U.S. patent number RE36,625 [Application Number 09/119,787] was granted by the patent office on 2000-03-21 for linear and cyclic polymers or oligomers having a photoreactive ethene group.
This patent grant is currently assigned to Rolic AG. Invention is credited to Rolf-Peter Herr, Stephen Kelly, Martin Schadt, Klauss Schmitt, Andreas Schuster.
United States Patent |
RE36,625 |
Herr , et al. |
March 21, 2000 |
Linear and cyclic polymers or oligomers having a photoreactive
ethene group
Abstract
The invention is concerned with linear and cyclic polymers or
oligomers having a photoreactive ethene group. The polymers are of
the formula ##STR1## wherein M.sub.a, M.sub.b, M.sub.c are monomer
units for homo- or copolymers; x, y, z are mole fractions of the
copolymers, whereby in each case 0<x.ltoreq.1;
0.ltoreq.y.ltoreq.1 and 0.ltoreq.z<1; S.sub.a, S.sub.b are
spacer units; Z.sub.a, Z.sub.b are molecular units which can
undergo photochemical isomerization/dimerization; n is a magnitude
of 4-100 000 and m is 0 or 1, The compounds are used as an
orienting layer for liquid cyrstals.
Inventors: |
Herr; Rolf-Peter
(Lorrach-Stetten, DE), Kelly; Stephen (Beverly,
GB), Schadt; Martin (Seltisberg, CH),
Schmitt; Klauss (Lorrach, DE), Schuster; Andreas
(Freiburg, DE) |
Assignee: |
Rolic AG (Allschwil,
CH)
|
Family
ID: |
25684718 |
Appl.
No.: |
09/119,787 |
Filed: |
July 21, 1998 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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Reissue of: |
191835 |
Feb 4, 1994 |
05539074 |
Jul 23, 1996 |
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Foreign Application Priority Data
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Feb 17, 1993 [CH] |
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488/93 |
Feb 23, 1993 [CH] |
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553/93 |
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Current U.S.
Class: |
526/245; 526/258;
526/292.1; 526/293; 526/304; 526/311; 526/328; 526/347; 526/326;
526/305; 526/297; 526/279 |
Current CPC
Class: |
C08G
77/38 (20130101); C08F 246/00 (20130101); G02F
1/133711 (20130101); G02F 1/133765 (20210101); C08F
220/305 (20200201); C08F 220/365 (20200201); G02F
1/133753 (20130101); G02F 1/133788 (20130101) |
Current International
Class: |
C08F
246/00 (20060101); C08G 77/00 (20060101); G02F
1/1337 (20060101); C08G 77/38 (20060101); G02F
1/13 (20060101); C08F 028/20 () |
Field of
Search: |
;526/245,258,279,292.1,293,297,304,305,311,326,328,347 |
References Cited
[Referenced By]
U.S. Patent Documents
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4974941 |
December 1990 |
Gibbons et al. |
5190687 |
March 1993 |
Hachiya et al. |
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Foreign Patent Documents
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0240276 |
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Oct 1987 |
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EP |
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445629 |
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Nov 1991 |
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EP |
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482985 |
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Apr 1992 |
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EP |
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Other References
Nishikubo et al., Macromolecules 18:2131-2135 (1985). .
Barley et al., Makomol. Chem. 192:2801-2810 (1991). .
Kawanishi et al., Polymers for Advanced Technologies 1:311-318
(1990). .
Derwent Abstract for EP 482 985. .
Schadt et al., "Surface-induced parallel alignment of liquid
crystals by linearly polymerized photopolymers" Jpn. J. Appl. Phys.
31:2155-2164 (1992). .
Ichimura et al., "Reversible change in alignment mode of nematic
liquid crystals regulated photochemically by command surfaces,
modified with an azobenzene monolayer", Langmuir 4:1214-1216
(1988). .
Seki et al., "Photochemical alignment regulation of a nematic
liquid crystals by Langmuir-Blodgett layers of azobenzene polymers
as command surfaces", Macromolecules 22:3505-3506 (1989). .
Ichimura et al., "Reversible alignment change of liquid crystals
induced by photochromic molecular films, reversible alignment of a
nematic liquid crystal induced by pendent azobenzene
groups--containing polymer thin films", Makromol. Chem., Rapid
Commun. 10:5-8 (1989). .
Ichimura et al., "Photocontrol of in-plane alignment of a nematic
liquid crystal by a photochromic spiropyran momolayer absorbing
linearly polarized light", Chemistry Letters, pp. 1063-1066 (1992).
.
Abstract 93-037881/05 for EP 525 477 (1993). .
Abstract 93-037882/05 for EP 525 478 (1993). .
Abstract 93-037877/05 for EP 525 473 (1993)..
|
Primary Examiner: Lipman; Bernard
Attorney, Agent or Firm: Finnegan, Henderson, Farabow,
Garrett & Dunner, L.L.P.
Claims
We claim:
1. A polymer of formula I ##STR8## wherein M.sub.a, M.sub.b,
M.sub.c are monomer units for homo- or copolymers;
x, y, z are mole fractions of the copolymers, whereby in each case
0<X.ltoreq.1; 0.ltoreq.y.ltoreq.1 and 0.ltoreq.z<1;
S.sub.a, S.sub.b are independently of one another, methylene,
1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene,
1,6-hexylene, 1,2-propylene, 1,3-butylene, cyclopentane-1,2-diyl,
cyclopentane-1,3-diyl, cyclohexane-1,3-diyl, cyclohexane-1,4-diyl,
piperidine-1,4-diyl, piperizine-1,4-diyl, 1,2-phenylene,
1,3-phenylene, 1,4-phenylene, ethyleneoxy, ethyleneoxycarbonyl,
ethylenecarboxy, CONH-- or --CONR' in which R.sup.1 is lower
alkyl;
Z.sub.a, Z.sub.b each independently are formula II ##STR9## wherein
ring A.sup.1 is 1,4-phenylene, which is unsubstituted or
substituted with at least one of halogen, cyano and nitro, or
pyridine-2,5-yl, pyrimidine-2-5-yl, 2,5-thiophenediyl,
2,5-furanylene, 1,4- or 2,6-naphthylene, in which a CH group can be
replaced by nitrogen;
ring A,A.sup.2 each individually are 1,4-phenylene, which is
unsubstituted or substituted with at least one of halogen, cyano,
and nitro, pyridine-2-5-yl, pyrimidine-2,5-yl, or
2,5-thiophenediyl, 2,5-furanylene, trans-1,4-cyclohexylene,
trans-1,3-dioxane-2,5-yl or 1,4-piperidyl;
A.sup.3 is --COO--, --CONH--, --CO--E--, 1,4-phenylene, which is
unsubstituted or substituted with at least one of halogen, cyano
and nitro, or pyridine-2,5-yl, pyrimidine-2-5-yl,
2,5-thiophenediyl, 2,5-furanylene, 1,4- or 2,6-naphthylene, in
which a CH group can be replaced by nitrogen;
E is 1,4-phenylene, which is unsubstituted or substituted with at
least one of halogen, cyano and nitro, or pyridine-2,5-yl,
pyrimidine-2,5-yl, 2,5-thiophenediyl, 2,5-furanylene, 1,4- or
2,6-naphthylene, in which a CH group can be replaced by
nitrogen;
Z,Z.sup.1 each independently are a single covalent bond, --CH.sub.2
CH.sub.2 --, COO--, --OOC--, --OCH.sub.2 --, CH.sub.2 O--,
--C.tbd.C--, --(CH.sub.2).sub.4, --O(CH.sub.2).sub.3 --,
--(CH.sub.2).sub.3 O-- or the trans form of --OCH.sub.2
CH.dbd.CH--, --CH.dbd.CHCH.sub.2 O--, --(CH.sub.2).sub.2
CH.dbd.CH-- or --CH.dbd.CH(CH.sub.2).sub.2 --;
R.sup.1 is hydrogen, halogen, cyano, nitro, NCS, alkyl with 1 to 12
carbon atoms, which is unsubstituted or substituted with fluorine
and in which 1 or 2 non-adjacent --CH.sub.2 -- groups can be
replaced by oxygen, --COO--, --OOC--, --CO-- and in which a
--CH.sub.2 CH.sub.2 -- group can be replaced by --CH.dbd.CH--;
n,p each independently are 0 or 1;
X,Y each independently are hydrogen, halogen, cyano, alkyl with 1
to 12 carbon atoms which is unsubstituted or substituted with
fluorine and in which 1 or 2 non-adjacent --CH.sub.2 -- groups can
be replaced by oxygen, --COO--, --OOC--, --CO-- and/or
--CH.dbd.CH--;
with the proviso that A.sup.3 is different from --COO--, when
simultaneously n and p each are 0, A.sup.1 is phenyl, R.sup.1 is
hydrogen or methoxy and S.sub.a and, respectively S.sub.b are a
single bond;
n' is from 4-100 000 and
m is 0 or 1.
2. A polymer according to claim 1 of formula 1-A: ##STR10## wherein
Ma, Sa, Za and n' have the significance given in claim 1.
3. A polymer according to of claim 1, wherein the
isomerization/dimerization units Z.sub.a and Z.sub.b each
independently are of formula ##STR11## wherein ring A.sup.1 is
1,4-phenylene, which is unsubstituted or substituted with halogen,
cyano and/or nitro, or pyrimidine-2,5-diyl, pyridine-2,5-diyl,
2,5-thiophenediyl, 2,5-furanylene, 1,4-naphthylene or
2,6-naphthylene;
ring A.sup.2 is 1,4-phenylene, which is unsubstituted or
substituted with halogen, cyano and/or nitro, or
pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenediyl,
2,5-furanylene, trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl
or 1,4-piperidyl;
ring A.sup.4 is 1,4-phenylene, which is unsubstituted or
substituted with halogen, cyano and/or nitro;
Z.sup.1 is a single covalent bond, --CH.sub.2 CH.sub.2 --, --COO--,
--OCH.sub.2 --, --(CH.sub.2).sub.4 --, --O(CH.sub.2).sub.3 -- or
--(CH.sub.2).sub.3 O--;
R.sup.1 is hydrogen, halogen, cyano, nitro, alkyl with 1 to 12
carbon atoms, which is optionally substituted with fluorine and in
which optionally 1 or 2 non-adjacent --CH.sub.2 -- groups can be
replaced by oxygen or --COO-- and/or a --CH.sub.2 CH.sub.2 -- group
can be replaced by --CH.dbd.CH--;
n is 0 or 1;
X is hydrogen or alkyl with 1 to 6 carbon atoms, which is
optionally substituted with halogen;
Y is hydrogen, cyano, --COO-alkyl, alkyl with 1 to 6 carbon atoms,
which is optionally substituted with fluorine; and
S.sub.a, S.sub.b are spacer units;
with the proviso that in formula II-A simultaneously n does not
signify 0, A.sup.1 does not signify phenyl, R.sup.1 does not
signify hydrogen or methoxy, X and Y do not signify hydrogen and
S.sub.a or S.sub.b does not signify a single bond.
4. A polymer according to claim 1, wherein the
isomerization/dimerization units Z.sub.a and Z.sub.b each
independently are of formula ##STR12## wherein R.sup.1 is hydrogen,
halogen, cyano, nitro, alkyl or alkoxy with 1 to 6 carbon atoms,
with the proviso that in formula IIa simultaneously R.sup.1 does
not signify hydrogen or methoxy and S.sub.a or S.sub.b does not
signify a single bond.
5. A polymer according to claim 1 selected from the group
consisting of:
poly(methacryloyloxyethyl-3-(E)-[4-cyano-4'-biphenyl]acrylate;
poly(methacryloyloxyethyl-3(E)-[4-cyanophenyl]acrylate;
poly(methacryloyloxyethyl-3(E)-[4-chlorophenyl]acrylate);
poly(methacryloyloxyethyl-3(E)-[4-methoxyphenyl]acrylate);
poly(methacryloyloxyethyl-3(E)-[4-nitrophenyl]acrylate);
poly(3-methacryloylaminopropyl-(E)-3-[4-cyano-phenyl]acrylamide)
poly[1-[1-[(E)-3-(4-methoxy-phenyl)-acryloyl]piperidine-4-yloxycarbonyl]-1-
methyl-ethylen]; and
poly(methacryloyloxyethyl-3-(E)-biphenylacrylate).
6. A polymer according to claim 5,
poly(methacryloyloxyethyl-3-(E)-[4-cyano-4'-biphenyl]acrylate.
.Iadd.
7. A polymer according to formula 1-A ##STR13## wherein M.sub.a is
a monomer unit for a homopolymer;
S.sub.a is an alkylene chain with 1 to 10 carbon atoms, a
cycloalkylene group with 3 to 8 carbon atoms in which optionally
one or two methylene groups can be replaced by NH groups, or
phenylene which can be substituted with lower alkyl, lower alkoxy,
--CN, --NO.sub.2, halogen, carbonate, an ester group, an amide
group, an ether group or a combination of said groups;
Z.sub.a is of formula II ##STR14## wherein, ring A.sup.1
1,4-phenylene, which is unsubstituted or substituted with at least
one of halogen, cyano and nitro, or pyridine-2,5-yl,
pyrimidine-2-5-yl, 2,5-thiophenediyl, 2,5-furanylene, 1,4- or
2,6-napthylene, in which a CH group can be replaced by
nitrogen;
ring A,A.sup.2 each individually are 1,4-phenylene, which is
unsubstituted or substituted with at least one of halogen, cyano
and nitro, pyridine-2-5-yl, pyrimidine-2,5-yl, or
2,5-thiophenediyl, 2,5-furanylene, trans-1,4-cyclohexylene,
trans-1,3-dioxane-2,5-diyl or 1,4-piperidyl;
A.sup.3 is --COO--, --CONH--, --CO--E--, 1,4-phenylene, which is
unsubstituted or substituted with at least one of halogen, cyano
and nitro, or pyridine-2,5-yl pyrimidine-2,5-yl, 2,5-thiophenediyl,
2,5-furanylene, 1,4- or 2,6-naphthylene, in which a CH group can be
replaced by nitrogen;
E is 1,4-phenylene, which is unsubstituted or substituted with at
least one of halogen, cyano and nitro, or pyridine-2,5-yl,
pyrimidine-2,5-yl, 2,5-thiophenediyl, 2,5-furanylene, 1,4- or
2,6-naphthylene, in which a CH group can be replaced by
nitrogen;
Z,Z.sup.1 each independently are a single covalent bond, --CH.sub.2
CH.sub.2 --, --COO--, --OOC--, --OCH.sub.2 --, --CH.sub.2 O--,
--C.tbd.C--, --(CH.sub.2).sub.4 --, --O(CH.sub.2).sub.3 --,
--(CH.sub.2).sub.3 O-- or the trans form of --OCH.sub.2
CH.dbd.CH--, --CH.dbd.CHCH.sub.2 O--, --(CH.sub.2).sub.2
CH.dbd.CH-- or --CH.dbd.CH(CH.sub.2).sub.2 --;
R.sup.1 is hydrogen, halogen, cyano, nitro, NCS, alkyl with 1 to 12
carbon atoms, which is optionally substituted with fluorine and in
which optionally 1 or 2 non-adjacent --CH.sub.2 -- groups can be
replaced by oxygen, --COO--, --OOC--, --CO-- and/or a --CH.sub.2
CH.sub.2 -- group can be replaced by --CH.dbd.CH--;
n,p each independently are 0 or 1;
X,Y each independently are hydrogen, halogen cyano, alkyl with 1 to
12 carbon atoms which is optionally substituted with fluorine and
in which optionally 1 or 2 non-adjacent --CH.sub.2 -- groups can be
replaced by oxygen, --COO--, --OOC--, --CO-- and/or
--CH.dbd.CH--,
with the proviso that A.sup.3 is different from --COO--, when
simultaneously n and p each are 0, A.sup.1 is phenyl, R.sup.1 is
hydrogen or methoxy and S.sub.a is a single bond;
n' is from 4-100 000. .Iaddend..Iadd.8. A polymer of the formula of
formula I ##STR15## wherein M.sub.a, M.sub.b, M.sub.c are monomer
units for homo- or copolymers;
x, y, z are mole fractions of the copolymers, whereby in each case
O<x.ltoreq.1; 0.ltoreq.y.ltoreq.1 and 0.ltoreq.z<1;
S.sub.a, S.sub.b are independently of one another, an alkylene
chain with 1 to 10 carbon atoms, a cycloalkylene group with 3 to 8
carbon atoms in which optionally one or two methylene groups can be
replaced by NH groups, or phenylene which can be substituted with
lower alkyl, lower alkoxy, --CN, --NO.sub.2 halogen, carbonate, an
ester group, an amide group, an ether group or a combination of
said groups;
Z.sub.a, Z.sub.b each independently are of formula II-A, ##STR16##
II-B, or ##STR17## II-C ##STR18## wherein ring A.sup.1 is
1,4-phenylene, which is unsubstituted or substituted with halogen,
cyano and/or nitro, or pyrimidine-2,5-diyl, pyridine-2,5-diyl,
2,5-thiophenediyl 2,5-furanylene, 1,4-naphthylene or
2,6-naphthylene;
ring A.sup.2 is 1,4-phenylene, which is unsubstituted or
substituted with halogen, cyano and/or nitro, or
pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenediyl,
2,5-furanylene, trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl
or 1,4-piperidyl;
ring A.sup.4 is 1,4-phenylene, which is unsubstituted or
substituted with halogen, cyano and/or nitro;
Z.sup.1 is a single covalent bond, --CH.sub.2 CH.sub.2 --, --COO--,
--OCH.sub.2 --, --(CH.sub.2).sub.4 --, --O(CH.sub.2).sub.3 -- or
--(CH.sub.2).sub.3 O--;
R.sup.1 is hydrogen, halogen, cyano, nitro, alkyl with 1 to 12
carbon atoms, which is optionally substituted with fluorine and in
which optionally 1 or 2 non-adjacent --CH.sub.2 -- groups can be
replaced by oxygen or --COO-- and/or a --CH.sub.2 CH.sub.2 -- group
can be replaced by --CH.dbd.CH--;
n is 0 or 1;
X is hydrogen or alkyl with 1 to 6 carbon atoms which is optionally
substituted with halogen;
Y is hydrogen, cyano, --COO-alkyl, alkyl with 1 to 6 carbon atoms,
which is optionally substituted with fluorine; and
with the proviso that in formula II-A simultaneously n does not
signify 0, A.sup.1 does not signify phenyl, R.sup.1 does not
signify hydrogen or methoxy, X and Y do not signify hydrogen and
S.sub.a or S.sub.b does not signify a single bond;
n' is from 4-100 000; and
m is 0 or 1. .Iaddend.
Description
FIELD OF THE INVENTION
The invention is concerned with novel linear and cyclic polymers or
oligomers having a photoreactive ethene group for use as
orientating layers for liquid crystals.
BACKGROUND OF THE ART
The alignment of liquid crystal phases in cells can be brought
about in various ways and is usually effected by rubbing a glass
plate coated with a polymer layer or by the inclined vapour
deposition of a SiO.sub.x layer on a glass plate. Generally
uniformly aligned layers are produced in this manner.
It is, however, also possible to obtain a structured orientation of
the liquid crystal phase. This can be achieved, for example, by
coating a glass plate with a polymer with which are admixed, for
example, photochemically orientatable dyestuff molecules or
photochemically dimerizable molecules, as described, for example,
in EP-A-0445629. These methods are, however, not optimal, since on
the one hand the solubility of such orientatable molecules in the
polymer is limited and on the other hand the stability with time
can not be guaranteed to a sufficient extent. A further possibility
for the production of photochemically orientatable polymer layers
is described, for example, in Jpn. J. Appl. Phys. Vol. 31 (1992),
2155 and comprises esterifying the free hydroxy groups on the
polymer with dimerizable units. A disadvantage of this method is,
however, the fact that the esterification of the free hydroxy
groups on the polymer with photochemically dimerizable units
usually leads to a non-reproducible and, above all, to an
incomplete conversion. The free hydroxy groups still present in the
orientating layer lead to an undesired ion solubility.
There is therefore a need to find an orientating layer which no
longer has the aforementioned disadvantages.
SUMMARY OF THE INVENTION
The present invention is directed to a polymer of formula I
##STR2## wherein M.sub.a, M.sub.b, M.sub.c are monomer units for
homo- or copolymers;
x, y, z are mole fractions of the copolymers, whereby in each case
0<x.ltoreq.1; 0.ltoreq.y.ltoreq.1 and 0.ltoreq.z<1;
S.sub.a, S.sub.b are spacer units;
Z.sub.a, Z.sub.b are molecule units which can undergo photochemical
isomerization/dimerization;
n is from 4-100 000 and
m is 0 or 1.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to a polymer having
isomerization/dimerization units of the general formula: ##STR3##
wherein M.sub.a, M.sub.b, M.sub.c signify monomer units for homo-
or copolymers;
x, y, z indicate mole fractions of the copolymers, whereby in each
case 0<x.ltoreq.1; 0.ltoreq.y.ltoreq.1 and 0.ltoreq.z<1;
S.sub.a, S.sub.b represent spacer units;
Z.sub.a, Z.sub.b represent molecule units which can undergo
photochemical isomerization/dimerization;
n is a magnitude of 4-100 000 and
m is 0 or 1.
The monomer units M.sub.a, M.sub.b and M.sub.c set forth in formula
I are units for the formation of homopolymers or copolymers and
have, in the is scope of the present invention, the structures
which are usual in polymer chemistry. Such monomer units are, for
example, acrylate, methacrylate, 2-chloroacrylate,
2-phenylacrylate, acryloylphenylene, acrylamide, methacrylamide,
2-choroacrylamide, 2-phenylacrylamide, vinyl ether, styrene
derivatives, vinyl ester, maleic acid derivatives, fumaric acid
derivatives, siloxanes, epoxides and the like. Acrylate,
methacrylate, 2-chloroacrylate, acrylamide, methacrylamide,
2-chloroacrylamide, styrene derivatives, siloxanes and the like are
preferred monomer units.
Under the term "copolymers" there are to be understood not only
statistical copolymers but also alternating copolymers, for example
alternating copolymers from maleic acid derivatives with styrene.
Statistical copolymers are preferably used. Homopolymers embrace
linear and cyclic polymers such as, for example, cyclic
polysiloxane.
Polymers in which z=0, but especially homopolymers of formula 1-A:
##STR4## are especially preferred.
The spacer units Sa and, respectively, S.sub.b join the
isomerization/dimerization unit (Z.sub.a and, respectively,
Z.sub.b) with the monomer unit (M.sub.a and, respectively,
M.sub.b). Such spacer units are known per se. In the present
instance the term "spacer units" S.sub.a and S.sub.b signifies, for
example, independently of one another, an alkylene chain with 1 to
10, preferably with 1 to 4, carbon atoms, a cycloalkylene group
with 3 to 8 carbon atoms, preferably with 5 or 6 carbon atoms, in
which optionally one or two methylene groups can be replaced by NH
groups, or phenylene, which can be substituted with lower alkyl,
lower alkoxy, --CN, --NO.sub.2, but especially with halogen, or
carbonate, an ester group, an amide group, an ether group and the
like or a combination of the said groups.
Methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene,
1,2-propylene, 1,3-butylene, cyclopentane-1,2-diyl,
cyclopentane-1,3-diyl, cyclohexane-1,3-diyl, cyclohexane-1,4-diyl,
piperidine-1,4-diyl, piperazine-1,4-diyl, 1,2-phenylene,
1,3-phenylene, 1,4-phenylene, ethyleneoxy, ethyleneoxycarbonyl,
ethylenecarboxyl, CONH-- and --CONR' in which R' signifies lower
alkyl are examples of preferred spacer units (S.sub.a and
S.sub.b).
The isomerization/dimerization units Z.sub.a and Z.sub.b are
molecule units which can undergo either photochemical
cis/trans-isomerization and photochemical [2+2] cycloaddition and
thus lead to a cross-linking of the polymer or oligomer. The
isomerization/dimerization units Z.sub.a and Z.sub.b are, as
already mentioned, linked via the spacer S.sub.a to the monomer
unit M.sub.a, or via a spacer S.sub.b to the monomer unit M.sub.b
and each independently have the general formula ##STR5## In formula
II, ring A.sup.1 signifies 1,4-phenylene, which is unsubstituted or
substituted with halogen, cyano and/or nitro and in which 1 or 2 CH
groups can be replaced by nitrogen, or 2,5-thiophenediyl,
2,5-furanylene, 1,4- or 2,6-naphthylene, in which a CH group can be
replaced by nitrogen;
ring A,A.sup.2 each individually signify 1,4-phenylene, which is
unsubstituted or substituted with halogen, cyano and/or nitro and
in which 1 or 2 CH groups can be replaced by nitrogen, or
2,5-thiophenediyl, 2,5-furanylene, trans-1,4-cyclohexylene,
trans-1,3-dioxane-2,5-diyl or 1,4-piperidyl;
A.sup.3 signifies --COO--, --CONH--, --CO--E--, 1,4-phenylene,
which is unsubstituted or substituted with halogen, cyano and/or
nitro and in which 1 or 2 CH groups can be replaced by nitrogen, or
2,5-thiophenediyl, 2,5-furanylene, 1,4- or 2,6-naphthylene, in
which a CH group can be replaced by nitrogen;
E signifies 1,4-phenylene, which is unsubstituted or substituted
with halogen, cyano and/or nitro and in which 1 or 2 CH groups can
be replaced by nitrogen, or 2,5-thiophenediyl, 2,5-furanylene, 1,4-
or 2,6-naphthylene, in which a CH group can be replaced by
nitrogen;
Z,Z.sup.1 each independently signify a single covalent bond,
--CH.sub.2 CH.sub.2 --, --COO--, --OOC--, --OCH.sub.2 --,
--CH.sub.2 O--, --C.tbd.C--, --(CH.sub.2).sub.4 --,
--O(CH.sub.2).sub.3 --, --(CH.sub.2).sub.3 O-- or the trans form of
--OCH.sub.2 CH.dbd.CH--, --CH.dbd.CHCH.sub.2 O--,
--(CH.sub.2).sub.2 CH.dbd.CH-- or --CH.dbd.CH(CH.sub.2).sub.2
--;
R.sup.1 signifies hydrogen, halogen, cyano, nitro, NCS, alkyl with
1 to 12 carbon atoms, which is optionally substituted with fluorine
and in which optionally 1 or 2 non-adjacent --CH.sub.2 -- groups
can be replaced by oxygen, --COO--, --OOC--, --CO-- and/or a
--CH.sub.2 CH.sub.2 -- group can be replaced by --CH.dbd.CH--;
n,p each independently signify 0 or 1;
X,Y each independently signify hydrogen, halogen cyano, alkyl with
1 to 12 carbon atoms which is optionally substituted with fluorine
and in which optionally 1 or 2 non-adjacent --CH.sub.2 -- groups
can be replaced by oxygen, --COO--, --OOC--, --CO-- and/or
--CH.dbd.CH--; and
S.sub.a, S.sub.b, signify spacer units;
with the proviso that A.sup.3 is different from --COO--, when n and
p each are 0, A.sup.1 signifies phenyl, R.sup.1 signifies hydrogen
or methoxy and S.sub.a and, respectively, S.sub.b signify a single
bond.
The ethene groups of the isomerization/dimerization units of
formula II which are not or only to a small extent incorporated
into the polymer under the polymerization conditions, can be
selectively aligned, after the application of the polymer layer to
a carrier, by irradiation with linear polarized light. This takes
place either by isomerization of the ethene group, by dimerization
of the ethene group or by simultaneous isomerization and
dimerization of these ethene groups. Very specific surface regions
can be aligned by the selective irradiation of the molecule units
of formula II and these regions are also simultaneously stabilized
by the dimerization. The term "1,4-phenylene, which is
unsubstituted or substituted with halogen, cyano and/or nitro and
in which 1 or 2 CH groups can be replaced by nitrogen" includes
1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene,
2,6-difluoro-1,4-phenylene, 2-chloro-1,4-phenylene,
2,3-dichloro-1,4-phenylene, 2,6-dichloro-1,4-phenylene,
2-cyano-1,4-phenylene, 2,3-dicyano-1,4-phenylene,
2-nitro-1,4-phenylene, 2,3-dinitro-1,4-phenylene,
2-bromo-1,4-phenylene, 2-methyl-1,4-phenylene, as well as
pyridine-2,5-diyl, pyrimidine-2,5-diyl and the like. 1,4-Phenylone,
2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene,
2,6-difluoro-1,4-phenylene, pyridine-2,5-diyl or pyrimidin-2,5-diyl
are especially preferred.
The term "1,4- or 2,6-naphthylene, in which a CH group can be
replaced by nitrogen" includes 1,4-naphthylene, 2,6-naphthylene,
1-benzazine-2,6-diyl and 2-benzazine-1,4-diyl.
The term "alkyl with 1 to 12 carbon atoms, which is optionally
substituted with fluorine and in which optionally 1 or 2
non-adjacent --CH.sub.2 -- groups can be replaced by oxygen,
--COO--, --OOC--, --CO-- and/or a --CH.sub.2 CH.sub.2 -- group can
be replaced by --CH.dbd.CH--" includes straight-chain and branched
(optionally chiral) residues such as alkyl, alkenyl, alkoxy,
alkenyloxy alkoxyalkyl, alkenyloxyalkyl, alkoxyalkenyl,
1-fluoroalkyl, 1,1-difluoroalkyl, 2-fluoroalkyl, 2-fluoroalkoxy,
terminal fluoroalkyl, terminal difluoromethylalkyl, terminal
trifluoromethylalkyl, terminal trifluoromethylalkoxy, and the like
with 1 or, respectively, 2 to 12 carbon atoms. Examples of
preferred residues are methyl, ethyl, propyl, butyl, pentyl, hexyl,
heptyl, octyl, 1-methylpropyl, 1-methylheptyl, 2-methylbutyl,
3-methylpentyl, vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl,
1E-hexenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 4-pentenyl,
4Z-hexenyl, 5-hexenyl, 6-heptenyl, 7-octenyl, methoxy, ethoxy,
propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy, octyloxy,
1-methylpropyloxy, 1-methylheptyloxy, 2-methylbutyloxy, allyloxy,
2E-butenyloxy, 2E-pentenyloxy, 3-butenyloxy, 3Z-pentenyloxy,
4-pentenyloxy, 5-hexenyloxy, 6-heptenyloxy, 7-octenyloxy,
2-methoxyethyl, 3-methoxypropyl, 3-methoxy-1E-propenyl,
1-fluoropropyl, 1-fluoropentyl, 2-fluoropropyl, 2,2-difluoropropyl,
3-fluoropropyl, 3,3-difluoropropyl, 3,3,3-trifluoropropyl,
2-fluoropropyloxy, 3-fluoropropyloxy, 2,2-difluorovinyl,
2-(3,3-difluoro)propenyl and the like. Especially preferred
residues have 1 or, respectively, 2 to 6 carbon atoms.
The term "halogen" includes fluorine, chlorine, bromine and iodine,
but especially fluorine and chlorine.
Preferred isomerization/dimerization units of formula II are
##STR6## in which formulae II-A, II-B and II-C ring A.sup.1
signifies 1,4-phenylene, which is unsubstituted or substituted with
halogen, cyano and/or nitro, or pyrimidine-2,5-diyl,
pyridine-2,5-diyl, 2,5-thiophenediyl, 2,5-furanylene,
1,4-naphthylene or 2,6-naphthylene;
ring A.sup.2 signifies 1,4-phenylene, which is unsubstituted or
substituted with halogen, cyano and/or nitro, or
pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenediyl,
2,5-furanylene, trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl
or 1,4-piperidyl;
ring A.sup.4 signifies 1,4-phenylene, which is unsubstituted or
substituted with halogen, cyano and/or nitro;
Z.sup.1 signifies a single covalent bond, --CH.sub.2 CH.sub.2 --,
--COO--, --OCH.sub.2 --, --(CH.sub.2).sub.4 --, --O(CH.sub.2).sub.3
-- or --(CH.sub.2).sub.3 O--;
R.sup.1 signifies hydrogen, halogen, cyano, nitro, alkyl with 1 to
12 carbon atoms, which is optionally substituted with fluorine and
in which optionally 1 or 2 non-adjacent --CH.sub.2 -- groups can be
replaced by oxygen or --COO-- and/or a --CH.sub.2 CH.sub.2 -- group
can be replaced by --CH.dbd.CH--;
n signifies 0 or 1;
X signifies hydrogen or alkyl with 1 to 6 carbon atoms, which is
optionally substituted with halogen;
Y signifies hydrogen, cyano, --COO-alkyl, alkyl with 1 to 6 carbon
atoms, which is optionally substituted with fluorine; and
S.sub.a, S.sub.b signify spacer units;
with the proviso that in formula II-A simultaneously n does not
signify 0, A.sup.1 does not signify phenyl, R.sup.1 does not
signify hydrogen or methoxy, X and Y do not signify hydrogen and
S.sub.a or S.sub.b does not signify a single bond.
Preferred compounds of formula II-A to II-C are those in which X
signifies hydrogen and Y signifies hydrogen, cyano or alkyl with 1
to 6 carbon atoms, which is optionally substituted with fluorine;
those in which X and Y represent hydrogen are, however, especially
preferred.
Particularly preferred isomerization/dimerization units are those
of formula II-A such as, for example, ##STR7## wherein R.sup.1
signifies hydrogen, halogen, cyano, nitro, alkyl or alkoxy with 1
to 6 carbon atoms, with the proviso that in formula IIa
simultaneously R.sup.1 does not signify hydrogen or methoxy and
S.sub.a or S.sub.b does not signify a single bond.
The polymers of formula I are readily accessible. The monomers are
firstly synthesized from the individual components, that is from
the isomerization/dimerization unit of formula II, the spacers
(S.sub.a, S.sub.b) and the polymerizable parts (M.sub.a, M.sub.b or
M.sub.c). The formation of the polymer is subsequently effected in
a manner known per se. The polymerization can be effected, for
example, in the melt or in solution with the exclusion of oxygen
and in the presence of a radical initiator which can generate
radicals thermally, photochemically or by a redox reaction. The
reaction can be effected in a temperature range of -10.degree. C.
to 120.degree. C., preferably in a range of 20.degree. C. to
100.degree. C.
For the production of polymer layers in regions selectively limited
by area, a solution of the polymer material obtained can, for
example, firstly be prepared and then spread out in a spin-coating
apparatus on a carrier coated with an electrode (for example, a
glass plate coated with indium-tin oxide) (ITC) such that
homogeneous layers of 0.05-50 .mu.m thickness result.
Simultaneously, irradiation can be applied to the region to be
isomerized and dimerized (to be crosslinked), for example with a
mercury high-pressure lamp, a xenon lamp or a pulsed UV laser using
a polarizer and optionally a mask for the formation of structures.
The duration of irradiation depends on the capacity of the
individual lamps and can vary from a few minutes to several hours.
The cross-linkage can, however, also be effected by irradiating the
homogeneous layer using filters which for example let through only
radiation suitable for the cross-linkage reaction.
The polymers in accordance with the invention are illustrated in
more detail by the following Examples. In the following Examples Tg
signifies the glass temperature, .DELTA.c.sub.p signifies the
change in the specific heat capacity at constant pressure, .DELTA.H
signifies the transition enthalpy, log I.sub.o /I signifies the
extinction, .epsilon. signifies the molar decadic absorption
coefficients, C signifies a crystalline phase, S signifies a
smectic phase, N signifies a nematic phase and I signifies the
isotropic phase.
EXAMPLE 1
1 g of methacryloyloxyethyl 3-(E)-[4-pentyl-4'-biphenyl]acrylate
and 0.002 g of azobisisobutyronitrile were dissolved in 4 ml of
tetrahydrofuran. The solution was flushed for 10 minutes with a
weak nitrogen stream and the reaction vessel was subsequently
closed air-tight. The solution was heated to 60.degree. C. for 24
hours. Thereafter, the reaction vessel was opened and the solution
was diluted with 5 ml of tetrahydrofuran while stirring.
Subsequently, the diluted solution was added dropwise to 450 ml of
diethyl ether while stirring at room temperature. The separated
polymer was filtered off, dried, dissolved in 30 ml of
dichlormethane and this solution was added dropwise to 450 ml of
diethyl ether. This procedure was repeated twice. Filtration and
drying at 50.degree. C. in a vacuum gave 0.4 g of
poly(methacryloyloxyethyl 3-(E)-[4-pentyl-4'-biphenyl]acrylate),
Tg. 123.degree. C., cl.p. (S-I) 160.degree. C.;
The methacryloyloxyethyl 3-(E)-[4-pentyl-4'-biphenyl]acrylate used
as the starting material was prepared as follows:
(a). A solution of 10 g of 4-pentyl-4'-cyanobiphenyl in 150 ml of
toluene was treated dropwise at 0.degree. C. with 65 ml of a 1M
solution of diisobutylaluminium hydride in toluene while gassing
with nitrogen. The reaction mixture was stirred at room temperature
overnight, then treated dropwise with 340 ml of 1N sulphuric acid,
stirred at room temperature for 1 hour, poured into 1,000 ml of
water and then extracted three times with 100 ml of ethyl acetate
each time. The combined organic phases were washed twice with 50 ml
of saturated sodium chloride solution each time, dried over
magnesium sulphate, filtered and subsequently concentrated.
Chromatographic purification of the residue on silica gel with
hexane/ethyl acetate (vol. 9:1) gave 10.1 g of
4-pentyl-4'-biphenylcarboxaldehyde.
(b). A mixture of 11.9 g of phosphonoacetic acid
P,P-diethyltrimethylsilyl ester in 370 ml of absolute
tetrahydrofuran was placed at 0.degree. C. while gassing with
nitrogen and then treated dropwise with 27.7 ml of a 1.6M solution
of butyllithium in hexane. The reaction mixture was stirred at room
temperature for 2 hours, then treated with a solution of 10.1 g of
4-pentyl-4'-biphenylcarboxaldehyde and 15 ml of absolute
tetrahydrofuran, stirred at room temperature for a further 1.5
hours, poured into 100 ml of water and then extracted three times
with 50 ml of ethyl acetate each time. The combined organic phases
were washed twice with 50 ml of saturated sodium chloride solution
each time, dried over magnesium sulphate, filtered and subsequently
concentrated. Two-fold recrystallization of the crude product from
ethyl alcohol gave 17.0 g of 3-(E)-[4-pentyl-4'-biphenyl]acrylic
acid, m.p. (C-N) 209.degree. C. and cl.p. (N-I) 284.degree. C.
(decompositon).
(c). 9.4 g of N,N'-dicyclohexylcarbodiimide were added at 0.degree.
C. within 15 minutes while stirring to a solution of 2-hydroxyethyl
methacrylate, 11.6 g of 3-(E)-[4-pentyl-4'-biphenyl]acrylic acid
and 1.21 g of 4-(dimethylamino)pyridine in 300 ml of
tetrahydrofuran. The reaction mixture was stirred at room
temperature overnight, then filtered, the filtrate was poured into
water and extracted three times with 50 ml of ethyl acetate each
time. The combined organic phases were washed twice with 50 ml of
saturated sodium chloride solution each time, is dried over
magnesium sulphate, filtered and subsequently concentrated.
Chromatographic purification of the residue on silica gel with
hexane/ethyl acetate (vol. 9:1) and two-fold recrystallization from
ethyl alcohol of the fractions which were pure according to
thin-layer chromotography gave 4.5 g of methacryloyloxyethyl
3-(E)-[4-pentyl-4'-biphenyl]acrylate, m.p. 72.degree. C.
The following compounds can be prepared in an analogous manner:
Poly(methacryloyloxyethyl
3-(E)-[4-methyl-4'-biphenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[4-ethyl-4'-biphenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[4-propyl-4'-biphenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[4-butyl-4'-biphenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[4-hexyl-4'-biphenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[4-heptyl-4'-biphenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[4-octyl-4'-biphenyl]acrylate);
poly(methacryloyloxypropyl
3-(E)-[4-pentyl-4'-biphenyl]acrylate);
poly(methacryloyloxybutyl
3-(E)-[4-pentyl-4'-biphenyl]acrylate);
poly(methacryloyloxypentyl
3-(E)-[4-pentyl-4'-biphenyl]acrylate);
poly(methacryloyloxyhexyl
3-(E)-[4-pentyl-4'-biphenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[4-methyloxy-4'-biphenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[4-ethoxy-4'-biphenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[4-propyloxy-4'-biphenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[4-butyloxy-4'-biphenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[4-hexyloxy-4'-biphenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[4-heptyloxy-4'-biphenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[4-octyloxy-4'-biphenyl]acrylate),
Tg. 106.degree. C., (S-I) 170.degree. C.;
poly(methacryloyloxypropyl
3-(E)-[4-octyloxy-4'-biphenyl]acrylate);
poly(methacryloyloxybutyl
3-(E)-[4-octyloxy-4'-biphenyl]acrylate);
poly(methacryloyloxypentyl
3-(E)-[4-octyloxy-4'-biphenyl]acrylate);
poly(methacryloyloxyhexyl
3-(E)-[4-octyloxy4'-biphenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[4-cyano-4'-biphenyl]acrylate), Tg.
134.degree. C.;
poly(methacryloyloxypropyl
3-(E)-[4-cyano-4'-biphenyl]acrylate);
poly(methacryloyloxybutyl 3-(E)-[4-cyano-4'-biphenyl]acrylate);
poly(acryloyloxybutyl
3-(E)-[4-[(R)-2-octyloxy]-4'-biphenyl]acrylate);
poly(methacryloyloxypentyl
3-(E)-[4-cyano-4'-biphenyl]acrylate);
poly(methacryloyloxyhexyl 3-(E)-[4-cyano-4'-biphenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[4-(trans-4-methylcyclohexyl)phenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[4-(trans-4-ethylcyclohexyl)phenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[4-(trans-4-propylcyclohexyl)phenyl]acrylate), Tg.
88.degree.;C.
poly(methacryloyloxyethyl
3-(E)-[4-(trans-4-butylcyclohexyl)phenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[4-(trans-4-pentylcyclohexyl)phenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[4-(trans-4-hexylcyclohexyl)phenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[4-(trans-4-heptylcyclohexyl)phenyl]acrylate);
poly(methacryloyloxypropyl
3-(E)-[4-(trans-4-pentylcyclohexyl)phenyl]acrylate);
poly(methacryloyloxybutyl
3-(E)-[4-(trans-4-pentylcyclohexyl)phenyl]acrylate);
poly(methacryloyloxypentyl
3-(E)-[4-(trans-4-pentylcyclohexyl)phenyl]acrylate);
poly(methacryloyloxyhexyl
3-(E)-[4-(trans-4-pentylcyclohexyl)phenyl]acrylate).
poly(methacryloyloxyethyl 3-(E)-biphenylacrylate), T.sub.g
=98.degree. C.;
poly(methacryloyloxypropyl 3-(E)-biphenylacrylate);
poly(methacryloyloxyethyl 3-(E)-phenylacrylate), T.sub.g
=60.degree. C.;
poly(methacryloyloxyethyl 3-(E)-[4-methylphenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[4-ethylphenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[4-methoxyphenyl]acrylate), T.sub.g
=69 .degree. C.;
poly(methacryloyloxyethyl 3-(E)-[4-ethoxyphenyl]acrylate);
poly(methacryloyloxypropyl 3-(E)-[4-methylphenyl]acrylate);
poly(methacryloyloxypropyl 3-(E)-[4-ethylphenyl]acrylate);
poly(methacryloyloxypropyl 3-(E)-[4-methoxyphenyl]acrylate);
poly(methacryloyloxypropyl 3-(E)-[4-ethoxyphenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[3-cyanophenyl]acrylate);
poly(methacryloyloxypropyl 3-(E)-[3-cyanophenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[4-cyanophenyl]acrylate), T.sub.g
=105.degree. C.;
poly(methacryloyloxypropyl 3-(E)-[4-cyanophenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[3-nitrophenyl]acrylate);
poly(methacryloyloxypropyl 3-(E)-[3-nitrophenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[4-nitrophenyl]acrylate), T.sub.g
=106.degree. C.;
poly(methacryloyloxypropyl 3-(E)-[4-nitrophenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[3-chlorophenyl]acrylate);
poly(methacryloyloxypropyl 3-(E)-[3-chlorophenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[4-chlorophenyl]acrylate), T.sub.g
=72.degree. C.;
poly(methacryloyloxypropyl 3-(E)-[4-chlorophenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[3-fluorophenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[4-fluorophenyl]acrylate);
poly(methacryloyloxypropyl 3-(E)-[4-fluorophenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[2,4-dimethylphenyl]acrylate);
poly(methacryloyloxypropyl 3-(E)-[2,4-dimethylphenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[2,3-dimethoxyphenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[2,4-dimethoxyphenyl]acrylate);
poly(methacryloyloxypropyl
3-(E)-[2,4-dimethoxyphenyl]acrylate);
poly (methacryloyloxyethyl
3-(E)-[3,4-dimethoxyphenyl]acrylate);
poly (methacryloyloxypropyl
3-(E)-[3,4-dimethoxyphenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[3,5-dimethoxyphenyl]acrylate);
poly(methacryloyloxypropyl
3-(E)-[3,5-dimethoxyphenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[3,4-dicyanophenyl]acrylate);
poly(methacryloyloxypropyl 3-(E)-[3,4-dicyanophenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[3,5-dicyanophenyl]acrylate);
poly(methacryloyloxypropyl 3-(E)-[3,5-dicyanophenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[2,4-dinitrophenyl]acrylate);
poly(methacryloyloxypropyl 3-(E)-[2,4-dinitrophenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[3,4-dichlorophenyl]acrylate);
poly(methacryloyloxypropyl 3-(E)-[3,4-dichlorophenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[3,5-dichlorophenyl]acrylate);
poly(methacryloyloxypropyl 3-(E)-[3,5-dichlorophenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[3,4-difluorophenyl]acrylate);
poly(methacryloyloxypropyl 3-(E)-[3,4-difluorophenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[3,5-difluorophenyl]acrylate);
poly(methacryloyloxypropyl 3-(E)-[3,5-difluorophenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[3-bromo-4-fluorophenyl]acrylate);
poly(methacryloyloxypropyl
3-(E)-[3-bromo-4-fluorophenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[5-bromo-2-methoxyphenyl]acrylate);
poly(methacryloyloxyethyl 3-(E)-[4-chloro
3-nitrophenyl]acrylate);
poly(methacryloyloxypropyl 3-(E)-[4-chloro
3-nitrophenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[2-chloro-4-fluorophenyl]acrylate);
poly(methacryloyloxypropyl
3-(E)-[2-chloro-4-fluorophenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[3-chloro-4-fluorophenyl]acrylate);
poly(methacryloyloxypropyl
3-(E)-[3-chloro-4-fluorophenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[3-fluoro-2-methylphenyl]acrylate);
poly(methacryloyloxypropyl
3-(E)-[3-fluoro-2-methylphenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[4-trifluoromethylphenyl]acrylate);
poly(methacryloyloxypropyl
3-(E)-[4-trifluoromethylphenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[4-trifluoromethoxyphenyl]acrylate);
poly(methacryloyloxypropyl
3-(E)-[4-trifluoromethoxyphenyl]acrylate);
poly(acryloyloxyethyl 3-(E)-biphenylacrylate);
poly(2-chloroacryloyloxyethyl 3-(E)-[4-methylphenyl]acrylate);
poly(acryloyloxyethyl 3-(E)-[4-methoxyphenyl]acrylate);
poly(acryloyloxypropyl 3-(E)-[4-ethoxyphenyl]acrylate);
poly(acryloyloxyethyl 3-(E)-[3-cyanophenyl]acrylate);
poly(acryloyloxypropyl 3-(E)-[4-cyanophenyl]acrylate);
poly(2-chloroacryloyloxyethyl 3-(E)-[3-nitrophenyl]acrylate);
poly(acryloyloxyethyl 3-(E)-[4-nitrophenyl]acrylate);
poly(acryloyloxybutyl 3-(E)-[3-chlorophenyl]acrylate);
poly(acryloyloxyethyl 3-(E)-[4-chlorophenyl]acrylate);
poly(acryloyloxyethyl 3-(E)-[3-fluorophenyl]acrylate);
poly(2-chloroacryloyloxypentyl 3-(E)-[4-fluorophenyl]acrylate);
poly(acryloyloxyethyl 3-(E)-[2,4-dimethylphenyl]acrylate);
poly(acryloyloxyethyl 3-(E)-[3,4-dimethoxyphenyl]acrylate);
poly(acryloyloxyethyl 3-(E)-[3,5-dimethoxyphenyl]acrylate);
poly(2-chloroacryloyloxypropyl
3-(E)-[3,4-dicyanophenyl]acrylate);
poly(acryloyloxyethyl 3-(E)-[3,5-dicyanophenyl]acrylate);
poly(acryloyloxybutyl 3-(E)-[2,4-dinitrophenyl]acrylate);
poly(acryloyloxypentyl 3-(E)-[3,4-dichlorophenyl]acrylate);
poly(acryloyloxyethyl 3-(E)-[3,5-dichlorophenyl]acrylate);
poly(acryloyloxyethyl 3-(E)-[3,4-difluorophenyl]acrylate);
poly(acryloyloxypropyl 3-(E)-[3,5-difluorophenyl]acrylate);
poly(acryloyloxyethyl 3-(E)-[4-chloro 3-nitro-phenyl]acrylate);
poly(2-chloroacryloyloxypropyl
3-(E)-[2-chloro-4-fluorophenyl]acrylate);
poly(acryloyloxyethyl
3-(E)-[3-chloro-4-fluoro-phenyl]acrylate);
poly(acryloyloxyhexyl
3-(E)-[3-fluoro-2-methyl-phenyl]acrylate);
poly(acryloyloxyethyl 3-(E)-[4-trifluoromethylphenyl]acrylate);
poly(acryloyloxyethyl
3-(E)-[4-trifluoromethoxyphenyl]acrylate).
EXAMPLE 2
1.5 g of 4-methacryloyloxybutyl (E)-3-[4-(4-methoxyphenyl
carbonyloxy)phenyl]acrylate and 0.003 g of azobisisobutyronitrile
were dissolved in 6.8 ml of tetrahydrofuran. The solution was
flushed for 10 minutes with a weak argon stream and subsequently
the reaction vessel was closed air-tight. The solution was heated
to 60.degree. C. for 20 hours. Thereafter, the reaction vessel was
opened and the solution was diluted with 3.5 ml of tetrahydrofuran
while stirring. Subsequently, the diluted solution was added
dropwise to 300 ml of diethyl ether at room temperature while
stirring. The separated polymer was filtered off, dried, dissolved
in 10 ml of dichlormethane and this solution was added dropwise to
300 ml of diethyl ether. This procedure was repeated twice.
Filtration and drying at 50.degree. C. in a vacuum gave 1.15 g of
poly(4-methacryloyloxybutyl
(E)-3-[4-(4-methoxyphenylcarbonyloxy)phenyl]acrylate). The polymer
has a glass stage at Tg=38.degree. C. (.DELTA.c.sub.p =0.17 J/gK)
and a clearing point (S.sub.A -I) at 202.degree. C. (.DELTA.H=6.9
J/g).
The 4-methacryloyloxybutyl
(E)-3-[4-(4-methoxyphenylcarbonyloxy)phenyl]acrylate used as the
starting material was prepared as follows:
a) 5 g of (E)-4-hydroxycinnamic acid were dissolved in a solution
of 2.8 g of potassium hydroxide in 25 ml of water. Four 1 g
portions of ethyl chloroformate were added to the ice-cooled
solution and the mixture was stirred intensively for 10 minutes
after each addition. The reaction mixture was stirred at 0.degree.
C. for a further 30 minutes and subsequently neutralized with 2N
hydrochloric acid. The crude product was filtered off and
recrystallised twice from ethanol/water (vol. 8:2). This gave 5.7 g
of 4-(E)-ethyloxycarbonyloxycinnamic acid, m.p.
173.degree.-176.degree. C.
b) A solution of 5.2 g of 4-(E)-ethyloxycarbonyloxycinnamic acid in
20 ml of thionyl chloride and 0.05 ml of N,N-dimethylformamide was
heated under reflux for 3 hours. Subsequently, excess thionyl
chloride was distilled off. 3.3 g of 4-hydroxybutyl methacrylate
were added dropwise to a solution of the resulting
4-(E)-ethyloxycarbonyloxycinnamoyl chloride in 15 ml of pyridine
while stirring at 0.degree. C. within 15 minutes. The reaction
mixture was stirred at room temperature for a further 12 hours,
then poured into water and extracted three times with 50 ml of
ethyl acetate each time. The combined organic phases were dried
over magnesium sulphate, filtered and subsequently concentrated.
Chromatographic purification on silica gel with hexane/ethyl
acetate (vol. 7:3) gave 3 g of 4-methacryloyloxybutyl
(E)-3-(4-ethoxycarbonyloxyphenyl)acrylate, m.p.
54.degree.-56.degree. C.
c) 5 g of 4-methacryloyloxybutyl
(E)-3-(4-ethoxycarbonyloxyphenyl)acrylate were dissolved in 40 ml
of pyridine and treated at room temperature with a mixture of 60 ml
of acetone and 7 ml of 25% aqueous ammonia solution. The reaction
mixture was stirred at room temperature for 12 hours. After
distillation of the acetone the mixture was neutralized with 2N
hydrochloric acid, diluted with 100 ml of water and subsequently
extracted 3 times with 100 ml of diethyl ether each time. The
combined organic phases were dried over sodium sulphate, filtered
and concentrated. Chromatographic purification of the residue on
silica gel with hexane/ethyl acetate (vol. 7:3) gave
4-methacryloyloxybutyl (E)-3-(4-hydroxyphenyl)acrylate.
d) 2.0 g of 4-methoxybenzoyl chloride in 25 ml of dichlormethane
were added dropwise at 0.degree. C. while stirring within 30 min.
to a solution of 3.5 g of 4-methacryloyloxybutyl
(E)-3-(4-hydroxyphenyl)acrylate and 1.2 g of triethylamine in 40 ml
of dichloromethane. The reaction mixture was stirred at room
temperature overnight, then filtered and subsequently concentrated.
Chromatographic purification of the residue on silica gel with
hexane/ethyl acetate (vol. 7:3) and two-fold recrystallization from
ethanol gave 4.5 g of 4-methacryloyloxybutyl
(E)-3-[4-(4-methoxyphenylcarbonyloxy)phenyl]acrylate, m.p.
89.degree.-90.degree. C.
The following compounds can be prepared in analogous manner:
poly(methacryloyloxyethyl
3-(E)-[4-(4-methoxybenzoyloxy)phenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[4-(4-ethoxybenzoyloxy)phenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[4-(4-propoxybenzoyloxy)phenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[4-(4-butyloxybenzoyloxy)phenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[4-(4-pentyloxybenzoyloxy)phenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[4-(4-hexyloxybenzoyloxy)phenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[4-(4-heptyloxybenzoyloxy)phenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[4-(4-octyloxybenzoyloxy)phenyl]acrylate);
poly(methacryloyloxypropyl
3-(E)-[4-(4-methoxybenzoyloxy)phenyl]acrylate);
poly(methacryloyloxypentyl
3-(E)-[4-(4-methoxybenzoyloxy)phenyl]acrylate);
poly(methacryloyloxyhexyl
3-(E)-[4-(4-methoxybenzoyloxy)phenyl]acrylate);
poly(methacryloyloxyethyl
3-(E)-[4-(4-[(S)-2-methylbutyloxy]benzoyloxy)phenyl]acrylate);
poly(acryloyloxybutyl
3-(E)-[4-(4-methoxybenzoyloxy)phenyl]acrylate).
EXAMPLE 3
2.5 g of methacryloyloxyethyl (E)-3-(4-methoxyphenyl)-acrylate) and
2.5 g of 2-methacryloyloxyethyl (E)-3-(4-chlorophenyl)acrylate as
well as 0.014 g of azobisisobutyronitrile were dissolved in 35 ml
of tetrahydrofuran. The solution was flushed for 10 minutes with a
weak argon stream and the reaction vessel was subsequently closed
air-tight. The solution was heated to 60.degree. C. for 24 hours.
Thereafter, the reaction vessel was opened and the solution was
diluted with 7.5 ml of tetrahydrofuran while stirring.
Subsequently, the diluted solution was added dropwise to 500 ml of
diethyl ether while stirring at room temperature. The separated
polymer was filtered off, dried, dissolved in 40 ml of
dichloromethane and this solution was added dropwise to 500 ml of
diethyl ether. This procedure was repeated twice. Filtration and
drying at 50.degree. C. in a vacuum gave 3.8 g of
poly(2-methacryloyloxyethyl
(E)-3-(4-methoxyphenyl)acrylate-co-2-methacryloyloxyethyl
(E)-3-(4-chlorophenyl)acrylate). The polymer has a glass stage at
Tg=74.degree. C. .lambda..sub.max. (0.586 mg/100 ml CH.sub.2
Cl.sub.2): 227 nm, (log I.sub.o /I)=0.213), 287.8 nm, (log I.sub.o
/I=0.367).
The monomers used as the starting materials were prepared as
follows:
50 g of 4-(E)-chlorocinnamic acid, 33.9 g of
2-hydroxyethylmethacrylate and 0.3 g of 4-dimethylaminopyridine
were placed in 200 ml of tetrahydrofuran. A solution of 57.2 g of
dicyclohexylcarbodiimide in 100 ml of tetrahydrofuran was added
dropwise at room temperature within 120 minutes. The mixture was
stirred at room temperature for a further 28 hours. Subsequently,
the precipitated N,N'-dicyclohexylurea was filtered off and washed
with 100 ml of tetrahydrofuran. After distillation of the
tetrahydrofuran the residue was dissolved in 300 ml of
dichloromethane. The dichloromethane solution was washed with 200
ml of 5% acetic acid and subsequently three times with 250 ml of
water each time and dried over sodium sulphate. After removing the
solvent the residue was recrystallized from ethanol at -50.degree.
C. This gave 20.4 g of 2methacryloyloxyethyl
(E)-3-(4-chlorphenyl)acrylate as white crystals with a melting
point of 58.degree.-60.degree. C.
2-Methacryloyloxyethyl (E)-3-(4-methoxyphenyl)-acrylate with a
melting point of 35.degree.-36.degree. C. was prepared analogously
thereto.
The following polymers can be prepared in an analogous manner:
Poly(2-methacryloyloxyethyl
(E)-3-(4-methoxyphenyl)acrylate-co-2-methacryloyloxyethyl
(E)-3-(4-nitrophenyl)acrylate), T.sub.g =89.degree. C.;
poly(2-methacryloyloxyethyl
(E)-3-(4-cyanophenyl)acrylate-co-2-methacryloyloxyethyl
(E)-3-(4-methoxyphenyl)acrylate);
poly(2-methacryloyloxyethyl
(E)-3-(4-methoxyphenyl)acrylate-co-2-acryloyloxyethyl
(E)-3-(4-nitrophenyl)acrylate);
poly(2-methacryloyloxypropyl
(E)-3-(4-cyanophenyl)acrylate-co-2-methacryloyloxyhexyl
(E)-3-(4-cyanophenyl)acrylate);
poly(2-acryloyloxyethyl
(E)-3-(4-methoxyphenyl)acrylate-co-2-methacryloyloxyethyl
(E)-3-(4-nitrophenyl)acrylate);
poly(acryloyloxybutyl
(E)-3-(4-cyanophenyl)acrylate-co-2-methacryloyloxyethyl
(E)-3-(4-methoxyphenyl)-(Z)-3-methylacrylate);
poly(acryloyloxybutyl
(E)-3-(4-methoxyphenyl)-2-carboxyethyl-acrylate-co-acryloyloxybutyl
(Z)-3-(4-methoxyphenyl)-2-carboxyethyl-acrylate);
poly(styryl-4-carbonyloxyhexyl
(E)-3-(4-cyanophenyl)acrylate-co-styryl-4-carbonyloxyhexyl
(E)-3-(4-methoxyphenyl)acrylate);
poly(2-methacryloyloxyethyl
(E)-3-(4-cyanophenyl)acrylate-co-2-methacryloyloxyethyl
(E)-3-(4-methoxyphenyl)acrylate);
poly(2-chloroacryloyloxyethyl
(E)-3-(4-chlorophenyl)acrylate-co-2-chloroacryloyloxyethyl
(E)-3-(4-methoxyphenyl)acrylate);
poly(2-methacrylamidoethyl
(E)-3-(4-cyanophenyl)acrylate-co-2-methacrylamidobutyl-3
(E)-[4-propyloxy-4'-biphenyl]acrylate]);
poly(2-chloroacrylamidohexyl
(E)-3-(4-cyano-4.degree.-biphenyl)acrylate-co-2-chloroacrylamidohexyl
3 (E)-[4-methyloxyphenyl]acrylate]);
poly(acrylamidomethyl
(E)-3-(4-butyloxyphenyl)acrylate-co-acrylamidobutyl-3
(E)-[4-butyloxy-4'-biphenyl]acrylate]);
poly(2-methacrylamidoethyl
(E)-3-(4-octyloxy-4'-biphenyl)acrylate-co-2-acrylamidobutyl
3-(E)-{4-[(R)-2-octyloxy]-4'-biphenyl}acrylate]);
poly(2-methacryloyloxybutyl
(E)-3-(4-ethyloxyphenyl)-(Z)-3-methyl-acrylate-co-2-methacryloyloxyethyl
(E)-3-(4-methoxy-4'-biphenyl)-2-cyanoacrylate);
poly(methacryloyloxybutyl-3
(E)-[4-(trans-4-butylcyclohexyl)phenyl]-3-(Z)-methylacrylate-co-styrene);
poly(acryloyloxyethyl-3
(E)-[4-octyloxy-4'-biphenyl]acrylate-co-methyl acrylate);
poly(ethyl methacrylate-co-methacryloyloxyethyl-3
(E)-[4-(4-propoxybenzoyloxy)phenyl]acrylate);
poly(methacrylamidoethyl (E)-3-(4-proyloxyphenyl)acrylate-co-methyl
methacrylamide);
poly(2-chloroacryloyloxyhexyl-3
(E)-[4-(trans-4-methylcyclohexyl)phenyl]acrylate-co-methyl
2-chloroacrylate);
poly(2-chloroacryloyloxypentyl
(E)-3-(4-methoxy-4'-biphenyl)-2-carboxyethyl-acrylate-co-2-chloroacryloylo
xybutyl-(Z)-3-(4-methoxy-4'-biphenyl)-2-carboxyethyl-acrylate-co-methyl
2chloroacrylate);
poly(ethyl 2-methacrylate-co-2-methacryloyloxypropyl
(E)-3-(4-pentyloxyphenyl)acrylate-co-2-methacryloyloxybutyl
(E)-3-(4-[(S)-2-methylbutyloxy]-4'-biphenyl)-2-carboxyethyl-acrylate);
poly(methacryloyloxypropyl-3
(E)-[4-(trans-4-butylcyclohexyl)phenyl]-3-(Z)-methylacrylate-co-2-methacry
loyloxypropyl
(E)-3-(4-(R)-2-octyloxy]phenyl)-3-(Z)-methylacrylate-co-styrene).
EXAMPLE 4
2.4 g of but-3-ene 3-phenylacrylate and 0.6 g of
poly(methylhydrogen-siloxane) were dissolved in 8 mi of toluene
(thiophene-free). The solution was flushed through a septum on the
reaction vessel for 10 minutes with a weak argon stream.
Subsequently, 20 .mu.l of a platinum-divinyltetramethyldisiloxane
solution (mfr. PETRARCH SYSTEMS, PC075) were sprayed into the
reaction mixture at room temperature while stirring. The reaction
mixture was stirred at room temperature for 30 minutes and at
60.degree. C. for 18 hours. Subsequently, the reaction mixture was
added dropwise to 200 ml of n-hexane while stirring. The
precipitated polymer was separated, dissolved in 10 ml of toluene
and again precipitated in 200 ml of n-hexane. This procedure was
repeated twice. Drying in a high vacuum gave 1.8 g of
poly[(butyl-3-phenylacrylate)-methylsiloxane] with a glass stage
T.sub.g =-25.degree. C., .DELTA.c.sub.p =0.31 J/gK.
The but-3-ene 3-phenylacrylate used as the starting material was
prepared as follows:
22.2 g of cinnamic acid, 12.5 g of but-3-en-1-al and 0.2 g of
4-N,N-dimethylaminopyridine were placed in 80 ml of
dichloromethane. A solution of 33.05 g of dicyclohexylcarbodiimide
in 80 ml of dichloromethane was added dropwise at
5.degree.-10.degree. C. within 120 minutes. The mixture was stirred
at room temperature for a further 18 hours. Subsequently, the
precipitated N,N'-dicyclohexylurea was filtered off and washed with
150 ml of dichloromethane. The dichloromethane solution was washed
with 200 ml of 5% acetic acid and subsequently three times with 250
ml of water each time, filtered and dried over sodium sulphate.
After concentrating the solution the residue was chromatographed on
silica gel with dichloromethane. Drying in a high vacuum gave 22.1
g of but-3-ene 3-phenylacrylate as a colourless liquid.
The following compounds can be prepared in an analogous manner:
Poly(methyl-[propyl-3-(E)-(4-methyloxy-4'-biphenyl)acrylate
siloxane);
poly(methyl-{pentyl-3-(E)-[4-(trans-4-propylcyclohexyl)phenyl]acrylate}silo
xane);
poly(methyl-{hexyl-3-(E)-[4-(4-methoxybenzoyl)phenyl]acrylate}siloxane);
1,3,5,7-tetra[butyl-3-(E)-(4-methoxy-4'-biphenyl)
acrylate]-1,3,5,7-tetramethyl-cyclotetrasiloxane;
poly(methyl-[butyl-3-(E)-(4-methyloxyphenyl)acrylate]siloxane);
poly
(methyl-[butyl-(E)-3-(4-methoxyphenyl)acrylate]siloxane-co-methyl-[propyl-
3-(E)-[4-ethyloxy-4'-biphenyl]acrylate]siloxane);
poly(dimethylsiloxane-co-methyl-[butyl-3-(E)-[4-methyloxy-4'-biphenyl]acryl
ate]siloxane);
poly(dimethylsiloxane-co-methyl-[propyl-(E)-3-(4-methoxyphenyl)-2-carboxyet
hyl-acrylate]siloxane-co-methyl-[propyl-3-(Z)-[4-methyloxyphenyl)-2-carboxy
ethyl-acrylate]siloxane);
poly(dimethylsiloxane-co-methyl-[octyl-3-(E)-(4-methyloxy-4'-biphenyl)acryl
ate]siloxane-co-[pentyl-(E)-3-(4-methoxyphenyl)acrylate]siloxane).
EXAMPLE 5
1.5 g of
(E)-3-(4-cyano-phenyl)-N-[3-(2-methyl-acryloylamino)propyl]acrylamide
and 0.0083 g of azobisisobutyronitrile were dissolved in 10 ml of
N,N-dimethylformamide. The solution was flushed for 10 minutes with
a weak argon stream. Subsequently, the reaction vessel was closed
air-tight. The solution was heated to 70.degree. C. for 16 hours.
Thereafter, the reaction vessel was opened and the solution was
added dropwise while stirring to 300 ml of diethyl ether at room
temperature. The separated polymer was filtered off, dried,
dissolved in 10 ml of N,N-dimethylformamide and this solution was
again added dropwise to 300 ml of diethyl ether. This procedure was
repeated twice. Filtration and drying at 50.degree. C. in a vacuum
gave 0.54 g of poly(3-methacryloylaminopropyl
(E)-3-[4-cyano-phenyl]acrylamide). The polymer has a glass stage at
T.sub.g =165.degree. C. (.DELTA.c.sub.p =0.46 J/gK).
The
(E)-3-(4-cyano-phenyl)-N-[3-(2-methyl-acryloylamino)propyl]-acrylamide
used at the starting material was prepared at follows:
4.12 g of 4-cyano-cinnamic acid were suspended in 35 ml of
methylene chloride and gassed for 10 min. with a weak argon stream.
After cooling to -15.degree. C. 3.8 ml of diphenylphosphinic acid
chloride and 3.3 ml of triethylamine were added dropwise in
succession while stirring. Subsequently, a suspension consisting of
4.25 g of N-(3aminopropyl)methacrylamide hydrochloride and 6.6 ml
of triethylamine in 40 ml of tetrahydrofuran were slowly added to
this reaction mixture. The reaction mixture was stirred overnight,
whereby the temperature rose to about 12.degree. C. For the
working-up, the reaction mixture was concentrated in a vacuum. The
residue which remained behind was precipitated in 200 ml of water,
filtered off and recrystallized from a mixture of 10 ml of ethanol
and 30 ml of water. This gave 3.13 g of
(E)-3-(4-cyano-phenyl)-N-[3-(2-methyl-acryloylamino)-propyl]-acrylamide.
.lambda..sub.max (ethanol)=284.3 nm (.epsilon.=32290 l mol.sup.-1
cm.sup.-1).
Having regard to Example 1b), the following compounds can be
prepared in an analogous manner:
Poly(2-methacryloylaminoethyl
(E)-3-[4-cyano-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[3-cyano-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[3-cyano-phenyl]acrylamide);
poly(2-methacryloylaminoethyl (E)-3-phenylacrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[4-methoxy-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[4-methoxy-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[4-ethoxy-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[4-ethoxy-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[4-methyl-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[4-methyl-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[4-ethyl-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[4-ethyl-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[4-trifluoromethyl-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[4-trifluoromethyl-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[4-trifluoromethoxy-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[4-trifluoromethoxy-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[3-nitro-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[3-nitro-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[4-nitro-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[4-nitro-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[2-chloro-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[3-chloro-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[4-chloro-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[4-chloro-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[3-fluoro-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[4-fluoro-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[4-fluoro-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[2,4-dimethyl-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[2,4-dimethyl-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[2,3-dimethoxy-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[2,4-dimethoxy-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[2,4-dimethoxy-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[3,4-dimethoxy-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[3,4-dimethoxy-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[3,5-dimethoxy-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[3,5-dimethoxy-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[3,4-dicyano-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[3,4-dicyano-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[3,5-dicyano-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[3,5-dicyano-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[2,4-dinitro-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[2,4-dinitro-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[3,4-dichloro-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-3,4-dichloro-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[3,5-dichloro-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[3,5-dichloro-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[3,4-difluoro-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[3,4-difluoro-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[3,5-difluoro-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[3,5-difluoro-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[4-chloro-3-nitro-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[4-chloro-3-nitro-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[2-chloro-4-fluoro-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[2-chloro-4-fluoro-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[3-chloro-4-fluoro-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[3-chloro-4-fluoro-phenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[3-fluoro-2-methyl-phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[3-fluoro-2-methyl-phenyl]acrylamide);
poly(3-methacryloylaminopropyl (E)-3-biphenyl-acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[4-methoxy-4'-biphenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[4-methoxy-4'-biphenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[4-cyano-4'-biphenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[4-cyano-4'-biphenyl]acrylamide);
poly(2-methacryloylaminoethyl
(E)-3-[4-(trans-4-methylocyclohexyl)phenyl]acrylamide);
poly(3-methacryloylaminopropyl
(E)-3-[4-(trans-4-methyl-cyclohexyl)phenyl]acrylamide);
poly(2-methacryloyloxyethyl (E)-3-[4-cyano-phenyl]acrylamide);
poly(3-methacryloyloxypropyl (E)-3-[4-cyano-phenyl]acrylamide);
poly(2-methacryloyloxyethyl (E)-3-[3-cyano-phenyl]acrylamide);
poly(3-methacryloyloxypropyl (E)-3-[3-cyano-phenyl]acrylamide);
poly(2-methacryloyloxyethyl
(E)-3-[4-methoxy-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[4-methoxy-phenyl]acrylamide);
poly(2-methacryloyloxyethyl (E)-3-[4-ethoxy-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[4-ethoxy-phenyl]acrylamide);
poly(2-methacryloyloxyethyl (E)-3-[4-methyl-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[4-methyl-phenyl]acrylamide);
poly(2-methacryloyloxyethyl (E)-3-[4-ethyl-phenyl]acrylamide);
poly(2-methacryloyloxyethyl
(E)-3-[4-trifluoromethyl-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[4-trifluoromethyl-phenyl]acrylamide);
poly(2-methacryloyloxyethyl
(E)-3-[4-trifluoromethoxy-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[4-trifluoromethoxy-phenyl]acrylamide);
poly(3-methacryloyloxypropyl (E)-3-[3-nitro-phenyl]acrylamide);
poly(2-methacryloyloxyethyl (E)-3-[4-nitro-phenyl]acrylamide);
poly(3-methacryloyloxypropyl (E)-3-[4-nitro-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[3-chloro-phenyl]acrylamide);
poly(2-methacryloyloxyethyl (E)-3-[4-chloro-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[4-chloro-phenyl]acrylamide);
poly(2-methacryloyloxyethyl (E)-3-[3-fluoro-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[3-fluoro-phenyl]acrylamide);
poly(2-methacryloyloxyethyl (E)-3-[4-fluoro-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[4-fluoro-phenyl]acrylamide);
poly(2-methacryloyloxyethyl
(E)-3-[2,4-dimethyl-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[2,4-dimethyl-phenyl]acrylamide);
poly(2-methacryloyloxyethyl
(E)-3-[2,4-dimethoxy-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[2,4-dimethoxy-phenyl]acrylamide);
poly(2-methacryloyloxyethyl
(E)-3-[3,4-dimethoxy-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[3,4-dimethoxy-phenyl]acrylamide);
poly(2-methacryloyloxyethyl
(E)-3-[3,5-dimethoxy-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[3,5-dimethoxy-phenyl]acrylamide);
poly(2-methacryloyloxyethyl
(E)-3-[3,4-dicyano-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[3,4-dicyano-phenyl]acrylamide);
poly(2-methacryloyloxyethyl
(E)-3-[3,5-dicyano-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[3,5-dicyano-phenyl]acrylamide);
poly(2-methacryloyloxyethyl
(E)-3-[2,4-dinitro-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[2,4-dinitro-phenyl]acrylamide);
poly(2-methacryloyloxyethyl
(E)-3-[3,4-dichloro-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-3,4-dichloro-phenyl]acrylamide);
poly(2-methacryloyloxyethyl
(E)-3-[3,5-dichloro-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[3,5-dichloro-phenyl]acrylamide);
poly(2-methacryloyloxyethyl
(E)-3-[3,4-difluoro-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[3,4-difluoro-phenyl]acrylamide);
poly(2-methacryloyloxyethyl
(E)-3-[3,5-difluoro-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[3,5-difluoro-phenyl]acrylamide);
poly(2-methacryloyloxyethyl
(E)-3-[3-bromo-4-fluoro-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[3-bromo-4-fluoro-phenyl]acrylamide);
poly(2-methacryloyloxyethyl
(E)-3-[5-bromo-2-methoxy-phenyl]acrylamide);
poly(2-methacryloyloxyethyl
(E)-3-[2-chloro-5-nitro-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[2-chloro-5-nitro-phenyl]acrylamide);
poly(2-methacryloyloxyethyl
(E)-3-[4-chloro-3-nitro-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[4-chloro-3-nitro-phenyl]acrylamide);
poly(2-methacryloyloxyethyl
(E)-3-[2-chloro-4-fluoro-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[2-chloro-4-fluoro-phenyl]acrylamide);
poly(2-methacryloyloxyethyl
(E)-3-[2-chloro-6-fluoro-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[2-chloro-6-fluoro-phenyl]acrylamide);
poly(2-methacryloyloxyethyl
(E)-3-[3-chloro-4-fluoro-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[3-chloro-4-fluoro-phenyl]acrylamide);
poly(2-methacryloyloxyethyl
(E)-3-[3-fluoro-2-methyl-phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[3-fluoro-2-methyl-phenyl]acrylamide);
poly(2-methacryloyloxyethyl (E)-3-biphenylacrylamide);
poly(2-methacryloyloxyethyl
(E)-3-[4-methoxy-4'-biphenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[4-methoxy-4'-biphenyl]acrylamide);
poly(2-methacryloyloxyethyl
(E)-3-[4-cyano-4'-biphenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[4-cyano-4'-biphenyl]acrylamide);
poly(2-methacryloyloxyethyl
(E)-3-[4-(trans-4-methyl-cyclohexyl)phenyl]acrylamide);
poly(3-methacryloyloxypropyl
(E)-3-[4-(trans-4-methyl-cyclohexyl)phenyl]acrylamide);
poly(2-methacryloylaminoethyl (E)-3-[4-cyano-phenyl]acrylate);
poly(3-methacryloylaminopropyl (E)-3-[4-cyano-phenyl]acrylate);
poly(2-methacryloylaminoethyl (E)-3-[3-cyano-phenyl]acrylate);
poly(3-methacryloylaminopropyl (E)-3-[3-cyano-phenyl]acrylate);
poly(2-methacryloylaminoethyl (E)-3-phenylacrylate);
poly(2-methacryloylaminoethyl
(E)-3-[4-methoxy-phenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[4-methoxy-phenyl]acrylate);
poly(2-methacryloylaminoethyl (E)-3-[4-ethoxy-phenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[4-ethoxy-phenyl]acrylate);
poly(2-methacryloylaminoethyl (E)-3-[4-methyl-phenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[4-methyl-phenyl]acrylate);
poly(2-methacryloylaminoethyl (E)-3-[4-ethyl-phenyl]acrylate);
poly(3-methacryloylaminopropyl (E)-3-[4-ethyl-phenyl]acrylate);
poly(2-methacryloylaminoethyl
(E)-3-[4-trifluoromethyl-phenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[4-trifluoromethyl-phenyl]acrylate);
poly(2-methacryloylaminoethyl
(E)-3-[4-trifluoromethoxy-phenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[4-trifluoromethoxy-phenyl]acrylate);
poly(2-methacryloylaminoethyl (E)-3-[3-nitro-phenyl]acrylate);
poly(3-methacryloylaminopropyl (E)-3-[3-nitro-phenyl]acrylate);
poly(2-methacryloylaminoethyl (E)-3-[4-nitro-phenyl]acrylate);
poly(3-methacryloylaminopropyl (E)-3-[4-nitro-phenyl]acrylate);
poly(2-methacryloylaminoethyl (E)-3-[3-chloro-phenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[3-chloro-phenyl]acrylate);
poly(2-methacryloylaminoethyl (E)-3-[4-chloro-phenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[4-chloro-phenyl]acrylate);
poly(2-methacryloylaminoethyl (E)-3-[3-fluoro-phenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[3-fluoro-phenyl]acrylate);
poly(2-methacryloylaminoethyl (E)-3-[4-fluoro-phenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[4-fluoro-phenyl]acrylate);
poly(2-methacryloylaminoethyl
(E)-3-[2,4-dimethyl-phenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[2,4-dimethyl-phenyl]acrylate);
poly(2-methacryloylaminoethyl
(E)-3-[2,4-dimethoxy-phenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[2,4-dimethoxy-phenyl]acrylate);
poly(2-methacryloylaminoethyl
(E)-3-[3,4-dimethoxy-phenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[3,4-dimethoxy-phenyl]acrylate);
poly(2-methacryloylaminoethyl
(E)-3-[3,5-dimethoxy-phenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[3,5-dimethoxy-phenyl]acrylate);
poly(2-methacryloylaminoethyl
(E)-3-[3,4-dicyano-phenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[3,4-dicyano-phenyl]acrylate);
poly(2-methacryloylaminoethyl
(E)-3-[3,5-dicyano-phenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[3,5-dicyano-phenyl]acrylate);
poly(2-methacryloylaminoethyl
(E)-3-[2,4-dinitro-phenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[2,4-dinitro-phenyl]acrylate);
poly(2-methacryloylaminoethyl
(E)-3-[3,4-dichloro-phenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-3,4-dichloro-phenyl]acrylate);
poly(2-methacryloylaminoethyl
(E)-3-[3,5-dichloro-phenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[3,5-dichloro-phenyl]acrylate);
poly(2-methacryloylaminoethyl
(E)-3-[3,4-difluoro-phenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[3,4-difluoro-phenyl]acrylate);
poly(2-methacryloylaminoethyl
(E)-3-[3,5-difluoro-phenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[3,5-difluoro-phenyl]acrylate);
poly(2-methacryloylaminoethyl
(E)-3-[3-bromo-4-fluoro-phenyl]acrylate);
poly(2-methacryloylaminoethyl
(E)-3-[4-chloro-3-nitro-phenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[4-chloro-3-nitro-phenyl]acrylate);
poly(2-methacryloylaminoethyl
(E)-3-[2-chloro-4-fluoro-phenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[2-chloro-4-fluoro-phenyl]acrylate);
poly(2-methacryloylaminoethyl
(E)-3-[3-chloro-4-fluoro-phenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[3-chloro-4-fluoro-phenyl]acrylate);
poly(2-methacryloylaminoethyl
(E)-3-[3-fluoro-2-methyl-phenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[3-fluoro-2-methyl-phenyl]acrylate);
poly(2-methacryloylaminoethyl
(E)-3-[4-methoxy-4'-biphenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[4-methoxy-4'-biphenyl]acrylate);
poly(2-methacryloylaminoethyl
(E)-3-[4-cyano-4'-biphenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[4-cyano-4'-biphenyl]acrylate);
poly(2-methacryloylaminoethyl
(E)-3-[4-(trans-4-methyl-cyclohexyl)phenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[4-(trans-4-methyl-cyclohexyl)phenyl]acrylate);
poly(3-methacryloylaminopropyl
(E)-3-[4-(trans-4-ethyl-cyclohexyl)phenyl]acrylate);
poly(2-acryloylaminoethyl (E)-3-[4-cyano-phenyl]acrylamide);
poly(3-acryloylaminopropyl (E)-3-[3-cyano-phenyl]acrylamide);
poly(4-acryloylaminobutyl (E)-3-phenylacrylamide);
poly(3-acryloylaminopropyl (E)-3-[4-methoxy-phenyl]acrylamide);
poly(2-acryloylaminoethyl (E)-3-[4-ethoxy-phenyl]acrylamide);
poly(2-acryloylaminoethyl (E)-3-[4-methyl-phenyl]acrylamide);
poly(4-acryloylaminobutyl (E)-3-[4-ethyl-phenyl]acrylamide);
poly(2-acryloylaminoethyl
(E)-3-[4-trifluoromethyl-phenyl]acrylamide);
poly(3-acryloylaminopropyl
(E)-3-[4-trifluoromethoxy-phenyl]acrylamide);
poly(2-acryloylaminoethyl (E)-3-[3-nitro-phenyl]acrylamide);
poly(2-acryloylaminoethyl (E)-3-[4-nitro-phenyl]acrylamide);
poly(3-acryloylaminopropyl (E)-3-[3-chloro-phenyl]acrylamide);
poly(2-acryloylaminoethyl (E)-3-[4-chloro-phenyl]acrylamide);
poly(2-acryloylaminoethyl (E)-3-[3-fluoro-phenyl]acrylamide);
poly(3-acryloylaminopropyl (E)-3-[4-fluoro-phenyl]acrylamide);
poly(4-acryloylaminobutyl
(E)-3-[2,4-di-methyl-phenyl]acrylamide);
poly(3-acryloylaminopropyl
(E)-3-[2,3-dimethoxy-phenyl]acrylamide);
poly(2-acryloylaminoethyl
(E)-3-[2,4-dimethoxy-phenyl]acrylamide);
poly(2-acryloylaminoethyl
(E)-3-[3,4-dimethoxy-phenyl]acrylamide);
poly(3-acryloylaminopropyl
(E)-3-[3,5-dimethoxy-phenyl]acrylamide);
poly(2-acryloylaminoethyl
(E)-3-[3,4-dicyano-phenyl]acrylamide);
poly(3-acryloylaminopropyl
(E)-3-[3,5-dicyano-phenyl]acrylamide);
poly(5-acryloylaminopentyl
(E)-3-[2,4-dinitro-phenyl]acrylamide);
poly(6-acryloylaminohexyl
(E)-3-[3,4-dichloro-phenyl]acrylamide);
poly(2-acryloylaminoethyl
(E)-3-[3,5-dichloro-phenyl]acrylamide);
poly(2-acryloylaminoethyl
(E)-3-[3,4-difluoro-phenyl]acrylamide);
poly(3-acryloylaminopropyl
(E)-3-[3,5-difluoro-phenyl]acrylamide);
poly(2-acryloylaminoethyl
(E)-3-[3-bromo-4-fluoro-phenyl]acrylamide);
poly(2-acryloylaminoethyl
(E)-3-[5-bromo-2-methoxy-phenyl]acrylamide);
poly(2-acryloylaminoethyl
(E)-3-[2-chloro-5-nitro-phenyl]acrylamide);
poly(3-acryloylaminopropyl
(E)-3-[4-chloro-3-nitro-phenyl]acrylamide);
poly(2-acryloylaminoethyl
(E)-3-[2-chloro-4-fluoro-phenyl]acrylamide);
poly(6-acryloylaminohexyl
(E)-3-[3-chloro-4-fluoro-phenyl]acrylamide);
poly(3-acryloylaminopropyl
(E)-3-[3-fluoro-2-methyl-phenyl]acrylamide);
poly(3-acryloylaminopropyl (E)-3-biphenyl-acrylamide);
poly(2-acryloylaminoethyl
(E)-3-[4-methoxy-4'-biphenyl]acrylamide);
poly(2-acryloylaminoethyl
(E)-3-[4-cyano-4'-biphenyl]acrylamide);
poly(3-acryloylaminopropyl
(E)-3-[4-(trans-4-methyl-cyclohexyl)phenyl]acrylamide);
poly(2-acryloylaminoethyl
(E)-3-[4-(trans-4-ethylocyclohexyl)-phenyl]acrylamide);
poly(2-acryloyloxyethyl (E)-3-[4-cyano-phenyl]acrylamide);
poly(4-acryloyloxybutyl (E)-3-[3-cyano-phenyl]acrylamide);
poly(3-acryloyloxypropyl (E)-3-phenylacrylamide);
poly(2-acryloyloxyethyl (E)-3-[4-methoxy-phenyl]acrylamide);
poly(2-acryloyloxyethyl (E)-3-[4-ethoxy-phenyl]acrylamide);
poly(3-acryloyloxypropyl (E)-3-[4-methyl-phenyl]acrylamide);
poly(3-acryloyloxypropyl (E)-3-[4-ethyl-phenyl]acrylamide);
poly(2-acryloyloxyethyl
(E)-3-[4-trifluoromethyl-phenyl]acrylamide);
poly(2-acryloyloxyethyl
(E)-3-[4-trifluoromethoxy-phenyl]acrylamide);
poly(6-acryloyloxyhexyl (E)-3-[3-nitro-phenyl]acrylamide);
poly(2-acryloyloxyethyl (E)-3-[4-nitro-phenyl]acrylamide);
poly(5-acryloyloxypentyl (E)-3-[3-chloro-phenyl]acrylamide);
poly(2-acryloyloxyethyl (E)-3-[4-chloro-phenyl]acrylamide);
poly(2-acryloyloxyethyl (E)-3-[3-fluoro-phenyl]acrylamide);
poly(3-acryloyloxypropyl (E)-3-[4-fluoro-phenyl]acrylamide);
poly(2-acryloyloxyethyl (E)-3-[2,4-dimethyl-phenyl]acrylamide);
poly(2-acryloyloxyethyl
(E)-3-[2,3-dimethoxy-phenyl]acrylamide);
poly(3-acryloyloxypropyl
(E)-3-[2,4-dimethoxy-phenyl]acrylamide);
poly(2-acryloyloxyethyl
(E)-3-[3,4-dimethoxy-phenyl]acrylamide);
poly(2-acryloyloxyethyl
(E)-3-[3,5-dimethoxy-phenyl]acrylamide);
poly(6-acryloyloxyhexyl (E)-3-[3,4-dicyano-phenyl]acrylamide);
poly(2-acryloyloxyethyl (E)-3-[3,5-dicyano-phenyl]acrylamide);
poly(2-acryloyloxyethyl (E)-3-[2,4-dinitro-phenyl]acrylamide);
poly(3-acryloyloxypropyl
(E)-3-[3,4-dichloro-phenyl]acrylamide);
poly(3-acryloyloxypropyl
(E)-3-[3,5-dichloro-phenyl]acrylamide);
poly(2-acryloyloxyethyl (E)-3-[3,4-difluoro-phenyl]acrylamide);
poly(2-acryloyloxyethyl (E)-3-[3,5-difluoro-phenyl]acrylamide);
poly(2-acryloyloxyethyl
(E)-3-[3-bromo-4-fluoro-phenyl]acrylamide);
poly(3-acryloyloxypropyl
(E)-3-[4-chloro-3-nitro-phenyl]acrylamide);
poly(4-acryloyloxybutyl
(E)-3-[2-chloro-4-fluoro-phenyl]acrylamide);
poly(2-acryloyloxyethyl
(E)-3-[3-chloro-4-fluoro-phenyl]acrylamide);
poly(3-acryloyloxypropyl
(E)-3-[3-fluoro-2-methyl-phenyl]acrylamide);
poly(3-acryloyloxypropyl (E)-3-biphenyl-acrylamide);
poly(2-acryloyloxyethyl
(E)-3-[4-methoxy-4'-biphenyl]acrylamide);
poly(2-acryloyloxyethyl (E)-3-[4-cyano-4'-biphenyl]acrylamide);
poly(3-acryloyloxypropyl
(E)-3-[4-(trans-4-methyl-cyclohexyl)-phenyl]acrylamide);
poly(5-acryloyloxypentyl
(E)-3-[4-(trans-4-ethyl-cyclohexyl)-phenyl]acrylamide);
poly(2-acryloylaminoethyl (E)-3-[4-cyano-phenyl]acrylate);
poly(3-acryloylaminopropyl (E)-3-[3-cyano-phenyl]acrylate);
poly(2-acryloylaminoethyl (E)-3-[4-methoxy-phenyl]acrylate);
poly(2-acryloylaminoethyl (E)-3-[4-ethoxy-phenyl]acrylate);
poly(2-acryloylaminoethyl (E)-3-[4-methyl-phenyl]acrylate);
poly(3-acryloylaminopropyl (E)-3-[4-ethylophenyl]acrylate);
poly(2-acryloylaminoethyl (E)-3-[4-propyl-phenyl]acrylate);
poly(2-acryloylaminoethyl
(E)-3-[4-trifluoromethyl-phenyl]acrylate);
poly(3-acryloylaminopropyl
(E)-3-[4-trifluoromethoxy-phenyl]acrylate);
poly(4-acryloylaminobutyl (E)-3-[3-nitro-phenyl]acrylate);
poly(2-acryloylaminoethyl (E)-3-[4-nitro-phenyl]acrylate);
poly(2-acryloylaminoethyl (E)-3-[3-chloro-phenyl]acrylate);
poly(3-acryloylaminopropyl (E)-3-[4-chloro-phenyl]acrylate);
poly(2-acryloylaminoethyl (E)-3-[3-fluoro-phenyl]acrylate);
poly(2-acryloylaminoethyl (E)-3-[4-fluoro-phenyl]acrylate);
poly(3-acryloylaminopropyl
(E)-3-[2,4-dimethyl-phenyl]acrylate);
poly(3-acryloylaminopropyl
(E)-3-[2,3-dimethoxy-phenyl]acrylate);
poly(2-acryloylaminoethyl
(E)-3-[2,4-dimethoxy-phenyl]acrylate);
poly(2-acryloylaminoethyl
(E)-3-[3,4-dimethoxy-phenyl]acrylate);
poly(6-acryloylaminohexyl
(E)-3-[3,5-dimethoxy-phenyl]acrylate);
poly(2-acryloylaminoethyl (E)-3-[3,4-dicyano-phenyl]acrylate);
poly(2-acryloylaminoethyl (E)-3-[3,5-dicyano-phenyl]acrylate);
poly(3-acryloylaminopropyl (E)-3-[2,4-dinitro-phenyl]acrylate);
poly(3-acryloylaminopropyl
(E)-3-[3,4-dichloro-phenyl]acrylate);
poly(2-acryloylaminoethyl (E)-3-[3,5-dichloro-phenyl]acrylate);
poly(2-acryloylaminoethyl (E)-3-[3,4-difluoro-phenyl]acrylate);
poly(5-acryloylaminopentyl
(E)-3-[3,5-difluoro-phenyl]acrylate);
poly(2-acryloylaminoethyl
(E)-3-[3-bromo-4-fluoro-phenyl]acrylate);
poly(2-acryloylaminoethyl
(E)-3-[4-chloro-3-nitro-phenyl]acrylate);
poly(3-acryloylaminopropyl
(E)-3-[2-chloro-4-fluoro-phenyl]acrylate);
poly(2-acryloylaminoethyl
(E)-3-[3-chloro-4-fluoro-phenyl]acrylate);
poly(2-acryloylaminoethyl
(E)-3-[3-fluoro-2-methyl-phenyl]acrylate);
poly(4-acryloylaminobutyl
(E)-3-[4-methoxy-4'-biphenyl]acrylate);
poly(2-acryloylaminoethyl (E)-3-[4-cyano-4'-biphenyl]acrylate);
poly(3-acryloylaminopropyl
(E)-3-[4-(trans-4-methyl-cyclohexyl)phenyl]acrylate);
poly(2-acryloylaminoethyl
(E)-3-[4-(trans-4-ethyl-cyclohexyl)-phenyl]acrylate).
EXAMPLE 6
1.63 g of 2-methyl-acrylic acid
(E)-1-[3-(4-methoxy-phenyl)acryloyl]-piperidin-4-yl ester and
0.0081 g of azobisisobutyronitrile were dissolved in 10 ml of
tetrahydrofuran. The solution was flushed for 10 minutes with a
weak argon stream. Subsequently, the reaction vessel was closed
air-tight. The mixture was heated to 60.degree. C.; for 19 hours.
Thereafter, the reaction vessel was opened and the solution was
added dropwise while stirring to 300 ml of diethyl ether at room
temperature. The separated polymer was filtered off, dried,
dissolved in 10 ml of tetrahydrofuran and this solution was again
added dropwise to 300 ml of diethyl ether. This procedure was
repeated twice. Filtration and drying at 50.degree. C. in a vacuum
gave 1.33 g of
poly[1-[1-[(E)-3-(4-methoxy-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-1
-methyl-ethylene]. The polymer has a glass stage at T.sub.g
=143.degree. C. (.DELTA.c.sub.p =0.30 J/gK).
The 2-methyl-acrylic acid
(E)-1-[3-(4-methoxy-phenyl)acryloyl]-piperidin-4-yl ester used as
the starting material was prepared as follows:
a) Firstly 2.1 g of cyanuric chloride and subsequently 3.2 ml of
triethylamine were slowly added at room temperature to a solution
of 4.06 g of p-methoxycinnamic acid in 100 ml of dry acetone. After
three hours the separated byproduct was filtered off and the
filtrate was concentrated to dryness. The p-methoxycinnamoyl
chloride which remained as the residue was taken up in 50 ml of dry
methylene chloride and processed immediately.
3.5 ml of trimethylsilyl chloride were added dropwise in an argon
atmosphere to a solution, cooled to 0.degree. C., of 2.8 g of
4-hydroxypiperidine in 100 ml of dry methylene chloride. After
stirring at 0.degree. C. for two hours the solution was treated
with 2 ml of triethylamine. The previously prepared
p-methoxycinnamoyl chloride in 50 ml of methylene chloride was
added dropwise to this mixture while cooling with ice. The reaction
mixture was stirred overnight and then warmed slowly to room
temperature. Subsequently, it was filtered over a thin layer of
silica gel. After the methylene chloride had been removed
completely in a vacuum the residue remaining was taken up in 50 ml
of methanol and, after the addition of 2.7 g of citric acid,
stirred at room temperature for three hours. For purification, the
mixture was evaporated to dryness in a vacuum, the crude product
was taken up in 100 ml of methylene chloride and washed with the
same amount of semi-saturated sodium hydrogen carbonate solution.
The aqueous phase was extracted twice with 50 ml of methylene
chloride each time. Subsequently, the organic phases were combined,
dried over magnesium sulphate, treated with 2 g of silica gel and
filtered. After removing the solvent 6.65g of
4-hydroxy-(E)-1-[3-(4-methoxyphenyl)-acryloyl]-piperidine remained
as a yellow oil.
b) A solution of 6.65 g of
4-hydroxy-(E)-1-[3-(4-methoxy-phenyl)acryloyl]-piperidine in 50 ml
of methylene chloride was treated with 4 ml of triethylamine at
0.degree. C. while gassing with argon. 2.7 ml of methacryloyl
chloride were added dropwise within 15 minutes. Subsequently, the
reaction mixture was concentrated to dryness in a vacuum.
Chromatographic purification of the residue on silica gel with
ether/hexane (vol. 4:1) gave 4.21 g of 2-methyl-acrylic acid
(E)-I-[3-(4-methoxy-phenyl)-acryloyl]-piperidin-4-yl ester as a
colourless oil. .lambda..sub.max (methylene chloride)=292.5 nm
(.epsilon.=22775 l mol.sup.-1 cm.sup.-1).
Having regard to Example 1b), the following compounds can be
prepared in an analogous manner:
Poly[1-[1-[(E)-3-phenyl-acryloyl]-piperidin-4-yloxycarbonyl]-1-methylethyle
ne];
poly[1-[1-[(E)-3-(4-methyl-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-1-m
ethyl-ethylene];
poly[1-[1-[(E)-3-(4-ethyl-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-1-me
thyl-ethylene];
poly[1-[1-[(E)-3-(4-ethoxy-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-1-m
ethyl-ethylene];
poly[1-[1-[(E)-3-(4-trifluoromethyl-phenyl)-acryloyl]-piperidin-4-yloxycarb
onyl]-1-methyl-ethylene];
poly[1-[1-[(E)-3-(4-trifluoromethoxy-phenyl)-acryloyl]-piperidin-4yloxycarb
onyl]-1-methyl-ethylene];
poly[1-[1-[(E)-3-(3-cyano-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-1-me
thyl-ethylene];
poly[1-[1-[(E)-3-(4-cyano-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-1-me
thyl-ethylene];
poly[1-[1-[(E)-3-(3-nitro-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-1-me
thyl-ethylene];
poly[1-[1-[(E)-3-(4-nitro-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-1-me
thyl-ethylene];
poly[1-[1-[(E)-3-(3-chloro-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-1-m
ethyl-ethylene];
poly[1-[1-[(E)-3-(4-chloro-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-1-m
ethyl-ethylene];
poly[1-[1-[(E)-3-(3-fluoro-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-1-m
ethyl-ethylene];
poly[1-[1-[(E)-3-(4-fluoro-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-1-m
ethyl-ethylene];
poly[1-[1-[(E)-3-(2,4-dimethyl-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]
-1-methyl-ethylene];
poly[1-[1-[(E)-3-(2,3-dimethoxy-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl
]-1-methyl-ethylene];
poly[1-[1-[(E)-3-(2,4-dimethoxy-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl
]-1-methyl-ethylene];
poly[1-[1-[(E)-3-(3,4-dimethoxy-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl
]-1-methyl-ethylene];
poly[1-[1-[(E)-3-(3,5-dimethoxy-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl
]-1-methyl-ethylene];
poly[1-[1-[(E)-3-(3,4-dicyano-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-
1-methyl-ethylene];
poly[1-[1-[(E)-3-(3,5-dicyano-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-
1-methyl-ethylene];
poly[1-[1-[(E)-3-(2,4-dinitro-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-
1-methyl-ethylene];
poly[1-[1-[(E)-3-(3,4-dichloro-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]
-1-methyl-ethylene];
poly[1-[1-[(E)-3-(3,5-dichloro-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]
-1-methyl-ethylene];
poly[1-[1-[(E)-3-(3,4-difluoro-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]
-1-methyl-ethylene];
poly[1-[1-[(E)-3-(3,5-difluoro-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]
-1-methyl-ethylene];
poly[1-[1-[(E)-3-(3-bromo-4-fluoro-phenyl)-acryloyl]-piperidin-4-yloxycarbo
nyl]-1-methyl-ethylene];
poly[1-[1-[(E)-3-(4-chloro-3-nitro-phenyl)-acryloyl]-piperidin-4-yloxycarbo
nyl]-1-methyl-ethylene];
poly[1-[1-[(E)-3-(2-chloro-4-fluoro-phenyl)-acryloyl]-piperidin-4-yloxycarb
onyl]-1-methyl-ethylene];
poly[1-[1-[(E)-3-(3-chloro-4-fluoro-phenyl)-acryloyl]-piperidin-4-yloxycarb
onyl]-1-methyl-ethylene];
poly[1-[1-[(E)-3-(3-fluoro-2-methyl-phenyl)-acryloyl]-piperidin-4-yloxycarb
onyl]-1-methyl-ethylene];
poly[1-[1-[(E)-3-(4-cyano-4'-biphenyl)-acryloyl]-piperidin-4-yloxycarbonyl]
-1-methyl-ethylene];
poly[1-[1-[(E)-3-[4-(trans-4-methyl-cyclohexyl)-phenyl]-acryloyl]-piperidin
-4-yloxycarbonyl]-1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-methyl-phenyl)-acryloyloxy]-piperidine]-1-me
thyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-methoxy-phenyl)-acryloyloxylpiperidine]-1-me
thyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-trifluoromethyl-phenyl)-acryloyloxy]piperidi
ne]-1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-trifluoromethoxy-phenyl)-acryloyloxy]piperid
ine]-1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3-cyano-phenyl)-acryloyloxy]-piperidine]-1-met
hyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-cyano-phenyl)-acryloyloxyl-piperidine]-1-met
hyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3-nitro-phenyl)-acryloyloxy]-piperidine]-1-met
hyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-nitro-phenyl)-acryloyloxy]-piperidine]-1-met
hyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3-chloro-phenyl)-acryloyloxy]-piperidine]-1-me
thyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-chloro-phenyl)-acryloyloxy]-piperidine]-1-me
thyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3-fluoro-phenyl)-acryloyloxy]-piperidine]-1-me
thyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-fluoro-phenyl)-acryloyloxy]-piperidine]-1-me
thyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(2,4-dimethyl-phenyl)-acryloyloxy]-piperidine]-
1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(2,3-dimethoxy-phenyl)-acryloyloxy]-piperidine]
-1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(2,4-dimethoxy-phenyl)-acryloyloxy]-piperidine]
-1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3,4-dimethoxy-phenyl)-acryloyloxy]-piperidine]
-1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3,5-dimethoxy-phenyl)-acryloyloxy]-piperidine]
-1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3,4-dicyano-phenyl)-acryloyloxy]-piperidine]-1
-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3,5-dicyano-phenyl)-acryloyloxy]-piperidine]-1
-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(2,4-dinitro-phenyl)-acryloyloxy]-piperidine]-1
-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3,4-dichloro-phenyl)-acryloyloxy]-piperidine]-
1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3,5-dichloro-phenyl)-acryloyloxy]-piperidine]-
1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3,4-difluoro-phenyl)-acryloyloxy]-piperidine]-
1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3,5-difluoro-phenyl)-acryloyloxy]-piperidine]-
1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3-bromo-4-fluoro-phenyl)-acryloyloxy]-piperidi
ne]-1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-chloro-3-nitro-phenyl)-acryloyloxy]-piperidi
ne]-1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(2-chloro-4-fluoro-phenyl)-acryloyloxy]-piperid
ine]-1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3-chloro-4-fluoro-phenyl)-acryloyloxy]-piperid
ine]-1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3-fluoro-2-methyl-phenyl)-acryloyloxy]-piperid
ine]-1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-biphenyl-acryloyloxy]-piperidine]-1-methyl-ethy
lene];
poly[1-[1-carbonyl-4-[(E)-3-(4-cyano-4'-biphenyl)-acryloyloxy]-piperidine]-
1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-[4-(trans-4-methyl-cyclohexyl)-phenyl]-acryloyl
oxy]-piperidine]-1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-phenyl-acryloyl]-piperazine]-1-methylethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-methyl-phenyl)-acryloyl]-piperazine]-1-methy
l-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-methoxy-phenyl)-acryloyl]-piperazine]-1-meth
yl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-trifluoromethyl-phenyl)-acryloyl]-piperazine
]-1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-trifluoromethoxy-phenyl)-acryloyl]-piperazin
e]-1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3-cyano-phenyl)-acryloyl]-piperazine]-1-methyl
-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-cyano-phenyl)-acryloyl]-piperazine]-1-methyl
-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3-nitro-phenyl)-acryloyl]-piperazine]-1-methyl
-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-nitro-phenyl)-acryloyl]-piperazine]-1-methyl
-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3-chloro-phenyl)-acryloyl]-piperazine]-1-methy
l-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-chloro-phenyl)-acryloyl]-piperazine]-1-methy
l-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3-fluoro-phenyl)-acryloyl]-piperazine]-1-methy
l-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-fluoro-phenyl)-acryloyl]-piperazine]-1-methy
l-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(2,4-dimethyl-phenyl)-acryloyl]-piperazine]-1-m
ethyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(2,3-dimethoxy-phenyl)-acryloyl]-piperazine]-1-
methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(2,4-dimethoxy-phenyl)-acryloyl]-piperazine]-1-
methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3,4-dimethoxy-phenyl)-acryloyl]-piperazine]-1-
methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3,5-dimethoxy-phenyl)-acryloyl]-piperazine]-1-
methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3
4-dicyano-phenyl)-acryloyl]-piperazine]-1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3
5-dicyano-phenyl)-acryloyl]-piperazine]-1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(2
4-dinitrophenyl)-acryloyl]-piperazine]-1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3
4-dichloro-phenyl)-acryloyl]-piperazine]-1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3
5-dichloro-phenyl)-acryloyl]-piperazine]-1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3
4-difluoro-phenyl)-acryloyl]-piperazine]-1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3,5-difluoro-phenyl)-acryloyl]-piperazine]-1-m
ethyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-chloro-3-nitro-phenyl)-acryloyl]-piperazine]
-1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(2-chloro-4-fluoro-phenyl)-acryloyl]-piperazine
]-1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3-chloro-4-fluoro-phenyl)-acryloyl]-piperazine
]-1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3-fluoro-2-methyl-phenyl)-acryloyl]-piperazine
]-1-methyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-cyano-4'-biphenyl)-acryloyl]-piperazine]-1-m
ethyl-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-[4-(trans-4-methyl-cyclohexyl)-phenyl]-acryloyl
]-piperazine]-1-methyl-ethylene];
poly[1-[1-[(E)-3-(4-methyl-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-eth
ylene];
poly[1-[1-[(E)-3-(4-methoxy-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-et
hylene];
poly[1-[1-[(E)-3-(4-trifluoromethyl-phenyl)-acryloyl]-piperidin-4-yloxycarb
onyl]-ethylene];
poly[1-[1-[(E)-3-(4-trifluoromethoxy-phenyl)-acryloyl]-piperidin-4-yloxycar
bonyl]-ethylene];
poly[1-[1-[(E)-3-(3-cyano-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-ethy
lene];
poly[1-[1-[(E)-3-(4-cyano-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-ethy
lene];
poly[1-[1-[(E)-3-(3-nitro-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-ethy
lene];
poly[1-[1-[(E)-3-(4-nitro-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-ethy
lene];
poly[1-[1-[(E)-3-(3-chloro-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-eth
ylene];
poly[1-[1-[(E)-3-(4-chloro-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-eth
ylene];
poly[1-[1-[(E)-3-(3-fluoro-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-eth
ylene];
poly[1-[1-[(E)-3-(4-fluoro-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-eth
ylene];
poly[1-[1-[(E)-3-(2,4-dimethyl-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]
-ethylene];
poly[1-[1-[(E)-3-(2,3-dimethoxy-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl
]-ethylene];
poly[1-[1-[(E)-3-(2,4-dimethoxy-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl
]-ethylene];
poly[1-[1-[(E)-3-(3,4-dimethoxy-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl
]-ethylene];
poly[1-[1-[(E)-3-(3,5-dimethoxy-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl
]-ethylene];
poly[1-[1-[(E)-3-(3,4-dicyano-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-
ethylene];
poly[1-[1-[(E)-3-(3,5-dicyano-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-
ethylene];
poly[1-[1-[(E)-3-(2,4-dinitro-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]-
ethylene];
poly[1-[1-[(E)-3-(3,4-dichloro-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]
-ethylene];
poly[1-[1-[(E)-3-(3,5-dichloro-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]
-ethylene];
poly[1-[1-[(E)-3-(3,4-difluoro-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]
-ethylene];
poly[1-[1-[(E)-3-(3,5-difluoro-phenyl)-acryloyl]-piperidin-4-yloxycarbonyl]
-ethylene];
poly[1-[1-[(E)-3-(3-bromo-4-fluoro-phenyl)-acryloyl]-piperidin-4-yloxycarbo
nyl]-ethylene];
poly[1-[1-[(E)-3-(4-chloro-3-nitro-phenyl)-acryloyl]-piperidin-4-yloxycarbo
nyl]-ethylene];
poly[1-[1-[(E)-3-(2-chloro-4-fluoro-phenyl)-acryloyl]-piperidin-4-yloxycarb
onyl]-ethylene];
poly[1-[1-[(E)-3-(3-chloro-4-fluoro-phenyl)-acryloyl]-piperidin-4-yloxycarb
onyl]-ethylene];
poly[1-[1-[(E)-3-(3-fluoro-2-methyl-phenyl)-acryloyl]-piperidin-4-yloxycarb
onyl]-ethylene];
poly[1-[1-[(E)-3-(4-cyano-4'-biphenyl)-acryloyl]-piperidin-4-yloxycarbonyl]
-ethylene];
poly[1-[1-[(E)-3-[4-(trans-4-methyl-cyclohexyl)-phenyl]-acryloyl]-piperidin
-4-yloxycarbonyl]-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-methyl-phenyl)-acryloyloxy]-piperidine]-ethy
lene];
poly[1-[1-carbonyl-4-[(E)-3-(4-methoxy-phenyl)-acryloyloxy]-piperidine]-eth
ylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-trifluoromethyl-phenyl)-acryloyloxy]-piperid
ine]-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-trifluoromethoxy-phenyl)-acryloyloxy]-piperi
dine]-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3-cyano-phenyl)-acryloyloxy]-piperidine]-ethyl
ene];
poly[1-[1-carbonyl-4-[(E)-3-(4-cyano-phenyl)-acryloyloxy]-piperidine]-ethyl
ene];
poly[1-[1-carbonyl-4-[(E)-3-(3-nitro-phenyl)-acryloyloxy]-piperidine]-ethyl
ene];
poly[1-[1-carbonyl-4-[(E)-3-(4-nitro-phenyl)-acryloyloxy]-piperidine]-ethyl
ene];
poly[1-[1-carbonyl-4-[(E)-3-(3-chloro-phenyl)-acryloyloxy]-piperidine]-ethy
lene];
poly[1-[1-carbonyl-4-[(E)-3-(4-chloro-phenyl)-acryloyloxy]-piperidine]-ethy
lene];
poly[1-[1-carbonyl-4-[(E)-3-(3-fluoro-phenyl)-acryloyloxy]-piperidine]-ethy
lene];
poly[1-[1-carbonyl-4-[(E)-3-(4-fluoro-phenyl)-acryloyloxy]-piperidine]-ethy
lene];
poly[1-[1-carbonyl-4-[(E)-3-(2,4-dimethyl-phenyl)-acryloyloxy]-piperidine]-
ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(2
3-dimethoxy-phenyl)-acryloyloxy]-piperidine]-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(2
4-dimethoxy-phenyl)-acryloyloxy]-piperidine]-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3
4-dimethoxy-phenyl)-acryloyloxy]-piperidine]-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3
5-dimethoxy-phenyl)-acryloyloxy]-piperidine]-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3
4-dicyano-phenyl)-acryloyloxy]-piperidine]-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3
5-dicyano-phenyl)-acryloyloxy]-piperidine]-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(2
4-dinitro-phenyl)-acryloyloxy]-piperidine]-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3
4-dichloro-phenyl)-acryloyloxy]-piperidine]-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3
5-dichloro-phenyl)-acryloyloxy]-piperidine]-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3,4-difluoro-phenyl)-acryloyloxy]-piperidine]-
ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3,5-difluoro-phenyl)-acryloyloxy]-piperidine]-
ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3-bromo-4-fluoro-phenyl)-acryloyloxy]-piperidi
ne]-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-chloro-3-nitro-phenyl)-acryloyloxy]-piperidi
ne]-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(2-chloro-4-fluoro-phenyl)-acryloyloxy]-piperid
ine]-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3-chloro-4-fluoro-phenyl)-acryloyloxy]-piperid
ine]-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-cyano-4'-biphenyl)-acryloyloxy]-piperidine]-
ethyene];
poly[1-[1-carbonyl-4-[(E)-3-[4-(trans-4-methyl-cyclohexyl)-phenyl]-acryloyl
oxy]-piperidine]ethylene];
poly[1-[1-carbonyl-4-[(E)-3-phenyl-acryloyl]-piperazine]-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-methyl-phenyl)-acryloyl]-piperazine]-ethylen
e];
poly[1-[1-carbonyl-4-[(E)-3-(4-methoxy-phenyl)-acryloyl]-piperazine]-ethyle
ne];
poly[1-[1-carbonyl-4-[(E)-3-(4-trifluoromethyl-phenyl)-acryloyl]-piperazine
]-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-trifluoromethoxy-phenyl)-acryloyl]-piperazin
e]-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3-cyano-phenyl)-acryloyl]-piperazine]-ethylene
];
poly[1-[1-carbonyl-4-[(E)-3-(4-cyano-phenyl)-acryloyl]-piperazine]-ethylene
];
poly[1-[1-carbonyl-4-[(E)-3-(3-nitro-phenyl)-acryloyl]-piperazine]-ethylene
];
poly[1-[1-carbonyl-4-[(E)-3-(4-nitro-phenyl)-acryloyl]-piperazine]-ethylene
];
poly[1-[1-carbonyl-4-[(E)-3-(3-chloro-phenyl)-acryloyl]-piperazine]-ethylen
e];
poly[1-[1-carbonyl-4-[(E)-3-(4-chloro-phenyl)-acryloyl]-piperazine]-ethylen
e];
poly[1-[1-carbonyl-4-[(E)-3-(2-fluoro-phenyl)-acryloyl]-piperazine]-ethylen
e];
poly[1-[1-carbonyl-4-[(E)-3-(3-fluoro-phenyl)-acryloyl]-piperazine]-ethylen
e];
poly[1-[1-carbonyl-4-[(E)-3-(4-fluoro-phenyl)-acryloyl]-piperazine]-ethylen
e];
poly[1-[1-carbonyl-4-[(E)-3-(2,4-dimethyl-phenyl)-acryloyl]-piperazine]-eth
ylene];
poly[1-[1-carbonyl-4-[(E)-3-(2,3-dimethoxy-phenyl)-acryloyl]-piperazine]-et
hylene];
poly[1-[1-carbonyl-4-[(E)-3-(2,4-dimethoxy-phenyl)-acryloyl]-piperazine]-et
hylene];
poly[1-[1-carbonyl-4-[(E)-3-(3,4-dimethoxy-phenyl)-acryloyl]-piperazine]-et
hylene];
poly[1-[1-carbonyl-4-[(E)-3-(3,5-dimethoxy-phenyl)-acryloyl]-piperazine]-et
hylene];
poly[1-[1-carbonyl-4-[(E)-3-(3,4-dicyano-phenyl)-acryloyl]-piperazine]-ethy
lene];
poly[1-[1-carbonyl-4-[(E)-3-(3,5-dicyano-phenyl)-acryloyl]-piperazine]-ethy
lene];
poly[1-[1-carbonyl-4-[(E)-3-(2,4-dinitro-phenyl)-acryloyl]-piperazine]-ethy
lene];
poly[1-[1-carbonyl-4-[(E)-3-(3,4-dichloro-phenyl)-acryloyl]-piperazine]-eth
ylene];
poly[1-[1-carbonyl-4-[(E)-3-(3,5-dichloro-phenyl)-acryloyl]-piperazine]-eth
ylene];
poly[1-[1-carbonyl-4-[(E)-3-(3,4-difluoro-phenyl)-acryloyl]-piperazine]-eth
ylene];
poly[1-[1-carbonyl-4-[(E)-3-(3,5-difluoro-phenyl)-acryloyl]-piperazine]-eth
ylene];
poly[1-[1-carbonyl-4-[(E)-3-(3-bromo-4-fluoro-phenyl)-acryloyl]-piperazine]
-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-chloro-3-nitro-phenyl)-acryloyl]-piperazine]
-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(2-chloro-4-fluoro-phenyl)-acryloyl]-piperazine
]-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(3-chloro-4-fluoro-phenyl)-acryloyl]-piperazine
]-ethylene];
poly[1-[1-carbonyl-4-[(E)-3-(4-cyano-4'-biphenyl)-acryloyl]-piperazine]-eth
ylene];
poly[1-[1-carbonyl-4-[(E)-3-[4-(trans-4-methyl-cyclohexyl)-phenyl]-acryloyl
]-piperazine]-ethylene].
* * * * *