Metal-polyorganosiloxanes

Patent metadata

Field	Value
Publication number	US-11021607-B2
Application number	US-201716087213-A
Country	US
Kind code	B2
Filing date	Mar 23, 2017
Priority date	Mar 23, 2016
Publication date	Jun 1, 2021
Grant date	Jun 1, 2021

Abstract

Metal-polyorganosiloxane materials, methods of making and using them, and manufactured articles and devices containing them are disclosed. The metal-polyorganosiloxane materials have improved thermal stability and comprises a metal-polyorganosiloxane mixture that is free of condensation-curable polyorganosiloxane and solid particles other than metal particles and ceramic particles, the metal-organosiloxane mixture otherwise comprising: (A) a polyorganosiloxane that is free of silicon-bonded organoheteryl groups; (B) a hydrocarbylene-based multipodal silane; and (C) metal particles.

First claim

What is claimed is:

1. A non-curable metal-polyorganosiloxane mixture that is free of condensation-curable polyorganosiloxane and solid particles other than metal particles and ceramic particles, the metal-organosiloxane mixture otherwise comprising constituents (A) to (C):
(A) a polyorganosiloxane that is free of silicon-bonded organoheteryl groups;
(B) a hydrocarbylene-based multipodal silane; and
(C) metal particles;
Wherein, when (B) is a multipodal silane having hydrolysable groups, (B) and (C) are capable of reacting to yield (B′-C′) hydrocarbylene-based multipodal silanoxy-functionalized metal particles; and wherein either the mixture is free of curable polyorganosiloxane or the mixture is free of a crosslinker.

2. The metal-polyorganosiloxane mixture of claim 1 :
wherein the constituent (A) is at least one polyorganosiloxane of formula (I):
[R 1 3 SiO 1/2 ] m [R 2 2 SiO 2/2 ] d [R 3 SiO 3/2 ] t [SiO 4/2 ] q [Z] z   (I),

wherein subscript m is a mole fraction from 0.0025 to 0.05; subscript d is a mole fraction from >0.90 to 0.9975; subscript t is a mole fraction from 0.00 to 0.05; subscript q is a mole fraction from 0.00 to 0.05; subscript z is from 0.00 to 0.05; the sum of m+d+t+q+z=1; each R 1 is independently hydrogen, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, or (C 2 -C 6 )alkynyl; each R 2 is independently hydrogen, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, or (C 6 -C 10 )aryl; each R 3 , when present, is independently hydrogen, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, or (C 6 -C 10 )aryl; and each Z, when present, is independently a hydrocarbon-diyl, wherein each radical is on a same or different carbon atom of the hydrocarbon-diyl and is bonded to a different silicon atom of the polyorganosiloxane of formula (I).

3. The metal-polyorganosiloxane mixture of claim 1 , wherein constituent (B) the hydrocarbylene-based multipodal silane is:
(i) a hydrocarbylene-based dipodal silane of formula (II):
X 3 Si—Y 1 —SiX 3   (II)

wherein Y 1 is a (C 2 -C 30 ) hydrocarbon-diyl and each silicon atom in formula (II) is bonded to a same or different carbon atom in Y1; or
(ii) a hydrocarbylene-based tripodal silane of formula (III)
X 3 Si—Y 2 (SiX 3 )—SiX 3   (III)

wherein Y 2 is a (C 2 -C 30 )hydrocarbon-diyl and each silicon atom in formula (III) is independently bonded to a same or different carbon atom in Y 2 ; and wherein in each formula (II) and (III), each X is independently a monovalent leaving group selected from halogen, (C 1 -C 6 )alkoxy, (C 2 -C 6 )carboxy, and (C 2 -C 6 )oximo.

4. The metal-polyorganosiloxane mixture of claim 2 , wherein constituent (B) the hydrocarbylene-based multipodal silane is any one of (i) to (xvi):
(i) a 1′,2′-bis(tri((C 1 -C 6 )alkoxy)silyl)ethyl-benzene;
(ii) a bis(tri((C 1 -C 6 )alkoxy)silyl)(C 1 -C 12 )alkane;
(iii) a bis(tri((C 1 -C 6 )alkoxy)silyl)(C 2 -C 12 )alkane;
(iv) a 1,2-bis(tri((C 1 -C 6 )alkoxy)silyl)(C 2 -C 12 )alkane;
(v) a 1,2-bis(tri((C 1 -C 6 )alkoxy)silyl)ethane;
(vii) a 1,2-bis(tri((C 1 -C 6 )alkoxy)silyl)propane;
(vii) a 1,2-bis(tri((C 1 -C 6 )alkoxy)silyl)butane;
(viii) a 1,2-bis(tri((C 1 -C 6 )alkoxy)silyl)pentane;
(ix) a 1,2-bis(tri((C 1 -C 6 )alkoxy)silyl) hexane;
(x) a 1,2-bis(tri((C 1 -C 6 )alkoxy)silyl)heptane;
(xi) a 1,2-bis(tri((C 1 -C 6 )alkoxy)silyl)octane;
(xii) a 1,2-bis(tri((C 1 -C 6 )alkoxy)silyl)nonane;
(xiii) a 1,2-bis(tri((C 1 -C 6 )alkoxy)silyl)decane;
(xiv) a 1,2-bis(tri((C 1 -C 6 )alkoxy)silyl)undecane;
(xv) a 1,2-bis(tri((C 1 -C 6 )alkoxy)silyl)dodecane; and
(xvi) a 1,3-substituted regioisomer of any one of (vi) to (xv).

5. The metal-polyorganosiloxane mixture of claim 1 , wherein the constituent (C) the metal particles comprise aluminum, wherein the aluminum particles have an average particle size of greater than 1 micrometer; beryllium; bismuth; cobalt; copper; gold; indium; iron; nickel; palladium; platinum; silver; tin; titanium; zinc; an alloy of any two of aluminum, beryllium; bismuth, cobalt, copper, gold, indium, iron, nickel, palladium, platinum, silver, tin, titanium, and zinc; or wherein the constituent (C) the metal particles have core-shell structure wherein the shell comprises aluminum, beryllium, bismuth, cobalt, copper, gold, indium, iron, nickel, palladium, platinum, silver, tin, titanium, or zinc; and the core comprises or consists essentially of a support material.

6. The metal-polyorganosiloxane mixture of claim 1 , further comprising:
at least one of optional constituents (D) to (R): (D) ceramic particles; (G) a catalyst inhibitor, which is effective at 23 degrees Celsius (° C.) for inhibiting curing catalyzed by constituent (F); (H) an adhesion promoter; (I) a rheology modifier; (J) an antioxidant; (K) a thixotropic agent; (L) a colorant; (M) a coupling initiator, which is effective for initiating a condensation reaction between constituent (B) and constituent (C); (N) a vehicle selected from a solvent, a diluent, and a dispersant; (O) a reactive diluent; (P) an acid acceptor; (Q) a corrosion inhibitor; (R) a radical cure initiator, which is effective for initiating a radical addition reaction between two or more molecules of constituent (A) wherein constituent (A) is a radical-curable polyorganosiloxane containing an average, per molecule, of at least 1 aliphatically unsaturated organic group.

7. The metal-polyorganosiloxane mixture of claim 1 or claim 6 ,
wherein, when the metal-polyorganosiloxane mixture does not comprise constituent (D) ceramic particles, the metal-polyorganosiloxane mixture is characterized by amounts of its constituents (A) to (C) plus any optional constituents, wherein the amount of the constituent (C) metal particles is from 40 to 95 weight percent of the metal-polyorganosiloxane mixture, the amount of constituent (B) the hydrocarbylene-based multipodal silane is from 0.01 to 2 weight percent of the metal-polyorganosiloxane mixture, and the sum of the amount of constituent (A) plus the amount(s) of any optional constituent(s) is from 3 to 58 weight percent of the metal-polyorganosiloxane mixture; all based on a total of 100 weight percent of the metal-polyorganosiloxane mixture; or
wherein, when the metal-polyorganosiloxane mixture comprises constituent (D) ceramic particles and the metal-polyorganosiloxane mixture is characterized by amounts of its constituents (A) to (D) plus any optional constituents, wherein the amount of the (C) metal particles is from 15 to 90 weight percent of the metal-polyorganosiloxane mixture, the amount of the (D) ceramic particles is from 5 to 25 weight percent of the metal-polyorganosiloxane mixture, the amount of (B) the hydrocarbylene-based multipodal silane is from 0.01 to 2 weight percent of the metal-polyorganosiloxane mixture, and the sum of the amount of constituent (A) plus the amount(s) of any constituent(s) other than constituents (A) to (D) is from 3 to 58 weight percent of the metal-polyorganosiloxane mixture; all based on a total of 100 weight percent of the metal-polyorganosiloxane mixture.

8. The metal-polyorganosiloxane composition of claim 1 wherein (B) is a multipodal silane having hydrolysable groups and (B) and (C) react to yield (B′-C′) hydrocarbylene-based multipodal silanoxy-functionalized metal particles.

9. The metal-polyorganosiloxane composition of claim 8 ,
(1) wherein the constituent (A) is a non-curable polyorganosiloxane and the metal-polyorganosiloxane composition is a non-curable metal-polyorganosiloxane composition; or
wherein the constituent (A) is an addition-curable polyorganosiloxane and the metal-polyorganosiloxane composition is an addition-curable metal-polyorganosiloxane composition; and/or
(2) wherein the constituent (B′-C′) is dispersed in the constituent (A).

10. A

Assignees

• Dow Silicones Corp

Inventors

• Bhagwagar Dorab E
• Kadleck Cameron J
• Zambova Adriana P

Classifications

• H10W40/251

  Organics · CPC title

• H10W40/70

  Fillings or auxiliary members in containers or in encapsulations for thermal protection or control · CPC title

• C08K9/06

  with silicon-containing compounds · CPC title

• C08L83/04 Primary

  Polysiloxanes · CPC title

• C09K5/14

  Solid materials, e.g. powdery or granular · CPC title