Tunable linear fluoropolymers

Patent metadata

Field	Value
Publication number	US-11597785-B2
Application number	US-201816764680-A
Country	US
Kind code	B2
Filing date	Nov 16, 2018
Priority date	Nov 17, 2017
Publication date	Mar 7, 2023
Grant date	Mar 7, 2023

Abstract

The present disclosure provides tunable fluoropolymers and methods for making them.

First claim

The invention claimed is:

1. A method of preparing a fluoropolymer comprising:
preparing a polymerization reaction mixture comprising a diene of formula VII with an α,ω-iodoperfluorocarbon of formula VIII:

and reacting the polymerization reaction mixture with sodium dithionite, thereby creating a fluoropolymer comprising repeat units according to formula I, Ia, or Ib:

wherein:
each R 1 is independently a divalent linker;
each R 3 is independently H, alkyl, alkenyl, alkynyl, alkoxy, allyl, aryl, heteroaryl, alkylthio, disulfide, OH, SH, SeH, CN, amino, carboxy, ester, thioester, amide, azide, phosphine, halogen, nitro, carbonyl, silyl, or boron; and
n is an integer from 1-100.

2. The method of claim 1 , wherein the method further comprises contacting the fluoropolymer with a cross linking agent, thereby creating a cross-linked fluoropolymer comprising repeat units according to formula Ic, Id, le, If, or Ig:

wherein each R 5 has the structure of:

each R 1 is independently a divalent linker;
each R 3 is independently H, alkyl, alkenyl, alkynyl, alkoxy, allyl, aryl, heteroaryl, alkylthio, disulfide, OH, SH, SeH, CN, amino, carboxy, ester, thioester, amide, azide, phosphine, halogen, nitro, carbonyl, silyl, or boron;
n is an integer from 1-100;
wherein:
each R 6 is independently an arylene or heteroarylene; and
z is 0-20.

3. The method of claim 2 , wherein the cross-linked fluoropolymer is a compound according to formula IIIc, IIId, or IIIe:

wherein m is l-5000;
each R 1 is independently a divalent linker;
each R 2 is independently H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, ester, acyloxy, alkoxy, alkylthio, disulfide, OH, SH, SeH, CN, amino, carboxy, thioester, amide, azide, phosphine, halogen, nitro, carbonyl, silyl, or boron;
each R 3 is independently H, alkyl, alkenyl, alkynyl, alkoxy, allyl, aryl, heteroaryl, alkylthio, disulfide, OH, SH, SeH, CN, amino, carboxy, ester, thioester, amide, azide, phosphine, halogen, nitro, carbonyl, silyl, or boron;
each R 4 independently comprises an alkylene, an ester, a carbonate, an ether, an acetal, a urea, an arylene, a heteroarylene, a thioether, a sulfoxide, a sulfone, a selenide, a selenoxide, a phosphodiester, boron, a boronic ester, a silyl, a siloxane, a diazo, an orthoester, a carbonyl, a disulfide, or an enol ester; and
n is an integer from 1-100.

4. The method of claim 3 , wherein m is 15-5000, 15-2000, 15-1000, 15-500, 50-5000, 50-2000, or 50-500.

5. The method of claim 2 , wherein the cross-linked fluoropolymer is a compound according to formula IV:

wherein,
each R 1 is independently a divalent linker;
each R 2 is independently H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, ester, acyloxy, alkoxy, alkylthio, disulfide, OH, SH, SeH, CN, amino, carboxy, thioester, amide, azide, phosphine, halogen, nitro, carbonyl, silyl, or boron;
each R 3 is independently H, alkyl, alkenyl, alkynyl, alkoxy, allyl, aryl, heteroaryl, alkylthio, disulfide, OH, SH, SeH, CN, amino, carboxy, ester, thioester, amide, azide, phosphine, halogen, nitro, carbonyl, silyl, or boron;
each R 4 independently comprises an alkylene, an ester, a carbonate, an ether, an acetal, a urea, an arylene, a heteroarylene, a thioether, a sulfoxide, a sulfone, a selenide, a selenoxide, a phosphodiester, boron, a boronic ester, a silyl, a siloxane, a diazo, an orthoester, a carbonyl, a disulfide, or an enol ester; and
n is an integer from 1-100;
each X 10 is independently O or S; and
y is 0-20.

6. The method of claim 5 , wherein y is 0, 2 or 10.

7. The method of claim 2 , wherein the cross-linked fluoropolymer polymer is a compound according to formula Vd:

wherein
each A is independently aryl or heteroaryl;
each R 1 is independently a divalent linker;
each R 3 is independently H, alkyl, alkenyl, alkynyl, alkoxy, allyl, aryl, heteroaryl, alkylthio, disulfide, OH, SH, SeH, CN, amino, carboxy, ester, thioester, amide, azide, phosphine, halogen, nitro, carbonyl, silyl, or boron;
each R 4 independently comprises an alkylene, an ester, a carbonate, an ether, an acetal, a urea, an arylene, a heteroarylene, a thioether, a sulfoxide, a sulfone, a selenide, a selenoxide, a phosphodiester, boron, a boronic ester, a silyl, a siloxane, a diazo, an orthoester, a carbonyl, a disulfide, or an enol ester; and
n is an integer from 1-100; and
m is 1-5000.

8. The method of claim 7 , wherein the fluoropolymer polymer is a compound according to formula VI:

wherein
each A is independently aryl or heteroaryl;
each R 1 is independently a divalent linker;
each R 3 is independently H, alkyl, alkenyl, alkynyl, alkoxy, allyl, aryl, heteroaryl, alkylthio, disulfide, OH, SH, SeH, CN, amino, carboxy, ester, thioester, amide, azide, phosphine, halogen, nitro, carbonyl, silyl, or boron;
each R 4 independently comprises an alkylene, an ester, a carbonate, an ether, an acetal, a urea, an arylene, a heteroarylene, a thioether, a sulfoxide, a sulfone, a selenide, a selenoxide, a phosphodiester, boron, a boronic ester, a silyl, a siloxane, a diazo, an orthoester, a carbonyl, a disulfide, or an enol ester; and
n is an integer from 1-100;
m is 1-5000; and
y is 0-20.

9. The method of claim 8 , wherein R 4 comprises a perfluoroalkylene.

10. The method of claim 1 , wherein the repeat unit further comprises an end group according to formula II, IIa, or IIb:

wherein:
R 4 is a divalent linker;
R 2 is H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, ester, acyloxy, alkoxy, alkylthio, disulfide, OH, SH, SeH, CN, amino, carboxy, thioester, amide, azide, phosphine, halo, nitro, carbonyl, silyl, or boron; and
each R 3 is independently H, alkyl, alkenyl, alkynyl, alkoxy, allyl, aryl, heteroaryl, alkylthio, disulfide, OH, SH, SeH, CN, amino, carboxy, ester, thioester, amide, azide, phosphine, halogen, nitro, carbonyl, silyl, or boron.

11. The method of claim 10 , wherein R 1 is the same as R 4 .

12. The method of claim 10 , wherein R 2 is alkenyl or halo.

13. The method of claim 10 , wherein R 2 is:

wherein A is an aryl or heteroaryl;
or R 2 is an amide.

14. The method of claim 10 , wherein R 4 comprises an alkylene, an ester, a carbonate, an ether, an acetal, a urea, an arylene, a heteroarylene, a thioether

Assignees

• Univ California

Inventors

• Sletten Ellen M
• Jaye Joseph A

Classifications

• C08F138/00 Primary

  Homopolymers of compounds having one or more carbon-to-carbon triple bonds · CPC title

• C08F120/40

  Esters of unsaturated alcohols {, e.g. allyl (meth)acrylate} · CPC title

• C08F118/12

  with unsaturated alcohols containing three or more carbon atoms · CPC title

• C08J3/243

  Two or more independent types of crosslinking for one or more polymers · CPC title

• C08F8/26

  Removing halogen atoms or halogen-containing groups from the molecule · CPC title