U.S. patent application number 10/835355 was filed with the patent office on 2004-12-09 for halogenated optical polymer composition.
Invention is credited to Blomquist, Robert M..
Application Number | 20040249081 10/835355 |
Document ID | / |
Family ID | 25432514 |
Filed Date | 2004-12-09 |
United States Patent
Application |
20040249081 |
Kind Code |
A1 |
Blomquist, Robert M. |
December 9, 2004 |
Halogenated optical polymer composition
Abstract
The invention provides polymeric optical materials that can be
cured in air and have low optical loss in both the C-band and the
L-band of the telecommunications spectrum. The polymeric materials
are made by the free radical polymerization of an at least
difunctional thiol compound with an at least difunctional
ethylenically unsaturated compound wherein at least one of the
thiol compound and the ethylenically unsaturated compound is at
least partially halogenated. The compositions of this invention may
be used to fabricate planar optical waveguides with low loss and
low birefringence.
Inventors: |
Blomquist, Robert M.;
(Whippany, NJ) |
Correspondence
Address: |
E I DU PONT DE NEMOURS AND COMPANY
LEGAL PATENT RECORDS CENTER
BARLEY MILL PLAZA 25/1128
4417 LANCASTER PIKE
WILMINGTON
DE
19805
US
|
Family ID: |
25432514 |
Appl. No.: |
10/835355 |
Filed: |
April 29, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10835355 |
Apr 29, 2004 |
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09912827 |
Jul 25, 2001 |
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6778753 |
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Current U.S.
Class: |
525/199 ; 522/1;
525/55 |
Current CPC
Class: |
C08G 65/007 20130101;
G02B 2006/121 20130101; G02B 6/138 20130101; C08F 2/46 20130101;
C08G 2650/16 20130101 |
Class at
Publication: |
525/199 ;
525/055; 522/001 |
International
Class: |
C08L 027/12 |
Claims
1. an energy curable composition comprising: an at least
difunctional thiol compound; and an at least difunctional
ethylenically unsaturated compound; wherein at least one of the
thiol compound and the ethylenically unsaturated compound is at
least partially halogenated, the ratio of thiol moieties to
ethylenically unsaturated moieties is between about 1:2 and about
2:1, and the thiol compound and the ethylenically unsaturated
compound account for between about 35% and about 99.9% by weight of
the energy curable composition.
2. The energy curable composition of claim 1 further comprising a
selected amount of a free radical initiator.
3. The energy curable composition of claim 1 wherein at least one
of the thiol compound and the ethylenically unsaturated compound
includes a perfluorinated moiety.
4. The energy curable composition of claim 1 further comprising a
C.sub.H of less than about 55 M.
5. The energy curable composition of claim 1 further comprising a
C.sub.H of less than about 35 M.
6. The energy curable composition of claim 1 further comprising a
C.sub.H of less than about 20 M.
7. The energy curable composition of claim 1 further comprising a
C.sub.H of less than about 15 M.
8. The energy curable composition of claim 1 wherein the ratio of
thiol moieties to ethylenically unsaturated moieties is between
about 9:10 and about 10:9.
9. The energy curable composition of claim 1 wherein the ratio of
thiol moieties to ethylenically unsaturated moieties is between
about 19:20 and about 20:19.
10. The energy curable composition of claim 1 wherein at least one
of the thiol compound and the ethylenically unsaturated compound is
at least trifunctional.
11. The energy curable composition of claim 1 wherein the
perfluorinated moiety is selected from the group consisting
of:--(CF.sub.2).sub.x--;--(C-
.sub.6F.sub.4).sub.x--;--(CF.sub.3).sub.2C--;--CF.sub.2O--[(CF.sub.2CF.sub-
.2O).sub.m(CF.sub.2O).sub.n]--CF.sub.2--;--CF(CF.sub.3)O(CF.sub.2).sub.4O[-
CF(CF.sub.3)CF.sub.2O].sub.pCF(CF.sub.3)--;
and--CF.sub.2O--(CF.sub.2CF.su- b.2O).sub.m--CF.sub.2--,wherein x
is an integer between 1 and about 10; m and n designate the number
of randomly distributed perfluoroethyleneoxy and
perfluoromethyleneoxy backbone repeating subunits, respectively;
and p designates the number of --CF(CF.sub.3)CF.sub.2O-- backbone
repeating subunits.
12. The energy curable composition of claim 11 wherein the
perfluorinated moiety is
--CF.sub.2O--[(CF.sub.2CF.sub.2O).sub.m(CF.sub.2O).sub.n]--CF.s-
ub.2-- and the ratio of m to n varies from about 0.5:1 to about
1.4:1.
13. The energy curable composition of claim 12 wherein the ratio of
m to n is about 1:1 and the molecular weight of the ethylenically
unsaturated compound is between about 2000 and about 2800.
14. The energy curable composition of claim 1 wherein the
ethylenically unsaturated moieties are selected from the group
consisting of acrylate, methacrylate, vinyl ether, allyl ether,
alkene, thioacrylate ester, thiomethacrylate ester, vinyl
thioether, allyl thioether, and maleimide.
15. The energy curable composition of claim 1 wherein the
ethylenically unsaturated compound has the
structure(A).sub.n-R--R.sub.f--R'-(A).sub.n'- ,wherein R.sub.f is a
perfluorinated moiety selected from the group consisting
of:--(CF.sub.2).sub.x--,--(C.sub.6F.sub.4).sub.x--,--(CF.sub.3-
).sub.2C--,--CF.sub.2O--[(CF.sub.2CF.sub.2O).sub.m(CF.sub.2O).sub.n]--CF.s-
ub.2--,--CF(CF.sub.3)O(CF.sub.2).sub.4O[CF(CF.sub.3)CF.sub.2O].sub.pCF(CF.-
sub.3)--,
and--CF.sub.2O--(CF.sub.2CF.sub.2O).sub.m--CF.sub.2--,wherein x is
an integer between 1 and about 10; m and n designate the number of
randomly distributed perfluoro-ethyleneoxy and
perfluoromethyleneoxy backbone repeating subunits, respectively;
and p designates the number of --CF(CF.sub.3)CF.sub.2O-- backbone
repeating subunits; R and R' are divalent or trivalent connecting
moieties selected individually from the group consisting of alkyl,
aryl, ester, ether, amide, amine, and urethane groups; A is an
ethylenically unsaturated group selected from the group consisting
ofCX.sub.2.dbd.C(X)COE-,CX.sub.2.dbd.C(CX.sub.3)COE-,CX.sub.2.-
dbd.CX--,CX.sub.2.dbd.CX-E-,
andCX.sub.2.dbd.CX--CH.sub.2-E-,wherein E=O or S; each X is
individually H, D, F, or Cl; n is 1 if R is divalent, and 2 if R is
trivalent; and n' is 1 if R' is divalent and 2 if R' is
trivalent.
16. The composition of claim 14 wherein the connecting groups R and
R' are individually selected from the group consisting of 15
17. The energy curable composition of claim 1 wherein the at least
difunctional thiol compound includes a perfluorinated moiety.
18. The energy curable composition of claim 17 wherein the at least
difunctional thiol compound has the
structure(HS).sub.n--R--R.sub.f--R'--- (SH).sub.n',wherein R.sub.f
is a perfluorinated moiety selected from the group consisting
of:--(CF.sub.2).sub.x--,--(C.sub.6F.sub.4).sub.x--,--(CF-
.sub.3).sub.2C--,--CF.sub.2O--[(CF.sub.2CF.sub.2O).sub.m(CF.sub.2O).sub.n]-
--CF.sub.2--,--CF(CF.sub.3)O(CF.sub.2).sub.4O[CF(CF.sub.3)CF.sub.2O].sub.p-
CF(CF.sub.3)--,
and--CF.sub.2O--(CF.sub.2CF.sub.2O).sub.m--CF.sub.2--,wher- ein x
is an integer between 1 and about 10; m and n designate the number
of randomly distributed perfluoro-ethyleneoxy and
perfluoromethyleneoxy backbone repeating subunits, respectively;
and p designates the number of --CF(CF.sub.3)CF.sub.2O-- backbone
repeating subunits; R and R' are divalent or trivalent connecting
moieties selected individually from the group consisting of alkyl,
aryl, ester, ether, amide, amine, and urethane groups; n is 1 if R
is divalent, and 2 if R is trivalent; and n' is 1 if R' is divalent
and 2 if R' is trivalent.
19. The energy curable composition of claim 18 wherein the divalent
or trivalent connecting moieties R and R' are selected individually
from the group consisting of 16
20. A polymeric material comprising: thioether moieties in a
concentration of at least about 0.05 M; and at least one
perhalogenated moiety.
21. The polymeric material of claim 20 further comprising a C.sub.H
of less than about 55 M.
22. The polymeric material of claim 20 wherein the perfluorinated
moiety is selected from the group consisting
of--(CF.sub.2).sub.x--,--(C.sub.6F.-
sub.4).sub.x--,--(CF.sub.3).sub.2C--,--CF.sub.2O--[(CF.sub.2CF.sub.2O).sub-
.m(CF.sub.2O).sub.n]--CF.sub.2--,--CF(CF.sub.3)O(CF.sub.2).sub.4O[CF(CF.su-
b.3)CF.sub.2O].sub.pCF(CF.sub.3)--,
and--CF.sub.2O--(CF.sub.2CF.sub.2O).su- b.m--CF.sub.2--,wherein x
is an integer between 1 and about 10; m and n designate the number
of randomly distributed perfluoroethyleneoxy and
perfluoromethyleneoxy backbone repeating subunits, respectively;
and p designates the number of --CF(CF.sub.3)CF.sub.2O-- backbone
repeating subunits.
23. Cancelled
24. Cancelled
25. Cancelled
26. (Cancelled)
27. Cancelled.
28. Cancelled
29. Cancelled
30. Cancelled.
31. (Cancelled)
32. (Cancelled)
33. (Cancelled)
34. (Cancelled)
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates generally to polymeric
materials, and more specifically to halogenated polymeric materials
useful in the construction of devices for telecommunications.
[0003] 2. Technical Background
[0004] In optical communication systems, messages are transmitted
by electromagnetic carrier waves at optical frequencies that are
generated by such sources as lasers and light-emitting diodes.
There is interest in such optical communication systems because
they offer several advantages over conventional communication
systems.
[0005] One preferred device for routing or guiding waves of optical
frequencies from one point to another is an optical waveguide. The
operation of an optical waveguide is based on the fact that when a
light-transmissive medium is surrounded or otherwise bounded by an
outer medium having a lower refractive index, light introduced
along the axis of the inner medium substantially parallel to the
boundary with the outer medium is highly reflected at the boundary,
trapping the light in the light transmissive medium and thus
producing a guiding effect between channels. A wide variety of
optical devices can be made which incorporate such light guiding
structures as the light transmissive elements. Illustrative of such
devices are planar optical slab waveguides, channel optical
waveguides, rib waveguides, optical couplers, optical splitters,
optical switches, optical filters, arrayed waveguide gratings,
waveguide Bragg gratings, variable attenuators and the like. For
light of a particular frequency, optical waveguides may support a
single optical mode or multiple modes, depending on the dimensions
of the inner light guiding region and the difference in refractive
index between the inner medium and the surrounding outer
medium.
[0006] Optical waveguide devices and other optical interconnect
devices may be constructed from organic polymeric materials.
Whereas single mode optical devices built from planar waveguides
made from glass are relatively unaffected by temperature, devices
made from organic polymers may show a significant variation of
properties with temperature. This is due to the fact that organic
polymeric materials have a relatively high thermo-optic coefficient
(dn/dT). Thus, as an organic polymer undergoes a change in
temperature, its refractive index changes appreciably. This
property can be exploited to make active, thermally tunable or
controllable devices incorporating light transmissive elements made
from organic polymers. One example of a thermally tunable device is
a 1.times.2 switching element activated by the thermo-optic effect.
Thus, light from an input waveguide may be switched between two
output waveguides by the application of a thermal gradient induced
by a resistive heater. Typically, the heating/cooling processes
occur over the span of one to several milliseconds.
[0007] Most polymeric materials, however, contain carbon-hydrogen
bonds, which absorb strongly in the 1550 nm wavelength range that
is commonly used in telecommunications applications, causing
devices made from such materials to have unacceptably high
insertion losses. By lowering the concentration of C--H bonds in a
material by replacement of C--H bonds with C-D or C-halogen bonds,
it is possible to lower the absorption loss at infrared
wavelengths. While planar waveguides made from fluorinated
polyimides and deuterated or fluorinated polymethacrylates have
achieved single mode losses of as little as 0.10 dB/cm at 1300 nm,
it is relatively difficult to make optical devices from these
materials. For example, the processes by which these waveguides
have typically been made includes the use of a reactive ion etching
process, which is cumbersome and can cause high waveguide loss due
to scattering. Further, deuteration is not an effective means of
reducing loss in the 1550 nm wavelength range. Fluorinated
polyimides and deuterated or fluorinated polymethacrylates have
higher losses in the telecommunications window near 1550 nm,
typically on the order of 0.6 dB/cm. O--H and N--H bonds also
contribute strongly to loss at wavelengths near 1310 nm and 1550
nm. Compositions are sought in which the concentrations of O--H and
N--H bonds are minimal.
[0008] Photopolymers have been of particular interest for optical
interconnect applications because they can be patterned using
standard photolithographic techniques. Photolithography involves
the selective polymerization of a layer of the photopolymer by
exposure of the material to a pattern of actinic radiation.
Material that is exposed to the actinic radiation is polymerized,
whereas material that is not exposed remains unpolymerized. The
patterned layer is developed, for example, by removal of the
unexposed, unpolymerized material by an appropriate solvent.
[0009] Among the many known photopolymers, acrylate materials have
been widely studied as waveguide materials because of their optical
clarity and low birefringence, and the ready availability of a wide
range of monomers. However, the performance of optical devices made
from many acrylate materials has been poor, due to high optical
losses, poor resistance to aging and yellowing and thermal
instability of the polymerized material. Further, acrylate
materials have relatively high losses, up to 1 dB/cm, in the L-band
(about 1565 nm to about 1620 nm), and do not cure efficiently in
air, necessitating the use of oxygen-free conditions.
[0010] In the attachment of optical fibers to highly fluorinated,
low refractive index polymer optical waveguides, a process known as
pigtailing, highly fluorinated, low refractive index adhesives are
desired. Most suitably, in order to reduce back reflections, the
refractive index of the adhesive lies between that of the
fluorinated polymer waveguide (about 1.33 to about 1.40) and the
optical fiber (about 1.46). Materials that are known to UV cure in
the presence of air, such as epoxies and vinyl ethers, generally
have higher refractive indices (about 1.47 to about 1.52). Further,
these materials are difficult to formulate with highly fluorinated
monomers to reduce their refractive index due to the insolubility
of the required cationic photoinitiators in nonpolar materials.
SUMMARY OF THE INVENTION
[0011] One aspect of the present invention relates to an energy
curable composition including an at least difunctional thiol
compound, an at least difunctional ethylenically unsaturated
compound having a perfluorinated moiety, and a selected amount of a
free radical initiator wherein at least one of the thiol compound
and the ethylenically unsaturated compound is at least partially
halogenated, the ratio of thiol moieties to ethylenically
unsaturated moieties is between about 1:2 and about 2:1, and the
thiol compound and the ethylenically unsaturated compound account
for between about 35% and about 99.9% of the energy curable
composition.
[0012] Another aspect of the present invention relates to a
polymeric material having thioether moieties in a concentration of
at least about 0.05 M; and at least one perhalogenated moiety.
[0013] Another aspect of the present invention relates to an
optical element having a polymeric core, said core including a
polymeric material including thioether moieties in a concentration
of at least 0.05 M and at least one at least partially halogenated
moiety.
[0014] Another aspect of the invention relates to a method of
making an optical element including the steps of (a) applying a
layer of a cladding composition to a substrate, the clad
composition including an at least difunctional thiol compound, an
at least difunctional ethylenically unsaturated compound, and an
effective amount of a free radical initiator wherein at least one
of the thiol compound and the ethylenically unsaturated compound is
at least partially halogenated, the ratio of thiol moieties to
isolated ethylenically unsaturated moieties is between about 1:2
and about 2:1 and the ethylenically unsaturated compound account
for between about 35% and about 99.9% of the cladding composition;
(b) at least partially curing the cladding composition to form a
polymeric cladding layer; (c) applying a photosensitive core
composition to the surface of the polymeric cladding layer to form
a core composition layer, the core composition including an at
least difunctional thiol compound, an at least difunctional
ethylenically unsaturated compound, and an effective amount of a
free radical initiator wherein at least one of the thiol compound
and the ethylenically unsaturated compound is at least partially
halogenated, the ratio of thiol moieties to isolated ethylenically
unsaturated moieties is between about 1:2 and about 2:1 and the
ethylenically unsaturated compound account for between about 35%
and about 99.9% of the core composition; (d) imagewise exposing the
photosensitive core composition layer to sufficient actinic
radiation to effect the at least partial polymerization of an
imaged portion and to form at least one non-imaged portion of the
photosensitive core composition layer; (e) removing the at least
one non-imaged portion without removing the imaged portion, thereby
forming a polymeric patterned core from the imaged portion; (f)
applying a photosensitive overclad composition onto the polymeric
patterned core; and (g) at least partially curing the overclad
composition to form a polymeric overclad layer, wherein the
polymeric overclad layer and the polymeric cladding layer have a
lower refractive index than the polymeric patterned core.
[0015] The compositions, methods, and devices of the present
invention result in a number of advantages over prior art
compositions, methods, and devices. For example, the compositions
of the present invention are far less sensitive to oxygen during
cure than analogous acrylate materials, and can be formulated to
cure substantially completely in the presence of air, thus
obviating the need for excluding oxygen during processing, such as
in the photolithographic exposure step of the waveguide
manufacturing process. The polymerized compositions of the present
invention have a low optical loss throughout both the C-band and
the L-band, allowing for the construction of optical waveguide
devices suitable for use in either band. Since they cure in air,
these compositions may also be used as adhesives, for example, in
the pigtailing of optical fibers to waveguide devices. The
compositions of the present invention may be formulated to have a
low refractive index, making them especially useful in the
pigtailing of optical fibers to highly fluorinated polymer optical
waveguide devices.
[0016] Additional features and advantages of the invention will be
set forth in the detailed description which follows, and in part
will be readily apparent to those skilled in the art from the
description or recognized by practicing the invention as described
in the written description and claims hereof, as well as the
appended drawings.
[0017] It is to be understood that both the foregoing general
description and the following detailed description are merely
exemplary of the invention, and are intended to provide an overview
or framework to understanding the nature and character of the
invention as it is claimed.
[0018] The accompanying drawings are included to provide a further
understanding of the invention, and are incorporated in and
constitute a part of this specification. The drawings illustrate
one or more embodiment(s) of the invention, and together with the
description serve to explain the principles and operation of the
invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] FIG. 1 is a schematic of a polymer system made from a
difunctional thiol compound and a difunctional ethylenically
unsaturated compound;
[0020] FIG. 2 is a schematic of a polymer system made from
trifunctional thiol compound and a difunctional ethylenically
unsaturated compound;
[0021] FIG. 3 is a cross-sectional view of an optical waveguide;
and
[0022] FIG. 4 is a view of two optical elements being affixed by an
adhesive of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0023] The invention provides an energy curable composition that
may be cured in the presence of air to form a polymeric material
which has a low optical loss in both the C-band and the L-band. As
used herein, an energy curable composition is one, which may be
cured by at least one of heat and actinic radiation. The energy
curable composition includes an at least difunctional thiol
compound, an at least difunctional ethylenically unsaturated
compound, and a selected amount of a free radical photoinitiator.
When initiated by a source of free radicals, thiols and ethylenic
unsaturated moieties can undergo an addition reaction to form a
thioether moiety. Without intending to be bound to any particular
explanation for this curing system, the mechanism for the reaction
is generally understood to be as follows: 1
[0024] This reaction is known commonly as the thiol-ene reaction.
In the initiation step of the reaction, an initiator-derived free
radical removes a hydrogen atom from a thiol to create a thiyl
radical. In the propagation steps, the thiyl radical reacts with a
carbon-carbon double bond of an ethylenically unsaturated moiety,
forming a thioether (R--S--CH.sub.2--) and a carbon-centered
radical intermediate. This carbon-centered radical intermediate
removes a hydrogen atom from another molecule of thiol, and the
propagation steps repeat. As will be appreciated by one of skill in
the art, the reaction may be terminated in any one of a number of
ways. In the reaction scheme given above, termination occurs
through combination of a thiyl radical with a carbon-centered
radical to give a bisthioether structure. However, termination may
occur in any other art-recognized fashion.
[0025] For this reaction to form a polymer, both the thiol compound
and the ethylenically unsaturated compound must be at least
difunctional. An at least difunctional ethylenically unsaturated
compound has at least two ethylenic unsaturations that are not
conjugated to one another and not part of an aromatic ring system.
Ethylenic unsaturations are generally carbon-carbon double bonds,
and include moieties such as, for example, acrylate, methacrylate,
vinyl ether, allyl ether, alkene, thioacrylate ester,
thiomethacrylate ester, vinyl thioether, allyl thioether,
norbornene and maleimide. Likewise, an at least difunctional thiol
compound has at least two thiol moieties. As shown in FIG. 1, the
reaction of difunctional thiols with difunctional ethylenically
unsaturated compounds yields a linear polymer. For this reaction to
form a crosslinked polymer, it is necessary that at least one of
the components be at least trifunctional. FIG. 2 shows a
crosslinked polymer made from a difunctional ethylenically
unsaturated compound and a trifunctional thiol.
[0026] Thiols for use in this invention must be at least
difunctional, having at least two reactive thiol (--SH) moieties.
Thiols may be aliphatic or aromatic, and may include other
functional groups such as, for example, ester, amide, ether,
thioether, thioester, and urethane. Examples of at least
difunctional thiols include, for example, 1,3-propanedithiol;
1,6-hexanedithiol; 2-mercaptoethyl ether; benzenedimethanethiols;
trimethylolpropane tri(3-mercaptopropionate); and ethylene glycol
di(3-mercaptopropionate).
[0027] In addition to thiols as described above, especially
suitable thiols for use in this invention are at least partially
halogenated. The thiols may include carbon-fluorine,
carbon-chlorine, and/or carbon-bromine bonds. The degree and type
of halogenation may be used to control the refractive index and
optical loss contributed by the thiol to the polymeric
material.
[0028] Desirable thiols for use in this invention include a
perhalogenated or substantially perhalogenated moiety. A
perhalogenated moiety is a halocarbon moiety in which C--H bonds
have been replaced by C--X bonds (X=F, Cl or Br) and may include
other elements such as oxygen, nitrogen and sulfur. The
perhalogenated moiety may be chosen from a number of structural
classes, such as, for example, perhaloaryl, perhaloarylene,
branched perhaloalkanes and -alkylenes, and straight chain
perhaloalkanes and -alkylenes.
[0029] Especially desirable thiols for use in this invention
include a perfluorinated moiety. A perfluorinated moiety is a
fluorocarbon moiety in which C--H bonds have been replaced by C--F
bonds, and may include other elements such as oxygen, nitrogen, and
sulfur. The perfluorinated moiety may be chosen from a number of
structural classes, such as perfluoroaryl, perfluoroarylene,
branched perfluoroalkanes and -alkylenes, and straight chain
perfluoroalkanes and -alkylenes.
[0030] As used herein, a substantially perhalogenated moiety is
defined as a moiety in which >75% of the C-H bonds are replaced
by C--X bonds. Likewise, a substantially perfluorinated moiety is
defined as a moiety in which >75% of the C--H bonds are replaced
by C--F bonds.
[0031] Especially suitable perfluorinated moieties for use in the
invention include, for example:
--(CF.sub.2).sub.x--;
--(C.sub.6F.sub.4).sub.x--;
--(CF.sub.3).sub.2C--;
--CF.sub.2O--[(CF.sub.2CF.sub.2O).sub.m(CF.sub.2O).sub.n]--CF.sub.2--;
--CF(CF.sub.3)O(CF.sub.2).sub.4O[CF(CF.sub.3)CF.sub.2O].sub.pCF(CF.sub.3)--
-; and
--CF.sub.2O--(CF.sub.2CF.sub.2O).sub.m--CF.sub.2--,
[0032] wherein x is an integer between 1 and about 10; m and n
designate the number of randomly distributed perfluoroethyleneoxy
and perfluoromethyleneoxy backbone repeating subunits,
respectively; and p designates the number of
--CF(CF.sub.3)CF.sub.2O-- backbone repeating subunits. The use of
other perfluorinated moieties, such as, for example,
tetrafluorophthaloyl, is also contemplated within the scope of this
invention.
[0033] Desirable thiol compounds for use in the invention have the
structure
(HS).sub.n--R--R.sub.f--R'--(SH).sub.n,
[0034] wherein R.sub.f is a perfluorinated moiety selected from the
group consisting of:
--(CF.sub.2).sub.x--;
--(C.sub.6F.sub.4).sub.x--;
--(CF.sub.3).sub.2C--;
--CF.sub.2O--[(CF.sub.2CF.sub.2O).sub.m(CF.sub.2O).sub.n]--CF.sub.2--;
--CF(CF.sub.3)O(CF.sub.2).sub.4O[CF(CF.sub.3)CF.sub.2O].sub.pCF(CF.sub.3)--
-; and
--CF.sub.2O--(CF.sub.2CF.sub.2O).sub.m--CF.sub.2--,
[0035] wherein x is an integer between 1 and about 10; m and n
designate the number of randomly distributed perfluoroethyleneoxy
and perfluoromethyleneoxy backbone repeating subunits,
respectively; and p designates the number of
--CF(CF.sub.3)CF.sub.2O-- backbone repeating subunits;
[0036] R and R' are divalent or trivalent connecting moieties
selected individually from the group consisting of alkyl, aryl,
ester, ether, amide, amine, urethane, thioester and thioether
groups; wherein n is 1 if R is divalent, and 2 if R is trivalent;
and n' is 1 if R' is divalent and 2 if R' is trivalent. Especially
suitable connecting moieties include --CH.sub.2-- and 2
[0037] In light of this disclosure, the skilled artisan will
recognize that a wide variety of connecting moieties could be used
in addition to those specifically listed herein.
[0038] Suitable thiol compounds including a perfluorinated moiety
for use in this invention include
HSCH.sub.2CF.sub.2O--[(CF.sub.2CF.sub.2O).sub.m-
(CF.sub.2O).sub.n]--CF.sub.2CH.sub.2SH, and 3
[0039] These compounds may be synthesized, for example, by
conversion of the corresponding diol or tetraol to the
corresponding bis- or tetrakis(nonafluoro-1-butanesulfonate),
followed by reaction with thiourea and saponification, as described
in the Example, below.
[0040] Other examples of desirable thiol compounds for use in this
invention include 4
[0041] These compounds may be synthesized, for example, by
esterification of the corresponding diol or tetraol with
mercaptopropionic acid, as would be recognized by a person of skill
in the art and as described in the Example below.
[0042] The use of at least difunctional thiols other than those
specifically described herein is contemplated within the scope of
the present invention. Halogenated or non-halogenated at least
difunctional thiols may be made by any method generally known in
the art, including, for example, esterification of an at least
difunctional alcohol with 3-mercaptopropionic acid, or reaction of
an at least difunctional bromide, p-toluenesulfonate, or
nonafluoro-1-butanesulfonate with thiourea followed by
saponification.
[0043] Ethylenically unsaturated compounds for use in this
invention include at least two ethylenically unsaturated moieties.
The ethylenically unsaturated moieties are chosen to be reactive in
the thiol-ene reaction, and may be, for example, acrylate,
methacrylate, vinyl ether, allyl ether, alkene, thioacrylate ester,
thiomethacrylate ester, vinyl thioether, allyl thioether, and
maleimide. The ethylenically unsaturated moieties may be able to
undergo free radical homopolymerization (e.g. methacrylate), or may
not homopolymerize by a free radical mechanism (e.g. vinyl
ether).
[0044] The ethylenically unsaturated moieties themselves may be
halogenated. For example, the use of species such as
2-(trifluoromethyl)acrylate, trifluoroacrylate, trifluorovinyl, and
trifluoroalkene may be desirable due to their low concentration of
C--H bonds and correspondingly low optical loss. For use herein,
the ethylenically unsaturated moiety may also be an alkyne.
[0045] Desirable ethylenically unsaturated compounds for use in
this invention are at least partially halogenated, and may include
carbon-fluorine, carbon-chlorine, and carbon-bromine bonds. The
degree and type of halogenation may be used to control the
refractive index and optical loss contributed by the ethylenically
unsaturated compound to the polymeric material.
[0046] Especially desirable ethylenically unsaturated compounds for
use in this invention include a perfluorinated moiety. A
perfluorinated moiety is a fluorocarbon moiety that has
substantially no carbon-hydrogen bonds, and may include other
elements such as oxygen, nitrogen, sulfur, chlorine and bromine.
The perfluorinated moiety may be chosen from a number of structural
classes, such as perfluoroaryl, perfluoroarylene, branched
perfluoroalkanes and -alkylenes, and straight chain
perfluoroalkanes and -alkylenes. Especially desirable ethylenically
unsaturated compounds for use in the invention have the
structure
(A).sub.n-R--R.sub.f--R'-(A).sub.n,
[0047] wherein R.sub.f is a perfluorinated moiety selected from the
group consisting of:
--(CF.sub.2).sub.x--,
--CF.sub.2O--[(CF.sub.2CF.sub.2O).sub.m(CF.sub.2O).sub.n]--CF.sub.2--,
--CF(CF.sub.3)O(CF.sub.2).sub.4O[CF(CF.sub.3)CF.sub.2O].sub.pCF(CF.sub.3)--
-, and
--CF.sub.2O--(CF.sub.2CF.sub.2O).sub.m--CF.sub.2--,
[0048] wherein x is an integer between 1 and about 10; m and n
designate the number of randomly distributed perfluoroethyleneoxy
and perfluoromethyleneoxy backbone repeating subunits,
respectively; and p designates the number of
--CF(CF.sub.3)CF.sub.2O-- backbone repeating subunits;
[0049] R and R' are divalent or trivalent connecting moieties
selected individually from the group consisting of alkyl, aryl,
ester, ether, amide, amine, urethane, thioester and thioether
groups; A is an ethylenically unsaturated group selected from the
group consisting of
CX.sub.2.dbd.C(X)COE-,
CX.sub.2.dbd.C(CX.sub.3)COE-,
CX.sub.2.dbd.CX--,
CX.sub.2.dbd.CX-E-, and
CX.sub.2.dbd.CX--CH.sub.2-E-,
[0050] wherein E=O or S; each X is individually H, D, F, or Cl; n
is 1 if R is divalent, and 2 if R is trivalent; and n' is 1 if R'
is divalent and 2 if R' is trivalent. Especially suitable
connecting moieties include, for example, 5
[0051] These and other suitable materials are described in commonly
owned and copending U.S. patent application Ser. No. 09/745,076,
which is incorporated herein by reference. In light of this
disclosure, the skilled artisan will recognize that a wide variety
of connecting moieties could be used in addition to those
specifically listed herein.
[0052] Ethylenically unsaturated compounds including a
perfluorinated moiety such as --(CF.sub.2).sub.n-- and a connecting
moiety such as --CH.sub.2-- may be made by, for example,
acrylation, methacrylation, vinylation, or allylation of the
fluorinated diols of the structure
HO--CH.sub.2--(CF.sub.2).sub.n--CH.sub.2--OH, where n is from 1 to
about 10. An example of such a material is
2,2,3,3,4,4,5,5-octafluorohexane-1,6- -diyl diacrylate. These
materials tend to produce relatively hard films of high crosslink
density. They have excellent adhesive properties but have higher
absorption losses than some of the other ethylenically unsaturated
compounds described for use herein.
[0053] When the perfluorinated moiety R.sub.f is
--CF.sub.2O--[(CF.sub.2CF-
.sub.2O).sub.m(CF.sub.2O).sub.n]--CF.sub.2--, the ratio of m:n
generally varies from about 0.5:1 to about 1.4:1. A sample of these
materials will include a distribution of molecules having different
numbers of repeating subunits. In such a sample, the average value
of m generally falls within the range of from about 6.34 to about
18.34, and the average value of n generally falls within the range
of from about 5.94 to about 13.93. Especially suitable materials
have a ratio of m:n of about 1, average values of m and n of about
10.3, and molecular weights between about 2000 and about 2800.
These materials may be made, for example, by acrylating,
methacrylating, vinylating, or allylating a perfluoropolyether diol
with the structure
HO--CH.sub.2CF.sub.2O--[(CF.sub.2CF.sub.2O).sub.m(CF.sub.2O-
).sub.n]--CF.sub.2CH.sub.2--OH, sold under the trade name
Fluorolink.RTM. D10 by Ausimont USA, or alternatively from a
perfluoropolyether tetraol with the structure
HO--CH.sub.2CH(OH)CH.sub.2OCH.sub.2CF.sub.2O--[(CF.sub-
.2CF.sub.2O).sub.m(CF.sub.2O).sub.n]--CF.sub.2CH.sub.2OCH.sub.2CH(OH)CH.su-
b.2--OH, sold under the trade name Fluorolink.RTM. T by Ausimont
USA. Typical art-recognized acrylation, methacrylation, vinylation,
and allylation methods maybe used. Examples of acrylation and
allylation of perfluoropolyethers are described herein below.
[0054] As stated above, the at least partially halogenated
ethylenically unsaturated compound may include chlorine or bromine.
Thus, an example of a suitable ethylenically unsaturated compound
is
(A).sub.n-R--R.sub.h--R'-(A).sub.n,
[0055] wherein R.sub.h is a halogenated moiety selected from the
group consisting of:
--(CF.sub.2CFX.sub.1).sub.a--CF.sub.2--,
--(CF.sub.2CFX.sub.1).sub.a--(CFX.sub.2CF.sub.2).sub.b--,
--(CF.sub.2CFX.sub.1).sub.a--(CFX.sub.2CF2).sub.b--CF.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.c--CF.sub.2,
[0056] 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; and a, b, and
c are independently integers from 1 to about 10; R and R' are
divalent or trivalent connecting moieties selected individually
from the group consisting of alkyl, aryl, ester, ether, amide,
amine, urethane, thioester and thioether groups; A is an
ethylenically unsaturated group selected from the group consisting
of
CX.sub.2.dbd.C(X)COE-,
CX.sub.2.dbd.C(CX.sub.3)COE-,
CX.sub.2.dbd.CX--,
CX.sub.2.dbd.CX-E-, and
CX.sub.2.dbd.CX--CH.sub.2-E-,
[0057] wherein E=O or S; each X is individually H, D, F, or Cl; n
is 1 if R is divalent, and 2 if R is trivalent; and n' is 1 if R'
is divalent and 2 if R' is trivalent. Especially suitable
connecting moieties include, for example, 6
[0058] These and other suitable materials are described in commonly
owned and copending U.S. patent application Ser. No. 08/842,783,
which is incorporated herein by reference. In light of this
disclosure, the skilled artisan will recognize that a wide variety
of connecting moieties could be used in addition to those
specifically listed herein. One purpose in incorporating chlorine
or bromine atoms in the structure is to raise the refractive index
and surface energy above that of a fully fluorinated system without
increasing optical loss due to C--H bond absorption.
[0059] At least partially halogenated thiomethacrylates,
thioacrylates, and vinyl and allyl thioethers may be made from the
corresponding thiols, including those described above, by methods
known and understood by the skilled artisan. For example,
thioacrylates may be synthesized by treating the corresponding
thiol with acryloyl chloride in the presence of base; and allyl
thioethers may be made by treating the corresponding thiol with
allyl bromide.
[0060] Other at least partially halogenated ethylenically
unsaturated compounds suitable for use in this invention include
2,2-bis(4-hydroxyphenyl)tetrafluoropropane diacrylate;
CH.sub.2.dbd.CHCO.sub.2--CH.sub.2CF(CF.sub.3)O(CF2).sub.4O[CF(CF.sub.3)CF-
.sub.2O].sub.pCF(CF.sub.3)CH.sub.2O.sub.2CCH.dbd.CH.sub.2 having
the trade name L-12043 available from 3M Specialty Chemicals
Division;
CH.sub.2.dbd.CHCO.sub.2--CH.sub.2CF.sub.2O--[(CF.sub.2CF.sub.2O).sub.m(CF-
.sub.2O).sub.n]--CF.sub.2CH.sub.2--O.sub.2CCH.dbd.CH.sub.2, sold
under the trade name L-9367 by 3M Specialty Chemicals Division; and
F(CF.sub.2).sub.7--CH.sub.2CH.sub.2--C(CO.sub.2CH.sub.2CH.sub.2CH.sub.2CH-
.sub.2O--CH.dbd.CH.sub.2).sub.2, sold under the trade name FAVE
4101 by Honeywell, and the chlorofluorinated polyester acrylate
7
[0061] described in commonly owned and copending U.S. patent
application Ser. No. 09/747,068, which is incorporated herein by
reference.
[0062] Additionally, non-halogenated at least difunctional
ethylenically unsaturated compounds may be used in the present
invention. The skilled artisan will appreciate that there exists in
the art a vast selection of such compounds, including, for example,
ethoxylated bisphenol A diacrylate, trimethylolpropane triacrylate,
diallyl phthalate, and poly(ethylene glycol) divinyl ether.
[0063] The energy curable composition may include a selected amount
of a free radical initiator. The free radical initiator can be a
photoinitiator, generating free radical species upon exposure to
actinic radiation. Any photoinitiator known to initiate the
thiol-ene reaction can be used. The photoinitiator is desirably
thermally inactive at common ambient temperatures, and is
preferably inactive below about 60.degree. C. Suitable free-radical
type photoinitiators nonexclusively include quinoxaline compounds;
the vicinal polyketaldonyl compounds; the alpha-carbonyls; the
acyloin ethers; the triarylimidazolyl dimers; the alpha-hydrocarbon
substituted aromatic acyloins; polynuclear quinones and
s-triazines.
[0064] Suitable photoinitiators include aromatic ketones such as
benzophenone, acrylated benzophenone, 2-ethylanthraquinone,
phenanthraquinone, 2-tert-butylanthraquinone,
1,2-benzanthraquinone, 2,3-benzanthraquinone,
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, methyl benzoin, ethyl benzoin and other
benzoins. Typical photoinitiators are 1-hydroxycyclohexyl phenyl
ketone (Irgacure.RTM. 184), benzoin, benzoin ethyl ether, benzoin
isopropyl ether, benzophenone, benzodimethyl ketal (Irgacure 651),
2,2-diethoxyacetophenon- e, 2-hydroxy-2-methyl-1-phenylpropan-1-one
(Darocur.RTM. 1173),
1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-propan-1-one
(Darocur 2959),
2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one
(Irgacure 907),
2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-on- e
(Irgacure 369),
poly{1-[4-(1-methylvinyl)phenyl]-2-hydroxy-2-methylpropa- n-1-one}
(Esacure.RTM. KIP), and [4-(4-methylphenylthio)-phenyl]phenylmeth-
anone (Quantacure.RTM. BMS from Great Lakes Fine Chemicals Limited
of London, England). The most desired photoinitiators are those
which tend not to yellow upon irradiation. Such photoinitiators
include benzodimethyl ketal (Irgacure.RTM. 651),
2-hydroxy-2-methyl-1-phenylpropa- n-1-one (Darocur 1173 available
from E. Merck of Darmstadt, Germany), 1-hydroxycyclohexyl phenyl
ketone (Irgacure 184), and
1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one
(Darocur 2959). For the more highly fluorinated energy curable
compositions, such as those including L-12043 and L-9367 from 3M, a
fluorinated photoinitiator such as
2-(1H,1H,2H,2H-heptadecafluoro-1-decoxy)-2-methyl--
1-phenylpropan-1-one, described in U.S. patent 5,391,587, which is
incorporated herein by reference, may be required.
[0065] Initiators for use in this invention may also include
selected amounts of thermal initiators, generating free radical
species upon exposure to heat. Suitable known thermal initiators
include, but are not limited to, substituted or unsubstituted
organic peroxides, azo compounds, pinacols, thiurams, and mixtures
thereof. Examples of operable organic peroxides include, but are
not limited to, benzoyl peroxide, p-chlorobenzoyl peroxide, methyl
ethyl ketone peroxide, tert-butyl perbenzoate, cumene
hydroperoxide, di-sec-butyl peroxide, and
1,1,-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane. Suitable azo
compound initiators include, but are not limited to,
2,2'-azobisisobutyronitrile, (1-phenylethyl)azodiphenylmethane,
dimethyl-2,2'-azobis(1-cyclohexanecarbonitrile), and
2,2'-azobis(2-methylpropane).
[0066] The free radical generating initiator, photo or thermal, may
be present in the energy curable composition in a selected amount
sufficient to effect polymerization of the composition upon
exposure to sufficient energy of an appropriate type. For example,
a photoinitiator is present in an amount sufficient to effect
polymerization upon exposure to sufficient actinic radiation. The
initiator is generally present in an amount of from about 0.01% to
about 10% by weight of the overall composition, or more usually
from about 0.1% to about 6% and suitably from about 0.5% to about
4% by weight based on the total weight of the composition. Mixtures
of initiators may also be used. In certain special cases, such as
when curing via exposure to electron beam radiation, the energy
curable composition may not require a free-radical initiator, since
said free-radicals may be generated in situ via the action of the
electron beam radiation.
[0067] Additional examples of photo- and thermal initiators may be
found in publications known to those skilled in the art; for
example, W. R. Sorenson and T. W. Campbell, Preparative Methods in
Polymer Chemistry, 2.sup.nd Ed. (Interscience Publishers, New York
1968).
[0068] Other additives may also be added to the energy curable
compositions depending on the purpose and the end use of the
compositions. Examples of these include solvents, antioxidants,
photostabilizers, volume expanders, fillers such as for example
silica, titania, glass spheres and the like (especially when in the
nanoscale regime, particle size less than about 100 nm), dyes, free
radical scavengers, contrast enhancers, nitrones and UV absorbers.
Antioxidants include such compounds as phenols and particularly
hindered phenols including Irganox.RTM. 1010 from Ciba Additives of
Tarrytown, N.Y.; sulfides; organoboron compounds; organophosphorous
compounds;
N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide)
available from Ciba Additives under the tradename Irganox 1098.
Photostabilizers and more particularly hindered amine light
stabilizers include but are not limited to
poly[(6-morpholino-s-triazine-2,4-diyl)[(2- ,2,6,6,
-tetramethyl-4-piperidyl)imino]-hexamethylene
[(2,2,6,6,-tetramethyl-4-piperidyl)imino]] available from Cytec
Industries of Wilmington, Del. under the trade name Cyasorb.RTM.
UV-3346. Volume expanding compounds include such materials as the
spiral monomers known as Bailey's monomer. Examples of dyes include
methylene green, methylene blue, and the like. Suitable free
radical scavengers include oxygen, hindered amine light
stabilizers, hindered phenols, 2,2,6,6-tetramethyl-1-piperidinyloxy
free radical (TEMPO), and the like. Suitable contrast enhancers
include other free radical scavengers such as nitrones. UV
absorbers include benzotriazole, hydroxybenzophenone, and the like.
Each of these additives may be included in quantities up to about
6%, based upon the total weight of the composition, and usually
from about 0.1% to about 1%.
[0069] As the person of skill in the art will recognize, more than
one ethylenically unsaturated compound, thiol compound, and
photoinitiator may be employed in a single composition. Blending of
different compounds allows for the tuning of the properties of the
energy curable composition and the polymeric material by the
skilled artisan. It may be desirable to formulate an energy curable
composition with a mixture of halogenated and non-halogenated
thiols and ethylenically unsaturated compounds. For example,
suitable energy curable compositions may include non-halogenated
thiols in admixture with halogenated ethylenically unsaturated
compounds. Alternatively, suitable energy curable compositions may
include halogenated thiols in admixture with non-halogenated
ethylenically unsaturated compounds. In the energy curable
compositions of the present inventions, at least one of the thiol
compound or the ethylenically unsaturated compound is at least
partially halogenated. In addition, it is also possible to include
the use of dissolved thermoplastic polymer materials in these
formulations. The use of alternative monomers and polymers is
limited strictly by their compatibility with the cured polymers of
this invention. Usually all components of the overall composition
are in admixture with one another, and most desirably in a
substantially uniform admixture.
[0070] Mixtures of ethylenically unsaturated compounds and/or thiol
compounds may be used to tune the refractive index of the energy
curable composition and the cured polymer derived therefrom. For
example, the refractive index of a composition may be controlled by
varying the compositional ratio of a low refractive index
perfluoropolyether acrylate and the higher refractive index
2,2,3,3,4,4,5,5-octafluorohexane-1,6-diyl diacrylate. The
refractive index of a composition may also be controlled by varying
the compositional ratio of a low refractive index
perfluoropolyether thiol and the higher refractive index
1,6-hexanedithiol. This is especially necessary in formulating
compositions for planar waveguides, in which the various layers
must have well-defined refractive indices.
[0071] As will be appreciated by the skilled artisan, mixtures of
ethylenically unsaturated compounds and/or thiol compounds may also
be used to tune other properties of the energy curable composition
and of the polymeric material, such as, for example, viscosity,
wettability, crosslink density, hardness, surface energy, and other
such properties. The compositional ratio of thiol moieties to
ethylenically unsaturated moieties chosen depends on the desired
properties of the cured polymer. Since the stoichiometry of the
thiol-ene reaction is 1:1 as described above, equal numbers of
thiol moieties and ethylenic unsaturated moieties may be used.
Suitable energy curable compositions have a ratio of thiol
moieties:ethylenic unsaturated moieties between about 9:10 and
about 10:9, and especially suitable energy curable compositions
have a ratio of thiol moieties:ethylenic unsaturated moieties
between about 19:20 and about 20:19. In embodiments wherein the
ethylenically unsaturated moieties cannot homopolymerize, a ratio
of thiol moieties:ethylenically unsaturated moieties of about 1:1
ensures highly efficient cure of all polymerizable groups of the
composition.
[0072] However, in many situations, it may be desired to use a
different ratio of thiol moieties to ethylenic unsaturated
moieties. For example, if it is desired to completely convert the
ethylenic unsaturated moieties to thioethers in the polymerization
process, an excess of thiol, up to a mole ratio of thiol
moieties:ethylenic unsaturated moieties of up to 2:1 may be used.
As the S--H bond does not absorb strongly at communications
wavelengths, unreacted thiols will not have a substantially
deleterious effect on the optical loss of the polymeric material.
If it is desired to convert all thiols to thioethers during
polymerization, a mole ratio of thiol moieties:ethylenic
unsaturated moieties of down to 1:2 may be used. In embodiments
wherein the ethylenically unsaturated moieties can homopolymerize,
a 1:1 ratio of thiol moieties:ethylenically unsaturated moieties is
not required for complete reaction of substantially all of the
thiol and the ethylenically unsaturated moieties. Efficient
reaction may occur with ratios of down to 1:2 when the
ethylenically unsaturated compound is capable of
homopolymerization. Such non-stochiometric ratios of thiol
moieties:ethylenically unsaturated compound can be effective in
lowering the concentration of unreacted carbon-carbon double bonds
in the polymeric material, and therefore in lowering the optical
loss of the polymeric material in the L-band. In evaluating the
relative merits of a particular ethylenically unsaturated compound
or thiol compound based on its structure, it is useful to determine
the molar concentration of light-absorbing bonds to hydrogen for a
particular candidate material. Since C--H, N--H, and O--H bond
stretching vibrational overtones are a major source of absorption
loss in the communications wavelengths, reduction of the
concentration of these bonds will reduce the material absorption
loss. The analogous overtone of sulfur-hydrogen bonds is very weak
and appears above 1900 nm, and thus is not a significant source of
absorption loss. The molar concentration of hydrogen (C.sub.H) for
a particular compound can be calculated from the number of C--H,
N--H, and O--H bonds per molecule (H); the molecular weight of the
compound (Mw), and the density of the material (.rho.), as shown in
the equation: 1 C H = H M w
[0073] The person of skill in the art will realize that the C.sub.H
for a formulated energy curable composition may be calculated as a
weighted average of the C.sub.H values of each individual
constituent. While an exact relationship between C.sub.H and the
absorption loss of a particular material or fabricated device is
unlikely, this relation gives an initial indication of which
materials may be useful in lowering optical loss values. When
carrying out these calculations for a polymeric material, it is
most appropriate to use the density of a cured film of the
compound, as it is the loss of the cured film that is of greatest
interest. However, since the measure of density of such films is
difficult, the density of the liquid can be used with the
understanding that the approximation does introduce a small amount
of error. Suitable energy curable compositions and polymeric
materials for use herein have a C.sub.H of below about 55 M.
Desirable energy curable compositions and polymeric materials have
a C.sub.H of below about 35 M. Especially desirable energy curable
compositions and polymeric materials have a C.sub.H of below about
20 M. For waveguide applications, most desirable compositions and
polymeric materials have a C.sub.H of below about 15 M. As will be
appreciated by the skilled artisan, C.sub.H may be controlled by
judicious formulation of halogenated and non-halogenated thiol
compounds and halogenated and non-halogenated ethylenically
unsaturated compounds of different chain lengths. C.sub.H values
for some exemplary materials are given in the Examples, below.
[0074] The energy curable compositions of the invention may be at
least partially polymerized by exposure to a suitable type and
amount of energy. For example, compositions formulated with a
thermal initiator may be polymerized by the application of heat.
Temperatures depend on the thermal initiator and usually range from
about 60.degree. C. to about 200.degree. C.; however, temperatures
between 70.degree. C. and 100.degree. C. are preferred. Thermal
polymerization times may vary from several seconds to several
hours, depending on the temperature and initiator used.
[0075] Compositions formulated with a photoinitiator may be
polymerized by exposure to actinic radiation, defined as light in
the visible, ultraviolet, or infrared regions of the
electromagnetic spectrum, as well as electron beam, ion or beam, or
X-ray radiation. Actinic radiation may be in the form of incoherent
light or coherent light, for example, from a laser. Sources of
actinic light and exposure procedures, times, wavelengths and
intensities may vary widely depending on the desired degree of
polymerization, the index of refraction of the material, and other
factors known to those of ordinary skill in the art. Such
conventional photopolymerization processes and their operational
parameters are well known in the art. Sources of actinic radiation
and the wavelength of the radiation may vary widely, and any
conventional wavelength and source can be used. It is preferable
that the photoinitiator require that photochemical excitation be
carried out with relatively short wavelength (high energy)
radiation, so that exposure to radiation normally encountered
before processing (e.g. room lights) will not prematurely
polymerize the energy curable composition. Thus, exposure to
ultraviolet light or deep ultraviolet light are useful.
[0076] Convenient sources include high pressure xenon or
mercury-xenon arc lamps filled with appropriate optical filters to
select the desired wavelengths for processing. Also, short
wavelength coherent radiation is useful for the practice of this
invention. An argon ion laser operating in the UV mode at several
wavelengths near 350 nm is desirable. Also, a frequency-double
argon ion laser with an output near 257 nm wavelength is highly
desirable. Electron beam or ion beam excitation may also be used.
Alternatively, the processing can utilize a multiphoton process
initiated by a high intensity source of actinic radiation, such as
a laser. Typical exposure times vary from a few tenths of seconds
to about several minutes depending on the actinic source. When
partial curing is desired, curing levels between about 50% and 90%
are generally preferred. Photopolymerization temperatures usually
range from about 10.degree. C. to about 60.degree. C.; however,
room temperature is preferred.
[0077] In the polymerization process, thiol moieties are converted
to thioether moieties, putatively by the mechanism detailed above.
As will be appreciated by the skilled artisan, the polymerization
parameters may be chosen to yield a partially polymerized material.
Partially polymerized means that not all thiol--ethylenic
unsaturated moiety pairs are converted to thioethers; thus some
ethylenically unsaturated moieties and some thiol moieties are
present after polymerization. This means that more than 0% but less
than 50%, and preferably less than 20% of the number of thiol
moieties or more than 0% but less than 50%, and preferably less
than 20% of the number of ethylenically unsaturated moieties remain
unreacted in the polymerization process. Partial polymerization is
especially useful in constructing layered structures; partial
polymerization of a first layer of an energy curable composition
prior to application of a second layer of an energy curable
composition allows the two layers to intermingle at their
interface. Reactive moieties in one layer will react with those in
a contiguous layer, improving interlayer adhesion. Further, a
gradient index between layers may be formed by the diffusion of
monomers between layers.
[0078] The concentration of thioether moieties in a sample of at
least partially polymerized material will depend on both the
concentration of thiol moieties in the original energy curable
composition and the degree of polymerization. In the case of a
polymer made by polymerizing a composition having a single thiol
compound and a single ethylenically unsaturated compound and having
excess thiol moieties, the concentration of thioether moieties may
be estimated using the formula: 2 Thioether concentration = ( y M w
e f e + y M w t f t ) DOC e N fru M w fru ( y M w e f e + x M w t f
t )
[0079] wherein x:y is the ratio of thiol moieties to ethylenically
unsaturated moieties in the composition, Mw.sub.t is the molecular
weight of the thiol compound, Mw.sub.e is the molecular weight of
the ethylenically unsaturated compound, f.sub.t is the
functionality of the thiol compound, f.sub.e is the functionality
of the ethylenically unsaturated compound, Mw.sub.fru is the
molecular weight of the fundamental repeat unit, N.sub.fru is the
number of thioether linkages in the fundamental repeat unit,
DOC.sub.e is the fraction of ethylenically unsaturated moieties
converted to thioethers in the polymerization process, and .rho. is
the density of the polymeric material.
[0080] In the case of a polymer made by polymerizing a composition
having a single thiol compound and a single ethylenically
unsaturated compound and having excess ethylenically unsaturated
moieties, the concentration of thioether moieties may be calculated
using the formula: 3 Thioether concentration = ( x M w e f e + x M
w t f t ) DOC t N fru M w fru ( y M w e f e + x M w t f t )
[0081] wherein DOC.sub.t is the fraction of thiol moieties
converted to thioethers in the polymerization process. As noted
above, the density of the initial energy curable composition may be
used as an approximation for the density of the cured material.
Further, the person of skill in the art will recognize that these
equations assume that the energy curable compositions consist
completely of thiol compound and ethylenically unsaturated
compound. The equations may be adjusted to reflect inventive
compositions that differ significantly from this assumption. Also,
polymers in accordance with this invention may be made from
compositions having more than one thiol compound and/or more than
one ethylenically unsaturated compound; the skilled artisan will
modify the given equations to reflect this fact. Thioether
concentrations of exemplary materials appear in the Examples,
below.
[0082] The compositions of the present invention undergo less
shrinkage upon curing than do analogous materials cured by reaction
of carbon-carbon double bonds (e.g. polyacrylates.) For example,
when 2,2,3,3,4,4,5,5,6,6-octafluorohexane-1,6-diyl diacrylate was
cured as a thick slab, the sample cracked due to stress and showed
a significant amount of shrinkage upon curing. A composition of the
difunctional ethylenically unsaturated compound
2,2,3,3,4,4,5,5,6,6-octafluorohexane-1- ,6-diyl diacrylate and the
trifunctional thiol trimethylolpropane tri(3-mercaptopropionate)
was cured to give an uncracked slab with significantly less
shrinkage. Further, the material was softer and more flexible than
the polyacrylate. The lower stress and shrinkage in the thiol-ene
derived materials is due to the separation of crosslinking sites in
the polymer structure. In the polyacrylate materials, crosslinking
branch points are only separated by one atom; in the materials of
the present invention, they are separated by the combined length of
the thiol compound main chain and the ethylenically unsaturated
compound main chain. In the example given above, the crosslinking
sites are separated by twenty five atoms, reducing the stress on
the system. Low shrinkage materials should have minimal
birefringence, making them beneficial for minimizing polarization
effects in optical devices.
[0083] The compositions and polymers of the present invention are
especially useful in the fabrication of planar optical waveguides.
A method for the fabrication of polymeric waveguides is disclosed
in commonly held and copending U.S. patent application Ser. No.
09/846,697, which is incorporated herein by reference. The
materials of the present invention are especially advantageous, as
they may be formulated to not require processing under oxygen-free
conditions. For example, energy curable compositions with a ratio
of thiols:ethylenically unsaturated moieties of 1:1 or greater are
much less sensitive to oxygen during curing than are the analogous
acrylate or methacrylate compositions. An example of a waveguide
structure appears in FIG. 3. In an embodiment of the present
invention, a suitable substrate 2 is rigorously chemically cleaned,
for example with concentrated aqueous sodium hydroxide. The
substrate 2 may then be primed with acrylate-, thiol-, amino-, or
isocyanato-functionalized chloro- or alkoxysilane compounds. For
example, it may be treated with (3-acryloxypropyl)trichlorosilane.
This is optionally followed by application via spin coating of a
photosensitive adhesion promoting tie layer composition. In this
and subsequent spin coating steps, the edge bead formed in the
spinning process may be removed by methods known by the skilled
artisan (e.g. rinsing the circumference of the wafer with a
suitable solvent during the final seconds of the spin). The tie
layer is preferably highly crosslinkable and contains either
ethylenically unsaturated moieties, thiol moieties, or both. If
used, the tie layer composition is exposed to sufficient actinic
radiation to cure the tie layer to at least a level above its gel
point. Alternatively, suitable tie layers may comprise other
polymers such as epoxies, polyacrylates, or poly(vinyl ethers).
Thereafter, a layer 4 of photosensitive buffer composition is
applied by spin coating. The buffer composition is formulated in
accordance with this invention, and is formulated, as described
above, to have a refractive index when cured of about 1% to about
3% lower than that of a core material. The buffer composition is
exposed to sufficient actinic radiation to partially cure it to a
level below full cure and above its gel point. Then, a
photosensitive clad composition 6 is applied to the surface 5 of
the polymeric buffer layer by spin coating. The clad composition is
formulated in accordance with this invention, and is formulated, as
described above, to have a refractive index when cured of about
0.3% to about 1.5% lower than that of the core material. The
laminate so constructed is exposed to sufficient actinic radiation
to partially cure the clad composition to a level below full cure
and above its gel point. Then, a layer of photosensitive core
composition, formulated in accordance with this invention, is
applied to the surface 7 of the polymeric clad layer by spin
coating. The core composition is then imagewise exposed to
sufficient actinic radiation to effect the at least partial
polymerization of an imaged portion and to form at least one
non-imaged portion of the core composition. For example, a
photomask may be used. In this process, a photomask is lowered to a
predetermined level above the core composition layer, usually less
than about 20 .mu.m above the core composition layer, and more
usually from about 5 .mu.m to about 20 .mu.m above the core
composition layer. The distance of the mask to the surface of the
core composition layer may be controlled by, for example, using
spacers such as thin wires of the desired thickness. Exposure
through the photomask with sufficient actinic radiation to
partially cure the core composition to a level below full cure and
above its gel point yields areas of exposed, partially polymerized
core, and unexposed liquid core composition. Alternatively, the
core composition may be imaged by writing with a well-defined beam
of actinic radiation, such as that generated by a laser. Regardless
of the method of exposure, the unexposed core composition may be
developed by rinsing with a suitable solvent, leaving the exposed,
partially polymerized patterned core 8. The patterned core may
define, for example, waveguide structures with a rectangular or
square cross-section. Then, a photosensitive overclad composition
10 is applied to the surface 9 of the core by spin coating. The
overclad composition coats the top and sides of the patterned core
features. The overclad composition is formulated in accordance with
this invention, and is formulated, as described above, to have a
refractive index when cured of about 0.3% to about 1.5% lower than
that of the core material. The structure is exposed to sufficient
actinic radiation to completely cure the film. Finally, the
structure may thermally annealed to ensure complete polymerization
of all layers and remove any residual volatile substances. Since
the polymerization process is less sensitive to oxygen, the
polymeric materials will be exhibit a higher degree of cure
relative to prior highly fluorinated acrylate compositions, which
will improve adhesion of metal to the polymer surface, adhesion of
the polymer to the substrate, and thermal stability.
[0084] A cross-sectional view of an example of a waveguide
structure in accordance with the present invention appears in FIG.
3. The structure includes a polymeric patterned core 8 including a
polymeric composition including thioether moieties in a
concentration of at least 0.05 M and at least one at least
partially halogenated moiety. The polymeric patterned core is
contiguous on at least one side with a polymeric clad layer 6, and
contiguous on at least one side with a polymeric overclad layer 10.
The clad layer is disposed above a substrate 2. The clad layer
either rests directly on the substrate, or rests upon a buffer
layer 4 that rests upon the substrate. The skilled artisan will
appreciate that the many alternative art-recognized waveguide
structures that can be made using the compositions and polymers
disclosed herein are contemplated within the scope of this
invention.
[0085] As will be appreciated by a person of skill in the art, the
thicknesses and refractive indices of the layers are critical to
waveguide device performance. The refractive indices of the layers
may be defined by judicious formulation of high and low refractive
thiol and ethylenically unsaturated compounds. Usually, the
refractive index of the core is in the range of from about 1.33 to
about 1.7, or more desirably from about 1.4 to about 1.55. The
refractive index of the polymeric materials of the present
invention will be higher than that of the analogous polymers made
by addition of carbon-carbon double bonds (e.g. acrylates) due to
the presence of sulfur. The refractive indices of the buffer, clad,
and overclad layers should be lower than that of the core, as
described above. Thicknesses of the layers are determined in the
spin coating step by spin speed and duration and by the viscosity
of the energy curable composition. The height of the waveguides of
the core layer is defined by the spin coating step, while the width
of the waveguides is determined by the dimensions of the features
of the photomask. The dimensions and refractive indices of the
layers are chosen by known methodologies to lend the desired
waveguiding properties to the final device. In an embodiment of the
invention, a single mode waveguide has core cross-sectional
dimensions of about 7 .mu.m by 7 .mu.m, core refractive index at
1550 nm of about 1.336, underclad thickness of about 2 .mu.m,
underclad refractive index at 1550 nm of about 1.329, buffer
thickness of about 10 .mu.m, buffer refractive index at 1550 nm of
about 1.313, overclad thickness of about 12 .mu.m, and overclad
refractive index at 1550 nm of about 1.329.
[0086] In order to produce waveguides having low loss and low
polarization dependence, planar optical waveguides preferably have
a polymeric core having a glass transition temperature of about
50.degree. C. or less, and more desirably about 0.degree. C. or
less. Desired photosensitive core compositions produce upon at
least partial polymerization a polymeric core having a glass
transition temperature of about 50.degree. C. or less, and more
desirably about 0.degree. C. or less. Desired planar optical
waveguides have a polymeric clad and overclad having a glass
transition temperature of about 40.degree. C. or less. Desired
photosensitive clad compositions and overclad compositions produce
upon at least partial polymerization polymeric materials having a
glass transition temperature of about 40.degree. C. or less. The
particular desired polymeric glass transition temperature may be
obtained by the skilled artisan by characterization and judicious
formulation of the energy curable formulations from which the
polymeric material is made. The glass transition temperature may
also be controlled by varying the irradiation exposure time and
temperatures at which polymerization is conducted.
[0087] Suitable polymer optical elements have low optical loss in
both the C-band and the L-band. For example, desired optical
elements have a polymeric core having an optical loss of less than
0.75 dB/cm at 1550 nm and less than 0.75 dB/cm at 1617 nm. Highly
desired optical elements have a polymeric core having an optical
loss of less than 0.5 dB/cm and at 1550 nm and less than 0.5 dB/cm
at 1617 nm. As the absorption loss is related to C.sub.H, the
person of skill will recognize that low optical loss polymeric
materials of the present invention may be made with a composition
made from compounds having a low C.sub.H. For example, a polymer
made from compounds based on Fluorolink T, which has a C.sub.H of
18.1 M, may have an optical loss of below 0.2 dB/cm.
[0088] Polymer optical waveguides may be made by processes other
than the one detailed above. For example, the photosensitive core
composition may be coated directly on the surface of a substrate of
lower refractive index, and exposed through a photomask and
overcladded as described above. Alternatively, processes such as UV
embossing or reactive ion etching may be used to define the
waveguide pattern.
[0089] The compositions and polymers of the present invention may
also find use as a tie layer to increase adhesion of a metal
electrode deposited on top of a device. For example, a tie layer
composition formulated in accordance with this invention will
adhere well to an underlying polyacrylate polymer layer, especially
if fabricated in the fashion described above. The tie layer should
be formulated to have a low refractive index so as not to perturb
the guiding properties of the underlying waveguide. The thiol-ene
derived tie layer can cure fully in the presence of oxygen, and
thus may have a high degree of surface cure. A deposited metal
layer will adhere well to the tie layer.
[0090] As the compositions and polymers of the present invention
cure fully in the presence of air and have low shrinkage upon
curing, they are also useful as adhesives. Low optical loss is less
important in adhesives than it is in waveguide polymers, so the
importance of minimizing C.sub.H is reduced. For use in pigtailing,
a refractive index between that of the optical fiber (about 1.46)
and that of the polymer optical waveguide (about 1.33 to about
1.40) is desired. These refractive indices are achievable using the
materials of this invention. A low index adhesive may be desired
for joining other optical elements; such use is contemplated within
the scope of this invention. FIG. 4 shows two elements joined by
the polymer of this invention. In the inventive method of affixing
a plurality of elements, an energy curable composition in
accordance with this invention is provided; the elements 12 are
arranged in a desired configuration; the energy curable composition
14 is applied to the area between and around the elements; and the
composition is exposed to an amount of energy sufficient to at
least partially polymerize the composition.
[0091] Other methods known to one of skill in the art may be used
to process the materials disclosed herein. For example, a layered
thin film structure may be fabricated by repeated spin/cure steps.
Monolithic elements may be made by casting into a mold followed by
curing. UV embossing may be used to fabricate thin films with
surface detail.
[0092] The following non-limiting examples serve to illustrate the
invention. It will be appreciated that variations in proportions
and alternatives in elements of the components of the energy
curable compositions and in material processing methods will be
apparent to those skilled in the art and are within the scope of
the present invention.
EXAMPLES
[0093] To formulate the energy curable compositions, the thiol
compound and the ethylenically unsaturated compound were mixed with
the initiator and any other additives and well stirred. To make the
polymers, the energy curable compositions were coated into thin
liquid films by spin coating, slot coating, or direct liquid
casting with appropriate spacers. The thickness of the film was
controlled by spinning speed or spacer thickness. The thickness of
films below 50 .mu.m was measured with a Sloan Dektak IIA
profilometer, and the thickness of films above 50 .mu.m was
measured with a microscope.
[0094] Some halogenated ethylenically unsaturated compounds for use
in this invention are commercially available. For example, as
described above, certain perfluoropolyether acrylates are available
from 3M Specialty Chemicals Division, St. Paul, Minn.
[0095] Alternatively, the fluorinated ethylenically unsaturated
compounds useful in this invention can be made from the
commercially available fluorinated polyols using methods generally
known to those skilled in the art. The tetrafunctional polyol 8
[0096] is available as Fluorolink T from Ausimont USA, Inc., of
Thorofare, N.J. Fluorinated alkanediols such as
2,2,3,3,4,4,5,5-octafluorohexane-1,6- -diol are available from
Lancaster Synthesis, Inc., of Windham, N.H. Thiol compounds for use
in this invention may be purchased commercially. Desirable
fluorinated thiol compounds may be synthesized by methods familiar
to those in the art. For example, fluorinated polyols may be
exhaustively esterified with 3-mercaptopropionic acid.
Alternatively, fluorinated polyols may be converted to the
corresponding polybromide, then reacted exhaustively with thiourea
and saponified to give the corresponding polyfunctional thiol
compound. As the person of skill in the art will recognize,
suitable non-halogenated thiol compounds and ethylenically
unsaturated compounds are commercially available, or may be
synthesized by known methods.
[0097] If the ethylenically unsaturated compounds or the thiol
compounds are synthesized from polyols, care should be taken to
remove as much as practicable any residual alcohols and amines or
other --OH or --NH bearing impurities, as O--H and N--H bonds
absorb strongly in the 1550 nm wavelength range that is commonly
used in telecommunications applications. A suitable product
purification technique is described in connection with Example
A.
Example A
[0098] A glass three-neck flask was fitted with a condenser and
stirrer. Fluorolink T brand fluorinated polyol (900 g) and
p-methoxyphenol (0.5 g) were added to the flask. The fluorinated
polyol used in this example can be described as having the
structure: 9
[0099] where the ratio of m:n varies from about 0.5:1 to 1.4:1, m
varies from about 6.45 to about 18.34 on average, and n varies from
about 5.94 to about 13.93 on average. Desirable materials have a
ratio of m:n of about 1, an average m and an average n of about
10.3.
[0100] Acryloyl chloride (170 g) was added, and the mixture was
vigorously stirred. The resulting exotherm brought the temperature
up to 70.degree. C. The temperature of the reaction mixture was
then raised to 90.degree. C. and the mixture was stirred for three
hours. The system was then placed under vacuum to remove the
hydrogen chloride generated by the reaction and the excess acryloyl
chloride. The mixture was cooled to room temperature. An infrared
spectrum of the material confirmed the disappearance of the broad
absorbance at 3500 cm.sup.-1, which is attributed to hydroxyl
groups on the polyol. Triethylamine (124 g) was slowly added to the
reaction flask over a half hour period. The material was filtered
to remove the triethylamine hydrochloride, which formed, then
washed twice with water. The resulting tetraacrylate has been named
UV-T and can be described as having the structure 10
[0101] where the ratio of m:n varies from about 0.5:1 to 1.4:1, m
varies from about 6.45 to about 18.34 on average, and n varies from
about 5.94 to about 13.93 on average. Desirable materials have a
ratio of m:n of about 1, an average m and an average n of about
10.3. These perfluoropolyether tetraacrylates have low refractive
index and can be useful in adjusting the crosslinking density of
the cured polymer to vary its physical properties. High molecular
weight versions of this material can be very low in loss. One
example of a perfluoropolyether tetraacrylate has a molecular
weight of 2400 g/mol, a liquid refractive index of 1.3362, a cured
homopolymer refractive index of 1.335, a liquid density of 1.663
g/mL, and a C.sub.H of about 18 M.
Example B
[0102] A three-neck glass flask was fitted with a condenser. The
diol 2,2,3,3,4,4,5,5-octafluorohexane-1,6-diol (300 g) and
p-methoxyphenol (0.5 g) were added to the flask. The flask was
heated to 70.degree. C. to melt the diol. Acryloyl chloride (228 g)
was added, and the mixture was vigorously stirred. The resulting
exotherm raised the temperature of the mixture to 90.degree. C. The
temperature was held at 90.degree. C., and the mixture was stirred
for three hours. The system was then placed under vacuum to remove
the hydrogen chloride generated by the reaction and the excess
acryloyl chloride. The mixture was cooled to room temperature. An
infrared spectrum of the material confirmed the disappearance of
the broad absorbance at 3500 cm.sup.-1, which is attributed to
hydroxyl groups on the polyol. Triethylamine (124 g) was slowly
added to the reaction flask over a 1/2 hour period. The material
was filtered to remove the triethylamine hydrochloride which
formed, then washed twice with water. The remaining water was then
removed under vacuum. The resulting acrylate,
2,2,3,3,4,4,5,5-octafluorohexane-1,6-diyl diacrylate, has been
named UV-8. This acrylate has a molecular weight of 370 g/mol, a
liquid refractive index of 1.42, a cured homopolymer refractive
index of 1.418, a liquid density of 1.433 g/mL, and a C.sub.H of
about 32.1 M.
Example C
[0103] A 250 mL three-neck flask was equipped with a dropping
funnel and a mechanical stirrer. Fluorolink T (104 g) was added,
followed by allylchloroformate (26 g). The mixture was stirred and
cooled to 5.degree. C. with an ice bath. Triethylamine (25.5 g) was
added dropwise, with the temperature being kept below 20.degree. C.
After the addition was complete, the reaction mixture was allowed
to stir for an additional hour. The mixture was washed three times
with methanol. Residual solvent was removed by rotary evaporation.
The resulting tetraallyl perfluoropolyether has been named A-T, and
can be described as having the structure 11
[0104] where the ratio of m:n varies from about 0.5:1 to 1.4:1, m
varies from about 6.45 to about 18.34 on average, and n varies from
about 5.94 to about 13.93 on average. Desirable materials have a
ratio of m:n of about 1, an average m and an average n of about
10.3. This material had an absorbance of 0.060 cm.sup.-1 at 1500
nm, and a CH of about 18 M.
Example D
[0105] A three-neck flask was equipped with a Dean-Stark condenser
and a magnetic stirrer. To the flask was added Fluorolink T (82 g)
and 3-mercaptopropionic acid. To the mixture was added one drop of
polyphosphoric acid and 100 mL of toluene. The flask was heated at
reflux with the water formed in the esterification reaction being
collected in the Dean-Stark condenser. After two days, the mixture
was cooled to room temperature and triethylamine (1 mL) was added
to neutralize any unreacted acid. The mixture was washed three
times with a mixture of 90 g of methanol and 10 g of water.
Residual solvent was removed by rotary evaporation. The relatively
high absorbance (0.085 cm.sup.-1 at 1550 nm) of this material was
attributed to incomplete esterification; infrared spectroscopy
confirmed the presence of residual hydroxyl groups. This material
has been named T-SH and can be described as having the structure
12
[0106] where the ratio of m:n varies from about 0.5:1 to 1.4:1, m
varies from about 6.45 to about 18.34 on average, and n varies from
about 5.94 to about 13.93 on average. Desirable materials have a
ratio of m:n of about 1, an average m and an average n of about
10.3. The material made from a Fluorolink T having a molecular
weight of 2400 g/mol has a C.sub.H of about 17 M.
Example E
[0107] In a 250 mL flask, 70 g of Fluorolink D10, a
perfluoropolyether diol with a molecular weight of 2000 g/mol,
available from Ausimont USA, are combined with 8 g of triethylamine
and 100 mL of 1,1,1-trichlorotrifluoroethane. Over a period of 2
hours, 24 g of nonafluoro-1-butanesulfonyl fluoride is added at
room temperature. After 12 hours, 150 mL of water is introduced,
and the heavy organic phase is dried in vacuo to yield the
bis(nonafluoro-1-butanesulfonate) of Fluorolink D10.
[0108] A 17 g sample of the bis(nonafluoro-1-butanesulfonate) of
Fluorolink D10 is dispersed in 20 mL of isopropanol, 1.2 g of
thiourea is added to the reaction mass, and the temperature is
raised to 80.degree. C. under an inert atmosphere. The reaction may
be monitored by infrared spectroscopy or .sup.19F NMR. After about
15 hours, conversion of the bis(nonafluoro-1-butanesulfonate) to
the corresponding bis(isothiouronium salt) is complete. The solvent
is eliminated by distillation, yielding the bis(isothiouronium
salt) of Fluorolink D10.
[0109] A 2.6 g sample of the bis(isothiouronium salt) of Fluorolink
D10 is dissolved in 10 mL of ethanol under nitrogen and treated
with 2.5 mL of 10% aqueous NaOH. The mass is allowed to react at
25.degree. C. for four hours, then 10 mL of 5% aqueous HCl is
introduced. The dithiol of Fluorolink D10 is isolated by extraction
with 1,1,1-trichlorotrifluoroeth- ane, and has the structure
HSCH.sub.2CF.sub.2O--[(CF.sub.2CF.sub.2O).sub.m-
(CF.sub.2O).sub.n]--CF.sub.2CH.sub.2SH. This compound has a C.sub.H
value of about 11 M.
Example F
[0110] A mixture of UV-8 (99% by weight) and Darocur 1173 (1% by
weight) was deposited as a 5 mm thick film on a glass substrate and
polymerized with a UV lamp in the presence of air to give a
polyacrylate film. A mixture of UV-8 (51% by weight),
trimethylolpropane tris(3-mercaptopropionate) (48% by weight), and
Darocur 1173 (1% by weight) was deposited as a 5 mm thick film on a
glass substrate and polymerized by a UV lamp in the presence of air
to give a thiol-ene derived film. FIG. 5 shows the absorbance
spectrum of the thiol compound trimethylolpropane
tris(3-mercaptopropionate), and FIG. 6 shows the absorbance spectra
of the two films with the glass removed. The thiol compound has a
relatively high loss due to C--H bond absorption, but has no sharp
transitions in the C-band or the L-band. As the trimethylolpropane
tris(3-mercaptopropionate) has a high concentration of
carbon-hydrogen bonds, the thiol-ene derived film has a higher
absorbance in the C-band (wavelengths of about 1530 nm to about
1560 nm) than does the polyacrylate film. However, the polyacrylate
film shows an absorption band at about 1617 nm, which is attributed
to an overtone of a C--H stretch on unreacted carbon-carbon double
bonds. The thiol-ene derived film has no sharp peak at about 1617
nm, suggesting that the carbon-carbon double bonds are
substantially completely reacted in the thiol-ene polymerization
reaction.
[0111] The thiol-ene composition of this example has a ratio of
thiol moieties to ethylenically unsaturated moieties of 1.31:1. The
cured polymer has a fundamental repeat unit of 13
[0112] Assuming 100% cure and a polymer density of 1.5 g/mL, the
thioether concentration of this material car be calculated to be
3.5 M. This material has a calculated C.sub.H of 51.2 M.
[0113] Thick slabs of the two energy curable compositions were
cured by UV radiation. The polyacrylate slab cracked and showed
substantial shrinkage. The thiol-ene derived slab did not crack,
and exhibited substantially less shrinkage than the polyacrylate
film. Further, the thiol-ene derived material was softer and more
flexible than the polyacrylate material.
Example G
[0114] An equimolar mixture of UV-T and T-SH with 1% by weight of
Darocur 1173 was cured to a polymer with UV radiation in the
presence of air. UV-T alone with 1% by weight of Darocur 1173 did
not cure in the presence of air. The thiol-ene derived material has
a fundamental repeat unit constructed from one molecule each of
UV-T and T-SH with four thioether bonds. Assuming a polymer density
of 1.7 g/mL, molecular weights of UV-T and T-SH of 2400 g/mol, and
an 80% degree of cure, the thioether concentration is calculated to
be about 1.1 M. The C.sub.H of this material is calculated to be
about 18 M.
Example H
[0115] An equimolar mixture of A-T and T-SH with 1% by weight of
Darocur 1173 was cured to a polymer with UV radiation in the
presence of air. Assuming a polymer density of 1.7 g/mL, molecular
weights of UV-T and T-SH of 2400 g/mol, and an 80% degree of cure,
the thioether concentration is calculated to be about 1.1 M. The
C.sub.H of this material is calculated to be about 18 M.
Example I
[0116] A mixture of T-SH, UV-T, and A-T (1:0.5:0.5 mole ratio) with
1% by weight of Darocur 1173 was cured to a polymer with UV
radiation in the presence of air. Assuming a polymer density of 1.7
g/mL, molecular weights of UV-T and T-SH of 2400 g/mol, and an 80%
degree of cure, the thioether concentration is calculated to be
about 1.1 M. The C.sub.H of this material is calculated to be about
18 M.
Example J
[0117] An 1:2 mole ratio mixture of T-SH and FAVE 4101 with 1% by
weight of Darocur 1173 was cured to a polymer with UV radiation in
the presence of air in 30 seconds using an Oriel model 8113 UV
curing unit, which has an intensity of 10 mW/cm.sup.2. As T-SH is
tetrafunctional, and FAVE 4101 is difunctional, this mixture had a
thiol:vinyl ratio of 1:1. A sample of FAVE 4101 mixed 1% by weight
of Daracure 1173 remained liquid even after 900 seconds in the same
curing unit in either the presence of air or when nitrogen
blanketed. This material has a thioether concentration of about 1.5
M, and a C.sub.H of about 42 M.
Example K
[0118] A suitable perfluoropolyether diisocyanate,
poly(tetrafluoroethylen- e oxide-co-difluoromethylene oxide)
alpha,omega-diisocyanate, was purchased from Sigma-Aldrich,
Milwaukee, Wis.
[0119] The perfluoropolyether bis(isocyanate) described above was
heated with 2.2 equivalents of 1,3-dimercapto-2-propanol in 1:1
ethyl perfluorobutyl ether/dimethylformamide with catalytic
dibutyltin dilaurate at reflux for four hours. The reaction was
followed by monitoring the disappearance of the isocyanate
stretching band and the growth of the carbonyl band by FTIR. Upon
completion of the reaction mixture was washed well with water.
Concentration by evaporation yielded the perfluoropolyether
bis(urethane dithiol), which has the putative formula: 14
Example L
[0120] 2-hydroxy-1-[4-(hydroxyethoxy)phenyl]-2-methyl-1-propanone
was allowed to react with 1.1 equivalents of perfluorobutyric
anhydride at reflux in tetrahydrofuran for 16 hours. The reaction
mixture was poured into water and, and the resulting mixture
extracted with ethyl perfluorobutyl ether. The solvent was
evaporated under reduced pressure to yield
2-hydroxy-1-[4-(2-heptafluorobutyroxyethoxy)phenyl]-2-methyl-1-p-
ropanone.
Example M
[0121] An adhesive composition was formulated with 1.0 g of UV-T,
0.8 g. of T-SH, 0.15 g of the perfluoropolyether bis(urethane
dithiol) of Example K, 0.05 g of
2-hydroxy-1-[4-(2-heptafluorobutyroxyethoxy)phenyl]--
2-methyl-1-propanone, 0.03 g of
(3-methacryloxypropyl)trimethoxysilane, and 0.03 g of
(3-glycidyloxypropyl)-trimethoxysilane. The composition has a
refractive index of 1.34 at 1.55 m. The adhesive composition was
used to pigtail an optical fiber to a low index fluoropolymer
waveguide. The adhesive was of an appropriate viscosity, and cured
well in air. The pigtail interface exhibited a return loss of about
-52 dB.
[0122] It will be apparent to those skilled in the art that various
modifications and variations can be made to the present invention
without departing from the spirit and scope of the invention. Thus,
it is intended that the present invention cover the modifications
and variations of this invention provided they come within the
scope of the appended claims and their equivalents.
* * * * *