Note: Descriptions are shown in the official language in which they were submitted.
_ 1 _
CYANATE FUNCTIONAL MALEIMIDES
: This invention pertains to thermosettable
compositions which simultaneously contain both a
maleimide group and a cyanate group.
Aromatic polycyanates which are thermosettable
to polytriazines are known, for example, from U.S.
. Patent Nos. 3,448,079; 3,553,244; 3,694,410; 3,740,348;
3,755,402; 4,0949852 and 4,097,455. Said polytriazines
: ~ 10 possess excellent heat resistance, however, an
: ~ improvement in their mechanical properties, especially
tensile strength and elongation would be desirable.
:~ F~urthermore, there is substantial room for im~rovement
: in the moisture resistanc~e of said polytriazines.
: : ; 15~
Polymaleimides which are thermosettable are
known, ~or example, from U.S. Patent No. 2,444,536 and
rom ew Industrial:Pol~mers, Rudolph D. Deanin
(editorj, ACS Symposium Serie~ 4 published by American
Chemical Society:,: Washi~ngton, D.C. (1972), pages 100-
;1:23. Sa:id polymaleimides are typically difficult to
process and cure due to high melting pointsj poor
:25~ ~ :
:~ : , ~ ,
34,329-F -1-
'
1~32~ 7~069-20
solvent solubility and slow curing rates. The thermoset (cured)
polymaleimides are very brittle and thus of limited utility.
Copolymerization products of compounds containing
two or more maleimide groups with compounds containing two or
more cyanate groups are also known, for example, ~rom Proc.
Electr./Electron. Insul. Conf., 1981, 15th, pages 168-171.
Representative of said copolymerization products is the bismale-
imide-triazine resin prepared ~y copolymerization of bisphenol A
dicyanate and N,N'-(methylenedi-p-phenylene) bismaleimide. Pre-
paration of said copolymerization products always requires
premixing or contactin~ together two separate components: the
polycyanate compound and the polymaleimide compound.
The present invention provides novel compositions
which simultaneously contain both a maleimide group and a cyanate
group. Said compositions are thermosettable to useful polymeric
~cured) compositions including castings, laminates, coatings and
the like. Many o~ the compositions of the present invention
possess improved mechanical properties and improved moisture
~ reslstance when compared to the polytriazines of the prior art.
In addition, improved processability is inherent to the composi-
tions of`the present invention.
One aspect o~ the present invention concerns a
; composition comprising at least one thermosettable compound which
contains a compound represented by the formulas
::
::
:;: lB
- "'
.
~L3~
- 3 ~ 74069-20
( I ) N = C-0 ~N~`
(~ )4
., , o
(II) N--C-0--~ (A)n ~ N~
(R' )4 ~R' )4
wherein each R and Rl is independently hydrogen or a hydrocarbyl
group having from 1 to 3 carbon atoms; each-R' is independently
hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to
10, preferably from 1 to 4 carbon atoms/ or halogen, preferably
chlorine or bromine; A is a divalent hydrocarbon group having
from 1 to 10, preferably from 1 to 4 carbon atoms,
:
O O O O
.. .. .. ..
~ O-, -C-, -S-, -S-S-, -S-, -S- or -O-C-O-; n has a value of
.~ ~ O
10 ~: : zero or 1.
The term hydrocarbyl as employed herein means any
aliphatic, cycloaliphatic, aromatic, aryl substituted aliphatic
or~allphatic substituted aromatic groups~ Likewise, the term
hydrocarbyloxy group~means hydrocarbyl group having an oxygen
: linkage between it and the object to which it is attached.
Another aspect of the present invention concerns the
product resulting from polymerizing the aforesaid composition.
:
,~
~3~ 8~
- 4 - 74069-20
A further aspect of the present invention concerns
a composition which comprises
(A) at least one thermosettable compound which simul-
taneously contains in the same molecule only one maleimide or
substituted maleimide group which grsups are represented by the
formula
o
~Rl
wherein each R and Rl is independently hydrogen or a hydrocarbyl
group having from 1 to 3 carbon atoms; and only one cyanate group
and
(B) at least one of
: Il) at least one aromatic polycyanate;
(2) at least one polymaleimide;
(3) at least one material having an average of
: more than one vicinal epoxide group per molecule or
(4) at least one polymerizable ethylenically
unsaturated material;
: wherein component (A) comprises from l to 99, preferably from 1
to 75, most preferably from~5 to 50 percent by weight of the
combined weight o~ components (A) and (B).
~ 20 An additional aspect of the present invention con-
;~ cerns the product resulting from copolymerizing the aforementioned
composition.
: ~
.: .
~3~S488
- 5 - 74069-20
Particularly suitable compositions include, for
example, 4~ 3-(2,5-dihydro-2,5-dioxo-lH-pyrrol-l-yl)phenyl)-
l-methylethyl)-phenyl cyanate; 4-(1-(4-(2,5-dihydro-2,5-dioxo-
lH-pyrrol-l-yl)phenyl)-l-methylethyl)phenyl cyanate; 4-(1-(4-(2,5-
; dihydro-2,5-dioxo-lH-pyrrol-l-yl)phenyl)ethyl)phenyl cyanate;
4-(4-(2,5-dihydro-2,5-dioxo-lH-pyrrol-l-yl)phenoxy)phenyl
cyanate; 4-((4-(2,5-dihydro-2,5-dioxo-lH-pyrrol-l-yl)phenyl)-
thio)phenyl cyanate; 4-(4~(2,5-dihydro-2,5-dioxo-lH-pyrrol-l-
yl)benzoyl)phenyl cyanate; 4-((4-(2,5-dihydro-2,5-dioxo-lH-
pyrrol-l-yl)phenyl)sulfonyl)phenyl cyanate, 4-tl-(4-(2,5-dihydro-
3-methyl-2,5-dioxo-lH-pyrrol-l-yl)phenyl)-l-methylethyl)phenyl
cyanate; 2,6-dibromo-4-(1-(3,5-dibromo-4-(2,5-dihydro-2,5-dioxo-
lH-pyrrol-ll-yl)phenyl)-l-methylethyl)phenyl cyanate; 4-(2,5-
dihydro-2,5-dioxo-lH-pyrrol l-yl~-3-methylphenyl cyanate; 4-
(2,5-dihydro-2,5-dioxo-lH-pyrrol-l-yl)phenyl cyanate and 3-(2,5-
dihydro-2,5-dioxo-lH-pyrrol-l-yl)phenyl cyanate.
:
:
::
: :~
; :
~ ~ B
.~ . .,
3t~S~
--6--
The compositions which simultaneously contain
both a male-imide group and a cyanate group can be
prapared by reacting a stoichiometric quantity of a
maleic anhydride per amine group of a
hydroxy(amino)aryl or a hydroxyarylaminoaryl compound
in the presence of a suitable solvent then cyanating
the resulting hydroxyaryl maleimide product.
Suitable maleic anhydrides include, for
example9 those represented by the formula
R ~ ~ (III)
O
wherein R and R1 are as hereinbefore de~ined.
Suitable maleic anhydrides include maleic
anhydride, methyl maleic anhydride, and mixtures
thereof. Most preferred as the maleic anhydride is
maleic anhydride, per se,
. ~ Suita~le hydroxy(amino)aryl and hydroxyaryl-
aminoaryl compounds include, for example, those repre-
3 sented by the formulas
~ .
:
: 35
: 34,32g-F -6-
- :
(IV)H0 ~ NH2
(R')4
10,
(V~H0 ~ (A)~ ~ -NH2
(R')4 (R')4
wherein R', A, and n are as hereinbefore defined.
: Suitable hydroxy(amino)aryl and hydroxyaryl-
aminoaryl compounds include o-aminophenol; m-
: 20 aminophenol; p-aminophenol; 2-methoxy-4-hydroxy 1-
: : aminobenzene; 3,5-dimethyl-4-hydroxy-1-aminobenzene; 3-
cyclohexyl-4-hydroxy-1-aminobenzene; 2,6-dibromo-4-
d hydroxy-1-aminobenzene; 5-butyl-4-hydroxy~
aminobenzene; 3-phenyl-4-hydroxy-1-aminobenzene; 4-(1-
~;~ 25 (3-aminophenyl)-1-methylethyl)phenol; 4-(1-(4-
aminophenyl~-1-methylethyl)phenol; 4~ (4-
aminophenyl)ethyl)phe~nol; 4-(4-aminophenoxy)phenol; 4-
4~aminophényl)thio)phenol; (4-aminophenyl)(4-hydroxy-
phenyl)methanone; 4-((4-aminophenyl)sulfonyl)phenol and
4-(1-(4-amino-3,5-dibromophenyl)-1-methylethyl)-2,6-di-
; bromophenol.~
: : Specific methods for preparing 2-(4'-hydroxy-
: aryl)-2-(4'-aminoaryl)propanes suitable for use as the
:: .
34,329-F -7-~
: : -
:~
~3~Si4
~8--
hydroxyarylaminoaryl compound are taught by U.S~ Patent
No. 4,374,272.
Suitable solvents inelude aliphatie monocar-
boxylic aeids such as acetic ae;d, propionie aeid, and
mixtures thereof. Most preferred as the solvent is
aeetie acid~ The maleamic acid resulting from reaction
of a maleie anhydride and a hydroxy(amino)aryl or
hydroxyarylaminoaryl eompound, typieally in an inert
solvent sueh as ehloroform, toluene or dioxane, may be
isolated then dehydrated in an aliphatic monoearboxylie
aeid to the eorresponding phenolie functional
maleimide. Alternately, the reaction may be performed
in a sin~le eontinuous step in the aliphatie
monoearboxylie aeid solvent. The produet resulting
from this reaetion is a phenolie funetional maleimide
represented by the formulas
0
(VI) H0 ~ N
(R')4
(R')4 (R')4 R
(VII) H0 ~ (A3n ~ - N
:
:~: :: :
34,329-F -8-
;; :
,.. , ~ .
':
" ~L3~4~8
g
wherein R, R1, R' 9 A, and n are as hereinbefore
defined.
Compounds which simultaneously contain both the
maleimide group and the cyanate group are conveniently
prepared by reacting a stoichiometric quantity or a
slight stoichiometric excess (up to 20 percent excess)
of a c~anogen halide with a phenolic functional
maleimide, such as those represented by formulas ~VI)
and (VII), in the presence of a stoichiometric quantity
o~ a base material.
Suitable cyanogen halides include cyanogen
bromide and cyanogen chloride. Alternately, the method
of Martin and Bauer described in Or~anic Synthesis,
Volume 61, pp. 35-68 ~1983) and published by lohn Wiley
and Sons can be used to generate the required cyanogen
halide in situ from sodium cyanide and a halogen such
as chlorine or bromine.
Suitable bases include both inorganic bases and
tertiary amines such as sodium hydroxide, potassium
hydroxide9 triethylamine, and mixtures thereof. Most
preferred as the base is triethylamine.
Suitable solvents include water, acetone,
chlorinated hydrocarbons, ketones and the like. Most
preferred solvents are acetone and methylene chloride.
Reaction temperatures of from -40 to 60C are operable
3 with temperatures of 20 to 25C being preferred.
Suitable materials having an average of more
than one vicinal epoxy group per molecule which can be
employed herein include7 for example7 the glycidyl
ethers represented by the formulas
'
34,329-F -9- -
```" ~3q~ 8
o~ ~
u ~
c~
0
c~l - ~ -
u ~
U ,L~ ~ ~ ~<~
H
O
H ~ ~a
34,329-F -10-
`^: `: ` ` :~ ` : `
:`
` - `' ` ` . ., . `
,
``` ~3~S488
N
0~ ~ _
U - 0S
U
O
=r~>
S~o
U
. N
~ ,
o
~r ,:
/
r
34 ,;3~29-F ~
:: : ~ : : : - : -:
~: , : : , :: -
:
:
~ 31~;4~3~
-12-
wherein A, R', and n are as hereinbe~ore defined; each
A' is independently a divalent hydrocarbon group having
from 1 to 6, pre~erably from 1 to 4 carbon atoms
or a ~ \~ J
p group; p has a value of from
zero to 10, preferably from zero to 3; each R" is
independently hydrogen or an alkyl group having from 1
to 4 carbon atoms; n' has a value of from zero to 30,
preferably from zero to 5; and n" has a value of from
0.001 to 6, preferably from 0001 to 3.
Particularly suitable polyepoxides which can be
employed herein include, for example, the diglycidyl
ethers of resorcinol, bisphenol A, 3,3',5,5'-
tetrabromobisphenol A, the triglycidyl ether of
tri~(hydroxyphenyl) methane, the polyglycidyl ether of
a phenolformaldehyde condensation product (novolac),
the polyglycidyl ether of a dicyclopentadiene and
phanol condensation product and the like. The
polyepoxides can be used either alone or in
combination.
The aforementioned polyepoxides represented by
3 ~ormulas (VIII), (IX), (X), and (XI) can be prepared by
reaction of a diphenol or polyphenol with an epihalo-
hydrin and a basic acting material. Said reaction
generally involves two distinct steps: couplin~
reaction of the epihalohydrin and diphenol or
polyphenol to provide a halohydrin intermediate and
; dehydrohalogenation reaction of the halohydrin
: ~ -
~ 34,329-F -12-
: ::: : :
.
..
~t~
-13-
intermediate to provide the glycidyl ether product.
Suitable catalysts and reaction conditions for
preparing polyepoxides are described in the
Handbook of Epoxy Resins by Lee and Neville, McGraw-
Hill (1967)-.
Suitable aromatic polycyanates which can be
employed herein include, for example, those represented
- by the formulas
~.
:
~ 35
.
34,329-F -13-
:
: ~ :
: '
~3~
-14-
(XII) N-C-O ~ O-C-N
(Z)4
(XIII) NsC-O ~ ~)n ~ ~ ~ O-CsN
(Z)4 (Z)4 (Z) m
/ O-C-N \
(XIV) N3C-O ~ A' ~ A' ~ O-C--N
(Z)4 ~ (Z)3 / (Z)4
n"
:: :
R:'
(Z)l~ I (Z~
(XV) N=C-O ~ I - ~ O-C--N
(Z)4 ~ ~ O-CsN
v,:
: : wherein each Z i9 independently hydrogen, a hydrocarbyl
or hydrocarbyloxy group having from 1 to 4 carbon
: atoms, chlorine, bromine, or a -O-C3N group; m has a
: value of fro~ zero to 100, pre~erably from zero to 10
and A, A', R', n, and n" are as hereinbefore defined.
34,329-F -14- :
,
,~
.
. .
:
:L3~S4~
-15-
Suitable aromatic polycyanates represented by
formulas (XII), (XIII), (XIV) and (XV) include, for
example, bis-phenol A dicyanate, the dicyanates of
4,4'-dihydroxydiphenyl oxide, resorcinol, 4,4'-thio-
diphenol, 4,4'-sulfonyldiphenol, 3,3',5,5'~tetrabromo-
bisphenol A, 2,2',6,6'-tetrabromobisphenol A, 3-phenyl
bisphenol A, 4,4'-dihydroxybiphenyl, 2,2'-dihydrcxybi-
phenyl, 2,2',4,4'-tetrahydroxydiphenyl methane,
2,2',6,6'-tetramethyl-3,3'~5,5'-tetrabromobisphenol A,
3,3'-dimethoxybisphenol A, the tetracyanate of
2,2'4,4'-tetrahydroxydiphenylmethane,
N-C-0 ~ 0-C-0 ~ 0-C-0 ~ 0-CaN
2~--C-O ~ ~ ¦ ~ O-CaN
the tricyanate of tris(hydroxyphenyl)methane, the
polycyanate of a phenolformaldehyde condensation
product (novolac), the polycyanate of a dicyclopenta-
:~ diene and phenol condensation product, and the like.
The aromatic polycyanates may be used either alone or
in any combination.
..
The aromatic polycyanates can be prepared by
reacting a stoichiometric quantity or slight stoichio-
metric excess (up to 20 percent excess) of a cyanogen
halide with an aromatic polyphenol in the presence of a
stoichiometric quantity of a base.
.
:~
34,329 F ~-15-
~:
, .~
, ' :
3~
-16-
Suitable aromatic polyphenols include, for
example, those represented by the formulas
:(XVI) HO ~ OH
(M)4
(XVII) HO ~ (A)n ~ (A) = OH
(M)4 (M)4 (M)4 m
/ OH
(XVIII) HO ~ A.' ~ A ~ OH
:(M)4 \ (M)3 /n" (M)4
(M)4 R' (M)4
(XIX) HO - ~ C ~ OH
(M)4 ~ = ~ OH
:: 35
, ~ ~ : : :
~::
34, ~29 -F - 1 6 -
~ ~ :
:
- - .
.
.
,~ . . .
~ ~ :' . ~ ' `,
.
1 L~5 48 8
-17-
wherein A, A', R', n, n" and m are as hereinbefore
defined, and each M is independently a hydrocarbyl or
hydrocarbyloxy group having ~rom 1 to 4 carbon atoms,
chlorine, bromine, a phenyl group or a hydroxyl group.
Suitable cyanogen halides inclùde cyanogen
bromide and cyanogen chloride. Alternately, the method
of Martin and Bauer described in 0
Volume 61, pp. 35-68 (1983) and published by John Wiley
and Sons can be used to generate the required cyanogen
halide in situ from sodium cyanide and a halogen such
as chlorine or bromine.
Suitable bases include hoth inorganic bases and
tertiary amines such as sodium hydroxide, potassium
hydroxide, triethylamine and mixtures thereo~. Most
preferred as the base is triethylamine.
Suitable solvents include water, acetone~
chlorinated hydrocarbons, ketones, and the like. Most
preferred solvents are acetone and methylene chloride.
Reaction temperatures of from -40 to 60C are
operable with temperatures of -20 to 25C being
preferred.
Suitable polymaleimides which can be employed
herein include, for example, those represented by the
formulas
34,329~F -17-
~3~
-18-
(XX) ~\ ~ -Q-N
(XXI)
R R1 R R1 R R1
(XXII)
~ N ~ N N
O I O / o I O ~ O I O
CH~ ~ CH
: / m1
wherein R and:R1 are as hereinbefore defined; Q is a
divalent hydrocarbyl group having from 2 to 12 carbon
30~ atoms:and ml has a value of 0.001 to 10; z1 is a direct
bond, a divalent hydrocarbyl group having from 1 to 5
carbon atoms, -S~ S-S~
::35:
34,329-F : -18
~: ,
:: : :
: ::
: . - . - .
.. , : . :
: . :
,
~3~;i;4~
- 1 9-
o o o o
,. .. .. ..
-0-, -S-, -S-, -C- or -O~C-0- O
O
Typical polymaleimides represented by formulas
XX, XXI and XXII include, N,N'-ethylenebismaleimide,
N,N'-ethylenebis(2-methylmaleimide), N,N'-
hexamethylenebismaleimide, N,N'-(oxydi-p-
phenylene)bismaleimide, N,N'-(methylenedi-p-
~ phenylene)bismaleimide, N,N'-(methylenedi-p-
phenylene)bis(2-methylmaleimide), N,N'-(thiodi-p-
phenylene)bism~leimide, N,N'-(sulfonyldi-m-phenylene)-
bismaleimide, N,N'-(isopropylidenedi-p-phenylene)bis-
maleimide, polymethylene polyphenylene polymaleimidesand the like. The polymaleimides may be used either
alone or in any combination.
The polymaleimides can be prepared by reacting
a stoichiometrio quantity of a maleic anhydride per
amine group of a polyamine in the presence of a
suitable sol~ent.
Suitable maleic anhydrides include those
previously delineated herein.
~;~ Suitable polyamines which can be employed to
prepare the polymaleimides include, for example, those
represented by the formu1as
; 30
~: :
`
34~329-F -19-
: : :
- ~
~3l~
-20-
(XXIII) H2N-Q-NH2
(XXIV) H2N - ~ z1 ~ NH2
; 15 wherein Q, z1 and m1 are as hereinbefore defined.
.
Suitable polyamines include 1,4-diaminobutane,
dodecyl diamine, methylene dianiline, diaminodiphenyl
ether, 2-methyl-4-ethyl-1,8-diaminooctane, aniline-
formaldehyde condensation products, and mixturesthereof.
,
Suitable solvents include aromatic
hydrocarbons, chlorinated hydrocarbons, M ? N-
dimethylformamide and the like. Most pre~erredsolvents are N,N-dimethylformamide, chloroform and
toluene. The polymaleamic;acid resulting from reaction
of a maleic anhydride and a poIyamine may be isolated
then dehydrated to the desired polymaleimide.
Alternately, the reaction may be performed in a single
continuous step. Detailed procedures for preparing
:
polymaleimides can be found in U.S. 2,444,536 and U.S.
2,46~2,835.
~ :: :
:
; ~ 34~329-F ~ -20-
~: :
,.".. ~,,~. . ,. . : . . i
.
., :
-
:~ : . ' :
5~
-21-
Suitable polymerizable ethylenically
unsaturated materials which can be employed herein
include those represented by the formula
(XXVI) (Ql) ~ (Q2)wl
wherein each Q1 is independently hydrogen, a
hydrocarbyl or hydrocarbyloxy group having from 1 to 4
carbon atoms, a vinyl group, an allyl group, chlorine
or bromine; each Q2 is independently hydrogen or a
hydrocarbyl or hydrocarbyloxy group having ~rom 1 to 4
carbon atoms; y1 is
: 20 R
-C-C-R1 or -C--C=CH wherein eaoh R, R1 and R is
R2 R1 R2
independently.hydrogen or a hydrocarbyl group having
~: ~ : 25 from 1 to 3 carbon atoms; and w and w1 are each
: positive integers, the sum of which is 5.
Typically ethylenically unsaturated compounds
:: represented by ~ormula XXVI include, for example,
3 ~tyrene, alpha-methylstyrene, chlorostyrene,
bromostyrene, t-butylstyrene, p-methylstyrene, p-
methoxystyrene, divinylbenzene, propylstyrene9 chloro-
: alpha--methylstyrene, m-methylstyrene, o-methylstyrene,
allylbenzene, methallylbenzene, p-allylstyrene,
: diallylbenzene, and mixtures thereof.
:
~ 34,329-F - -21-
:
~, ' ' -
~3~5~
-22-
Equally preferred as the polymerizable ethylen-
ically unsaturated material which can be employed
include herein the acrylate esters represented by the
formula
O R4 O
ll l
(XXVII) R3-o-C-C~CH2
wherein R3 is a hydrocarbyl group having from 2 to 25
carbon atoms and may be branched, cyclic or polycyclic
and R is hydrogen or a methyl group.
Typical acrylate esters represented by formula
XXVII include ethyl acrylate, n-butyl acrylate, n-butyl
methacrylate 9 sec-butyl acrylate, 2-ethylhexyl
acrylate, 2-ethylhexyl methacrylate, n-dodecyl
acrylate, cyclohexyl acryIate, methyl cyclohexyl
acrylate, norbornyl acrylate, dicyclopentadiene
acrylate, methyl dicyclopentadiene acrylate, and
mixtures thereof.
Although less preferred, any other of the known
polymerizable ethylenically unsaturated compounds can
be employed herein either alone or in any combination.
Typical of these compounds are acrylonitrile, diallyl-
phthalate, vinyl chloride, vinyl bromide, vinyl
acetate, vinyl naphthalene, the poly(ethoxy)acrylate of
dicyclopentadiene, and mixtures thereof.
Compositions which comprise at least one
thermosettable compound which simultaneously contains
both a maleimide group and a cyanate group (Formulas I,
II) may be cured (polymerized) by heating from 50 to
350C or more, preferably by heating from 70 to 200C
and optionally in the presence of 0.001 to 5 percent by
weight of a suitable cyclization catalyst. Operable
34,329-F -22- --
:
.
.
-23-
cyclization catalysts include those taught by U.S.
Patent Nos. 3,694,410 and 4,094,852. Most preferred
cyclization catalysts are cobalt naphthenate an~ cobalt
octoate. The quantity depends upon the particular
cyclization catalyst, cure time 9 cure temperature and
structure of the specific compound being cured.
Prepolymerization or B-staging of the composi-
tions can be accomplished by using lower temperatures
and/or shorter curing times. Curing of the thus formed
prepolymerized or B-staged resin can then be completed
at a later time or immediately following prepolymeriza-
tion or B-staging by increasing the temperature and/or
curing timeO
The cured (polymerized) products prepared from
at least one thermosettable compound which simul-
taneously contain both a maleimide group and a cyanate
group can posses a complex variety of curing structures
including the cyanate group homopolymerization
structure
:
N~
0~0
N ~ ~
, ~
the maleimide group homopolymerization structure
~:
:
~ 35
: ::::: ;
.
34,329-F -23
.
-24-
H H H H
' ' '
C--C - C C
~ N ~ ~ N ~
and cyanate group and maleimide group copolymerization
structures such a3, ~or example
:0
H "
- 0-C ~ \ j \N -
:20 ~ C ~ ''
H o
--O
H
C \ C / ~ N
. - N
C - C ~ / C-H
: ::30 : //
; 0/ H H ~ ~ CoO
~: ~ O
~, ~
::35~
34,329-F -24-
., ~ - ., . ., : ,
: ' :
~ 3~ 8
-25-
Compositions which comprise at least one
thermosettable compound which simultaneously contzins
both a maleimide group and a cyanate group (Formulas I,
II) and at least one compound selected from the group
consisting of an aromatic polycyanate, (Formulas XII,
XIII, XIV, XV), a polymaleimide (Formulas XX, XXI,
XXII), a polyepoxide (Formulas VIII, IX, X, XI) or a
polymerizable ethylenically unsaturated material
(Formulas XXVI, XXVII) may be cured (copolymerized) by
heating from 5Q to 350C or more, preferably from 70 to
200C and, optionally, in the presence of 0.001 to 5
percent o~ a suitable cyclization catalyst and,
optionally, 0.001 to 3 percent of a suitable free
radical forming catalyst~
Suitable cyclization catalysts include those
previously delineated herein while suitable free
radical forming catalysts include the organic
peroxides, hydroperoxides, azo compounds and diazo
compounds. Most preferred free radical forming
catalysts include t-butyl peroxybenzoate, azo-
bisiosbutyronitrile, dicumylperoxide and di-t-
butylperoxide. The quantity depends upon the
particular free radical forming catalyst, cure
temperature, cure time and the particular compounds
being copoIymerized.
Prepolymerization or B-staging of the composi-
tions can be accomplished as was previously described.
The cured (copolymerized) products possess acomplex variety of curing structures which depend, in
part, upon the amounts and types of compounds being
copolymerized, cure time, cure tempèrature, presence or
absence of a cyclization catalyst ? presence or absence
34,329-F -25- -
-26-
of a free radical forming catalyst and other known
variables.
Compositions whic~ contain at least one
thermosettable compound which simultaneously contains
both a maleimide group and a cyanate group (`Formulas I,
II) and either an aromatic polycyanate (Formulas XII,
XIII, XIV, XV) or a polymaleimide (Formulas XX, XXI,
XXII) or both can copolymerize to produce the
aforementioned curing structures delineatèd for
thermosettable compounds which simultaneously contain
both a maleimide group and a cyanate. group. It should
be noted, however, that the relative mole ratio of
cyanate groups to maleimide groups can influence the
amounts of the various curing structures in the cured
product. For example, a large excess o~ cyanate
: groups, provided by using an aromatic polycyanate in
the copolymerizable composition, increases the amount
of triaæine curing structure in the cured product.
'
Compositions which contain at least one
thermosettable compound which simultaneously contains ~
~ both a maleimide group and a cyanate group (Formulas I,
:: 25 II) and a polyepoxide (Formulas VIII, IX, X, XI)
~ pos~ess complex curing structures including those
:~ derived from copolymerization reaction of the cyanate
~: group and the glycidyl ether
`:~
0
:
I ~
; : group (-0-CH2-C-CH2).
: R"
35 -
~:: 34,329-F -26- -
~;3~
-27-
Compositions whîch contain at least one
thermosettable compound which simultaneously contains
both a malei~ide group and a cyanate group (Formulas I,
I~) and a polymerizable ethylenically unsaturated
material (Formulas XXVI, XXVII) car, possess curing
structures derived from copolymerization reaction of
the maleimide-group and the polymerizable ethylenically
unsaturated group, from copolymerization reaction of
the maleimide group and the cyanate group, as well as
from copolymerization reaction of the cyanate group and
the polymerizable ethylenically unsaturated group.
Additionally present may be curing structures derived
from homopolymerization of the polymerizable
ethylenically unsaturated groups, from
homopolymerization of the maleimide groups, as well as
from homopolymerization of the cyanate groups.
The terms homopolymerization and copolymeriza-
tion are also meant to include both dimerization andoligomerization.
The compositions which comprise at least one
thermosettable compound which simultaneously contains
both a maleimide group and a cyanate group (Formulas I,
II) and at least one compound from the group consisting
of an aromatic polycyanate (Formulas XII, XIII, XIV,
XV), a polymaleimide (Formulas XX, XXI, XXII), a poly-
epoxide (For~ulas VIII, IX, X, XI) or a polymerizable
ethylenically unsaturated material (Formulas
XXVI,XXVII) may be copolymerized either simultaneously
or in stages.
In a preferred process of the present
invention, a thermosettable compound which
simultaneously contains both a maIeimide group and a
, . .
34,329-F -27- -
, ", ,
-28-
cyanate group (Formulas I, II) and a polymerizable
ethylenically unsaturated material are first
copolymerized in the presence of 0.001 to 2 percent of
a suitable free radical forming catalyst and at a
suitable reaction temperature while in solution in an
aromatic polycyanate (Formulas XII, XIII, XIV, XV).
Operable free radical forming catalysts are as
hereinbefore describedO Suitable reaction temperatures
are from 65C to 125C. The compound which
simultaneously contains both a maleimide group and a
cyanate group and the polymerizable ethylenically
unsaturated material may first be mixed to form a
solution which is then added to the polycyanate.
Alternately, the polymerizable ethylenically
unsaturated material may be added to a solution of the
compound which simultaneously contains both a maleimide
group and a c~anate group and the polycyanate. The
product resulting from this copolymerization is a
copolymer of the polymerizable ethylenically
unsaturated ~aterial with the maleimide groups of the
compound which simultaneously contains both a maleimide
group and a cyanate group dissolved in or mixed with a
polycyanate. This product may be cured
(homopolymerized) as previously described herein or
copolymerized, for example, with a polyepoxide, as
previously described herein.
As a specific example, copolymerization of
3 styrene and 3-(2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl)-
phenyl cyanate in the presence of a free radical
forming catalyst while in solution in bisphenol A
; dicyanate provides a copolymer of the following
structure dissolved in or mixed with the bisphenol A
dicyanate:
:
~ 34,329-F -28-
~3~
-29-
H H H H
~ C C - C C I
S C~
N-C-0 ~
Depending on the amounts of the styrene and 3-(2,5-
: dihydro-2,5-dioxo-1H-pyrrol-1-yl)phenyl cyanate used,
signi~icant amounts of homopolymer of either of the
- aforementioned compounds may also be present.
In another preferred process of the present
~: invention, a thermosettable compound which
20: simultaneously contains both a maleimide group and a
: :~ cyanate group (Formulas I, II):and a polymerizable
ethylenically unsaturated material are copolymeri7.ed in
the presence of 0.001 to 3 percent of a suitable ~ree
~radical forming catalyst and at a~suitable reaction
~: : 25 temperature optionally:in the presence of an inert
~ ~ ~ solvent. The product resulting f:rom this
: ~: copolymerization is a copolymer of the ethylenically
Z ~ :unsaturated material with the maleimide groups of the
compound which~simultaneously contains both a maleimide
30: group and a cyanate group. This product may be cured
(homopolymerized) as previously described herein or
copolymer~ized,~ for example, with a polycyanate and/or a
polyepoxide, as previously descrlbed herein.
: In those instances where R' is chlorine or
: ~ bromine ~Formulas I, II, VIII, IX, X, XI, XV), Z is
:
:
: ::; : :
:~ : 34,329-F -29-
:,: ~ , ~
`:
:. .
-3o-
chlorine or bromine (Formulas XII, XIII, XIV, XV)
and/or Q1 is chlorine or bromine (Formula XXVI) the
halogen(s) are incorporated into the copolymers by the
polymerization of monomer(s) containing said group(s).
Furthermore, the halogen groups can be incorporated
into the copolymers in a specific location within the
polymer structure. As a specific example,
copolymerization of 3-(2,5-dihydro-2,5-dioxo-lH-pyrrol-
1-yl)phenyl cyanate, bisphenol A dicyanate and
chlorostyrene provide a copolymer wherein 21 is
chlorine and Q1 is specifically present only on the
styrene aromatic rings within the polymer chains. Said
halogen containing copolymers are useful as fire
retardant polymers.
I~ desired, the compositions can contain
fillers, pigments, dyes, reinforcing materials, other
additives and the like.
The compositions of the present invention are
useful in the preparation of castings, structural or
electrical laminates or composites, coatings, and the
like.
Laminates or composites can be prepared from
the compositions of the present invention employing any
facing and/or reinforcing materials such as9 for
example, metallic sheets, woven or mat materials, such
as fiberglass, graphite, asbestos, aramids, carbon
combinations thereof and the like.
The following examples are illus~rative of the
invention but are not to be construed as to limiting
the scope thereof in any manner.
34,329-F ~3-
"~" ~j. ... .
~ 3~
- 3 1 -
EXAMPLE 1
A. Synthesis of a Phenolic Functional Maleimide
A 54.57 gram portion of m-aminophenol (0.50
mole) and 650 milliliters of acetic acid were added to
a reactor and maintained under a nitrogen atmosphere
with stirring. The stirred solution was maintained at
25C, then 49.03 grams of maleic anhydride (0.50 mole)
dissolved in 100 milliliters of acetic acid was added
to the reactor and heating to 110C commenced. The
110C reaction temperature was maintained for 14 hours
then the product was dried under vacuum by rotary
evaporation at 120C for 30 minutes to a dark brown
solid~ The crude product was extracted with two 250
milliliter portions of o-dichlorobenzene at 120C. The
combined extracts were maintained at 2C for 24 hours
then the light yellow orange colored crystalline
product was recovered by filtration and dried under
vacuum at 60C for 24 hours to provide 35.0 grams of N-
(3-hydroxyphenyl) maleimide. Infrared
spectrophotometric analysis of a film sample of the
product confirmed the product structure.
~ r~ B. Preparation of 3-(2,5-dihydro-2,5-dioxo-1H-pyrrol-
yl)Phen~l cyanate
A 34.05 gram portion of N-(3-hydroxyphenyl)-
maleimide (0.18 mole), 20.02 grams of cyanogen bromide
3 (0.189 mole) and 300 milliliters of acetone were added
to a reactor and maintained under a nitrogen atmosphere
with stirring. The stirred solution was cooled to -10C
then 18.31 grams of triethylamine (0.1809 mole) was
added to the reactor over a fifteen minute period and
so as to maintain the reaction temperature at -5 to
34,329-F ~31-
.,.~
-32-
-4C. After completion o~ the triethylamine addition,
the reactor was maintained at -5 to -3C for an
additional thirty minutes, followed by addition of the
reactor contents to 1500 milliliters of deionized
water. After five minutes, the water and product
mixture was multiplynextracted with three 100
milliliter volumes of methylene chloride. The combined
methylene chloride extract was washed with 500
milliliters of 0.05 percent aqueous hydrochloric acid
followed by washing with 500 milliliters of deionized
water then drying over anhydrous sodium sulfate. The
dry methylene chloride extract was filtered and solvent
removed by rotary evaporation under vacuum for 60
minutes at 60C. 3-(2,5-dihydro-2,5-dioxo-lH-pyrrol-1-
-yl)phenyl cyanate (34.25 grams) was recovered in 88.9
percent yield as a light tan colored powder. Infrared
spectrophotometric analysis of a film sample of the
product confirmed the product structure (disappearance
of phenolic hydroxyl absorbance, appearance of cyanate
absorbance at 2232 and 2274 cm~1, maintenance of
~ maleimide carbonyl absorbance at 1714 cm~1).
:; :
C. Mass Spectroscopic Anal~sis of 3-(2,5-dihydro-2,5-
-dioxo-1H-pyrrol-1-yl!phenyl cyanate
3-(2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl)-
phenyl cyanate~from B above was analyzed by mass
spectroscopy using a Finnigan 4500 MS and direct probe
30~introduction of the sample. Sample ions were observed
at the ambient temperature (150G) of the ion source.
The moleoular ion observed at m/z 214 confirmed the
product structure.
~ ;
::
~ 34,329-F -32-
'
~" 3~ ~ L~
-33- -
EXAMPLE 2
A. Preparation of 4~ (4-aminoQhenyl)-l-methyleth~l ?
phenol
A mixture of 134.0 grams (1.0 mole) of p-iso-
propenylphenol and 186.0 grams (2.0 moles) of aniline
was stirred and heated to 150C. To the mixture was
added 5.0 grams of a solution obtained by adding 1.28
grams of 10% hydrochloric acid to 93 grams of aniline
and stirring the mixture well. The reaction was carried
out for 3.0 hours at the 150C reaction temperature.
The reaction product was cooled to 120C then 350
milliliters of toluene was added. The product was then
cooled to 25C and the solid precipitated product was
recovered by ~iltration. The crude product was
slurried into 350 milliliters of methanol and heated to
a reflux then maintained for 15 minutes. After
cooling, the product was recovered by filtration and
dried under vacuum to yield 4-(1-(4-aminophenyl)-1-
methylethyl)phenol as a white powder.
,,
B. Synthesis of a Phenolic_Functional Maleimide
A 45.46 gram portion of 4-(1-(4-aminophenyl)-1-
methylethyl)phenol (0.20 mole) and 500 milliliters of
acetic acid were added to a reactor and maintained
under a nitrogen atmosphere with stirring. The stirred
solution was maintained at 25C, then 19.61 grams of
3 maleic anhydride (0.20 mole) dissolved in 100
milliliters of acetic acid was added to the reactor and
heating to a reflux commenced. The 126C reflux
temperature was maintained for 15 hours, then the
product was dried under vacuum by rotary evaporation at
100C for 60 minutes. The crude product was dissolved
34,329-F -33-
~: :
::
.
-34-
in 250 milliliters uf o-dichlorobenzene at 120C and
then cooled to 25C. The light yellow colored solution
was decanted away from a brown colored oil layer and
dried under vacuum by rotary evaporation at 100C for 60
minutes to provide 31.4 grams of 4~ (4-(2,5-dihy.dro-
2,5-dioxo-1H-pyrrol-1-yl)phenyl)-1--methylethyl)phenol
as a bright yellow colored powder. Infrared
spectrophotometric analysis of a film sample of the
product confirmed the product structure.
C~ PreRaration of 4-(1-~4-(2,5-dih~dro-2,5 dioxo-1H-
-pyrrol-1-yl)phenyl)-1-methylethyl)phenyl cyanate
A 21.70 gram portion o~ 4~ (4-(2,5-dihydro-
2,5~dioxo-1H-pyrrol-1-yl)phenyl)-1-methylethyl)phenol
(0~1037 mole), 11.53 grams of cyanogen bromide (0.1089
mole) and 250 milliliters of acetone were added to a
reactor and maintained under a nitrogen atmosphere with
stirring. The stirred solution was cooled to -5C then
10.55 grams oP triethylamine (0.1043 mole) was added to
the reactor over a eight minute period and so as to
maintain the reaction temperature at -5 to -3C~. A~ter
completion of the triethylamine addition, the reactor
was maintained at -5 to -3C for an additional 37
minutes, followed by addition of the reactor contents
to 1500 milliliters of deionized water. After 5
minutes, the water and product mixture was multiply
extracted with three 100 mi-lliliter volumes of
methylene ohloride. The combined methylene chloride
extract was washed with 500 milliliters of 0.05 percent
aqueous hydrochloric acid followed by washing with 500
milliliters of deionized water then drying over
anhydrous sodium ~sul~ate. The dry methylene chloride
extract was filtered and solvent removed by rotary
:
~ evaporation under vacuum for 30 minutes at 90C. 4-(1-
~: ~- ::
34,32~-F ~ -34-
~: .
~ ~ ,
~'
'' ~
~ ~ 3~
-35-
(4-(2,5-dihydro-2,5-dioxo-1H-pyrrol l-yl)phenyl)-l-
methylethyl)pheny-l cyanate (22.2 grams) was recovered
in 91.4 percent yield as a light amber colored oil.
Infrared spectrophotometric analysis of a film sample
of the product confirmed the product structure
(disappearance of phenolic hydroxyl absorbance7
appearance of cyanate absorbance at 2242 and 2271 cm~1,
maintenance of maleimide carbonyl absorbance at 1722
cm~l)O
D Preparation o~ Bisphenol A Dic~ ate
A 456.60 gram portion of 4,4'-isopropylidene
diphenol (2.00 moles), 444.91 grams of cyanogen bromide
(4.20 moles) and 1,100 milliliters of acetone were
added to a reactor and maintained under a nitrogen
atmosphere with stirring. The stirred solution was
aooled to -5C, then 406.82 grams oP triethylamine (4.02
moles) was added to the reactor over a 60 minute period
and so as to maintain the reaction temperature at -5 to
-3C. After completion of the triethylamine addition,
the reactor was maintained at -5 to -3C for an
additional twenty-five minutes followed by addition of
the reactor contents to 1.5 gallons (5.685 1) of
deionized water. After 5 minutes, the water and
product mixture was multiply extracted with three 500
milliliter volumes of methylene chloride. The combined
methylene chloride extract was washed with 500
milliliters of 0.05 percent by weight aqueous
hydrochloric acid ~ollowed by washing with 500
~ milliliters of deionized water, then drying over
; anhydrous sodium sul~ate. The dry methylene chloride
extract was filtered and solvent removed by rotary
evaporation under vacuum for 60 minutes at 100C.
; Bisphenol A dicyanate (545~8 grams) was recovered in
: ~ :
: : ~:
34,~29-F -35-
. :
.' . : " '
- : '
-36-
98.1 percent yield as a light tan colored, crystalline
solid. Infrared spectrophotometric analysis of a film
sample of the product confirmed the product structure
(disappearance of phenolic hydroxyl absorbance,
appearance of cyanate absorbance).
E. __Preparation and Copol~merization of 4~ (4-
-(2,5-dih~dro-2,5-dioxo-lH-e,yrrol-l-yl)phenyl)-
-1-methylethyl)phenyl c~nate and Bisphenol A
Dicyanate Solution
A 22.2 gram portion of 4~ (4-(2,5-dihydro-
2,5wdioxo-lH-pyrrol-1-yl)phenyl-1-methylethyl)-phenyl
cyanate from C above and 88.8 grams of bisphenol A
dicyanate from D above were combined and heated to 100C
with stirring to form a solution. The solution was
cooled to 50C, then 0.11 gram of cobalt naphthenate
(6.0 percent active) was mixed in. This solution was
reheated to 100C, filtered, then poured into a 1/8 inch
(o.3 cm) mold made from a pair of glass plates and then
placed in an oven and maintained at 125C for 2 hours,
177C ~or 4 hours, 200C for 4 hours, then 250C for 2
hours. The transparent, light amber colored, clear,
unfilled casting was demolded and used to prepare test
pieces for tensile and flexural strength, flexural
modulus, percent elongation and average Barcol hardness
(934-1 scale determinations). Mechanical properties of
tensile and flexural test pieces were determined using
an Instron machine with standard test methods (ASTM D-
638 and D-790~. The results are reported in Table I.
COMPARATIVE EXPERIMENT A
Homopo~ on of Bisphenol A Dicyanate
.
- 34,329-F -36-
.
-37-
A 200.0 gram portion of bisphenol A dicyanate
prepared using the method of Example 2-D was heated to
100C to form a solution, cooled to 50C, then 0.20 gram
of cobalt naphthenate (6.0 percent active) was added.
This solution was reheated to 100C, filtered, then
poured into a 1/8 inch (0.3 cm) mold and cured using
the method o~ Example 2-E. The transparent, light
amber colored, clear, unfilled casting was demolded and
used to prepare test pieces which were tested using the
method o~ Example 2-E. The results are reported in
Table I.
TABLE I
Comparative
~xam~ E
ExDeriment A
~arcol Hardness 49 48
Tensile Strength,
psi/kPa 13,590/93,699 13,080/90,184
Elongation, & 3 .12 3 . 26
Flexural Strength, 22,348/154,085 19,176~132,215
psi/kPa
Flexural Modulus, 571,000/3,936,906 555,000/3,826,590
psi~kPa
:25
~ .
EXAMPLE 3
Co~olymerization of 2-Ethylhexyl Acrylate and
~:~ 3 3-(295-dih~dro-2,5-dioxo-1H-p~rrol-1-vl)phen~l
cyanate in a Bi~phenol A Dicyanate Solution
A 175.0 gram (81.28 percent by weight, pbw)
portion of bisphenol A dicyanate prepared using the
: method of Example 2-D and a 8.0 gram (3.72 pbw) portion
of 3-~2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl)phenyl
34,329-F ~37~
:~ :
.
:
- ~3~
cyanate prepared using the method of Example I-B were
added to a reactor and maintained under a nitrogen
atmosphere. The reactor contents were heated to a 110C
solution then stirring commenced and dropwise addition
of 32.29 grams (15.0 pbw) of 2-ethylhexyl acrylate and
0O43 gram of azobisisobutyronitrile as a solution
commenced and was completed over a fifteen minute
period. After an additional 80 minutes of reaction at
the 110C reaotion temperature, the product was
recovered as a slightly hazy, light amber colored
solution. A portion (0.2 grams) of the copoly(2-
ethylhexyl acrylate and 3-(2,5-dihydro-2,5-dioxo-lH--
pyrrol-1-yl)phenyl cyanate) in bisphenol A dicyanate
solution was analyzed by gel permeation chromatography
using polystyrene standards. The weight average
molecular weight of the 2-ethylhexyl acrylate and 3-
(2,5-dihydro-2,5-dioxo-lH-pyrrol-l-yl)phenyl cyanate
copolymer portion of the solution was 11,789 and the
polydispersity ratio was 8098.
EXAMPLE 4
A. _Copol~_rization of 2-Ethylhexyl Acrvlate and
3-(2,5-dihydro-2,5-dioxo-lH-pyrrol-l-yl)phenyl
cyanate in a Bi~phenol A Dic~anate Solution
A 180.0 gram (80 percent by weight, pbw)
portion of bisphenol A dicyanate prepared using the
method of Example 2-D and an 11.25 gram (5 pbw) portion
; ~ of 3-(2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl)phenyl
cyanate prepared using the method of Example 1-B were
added to a reactor and maintained under a nitrogen
atmosphere The reactor contents were heated to a 110C
solution. Then stirring commenced and dropwise
addition of 33.75 grams (15 pbw) of 2-ethylhexyl
:
34,329-F -38-
`` ~ 3
-39-
acrylate ~nd 0.45 gram of azobisisobutyronitrile as a
solution commenced over a 35 minute period. After an
additional 120 minutes of reaction at the 110C reaction
temperature, the product was recovered as a hazy, light
amber colored solution.
B. Polymerization of Copoly(2-ethvlhexyl_acrylate
and 3-(2,5-dih~dro-2,5-dioxo-lH-~rrol-1-yl)phenyl
cyanate) in Bisphenol A DicJy nate Solution
A 210.0 gram portion of copoly(2-eth~lhexyl
acrylate and 3~(2,5-dihydro-2,5-dioxo-1H-pyrrol-1-
yl)phenyl cyanate) in bisphenol A dicyanate from A
above was heated to 50C, then 0.21 gram of cobalt
naphthenate (6.0 percent active) was added. This
solution was heated to 100~C, filtered, then poured i-nto
a 1/8 inch (0.3 cm) mold and cured using the method of
Example 2-E. The opaque, light amber colored, unfilled
casting was demolded and used to prepare test pieces
which were tested using the method of Example 2-E. A
pair of heat distortion temperature test pieces were
also prepared from the casting and heat distortion
temperature was determined using an Aminco Piastic
Deflection Tester (American Instrument Co.) with
standard methods (ASTM D-648 modified). The results
~ ~ are reported in Table II.
: . :
: ::
; ~35
.~ .
34,329-F -39-
;: :
, ~ .: . :
;
':
,a
~ 3~
- -40-
TABLE II
Barcol Hardness 36
Heat Distortion Temperature,
~F/C 455/235
Tensile Strength
psi,kPa 10,525/72,568
Elongation, % 4.49
Flexural Strength,
psi/kPa 17,516/120,769
Flexural Modulus,
psi/kPa 422,000/2,909,587
EXAMPLE 5
Polymerization of 3-(2,5-dihydro-2,5-dioxo-1H-p~rrol-
yl)phenyl cyanate; Bisphenol A Dicyanate and Styrene
SOlUtlon
A 9.25 gram portion of 3-(2,5-dihydro-2,5 -
dioxo-1H-pyrrol-1-yl)phenyl cyanate (4.15 pbw) prepared
using the method of Example 1-B; 168.75 grams of
bisphenol A dicyanate (75.67 pbw) prepared using the
method of Example 2-D; and 45.0 grams of styrene (20.18
pbw) were combined and heated to 100C with stirring to
form a solution. The solution was cooled to 60~C, then
0.22 gram o~ cobalt naphthenate (6.0 percent active)
3 was mixed in. This solution was reheated to 100CC,
filtered, then poured into a 1/8 inch (0.3 cm) mold and
cured using the method o~ Example 2-E. The
trans~arent, light amber colored,~clear, unfilled
casting was demolded and used to prepare test pieces
~ which were evaluated using the method of Example 2-E.
- ~ A pair of heat distortion temperature test pieces were
~ 34,3Z9-F -40_
~ .
. .
3~
-41-
also prepared and tested using the method of Example 4-
Bo The results are reported in Table IIIo
TABLE III
Barcol Hardness 51
Heat Distortion Temperature, 379.9/193.3
F/C
Tensile Strength, psi/kPa 129909/89,005
Elongation, % 2.81
Flexural Strength, psi/kPa 18,476/127,388
Flexural Modulus, psi/kPa 522,200/3,600,465
EXAMPLE 6
Homopolvmerization of 3-(295~dihydro-2,5-dioxo-lH-
-pyrrol-1-yl)phenyl cyanate
A portion (1.0 gram) of 3-(2,5-dihydro-2,5-
: dioxo-1H-pyrrol~1-yl)phenyl cyanate from Example 1-B,
0.0001 gram of cobalt naphthenate (6.0 percent active)
and 3.0 grams of acetone were thoroughly mixed to form
a solution. The solution was devolatilized and then
cured using the method of Example 2-E. A portion (9.54
: milligrams) of the resulting transparent, light amber
colored film was analyzed by thermogravimetric analysis
(`TGA), Weight loss was recorded as a function of
temperature at a 10C per minute rate of increase in a
; stream of nitrogen:flowing at 35 cubic centimeters per
: : minute. As a comparative experiment, a portion (9.80
~3 m1lligrams) of the homopolymerized bisphenol A
: : dicyanate of Comparative Experiment A was also analyzed
~: : by TGA. The resuIts are reported in Table IV.
~ 35
34,329-F -41-
~'` ' '" "" '.
:
: :
~3a~$9~
-112 -
Table IV.
Weiqht Loss
Sa~npl e
Desiqnation
l00C 300C 350C 400C 450C 500C 700C
Exampl~ 6 0 1.0 1.2 1.726.2 32 4905
Compara t ive
Experiment A0.2 1.5 2.0 3.63û.5 49 62.2
EXAMPLE 7
Sets of four flexural strength test pieces
prepared from the castings of Examples 2-E, 4-B, 5 and
Comparative Experiment A were weighed, then immersed in
deionized water contained in individual jars and main-
tained at 92C. The test pieces were weighed at the
indicated intervals and the percent weight gain
: 20 calculated as follows: 100 ~(exposed weight - initial
weight)/initial weight]. An average of the percent
: weight gain was then calculated. After a total of 94
hours of exposure to the 92C deionized water, the
~: 25: flexural strength, flexural modulus and average Barcol
hardness were determined using the method of Example 2-
E. The results are reported in Table V.
~: 30:
:: :
: 34,329-F -42- .
::
~3~
o r~l
a~ o
J N Irl N
` CO r~
~ r~
V ~1 ~I t~
(~I E ~ ~ O O
~a 4 ~ o o t~
E Q r~ N O O
O x
U l~ ~ ~, et~ N ~1 00 ~ ~
117 ~D + ~ ~ N N t`i
r ~
0 ~ o
r-7 1~ al o
u~ r~
~`I N
a) .-1 ~I t`l '?
~1 u~ 1` Q o
E I` ~ o o "' ~ cn el~ N u:~
~1 ~ N N 1~ 1 0
_I + ~ O ~ 0
U~ ~O +
r- Ir~
u~ r-
m r N O
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-44-
COMPARATIVE EXPERIMENT B
A clear, unfilled 1/8 inch (0.3 cm) casting of
a bismaleimide--triazine resin (BT 2600 Resin, Mitsu-
bishi Gas Chemical Co., Inc.) was prepared using the
method of Example 2-E with the exception that cobalt
acetoacetonate catalyst was used to provide.131 ppm
cobalt and curing was completed at 175C ~or 1 hour and
225C for 2 hours. Flexural strength and flexural
modulus of test pieces prepared from the transparent,
amber colored casting were evaluated using the method
of Example 2-E. A second set of flexural strength test
pieces were prepared and immersed in 92C deionized
water then evaluated using the method of Example 7.
The results are reported in Table VI and may be
compared with the results reported in Example 7.
TABLE VI
Flexural Strength, psi/kPa
; initial 16,200/111,696
: exposed 13,130/90,529
; percent change -18.95
25 Flexural Modulus, psi/kPa
initial 673,000/4,640,171
exposed 760,000/5,240,015
: percent change +12.93
: Barcol Hardness
initial 60
exposed 56
3 percent change 6.67
: Percent Weight Gain
after 24 hours of exposure 1.31
~ after 48 hours of exposure 1.66
: a~ter 72 hours of:exposure 1.87
; after 94 hours of exposure 2.04
: ~ 34,329~F _44
:::
