IP Library › Granted Patent US 9,512,150
Granted Patent B2
US 9,512,150 · App. 14/448,938 · Granted Dec 6, 2016

Thermal conductive compositions and methods for their preparation and use

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Quick Facts
Patent No.
US 9,512,150
App. No.
14/448,938
Granted
Dec 6, 2016
Kind
B2
Abstract

Thermal conductive compositions, methods for their preparation, and use are provided, which include, for example, as thermal sinks and other uses.

Claims (168)

1. A thermal conductive composition comprising at least one of a compound of Formula (I):

wherein:

M is Al, Ga, Si, Ge, In, or Sn;

R 1 , R 2 , R 3 , and R 4 are each independently —H, or —NH 2 , —Si(OR 5 ) 3 , —Si(OR 5 ) 2 CH 2 CH 2 NH 2 , —Si(R 5 ) 2 CH 2 CH 2 NH 2 , —N + (CH 3 ) 3 − OH, —CH 2 CH(O)CH 2 , —Si(R 5 ) 2 CH 2 CH(O)CH 2 , —CH 3 , —CH═CH 2 , —CH 2 CH═CH 2 , —CH═CH—CN, —OCN, —CH 2 OH, CH 2 X, CH 2 OCN, —CH(═O), provided that R 1 , R 2 , R 3 , and R 4 are not all H,

wherein:

X is halo;

R 5 is C 1 -C 6 alkyl;

and a compound of Formula (II):

wherein:

y is about 10 to about 500;

R 6 is C 1 -C 6 alkyl or halo;

each R 7 is independently —H, or —NH 2 , —Si(OR 9 ) 3 , —Si(OR 9 ) 2 CH 2 CH 2 NH 2 , —Si(R 9 ) 2 CH 2 CH 2 NH 2 , —N + (CH 3 ) 3 − OH, —CH 2 CH(O)CH 2 , —Si(R 9 ) 2 CH 2 CH(O)CH 2 , —CH 3 , —CH═CH 2 , —CH 2 CH═CH 2 , —CH═CH—CN, —OCN, —CH 2 OH, CH 2 X, CH 2 OCN, or —CH(═O), provided that each R 7 are not both H;

R 8 is —NH—CH 2 —CH 2 —NH 2 or Al(R 10 ) 2 ;

R 9 is C 1 -C 6 alkyl; and

R 10 is C 1 -C 6 alkyl or halo.

2. The thermal conductive composition of claim 1 , wherein R 1 , R 2 , R 3 , and R 4 are each independently H, or NH 2 , —Si(OR 5 )2CH 2 CH 2 NH 2 , Si(OR 5 ) 3 , N(CH 3 ) 3 OH, CH 2 CH(O)CH 2 , —CH 3 , —CH═CH 2 , —CH 2 CH═CH 2 , —CH 2 CH(O)CH 2 , —CH═CH—CN, —OCN, —CH 2 OH, CH 2 Cl, CH 2 OCN, or —CH(═O).

3. The thermal conductive composition of claim 1 , wherein R 7 is H, or NH 2 , —Si(OR 9 ) 2 CH 2 CH 2 NH 2 , Si(OR 9 ) 3 , —N + (CH 3 ) 3 − OH, CH 2 CH(O)CH 2 , —CH 3 , —CH═CH 2 , —CH 2 CH═CH 2 , —CH 2 CH(O)CH 2 , —CH═CH—CN, —OCN, —CH 2 OH, CH 2 Cl, CH 2 OCN, or —CH(═O).

4. The thermal conductive composition of claim 1 , wherein the composition is a siloxane polymer cross linked or cured with a compound of Formula (I) or (II).

5. The thermal conductive composition of claim 4 , wherein the siloxane polymer cured or cross linked with a compound of Formula (I) or (II) has a formula of:

wherein

each R 12 is alkenyl, alkenylaryl, aryl or alicyclic; and

each z is independently about 1 to about 100.

6. The thermal conductive composition of claim 1 , wherein the composition is a polyurethane cross linked with a compound of Formula (I) or (II).

7. The thermal conductive composition of claim 6 , wherein the polyurethane cross linked with a compound of Formula (I) or (II) is a compound of Formula (III):

wherein:

M is Al, Ga, Si, Ge, In, or Sn;

R 2 , R 3 , and R 4 are each independently —H, or —NH 2 , —Si(OR 5 ) 3 , —Si(OR 5 ) 2 CH 2 CH 2 NH 2 , —Si(R 5 ) 2 CH 2 CH 2 NH 2 , —N + (CH 3 ) 3 − OH, —CH 2 CH(O)CH 2 , —Si(R 5 ) 2 CH 2 CH(O)CH 2 , —CH 3 , —CH═CH 2 , —CH 2 CH═CH 2 , —CH═CH—CN, —OCN, —CH 2 OH, CH 2 X, CH 2 OCN, —CH(═O);

wherein:

X is halo;

R 5 is C 1 -C 6 alkyl; and

R 11 is a polyurethane chain.

8. The thermal conductive composition of claim 1 , wherein the composition is a polyolefin copolymerized or grafted with a compound of Formula (I) or (II).

9. The thermal conductive composition of claim 8 , wherein the composition has a formula of:

wherein

M is Al, Ga, Si, Ge, In, or Sn; and

q is about 100 to about 10000.

10. A heat sink comprising at least one of a compound of Formula (I)

wherein:

M is Al, Ga, Si, Ge, In, or Sn;

R 1 , R 2 , R 3 , and R 4 are each independently —H, or —NH 2 , —Si(OR 5 ) 3 , —Si(OR 5 ) 2 CH 2 CH 2 NH 2 , —Si(R 5 ) 2 CH 2 CH 2 NH 2 , —N + (CH 3 ) 3 − OH, —CH 2 CH(O)CH 2 , —Si(R 5 ) 2 CH 2 CH(O)CH 2 , —CH 3 , —CH═CH 2 , —CH 2 CH═CH 2 , —CH═CH—CN, —OCN, —CH 2 OH, CH 2 X, CH 2 OCN, —CH(═O), provided that R 1 , R 2 , R 3 , and R 4 are not all H,

wherein:

X is halo;

R 5 is C 1 -C 6 alkyl;

and a compound of Formula (II):

wherein:

y is about 10 to about 500;

R 6 is C 1 -C 6 alkyl or halo;

each R 7 is independently —H, or —NH 2 , —Si(OR 9 ) 3 , —Si(OR 9 ) 2 CH 2 CH 2 NH 2 , —Si(R 9 ) 2 CH 2 CH 2 NH 2 , —N + (CH 3 ) 3 − OH, —CH 2 CH(O)CH 2 , —Si(R 9 ) 2 CH 2 CH(O)CH 2 , —CH 3 , —CH═CH 2 , —CH 2 CH═CH 2 , —CH═CH—CN, —OCN, —CH 2 OH, CH 2 X, CH 2 OCN, or —CH(═O), provided that each R 7 are not both H;

R 8 is —NH—CH 2 —CH 2 —NH 2 or Al(R 10 ) 2 ;

R 9 is C 1 -C 6 alkyl; and

R 10 is C 1 -C 6 alkyl or halo.

11. The heat sink of claim 10 , wherein R 7 is H, —NH 2 , —Si(OR 9 ) 2 CH 2 CH 2 NH 2 , —Si(OR 9 ) 3 , —N + (CH 3 ) 3 − OH, —CH 2 CH(O)CH 2 , —CH 3 , —CH═CH 2 , —CH 2 CH═CH 2 , —CH 2 CH(O)CH 2 , —CH═CHCN, —OCN, —CH 2 OH, —CH 2 Cl, —CH 2 OCN, —CH(═O).

12. The heat sink of claim 10 , wherein the composition is a siloxane polymer cured or cross linked with a compound of Formula (I) or (II).

13. The heat sink of claim 12 , wherein the siloxane polymer cured or cross linked with a compound of Formula (I) or (II) a formula of:

wherein

each R 12 is alkenyl, alkenylaryl, aryl or alicyclic; and

each z is independently about 10 to about 1000.

14. The heat sink of claim 10 , wherein the composition is a polyurethane cross linked with a compound of Formula (I) or (II).

15. The heat sink of claim 14 , wherein the polyurethane cross linked with a compound of Formula (I) or (II) is a compound of Formula (III):

wherein:

M is Al, Ga, Si, Ge, In, or Sn;

R 2 , R 3 , and R 4 are each independently —H, or —NH 2 , —Si(OR 5 ) 3 , —Si(OR 5 ) 2 CH 2 CH 2 NH 2 , —Si(R 5 ) 2 CH 2 CH 2 NH 2 , —N + (CH 3 ) 3 − OH, —CH 2 CH(O)CH 2 , —Si(R 5 ) 2 CH 2 CH(O)CH 2 , —CH 3 , —CH═CH 2 , —CH 2 CH═CH 2 , —CH═CH—CN, —OCN, —CH 2 OH, CH 2 X, CH 2 OCN, —CH(═O);

wherein:

X is halo;

R 5 is C 1 -C 6 alkyl; and

R 11 is a polyurethane chain.

16. The heat sink of claim 10 , wherein the composition is a polyolefin copolymerized or grafted with a compound of Formula (I) or (II).

17. The heat sink of claim 16 , wherein the polyolefin copolymerized or grafted with a compound of Formula (I) or (II) has a formula of:

wherein

M is Al, Ga, Si, Ge, In, or Sn; and

q is about 100 to about 10000.

18. A heat transfer system or an electronic device:

the heat transfer system comprising:

at least one heat source;

at least one heat sink; and

at least one thermal conductive composition comprising at least one of a compound of Formula (I)

wherein:

M is Al, Ga, Si, Ge, In, or Sn;

R 1 , R 2 , R 3 , and R 4 are each independently —H, or —NH 2 , —Si(OR 5 ) 3 , —Si(OR 5 ) 2 CH 2 CH 2 NH 2 , —Si(R 5 ) 2 CH 2 CH 2 NH 2 , —N + (CH 3 ) 3 − OH, —CH 2 CH(O)CH 2 , —Si(R 5 ) 2 CH 2 CH(O)CH 2 , —CH 3 , —CH═CH 2 , —CH 2 CH═CH 2 , —CH═CH—CN, —OCN, —CH 2 OH, CH 2 X, CH 2 OCN, —CH(═O), provided that R 1 , R 2 , R 3 , and R 4 are not all H,

wherein:

X is halo;

R 5 is C 1 -C 6 alkyl;

or a compound of Formula (II):

wherein:

y is about 10 to about 500;

R 6 is C 1 -C 6 alkyl or halo;

each R 7 is independently —H, or —NH 2 , —Si(OR 9 ) 3 , —Si(OR 9 ) 2 CH 2 CH 2 NH 2 , —Si(R 9 ) 2 CH 2 CH 2 NH 2 , —N + (CH 3 ) 3 − OH, —CH 2 CH(O)CH 2 , —Si(R 9 ) 2 CH 2 CH(O)CH 2 , —CH 3 , —CH═CH 2 , —CH 2 CH═CH 2 , —CH═CH—CN, —OCN, —CH 2 OH, CH 2 X, CH 2 OCN, or —CH(═O), provided that each R 7 are not both H;

R 8 is —NH—CH 2 —CH 2 —NH 2 or Al(R 10 ) 2 ;

R 9 is C 1 -C 6 alkyl; and

R 10 is C 1 -C 6 alkyl or halo;

wherein at least a portion of the thermal conductive composition is positioned substantially between the heat source and the heat sink and provides thermal communication between the heat source and heat sink; or

an electronic device, the electronic device at least partially encapsulated by a thermal conductive composition comprising at least one of a compound of Formula (I):

wherein:

M is Al, Ga, Si, Ge, In, or Sn;

R 1 , R 2 , R 3 , and R 4 are each independently —H, or —NH 2 , —Si(OR 5 ) 3 , —Si(OR 5 ) 2 CH 2 CH 2 NH 2 , —Si(R 5 ) 2 CH 2 CH 2 NH 2 , —N + (CH 3 ) 3 − OH, —CH 2 CH(O)CH 2 , —Si(R 5 ) 2 CH 2 CH(O)CH 2 , —CH 3 , —CH═CH 2 , —CH 2 CH═CH 2 , —CH═CH—CN, —OCN, —CH 2 OH, CH 2 X, CH 2 OCN, —CH(═O), provided that R 1 , R 2 , R 3 , and R 4 are not all H,

wherein:

X is halo;

R 5 is C 1 -C 6 alkyl;

and a compound of Formula (II):

wherein:

y is about 10 to about 500;

R 6 is C 1 -C 6 alkyl or halo;

each R 7 is independently —H, or —NH 2 , —Si(OR 9 ) 3 , —Si(OR 9 ) 2 CH 2 CH 2 NH 2 , —Si(R 9 ) 2 CH 2 CH 2 NH 2 , —N + (CH 3 ) 3 − OH, —CH 2 CH(O)CH 2 , —Si(R 9 ) 2 CH 2 CH(O)CH 2 , —CH 3 , —CH═CH 2 , —CH 2 CH═CH 2 , —CH═CH—CN, —OCN, —CH 2 OH, CH 2 X, CH 2 OCN, or —CH(═O), provided that each R 7 are not both H;

R 8 is —NH—CH 2 —CH 2 —NH 2 or Al(R 10 ) 2 ;

R 9 is C 1 -C 6 alkyl; and

R 10 is C 1 -C 6 alkyl or halo.

19. A method of preparing:

a polyurethane cross-linked compound of Formula (I) or (II), the method comprising contacting a compound of Formula (I) or Formula (II)

wherein:

M is Al, Ga, Si, Ge, In, or Sn;

R 1 , R 2 , R 3 , and R 4 are each independently —H, or —NH 2 , —Si(OR 5 ) 3 , —Si(OR 5 ) 2 CH 2 CH 2 NH 2 , —Si(R 5 ) 2 CH 2 CH 2 NH 2 , —N + (CH 3 ) 3 − OH, —CH 2 CH(O)CH 2 , —Si(R 5 ) 2 CH 2 CH(O)CH 2 , —CH 3 , —CH═CH 2 , —CH 2 CH═CH 2 , —CH═CH—CN, —OCN, —CH 2 OH, CH 2 X, CH 2 OCN, —CH(═O), provided that R 1 , R 2 , R 3 , and R 4 are not all H,

wherein:

X is halo;

R 5 is C 1 -C 6 alkyl;

wherein:

y is about 10 to about 500;

R 6 is C 1 -C 6 alkyl or halo;

each R 7 is independently —H, or —NH 2 , —Si(OR 9 ) 3 , —Si(OR 9 ) 2 CH 2 CH 2 NH 2 , —Si(R 9 ) 2 CH 2 CH 2 NH 2 , —N + (CH 3 ) 3 − OH, —CH 2 CH(O)CH 2 , —Si(R 9 ) 2 CH 2 CH(O)CH 2 , —CH 3 , —CH═CH 2 , —CH 2 CH═CH 2 , —CH═CH—CN, —OCN, —CH 2 OH, CH 2 X, CH 2 OCN, or —CH(═O), provided that each R 7 are not both H;

R 8 is —NH—CH 2 —CH 2 —NH 2 or Al(R 10 ) 2 ;

R 9 is C 1 -C 6 alkyl; and

R 10 is C 1 -C 6 alkyl or halo,

with a diisocyanate and a polyol under conditions sufficient to form a polyurethane cross-linked compound of Formula (I) or (II); or,

a siloxane polymer cross linked or cured with a compound of Formula (I) or (II), the method comprising contacting a compound of Formula (I) or (II)

wherein:

M is Al, Ga, Si, Ge, In, or Sn;

R 1 , R 2 , R3, and R 4 are each independently —H, or —NH 2 , —Si(OR 5 ) 3 , —Si(OR 5 ) 2 CH 2 CH 2 NH 2 , —Si(R 5 ) 2 CH 2 CH 2 NH 2 , —N + (CH 3 ) 3 − OH, —CH 2 CH(O)CH 2 , —Si(R 5 ) 2 CH 2 CH(O)CH 2 ,—CH 3 , —CH═CH 2 , —CH 2 CH═CH 2 , —CH═CH—CN, —OCN, —CH 2 OH, CH 2 X, CH 2 OCN, —CH(═O), provided that R 1 , R 2 , R 3 , and R 4 are not all H,

wherein:

X is halo;

R 5 is C 1 -C 6 alkyl;

wherein:

y is about 10 to about 500;

R 6 is C 1 -C 6 alkyl or halo;

each R 7 is independently —H, or —NH 2 , —Si(OR 9 ) 3 , —Si(OR 9 ) 2 CH 2 CH 2 NH 2 , —Si(R 9 ) 2 CH 2 CH 2 NH 2 ,

—N + (CH 3 ) 3 − OH, —CH 2 CH(O)CH 2 , —Si(R 9 ) 2 CH 2 CH(O)CH 2 , —CH 3 , —CH═CH 2 , —CH 2 CH═CH 2 , —CH═CH—CN, —OCN, —CH 2 OH, CH 2 X, CH 2 OCN, or —CH(═O), provided that each R 7 are not both H;

R 8 is —NH—CH 2 —CH 2 —NH 2 or Al(R 10 ) 2 ;

R 9 is C 1 -C 6 alkyl; and

R 10 is C 1 -C 6 alkyl or halo,

with a siloxane cyclic monomer or silicone oil in the presence of a crosslinking agent to form the siloxane polymer cross linked or cured with a compound of Formula (I) or (II); or

polyolefin copolymerized or grafted with a compound of Formula (I) or (II), the method comprising contacting a compound of a compound of Formula (I) or (II)

wherein:

M is Al, Ga, Si, Ge, In, or Sn;

R 1 , R 2 , R 3 , and R 4 are each independently —CH 2 ═CH—, CH 2 ═CH CH 2 —, or —CH 2 ═CH(CN),

wherein:

X is halo;

R 5 is C 1 -C 6 alkyl;

wherein:

y is about 10 to about 500;

R 6 is C 1 -C 6 alkyl or halo;

each R 7 is independently CH 2 ═CH—, or CH 2 ═CHCH 2 —, or CH 2 ═CH(CN)—;

R 8 is —NH—CH 2 —CH 2 —NH 2 or Al(R 10 ) 2 ;

R 9 is C 1 -C 6 alkyl; and

R 10 is C 1 -C 6 alkyl or halo,

with an olefin monomer under conditions suitable for free radical polymerization or anionic polymerization; or

polyolefin grafted with a compound of Formula (I) or (II), the method comprising contacting a polyolefin with a compound of Formula (I) or (II),

wherein:

M is Al, Ga, Si, Ge, In, or Sn;

R 1 , R 2 , R 3 , and R 4 are —CH 3 ,

wherein:

X is halo;

R 5 is C 1 -C 6 alkyl;

wherein:

y is about 10 to about 500;

R 6 is C 1 -C 6 alkyl or halo;

R 7 is —CH 3 ;

R 8 is —NH—CH 2 —CH 2 —NH 2 or Al(R 10 ) 2 ;

R 9 is C 1 -C 6 alkyl; and

R 10 is C 1 -C 6 alkyl or halo,

in the presence of a peroxide in a reactive extruder.

Assignments (6)
SECURITY INTEREST Recorded Jan 29, 2019
From: EMPIRE TECHNOLOGY DEVELOPMENT LLC
To: CRESTLINE DIRECT FINANCE, L.P.
Reel/Frame 048373/0217 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 31, 2014
From: ADAM, GEORGIUS ABIDAL
To: ADAMS INVENTION CONSULTING PTY LTD
Reel/Frame 033439/0583 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 31, 2014
From: MARGALIT, MORDEHAI
To: MORDEHAI MARGALIT HOLDINGS LTD.
Reel/Frame 033439/0640 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 31, 2014
From: MORDEHAI MARGALIT HOLDINGS LTD.
To: EMPIRE TECHNOLOGY DEVELOPMENT LLC
Reel/Frame 033439/0645 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 31, 2014
From: ROBERTS, BRADLEY KIRK; WAN, FENG
To: EMPIRE TECHNOLOGY DEVELOPMENT LLC
Reel/Frame 033439/0668 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 31, 2014
From: ADAMS INVENTION CONSULTING PTY LTD
To: EMPIRE TECHNOLOGY DEVELOPMENT LLC
Reel/Frame 033453/0449 →