U.S. patent application number 13/952694 was filed with the patent office on 2014-01-09 for nanotextured surfaces.
This patent application is currently assigned to INNOVATIVE SURFACE TECHNOLOGIES, INC.. The applicant listed for this patent is INNOVATIVE SURFACE TECHNOLOGIES, INC.. Invention is credited to Patrick E. Guire, Laurie R. Lawin, Kristin Taton, Jie Wen.
Application Number | 20140011938 13/952694 |
Document ID | / |
Family ID | 37669395 |
Filed Date | 2014-01-09 |
United States Patent
Application |
20140011938 |
Kind Code |
A1 |
Guire; Patrick E. ; et
al. |
January 9, 2014 |
NANOTEXTURED SURFACES
Abstract
The invention describes novel compositions that include a cross
linking compound, a polymer and a 1 nm to about a 25 micron sized
particle optionally with an oxide layer. In particular, the
particle is a silica and one which has been pretreated with a
silane.
Inventors: |
Guire; Patrick E.; (Hopkins,
MN) ; Taton; Kristin; (Little Canada, MN) ;
Wen; Jie; (Eden Prairie, MN) ; Lawin; Laurie R.;
(New Brighton, MN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
INNOVATIVE SURFACE TECHNOLOGIES, INC. |
St. Paul |
MN |
US |
|
|
Assignee: |
INNOVATIVE SURFACE TECHNOLOGIES,
INC.
St. Paul
MN
|
Family ID: |
37669395 |
Appl. No.: |
13/952694 |
Filed: |
July 29, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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13167104 |
Jun 23, 2011 |
8496857 |
|
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13952694 |
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11457170 |
Jul 13, 2006 |
7989619 |
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13167104 |
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60807143 |
Jul 12, 2006 |
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60699200 |
Jul 14, 2005 |
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Current U.S.
Class: |
524/493 |
Current CPC
Class: |
Y10T 428/31551 20150401;
Y10T 428/31993 20150401; Y10T 428/31721 20150401; Y10T 428/31989
20150401; C08K 5/0025 20130101; Y10T 428/31855 20150401; Y10T
428/31725 20150401; Y10T 428/31507 20150401; C09D 7/63 20180101;
Y10T 428/31511 20150401; Y10T 428/31678 20150401 |
Class at
Publication: |
524/493 |
International
Class: |
C09D 7/12 20060101
C09D007/12 |
Claims
1. A composition comprising a compound of formula:
L-(D-CH.sub.2CH(OP)CH.sub.2GR.sup.3C(.dbd.O)R.sup.4).sub.m wherein
L is a branched or unbranched alkyl chain having between about 2
and about 10 carbon atoms, ##STR00032## R.sup.12, R.sup.13,
R.sup.14, R.sup.15, R.sup.16, R.sup.17 are each independently a
hydrogen atom, an alkyl or aryl group or denotes a bond with D,
provided at least two of R.sup.12, R.sup.13, R.sup.14, R.sup.15,
R.sup.16, R.sup.17 are bonded with two different D and each K,
independently, is CH or N, ##STR00033## R.sup.20 and R.sup.21 are
each individually a hydrogen atom, an alkyl group or an aryl group,
a urea, a uracil, or a mannitol; D is O; P is a hydrogen atom or a
protecting group; G is O; R.sup.3 and R.sup.4 are, each
independently, aryl; and m is an integer from 2 to about 10; a
polymer; and a particle having a particle size of between about 1
nm to about 25 microns.
2. The composition of claim 1, wherein the particles are fabricated
from material selected from the group of aluminum oxide, titanium
oxide, zirconium oxide, gold, silver, nickel, iron oxide, and
alloys, polystyrene, (meth) acrylate, PTFE, silica, polyolefin,
polycarbonate, polysiloxane, silicone, polyester, polyamide,
polyurethane, ethylenically unsaturated polymers, polyanhydride,
polycaprolactone, polylactideglycolide, or combinations
thereof.
3. The composition of claim 1, wherein the particles are selected
from the group of nanofibers, nanotubes, nanowires, or combinations
thereof.
4. The composition of claim 1, wherein the composition is super
hydrophobic and has a water contact angle above 150.degree..
5. The composition of claim 1, wherein the composition is ultra
hydrophobic and has a water contact angle of 120.degree. to
150.degree..
6. A method to modify a substrate comprising the step of applying a
composition comprising the compound, polymer and particle of claim
1 to a surface of a substrate, such that the substrate surface is
modified.
7. The method of claim 6, wherein the compound is photoactivated
such that at least one photoactivatable group within the compound
forms a bond with the surface of the substrate.
8. A composition comprising a compound of formula:
L-(T-C(R.sup.1)(XP)CHR.sup.2GR.sup.3C(.dbd.O)R.sup.4).sub.m wherein
L is a branched or unbranched alkyl chain having between about 2
and about 10 carbon atoms, ##STR00034## R.sup.12, R.sup.13,
R.sup.14, R.sup.15, R.sup.16, R.sup.17 are each independently a
hydrogen atom, an alkyl or aryl group or denotes a bond with T,
provided at least two of R.sup.12, R.sup.13, R.sup.14, R.sup.15,
R.sup.16, R.sup.17 are bonded with two different T and each K,
independently, is CH or N, ##STR00035## R.sup.20 and R.sup.21 are
each individually a hydrogen atom, an alkyl group or an aryl group,
a urea, a uracil, or a mannitol; T is (--CH.sub.2--).sub.x, or
forms a bond; R.sup.1 is a hydrogen atom, an alkyl, alkyloxyalkyl,
aryl, aryloxyalkyl or aryloxyaryl group; X is O, P is a hydrogen
atom or a protecting group; R.sup.2 is a hydrogen atom, an alkyl,
alkyloxyalkyl, aryl, aryloxyalkyl or aryloxyaryl group; G is O;
R.sup.3 and R.sup.4 are, each independently, aryl; x is an integer
from 1 to about 500; m is an integer from 2 to about 10; a polymer;
and a particle having a particle size of between about 1 nm to
about 25 microns.
9. The composition of claim 8, wherein the particles are fabricated
from material selected from the group of aluminum oxide, titanium
oxide, zirconium oxide, gold, silver, nickel, iron oxide, and
alloys, polystyrene, (meth) acrylate, PTFE, silica, polyolefin,
polycarbonate, polysiloxane, silicone, polyester, polyamide,
polyurethane, ethylenically unsaturated polymers, polyanhydride,
polycaprolactone, polylactideglycolide, or combinations
thereof.
10. The composition of claim 8, wherein the particles are selected
from the group of nanofibers, nanotubes, nanowires, or combinations
thereof.
11. The composition of claim 8, wherein the composition is super
hydrophobic and has a water contact angle above 150.degree..
12. The composition of claim 8, wherein the composition is ultra
hydrophobic and has a water contact angle of 120.degree. to
150.degree..
13. A method to modify a substrate comprising the step of applying
a composition comprising the compound, polymer and particle of
claim 8 to a surface of a substrate, such that the substrate
surface is modified.
14. The method of claim 13, wherein the compound is photoactivated
such that at least one photoactivatable group within the compound
forms a bond with the surface of the substrate.
15. A composition comprising a compound of formula:
L-(TGQR.sup.3C(.dbd.O)R.sup.4).sub.m wherein L is a branched or
unbranched alkyl chain having between about 2 and about 10 carbon
atoms, ##STR00036## R.sup.12, R.sup.13, R.sup.14, R.sup.15,
R.sup.16, R.sup.17 are each independently a hydrogen atom, an alkyl
or aryl group or denotes a bond with T, provided at least two of
R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, R.sup.17 are
bonded with two different T and each K, independently, is CH or N,
##STR00037## R.sup.20 and R.sup.21 are each individually a hydrogen
atom, an alkyl group or an aryl group, a urea, a uracil, or a
mannitol; T is (--CH.sub.2--).sub.x, or forms a bond; G is O; Q is
(--CH.sub.2--).sub.p, (--CH.sub.2CH.sub.2--O--).sub.p,
(--CH.sub.2CH.sub.2CH.sub.2--O--).sub.p or
(--CH.sub.2CH.sub.2CH.sub.2CH.sub.2--O--).sub.p; R.sup.3 and
R.sup.4 are, each independently, aryl; p is an integer from 1 to
about 10; x is an integer from 1 to about 500; and m is an integer
from 2 to about 10; a polymer; and a particle having a particle
size of between about 1 nm to about 25 microns.
16. The composition of claim 15, wherein the particles are
fabricated from material selected from the group of aluminum oxide,
titanium oxide, zirconium oxide, gold, silver, nickel, iron oxide,
and alloys, polystyrene, (meth) acrylate, PTFE, silica, polyolefin,
polycarbonate, polysiloxane, silicone, polyester, polyamide,
polyurethane, ethylenically unsaturated polymers, polyanhydride,
polycaprolactone, polylactideglycolide, or combinations
thereof.
17. The composition of claim 15, wherein the particles are selected
from the group of nanofibers, nanotubes, nanowires, or combinations
thereof.
18. The composition of claim 15, wherein the composition is super
hydrophobic and has a water contact angle above 150.degree..
19. The composition of claim 15, wherein the composition is ultra
hydrophobic and has a water contact angle of 120.degree. to
150.degree..
20. A method to modify a substrate comprising the step of applying
a composition comprising the compound, polymer and particle of
claim 15 to a surface of a substrate, such that the substrate
surface is modified.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Continuation of U.S. patent
application Ser. No. 13/167,104, filed Jun. 23, 2011, entitled
"Nanotextured Surfaces", which is a Continuation of U.S. patent
application Ser. No. 11/457,170, filed Jul. 13, 2006, entitled
"Nanotextured Surfaces", issued as U.S. Pat. No. 7,989,619, which
claims benefit under 35 U.S.C. .sctn.119(e) to U.S. Ser. Nos.
60/699,200, entitled "Nanotextured Surfaces", filed Jul. 14, 2005
(attorney docket number 186805/US) and 60/807,143, entitled
"Nanotextured Surfaces", filed Jul. 12, 2006 (attorney docket
number 186805/US/2), the contents of which are incorporated herein
by reference in their entirety.
FIELD OF THE INVENTION
[0002] The invention relates generally to super hydrophobic or
ultra hydrophobic coatings that include a cross linker with
photoactivatable groups, a polymer and a 1 nm to about a 25 micron
sized particle, optionally with an oxide layer, such as a porous or
non-porous silica. The compositions are useful as surface coating
agents alone or in combination with other target molecules such as
polymers, biomolecules and the like.
BACKGROUND OF THE INVENTION
[0003] There exist many ways to coat, adhere, adsorb, modify, etc.
a surface with a material, such that the material changes the
characteristics of the surface. For example, suitable coatings can
be prepared that when applied to a given surface render the surface
hydrophobic. In other instances, the coating may provide enhanced
ability to bind with a target molecule, such as a protein.
[0004] In particular, there are known cross linking materials that
include a latent reactive group, such as a photoactivatable group.
The cross linking material has, in general, at least two
photoactivatable groups, such that one group can be activated and
attached to the surface of the substrate. The remaining latent
group, can then later be, or simultaneously with the surface
attachment, activated to react with a target molecule such as a
polymer or a biomolecule.
[0005] Unfortunately, the cross linking materials themselves are
generally not hydrophobic and thus lessen the hydrophobic nature of
the treated surface.
[0006] Therefore, a need exists for coating compositions that
include photoactivatable crosslinking groups that do not detract
from the desired hydrophobic nature of the treated surface.
BRIEF SUMMARY OF THE INVENTION
[0007] The present invention surprisingly provides unique
hydrophobic or ultra hydrophobic compositions that include a
crosslinker with photoactivatable (photoreactive) groups, a polymer
and a 1 nm to about a 25 micron sized particle, optionally having
an oxide layer, such as a porous or non-porous particles including,
aluminum oxides (alumina), titanium oxide, zirconium oxide, gold
(treated with thiols), silver (thiol or silane treated), nickel,
iron oxide, and alloys (all treated with silane), polystyrene
particles, (meth)acrylates particles, PTFE particles, silica
particles, polyolefin particles, polycarbonate particles,
polysiloxane particles, silicone particles, polyester particles,
polyamide particles, polyurethane particles, ethylenically
unsaturated polymer particles, polyanhydride particles and
biodegradable particles such as polycaprolactone (PCL) and
polylactideglycolide (PLGA), and nanofibers, nanotubes, or
nanowires. Generally inorganic particles, porous or non-porous, are
pretreated with a silane to promote hydrophobicity.
[0008] One unique cross linking molecular family includes compounds
having the formula:
L-((D-T-C(R.sup.1)(XP)CHR.sup.2GR.sup.3C(.dbd.O)R.sup.4)).sub.m.
[0009] L is a linking group. D is O, S, SO, SO.sub.2, NR.sup.5 or
CR.sup.6R.sup.7. T is (--CH.sub.2--).sub.x,
(--CH.sub.2CH.sub.2--O--).sub.x,
(--CH.sub.2CH.sub.2CH.sub.2--O--).sub.x,
(--CH.sub.2CH.sub.2CH.sub.2CH.sub.2--O--).sub.x or forms a bond.
R.sup.1 is a hydrogen atom, an alkyl, alkyloxyalkyl, aryl,
aryloxyalkyl or aryloxyaryl group. X is O, S, or NR.sup.8R.sup.9. P
is a hydrogen atom or a protecting group, with the provisio that P
is absent when X is NR.sup.8R.sup.9. R.sup.2 is a hydrogen atom, an
alkyl, alkyloxyalkyl, aryl, aryloxylalkyl or aryloxyaryl group. G
is O, S, SO, SO.sub.2, NR.sup.10, (CH.sub.2).sub.t--O-- or C.dbd.O.
R.sup.3 and R.sup.4 are each independently an alkyl, aryl,
arylalkyl, heteroaryl, or an heteroarylalkyl group, or optionally,
R.sup.3 and R.sup.4 can be tethered together via
(--CH.sub.2--).sub.q,
(--CH.sub.2--).sub.rC.dbd.O(--CH.sub.2--).sub.s,
(--CH.sub.2--).sub.rS(--CH.sub.2--).sub.s,
(--CH.sub.2--).sub.rS.dbd.O(--CH.sub.2--).sub.s,
(--CH.sub.2--).sub.rS(O).sub.2(--CH.sub.2--).sub.s, or
(--CH.sub.2--).sub.rNR(--CH.sub.2--).sub.s. R.sup.5 and R.sup.10
are each independently a hydrogen atom or an alkyl, aryl, or
arylalkyl group. R.sup.6 and R.sup.7 are each independently a
hydrogen atom, an alkyl, aryl, arylalkyl, heteroaryl or
heteroarylalkyl group. R.sup.8 and R.sup.9 are each independently a
hydrogen atom, an alkyl, aryl, or arylalkyl group, R is a hydrogen
atom, an alkyl group or an aryl group, q is an integer from 1 to
about 7, r is an integer from 0 to about 3, s is an integer from 0
to about 3, m is an integer from 2 to about 10, t is an integer
from 1 to about 10 and x is an integer from 1 to about 500.
[0010] In one aspect, L is a branched or unbranched alkyl chain
having between about 2 and about 10 carbon atoms.
[0011] In another aspect, D is an oxygen atom (O).
[0012] In still another aspect, T is (--CH.sub.2--).sub.x or
(--CH.sub.2CH.sub.2--O--).sub.x and x is 1 or 2.
[0013] In still yet another aspect, R.sup.1 is a hydrogen atom.
[0014] In yet another aspect, X is an oxygen atom, 0, and P is a
hydrogen atom.
[0015] In another aspect, R.sup.2 is a hydrogen atom.
[0016] In still another aspect, G is an oxygen atom, O.
[0017] In still yet another aspect, R.sup.3 and R.sup.4 are each
individually aryl groups, which can be further substituted, and m
is 3.
[0018] In one particular aspect, L is
##STR00001##
D is O, T is (--CH.sub.2--).sub.x, R.sup.1 is a hydrogen atom, X is
O, P is a hydrogen atom, R.sup.2 is a hydrogen atom, G is O,
R.sup.3 and R.sup.4 are phenyl groups, m is 3 and x is 1.
[0019] In yet another particular aspect, L is (--CH.sub.2--).sub.y,
D is O, T is (--CH.sub.2--).sub.x, R.sup.1 is a hydrogen atom, X is
O, P is a hydrogen atom, R.sup.2 is a hydrogen atom, G is O,
R.sup.3 and R.sup.4 are phenyl groups, m is 2, x is 1 and y is an
integer from 2 to about 6, and in particular, y is 2, 4 or 6.
[0020] A second unique cross linking molecular family includes
compounds having the formula:
L-((T-C(R.sup.1)(XP)CHR.sup.2GR.sup.3C(.dbd.O)R.sup.4)).sub.m.
[0021] L is a linking group. T is (--CH.sub.2--).sub.x,
(--CH.sub.2CH.sub.2--O--).sub.x,
(--CH.sub.2CH.sub.2CH.sub.2--O--).sub.x,
(--CH.sub.2CH.sub.2CH.sub.2CH.sub.2--O--).sub.x or forms a bond.
R.sup.1 is a hydrogen atom, an alkyl, alkyloxyalkyl, aryl,
aryloxyalkyl or aryloxyaryl group. X is O, S, or NR.sup.8R.sup.9. P
is a hydrogen atom or a protecting group, with the provisio that P
is absent when X is NR.sup.8R.sup.9. R.sup.2 is a hydrogen atom, an
alkyl, alkyloxyalkyl, aryl, aryloxylalkyl or aryloxyaryl group. G
is O, S, SO, SO.sub.2, NR.sup.10, (CH.sub.2).sub.t--O-- or C.dbd.O.
R.sup.3 and R.sup.4 are each independently an alkyl, aryl,
arylalkyl, heteroaryl, or an heteroarylalkyl group, or optionally,
R.sup.3 and R.sup.4 can be tethered together via
(--CH.sub.2--).sub.q,
(--CH.sub.2--).sub.rC.dbd.O(--CH.sub.2--).sub.s,
(--CH.sub.2--).sub.rS(--CH.sub.2--).sub.s,
(--CH.sub.2--).sub.rS.dbd.O(--CH.sub.2--).sub.s,
(--CH.sub.2--).sub.rS(O).sub.2(--CH.sub.2--).sub.s, or
(--CH.sub.2--).sub.rNR(--CH.sub.2--).sub.s. R.sup.10 is a hydrogen
atom or an alkyl, aryl, or arylalkyl group. R.sup.8 and R.sup.9 are
each independently a hydrogen atom, an alkyl, aryl, or arylalkyl
group. R is a hydrogen atom, an alkyl group or an aryl group, q is
an integer from 1 to about 7, r is an integer from 0 to about 3, s
is an integer from 0 to about 3, m is an integer from 2 to about
10, t is an integer from 1 to about 10 and x is an integer from 1
to about 500.
[0022] In one aspect, L has a formula according to structure
(I):
##STR00002##
[0023] A and J are each independently a hydrogen atom, an alkyl
group, an aryl group, or together with B form a cyclic ring,
provided when A and J are each independently a hydrogen atom, an
alkyl group, or an aryl group then B is not present, B is
NR.sup.11, O, or (--CH.sub.2--).sub.z, provided when A, B and J
form a ring, then A and J are (--CH.sub.2--).sub.z or C.dbd.O,
R.sup.11 is a hydrogen atom, an alkyl group, an aryl group or
denotes a bond with T, each z independently is an integer from 0 to
3 and provided when either A or J is C.dbd.O, then B is NR.sup.11,
O, or (--CH.sub.2--).sub.z and z must be at least 1.
[0024] In another aspect T is --CH.sub.2--.
[0025] In still another aspect, R.sup.1 is a hydrogen atom.
[0026] In still yet another aspect, X is O and P is a hydrogen
atom.
[0027] In still another aspect, R.sup.2 is a hydrogen atom.
[0028] In yet another aspect, G is O.
[0029] In another aspect, R.sup.3 and R.sup.4 are each individually
aryl groups.
[0030] In still yet another aspect, m is 3, and in particular, A
and J are both C.dbd.O and B is N or A and J are both hydrogen
atoms.
[0031] A third unique cross linking molecular family includes
compounds having the formula: [0032]
L-((TGQR.sup.3C(.dbd.O)R.sup.4)).sub.m.
[0033] L is a linking group. T is (--CH.sub.2--).sub.x,
(--CH.sub.2CH.sub.2--O--).sub.x,
(--CH.sub.2CH.sub.2CH.sub.2--O--).sub.x,
(--CH.sub.2CH.sub.2CH.sub.2CH.sub.2--O--).sub.x or forms a bond. G
is O, S, SO, SO.sub.2, NR.sup.10, (CH.sub.2).sub.t--O-- or C.dbd.O.
Q is (--CH.sub.2--).sub.p, (--CH.sub.2CH.sub.2--O--).sub.p,
--(CH.sub.2CH.sub.2CH.sub.2--O--).sub.p or
(--CH.sub.2CH.sub.2CH.sub.2CH.sub.2--O--).sub.p. R.sup.3 and
R.sup.4 are each independently an alkyl, aryl, arylalkyl,
heteroaryl, or an heteroarylalkyl group, or optionally, R.sup.3 and
R.sup.4 can be tethered together (--CH.sub.2--).sub.q,
(--CH.sub.2--).sub.rC.dbd.O(--CH.sub.2--).sub.s,
(--CH.sub.2--).sub.rS(--CH.sub.2--).sub.s,
(--CH.sub.2--).sub.rS.dbd.O(--CH.sub.2--).sub.s,
(--CH.sub.2--).sub.rS(O).sub.2(--CH.sub.2--).sub.s, or
(--CH.sub.2--).sub.rNR(--CH.sub.2--).sub.s. R.sup.10 is a hydrogen
atom or an alkyl, aryl, alkylaryl or arylalkyl group. R is a
hydrogen atom, an alkyl group or an aryl group, q is an integer
from 1 to about 7, r is an integer from 0 to about 3, s is an
integer from 0 to about 3, m is an integer from 2 to about 10, p is
an integer from 1 to about 10, t is an integer from 1 to about 10
and x is an integer from 1 to about 500.
[0034] In one aspect, L has a formula according to structure
(I):
##STR00003##
[0035] A and J are each independently a hydrogen atom, an alkyl
group, an aryl group, or together with B form a cyclic ring,
provided when A and J are each independently a hydrogen atom, an
alkyl group, or an aryl group then B is not present, B is
NR.sup.11, O, or (--CH.sub.2--).sub.z, provided when A, B and J
form a ring, then A and J are (--CH.sub.2--).sub.z or C.dbd.O,
R.sup.11 is a hydrogen atom, an alkyl group, an aryl group or
denotes a bond with T, each z independently is an integer from 0 to
3 and provided when either A or J is C.dbd.O, then B is NR.sup.11,
0, or (--CH.sub.2--).sub.z and z must be at least 1.
[0036] In one aspect, T is --CH.sub.2--.
[0037] In another aspect, G is an oxygen atom, O.
[0038] In still another aspect, R.sup.3 and R.sup.4 are each
individually aryl groups, which can be substituted, and m is 2.
[0039] In still yet another aspect, A and J are both C.dbd.O and B
is NR.sup.11.
[0040] In another aspect, A and J are both hydrogen atoms.
[0041] In yet another aspect, L has a formula according to
structure (II):
##STR00004##
[0042] R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, R.sup.17
are each independently a hydrogen atom, an alkyl or aryl group or
denotes a bond with T, provided at least two of R.sup.12, R.sup.13,
R.sup.14, R.sup.15, R.sup.16, R.sup.17 are bonded with T and each
K, independently is CH or N.
[0043] A fourth unique cross linking molecular family includes
compounds having the formula:
L-((GTZR.sup.3C(.dbd.O)R.sup.4)).sub.m
[0044] L is a linking group. T is (--CH.sub.2--).sub.x,
(--CH.sub.2CH.sub.2--O--).sub.x,
(--CH.sub.2CH.sub.2CH.sub.2--O--).sub.x,
(--CH.sub.2CH.sub.2CH.sub.2CH.sub.2--O--).sub.x or forms a bond. G
is O, S, SO, SO.sub.2, NR.sup.10, (CH.sub.2).sub.r--O-- or C.dbd.O.
Z can be a C.dbd.O, COO or CONH when T is (--CH.sub.2--).sub.x.
R.sup.3 and R.sup.4 are each independently an alkyl, aryl,
arylalkyl, heteroaryl, or an heteroarylalkyl group, or optionally,
R.sup.3 and R.sup.4 can be tethered together via
(--CH.sub.2--).sub.q,
(--CH.sub.2--).sub.rC.dbd.O(--CH.sub.2--).sub.s,
(--CH.sub.2--).sub.rS(--CH.sub.2--).sub.s,
(--CH.sub.2--).sub.rS.dbd.O(--CH.sub.2--).sub.s,
(--CH.sub.2--).sub.rS(O).sub.2(--CH.sub.2--).sub.s, or
(--CH.sub.2--).sub.rNR(--CH.sub.2--).sub.s. R.sup.10 is a hydrogen
atom or an alkyl, aryl, alkylaryl or arylalkyl group. R is a
hydrogen atom, an alkyl group or an aryl group, q is an integer
from 1 to about 7, r is an integer from 0 to about 3, s is an
integer from 0 to about 3, m is an integer from 2 to about 10, p is
an integer from 1 to about 10, t is an integer from 1 to about 10
and x is an integer from 1 to about 500.
[0045] In one aspect, L has a formula according to structure
(I):
##STR00005##
[0046] A and J are each independently a hydrogen atom, an alkyl
group, an aryl group, or together with B form a cyclic ring,
provided when A and J are each independently a hydrogen atom, an
alkyl group, or an aryl group then B is not present, B is
NR.sup.11, O, or (--CH.sub.2--).sub.z, provided when A, B and J
form a ring, then A and J are (--CH.sub.2--).sub.z or C.dbd.O,
R.sup.11 is a hydrogen atom, an alkyl group, an aryl group or
denotes a bond with T, each z independently is an integer from 0 to
3 and provided when either A or J is C.dbd.O, then B is NR.sup.11,
O, or (--CH.sub.2--).sub.z and z must be at least 1.
[0047] In one aspect, T is --CH.sub.2--.
[0048] In another aspect, G is an oxygen atom, O.
[0049] In still another aspect, R.sup.3 and R.sup.4 are each
individually aryl groups, which can be substituted, and m is 2.
[0050] In still yet another aspect, A and J are both C.dbd.O and B
is NR.sup.11.
[0051] In another aspect, A and J are both hydrogen atoms.
[0052] In yet another aspect, L has a formula according to
structure (II):
##STR00006##
[0053] R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, R.sup.17
are each independently a hydrogen atom, an alkyl or aryl group or
denotes a bond with T, provided at least two of R.sup.12, R.sup.13,
R.sup.14, R.sup.15, R.sup.16, R.sup.17 are bonded with T and each
K, independently is CH or N.
[0054] In still yet another aspect, compounds of the present
invention provide that R.sup.3 and R.sup.4 are both phenyl groups
and are tethered together via a CO, a S or a CH.sub.2.
[0055] In yet another aspect, compounds of the present invention
provide when R.sup.3 and R.sup.4 are both phenyl group, the phenyl
groups can be substituted with at least one
CH.sub.3OCH.sub.2CH.sub.2O--.
[0056] The compositions of the invention include the crosslinkers
described throughout the specification in combination with a
polymer, in particular a hydrophobic polymer, and a particle having
a particle size between about 1 nm to about a 25 microns, such as a
porous or non-porous silica. In one embodiment, the particle has
been treated with a silane.
[0057] The compositions of the invention have broad applications.
The compositions can be used in surface modifications. The
combination of the crosslinker, polymer, and particle, optionally
treated with silane, having a size between about 1 nm to about a 25
microns, such as silica, provide hydrophobic coatings. This
physical attribute provides that the compositions can be used where
hydrophobic agents are favored.
[0058] The inclusion of photoreactive moieties within the
compositions provides that the composition can be used with a wide
range of support surfaces. The compositions can be used alone or in
combination with other materials to provide a desired surface
characteristic. The compositions, alone or in combination with
another material, provides the treated surface having a hydrophobic
surface.
[0059] While multiple embodiments are disclosed, still other
embodiments of the present invention will become apparent to those
skilled in the art from the following detailed description. As will
be apparent, the invention is capable of modifications in various
obvious aspects, all without departing from the spirit and scope of
the present invention. Accordingly, the detailed descriptions are
to be regarded as illustrative in nature and not restrictive.
DETAILED DESCRIPTION
[0060] The present invention surprisingly provides unique cross
linking molecule families that include photoactivatable groups,
that in combination with a polymer and a 1 nm to about a 25 micron
sized particle, such as silica, provide hydrophobic (e.g., super
hydrophobic or ultra hydrophobic) compositions that can be used to
treat surfaces.
[0061] The compositions of the invention are useful as coating
agents. As described throughout the specification, the compositions
include a unique crosslinker, a polymer and a particle having a
particle size between about 1 nm to about a 25 microns. In one
embodiment, the particle has an oxide coating. In another aspect,
the particle is pretreated with a silane. In still another aspect,
the particle, with the oxide layer has been pretreated with a
silane. The intent being that the particle exhibits some degree of
hydrophobicity.
[0062] The particles include those particles having a particle size
of between about 1 nm and about 25 micron sized particles that can
be porous or non-porous particles derived from aluminum oxides
(alumina), titanium oxide, zirconium oxide, gold (treated with
thiols), silver (thiol or silane treated), nickel, iron oxide, and
alloys (all treated with silane), polystyrene particles,
(meth)acrylates particles, PTFE particles, silica particles,
polyolefin particles, polycarbonate particles, polysiloxane
particles, silicone particles, polyester particles, polyamide
particles, polyurethane particles, ethylenically unsaturated
polymer particles, polyanhydride particles and biodegradable
particles such as polycaprolactone (PCL) and polylactideglycolide
(PLGA), and nanofibers, nanotubes, or nanowires and combinations
thereof. Appropriate treatments of the metals, such as gold,
silver, and other nobel metals and alloys are generally include use
of alkylthiols, more particularly fluoroalkylthiols.
[0063] Super hydrophobicity, and ultra hydrophobicity are defined
as surfaces which have a water contact angle above 150.degree. and
120.degree.-150.degree. respectively. In nature, lotus leaves are
considered super hydrophobic. Water drops roll off the leaves
collecting dirt along the way to give a "self-cleaning" surface.
This behavior is believed to be a result of nanotextured surfaces,
as well as a wax layer present on the leaf. However, super
hydrophobic surfaces cannot be derived from simply coating
hydrophobic or oleophobic substances on surfaces, but also require
nanotexture, small protrusions on the surface giving a topography
on the order of 1-1000 nm. When nanotexture is added to a
hydrophobic surface, water contact angles rise from 100-120.degree.
to over 150.degree.. Not to be limited by theory, it is believed
that the nanotexture produces this effect by trapping air in the
spaces between structural features. Water droplets interact with
both the very small hydrophobic tips of the particles and the
larger valleys between particles where only air remains. Air is
also highly hydrophobic. The water contacts the particle tips and
does not penetrate into the air pockets. As a result the water
cannot remain still on the surface and "dances" away.
[0064] The present invention provides unique compositions and
methods for preparing photocrosslinked super hydrophobic or ultra
hydrophobic surfaces. Such surfaces may be useful for coatings for
a variety of applications including automotive, RF coatings for
satellite dishes, fabrics, filters, transportation, building
materials, and others. There are few low cost methods of
manufacturing super or ultra hydrophobic surfaces and these current
methods generally lack durability. Introducing photoreactive
crosslinkers into a polymer-particle matrix and photolyzing the
crosslinker, crosslinks the matrix and greatly improves durability
and use time of the coatings.
[0065] The coatings of the invention can be applied to a large
variety of substrates including but not limited to plastics
(polyethylene, PVC, polystyrene, polyurethane, etc), glass, wood,
paper, ceramics and metals. The polymer is optimally hydrophobic
(WCA)>70.degree. and may contain reactive groups such as double
bonds, but is not required to. The photocrosslinker may be
hydrophobic, amphiphilic, or hydrophilic as it is added in smaller
quantities. The nanoparticles should also be hydrophobic. The
polymer matrix entraps the nanoparticles on the surface to give the
needed nanotexture. It also provides the surface
hydrophobicity.
[0066] Photopolymerization can be defined as a phenomenon whereby
low molecular weight substances are joined together to create a new
larger structure by way of the action of light. When light is
absorbed, electrons populate excited states in molecules. These
excited states are generally quite short-lived and terminate by one
of three pathways. The excited state can emit a photon from either
a singlet state (fluorescence) or a triplet state
(phosphorescence), lose its energy via vibrations in the form on
heat, or react chemically. Because the absorption of a photon
highly excites a molecule, there is a much wider variety of
reactions possible than standard thermochemical means.
Photocrosslinking uses these reactions to link small molecules to
other small molecules, large molecules to small molecules, and
large molecules to each other (photocoupling of polymers), as well
as large and small molecules to substrates or particles
(photobonding to surfaces). During photocrosslinking each increase
in molecular weight is initiated by its own photochemical reaction
and the coupling of radicals can result in the formation of
crosslinks, especially in the solid state. The crosslinking is
generally between pre-existing polymer chains and includes
polycondensation, which is also referred to as step growth
polymerization. Photocrosslinking can usually be classified into
two types.
[0067] The first type is where crosslinks are formed by the direct
reaction of an excited molecule. Representative reactions would be
a photo 2+2 cycloaddition (or 4+4) and cis-trans isomerization of
double bonds. Examples of this type are demonstrated by the
cyclodimerization of cinnamic acid and derivatives, chalcones and
stilbenes, anthracenes, maleimides and strained cycloalkenes. In
another large class of reactions, the triplet, T.sub.1 excited
state of carbonyl groups in ketones can result in either
fragmentation (Norrish Type I reaction) or hydrogen abstraction
(Norrish type II reaction). Both of these photoreactions create two
radicals which can then subsequently react with surrounding
molecules. For example, aromatic ketones, such as benzophenone,
readily undergo hydrogen abstraction reactions with any preformed
polymer possessing C--H bonds. A possible mechanism is shown in the
Scheme which follows.
(C.sub.6H.sub.5).sub.2C.dbd.O)(T.sub.1)+Rp-H.fwdarw.(C.sub.6H.sub.5).sub-
.2C.--OH)+Rp.
Rp.+(C.sub.6H.sub.5).sub.2C.--OH).fwdarw.(C.sub.6H.sub.5).sub.2C--(Rp)-O-
H)
[0068] Scheme. Possible photolysis mechanism with benzophenone as
an example of a non cross linking photoreactive moiety. It should
be understood that incorporation of two or more photoreactive
moieties, such as a benzophenone, would provide a multifunctional
cross linking photoreactive group.
[0069] The second usual type of photocrosslinking is where
crosslinks occur through the action of a photogenerated reactive
species. Examples of the second type include the use of nitrenes
that are formed from organic azides, carbenes.
[0070] Whether through direct excited state reaction or reactive
intermediates, photolysis of photoreactive cross linking groups can
begin a process of bond formation throughout a mixture. In most
cases this will be a solid mixture of polymers, particles, and
photoreactive cross linking groups designed to give a nanotextured
surface. The act of cross linking will serve to increase the
durability of this surface. Bonds will be formed between polymer
and photoreactive cross linking group, and between polymer,
photoreactive cross linking group and the surface and/or particles.
Bond formation may take place by many means within the various
systems. In many cases radicals are formed through photolysis.
Radicals can form new bonds through radical-radical recombination,
addition to unsaturated bonds, hydrogen abstraction and subsequent
recombination or addition, further fragmentation, oxygen addition,
or disproportionation, as well as possible electron transfer
reactions. Similarly, photoreactive cross linking group and polymer
can be bonded to the surface of the substrate or the particles. All
of these newly formed covalent bonds increase the durability and
stability of the matrix. In cases which generate carbenes and
nitrenes, bonds would be formed typically by insertion, hydrogen
abstraction to form radicals, rearrangements, etc. The excited
states of some dienes and other unsaturated compounds may directly
react with relevant groups on a polymer chain, as when cinnamic
acid forms a 2+2 photoadduct with polybutadiene or other polymer
(or surface) containing double bonds. The invention is not limited
to these mechanisms, and in fact, many mechanisms may be at work
within one polymer-particle-photoreactive cross linking group
matrix.
[0071] In one embodiment the crosslinker has the formula:
L-((D-T-C(R.sup.1)(XP)CHR.sup.2GR.sup.3C(.dbd.O)R.sup.4)).sub.m.
[0072] L is a linking group. D is O, S, SO, SO.sub.2, NR.sup.5 or
CR.sup.6R.sup.7. T is (--CH.sub.2--).sub.x,
(--CH.sub.2CH.sub.2--O--).sub.x,
(--CH.sub.2CH.sub.2CH.sub.2--O--).sub.x,
(--CH.sub.2CH.sub.2CH.sub.2CH.sub.2--O--).sub.x or forms a bond.
R.sup.1 is a hydrogen atom, an alkyl, alkyloxyalkyl, aryl,
aryloxyalkyl or aryloxyaryl group. X is O, S, or NR.sup.8R.sup.9. P
is a hydrogen atom or a protecting group, with the provisio that P
is absent when X is NR.sup.8R.sup.9. R.sup.2 is a hydrogen atom, an
alkyl, alkyloxyalkyl, aryl, aryloxylalkyl or aryloxyaryl group. G
is O, S, SO, SO.sub.2, NR.sup.10, (CH.sub.2).sub.t--O-- or C.dbd.O.
R.sup.3 and R.sup.4 are each independently an alkyl, aryl,
arylalkyl, heteroaryl, or a heteroarylalkyl group, or optionally,
R.sup.3 and R.sup.4 can be tethered together via
(--CH.sub.2--).sub.q,
(--CH.sub.2--).sub.rC.dbd.O(--CH.sub.2--).sub.s,
(--CH.sub.2--).sub.rS(--CH.sub.2--).sub.s,
(--CH.sub.2--).sub.rS.dbd.O(--CH.sub.2--).sub.s,
(--CH.sub.2--).sub.rS(O).sub.2(--CH.sub.2--).sub.s, or
(--CH.sub.2--).sub.rNR(--CH.sub.2--).sub.s. R.sup.5 and R.sup.10
are each independently a hydrogen atom or an alkyl, aryl, or
arylalkyl group. R.sup.6 and R.sup.7 are each independently a
hydrogen atom, an alkyl, aryl, arylalkyl, heteroaryl or
heteroarylalkyl group. R.sup.8 and R.sup.9 are each independently a
hydrogen atom, an alkyl, aryl, or arylalkyl group, R is a hydrogen
atom, an alkyl group or an aryl group, q is an integer from 1 to
about 7, r is an integer from 0 to about 3, s is an integer from 0
to about 3, m is an integer from 2 to about 10, t is an integer
from 1 to about 10 and x is an integer from 1 to about 500.
[0073] In one aspect, L is a branched or unbranched alkyl chain
having between about 2 and about 10 carbon atoms.
[0074] In another aspect, D is an oxygen atom (O).
[0075] In still another aspect, T is (--CH.sub.2--).sub.x or
(--CH.sub.2CH.sub.2--O--).sub.x and x is 1 or 2.
[0076] In still yet another aspect, R.sup.1 is a hydrogen atom.
[0077] In yet another aspect, X is an oxygen atom, O, and P is a
hydrogen atom.
[0078] In another aspect, R.sup.2 is a hydrogen atom.
[0079] In still another aspect, G is an oxygen atom, O.
[0080] In still yet another aspect, R.sup.3 and R.sup.4 are each
individually aryl groups, which can be further substituted, and m
is 3.
[0081] In one particular aspect, L is
##STR00007##
D is O, T is (--CH.sub.2--).sub.x, R.sup.1 is a hydrogen atom, X is
O, P is a hydrogen atom, R.sup.2 is a hydrogen atom, G is O,
R.sup.3 and R.sup.4 are phenyl groups, m is 3 and x is 1.
[0082] In yet another particular aspect, L is (--CH.sub.2--).sub.y,
D is O, T is (--CH.sub.2--).sub.x, R.sup.1 is a hydrogen atom, X is
O, P is a hydrogen atom, R.sup.2 is a hydrogen atom, G is O,
R.sup.3 and R.sup.4 are phenyl groups, m is 2, x is 1 and y is an
integer from 2 to about 6, and in particular, y is 2, 4 or 6.
[0083] In certain embodiments, x is an integer from about 1 to
about 500, more particularly from about 1 to about 400, from about
1 to about 250, from about 1 to about 200, from about 1 to about
150, from about 1 to about 100, from about 1 to about 50, from
about 1 to about 25 or from about 1 to about 10.
[0084] In another embodiment, the crosslinker has the formula:
L-((T-C(R.sup.1)(XP)CHR.sup.2GR.sup.3C(.dbd.O)R.sup.4)).sub.m.
[0085] wherein L, T, R.sup.1, X, P, R.sup.2, G, R.sup.3, R.sup.4,
R.sup.8, R.sup.9, R.sup.10, R, q, r, s, m and x are as defined
above.
[0086] In one aspect, L has a formula according to structure
(I):
##STR00008##
[0087] A and J are each independently a hydrogen atom, an alkyl
group, an aryl group, or together with B form a cyclic ring,
provided when A and J are each independently a hydrogen atom, an
alkyl group, or an aryl group then B is not present, B is
NR.sup.11, O, or (--CH.sub.2--).sub.z, provided when A, B and J
form a ring, then A and J are (--CH.sub.2--).sub.z or C.dbd.O,
R.sup.11 is a hydrogen atom, an alkyl group, an aryl group or
denotes a bond with T, each z independently is an integer from 0 to
3 and provided when either A or J is C.dbd.O, then B is NR.sup.11,
O, or (--CH.sub.2--).sub.z and z must be at least 1.
[0088] In another aspect T is --CH.sub.2--.
[0089] In another embodiment, the family has the formula:
L-((GTZR.sup.3C(.dbd.O)R.sup.4)).sub.m
[0090] wherein L, T, G, R.sup.3, R.sup.4, R.sup.10, R, q, r, s, m
and x are as defined above. Z can be a C.dbd.O, COO or CONH when T
is (--CH.sub.2--).sub.x.
[0091] In one aspect, L has a formula according to structure
(I):
##STR00009##
[0092] wherein A, B, J, R.sup.11, and z are as defined above.
[0093] In another aspect, L has a formula according to structure
(II):
##STR00010##
[0094] R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, R.sup.17
are each independently a hydrogen atom, an alkyl or aryl group or
denotes a bond with T, provided at least two of R.sup.12, R.sup.13,
R.sup.14, R.sup.15, R.sup.16, R.sup.17 are bonded with T and each
K, independently is CH or N.
[0095] In another embodiment, the family has the formula:
L-((TGQR.sup.3C(.dbd.O)R.sup.4)).sub.m
[0096] wherein L, G, R.sup.3, R.sup.4, R.sup.10, R, q, r, s, m and
x are as defined above. T is (--CH.sub.2--).sub.x,
(--CH.sub.2CH.sub.2--O--).sub.x,
(--CH.sub.2CH.sub.2CH.sub.2--O--).sub.x,
(--CH.sub.2CH.sub.2CH.sub.2CH.sub.2--O--).sub.x or forms a bond. Q
is (--CH.sub.2--).sub.p, (--CH.sub.2CH.sub.2--O--).sub.p,
(--CH.sub.2CH.sub.2CH.sub.2--O--).sub.p or
(--CH.sub.2CH.sub.2CH.sub.2CH.sub.2--O--).sub.p and p is an integer
from 1 to about 10.
[0097] In one aspect, L has a formula according to structure
(I):
##STR00011##
[0098] wherein A, B, J, R.sup.11, and z are as defined above.
[0099] In another aspect, L has a formula according to structure
(II):
##STR00012##
[0100] R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, R.sup.17
are each independently a hydrogen atom, an alkyl or aryl group or
denotes a bond with T, provided at least two of R.sup.12, R.sup.13,
R.sup.14, R.sup.15, R.sup.16, R.sup.17 are bonded with T and each
K, independently is CH or N.
[0101] In still yet another aspect, compounds of the present
invention provide that R.sup.3 and R.sup.4 are both phenyl groups
and are tethered together via a CO, a S or a CH.sub.2.
[0102] In yet another aspect, compounds of the present invention
provide when R.sup.3 and R.sup.4 are phenyl groups, the phenyl
groups can each independently be substituted with at least one
alkyloxyalkyl group, such as
CH.sub.3O--(CH.sub.2CH.sub.2O--).sub.n--, or
CH.sub.3O(--CH.sub.2CH.sub.2CH.sub.2O--).sub.n-- a hydroxylated
alkoxy group, such as HO--CH.sub.2CH.sub.2O--,
HO(--CH.sub.2CH.sub.2O--).sub.n-- or
HO(--CH.sub.2CH.sub.2CH.sub.2O--).sub.n--, etc. wherein n is an
integer from 1 to about 10.
[0103] In another embodiment the family has the formula:
L-((-CH.sub.2--).sub.xxC(R.sup.1)(GR.sup.3C(.dbd.O)R.sup.4).sub.2).sub.m
[0104] wherein L, each R, R.sup.1, each G, each R.sup.3, each
R.sup.4, each R.sup.10, each q, each r, each s, each t and m are as
defined above and xx is an integer from 1 to about 10.
[0105] In one aspect, L has a formula according to structure
(I):
##STR00013##
[0106] wherein A, B, J, R.sup.11, and z are as defined above.
[0107] In another aspect, A and J are both hydrogen atoms.
[0108] In still another aspect, xx is 1.
[0109] In yet another aspect, R.sup.1 is H.
[0110] In still yet another aspect, G is (--CH.sub.2--).sub.tO--
and t is 1.
[0111] In another aspect, R.sup.3 and R.sup.4 are each individually
aryl groups.
[0112] In still yet another embodiment, xx is 1, R.sup.1 is H, each
G is (--CH.sub.2--).sub.tO--, t is 1 and each of R.sup.3 and
R.sup.4 are each individually aryl groups.
[0113] In another embodiment of the invention, the family has the
formula:
L-((-C(R.sup.1)(XP)CHR.sup.2GR.sup.3C(.dbd.O)R.sup.4).sub.m
[0114] where L, R, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.8,
R.sup.9, R.sup.10, X, P, G, q, r, s, t, and m are as defined
above.
[0115] In one aspect, L is
##STR00014##
and R.sup.20 and R.sup.21 are each individually a hydrogen atom, an
alkyl group or an aryl group.
[0116] In another aspect, R.sup.1 is H.
[0117] In still another aspect, X is O.
[0118] In yet another aspect, P is H.
[0119] In still yet another aspect, R.sup.2 is H.
[0120] In another aspect, G is (--CH.sub.2--)tO-- and t is 1.
[0121] In still another aspect, R.sup.3 and R.sup.4 are each
individually aryl groups.
[0122] In yet another aspect, R.sup.1 is H, X is O, P is H, R.sup.2
is H, G is (--CH.sub.2--).sub.tO--, t is 1, R.sup.3 and R.sup.4 are
each individually aryl groups and R.sup.20 and R.sup.21 are both
methyl groups.
[0123] In yet another embodiment, the present invention provides a
family of compounds having the formula:
L-((GR.sup.3C(.dbd.O)R.sup.4)).sub.m
[0124] where L, G, R, R.sup.3, R.sup.4, R.sup.10, q, r, s, m and t
are as defined above.
[0125] In one aspect, L is
##STR00015##
[0126] In another aspect, G is C.dbd.O.
[0127] In still another aspect, R.sup.3 and R.sup.4 are each
individually aryl groups.
[0128] In yet another aspect, G is C.dbd.O and R.sup.3 and R.sup.4
are each individually aryl groups.
[0129] In still yet another embodiment, the present invention
provides a family of compounds having the formula:
L-((ZZ-D-T-C(R.sup.1)(XP)CHR.sup.2GR.sup.3C(.dbd.O)R.sup.4)).sub.m
[0130] where L is as described above or CH.
[0131] T, R.sup.1, X, P, R.sup.2, G, R.sup.3, R.sup.4 and m are as
described above.
[0132] ZZ is a linking group as described above for L, and in
particular is an aryl or alkyl group. In particular ZZ is a phenyl
group.
[0133] In one aspect, m is 3.
[0134] In another aspect, L is CH, ZZ is phenyl, D is O, T is
CH.sub.2, R.sup.1 is H, P is H, R.sup.2 is H, G is O, R.sup.3 is
phenyl, R.sup.4 is phenyl with a --OC.sub.8H.sub.17 (an alkoxide)
substituent and m is 3.
[0135] "Alkyl" by itself or as part of another substituent refers
to a saturated or unsaturated branched, straight-chain or cyclic
monovalent hydrocarbon radical having the stated number of carbon
atoms (i.e., C1-C6 means one to six carbon atoms) that is derived
by the removal of one hydrogen atom from a single carbon atom of a
parent alkane, alkene or alkyne. Typical alkyl groups include, but
are not limited to, methyl; ethyls such as ethanyl, ethenyl,
ethynyl; propyls such as propan-1-yl, propan-2-yl,
cyclopropan-1-yl, prop-1-en-1-yl, prop-1-en-2-yl, prop-2-en-1-yl,
cycloprop-1-en-1-yl; cycloprop-2-en-1-yl, prop-1-yn-1-yl,
prop-2-yn-1-yl, etc.; butyls such as butan-1-yl, butan-2-yl,
2-methyl-propan-1-yl, 2-methyl-propan-2-yl, cyclobutan-1-yl,
but-1-en-1-yl, but-1-en-2-yl, 2-methyl-prop-1-en-1-yl,
but-2-en-1-yl, but-2-en-2-yl, buta-1,3-dien-1-yl,
buta-1,3-dien-2-yl, cyclobut-1-en-1-yl, cyclobut-1-en-3-yl,
cyclobuta-1,3-dien-1-yl, but-1-yn-1-yl, but-1-yn-3-yl,
but-3-yn-1-yl, etc.; and the like. Where specific levels of
saturation are intended, the nomenclature "alkanyl," "alkenyl"
and/or "alkynyl" is used, as defined below. "Lower alkyl" refers to
alkyl groups having from 1 to 6 carbon atoms.
[0136] "Alkanyl" by itself or as part of another substituent refers
to a saturated branched, straight-chain or cyclic alkyl derived by
the removal of one hydrogen atom from a single carbon atom of a
parent alkane. Typical alkanyl groups include, but are not limited
to, methanyl; ethanyl; propanyls such as propan-1-yl, propan-2-yl
(isopropyl), cyclopropan-1-yl, etc.; butanyls such as butan-1-yl,
butan-2-yl (sec-butyl), 2-methyl-propan-1-yl (isobutyl),
2-methyl-propan-2-yl (t-butyl), cyclobutan-1-yl, etc.; and the
like.
[0137] "Alkenyl" by itself or as part of another substituent refers
to an unsaturated branched, straight-chain or cyclic alkyl having
at least one carbon-carbon double bond derived by the removal of
one hydrogen atom from a single carbon atom of a parent alkene. The
group may be in either the cis or trans conformation about the
double bond(s). Typical alkenyl groups include, but are not limited
to, ethenyl; propenyls such as prop-1-en-1-yl, prop-1-en-2-yl,
prop-2-en-1-yl, prop-2-en-2-yl, cycloprop-1-en-1-yl;
cycloprop-2-en-1-yl; butenyls such as but-1-en-1-yl, but-1-en-2-yl,
2-methyl-prop-1-en-1-yl, but-2-en-1-yl, but-2-en-2-yl,
buta-1,3-dien-1-yl, buta-1,3-dien-2-yl, cyclobut-1-en-1-yl,
cyclobut-1-en-3-yl, cyclobuta-1,3-dien-1-yl, etc.; and the
like.
[0138] "Alkyloxyalkyl" refers to a moiety having two alkyl groups
tethered together via an oxygen bond. Suitable alkyloxyalkyl groups
include polyoxyalkylenes, such as polyethyleneoxides,
polypropyleneoxides, etc. that are terminated with an alkyl group,
such as a methyl group. A general formula for such compounds can be
depicted as R'-(OR'').sub.n or (R'O).sub.n--R'' wherein n is an
integer from 1 to about 10, and R' and R'' are alkyl or alkylene
groups.
[0139] "Alkynyl" by itself or as part of another substituent refers
to an unsaturated branched, straight-chain or cyclic alkyl having
at least one carbon-carbon triple bond derived by the removal of
one hydrogen atom from a single carbon atom of a parent alkyne.
Typical alkynyl groups include, but are not limited to, ethynyl;
propynyls such as prop-1-yn-1-yl, prop-2-yn-1-yl, etc.; butynyls
such as but-1-yn-1-yl, but-1-yn-3-yl, but-3-yn-1-yl, etc.; and the
like.
[0140] "Alkyldiyl" by itself or as part of another substituent
refers to a saturated or unsaturated, branched, straight-chain or
cyclic divalent hydrocarbon group having the stated number of
carbon atoms (i.e., C1-C6 means from one to six carbon atoms)
derived by the removal of one hydrogen atom from each of two
different carbon atoms of a parent alkane, alkene or alkyne, or by
the removal of two hydrogen atoms from a single carbon atom of a
parent alkane, alkene or alkyne. The two monovalent radical centers
or each valency of the divalent radical center can form bonds with
the same or different atoms. Typical alkyldiyl groups include, but
are not limited to, methandiyl; ethyldiyls such as ethan-1,1-diyl,
ethan-1,2-diyl, ethen-1,1-diyl, ethen-1,2-diyl; propyldiyls such as
propan-1,1-diyl, propan-1,2-diyl, propan-2,2-diyl, propan-1,3-diyl,
cyclopropan-1,1-diyl, cyclopropan-1,2-diyl, prop-1-en-1,1-diyl,
prop-1-en-1,2-diyl, prop-2-en-1,2-diyl, prop-1-en-1,3-diyl,
cycloprop-1-en-1,2-diyl, cycloprop-2-en-1,2-diyl,
cycloprop-2-en-1,1-diyl, prop-1-yn-1,3-diyl, etc.; butyldiyls such
as, butan-1,1-diyl, butan-1,2-diyl, butan-1,3-diyl, butan-1,4-diyl,
butan-2,2-diyl, 2-methyl-propan-1,1-diyl, 2-methyl-propan-1,2-diyl,
cyclobutan-1,1-diyl; cyclobutan-1,2-diyl, cyclobutan-1,3-diyl,
but-1-en-1,1-diyl, but-1-en-1,2-diyl, but-1-en-1,3-diyl,
but-1-en-1,4-diyl, 2-methyl-prop-1-en-1,1-diyl,
2-methanylidene-propan-1,1-diyl, buta-1,3-dien-1,1-diyl,
buta-1,3-dien-1,2-diyl, buta-1,3-dien-1,3-diyl,
buta-1,3-dien-1,4-diyl, cyclobut-1-en-1,2-diyl,
cyclobut-1-en-1,3-diyl, cyclobut-2-en-1,2-diyl,
cyclobuta-1,3-dien-1,2-diyl, cyclobuta-1,3-dien-1,3-diyl,
but-1-yn-1,3-diyl, but-1-yn-1,4-diyl, buta-1,3-diyn-1,4-diyl, etc.;
and the like. Where specific levels of saturation are intended, the
nomenclature alkanyldiyl, alkenyldiyl and/or alkynyldiyl is used.
Where it is specifically intended that the two valencies be on the
same carbon atom, the nomenclature "alkylidene" is used. A "lower
alkyldiyl" is an alkyldiyl group having from 1 to 6 carbon atoms.
In preferred embodiments the alkyldiyl groups are saturated acyclic
alkanyldiyl groups in which the radical centers are at the terminal
carbons, e.g., methandiyl (methano); ethan-1,2-diyl (ethano);
propan-1,3-diyl (propano); butan-1,4-diyl (butano); and the like
(also referred to as alkylenes, defined infra).
[0141] "Alkylene" by itself or as part of another substituent
refers to a straight-chain saturated or unsaturated alkyldiyl group
having two terminal monovalent radical centers derived by the
removal of one hydrogen atom from each of the two terminal carbon
atoms of straight-chain parent alkane, alkene or alkyne. The locant
of a double bond or triple bond, if present, in a particular
alkylene is indicated in square brackets. Typical alkylene groups
include, but are not limited to, methylene (methano); ethylenes
such as ethano, etheno, ethyno; propylenes such as propano,
prop[1]eno, propa[1,2]dieno, prop[1]yno, etc.; butylenes such as
butano, but[1]eno, but[2]eno, buta[1,3]dieno, but[1]yno, but[2]yno,
buta[1,3]diyno, etc.; and the like. Where specific levels of
saturation are intended, the nomenclature alkano, alkeno and/or
alkyno is used. In preferred embodiments, the alkylene group is
(C1-C6) or (C1-C3) alkylene. Also preferred are straight-chain
saturated alkano groups, e.g., methano, ethano, propano, butano,
and the like.
[0142] "Aryl" by itself or as part of another substituent refers to
a monovalent aromatic hydrocarbon group having the stated number of
carbon atoms (i.e., C5-C15 means from 5 to 15 carbon atoms) derived
by the removal of one hydrogen atom from a single carbon atom of a
parent aromatic ring system. Typical aryl groups include, but are
not limited to, groups derived from aceanthrylene, acenaphthylene,
acephenanthrylene, anthracene, azulene, benzene, chrysene,
coronene, fluoranthene, fluorene, hexacene, hexaphene, hexylene,
as-indacene, s-indacene, indane, indene, naphthalene, octacene,
octaphene, octalene, ovalene, penta-2,4-diene, pentacene,
pentalene, pentaphene, perylene, phenalene, phenanthrene, picene,
pleiadene, pyrene, pyranthrene, rubicene, triphenylene,
trinaphthalene, and the like, as well as the various hydro isomers
thereof. In preferred embodiments, the aryl group is (C5-C15) aryl,
with (C5-C10) being even more preferred. Particularly preferred
aryls are phenyl and naphthyl.
[0143] "Arylalkyl" by itself or as part of another substituent
refers to an acyclic alkyl radical in which one of the hydrogen
atoms bonded to a carbon atom, typically a terminal or sp.sup.3
carbon atom, is replaced with an aryl group. Typical arylalkyl
groups include, but are not limited to, benzyl, 2-phenylethan-1-yl,
2-phenylethen-1-yl, naphthylmethyl, 2-naphthylethan-1-yl,
2-naphthylethen-1-yl, naphthobenzyl, 2-naphthophenylethan-1-yl and
the like. Where specific alkyl moieties are intended, the
nomenclature arylalkanyl, arylalkenyl and/or arylalkynyl is used.
Preferably, an arylalkyl group is (C.sub.7-C.sub.30) arylalkyl,
e.g., the alkanyl, alkenyl or alkynyl moiety of the arylalkyl group
is (C.sub.1-C.sub.10) and the aryl moiety is (C.sub.6-C.sub.20),
more preferably, an arylalkyl group is (C.sub.7-C.sub.20)
arylalkyl, e.g., the alkanyl, alkenyl or alkynyl moiety of the
arylalkyl group is (C.sub.1-C.sub.8) and the aryl moiety is
(C.sub.6-C.sub.12).
[0144] "Aryloxyalkyl" refers to a moiety having an aryl group and
an alkyl group tethered together via an oxygen bond. Suitable
aryloxyalkyl groups include phenyloxyalkylenes, such as
methoxyphenyl, ethoxyphenyl, etc.
[0145] "Cycloalkyl" by itself or as part of another substituent
refers to a cyclic version of an "alkyl" group. Typical cycloalkyl
groups include, but are not limited to, cyclopropyl; cyclobutyls
such as cyclobutanyl and cyclobutenyl; cyclopentyls such as
cyclopentanyl and cycloalkenyl; cyclohexyls such as cyclohexanyl
and cyclohexenyl; and the like.
[0146] "Cycloheteroalkyl" by itself or as part of another
substituent refers to a saturated or unsaturated cyclic alkyl
radical in which one or more carbon atoms (and any associated
hydrogen atoms) are independently replaced with the same or
different heteroatom. Typical heteroatoms to replace the carbon
atom(s) include, but are not limited to, N, P, O, S, Si, etc. Where
a specific level of saturation is intended, the nomenclature
"cycloheteroalkanyl" or "cycloheteroalkenyl" is used. Typical
cycloheteroalkyl groups include, but are not limited to, groups
derived from epoxides, imidazolidine, morpholine, piperazine,
piperidine, pyrazolidine, pyrrolidine, quinuclidine, and the
like.
[0147] "Halogen" or "Halo" by themselves or as part of another
substituent, unless otherwise stated, refer to fluoro, chloro,
bromo and iodo.
[0148] "Haloalkyl" by itself or as part of another substituent
refers to an alkyl group in which one or more of the hydrogen atoms
are replaced with a halogen. Thus, the term "haloalkyl" is meant to
include monohaloalkyls, dihaloalkyls, trihaloalkyls, etc. up to
perhaloalkyls. For example, the expression "(C1-C2) haloalkyl"
includes fluoromethyl, difluoromethyl, trifluoromethyl,
1-fluoroethyl, 1,1-difluoroethyl, 1,2-difluoroethyl,
1,1,1-trifluoroethyl, perfluoroethyl, etc.
[0149] "Heteroalkyl, Heteroalkanyl, Heteroalkenyl, Heteroalkynyl"
by itself or as part of another substituent refer to alkyl,
alkanyl, alkenyl and alkynyl radical, respectively, in which one or
more of the carbon atoms (and any associated hydrogen atoms) are
each independently replaced with the same or different heteroatomic
groups. Typical heteroatomic groups include, but are not limited
to, --O--, --S--, --O--O--, --S--S--, --O--S--, --NR'--,
.dbd.N--N.dbd., --N.dbd.N--, --N.dbd.N--NR'--, --PH--,
--P(O).sub.2--, --O--P(O).sub.2--, --S(O)--, --S(O).sub.2--,
--SnH.sub.2-- and the like, where R' is hydrogen, alkyl,
substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl or
substituted aryl.
[0150] "Heteroaryl" by itself or as part of another substituent,
refers to a monovalent heteroaromatic radical derived by the
removal of one hydrogen atom from a single atom of a parent
heteroaromatic ring system. Typical heteroaryl groups include, but
are not limited to, groups derived from acridine, arsindole,
carbazole, .beta.-carboline, benzoxazine, benzimidazole, chromane,
chromene, cinnoline, furan, imidazole, indazole, indole, indoline,
indolizine, isobenzofuran, isochromene, isoindole, isoindoline,
isoquinoline, isothiazole, isoxazole, naphthyridine, oxadiazole,
oxazole, perimidine, phenanthridine, phenanthroline, phenazine,
phthalazine, pteridine, purine, pyran, pyrazine, pyrazole,
pyridazine, pyridine, pyrimidine, pyrrole, pyrrolizine,
quinazoline, quinoline, quinolizine, quinoxaline, tetrazole,
thiadiazole, thiazole, thiophene, triazole, xanthene, and the like.
Preferably, the heteroaryl group is from 5-20 membered heteroaryl,
more preferably from 5-10 membered heteroaryl. Preferred heteroaryl
groups are those derived from thiophene, pyrrole, benzothiophene,
benzofuran, indole, pyridine, quinoline, imidazole, oxazole and
pyrazine.
[0151] "Heteroarylalkyl" by itself or as part of another
substituent refers to an acyclic alkyl group in which one of the
hydrogen atoms bonded to a carbon atom, typically a terminal or
sp.sup.3 carbon atom, is replaced with a heteroaryl group. Where
specific alkyl moieties are intended, the nomenclature
heteroarylalkanyl, heteroarylakenyl and/or heteroarylalkynyl is
used. In preferred embodiments, the heteroarylalkyl group is a 6-21
membered heteroarylalkyl, e.g., the alkanyl, alkenyl or alkynyl
moiety of the heteroarylalkyl is (C1-C6) alkyl and the heteroaryl
moiety is a 5-15-membered heteroaryl. In particularly preferred
embodiments, the heteroarylalkyl is a 6-13 membered
heteroarylalkyl, e.g., the alkanyl, alkenyl or alkynyl moiety is
(C1-C3) alkyl and the heteroaryl moiety is a 5-10 membered
heteroaryl.
[0152] "Hydroxyalkyl" by itself or as part of another substituent
refers to an alkyl group in which one or more of the hydrogen atoms
are replaced with a hydroxyl substituent. Thus, the term
"hydroxyalkyl" is meant to include monohydroxyalkyls,
dihydroxyalkyls, trihydroxyalkyls, etc.
[0153] "Parent Aromatic Ring System" refers to an unsaturated
cyclic or polycyclic ring system having a conjugated .pi. electron
system. Specifically included within the definition of "parent
aromatic ring system" are fused ring systems in which one or more
of the rings are aromatic and one or more of the rings are
saturated or unsaturated, such as, for example, fluorene, indane,
indene, phenalene, tetrahydronaphthalene, etc. Typical parent
aromatic ring systems include, but are not limited to,
aceanthrylene, acenaphthylene, acephenanthrylene, anthracene,
azulene, benzene, chrysene, coronene, fluoranthene, fluorene,
hexacene, hexaphene, hexylene, indacene, s-indacene, indane,
indene, naphthalene, octacene, octaphene, octalene, ovalene,
penta-2,4-diene, pentacene, pentalene, pentaphene, perylene,
phenalene, phenanthrene, picene, pleiadene, pyrene, pyranthrene,
rubicene, tetrahydronaphthalene, triphenylene, trinaphthalene, and
the like, as well as the various hydro isomers thereof.
[0154] "Parent Heteroaromatic Ring System" refers to a parent
aromatic ring system in which one or more carbon atoms (and any
associated hydrogen atoms) are independently replaced with the same
or different heteroatom. Typical heteroatoms to replace the carbon
atoms include, but are not limited to, N, P, O, S, Si, etc.
Specifically included within the definition of "parent
heteroaromatic ring systems" are fused ring systems in which one or
more of the rings are aromatic and one or more of the rings are
saturated or unsaturated, such as, for example, arsindole,
benzodioxan, benzofuran, chromane, chromene, indole, indoline,
xanthene, etc. Typical parent heteroaromatic ring systems include,
but are not limited to, arsindole, carbazole, .beta.-carboline,
chromane, chromene, cinnoline, furan, imidazole, indazole, indole,
indoline, indolizine, isobenzofuran, isochromene, isoindole,
isoindoline, isoquinoline, isothiazole, isoxazole, naphthyridine,
oxadiazole, oxazole, perimidine, phenanthridine, phenanthroline,
phenazine, phthalazine, pteridine, purine, pyran, pyrazine,
pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolizine,
quinazoline, quinoline, quinolizine, quinoxaline, tetrazole,
thiadiazole, thiazole, thiophene, triazole, xanthene, and the
like.
[0155] "Leaving group" is a group that is displaced during a
reaction by a nucleophilic reagent. Suitable leaving groups include
S(O).sub.2Me, --SMe or halo (e.g., F, Cl, Br, I).
[0156] "Linking group" is a group that serves as an intermediate
locus between two or more end groups. The nature of the linking
group can vary widely, and can include virtually any combination of
atoms or groups useful for spacing one molecular moiety from
another. For example, the linker may be an acyclic hydrocarbon
bridge (e.g, a saturated or unsaturated alkyleno such as methano,
ethano, etheno, propano, prop[1]eno, butano, but[1]eno, but[2]eno,
buta[1,3]dieno, and the like), a monocyclic or polycyclic
hydrocarbon bridge (e.g., [1,2]benzeno, [2,3]naphthaleno, and the
like), a simple acyclic heteroatomic or heteroalkyldiyl bridge
(e.g., --O--, --S--, --S--O--, --NH--, --PH--, --C(O)--,
--C(O)NH--, --S(O)--, --S(O).sub.2--, --S(O)NH--, --S(O).sub.2NH--,
--O--CH.sub.2--, --CH.sub.2--O--CH.sub.2--,
--O--CH.dbd.CH--CH.sub.2--, and the like), a monocyclic or
polycyclic heteroaryl bridge (e.g., [3,4]furano, pyridino,
thiopheno, piperidino, piperazino, pyrazidino, pyrrolidino, and the
like) or combinations of such bridges.
[0157] "Protecting group" is a group that is appended to, for
example, a hydroxyl oxygen in place of a labile hydrogen atom.
Suitable hydroxyl protecting group(s) include esters (acetate,
ethylacetate), ethers (methyl, ethyl), ethoxylated derivatives
(ethylene glycol, propylene glycol) and the like that can be
removed under either acidic or basic conditions so that the
protecting group is removed and replaced with a hydrogen atom.
Guidance for selecting appropriate protecting groups, as well as
synthetic strategies for their attachment and removal, may be
found, for example, in Greene & Wuts, Protective Groups in
Organic Synthesis, 3d Edition, John Wiley & Sons, Inc., New
York (1999) and the references cited therein (hereinafter "Greene
& Wuts").
[0158] The compositions of the invention that can be used as
coating agents include one or more moieties that render the
molecule hydrophobic in nature.
[0159] Photoreactive species are as described herein, and are
sufficiently stable to be stored under conditions in which they
retain such properties. See, e.g., U.S. Pat. No. 5,002,582, the
disclosure of which is incorporated herein by reference. Latent
reactive groups can be chosen that are responsive to various
portions of the electromagnetic spectrum, with those responsive to
ultraviolet, infrared and visible portions of the spectrum
(referred to herein as "photoreactive").
[0160] Photoreactive groups respond to external stimuli and undergo
active specie generation with the formation of a covalent bond to
an adjacent chemical structure, e.g., as provided by the same or a
different molecule. Photoreactive groups are those groups of atoms
in a molecule that retain their covalent bonds during storage but,
upon activation by an external energy source, form covalent bonds
with other molecules.
[0161] Photoreactive groups generate active species such as free
radicals and particularly nitrenes, carbenes, and excited states of
ketones upon absorption of electromagnetic energy. Photoreactive
groups can be chosen to be responsive to various portions of the
electromagnetic spectrum, and photoreactive species that are
responsive to electromagnetic radiation, including, but not limited
to ultraviolet, infrared and visible portions of the spectrum, are
referred to as a "photochemical group" or "photogroup."
[0162] Free radical photoreactive groups can be classified by the
following two types.
[0163] Type A. Compounds directly produce radicals by unimolecular
fragmentation after light absorption. The radicals result from a
homolytic or heterolytic cleavage of a sigma bond inside the
molecule itself. Common examples include but are not limited to
peroxides, and peroxy compounds, benzoin derivatives (including
ketoxime esters of benzoin), acetophenone derivatives,
benzilketals, .alpha.-hydroxyalkylphenones and
.alpha.-aminoalkylphenones, O-acyl .alpha.-oximinoketones,
acylphosphine oxides and acylphosphonates, thiobenzoic S-esters,
azo and azide compounds, triazines and biimidazoles.
[0164] Type B. Compounds generate free radicals by bimolecular
hydrogen abstraction after light absorption. The hydrogen
abstraction photoreactive group enters an excited state and undergo
an intermolecular reaction with a hydrogen donor to generate free
radicals. This leads to the formation of a pair of radicals
originating from two different molecules. The coupling of radicals
can be used to form crosslinks, especially in the solid state in
the absence of solvents. Common examples include but are not
limited to the following chemical classes. Quinones, benzophenones,
xanthones and thioxanthones, ketocoumarins, aromatic 1,2 diketones
and phenylglyoxylates. Hydrogen abstraction reactions can also
occur intramolecularly. The reactions are not effective for the
direct initiation of polymerization and are used internally for the
formation of an intermediate. This intermediate may be effective
for further cross linking depending on its structure.
[0165] Photoreactive crosslinkers are defined as
multiphotofunctional photoreactive compounds containing a minimum
of two photoreactive groups that can be homo- or hetero-functional.
The photocrosslinkers undergo reactions with pre-existing polymer
or oligomer chains to produce crosslinks, for example, a
multiphotofunctional reactive compound containing multiple
benzophenone functionality. These photoreactive crosslinkers are
expected to be more efficient at creating covalent bonds within a
matrix. Photocrosslinkers can also crosslink polymer to the
substrate surface and the surface of the particles to create a more
durable matrix.
[0166] The various photoreactive groups listed above can be
incorporated into moieties that have at least 2 (or more) of such
photoreactive groups to afford photoreactive cross linking groups
useful with the present invention. It should be understood that the
photoreactive crosslinker may contain two or more types of
photoreactive groups.
[0167] Bis-azido benzylidene methylcyclohexanone, (ABC), (Structure
X) is an example of a multifunctional photocrosslinker based on
phenyl azide that is available from Aldrich Chemicals. Many
heterodifunctional-initiators capable of cross linking through a
photo and a non-photo initiated mechanism are available from Pierce
(Rockford, Ill.). Pierce supplies a photoreactive crosslinker that
is a homodifunctional-initiator,
bis-[b-(4-azidosalicylamido)ethyl]disulfide.
[0168] The photolysis of organic azides has been shown to result in
N.sub.2 loss, producing nitrenes as reactive intermediates.
Nitrenes are known to undergo five general reactions. 1) Addition
to double bonds is observed for both singlet and triplet nitrenes
which in the case of arylnitrenes results in rearrangement of the
aziridine to a secondary amine as a conceivable mechanism. 2)
Insertion of a nitrene into a carbon-hydrogen bond to give a
secondary amine which is observed for singlet nitrenes. 3) Hydrogen
abstraction is the most common reaction of triplet nitrenes in
solution where the formed amino radical and carbon radical
generally diffuse apart and the amino radical abstracts a second
hydrogen atom to give a primary amine. 4) Nitrene dimerization 5)
Attack on heteroatom, for example nitrenes react with azides and
oxygen.
##STR00016##
[0169] Eight commercially available multifunctional
photocrosslinkers based on trichloromethyl triazine are available
either from Aldrich Chemicals, Produits Chimiques Auxiliaires et de
Syntheses, (Longjumeau, France), Shin-Nakamara Chemical, Midori
Chemicals Co., Ltd. or Panchim S.A. (France). The eight compounds
include 2,4,6-tris(trichloromethyl)-1,3,5 triazine,
2-(methyl)-4,6-bis(trichloromethyl)-1,3,5-triazine,
2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine,
2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine,
4-(4-carboxylphenyl)-2,6-bis(trichloromethyl)-1,3,5-triazine,
2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine,
2-(1-ethen-2-2'-furyl)-4,6-bis(trichloromethyl)-1,3,5-triazine and
2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine.
[0170] For example,
2-(4-Methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine,
(Aldrich Chemical) (Structure XI) is a type A photo initiator.
##STR00017##
[0171] Upon direct excitation the homolytic cleavage of one of the
carbon-chlorine bonds occurs yielding a radical pair. The highly
reactive chlorine atom formed in this reaction abstracts a hydrogen
atom to form a carbon radical and hydrogen chloride as shown in the
following Scheme. The trichloromethyl triazine can serve as a
photocrosslinker since it contains two reactive groups.
##STR00018##
[0172] The di-azide compound (Structure X) and the triazine
compound (Structure XI) were evaluated in nanostructured surfaces
and the coatings were shown to have improved durability over
coatings that did not contain a photocrosslinker. (See
Examples)
[0173] The use of photoreactive groups in the form of photoreactive
aryl ketones are useful in photoreactive crosslinkers, such as
acetophenone, benzophenone, anthraquinone, anthrone, and
anthrone-like heterocycles (i.e., heterocyclic analogs of anthrone
such as those having N, O, or S in the 10-position), or their
substituted (e.g., ring substituted) derivatives. Examples of aryl
ketones include heterocyclic derivatives of anthrone, including
acridone, xanthone, and thioxanthone, and their ring substituted
derivatives. In particular, thioxanthone, and its derivatives,
having excitation energies greater than about 360 nm are
useful.
[0174] The photoreactive groups of such ketones are preferred since
they are readily capable of undergoing an
activation/inactivation/reactivation cycle. Benzophenone,
acetophenone and anthraquinone are examples of photoreactive
moieties, since they are capable of photochemical excitation with
the initial formation of an excited singlet state that undergoes
intersystem crossing to the triplet state. The excited triplet
state can insert into carbon-hydrogen bonds by abstraction of a
hydrogen atom (from a support surface, for example), thus creating
a radical pair. Subsequent collapse of the radical pair leads to
formation of a new carbon-carbon bond. If a reactive bond (e.g.,
carbon-hydrogen) is not available for bonding, the ultraviolet
light-induced excitation of the benzophenone, acetophenone or
anthraquinone group is reversible and the molecule returns to
ground state energy level upon removal of the energy source.
Photoactivatible aryl ketones such as benzophenone, anthraquinone
and acetophenone are of particular importance inasmuch as these
groups are subject to multiple reactivation in water and hence
provide increased coating efficiency.
[0175] The compositions of the invention can be applied to a
surface of interest in any suitable manner. For example, the
composition can be applied by dip coating or by dispersing the
compound on the surface (for example, by spray coating). Suitable
methods of application include application in solution, dipping,
spray coating, knife coating, and roller coating. In one aspect,
the compound is applied to the surface via spray coating, as this
application method provides increased density of the compound on
the support surface, thereby improving durability.
[0176] Cross linking agents can be used in any suitable manner,
including by the simultaneous or sequential attachment of a
chemical compound to a surface. Cross linking agents of the present
invention can be used to modify any suitable surface. Where the
latent reactive group of the agent is a photoreactive group of the
preferred type, it is particularly preferred that the surface
provide abstractable hydrogen atoms suitable for covalent bonding
with the activated group.
[0177] Plastics such as polyolefins, polystyrenes,
poly(methyl)methacrylates, polyacrylonitriles, poly(vinylacetates),
poly (vinyl alcohols), chlorine-containing polymers such as
poly(vinyl) chloride, polyoxymethylenes, polycarbonates,
polyamides, polyimides, polyurethanes, phenolics, amino-epoxy
resins, polyesters, silicones, cellulose-based plastics, and
rubber-like plastics can all be used as supports, providing
surfaces that can be modified as described herein. See generally,
"Plastics", pp. 462-464, in Concise Encyclopedia of Polymer Science
and Engineering, Kroschwitz, ed., John Wiley and Sons, 1990, the
disclosure of which is incorporated herein by reference. In
addition, supports such as those formed of pyrolytic carbon,
parylene coated surfaces, and silylated surfaces of glass, ceramic,
or metal are suitable for surface modification.
[0178] Cross linking compounds encompassed by the present invention
can be prepared by selection of an appropriate aryl group with a
photoactivatable group and at least one group that can either act
as a nucleophilic site or can be acted upon in a nucleophilic
displacement reaction with a linking agent (L) having at least two
opposing groups, either a leaving group(s) or a nucleophilic
group(s). General synthetic schemes detailed below demonstrate two
approaches suitable to prepare compounds of the invention.
##STR00019##
Or
##STR00020##
[0179] wherein X is an integer equivalent to "n" and n is an
integer between 2 and about 6, R.sup.3 and R.sup.4 are as defined
above, "Y" is a leaving group or a group that can be acted upon by
a nucleophilic group, such as an ester, carboxylic acid halide,
etc. and "Nuc" is a nucleophilic group, as described in further
detail below. Alternatively, the reaction between "Y" and "Nuc" can
be a condensation reaction, such as the reaction between, for
example, a hydroxyl group and a carboxylic acid.
[0180] It should be understood in schemes I and II, that R.sup.3
and R.sup.4 are interchangeable.
[0181] Suitable nucleophilic groups (Nuc) include, for example,
amines, hydroxyl, thiol, etc.
[0182] Suitable leaving groups, or groups susceptible to
nucleophilic attack, include esters, ethers, epoxides, halides,
isocyanates, isothiocyanates, sulfonyl chlorides, anhydrides,
carboxylic acid halides, carboxylic acid esters, and aldehydes.
[0183] Resultant functional moieties from the reaction between the
nucleophilic group and leaving (or condensation group) include, for
example, esters, ethers, carbamates, thiocarbamates, sulfones,
amides, ureas, thiourea, amines, sulfonamides, imines (that can be
further reduced with a reducing agent such as sodium borohydride to
an amine), etc.
[0184] Suitable reaction conditions for such condensations or
nucleophilic displacements are known in the art. For example,
hydroxyl containing moieties can be condensed with a carboxylic
acid under dehydrating conditions (refluxing toluene, acid
catalyst, Dean Stark trap) to form esters. Reactive halides can be
displaced by hydroxyl groups under basic conditions. An isocyanate
reacts with a hydroxyl group with heat to form carbamates.
Likewise, an isothiocyanates reacts with a hydroxyl group to form a
thiocarbamate. Under deprotonation conditions, a hydroxide ion
reacts with an epoxide to form an ether linkage and forming a new
hydroxyl group. Reaction between a hydroxyl and a sulfonyl chloride
forms a sulfone. Reaction between a hydroxyl and an anhydride will
form a ester with a carboxylic acid portion as well. Reaction
between a hydroxyl group and an ester will also form an ester, with
the removal of a corresponding displaced alcohol, generally under
conditions that drive off the displaced alcohol.
[0185] Much like the reactions with hydroxyl groups, amines serve
in similar manner. For example, an amine can react with an
activated carboxylic acid for form an amide. Activation of a
carboxylic acid can be facilitated by various methods in the art,
including for example, use of dicyclohexylcarbodiimide (DCC) that
generates urea as a side product. An isocyanate reacts with an
amine to form a urea and an isothiocyanate reacts with an amine to
form a thiourea.
[0186] Reaction between an amine and an epoxide will form an amine
with an appended hydroxyl group from the nucleophilic displacement
of the epoxide ring. Reaction between an amine and a sulfonyl
chloride will form a sulfonamide. Reaction between an anhydride and
an amine will afford an amide with a carboxylic portion attached to
the product. Reaction between an aldehyde and an amine will form an
imine which can be further reduced to an amine. Reaction between a
carboxylic acid halide and an amine will form an amide, as well as
the reaction between a carboxylic ester and amine. Lastly, melamine
type compounds can react with an amine to form amine linkages.
[0187] Reaction conditions to form the compounds of the invention
are known in the art. For example, suitable reaction conditions are
described in "March's Advanced Organic Chemistry: Reactions,
Mechanisms, and Structure, 5th Edition, John Wiley & Sons,
Michael B. Smith & Jerry March; Fieser and Fieser's Reagents
for Organic Synthesis" John Wiley & Sons, NY; Vogel's
[0188] Textbook of Practical Organic Chemistry (Fifth Edition) by
A. I. Vogel, B. S. Furniss, A. J. Hannaford, P. W. G. Smith, and A.
R. Tatchell, Longman Scientific and Technical, Longman Group UK;
and Advanced Organic Chemistry parts A and B" Third Edition, F. A.
Carey, R. S. Sundberg, Plenum Press, NY, 1990, the contents of
which are incorporated herein by reference in their entirety.
[0189] It should also be understood that each "Y" independently can
be different. Therefore, it is possible to have reaction products
that include an ether linkage as well as an ester linkage to the
carbonyl containing photoactivatable group.
[0190] An exemplary non-limiting reaction is depicted in Scheme
III, in which a hydroxyl group undergoes nucleophilic addition to
an ester or acid halide or can undergo a condensation reaction
between the hydroxyl group and a carboxylic acid.
##STR00021##
[0191] A second class of photocrosslinkers that undergo 2+2
cycloadditions when photolyzed can be synthesized with the
following general scheme.
R1-CH.dbd.CH--R3-X+YR2Y.fwdarw.R1-CH.dbd.CH--R3-Z-R2-Z-CH.dbd.CH--R1
[0192] X, Y, and Z are functional groups described above as
nucleophiles and leaving groups. R1 is typically substituted or
unsubstituted aryl or contains substituted allylic groups or
carbonyl groups which are conjugated with the main alkene. R3 is a
substituted aryl or alkyl substituent which may include other
functionalities such as esters, amides, ethers, etc. R2 is any
linking agent, such as those shown above. Similarly, the X group
may reside on the R1 component instead of the R3, giving additional
photocrosslinkers.
[0193] In some cases, one arm of the photocrosslinker will be as
the above alkene and one arm will be from the aryl ketone scheme
described above. This may be particularly advantageous because
alkene 2+2 photochemistry generally requires an additional alkene
from the polymer or substrate for reaction. If a crosslinker with
one alkene and one benzophenone was used, the benzophenone would be
available for broad coupling to the polymer, while the alkene would
be available for the more specific coupling of alkene to alkene on
two crosslinkers, thus crosslinking the polymer matrix.
[0194] Other classes of photocrosslinkers include azides,
trichloromethyl-substituted compounds and peroxides. A method to
synthesize the bis(trichloromethyl)-1,3,5-triazine crosslinkers
that contain multiple triazine groups could include of the use of
4-(4-carboxylphenyl)-2,6-bis-(trichloromethy)-1,3,5-triazine which
can be converted to the acid chloride and reacted with a linker, as
described throughout.
[0195] Many methods to synthesize multifunctional azide type
crosslinkers are possible. Alkyl azides are best prepared by
nucleophilic displacement on alkyl halides using sodium azide.
Other ways to prepare azides include reactions between hydrazines
and nitrous acid, reactions of amine anions with tosyl azide,
reactions of diazonium salts with sodium azide and substitution
reactions with compounds containing a double bond. For the
synthesis of multifunctional azide containing reagents the
conversion to the azide would generally be the last step in the
synthetic scheme utilizing a bifunctional or multifunctional
reagent.
[0196] The synthesis of multifunctional peroxide type crosslinkers
containing diacyl peroxides and acyl hydroperoxides can be prepared
from compounds containing multiple functional groups such as
carboxylic acids, acyl halides, or anhydrides. Mixed alkyl-acyl
peroxides, (peresters) can be prepared from acyl halides and
hydroperoxides, or through reaction of an acid and hydroperoxide
with DCC. As with the multifunctional azide type crosslinkers, the
formation of the peroxide would generally be the last step in the
synthetic scheme. Multifunctional acids could serve as the core
linker.
[0197] Suitable polymers useful in combination with the
crosslinkers noted throughout the specification include those
described in U.S. Pat. No. 6,683,126, issued Jan. 27, 2004 to
Keller et al., described as binders, the contents of which are
included herein in their entirety.
[0198] As described above, the particle can be virtually any type
of particle that has a particle size of between about 1 nm and
about 25 microns and up to 1000 nm). The particle can be porous or
non-porous. Generally, the particle has an oxide layer but in
particular has been treated with a silane reagent to provide
hydrophobicity. Suitable materials include, but are not limited to,
particles derived from aluminum oxides (alumina), titanium oxide,
zirconium oxide, gold (treated with thiols), silver (thiol or
silane treated), nickel, iron oxide, and alloys (all treated with
silane), polystyrene particles, (meth)acrylates particles, PTFE
particles, silica particles, polyolefin particles, polycarbonate
particles, polysiloxane particles, silicone particles, polyester
particles, polyamide particles, polyurethane particles,
ethylenically unsaturated polymer particles, polyanhydride
particles and biodegradable particles such as polycaprolactone
(PCL) and polylactideglycolide (PLGA), and nanofibers, nanotubes,
or nanowires and combinations thereof.
[0199] The particles may also be used to give properties to the
surface other than hydrophobicity. For example, inclusion of silver
particles may give anti-bacterial properties to the surface. Silver
has long been known to have broad spectrum antimicrobial
properties. The silver cation binds to thiols and other groups,
denaturing proteins. When bound to proteins in the bacterial cell
wall, rupture can ensue, killing the bacteria. Silver may also bind
respiratory enzymes and DNA leading to further cell death. Its use
in the particle aspect of these matrices may provide additional
benefits beyond texture. Similarly, gold nanoparticles may give
effects common to gold nanoparticles such as fluorescence quenching
or surface plasmon resonance. Polymer matrix coatings may be
tailored with these additional features in mind.
[0200] As noted throughout the specification, the particle can be
pretreated with a silane to help increase hydrophobicity of the
ultimate composition. Silanation of surfaces is known in the art.
Generally, any hydrophobic silane that can react with a surface can
be used with the particles described herein
[0201] For example, Cab-O-Sil TS 720 (Cabot, a silica product, uses
a dimethyl silicone (polydimethylsiloxane) according to the MSDS.
Other silanating agents used on Cab-O-Sil products include
hexamethyldisilazane and dichlorodimethylsilane. Similar silica
products are available from Degussa (www.degussa.com, Duesseldorf,
Germany), under their Aerosil R and LE lines that are silanated
with various silane reagents, including
octamethylcyclotetrasiloxane.
[0202] Not to be limited by the following, it is possible to treat
uncoated particles using a solution phase reaction. A long chain
alkanesilane, such as octadecyltrichlorosilane,
decyltrichlorosilane, etc. can be used. The chain length can be
varied from about 1 to 20, though the 18 is very common.
Additionally there are aryl silanes, such as
tolyldimethylchlorosilane, phenyltrichlorosilane, etc. and
fluoroalkylsilanes like heptadecafluorodecyltrichlorosilane
(fluorosilanes) having the same chain length range as straight
alkyl chains, with complete or almost complete fluorination.
[0203] The silanes react with the particle surface through reactive
groups, such as chloro groups (mono, di, and tri-chloro) or through
alkoxy groups (mono-methoxy, di-methoxy, trimethoxy or ethoxy
versions typically). They can have one, two, or three chains,
though it is more common to have one chain, and one or two methyl
groups. Such silanes are sold commercially from Gelest Inc.,
Morrisville, Pa. www.gelest.com. Application procedures are found
in the Gelest catalog, the contents of which are incorporated
herein by reference
[0204] Typically, to treat a particle with a chlorosilane, a 1-5 wt
% solution is prepared in anhydrous alcohol or acetone solution.
The particles are added in the same solvent, and mixed until HCl
production is completed. Alkoxy silanes can be applied in a
solution of 95:5 ethanol:water at pH 4-5. The silane is applied to
the particles generally at a 2% concentration, stirred for a period
of time, and the solvent removed. Generally, pretreated "silanated"
particles are commercially available.
[0205] Any type of silica particle can be used in the compositions
of the invention. The silica can be porous or non-porous and in
particular can be treated with a silane to help improve
hydrophobicity. Suitable silica particles are included as described
in U.S. Pat. No. 6,683,126, the contents of which are included
herein in their entirety.
[0206] In a first embodiment, the present invention pertains to a
composition comprising a cross linking compound comprising a
formula:
L-((D-T-C(R.sup.1)(XP)CHR.sup.2GR.sup.3C(.dbd.O)R.sup.4)).sub.m
wherein L is a linking group;
[0207] D is O, S, SO, SO.sub.2, NR.sup.5 or CR.sup.6R.sup.7;
[0208] T is (--CH.sub.2--).sub.x, (--CH.sub.2CH.sub.2--O--).sub.x,
(--CH.sub.2CH.sub.2CH.sub.2--O--).sub.x,
(--CH.sub.2CH.sub.2CH.sub.2CH.sub.2--O--).sub.x or forms a
bond;
[0209] R.sup.1 is a hydrogen atom, an alkyl, alkyloxyalkyl, aryl,
aryloxyalkyl or aryloxyaryl group;
[0210] X is O, S, or NR.sup.8R.sup.9;
[0211] P is a hydrogen atom or a protecting group, with the
provisio that P is absent when X is NR.sup.8R.sup.9;
[0212] R.sup.2 is a hydrogen atom, an alkyl, alkyloxyalkyl, aryl,
aryloxyalkyl or aryloxyaryl group;
[0213] G is O, S, SO, SO.sub.2, NR.sup.10, (CH.sub.2).sub.t--O-- or
C.dbd.O;
[0214] R.sup.3 and R.sup.4 are each independently an alkyl, aryl,
arylalkyl, heteroaryl, or an heteroarylalkyl group or, optionally,
R.sup.3 and R.sup.4 can be tethered together via
(--CH.sub.2--).sub.q,
(--CH.sub.2--).sub.rC.dbd.O(--CH.sub.2--).sub.s,
(--CH.sub.2--).sub.rS(--CH.sub.2--).sub.s,
(--CH.sub.2--).sub.rS.dbd.O(--CH.sub.2--).sub.s or
(--CH.sub.2--).sub.rS(O).sub.2(--CH.sub.2--).sub.s,
(--CH.sub.2--).sub.rNR(--CH.sub.2--).sub.s;
[0215] R.sup.5 and R.sup.16 are each independently a hydrogen atom
or an alkyl, aryl or arylalkyl group;
[0216] R.sup.6 and R.sup.7 are each independently a hydrogen atom,
an alkyl, aryl, arylalkyl, heteroaryl or heteroarylalkyl group;
[0217] R.sup.8 and R.sup.9 are each independently a hydrogen atom,
an alkyl, aryl, or arylalkyl group;
[0218] R is a hydrogen atom, an alkyl or an aryl group;
[0219] q is an integer from 1 to about 7;
[0220] r is an integer from 0 to about 3;
[0221] s is an integer from 0 to about 3;
[0222] m is an integer from 2 to about 10;
[0223] t is an integer from 1 to about 10;
[0224] x is an integer from 1 to about 500;
[0225] a polymer; and
[0226] a particle having a particle size of between about 1 nm to
about 25 microns.
[0227] In a second embodiment of the first embodiment, L is a
branched or unbranched alkyl chain having between about 2 and about
10 carbon atoms.
[0228] In a third embodiment of either of the first or second
embodiments, D is O.
[0229] In a fourth embodiment of any of the first through third
embodiments, T is (--CH.sub.2--).sub.x or
(--CH.sub.2CH.sub.2--O--).sub.x and x is 1 or 2.
[0230] In a fifth embodiment of the any of the first through fourth
embodiments, R.sup.1 is a hydrogen atom.
[0231] In a sixth embodiment of any of the first through fifth
embodiments, X is O and P is a hydrogen atom.
[0232] In a seventh embodiment of any of the first through the
sixth embodiments, R.sup.2 is a hydrogen atom.
[0233] In an eighth embodiment of any of the first through the
seventh embodiments, G is O.
[0234] In a ninth embodiment of any of the first through the eighth
embodiments, R.sup.3 and R.sup.4 are each individually aryl
groups.
[0235] In a tenth embodiment of any of the first through the ninth
embodiments, m is 3.
[0236] In an eleventh embodiment of the first embodiment, L is
##STR00022##
D is O, T is (--CH.sub.2--).sub.x, R.sup.1 is a hydrogen atom, X is
O, P is a hydrogen atom, R.sup.2 is a hydrogen atom, G is O,
R.sup.3 and R.sup.4 are phenyl groups, m is 3 and x is 1.
[0237] In a twelfth embodiment of the first embodiment, L is
(--CH.sub.2--).sub.y, D is O, T is (--CH.sub.2--).sub.x, R.sup.1 is
a hydrogen atom, X is O, P is a hydrogen atom, R.sup.2 is a
hydrogen atom, G is O, R.sup.3 and R.sup.4 are phenyl groups, m is
2, x is 1 and y is an integer from 2 to about 6.
[0238] In a thirteenth embodiment of the twelfth embodiment, y is
2, 4 or 6.
[0239] In a fourteenth embodiment, the present invention pertains
to a composition comprising a cross linking compound comprising a
formula:
L-((T-C(R.sup.1)(XP)CHR.sup.2GR.sup.3C(.dbd.O)R.sup.4)).sub.m
[0240] wherein L, T, R.sup.1, X, R.sup.8, R.sup.9, P (with the
provisio that P is absent when X is NR.sup.8R.sup.9), R.sup.2, G,
R.sup.3, R.sup.4, R.sup.10, R, q, r, s, m, t, and x are as defined
above.
[0241] In a fifteenth embodiment of the fourteenth embodiment L has
a formula according to structure (I):
##STR00023##
[0242] wherein A and J are each independently a hydrogen atom, an
alkyl group, an aryl group, or together with B form a cyclic ring,
provided when A and J are each independently a hydrogen atom, an
alkyl group, or an aryl group then B is not present;
[0243] B is NR.sup.11, O, or (--CH.sub.2--).sub.z;
[0244] provided when A, B and J form a ring, then A and J are
(--CH.sub.2--).sub.z or C.dbd.O;
[0245] R.sup.11 is a hydrogen atom, an alkyl group, an aryl group
or denotes a bond with T;
[0246] each z independently is an integer from 0 to 3;
[0247] provided when either A or J is C.dbd.O, then B is NR.sup.11,
O, or (--CH.sub.2--).sub.z and z must be at least 1;
[0248] a polymer; and
[0249] a particle having a particle size of between about 1 nm to
about 25 microns.
[0250] In a sixteenth embodiment of either the fourteenth or
fifteenth embodiments, T is --CH.sub.2--.
[0251] In a seventeenth embodiment of any of the fourteenth through
sixteenth embodiments, R.sup.1 is a hydrogen atom.
[0252] In an eighteenth embodiment of any of the fourteenth through
seventeenth embodiments, X is O and P is a hydrogen atom.
[0253] In a nineteenth embodiment of any of the fourteenth through
eighteenth embodiments, R.sup.2 is a hydrogen atom.
[0254] In a twentieth embodiment of any of the fourteenth through
nineteenth embodiments, G is O.
[0255] In a twenty first embodiment of any of the fourteenth
through twentieth embodiments, R.sup.3 and R.sup.4 are each
individually aryl groups.
[0256] In a twenty second embodiment of any of the fourteenth
through twenty first embodiments, m is 3.
[0257] In a twenty third embodiment of the fifteenth embodiment, A
and J are both C.dbd.O and B is N.
[0258] In a twenty fourth embodiment of the fifteenth embodiment, A
and J are both hydrogen atoms.
[0259] In a twenty fifth embodiment, the present invention pertains
to a composition comprising a cross liking compound comprising a
formula:
L-((GTZR.sup.3C(.dbd.O)R.sup.4)),
[0260] wherein Z is C.dbd.O, COO, or CONH when T
(--CH.sub.2--).sub.x;
[0261] L, T, G, R.sup.3, R.sup.4, R.sup.10, R, q, r, s, m, t, and x
are as defined above;
[0262] a polymer; and
[0263] a particle having a particle size of between about 1 nm to
about 25 microns.
[0264] In a twenty sixth embodiment of the twenty fifth embodiment,
L has the formula according to structure (I) as defined above.
[0265] In a twenty seventh embodiment of either the twenty fifth or
twenty sixth embodiments, T is --CH.sub.2--.
[0266] In a twenty eighth embodiment of any of the twenty fifth
through the twenty seventh embodiments, G is O.
[0267] In a twenty ninth embodiment of any of the twenty fifth
through twenty eighth embodiments, R.sup.3 and R.sup.4 are each
individually aryl groups.
[0268] In a thirtieth embodiment of any of the twenty fifth through
twenty ninth embodiments, wherein m is 2.
[0269] In a thirty first embodiment of any of the twenty sixth
through thirtieth embodiments, A and J are both C.dbd.O and B is
NR.sup.11.
[0270] In a thirty second embodiment of the twenty sixth
embodiment, A and J are both hydrogen atoms.
[0271] In a thirty third embodiment of the twenty fifth embodiment,
L has a formula according to structure (II):
##STR00024##
[0272] wherein R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16,
R.sup.17 are each independently a hydrogen atom, an alkyl or aryl
group or denotes a bond with T, provided at least two of R.sup.12,
R.sup.13, R.sup.14, R.sup.15, R.sup.16, R.sup.17 are bonded with T
and each K, independently, is CH or N.
[0273] In a thirty fourth embodiment of the twenty fifth
embodiment, L is C.dbd.O.
[0274] In a thirty fifth embodiment of the thirty fourth
embodiment, G is NH.
[0275] In a thirty sixth embodiment of either the thirty fourth or
thirty fifth embodiments, T is --CH.sub.2CH.sub.2O--.
[0276] In a thirty seventh embodiment of any of the thirty fourth
through thirty sixth embodiments, Z is C.dbd.O.
[0277] In a thirty eighty embodiment of any of the thirty fourth
through thirty seventh embodiments, R.sup.3 is an aryl group.
[0278] In a thirty ninth embodiment of any of the thirty fourth
through thirty eighth embodiments, R.sup.4 is an aryl group.
[0279] In a fortieth embodiment, the present invention pertains to
a composition comprising a cross linking compound comprising a
formula:
L-((TGQR.sup.3C(.dbd.O)R.sup.4)).sub.m
[0280] wherein L, T, G, R.sup.3, R.sup.3, R.sup.4, R.sup.10, R, q,
r, s, m, t and x are as defined above and Q is
(--CH.sub.2--).sub.p, (--CH.sub.2CH.sub.2--O--).sub.p,
(--CH.sub.2CH.sub.2CH.sub.2--O--).sub.p or
(--CH.sub.2CH.sub.2CH.sub.2CH.sub.2--O--)p and p is an integer from
1 to about 10;
[0281] a polymer; and
[0282] a particle having a particle size of between about 1 nm to
about 25 microns.
[0283] In a forty first embodiment of the fortieth embodiment, L
has the formula according to structure (I) as defined above.
[0284] In a forty second embodiment if either the fortieth or forty
first embodiments, T is --CH.sub.2--.
[0285] In a forty third embodiment of any of the fortieth through
forty second embodiments, G is O.
[0286] In a forty fourth embodiment of any of the fortieth through
the forty third embodiments, R.sup.3 and R.sup.4 are each
individually aryl groups.
[0287] In a forty fifth embodiment of any of the fortieth through
forty fourth embodiments, m is 2.
[0288] In a forty sixth embodiment of any of the forty first
through forty fifth embodiments, A and J are both C.dbd.O and B is
NR.sup.11.
[0289] In a forty seventh embodiment of any of the forty first
through forty fifth embodiments, A and J are both hydrogen
atoms.
[0290] In a forty eighth embodiment of the fortieth embodiment, L
has the formula according to structure (II) as defined above.
[0291] In a forty ninth embodiment, the present invention pertains
to a composition comprising a cross linking compound comprising a
formula:
L-((-CH.sub.2--).sub.xxC(R.sup.1)(GR.sup.3C(.dbd.O)R.sup.4).sub.2).sub.m
[0292] wherein L, R.sup.1, G, R.sup.3, R.sup.4, R.sup.10, R, q, r,
s, m, t are as defined above and xx is an integer from 1 to about
10;
[0293] a polymer; and
[0294] a particle having a particle size of between about 1 nm to
about 25 microns.
[0295] In a fiftieth embodiment of the forty ninth embodiment, L
has the formula according to structure (I) as defined above.
[0296] In a fifty first embodiment of the fiftieth embodiment, A
and J are both hydrogen atoms.
[0297] In a fifty second embodiment of any of the forty ninth
through fifty first embodiments, wherein xx is 1.
[0298] In a fifty third embodiment of any of the forty ninth
through fifty second embodiment, wherein each R.sup.1 is H.
[0299] In a fifty fourth embodiment of any of the forty ninth
through fifty third embodiments, wherein each G is
(--CH.sub.2--).sub.tO-- and t is 1.
[0300] In a fifty fifth embodiment of any of the forty ninth
through fifty fourth embodiments, each R.sup.3 and R.sup.4 are each
individually aryl groups.
[0301] In a fifty sixth embodiment of any of the forty ninth
through fifty fifth embodiments, wherein xx is 1, each G is
(--CH.sub.2--).sub.tO-- and t is 1, each R.sup.1 is H and each
R.sup.3 and R.sup.4 are each individually aryl groups.
[0302] In a fifty seventh embodiment, the present invention
pertains to a composition comprising a cross linking compound
comprising the formula:
L-((-C(R.sup.1)(XP)CHR.sup.2GR.sup.3C(.dbd.O)R.sup.4)).sub.m
[0303] wherein L, R.sup.1, X, P, R.sup.8, R.sup.9, R.sup.2,
R.sup.10, G, R.sup.3, R.sup.4, R, q, r, s, m and t are as defined
as above;
[0304] a polymer; and
[0305] a particle having a particle size of between about 1 nm to
about 25 microns.
[0306] In a fifty eighty embodiment of the fifty seventh
embodiment, L is
##STR00025##
and R.sup.20 and R.sup.21 are each individually a hydrogen atom, an
alkyl group or an aryl group.
[0307] In a fifty ninth embodiment of either the fifty seventh or
fifty eighth embodiments, wherein R.sup.1 is H.
[0308] In a sixtieth embodiment of any of the fifty seventh through
fifty ninth embodiments, wherein X is O.
[0309] In a sixty first embodiment of any of the fifty seventh
through sixtieth embodiments, P is H.
[0310] In a sixty second embodiment of any of the fifty seventh
through sixty first embodiments, R.sup.2 is H.
[0311] In a sixty third embodiment of any of the fifty seventh
through sixty second embodiments, G is (--CH.sub.2--).sub.tO-- and
t is 1.
[0312] In a sixty fourth embodiment of any of the fifty seventh
through sixty third embodiments, R.sup.3 and R.sup.4 are each
individually aryl groups.
[0313] In a sixty fifth embodiment of the fifty eight embodiment,
R.sup.1 is H, X is O, P is H, R.sup.2 is H, G is
(--CH.sub.2--).sub.tO--, t is 1, R.sup.3 and R.sup.4 are each
individually aryl groups and R.sup.20 and R.sup.21 are both methyl
groups.
[0314] In a sixty sixth embodiment, the present invention pertains
to a composition comprising a cross linking compound comprising the
formula:
L-((GR.sup.3C(.dbd.O)R.sup.4)).sub.m;
[0315] wherein L, G, R.sup.3, R.sup.4, R.sup.10, R, q, r, s, m and
t are as defined above;
[0316] a polymer; and
[0317] a particle having a particle size of between about 1 nm to
about 25 microns.
[0318] In a sixty seventh embodiment, L is
##STR00026##
[0319] In a sixty eighth embodiment of either the sixty sixth or
sixty seventh embodiments, G is C.dbd.O.
[0320] In a sixty ninth embodiment of any of sixty sixth through
sixty eighth embodiments, R.sup.3 and R.sup.4 are each individually
aryl groups.
[0321] In a seventieth embodiment of any of the sixty sixth through
sixty ninth embodiments, G is C.dbd.O and R.sup.3 and R.sup.4 are
each individually aryl groups.
[0322] In a seventy first embodiment, the present invention
pertains to a composition comprising a cross linking compound
comprising a formula:
L-((ZZ-D-T-C(R.sup.1)(XP)CHR.sup.2GR.sup.3C(.dbd.O)R.sup.4)).sub.m
[0323] wherein L, D, T, R.sup.1, R.sup.5, R.sup.6, R.sup.7, T, X,
P, N.sup.8, N.sup.9, R.sup.2, G, R.sup.10, R.sup.3, R.sup.4, R, q,
r, s, m, t, x are as defined above;
[0324] ZZ is a phenyl group;
[0325] a polymer; and
[0326] a particle having a particle size of between about 1 nm to
about 25 microns.
[0327] In a seventy second embodiment of the seventy first
embodiment, m is 3.
[0328] In a seventy third embodiment of the seventy first or
seventy second embodiments, L is CH.
[0329] In a seventy fourth embodiment of the seventy first
embodiment, L is CH, ZZ is phenyl, D is O, T is CH.sub.2, R.sup.1
is H, P is H, R.sup.2 is H, G is O, R.sup.3 is phenyl, R.sup.4 is
phenyl substituted with a --OC.sub.8H.sub.17 and m is 3.
[0330] In a seventy fifth embodiment of any of the first through
seventy fourth embodiments, R.sup.3 and R.sup.4 are both phenyl
groups and are tethered together via a CO, a S or a CH.sub.2.
[0331] In a seventy sixth embodiment of any of the first through
seventy fourth embodiments, R.sup.3 and R.sup.4 are both phenyl
groups and include at least one CH.sub.3OCH.sub.2CH.sub.2O--.
[0332] In a seventy seventh embodiment of any of the first through
seventy fourth embodiments, the particle is a porous or non-porous
particle comprising aluminum oxides (alumina), titanium oxide,
zirconium oxide, gold (treated with thiols), silver (thiol or
silane treated), nickel, iron oxide, and alloys (all treated with
silane), polystyrene particles, (meth)acrylates particles, PTFE
particles, silica particles, polyolefin particles, polycarbonate
particles, polysiloxane particles, silicone particles, polyester
particles, polyamide particles, polyurethane particles,
ethylenically unsaturated polymer particles, polyanhydride
particles and biodegradable particles such as polycaprolactone
(PCL) and polylactideglycolide (PLGA), and nanofibers, nanotubes,
or nanowires, and combinations thereof.
[0333] In a seventy eighth embodiment of any of the first through
seventy seventh embodiments, the particle is pretreated with a
silane.
[0334] In a seventy ninth embodiment, the present invention
pertains to a method to modify a substrate comprising the step of
applying a composition of any of claims first through seventy
eighth embodiments to the surface, such that the substrate surface
is modified.
[0335] In an eightieth embodiment, the method of the seventy ninth
embodiment is photoactivated such that at least one
photoactivatable group within the composition forms a covalent bond
with the surface of the substrate.
[0336] In an eighty first embodiment, the method of the seventy
ninth embodiment is photoactivated such that a coating is formed
from interpolymer cross linking.
[0337] In an eighty second embodiment, the present invention
pertains to a super hydrophobic composition comprising a
photoreactive cross linking compound, a polymer and a particle
having a particle size of between about 1 nm to 25 microns. The
cross linking compound is any of those described in any of the
first through seventy eighth embodiments.
[0338] In an eighty third embodiment of the eighty second
embodiment, the photoreactive moiety of the cross linking compound
is selected from the group consisting of benzoin derivatives
(including ketoxime esters of benzoin), acetophenone derivatives,
benzilketals, .alpha.-hydroxyalkylphenones,
.alpha.-aminoalkylphenones, O-acyl .alpha.-oximinoketones,
acylphosphine oxides, acylphosphonates, thiobenzoic S-esters, azo,
azide compounds, triazines, biimidazoles, quinones, benzophenones,
xanthones and thioxanthones, coumarins, aromatic 1,2 diketones,
peroxides, trichloromethyl substituted compounds, aryl ketones,
phenyl glyoxylate and 2+2 photogroups.
[0339] In an eighty fourth embodiment, the present invention
pertains to an ultra hydrophobic composition comprising a
photoreactive cross linking compound, a polymer and a particle
having a particle size of between about 1 nm to 25 microns.
[0340] In an eighty fifth embodiment of the eighty fourth
embodiment, the photoreactive moiety of the cross linking compound
is selected from the group consisting of benzoin derivatives
(including ketoxime esters of benzoin), acetophenone derivatives,
benzilketals, .alpha.-hydroxyalkylphenones,
.alpha.-aminoalkylphenones, O-acyl .alpha.-oximinoketones,
acylphosphine oxides, acylphosphonates, thiobenzoic S-esters, azo,
azide compounds, triazines, biimidazoles, quinones, benzophenones,
xanthones and thioxanthones, coumarins, aromatic 1,2 diketones,
peroxides, trichloromethyl substituted compounds, aryl ketones and
2+2 photogroups.
[0341] The invention will be further described with reference to
the following non-limiting Examples. It will be apparent to those
skilled in the art that many changes can be made in the embodiments
described without departing from the scope of the present
invention. Thus the scope of the present invention should not be
limited to the embodiments described in this application, but only
by embodiments described by the language of the claims and the
equivalents of those embodiments. Unless otherwise indicated, all
percentages are by weight.
Example 1
Synthesis of Trifunctional Triazine Crosslinker
[0342] 1.2 g (4 mmol) of triglycidyl isocyanurate (Aldrich
Chemicals, Milwaukee, Wis.) and 2.4 g (12 mmol) of
4-hydroxybenzophenone (Aldrich Chemicals, Milwaukee, Wis.) were
mixed in a 50-ml round bottom flask containing a magnetic stir bar.
The flask was flushed with argon for 10 min and heated to
130.degree. C. in an oil bath. Once the reaction mixture melted, 6
mg (0.02 mmol) of triphenylphosphine (Aldrich Chemicals, Milwaukee,
Wis.) was added. The mixture was stirred for another 2 minutes
under argon and cooled to room temperature. The reaction residue
was dissolved in 30 ml chloroform, then washed with 4N NaOH (30
ml.times.3) and deionized water (30 ml.times.3). The organic layer
was dried over magnesium sulfate and concentrated to dryness on the
under reduced pressure. The product was purified by column
chromatography (silica gel, 230-400 mesh, Whatman, Inc.) using
ethyl acetate as eluent (R.sub.f.about.4.5). The fractions
containing the pure product were combined and concentrated under
reduced pressure and a white powder was obtained after drying under
vacuum (yield 70%).
##STR00027##
[0343] The crosslinker is soluble in most common solvents including
chloroform, methylene chloride, acetone, ethyl acetate,
isopropanol, etc. .sup.1H NMR (CDCl.sub.3) confirmed the structure
of the product. The peaks at d 7.78 ppm (m, 12H), 7.46 ppm (m, 9H),
6.98 ppm (m, 6H) were the typical signals from 4-substituted
benzophenone. The peak at d 4.35 ppm (m, 6H) was assigned to the
protons of methylene connected to phenoxy group. The peak at d 4.13
ppm (m, 9H) was a combination of 6 protons of 3 methylene groups
connected to nitrogen atom and 3 protons from 3 methine groups. The
peak at d 3.00 ppm (s, 3H) corresponded to hydroxyl groups.
Example 2
Application of Triazine Crosslinker to Create a Photoreactive
Surface
[0344] A photoreactive poly(.epsilon.-caprolactone) (PCL) film was
prepared by incorporating the crosslinker in a film casting polymer
solution. A solution containing 20 mg/ml PCL (Aldrich Chemicals,
Milwaukee, Wis.) and 0.4 mg/ml triazine crosslinker (as prepared in
Example 1) was cast onto a glass slide. 10 .mu.l of 50 mg/ml
poly(vinylpyrrolidone) (PVP, 30K, Kollidon K30 BASF, NJ) in
isopropanol solution was added onto the film. After complete
evaporation of the isopropanol, the film was illuminated under UV
for 20 minutes (UV Crosslinker, UVP CL-1000, Upland, Calif., 254 nm
light, 120,000 .mu.J/cm.sup.2). The coated film was incubated in
deionized water on a shaker for 3 hours to remove unbound PVP. A
homogeneous PVP coating could be seen on the PCL film by staining
with a solution of Congo Red (0.5% w/v aqueous solution) indicating
a uniform distribution of crosslinker on the film surface. A PCL
film without triazine crosslinker added showed no staining,
indicating all unbound PVP was removed by the rinse.
Example 3
Synthesis of Photoreactive Glycol Crosslinker
[0345] 2.26 g 4-hydroxybenzophenone (Aldrich Chemicals, Milwaukee,
Wis.) was dissolved in 50 ml of acetone, and 0.532 ml of glycerol
triglycidyl ether (Polysciences, Warrington, Pa.), and 3.3 g
potassium carbonate (Aldrich Chemicals, Milwaukee, Wis.) were added
to the solution. The reaction mixture was heated to reflux over 24
hours. After 24 hours of heating, thin layer chromatography (TLC)
showed consumption of the glycerol starting material (eluent 20:1
Chloroform:methanol) and the emergence of three uv active spots.
The acetone was removed by rotary evaporation and the residue was
dissolved in chloroform, and filtered. The resulting chloroform
solution was washed three times with 4N NaOH aqueous solution, once
with deionized water, then twice with 1N HCl aqueous solution, and
three times again with deionized water. The chloroform solution was
dried over magnesium sulfate, filtered, and the solvent removed by
rotary evaporation. The resulting oil was washed three times with
diethyl ether and dried. This treatment removed all
4-hydroxybenzophenone starting material, with TLC revealing the
same three uv active spots. These three products presumably
correspond to single, double, and triple substitution of
benzophenone on the glycerol compound.
[0346] Coating Composition A
[0347] 320 mg of polycaprolactone (Aldrich Chemicals, Milwaukee,
Wis., Mn=80,000) and 13 mg triazine crosslinker (Example 1) were
dissolved in 20 ml methylene chloride. 330 mg of CAB-O-SIL.RTM.
TS-720 silica nanoparticles (Cabot Corp. Tuscola, Ill.) were
dispersed in the solution with intensive vortexing. The coating
composition was sprayed on a LNB surface (provided by King
Controls, Bloomington, Minn.) using a commercial hair spray. After
the solvent evaporated, the LNB was irradiated under UV (UVP
CL-1000 Ultraviolet Crosslinker, 40 watt, 254 nm, 10 cm from light
source) for 20 min.
[0348] Coating Composition B
[0349] 160 mg of polybutyl methacrylate (Aldrich Chemicals,
Milwaukee, Wis., Mw=337,000), 160 mg of polycaprolactone (Aldrich
Chemicals, Milwaukee, Wis., Mn=80,000) and 13 mg triazine
crosslinker (Example 1) were dissolved in 20 ml methylene chloride.
330 mg of CAB-O-SIL.RTM. TS-720 silica nanoparticles (Cabot Corp.
Tuscola, Ill.) were dispersed in the solution with intensive
vortexing. The coating composition was sprayed on a LNB surface
(provided by King Controls, Bloomington, Minn.) using a commercial
hair spray. After the solvent evaporated, the LNB was irradiated
under UV (UVP CL-1000 Ultraviolet Crosslinker, 40 watt, 254 nm, 10
cm from light source) for 20 min.
[0350] Coating Composition C
[0351] 150 mg of polystyrene (Aldrich Chemicals, Milwaukee, Wis.,
Mw=280,000) and 30 mg triazine crosslinker (Example 1) were
dissolved in 20 ml methylene chloride. 250 mg of CAB-O-SIL.RTM.
TS-720 silica nanoparticles (Cabot Corp. Tuscola, Ill.) were
dispersed in the solution with intensive vortexing. The coating
composition was sprayed on a LNB surface (provided by King
Controls, Bloomington, Minn.) using a commercial hair spray. After
the solvent evaporated, the LNB was irradiated under UV (UVP
CL-1000 Ultraviolet Crosslinker, 40 watt, 254 nm, 10 cm from light
source) for 20 min.
[0352] Coating Composition D
[0353] 200 mg of polystyrene (Aldrich Chemicals, Milwaukee, Wis.,
Mw=280,000) and 40 mg triazine crosslinker (Example 1) were
dissolved in 20 ml methylene chloride. 250 mg of CAB-O-SIL.RTM.
TS-720 silica nanoparticles (Cabot Corp. Tuscola, Ill.) were
dispersed in the solution with intensive vortexing. The coating
composition was sprayed on a LNB surface (provided by King
Controls, Bloomington, Minn.) using a commercial hair spray. After
the solvent evaporated, the LNB was irradiated under UV (UVP
CL-1000 Ultraviolet Crosslinker, 40 watt, 254 nm, 10 cm from light
source) for 20 min.
[0354] Coating Composition E
[0355] 130 mg of polyisobutylene (Aldrich Chemicals, Milwaukee,
Wis., Mw=500,000) and 6 mg triazine crosslinker were dissolved in
20 ml THF. 156 mg of CAB-O-SIL.RTM. TS-720 silica nanoparticles
(Cabot Corp. Tuscola, Ill.) were dispersed in the solution with
intensive vortex mixing. The coating composition was sprayed on a
LNB surface (provided by King Controls, Bloomington, Minn.) using a
commercial hair spray. After the solvent evaporated, the LNB was
irradiated under UV (UVP CL-1000 Ultraviolet Crosslinker, 40 watt,
254 nm, 10 cm from light source) for 20 min.
[0356] Coating Composition F
[0357] 133 mg of polyisobutylene (BASF Corp. Florham Park, N.J.,
Mw=2,000,000) and 6 mg triazine crosslinker were dissolved in 120
ml THF. 160 mg of CAB-O-SIL.RTM. TS-720 silica nanoparticles (Cabot
Corp. Tuscola, Ill.) were dispersed in the solution with intensive
vortex mixing. The coating composition was sprayed on a LNB surface
(provided by King Controls, Bloomington, Minn.) using a commercial
hair spray. After the solvent evaporated, the LNB was irradiated
under UV (UVP CL-1000 Ultraviolet Crosslinker, 40 watt, 254 nm, 10
cm from light source) for 20 min.
[0358] Super Hydrophobicity Test
[0359] Coatings A, B, C, D, E and F showed comparable super
hydrophobicity to a commercial super hydrophobic coating
product--King's Rain Shield (King Controls, Bloomington, Minn.)
with water contact angles higher than 150.degree.. Water drops
could hardly sit on the coatings.
[0360] Coating Durability Test
[0361] The durability of coatings A, B, C, D, E and F all showed
improved durability against rub, touch and water flow compared to
King's Rain Shield.
[0362] A three-month weather stability study was conducted using
satellite dish LNBs provided by King Controls, Inc. The LNBs were
spray coated using a formulation containing 20 mg/mL of
polycaprolactone (Aldrich Chemicals, Milwaukee, Wis., Mw=80,000),
240 mg/mL CAB-O-SIL.RTM. TS-720 silica nanoparticles (Cabot Corp.
Tuscola, Ill.), 0.8 mg/mL triazine crosslinker in THF, allowed to
evaporate, and then irradiated with ultraviolet light (300 to 400
nm) for 5 minutes (Harland Medical UVM400, Eden Prairie, Minn.).
Three LNBs were coated with a commercial water repellent product
(King's Rain Shield, King Controls, Inc., Bloomington, Minn.) as
control. The coated samples and controls were placed outdoors for
weather exposure. At regular intervals the sample LNBs were tested
using several drops of DI water to determine super hydrophobicity
of the coated surface. The results showed that after eight days the
commercial coatings lost super hydrophobicity whereas
PCL/nanoparticle/triazine crosslinker coatings remained super
hydrophobic for greater than three months.
Example 4
Synthesis of Photoreactive Glycol Crosslinker
[0363] 2.26 g 4-hydroxybenzophenone (Aldrich Chemicals, Milwaukee,
Wis.) was dissolved in 50 ml of acetone, and 0.532 ml of glycerol
triglycidyl ether (Polysciences, Warrington, Pa.), and 3.3 g
potassium carbonate (Aldrich Chemicals, Milwaukee, Wis.) were added
to the solution. The reaction mixture was heated to reflux over 24
hours. After 24 hours of heating, thin layer chromatography (TLC)
showed consumption of the glycerol starting material (eluent 20:1
Chloroform:methanol) and the emergence of three uv active spots.
The acetone was removed by rotary evaporation and the residue was
dissolved in chloroform, and filtered. The resulting chloroform
solution was washed three times with 4N NaOH aqueous solution, once
with deionized water, then twice with 1N HCl aqueous solution, and
three times again with deionized water. The chloroform solution was
dried over magnesium sulfate, filtered, and the solvent removed by
rotary evaporation. The resulting oil was washed three times with
diethyl ether and dried. This treatment removed all
4-hydroxybenzophenone starting material, with TLC revealing the
same three uv active spots. These three products presumably
correspond to single, double, and triple substitution of
benzophenone on the glycerol compound.
Example 5
Diethylene Glycol Photocrosslinker Synthesis
[0364] 4-Hydroxybenzophenone, 2.2758 g (11.4811 mMol, 2 mol eq,
Alfa Aesar, Ward Hill, Mass.), was added to a 100 mL round bottom
flask equipped with a reflux condenser and dissolved in 75 mL of
acetone. Ethylene glycol diglycidyl ether, 1.0000 g (5.7405 mMol, 1
mol eq Aldrich Chemicals, Milwaukee, Wis.) followed by potassium
carbonate, 3.1736 g (22.9621 mMol, 4 mol eq), was then added to the
mixture and was heated at reflux overnight. After cooling, the
remaining solid was filtered and organic layer was removed in
vacuo. The crude product mixture was redissolved in 60 mL of
chloroform and the residual 4-Hydroxybenzophenone was removed by
washing with a 4N NaOH aqueous solution. The organic layer was then
dried over MgSO.sub.4 and filtered to remove drying agent. A
portion of the chloroform solvent was removed in vacuo until 5 mL
remained. The product was isolated by silica column (EMD Silica Gel
0.040-0.063 mm, 230-400 mesh, 60 .ANG.) using (9:1) Ethyl
Acetate:Hexane as eluent. Elution was monitored by TLC. R.sub.f
value of desired product was 0.40 in same eluent. .sup.1H NMR
(CDCl.sub.3): .delta.=7.7-7.9, 7.4-7.6, 6.9-7.1 (m, characteristic
of benzophenone), 4.2-4.3 (m), 4.0-4.2 (m), 3.6-3.8 ppm (m).
Example 6
Synthesis of Urea Photo-Crosslinker
[0365] Bis-2,3-dihydroxypropylurea, 0.3000 g (1.4408 mMol, 1 mol
equiv. Aldrich Chemicals, Milwaukee, Wis.), was added to a 50 mL
round bottom flask under argon sweep and dissolved in 20 mL of DMF
(Fisher Scientific, Pittsburgh, Pa.). Sodium hydride (60%
dispersion in mineral oil, Aldrich Chemicals, Milwaukee, Wis.),
0.2305 g (5.7633 mMol, 4 mol eq), was then added and stirred at
room temperature for 20 minutes. 4-(Bromomethyl)benzophenone,
1.5858 g (5.7633 mMol, 4 mol equiv. Aldrich Chemicals, Milwaukee,
Wis.), was added to the mixture and heated at reflux under positive
argon pressure for five hours. After cooling, the reaction mixture
was dissolved in 200 mL of deionized water and the crude product
was extracted with chloroform. The organic layer was then dried
over magnesium sulfate and filtered to remove the drying agent. The
chloroform was removed in vacuo and the crude product was
redissolved in a minimal amount of (85:15) CHCl.sub.3:MeOH. The
product was isolated by silica gel column (EMD Silica Gel
0.040-0.063 mm, 230-400 mesh, 60 .ANG.) using (85:15)
CHCl.sub.3:MeOH as eluent. Elution was monitored by TLC. R.sub.f
value of desired product was 0.74 in the same eluent. Several spots
were isolated together and may represent two, three, and four
functionalized crosslinkers. .sup.1H NMR (CDCl.sub.3):
.delta.=7.3-7.9 (m, characteristic benzophenone pattern), 4.5-4.7
(m), 3.5-3.8 ppm (m).
Example 7
Synthesis of Polyalcohol Photo-Crosslinker
[0366] 3,4-O-Isopropylidene-D-mannitol, 0.5000 g (2.2498 mMol, 1
mol eq, Aldrich Chemicals, Milwaukee, Wis.), was added to a 50 mL
round bottom flask equipped with a reflux condenser and dissolved
in 25 mL of chloroform under argon sweep. NaH (with 60% dispersion
in mineral oil, Aldrich Chemicals, Milwaukee, Wis.), 0.2700 g
(6.7495 mMol, 3 mol eq), was added and then stirred for 30 minutes.
4-(Bromomethyl)benzophenone (Aldrich Chemicals, Milwaukee, Wis.),
0.1.23808 g (4.4996 mMol, 2 mol eq), was added to the mixture and
heated at reflux overnight under positive argon pressure. After
cooling, the organic layer was filtered to remove precipitate. A
portion of the chloroform solvent was removed in vacuo until 5 mL
remained. The product was isolated by silica gel column (EMD Silica
Gel 0.040-0.063 mm, 230-400 mesh, 60 .ANG.) using chloroform as
eluent. Elution was monitored by TLC. R.sub.f value of desired
product was 0.40 in the same eluent. Three compounds were isolated
and may represent different isomers of the compound. .sup.1H NMR
(CDCl.sub.3): .delta.=7.3-7.9 (m, characteristic of benzophenone
pattern), 4.6-5.0 (dd), 4.5-4.6 (s), 3.6-3.9 (m), 1.5-1.6 ppm
(s).
Example 8
Synthesis of Photo-Uracil Crosslinker
[0367] 6-Aminouracil, 0.1091 g (0.8581 mMol, 1 mol eq, Aldrich
Chemicals, Milwaukee, Wis.), was added to a 100 mL round bottom
flask equipped with a reflux condenser and dissolved in 50 mL of
chloroform under argon sweep. 4-(Benzoyl)benzoic acid chloride,
0.4199 g (1.7161 mMol, 2 mol eq, Aldrich Chemicals, Milwaukee,
Wis.), 4-Dimethylaminopyridine, 0.01260 g (3-5 wt % of
4-(Benzoyl)benzoic acid chloride, Aldrich Chemicals, Milwaukee,
Wis.), and Triethylamine, 0.1042 g (1.02969 mMol, 1.2 mol eq,
Aldrich Chemicals, Milwaukee, Wis.) were heated at reflux under
positive argon pressure overnight. After cooling, the reaction
mixture was filtered to remove precipitate. The organic layer was
removed in vacuo and the remaining crude reaction mixture was
redissolved in a minimal amount of (9:1) CHCl.sub.3:MeOH. The
desired product was isolated by silica gel column (EMD Silica Gel
0.040-0.063 mm, 230-400 mesh, 60 .ANG.) using the (9:1)
CHCl.sub.3:MeOH as eluent. Monitor elution by TLC. R.sup.f value of
desired product was 0.56 in the same eluent.
Example 9
Synthesis of TOB Crosslinker
[0368] 6 g of triglycidyl isocyanurate (Aldrich Chemicals,
Milwaukee, Wis.) and 19.6 g of 2-hydroxy-4-(octyloxy)-benzophenone
(Aldrich Chemicals, Milwaukee, Wis.) were mixed in a 50-ml round
bottom flask containing a magnetic stir bar. The flask was flushed
with argon for 10 min and heated to 130.degree. C. in an oil bath.
Once the reaction mixture melted, 26 mg of triphenylphosphine
(Aldrich Chemicals, Milwaukee, Wis.) was added. The mixture was
stirred under argon for three days and cooled to room temperature.
The product was purified by column chromatography (silica gel,
230-400 mesh, Whatman, Inc.) using 18:17 ethyl acetate/hexane as
eluent (R.sub.f.about.0.66). The fractions containing the pure
product were combined and concentrated under reduced pressure and a
yellowish syrup was obtained after drying under vacuum (yield
68%).
[0369] The crosslinker is soluble in most common solvents including
chloroform, methylene chloride, acetone, ethyl acetate,
isopropanol, etc. .sup.1H NMR (CDCl.sub.3) confirmed the structure
of the product. The peaks at 7.72 ppm, 7.40 ppm, 6.52 ppm (m, 24H)
were the typical signals from benzophenone. The peak at d 4.05 ppm
(m, 15H) was assigned to the protons of methylene and methine
groups at the ring opening site of epoxide. The peaks 0.9-1.8 ppm
(m, 45H) belonged to octyl group.
##STR00028##
Example 10
Synthesis of BOB Crosslinker
[0370] Triphenylolmethane triglycidyl ether, 1.62 g (3.5 mMol), was
added to a dry 50 mL round bottom flask, followed by the addition
of 2-hydroxy-4-(octyloxy)-benzophenone, 2.88 g (8.8 mMol).
Triphenylphosphine, 0.14 g (0.55 mMol), was then added and the
mixture was heated at 125.degree. C. under positive argon pressure
overnight. After cooling to room temperature, the product was
purified by silica gel column (EMD Silica Gel, 0.040-0.063 mm,
230-400 mesh, 60 .ANG.) to give a pale, yellow translucent syrup.
Hexane:ethyl acetate (27:20) was used as eluent. R.sub.f of desired
product was 0.47 in the same eluent.
[0371] The product is soluble in most common organic solvents such
as THF, IPA, CH.sub.2Cl.sub.2, CHCl.sub.3, acetone and ethyl
acetate and is partially soluble in hexane. .sup.1H NMR
(CDCl.sub.3): The peaks at 7.75 ppm, 7.45 ppm, 6.55 ppm (m, 24H)
were the typical signals from benzophenone. The peaks at 6.6-7.0
ppm (m, 12H) were assigned to the protons of benzene. The peaks at
3.5-4.1 ppm (m, 15H) corresponded to the protons of methylene and
methine groups at the ring opening site of epoxide. The peaks
1.2-1.9 ppm (m, 45H) belonged to octyl group.
##STR00029##
Example 11
Synthesis of TEG Crosslinker
[0372] 1.94 g of tetraethylene glycol (Aldrich Chemicals,
Milwaukee, Wis.) was dried under vacuum at 50.degree. C. for 2 h
and dissolved in 50 ml anhydrous tetrahydrofuran. 6.8 g of
4-(bromomethyl)benzophenone (Aldrich Chemicals, Milwaukee, Wis.)
and 1.8 g sodium hydride (60% in mineral oil, Aldrich Chemicals,
Milwaukee, Wis.) were added to the solution. The mixture was
stirred overnight under reflux and argon protection. The reaction
solution was cooled to room temperature and filtered. The filtrate
was concentrated by rotary evaporation and the residue was purified
by column chromatography (silica gel, 230-400 mesh, Whatman, Inc.)
using 25:1 chloroform/methanol mixture as eluent. The fractions
containing the pure product were combined and concentrated to
dryness by rotary evaporation to yield yellowish oil (yield
80%).
[0373] The TEG crosslinker is soluble in most common solvents
including chloroform, methylene chloride, tetrahydrofuran, acetone,
ethyl acetate, isopropanol, etc. .sup.1H NMR (CDCl.sub.3) confirmed
the structure of the product. The peaks at 7.49.about.7.79 ppm (m,
18H) were the typical signals from 4-substituted benzophenone. The
peak at 4.66 ppm (s, 4H) was assigned to the protons of methylene
connected to benzophenone groups. The peak at 3.70 ppm (m, 16H)
corresponded to ethylene groups.
##STR00030##
Example 12
Synthesis of HEG Crosslinker
[0374] 1.70 g of hexaethylene glycol (Aldrich Chemicals, Milwaukee,
Wis.) was dried under vacuum at 50.degree. C. for 2 h and dissolved
in 50 ml anhydrous tetrahydrofuran. 3.7 g of
4-(bromomethyl)benzophenone (Aldrich Chemicals, Milwaukee, Wis.)
and 1.5 g sodium hydride (60% in mineral oil, Aldrich Chemicals,
Milwaukee, Wis.) were added to the solution. The mixture was
stirred overnight under reflux and argon protection. The reaction
solution was cooled to room temperature and filtered. The filtrate
was concentrated by rotary evaporation and the residue was purified
by column chromatography (silica gel, 230-400 mesh, Whatman, Inc.)
using 25:1 chloroform/methanol mixture as eluent. The fractions
containing the pure product were combined and concentrated to
dryness by rotary evaporation to provide yellowish oil (yield
70%).
[0375] The HEG crosslinker is very soluble in most common solvents
including chloroform, methylene chloride, tetrahydrofuran, acetone,
ethyl acetate, isopropanol, etc and slightly soluble in water.
.sup.1H NMR (CDCl.sub.3) confirmed the structure of the product.
The peaks at 7.26.about.7.79 ppm (m, 18H) were the typical signals
from 4-substituted benzophenone. The peak at 4.64 ppm (s, 4H) was
assigned to the protons of methylene connected to benzophenone
groups. The peak at 3.66 ppm (m, 24H) corresponded to ethylene
groups.
##STR00031##
Example 13
Coating with Different Binder Polymers and Crosslinkers
[0376] Super Hydrophobic Coating with TOB Crosslinker
[0377] 400 mg of polyisobutylene (BASF Corp. Florham Park, N.J.,
Mw=2,000,000) and 23 mg TOB crosslinker were dissolved in 60 ml
THF. 480 mg of CAB-O-SIL.RTM. TS-720 silica nanoparticles (Cabot
Corp. Tuscola, Ill.) were dispersed in the solution with intensive
vortex mixing. N-octyltrimethoxysilane (Dow Corning, Midland,
Mich.) treated glass slides were dip coated by immersing the slides
in the coating solution for 30 seconds, then extracting at 0.5
cm/sec. The slides were air dried at room temperature for 5
minutes, then irradiated with ultraviolet light (300 to 400 nm) for
5 minutes (Harland Medical UVM400, Eden Prairie, Minn.).
[0378] 600 mg of polycaprolactone (Aldrich Chemicals, Milwaukee,
Wis., Mw=80,000) and 35 mg TOB crosslinker were dissolved in 30 ml
THF. 720 mg of CAB-O-SIL.RTM. TS-720 silica nanoparticles (Cabot
Corp. Tuscola, Ill.) were dispersed in the solution with intensive
vortexing. N-octyltrimethoxysilane (Dow Corning, Midland, Mich.)
treated glass slides were dip coated by immersing the slides in the
coating solution for 30 seconds, then extracting at 0.5 cm/sec. The
slides were air dried at room temperature for 5 minutes, then
irradiated with ultraviolet light (300 to 400 nm) for 5 minutes
(Harland Medical UVM400, Eden Prairie, Minn.).
[0379] Super Hydrophobic Coating with TEG Crosslinker
[0380] 400 mg of polyisobutylene (BASF Corp. Florham Park, N.J.,
Mw=2,000,000) and 16 mg TEG crosslinker were dissolved in 60 ml
THF. 480 mg of CAB-O-SIL.RTM. TS-720 silica nanoparticles (Cabot
Corp. Tuscola, Ill.) were dispersed in the solution with intensive
vortex mixing. N-octyltrimethoxysilane (Dow Corning, Midland,
Mich.) treated glass slides were dip coated by immersing the slides
in the coating solution for 30 seconds, then extracting at 0.5
cm/sec. The slides were air dried at room temperature for 5
minutes, then irradiated with ultraviolet light (300 to 400 nm) for
5 minutes (Harland Medical UVM400, Eden Prairie, Minn.).
[0381] 600 mg of polycaprolactone (Aldrich Chemicals, Milwaukee,
Wis., Mw=80,000) and 24 mg TEG crosslinker were dissolved in 30 ml
THF. 480 mg of CAB-O-SIL.RTM. TS-720 silica nanoparticles (Cabot
Corp. Tuscola, Ill.) were dispersed in the solution with intensive
vortex mixing. N-octyltrimethoxysilane (Dow Corning, Midland,
Mich.) treated glass slides were dip coated by immersing the slides
in the coating solution for 30 seconds, then extracting at 0.5
cm/sec. The slides were air dried at room temperature for 5
minutes, then irradiated with ultraviolet light (300 to 400 nm) for
5 minutes (Harland Medical UVM400, Eden Prairie, Minn.).
[0382] Super Hydrophobic Coating with HEG Crosslinker
[0383] 400 mg of polyisobutylene (BASF Corp. Florham Park, N.J.,
Mw=2,000,000) and 18 mg HEG crosslinker were dissolved in 60 ml
THF. 480 mg of CAB-O-SIL.RTM. TS-720 silica nanoparticles (Cabot
Corp. Tuscola, Ill.) were dispersed in the solution with intensive
vortex mixing. N-octyltrimethoxysilane (Dow Corning, Midland,
Mich.) treated glass slides were dip coated by immersing the slides
in the coating solution for 30 seconds, then extracting at 0.5
cm/sec. The slides were air dried at room temperature for 5
minutes, then irradiated with ultraviolet light (300 to 400 nm) for
5 minutes (Harland Medical UVM400, Eden Prairie, Minn.).
[0384] 600 mg of polycaprolactone (Aldrich Chemicals, Milwaukee,
Wis., Mw=80,000) and 27 mg HEG crosslinker were dissolved in 30 ml
THF. 480 mg of CAB-O-SIL.RTM. TS-720 silica nanoparticles (Cabot
Corp. Tuscola, Ill.) were dispersed in the solution with intensive
vortexing. N-octyltrimethoxysilane (Dow Corning, Midland, Mich.)
treated glass slides were dip coated by immersing the slides in the
coating solution for 30 seconds, then extracting at 0.5 cm/sec. The
slides were air dried at room temperature for 5 minutes, then
irradiated with ultraviolet light (300 to 400 nm) for 5 minutes
(Harland Medical UVM400, Eden Prairie, Minn.).
[0385] Super Hydrophobic Coating with BOB Crosslinker
[0386] 400 mg of polyisobutylene (BASF Corp. Florham Park, N.J.,
Mw=2,000,000) and 26 mg BOB crosslinker were dissolved in 60 ml
THF. 480 mg of CAB-O-SIL.RTM. TS-720 silica nanoparticles (Cabot
Corp. Tuscola, Ill.) were dispersed in the solution with intensive
vortex mixing. N-octyltrimethoxysilane (Dow Corning, Midland,
Mich.) treated glass slides were dip coated by immersing the slides
in the coating solution for 30 seconds, then extracting at 0.5
cm/sec. The slides were air dried at room temperature for 5
minutes, then irradiated with ultraviolet light (300 to 400 nm) for
5 minutes (Harland Medical UVM400, Eden Prairie, Minn.).
[0387] 600 mg of polycaprolactone (Aldrich Chemicals, Milwaukee,
Wis., Mw=80,000) and 39 mg BOB crosslinker were dissolved in 30 ml
THF. 480 mg of CAB-O-SIL.RTM. TS-720 silica nanoparticles (Cabot
Corp. Tuscola, Ill.) were dispersed in the solution with intensive
vortex mixing. N-octyltrimethoxysilane (Dow Corning, Midland,
Mich.) treated glass slides were dip coated by immersing the slides
in the coating solution for 30 seconds, then extracting at 0.5
cm/sec. The slides were air dried at room temperature for 5
minutes, then irradiated with ultraviolet light (300 to 400 nm) for
5 minutes (Harland Medical UVM400, Eden Prairie, Minn.).
[0388] Super Hydrophobic Coating with ABC Crosslinker
[0389] 400 mg of polyisobutylene (BASF Corp. Florham Park, N.J.,
Mw=2,000,000) and 10 mg
2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone (ABC, Aldrich
Chemicals, Milwaukee, Wis.) were dissolved in 60 ml THF. 480 mg of
CAB-O-SIL.RTM. TS-720 silica nanoparticles (Cabot Corp. Tuscola,
Ill.) were dispersed in the solution with intensive vortex mixing.
N-octyltrimethoxysilane (Dow Corning, Midland, Mich.) treated glass
slides were dip coated by immersing the slides in the coating
solution for 30 seconds, then extracting at 0.5 cm/sec. The slides
were air dried at room temperature for 5 minutes, then irradiated
with ultraviolet light (300 to 400 nm) for 5 minutes (Harland
Medical UVM400, Eden Prairie, Minn.).
[0390] 600 mg of polycaprolactone (Aldrich Chemicals, Milwaukee,
Wis., Mw=80,000) and 15 mg
2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone (ABC, Aldrich
Chemicals, Milwaukee, Wis.) were dissolved in 30 ml THF. 480 mg of
CAB-O-SIL.RTM. TS-720 silica nanoparticles (Cabot Corp. Tuscola,
Ill.) were dispersed in the solution with intensive vortex mixing.
N-octyltrimethoxysilane (Dow Corning, Midland, Mich.) treated glass
slides were dip coated by immersing the slides in the coating
solution for 30 seconds, then extracting at 0.5 cm/sec. The slides
were air dried at room temperature for 5 minutes, then irradiated
with ultraviolet light (300 to 400 nm) for 5 minutes (Harland
Medical UVM400, Eden Prairie, Minn.).
[0391] Super Hydrophobic Coating with MBT
[0392] 400 mg of polyisobutylene (BASF Corp. Florham Park, N.J.,
Mw=2,000,000) and 10 mg
2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine (MBT,
Aldrich Chemicals, Milwaukee, Wis.) were dissolved in 60 ml THF.
480 mg of CAB-C.sub.1--Sift TS-720 silica nanoparticles (Cabot
Corp. Tuscola, Ill.) were dispersed in the solution with intensive
vortex mixing. N-octyltrimethoxysilane (Dow Corning, Midland,
Mich.) treated glass slides were dip coated by immersing the slides
in the coating solution for 30 seconds, then extracting at 0.5
cm/sec. The slides were air dried at room temperature for 5
minutes, then irradiated with ultraviolet light (300 to 400 nm) for
5 minutes (Harland Medical UVM400, Eden Prairie, Minn.).
[0393] 600 mg of polycaprolactone (Aldrich Chemicals, Milwaukee,
Wis., Mw=80,000) and 18 mg
2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine (MBT,
Aldrich Chemicals, Milwaukee, Wis.) were dissolved in 30 ml THF.
480 mg of CAB-O-SIL.RTM. TS-720 silica nanoparticles (Cabot Corp.
Tuscola, Ill.) were dispersed in the solution with intensive vortex
mixing. N-octyltrimethoxysilane (Dow Corning, Midland, Mich.)
treated glass slides were dip coated by immersing the slides in the
coating solution for 30 seconds, then extracting at 0.5 cm/sec. The
slides were air dried at room temperature for 5 minutes, then
irradiated with ultraviolet light (300 to 400 nm) for 5 minutes
(Harland Medical UVM400, Eden Prairie, Minn.).
[0394] Super Hydrophobicity of Coated Slides
[0395] All formulations were able to create surfaces with water
contact angle greater than 150.degree., indicating the coatings
were all super hydrophobic.
[0396] Solvent Challenging Test
[0397] The coated slides were sonicated on a probe sonicator for 1
min in THF. The slides were taken out and air dried. Water contact
angles were measured on each coated surface. The results showed
that all the crosslinked surfaces remained super hydrophobic after
THF challenging, while the non-crosslinked (same composition
without crosslinker) coatings were washed away.
Example 14
Coating with Microparticles
[0398] 200 mg of polyisobutylene (BASF Corp. Florham Park, N.J.,
Mw=2,000,000) was dissolved in 30 ml hexane. Coating solutions with
three different polymer/particle ratios were made by dispersing 100
mg, 200 mg and 400 mg of polystyrene beads (105.about.125 micro,
Polysciences, Inc, Warrington, Pa.) in the 30 ml
polyisobutylene/hexane solution with intensive vortex mixing.
N-octyltrimethoxysilane (Dow Corning, Midland, Mich.) treated glass
slides were dip coated by immersing the slides in the coating
solution for 30 seconds, then extracting at 0.5 cm/sec. The slides
were air dried at room temperature for 5 minutes and water contact
angles were measured. The results showed that none of the
microparticle coating formulations could create a super hydrophobic
or ultra hydrophobic surface.
Example 15
Ultra Hydrophobic Coating of Fiber Membrane
[0399] A coating formulation containing 2.2 mg/ml polyisobutylene
(BASF Corp. Florham Park, N.J., Mw=2,000,000), 2.6 mg/ml
CAB-O-SIL.RTM. TS-720 silica nanoparticles (Cabot Corp. Tuscola,
Ill.) and 0.1 mg/ml triazine crosslinker was made in
tetrahydrofuran. 2.times.2 inch Reemay 2011 fiber membrane (BBA
Fiberweb, Green Bay, Wis.) was coated by dipping the membrane in
coating solution three times with 1 min interval. The membranes
were air dried at room temperature for 5 min and irradiated under
UV (UVP CL-1000 Ultraviolet Crosslinker, 40 watt, 254 nm, 10 cm
from light source) for 20 min. Coatings without crosslinker were
made as control.
Example 16
Ultra Hydrophobicity of the Coated Fiber Membrane
[0400] Both formulations (with and without triazine crosslinker)
were able to create surfaces with water contact angle greater than
140.degree. on fiber membrane, indicating the coatings were all
ultra hydrophobic.
Example 17
Solvent Challenging Test of Coated Fiber Membrane
[0401] Solvent resistance of coatings with and without crosslinker
was tested as follows. Coated samples were sonicated on a probe
sonicator for 30 seconds in methylene chloride. After rinsing with
fresh methylene chloride the samples were air dried. Water contact
angles were measured on the treated samples. The results showed
that the crosslinked coatings remained ultra hydrophobic while the
non-crosslinked coatings lost ultra hydrophobicity after solvent
challenging.
Example 18
Separation of Aqueous/Organic Mixture Using Ultra Hydrophobic Fiber
Membrane
[0402] Reemay 2011 fiber membrane was coated and crosslinked as
described above. The membrane was installed on the bottom of a
stainless steel cylinder with an O-ring seal. 10 ml water and 10 ml
methylene chloride were mixed and added on top of the coated
membrane. Methylene chloride passed though the membrane
successfully and completely with 10 ml water left on top of the
membrane. The uncoated membrane allowed both methylene chloride and
water to pass through.
[0403] Although the present invention has been described with
reference to preferred embodiments, persons skilled in the art will
recognize that changes may be made in form and detail without
departing from the spirit and scope of the invention. All
references cited throughout the specification, including those in
the background, are incorporated herein in their entirety. Those
skilled in the art will recognize, or be able to ascertain, using
no more than routine experimentation, many equivalents to specific
embodiments of the invention described specifically herein. Such
equivalents are intended to be encompassed in the scope of the
following claim.
* * * * *
References