Polymers containing metathesized natural oil derivatives
View Patent ↗Polymers containing natural oil derivatives are generally disclosed. Methods of forming such polymers are also generally disclosed. In some embodiments, the polymer is a polyurethane. In some embodiments, the natural oil derivative is a cross-linking group that links two or more polymer chains together.
1. A polyurethane, comprising one or more constitutional units according to formula (I):
wherein:
R 1 and R 2 are independently C 1-20 alkylene, C 2-20 alkenylene, C 3-14 cycloaklylene, C 6-14 arylene, C 1-20 heteroalkylene, C 2-20 heteroalkenylene, C 3-14 heterocycloaklylene, C 6-14 hetero-arylene, or any combination thereof, each of which is optionally substituted one or more times by groups selected independently from R 3 ;
R 3 is a halogen, C 1-6 alkyl, —OH, C 1-6 alkoxy, —NH 2 , —NH(C 1-6 alkyl), —N(C 1-6 alkyl) 2 , C 1-6 haloalkyl, or C 1-6 haloalkoxy;
X 1 is 8-nonenyl, 9-decenyl, or 10-undecenyl, each of which is optionally substituted one or more times by groups selected independently from R 3 ; or X 1 is —X 2 -G 1 ;
X 2 is C 4-28 alkylene or C 4-28 alkenylene, each of which is optionally substituted one or more times by groups selected independently from R 3 ;
G 1 is
R 4 and R 5 are independently C 1-20 alkylene, C 2-20 alkenylene, C 3-14 cycloaklylene, C 6-14 arylene, C 1-20 heteroalkylene, C 2-20 heteroalkenylene, C 3-14 heterocycloaklylene, C 6-14 hetero-arylene, or any combination thereof, each of which is optionally substituted one or more times by groups selected independently from R 3 ; and
X 4 and X 5 are independently a hydrogen atom or a polymer or polymer sequence, which is a polyurethane, a polyether, or a polyester.
2. The polyurethane of claim 1 , wherein R 1 and R 2 are independently C 1-8 alkylene, which is optionally substituted one or more times with substituents selected independently from R 3 .
3. The polyurethane of claim 2 , wherein R 1 and R 2 are independently —CH 2 —, —(CH 2 ) 2 —, —(CH 2 ) 3 —, —(CH 2 ) 4 —, —(CH 2 ) 5 , or —(CH 2 ) 6 —.
4. The polyurethane of any one of claim 1 , wherein X 1 is —X 2 -G 1 .
5. The polyurethane of claim 4 , wherein X 2 is —(CH 2 ) 7 —CH═CH—(CH 2 ) 7 —, —(CH 2 ) 7 —CH═CH—(CH 2 ) 8 —, —(CH 2 ) 7 —CH═CH—(CH 2 ) 9 —, —(CH 2 ) 8 —CH═CH—(CH 2 ) 7 —, —(CH 2 ) 8 —CH═CH—(CH 2 ) 8 —, —(CH 2 ) 8 —CH═CH—(CH 2 ) 9 —, —(CH 2 ) 9 —CH═CH—(CH 2 ) 7 —, —(CH 2 ) 9 —CH═CH—(CH 2 ) 8 —, or —(CH 2 ) 9 —CH═CH—(CH 2 ) 9 —.
6. The polyurethane of claim 4 , wherein R 4 and R 5 are independently C 1-8 alkylene, which is optionally substituted one or more times with substituents selected independently from R 3 .
7. The polyurethane of claim 6 , wherein R 4 and R 5 are independently —CH 2 —, —(CH 2 ) 2 —, —(CH 2 ) 3 —, —(CH 2 ) 4 —, —(CH 2 ) 5 , or —(CH 2 ) 6 —.
8. The polyurethane of claim 1 , wherein the polyurethane is a block copolymer comprising a first block and a second block.
9. The polyurethane of claim 8 , wherein the first block is formed from a reaction mixture comprising a short-chain diol, a diisocyanate, and a compound of formula (Ia):
wherein R 1 , R 2 ,and X 1 are the same as defined in any one of claims 1 to 10 .
10. The polyurethane of claim 9 , wherein X 4 and X 5 are hydrogen.
11. The polyurethane of claim 9 , wherein the mole-to-mole ratio of the short-chain diol to the compound of formula (Ia) in the reaction mixture is at least 10:1.
12. The polyurethane of claim 9 , wherein the short-chain diol is a compound of formula (II):
HO—X 11 —OH (II),
wherein:
X 11 is C 1-20 alkylene, C 2-20 alkenylene, C 3-14 cycloaklylene, C 6-14 arylene, C 1-20 heteroalkylene, C 2-20 heteroalkenylene, C 3-14 heterocycloaklylene, C 6-14 hetero-arylene, or any combination thereof, each of which is optionally substituted one or more times by groups selected independently from R 11 ; and
R 11 is halogen, C 1-6 alkyl, —OH, C 1-6 alkoxy, —NH 2 , —NH(C 1-6 alkyl), —N(C 1-6 alkyl) 2 , C 1-6 haloalkyl, or C 1-6 haloalkoxy.
13. The polyurethane of claim 12 , wherein X 11 is C 1-20 alkylene or C 2-20 polyalkyleneoxide.
14. The polyurethane of claim 12 , wherein the short-chain diol is ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexane-dimethanol, hydroquinone bis(2-hydroxyethyl)ether, or p-di-(2-hydroxyethoxy)benzene.
15. The polyurethane of claim 9 , wherein the diisocyanate is a toluene diisocyanate, a methylene diphenyl diisocyanate, a naphthalene diisocyanate, or hexamethylene diisocyanate.
16. The polyurethane of claim 8 , wherein the second block comprises a polymer sequence selected from the group consisting of: a polyether, a polyester, a polycarbonate, a polycaprolactone, a polybutadiene, and a polysulfide; and
wherein the polymer sequence has a molecular weight of 1,000 Da to 20,000 Da.
17. The polyurethane of claim 16 , wherein the polymer sequence is a polyether or a polyester.
18. A method of making a polyurethane resin, the method comprising:
forming a reaction mixture comprising a short-chain diol, a diisocyanate, a long-chain polyol, and a compound of formula (Ia):
and
forming a product mixture comprising a polyurethane resin formed from the short-chain diol, the diisocyanate, the long-chain polyol, and the compound of formula (Ia); wherein:
R 1 and R 2 are independently C 1-20 alkylene, C 2-20 alkenylene, C 3-14 cycloaklylene, C 6-14 arylene, C 1-20 heteroalkylene, C 2-20 heteroalkenylene, C 3-14 heterocycloaklylene, C 6-14 hetero-arylene, or any combination thereof, each of which is optionally substituted one or more times by groups selected independently from R 3 ;
R 3 is a halogen, C 1-6 alkyl, —OH, C 1-6 alkoxy, —NH 2 , —NH(C 1-6 alkyl), —N(C 1-6 alkyl) 2 , C 1-6 haloalkyl, or C 1-6 haloalkoxy;
X 1 is 8-nonenyl, 9-decenyl, or 10-undecenyl, each of which is optionally substituted one or more times by groups selected independently from R 3 ; or X 1 is —X 2 -G 1 ;
X 2 is C 4-28 alkylene or C 4-28 alkenylene, each of which is optionally substituted one or more times by groups selected independently from R 3 ;
G 1 is
R 4 and R 5 are independently C 1-20 alkylene, C 2-20 alkenylene, C 3-14 cycloaklylene, C 6-14 arylene, C 1-20 heteroalkylene, C 2-20 heteroalkenylene, C 3-14 heterocycloaklylene, C 6-14 hetero-arylene, or any combination thereof, each of which is optionally substituted one or more times by groups selected independently from R 3 ; and
X 4 and X 5 are independently a hydrogen atom or a polymer or polymer sequence, which is a polyurethane, a polyether, or a polyester.
19. The method of claim 18 , wherein X 1 is —X 2 -G 1 .
20. The polyurethane of claim 9 , wherein the compound of formula (Ia) is formed from a reaction mixture comprising a dialkanol amine and an ester or acid compound, wherein the ester or acid compound is formed from the metathesis of a natural oil.
21. The method of claim 18 , wherein the compound of formula (Ia) is formed from a reaction mixture comprising a dialkanol amine and an ester or acid compound, wherein the ester or acid compound is formed from the metathesis of a natural oil.
22. The polyurethane of claim 1 , wherein X 1 is unsubstituted 8-nonenyl, 9-decenyl, or 10-undecenyl.
23. The polyurethane of claim 22 , wherein X 1 is 8-nonenyl.
24. The polyurethane of claim 22 , wherein R 1 and R 2 are both —(CH 2 ) 2 —.
25. The polyurethane of claim 23 , wherein R 1 and R 2 are both —(CH 2 ) 2 —.
26. The method of claim 18 , wherein X 1 is unsubstituted 8-nonenyl, 9-decenyl, or 10-undecenyl.
27. The method of claim 26 , wherein X 1 is 8-nonenyl.
28. The method of claim 26 , wherein R 1 and R 2 are both —(CH 2 ) 2 —.
29. The method of claim 27 , wherein R 1 and R 2 are both —(CH 2 ) 2 —.