U.S. patent application number 16/376289 was filed with the patent office on 2019-12-19 for bis(benzoxazinyl)phthalimidine and associated curable composition and composite.
The applicant listed for this patent is SABIC Global Technologies B.V.. Invention is credited to Prakash Sista.
Application Number | 20190382393 16/376289 |
Document ID | / |
Family ID | 62636111 |
Filed Date | 2019-12-19 |
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United States Patent
Application |
20190382393 |
Kind Code |
A1 |
Sista; Prakash |
December 19, 2019 |
BIS(BENZOXAZINYL)PHTHALIMIDINE AND ASSOCIATED CURABLE COMPOSITION
AND COMPOSITE
Abstract
A bis(benzoxazinyl)phthalimidine has the structure ##STR00001##
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, j, and k are defined
herein. The bis(benzoxazinyl)phthalimidine is useful as a component
of a curable composition. It exhibits a high melting temperature
and a high exotherm onset temperature. Also described is a
composite that includes a reinforcing filler and the curing product
of the bis(benzoxazinyl)phthalimidine.
Inventors: |
Sista; Prakash; (Evansville,
IN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SABIC Global Technologies B.V. |
Bergen op Zoom |
|
NL |
|
|
Family ID: |
62636111 |
Appl. No.: |
16/376289 |
Filed: |
April 5, 2019 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07D 413/14 20130101;
C07D 405/14 20130101; C08K 5/357 20130101 |
International
Class: |
C07D 413/14 20060101
C07D413/14; C07D 405/14 20060101 C07D405/14 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 14, 2018 |
EP |
18177776.4 |
Claims
1. A bis(benzoxazinyl)phthalimidine having the structure
##STR00009## wherein R.sup.1 is hydrogen, C.sub.1-C.sub.6 alkyl,
phenyl, or phenyl substituted with up to five substituents
independently selected from halogen and C.sub.1-C.sub.6 alkyl; each
occurrence of R.sup.2 is independently selected from the group
consisting of unsubstituted or substituted C.sub.1-C.sub.30
hydrocarbyl; each occurrence of R.sup.3 is independently
C.sub.1-C.sub.6 alkyl; j is 0, 1, 2, 3, or 4; each occurrence of
R.sup.4 is independently selected from the group consisting of
C.sub.1-C.sub.12 alkyl, C.sub.2-C.sub.12 alkenyl, and
C.sub.1-C.sub.12 alkoxyl; and each occurrence of k is independently
0, 1, 2, or 3.
2. The bis(benzoxazinyl)phthalimidine of claim 1, wherein R.sup.1
is phenyl, or phenyl substituted with 1, 2, 3, 4, or 5 substituents
independently selected from halogen and C.sub.1-C.sub.6 alkyl.
3. The bis(benzoxazinyl)phthalimidine of claim 1, wherein R.sup.1
is phenyl.
4. The bis(benzoxazinyl)phthalimidine of claim 1, wherein each
occurrence of R.sup.2 is independently selected from the group
consisting of C.sub.1-C.sub.12 alkyl, anthracenyl, biphenyl,
cyclohexenyl, cyclopentenyl, indanyl, naphthyl, and phenyl.
5. The bis(benzoxazinyl)phthalimidine of claim 1, wherein each
occurrence of R.sup.2 is C.sub.1-C.sub.12 alkyl or phenyl.
6. The bis(benzoxazinyl)phthalimidine of claim 1, wherein j is 0,
and each occurrence of k is 0.
7. The bis(benzoxazinyl)phthalimidine of claim 1, wherein R.sup.1
is phenyl, each occurrence of R.sup.2 is phenyl, j is 0, and each
occurrence of k is 0.
8. A curable composition comprising the
bis(benzoxazinyl)phthalimidine of claim 1.
9. The curable composition of claim 8, further comprising an epoxy
resin selected from the group consisting of aliphatic epoxy resins,
cycloaliphatic epoxy resins, aromatic epoxy resins,
dicyclopentadiene-type (DCPD-type) epoxy resins, and combinations
thereof.
10. The curable composition of claim 9, wherein the epoxy resin is
selected from the group consisting of bisphenol-A diglycidyl ether,
bisphenol-F diglycidyl ether, neopentylglycol diglycidyl ether,
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate,
N,N-diglycidyl-4-glycidyloxyaniline,
N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane,
2-phenyl-3,3-bis(4-glycidyloxyphenyl)phthalimidine, and
combinations thereof.
11. The curable composition of claim 9, wherein the epoxy resin is
a diglycidyl ether compound having the structure ##STR00010##
wherein R.sup.1 is hydrogen, C.sub.1-C.sub.6 alkyl, phenyl, or
phenyl substituted with up to five substituents independently
selected from halogen and C.sub.1-C.sub.6 alkyl; each occurrence of
R.sup.3 is independently C.sub.1-C.sub.6 alkyl; j is 0, 1, 2, 3, or
4; each occurrence of R.sup.4 is independently selected from the
group consisting of C.sub.1-C.sub.12 alkyl, C.sub.2-C.sub.12
alkenyl, and C.sub.1-C.sub.12 alkoxyl; and each occurrence of m is
independently 0, 1, 2, 3, or 4.
12. The curable composition of claim 7, comprising the
bis(benzoxazinyl)phthalimidine of claim 7.
13. A composite comprising a reinforcing filler and a curing
product of the bis(benzoxazinyl)phthalimidine of claim 1.
14. The composite of claim 13, comprising a reinforcing filler and
a curing product of the bis(benzoxazinyl)phthalimidine of claim 7.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority from European Patent
Application No. 18177776.4 filed on Jun. 14, 2018, which is
incorporated by reference herein in its entirety.
BACKGROUND OF THE INVENTION
[0002] Benzoxazines are a class of thermoset materials that are
useful in the fabrication of electronic devices and other
composites. Benzoxazines can undergo thermal curing with or without
a curing catalyst to form polybenzoxazines. Relative to epoxy
thermosets, benzoxazines typically cure at lower temperatures and
do not require curing catalysts or hardening agents. Cured
thermosets derived from benzoxazines also absorb much less moisture
than those derived from epoxies. Benzoxazines also demonstrate
near-zero shrinkage during curing (which is a significant
improvement from epoxy resins), and no volatiles are released
during curing reactions. Polybenzoxazines offer a low melt
viscosity, high glass transition temperature, high thermal
stability, good mechanical strength, low dielectric constant and
good resistance to burning. In addition, the cure exotherms for
benzoxazines are much lower than those of epoxies, thereby allowing
fabrication of thicker sections, longer injection times, and larger
parts.
[0003] Compounds containing two benzoxazine groups (i.e.,
bis(benzoxazinyl) compounds) are known. See, for example, U.S.
Patent Application No. US 2011/0152453 A1 of Tietze et al., which
describes bis(benzoxazinyl) derivatives of phenolphthalein.
However, there is a desire for bis(benzoxazinyl) compounds
exhibiting higher melting temperatures and higher exotherm onset
temperatures.
BRIEF SUMMARY OF EMBODIMENTS OF THE INVENTION
[0004] One embodiment is a bis(benzoxazinyl)phthalimidine having
the structure
##STR00002##
wherein R.sup.1 is hydrogen, C.sub.1-C.sub.6 alkyl, phenyl, or
phenyl substituted with up to five substituents independently
selected from halogen and C.sub.1-C.sub.6 alkyl; each occurrence of
R.sup.2 is independently selected from the group consisting of
unsubstituted or substituted C.sub.1-C.sub.30 hydrocarbyl; each
occurrence of R.sup.3 is independently C.sub.1-C.sub.6 alkyl; j is
0, 1, 2, 3, or 4; each occurrence of R.sup.4 is independently
selected from the group consisting of C.sub.1-C.sub.12 alkyl,
C.sub.2-C.sub.12 alkenyl, C.sub.1-C.sub.12 alkoxyl; and each
occurrence of k is independently 0, 1, 2, or 3.
[0005] Another embodiment is a curable composition comprising the
bis(benzoxazinyl)phthalimidine in any of its variations.
[0006] Another embodiment is a composite comprising a reinforcing
filler and a curing product of the bis(benzoxazinyl)phthalimidine
in any of its variations.
[0007] These and other embodiments are described in detail
below.
BRIEF DESCRIPTION OF THE DRAWING
[0008] The FIGURE is a chemical scheme for the synthesis of
2-phenyl-3,3-bis(3-phenyl-3,4-dihydro-2H-benzo[e][1,3]oxazin-6-yl)isoindo-
lin-1-one.
DETAILED DESCRIPTION OF THE INVENTION
[0009] The present inventors have determined that a
bis(benzoxazinyl)phthalimidine compound exhibits a higher melting
temperature and higher exotherm onset temperature than a
corresponding bis(benzoxazinyl)phenophthalein compound.
[0010] One embodiment is a bis(benzoxazinyl)phthalimidine having
the structure
##STR00003##
wherein R.sup.1 is hydrogen, C.sub.1-C.sub.6 alkyl, phenyl, or
phenyl substituted with up to five substituents independently
selected from halogen and C.sub.1-C.sub.6 alkyl; each occurrence of
R.sup.2 is independently selected from the group consisting of
unsubstituted or substituted C.sub.1-C.sub.30 hydrocarbyl; each
occurrence of R.sup.3 is independently C.sub.1-C.sub.6 alkyl; j is
0, 1, 2, 3, or 4; each occurrence of R.sup.4 is independently
selected from the group consisting of C.sub.1-C.sub.12 alkyl,
C.sub.2-C.sub.12 alkenyl, and C.sub.1-C.sub.12 alkoxyl; and each
occurrence of k is independently 0, 1, 2, or 3.
[0011] As used herein, the term "hydrocarbyl", whether used by
itself, or as a prefix, suffix, or fragment of another term, refers
to a residue that contains only carbon and hydrogen unless it is
specifically identified as "substituted hydrocarbyl". The
hydrocarbyl residue can be aliphatic or aromatic, straight-chain,
cyclic, bicyclic, branched, saturated, or unsaturated. It can also
contain combinations of aliphatic, aromatic, straight chain,
cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon
moieties. When the hydrocarbyl residue is described as substituted,
it can contain heteroatoms in addition to carbon and hydrogen.
[0012] As used herein, the term "alkyl" includes linear, branched,
cyclic, and polycyclic alkyl groups, as well as alkyl groups having
a combination of at least two types of linear, branched, cyclic,
and polycyclic alkyl fragments.
[0013] As used herein, the term "halogen" means fluoro, chloro,
bromo, or iodo.
[0014] When not otherwise expressly defined, the term "substituted"
means including at least one substituent such as a halogen,
hydroxyl, amino, thiol, carboxyl, carboxylate, amide, cyano,
sulfide, disulfide, nitro, C.sub.1-C.sub.18 alkyl, C.sub.1-C.sub.18
alkoxyl, C.sub.6-C.sub.18 aryl, C.sub.6-C.sub.18 aryloxyl,
C.sub.7-C.sub.18 alkylaryl, or C.sub.7-C.sub.18 alkylaryloxyl.
"Substituted" further means including at least one heteroatom
within the carbon framework, as contrasted with pendant to the
carbon framework. For example, substituted aryl includes
pyridyl.
[0015] In some embodiments of the bis(benzoxazinyl)phthalimidine,
R.sup.1 is phenyl, or phenyl substituted with 1, 2, 3, 4, or 5
substituents independently selected from halogen and
C.sub.1-C.sub.6 alkyl. In some embodiments, R.sup.1 is phenyl.
[0016] In some embodiments of the bis(benzoxazinyl)phthalimidine,
each occurrence of R.sup.2 is independently selected from the group
consisting of C.sub.1-C.sub.12 alkyl (including, for example,
cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and
cyclooctyl), anthracenyl, biphenyl, cyclohexenyl, cyclopentenyl,
indanyl, naphthyl, and phenyl. In some embodiments, each occurrence
of R.sup.2 is C.sub.1-C.sub.12 alkyl or phenyl. In some
embodiments, each occurrence of R.sup.2 is phenyl. In some
embodiments, R.sup.1 is phenyl, and each occurrence of R.sup.2 is
phenyl.
[0017] In some embodiments, j is 0. In some embodiments, each
occurrence of k is 0. In some embodiments, j is 0, and each
occurrence of k is 0.
[0018] A representative synthesis of a
bis(benzoxazinyl)phthalimidine is provided in the working examples
below. In general, the bis(benzoxazinyl)phthalimidine can be
synthesized by reacting a 3,3-bis(4-hydroxyphenyl)phthalimidine
substituted in the 2-position with the desired R.sup.1 group with
at least two equivalents of paraformaldehyde or other formaldehyde
equivalent, and with at least two equivalents of an amine
substituted with the desired R.sup.2 group. The resulting product
bis(benzoxazinyl)phthalimidine can be purified by conventional
methods, including chromatography, precipitation,
recrystallization, and combinations thereof.
[0019] Another embodiment is a curable composition comprising the
bis(benzoxazinyl)phthalimidine in any of its above-described
variations. The bis(benzoxazinyl)phthalimidine can be cured in the
absence of any curing catalyst or curing agent. So, it is possible
for the curable composition to consist of the
bis(benzoxazinyl)phthalimidine.
[0020] In other embodiments, the curable composition comprises, in
addition to the bis(benzoxazinyl)phthalimidine, an epoxy compound.
The bis(benzoxazinyl)phthalimidine and the epoxy compound can be
co-cured without the need for any of the curing agents or curing
catalysts typically required by epoxy compounds.
[0021] Epoxy compounds include, for example, aliphatic epoxy
resins, cycloaliphatic epoxy resins, aromatic epoxy resins
(including bisphenol-A epoxy resins, bisphenol-F epoxy resins,
phenol novolac epoxy resins, cresol-novolac epoxy resins, biphenyl
epoxy resins, triglycidyl p-aminophenol, tetraglycidyl diamino
diphenyl methane, naphthalene epoxy resins,
2-glycidylphenylglycidyl ether, 4-glycidylphenylglycidyl ether,
2-phenyl-3,3-bis(4-glycidyloxyphenyl)phthalimidine, and
multi-aromatic resin (MAR-type) epoxy resins),
dicyclopentadiene-type (DCPD-type) epoxy resins, and combinations
thereof.
[0022] In some embodiments, the epoxy compound is selected from the
group consisting of bisphenol-A epoxy resins, bisphenol-F epoxy
resins, neopentylglycol epoxy resins,
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate,
N,N-diglycidyl-4-glycidyloxyaniline,
N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane,
2-phenyl-3,3-bis(4-glycidyloxyphenyl)phthalimidine, and
combinations thereof.
[0023] In some embodiments, the curable composition further
comprises, in addition to the bis(benzoxazinyl)phthalimidine, a
diglycidyl ether compound having the structure
##STR00004##
wherein R.sup.1 is hydrogen, C.sub.1-C.sub.6 alkyl, phenyl, or
phenyl substituted with up to five substituents independently
selected from halogen and C.sub.1-C.sub.6 alkyl; each occurrence of
R.sup.3 is independently C.sub.1-C.sub.6 alkyl; j is 0, 1, 2, 3, or
4; each occurrence of R.sup.4 is independently selected from the
group consisting of C.sub.1-C.sub.12 alkyl, C.sub.2-C.sub.12
alkenyl, and C.sub.1-C.sub.12 alkoxyl; and each occurrence of m is
independently 0, 1, 2, 3, or 4.
[0024] In some embodiments of the diglycidyl ether compound,
R.sup.1 is phenyl, or phenyl substituted with 1, 2, 3, 4, or 5
substituents independently selected from halogen and
C.sub.1-C.sub.6 alkyl. In some embodiments, R.sup.1 is phenyl.
[0025] In some embodiments of the diglycidyl ether compound, j is
0. In some embodiments of the diglycidyl ether compound, each
occurrence of k is 0. In some embodiments of the diglycidyl ether
compound, j is 0, and each occurrence of k is 0.
[0026] In a very specific embodiment of the curable composition,
the bis(benzoxazinyl)phthalimidine has the structure
##STR00005##
wherein R.sup.1 is phenyl, and each occurrence of R.sup.2 is
C.sub.1-C.sub.12 alkyl or phenyl. In some embodiments, each
occurrence of R.sup.2 is phenyl.
[0027] The curable composition comprises the
bis(benzoxazinyl)phthalimidine in an amount of 10 to 100 weight
percent, based on the total weight of the curable composition.
Within this range, the amount of bis(benzoxazinyl)phthalimidine can
be 25 to 100 weight percent, or 50 to 100 weight percent, or 75 to
100 weight percent, or 90 to 100 weight percent, or 95 to 100
weight percent.
[0028] When the curable composition comprises the
bis(benzoxazinyl)phthalimidine and the diglycidyl ether compound,
the composition can comprise 10 to 90 weight percent of the
bis(benzoxazinyl)phthalimidine and 10 to 90 weight percent of the
diglycidyl ether compound, based on the total weight of the curable
composition. Within these ranges, the curable composition can
comprise 25 to 75 weight percent of the
bis(benzoxazinyl)phthalimidine and 25 to 75 weight percent of the
diglycidyl ether compound, or 40 to 60 weight percent of the
bis(benzoxazinyl)phthalimidine and 40 to 60 weight percent of the
diglycidyl ether compound.
[0029] The curable composition can, optionally, further comprise
one or more thermoset additives. Such additive include, for
example, flame retardants, lubricants, mold release agents,
antioxidants, thermal stabilizers, ultraviolet stabilizers,
colorants (including pigments and dyes), anti-static agents, and
combinations thereof. When present, such additives can be used in a
total amount of 1 part per million by weight to 20 weight percent,
based on the total weight of the composition. Within this range,
the total amount of colorants can be 0.1 to 10 weight percent, or
0.2 to 5 weight percent.
[0030] The curable composition can, optionally, further include a
filler. Fillers include, for example, silica, boron nitride,
boron-silicate, alumina, aluminum diboride, magnesium oxide,
wollastonite, calcium sulfate, calcium carbonate, talc, basalt,
glass fibers, glass flakes, glass spheres, kaolin, mica, feldspar,
nepheline syenite, flue dust, cenospheres, fillite, natural silica
sand, quartz, quartzite, perlite, tripoli, diatomaceous earth,
silicon carbide, molybdenum sulfide, zinc sulfide, aluminum
silicate (mullite), calcium silicate, zirconium silicate, barium
titanate, barium ferrite, barium sulfate, particulate and fibrous
aluminum, particulate and fibrous bronze, particulate and fibrous
zinc, particulate and fibrous copper, particulate and fibrous
nickel, particulate and fibrous steel, particulate and fibrous
conductive carbon, polyester fibers, aromatic polyamide fibers,
polyimide fibers, poly(phenylene sulfide) fibers, polyether ether
ketone fibers, and combinations thereof.
[0031] In some embodiments, the filler is a reinforcing filler.
Reinforcing fillers include, for example, metal fibers, metallized
inorganic fibers, metallized synthetic fibers, glass fibers,
graphite fibers, carbon fibers, ceramic fibers, mineral fibers,
basalt fibers, polymer fibers having a melting or glass transition
temperature at least 100.degree. C. higher than decomposition onset
temperature of the bis(benzoxazinyl)phthalimidine (including aramid
fibers), and combinations thereof. It will be understood that the
reinforcing fillers can be in the form of woven fabrics (including
plain weave fabrics, satin weave fabrics, and non-crimp fabrics),
non-woven fabrics, unidirectional fibers, braided fibers, fiber
tow, and fiber ropes.
[0032] When present, the fillers can be used in an amount of 0.5 to
1000 weight parts, based on 100 parts by weight of the
bis(benzoxazinyl)phthalimidine. Within this range, the filler
amount can be 10 to 500 weight parts, or 20 to 400 weight
parts.
[0033] Another embodiment is a composite comprising a reinforcing
filler and the curing product of the bis(benzoxazinyl)phthalimidine
in any of its above-described variations.
[0034] Reinforcing fillers are describe above in the context of the
curable composition. In some embodiments, the reinforcing filler is
selected from the group consisting of glass fiber, carbon fiber,
and combinations thereof.
[0035] In a very specific embodiment of the composite, the
bis(benzoxazinyl)phthalimidine has the structure
##STR00006##
wherein R.sup.1 is phenyl, and each occurrence of R.sup.2 is
phenyl.
[0036] In addition to the reinforcing filler and a curing product
of the bis(benzoxazinyl)phthalimidine, the composite can,
optionally, further comprise a curing product of an epoxy compound.
Epoxy compounds are describe above in the context of the curable
composition.
[0037] The composite comprises the reinforcing filler in an amount
of 0.5 to 1000 weight parts, based on 100 parts by weight of a
curing product of the bis(benzoxazinyl)phthalimidine and a curing
product of the optional epoxy compound. Within this range, the
filler amount can be 10 to 500 weight parts, or 20 to 400 weight
parts.
[0038] The invention includes at least the following
embodiments.
[0039] Aspect 1: A bis(benzoxazinyl)phthalimidine having the
structure
##STR00007##
wherein R.sup.1 is hydrogen, C.sub.1-C.sub.6 alkyl, phenyl, or
phenyl substituted with up to five substituents independently
selected from halogen and C.sub.1-C.sub.6 alkyl; each occurrence of
R.sup.2 is independently selected from the group consisting of
unsubstituted or substituted C.sub.1-C.sub.30 hydrocarbyl; each
occurrence of R.sup.3 is independently C.sub.1-C.sub.6 alkyl; j is
0, 1, 2, 3, or 4; each occurrence of R.sup.4 is independently
selected from the group consisting of C.sub.1-C.sub.12 alkyl,
C.sub.2-C.sub.12 alkenyl, and C.sub.1-C.sub.12 alkoxyl; and each
occurrence of k is independently 0, 1, 2, or 3.
[0040] Aspect 2: The bis(benzoxazinyl)phthalimidine of aspect 1,
wherein R.sup.1 is phenyl, or phenyl substituted with 1, 2, 3, 4,
or 5 substituents independently selected from halogen and
C.sub.1-C.sub.6 alkyl.
[0041] Aspect 3: The bis(benzoxazinyl)phthalimidine of aspect 1,
wherein R.sup.1 is phenyl.
[0042] Aspect 4: The bis(benzoxazinyl)phthalimidine of any one of
aspects 1-3, wherein each occurrence of R.sup.2 is independently
selected from the group consisting of C.sub.1-C.sub.12 alkyl
(including, for example, cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, cycloheptyl, and cyclooctyl), anthracenyl, biphenyl,
cyclohexenyl, cyclopentenyl, indanyl, naphthyl, and phenyl.
[0043] Aspect 5: The bis(benzoxazinyl)phthalimidine of any one of
aspects 1-3, wherein each occurrence of R.sup.2 is C.sub.1-C.sub.12
alkyl or phenyl.
[0044] Aspect 6: The bis(benzoxazinyl)phthalimidine of any one of
aspects 1-5, wherein j is 0, and each occurrence of k is 0.
[0045] Aspect 7: The bis(benzoxazinyl)phthalimidine of aspect 1,
wherein R.sup.1 is phenyl, each occurrence of R.sup.2 is phenyl, j
is 0, and each occurrence of k is 0.
[0046] Aspect 8: A curable composition comprising the
bis(benzoxazinyl)phthalimidine of any one of aspects 1-7.
[0047] Aspect 9: The curable composition of aspect 8, further
comprising an epoxy resin selected from the group consisting of
aliphatic epoxy resins, cycloaliphatic epoxy resins, aromatic epoxy
resins, dicyclopentadiene-type (DCPD-type) epoxy resins, and
combinations thereof.
[0048] Aspect 10: The curable composition of aspect 9, wherein the
epoxy resin is selected from the group consisting of bisphenol-A
diglycidyl ether, bisphenol-F diglycidyl ether, neopentylglycol
diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane
carboxylate, N,N-diglycidyl-4-glycidyloxyaniline,
N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane,
2-phenyl-3,3-bis(4-glycidyloxyphenyl)phthalimidine, and
combinations thereof.
[0049] Aspect 11: The curable composition of aspect 9, wherein the
epoxy resin is a diglycidyl ether compound having the structure
##STR00008##
wherein R.sup.1 is hydrogen, C.sub.1-C.sub.6 alkyl, phenyl, or
phenyl substituted with up to five substituents independently
selected from halogen and C.sub.1-C.sub.6 alkyl; each occurrence of
R.sup.3 is independently C.sub.1-C.sub.6 alkyl; j is 0, 1, 2, 3, or
4; each occurrence of R.sup.4 is independently selected from the
group consisting of C.sub.1-C.sub.12 alkyl, C.sub.2-C.sub.12
alkenyl, and C.sub.1-C.sub.12 alkoxyl; and each occurrence of m is
independently 0, 1, 2, 3, or 4.
[0050] Aspect 12: The curable composition of any one of aspects
7-10, comprising the bis(benzoxazinyl)phthalimidine of aspect
7.
[0051] Aspect 13: A composite comprising a reinforcing filler and a
curing product of the bis(benzoxazinyl)phthalimidine of any one of
aspects 1-7.
[0052] Aspect 14: The composite of aspect 13, comprising a
reinforcing filler and a curing product of the
bis(benzoxazinyl)phthalimidine of aspect 7.
[0053] All ranges disclosed herein are inclusive of the endpoints,
and the endpoints are independently combinable with each other.
Each range disclosed herein constitutes a disclosure of any point
or sub-range lying within the disclosed range.
[0054] The invention is further illustrated by the following
non-limiting examples.
EXAMPLES
[0055] Synthesis of
2-Phenyl-3,3-bis(3-phenyl-3,4-dihydro-2H-benzo[e][1,3]oxazin-6-yl)isoindo-
lin-1-one (PPPBP-BZ). The FIGURE is a chemical scheme for the
synthesis. 2-Phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine (PPPBP,
25 grams, 0.0636 mole) was added to a 500 milliliter 3-neck flask
equipped with a Dean-Stark apparatus and a condenser. The PPPBP was
allowed to partially dissolve in 45 milliliters of toluene at
80.degree. C. for about 30 minutes. To this mixture,
paraformaldehyde (12.4 grams, 0.4 mole) was added followed by
aniline (13 milliliters, 0.1424 mole) and 15 milliliters of
ethanol. The reaction mixture was allowed to stir for 24 hours at
85 to 90.degree. C. The solution was allowed to cool to room
temperature and the solvent was removed under reduced pressure to
yield an oil. The oil was dispersed in a small amount of methylene
chloride and precipitated into hexane to yield a white powder
(crude yield 33 grams, 82.64%). The crude product was purified
using a silica plug (solvent: hexane+ethyl acetate), where PPPBP-BZ
was retained in the silica gel. The pure product was obtained by
washing the silica gel with chloroform and filtering out the silica
gel. The filtrate was then precipitated in hexane and dried. A
proton nuclear magnetic resonance (.sup.1H NMR) spectrum confirmed
the formation of pure PPPBP-BZ as the product. The .sup.1H NMR
spectrum was obtained using a Mercury Plus 400 Megahertz
.sup.1H-NMR spectrometer.
[0056] Synthesis of
3,3-bis(3-phenyl-3,4-dihydro-2H-benzo[e][1,3]oxazin-6-yl)isobenzofuran-1(-
3H)-one (Phen-BZ, Phenolphthalein bis(benzoxazine)). The synthesis
of phenolphthalein bis(benzoxazine) was performed according to
literature reports. See, P. Yang and Y. Gu, Journal of Polymer
Research, 2011, volume 18, pages 1725-1733; P. Yang, X. Wang, and
Y. Gu, Journal of Polymer Research, 2012, volume 19, page 9901; and
R. Tietz, D. Orser, Y. Blyakhman, M. Bryant, and B.-S. Lin,
"Benzoxazine Compounds Derivated from Phenolphthalein Having
Flame-Retardant Properties and a Process for Their Preparation,"
European Patent No., EP 1 797 081 B1, 2005. Phenolphthalein (19.91
grams, 0.0626 mole) was added to a 500 milliliter 3-neck flask
equipped with a Dean-Stark apparatus and a condenser. The
phenolphthalein was allowed to partially dissolve in 45 milliliters
toluene at 80.degree. C. for about 30 minutes. To this solution,
paraformaldehyde (12.4 grams, 0.4 mole) was added, followed by
aniline (13 milliliters, 0.14 moles) and 15 milliliters of ethanol.
The reaction was allowed to stir for 24 hours at 85 to 90.degree.
C. The solution was allowed to cool to room temperature and the
solvent was removed under reduced pressure to yield an oil. The oil
was dispersed in small amount of methylene chloride and
precipitated into hexane to yield yellow powder (crude yield 39
grams, 114.7%). The crude product was purified using preparatory
HPLC in hexane and ethyl acetate solvent. The pure fractions were
mixed and concentrated in vacuum to yield a colorless oil which was
mixed with methylene chloride and precipitated into hexane to yield
a pale off-white solid. .sup.1H NMR spectrum confirmed the
formation of pure Phen-BZ as the product.
[0057] Cured thermosets were prepared by the following method. A
small amount of the solid (.about.60 mg) in an aluminum pan was
placed in a Blue M Oven from Thermal Product Solutions and cured at
atmospheric pressure according to the curing protocol detailed
below in Table 1.
TABLE-US-00001 TABLE 1 Step No. Temperature (.degree. C.)
Equilibration Time (min) 1 140 60 2 160 60 3 180 60 4 200 30 5 220
30
[0058] Differential Scanning calorimetry (DSC) according to ASTM
D3418-15 was used to determine the melting temperatures (T.sub.m)
of the bis(benzoxazine) compounds, and the glass transition
temperatures (T.sub.g) of the cured products of the
bis(benzoxazine) compounds. Testing was performed using a Q1000
differential scanning calorimeter from TA Instruments. In a typical
procedure, a polymer sample (10-20 milligrams) was heated from
40.degree. C. to 325.degree. C. at 20.degree. C./minute, held at
325.degree. C. for 1 minute, cooled back to 40.degree. C. at
20.degree. C./minute, then held at 40.degree. C. for 1 minute.
T.sub.m values for the bis(benzoxazine) compounds were determined
based on the heating portion of this first thermal cycle, and
curing occurred in the high temperature portion of the cycle. A
second thermal cycle was conducted under the same conditions, and
the heating portion of this second thermal cycle was used to
determine T.sub.g values for the cured products of the
bis(benzoxazine) compounds.
[0059] Thermal Gravimetric Analysis (TGA) was performed with a TA
Q800 TGA. The samples were scanned from 40.degree. C. to
800.degree. C. under nitrogen and air with a heating rate of
20.degree. C./minute. This analysis was also used to determine the
temperature of peak decomposition (also referred as the onset
decomposition temperature), and the char yield at the end of the
TGA run.
[0060] The property results in Table 2 show that the
bis(benzoxazinyl)phthalimidine exhibits a substantially higher
melting temperature and a substantially higher exotherm onset
temperature relative to the corresponding
bis(benzoxazinyl)phenophthalein.
TABLE-US-00002 TABLE 2 PPPBP-BZ Phen-BZ Melting temperature
(.degree. C.) 139.5 ~95 Onset of Exotherm (.degree. C.) ~210 ~190
T.sub.g of cured material (.degree. C.) 238 235 Onset of
decomposition (.degree. C.) N.sub.2 349 320 air 383 300 1% weight
loss (.degree. C.) N.sub.2 203 276 air 76 267 5% weight loss
(.degree. C.) N.sub.2 350 357 air 369 381 Char yield (%) N.sub.2
44.97 59.45 air 0.89 0
* * * * *