Farnesene-based macromonomers and methods of making and using the same

Patent metadata

Field	Value
Publication number	US-10544241-B2
Application number	US-201615266330-A
Country	US
Kind code	B2
Filing date	Sep 15, 2016
Priority date	Sep 15, 2016
Publication date	Jan 28, 2020
Grant date	Jan 28, 2020

Abstract

A macromonomer precursor is provided that includes a polymeric chain derived from farnesene and a single functional terminal end. The functional terminal end may include a hydroxyl group, an amino group, an epoxy group, an isocyanato group, or a carboxylic acid group. The terminal end of the macromonomer precursor may then be reacted with a (meth)acrylate to form a macromonomer having a (meth)acrylate functionalized terminal end that may be (co)polymerized with radically polymerizable monomers, such as alkyl(meth)acrylate monomers. Alternatively, a copolymer may be obtained by first deriving a poly(meth)acrylate from (meth)acrylate monomers having reactive groups that would allow the macromonomer precursors to be grafted onto the poly(meth)acrylate in a second step. The resulting copolymer may be incorporated as an additive in various formulations, such as a lubricant, a hydraulic fluid, a cosmetic composition, and an adhesive composition.

First claim

We claim:

1. A macromonomer precursor consisting of:
a polymeric chain derived from monomers consisting of farnesene and, optionally, at least one diene;
wherein the polymeric chain has terminal ends and wherein only one of the terminal ends is functionalized with a hydroxyl group, an amino group, an epoxy group, an isocyanato group, or a carboxylic acid group.

2. The macromonomer precursor of claim 1 , wherein the polymeric chain has been hydrogenated and has a degree of unsaturation less than or equal to 10% and wherein degree of unsaturation is equal to the ratio of the Iodine value after hydrogenation to the Iodine value before hydrogenation.

3. The macromonomer precursor of claim 1 , wherein the farnesene comprises at least 25 wt. % of the macromonomer precursor.

4. The macromonomer precursor of claim 1 having a weight average molecular weight of from 1,000 to 100,000.

5. The macromonomer precursor of claim 1 , wherein the polymeric chain is derived solely from farnesene.

6. A method of preparing a copolymer comprising:
reacting a macromonomer precursor according to claim 1 with a reactant according to formula (II):

wherein R 2 is hydrogen or methyl, and R 3 is selected from the group consisting of a hydroxyl, a halogen, and —OR 4 , wherein R 4 is a substituted hydrocarbyl to provide a (meth)acrylate terminated polyfarnesene macromonomer; and
copolymerizing the (meth)acrylate terminated polyfarnesene macromonomer with one or more radically polymerizable monomers.

7. The method of claim 6 , wherein the macromonomer precursor is at least partially saturated prior to the reacting step.

8. The method of claim 6 , wherein the optionally substituted hydrocarbyl is a linear, branched or cyclic alkyl residue having 1 to 5 carbon atoms.

9. A method of preparing a copolymer comprising:
reacting a macromonomer precursor according to claim 1 which is functionalized with a hydroxyl group, an amino group, or a carboxylic acid group with glycidyl (meth)acrylate to provide a (meth)acrylate terminated polyfarnesene macromonomer; and
copolymerizing the (meth)acrylate terminated polyfarnesene macromonomer with one or more radically polymerizable monomers.

10. The method of claim 9 , wherein the macromonomer precursor is at least partially saturated prior to the reacting step.

11. A method of preparing a copolymer comprising:
reacting a macromonomer precursor according to claim 1 which is functionalized with a hydroxyl group, an amino group, an epoxy group, or a carboxylic acid group with an acrylated isocyanate compound to provide a (meth)acrylate terminated polyfarnesene macromonomer; and
copolymerizing the (meth)acrylate terminated polyfarnesene macromonomer with one or more radically polymerizable monomers.

12. The method of claim 11 , wherein the macromonomer precursor is at least partially saturated prior to the reacting step.

13. A method of preparing a copolymer comprising:
radically polymerizing monomers according to formula (II) to form a poly(meth)acrylate):

wherein R 2 is hydrogen or methyl, and R 3 is selected from the group consisting of a hydroxyl, a halogen, and —OR 4 , wherein R 4 is an alcohol, an amino-alkyl, an isocyanato alkyl, or an optionally substituted hydrocarbyl; and
reacting the poly(meth)acrylate with the macromonomer precursor of claim 1 .

14. The method of preparing a copolymer according to claim 13 , wherein the monomers according to formula (II) are radically polymerized with monomers selected from the group consisting of vinyl aromatics, fumarates, maleates, vinyl esters, acrylonitriles, ethylene, and combinations thereof.

15. A copolymer made according to claim 13 .

16. A lubricant composition comprising
base oil containing at least one of an ester oil and a hydrocarbon oil; and
the copolymer of claim 15 .

17. A hydraulic fluid composition comprising the copolymer of claim 15 .

18. A cosmetic composition comprising the copolymer of claim 15 .

19. An adhesive composition comprising the copolymer of claim 15 .

Assignees

• Fina Technology

Inventors

• Henning Steven K
• Yoo Taejun
• Chao Herbert S

Classifications

• C08F136/22

  the radical having three or more carbon-to-carbon double bonds · CPC title

• C08C19/38

  with hydroxy radicals · CPC title

• C08C19/44

  of polymers containing metal atoms exclusively at one or both ends of the skeleton · CPC title

• A61K8/8194

  Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers · CPC title

• A61K2800/10

  General cosmetic use · CPC title