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US 2001/0044481 A1Published application
New photocurable halofluorinated acrylates
OwnerChengjiu Wu, Baopei Xu +2inventors
InventorsChengjiu Wu, Baopei Xu, Jianhui Shan, James T. Yardley
Life of this patent
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Abstract
This invention relates to a novel class of halofluorinated acrylates and more particularly to chlorofluorinated or bromofluorinated acrylates characterized by a chlorofluorinated or bromofluorinated alkylene moiety with acrylate functions at both terminals. These chlorofluorinated acrylates may be photocured in the presence of a photoinitiator into transparent polymers useful as optical waveguiding materials.
Claims26
A photocurable compound of the formula:
- 6
- wherein
- RF=—CF2CFX1)aCF2—, —(CF2CFX1)a—(CFX2CF2)b—, —(CF2CFX1)a—(CF2CFX2)bCF2—, or —(CF2CFX1)a—(CH2CY1Y2)b—(CF2CFX1)cCF2-
- wherein X1═Cl or Br;
- X2═F, Cl, or Br;
- Y1 and Y2 are independently H. CH3, F, Cl, or Br;
- a, b, and c are independently integers from 1 to about 10.
4 more elements
A process for the production of an α,ω-diol of the formula HOCH2—PF—CH2OF which comprises reacting an Ct,co-diester of the formula
- 7
- with aluminum hydride under conditions sufficient to produce said α,ω-diol;
- wherein
- R1 is a straight or branched chain alkyl group of from 1 to about 10 carbon atoms, and
- RF=—(CF2CFX1)aCF2—,—(CF2CFX1)a—(CFX2CF2)b—, —(CF2CFX1)a—(CF2CFX2)bCF2-, or —(CF2CFX1)a(CH2CY1Y2)b—(CF2CFX1)cCF2-
- wherein X1=Cl or Br;
- X2=F, Cl, or Br;
- Y1 and Y2 are independently H, CH3, F, Cl, or Br;
- a, b, and c are independently integers from 1 to about 10.
6 more elements
A process for producing at least one di-, tri-, or tetraacrylate which comprises:
- A) reducing an α,ω-diester of the formula:
- 8
- with AlH3 under conditions sufficient to produce an α,ω-diol of the formula:
- HOCH2—RF—CH2OH;
- and then
- B) performing either step a, b, or c:
- a) reacting the α,ω-diol produced by step A with at least one acryloyl halide in the presence of at least one organic base and at least one anhydrous aprotic solvent, under conditions sufficient to produce a diacrylate of the formula:
- 9
- b) i) reacting the α,107 -diol produced by step A with at least one metal hydroxide base or metal alkoxide base under conditions sufficient to produce a metal salt of the α,ω-diol;
- and then
- ii) reacting the metal salt produced by step b)i) with about one molar equivalent of an allyl halide per molar equivalent of molar salt under conditions sufficient to produce an allyl ether of the α,ω-diol;
- and then
- iii) reacting the allyl ether produced by step b)ii) with at least one peroxyacid under conditions sufficient to produce a triol of the formula:
- 10
- iv)reacting the triol produced by step b)iii) with at least one acryloyl halide in the presence of at least one organic base and at least one anhydrous aprotic solvent, under conditions sufficient to produce a triacrylate of the formula:
- 11
- c)i) reacting the α,ω-diol produced by step A with at least one metal hydroxide presence of at least one organic base der conditions sufficient to produce a metal salt of the α,ω-diol and then
- ii) reacting the metal salt produced by step c)i) with about two molar equivalents of an allyl halide per molar equivalent of metal salt under conditions sufficient to produce an allyl ether of the α,ω-diol;
- and then
- iii) reacting the allyl ether produced by step c)ii) with at least one peroxyacid under conditions sufficient to produce a tetraol of the formula:
- 12
- iv) reacting the tetraol produced by step c)iii) with at least one acryloyl halide in the presence of at least one organic base and at least one anhydrous aprotic solvent under conditions sufficient to produce a tetraacrylate of the formula:
- 13
- wherein
- R1 is a straight or branched chain alkyl group of from 1 to about 10 carbon atoms;
- RF=—(CF2CFX1)aCF2—, —(CF2CFX1)a—(CFX2CF2)b—, —(CF2CFX1)a—(CF2CFX2)bCF2—, or —(CF2CFX1)a—(CH2CY1Y2)b—(CF2CFX1)cCF2—
- wherein X1═Cl or Br;
- X2=F, Cl, or Br:
- Y1 and Y2 are independently H, CH3, F, Cl, or Br;
- a, b, and c are independently integers from 1 to about 10.
27 more elements
A process for producing at least one diacrylate which comprises:
- A) reducing an α,+107-DIESTER of the formula:
- 14
- with AlH3 under conditions sufficient to produce an α,ω-diol of the formula:
- HOCH2—RF—CH2OH;
- and then
- B) reacting the α,ω-diol produced by step A with at least one acryloyl halide in the presence of at least one organic base and at least one anhydrous aprotic solvent, under conditions sufficient to produce a diacrylate of the formula:
- 15
- wherein
- R1 is a straight or branched chain alkyl group of from 1 to about 10 carbon atoms,
- RF=—(CF2CFX1)aCF2—, —(CF2CFX1)a—(CFX2CF2)b—, —(CF2CFX1)a—(CF2CFX2)bCF2—, or —(CF2CFX1)a—(CH2CY1Y2)b—(CF2CFX1)cCF2—
- wherein X1═Cl or Br;
- X2═F, Cl, or Br;
- Y1 and Y2 are independently H, CH3, F, Cl, or Br;
- a, b, and c are independently integers from 1 to about 10.
11 more elements
A process for producing at least one triacrylate which comprises:
- A) reducing an α,ω-diester of the formula:
- 16
- with AlH3 under conditions sufficient to produce an α,ω-diol of the formula:
- HOCH2—RF—CH2OH;
- and then
- B) i) reacting the α,ω-diol produced by step A with at least one metal hydroxide base or metal alkoxide base under conditions sufficient to produce a metal salt of the α,ω-diol;
- and then
- ii) reacting the metal salt produced by step i) with about one molar equivalent of an allyl halide per molar equivalent of molar salt under conditions sufficient to produce an allyl ether of the α,ω-diol;
- and then
- iii) reacting the allyl ether produced by step ii) with at least one peroxyacid under conditions sufficient to produce a triol of the formula:
- 17
- iv) reacting the triol produced by step iii) with at least one acryloyl halide in the presence of at least one organic base and at least one anhydrous aprotic solvent, under conditions sufficient to produce a triacrylate of the formula:
- 18
- wherein
- R1 is a straight or branched chain alkyl group of from 1 to about 10 carbon atoms;
- RF=—(CF2CFX1)aCF2+13,—(CF2CFX1)a—(CFX2CF2)b—, —(CF2CFX1)a—(CF2CFX2)bCF2—, or —(CF2CFX1)a—(CH2CY1Y2)b—(CF2CFX1)cCF2—
- wherein X1=Cl or Br;
- X2 =F, Cl, or Br;
- Y1 and Y2 are independently H, CH3, F, Cl, or Br;
- a, b, and c are independently integers from 1 to about 10.
17 more elements
A process for producing at least one tetraacrylate which comprises:
- A) reducing an α,ω-diester of the formula:
- 19
- with AlH3 under conditions sufficient to produce an α,ω-diol of the formula:
- HOCH2—RF—CH2OH;
- and then
- B) i) reacting the α,ω-diol produced by step A with at least one metal hydroxide base or metal alkoxide base under conditions sufficient to produce a metal salt of the α,ω-diol;
- and then
- ii) reacting the metal salt produced by step i) with about two molar equivalents of an allyl halide per molar equivalent of metal salt under conditions sufficient to produce an allyl ether of the α,ω-diol;
- and then
- iii) reacting the allyl ether produced by step ii) with at least one peroxyacid under conditions sufficient to produce a tetraol of the formula:
- 20
- iv) reacting the tetraol produced by step iii) with at least one acryloyl halide in the presence of at least one organic base and at least one anhydrous aprotic solvent under conditions sufficient to produce a tetraacrylate of the formula:
- 21
- wherein
- R is a straight or branched chain alkyl group of from 1 to about 10 carbon atoms;
- RF=—(CF2CFX1)aC2—, —(CF2CFX1)a—(CFX2CF2)b—, —(CF2CFX1)a—(CF2CFX2)bCF2—, or —(CF2CFX1)a—(CH2CY1Y2)b—(CF2CFX1)cCF2-
- wherein X1=Cl or Br;
- X2=F, Cl, or Br;
- Y1 and Y2 are independently H, CH3, F, Cl, or Br;
- a, b, and c are independently integers from 1 to about 10.
17 more elements
Dependencies are inferred from the claim text.