U.S. patent application number 15/858904 was filed with the patent office on 2018-05-03 for multi-functional phenolic resins.
This patent application is currently assigned to EMPIRE TECHNOLOGY DEVELOPMENT LLC. The applicant listed for this patent is EMPIRE TECHNOLOGY DEVELOPMENT LLC. Invention is credited to Georgius Abidal ADAM.
Application Number | 20180118645 15/858904 |
Document ID | / |
Family ID | 52022617 |
Filed Date | 2018-05-03 |
United States Patent
Application |
20180118645 |
Kind Code |
A1 |
ADAM; Georgius Abidal |
May 3, 2018 |
MULTI-FUNCTIONAL PHENOLIC RESINS
Abstract
Disclosed herein are compositions and methods of making phenolic
compounds and phenolic resins. The resins include multifunctional
epoxies, amino glycidyl derivatives, alkanoate derivatives, alkyl
ether derivatives, and multi-functional amines prepared from
hydroxymethyl derivatives of novolac resin.
Inventors: |
ADAM; Georgius Abidal;
(Edensor Park, AU) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
EMPIRE TECHNOLOGY DEVELOPMENT LLC |
Wilmington |
DE |
US |
|
|
Assignee: |
EMPIRE TECHNOLOGY DEVELOPMENT
LLC
Wilmington
DE
|
Family ID: |
52022617 |
Appl. No.: |
15/858904 |
Filed: |
December 29, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14898420 |
Dec 14, 2015 |
9868683 |
|
|
PCT/US13/45579 |
Jun 13, 2013 |
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15858904 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07C 41/01 20130101;
C08G 8/08 20130101; C07D 301/28 20130101; C07C 233/20 20130101;
C07D 303/30 20130101; C07C 43/1783 20130101; C07C 265/08 20130101;
C07C 213/02 20130101; C07C 67/00 20130101; C07C 215/50 20130101;
C08L 61/14 20130101; C07C 69/54 20130101; C07D 303/36 20130101;
C08G 8/28 20130101; C07C 231/02 20130101; C07C 37/20 20130101; C07C
39/15 20130101; C07C 263/10 20130101 |
International
Class: |
C07C 39/15 20060101
C07C039/15; C07C 37/20 20060101 C07C037/20; C08G 8/28 20060101
C08G008/28; C08L 61/14 20060101 C08L061/14; C07C 41/01 20060101
C07C041/01; C07C 43/178 20060101 C07C043/178; C07C 67/00 20060101
C07C067/00; C07C 69/54 20060101 C07C069/54; C07C 213/02 20060101
C07C213/02; C07C 215/50 20060101 C07C215/50; C07C 231/02 20060101
C07C231/02; C07C 233/20 20060101 C07C233/20; C07C 263/10 20060101
C07C263/10; C07C 265/08 20060101 C07C265/08; C07D 301/28 20060101
C07D301/28; C07D 303/30 20060101 C07D303/30; C07D 303/36 20060101
C07D303/36; C08G 8/08 20060101 C08G008/08 |
Claims
1. A method of preparing a compound of formula I, ##STR00008##
wherein: a is an integer from 1 to 10; R.sub.1 is H, Z,
--C(.dbd.O)--CH.dbd.CH.sub.2, --(CH.sub.2--CH.sub.2--O).sub.nH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.nH, or
--(CH.sub.2--CH.sub.2--O).sub.n--(CH.sub.2--CH(CH.sub.3)--O).sub.nH,
where each n is, independently, an integer from 1 to 18; each
R.sub.2 is, independently, H, Z, --C(.dbd.O)--CH.dbd.CH.sub.2,
--(CH.sub.2--CH.sub.2--O).sub.pH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.pH, or
--(CH.sub.2--CH.sub.2--O).sub.p--(CH.sub.2--CH(CH.sub.3)--O).sub.pH,
where each p is, independently, an integer from 1 to 18; R.sub.3 is
H, Z, --C(.dbd.O)--CH.dbd.CH.sub.2,
--(CH.sub.2CH.sub.2--CH.sub.2--O).sub.qH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.qH, or
--(CH.sub.2--CH.sub.2--O).sub.q--(CH.sub.2--CH(CH.sub.3)--O).sub.qH,
where each q is, independently, an integer from 1 to 18; R.sub.4 is
--NH.sub.2, --O--Z, --N(Z).sub.2, --N(CH.sub.2--O--Z).sub.2,
--N(CH.sub.2OH).sub.2, --N(CH.sub.2CH.sub.2--O--Z).sub.2,
--N(CH.sub.2NH.sub.2).sub.2, --N(CH.sub.2CH.sub.2OH).sub.2,
--CH.sub.2--O--Z, --CH.sub.2--OH, --CH.sub.2--NH.sub.2,
--N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3, --CH.sub.2--Y, --NCO,
--O--C(.dbd.O)--(CH.sub.2).sub.r--CH.sub.3, --NH--Z,
--N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
--NH--C(.dbd.O)CH.dbd.CH.sub.2, --CH.sub.2CH.sub.2--O--Z,
--CH.sub.2CH.sub.2OH, --O--C(.dbd.O)--CH.dbd.CH.sub.2,
--N(CH.sub.2--CH.sub.2--NH.sub.2).sub.2,
--(CH.sub.2--CH.sub.2--O).sub.rH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.rH,
--N[CH.sub.2--CH.sub.2--O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2, or
--N[CH.sub.2--CH.sub.2--NH--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
where each r is, independently, an integer from 1 to 18; R.sub.5 is
--OH, --NH.sub.2, --O--Z, --N(Z).sub.2, --N(CH.sub.2--O--Z).sub.2,
--N(CH.sub.2OH).sub.2, --N(CH.sub.2CH.sub.2--O--Z).sub.2,
--N(CH.sub.2NH.sub.2).sub.2, --N(CH.sub.2CH.sub.2OH).sub.2,
--CH.sub.2--O--Z, --CH.sub.2--OH, --CH.sub.2--NH.sub.2,
--N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3, --CH.sub.2--Y, --NCO,
--O--C(.dbd.O)--(CH.sub.2).sub.t--CH.sub.3, --NH--Z,
--N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
--NH--C(.dbd.O)CH.dbd.CH.sub.2, --CH.sub.2CH.sub.2--O--Z,
--CH.sub.2CH.sub.2OH, --O--C(.dbd.O)--CH.dbd.CH.sub.2,
--N(CH.sub.2--CH.sub.2--NH.sub.2).sub.2,
--(CH.sub.2--CH.sub.2--O).sub.tH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.tH,
--N[CH.sub.2--CH.sub.2--O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2, or
--N[CH.sub.2--CH.sub.2--NH--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
where each t is, independently, an integer from 1 to 18; R.sub.6 is
--OH, --NH.sub.2, --O--Z, --N(Z).sub.2, --N(CH.sub.2--O--Z).sub.2,
--N(CH.sub.2OH).sub.2, --N(CH.sub.2CH.sub.2--O--Z).sub.2,
--N(CH.sub.2NH.sub.2).sub.2, --N(CH.sub.2CH.sub.2OH).sub.2,
--CH.sub.2--O--Z, --CH.sub.2--OH, --CH.sub.2--NH.sub.2,
--N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3, --CH.sub.2--Y, --NCO,
--O--C(.dbd.O)--(CH.sub.2).sub.v--CH.sub.3, --NH--Z,
--N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
--NH--C(.dbd.O)CH.dbd.CH.sub.2, --CH.sub.2CH.sub.2--O--Z,
--CH.sub.2CH.sub.2OH, --O--C(.dbd.O)--CH.dbd.CH.sub.2,
--N(CH.sub.2--CH.sub.2--NH.sub.2).sub.2,
--(CH.sub.2--CH.sub.2--O).sub.vH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.vH,
--N[CH.sub.2--CH.sub.2--O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2, or
--N[CH.sub.2--CH.sub.2--NH--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
where each v is, independently, an integer from 1 to 18; each
R.sub.7 is, independently, --OH, --NH.sub.2, --O--Z, --N(Z).sub.2,
--N(CH.sub.2--O--Z).sub.2, --N(CH.sub.2OH).sub.2,
--N(CH.sub.2CH.sub.2--O--Z).sub.2, --N(CH.sub.2NH.sub.2).sub.2,
--N(CH.sub.2CH.sub.2OH).sub.2, --CH.sub.2--O--Z,
--CH.sub.2--NH.sub.2, --N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3,
--CH.sub.2--Y, --NCO, --O--C(.dbd.O)--(CH.sub.2).sub.w--CH.sub.3,
--NH--Z, --N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
--NH--C(.dbd.O)CH.dbd.CH.sub.2, --CH.sub.2CH.sub.2--O--Z,
--CH.sub.2CH.sub.2OH, --O--C(.dbd.O)--CH.dbd.CH.sub.2,
--N(CH.sub.2--CH.sub.2--NH.sub.2).sub.2,
--(CH.sub.2--CH.sub.2--O).sub.wH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.wH,
--N[CH.sub.2--CH.sub.2--O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2, or
--N[CH.sub.2--CH.sub.2--NH--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
where each w is, independently, an integer from 1 to 18; R.sub.8 is
--OH, --NH.sub.2, --O--Z, --N(Z).sub.2, --N(CH.sub.2--O--Z).sub.2,
--N(CH.sub.2OH).sub.2, --N(CH.sub.2CH.sub.2--O--Z).sub.2,
--N(CH.sub.2NH.sub.2).sub.2, --N(CH.sub.2CH.sub.2OH).sub.2,
--CH.sub.2--O--Z, --CH.sub.2--OH, --CH.sub.2--NH.sub.2,
--N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3, --CH.sub.2--Y, --NCO,
--O--C(.dbd.O)--(CH.sub.2).sub.x--CH.sub.3, --NH--Z,
--N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
--NH--C(.dbd.O)CH.dbd.CH.sub.2, --CH.sub.2CH.sub.2--O--Z,
--CH.sub.2CH.sub.2OH, --O--C(.dbd.O)--CH.dbd.CH.sub.2,
--N(CH.sub.2--CH.sub.2--NH.sub.2).sub.2,
--(CH.sub.2--CH.sub.2--O).sub.xH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.xH,
--N[CH.sub.2--CH.sub.2--O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2, or
--N[CH.sub.2--CH.sub.2--NH--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
where each x is, independently, an integer from 1 to 18; Z is
##STR00009## and Y is Cl, Br, F, or I, the method comprising:
contacting a novolac compound with a formaldehyde or a
paraformaldehyde to form a hydroxymethyl compound; and contacting
the hydroxymethyl compound with an epihalohydrin, an acrylic
compound, an alkanoyl halide, an alkyl halide, ammonia, phosgene,
or a dialkyl amine to form the compound.
2. The method of claim 1, wherein contacting the novolac compound
with the formaldehyde or the paraformaldehyde comprises contacting
about 1 mole of the novolac compound with about 3 moles to about 10
moles of the formaldehyde or the paraformaldehyde in presence of a
basic catalyst.
3. The method of claim 2, wherein contacting the novolac compound
with the formaldehyde or the paraformaldehyde in presence of the
basic catalyst comprises mixing the novolac compound, the
formaldehyde or the paraformaldehyde, and the basic catalyst in a
solution having a pH of about 8 to a pH of about 11.
4. The method of claim 2, wherein contacting the novolac compound
with the formaldehyde or the paraformaldehyde in presence of the
basic catalyst comprises mixing the novolac compound, the
formaldehyde or the paraformaldehyde, and the basic catalyst in a
solution for about 2 hours to about 6 hours.
5. The method of claim 2, wherein contacting the novolac compound
with the formaldehyde or the paraformaldehyde in presence of the
basic catalyst comprises heating the novolac compound, the
formaldehyde or the paraformaldehyde, and the basic catalyst to a
temperature of about 50 C to about 70 C.
6. The method of claim 1, wherein contacting the hydroxymethyl
compound with the dialkyl amine comprises contacting with a dialkyl
amine comprising dimethyl amine, diethyl amine, dipropyl amine,
dibutyl amine, or any combination thereof.
7. The method of claim 1, wherein contacting the hydroxymethyl
compound with the acrylic compound comprises contacting with an
acrylic compound comprising acrylic anhydride, acrylic acid,
acryloyl chloride, or any combination thereof.
8. The method of claim 1, wherein contacting the hydroxymethyl
compound with the alkyl halide comprises contacting with an alkyl
halide comprising isooctyl chloride, decyl chloride, hexyl
chloride, heptyl chloride, nonyl chloride, or any combination
thereof.
9. The method of claim 1, wherein contacting the hydroxymethyl
compound with the alkanoyl halide comprises contacting with an
alkanoyl halide comprising isooctanoyl chloride, decanoyl chloride,
hexanoyl chloride, lauroyl chloride, nonanoyl chloride, palmitoyl
chloride, or any combination thereof.
10. The method of claim 1, wherein contacting the hydroxymethyl
compound comprises contacting the hydroxymethyl compound with the
epihalohydrin, the acrylic compound, the alkanoyl halide, the alkyl
halide, the ammonia, the phosgene, or the dialkyl amine, in a molar
ratio of about 1:3 to about 1:10.
11. The method of claim 10, wherein contacting the hydroxymethyl
compound further comprises contacting the hydroxymethyl compound
with the epihalohydrin or the dialkyl amine in presence of a
reaction catalyst.
12. The method of claim 11, wherein the reaction catalyst is
selected from the group consisting of MgClO.sub.4, LiCl, LiOH,
SnF.sub.2, LiClO.sub.4, and any combination thereof.
13. The method of claim 11, wherein contacting the hydroxymethyl
compound with the epihalohydrin compound in presence of the
reaction catalyst further comprises heating the hydroxymethyl
compound, the epihalohydrin, and the reaction catalyst along with a
phase transfer catalyst.
14. The method of claim 13, wherein the phase transfer catalyst is
selected from the group consisting of benzyltrimethylammonium
bromide, cetyltrimethylammonium bromide, tetrabutylammonium
hydroxide, tetrabutyl ammonium chloride, and any combination
thereof.
15. The method of claim 11, wherein contacting the hydroxymethyl
compound with the epihalohydrin compound in presence of the
reaction catalyst further comprises adding an organic solvent.
16. The method of claim 15, wherein the organic solvent is selected
from the group consisting of 1-butanol, a secondary butanol,
2-methoxyethanol, 2-ethoxyethanol, 2-phenoxyethanol, 1,4-dioxane,
1,3-dioxane, diethoxyethane, acetonitrile, dimethyl sulfoxide,
dimethyl formamide, and any combination thereof.
17. The method of claim 10, wherein contacting the hydroxymethyl
compound further comprises contacting the hydroxymethyl compound
with the acrylic compound in presence of an antioxidant and an
inhibitor.
18. The method of claim 17, wherein the inhibitor is a substituted
or a non-substituted quinone, hydroquinone, butylated hydroxyl
toluene, or any combination thereof.
19. The method of claim 17, wherein the antioxidant is
tert-butylhydroquinone, a substituted quinone, butylated hydroxyl
toluene, or any combination thereof.
20. The method of claim 10, wherein contacting the hydroxymethyl
compound further comprises contacting the hydroxymethyl compound
with the ammonia or the phosgene in an autoclave.
21. The method of claim 20, wherein contacting the hydroxymethyl
compound comprises contacting the hydroxymethyl compound and the
ammonia or the phosgene under a pressure of about 1 atmospheric
pressure to about 1.5 atmospheric pressure.
22. The method of claim 10, wherein contacting the hydroxymethyl
compound comprises contacting the hydroxymethyl compound with the
epihalohydrin, the acrylic compound, the alkanoyl halide, the alkyl
halide, the ammonia, the phosgene, or the dialkyl amine at a
temperature of about 50 C to about 90 C.
23. The method of claim 10, wherein contacting the hydroxymethyl
compound contacting the hydroxymethyl compound with the
epihalohydrin, the acrylic compound, the alkanoyl halide, the alkyl
halide, the ammonia, the phosgene, or the dialkyl amine for about 2
hours to about 6 hours.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This patent application is a Divisional patent application
under 35 U.S.C. .sctn. 121 of U.S. patent application Ser. No.
14/898,420 filed on Dec. 14, 2015, which is a U.S. National Stage
filing under 35 U.S.C. .sctn. 371 of International Patent
Application No. PCT/US2013/045579 filed on Jun. 13, 2013, entitled
"MULTI-FUNCTIONAL PHENOLIC RESINS," which are incorporated herein
by reference in their entirety.
BACKGROUND
[0002] Over 6 million tons of phenolic resins are produced each
year globally. They are relatively inexpensive and possess
excellent properties, making them suitable for a wide range of
applications. Phenolic resins exhibit good heat resistance, high
mechanical strength, electrical insulation, excellent creep
resistance, good processability, and flame resistance.
[0003] Phenol-formaldehyde resins generally occur in two forms:
resole (viscous liquid) and novolac (solid). Resoles have a
formaldehyde to phenol ratio of greater than one. Resoles are
self-curing without requiring any cross-linkers, and can be easily
compounded with additives, fillers, or fibers. Curing of resole
occurs by the loss of 1.5 moles of formaldehyde per mole of resole,
which is usually released as a toxic gas. The shelf-life of resole
is 6-8 months when stabilized and stored under ideal conditions.
Novolacs, on the other hand, have a formaldehyde-to-phenol molar
ratio of less than one. Novolacs require curing agents and is
usually mixed with hexamine derivatives.
[0004] Several curing agents for novolac resins are known in the
art, including formaldehyde, paraformaldehyde, and
hexamethylenetetramine. The most common curing agent is
hexamethylenetetramine, which reacts upon heating to yield ammonia,
formaldehyde, methylene amine derivatives, and a cured resin. These
curing agents complete the cross-linking reaction to convert a
thermoplastic novolac resin to an insoluble infusible state.
However, each of these novolac curing agents has certain
disadvantages. For instance, where hexamethylenetetramine or
formaldehyde are used to cure a novolac resin, volatile reaction
products are emitted during the cure reaction. Specifically, when
the curing agent is hexamethylenetetramine, toxic gas such as
ammonia and formaldehyde are released during curing of the novolac
resin. Further, hexamethylene derivatives are highly explosive, and
require storing the cured resins under temperature regulated
conditions, which are not economical. In addition, novolac curing
agents like hexamethylenetetramine typically require curing
temperatures as high as 150.degree. C. Cure temperatures can be
lowered by the addition of acids, but this often introduces other
problems such as die staining, die sticking, and sublimation of
organic acids into the atmosphere.
[0005] Whilst both of these phenolic resins are used ubiquitously,
the issues outlined above concerning their handling, storage, and
the necessary curing with dangerous chemicals creates an
opportunity for improvements. Furthermore, it is possible to
further enhance the physical, chemical, and mechanical properties
of these resins. Accordingly, there is a need for the production of
new resins with enhanced functionality and improved safety which
can be used in a wide variety of industrial applications.
SUMMARY
[0006] The present disclosure is directed to various phenolic
resins and phenolic compounds with multi-functional groups. In one
embodiment, a compound is of formula I
##STR00001##
[0007] wherein:
[0008] a is an integer from 1 to 10;
[0009] R.sub.1 is H, Z, --C(.dbd.O)--CH.dbd.CH.sub.2,
--(CH.sub.2--CH.sub.2--O).sub.nH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.nH, or
--(CH.sub.2--CH.sub.2--O).sub.n--(CH.sub.2--CH(CH.sub.3)--O).sub.nH,
where each n is, independently, an integer from 1 to 18;
[0010] each R.sub.2 is, independently, H, Z,
--C(.dbd.O)--CH.dbd.CH.sub.2, --(CH.sub.2--CH.sub.2--O).sub.pH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.pH, or
--(CH.sub.2--CH.sub.2--O).sub.p--(CH.sub.2--CH(CH.sub.3)--O).sub.pH,
where each p is, independently, an integer from 1 to 18;
[0011] R.sub.3 is H, Z, --C(.dbd.O)--CH.dbd.CH.sub.2,
--(CH.sub.2--CH.sub.2--O).sub.qH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.qH, or
--(CH.sub.2--CH.sub.2--O).sub.q--(CH.sub.2--CH(CH.sub.3)--O).sub.qH,
where each q is, independently, an integer from 1 to 18;
[0012] R.sub.4 is --OH, --NH.sub.2, --O--Z, --N(Z).sub.2,
--N(CH.sub.2--O--Z).sub.2, --N(CH.sub.2OH).sub.2,
--N(CH.sub.2CH.sub.2--O--Z).sub.2, --N(CH.sub.2NH.sub.2).sub.2,
--N(CH.sub.2CH.sub.2OH).sub.2, --CH.sub.2--O--Z, --CH.sub.2--OH,
--CH.sub.2--NH.sub.2, --N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3,
--CH.sub.2--Y, --NCO, --O--C(.dbd.O)--(CH.sub.2).sub.r--CH.sub.3,
--NH--Z, --N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
--NH--C(.dbd.O)CH.dbd.CH.sub.2, --CH.sub.2CH.sub.2--O--Z,
--CH.sub.2CH.sub.2OH, --O--C(.dbd.O)--CH.dbd.CH.sub.2,
--N(CH.sub.2--CH.sub.2--NH.sub.2).sub.2,
--(CH.sub.2--CH.sub.2--O).sub.rH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.rH,
--N[CH.sub.2--CH.sub.2--O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2, or
--N[CH.sub.2--CH.sub.2--NH--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
where each r is, independently, an integer from 1 to 18;
[0013] R.sub.5 is --OH, --NH.sub.2, --O--Z, --N(Z).sub.2,
--N(CH.sub.2--O--Z).sub.2, --N(CH.sub.2OH).sub.2,
--N(CH.sub.2CH.sub.2--O--Z).sub.2, --N(CH.sub.2NH.sub.2).sub.2,
--N(CH.sub.2CH.sub.2OH).sub.2, --CH.sub.2--O--Z, --CH.sub.2--OH,
--CH.sub.2--NH.sub.2, --N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3,
--CH.sub.2--Y, --NCO, --O--C(.dbd.O)--(CH.sub.2).sub.t--CH.sub.3,
--NH--Z, --N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
--NH--C(.dbd.O)CH.dbd.CH.sub.2, --CH.sub.2CH.sub.2--O--Z,
--CH.sub.2CH.sub.2OH, --O--C(.dbd.O)--CH.dbd.CH.sub.2,
--N(CH.sub.2--CH.sub.2--NH.sub.2).sub.2,
--(CH.sub.2--CH.sub.2--O).sub.tH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.tH,
--N[CH.sub.2--CH.sub.2--O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2, or
--N[CH.sub.2--CH.sub.2--NH--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
where each t is, independently, an integer from 1 to 18;
[0014] R.sub.6 is --OH, --NH.sub.2, --O--Z, --N(Z).sub.2,
--N(CH.sub.2--O--Z).sub.2, --N(CH.sub.2OH).sub.2,
--N(CH.sub.2CH.sub.2--O--Z).sub.2, --N(CH.sub.2NH.sub.2).sub.2,
--N(CH.sub.2CH.sub.2OH).sub.2, --CH.sub.2--O--Z, --CH.sub.2--OH,
--CH.sub.2--NH.sub.2, --N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3,
--CH.sub.2--Y, --NCO, --O--C(.dbd.O)--(CH.sub.2).sub.v--CH.sub.3,
--NH--Z, --N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
--NH--C(.dbd.O)CH.dbd.CH.sub.2, --CH.sub.2CH.sub.2--O--Z,
--CH.sub.2CH.sub.2OH, --O--C(.dbd.O)--CH.dbd.CH.sub.2,
--N(CH.sub.2--CH.sub.2--NH.sub.2).sub.2,
--(CH.sub.2--CH.sub.2--O).sub.vH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.vH,
--N[CH.sub.2--CH.sub.2--O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2, or
--N[CH.sub.2--CH.sub.2--NH--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
where each v is, independently, an integer from 1 to 18; [0015]
each R.sub.7 is, independently, --OH, --NH.sub.2, --O--Z,
--N(Z).sub.2, --N(CH.sub.2--O--Z).sub.2, --N(CH.sub.2OH).sub.2,
--N(CH.sub.2CH.sub.2--O--Z).sub.2, --N(CH.sub.2NH.sub.2).sub.2,
--N(CH.sub.2CH.sub.2OH).sub.2, --CH.sub.2--O--Z, --CH.sub.2--OH,
--CH.sub.2--NH.sub.2, --N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3,
--CH.sub.2--Y, --NCO, --O--C(.dbd.O)--(CH.sub.2).sub.w--CH.sub.3,
--NH--Z, --N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
--NH--C(.dbd.O)CH.dbd.CH.sub.2, --CH.sub.2CH.sub.2--O--Z,
--CH.sub.2CH.sub.2OH, --O--C(.dbd.O)--CH.dbd.CH.sub.2,
--N(CH.sub.2--CH.sub.2--NH.sub.2).sub.2,
--(CH.sub.2--CH.sub.2--O).sub.wH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.wH,
--N[CH.sub.2--CH.sub.2--O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2, or
--N[CH.sub.2--CH.sub.2--NH--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
where each w is, independently, an integer from 1 to 18;
[0016] R.sub.8 is --OH, --NH.sub.2, --O--Z, --N(Z).sub.2,
--N(CH.sub.2--O--Z).sub.2, --N(CH.sub.2OH).sub.2,
--N(CH.sub.2CH.sub.2--O--Z).sub.2, --N(CH.sub.2NH.sub.2).sub.2,
--N(CH.sub.2CH.sub.2OH).sub.2, --CH.sub.2--O--Z, --CH.sub.2--OH,
--CH.sub.2--NH.sub.2, --N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3,
--CH.sub.2--Y, --NCO, --O--C(.dbd.O)--(CH.sub.2).sub.x--CH.sub.3,
--NH--Z, --N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
--NH--C(.dbd.O)CH.dbd.CH.sub.2, --CH.sub.2CH.sub.2--O--Z,
--CH.sub.2CH.sub.2OH, --O--C(.dbd.O)--CH.dbd.CH.sub.2,
--N(CH.sub.2--CH.sub.2--NH.sub.2).sub.2,
--(CH.sub.2--CH.sub.2--O).sub.xH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.xH,
--N[CH.sub.2--CH.sub.2--O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2, or
--N[CH.sub.2--CH.sub.2--NH--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
where each x is, independently, an integer from 1 to 18;
[0017] Z is
##STR00002##
and
[0018] Y is Cl, Br, F, or I.
[0019] In an additional embodiment, a composition may include any
one or more of the compounds of formula I as described herein. In
some embodiments, the composition may be or include an absorbent
polymer, or a carbon fiber resin comprising any one or more of the
compounds of formula I as described herein. In a further
embodiment, an article may include any one or more of the compounds
of formula I as described herein. In a further embodiment, a resin
may include any one or more of the compounds of formula I as
described herein.
[0020] In a further embodiment, methods of preparing a compound may
include: contacting a novolac compound with a formaldehyde or
paraformaldehyde to form a hydroxymethyl compound; and contacting
the hydroxymethyl compound with an epihalohydrin, an acrylic
compound, an alkanoyl halide, an alkyl halide, ammonia, phosgene,
or a dialkylamine to form the compound.
[0021] In an additional embodiment, a method to enhance thermal
stability, glass transition temperature or chemical resistance of a
resin may include incorporating any one or more of the compounds of
formula I as described herein in the resin.
BRIEF DESCRIPTION OF THE FIGURES
[0022] FIG. 1 illustrates reaction steps according to an
embodiment.
[0023] FIG. 2A depicts a DSC thermogram of compound 1 measured at
10.degree. C./minute under N.sub.2 atmosphere according to an
embodiment; FIG. 2B shows a DSC thermogram of novolac cured with
hexamine according to an embodiment.
[0024] FIG. 3 depicts the TGA curves of compound 1 according to an
embodiment.
[0025] FIG. 4 depicts the isothermal DSC curing curves of compound
4 at temperatures 40.degree. C., 50.degree. C., 60.degree. C. and
80.degree. C., according to an embodiment.
[0026] FIG. 5 depicts DSC curing curves of compound 7 at
temperatures 40.degree. C. and 60.degree. C., according to an
embodiment.
[0027] FIG. 6 depicts the thermomechanical curve showing high glass
transition temperature and expansion coefficient of a cured epoxy
resin according to an embodiment.
[0028] FIG. 7 represents DSC curing curves of acrylate resin at
temperatures 40.degree. C. and 60.degree. C. according to an
embodiment.
DETAILED DESCRIPTION
[0029] This disclosure is not limited to the particular systems,
devices and methods described, as these may vary. The terminology
used in the description is for the purpose of describing the
particular versions or embodiments only, and is not intended to
limit the scope.
[0030] As used herein, "alkylene" refers to a bivalent alkyl moiety
having the general formula --(CH.sub.2).sub.n--, where n is from
about 1 to about 25, about 1 to about 20, or about 4 to about 20.
By bivalent, it is meant that the group has two open sites each of
which bonds to another group. Non-limiting examples include, but
are not limited to, methylene, ethylene, trimethylene,
pentamethylene, and hexamethylene. Alkylene groups can be
substituted or unsubstituted, linear or a branched bivalent alkyl
groups.
[0031] As used herein, the term "alkyl" refers to a saturated
hydrocarbon group which is straight-chained or branched. An alkyl
group can contain from 1 to 20 carbon atoms, from 2 to 20 carbon
atoms, from 1 to 10 carbon atoms, from 2 to 10 carbon atoms, from 1
to 8 carbon atoms, from 2 to 8 carbon atoms, from 1 to 6 carbon
atoms, from 2 to 6 carbon atoms, from 1 to 4 carbon atoms, from 2
to 4 carbon atoms, from 1 to 3 carbon atoms, or 2 carbon atoms, or
3 carbon atoms. Examples of alkyl groups include, but are not
limited to, methyl (Me), ethyl (Et), propyl (example, n-propyl and
isopropyl), butyl (example, n-butyl, t-butyl, isobutyl), pentyl
(example, n-pentyl, isopentyl, neopentyl), hexyl, isohexyl, heptyl,
4,4 dimethylpentyl, octyl, 2,2,4-trimethylpentyl, nonyl, decyl,
undecyl, dodecyl, 2-methyl-1-propyl, 2-methyl-2-propyl,
2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-3-butyl,
2-methyl-1-pentyl, 2,2-dimethyl-1-propyl, 3-methyl-1-pentyl,
4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl,
4-methyl-2-pentyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl,
2-ethyl-1-butyl, and the like.
[0032] Disclosed herein are compositions and methods for making
various phenolic resins and compounds with multi-functional groups.
In some embodiments, the phenolic compound is of formula I:
##STR00003##
[0033] wherein:
[0034] a is an integer from 1 to 10;
[0035] R.sub.1 is H, Z, --C(.dbd.O)--CH.dbd.CH.sub.2,
--(CH.sub.2--CH.sub.2--O).sub.nH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.nH, or
--(CH.sub.2--CH.sub.2--O).sub.n--(CH.sub.2--CH(CH.sub.3)--O).sub.nH,
where each n is, independently, an integer from 1 to 18; each
R.sub.2 is, independently, H, Z, --C(.dbd.O)--CH.dbd.CH.sub.2,
--(CH.sub.2--CH.sub.2--O).sub.pH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.pH, or
--(CH.sub.2--CH.sub.2--O).sub.p--(CH.sub.2--CH(CH.sub.3)--O).sub.pH,
where each p is, independently, an integer from 1 to 18;
[0036] R.sub.3 is H, Z, --C(.dbd.O)--CH.dbd.CH.sub.2,
--(CH.sub.2--CH.sub.2--O).sub.qH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.qH, or
--(CH.sub.2--CH.sub.2--O).sub.q--(CH.sub.2--CH(CH.sub.3)--O).sub.qH,
where each q is, independently, an integer from 1 to 18;
[0037] R.sub.4 is --OH, --NH.sub.2, --O--Z, --N(Z).sub.2,
--N(CH.sub.2--O--Z).sub.2, --N(CH.sub.2OH).sub.2,
--N(CH.sub.2CH.sub.2--O--Z).sub.2, --N(CH.sub.2NH.sub.2).sub.2,
--N(CH.sub.2CH.sub.2OH).sub.2, --CH.sub.2--O--Z, --CH.sub.2--OH,
--CH.sub.2--NH.sub.2, --N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3,
--CH.sub.2--Y, --NCO, --O--C(.dbd.O)--(CH.sub.2).sub.r--CH.sub.3,
--NH--Z, --N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
--NH--C(.dbd.O)CH.dbd.CH.sub.2, --CH.sub.2CH.sub.2--O--Z,
--CH.sub.2CH.sub.2OH, --O--C(.dbd.O)--CH.dbd.CH.sub.2,
--N(CH.sub.2--CH.sub.2--NH.sub.2).sub.2,
--(CH.sub.2--CH.sub.2--O).sub.rH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.rH,
--N[CH.sub.2--CH.sub.2--O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2, or
--N[CH.sub.2--CH.sub.2--NH--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
where each r is, independently, an integer from 1 to 18;
[0038] R.sub.5 is --OH, --NH.sub.2, --O--Z, --N(Z).sub.2,
--N(CH.sub.2--O--Z).sub.2, --N(CH.sub.2OH).sub.2,
--N(CH.sub.2CH.sub.2--O--Z).sub.2, --N(CH.sub.2NH.sub.2).sub.2,
--N(CH.sub.2CH.sub.2OH).sub.2, --CH.sub.2--O--Z, --CH.sub.2--OH,
--CH.sub.2--NH.sub.2, --N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3,
--CH.sub.2--Y, --NCO, --O--C(.dbd.O)--(CH.sub.2).sub.t--CH.sub.3,
--NH--Z, --N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
--NH--C(.dbd.O)CH.dbd.CH.sub.2, --CH.sub.2CH.sub.2--O--Z,
--CH.sub.2CH.sub.2OH, --O--C(.dbd.O)--CH.dbd.CH.sub.2,
--N(CH.sub.2--CH.sub.2--NH.sub.2).sub.2,
--(CH.sub.2--CH.sub.2--O).sub.tH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.tH,
--N[CH.sub.2--CH.sub.2--O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2, or
--N[CH.sub.2--CH.sub.2--NH--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
where each t is, independently, an integer from 1 to 18;
[0039] R.sub.6 is --OH, --NH.sub.2, --O--Z, --N(Z).sub.2,
--N(CH.sub.2--O--Z).sub.2, --N(CH.sub.2OH).sub.2,
--N(CH.sub.2CH.sub.2--O--Z).sub.2, --N(CH.sub.2NH.sub.2).sub.2,
--N(CH.sub.2CH.sub.2OH).sub.2, --CH.sub.2--O--Z, --CH.sub.2--OH,
--CH.sub.2--NH.sub.2, --N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3,
--CH.sub.2--Y, --NCO, --O--C(.dbd.O)--(CH.sub.2)--CH.sub.3,
--NH--Z, --N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
--NH--C(.dbd.O)CH.dbd.CH.sub.2, --CH.sub.2CH.sub.2--O--Z,
--CH.sub.2CH.sub.2OH, --O--C(.dbd.O)--CH.dbd.CH.sub.2,
--N(CH.sub.2--CH.sub.2--NH.sub.2).sub.2,
--(CH.sub.2--CH.sub.2--O).sub.vH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.vH,
--N[CH.sub.2--CH.sub.2--O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2, or
--N[CH.sub.2--CH.sub.2--NH--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
where each v is, independently, an integer from 1 to 18; [0040]
each R.sub.7 is, independently, --OH, --NH.sub.2, --O--Z,
--N(Z).sub.2, --N(CH.sub.2--O--Z).sub.2, --N(CH.sub.2OH).sub.2,
--N(CH.sub.2CH.sub.2--O--Z).sub.2, --N(CH.sub.2NH.sub.2).sub.2,
--N(CH.sub.2CH.sub.2OH).sub.2, --CH.sub.2--O--Z, --CH.sub.2--OH,
--CH.sub.2--NH.sub.2, --N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3,
--CH.sub.2--Y, --NCO, --O--C(.dbd.O)--(CH.sub.2).sub.w--CH.sub.3,
--NH--Z, --N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
--NH--C(.dbd.O)CH.dbd.CH.sub.2, --CH.sub.2CH.sub.2--O--Z,
--CH.sub.2CH.sub.2OH, --O--C(.dbd.O)--CH.dbd.CH.sub.2,
--N(CH.sub.2--CH.sub.2--NH.sub.2).sub.2,
--(CH.sub.2--CH.sub.2--O).sub.wH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.wH,
--N[CH.sub.2--CH.sub.2--O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2, or
--N[CH.sub.2--CH.sub.2--NH--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
where each w is, independently, an integer from 1 to 18;
[0041] R.sub.8 is --OH, --NH.sub.2, --O--Z, --N(Z).sub.2,
--N(CH.sub.2--O--Z).sub.2, --N(CH.sub.2OH).sub.2,
--N(CH.sub.2CH.sub.2--O--Z).sub.2, --N(CH.sub.2NH.sub.2).sub.2,
--N(CH.sub.2CH.sub.2OH).sub.2, --CH.sub.2--O--Z, --CH.sub.2--OH,
--CH.sub.2--NH.sub.2, --N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3,
--CH.sub.2--Y, --NCO, --O--C(.dbd.O)--(CH.sub.2).sub.x--CH.sub.3,
--NH--Z, --N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
--NH--C(.dbd.O)CH.dbd.CH.sub.2, --CH.sub.2CH.sub.2--O--Z,
--CH.sub.2CH.sub.2OH, --O--C(.dbd.O)--CH.dbd.CH.sub.2,
--N(CH.sub.2--CH.sub.2--NH.sub.2).sub.2,
--(CH.sub.2--CH.sub.2--O).sub.xH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.xH,
--N[CH.sub.2--CH.sub.2--O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2, or
--N[CH.sub.2--CH.sub.2--NH--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
where each x is, independently, an integer from 1 to 18;
[0042] Z is
##STR00004##
and
[0043] Y is Cl, Br, F, or I.
[0044] In some embodiments, a is an integer from 1 to 5, an integer
from 1 to 3 or an integer from 3 to 5. In some embodiments, a is 1.
In some embodiments, a is 5.
[0045] In some embodiments, R.sub.1 may be H, Z,
--C(.dbd.O)--CH.dbd.CH.sub.2, --(CH.sub.2--CH.sub.2--O).sub.nH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.nH, or
--(CH.sub.2--CH.sub.2--O).sub.n--(CH.sub.2--CH(CH.sub.3)--O).sub.nH,
where each n is, independently, an integer from 1 to 18. In some
embodiments, R.sub.1 may be H, Z, or --C(.dbd.O)--CH.dbd.CH.sub.2,
--(CH.sub.2--CH.sub.2--O).sub.nH.
[0046] In some embodiments, each R.sub.2 may be H, Z,
--C(.dbd.O)--CH.dbd.CH.sub.2, --(CH.sub.2--CH.sub.2--O).sub.pH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.pH, or
--(CH.sub.2--CH.sub.2--O).sub.p--(CH.sub.2--CH(CH.sub.3)--O).sub.pH,
where each p is, independently, an integer from 1 to 18. In some
embodiments, each R.sub.2 may be H, Z,
--C(.dbd.O)--CH.dbd.CH.sub.2, or
--(CH.sub.2--CH.sub.2--O).sub.pH.
[0047] In some embodiments, R.sub.3 may be H, Z,
--C(.dbd.O)--CH.dbd.CH.sub.2, --(CH.sub.2--CH.sub.2--O).sub.qH,
(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.qH, or
--(CH.sub.2--CH.sub.2--O).sub.q--(CH.sub.2--CH(CH.sub.3)--O).sub.qH,
where each q is, independently, an integer from 1 to 18. In some
embodiments, R.sub.3 may be H, Z, --C(.dbd.O)--CH.dbd.CH.sub.2,
--(CH.sub.2--CH.sub.2--O).sub.qH.
[0048] In some embodiments, R.sub.4 may be --OH, --NH.sub.2,
--O--Z, --N(Z).sub.2, --N(CH.sub.2--O--Z).sub.2,
--N(CH.sub.2OH).sub.2, --N(CH.sub.2CH.sub.2--O--Z).sub.2,
--N(CH.sub.2NH.sub.2).sub.2, --N(CH.sub.2CH.sub.2OH).sub.2,
--CH.sub.2--O--Z, --CH.sub.2--OH, --CH.sub.2--NH.sub.2,
--N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3, --CH.sub.2--Y, --NCO,
--O--C(.dbd.O)--(CH.sub.2).sub.r--CH.sub.3, --NH--Z,
--N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
--NH--C(.dbd.O)CH.dbd.CH.sub.2, --CH.sub.2CH.sub.2--O--Z,
--CH.sub.2CH.sub.2OH, --O--C(.dbd.O)--CH.dbd.CH.sub.2,
--N(CH.sub.2--CH.sub.2--NH.sub.2).sub.2,
--(CH.sub.2--CH.sub.2--O).sub.rH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.rH,
--N[CH.sub.2--CH.sub.2--O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2, or
--N[CH.sub.2--CH.sub.2--NH--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
where each r is, independently, an integer from 1 to 18. In some
embodiments, R.sub.4 may be --OH, --NH.sub.2, --O--Z, --N(Z).sub.2,
--N(CH.sub.2--O--Z).sub.2, --N(CH.sub.2OH).sub.2,
--N(CH.sub.2CH.sub.2--O--Z).sub.2, --N(CH.sub.2NH.sub.2).sub.2,
--N(CH.sub.2CH.sub.2OH).sub.2, --CH.sub.2--O--Z, --CH.sub.2--OH,
--CH.sub.2--NH.sub.2, --N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3,
--CH.sub.2--Y, --NCO, --O--C(.dbd.O)--(CH.sub.2).sub.r--CH.sub.3,
--NH--Z, --N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
--NH--C(.dbd.O)CH.dbd.CH.sub.2, --CH.sub.2CH.sub.2--O--Z,
--CH.sub.2CH.sub.2OH, --O--C(.dbd.O)--CH.dbd.CH.sub.2, or
--N(CH.sub.2--CH.sub.2--NH.sub.2).sub.2. In some embodiments,
R.sub.4 may be --OH, --NH.sub.2, --O--Z, --N(Z).sub.2,
--N(CH.sub.2--O--Z).sub.2, --N(CH.sub.2OH).sub.2,
--N(CH.sub.2CH.sub.2--O--Z).sub.2, --N(CH.sub.2NH.sub.2).sub.2,
--N(CH.sub.2CH.sub.2OH).sub.2, --CH.sub.2--O--Z, --CH.sub.2--OH,
--CH.sub.2--NH.sub.2, --N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3,
--CH.sub.2--Y, --NCO, --O--C(.dbd.O)--(CH.sub.2).sub.r--CH.sub.3,
--NH--Z, --N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2, or
--NH--C(.dbd.O)CH.dbd.CH.sub.2.
[0049] In some embodiments, R.sub.5 may be --OH, --NH.sub.2,
--O--Z, --N(Z).sub.2, --N(CH.sub.2--O--Z).sub.2,
--N(CH.sub.2OH).sub.2, --N(CH.sub.2CH.sub.2--O--Z).sub.2,
--N(CH.sub.2NH.sub.2).sub.2, --N(CH.sub.2CH.sub.2OH).sub.2,
--CH.sub.2--O--Z, --CH.sub.2--OH, --CH.sub.2--NH.sub.2,
--N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3, --CH.sub.2--Y, --NCO,
--O--C(.dbd.O)--(CH.sub.2).sub.t--CH.sub.3, --NH--Z,
--N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
--NH--C(.dbd.O)CH.dbd.CH.sub.2, --CH.sub.2CH.sub.2--O--Z,
--CH.sub.2CH.sub.2OH, --O--C(.dbd.O)--CH.dbd.CH.sub.2,
--N(CH.sub.2--CH.sub.2--NH.sub.2).sub.2,
--(CH.sub.2--CH.sub.2--O).sub.tH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.tH,
--N[CH.sub.2--CH.sub.2--O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2, or
--N[CH.sub.2--CH.sub.2--NH--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
where each t is, independently, an integer from 1 to 18. In some
embodiments, R.sub.5 may be --OH, --NH.sub.2, --O--Z, --N(Z).sub.2,
--N(CH.sub.2--O--Z).sub.2, --N(CH.sub.2OH).sub.2,
--N(CH.sub.2CH.sub.2--O--Z).sub.2, --N(CH.sub.2NH.sub.2).sub.2,
--N(CH.sub.2CH.sub.2OH).sub.2, --CH.sub.2--O--Z, --CH.sub.2--OH,
--CH.sub.2--NH.sub.2, --N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3,
--CH.sub.2--Y, --NCO, --O--C(.dbd.O)--(CH.sub.2).sub.t--CH.sub.3,
--NH--Z,
--N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2--NH--C(.dbd.O)C-
H.dbd.CH.sub.2, --CH.sub.2CH.sub.2--O--Z, --CH.sub.2CH.sub.2OH,
--O--C(.dbd.O)--CH.dbd.CH.sub.2, or
--N(CH.sub.2--CH.sub.2--NH.sub.2).sub.2. In some embodiments,
R.sub.5 may be --OH, --NH.sub.2, --O--Z, --N(Z).sub.2,
--N(CH.sub.2--O--Z).sub.2, --N(CH.sub.2OH).sub.2,
--N(CH.sub.2CH.sub.2--O--Z).sub.2, --N(CH.sub.2NH.sub.2).sub.2,
--N(CH.sub.2CH.sub.2OH).sub.2, --CH.sub.2--O--Z, --CH.sub.2--OH,
--CH.sub.2--NH.sub.2, --N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3,
--CH.sub.2--Y, --NCO, --O--C(.dbd.O)--(CH.sub.2).sub.t--CH.sub.3,
--NH--Z, --N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2, or
--NH--C(.dbd.O)CH.dbd.CH.sub.2.
[0050] In some embodiments, R.sub.6 may be --OH, --NH.sub.2,
--O--Z, --N(Z).sub.2, --N(CH.sub.2--O--Z).sub.2,
--N(CH.sub.2OH).sub.2, --N(CH.sub.2CH.sub.2--O--Z).sub.2,
--N(CH.sub.2NH.sub.2).sub.2, --N(CH.sub.2CH.sub.2OH).sub.2,
--CH.sub.2--O--Z, --CH.sub.2--OH, --CH.sub.2--NH.sub.2,
--N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3, --CH.sub.2--Y, --NCO,
--O--C(.dbd.O)--(CH.sub.2).sub.v--CH.sub.3, --NH--Z,
--N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
--NH--C(.dbd.O)CH.dbd.CH.sub.2, --CH.sub.2CH.sub.2--O--Z,
--CH.sub.2CH.sub.2OH, --O--C(.dbd.O)--CH.dbd.CH.sub.2,
--N(CH.sub.2--CH.sub.2--NH.sub.2).sub.2,
--(CH.sub.2--CH.sub.2--O).sub.vH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.vH,
--N[CH.sub.2--CH.sub.2--O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2, or
--N[CH.sub.2--CH.sub.2--NH--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
where each v is, independently, an integer from 1 to 18.
[0051] In some embodiments, R.sub.6 may be --OH, --NH.sub.2,
--O--Z, --N(Z).sub.2, --N(CH.sub.2--O--Z).sub.2,
--N(CH.sub.2OH).sub.2, --N(CH.sub.2CH.sub.2--O--Z).sub.2,
--N(CH.sub.2NH.sub.2).sub.2, --N(CH.sub.2CH.sub.2OH).sub.2,
--CH.sub.2--O--Z, --CH.sub.2--OH, --CH.sub.2--NH.sub.2,
--N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3, --CH.sub.2--Y, --NCO,
--O--C(.dbd.O)--(CH.sub.2).sub.v--CH.sub.3, --NH--Z,
--N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
--NH--C(.dbd.O)CH.dbd.CH.sub.2, --CH.sub.2CH.sub.2--O--Z,
--CH.sub.2CH.sub.2OH, --O--C(.dbd.O)--CH.dbd.CH.sub.2, or
--N(CH.sub.2--CH.sub.2--NH.sub.2).sub.2. In some embodiments,
R.sub.6 may be --OH, --NH.sub.2, --O--Z, --N(Z).sub.2,
--N(CH.sub.2--O--Z).sub.2, --N(CH.sub.2OH).sub.2,
--N(CH.sub.2CH.sub.2--O--Z).sub.2, --N(CH.sub.2NH.sub.2).sub.2,
--N(CH.sub.2CH.sub.2OH).sub.2, --CH.sub.2--O--Z, --CH.sub.2--OH,
--CH.sub.2--NH.sub.2, --N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3,
--CH.sub.2--Y, --NCO, --O--C(.dbd.O)--(CH.sub.2).sub.v--CH.sub.3,
--NH--Z, or --N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2.
[0052] In some embodiments, each R.sub.7 may be --OH, --NH.sub.2,
--O--Z, --N(Z).sub.2, --N(CH.sub.2--O--Z).sub.2,
--N(CH.sub.2OH).sub.2, --N(CH.sub.2CH.sub.2--O--Z).sub.2,
--N(CH.sub.2NH.sub.2).sub.2, --N(CH.sub.2CH.sub.2OH).sub.2,
--CH.sub.2--O--Z, --CH.sub.2--OH, --CH.sub.2--NH.sub.2,
--N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3, --CH.sub.2--Y, --NCO,
--O--C(.dbd.O)--(CH.sub.2).sub.w--CH.sub.3, --NH--Z,
--N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2--NH--C(.dbd.O)C-
H.dbd.CH.sub.2, --CH.sub.2CH.sub.2--O--Z, --CH.sub.2CH.sub.2OH,
--O--C(.dbd.O)--CH.dbd.CH.sub.2,
--N(CH.sub.2--CH.sub.2--NH.sub.2).sub.2,
--(CH.sub.2--CH.sub.2--O).sub.wH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.wH,
--N[CH.sub.2--CH.sub.2--O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2, or
--N[CH.sub.2--CH.sub.2--NH--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
where each w is, independently, an integer from 1 to 18. In some
embodiments, each R.sub.7 may be --OH, --NH.sub.2, --O--Z,
--N(Z).sub.2, --N(CH.sub.2--O--Z).sub.2, --N(CH.sub.2OH).sub.2,
--N(CH.sub.2CH.sub.2--O--Z).sub.2, --N(CH.sub.2NH.sub.2).sub.2,
--N(CH.sub.2CH.sub.2OH).sub.2, --CH.sub.2--O--Z, --CH.sub.2--OH,
--CH.sub.2--NH.sub.2, --N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3,
--CH.sub.2--Y, --NCO, --O--C(.dbd.O)--(CH.sub.2).sub.w--CH.sub.3,
--NH--Z, --N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
--NH--C(.dbd.O)CH.dbd.CH.sub.2, --CH.sub.2CH.sub.2--O--Z,
--CH.sub.2CH.sub.2OH, --O--C(.dbd.O)--CH.dbd.CH.sub.2, or
--N(CH.sub.2--CH.sub.2--NH.sub.2).sub.2. In some embodiments, each
R.sub.7 may be --OH, --NH.sub.2, --O--Z, --N(Z).sub.2,
--N(CH.sub.2--O--Z).sub.2, --N(CH.sub.2OH).sub.2,
--N(CH.sub.2CH.sub.2--O--Z).sub.2, --N(CH.sub.2NH.sub.2).sub.2,
--N(CH.sub.2CH.sub.2OH).sub.2, --CH.sub.2--O--Z, --CH.sub.2--OH,
--CH.sub.2--NH.sub.2, --N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3,
--CH.sub.2--Y, --NCO, --O--C(.dbd.O)--(CH.sub.2).sub.w--CH.sub.3,
--NH--Z, --N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2, or
--NH--C(.dbd.O)CH.dbd.CH.sub.2.
[0053] In some embodiments, R.sub.8 may be --OH, --NH.sub.2,
--O--Z, --N(Z).sub.2, --N(CH.sub.2--O--Z).sub.2,
--N(CH.sub.2OH).sub.2, --N(CH.sub.2CH.sub.2--O--Z).sub.2,
--N(CH.sub.2NH.sub.2).sub.2, --N(CH.sub.2CH.sub.2OH).sub.2,
--CH.sub.2--O--Z, --CH.sub.2--OH, --CH.sub.2--NH.sub.2,
--N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3, --CH.sub.2--Y, --NCO,
--O--C(.dbd.O)--(CH.sub.2).sub.x--CH.sub.3, --NH--Z,
--N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2--NH--C(.dbd.O)C-
H.dbd.CH.sub.2, --CH.sub.2CH.sub.2--O--Z, --CH.sub.2CH.sub.2OH,
--O--C(.dbd.O)--CH.dbd.CH.sub.2,
--N(CH.sub.2--CH.sub.2--NH.sub.2).sub.2,
--(CH.sub.2--CH.sub.2--O).sub.xH,
--(CH.sub.2--CH.sub.2--CH.sub.2--O).sub.xH,
--N[CH.sub.2--CH.sub.2--O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2, or
--N[CH.sub.2--CH.sub.2--NH--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2,
where each x is, independently, an integer from 1 to 18. In some
embodiments, R.sub.8 may be --OH, --NH.sub.2, --O--Z, --N(Z).sub.2,
--N(CH.sub.2--O--Z).sub.2, --N(CH.sub.2OH).sub.2,
--N(CH.sub.2CH.sub.2--O--Z).sub.2, --N(CH.sub.2NH.sub.2).sub.2,
--N(CH.sub.2CH.sub.2OH).sub.2, --CH.sub.2--O--Z, --CH.sub.2--OH,
--CH.sub.2--NH.sub.2, --N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3,
--CH.sub.2--Y, --NCO, --O--C(.dbd.O)--(CH.sub.2).sub.x--CH.sub.3,
--NH--Z,
--N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2--NH--C(.dbd.O)C-
H.dbd.CH.sub.2, --CH.sub.2CH.sub.2--O--Z, --CH.sub.2CH.sub.2OH,
--O--C(.dbd.O)--CH.dbd.CH.sub.2, or
--N(CH.sub.2--CH.sub.2--NH.sub.2).sub.2. In some embodiments,
R.sub.8 may be --OH, --NH.sub.2, --O--Z, --N(Z).sub.2,
--N(CH.sub.2--O--Z).sub.2, --N(CH.sub.2OH).sub.2,
--N(CH.sub.2CH.sub.2--O--Z).sub.2, --N(CH.sub.2NH.sub.2).sub.2,
--N(CH.sub.2CH.sub.2OH).sub.2, --CH.sub.2--O--Z, --CH.sub.2--OH,
--CH.sub.2--NH.sub.2, --N(CH.sub.3).sub.2, --O-(alkylene)-CH.sub.3,
--CH.sub.2--Y, --NCO, --O--C(.dbd.O)--(CH.sub.2).sub.x--CH.sub.3,
--NH--Z, --N[CH.sub.2O--C(.dbd.O)--CH.dbd.CH.sub.2].sub.2, or
--NH--C(.dbd.O)CH.dbd.CH.sub.2.
[0054] In some embodiments, Z is
##STR00005##
In some embodiments, Y is Cl, Br, F, or I.
[0055] In some embodiments, compounds of formula I may have the
following substitutions at each of, independently, R.sub.1,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.8
as shown in Table 1.
TABLE-US-00001 TABLE 1 R.sub.1 R.sub.2 R.sub.3 R.sub.4 R.sub.5 H,
H, H, --OH, --OH, Z, Z, Z, --NH.sub.2, --NH.sub.2, --C(.dbd.O)--
--C(.dbd.O)-- --C(.dbd.O)-- --O--Z, --O--Z, CH.dbd.CH.sub.2,
CH.dbd.CH.sub.2, CH.dbd.CH.sub.2, --N(Z).sub.2, --N(Z).sub.2,
--(CH.sub.2--CH.sub.2-- --(CH.sub.2-- --(CH.sub.2--CH.sub.2--
--N(CH.sub.2--O-- --N(CH.sub.2--O-- O).sub.nH, CH.sub.2--O).sub.pH,
O).sub.qH, Z).sub.2, Z).sub.2, --(CH.sub.2--CH.sub.2--
--(CH.sub.2--CH.sub.2-- --(CH.sub.2--CH.sub.2-- --N(CH.sub.2
--N(CH.sub.2 CH.sub.2--O).sub.nH, CH.sub.2--O).sub.pH,
CH.sub.2--O).sub.qH, OH).sub.2, OH).sub.2, or or or --N(CH.sub.2
--N(CH.sub.2 --(CH.sub.2--CH.sub.2-- --(CH.sub.2--CH.sub.2--
--(CH.sub.2--CH.sub.2-- CH.sub.2--O--Z).sub.2,
CH.sub.2--O--Z).sub.2, O).sub.n--(CH.sub.2-- O).sub.p--(CH.sub.2--
O).sub.q--(CH.sub.2-- --N(CH.sub.2 --N(CH.sub.2 CH(CH.sub.3)--
CH(CH.sub.3)-- CH(CH.sub.3)-- NH.sub.2).sub.2, NH.sub.2).sub.2,
O).sub.nH, O).sub.pH, O).sub.qH, --N(CH.sub.2 --N(CH.sub.2 where
each where each where each CH.sub.2OH).sub.2, CH.sub.2OH).sub.2, n
is, p is, q is, --CH.sub.2--O--Z, --CH.sub.2--O--Z, independently,
independently, independently, --CH.sub.2--OH, --CH.sub.2--OH, an an
an --CH.sub.2--NH.sub.2, --CH.sub.2--NH.sub.2, integer from integer
integer --N(CH.sub.3).sub.2, --N(CH.sub.3).sub.2, 1 to 18. from 1
to from 1 to --O-- --O-- 18. 18. (alkylene) - (alkylene) -
CH.sub.3, CH.sub.3, --CH.sub.2--Y, --CH.sub.2--Y, --NCO, --NCO,
--O--C(.dbd.O)-- --O--C(.dbd.O)-- (CH.sub.2).sub.r--CH.sub.3,
(CH.sub.2).sub.t--CH.sub.3, --NH--Z, --NH--Z, --N[CH.sub.2O--
--N[CH.sub.2O-- C(.dbd.O)-- C(.dbd.O)-- CH.dbd.CH.sub.2].sub.2,
CH.dbd.CH.sub.2].sub.2, --NH-- --NH-- C(.dbd.O)CH.dbd.
C(.dbd.O)CH.dbd. CH.sub.2, CH.sub.2, --CH.sub.2CH.sub.2--
--CH.sub.2CH.sub.2-- O--Z, O--Z, --CH.sub.2CH.sub.2
--CH.sub.2CH.sub.2 OH, OH, --O--C(.dbd.O)-- --O--C(.dbd.O)--
CH.dbd.CH.sub.2, CH.dbd.CH.sub.2, --N(CH.sub.2-- --N(CH.sub.2--
CH.sub.2--NH.sub.2).sub.2, CH.sub.2--NH.sub.2).sub.2,
--(CH.sub.2--CH.sub.2-- --(CH.sub.2--CH.sub.2-- O).sub.rH,
O).sub.tH, --(CH.sub.2-- --(CH.sub.2-- CH.sub.2--CH.sub.2--
CH.sub.2--CH.sub.2-- O).sub.rH, O).sub.tH, --N[CH.sub.2--
--N[CH.sub.2-- CH.sub.2--O-- CH.sub.2--O-- C(.dbd.O)-- C(.dbd.O)--
CH.dbd.CH.sub.2].sub.2, CH.dbd.CH.sub.2].sub.2, or or
--N[CH.sub.2-- --N[CH.sub.2-- CH.sub.2--NH-- CH.sub.2--NH--
C(.dbd.O)-- C(.dbd.O)-- CH.dbd.CH.sub.2].sub.2,
CH.dbd.CH.sub.2].sub.2, where each where each r is, t is,
independently, independently, an an integer integer from 1 to from
1 to 18. 18.. Z, Z, Z, --NH.sub.2, --NH.sub.2, --C(.dbd.O)--
--C(.dbd.O)-- --C(.dbd.O)-- --N(CH.sub.3).sub.2,
--N(CH.sub.3).sub.2, CH.dbd.CH.sub.2, CH.dbd.CH.sub.2,
CH.dbd.CH.sub.2, --O--C(.dbd.O)-- --O--C(.dbd.O)-- or or or
CH.dbd.CH.sub.2, CH.dbd.CH.sub.2, --(CH.sub.2--CH.sub.2--
--(CH.sub.2--CH.sub.2-- --(CH.sub.2--CH.sub.2-- --NCO, --NCO,
O).sub.nH. O).sub.pH. O).sub.qH. --O--C(.dbd.O)-- --O--C(.dbd.O)--
(CH.sub.2).sub.r--CH.sub.3, (CH.sub.2).sub.t--CH.sub.3, --NH--
--NH-- C(.dbd.O)CH.dbd. C(.dbd.O)CH.dbd. CH.sub.2, CH.sub.2,
--O--Z, --O--Z, --O--(CH.sub.2).sub.7-- --O--(CH.sub.2).sub.7--
CH.sub.3, CH.sub.3, --NH--Z, or --NH--Z, or --N(CH.sub.2--
--N(CH.sub.2-- CH.sub.2--OH).sub.2. CH.sub.2--OH).sub.2. H, H, H,
--OH, --OH, Z, or Z, or Z, or --NH.sub.2, --NH.sub.2, --C(.dbd.O)--
--C(.dbd.O)-- --C(.dbd.O)-- --O--Z, --O--Z, CH.dbd.CH.sub.2.
CH.dbd.CH.sub.2. CH.dbd.CH.sub.2. --N(Z).sub.2, --N(Z).sub.2,
--N(CH.sub.2--O-- --N(CH.sub.2--O-- Z).sub.2, or Z).sub.2, or
--N(CH.sub.2 --N(CH.sub.2 OH).sub.2. OH).sub.2. --C(.dbd.O)--
--C(.dbd.O)-- --C(.dbd.O)-- --N(Z).sub.2, --N(Z).sub.2,
CH.dbd.CH.sub.2, CH.dbd.CH.sub.2, CH.dbd.CH.sub.2, --N(CH.sub.2
--N(CH.sub.2 or or or CH.sub.2--O--Z).sub.2, CH.sub.2--O--Z).sub.2,
--(CH.sub.2--CH.sub.2-- --(CH.sub.2--CH.sub.2--
--(CH.sub.2--CH.sub.2-- --N(CH.sub.2 --N(CH.sub.2 O).sub.nH.
O).sub.pH. O).sub.qH. CH.sub.2--NH.sub.2).sub.2,
CH.sub.2--NH.sub.2).sub.2, or or --O--C(.dbd.O)-- --O--C(.dbd.O)--
CH--CH.sub.2. CH--CH.sub.2. --C(.dbd.O)-- --C(.dbd.O)--
--C(.dbd.O)-- --N(CH.sub.2 --N(CH.sub.2 CH.dbd.CH.sub.2,
CH.dbd.CH.sub.2, CH.dbd.CH.sub.2, CH.sub.2--O--Z).sub.2,
CH.sub.2--O--Z).sub.2, or or or --N(CH.sub.2 --N(CH.sub.2
--(CH.sub.2--CH.sub.2-- --(CH.sub.2--CH.sub.2-- --
(CH.sub.2--CH.sub.2-- NH.sub.2).sub.2, NH.sub.2).sub.2, O).sub.nH.
O).sub.pH. O).sub.qH. --N(CH.sub.2 --N(CH.sub.2 CH.sub.2OH).sub.2,
CH.sub.2OH).sub.2, --CH.sub.2--O--Z, --CH.sub.2--O--Z,
--CH.sub.2--OH, --CH.sub.2--OH, --CH.sub.2--NH.sub.2,
--CH.sub.2--NH.sub.2, --N(CH.sub.3).sub.2, --N(CH.sub.3).sub.2,
--O-- --O-- (alkylene) - (alkylene) - CH.sub.3, or CH.sub.3, or
--CH.sub.2--Y. --CH.sub.2--Y. --(CH.sub.2--CH.sub.2--
--(CH.sub.2--CH.sub.2-- --(CH.sub.2--CH.sub.2-- --NCO, --NCO,
O).sub.n--(CH.sub.2-- O).sub.n--(CH.sub.2-- O).sub.n--(CH.sub.2--
--O--C(.dbd.O)-- --O--C(.dbd.O)-- CH(CH.sub.3)-- CH(CH.sub.3)--
CH(CH.sub.3)-- (CH.sub.2).sub.r--CH.sub.3,
(CH.sub.2).sub.t--CH.sub.3, O).sub.nH O).sub.pH O).sub.qH --NH--Z,
--NH--Z, --N[CH.sub.2O-- --N[CH.sub.2O-- C(.dbd.O)-- C(.dbd.O)--
CH.dbd.CH.sub.2].sub.2, CH.dbd.CH.sub.2].sub.2, --NH-- --NH--
C(.dbd.O)CH.dbd. C(.dbd.O)CH.dbd. CH.sub.2, CH.sub.2,
--CH.sub.2CH.sub.2-- --CH.sub.2CH.sub.2-- O--Z, O--Z, or or
--CH.sub.2CH.sub.2 --CH.sub.2CH.sub.2 OH. OH. C(.dbd.O)--
--C(.dbd.O)-- --C(.dbd.O)-- --N(Z).sub.2, --N(Z).sub.2,
CH.dbd.CH.sub.2 CH.dbd.CH.sub.2 CH.dbd.CH.sub.2 --N(CH.sub.2--O--
--N(CH.sub.2--O-- or or or Z).sub.2, Z).sub.2,
--(CH.sub.2--CH.sub.2-- --(CH.sub.2-- --(CH.sub.2-- --N(CH.sub.2--
--N(CH.sub.2-- O).sub.nH. CH.sub.2--O).sub.pH. CH.sub.2--O).sub.qH.
CH.sub.2--NH.sub.2).sub.2 CH.sub.2--NH.sub.2).sub.2 or or
--O--C(.dbd.O)-- --O--C(.dbd.O)-- CH.dbd.CH.sub.2. CH.dbd.CH.sub.2.
H H H --O--C(.dbd.O)-- --O--C(.dbd.O)-- CH.dbd.CH.sub.2
CH.dbd.CH.sub.2 H H H --N(CH.sub.3).sub.2 --N(CH.sub.3).sub.2 Z Z Z
--O--Z --O--Z H H H --NH.sub.2 --NH.sub.2 H H H --NCO --NCO H H H
--O--C(.dbd.O)-- --O--C(.dbd.O)-- (CH.sub.2).sub.6--CH.sub.3
(CH.sub.2).sub.6--CH.sub.3 H H H --NH-- --NH-- C(.dbd.O)CH.dbd.
C(.dbd.O)CH.dbd. CH.sub.2 CH.sub.2 H H H --O--(CH.sub.2).sub.7--
--O--(CH.sub.2).sub.7-- CH.sub.3 CH.sub.3 Z Z Z --NH--Z --NH--Z
--(CH.sub.2--CH.sub.2-- --(CH.sub.2--CH.sub.2--
--(CH.sub.2--CH.sub.2-- --N(CH.sub.2 --N(CH.sub.2
O).sub.n--(CH.sub.2-- O).sub.p--(CH.sub.2-- O).sub.q--(CH.sub.2--
CH.sub.2OH).sub.2 CH.sub.2OH).sub.2 CH(CH.sub.3)-- CH(CH.sub.3)--
CH(CH.sub.3)-- O).sub.nH O).sub.pH O).sub.q H Z Z Z --NCO --NCO
R.sub.6 R.sub.7 R.sub.8 --OH, --OH, --OH, --NH.sub.2, --NH.sub.2,
--NH.sub.2, --O--Z, --O--Z, --O--Z, --N(Z).sub.2, --N(Z).sub.2,
--N(Z).sub.2, --N(CH.sub.2--O-- --N(CH.sub.2--O-- --N(CH.sub.2--O--
Z).sub.2, Z).sub.2, Z).sub.2, --N(CH.sub.2 --N(CH.sub.2
--N(CH.sub.2 OH).sub.2, OH).sub.2, OH).sub.2, --N(CH.sub.2
--N(CH.sub.2 --N(CH.sub.2 CH.sub.2--O--Z).sub.2,
CH.sub.2--O--Z).sub.2, CH.sub.2--O--Z).sub.2, --N(CH.sub.2
--N(CH.sub.2 --N(CH.sub.2 NH.sub.2).sub.2, NH.sub.2).sub.2,
NH.sub.2).sub.2, --N(CH.sub.2 --N(CH.sub.2 --N(CH.sub.2
CH.sub.2OH).sub.2, CH.sub.2OH).sub.2, CH.sub.2OH).sub.2,
--CH.sub.2--O--Z, --CH.sub.2--O--Z, --CH.sub.2--O--Z,
--CH.sub.2--OH, --CH.sub.2--OH, --CH.sub.2--OH,
--CH.sub.2--NH.sub.2, --CH.sub.2--NH.sub.2, --CH.sub.2--NH.sub.2,
--N(CH.sub.3).sub.2, --N(CH.sub.3).sub.2, --N(CH.sub.3).sub.2,
--O-- --O-- --O-- (alkylene) - (alkylene) - (alkylene) - CH.sub.3,
CH.sub.3, CH.sub.3, --CH.sub.2--Y, --CH.sub.2--Y, --CH.sub.2--Y,
--NCO, --NCO, --NCO, --O--C(.dbd.O)-- --O--C(.dbd.O)--
--O--C(.dbd.O)-- (CH.sub.2).sub.v-- (CH.sub.2).sub.w--
(CH.sub.2).sub.x--CH.sub.3, CH.sub.3, CH.sub.3, --NH--Z, --NH--Z,
--NH--Z, --N[CH.sub.2O-- --N[CH.sub.2O-- --N[CH.sub.2O--
C(.dbd.O)-- C(.dbd.O)-- C(.dbd.O)-- CH.dbd.CH.sub.2].sub.2,
CH.dbd.CH.sub.2].sub.2, CH.dbd.CH.sub.2].sub.2, --NH-- --NH--
--NH-- C(.dbd.O)CH.dbd.C C(.dbd.O)CH.dbd. C(.dbd.O)CH.dbd. H.sub.2,
CH.sub.2, CH.sub.2, --CH.sub.2CH.sub.2-- --CH.sub.2CH.sub.2--
--CH.sub.2CH.sub.2-- O--Z, O--Z, O--Z, --CH.sub.2CH.sub.2
--CH.sub.2CH.sub.2 --CH.sub.2CH.sub.2 OH, OH, OH, --O--C(.dbd.O)--
--O--C(.dbd.O)-- --O--C(.dbd.O)-- CH.dbd.CH.sub.2, CH.dbd.CH.sub.2,
CH.dbd.CH.sub.2, --N(CH.sub.2-- --N(CH.sub.2-- --N(CH.sub.2--
CH.sub.2--NH.sub.2).sub.2, CH.sub.2--NH.sub.2).sub.2,
CH.sub.2--NH.sub.2).sub.2, --(CH.sub.2--CH.sub.2--
--(CH.sub.2--CH.sub.2-- --(CH.sub.2--CH.sub.2-- O).sub.xH,
O).sub.vH, O).sub.wH, --(CH.sub.2--CH.sub.2-- --(CH.sub.2--
--(CH.sub.2-- CH.sub.2-- O).sub.xH, CH.sub.2--CH.sub.2--
CH.sub.2--CH.sub.2-- --N[CH.sub.2-- O).sub.vH, O).sub.wH,
CH.sub.2--O-- --N[CH.sub.2-- --N[CH.sub.2-- C(.dbd.O)--
CH.sub.2--O-- CH.sub.2--O-- CH.dbd.CH.sub.2].sub.2, C(.dbd.O)--
C(.dbd.O)-- or CH.dbd.CH.sub.2].sub.2, CH.dbd.CH.sub.2].sub.2,
--N[CH.sub.2-- or or CH.sub.2--NH-- --N[CH.sub.2-- --N[CH.sub.2--
C(.dbd.O)-- CH.sub.2--NH-- CH.sub.2--NH-- CH.dbd.CH.sub.2].sub.2,
C(.dbd.O)-- C(.dbd.O)-- where each x CH.dbd.CH.sub.2].sub.2,
CH.dbd.CH.sub.2].sub.2, is, where each where each independently, v
is, w is, an integer independently, independently, from 1 to an an
18.. integer integer from 1 to from 1 to 18. 18.. --NH.sub.2,
--NH.sub.2, --NH.sub.2, --N(CH.sub.3).sub.2, --N(CH.sub.3).sub.2,
--N(CH.sub.3).sub.2, --O--C(.dbd.O)-- --O--C(.dbd.O)--
--O--C(.dbd.O)-- CH.dbd.CH.sub.2, CH.dbd.CH.sub.2, CH.dbd.CH.sub.2,
--NCO, --NCO, --NCO, --O--C(.dbd.O)-- --O--C(.dbd.O)--
--O--C(.dbd.O)--
(CH.sub.2).sub.v--CH.sub.3, (CH.sub.2).sub.w--CH.sub.3,
(CH.sub.2).sub.x--CH.sub.3, --NH-- --NH-- --NH-- C(.dbd.O)CH.dbd.
C(.dbd.O)CH.dbd. C(.dbd.O)CH.dbd.C CH.sub.2, CH.sub.2, H.sub.2,
--O--Z, --O--Z, --O--Z, --O--(CH.sub.2).sub.7--
--O--(CH.sub.2).sub.7-- --O--(CH.sub.2).sub.7-- CH.sub.3, CH.sub.3,
CH.sub.3, --NH--Z, or --NH--Z, or --NH--Z, or --N(CH.sub.2--
--N(CH.sub.2-- --N(CH.sub.2-- CH.sub.2--OH).sub.2.
CH.sub.2--OH).sub.2. CH.sub.2--OH).sub.2. --OH, --OH, --OH,
--NH.sub.2, --NH.sub.2, --NH.sub.2, --O--Z, --O--Z, --O--Z,
--N(Z).sub.2, --N(Z).sub.2, --N(Z).sub.2, --N(CH.sub.2--O--
--N(CH.sub.2--O-- --N(CH.sub.2--O-- Z).sub.2, or Z).sub.2, or
Z).sub.2, or --N(CH.sub.2 --N(CH.sub.2 --N(CH.sub.2 OH).sub.2.
OH).sub.2. OH).sub.2. --N(Z).sub.2, --N(Z).sub.2, --N(Z).sub.2,
--N(CH.sub.2 --N(CH.sub.2 --N(CH.sub.2 CH.sub.2--O--Z).sub.2,
CH.sub.2--O--Z).sub.2, CH.sub.2--O--Z).sub.2, --N(CH.sub.2
--N(CH.sub.2 --N(CH.sub.2 CH.sub.2--NH.sub.2).sub.2,
CH.sub.2--NH.sub.2).sub.2, CH.sub.2--NH.sub.2).sub.2, or or or
--O--C(.dbd.O)-- --O--C(.dbd.O)-- --O--C(.dbd.O)-- CH--CH.sub.2.
CH--CH.sub.2. CH--CH.sub.2. --N(CH.sub.2 --N(CH.sub.2 --N(CH.sub.2
CH.sub.2--O--Z).sub.2, CH.sub.2--O--Z).sub.2,
CH.sub.2--O--Z).sub.2, --N(CH.sub.2 --N(CH.sub.2 --N(CH.sub.2
NH.sub.2).sub.2, NH.sub.2).sub.2, NH.sub.2).sub.2, --N(CH.sub.2
--N(CH.sub.2 --N(CH.sub.2 CH.sub.2OH).sub.2, CH.sub.2OH).sub.2,
CH.sub.2OH).sub.2, --CH.sub.2--O--Z, --CH.sub.2--O--Z,
--CH.sub.2--O--Z, --CH.sub.2--OH, --CH.sub.2--OH, --CH.sub.2--OH,
--CH.sub.2--NH.sub.2, --CH.sub.2--NH.sub.2, --CH.sub.2--NH.sub.2,
--N(CH.sub.3).sub.2, --N(CH.sub.3).sub.2, --N(CH.sub.3).sub.2,
--O-- --O-- --O-- (alkylene) - (alkylene) - (alkylene) - CH.sub.3,
or CH.sub.3, or CH.sub.3, or --CH.sub.2--Y. --CH.sub.2--Y.
--CH.sub.2--Y. --NCO, --NCO, --NCO, --O--C(.dbd.O)--
--O--C(.dbd.O)-- --O--C(.dbd.O)-- (CH.sub.2).sub.v--
(CH.sub.2).sub.w-- (CH.sub.2).sub.x--CH.sub.3, CH.sub.3, CH.sub.3,
--NH--Z, --NH--Z, --NH--Z, --N[CH.sub.2O-- --N[CH.sub.2O--
--N[CH.sub.2O-- C(.dbd.O)-- C(.dbd.O)-- C(.dbd.O)--
CH.dbd.CH.sub.2].sub.2, CH.dbd.CH.sub.2].sub.2,
CH.dbd.CH.sub.2].sub.2, --NH-- --NH-- --NH-- C(.dbd.O)CH.dbd.C
C(.dbd.O)CH.dbd. C(.dbd.O)CH.dbd. H.sub.2, CH.sub.2, CH.sub.2,
--CH.sub.2CH.sub.2-- --CH.sub.2CH.sub.2-- --CH.sub.2CH.sub.2--
O--Z, O--Z, O--Z, or or or --CH.sub.2CH.sub.2 --CH.sub.2CH.sub.2
--CH.sub.2CH.sub.2 OH. OH. OH. --N(Z).sub.2, --N(Z).sub.2,
--N(Z).sub.2, --N(CH.sub.2--O-- --N(CH.sub.2--O-- --N(CH.sub.2--O--
Z).sub.2, Z).sub.2, Z).sub.2, --N(CH.sub.2-- --N(CH.sub.2--
--N(CH.sub.2-- CH.sub.2--NH.sub.2).sub.2 CH.sub.2--NH.sub.2).sub.2
CH.sub.2--NH.sub.2).sub.2 or or or --O--C(.dbd.O)--
--O--C(.dbd.O)-- --O--C(.dbd.O)-- CH.dbd.CH.sub.2. CH.dbd.CH.sub.2.
CH.dbd.CH.sub.2. --O--C(.dbd.O)-- --O--C(.dbd.O)-- --O--C(.dbd.O)--
CH.dbd.CH.sub.2 CH.dbd.CH.sub.2 CH.dbd.CH.sub.2 --N(CH.sub.3).sub.2
--N(CH.sub.3).sub.2 --N(CH.sub.3).sub.2 --O--Z --O--Z --O--Z
--NH.sub.2 --NH.sub.2 --NH.sub.2 --NCO --NCO --NCO --O--C(.dbd.O)--
--O--C(.dbd.O)-- --O--C(.dbd.O)-- (CH.sub.2).sub.6--CH.sub.3
(CH.sub.2).sub.6--CH.sub.3 (CH.sub.2).sub.6--CH.sub.3 --NH-- --NH--
--NH-- C(.dbd.O)CH.dbd. C(.dbd.O)CH.dbd. C(.dbd.O)CH.dbd.C CH.sub.2
CH.sub.2 H.sub.2 --O--(CH.sub.2).sub.7-- --O--(CH.sub.2).sub.7--
--O--(CH.sub.2).sub.7-- CH.sub.3 CH.sub.3 CH.sub.3 --NH--Z --NH--Z
--NH--Z --N(CH.sub.2 --N(CH.sub.2 --N(CH.sub.2 CH.sub.2OH).sub.2
CH.sub.2OH).sub.2 CH.sub.2OH).sub.2 --NCO --NCO --NCO
[0056] Non-limiting examples of phenolic compounds represented by
formula I include, but are not limited to, the following
compounds:
##STR00006## ##STR00007##
[0057] In some embodiments, methods for preparing compounds
described herein may comprise: contacting a novolac compound with a
formaldehyde or paraformaldehyde to form a hydroxymethyl compound;
and contacting the hydroxymethyl compound with an epihalohydrin, an
acrylic compound, an alkanoyl halide, an alkyl halide, ammonia,
phosgene, or dialkylamine to form the compound. One example of such
a reaction mechanism, outlined in FIG. 1, shows that novolac
compound is reacted with formaldehyde to obtain compound 1.
Compound 1 may be reacted with ammonia, diethylamine, acrylic
anhydride, phosgene, isooctanoyl chloride, epichlorohydrin, or
isooctyl chloride to obtain compounds 2, 3, 4, 5, 6, 8, and 9,
respectively. Compound 2 may be reacted with any one of acrylic
anhydride or epichlorohydrin to obtain compounds 7 and 10,
respectively.
[0058] In some embodiments, contacting the phenolic compound with
the formaldehyde or paraformaldehyde is performed in the presence
of a basic catalyst. Examples of basic catalysts include, but are
not limited to, alkali metal hydroxides, such as KOH, LiOH, NaOH,
and the like. The phenolic compound and the formaldehyde or
paraformaldehyde may be reacted in a molar ratio from about 1:3 to
about 1:10, about 1:3 to about 1:8, about 1:3 to about 1:5, or
about 1:3 to about 1:4. Examples also include about 1:10, about
1:8, about 1:6, about 1:4, about 1:3, and ranges between any two of
these values (including their endpoints). During the reaction of
the phenolic compound and the formaldehyde or paraformaldehyde, the
pH of the solution may be maintained between about pH 8 to about pH
11, about pH 8 to about pH 10, about pH 8 to about pH 9, or about
pH 8 to about pH 8.5. Examples also include about pH 8, about pH
8.5, about pH 9, about pH 10, about pH 11, and ranges between any
two of these values (including their endpoints).
[0059] During the reaction of the phenolic compound and the
formaldehyde or paraformaldehyde, the reaction mixture may be
heated to an elevated temperature, such as a temperature of about
50.degree. C. to about 70.degree. C., about 50.degree. C. to about
65.degree. C., or about 50.degree. C. to about 60.degree. C.
Examples also include temperatures of about 50.degree. C., about
55.degree. C., about 60.degree. C., about 65.degree. C., about
70.degree. C., and ranges between (and including the endpoints of)
any two of these values. The heating may be performed for a variety
of times, such as about 2 hours to about 6 hours, for about 2 hours
to about 5 hours, for about 2 hours to about 4 hours, or for about
2 hours to about 3 hours. Examples also include about 2 hours,
about 3 hours, about 4 hours, about 5 hours, about 6 hours, and
ranges between (an including the endpoints of) any two of these
values. The reaction time may vary with the reaction temperature
inversely. For example, if the reaction temperature is higher, the
reaction time period may be shorter.
[0060] In some embodiments, novolac compounds with epoxy groups may
be prepared by reacting a hydroxymethyl compound with an
epihalohydrin compound in a molar ratio from about 1:3 to about
1:10, about 1:3 to about 1:7, about 1:3 to about 1:6, or about 1:3
to about 1:4. Examples also include about 1:3, about 1:4, about
1:6, about 1:8, about 1:10, and ranges between any two of these
values (including their endpoints). The molar ratio of
epihalohydrin to the hydroxymethyl compound may also depend on the
number of hydroxyl groups present on the hydroxymethyl compound,
and taking into consideration that one epichlorohyrdin molecule may
react with one hydroxyl group. In some embodiments, the
epihalohydrin molecule may be used in molar excess of the hydroxyl
groups. Examples of the epihalohydrin compound that may be used in
the reaction include, but are not limited to, epichlorohydrin,
epibromohydrin and methylepichlorohydrin. In some embodiments, the
hydroxymethyl compound and the epihalohydrin compound may be heated
to an elevated temperature, such as a temperature of about
50.degree. C. to about 90.degree. C., about 50.degree. C. to about
75.degree. C., about 50.degree. C. to about 70.degree. C., or about
50.degree. C. to about 60.degree. C. Examples also include about
50.degree. C., about 65.degree. C., about 70.degree. C., about
80.degree. C., about 85.degree. C., about 90.degree. C., and ranges
between (and including the endpoints of) any two of these values.
The heating may be performed for a variety of times, such as about
2 hours to about 6 hours, for about 2 hours to about 5 hours, for
about 2 hours to about 4 hours, or for about 2 hours to about 3
hours. Examples also include about 2 hours, about 3 hours, about 4
hours, about 5 hours, about 6 hours, and ranges between (an
including the endpoints of) any two of these values. In some
embodiments, the reaction may involve a two-step heating process:
heating the reaction mixture to a first lower temperature, and
heating the reaction mixture to a second higher temperature to
obtain a high degree of condensation of epihalohydrin and
hydroxymethyl compound.
[0061] The reactions between the hydroxymethyl compound and the
epihalohydrin compound may be performed in the presence of a
reaction catalyst. Suitable reaction catalysts include, but are not
limited to, MgClO.sub.4, LiCl, LiOH, SnF.sub.2, LiClO.sub.4, or a
combination thereof. In addition, the reaction rate may be
increased by adding an organic solvent and performing the reaction
in an emulsion system. Examples of organic solvents include, but
are not limited to, 1-butanol, secondary butanols, glycol ethers
such as 2-methoxyethanol, 2-ethoxyethanol, and 2-phenoxyethanol,
ethers such as 1,4-dioxane, 1,3-dioxane and diethoxyethane, and
aprotic polar solvents such as acetonitrile, dimethyl sulfoxide,
and dimethyl formamide. These organic solvents may be used alone or
in combination so as to adjust polarity.
[0062] For the purpose of, for example, improving the reaction
rate, the reaction may be conducted in the presence of a phase
transfer catalyst, such as, for example, quaternary ammonium salts.
Examples include, but are not limited to, benzyltrimethylammonium
bromide, cetyltrimethylammonium bromide, tetrabutylammonium
hydroxide, tetrabutyl ammonium chloride, and any combination
thereof.
[0063] The reaction product obtained from the above methods
described herein may be washed with, for example, water. Using the
resulting product of the reaction between the hydroxymethyl
compound and the epihalohydrin compound as an example, the
unreacted epihalohydrin compound and the organic solvent may be
distilled off by distillation with heating under reduced pressure.
To obtain a compound containing a small amount of a hydrolysable
halogen, the dehydrochlorination step may be performed under
optimum conditions so that all the chlorohydrin derivatives are
converted to epoxides. To remove the salt content, the resulting
product may be dissolved in an organic solvent, such as toluene,
methyl isobutyl ketone or methyl ethyl ketone, and the salt can be
removed by filtration or by washing with water. The organic solvent
may be distilled off by heating under reduced pressure to obtain a
high-purity epoxy resin. An example compound prepared by this
method is compound 7.
[0064] In some embodiments, novolac compounds with amino groups may
be prepared by contacting the hydroxymethyl compound with ammonia
in a molar ratio from about 1:3 to about 1:10, about 1:3 to about
1:8, about 1:3 to about 1:6, or about 1:3 to about 1:4. Examples
also include about 1:3, about 1:5, about 1:7, about 1:8, about
1:10, and ranges between any two of these values (including their
endpoints). The hydroxymethyl compound and the ammonia may be
heated to an elevated temperature, such as a temperature of about
50.degree. C. to about 70.degree. C., about 50.degree. C. to about
65.degree. C., about 50.degree. C. to about 60.degree. C., or about
50.degree. C. to about 55.degree. C. Examples also include about
50.degree. C., about 55.degree. C., about 65.degree. C., about
70.degree. C., and ranges between (and including the endpoints of)
any two of these values. In some embodiments, the hydroxymethyl
compound and the ammonia may be heated under an elevated pressure,
such as a pressure of about 1 atmosphere to about 1.5 atmospheres,
about 1 atmosphere to about 1.35 atmospheres, or about 1 atmosphere
to about 1.15 atmospheres. Examples also include about 1
atmosphere, about 1.15 atmospheres, about 1.25 atmospheres, about
1.35 atmospheres, about 1.5 atmospheres, and ranges between (and
including the endpoints of) any two of these values. One example of
such a compound prepared by this method is compound 2. In some
embodiments, a novolac compound with primary amine, secondary
amine, quaternary ammonium salts, or polyamine groups may be
prepared by the methods described herein.
[0065] In some embodiments, novolac compounds with acrylate
functional groups may be prepared by contacting a hydroxymethyl
compound with an acrylic compound in a molar ratio from about 1:3
to about 1:10, from about 1:3 about 1:7, from about 1:3 to about
1:6, or from about 1:3 to about 1:5. Examples also include, but are
not limited to, about 1:3, about 1:5, about 1:7, about 1:9, about
1:10, and ranges between any two of these values (including their
endpoints). The acrylic compound may be acrylic anhydride, acryloyl
chloride, acrylic acid, or any combination thereof. In some
embodiments, the contacting step may be carried out in the presence
or absence of an antioxidant, such as tert-butylhydro-quinone,
substituted quinones, butylated hydroxyl toluene, or any
combination thereof.
[0066] In some embodiments, the reaction of hydroxymethyl compound
and the acrylic compound may be brought to about completion by
heating the reaction mixture to an elevated temperature, such as a
temperature of about 25.degree. C. to about 90.degree. C., of about
25.degree. C. to about 75.degree. C., of about 25.degree. C. to
about 70.degree. C., of about 25.degree. C. to about 60.degree. C.,
or of about 25.degree. C. to about 40.degree. C. Examples also
include, but are not limited to, about 25.degree. C., about
50.degree. C., about 65.degree. C., about 70.degree. C., about
80.degree. C., about 85.degree. C., about 90.degree. C., and ranges
between (and including the endpoints of) any two of these values.
The heating may be performed for a variety of times, such as about
2 hours to about 6 hours, for about 2 hours to about 5 hours, for
about 2 hours to about 4 hours, or for about 2 hours to about 3
hours. Examples also include, but are not limited to, about 2
hours, about 3 hours, about 4 hours, about 5 hours, about 6 hours,
and ranges between (and including the endpoints of) any two of
these values. An example of such a compound prepared by this method
is compound 4. In addition, the phenolic hydroxyl groups of
compound 4 can be acrylated or epoxidized to produce acrylate epoxy
alloys or reacted with ethoxylated ethers to produce hydrophilic
acrylate emulsions for self-cleaning smart hydrophilic paints.
[0067] In some embodiments, novolac compounds with dialkylamino
groups may be prepared by contacting a hydroxymethyl compound with
a dialkylamine in a molar ratio from about 1:3 to about 1:10, about
1:3 to about 1:7, about 1:3 to about 1:6, or about 1:3 to about
1:5. Examples also include about 1:3, about 1:4, about 1:6, about
1:8, about 1:10, and ranges between any two of these values
(including their endpoints). The molar ratio of dialkylamine to the
hydroxymethyl compound may also depend on the number of the
hydroxyl groups present on the hydroxymethyl compound, and taking
into consideration that one dialkylamine molecule may react with
one hydroxyl group. In some embodiments, the dialkylamine molecule
may be used in molar excess of the hydroxyl groups. Non-limiting
examples of dialkyl amine include dimethyl amine, diethyl amine,
dipropyl amine, dibutyl amine, or any combination thereof. In some
embodiments, the hydroxymethyl compound and the dialkylamine may be
heated to a temperature of about 50.degree. C. to about 70.degree.
C., about 50.degree. C. to about 65.degree. C., about 50.degree. C.
to about 60.degree. C., or about 50.degree. C. to about 55.degree.
C. Examples also include about 50.degree. C., about 55.degree. C.,
about 60.degree. C., about 70.degree. C., and ranges between (and
including the endpoints of) any two of these values. The heating
may be performed for about 2 hours to about 6 hours, for about 2
hours to about 5 hours, for about 2 hours to about 4 hours, or for
about 2 hours to about 3 hours. Examples also include about 2
hours, about 3 hours, about 4 hours, about 5 hours, about 6 hours,
and ranges between (an including the endpoints of) any two of these
values.
[0068] The reactions between hydroxymethyl compounds and dialkyl
amine compounds may be performed in the presence of a reaction
catalyst. Suitable reaction catalysts include, but are not limited
to, MgClO.sub.4, LiCl, LiOH, SnF.sub.2, LiClO.sub.4, or a
combination thereof. In addition, the reaction rate may be
increased by adding an organic solvent and performing the reaction
in an emulsion system. Examples of organic solvents include, but
are not limited to, acetone, methyl ethyl ketone, methanol,
tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, diethoxyethane, dimethyl
sulfoxide, dimethyl formamide, and combinations thereof. An
exemplary compound prepared by this method is compound 3.
Dialkylamino novolac compounds (compound 3) may have a wide range
of applications, such as an activator, a hardener for epoxy resins,
a potential catalyst for polyurethane and silicon polymers, a
cation exchange resin, and as a septiciding agent.
[0069] In some embodiments, novolac compounds with alkanoate
functional groups may be prepared by reacting a hydroxymethyl
compound and an alkanoyl halide in a molar ratio from about 1:3 to
about 1:10, about 1:3 to about 1:7, about 1:3 to about 1:6, or
about 1:3 to about 1:5. Examples also include about 1:3, about 1:4,
about 1:6, about 1:8, about 1:10, and ranges between any two of
these values (including their endpoints). Non-limiting examples of
alkanoyl halide include isooctanoyl chloride, decanoyl chloride,
hexanoyl chloride, lauroyl chloride, nonanoyl chloride, palmitoyl
chloride, or any combination thereof. In some embodiments, the
hydroxymethyl compound and the dialkylamine may be heated to a
temperature of about 50.degree. C. to about 90.degree. C., about
50.degree. C. to about 85.degree. C., about 50.degree. C. to about
70.degree. C., or about 50.degree. C. to about 55.degree. C.
Examples also include about 50.degree. C., about 65.degree. C.,
about 70.degree. C., about 80.degree. C., about 90.degree. C., and
ranges between (and including the endpoints of) any two of these
values. The heating may be performed for about 2 hours to about 6
hours, for about 2 hours to about 5 hours, for about 2 hours to
about 4 hours, or for about 2 hours to about 3 hours. Examples also
include about 2 hours, about 3 hours, about 4 hours, about 5 hours,
about 6 hours, and ranges between (and including the endpoints of)
any two of these values. An exemplary compound prepared by this
method is compound 6. Compound 6 may have a wide range of
applications, such as a plasticizer, an anti-oxidant, or a
vibration damping resin.
[0070] In some embodiments, novolac compounds with alkyl ether
groups may be prepared by contacting a hydroxymethyl compound and
an alkyl halide in a molar ratio from about 1:3 to about 1:10,
about 1:3 to about 1:7, about 1:3 to about 1:6, or about 1:3 to
about 1:5. Examples include about 1:3, about 1:4, about 1:6, about
1:8, about 1:10, and ranges between any two of these values
(including their endpoints). Non-limiting examples of alkyl halide
include isooctyl chloride, decyl chloride, hexyl chloride, heptyl
chloride, nonyl chloride, or any combination thereof. In some
embodiments, the hydroxymethyl compound and the dialkylamine may be
heated to a temperature of about 50.degree. C. to about 90.degree.
C., about 50.degree. C. to about 85.degree. C., about 50.degree. C.
to about 70.degree. C., or about 50.degree. C. to about 55.degree.
C. Examples also include about 50.degree. C., about 65.degree. C.,
about 70.degree. C., about 80.degree. C., about 90.degree. C., and
ranges between (and including the endpoints of) any two of these
values. The heating may be performed for about 2 hours to about 6
hours, for about 2 hours to about 5 hours, for about 2 hours to
about 4 hours, or for about 2 hours to about 3 hours. Examples also
include about 2 hours, about 3 hours, about 4 hours, about 5 hours,
about 6 hours, and ranges between (an including the endpoints of)
any two of these values. An exemplary compound prepared by this
method is compound 9. Compound 9 may have a wide range of
applications, such as plasticizers, anti-oxidants, or vibration
damping resins.
[0071] In some embodiments, novolac compounds with isocyanate
functional groups may be prepared by contacting a hydroxymethyl
compound and phosgene in a molar ratio from about 1:3 to about
1:10, about 1:3 to about 1:8, about 1:3 to about 1:6, or about 1:3
to about 1:4. Examples include about 1:3, about 1:5, about 1:7,
about 1:8, about 1:10, and ranges between any two of these values
(including their endpoints). The hydroxymethyl compound and the
phosgene may be heated to a temperature of about 50.degree. C. to
about 70.degree. C., about 50.degree. C. to about 65.degree. C.,
about 50.degree. C. to about 60.degree. C., or about 50.degree. C.
to about 55.degree. C. Examples also include about 50.degree. C.,
about 55.degree. C., about 65.degree. C., about 70.degree. C., and
ranges between (and including the endpoints of) any two of these
values. In some embodiments, the hydroxymethyl compound and the
phosgene may be heated under a pressure of about 1 atmosphere to
about 1.5 atmospheres, about 1 atmosphere to about 1.35
atmospheres, or about 1 atmosphere to about 1.15 atmospheres.
Examples include about 1 atmosphere, about 1.15 atmospheres, about
1.25 atmospheres, about 1.35 atmospheres, about 1.5 atmospheres,
and ranges between (and including the endpoints of) any two of
these values. In some embodiments, CO.sub.2 may be substituted for
phosgene. In some embodiments, the phenolic --OH groups on compound
5 can be pre-reacted to form epoxy glycidyl ether or acrylate as a
new source for polymeric alloys (acrylate-urethane, epoxy-urethane
or epoxy-acrylate urethane) or polyethyleneoxide. An exemplary
compound prepared by this method is compound 5. Compound 5 can also
be used as a blocking agent to protect isocyanate groups in
water-based applications.
[0072] Compounds of the present disclosure may be used as, for
example, thermosets, electrical insulators for high-voltage
generators, curing agents for manufacturing brake pads, hydrogels,
hydrogel surfactants, binding resins for ablative thermal
insulators, ceramics, catalysts, hardeners, surfactants, vibration
damping agents, plasticizers, anti-oxidants, insecticides,
crosslinking agents, or any combinations thereof. These compounds
may enhance the thermal stability, glass transition temperature
and/or the chemical resistance of the resins due to the aromatic
structures and multi-functionality. Examples of such resins in
which the compounds may be incorporated include, but are not
limited to, polyurethanes, silicones, commercial epoxy resins,
urea-formaldehyde resins, melamine-formaldehyde resins,
hydroxymethyl urea-formaldehyde resins, hydroxymethyl
melamine-formaldehyde resins, and the like.
[0073] In addition, compounds of the present disclosure may be
cured to form resins. A variety of curing agents may be used for
this process. Curing agents include acid catalysts, peroxides, or
any commercially available hardeners. In some embodiments,
compounds described herein may themselves be used as curing agents.
For example, compound 2 may be used as a curing agent for epoxy
resin derivatives.
[0074] Resins manufactured from the compounds of the present
disclosure may be blended with, for example, other materials such
as solvents or diluents, fillers, pigments, dyes, flow modifiers,
thickeners, reinforcing agents, mold release agents, wetting
agents, stabilizers, fire retardant agents, surfactants and
combinations thereof. These additives may be added in functionally
equivalent amounts to obtain the desired properties.
[0075] The poly-functional epoxy and amine resins prepared
according to the disclosure may have a high glass transition
temperature and may display high thermal stability. Resins with
such properties may be well suited for use as, for example, binders
for composite materials. Further, the multi-functional epoxy resins
may have a higher degree of cross-linking resulting in improved
resistance to solvents and/or corrosive chemicals. The resins made
from the compounds of the present disclosure may have improved
water miscibility when compared to the common aromatic epoxy
resins, and accordingly such a resin may be used for applications
in, for example, in a humid environment, on a wet surface, as a
water-based epoxy for construction work and as a water-based
paint.
[0076] The resins of the present disclosure may be employed in, for
example, encapsulations, electronic or structural laminates or
composites, filament winding, molding, semiconductor encapsulating
materials, under-fill materials, conductive pastes, laminates,
resin compositions used for electronic circuit boards, resin
casting materials, adhesives, interlayer insulation materials for
buildup substrates, and coating materials, such as insulating
paint. Further, these resins may also be used as linings in
articles of manufacture including, but not limited to, tanks, cars,
drums, pails, pipes, down-hole oilfield tubings, and food cans. In
addition, the resins may be used as, for example, laminated epoxy
structures for concrete molds, honeycomb cores, wood and metal
assemblies, and reinforced pipes.
[0077] Epoxy resins of the present disclosure may be used with, for
example, acrylic systems to provide excellent coatings for articles
of manufacture, such as appliances, kitchen cabinets, outdoor
furniture, aluminum siding, and other metal products. The
poly-functional epoxy and amine resins may be used as, for example,
a powder coating for anti-corrosion or a high sheen decorative
coating. Such coatings may find applications in articles of
manufacture such as, washing machines, appliances, ships, bridges,
pipelines, chemical plants, automobiles, farm implements,
containers, and floor surfaces.
[0078] The phenolic compounds with acrylate functional groups may
be used, for example, as binders in paints and coatings. In
addition, various additives, such as pigments, coalescing agents,
rheology modifiers, fungicides, plasticizers, nitrates, and the
like, may be added to the coatings. Paints with multi-functional
acrylate binders may display high glass transition temperatures,
and may be resistant to abrasion, and easily cure at room
temperature. The coatings may generally be applied to any
substrate. The substrate may be, for example, an article, an
object, a vehicle or a structure. Although no particular limitation
is imposed on the substrate to be used in the present disclosure,
examples of such substrates include, building exteriors, vehicles,
bridges, airplanes, metal railings, fences, glasses, plastics,
metals, ceramics, wood, stones, cement, fabric, paper, leather, and
combinations or laminations thereof may be used. The coating may be
applied to a substrate by, for example, spraying, dipping, rolling,
brushing, or any combination thereof.
[0079] The resins formed from the acrylate compounds described
herein may be used for production of composites, either alone or as
interpenetrating polymer networks (IPNs) with other thermosets,
such as epoxy and unsaturated polyesters. Further, these resins may
also find use in, for example, hydrogels, polyacrylate super
absorbent polymers (SAPs), adhesives, composites, sealants,
fillers, fire retardants, crosslinking agents, and the like. In
addition, resins may be prepared with different functionality such
that a different number of acrylate functional groups per monomer
are exhibited. For example, by using a resole precursor a resin
with 4 acrylate groups per monomer may be prepared. In contrast, a
melamine precursor may result in 6 acrylate groups per monomer.
Such resins with tailored functionality may be used to improve the
physical, mechanical and/or chemical properties, and curing
characteristics of acrylate emulsions. The resins described herein
may be used as a crosslinking agent for commercial acrylate resins,
and/or as a wetting polymeric surfactant, and such properties may
find applications in super absorbent polymers for soil
treatment.
[0080] The compounds of the present disclosure may also be used as
a precursor for developing new and improved products for
hydrophobic soil treatment, or for use in water and sewage
treatment facilities with compounds that act as water-clarification
agents. Further, compounds described herein may find use in carbon
fibers, crosslinking agents for SAPs, adhesives, lamination, photo
printing, room-temperature curing applications, photo curing, and
the like.
EXAMPLES
Example 1: Preparation of Hydroxymethyl Compound-Resolac (Compound
1)
[0081] About 150 grams of low molecular weight novolac and 200
grams of formalin solution (37% by weight) were mixed in a
five-neck reaction flask fitted with a condenser, a mechanical
stirrer, dropping funnel, and a thermometer. The reaction was
started by adding 150 mL of 10% (by weight) sodium hydroxide
solution drop wise, and the pH of the reaction mixture was adjusted
between pH 9-10. The reaction mixture was heated to about
65.degree. C. for 3 hours. At the end of this period, the reaction
mixture was cooled and neutralized with a cold (5-10.degree. C.)
solution of sodium dihydrogen phosphate. A golden colored resin
layer was separated from the reaction mixture, dissolved in
ethanol, desalted, and dried with molecular sieves. The product was
evaporated by rotary evaporators and dried under vacuum to obtain
compound 1. The product was characterized and its curing properties
were investigated by differential scanning calorimetry (DSC). A
typical DSC thermogram for compound 1 measured at a constant rate
of change in temperature (10.degree. C./minute under N.sub.2
atmosphere) is shown in FIG. 2A. For comparison, a DSC thermogram
of novolac cured with hexamine is shown in FIG. 2B. A
representative thermogravimetric analysis (TGA) of compound 1 is
shown in FIG. 3.
Example 2: Preparation of Amino Novolac Compound (Compound 2)
[0082] About 30.6 grams of compound 1 was mixed with 150 mL of
ethanol in a one liter autoclave system from Analis (Belgium) that
is fitted with a mechanical stirrer, and which could be operated
under controlled temperature and pressure. The system was secured
and connected to an ammonia gas cylinder. The system was flushed
with N.sub.2, and mixed for 10 minutes to dissolve the compound.
Ammonia gas was fed to the autoclave until the pressure reached 1.5
atmospheres. The reaction temperature was maintained at
50-70.degree. C. via the cooling jacket of the autoclave for 2
hours. At the end of this period, the system was cooled to room
temperature and the system was flushed with N.sub.2 gas to remove
unreacted ammonia gas. The white milky syrup product was evaporated
and dried under vacuum to obtain compound 2. The number of amino
groups present, based on the percent N content, was determined by
CHN microanalysis. The CHN data showed that the number of amino
groups (based on percent N content) were 10 and 5, for novolacs of
molecular weight 700 and 1000, respectively. The purified resin was
used as a hardening agent for epoxies, and as a catalyst and
crosslinking agent for polyurethanes and siloxanes.
Example 3: Preparation of Diethylamino Derivative (Compound 3)
[0083] About 45 grams of compound 1 was refluxed with 300 grams of
diethylamine (DEA) for three hours. At the end of this period, the
product was cooled to room temperature, and the unreacted DEA was
extracted with water several times. The obtained oily resin was
dissolved in ethanol and dried with molecular sieves. The product
was evaporated by rotary evaporator and dried under vacuum at
80.degree. C. and 0.1 mm Hg for 3 hours to obtain compound 3. The
number of diethylamine groups was determined from CHN
microanalysis. The number of substituted aminogroups was less than
the number of hydroxymethyl groups by 20-30%, due to the catalytic
polymerization of resolac in the presence of DEA. The number of
estimated DEA groups was about 5-7 groups per resolac molecule.
Example 4: Preparation of Acrylate Compound (Compound 4)
[0084] About 22 grams of compound 1 was diluted with 10% THF and
mixed with 86 grams (0.4 mole) of acrylic anhydride (analar grade)
and 0.1 gram of tert-butylhydroquinone in a reaction vessel. The
reaction mixture was heated to about 60.degree. C. The reaction was
continued at about 60.degree. C. for two hours, and at the end of
this period the temperature was raised to about 80.degree. C. and
heated for one more hour. Excess unreacted acrylic anhydride and
acrylic acid by-products were distilled under vacuum, and a pale
yellow viscous acrylated compound (compound 4) was obtained. The
product was characterized and evaluated by DSC. The isothermal DSC
curing curves for compound 4 at 40.degree. C. (a), 50.degree. C.
(b), 60.degree. C. (c), and 80.degree. C. (d) are shown in FIG. 4.
The measured glass transition temperature of compound 4 was
144.degree. C.
[0085] The above product can also be prepared by substituting
acrylic acid with acryloyl chloride and carrying out the reaction
in the presence of triethylamine as HCl acceptor at ambient
temperature (25.degree. C.).
Example 5: Preparation of Polyisocyanate Compound (Compound 5)
[0086] About 45 grams of compound 1 dissolved in 150 mL of dry
methylene chloride and about 20 grams of triethylamine as HCl
acceptor are placed in 500 mL autoclave, as used in Example 2. The
autoclave is secured and flushed with nitrogen. Phosgene is fed to
the solution, and the reaction is continued under phosgene
atmosphere for two hours. At the end of the reaction period, the
system is flushed again with nitrogen, and unreacted phosgene is
bubbled through a saturated solution of alcoholic potassium
hydroxide. The product is separated to obtain compound 5. The
isocyanate equivalent is determined by titration adopting standard
methods and will be about 30-40% by weight.
Example 6: Preparation of Isooctanoate Compound (Compound 6)
[0087] A 500 mL three-neck reaction vessel fitted with a condenser,
a dropping funnel, and a mechanical stirrer was immersed in a water
bath. The dropping funnel was charged with about 22 grams of
compound 1 diluted with 20 grams of triethylamine as a HCl acid
acceptor. The reaction vessel was charged with about 30 grams of
isooctanoyl chloride, and the reaction vessel was heated to
60.degree. C. Compound 1 was added from the dropping funnel drop
wise with efficient mixing over one hour. The reaction was
continued at 60.degree. C. for two hours. Later, the temperature
was raised to 80.degree. C. and the reaction was continued for one
more hour. Excess unreacted isooctanoyl chloride and its amine
adduct were separated. A yellow viscous resolac isooctanoate
compound (compound 6) was obtained. The compound was characterized
by IR, CHN, and cryoscopic molecular weight determination
apparatus. The obtained molecular weight of the compound was
between 3500-4200.
Example 7: Preparation of Acrylamide Compound (Compound 7)
[0088] The reaction set up of Example 6 was used. The dropping
funnel was charged with about 45 grams of compound 2 diluted with
10% THF. The reaction vessel was charged with 0.2 mole (44 grams)
of acrylic anhydride and 0.2 grams of butylated hydroquinone. The
reaction mixture was heated to 80.degree. C., with slow addition of
compound 2 for one hour. After the addition of the compound, the
reaction was continued for further one hour. Excess unreacted
acrylic anhydride and acrylic acid by-products were distilled under
vacuum, and a pale yellow viscous acrylated compound (compound 7)
was obtained. The product was characterized and evaluated by DSC.
The compound is further polymerized to form a hydrogel wetting
surfactant by modifying the phenolic groups to phenoxypoly ether,
which is suitable for the treatment of hydrophobic soils. The above
product can also be prepared by substituting acrylic anhydride with
acryloyl chloride and carrying out the reaction in the presence of
triethylamine as HCl acceptor at ambient temperature (25.degree.
C.). A representative DSC thermogram showing the curing of compound
7 (at 40.degree. C. (a) and at 60.degree. C. (b), measured at
10.degree. C./minute), is shown in FIG. 5.
Example 8: Preparation of Epoxy Compound (Compound 8)
[0089] About 100 grams (0.2 mol) of compound 1 was combined with 1
gram of MgClO.sub.4 dissolved in 5 mL of 2-methoxy ethanol, and 231
grams (2.5 mol) of epichlorohydrin. The system was flashed with
nitrogen for 10 minutes with continuous mixing. The reaction
temperature was raised to 60.degree. C., and the reaction was
continued for two hours. At the end of this period, the temperature
was raised to 80-85.degree. C., and the reaction was continued for
1 more hour. Later, the reaction mixture was cooled to 60.degree.
C., and about 12 grams of tetrabutyl ammonium chloride dissolved in
25 mL of water was added with continuous mixing, followed by
addition of 250 ml of 50% (by weight) NaOH solution. The reaction
mixture was stirred for 1 hour, and the mixture of epichlorohydrin
and water was separated by azeotropic distillation. Separated
epichlorohydrin was again introduced back into the reaction
mixture, and the mixture was further heated to 70.degree. C. for 60
minutes. The excess of unreacted epichlorohydrin was distilled
under vacuum, and the reaction mixture was cooled to room
temperature. The epoxy product formed was dissolved in toluene,
filtered, washed with 1% (by weight) acetic acid, washed with water
and dried with molecular sieves. The product was evaporated by
rotary evaporators and dried under vacuum at 0.1 millimeter Hg at
40.degree. C. for 6 hours to obtain a brownish colored viscous
compound 8. The epoxy equivalent of the compound was determined
adopting standard methods. The epoxy equivalent was found to be 86
grams/equivalent (epoxy equivalent=4.8 eq/kilogram), viscosity at
40.degree. C. was 315.4 Pas, and active chlorine content was 1.3%
by weight.
Example 9: Preparation of Isooctyl Ether Compound (Compound 9)
[0090] About 20 grams of resolac compound 1 is dissolved in
tetrahydrofuran and modified to a sodium ether adduct by treating
with sodium wire. Under dry conditions, the sodium resolac oxide
derivative is reacted with isooctyl chloride, and the reaction is
continued for two hours with efficient mixing. The oily yellow
color ether plasticizer obtained is separated, washed with ethanol
to decompose the unreacted sodium. The product is washed with
water, and dried with molecular sieves to obtain compound 9. The
product is evaluated for plasticizer and vibration damping agent
properties.
Example 10: Preparation of Glycidylamine Compound (Compound 10)
[0091] About 45 grams of compound 2 is dissolved in 100 mL of DMF
and combined with 1 gram of MgClO.sub.4 dissolved in 5 mL of
2-methoxy ethanol, and 231 grams (2.5 mol) of epichlorohydrin. The
system is flashed with nitrogen for 10 minutes with continuous
mixing. The reaction temperature is raised to 60.degree. C., and
the reaction is continued for two hours. At the end of this period,
the temperature is further raised to 80-85.degree. C., and the
reaction is continued for 1 more hour. Later, the reaction mixture
is cooled to 60.degree. C., and about 12 grams of tetrabutyl
ammonium chloride dissolved in 25 mL water is added with continuous
mixing, followed by addition of 250 ml of 50% (by weight) NaOH
solution. The reaction mixture is stirred for 1 hour, and the
mixture of epichlorohydrin and water is separated by azeotropic
distillation. Separated epichlorohydrin is again introduced back
into the reaction mixture, and the mixture is further heated to
70.degree. C. for 60 minutes. The excess of unreacted
epichlorohydrin is distilled under vacuum, and the reaction mixture
is cooled to room temperature. The epoxy product formed is
dissolved in toluene, filtered, washed with 1% (by weight) acetic
acid, washed with water and dried with molecular sieves. The
product is evaporated by rotary evaporators and dried under vacuum
at 0.1 millimeter Hg at 40.degree. C. for 6 hours to obtain a
brownish colored viscous compound 10. The epoxy equivalent of the
compound is determined adopting standard methods and will be 4-5
epoxy equivalent per kilogram of the compound.
Example 11: Use of Compound 1 as a Binder
[0092] A composition comprising 90% by weight fine silica sand
(80-200 microns in diameter), 2.5% by weight rock wool, 2.5% by
weight waste paper, and 5% by weight compound 1 was dissolved in
10% (v/v) ethanol. The composition was mixed until a homogenous
product was obtained. The product was placed in a mold to form
various shapes, such as a plate of dimension 80.times.80.times.5
centimeters, nozzles, and other refractory products. The cast
products were cured in an oven at 80-100.degree. C. for 2 hours.
The products were removed from the mold and used in refractory
applications.
Example 12: Use of Compound 1 and Compound 2 as a Binder
[0093] A composition comprising 90% by weight fine silica sand
(80-200 microns in diameter), 2.5% by weight rock wool, 2.5% by
weight waste paper, 2.5% by weight compound 2, and 2.5% by weight
compound 1 was dissolved in 10% (v/v) ethanol. The composition was
mixed until homogenous product was obtained. The product was placed
in a mold to form various shapes, such as a plate of dimension
80.times.80.times.5 centimeters, nozzles, and other refractory
products. The cast products were cured at room temperature
overnight. The products were removed from the mold and used in
refractory applications.
Example 13: Use of Compounds as an Electrical Insulators
[0094] A composition comprising compound 1 and compound 2 in a
ratio of about 1:1 was prepared and diluted with 5% (v/v) ethanol.
The mixture was applied to electrical coils as insulators, and
cured at room temperature. The mixture exhibited excellent
electrical resistivity, and were resistant to high temperatures.
These coils were used in electrical transformers.
Example 14: Evaluation of Resolac Plasticizers
[0095] Several compositions comprising a mixture of polyvinyl
chloride (PVC), (5-10% by weight) compound 2 and (5-10% by weight)
compound 6 was prepared. The rheological properties and thermal
stability of the obtained compositions were measured by rheometer
and melt flow rate. Compounds 2 and 6 showed remarkable efficiency
in improving the melt flow rate of PVC when compared with
commercial plasticizers, such as dioctylphthalate.
Example 15: An Article Coated with Epoxy Coating
[0096] A cast iron rod is coated with an epoxy paint prepared from
compound 8. A similar rod is also coated with a commercially
available non-epoxy paint. The paint is allowed to dry and scribed
with an X through the paint down to the metal. The rods are placed
in a salt fog chamber (5% by volume NaCl, 35.degree. C.) for 200
hours. At the end of this period, the rods are visually inspected
for corrosion and peeling of the paint at the site of damage. The
rod sprayed with epoxy paint will display less corrosion and
peeling of the paint, when compared to the rod sprayed with a
non-epoxy paint.
Example 16: Preparation of a Hydrogel
[0097] About 10 grams of compound 7 was mixed with 2 grams of
polyacrylate, 0.05 grams of benzoylperoxide and 0.02 grams of
cobalt octanoate and left to cure at ambient temperature. The cured
resin was later neutralized with potassium hydroxide. About 10
grams of the neutralized resin was immersed in distilled water. The
product swelled in volume (about 200% increase in weight) due to
absorption of water.
Example 17: Curing of an Epoxy Compound
[0098] 10 grams of compound 8 was mixed with 3 grams of the
commercial hardener 8050. The mixture was left to cure overnight to
form a hard resin with a glass transition temperature of about
90.degree. C. to about 100.degree. C. The thermomechanical curve
showing high glass transition temperature and expansion coefficient
of the cured resin at various temperature ranges is depicted in
FIG. 6.
Example 18: Curing of Acrylate Resins
[0099] 10 grams of acrylate compound 4 was mixed with 0.05 grams of
benzoylperoxide and 0.02 grams of cobalt octanoate. The mixture was
left to cure at ambient temperature for about 6 hours to about 12
hours. The cured polyacrylate resin had a glass transition
temperature of 120-150.degree. C. and a thermal decomposition
temperature of 430.degree. C. As will be appreciated, the acrylate
resin can be easily cured at ambient temperature. The acrylate
resin displays high glass transition and thermal decomposition
temperatures. The DSC isothermal curing curves for acrylate resins
at 40.degree. C. and 60.degree. C. are shown in FIG. 7.
Example 19: Manufacture of a Brake Pad
[0100] About 15 grams of resolac compound 1 is mixed with a filler
composition made up of 10 grams of barium sulphate, 3.5 grams of
asbestos, 1.5 grams of brass fillings, 5.5 grams of graphite
powder, 5 grams of carbon fibers, 5 grams of ceramic microspheres,
2 grams of copper, 5 grams of fiberglass, 0.5 grams of calcium
hydroxide, 12 grams of aluminum oxide, 0.2 grams of copper
sulphide, 12 grams of quartz, 5 grams of rock wool, and 5 grams of
recycled rubber scrap. The composition is mixed well and about 10
grams of compound 2 is added to this composition and remixed to get
homogenous mixture. The mixture is pressed into a mold by a metal
plate and then left to cure at room temperature for 6 hours. The
product is further cured at 80.degree. C. for 1 hour. A brake pad
is obtained with good friction properties.
[0101] In the above detailed description, reference is made to the
accompanying drawings, which form a part hereof. In the drawings,
similar symbols typically identify similar components, unless
context dictates otherwise. The illustrative embodiments described
in the detailed description, drawings, and claims are not meant to
be limiting. Other embodiments may be used, and other changes may
be made, without departing from the spirit or scope of the subject
matter presented herein. It will be readily understood that the
aspects of the present disclosure, as generally described herein,
and illustrated in the Figures, can be arranged, substituted,
combined, separated, and designed in a wide variety of different
configurations, all of which are explicitly contemplated
herein.
[0102] The present disclosure is not to be limited in terms of the
particular embodiments described in this application, which are
intended as illustrations of various aspects. Many modifications
and variations can be made without departing from its spirit and
scope, as will be apparent to those skilled in the art.
Functionally equivalent methods and apparatuses within the scope of
the disclosure, in addition to those enumerated herein, will be
apparent to those skilled in the art from the foregoing
descriptions. Such modifications and variations are intended to
fall within the scope of the appended claims. The present
disclosure is to be limited only by the terms of the appended
claims, along with the full scope of equivalents to which such
claims are entitled. It is to be understood that this disclosure is
not limited to particular methods, reagents, compounds,
compositions or biological systems, which can, of course, vary. It
is also to be understood that the terminology used herein is for
the purpose of describing particular embodiments only, and is not
intended to be limiting.
[0103] As used in this document, the singular forms "a," "an," and
"the" include plural references unless the context clearly dictates
otherwise. Unless defined otherwise, all technical and scientific
terms used herein have the same meanings as commonly understood by
one of ordinary skill in the art. Nothing in this disclosure is to
be construed as an admission that the embodiments described in this
disclosure are not entitled to antedate such disclosure by virtue
of prior invention. As used in this document, the term "comprising"
means "including, but not limited to."
[0104] While various compositions, methods, and devices are
described in terms of "comprising" various components or steps
(interpreted as meaning "including, but not limited to"), the
compositions, methods, and devices can also "consist essentially
of" or "consist of" the various components and steps, and such
terminology should be interpreted as defining essentially
closed-member groups.
[0105] With respect to the use of substantially any plural and/or
singular terms herein, those having skill in the art can translate
from the plural to the singular and/or from the singular to the
plural as is appropriate to the context and/or application. The
various singular/plural permutations may be expressly set forth
herein for sake of clarity.
[0106] It will be understood by those within the art that, in
general, terms used herein, and especially in the appended claims
(e.g., bodies of the appended claims) are generally intended as
"open" terms (e.g., the term "including" should be interpreted as
"including but not limited to," the term "having" should be
interpreted as "having at least," the term "includes" should be
interpreted as "includes but is not limited to," etc.). It will be
further understood by those within the art that if a specific
number of an introduced claim recitation is intended, such an
intent will be explicitly recited in the claim, and in the absence
of such recitation no such intent is present. For example, as an
aid to understanding, the following appended claims may contain
usage of the introductory phrases "at least one" and "one or more"
to introduce claim recitations. However, the use of such phrases
should not be construed to imply that the introduction of a claim
recitation by the indefinite articles "a" or "an" limits any
particular claim containing such introduced claim recitation to
embodiments containing only one such recitation, even when the same
claim includes the introductory phrases "one or more" or "at least
one" and indefinite articles such as "a" or "an" (e.g., "a" and/or
"an" should be interpreted to mean "at least one" or "one or
more"); the same holds true for the use of definite articles used
to introduce claim recitations. In addition, even if a specific
number of an introduced claim recitation is explicitly recited,
those skilled in the art will recognize that such recitation should
be interpreted to mean at least the recited number (e.g., the bare
recitation of "two recitations," without other modifiers, means at
least two recitations, or two or more recitations). Furthermore, in
those instances where a convention analogous to "at least one of A,
B, and C, etc." is used, in general such a construction is intended
in the sense one having skill in the art would understand the
convention (e.g., "a system having at least one of A, B, and C"
would include but not be limited to systems that have A alone, B
alone, C alone, A and B together, A and C together, B and C
together, and/or A, B, and C together, etc.). In those instances
where a convention analogous to "at least one of A, B, or C, etc."
is used, in general such a construction is intended in the sense
one having skill in the art would understand the convention (e.g.,
"a system having at least one of A, B, or C" would include but not
be limited to systems that have A alone, B alone, C alone, A and B
together, A and C together, B and C together, and/or A, B, and C
together, etc.). It will be further understood by those within the
art that virtually any disjunctive word and/or phrase presenting
two or more alternative terms, whether in the description, claims,
or drawings, should be understood to contemplate the possibilities
of including one of the terms, either of the terms, or both terms.
For example, the phrase "A or B" will be understood to include the
possibilities of "A" or "B" or "A and B."
[0107] In addition, where features or aspects of the disclosure are
described in terms of Markush groups, those skilled in the art will
recognize that the disclosure is also thereby described in terms of
any individual member or subgroup of members of the Markush
group.
[0108] As will be understood by one skilled in the art, for any and
all purposes, such as in terms of providing a written description,
all ranges disclosed herein also encompass any and all possible
subranges and combinations of subranges thereof. Any listed range
can be easily recognized as sufficiently describing and enabling
the same range being broken down into at least equal halves,
thirds, quarters, fifths, tenths, etc. As a non-limiting example,
each range discussed herein can be readily broken down into a lower
third, middle third and upper third, etc. As will also be
understood by one skilled in the art all language such as "up to,"
"at least," and the like include the number recited and refer to
ranges which can be subsequently broken down into subranges as
discussed above. Finally, as will be understood by one skilled in
the art, a range includes each individual member. Thus, for
example, a group having 1-3 cells refers to groups having 1, 2, or
3 cells. Similarly, a group having 1-5 cells refers to groups
having 1, 2, 3, 4, or 5 cells, and so forth.
[0109] Various of the above-disclosed and other features and
functions, or alternatives thereof, may be combined into many other
different systems or applications. Various presently unforeseen or
unanticipated alternatives, modifications, variations or
improvements therein may be subsequently made by those skilled in
the art, each of which is also intended to be encompassed by the
disclosed embodiments.
* * * * *