Fluorinated block copolymers

Patent metadata

Field	Value
Publication number	US-11261280-B2
Application number	US-201816477019-A
Country	US
Kind code	B2
Filing date	Jan 12, 2018
Priority date	Jan 18, 2017
Publication date	Mar 1, 2022
Grant date	Mar 1, 2022

Abstract

Described herein is a millable fluorinated block copolymer having (a) at least one A block, wherein the A block is a semi-crystalline segment comprising repeating divalent monomeric units derived from at least TFE, HFP and VDF; (b) at least one B block, wherein the B block is a segment comprising repeating divalent monomeric units derived from at least HFP and VDF; and (c) a bisolefin monomer, wherein at least (i) the semi-crystalline segment of the A block comprises repeating divalent monomeric units derived from TFE, HFP, VDF, and the bisolefin monomer, (ii) the segment of the B block comprises repeating divalent monomeric units derived from HFP, VDF, and the bisolefin monomer, or (iii) a combination thereof; and wherein the millable fluorinated block copolymer has a modulus of 0.1 to 2.5 MPa at 100° C.

First claim

What is claimed is:

1. A curable composition comprising:
a millable fluorinated block copolymer having
(a) at least one A block, wherein the A block is a semi-crystalline segment comprising repeating divalent monomeric units derived from at least TFE, HFP and VDF;
(b) at least one B block, wherein the B block is a segment comprising repeating divalent monomeric units derived from at least HFP and VDF; and
(c) a bisolefin monomer, wherein at least (i) the semi-crystalline segment of the A block comprises repeating divalent monomeric units derived from TFE, HFP, VDF, and the bisolefin monomer, (ii) the segment of the B block comprises repeating divalent monomeric units derived from HFP, VDF, and the bisolefin monomer, or (iii) a combination thereof; and
wherein the millable fluorinated block copolymer has a modulus of 0.1 to 2.5 MPa at 100° C.

2. The curable composition of claim 1 , wherein the bisolefin monomer is of the formula
(I)
wherein R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently H, a C1-C5 alkyl group, or a C1-C5 fluorinated alkyl group; and Z is an alkylene or cycloalkylene C1-C18 radical, which is linear or branched, optionally containing oxygen atoms and optionally fluorinated.

3. The curable composition of claim 2 , wherein the bisolefin monomer is at least one of: CH2═CH(CF 2 ) 4 CH═CH 2 , CH2═CH(CF 2 ) 6 CH═CH 2 , CH 2 ═CH(CF 2 ) 8 CH═CH 2 .

4. The curable composition of claim 2 , wherein the bisolefin monomer is at least one of: CF 2 ═CF—O—(CF 2 ) 2 —O—CF═CF 2 , CF 2 ═CF—O—(CF 2 ) 3 —O—CF═CF 2 , CF 2 ═CF—O—(CF 2 ) 4 —O—CF═CF 2 , CF 2 ═CF—O—(CF 2 ) 5 —O—CF═CF 2 , CF 2 ═CF—O—(CF 2 ) 6 —O—CF═CF 2 , CF 2 ═CF—CF 2 —O—(CF 2 ) 2 —O—CF═CF 2 , CF 2 ═CF—CF 2 —O—(CF 2 ) 3 —O—CF═CF 2 , CF 2 ═CF—CF 2 —O—(CF 2 ) 4 —O—CF═CF 2 , CF 2 ═CF—CF 2 —O—(CF 2 ) 4 —O—CF═CF 2 , CF 2 ═CF—CF 2 —O—(CF 2 ) 5 —O—CF═CF 2 , CF 2 ═CF—CF 2 —O—(CF 2 ) 6 —O—CF═CF 2 , CF 2 ═CF—CF 2 —O—(CF 2 ) 2 —O—CF 2 —CF═CF 2 , CF 2 ═CF—CF 2 —O—(CF 2 ) 3 —O—CF 2 —CF═CF 2 , CF 2 ═CF—CF 2 —O—(CF 2 ) 4 —O—CF 2 —CF═CF 2 , CF 2 ═CF—CF 2 —O—(CF 2 ) 5 —O—CF 2 —CF═CF 2 , CF 2 ═CF—CF 2 —O—(CF 2 ) 6 —O—CF 2 —CF═CF 2 , CF 2 ═CF—CF 2 —O—CF 2 CF 2 —CH═CH 2 , CF 2 ═CF—(OCF(CF 3 )CF 2 )—O—CF 2 CF 2 —CH═CH 2 , CF 2 ═CF—(OCF(CF 3 )CF 2 ) 2 —O—CF 2 CF 2 —CH═CH 2 , CF 2 ═CFCF 2 —O—CF 2 CF 2 —CH═CH 2 , CF 2 ═CF—CF 2 —(OCF(CF 3 )CF 2 —O—CF 2 CF 2 —CH═CH 2 , CF 2 ═CFCF 2 —(OCF(CF 3 )CF 2 ) 2 —O—CF 2 CF 2 —CH═CH 2 , CF 2 ═CF—CF 2 —CH═CH 2 , CF 2 ═CF—O—(CF 2 ) c —O—CF 2 —CF 2 —CH═CH 2 wherein c is an integer selected from 2 to 6, CF 2 ═CFCF 2 —O—(CF 2 ) c —O—CF 2 —CF 2 —CH═CH 2 wherein c is an integer selected from 2 to 6, CF 2 ═CF—(OCF(CF 3 )CF 2 ) b —O—CF(CF 3 )—CH═CH 2 wherein b is 0, 1, or 2, CF 2 ═CF—CF 2 —(OCF(CF 3 )CF 2 ) b —O—CF(CF 3 )—CH═CH 2 wherein b is 0, 1, or 2, CH 2 ═CH—(CF 2 ) n —O—CH═CH 2 wherein n is an integer from 1-10, and CF 2 ═CF—(CF 2 ) a —(O—CF(CF 3 )CF 2 ) b —O—(CF 2 ) c —(OCF(CF 3 )CF 2 ) f —O—CF═CF 2 wherein a is 0 or 1, b is 0, 1, or 2, c is 1, 2, 3, 4, 5, or 6, and f is 0, 1, or 2.

5. The curable composition of claim 1 , wherein the fluorinated block copolymer has a melting point of at least 100° C. and at most 275° C.

6. The curable composition of claim 1 , wherein the B block is semi-crystalline.

7. The curable composition of claim 1 , wherein the B block is amorphous.

8. The curable composition of claim 1 , wherein the Tg of the A block is greater than 0° C. and less 80° C.

9. The curable composition of claim 1 , wherein the Tg of the B block is less than 0° C.

10. The curable composition of claim 1 , further comprising a peroxide cure system.

11. The curable composition of claim 1 , wherein the glass transition temperature of the millable fluorinated block copolymer is less than −20° C.

12. A cured article derived from the curable composition of claim 1 .

13. The cured article of claim 12 , wherein the article is a packer, an o-ring, a seal, a gasket, a hose, or a sheet.

14. The curable composition of claim 1 , wherein the A block comprises repeating divalent monomeric units further derived from at least one of a perfluorovinyl ether monomer, and a perfluoroallyl ether monomer.

15. The curable composition of claim 14 , wherein the perfluorovinyl ether is selected from at least one of: perfluoro (methyl vinyl) ether (PMVE), perfluoro (ethyl vinyl) ether (PEVE), perfluoro (n-propyl vinyl) ether (PPVE-1), perfluoro-2-propoxypropylvinyl ether (PPVE-2), perfluoro-3-methoxy-n-propylvinyl ether, perfluoro-2-methoxy-ethylvinyl ether, CF 2 ═CFOCF 2 OCF 3 , CF 2 ═CFOCF 2 OCF 2 CF 3 , and CF 3 —(CF 2 ) 2 —O—CF(CF 3 )—CF 2 —O—CF(CF 3 )—CF 2 —O—CF═CF 2 .

16. The curable composition of claim 14 , wherein the perfluoroallyl ether is selected from at least one of: perfluoro (methyl allyl) ether (CF 2 ═CF—CF 2 —O—CF 3 ), perfluoro (ethyl allyl) ether, perfluoro (n-propyl allyl) ether, perfluoro-2-propoxypropyl allyl ether, perfluoro-3-methoxy-n-propylallyl ether, perfluoro-2-methoxy-ethyl allyl ether, perfluoro-methoxy-methyl allyl ether, and CF 3 —(CF 2 ) 2 —O—CF(CF 3 )—CF 2 —O—CF(CF 3 )—CF 2 —O—CF 2 CF═CF 2 .

17. The curable composition of claim 1 , wherein the B block segment further comprises repeating divalent monomeric units derived from TFE, a cure site monomer, a perfluorovinyl ether monomer, a perfluoroallyl ether monomer, and combinations thereof.

18. The curable composition of claim 17 , wherein the cure site monomer is selected from at least one of: CF 2 ═CFCF 2 I, CF 2 ═CFCF 2 CF 2 I, CF 2 ═CFOCF 2 CF 2 I, CF 2 ═CFOCF 2 CF 2 CF 2 I, CF 2 ═CFOCF 2 CF 2 CH 2 I, CF 2 ═CFCF 2 OCH 2 CH 2 I, CF 2 ═CFO(CF 2 ) 3 —OCF 2 CF 2 I, CF 2 ═CFCF 2 Br, CF 2 ═CFOCF 2 CF 2 Br, CF 2 ═CFCl, CF 2 ═CFCF 2 Cl, and combinations thereof.

19. The curable composition of claim 1 , wherein the millable fluorinated block copolymer comprises about 0.05 wt % to about 1 wt % of iodine based on the weight of the millable fluorinated block copolymer.

Assignees

• 3M Innovative Properties Co

Inventors

• Mitchell Michael H
• Duchesne Denis
• Fukushi Tatsuo
• Last Larry A
• Scott Peter J
• Weilandt Karl D

Classifications

• C08F214/28 Primary

  Hexyfluoropropene · CPC title

• C08F214/16

  Monomers containing bromine or iodine · CPC title

• C08F2438/01

  Atom Transfer Radical Polymerization [ATRP] or reverse ATRP · CPC title

• C08F293/005 Primary

  using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent · CPC title

• C08K5/14

  Peroxides · CPC title