U.S. patent application number 10/602805 was filed with the patent office on 2004-04-08 for hydroxyaliphatic functional epoxy resins.
Invention is credited to Clement, Katherine S., Hefner, Robert E. JR., Walker, Louis L..
Application Number | 20040068062 10/602805 |
Document ID | / |
Family ID | 22519821 |
Filed Date | 2004-04-08 |
United States Patent
Application |
20040068062 |
Kind Code |
A1 |
Walker, Louis L. ; et
al. |
April 8, 2004 |
Hydroxyaliphatic functional epoxy resins
Abstract
The present invention concerns hydroxyaliphatic functional
diglycidyl ethers of bisphenols (epoxy resins); curable
(thermosettable) mixtures of at least one hydroxyaliphatic
functional epoxy resin and at least one curing agent and/or
catalyst therefor, as well as cured (thermoset) compositions
prepared therefrom; and derivatives prepared therefrom. The
bisphenol precursor to the diglycidyl ether contains a
hydroxyaliphatic group linkage between the two aromatic rings of
the bisphenol.
Inventors: |
Walker, Louis L.; (Clute,
TX) ; Hefner, Robert E. JR.; (Lake Jackson, TX)
; Clement, Katherine S.; (Lake Jackson, TX) |
Correspondence
Address: |
THE DOW CHEMICAL COMPANY
INTELLECTUAL PROPERTY SECTION
P. O. BOX 1967
MIDLAND
MI
48641-1967
US
|
Family ID: |
22519821 |
Appl. No.: |
10/602805 |
Filed: |
June 24, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10602805 |
Jun 24, 2003 |
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09991026 |
Nov 16, 2001 |
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6613849 |
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09991026 |
Nov 16, 2001 |
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09625933 |
Jul 26, 2000 |
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6353079 |
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60146974 |
Aug 3, 1999 |
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Current U.S.
Class: |
525/531 |
Current CPC
Class: |
C07D 303/24 20130101;
C08F 290/061 20130101; C08F 22/1006 20200201; C08G 59/245 20130101;
C08G 59/1466 20130101; C08F 290/06 20130101; C08F 290/064
20130101 |
Class at
Publication: |
525/531 |
International
Class: |
C08G 059/16 |
Claims
What is claimed is:
1. A resin having the structural Formula I 8wherein each R is
independently selected from the group consisting of hydrogen, a
hydrocarbyl or hydrocarbyloxy group having from one to about 10
carbon atoms, a halogen atom, a nitro group, a nitrile group and a
--CO--R.sup.2 group; each E is independently selected from the
group consisting of 9each R.sup.1 is independently selected from
the group consisting of hydrogen and a hydrocarbyl group having
from one to about 10 carbon atoms; X is independently selected from
the group consisting of 10each R.sup.2 is independently selected
from the group consisting of hydrogen and a hydrocarbyl group
having from one to about 10 carbon atoms; R.sup.3 is a hydrocarbyl
group having from one to about 10 carbon atoms; and n has a value
of from one to about 10.
2. A resin of claim 1 wherein E is 11
3. A resin of claim 1 wherein E is 12
4. A resin of claim 1 wherein each R is hydrogen.
5. A resin of claim 1 wherein R.sup.1 is hydrogen.
6. A resin of claim 1 wherein X is 13
7. A resin of claim 1 wherein X is 14
8. A resin of claim 1 wherein X is 15
9. A resin prepared by advancing a resin of Formula I wherein E is
16
10. A resin having the structural Formula II 17wherein each R is
independently selected from the group consisting of hydrogen, a
hydrocarbyl or hydrocarbyloxy group having from one to about 10
carbon atoms, a halogen atom, a nitro group, a nitrile group and a
--CO--R.sup.2 group; each E is independently selected from the
group consisting of 18each R.sup.1 is independently selected from
the group consisting of hydrogen and a hydrocarbyl group having
from one to about 10 carbon atoms; each R.sup.2 is independently
selected from the group consisting of hydrogen and a hydrocarbyl
group having from one to about 10 carbon atoms; R.sup.3 is a
hydrocarbyl group having from one to about 10 carbon atoms; n has a
value of from one to about 10; and X.sup.1 is selected from the
group consisting of 19E.sup.1 is a moiety containing a
polymerizable ethylenically unsaturated group wherein the oxygen
atom attached to E.sup.1 is part of an ester or a urethane
linkage.
11. A resin of claim 10 wherein E is 20
12. A resin of claim 10 wherein E is 21
13. A resin of claim 10 wherein each R is hydrogen.
14. A resin of claim 10 wherein R.sup.1 is hydrogen.
15. A resin of claim 10 wherein X.sup.1 is 22
16. A resin of claim 10 wherein X.sup.1 is 23
17. A resin of claim 10 wherein X.sup.1 is 24
18. A composition comprising a resin of Formula and a resin of
Formula II.
19. A polymer modified epoxy resin prepared by polymerizing an
epoxy resin of the composition of claim 18 with one or more
polymerizable ethylenically unsaturated monomers.
20. A polymer modified vinyl ester resin prepared from the resin of
claim 19.
21. A resin having the structural Formula III 25wherein each R is
independently selected from the group consisting of hydrogen, a
hydrocarbyl or hydrocarbyloxy group having from one to about 10
carbon atoms, a halogen atom, a nitro group, a nitrile group and a
--CO--R.sup.2 group; each E is independently selected from the
group consisting of 26each R.sup.1 is independently selected from
the group consisting of hydrogen and a hydrocarbyl group having
from one to about 10 carbon atoms; each R.sup.2 is independently
selected from the group consisting of hydrogen and a hydrocarbyl
group having from one to about 10 carbon atoms; R.sup.3 is a
hydrocarbyl group having from one to about 10 carbon atoms; n has a
value of from one to about 10; E.sup.3 is a direct bond or a
hydrocarbyl group having from one to about 30 carbon atoms; and
X.sup.2 is selected from the group consisting of 27
22. A resin of claim 21 wherein E is 28
23. A resin of claim 21 wherein E is 29
24. A resin of claim 21 wherein each R is hydrogen.
25. A resin of claim 21 wherein R.sup.1 is hydrogen.
26. A resin of claim 21 wherein X.sup.2 is 30
27. A resin of claim 21 wherein X.sup.2 is 31
28. A resin of claim 21 wherein X.sup.2 is 32
29. A resin of claim 21 wherein E.sup.3 is
--(CH.sub.2).sub.4--.
30. A resin having the structural Formula IV 33wherein each R is
independently selected from the group consisting of hydrogen, a
hydrocarbyl or hydrocarbyloxy group having from one to about 10
carbon atoms, a halogen atom, a nitro group, a nitrile group and a
--CO--R.sup.2 group; each E is independently selected from the
group consisting of 34each R.sup.1 is independently selected from
the group consisting of hydrogen and a hydrocarbyl group having
from one to about 10 carbon atoms; each R.sup.2 is independently
selected from the group consisting of hydrogen and a hydrocarbyl
group having from one to about 10 carbon atoms; R.sup.3 is a
hydrocarbyl group having from one to about 10 carbon atoms; n has a
value of from one to about 10; E.sup.4 is a hydrocarbyl group
having from about 4 to about 35 carbon atoms; X.sup.2 is selected
from the group consisting of 35
31. A resin of claim 30 wherein E is 36
32. A resin of claim 30 wherein E is 37
33. A resin of claim 30 wherein each R is hydrogen.
34. A resin of claim 30 wherein R.sup.1 is hydrogen.
35. A resin of claim 30 wherein X.sup.2 is 38
36. A resin of claim 30 wherein X.sup.2 is 39
37. A resin of claim 30 wherein X.sup.2 is 40
38. A resin of claim 30 wherein E.sup.4 is
-p-C.sub.6H.sub.4--CH.sub.2--P-- -C.sub.6H.sub.4--.
39. A polymer modified epoxy resin prepared by polymerizing an
epoxy resin of Formula II with one or more polymerizable
ethylenically unsaturated monomers.
40. A polymer modified vinyl ester resin prepared from the resin of
claim 39.
Description
[0001] This application claims the benefit of U.S. Provisional
Application No. 60/146,974, filed Aug. 3, 1999.
FIELD OF THE INVENTION
[0002] The present invention concerns hydroxyaliphatic functional
diglycidyl ethers of bisphenols (epoxy resins); curable
(thermosettable) mixtures of at least one hydroxyaliphatic
functional epoxy resin and at least one curing agent and/or
catalyst therefor, as well as cured (thermoset) compositions
prepared therefrom; and derivatives prepared therefrom. The
bisphenol precursor to the diglycidyl ether contains a
hydroxyaliphatic group linkage between the two aromatic rings of
the bisphenol.
BACKGROUND AND SUMMARY OF THE INVENTION
[0003] The present invention provides novel hydroxyaliphatic epoxy
resins, curable mixtures of at least one hydroxyaliphatic
functional epoxy resin and at least one curing agent and/or
catalyst therefor, as well as the cured (thermoset) compositions
prepared therefrom. Epoxy resins are well established as a class of
curable compositions which find efficacy in a myriad of
applications. The curing of epoxy resins is effected by a wide
range of curing agents including, for example, the primary and
secondary aliphatic, cycloaliphatic and aromatic polyamines;
dicarboxylic acids and the anhydrides thereof; aromatic hydroxyl
containing compounds; imidazoles; guanidines; urea-aldehyde resins
and alkoxylated derivatives thereof; melamine-aldehyde resins and
alkoxylated derivatives thereof; amidoamines; epoxy resin adducts;
and various combinations thereof. In addition to said curing
agents, one or more catalysts, such as a quaternary ammonium or
phosphonium salts are frequently added to accelerate the cure rate
as well as to insure completeness of the cure. While the curing of
epoxy resins may be effected via the usual epoxy resin curing
agents and catalysts, a number of additional factors are critical
to and interrelate to the curing process for epoxy resins. These
factors include the processing time and temperature profile
employed, the epoxide equivalent weight (EEW) of the epoxy resin
component(s) employed, the active hydrogen equivalent weight of the
curing agent component(s) employed, the final configuration of the
curable mixture, and other such variables and combinations of
variables. For many of the applications served by epoxy resins, it
would be desirable to possess controlled higher reactivity during
the curing process, while maintaining, or even improving one or
more of the physical and/or mechanical and/or thermal properties of
the cured products thereof. The hydroxyaliphatic epoxy resins of
the present invention impart controlled higher reactivity during
the curing process, while using a wide variety of conventional
curing agents and/or catalysts.
[0004] The hydroxyaliphatic epoxy resins of the present invention
possess a unique molecular structure heretofore unavailable in an
epoxy resin. The key feature of the molecular structure inherent to
the hydroxyaliphatic epoxy resins of the present invention is the
presence of the hydroxy group attached to the aliphatic linkage
between the two aromatic rings each bearing a glycidyloxy group.
The hydroxy group inherent to the hydroxyaliphatic epoxy resins of
the present invention provides curable epoxy resin compositions,
with outstanding processability through acceleration of the cure
and cured epoxy resin compositions thereof, with substantial
improvements in one or more physical and/or mechanical and/or
thermal properties. A specific mechanical property expected to be
improved by the presence of the aliphatic hydroxy group is
adhesion. Furthermore, this improvement is expected, without
significantly diminishing the glass transition temperature of the
cured epoxy resin. One conventional method for incorporation of
aliphatic hydroxy groups into an epoxy resin specifically used to
promote adhesion involves partial hydrolysis of epoxide groups to
.alpha.-glycol groups. However, this markedly lowers the glass
transition temperature of the cured epoxy resin by removal of
available epoxide groups for reaction with curing agent (lowers the
crosslink density). The second conventional method for the
incorporation of aliphatic hydroxy groups into an epoxy resin
involves advancement of the epoxy resin to produce secondary
aliphatic hydroxy groups. This again markedly lowers the glass
transition temperature of the cured epoxy resin by forming highly
flexible linkages (for example, diether linkages if a diphenol is
used in the advancement reaction) between aromatic ring pairs.
[0005] Additionally, the hydroxy group inherent to the
hydroxyaliphatic epoxy resins of the present invention is present
in an exact and defined stoichiometry and thus serves as a
convenient reactive site for conversion to a myriad of other
functional moieties, thus providing additional epoxy resin
compositions of the present invention. Thus, for example,
esterification of the hydroxy group with an ethylenically
unsaturated carboxylic acid halide, provides a novel thermosettable
composition containing both diglycidyl ether and polymerizable
ethylenic unsaturation. The resulting diglycidyl ether containing a
polymerizable ethylenic unsaturation may be further reacted with an
ethylenically unsaturated monocarboxylic acid, such as methacrylic
acid, to provide vinyl ester resins containing three or four
polymerizable ethylenically unsaturated groups. These novel vinyl
ester resins may be thermoset to provide highly crosslinked
products. The diglycidyl ether compositions of the present
invention containing polymerizable ethylenic unsaturation may be
further converted to a polymer modified epoxy resin, via
copolymerization with one or more ethylenically unsaturated
monomers. Reaction of a polymer modified epoxy resin with an
ethylenically unsaturated monocarboxylic acid provides the polymer
modified vinyl ester resins of the present invention.
[0006] As a further embodiment of the present invention, coupling
of a pair of the hydroxyaliphatic epoxy resin molecules, for
example via esterification with a diacid halide or, via reaction
with a diisocyanate, provides novel tetraglycidyl ethers which can
be thermoset to highly crosslinked products. These tetraglycidyl
esters may be further reacted with ethylenically unsaturated
monocarboxylic acid, such as acrylic acid or methacrylic acid, to
provide vinyl ester resins containing four polymerizable
ethylenically unsaturated groups. Such polyfunctional vinyl esters
are thermosettable to provide highly crosslinked products.
[0007] One aspect of the present invention pertains to
hydroxyaliphatic epoxy resins or vinyl ester resins represented by
the following Formula I 1
[0008] wherein each R is independently hydrogen or a hydrocarbyl or
hydrocarbyloxy group having from one to about 10, preferably one to
about 4, carbon atoms, a halogen atom, preferably chlorine, bromine
or fluorine, a nitro group, a nitrile group or a --CO--R.sup.2
group; E is a 2
[0009] group; each R.sup.1 is independently hydrogen or a
hydrocarbyl group having from one to about 10, preferably one to
about 6, carbon atoms; X is a 3
[0010] group, each R.sup.2 is independently hydrogen or a
hydrocarbyl group having from one to about 10, preferably one to
about 2, carbon atoms; R.sup.3 is a hydrocarbyl group having from
one to about 10, preferably one to about 2, carbon atoms; n has a
value of from one to about 10, preferably one to about 2.
[0011] A further aspect of the present invention pertains to
advanced epoxy resins prepared using (A) one or more
hydroxyaliphatic epoxy resins, optionally, (B) one or more epoxy
resins, and (C) one or more compounds having an average of more
than one hydrogen atom per molecule which is reactive with an
epoxide group.
[0012] Another aspect of the present invention pertains to curable
(thermosettable) compositions comprising (A) one or more
hydroxyaliphatic epoxy resins, advanced hydroxyaliphatic epoxy
resins, or a mixture thereof; optionally, (B) one or more epoxy
resins; and (C) a curing amount of one or more curing agents and/or
catalysts therefor.
[0013] A further aspect of the present invention pertains to
products resulting from curing the aforementioned curable
compositions.
[0014] Another aspect of the present invention pertains to curable
(thermosettable) compositions comprising (A) one or more
hydroxyaliphatic vinyl ester resins, optionally, (B) one or more
vinyl ester resins, optionally, (C) one or more polymerizable
ethylenically unsaturated monomers, (D) a curing amount of one or
more free radical forming catalysts, and, optionally, (E) one or
more curing accelerators.
[0015] A further aspect of the present invention pertains to
products resulting from curing the aforementioned curable
compositions.
[0016] A further aspect of the present invention pertains to
totally or partially vinylized epoxy and vinyl ester resins
represented by the following Formula II (this formula shows total
vinylization for the sake of simplicity). 4
[0017] wherein n, E, R, R.sup.1, R.sup.2, R.sup.3 are as
hereinbefore defined, X.sup.1 is a 5
[0018] group, E.sup.1 is a moiety containing a polymerizable
ethylenically unsaturated group wherein the oxygen atom attached to
E.sup.1 is part of an ester or a urethane linkage.
[0019] Another aspect of the present invention pertains to curable
(thermosettable) compositions comprising (A) one or more totally or
partially vinylized hydroxyaliphatic epoxy resins, optionally, (B)
one or more epoxy resins, (C) a curing amount of one or more curing
agents and/or catalysts therefor, (D) a curing amount of one or
more free radical forming catalysts, and, optionally, (E) one or
more curing accelerators.
[0020] A further aspect of the present invention pertains to
products resulting from curing the aforementioned curable
compositions.
[0021] Another aspect of the present invention pertains to curable
(thermosettable) compositions comprising (A) one or more totally or
partially vinylized hydroxyaliphatic vinyl ester resins,
optionally, (B) one or more vinyl ester resins, optionally, (C) one
or more polymerizable ethylenically unsaturated monomers, (D) a
curing amount of one or more free radical forming catalysts, and,
optionally, (E) one or more curing accelerators.
[0022] A further aspect of the present invention pertains to
products resulting from curing the aforementioned curable
compositions.
[0023] A further aspect of the present invention pertains to
tetrafunctional epoxy and vinyl ester resins represented by the
following Formulas III and IV 6
[0024] wherein n, E, R, R.sup.1, R.sup.2, R.sup.3 are as
hereinbefore defined, E.sup.3 is a direct bond or a hydrocarbyl
group having from one to about 30, preferably one to about 12,
carbon atoms; E is a hydrocarbyl group having from about 4 to about
35, preferably six to about 15 carbon atoms; X.sup.2 is a 7
[0025] group.
[0026] Another aspect of the present invention pertains to curable
(thermosettable) compositions comprising (A) one or more
tetrafunctional epoxy resins, optionally, (B) one or more epoxy
resins; and (C) a curing amount of one or more curing agents and/or
catalysts therefor.
[0027] A further aspect of the present invention pertains to
products resulting from curing the aforementioned curable
compositions.
[0028] Another aspect of the present invention pertains to curable
(thermosettable) compositions comprising (A) one or tetrafunctional
vinyl ester, optionally, (B) one or more vinyl ester resins,
optionally, (C) one or more polymerizable ethylenically unsaturated
monomers, (D) a curing amount of one or more free radical forming
catalysts, and, optionally, (E) one or more curing
accelerators.
[0029] A further aspect of the present invention pertains to
products resulting from curing the aforementioned curable
compositions.
[0030] A further aspect of the present invention pertains to
polymer modified epoxy and vinyl ester resins prepared via
copolymerization of a partially or totally vinylized
monohydroxyaliphatic epoxy resin of Formula II and one or more
polymerizable ethylenically unsaturated monomers.
[0031] Another aspect of the present invention pertains to curable
(thermosettable) compositions comprising (A) one or more polymer
modified epoxy resins, optionally, (B) one or more epoxy resins;
and (C) a curing amount of one or more curing agents and/or
catalysts therefor.
[0032] A further aspect of the present invention pertains to
products resulting from curing the aforementioned curable
compositions.
[0033] Another aspect of the present invention pertains to curable
(thermosettable) compositions comprising (A) one or more polymer
modified vinyl ester resins, optionally, (B) one or more vinyl
ester resins, optionally, (C) one or more polymerizable
ethylenically unsaturated monomers, (D) a curing amount of one or
more free radical forming catalysts, and, optionally, (E) one or
more curing accelerators.
[0034] A further aspect of the present invention pertains to
products resulting from curing the aforementioned curable
compositions.
DETAILED DESCRIPTION OF THE INVENTION
[0035] Definitions
[0036] The term "hydrocarbyl" as employed herein means any
aliphatic, cycloaliphatic, aromatic, aryl substituted aliphatic or
cycloaliphatic or aliphatic or cycloaliphatic substituted aromatic
groups. The aliphatic or cycloaliphatic groups can be saturated or
unsaturated. The aliphatic groups can be straight chained or
branched. Likewise, the term "hydrocarbyloxy" means a hydrocarbyl
group having an oxygen linkage between it and the carbon atom to
which it is attached.
[0037] The term "hydroxyaliphatic" means an aliphatic group, such
as an alkylene or alkenylene, which is substituted with one or more
hydroxy groups and is divalent, that is, it has two attachment
points as shown for X in Formula I and X.sup.1 in Formula II.
[0038] The terms "curable" and "thermosettable" are used
synonymously throughout and mean that the composition is capable of
being subjected to conditions which will render the composition to
a cured or thermoset state or condition.
[0039] The terms "cured" and "thermoset" are used synonymously
throughout. The term "thermoset" is defined by L. R. Whittington in
Whittington's Dictionary of Plastics (1968) on page 239: "Resin or
plastics compounds which in their final state as finished articles
are substantially infusible and insoluble. Thermosetting resins are
often liquid at some stage in their manufacture or processing,
which are cured by heat, catalysis, or some other chemical means.
After being fully cured, thermosets cannot be resoftened by heat.
Some plastics which are normally thermoplastic can be made
thermosetting by means of crosslinking with other materials."
[0040] Hydroxyaliphatic Epoxy Resins and Advanced Epoxy Resins
[0041] The hydroxyaliphatic epoxy resins of the present invention
can be prepared using known methods. Thus, hydroxyaliphatic epoxy
resins are generally prepared by reacting a
bis(hydroxyphenyl)hydroxyaliphatic compound with an epihalohydrin
in the presence of a suitable catalyst and in the presence or
absence of a suitable solvent at a temperature suitably from about
0.degree. C. to about 100.degree. C., more suitably from about
20.degree. C. to about 80.degree. C., most suitably from about
20.degree. C. to about 65.degree. C.; at pressures suitably from
about 30 mm Hg vacuum to about 100 psia, more suitably from about
30 Hg vacuum to about 50 psia, most suitably from about 60 mm Hg
vacuum to about atmospheric pressure; for a time sufficient to
complete the reaction, usually from about 0.5 to about 24, more
usually from about 1 to about 12, most usually from about 1 to
about 8 hours; and using from about 1.5:1 to 100:1, preferably from
about 2:1 to about 50:1, most preferably from about 3:1 to about
20:1 moles of epihalohydrin per phenolic hydroxy group. This
initial reaction, unless the catalyst is an alkali metal or
alkaline earth metal hydroxide employed in stoichiometric
quantities, produces a halohydrin intermediate which is then
reacted with a basic acting substance to convert the vicinal
halohydrin groups to epoxide groups. The resultant product is a
glycidyl ether compound, wherein the aliphatic hydroxy group
remains essentially unchanged. Details concerning preparation of
epoxy resins are given in U.S. Pat. No. 5,736,620; Handbook of
Epoxy Resins by Lee and Neville, McGraw-Hill (1967); and Journal of
Applied Polymer Science, volume 23, pages 1355-1372 (1972) all of
which are incorporated herein by reference in their entirety.
[0042] The hydroxyaliphatic epoxy resin's chain may be linearly
extended via an advancement reaction. Such advancement may be
desirable to increase molecular weight. The increase in molecular
weight is useful to vary the mechanical properties and to control
the degree of crosslinking.
[0043] Advancement reaction of a hydroxyaliphatic epoxy resin can
be performed using known methods which usually includes combining
one or more suitable compounds having an average of more than one
hydrogen atom per molecule which is reactive with an epoxide group,
including, for example, dihydroxy aromatic, dithiol, disulfonamide
or dicarboxylic acid compounds or compounds containing one primary
amine or amide group, two secondary amine groups, one secondary
amine group and one phenolic hydroxy group, one secondary amine
group and one carboxylic acid group, or one phenolic hydroxy group
and one carboxylic acid group and the hydroxyaliphatic epoxy resin
in the presence or absence of a suitable solvent with the
application of heat and mixing to effect the advancement reaction.
The compound having more than one hydrogen atom per molecule which
is reactive with an epoxide group and the hydroxyaliphatic epoxy
resin are reacted in amounts which provide suitably from about
0.01:1 to about 0.95:1, more suitably from about 0.05:1 to about
0.8:1, most suitably from about 0.10:1 to about 0.5:1 reactive
hydrogen atoms per epoxide group. The advancement reaction can be
conducted at atmospheric, superatmospheric or subatmospheric
pressures at temperatures of from about 20.degree. C. to about
260.degree. C., more suitably from about 80.degree. C. to about
240.degree. C., most suitably from about 100.degree. C. to about
200.degree. C. The time required to complete the advancement
reaction depends upon the temperature employed, the structure of
the active hydrogen-containing compound employed, the structure of
the hydroxyaliphatic epoxy resin employed and other such variables.
Higher temperatures require shorter periods of time whereas lower
temperatures require longer periods of time. Generally, times of
from about 5 minutes to about 24 hours, more suitably from about 30
minutes to about 8 hours, most suitably from about 30 minutes to
about 4 hours are employed. A catalyst, including, for example,
phosphines, quaternary ammonium compounds, phosphonium compounds
and tertiary amines, is frequently added to facilitate the
advancement reaction and is usually employed in quantities of from
about 0.01 to about 3, preferably from about 0.03 to about 1.5,
most preferably from about 0.05 to about 1.5 percent by weight
based upon the weight of the hydroxyaliphatic epoxy resin. Details
concerning advancement reaction are given in the aforementioned
U.S. Pat. No. 5,736,620 and Handbook of Epoxy Resins.
[0044] The curable compositions of the present invention are
prepared by mixing together one or more of the hydroxyaliphatic
epoxy resins, advanced hydroxyaliphatic epoxy resins, mixtures
thereof, or mixtures with epoxy resins and one or more curing
agents and/or curing catalysts therefor in amounts which will
effectively cure the mixture, with the understanding that these
amounts will depend upon the particular epoxy resin and curing
agent employed. Generally, suitable amounts of curing agents are
from about 0.80:1 to about 1.50:1, preferably from about 0.95:1 to
about 1.05:1 equivalents of hydrogen in the curing agent which is
reactive with an epoxide group per equivalent of epoxide group in
the hydroxyaliphatic epoxy resin at the conditions employed for
curing.
[0045] The curing of the curable compositions of the present
invention can be conducted at atmospheric, superatmospheric or
subatmospheric pressures at temperatures of from about 0.degree. C.
to about 300.degree. C., preferably from about 50.degree. C. to
about 200.degree. C., more preferably from about 80.degree. C. to
about 175.degree. C. The time required to complete curing depends
upon the temperature employed. Higher temperatures require shorter
periods of time whereas lower temperatures require longer periods
of time. Generally, however, times of from about one minute to
about 48 hours, preferably from about 15 minutes to about 8 hours,
more preferably from about 30 minutes to about 3 hours are
suitable. It is also operable to partially cure (B-stage) the
curable compositions of the present invention and then complete the
curing at a later time.
[0046] The curable mixtures of the present invention may be
prepared using the known conventional curing agents and/or
catalysts for curing epoxy resins, such as, for example, aliphatic,
cycloaliphatic, polycycloaliphatic or aromatic primary monoamines;
aliphatic, cycloaliphatic, polycycloaliphatic or aromatic primary
and secondary polyamines; carboxylic acids and anhydrides thereof;
aromatic hydroxyl containing compounds; imidazoles; guanidines;
urea-aldehyde resins; melamine-aldehyde resins; alkoxylated
urea-aldehyde resins; alkoxylated melamine-aldehyde resins;
amidoamines; epoxy resin adducts; combinations thereof and the
like. Particularly suitable curing agents include, for example,
methylenedianiline, 4,4'-diaminostilbene,
4,4'-diamino-.alpha.-methylstilbene, 4,4'-diaminobenzanilide,
dicyandiamide, ethylenediamine, diethylenetriamine,
triethylenetetramine, tetraethylenepentamine, urea-formaldehyde
resins, melamine-formaldehyde resins, methylolated
urea-formaldehyde resins, methylolated melamine-formaldehyde
resins, phenol-formaldehyde novolac resins, cresol-formaldehyde
novolac resins, sulfanilamide, diaminodiphenylsulfone,
diethyltoluenediamine, t-butyltoluenediamine,
bis-4-aminocyclohexylamine, isophoronediamine, diaminocyclohexane,
hexamethylenediamine, piperazine, aminoethylpiperazine,
2,5-dimethyl-2,5-hexanediamine, 1,12-dodecanediamine,
tris-3-aminopropylamine, combinations thereof and the like.
[0047] Particularly suitable curing catalysts include boron
trifluoride, boron trifluoride etherate, aluminum chloride, ferric
chloride, zinc chloride, silicon tetrachloride, stannic chloride,
titanium tetrachloride, antimony trichloride, boron trifluoride
monoethanolamine complex, boron trifluoride triethanolamine
complex, boron trifluoride piperidine complex, pyridine-borane
complex, diethanolamine borate, zinc fluoroborate, mixtures thereof
and the like.
[0048] The curing catalysts are employed in amounts which will
effectively cure the curable composition, however, these amounts
will depend upon the particular hydroxyaliphatic epoxy resin
employed and curing agent, if used. Generally suitable amounts
include, for example, 0.001 to about 2 percent by weight of the
total hydroxyaliphatic epoxy resin used. It is frequently of
benefit to employ one or more of the curing catalysts in the curing
of the curable compositions of the present invention. This is
generally done to accelerate or otherwise modify the curing
behavior obtained when a curing catalyst is not used.
[0049] Phenoxy Resins
[0050] Phenoxy resins of the present invention are prepared via
advancement reaction of at least one hydroxyaliphatic epoxy resin
and at least one compound having more than one hydrogen atom per
molecule which is reactive with an epoxide group, wherein said
difunctional monomer and said diglycidyl ether are reacted in
amounts which provide suitably from about 0.96:1 to about 1.05:1,
more suitably from about 0.98:1 to about 1.03:1, most suitably
about 1:1 reactive hydrogen atoms per epoxide group. The resulting
phenoxy resin is a substantially thermoplastic, resinous product
which contains little, if any, residual curable epoxide
functionality and may even contain an active hydrogen
functionality, depending on which component, if any, is employed in
excess, the hydroxyaliphatic epoxy resin or the epoxide reactive
hydrogen-containing compound. Details concerning advancement
reaction to produce phenoxy resins are given in the aforementioned
U.S. Pat. No. 5,736,620 and in U.S. Pat. No. 5,686,551 which is
incorporated herein by reference in its entirety. Additionally,
residual epoxide groups, if present in the phenoxy resin, may be
"end-capped" via reaction with monofunctional reactants (compounds
having one hydrogen atom which is reactive with an epoxide group)
such as carboxylic acids, thiols, monofunctional sulfonamides,
secondary amines, and monohydric phenols. Preferred monofunctional
reactants include acetic acid, benzoic acid, thiophenol,
N-methylbenzensulfonamide, diethanolamine,
N-(2-hydroxyethyl)piperazine, N-methylpiperazine, phenol, and
tert-butylphenol. Reaction conditions for conducting said
end-capping reaction are identical to those previously delineated
herein for the advancement reaction. In fact, end-capping reaction
with the monofunctional reactant may be performed as an integral
part of the advancement reaction, for example, by adding said
monofunctional compound at or near the completion of the
advancement reaction. It is frequently advantageous to end-cap the
phenoxy resin of the present invention to remove residual epoxide
groups which may react during processing to form crosslinks which
are deleterious to thermoplastic character.
[0051] Hydroxyaliphatic Vinyl Ester Resins
[0052] The hydroxyaliphatic vinyl ester resins of the present
invention can be prepared using known methods. Thus, the
hydroxyaliphatic epoxy resins, advanced hydroxyaliphatic epoxy
resins, mixtures thereof, or mixtures with epoxy resins are
generally reacted with one or more suitable monounsaturated
monocarboxylic acids, namely acrylic acid or methacrylic acid.
Other less preferred, but operable monounsaturated monocarboxylic
acids include cyanoacrylic acid, crotonic acid,
.alpha.-phenylacrylic acid, methoxyacrylic acid, monomethyl ester
of maleic acid, monomethyl ester of fumaric acid, mixtures thereof
and the like. Methacrylic acid is the most preferred
monounsaturated monocarboxylic acid. A mole ratio of 0.9:1.1
monounsaturated monocarboxylic acid per epoxide group is preferred,
with a mole ratio of 0.95:1.00 being most preferred. The reaction
between the carboxylic acid group and the epoxide group is
typically performed in the presence of one or more catalysts.
Chromium trichloride and tris(dimethylaminoethyl)pheno- l are most
preferred as the catalysts. A quantity of from about 0.01 to about
2 percent by weight has been found to be a suitable quantity of
catalyst with concentrations of 0.1 to 0.3 weight percent of the
total reactants used being most preferred. A suitable process
inhibitor is typically used in the reaction between the epoxide
group and the carboxylic acid group to prevent gelation.
Hydroquinone activated with air is a most preferred inhibitor at
concentrations of from about 100 ppm to about 500 ppm based on the
total weight of the reactants used. The reaction to produce the
hydroxyaliphatic vinyl ester compositions of the present invention
is optionally conducted in one or more organic solvents inert to
the other reactants and the vinyl ester product. Typical of the
inert organic solvents are the aliphatic ketones, such as
methylisobutyl ketone; the chlorinated aliphatics, such as
perchloroethylene; and the aromatic hydrocarbons, such as toluene.
The reaction to produce the hydroxyaliphatic vinyl ester resin is
usually conducted at a temperature of from about 50.degree. C. to
about 125.degree. C., preferably from about 80.degree. C. to about
120.degree. C. for from about 90 minutes to 720 minutes, preferably
from about 120 minutes to about 420 minutes. While reaction times
and temperatures can vary substantially, the most preferred
hydroxyaliphatic vinyl esters are produced by reacting to a
specific conversion, typically 1.5 to 0.25 percent carboxylic
acid.
[0053] The vinyl ester is typically combined with a reactive
diluent, a copolymerizable ethylenically unsaturated monomer, to
alter the viscosity of the mixture, to vary properties of the cured
resin, or for other known reasons. Suitable ethylenically
unsaturated monomers which can be employed herein can be selected
from the many known classes of polymerizable monomers. Suitable
such monomers include, for example, the vinyl aromatic compounds,
such as styrene, .alpha.-methylstyrene, vinyl toluenes, halogenated
styrenes, t-butylstyrenes, vinyl naphthalenes, and divinylbenzenes.
Other suitable monomers include the methyl, ethyl, isopropyl,
octyl, etc. esters of acrylic and methacrylic acid, hydroxyethyl
acrylate and methacrylate, hydroxypropyl acrylate and methacrylate;
acidic monomers, such as acrylic acid, methacrylic acid and
crotonic acid; amide monomers, such as, acrylamide and
N-alkylacrylamides; allyl monomers, such as diallylphthalate,
triallylisocyanurate, diallylmaleate and dimethallyl fumarate;
vinyl acetate; mixtures thereof and the like. The reactive diluent
present in the copolymerizable mixtures of the present invention
can consist of 1 to 99, preferably from about 20 to about 80, most
preferably 30 to about 70 percent by weight of the combined weight
of said reactive diluent and vinyl ester. If an inert organic
solvent is used in the preparation of the vinyl ester, it is
preferably removed, for example by distillation under vacuum, prior
to the addition of one or more ethylenically unsaturated
monomers.
[0054] The vinyl ester and the blend of the vinyl ester with an
ethylenically unsaturated monomer are curable, typically by mixing
in a free radical forming catalyst and applying heat and/or
pressure and/or adding an accelerator. Catalysts that can be used
for the curing include the peroxide catalysts, such as benzoyl
peroxide, lauroyl peroxide, tert-butylhydroperoxide, methyl ethyl
ketone peroxide, tert-butylperoxybenzoate, potassium persulfate,
mixtures thereof and the like. The amount of catalyst added will
vary from 0.1 to about 2 percent by weight, preferably from about
0.75 to 1.5 percent by weight. Temperatures employed can vary over
a considerable range but are usually in the range of 20.degree. C.
to 250.degree. C. Additionally, more rapid curing of the vinyl
ester compositions can be accomplished by the addition of one or
more accelerators, such as lead or cobalt naphthenate,
N,N,-dimethylaniline, mixtures thereof and the like, usually in
concentrations ranging from about 0.01 to about 2 percent by
weight, preferably 0.05 to 0.5 percent by weight. Details
concerning preparation of vinyl ester resins are given in U.S. Pat.
Nos. 3,367,992; 3,066,112; 3,179,623; 3,301,743; 3,256,226;
3,892,819; 5,164,464 all of which are incorporated herein by
reference in their entirety.
[0055] Vinylized Epoxy and Vinyl Ester Resins Derived from
Hydroxyaliphatic Epoxy Resins
[0056] Vinylized epoxy and vinyl ester resins are prepared via
reaction of one or more hydroxyaliphatic epoxy resins with one or
more compounds possessing a group reactive with the hydroxy
group(s) in said hydroxyaliphatic epoxy resin and a single
polymerizable ethylenically unsaturated group. It is understood, as
a specific embodiment of the present invention, that all or only a
part of said hydroxy group(s) may be reacted (vinylized) to a
polymerizable ethylenic unsaturated group. The resulting product is
an epoxy resin containing polymerizable ethylenic unsaturation,
wherein all or only a part of the hydroxy group(s) have been
converted to groups containing polymerizable ethylenic
unsaturation. The vinylized vinyl ester resins of the present
invention are prepared using the partially or totally vinylized
epoxy resins and methods previously delineated herein for the
preparation of vinyl ester resins.
[0057] Suitable compounds which are reacted with the
hydroxyaliphatic epoxy resin to provide the vinylized epoxy resin
include most any compound possessing a group reactive with the
hydroxy group in said hydroxyaliphatic epoxy resin and a
polymerizable ethylenically unsaturated group. Representative of
said compounds are the ethylenically unsaturated carboxylic acid
halides, such as, for example, acryloyl chloride, methacryloyl
bromide, methacryloyl chloride; the monoesterified
.alpha.,.beta.-unsaturated dicarboxylic acid halides, such as, for
example, fumaric acid chloride methyl monoester, itaconic acid
chloride ethyl monoester; and the ethylenically unsaturated
monoisocyanates, such as, for example, p-isopropenyl
phenylisocyanate, isocyanatoethylmethacryl- ate. Most preferred as
the compound for the vinylization of the hydroxyaliphatic epoxy
resin is acryloyl chloride or methacryloyl chloride. These
compounds containing a group reactive with the hydroxy group in the
hydroxyaliphatic epoxy resin and a polymerizable ethylenically
unsaturated group are employed in amounts which result in the
desired degree of vinylization. Thus, using less than the
stoichiometric amount of the compound containing a group reactive
with the hydroxy group in the hydroxyaliphatic epoxy resin and a
polymerizable ethylenically group per hydroxy group contained in
the hydroxyaliphatic epoxy resin results in partial vinylization.
Likewise, stoichiometric (or slight stoichiometric excess) use of
these reactants results in total vinylization of the
hydroxyaliphatic epoxy resin. The vinylization reaction is usually
conducted at temperatures of from about -20.degree. C. to about
80.degree. C., preferably from about 0.degree. C. to about
50.degree. C., more preferably from about 10.degree. C. to about
30.degree. C. A suitable basic acting substance is employed to
facilitate reaction of an ethylenically unsaturated carboxylic acid
halide or monoesterified .alpha.,.beta.-unsaturated dicarboxylic
acid halide with the hydroxy group of the hydroxyaliphatic epoxy
resin. Said basic acting substance additionally serves to scavenge
hydrogen halide generated during the vinylization reaction, thus
preventing undesirable reaction with epoxide groups. Suitable basic
acting substances include the alkali metal or alkaline earth metal
hydroxides, carbonates and bicarbonates, trialkyl monoamines, or
mixtures thereof. Particularly suitable such compounds include
sodium carbonate, potassium carbonate, sodium bicarbonate,
potassium bicarbonate, magnesium carbonate, calcium carbonate,
triethylamine, tri-n-butylamine, tri-tert-butylamine, mixtures
thereof and the like. Care should be taken to utilize only those
basic acting substances which are inert to reaction with any of the
reactants employed in the vinylization reaction or the product
formed therefrom. The vinylization reaction is advantageously
conducted in the presence of one or more solvents. Suitable such
solvents include aliphatic and aromatic hydrocarbons, halogenated
aliphatic hydrocarbons, aliphatic ethers, cyclic ethers, ketones,
esters, amides, sulfoxides, combinations thereof and the like.
Particularly suitable solvents include pentane, hexane, octane,
toluene, methyl ethyl ketone, methylisobutyl ketone,
dimethylformamide, dimethylsulfoxide, diethyl ether, methyl
acetate, ethyl acetate, tetrahydrofuran, 1,4-dioxane, methylene
chloride, chloroform, ethylene dichloride, methyl chloroform,
ethylene glycol dimethyl ether, combinations thereof and the like.
The solvent may be removed at the completion of the reaction using
conventional means, such as, for example, vacuum distillation. Care
should be taken to utilize only those solvents which are inert to
reaction with any of the reactants employed in the vinylization
reaction or the product formed therefrom.
[0058] Tetrafunctional Epoxy and Vinyl Ester Resins Derived from
Hydroxyaliphatic Epoxy Resins
[0059] Tetrafunctional epoxy and vinyl ester resins are prepared
via coupling reaction of one or more monohydroxyaliphatic epoxy
resins with one or more compounds possessing two groups reactive
with the hydroxy group in said hydroxyaliphatic epoxy resin. The
resulting product is a tetrafunctional epoxy resin wherein a pair
of the hydroxyaliphatic epoxy resin molecules have been linked
together through either ester or urethane linkages formed via
reaction of the hydroxy group. The tetrafunctional vinyl ester
resins of the present invention are prepared using the
tetrafunctional epoxy resins and methods previously delineated
herein for the preparation of vinyl ester resins.
[0060] Suitable compounds which are reacted with the
hydroxyaliphatic epoxy resin to provide the tetrafunctional epoxy
resin include most any compound possessing two groups reactive with
the hydroxy group in said hydroxyaliphatic epoxy resin.
Representative of said compounds are the dicarboxylic acid halides,
such as, for example, oxalyl chloride, oxalyl bromide, adipoyl
chloride, suberoyl chloride, sebacoyl chloride, dodecanedioyl
dichloride, cyclohexanediacetic acid chloride,
trans-1,4-cyclohexanedicarboxylic acid chloride,
dicyclopentadienedicarbo- xylic acid chloride, terephthaloyl
chloride, isophthaloyl dichloride, 1,4-phenylenediacetic acid
chloride, 1,2-phenylenediacetic acid chloride, mixtures thereof and
the like. These dicarboxylic acid halides provide the tetraepoxy
resin compositions of Formula III. Additional representatives of
said compounds are the diisocyanates, such as, for example,
1,6-diisocyanatohexane, 1,12-diisocyanatododecane,
1,4-diisocyanatocyclohexane, dicyclopentadiene diisocyanate,
toluene-diisocyanate, diphenylmethane diisocyanate, biphenyl
diisocyanate, mixtures thereof and the like. These diisocyanates
provide the tetraepoxy resin compounds of Formula IV. In the
reaction to produce the tetraepoxy resin compositions of the
present invention, both the dicarboxylic acid halides and the
diisocyanates are employed in essentially stoichiometric amounts,
with respect to the hydroxyl group contained in the
hydroxyaliphatic epoxy resin (1:1 isocyanate group:hydroxy group or
acid halide group). The coupling reaction is usually conducted at
temperatures of from about -20.degree. C. to about 80.degree. C.,
preferably from about 0.degree. C. to about 50.degree. C., more
preferably from about 10.degree. C. to about 30.degree. C. A
suitable basic acting substance is employed to facilitate reaction
of a dicarboxylic acid halide with the hydroxy group of the
hydroxyaliphatic epoxy resin. Said basic acting substance
additionally serves to scavenge hydrogen halide generated during
the vinylization reaction, thus preventing undesirable reaction
with epoxide groups. Suitable basic acting substances include the
alkali metal or alkaline earth metal hydroxides, carbonates and
bicarbonates and the trialkyl monoamines. Particularly suitable
such compounds include sodium carbonate, potassium carbonate,
sodium bicarbonate, potassium bicarbonate, magnesium carbonate,
calcium carbonate, triethylamine, tri-n-butylamine,
tri-tert-butylamine, mixtures thereof and the like. Care should be
taken to utilize only those basic acting substances which are inert
to reaction with any of the reactants employed in the vinylization
reaction or the product formed therefrom. The coupling reaction is
advantageously conducted in the presence of one or more solvents.
Suitable such solvents include aliphatic and aromatic hydrocarbons,
halogenated aliphatic hydrocarbons, aliphatic ethers, cyclic
ethers, ketones, esters, amides, sulfoxides, combinations thereof
and the like. Particularly suitable solvents include pentane,
hexane, octane, toluene, methyl ethyl ketone, methylisobutyl
ketone, dimethylformamide, dimethylsulfoxide, diethyl ether, methyl
acetate, ethyl acetate, tetrahydrofuran, 1,4-dioxane, methylene
chloride, chloroform, ethylene dichloride, methyl chloroform,
ethylene glycol dimethyl ether, combinations thereof and the like.
The solvent may be removed at the completion of the reaction using
conventional means, such as, for example, vacuum distillation. Care
should be taken to utilize only those solvents which are inert to
reaction with any of the reactants employed in the coupling
reaction or the product formed therefrom.
[0061] Polymer Modified Epoxy and Vinyl Ester Resins Derived from
Hydroxyaliphatic Epoxy Resins
[0062] The polymer modified epoxy resins of the present invention
are prepared via copolymerization of (A) one or more partially or
totally vinylized epoxy resins derived from the vinylization
reaction of one or more monohydroxyaliphatic epoxy resins and (B)
one or more polymerizable ethylenically unsaturated monomers. The
copolymerization is effected in the usual fashion, that is, by
application of heat and/or pressure, typically in the presence of
one or more free radical-forming catalysts. One or more inert
solvents may optionally be used in the copolymerization reaction.
(The term "inert" means that little, if any, reaction between the
solvent and reactants or copolymer product occurs.). Suitable
polymerizable ethylenically unsaturated monomers include those
previously delineated herein for the preparation of vinyl ester
resins. When two or more polymerizable ethylenically unsaturated
monomers are used in the copolymerization with the vinylized epoxy
resin, they can be preblended and then copolymerized with the
vinylized epoxy resin. Alternately, they can be added in separate
additions such that blocks from each respective monomer are
predominately produced. The additions are made in aliquots or
continuously. These monomers or monomer mixtures are employed in an
amount which provides from about 0.1 to about 150, preferably from
about 1 to about 80, more preferably from about 2 to about 40
percent by weight based on the combined weight of such monomers and
the vinylized epoxy resin. Suitable free radical-forming catalysts
are the well known organic peroxides and hydroperoxides, and
include, for example, benzoyl peroxide, di-tert-butylperoxide,
tert-butylperoxybenzoate, tert-butylhydroperoxide; the azo and
diazo compounds, such as, for example, azobis(isobutyronitrile);
and mixtures of said free radical-forming catalysts. Said catalysts
are typically used in amounts of from about 0.01 to about 5 percent
by weight of the total reactants used. Reaction temperatures of
from about 20.degree. C. to about 200.degree. C. are used for the
copolymerization reaction, with temperatures of from about
30.degree. C. to about 120.degree. C. being preferred. Reaction
times of from about 15 minutes to about 8 hours are used for the
copolymerization, with times of from about 30 minutes to about 4
hours being preferred. The solvent used, if any, may be removed
before further use of the copolymerization product, using
conventional methods such as, for example, vacuum distillation. The
copolymerization reaction may be carried out in the presence of
from about 0.01 to about 2 percent by weight of one or more chain
transfer agents, although this is not generally preferred.
Representative chain transfer agents include the alkyl mercaptans
such as butyl mercaptan and stearyl mercaptan; the disulfides and
halogenated compounds, especially those containing bromine.
[0063] The product resulting from the copolymerization is a polymer
modified epoxy resin, a portion or all of which contains chemically
bonded (grafted) polymeric chains derived from the copolymerization
of one or more polymerizable ethylenically monomers with the vinyl
groups present in the vinylized epoxy resin. Said product can also
contain homooligomer (cooligomer) and/or homopolymer (copolymer) of
the ethylenically unsaturated monomers. Likewise, said product can
also contain homooligomer (cooligomer) and/or homopolymer
(copolymer) of the vinylized epoxy resin. Methodology for radical
and ionic chain polymerizations are delineated by G. G. Odian in
Principles of Polymerization published by John Wiley and Sons, New
York (1981) on pages 179-507 which are incorporated herein by
reference. The polymer modified vinyl ester resins of the present
invention are prepared using the polymer modified epoxy resins and
methods previously delineated herein for the preparation of vinyl
ester resins.
[0064] Conventional Epoxy Resins and Vinyl Ester Resins
[0065] One or more epoxy resins may be mixed with the
hydroxyaliphatic functional epoxy resins, the totally or partially
vinylized hydroxyaliphatic epoxy resins, the tetrafunctional epoxy
resins or the polymer modified epoxy resins to prepare curable
mixtures of the present invention. The epoxy resins which can be
employed to prepare the curable compositions of the present
invention include essentially any epoxy-containing compound which
contains an average of more than one vicinal epoxide group per
molecule. The epoxide groups can be attached to any oxygen, sulfur
or nitrogen atom or the single bonded oxygen atom attached to the
carbon atom of a --CO--O-- group in which said oxygen, sulfur or
nitrogen atom or the carbon atom of the --CO--O-- group is attached
to an aliphatic, cycloaliphatic, polycycloaliphatic or aromatic
hydrocarbon group which hydrocarbon group can be substituted with
any inert substituent including, but not limited to, halogen atoms,
preferably fluorine, bromine or chlorine, nitro groups, and the
like or such groups can be attached to the terminal carbon atoms of
a compound containing an average of more than one
--(O--CHR.sup.a--CHR.sup.a).sub.t-- - group where each R.sup.a is
independently hydrogen or an alkyl or haloalkyl group, containing
from one to about 2 carbon atoms, with the proviso that only one
R.sup.a group can be a haloalkyl group, and t has a value from one
to about 100, preferably from one to about 20, more preferably from
one to about 10, most preferably from one to about 5.
[0066] Said epoxy resins include, for example, the diglycidyl
ethers of: resorcinol, hydroquinone, 4,4'-isopropylidenediphenol
(bisphenol A), 4,4'-dihydroxydiphenylmethane,
4,4'-dihydroxybenzophenone,
3,3'5,5'-tetrabromo-4,4'-isopropylidenediphenol, 4,4'-thiodiphenol,
4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl oxide,
1,1-bis(4-hydroxyphenyl)-1-phenylethane,
3,3',5,5'-tetrachloro-4,4'-isopr- opylidenediphenol A,
3,3'-dimethoxy-4,4'-isopropylidenediphenol,
4,4'-dihydroxy-.alpha.-methylstilbene, 4,4'-dihydroxybenzanilide,
4,4'-dihydroxyazoxybenzene, 4,4'-dihydroxybiphenyl,
4,4'-dihydroxydiphenylazomethine, 4,4'-dihydroxydiphenylacetylene,
4,4'-dihydroxystilbene, 4,4'-dihydroxy-.alpha.-cyanostilbene,
4,4'-dihydroxyazobenzene, 4,4'-dihydroxyazoxybenzene,
4,4'-dihydroxychalcone, 4-hydroxyphenyl-4-hydroxybenzoate,
dipropylene glycol, poly(propylene glycol), thiodiglycol; the
triglycidyl ether of tris(hydroxyphenyl)methane; the polyglycidyl
ethers of a phenol or alkyl or halogen substituted phenol-aldehyde
acid catalyzed condensation product (novolac resins); the
tetraglycidyl amines of: 4,4'-diaminodiphenylmethane,
4,4'-diaminostilbene, N,N'-dimethyl-4,4'-diaminostilbene,
4,4'-diaminobenzanilide, 4,4'-diaminobiphenyl,
4,4'-diamino-.alpha.-methylstilbene; the polyglycidyl ether of the
condensation product of a dicyclopentadiene or an oligomer thereof
and a phenol or alkyl or halogen substituted phenol; the
advancement reaction products of the aforesaid di and polyglycidyl
ethers with aromatic di and polyhydroxyl or carboxylic acid
containing compounds including, for example hydroquinone,
resorcinol, catechol, 2,4-dimethylresorcinol, 4-chlororesorcinol,
tetramethylhydroquinone, 4,4'-isopropylidenediphenol (bisphenol A),
4,4'-dihydroxydiphenylmethane, 4,4'-thiodiphenol,
4,4'-sulfonyldiphenol, 2,2'-sulfonyldiphenol,
4,4'-dihydroxydiphenyl oxide, 4,4'-dihydroxybenzophenone,
1,1-bis(4-hydroxyphenyl)-1-phenylethane,
4,4'-bis(4(4-hydroxyphenoxy)-phe- nylsulfone)diphenyl ether,
4,4'-dihydroxydiphenyl disulfide,
3,3',3,5'-tetrachloro-4,4'-isopropylidenediphenol,
3,3',3,5'-tetrabromo-4,4'-isopropylidenediphenol,
3,3'-dimethoxy-4,4'-iso- propylidenediphenol,
4,4'-dihydroxybiphenyl, 4,4'-dihydroxy-.alpha.-methyl- stilbene,
4,4'-dihydroxybenzanilide, bis(4-hydroxyphenyl)terephthalate,
N,N'-bis(4-hydroxyphenyl)terephthalamide,
bis(4'-hydroxybiphenyl)terephth- alate,
4,4'-dihydroxyphenylbenzoate,
bis(4'-hydroxyphenyl)-1,4-benzenediim- ine;
1,1'-bis(4-hydroxyphenyl)cyclohexane, phloroglucinol, pyrogallol,
2,2',5,5'-tetrahydroxydiphenyl sulfone, tris(hydroxyphenyl)methane,
dicyclopentadiene diphenol, tricyclopentadiene diphenol,
terephthalic acid, isophthalic acid, 4,4'-benzanilidedicarboxylic
acid, 4,4'-phenylbenzoatedicarboxylic acid,
4,4'-stilbenedicarboxylic acid, adipic acid; and any combination of
the aforementioned epoxy resins and the like.
[0067] One or more vinyl ester resins may be mixed with the
hydroxyaliphatic functional vinyl ester resins, the totally or
partially vinylized hydroxyaliphatic vinyl ester resins, the
tetrafunctional vinyl ester resins or the polymer modified vinyl
ester resins to prepare curable mixtures of the present invention.
Said vinyl ester resins are prepared using the aforementioned epoxy
resins and the methods previously delineated herein for the
preparation of hydroxyaliphatic vinyl ester resins.
[0068] Other Components
[0069] The curable blends containing one or more hydroxyaliphatic
functional epoxy or vinyl ester resins, totally or partially
vinylized hydroxyaliphatic epoxy or vinyl ester resins, the
tetrafunctional epoxy or vinyl ester resins or the polymer modified
epoxy or vinyl ester resins, can be blended with 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 or
any combination thereof and the like.
[0070] These additives are added in functionally equivalent
amounts, e.g., the pigments and/or dyes are added in quantities
which will provide the composition with the desired color; however,
they are suitably employed in amounts of from about zero to about
20, more suitably from about 0.5 to about 5, most suitably from
about 0.5 to about 3 percent by weight based upon the weight of the
total blended compositions.
[0071] Solvents or diluents which can be employed herein include,
for example, hydrocarbons, ketones, glycol ethers, aliphatic
ethers, cyclic ethers, esters, amides, combinations thereof and the
like. Particularly suitable solvents or diluents include, for
example, toluene, xylene, methyl ethyl ketone, methyl isobutyl
ketone, diethylene glycol methyl ether, dipropylene glycol methyl
ether, dimethylformamide, N-methylpyrrolidinone, tetrahydrofuran,
1,4-dioxane, propylene glycol methyl ether or any combination
thereof and the like.
[0072] The modifiers such as thickeners, flow modifiers and the
like can be suitably employed in amounts of from zero to about 10,
more suitably from about 0.5 to about 6, most suitably from about
0.5 to about 4 percent by weight based upon the weight of the total
composition.
[0073] Reinforcing materials which can be employed herein include
natural and synthetic fibers in the form of woven fabric, mats,
monofilament, multifilament, unidirectional fibers, rovings, random
fibers or filaments, inorganic fillers or whiskers, hollow spheres,
and the like. Suitable reinforcing materials include glass,
ceramics, nylon, rayon, cotton, aramid, graphite, polyalkylene
terephthalates, polyethylene, polypropylene, polyesters or any
combination thereof and the like.
[0074] Suitable fillers which can be employed herein include, for
example, inorganic oxides, ceramic microspheres, plastic
microspheres, glass microspheres, inorganic whiskers, calcium
carbonate or any combination thereof and the like.
[0075] The fillers can be employed in amounts suitably from about
zero to about 95, more suitably from about 10 to about 80, most
suitably from about 40 to about 60 percent by weight based upon the
weight of the total composition.
[0076] The curable blends of the present invention can be employed
in coating, casting, encapsulation, electronic or structural
laminate or composite, filament winding, molding, and the like
applications.
[0077] The following examples are illustrative of the present
invention, but are not to be construed as to limiting its scope in
any manner.
EXAMPLE 1
Copolymerization of Diglycidyl Ether of
1,2-bis(4-Hydroxyphenyl)-2-hydroxy- propane and Sulfanilamide.
[0078] A portion (26.9 milligrams, 0.000139 epoxide equivalent) of
distilled diglycidyl ether of
1,2-bis(4-hydroxyphenyl)-2-hydroxypropane having an epoxide,
equivalent weight (EEW) of 193.56 and sulfanilamide (6.0
milligrams, 0.000139 N--H equivalent) were combined in an aluminum
pan used for differential scanning calorimetry analysis. A second
sample was prepared by combining a portion (29.2 milligrams,
0.000151 epoxide equivalent) of the distilled diglycidyl ether of
1,2-bis(4-hydroxyphenyl)- -2-hydroxypropane and sulfanilamide (6.5
milligrams, 0.000151 N--H equivalent) in an aluminum pan used for
differential scanning calorimetry analysis. Differential scanning
calorimetry was completed by heating at a rate of 10.degree. C. per
minute under a stream of nitrogen flowing 35 cubic centimeters per
minute from 30.degree. C. to 300.degree. C. with the average values
of the two samples reported. This analysis revealed a cure exotherm
with an onset of 131.3.degree. C. and a maximum at 172.0.degree. C.
immediately followed by a second cure exotherm with an onset of
223.2.degree. C. and a maximum of 242.0.degree. C. The collective
enthalpy for the pair of merged exotherms was 189.5 joules per
gram. A second differential scanning calorimetry analysis was
completed using the aforementioned conditions and revealed a glass
transition temperature of 174.1.degree. C. The rigid, transparent,
light amber colored product recovered from the differential
scanning calorimetry was featureless (non-birefringent) when
observed by optical microscopy under crosspolarized light.
COMPARATIVE EXAMPLE 1
Copolymerization of Diglycidyl Ether of Bisphenol A
(4,4'-Isopropylidenediphenol) and Sulfanilamide
[0079] A portion (24.09 milligrams, 0.0001414 epoxide equivalent)
of a crystalline diglycidyl ether of bisphenol A having an epoxide
equivalent weight (EEW) of 170.4 and sulfanilamide (6.09
milligrams, 0.0001414 N--H equivalent) were combined in an agate
mortar and ground to a homogeneous powder. Portions (17.5 and 26.4
milligrams) of the curable blend were analyzed by differential
scanning calorimetry by heating at a rate of 10.degree. C. per
minute under a stream of nitrogen flowing 35 cubic centimeters per
minute from 30.degree. C. to 300.degree. C. with the average values
of the two samples reported. This analysis revealed a sharp melting
point endotherm with a minimum at 56.3.degree. C. and an enthalpy
of 58.8 joules per gram. This analysis additionally revealed a
broad cure exotherm with an onset of 154.0.degree. C. and a maximum
at 172.0.degree. C. immediately followed by a second cure exotherm
with an onset which could not be measured due to overlap with the
initial cure exotherm and a maximum of 242.2.degree. C. The
collective enthalpy for the pair of merged exotherms was of 184.8
joules per gram. A second differential scanning calorimetry
analysis was completed using the aforementioned conditions and
revealed a glass transition temperature of 181.6.degree. C. The
rigid, transparent, light amber colored product recovered from the
differential scanning calorimetry was featureless
(non-birefringent) when observed by optical microscopy under
crosspolarized light.
EXAMPLE 2
[0080] A. Isolation of
1,2-bis(4-Hydroxyphenyl)-2-hydroxypropane
[0081] A wet cake containing
1,2-bis(4-hydroxyphenyl)-2-hydroxypropane was recovered from the
reaction of 1,2-bis(4-hydroxyphenyl)-2-chloropropane and calcium
carbonate in aqueous media. High pressure liquid chromatographic
(HPLC) analysis demonstrated the presence of 97.7 area %
1,2-bis(4-hydroxyphenyl)-2-hydroxypropane, 1.78 area %
4,4'-dihydroxy-alpha-methylstilbene and 0.51 area % of an unknown
compound. A portion of the wet cake was placed in an aluminum dish,
then dried 20 hours at 25.degree. C.-27.degree. C. in a vacuum oven
to give a constant weight. The HPLC analysis of the recovered dry
product was essentially unchanged (97.7 area %
1,2-bis(4-hydroxyphenyl)-2-hydroxyprop- ane, 1.92 area %
4,4'-dihydroxy-alpha-methylstilbene and 0.40 area % of an unknown
compound).
[0082] B. Uncatalyzed Copolymerization of Diglycidyl Ether of
1,2-bis(4-Hydroxyphenyl)-2-hydroxpropane and
1,2-bis(4-Hydroxyphenyl)-2-h- ydroxypropane: In Situ Phenoxy Resin
Synthesis
[0083] A portion (17.3 milligrams, 0.000089 epoxide equivalent) of
distilled diglycidyl ether of
1,2-bis(4-hydroxyphenyl)-2-hydroxypropane having an epoxide
equivalent weight (EEW) of 193.56 and
1,2-bis(4-hydroxyphenyl)-2-hydroxypropane (10.92 milligrams,
0.000089 phenolic hydroxyl equivalent) were combined in an aluminum
pan used for differential scanning calorimetry analysis. A second
sample was prepared by combining a portion (18.7 milligrams,
0.000097 epoxide equivalent) of the distilled diglycidyl ether of
1,2-bis(4-hydroxyphenyl)-2-hydroxypropa- ne and
1,2-bis(4-hydroxyphenyl)-2-hydroxypropane (11.8 milligrams,
0.000097 phenolic hydroxyl equivalent) in an aluminum pan used for
differential scanning calorimetry analysis. Differential scanning
calorimetry was completed by heating at a rate of 10.degree. C. per
minute under a stream of nitrogen flowing 35 cubic centimeters per
minute from 30.degree. C. to 300.degree. C. with the average values
of the two samples reported. This analysis revealed a cure exotherm
with an onset of 115.7.degree. C. and a maximum at 210.0.degree. C.
The enthalpy for the exotherm was 213.8 joules per gram. A second
differential scanning calorimetry analysis was completed using the
aforementioned conditions and revealed a glass transition
temperature of 89.8.degree. C. There was no residual exothermic
cure noted in this second scan. The results are also summarized in
Table 1.
COMPARATIVE EXAMPLE 2
Uncatalyzed Copolymerization of Diglycidyl Ether of Bisphenol A and
Bisphenol A: In Situ Phenoxy Resin Synthesis
[0084] A portion (14.48 milligrams, 0.000085 epoxide equivalent) of
a crystalline diglycidyl ether of bisphenol A having an epoxide
equivalent weight (EEW) of 170.4 and bisphenol A (9.70 milligrams,
0.000085 phenolic hydroxyl equivalent) were combined in an agate
mortar and ground to a homogeneous powder. The bisphenol A used was
a commercial grade product containing in excess of 99%
4,4'-isopropylidenediphenol. Portions (16.9 and 17.1 milligrams) of
the curable blend were analyzed by differential scanning
calorimetry by heating at a rate of 10.degree. C. per minute under
a stream of nitrogen flowing 35 cubic centimeters per minute from
30.degree. C. to 300.degree. C. with the average values of the two
samples reported. This analysis revealed a sharp melting point
endotherm with a minimum at 52.3.degree. C. and an enthalpy of 43.0
joules per gram. A very broad cure exotherm with an onset of
154.0.degree. C. and a maximum in excess of the 300.degree. C.
upper temperature limit for the analysis was additionally observed.
The enthalpy for the exotherm could not be measured due to the
incomplete cure under the conditions of the analysis. A second
differential scanning calorimetry analysis was completed using the
aforementioned conditions and revealed the presence of residual
exothermic cure. The results are also summarized in Table 1.
1 TABLE 1 Comparative Property Example 2 Example 2 Initial Scan:
Minimum of melting point endotherm none 52.3 (.degree. C.) Enthalpy
(joules/gram) none 43.0 Onset to exothermic cure (.degree. C.)
115.7 226.0 Maximum of cure exotherm (.degree. C.) 210.0 >300
Enthalpy (joules/gram) 213.8 unknown Second Scan: Glass Transition
Temperature (.degree. C.) 89.8 none Residual cure energy none
present
EXAMPLE 3
Catalyzed Copolymerization of Diglycidyl Ether of
1.2-bis(4-Hydroxyphenyl)- -2-hydroxypropane and
1,2-bis(4-Hydroxyphenyl)-2-hydroxypropane: In Situ Phenoxy Resin
Synthesis
[0085] Distilled diglycidyl ether of
1,2-bis(4-hydroxyphenyl)-2-hydroxypro- pane (1.9356 gram, 0.01
epoxide equivalent) having an epoxide equivalent weight (EEW) of
193.56 and tetrabutylphosphonium acetate-acetic acid complex as a
70.69 weight % solids solution in methanol (0.0107 gram, 0.002
equivalent per epoxide equivalent) were thoroughly mixed together
to provide a homogeneous solution. A portion (18.80 milligrams,
0.000097 epoxide equivalent) of the precatalyzed diglycidyl ether
of 1,2-bis(4-hydroxyphenyl)-2-hydroxypropane and
1,2-bis(4-hydroxyphenyl)-2-- hydroxypropane (11.86 milligrams,
0.000097 phenolic hydroxyl equivalent) were combined in an aluminum
pan used for differential scanning calorimetry analysis. A second
sample was prepared by combining a portion (21.6 milligrams,
0.000112 epoxide equivalent) of the distilled diglycidyl ether of
1,2-bis(4-hydroxyphenyl)-2-hydroxypropane and
1,2-bis(4-hydroxyphenyl)-2-hydroxypropane (13.60 milligrams,
0.000112 phenolic hydroxyl equivalent) in an aluminum pan used for
differential scanning calorimetry analysis. Differential scanning
calorimetry was completed by heating at a rate of 10.degree. C. per
minute under a stream of nitrogen flowing 35 cubic centimeters per
minute from 30.degree. C. to 300.degree. C. with the average values
of the two samples reported. This analysis revealed a cure exotherm
with an onset of 110.5.degree. C. and a maximum at 181.9.degree. C.
The enthalpy for the exotherm was 206.1 joules per gram. A second
differential scanning calorimetry analysis was completed using the
aforementioned conditions and revealed a glass transition
temperature of 98.4.degree. C. There was no residual exothermic
cure noted in this second scan. The results are also summarized in
Table 2.
COMPARATIVE EXAMPLE 3
Catalyzed Copolymerization of Diglycidyl Ether of Bisphenol A and
Bisphenol A: In Situ Phenoxy Resin Synthesis
[0086] Crystalline diglycidyl ether of bisphenol A (1.7040 grams,
0.01 epoxide equivalent) having an epoxide equivalent weight (EEW)
of 170.4 and tetrabutylphosphonium acetate-acetic acid complex as a
70.69 weight % solids solution in methanol (0.0107 gram, 0.002
equivalent per epoxide equivalent) were combined and then mixed
with gentle heating to 50.degree. C. to provide a homogeneous
solution. Bisphenol A (1.1414 grams, 0.01 phenolic hydroxyl
equivalent) was added to the warm precatalyzed diglycidyl ether
with mixing until a homogeneous paste formed. The bisphenol A used
was a commercial grade product containing in excess of 99%
4,4-isopropylidenediphenol. Portions (31.7 and 35.1 milligrams) of
the curable blend were analyzed by differential scanning
calorimetry by heating at a rate of 10.degree. C. per minute under
a stream of nitrogen flowing 35 cubic centimeters per minute from
30.degree. C. to 300.degree. C. with the average values of the two
samples reported. This analysis revealed a cure exotherm with an
onset of 119.0.degree. C. and a maximum at 184.2.degree. C. The
enthalpy for the exotherm, was 199.2 joules per gram. A second
differential scanning calorimetry analysis was completed using the
aforementioned conditions and revealed a glass transition
temperature of 70.4.degree. C. There was no residual exothermic
cure noted in this second scan. The results are also summarized in
Table 2.
2 TABLE 2 Comparative Property Example 3 Example 3 Initial Scan:
Onset to exothermic cure (.degree. C.) 110.5 119.0 Maximum of cure
exotherin (.degree. C.) 181.9 184.2 Enthalpy (joules/gram) 206.1
199.2 Second Scan: Glass Transition Temperature (.degree. C.) 98.4
70.4 Residual cure energy none none
EXAMPLE 4
Copolymerization of Diglycidyl Ether of
1,2-bis(4-Hydroxyphenyl)-2-hydroxy- propane with an
Aliphatic/Cycloaliphatic Diamine Mixture
[0087] The diglycidyl ether of
1,2-bis(4-hydroxyphenyl)-2-hydroxypropane and an
aliphatic/cycloaliphatic diamine mixture were combined in 1:1
epoxide:N--H stoichiometry and mixed to give a homogeneous
solution. The aliphatic/cycloaliphatic diamine mixture used was a
commercial grade product containing 90 weight %
diethyltoluenediamine and 10 weight % 1,2-diaminocyclohexane.
Viscosity of the curable solution was monitored as a function of
time at 50.degree. C. The results are given in Table 3.
COMPARATIVE EXAMPLE 4
Copolymerization of Diglycidyl Ether of Bisphenol A
(4,4'-Isopropylienediphenol) with an Aliphatic/Cycloaliphatic
Diamine Mixture
[0088] A diglycidyl ether of bisphenol A and an
aliphatic/cycloaliphatic diamine mixture were combined in 1:1
epoxide:N--H stoichiometry and mixed for one minute at room
temperature to give a homogeneous solution. The diglycidyl ether of
bisphenol A used was a commercial grade product with an EEW
specification of 176 to 183. The aliphatic/cycloaliphatic diamine
mixture used was a commercial grade product containing 90 weight %
diethyltoluenediamine and 10 weight % 1,2-diaminocyclohexane.
Brookfield viscosity of the curable solution was monitored as a
function of time at 50.degree. C. The results are given in Table
3.
3TABLE 3 Designation Time at 50.degree. C. (min.) Viscosity (cps)
Example 4 0 1444 5 1779 10 2184 15 2655 20 3165 25 3701 30 4303 35
4918 40 5598 45 6304 50 7089 Comparative Example 0 233 4 5 315 10
330 15 349 20 370 25 392 30 416 35 441 40 464 45 488 50 514 120
908
EXAMPLE 5
[0089] A. Condensation Reaction of 5-Chloro-2-pentanone and
Phenol
[0090] 5-Chloro-2-pentanone (36.17 grams, 0.30 mole) and phenol
(282.3 grams, 3.0 mole) were added to a three-neck, round-bottom,
one liter, glass reactor and heated to 35.degree. C. with magnetic
stirring under a nitrogen atmosphere (0.5 liter per minute) and
under a condenser chilled to -10.degree. C.
3-Mercaptopropanesulfonic acid (9.37 grams, 0.06 mole) was added to
the solution which was then maintained for the 15.8 hours at a
temperature of 34.degree. C.-37.degree. C. The product solution was
recovered from the reactor and added to stirred, deionized water
(3.5 liters). The stirred slurry was then added to a separatory
funnel and the organic layer allowed to settle out. The recovered
organic layer was then added back into the clean separatory funnel
and washed with a solution of sodium bicarbonate (30 grams) in
deionized water (800 milliliters). The organic layer which settled
out was recovered, added back into the clean separatory funnel,
then washed with deionized water (800 milliliters). The resulting
organic layer which settled out (99.1 grams) was added to a
single-neck, round-bottom flask along with sodium bicarbonate (5
grams), then rotary evaporated using final conditions of 1 mm Hg
vacuum at 95.degree. C. for 3.8 hours. The recovered product was
dissolved into ethyl acetate (250 milliliters) then twice washed in
a separatory funnel with deionized water (150 grams per portion).
The washed ethyl acetate solution was recovered and rotary
evaporated to provide 46.0 grams of a transparent, amber colored,
glassy product (at room temperature). HPLC analysis (unnormalized)
revealed a single major product peak comprising 88 area %, 6 area %
phenol and several minor peaks comprising the balance.
[0091] B. Acetoxylation of
2,2'-bis(4-Hydroxphenyl)-5-chloropentane
[0092] A portion (43.7 grams) of the
2,2'-bis(4-hydroxyphenyl)-5-chloropen- tane from A above, acetic
acid (250 milliliters), acetic anhydride (50 milliliters) and
potassium acetate (46.8 grams, 0.475 mole) were added to a
three-neck, round-bottom, one liter, glass reactor and heated to
reflux with magnetic stirring under a nitrogen atmosphere (0.5
liter per minute) and under a condenser chilled to -10.degree. C.
After 3.2 hours, the product slurry was sampled for HPLC analysis
(unnormalized) and revealed the presence of a single major product
peak for the acetoxylated product comprising 82 area % with several
minor peaks comprising the balance and complete conversion of the
2,2'-bis(4-hydroxyphenyl)-5-chloropentane. At this time, the
reactor was cooled to 25.degree. C. and the product diluted with
methylene chloride (150 milliliters). The product solution was
recovered from the reactor then added to a separatory funnel and
twice washed with deionized water (100 milliliters). The organic
layer which settled out was recovered, then rotary evaporated to
provide 34.9 grams of a transparent, amber colored, viscous liquid
product (at room temperature). HPLC analysis (unnormalized)
revealed a single major product peak comprising 90 area %, with
several minor peaks comprising the balance.
[0093] C. Hydrolysis of Acetoxylated
2,2'-bis(4-Hydroxyphenyl)-5-chloropen- tane
[0094] A portion (34.0 grams) of the acetoxylated
2,2'-bis(4-hydroxyphenyl- )-5chloropentane from B above and sodium
hydroxide (21.0 grams, 0.526 mole) dissolved in deionized water
(400 milliliters) were added to a three-neck, round-bottom, one
liter, glass reactor and heated to reflux with magnetic stirring
under a nitrogen atmosphere (0.5 liter per minute) and under a
condenser chilled to 10.degree. C. After 3 hours at the 98.degree.
C. reflux temperature, the product slurry was sampled for HPLC
analysis (unnormalized, sample acidified with aqueous hydrochloric
acid) and revealed the presence of a single major product peak for
the hydrolyzed product comprising 87 area %, 3 area % phenol and
several minor peaks comprising the balance and complete conversion
of the acetoxylated 2,2-bis(4-hydroxyphenyl)-5-chloropentane. At
this time, the reactor was cooled to 25.degree. C. and the product
neutralized using aqueous hydrochloric acid followed by rotary
evaporation to remove water. The resultant solid product was
diluted with ethyl acetate (200 milliliters) and the product slurry
obtained was recovered then added to a separatory funnel and twice
washed with deionized water (100 milliliters). The organic layer
which settled out was recovered, then rotary evaporated to provide
19.7 grams of a transparent, amber colored, glassy product (at room
temperature). HPLC analysis (unnormalized) revealed a single major
product peak comprising 90 area %, 0.86 area % phenol, with several
minor peaks comprising the balance.
[0095] D. Epoxidation of
2,2'-bis(4-Hydroxyphenyl)-5-hydroxypentane
[0096] A portion (0.136 phenolic hydroxyl equivalent, 18.55 grams)
of the 2,2'-bis(4-hydroxyphenyl)-5-hydroxypentane from C above,
epichlorohydrin (63.0 grams, 0.68 mole), ethanol (35 weight % of
the epichlorohydrin used, 22.1 grams), and deionized water (8
weight % of the epichlorohydrin used) were added to a three-neck,
round-bottom, one liter, glass reactor and heated to a 60.degree.
C. solution with magnetic stirring under a nitrogen atmosphere (0.5
liter per minute) and under a condenser chilled to -10.degree. C.
Once the 60.degree. C. temperature was achieved, dropwise addition
of a solution of 97+% sodium hydroxide (4.90 grams, 0.123 mole)
dissolved in deionized water (24.5 milliliters) commenced and was
completed over a 45 minute period with maintenance of the reaction
temperature at 58.degree. C.-60.degree. C. Ten minutes after
completion of the aqueous sodium hydroxide addition, stirring
ceased and the aqueous brine layer settled out and was pipetted off
and discarded. Fifteen minutes after the completion of the aqueous
sodium hydroxide addition, a second solution of 97+% sodium
hydroxide (2.2 grams, 0.055 mole) dissolved in deionized water
(10.9 milliliters) commenced and was completed over a 20 minute
period with maintenance of the reaction temperature at 57.degree.
C.-61.degree. C. Fifteen minutes after completion of the aqueous
sodium hydroxide addition, the product mixture was recovered from
the reactor and added to a separatory funnel and the aqueous layer
allowed to settle out. After removal of the aqueous layer, the
remaining organic layer was sequentially washed four times in a
separatory funnel with deionized water (100 grams per portion). The
washed organic layer was recovered and rotary evaporated using
final conditions of 1 mm Hg vacuum at 85.degree. C. for 45 minutes
to provide 24.6 grams of a transparent, light amber colored, tacky
solid (at room temperature). HPLC analysis (unnormalized) revealed
a single major product peak (with a second peak as a shoulder)
comprising 92.3 area %, 0.61 area % phenyl glycidyl ether and a
pair of minor peaks comprising the balance. Fourier transform
infrared spectrophotometric analysis of a neat film of the epoxy
resin on a potassium bromide plate confirmed the presence of the
expected aliphatic hydroxyl functionality. Titration for percent
epoxide versus a standard diglycidyl ether of
4,4'-isopropylidenediphenol revealed the presence of 22.13% epoxide
(194.5 EEW).
EXAMPLE 6
Uncatalyzed Copolymerization of Diglycidyl Ether of
2,2'-bis(4-Hydroxyphenyl)-5-hydroxypentane and
2,2'-bis(4-Hydroxyphenyl)-- 5-hydroxypentane: In Situ Phenoxy Resin
Synthesis
[0097] A portion (0.2326 gram, 0.001196 epoxide equivalent) of the
diglycidyl ether of 2,2'-bis(4-hydroxyphenyl)-5-hydroxypentane from
5-D above having an EEW of 194.5 and
2,2'-bis(4-hydroxyphenyl)-5-hydroxypenta- ne (0.1628 gram, 0.001196
phenolic hydroxyl equivalent) from 5-C above were thoroughly mixed
together to provide a homogeneous paste. Portions (17.0 and 35.8
milligrams) of the homogeneous paste were used for differential
scanning calorimetry analysis. Differential scanning calorimetry
was completed by heating at a rate of 10.degree. C. per minute
under a stream of nitrogen flowing 35 cubic centimeters per minute
from 30.degree. C. to 300.degree. C. with the average values of the
two samples reported. This analysis revealed a cure exotherm with
an onset of 134.5.degree. C. and a maximum at 282.8.degree. C. A
second differential scanning calorimetry analysis was completed
using the aforementioned conditions and revealed a glass transition
temperature of 82.7.degree. C. There was no residual exothermic
cure noted in this second scan. The results are also summarized in
Table 4.
4 TABLE 4 Comparative Property Example 6 Example 2 Initial Scan:
Minimum of melting point none 52.3 endotherm (.degree. C.) Enthalpy
(joules/gram) none 43.0 Onset to exothermic cure (.degree. C.)
134.5 226.0 Maximum of cure exotherm (.degree. C.) 282.8 >300
Enthalpy (joules /gram) unknown Unknown Second Scan: Glass
Transition Temperature (.degree. C.) 82.7 None Residual cure energy
none Present
EXAMPLE 7
Copolymerization of Diglycidyl Ether of
2,2'-bis(4-Hydroxyphenyl)-5-hydrox- ypentane with an
Aliphatic/Cycloaliphatic Diamine Mixture
[0098] The diglycidyl ether of
2,2'-bis(4-hydroxyphenyl)-5-hydroxypentane from 5-D above and an
aliphatic/cycloaliphatic diamine mixture were combined in 1:1
epoxide:N--H stoichiometry and mixed to give a homogeneous
solution. The aliphatic/cycloaliphatic diamine mixture used was a
commercial grade product containing 90 weight %
diethyltoluenediamine and 10 weight % 1,2-diaminocyclohexane.
Viscosity of the curable solution was monitored as a function of
time at 50.degree. C. The results are given in Table 5. These
results may be compared directly with those given in Comparative
Example 4 (Table 3).
5TABLE 3 Designation Time at 50.degree. C. (min.) Viscosity (cps)
Example 7 1 4403 2 5426 3 6881 4 8925 5 11,750 6 15,610 7 20,950 8
28,460 9 38,960 10 53,860 11 74,550
EXAMPLE 8
Methacrylation of Diglycidyl Ether of
2,2'-bis(4-Hydroxyphenyl)-5-hydroxyp- entane
[0099] A portion (3.89 grams, 0.01 aliphatic hydroxyl equivalent)
of the diglycidyl ether of
2,2'-bis(4-hydroxyphenyl)-5-hydroxypentane from 5-D above having an
EEW of 194.5, anhydrous tetrahydrofuran (150 grams) and anhydrous
-325 mesh potassium carbonate (1.52 grams, 0.011 mole) were added
to a three-neck, round-bottom, one liter, glass reactor and
maintained at room temperature (22.degree. C.) with magnetic
stirring under a nitrogen atmosphere (0.5 liter per minute) and
under a condenser chilled to -15.degree. C. Methacryloyl chloride
(1.15 grams, 0.011 mole) was added to the stirred slurry, followed
five minutes later by addition of triethylamine (1.11 gram, 0.011
mole). After 16 hours, the product slurry was sampled for HPLC
analysis and revealed the presence of a single major product peak
for the methacrylate product accompanied by complete conversion of
the diglycidyl ether of 2,2'-bis(4-hydroxyphenyl)--
5-hydroxypentane.
EXAMPLE 9
Coupling of Diglycidyl Ether of
1,2-bis(4-Hydroxyphenyl)-2-hydroxypropane with
4,4'-Diisocyanatodiphenyl Methane
[0100] A portion (3.56 grams, 0.01 aliphatic hydroxy equivalent) of
distilled diglycidyl ether of
1,2-bis(4-hydroxyphenyl)-2-hydroxypropane having an EEW of 193.56
was added to a predried, single-neck, 250 milliliter, glass reactor
containing a dried magnetic stir bar and maintained in a dry
nitrogen glovebox. Anhydrous, inhibitor free tetrahydrofuran (50
grams) which had been chromatographically purified over dry alumina
in the dry, nitrogen glovebox was added to the reactor and magnetic
stirring initiated to form a solution. Dibutyltin dilaurate
catalyst (0.097 gram, 2.0 weight percent of the reactants used) was
added to the magnetically stirred solution, followed by the
dropwise addition of molten, dimer free=4,4'-diisocyanatodiphenyl
methane (1.31 grams, 0.0105 isocyanate equivalent). The reaction
mixture was heated at 40.degree. C. for 30 minutes, followed by
HPLC analysis of a portion of the product. The HPLC analysis
revealed complete conversion of the
1,2-bis(4-hydroxyphenyl)-2-hydroxypropane and the
4,4'-diisocyanatodiphen- yl methane to a single product peak
proposed to be the tetraglycidyl ether.
* * * * *