Granted Patent B2

US 9,512,150 · App. 14/448,938 · Granted Dec 6, 2016

Inventors: Georgius Abidal Adam (Edensor Park, AU); Mordehai Margalit (Zichron Ya'akov, IL); Bradley Kirk Roberts (Seattle, WA); Feng Wan (Issaquah, WA)

Assignee: Empire Technology Development LLC

C07F5/069C08F110/06C08G18/42C08G18/7621C08G77/04C08G79/10

Abstract

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 (8)

Continuity (1)