Control of polymer architectures by living ring-opening metathesis copolymerization

Patent metadata

Field	Value
Publication number	US-11053356-B2
Application number	US-201815914762-A
Country	US
Kind code	B2
Filing date	Mar 7, 2018
Priority date	Mar 7, 2017
Publication date	Jul 6, 2021
Grant date	Jul 6, 2021

Abstract

In an aspect, a method of synthesizing a graft copolymer comprises the steps of: copolymerizing a first macromonomer and a first reactive diluent; wherein said first macromonomer comprises a first backbone precursor directly or indirectly covalently linked to a first polymer side chain group; wherein said reactive diluent is provided in the presence of the first macromonomer at an amount selected so as to result in formation said graft copolymer having a first backbone incorporating said diluent and said first macromonomer in a first polymer block characterized by a preselected first graft density or a preselected first graft distribution of said first macromonomer. In some embodiments of this aspect, said preselected first graft density is any value selected from the range of 0.05 to 0.75. In some methods, the composition and amount of said diluent is selected to provide both a first preselected first graft density and a first preselected first graft distribution.

First claim

We claim:

1. A method of synthesizing a graft copolymer, said method comprising the steps of:
copolymerizing a first macromonomer and a first reactive diluent; wherein said first macromonomer comprises a first backbone precursor directly or indirectly covalently linked to a first polymer side chain group;
wherein said first reactive diluent is provided in the presence of the first macromonomer at an amount selected so as to result in formation of said graft copolymer having a first backbone incorporating said first reactive diluent and said first macromonomer in a first polymer block characterized by a preselected first graft density and/or a preselected first graft distribution of said first macromonomer;
wherein said graft copolymer is a graft block copolymer; and wherein said method further comprises a step of:
copolymerizing a second macromonomer and a second reactive diluent;
wherein said second macromonomer comprises a second backbone precursor directly or indirectly covalently linked to a second polymer side chain group;
thereby resulting in formation of said graft copolymer having a second backbone incorporating said second reactive diluent and said second macromonomer in a second polymer block; wherein said second polymer block is directly or indirectly covalently linked to said first polymer block along said backbone; and wherein said second polymer block has a different composition than said first polymer block; and wherein said second reactive diluent is provided in the presence of the second macromonomer at an amount selected so as to result in said second polymer block being characterized by a preselected second graft density and/or a preselected second graft distribution of said second macromonomer;
wherein said first reactive diluent, said second reactive diluent, or each of said first reactive diluent and said second reactive diluent independently is defined by the formula (FX1a), (FX1b), or (FX1c):

wherein:
B 1 is a second backbone precursor group having a strained olefin;
each A 1 is independently an anchor group having the formula (FX3a) or (FX3b):

each L 1 is independently a linker group selected from the group consisting of a single bond, —O—, C 1 -C 10 alkyl, C 2 -C 10 alkenylene, C 3 -C 10 arylene, C 1 -C 10 alkoxy, C 1 -C 10 acyl, triazole, diazole, pyrazole, and any combination thereof;
and each D 1 is independently a dangling group that is a substituted or unsubstituted C 1 -C 30 alkyl, C 3 -C 30 cycloalkyl, C 5 -C 30 aryl, C 5 -C 30 heteroaryl, C 1 -C 30 acyl, C 1 -C 30 hydroxyl, C 1 -C 30 alkoxy, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 5 -C 30 alkylaryl, —CO 2 R 3 , —CONR 4 R 5 , —COR 6 , —SOR 7 , —OSR 8 , —SO 2 R 9 , —OR 10 , —SR 11 , —NR 12 R 13 , —NR 14 COR 15 , C 1 -C 30 alkyl halide, phosphonate, phosphonic acid, silane, siloxane, silsesquioxane, C 2 -C 30 halocarbon chain, C 2 -C 30 perfluorocarbon, C 2 -C 30 polyethylene glycol, a metal, or a metal complex, wherein each of R 3 -R 15 is independently H, C 5 -C 10 aryl or C 1 -C 10 alkyl; and
wherein said first macromonomer, said second macromonomer, or each of said first macromonomer and said second macromonomer independently is defined by the formula (FX6a), (FX6b), or (FX6c):

where:
B 1 is said second backbone precursor group having a strained olefin;
each A 1 is independently an anchor group having the formula (FX3a) or (FX3b):

each L 1 is independently a linker group selected from the group consisting of a single bond, —O—, C 1 -C 10 alkyl, C 2 -C 10 alkenylene, C 3 -C 10 arylene, C 1 -C 10 alkoxy, C 1 -C 10 acyl, triazole, diazole, pyrazole, and any combination thereof;
and each P 1 is independently said second polymer side chain group.

2. The method of claim 1 further comprising one or more additional copolymerization steps, so as to result in said graft copolymer having one or more additional polymer blocks directly or indirectly covalently linked to said first backbone of said first polymer block.

3. The method of claim 1 , wherein said second polymer side chain group is different from said first polymer side chain group and wherein said second reactive diluent is different from said first reactive diluent.

4. The method of claim 1 further comprising a step of copolymerizing a third polymer block, said third polymer block having a third backbone, wherein said third backbone of said third polymer block is directly or indirectly covalently linked to said first backbone of said first polymer block or to said second backbone of said second polymer block; wherein the composition of said third block is different from the composition said first polymer block, said second polymer block or both; and wherein said third polymer block comprises one or more third polymer side chain groups, and wherein said third reactive diluent is provided in the presence of the third macromonomer at an amount selected so as to result in formation of said third polymer block characterized by a preselected third graft density and/or a preselected third graft distribution of said one or more third polymer side chain groups.

5. The method of claim 1 , wherein said first graft density of said first macromonomer in said first polymer block is equal to [M a 1 ] 0 /([M a 1 ] 0 +[M a 2 ] 0 ), where:
[M a 1 ] 0 and [M a 2 ] 0 are initial concentrations of said first macromonomer and said first reactive diluent, respectively; and wherein said first graft density is selected from the range of 0.05 to 0.75.

6. The method of claim 5 , wherein said first graft density is selected from the range of 0.05 to 0.32, 0.34 to 0.49, 0.51 to 0.65, or 0.68 to 0.75.

7. The method of claim 1 , where:
r a 1 is a reactivity ratio of said first macromonomer; and
r a 2 is a reactivity ratio of said first reactive diluent;
wherein:
said first graft distribution of said first macromonomer is an alternating graft distribution when r a 1 is less than 1 and r a 2 is less than 1;
said first graft distribution of said first macromonomer is a blocky graft distribution when r a 1 is greater than 1 and r a 2 is greater than 1; wherein the first polymer block characterized by the blocky graft distribution comprises four or more identical first repeating units followed by four or more identical second repeating units, wherein each of the first repeating units or each of the second repeating units comprises the first polymer side chain group of said first macromonomer;
said first graft distribution of said first macromonomer is a random graft distribution when r a 1 is within 10% of or equal to 1 and r a 2 is within 10% of or equal to 1; or
said first graft distribution of said first macromonomer is a gradient graft distribution when r a 1 is less than 1 and r a 2 is greater than 1;
wherein said step of copolymerizing said first macromonomer is performed in the presence of a catalyst; and wherein first polymer block has a preselected first degree of polymerization, said first degree of polymerization being equal to ([M a 1 ] 0 +[M a 2 ] 0 )/[Cat] 0 ; where:
[Cat] 0 is an initial concentration of said catalyst; and [M a 1 ] 0 and [M a 2 ] 0 are initial concentrations of said first macromonomer and said first reactive diluent, respectively.

8. The method of claim

Assignees

• California Inst Of Techn

Inventors

• Grubbs Robert H
• Lin Tzu-Pin
• Chang Alice
• Chen Hsiang-Yun
• Bates Christopher M

Classifications

• C08F290/04 Primary

  Polymers provided for in subclasses C08C or C08F · CPC title

• C08G2261/1428

  containing acyl groups · CPC title

• C08F290/06

  Polymers provided for in subclass C08G · CPC title

• C08F2500/09

  Long chain branches · CPC title

• C08G2261/722

  Sulfonation · CPC title