U.S. patent application number 09/880466 was filed with the patent office on 2001-11-22 for new photocurable halofluorinated acrylates.
Invention is credited to Shan, Jianhui, Wu, Chengjiu, Xu, Baopei, Yardley, James T..
Application Number | 20010044481 09/880466 |
Document ID | / |
Family ID | 25288229 |
Filed Date | 2001-11-22 |
United States Patent
Application |
20010044481 |
Kind Code |
A1 |
Wu, Chengjiu ; et
al. |
November 22, 2001 |
New photocurable halofluorinated acrylates
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.
Inventors: |
Wu, Chengjiu; (Morristown,
NJ) ; Xu, Baopei; (Lake Hiawatha, NJ) ; Shan,
Jianhui; (High Bridge, NJ) ; Yardley, James T.;
(Morristown, NJ) |
Correspondence
Address: |
NIXON PEABODY LLP
ATTENTION: DAVID RESNICK
101 FEDERAL STREET
BOSTON
MA
02110
US
|
Family ID: |
25288229 |
Appl. No.: |
09/880466 |
Filed: |
June 13, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09880466 |
Jun 13, 2001 |
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08842783 |
Apr 17, 1997 |
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Current U.S.
Class: |
522/153 |
Current CPC
Class: |
G02B 1/046 20130101;
C07C 29/147 20130101; C07C 29/48 20130101; C07C 29/147 20130101;
C07C 69/653 20130101; C07C 29/48 20130101; G02B 1/046 20130101;
C07C 31/42 20130101; C07C 43/137 20130101; C08L 33/16 20130101;
C07C 31/42 20130101 |
Class at
Publication: |
522/153 |
International
Class: |
C08F 120/10 |
Claims
In the claims:
1. A photocurable compound of the formula: 6wherein
R.sub.F=--CF.sub.2CFX.sub.1).sub.aCF.sub.2--,
--(CF.sub.2CFX.sub.1).sub.a- --(CFX.sub.2CF.sub.2).sub.b--,
--(CF.sub.2CFX.sub.1).sub.a--(CF.sub.2CFX.s- ub.2).sub.bCF.sub.2--,
or --(CF.sub.2CFX.sub.1).sub.a--(CH.sub.2CY.sub.1Y.-
sub.2).sub.b--(CF.sub.2CFX.sub.1).sub.cCF.sub.2- wherein
X.sub.1.dbd.Cl or Br; X.sub.2.dbd.F, Cl, or Br; Y.sub.1 and Y.sub.2
are independently H. CH.sub.3, F, Cl, or Br; a, b, and c are
independently integers from 1 to about 10.
2. The photocurable compound of claim 1 wherein a, b, and c are
independently integers from 1 to about 7.
3. The photocurable compound of claim 1 comprising
chlorotrifluoroethylene or bromotrifluoroethylene repeating units
and having at least two terminal acrvlate groups.
4. The photocurable compound of claim 1 which comprises
CH.sub.2.dbd.CHCO.sub.2CH.sub.2(CF.sub.2CFCl).sub.2CF.sub.2CH.sub.2OC(O)C-
H.dbd.CH.sub.2; CH.sub.2.dbd.CCl
CO.sub.2CH.sub.2(CF.sub.2CFCl).sub.2CF.su- b.2CH.sub.2OC(O)CCl
.dbd.CH.sub.2; CH.sub.2.dbd.CHCO.sub.2CH.sub.2(CF.sub.-
2CFCl).sub.4CF.sub.2CH.sub.2OC(O)CH.dbd.CH.sub.2;
CH.sub.2.dbd.CHCO.sub.2C-
H.sub.2CH[OC(O)CH.dbd.CH.sub.2]CH.sub.2OCH.sub.2(CF.sub.2CFCl).sub.3CF.sub-
.2CH.sub.2OCH.sub.2CH[OC(O)CH.dbd.CH.sub.2]CH.sub.2OOC(O)
CH.dbd.CH.sub.2; CH.sub.2.dbd.CClCO.sub.2CH.sub.2CH [OC (O)
CC1.dbd.CH.sub.2] CH.sub.2OCH.sub.2
(CF.sub.2CFC1).sub.3CF.sub.2CH.sub.2OCH.sub.2CH
[OC(O)CC1.dbd.CH.sub.2] CH.sub.2OOC(O)CC1=CH.sub.2;
CH.sub.2.dbd.CHCO.sub.2CH.sub.2(CF.sub.2CFCl).sub.3CF.sub.2CH.sub.2OCH.su-
b.2CH[OC(O)CH.dbd.CH.sub.2]CH.sub.2OOC(O)CH .dbd.CH.sub.2;
[CH.sub.2.dbd.CHCO.sub.2CH.sub.2(CF.sub.2CFCl.sub.2].sub.2;
CH.sub.2.dbd.CHCO.sub.2CH.sub.2CH[OC(O)CH.dbd.CH.sub.2]CH.sub.2OCH.sub.2(-
CF.sub.2CFCl).sub.3CF.sub.2CH.sub.2OCH.sub.2CH[CO(O)CH.dbd.CH.sub.2]CH.sub-
.2OOC(O) CH.dbd.CH.sub.2;
CH.sub.2.dbd.CClCO.sub.2CH.sub.2(CF.sub.2CFCl).s-
ub.4CF.sub.2CH.sub.2OC(O)CC1.dbd.CH.sub.2;
H.sub.2C.dbd.CHCO.sub.2CH.sub.2-
(CF.sub.2CFCl).sub.3CF.sub.2CH.sub.2OC(O)CH.dbd.CH.sub.2;
H.sub.2C.dbd.CHCO.sub.2CH.sub.2(CF.sub.2CFCl).sub.3CF.sub.2CH.sub.2OC(O)C-
H.dbd.CH.sub.2 and niixtures thereof.
5. A photocurable composition comprising at least one photocurable
compound according to claim 1 and at least one photoinitiator.
6. The photocurable composition of claim 5 wherein the photocurable
compound is present in an amount of from about 35% to about 99.9%
by weight of the photocurable composition.
7. The photocurable composition of claim 6 further comprising at
least one ethylenically unsaturated monomer, oligomer, or polymer
compound.
8. The photocurable composition of claim 7 wherein the photocurable
compound and the at least one ethylenically unsaturated monomer,
oligomer, or polymer compound are present in a total amount from
about 35% to about 99.9% by weight of the photocurable composition
and at a weight ratio of the photocurable compound to the at least
one ethylenically unsaturated monomer, oligomer, or polymer
compound of from about 1:9 to about 9:1.
9. The photocurable composition of claim 5 wherein the
photoinitiator is present in an amount of from about 0.01% to about
10% by weight of the overall composition.
10. The photocurable composition of claim 5 further comprising one
or more additives selected from the group consisting of
antioxidants, photostabilizers, volume expanders, fillers, dyes,
free radical scavengers, contrast enhancers and UV absorbers.
11. The photocurable composition of claim 10 wherein the one or
more additives are present in an amount from about 0.1% to about 6%
by weight of the overall composition.
12. A process for producing an optical device which comprises
applying a layer of the photocurable composition of claim 5 onto a
substrate, imagewise exposing the photocurable composition to
actinic radiation to form exposed and nonexposed areas on the
substrate, and removing the imagewise nonexposed areas while
leaving the imagewise exposed areas on the substrate.
13. The process of claim 12 wherein the imagewise nonexposed areas
are removed with a solvent developer.
14. The optical device produced according to the process of claim
12.
15. The optical device of claim 14 which is a waveguide, a
splitter, a router, a coupler or a combiner.
16. An optical device which comprises a layer of a patterned and
photocured composition according to claim 5.
17. An optical device which comprises a substrate, and a layer of a
patterned and photocured composition according to claim 5 on the
substrate.
18. The optical device of claim 17 wherein the substrate comprises
silicon, silicon oxide, or gallium arsenide.
19. A process for the production of an .alpha.,.omega.-diol of the
formula HOCH.sub.2--P.sub.F--CH.sub.2OF which comprises reacting an
Ct,co-diester of the formula 7with aluminum hydride under
conditions sufficient to produce said .alpha.,.omega.-diol; wherein
R.sub.1 is a straight or branched chain alkyl group of from 1 to
about 10 carbon atoms, and
RF=--(CF.sub.2CFX.sub.1).sub.aCF.sub.2--,--(CF.sub.2CFX.sub.1).sub.a--(CF-
X.sub.2CF.sub.2).sub.b--,
--(CF.sub.2CFX.sub.1).sub.a--(CF.sub.2CFX.sub.2)- .sub.bCF.sub.2-,
or --(CF.sub.2CFX.sub.1).sub.a(CH.sub.2CY.sub.1Y.sub.2).s-
ub.b--(CF.sub.2CFX.sub.1).sub.cCF.sub.2- wherein X.sub.1=Cl or Br;
X.sub.2=F, Cl, or Br; Y.sub.1 and Y.sub.2 are independently H,
CH.sub.3, F, Cl, or Br; a, b, and c are independently integers from
1 to about 10.
20. A process for producing at least one di-, tri-, or
tetraacrylate which comprises: A) reducing an
.alpha.,.omega.-diester of the formula: 8with AlH.sub.3 under
conditions sufficient to produce an .alpha.,.omega.-diol of the
formula: HOCH.sub.2--R.sub.F--CH.sub.2OH; and then B) performing
either step a, b, or c: a) reacting the .alpha.,.omega.-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: 9b) i) reacting the .alpha.,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 .alpha.,.omega.-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 .alpha.,.omega.-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: 10iv)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: 11c)i) reacting the .alpha.,.omega.-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 .alpha.,.omega.-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 .alpha.,.omega.-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: 12iv) 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: 13wherein R.sub.1 is a straight or branched chain alkyl
group of from 1 to about 10 carbon atoms;
R.sub.F=--(CF.sub.2CFX.sub.1).sub.aCF- .sub.2--,
--(CF.sub.2CFX.sub.1).sub.a--(CFX.sub.2CF.sub.2).sub.b--,
--(CF.sub.2CFX.sub.1).sub.a--(CF.sub.2CFX.sub.2).sub.bCF.sub.2--,
or
--(CF.sub.2CFX.sub.1).sub.a--(CH.sub.2CY.sub.1Y.sub.2).sub.b--(CF.sub.2CF-
X.sub.1).sub.cCF.sub.2--wherein X.sub.1.dbd.Cl or Br; X.sub.2=F,
Cl, or Br: Y.sub.1 and Y.sub.2 are independently H, CH.sub.3, F,
Cl, or Br; a, b, and c are independently integers from 1 to about
10.
21. The process of claim 20 which comprises performing step a to
produce the diacrylate.
22. The process of claim 20 which comprises performing step b to
produce the triacrylate.
23. The process of claim 20 which comprises performing step c to
produce the tetraacrylate.
24. A process for producing at least one diacrylate which
comprises: A) reducing an .alpha.,+107-DIESTER of the formula:
14with AlH.sub.3 under conditions sufficient to produce an
.alpha.,.omega.-diol of the formula:
HOCH.sub.2--R.sub.F--CH.sub.2OH; and then B) reacting the
.alpha.,.omega.-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: 15wherein R.sub.1 is a
straight or branched chain alkyl group of from 1 to about 10 carbon
atoms, R.sub.F=--(CF.sub.2CFX.sub.1).s- ub.aCF.sub.2--,
--(CF.sub.2CFX.sub.1).sub.a--(CFX.sub.2CF.sub.2).sub.b--,
--(CF.sub.2CFX.sub.1).sub.a--(CF.sub.2CFX.sub.2).sub.bCF.sub.2--,
or
--(CF.sub.2CFX.sub.1).sub.a--(CH.sub.2CY.sub.1Y.sub.2).sub.b--(CF.sub.2CF-
X.sub.1).sub.cCF.sub.2--wherein X.sub.1.dbd.Cl or Br;
X.sub.2.dbd.F, Cl, or Br; Y.sub.1 and Y.sub.2 are independently H,
CH.sub.3, F, Cl, or Br; a, b, and c are independently integers from
1 to about 10.
25. A process for producing at least one triacrylate which
comprises: A) reducing an .alpha.,.omega.-diester of the formula:
16with AlH.sub.3 under conditions sufficient to produce an
.alpha.,.omega.-diol of the formula:
HOCH.sub.2--R.sub.F--CH.sub.2OH; and then B) i) reacting the
.alpha.,.omega.-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 .alpha.,.omega.-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
.alpha.,.omega.-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: 17iv) 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: 18wherein R.sub.1 is a straight or
branched chain alkyl group of from 1 to about 10 carbon atoms;
R.sub.F=--(CF.sub.2CFX.sub.1).sub.aCF.sub.2+13,--(CF.sub.2CFX1).sub.a--(C-
FX.sub.2CF.sub.2).sub.b--,
--(CF.sub.2CFX.sub.1).sub.a--(CF.sub.2CFX.sub.2- ).sub.bCF.sub.2--,
or --(CF.sub.2CFX.sub.1).sub.a--(CH.sub.2CY.sub.1Y.sub.-
2).sub.b--(CF.sub.2CFX.sub.1).sub.cCF.sub.2--wherein X.sub.1=Cl or
Br; X.sub.2 =F, Cl, or Br; Y.sub.1 and Y.sub.2 are independently H,
CH.sub.3, F, Cl, or Br; a, b, and c are independently integers from
1 to about 10.
26. A process for producing at least one tetraacrylate which
comprises: A) reducing an .alpha.,.omega.-diester of the formula:
19with AlH.sub.3 under conditions sufficient to produce an
.alpha.,.omega.-diol of the formula:
HOCH.sub.2--R.sub.F--CH.sub.2OH; and then B) i) reacting the
.alpha.,.omega.-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 .alpha.,.omega.-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
.alpha.,.omega.-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: 20iv) 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: 21wherein R is a straight or branched
chain alkyl group of from 1 to about 10 carbon atoms;
R.sub.F=--(CF.sub.2CFX.sub.1).sub.aC.sub.2--,
--(CF.sub.2CFX.sub.1).sub.a- --(CFX.sub.2CF.sub.2).sub.b--,
--(CF.sub.2CFX.sub.1).sub.a--(CF.sub.2CFX.s- ub.2).sub.bCF.sub.2--,
or --(CF.sub.2CFX.sub.1).sub.a--(CH.sub.2CY.sub.1Y.-
sub.2).sub.b--(CF.sub.2CFX.sub.1).sub.cCF.sub.2- wherein X.sub.1=Cl
or Br; X.sub.2=F, Cl, or Br; Y.sub.1 and Y.sub.2 are independently
H, CH.sub.3, F, Cl, or Br; a, b, and c are independently integers
from 1 to about 10.
Description
BACKGROUND OF THE INVENTION
[0001] This invention relates to a novel class of halofluorinated
acrylates and more particularly to chlorofluorinated or
bromofluorinated acrylates characterized by achlorofluorinated
alkylene moiety with acrylate functions at both terminals. These
chlorofluorinated or bromofluorinated acrylates may be photocured
in the presence of a photoinitiator into transparent polymers
useful as optical waveguiding materials.
[0002] The use of photocuring technology has grown rapidly within
the last decade. Photocuring involves the radiation induced
polymerization or crosslinking of monomers into a three dimensional
network. The polymerization mechanism can be either radical or
cationic. Radical initiated polymerization is the most common. Most
commercial photocuring systems consist of multifuinctional acrylate
monomers and free radical photoinitiators. Photocuring has a number
of adavantages including: a 100% conversion to a solid composition,
short cycle times and limited space and capital requirements.
[0003] Photocuring technology has recently been applied in planar
waveguide applications. See, B. M. Monroe and W. K. Smothers, in
Polymers for Lightwave and Integrated Optics, Technology and
Applications, L. A. Hornak, ed., p. 145, Dekker, 1992. In its
simplest application, a photocurable composition is applied to a
substrate and irradiated with light in a predetermined pattern to
produce (the light transmissive) or waveguide portion on the
substrate. Photocuring permits one to record fine patterns (<1
um) directly with light. The refractive index difference between
the substrate and the light transmissive portion of the substrate
can be controlled by either regulating the photocurable composition
or the developing conditions.
[0004] Because of the dramatic growth in the telecommunications
industry there is a need to develop photocurable compositions for
optical waveguide and interconnect applications. In order to be
useful in these applications, the photocurable composition must be
highly transparent at the working wavelength and possess low
intrinsic absorption and scattering loss. Unfortunately, in the
near-infrared region, among which the 1300 and the 1550 nm
wavelengths are preferred for optical communications, conventional
photocurable materials possess neither the required transparency or
low intrinsic absorption loss.
[0005] The absorption loss in the near-infrared stems from the high
harmonics of bond vibrations of the C--H bonds which comprise the
basic molecules in conventional acrylate photopolymers. One way to
shift the absorption bands to higher wavelength, is to replace
most, if not all, of the hydrogen atoms in the conventional
materials with heavier elements such as deuterium, fluorine, and
chlorine. See, T. Kaino, in Polymers for Lightwave and Integrated
Optics, Technology and Applications, L. A. Hornak, ed., p. 1,
Dekker, 1992. The replacement of hydrogen atoms with fluorine atoms
is the easiest of these methods. It is known in the art that
optical loss at 1300 and 1550nm can be significantly reduced by
increasing the fluorine to hydrogen ratio in the polymer. It was
recently reported that some perfluorinated polyimide polymers have
very low absorption over the wavelengths used in optical
communications. See, S. Ando, T. Matsuda, and 5. Sasaki, Chemtech,
1994-12, p.20. Unfortunately, these materials are not
photocurable.
[0006] U.S. Pat. No. 5,274,174 discloses a new class of
photocurable compositions comprised of certain fluorinated monomers
such as diacrylates with perfluoro or perfluoropolyether chains
which possess low intrinsic absorption loss. It is, therefore,
possible to make low loss optical interconnects from a photocurable
system include these materials.
[0007] Fluorine substitution in the polymer structure, however,
also induces some other less desirable changes in the polymer's
physical properties. One such change is the decrease in refractive
index. For a highly fluorinated acrylate photopolymer, the
refractive index decreases to the 1.32 region when the H/F mole
ratio reaches 0.25. For optical interconnect applications, to avoid
loss of light, it is important that the refractive index of the
core of a planar waveguide approximate and preferably match that of
the optical fiber (generally 1.45). Another problem with fluorine
substitution in the polymer is the decrease of the surface energy
of the resulting photopolymer film which results in its reduced
adhesion to other materials like substrates.
[0008] It is also important to be abovel to precisely control and
fine tune the refractive index of the photopolymer at the working
wavelength in optical waveguide and interconnect applications. A
desired index of refraction can be produced by mixing photocurable
monomers with different refractive indices. Most photopolymers made
from conventional photocurable monomers have refractive indices in
the region of 1.45-1.55. Depending on the application, it is often
desirable to lower a photopolymer's refractive index. One way to do
this is to mix low refractive index fluorinated monomers with
conventional hydrocarbon-based monomers. Unfortunately this is
difficult to accomplish because of the incompatibility or
insolubility of the different monomer systems. Thus, there is a
need for photocurable compositions which: (i) possess low optical
loss in the near-infrared region, (ii) possess a refractive index
approaching traditional optical fibers; and (iii) are compatible
with both conventional hydrocarbon-based and highly fluorinated
monomers.
DESCRIPTION OF THE INVENTION
[0009] The photocurable monomer of the invention is a di-, tri- or
tetra-acrylate which contains a chlorofluorinated or
bromofluorinated alkylene chain and has the formula: 1
[0010] wherein 0 in an integer of from 2-4; X is H, F, CH.sub.3 or
Cl and is preferably H, or Cl. 2
[0011] and
[0012]
R.sub.F=--(CF.sub.2CFX.sub.1).sub.aCF.sub.2,(CF.sub.2CFX.sub.1).sub-
.a(CFX.sub.2CF.sub.2).sub.b,
(CF.sub.2CFX.sub.1).sub.a(CF.sub.2CFX.sub.2).- sub.bCF.sub.2, and
--(CF.sub.2CFX.sub.1).sub.a--(CH.sub.2CY.sub.1Y.sub.2).-
sub.b--(CF.sub.2CFX.sub.1).sub.dCF.sub.2--
[0013] wherein X.sub.1 is Cl or Br; X.sub.2 is F, Cl or Br; Y.sub.1
and Y.sub.2 are the same or different and are H, CH.sub.3, F, Cl or
Br; and a, b, and c are the same or different and are integers of
from 1-10 and preferably integers of from 1-7.
[0014] In the preferred embodiments, the above mentioned monomers
contain chlorofluorinated or bromofluorinated alkylene chains which
comprise chlorotrifluoroethylene or bromotrifluoroethylene
repeating units and at least two terminal acrylate groups.
[0015] These monomers contain much less hydrogen than conventional
photocurable monomers such that their inherent carbon-hydrogen bond
absorption is greatly reduced. In addition, the introduction of
chlorine or bromine atoms into the molecule offsets the effect of
fluorine on the refractive index of the monomer producing a
material with an index of refraction between about 1.40-1.48 As a
result, the monomers of the invention are particularly useful in
optical applications in the 1300-1550 nm wavelength region. The
monomers are also compatible with both conventional
hydrocarbon-based and highly fluorinated monomers. Because of this
compatibility, it becomes possible to fine tune the refractive
index and other physical properties of photocurable compositions
containing these photocurable monomer.
[0016] In a second embodiment, the invention relates to a
photocurable composition comprising at least one photocurable
monomer of the invention and a photoinitiator.
[0017] In another embodiment, the invention relates to a process
for producing an optical device containing a light transmissive
region comprising:
[0018] a) applying a film of a photocurable composition comprising
a photocurable monomer of the invention and a photoinitiator to a
substrate; b) imagewise exposing said composition to sufficient
actinic radiation to form exposed and unexposed areas on the
substrate; and c) removing the unexposed portions of the
composition.
[0019] In still another embodiment, the invention relates to an
optical device comprising a light transmissive region wherein said
light transmissive region comprises a photocurable composition of
the invention.
[0020] In yet another embodiment, the invention relates to a
process for the manufacture of an .alpha.,.omega. Diol of the
formula:
HOCH.sub.2--R.sub.F--CH.sub.2OH
[0021] comprising reacting a .alpha.,.omega.-Diester of the
formula: 3
[0022] with aluminum hydride under conditions sufficient to produce
said .alpha.,.omega. Diol.
[0023] In still another embodiment the invention relates to a
process for the production of an .alpha.,.omega.-diol of the
formula HOCH.sub.2--R.sub.F--CH.sub.2OF which comprises reacting an
.alpha.,.omega.-diester of the formula 4
[0024] with aluminum hydride under conditions sufficient to produce
said .alpha.,.omega.-diol;
[0025] wherein
[0026] R.sub.1 is a straight or branched chain alkyl group of from
1 to about 10 carbon atoms; and
[0027]
R.sub.F=--(CF.sub.2CFX.sub.1).sub.aCF.sub.2--,--(CF.sub.2CFX.sub.1)-
.sub.a--(CFX.sub.2CF.sub.2).sub.b--,
--(CF.sub.2CFX.sub.1).sub.a--(CF.sub.- 2CFX.sub.2).sub.bCF.sub.2--,
or --(CF.sub.2CFX.sub.1).sub.a--(CH.sub.2CY.s-
ub.1Y.sub.2).sub.b--(CF.sub.2CFX.sub.1).sub.cCF.sub.2--
[0028] wherein X.sub.1=Cl or Br; X.sub.2=F, Cl, or Br; Y.sub.1 and
Y.sub.2 are independently H, CH.sub.3, F, Cl, or Br; a, b, and c
are independently integers from 1 to about 10.
[0029] All of the photocurable monomers of the invention may be
made by using or adapting methods known in the art. Methods for the
preparation of certain .alpha.,.omega.-diols with chlorofluorinated
backbones are known. See, B. Boutevin, A. Rousseau, and D. Bosc,
Jour. Polym. Sci., Part A, Polym. Chem., 30, 1279, 1993; B.
Boutevin, A. Rousseau, and D. Bosc, Fiber and Integrated Optics,
13, 309, 1994; and B. Boutevin and Y. Pietrasanta, European Polym.
Jour., 12, p.231, 1976.
[0030] The photocurable monomers of the invention may be prepared
by following the general reaction scheme outlined below wherein
R.sub.F, and X have the meanings set forth above and R.sub.1 is a
straight or branched chain alkyl group of from 1-10 and preferably
1-3 carbon atoms. 5
[0031] Preparation of the .alpha.,.omega.-Diester.
[0032] Methods for the preparation of the .alpha.,.omega.-diester
are known in the art. The diester may be prepared, for example by
reducing with lithium aluminum hydride the appropriate telomer of a
halotrifluoroethylene monomer. Examples of suitable
halotrifluoroethylene monomers include: chlorotrifluoroethylene (or
bromotrifluoroethylene), alone or mixture with other vinyl monomers
such as bromotrifluoroethylene (or chlorotrifluoroethylene),
tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl
fluoride, vinyl chloride, vinylidene chloride, ethylene, and
propylene. Preparation of .alpha.,.omega.-diesters with a
chlorofluorinated alkylene chain composed of
chlorotrifluoroethylene monomer units is described in U.S. Pat.
Nos. 2,806,865 and 2,806,866.
[0033] The prior art processes discussed above produce mixtures of
.alpha.,.omega.-diols because of the partial reduction of chlorine
and bromine in the .alpha.,.omega.-diester to hydrogen. Applicants
have unexpectedly found that a pure (not a mixture)
.alpha.,.omega.-diol can be obtained by using an aluminum hydride
reducing agent. Compare Example 1 and Examples 2-4 below.
[0034] Preparation of Triols and Tetraols.
[0035] The .alpha.,.omega.-diols can be converted to triols and
tetraols by methods known in the art. For example,
.alpha.,.omega.-triol can be obtained by: reacting the
.alpha.,.omega.-diol with a metal hydroxide base or a metal
alkoxide base to produce a metal salt of the .alpha.,.omega.-diol;
reacting the metal salt with an allyl halide to produce an allyl
ether of the .alpha.,.omega.-diol; and finally reacting the allyl
ether with a peroxyacid to produce a .alpha.,.omega.-triol. See,
Turri, S.; Scicchitano, M.; and Tonelli, C., Jour. Polymer Science:
Part A: Polymer Chemistry, 1966, 34, p.3263.
[0036] Preparation of the Di-, Tri- and Tetra- acrylates.
[0037] The di-, tri-, and tetra- acrylates can also be prepared by
methods known in the art. For example, a triacrylate of the
invention may be prepared by reacting the triol described above
with an acryloyl halide in the presence of an organic base and an
anhydrous aprotic solvent.
[0038] In addition to the photocurable monomer described above,
other photocurable compounds which are known in the art may be
incorporated into the photocurable compositions of the invention.
These compounds include monomers, oligomers and polymers containing
at least one terminal ethylenically unsaturated group and being
capable of forming a high molecular weight polymer by free radical
initiated, chain propagating addition polymerization.
[0039] Suitable monomers include, but are not limited to, ethers,
esters and partial esters of: acrylic and methacrylic acid;
aromatic and aliphatic polyols containing from about 2 to about 30
carbon atoms; and cycloaliphatic polyols containing from about 5 to
about 6 ring carbon atoms. Specific examples of compounds within
these classes are: ethylene glycol diacrylate and dimethacrylate,
diethylene glycol diacrylate and dimethacrylate, triethylene glycol
diacrylate and dimethacrylate, hexane diacrylate and
dimethacrylate, trimethylolpropane triacrylate and trimethacrylate,
dipentaerythritol pentaacrylate, pentaerythritol triacrylate and
trimethacrylate, alkoxylated bisphenol-A diacrylates and
dimethacrylates (e.g, ethoxylated bisphenol-A di-acrylate and
dimethacrylate), propoxylated bisphenol-A diacrylates and
dimethacrylates, ethoxylated hexafluorobisphenol-A diacrylates and
dimethacrylates and mixtures of the above compounds. Preferred
monomers include multifunctional aryl acrylates and methacrylates.
More preferred aryl acrylate monomers include di-, tri- and tetra-
acrylates and methacrylates based on the bisphenol-A structure.
Most preferred aryl acrylate monomers are alkoxylated bisphenol-A
diacrylates and dimethacrylates such as ethoxylated bisphenol-A
di-acrylates and dimethacrylates, and ethoxylated
hexafluorobisphenol-A diacrylates and dimethacrylates.
[0040] Suitable oligomers include, but are not limited to, epoxy
acrylate oligomers, aliphatic and aromatic urethane acrylate
oligomers, polyester acrylate oligomers, and acrylated acrylic
oligomers. Epoxy acrylate oligomers (such as Ebercryl 600 by
Radcure) are preferred.
[0041] Suitable polymers include, but are not limited to, acrylated
polyvinyl alcohol, polyester acrylates and methacrylates, acrylated
and methacrylated styrene-maleic acid copolymers. Acrylated
styrene-maleic acid copolymers such as Sarbox SR-454 sold by
Sartomer are preferred.
[0042] The photocurable component is comprised of photocurable
monomer A+EE, and optionally the other photocurable compounds
described above. The photocurable component is present in an amount
sufficient to photocure and provide image differentiation upon
exposure to sufficient actinic radiation. The amount of the
photocurable component in the photocurable composition may vary
widely. Typically the photocurable component is present in an
amount of from about 35 to about 99% by weight of the overall
composition. In a preferred embodiment, the photocurable component
is present in an amount of from about 80 to about 99% by weight and
more preferably from about 95 to about 99% by weight in the overall
composition. The weight ratio of monomer A to the other
photocurable compounds may vary from about 1:9 to about 9:1.
Preferably the weight ratio ranges from about 1:1 to about 9:1.
[0043] The photocurable composition further comprises at least one
photoinitiator which photolytically generates activated species
capable of inducing polymerization. Any photoinitiator known to be
useful in the polymerization of acrylates or methacrylates may be
used in the photocurable compositions of the invention. Suitable
photoinitiators include aromatic ketone derivatives such as
benzophenone, acrylated benzophenone, phenanthraquinone,
2,3-dichloronaphthoquinone, benzyl dimethyl ketal and other
aromatic ketones (e.g. benzoin), benzoin ethers such as benzoin
methyl ether, benzoin ethyl ether, benzoin isobutyl ether and
benzoin phenyl ether. Preferred photoinitiators include
1-hydroxy-cyclohexyl-phenyl ketone (Irgacure 184), benzoin, benzoin
ethyl ether, benzoin isopropyl ether, benzophenone, benzodimethyl
ketal (Irgacure 651), .alpha.,.alpha.-diethyloxy acetophenone,
.alpha.,.alpha.-dimethyloxy-.alpha.-hydroxyacetophenone (Darocur
1173), 1-[4-(2-hydroxyethoxy)
phenyl]-2-hydroxy-2-methyl-propan-1-one (Darocur 2959),
2-methyl-1-[4-methylthio) phenyl]-2-morpholino-propan-1-one
(Irgacure 907),
2-benzyl-2-dimethylarmino-1-(4-morpholinophenyl)-butan- 1-one
(Irgacure 369), poly
{1-[4-(1-methylvinyl)phenyl]-2-hydroxy-2-methy- l-propan- 1-one }
(Esacure KIP), [4-(4-methylphenylthio)-phenyl]- phenylmethanone
(Quantacure BMS), and dicampherquinone. The most preferred
photoinitiators are those which tend not to yellow upon
irradiation. Such photoinitiators include benzodimethyl ketal
(Irgacure 651), .alpha.,.alpha.-dimethyloxy-.alpha.-hydroxy
acetophenone (Darocur 1173), 1-hydroxy-cyclohexyl-phenyl ketone
(Irgacure 184), and
1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-propan-1-one
(Darocur 2959).
[0044] The photoinitiator is present in an amount sufficient to
effect photopolymerization of the photocurable compound upon
exposure to sufficient actinic radiation. The photoinitiator may
comprise from about 0.01 to about 10% by weight preferably from
about 0.1 to about 6% by weight and most preferably from about 0.5
to about 4% by weight based upon the total weight of the
photocurable composition.
[0045] Various optional additives may also be added to the
photocurable compositions of the invention depending upon the
application in which such they are to be used. Examples of these
optional additives include antioxidants, photostabilizers, volume
expanders. fillers (e.g., silica and glass spheres), dyes, free
radical scavengers, contrast enhancers and UV absorbers.
Antioxidants include such compounds as phenols and particularly
hindered phenols including Irganox 1010 from Ciba-Geigy; sulfides;
organoboron compounds; organophosphorous compounds; and N,
N'-hexamethylenebis(3,5-di-ter(-butyl-4-hydroxyhydrocinnamamide)
available from Ciba-Geigy under the tradename Irganox 1098.
Photostabilizers and more particularly hindered amine light
stabilizers include, but are not limited to, poly[(6-hexamethylene
[2,2,6,6,-tetramethyl-4-piperidyl)imino)] available from Cytec
Industries under the tradename Cyasorb UV3346. Volume expanding
compounds include such materials as the spiral monomers known as
Bailey's monomer. Suitable dyes include methylene green, methylene
blue, and the like. Suitable free radical scavengers include
oxygen, hindered amine light stabilizers, hindered phenols, and
2,2,6,6-tetramethyl-1-piperidinyloxy free radical (TEMPO). Suitable
contrast enhancers include other free radical scavengers. UV
absorbers include benzotriazoles and hydroxybenzophenone. These
additives may be included in quantities, based upon the total
weight of the composition, of from about 0 to about 6%, and
preferably from about 0.1% to about 1%. Preferably all components
of the photocurable composition are in admixture with one another
and more preferably in a substantially uniform admixture.
[0046] The photocurable compositions of this invention can be used
in the formation of the light transmissive element of an optical
device. Illustrative of such devices are planar optical slab
waveguides, channel optical waveguides, ribbed waveguides, optical
couplers, and splitters. The photocurable composition of this
invention can also be used in the formation of negative working
photoresists and other lithographic elements such as printing
plates. In a preferred embodiment of the invention, the
photocurable composition is used for producing a waveguide
comprising a substrate containing a light transmissive element.
Such waveguides are formed by applying a film of the photocurable
composition of the invention to the surface of a suitable
substrate. The film may be formed by any method known in the art,
such as spin coating, dip coating, slot coating, roller coating,
doctor blading, and evaporation.
[0047] The substrate may be any material on which it is desired to
establish a waveguide including semiconductor materials such as
silicon, silicon oxide and gallium arsenide. In the event that the
light transmissive region on the substrate is to be made from a
photocurable material which has an index of refraction which is
lower than that of the substrate, an intermediate buffer layer
possessing an index of refraction which is lower than the substrate
must be applied to the substrate before the photocurable
composition is added. Otherwise, the light loss in the waveguide
will be unacceptable. Suitable buffers are made from semiconductor
oxides, lower refractive index polymers or spin-on silicon dioxide
glass materials.
[0048] Once a film of the photocurable composition is applied to
the substrate, actinic radiation is directed onto the film in order
to delineate the light transmissive region. That is, the position
and dimensions of the light transmissive device are determined by
the pattern of the actinic radiation upon the surface of the film
on the substrate. The photopolymers of the invention are
conventionally prepared by exposing the photocurable composition to
sufficient actinic radiation. For purposes of this invention,
"sufficient actinic radiation" means light energy of the required
wavelength, intensity and duration to produce the desired degree of
polymerize action in the photocurable composition. Suitable sources
of actinic radiation include light in the visible, ultraviolet or
infrared regions of the spectrum, as well as electron beam, ion or
neutron beam or X-ray radiation. Actinic radiation may be in the
form of incoherent light or coherent light such as light from a
laser.
[0049] Sources of actinic light, exposure procedures, times,
wavelengths and intensities may vary widely depending on the
desired degree of polymerization, the index of refraction of the
photopolymer and other factors known to those of ordinary skill in
the art. The selection and optimization of these factors are well
known to those skilled in the art.
[0050] It is preferred that the photochemical excitation be carried
out with relatively short wavelengths (or high energy) radiation so
that exposure to radiation normally encountered before processing
(e.g., room lights) will not prematurely polymerize the
polymerizable material. The energy necessary to polymerize the
photocurable compositions of the invention generally ranges from
about 5 mW/cm.sup.2 to about 100 mW/cm.sup.2 with typical exposure
times ranging from about 0.1 second to about 5 minutes.
[0051] After the photocurable composition has been polymerized to
form a predetermined pattern on the surface of the substrate, the
pattern is then developed to remove the nonimage areas. Any
conventional development method can be used such as flushing the
unirradiated composition with a solvent. Suitable solvents include
polar solvents, such as alcohols and ketones. The most preferred
solvents are acetone, methanol, tetrahydrofuran and ethyl
acetate.
[0052] The following non-limiting examples serve to illustrate the
invention.
EXAMPLE 1
Preparation and Reduction of
CH.sub.3OC(O)(CF.sub.2CFCl).sub.2CF.sub.2CO.s- ub.2CH.sub.3
.alpha.,.omega.-diester by aluminum hydride
[0053] A. Preparation of
CH.sub.3OC(O)(CF.sub.2CFCl).sub.2CF.sub.2CO.sub.2- CH.sub.3
[0054] To 225 parts of CCl.sub.3(CF.sub.2CFCl).sub.3Br was added
290 parts of fuming sulfuric acid containing 50% sulfur trioxide.
The mixture was stirred and heated gradually from room temperature
to 170.degree. C. The mixture was maintained at that temperature
for 6 hours and then cooled to 0.degree. C. After this cooling, 240
parts of methanol was added dropwise to the mixture. The solution
was then heated to 150.degree. C. for 2 hours, cooled to room
temperature and poured into 200 parts of ice-water. Then, the
solution was extracted with ether after which the ether layer was
evaporated ("ether workup"). The solution was next distilled to
yield 133 parts of the dimethylester,
[0055] CH.sub.3OC(O)(CF.sub.2CFCl).sub.2CF.sub.2COOCH.sub.3 (81%
yield) was obtained. The characterization results of this product
are consistent with the indicated structure.
[0056] B. Reduction of
CH.sub.3OC(O)(CF.sub.2CFCl).sub.2CF.sub.2CO.sub.2CH- .sub.3 to
HOCH.sub.2(CF.sub.2CFCl).sub.2CF.sub.2CH.sub.2OH with aluminum
hydride
[0057] A solution of 310 part of 1.04M LiAlH.sub.4 in
tetrahydrofuran was stirred at 0.degree. C. under nitrogen. To this
solution was added slowly 17.8 parts of 100% sulfuric acid. The
solution was stirred for an additional hour at room temperature.
After settlement of the lithium sulfate precipitate, 240 parts of
the clear supernatant solution of A1H.sub.3 (0.91 M) was collected.
To this 240 parts of A1H3 solution which was stirred at 0.degree.
C. was slowly added a solution of 33.7 parts of the above prepared
diester in 450 parts of tetrahydrofuran. The mole ratio of
AlH.sub.3 to CH.sub.3OC(O)(CF.sub.2CFCl).sub.2CF.sub.2CO.su-
b.2CH.sub.3 was 2.6:1. After one hour, the excess hydride was
carefully hydrolyzed with 20 parts of a 1:1 mixture of
tetrahydrofuran and water. After ether workup and distillation, 28
parts of the diol,
HOCH.sub.2(CF.sub.2CFCl).sub.2CF.sub.2CH.sub.2OH, was obtained
(quantitative). The characterization results of this product are
consistent with the indicated structure.
EXAMPLE 2
Reduction of
CH.sub.3OC(O)(CF.sub.2CFCl).sub.2CF.sub.2CO.sub.2CH.sub.3
.alpha.,.omega.-diester by lithium aluminum hydride
[0058] A solution of 180 part of 1.04M LiAlH.sub.4 in
tetrahydrofuran was stirred at 0.degree. C. under nitrogen. To this
solution was slowly added a solution of 30 parts of the diester
CH.sub.3OC(O)(CF.sub.2CFCl).sub.2CF- .sub.2CO.sub.2CH.sub.3 in 450
parts of tetrahydrofuran. The mole ratio of LiAlH.sub.4 to the
diester was 2.6:1. After one hour, the excessive hydride was
carefully hydrolyzed with 20 parts of a 1:1 mixture of
tetrahydrofuran and water. After ether workup, 25 parts of crude
product was obtained. GC-MS analysis identified this crude product
as a mixture of 3 main products: the target diol in which only the
ester groups were reduced,
HOCH.sub.2(CF.sub.2CFCl).sub.2CF.sub.2CH.sub.2OH;
HOCH.sub.2CF.sub.2CFHCF.sub.2CFClCF.sub.2CH.sub.2OH diol in which
one chlorine atom was reduced and
HOCH.sub.2(CF.sub.2CFH).sub.2CF.sub.2CH.sub- .2OH in which both
chlorine atoms were reduced. The products were produced in a ratio
of 60:35:5 respectively.
EXAMPLE 3
Reduction of
CH.sub.3OC(O)(CF.sub.2CFCl).sub.2CF.sub.2CO.sub.2CH.sub.3
.alpha.,.omega.-diester with lithium aluminum hydridealuminum
chloride complex
[0059] A solution of 165 parts of 1.04M LiAlH.sub.4 in
tetrahydrofuran was stirred at 0.degree. C. under nitrogen. To this
solution was slowly added 22 parts of anhydrous aluminum chloride.
The mixture was stirred for one hour. A solution of 30 parts of the
diester CH.sub.3OC(O)(CF.sub.2CFCl).s- ub.2CF.sub.2CO.sub.2CH.sub.3
in 450 parts of tetrahydrofuran was then slowly added. The mole
ratio of LiAlH.sub.4: AlCl.sub.3 :
CH.sub.3OC(O)(CF.sub.2CFCl).sub.2CF.sub.2CO.sub.2CH.sub.3 was
2.2:2.2:1 respectively. GC-MS analysis identified the presence of
the chlorine reduced diol in the crude product.
EXAMPLE 4
Reduction of
CH.sub.3OC(O)(CF.sub.2CFCl).sub.2CF.sub.2CO.sub.2CH.sub.3 by sodium
borohydride
[0060] To a stirred solution of 30 parts of the diester
CH.sub.3OC(O)(CF.sub.2CFCl).sub.2CF.sub.2CO.sub.2CH.sub.3 in 450
parts of tetrahydrofuiran at 0.degree. C. and under nitrogen, was
slowly added 150 parts of 0.5M sodium borohydride in 2-methoxyethyl
ether. The mole ratio of NaBH.sub.4 to
CH.sub.3OC(O)(CF.sub.2CFCl).sub.2CF.sub.2CO.sub.2CH.sub.- 3 was
2.0:1. GC-MS analysis identified the presence of the chlorine
reduced diol in the crude product.
[0061] The results from Examples 1-4 are described in Table 1
below.
1TABLE 1 Example: EX. 1 EX. 2 EX. 3 EX. 4 Reducing agent AlH.sub.3
LiAlH.sub.4 LiAlH.sub.4/AlCl.sub.3 NaBH.sub.4 (RA)* Ratio
RA:diester: Theoretical 1.5:1 2:1 2:1 2:1 Actual 2.6:1 2.5:1 2.2:1
2:1 Reduction of chlorine - + + + *all runs were in THF, 0.degree.
C.
[0062] The results show that even when present in excess, aluminum
hydride does not result in reduction of chlorine atoms in the
reduced diol.
EXAMPLE 5
Preparation of
CH.sub.2=CHCO.sub.2CH.sub.2(CF.sub.2CFCl).sub.2CFCH.sub.2OC-
(O)CH=CH.sub.2 diacrylate
[0063] 80 parts of the diol prepared in Example 1 were mixed with
56.3 parts of triethylamine and 100 parts of methylene chloride and
cooled to 0.degree. C. To this solution was slowly added with
stirring and under nitrogen 50 parts of freshly distilled acryloyl
chloride in 100 parts of methylene chloride. After addition, the
mixture was stirred for an additional 24 hours and the temperature
was returned to ambient. The mixture was treated with water and
worked up with ethyl ether. The crude product was purified by
silica gel column chromatography (Merck #60) eluted with an ethyl
acetate and hexane mixture. 28 parts of the purified diacrylate,
CH.sub.2.dbd.CHCO.sub.2CH.sub.2(CF.sub.2CFCl).sub.2CF.sub.2CH-
.sub.2OC(O)CH.dbd.CH.sub.2 was obtained. The characterization
results are consistent with the indicated structure. .sup.19F-NMR
[.delta. (CF.sub.3COOH), ppm]: 31.1 (2F), 35.5 (4F), and 53.6 (2F);
.sup.1H-NMR [.delta., ppm]: 4.66 (t, 4H), 6.13 (ABX, 6H); Mass
spectra: 454 (M, 0.35%), 452 (M, 0.57%), 426 ([M--CO or
M--C.sub.2H.sub.4].sup.+, 0.42%), 424 ([M--CO or
M-C.sub.2H.sub.4].sup.+, 0.63%), 383
([M--CH.sub.2.dbd.CHCO.sub.2].sup.+, 0.21%), 381
([M--CH.sub.2=CHCO.sub.2- ].sup.+, 0.31%), 85
([CH.sub.2.dbd.CHCO.sub.2CH.sub.2]+.sup.+, 5.13%), 55
([CH.sub.2=CHCO].sup.+, 100%); IR [film, cm.sup.-1]: 2982 (w),
1747(vs), 1637(m), 1412(vs), 1299(s), 1262(s), 1165(vs), 1110(s),
974(s), 806(m).
EXAMPLE 6
Preparation of
CH.sub.2=CClCO.sub.2CH.sub.2(CF.sub.2CFCl).sub.2CF.sub.2CH.-
sub.2OC(O)CCl.dbd.CH.sub.2 a, Cl-diacrylate
[0064] The following materials were reacted according to the
procedure set forth in Example 5 above: 44.5 parts of the diol
prepared in Example 1, 31.3 parts of triethylamine, 14 parts of
.alpha.-chloroacryloyl chloride and 100 parts of methylene
chloride. 31 parts of CH.sub.2=CClCO.sub.2CH.s-
ub.2(CF.sub.2CFCl).sub.2CF.sub.2CH.sub.2OC(O)CC1.dbd.CH.sub.2 were
obtained. The characterization results are consistent with the
indicated structure
EXAMPLE 7
Preparation of
CH.sub.2=CHCO.sub.2CH.sub.2(CF.sub.2CFCl).sub.4CF.sub.2CH.s-
ub.2OC(O)CH.dbd.CH.sub.2 diacrylate
[0065] The following materials were reacted according to the
procedure set forth in Example 5 above: 93 parts of
HOCH.sub.2(CF.sub.2CFCl).sub.3CF.su- b.2CH.sub.2OH, diol (prepared
according to Example 1) 54 parts of triethylamine, 61 parts of
acryloyl chloride and 250 parts of methylene chloride. 22 parts of
pure CH.sub.2=CHCO.sub.2CH.sub.2(CF.sub.2CFCl).sub.-
4CF.sub.2CH.sub.2OC(O)CH.dbd.CH.sub.2 diacrylate were obtained. The
characterization results are consistent with the indicated
structure. .sup.19F-NMR [.delta.(CF.sub.3COOH), ppm]:
29.5.about.32.0(m. 6F), 36.0(s, 4F), 49.6.about.55.0(m, 4F);
.sup.1H-NMR [.delta., ppm] 4.6(t, J=13.6 Hz, 4H), 6.1(ABX system,
6H); MS: 684 (M, 0.25), 576
([HOCH.sub.2(CF.sub.2CFCl).sub.4CF.sub.2CH.sub.2OH].sup.+, 1.60),
460 ([HOCH.sub.2(CF.sub.2CFCl).sub.3CF.sub.2CH.sub.2OH].sup.+,
1.67), 433
([CH.sub.2=CHCO.sub.2CH.sub.2(CF.sub.2CFCl).sub.3].sup.+), 344
([HOCH.sub.2(CF.sub.2CFCl).sub.2CF.sub.2CH.sub.2OH].sup.+, 0.71),
317 ([CH.sub.2.dbd.CHCO.sub.2CH.sub.2(CF.sub.2CFCl).sub.2].sup.-,
0.24), 135 ([CH.sub.2=CHCO.sub.2CH.sub.2CF.sub.2].sup.-, 4.93), 85
([CH.sub.2.dbd.CHCO.sub.2CH.sub.2].sup.+, 7.13), 55
([CH2=CHCO].sup.-, 100); IR [film, cm.sup.-1]: 2983(w), 1748(vs).
1637(m). 1411(s), 1261(s), 1165(vs), 1122(vs), 971(vs), 806(s).
EXAMPLE 8
Preparation of
[CH.sub.2=CHCO.sub.2CH.sub.2(CF.sub.2CFCl).sub.2].sub.2
diacrylate
[0066] A. Preparation of
Cl.sub.3CCF.sub.2CFClCF.sub.2CFClCFClCF.sub.2CFCl-
CF.sub.2CC1.sub.3 (precursor of .alpha.,.omega.-diester)
[0067] A mixture of 86 parts of acetic anhydride, 105 parts of
dichloromethane, 12.7 parts of granular zinc, and 81.8 parts of
Cl.sub.3C(CF.sub.2CFCl).sub.2Br were stirred at 45.degree. C. for 2
hours. The unreacted zinc was removed from the mixture and 40 parts
of water were added. The acetic anhydride was then hydrolyzed by
the dropwise addition of 50 parts of 3N H.sub.2SO.sub.4 and the
mixture was washed with aqueous sodium carbonate, worked up with
ether and then distilled. 13.4 parts of the unreacted
Cl.sub.3C(CF.sub.2CFCl).sub.2Br, and 44.1 parts of the residue,
showed two GC peaks with a relative intensity of 1:6. The residue
was then transferred into a quartz tube with 125 parts of
1,1,2-trichlorotrifluoroethane. Chlorine gas was bubbled through
the mixture for 4 hours while the tube was irradiated with a UV
lamp at room temperature. After removal of solvent and fractional
distillation, 44.5 parts of a single coupling product, C1.sub.3CCFl
CFClCF.sub.2CFClCFClCF.sub.2CFClCF.sub.2CC1.sub.3, was obtained.
.sup.19F-NMR (.delta..sub.CF3COOH ppm): 17.3-29.2 (8F), 41.0-48.6
(4F).
[0068] B. Preparation of
H.sub.3CO.sub.2C(CF.sub.2CFCl).sub.2-(CFClCF.sub.-
2).sub.2CF.sub.2CO.sub.2CH.sub.3.alpha.,.omega.-diester 44.5 parts
of
Cl.sub.3CCF.sub.2CFClCF.sub.2CFClCFClCF.sub.2CFClCF.sub.2CCl.sub.3,
was reacted according to the procedure set forth in Example 1A
above to yield 30 parts of
H.sub.3CO.sub.2C(CF.sub.2CFCl).sub.2-(CFClCF.sub.2).sub.2CF.s-
ub.2CO.sub.2CH.sub.3 .alpha.,.omega.-diester. Characterization
results are consistant with the indicated structure.
[0069] C. Preparation of
HOCH.sub.2(CF.sub.2CFCl).sub.2-(CFClCF.sub.2).sub-
.2CF.sub.2CH.sub.2OH .alpha.,.omega.-diol
[0070] 30 parts of
H.sub.3CO.sub.2C(CF.sub.2CFCl)2-(CFClCF.sub.2).sub.2CF.-
sub.2CO.sub.2CH.sub.3 were reacted according to the procedure set
forth in Example 1B above to yield 26 parts of
HOCH.sub.2(CF.sub.2CFCl).sub.2-(CFC- l
CF.sub.2).sub.2CF.sub.2CH.sub.2OH .alpha.,.omega.-diol. The
characterization results are consistant with the indicated
structure.
[0071] D. Preparation of
[CH2.dbd.CHCO.sub.2CH.sub.2(CF.sub.2CFC1).sub.2-[- .sub.2
diacralate
[0072] 13 parts of HOCH.sub.2(CF.sub.2CFCl).sub.2-(CFCl
CF.sub.2).sub.2CF.sub.2CH.sub.2OH was reacted according to the
procedure set forth in Example 5 above to yield 15 parts of
[CH2.dbd.CHCO.sub.2CH.s- ub.2(CF.sub.2CFCl).sub.2-].sub.2 were
obtained. The characterization results are consistant with the
indicated structure.
EXAMPLE 9
Preparation of
HOCH.sub.2CH(OH)CH.sub.2OCH.sub.2(CF.sub.2CFCl).sub.3CF.sub-
.2OCH.sub.2CH(OH)CH.sub.2OH .alpha.,.omega.-tetraol
[0073] HOCH.sub.2(CF.sub.2CFCl).sub.3CF.sub.2CH.sub.2OH diol was
prepared according to the procedure outline in Example 1 above.
Then, to a stirred solution of 46.1 parts of the
HOCH.sub.2(CF.sub.2CFCl).sub.3CF.sub.2CH.su- b.2OH diol in 200
parts of anhydrous t-butanol was slowly added at 0.degree. C. a
solution of 21.6 parts of potassium t-butoxide in 100 parts of
t-butanol. After 2 hours, the temperature of the mixture was raised
to 30.degree. C. and 25 parts of allyl bromide was added. The
mixture was stirred overnight. After filtration and vacuum removal
of excess allyl bromide and most of the t-butanol, the residue was
poured into 300 parts of water. After ether workup, 54 parts of
diallyl product was obtained. .sup.19F and .sup.1H-NMR proved the
completeness of the allylation.
[0074] 54 parts of the diallyl product was then dissolved in 200
parts of methylene chloride and a mixture of 20 parts of
triethylammonium trifluoroacetate with 10 parts of trifluoroacetic
acid was added. To this chilled mixture was then added a
trifluoroperoxyacetic acid solution (which was made by slowly
adding 11 parts of 35% hydrogen peroxide to 25 parts of
trifluoroacetic anhydride at 0.degree. C.). The resulting mixture
wax stirred for 2 hours. After 6 hours, the mixture was poured into
ice-water. The organic layer was further washed with water and
vacuum dried to yield 50 parts of
[0075]
HOCH.sub.2CH(OH)CH.sub.2OCH.sub.2(CF.sub.2CFCl).sub.3CF.sub.2CH.sub-
.2OCH.sub.2CH(OH)CH.sub.2OH tetraol. The characterization results
are consistant with the indicated structure.
EXAMPLE 10
Preparation of
CH.sub.2=CHCO.sub.2CH.sub.2CH[OC(O)CH.dbd.CH.sub.2]CH.sub.2-
OCH.sub.2(CF.sub.2CFCl).sub.3CF.sub.2CH.sub.2OCH.sub.2CH[OC(O)CH=CH.sub.2]-
CH.sub.2OOC(O)CH=CH.sub.2 tetracrylate
[0076] 25 parts of
HOCH.sub.2CH(OH)CH.sub.2OCH.sub.2(CF.sub.2CFCl).sub.3CF-
.sub.2CH.sub.2OCH2CH(OH)CH.sub.2OH were reacted according to the
procedure set forth in Example 5 above to yield 15 parts of
CH.sub.2.dbd.CHCO.sub.2-
CH.sub.2CH[OC(O)CH.dbd.CH.sub.2]CH.sub.2OCH.sub.2(CF.sub.2CFCl).sub.3CF.su-
b.2CH.sub.2OCH.sub.2CH[OC(O)CH=CH.sub.2]CH.sub.2OOC(O)CH.dbd.CH.sub.2
tetracrylate. The characterization results are consistant with the
indicated structure.
EXAMPLE 11
[0077] Prepartion of
CH.sub.2.dbd.CClCO.sub.2CH.sub.2CH[OC(O)CCl.dbd.CH.su-
b.2]CH.sub.2OCH.sub.2(CF.sub.2CFC1).sub.3CF.sub.2CH.sub.2OCH.sub.2CH[OC(O)-
CC1=CH.sub.2]CH.sub.2OOC(O)CC1=CH.sub.2 tetra-a-Cl-acrylate
[0078] 25 parts of
HOCH.sub.2CH(OH)CH.sub.2OCH.sub.2(CF.sub.2CFCl).sub.3CF-
.sub.2CH.sub.2OCH2CH(OH)CH.sub.2OH were reacted according to the
procedure set forth in Example 6 above to yield 12 parts of
CH.sub.2.dbd.CClCO.sub.-
2CH.sub.2CH[OC(O)CC.dbd.CH.sub.2]CH.sub.2OCH.sub.2(CF.sub.2CFCl).sub.3CF.s-
ub.2CH.sub.2OCH.sub.2CH[OC(O)CC1=CH.sub.2]CH.sub.2OOC(O)CC1=CH.sub.2.
tetra-.alpha.-Cl-acrylate. The characterization results are
consistant with the indicated structure.
EXAMPLE 12
Preparation of
CH.sub.2.dbd.CHCO.sub.2CH.sub.2(CF.sub.2CFCl).sub.3CF.sub.2-
CH.sub.2OCH2CH[OC(O)CH=CH.sub.2]CH.sub.2OOC(O)CH=CH.sub.2triacrylate
[0079] 25 parts of
HOCH.sub.2(CF.sub.2CFCl).sub.3CF.sub.2CH.sub.2OCH2CH(OH-
)CH.sub.2OH triol (prepared according to the procedure outlined in
Example 9 above except that the amount of the diol starting
material was doubled (92 parts)) were reacted according to the
procedure set forth in Example 5 above to yield 10 parts of
CH.sub.2.dbd.CHCO.sub.2CH.sub.2(CF.sub.2CFCl-
).sub.3CF.sub.2CH.sub.2OCH2CH[OC(O)CH=CH.sub.2]CH.sub.2OOC(O)CH=CH.
triacrylate. The characterization results are consistant with the
indicated structure.
EXAMPLE 13
Comparison of the refractive indices and near-IR absorption of
conventional hydrocarbon-based diacrylates, highly fluorinated
diacrylates and the chlorofluorodiacrylates of the invention.
[0080] The refractive indices and near-IR absorption of three
diacrylate monomers are compared in Table 2 below:
2 TABLE 2 Index of Near IR Refraction* Absorption**
H.sub.2C.dbd.CHCO.sub.2CH.sub.2(CF.s-
ub.2CFCl).sub.2CF.sub.2CH.sub.2OC(O)CH.dbd.CH.sub.2 1.4221 lowest
H.sub.2C.dbd.CHCO.sub.2CH.sub.2(CF.sub.2).sub.4CH.sub.2OC(O)CH.dbd.CH.sub-
.2 1.3891 medium
H.sub.2C.dbd.CHCO.sub.2CH.sub.2(CH.sub.2).sub.4CH.-
sub.2OC(O)CH.dbd.CH.sub.2 1.4560 highest *measured using an Abbe
refractometer at 589 nm
[0081] (**) relative comparison of the 1300 and the 1550 nm
absorption of the three monomers in a 2 mm quartz cell.
[0082] This example demonstrates that the chlorofluoroacrylates of
the invention have indices of refraction which approximate the
indices of refraction of optical fibers making them more suitable
for optical interconnect applications than the highly fluorinated
diacrylates. The data also show that the diacrylates of the
invention have lower IR absorption which makes them suitable for
low loss optical applications.
EXAMPLES 14-22
General procedure used to prepare the photopolymers described
below
[0083] The photocurable monomer(s) and photoinitiator used in the
examples which follow were stirred at 30-50.degree. C. in a brown
glass container under nitrogen for 5-8 hours. The mixture was then
pressure-filtered through a 0.2 micron PTFE membrane to obtain a
homogeneous clear photocurable composition. The composition was
spin-coated onto a silicon wafer or a quartz plate to form a 2-10
micron thick liquid layer. The plate was then irradiated under
medium pressure mercury LTV lamp in a nitrogen atmosphere for
0.1-60 seconds to obtain a tough solid coating.
EXAMPLE 14
Preparation of
H.sub.2C.dbd.CHCO.sub.2CH.sub.2(CF.sub.2CFCl).sub.2CF.sub.2-
CH.sub.2OC(O)CH.dbd.CH.sub.2photopolymer
[0084] The monomer prepared in Example 5 above was mixed with 2.0
wt. % of .alpha.,.alpha.-dimethyloxy-.alpha.-hydroxyacetophenone
(Darocur 1173) into a homogenous composition and photocured
according to the procedure set forth above The resulting product
was a clear, tough, solid polymer film. The refractive indices of
the monomer and the polymer are 1.4221(at 589 nm) and 1.4586(at 633
nm) respectively.
EXAMPLE 15
Preparation of
H.sub.2C.dbd.CClCO.sub.2CH.sub.2(CF.sub.2CFCl).sub.2CF.sub.-
2CH.sub.2OC(O)CC1.dbd.CH.sub.2photopolymer
[0085] The monomer prepared in Example 6 above was mixed with 2.0
wt. % of benzodimethyl ketal (Irgacure 651) into a homogeneous
composition and photocured according to the procedure set forth
above. The resulting product was a clear, tough, solid polymer
film.
EXAMPLE 16
Preparation of
H.sub.2C.dbd.CHCO.sub.2CH.sub.2(CF.sub.2CFCl).sub.4F.sub.2C-
H.sub.2OC(O)CH=CH.sub.2photopolymer
[0086] The monomer prepared in Example 7 above was mixed with 1 wt.
% LR 8893X (Ciba-Geigy) into a homogeneous composition and
photocured according to the procedure set forth above. The
resulting product was a clear, tough, solid polymer film. The
refractive indices of the monomer and the polymer are 1.4232(at 589
nm) and 1.4416(at 810 nm) respectively.
EXAMPLE 17
Preparation of
[CH.sub.2.dbd.CHCO.sub.2CH.sub.2(CF.sub.2CFCl).sub.2-].sub.-
2photopolymer
[0087] The monomer prepared in Example 8 above was mixed with 1.5
wt % of benzodimethyl ketal (Irgacure 651) into a homogeneous
composition and photocured according to the procedure set forth
above. The resulting product was a clear, tough, solid polymer
film. The refractive indices of the monomer and the polymer are
1.4482(at 589 nm) and 1.4724(at 633 nm) respectively.
EXAMPLE 18
Preparation of
CH.sub.2.dbd.CHCO.sub.2CH.sub.2CH[OC(O)CH.dbd.CH.sub.2]CH.s-
ub.2OCH.sub.2(CF.sub.2CFC1).sub.3CF.sub.2CH.sub.2OCH.sub.2CH[OC(O)CH=CH.su-
b.2]CH.sub.2OOC(O)CH.dbd.CH. tetracrylate
[0088] The monomer produced in Example 10 was mixed with 1.5 wt %
of benzodimethyl ketal (Irgacure 651) to produce a homogeneous
composition. The composition was photocured according to the
procedure set forth above. The resulting product was a clear,
tough, solid polymer film.
EXAMPLE 19
Preparation of a mixture of
H.sub.2C.dbd.CHCO.sub.2CH.sub.2(CF.sub.2CFCl).-
sub.4CF.sub.2CH.sub.2OC(O)CH.dbd.CHH.sub.2 (A) and
H.sub.2C.dbd.CClCO.sub.-
2CH.sub.2(CF.sub.2CFCl).sub.4CF.sub.2CH.sub.2OC(O)CC1.dbd.CH.sub.2
(B)
[0089] Monomers A and B were mixed together in three weight ratios:
10.3/89.7; 32.6/67.4; and 49.4/50.6 and each of the resulting
mixtures was combined with 1 wt. % of LR 8893X as photoinitiator.
Each composition was photocured according to the procedure set
forth above. The refractive indices of resulting photocurable
compositions and the photocured polymers made from these
compositions are listed in Table 3 below:
3 TABLE 3 Ratio of Refractive Refractive monomers in Refractive
Index of, index of photocurable index of photocured photocured
composition photocurable polymer polymer (A/B) composition at 810
nm at 1550 nm 10.3/89.7 1.4377 1.4552 1.4505 32.6/67.4 1.4349
1.4498 1.4470 49.4/50.6 -- 1.4488 1.4425
[0090] This example shows that the diacrylates of the invention may
be combined to produce a polymer of desired refractive index.
EXAMPLE 20
Preparation of a mixture of
H.sub.2C.dbd.CHCO.sub.2CH.sub.2(CF.sub.2CFCl).-
sub.3CF.sub.2CH.sub.2OC(O)CH.dbd.CH.sub.2 and a hydrocarbon
diacrylate
[(CH.sub.3)CC.sub.6H.sub.4O(CH.sub.2).sub.2O.sub.2CCH.dbd.CH.sub.2].sub.2
(EBDA) SR-349)
[0091]
H.sub.2C.dbd.CHCO.sub.2CH.sub.2(CF.sub.2CFCl).sub.3CF.sub.2CH.sub.2-
OC(O)CH.dbd.CH.sub.2 monomer was mixed with
[(CH.sub.3)CC.sub.6H.sub.4O(CH-
.sub.2).sub.2O.sub.2CCH.dbd.CH.sub.2].sub.2 (ethoxylated
bisphenol-A diacrylate, EBDA, Sartomer SR349) in a weight ratio of
11.2/88.8, respectively, to give a homogeneous mixture LR 8893X
(0.7 wt % ) was added to this mixture as the photoinitiator. The
composition was photocured according to the procedure set forth in
Example 21 above. The resulting product was a clear, tough, solid
polymer film. The refractive indices of the photocurable
composition and the photopolymer are 1.4429(at 589 nm) and 1.4512
(at 1550 nm), respectively.
[0092] This example shows that the diacrylates of the invention may
be combined with (are compatible with) other conventional
hydrocarbon-based monomers.
EXAMPLE 21
Preparation of a mixture of
H.sub.2C.dbd.CHCO.sub.2CH.sub.2(CF.sub.2CFCl).-
sub.3CF.sub.2CH.sub.2OC(O)CH=CH.sub.2 and a fluorinated diacrylate
[CH.sub.2.dbd.CHCO.sub.2CH.sub.2CF(CF.sub.3)O(CF(CF.sub.3)CF.sub.2O).sub.-
2CF.sub.2CF.sub.2].sub.2
[0093]
H.sub.2C.dbd.CHCO.sub.2CH.sub.2(CF.sub.2CFCl).sub.3CF.sub.2CH.sub.2-
OC(O)CH=CH.sub.2 monomer was mixed with a highly fluorinated
diacrylate,
[0094]
[CH.sub.2.dbd.CHCO.sub.2CH.sub.2CF(CF.sub.3)O(CF(CF.sub.3)CF.sub.2O-
).sub.2CF.sub.2CF.sub.2].sub.2, in a weight ratio of {fraction
(70/30)}, respectively, to give a homogeneous mixture. LR 8893X,
0.7 wt. %, was added to this composition as photoinitiator. The
composition was photocured according to the procedure set forth
above. The resulting product was a clear, tough, solid polymer
film. The refractive indices of the photocurable composition and
the photocured polymer are 1.4092 (at 589 nm) and 1.4289 (at 633
nm), respectively.
[0095] The refractive indices of the two homopolymers,
H.sub.2C.dbd.CHCO.sub.2CH.sub.2(CF.sub.2CFCl).sub.3CF.sub.2CH.sub.2OC(O)C-
H=CH.sub.2 and
[CH.sub.2.dbd.CHCO.sub.2CH.sub.2CF(CF.sub.3)O(CF(CF.sub.3)C-
F.sub.2O).sub.2CF.sub.2CF.sub.2].sub.2, are 1.4435 (at 633 nm) and
1.3484 (at 633 nm), respectively.
[0096] This example shows that the diacrylates of the invention may
be combined with (are compatible with) highly fluorinated
monomers.
EXAMPLE 22
Preparation of a polymer waveguide using a chlorofluorinated
diacrylate of the invention
[0097] The photcurable compositions of each of Examples 14-21 is
coated onto a glass substrate to a thickness of 6 to 10 .mu.m. The
coating is irradiated in a nitrogen atmosphere for 30 seconds
through a quartz mask with light from a mercury-xenon arc lamp at
11.3 mW/cm.sup.2. The mask is designed to produce a single-mode
star coupler consisting of tapered waveguides of from 5.5 to 8.5
.mu.m width having decreasing spacing between the guides down to
3.5 .mu.m. Following exposure, the coating is developed by flushing
with acetone from end to end to produce free-standing rib
waveguides of about 5 to 9 .mu.m width.
* * * * *