preferably not more than 400, preferably not more than 300, preferably not more than 200, preferably not more than 150 of these units ([ R)²R³SiO_2/2]Units or D units) are part of the polysiloxane chain. Preferably, R²And R³Independently represent C₁-C₁₂Alkyl or C₆-C₁₂Aryl, preferably phenyl or C₁-C₁₂Alkyl, preferably phenyl or C₁-C₄Alkyl, preferably C₁-C₁₂Alkyl, preferably C₁-C₆Alkyl, preferably C₁-C₄Alkyl, preferably methyl or ethyl, preferably methyl. Preferably, R²And R³Represent the same alkyl group. Preferably, R⁴And R⁵Independently represent C₁-C₁₂Alkyl or C₆-C₁₂Aryl, preferably phenyl or C₁-C₁₂Alkyl, preferably C₁-C₁₂Alkyl, preferably C₁-C₆Alkyl, preferably C₁-C₄Alkyl, preferably methyl or ethyl, preferably methyl. A bond ending with "- -" or "- - -" is understood to be a silicon atom which is linked to another siloxane unit, or to hydrogen.

Preferably, R¹Is C₂-C₁₂Alkenyl, preferably C₂-C₈Alkenyl, preferably C₂-C₆Alkenyl, preferably C₂-C₄Alkenyl, preferably vinyl. Preferably, when R is¹Greater than vinyl, double bonds being terminalEnd positions. Preferably, R¹Is acyclic. Comprising R¹The siloxane unit of (A) is designated as [ R ]¹SiO_3/2]Units or T-alkenyl or T^{Alkenyl radical}And (4) units.

Preferably, Ar is C₆-C₁₄Aryl, preferably C₆-C₁₂Aryl, preferably C₆-C₁₀Aryl, preferably phenyl. Preferably, Ar does not contain a heterocyclic aromatic ring. Preferably, Ar does not comprise heteroatoms. Preferably, Ar does not contain fused rings. Preferably, any substituents on the Ar group are limited to C₁-C₄An alkyl or alkoxy group. Preferably, the Ar group is unsubstituted. Siloxane units containing Ar are known as [ ArSiO ]_3/2]Units or T-aryl or T^{Aryl radicals}And (4) units.

Preferably, the polysiloxane comprises from 0.5 to 4.5 mol%, preferably from 0.8 to 4 mol%, preferably from 1 to 3 mol%, preferably from 1 to 2.5 mol% of C containing at least one carbon-carbon double bond₁-C₂₀A hydrocarbyl group. Preferably, the polysiloxane comprises from 20 to 60 mole%, preferably at least 25 mole%, preferably at least 28 mole%, preferably not more than 55 mole%, preferably not more than 52 mole% of T^{Aryl radicals}And (4) units. Preferably, the polysiloxane comprises from 0.5 to 4.5 mole%, preferably at least 0.8 mole%, preferably at least 1.0 mole%, preferably no more than 4 mole%, preferably no more than 3 mole%, preferably no more than 2.5 mole% of T^{Alkenyl radical}And (4) units. Preferably, the polysiloxane comprises from 40 to 80 mole%, preferably at least 45 mole%, preferably at least 48 mole%, preferably no more than 75 mole%, preferably no more than 72 mole% of D units. Preferably, T^{Aryl radicals}The units are arranged in nonlinear blocks, preferably having a molecular weight of at least 500 g/mole. Preferably, the polysiloxane has a weight average molecular weight of at least 20,000 g/mole. Preferably, at least 50 mol%, preferably at least 60 mol%, preferably at least 70 mol%, preferably at least 80 mol%, preferably at least 90 mol% of units having a carbon-carbon double bond (this excluding aryl groups)Unit) exists as a T unit.

Preferably, the hydrosilylation-curable polysiloxane comprises units of formula (I). Preferably, less than 50 mole%, preferably less than 25 mole%, preferably less than 10 mole%, preferably less than 5 mole%, preferably less than 1 mole% of R in the hydrosilylation-curable polysiloxane¹The radical is derived from a unit of formula (II).

In a preferred embodiment of the present invention, the hydrosilylation-curable polysiloxane comprises units of formula (III).

In a preferred embodiment of the present invention, the hydrosilylation-curable polysiloxane comprises units of formula (IV).

The present invention also relates to a curable silicone composition comprising the hydrosilylation-curable polysiloxane. Preferably, the composition further comprises a hydrosilylation catalyst and a crosslinking agent.

Preferably, the hydrosilylation catalyst is present in the curable silicone composition in a catalytic amount along with an amount of polysiloxane sufficient to promote curing of the composition. Suitable hydrosilylation catalysts include, but are not limited to, platinum group metals including platinum, rhodium, ruthenium, palladium, osmium, or iridium metals or organometallic compounds thereof and combinations of any two or more thereof. In a preferred embodiment, the hydrosilylation catalyst is platinum black, platinum compounds such as chloroplatinic acid, chloroplatinic acid hexahydrate, the reaction product of chloroplatinic acid with a monohydric alcohol, platinum bis (ethylacetoacetate), platinum bis (acetylacetonate), platinum dichloride, and complexes of platinum compounds with olefins or low molecular weight organopolysiloxanes or platinum compounds microencapsulated in a matrix or core-shell type structure.

Preferably, the hydrosilylation catalyst is present in the composition in an amount of from 0.1 to 5ppm, preferably at least 0.2ppm, preferably at least 0.25ppm, preferably not more than 3ppm, preferably not more than 2ppm, preferably not more than 1.5ppm, preferably not more than 1ppm, preferably not more than 0.7ppm, preferably not more than 0.5 ppm.

Preferably, the cross-linking agent is a polysiloxane containing at least two, preferably at least three, silicon-bonded hydrogen atoms. Preferably, the silicon-bonded group other than silicon-bonded hydrogen is phenyl or C_1-10Alkyl groups in an amount to provide from about 0.8 moles to about 2.5 moles, preferably from 0.8 moles to 1.5 moles, preferably from 0.9 moles to 1.2 moles of silicon-bonded hydrogen per 1 mole of total alkenyl groups in the organopolysiloxane. Preferably, the crosslinking agent itself is an organopolysiloxane containing about 0.3 to 2.0 mass% silicon-bonded hydrogen. Preferably, contains RSiO_3/2Unit, R₂SiO_2/2Unit, R₃SiO_1/2And HR₂SiO_1/2And/or HRSiO_2/2Wherein the silicon-bonded R group is phenyl or C_1-C₁₀Alkyl, preferably phenyl or methyl. A preferred crosslinking agent is M^H _0.6T^Ph _0.4("M" units unspecified for any group being methyl, e.g. M^HIs MH^(CH ₃ ⁾ ₂)