Note: Descriptions are shown in the official language in which they were submitted.
RD-14,199
POLYAMIDE MOLDING CAPSTONES
Background of the Invention
Bi~maleimides have been utilized with epoxy monomers and aromatic
amine to provide polyamide molding compositions with high heat disk
torsion temperatures, as disclosed in US. Patents 4,294,723 and
4,294,877. A disadvantage that is characteristic of these molding
compositions is that they have a slow cure rate, typically
requiring about 0.5-2 hours to cure.
Malefic android has been known to react rapidly with aliphatic
vinyl ethers, as disclosed by Leonard, Ed Vinyl and Dine Monomers.
- Vol. 24, Part I, NY: Wiley Intrusions, 1970, pp. 39g-401~ However,
the cured product obtained with maleimide and aliphatic vinyl ethers
are not attractive because of low heat distortion temperatures. In
addition, these aliphatic vinyl ethers are liquid at room temperature
and are not amenable to the formulation of solid molding compositions,
making such compositions difficult to process into finished products.
The present invention is based on the discovery that maleimides
copolymerize rapidly with aromatic vinyl ethers. The resulting
copolymers have high oxidative stability and high heat distortion
temperatures which overcome the disadvantages characteristic of
polyamide molding compositions known to the art.
Statement of the Invention
The invention provides a molding composition comprising an
aromatic vinyl ether and maleimide. The preferred molding
compositions comprise:
(A) aromatic vinyl ether of the formula
R3
A GROW OKAY / J n (I) and
R4 R ,
Jo 1
ROD 14,199
(~) maleimide having at least one chemically
combined unit of the formula
o
R5-C-C
11 \
6 i (II)
R -C-C
o
h i R2 R3 R4 R5 d R6 are selected from the group
consisting of hydrogen, halogen and alkyd radicals of from
1 to 8 carbon atoms, Al is an alkaline radical of from 1
to 8 carbon atoms, G is selected from the group consisting
O
of -O-, -C-O-, and mixtures thereof, A is selected from
a group of monovalent and polyvalent aromatic radicals
having from 6 to 130 carbon atoms, and n is an integer
equal to 1-10 inclusive.
Examples of maleimides suitable for use in the
molding compositions comprising this invention are
described by Holub et at in the following US. Patents:
3,558,741, issued January 26, 1971 and 3,787,439, issued
January 22, 1974 (maleimide substituted organ polyp
selection); 3,652,716, issued March 28, 1972 and 3,729,446,
issued April 24, 1973 ~maleimide substituted polyesters);
3,6~9,464, issued July 5, 1972 and 3,763,273, issued
October 2, 1973 (maleimide substituted polyamides) and
3,576,031, issued April 20, 1971 (male.imide substituted
organosilanes). All of the above-identified patents are
assigned to the same assignee as the present invention.
Other suitable maleimides include bismaleimide
of the formula:
O O
5 " " 5
R -C-C C-C-R
¦¦ NUN ¦¦
O O
-- 2
RD-14,199
and monofunctional mateimide of the formula:
0
R5-C-C\
R5-C-C
o
wherein R5 and I are selected from the group consisting of hydrogen,
hygiene and alkyd radicals of from 1 to 8 carbon atoms, X is
selected from a group consisting of diva lent hydrocarbon radicals
of from 1-35 carbon atoms and diva lent groups of the formula
I
where Z is selected from the class of diva lent radicals con-
sitting of hydrocarbon radicals of prom 0 to 15 carbon atoms ,
R7
10 -S- , -O- , -S2- -C- , -N-, and N ; where R7 is a
monovalent alkyd radical of from 1-6 carbon atoms; and Y is
a monovalent hydrocarbon radical selected from the group
consisting of aliphatic radicals of from 1-8 carbon atoms and
aromatic radicals of from 6-20 carbon atoms;
lo Some bismaleimides may be prepared by effecting reaction
between a Damon compound of the formula NH2-X-NH~ and malefic
android to form the maleamic acid, where X has the meaning
given above. The maleamic acid is treated with acetic
android and catalyst composition, such. as a mixture of nickel
acetate and triethyl amine, to produce the corresponding
bismaleimide.
Same monofunctional maleimides can be made in a similar
fashion by utilizing an amine of the following formula NOAH
and malefic androids to form the maleamic acid, where Y is a
group of monovalent radicals defined above.
. In addition to hismaleimides and monofunctional
maleimides, maleimide oligomers of the following formula are
suitable for use in the molding compositions of this invention.
Jo
ROD 14,199
_
H O O H
R -C-C C-C-R
I > -X-N \
-N~l-X'-NH-C-C O R5
_ m
R60 0
¦ N-X-N \ ¦¦
- C-C-R
R O O O o R6
R -C-C \ / C-C-NH-X'-NH~-
if N-X-N
If / \ I
R5-C-C C C-H
O O R
wherein X, R6 and R5 are as previously defined and X' is
selected from the same group of diva lent organic radicals
from which X is selected, and m is an integer of from l
to lo inclusive.
These oligomers may be prepared ho effecting
a condensation reaction between bismaleimide and Damon
of the formula NH2-X'-NH2, where X' is selected prom a
group of diva lent radicals as defined above. A statue-
lo metric deficient quantity of Damon is utilized to
prevent complete polymerization of the bismaleimides.
The maleimide monomers and oligomers can be varied
widely, as can the organic radicals represented by X, X' and
Y which are present therein. Among the devaluate groups whirl-
X and X' may more specifically represent are, for example,
diva lent saturated alkaline radicals of up to 15 carbon atoms
having linear, branched and cyclic structures
- 4 -
9~L~36
RD-14,199
including, ethylene, ethylene, propylene, battalion, isopropyl-
Irene, hexylene, cyclohexylene, ne3pentylene, etc. lye members of
the diva lent groups, X and X', also include diva lent radicals
of the formula -CH2-CH2-0-CH2-CH2-. Diva lent aromatic radicals
within the scope of X and X' include, for example, m-
phenylene, p-phenylene, 2,6-naphthylene, 2-methyl-1,3-phenylene,
dichlorophenylene and diary groups such as p,p'-biphenylene
m,m'-biphenylene, diphenylene ethylene, diphenylene oxide,
diphenylene cellophane, diphenylene sulfide, ketobiphenylene, etc.
These diary radicals may be attached to the nitrogens through
ortho, mote or pane positions.
Typical examples of bismaleimides which can
be utilized in the molding compositions of this invention or
be converted to oligomers include, for example,
N,N'-1,2-ethylene-bismaleimide,
N,N'-methylene bismaleimide,
N,N'-1,4-butylene-bismaleimide,
N,N'-1,6-hexamethylene-bismaleimide,
N,N'-1,4'-phenylene-b;smaleim;de,
N,N'-1,3'-phenylene-bismaleimide,
Jo N,N'-2-methyl-1,3-phenylene-bismaleimide,
N,N'-4,4'-diphenylmethyl bismaleimide,
N,N'-4,4'-diphenylether bismaleimide,
N,N'-4,4'-diphenylsulfone bismaleimide,
N,N'-4,4'-diphenyl sulfide-bismaleimide,
N,N'-4,4'-dicyclohexylmethane-bismaleimide,
N,N'-1,3-xylene-bismaleimide,
N,N'-4,4'-benzophenone-bismaleimide,
N,N'-~3,3'-dichloro-4,4'-biphenylene~bismaleimide..
The above list of bismaleimides are typically prepared
by reacting l mole of a Damon compound having the corresponding
diva lent radical X with 2 moles of malefic android. other
androids, such as substituted malefic androids, may be
utilized for making the bismaleimides. For example, citraconic android
and pyrocinchonic android can be utilized to produce bismaleimides,
such as N,N'-4,4'-diphenyl methane-bis~methyl-maleimide) and
N,N'-4,4'-diphenyl methane-bis(dimethylmaleimide) with
I
RD-14.199
Damon diphenyl methane. Mixtures of androids and or
mixtures of Damon compounds may be employed for making
mixtures of bismaleimides. Such mixtures of bismaleimide
are suitable for use in the molding composition comprising
this invention and for producing oligomers suitable for sub-
sequent use in this invention. Halogenated bismaleimides, where
halogen is on the diva lent radical X and X' or the monovalent
radicals R5 and R6, can be employed without departing from
the scope of this invention. For example, NOAH
dichloro-4,4'-diphenyloxy-bismaleimide), No
(3,3'-dibromo-4,4-diphenylmethane)-bismaleimide, etc. are
suitable maleimides for use in the molding compositions
comprising this invention.
Monofunctional maleimides can also be varied widely
depending on the organic radicals which are present therein.
Among the monovalent radicals which Y may more specifically
represent are, for example, monovalent saturated alkyd radicals
of up to 8 carbon atoms having linear and branch structures.
The suitable alkyd radicals include, for example, methyl,
ethyl, propel, bottle, isopropyl, ponytail, Huxley, etc. The
monovalent radicals represented by Y also include aromatic
radicals of from 6-20 carbon atoms. Included in this group,
are, for example, phenol, 3-methyl phenol, naphthyl, biphenyl,
etc.
The aromatic vinyl ethers of the molding compositions
comprising this invention can be varied widely due to the many
different aromatic units which can be present therein. A
portion of the vinyl ether monomers suitable for the molding
composition of this invention are more particularly defined
my Crivello in US. Patent 4,388,450, which issued
June 14, 1983. Some of the aromatic polyvinyl
ether monomers within the scope of this invention are more
particularly defined below. The aromatic vinyl ethers which are
suitable for use in this invention also include aromatic vinyl
ethers having only one vinyl ether moiety.
~Z29~
RD-14,199
. Radicals included within the scope of A of formula I
are, for example, polyvalent aromatic radicals such as phenylene,
tolylene, xylylene, naphthylene, zanily, anthrylene, and
diary groups of the formula
Q
O Q
where Q is selected from -O-, -S-, -C-, -S-, alkaline radicals
of from 1-8 carbon atoms and a diva lent aromatic group of the
formula
Jo '
Polyvalent aromatic radicals also included within the scope of
A include those of the formula
n OH and
tCH2-CH etc. ,
3L2~ Lo
-
RD-14,199
where no is an integer of from 1 to 10 inclusive.
Monovalent aromatic radicals within the scope of A
include phenol, naphthyl, xylyl and ~iaryl groups of the formula
Q
where Q is as previously defined.
Suitable aromatic vinyl ethers also vary with the
radicals which are present on the vinyl ether group.
The diva lent radicals included within the scope of
Al of formula I are alkaline radicals of 1-8 carton atoms,
such as ethylene, ethylene, trim ethylene, tetramethylene, etc.
Radicals within the scope of R3, R2 and R4 are, for example,
hydrogen, monovalent alkyd radicals of 1-8 carbon atoms, such
as methyl, ethyl, propel, etc. and halogen radicals such as,
sheller, broom, etc.
Halogenated derivatives of the aromatic radicals
previously described are also within the scope of A, for
example, chlorophenylene, bromotolylene, chlorophenyl, bromophenyl,
etc. Specific examples of aromatic polyvinyl ethers of
formula I include compounds such as,
CH2=CH-0-CH2CH2-0 C -CH2-CH2-0-cH=cH2
CH2=CH-O-CH2CH2-O O-CH2CH2-O-cH=cH29
CH3-CH=CH-O-cH2-cH2-o Shea O-CH2-CH2-O-CH=CH-CH3
. ..
9~L~6
RD-14~199
CH2=CH-O~CH2CH2-O 0 CH.2-CH2 O-CH=CH2~
I,
CH2=CH-O-cH2-cH2-o S _ O-CH2-CH2-O-cH=cH2
p-CH2-CH2-O-cH-cH2
CH2=CH-O-CH2- SHEA O-cH2-cH2-o-c~l=cH2
CH2=CH-O-CH2-CH2-O SHEA O-cH2-cHz-o-cH=cH2
CMz=CHO-CH2-CH2-O O-cH2-cH2-o-cH=cH2
0
SCHICK O-CH2-CH;O CH3~o-CH;CH2-O-c~5H2~
p-CH2-CH2-O-CH=CH2 O-CH2-CHz~O~cH=cH2 ,O-CH2-CH2-O-cH=cH2
n
: SHEA SHEA SHEA
LO
RD-14,199
CH2=CH-O~CH2-CH2-3--~ O-CH2-CH2-O-cH=cH2~
O-CH2-CH2-O-C~=cH2 O-cH2-cH2-o-cH-cH2 O-CH2-C112-O-CH=cH2
-$ SHEA SHEA
One method of making some of the aromatic vinyl
ethers of formula I is to condense an alkali metal salt of an
aureole hydroxide or carboxylic acid with a halo-alkyl vinyl ether
in the presence of dimethylsulfoxide as shown by the following
equation:
Amman + nBRlOC(R4) = CROWER) formula
where h? I. Al, R2, R3 and R4 and n are as previously defined,
B is a halogen radical and M is an alkali metal ion.
Once the desired aromatic vinyl ether and maleimide
compounds have been obtained, the molding composition can be
prepared by melt mixing these two components at temperatures
below about 110C. In addition to the maleimide compounds
and the aromatic vinyl ethers, the molding composition may
contain a peroxide or aza^catalystto reduce the curing
temperature or curing time necessary. Typical organic
peroxides suitable for catalysis are, for example, kitten
peroxides, proxy acids, dibasic acid peroxides, alluded
I peroxides, alkyd peroxides, hydra peroxides, alkyd proxy-
esters, diperoxide derivatives, for example, t-butyl proxy
pivalate, 2,4-dichlorobenzoyl peroxide, caprylyl peroxide,
-
RD-14,199
laurel peroxide, decanoyl peroxide, Dropionyl peroxide, acutely
peroxide, t-butyl peroxyisobutyrate, p-chlorobenzoyl peroxide,
bouncily peroxide, hydroxyheptyl peroxide, cyclohexanone
peroxide, 2,5-dimethylhexyl-2,5-di~peroxybenzoate), dirt-
bottle diperphthalate, t-butylhydroperoxide, di-t-butylperoxide,
methyl ethyl kitten peroxide, p-methane hydroperoxide, cumin
hydroperoxide, 2,5-dimethyl hexyl-2,5-dihydroperoxide, t-
butyl-hydroperoxide, parasitic acid, perbenzoic acid, m-chloro
perbenzoic acid, etc.
In addition to these organic peroxides, some
azo-compounds are suitable for catalysis in the molding
composition of this invention. Such azo-compounds include
azo-bis-alkyl nitrites and azo-compounds of the formulas:
SHEA SHEA ,c,~3
CH3-C-N=N-C-CH3 , CHICANO
SHEA SHEA SHEA ON
N N (C6H5)3C-N=~ C~C6H5)3
SHEA SHEA SHEA SHEA
CH3-C-N=N-C-CH3 , C2H5-C-N=N-C-C2H5 , etc.;
SHEA SHEA SHEA SHEA
and
~,29~
RD-14,199
quinines, such as
Of ON 1 0 C
O Of
Clue 1
o
Besides a catalyst, the molding composition may also contain
fillers, such as clay, silica, calcium carbonate, aluminum
trihydrite, carbon black, talc, calcium sulfate, wollastonite,
etc. Suitable weight ratios of filler to active ingredients fall
within the range ox 0 to 300 parts filler per 100 parts active
ingredients. These molding compositions may also contain other
additives such as antioxidant flame retardants, impact
modifiers, etc.
Once the molding composition is prepared by melt
mixing the aromatic vinyl ethers and maleimide compounds
together with the desired additives, the molding composition
is cured by raising the temperature from 14~ to about
170C. Rapid polymerization results from the application of
such temperatures. This heat activated polymerization is
usually accomplished within a mold under pressure. Such
pressures can range from about 200 psi to about 600 psi. Cure
times typically fall within the range of about 1-4.5 minutes.
Although this polymerization is rapid at relatively low
temperatures in absence of a catalyst, the cure temperature or
the cure time can be reduced upon addition of a peroxide or
azo-catalyst indicated above. The cusp time or such molding
compositions containing catalysts are typically reduced to
within the range of about 1 minute to about 2 minutes.
12
go
RD-14,199
This enables the polyamide molding compositions of this invention
to be used as photo curable coatings and to be employed as
photo resists. A photo-initiated cure can be achieved with
conventional free radical photo-initiators, such as bottle
Bunsen ether, added to the mixture of aromatic vinyl ether
monomers and maleimide monomers. A photo-initiated cure can
be achieved for mixtures containing the above-identified
bottle Bunsen ether where a molding composition is radiated for
30 seconds at a distance of 6 inches from a mercury arc lamp.
When intending to cure by photo initiation, it is preferable to
use maleimide monomers having low melting points to aid volubility
with the aromatic vinyl ethers at room temperature.
An alternative to mixing the maleimide compounds and
aromatic vinyl ether monomers as identified above is to
dissolve both the aromatic vinyl ether monomers and the maleimide
compounds in a common organic solvent; such as acetone, and
impregnate a fiber matrix such as fiber glass cloth, with the
solution. The organic solvent is then evaporated off the
fiber matrix producing a dry fiber matrix impregnated with the
maleimide compounds and the vinyl ether monomers, herein
referred to as "prepreg". These prepregs are cut, stacked and
heated to initiate polymerization. Suitable cure temperatures
fall within the range ox about 1~0C to about 170C. These
prepregs can be molded when pressed together under such curing
temperatures for about 2-3 minutes and pressures of about 400-600 psi.
An alternative to curing a melt mixture comprised
substantially of maleimide and the aromatic vinyl ether is to
granulate and pullets the mixture to make solid thermosetting
compositions for injection, compression and transfer molding.
Optimum cross linking densities are typically obtained
from a molding composition having a 1:1 mole ratio of maleimide
having more than 1 electron deficient group, such as bismaleimidPs,
RD-14,199
to aromatic vinyl ether having more than one vinyl group, such
as aromatic bus vinyl ether. However, the stoichiometry of the
molding composition is variable within wide tolerances and a
suitable cured composition may be achieved with molding
compositions where the ratio of maleimide functional groups of
formula II to vinyl groups can have a value in the range of
about 0.25 to about 4.
The mechanical properties of the cured molding come
position can be altered to desired values by varying the
stoichiometry of the molding composition and by altering the
constituents of the molding composition. For example, where
improved flexural strength and elongation is desired, maleimide
oligomers may be preferred over the maleimide monomers.
Variations of the stoichiometry can provide changes in the
flexural strength, elongation and tensile strength also.
Cure temperatures are preferably within the range of
about 140 to about 170C. Higher temperatures are suitable,
however, such higher temperatures may cause unnecessary
degradation of the aromatic vinyl ethers or additives present
within the molding compounds. Cure times at these temperatures
vary within the range of 1 minute to I minutes depending on the
presence of catalysts and the quantity of such catalysts.
The cured molding compositions typically exhibit
high heat distortion temperatures of approximately 220C and
suitable engineering properties such as percent elongation,
tensile strength, tensile modulus, flexural strength etc.
The following experimental procedures were used to
produce selected constituents of particular thermoplastic
compositions comprising this invention. These procedures are
provided to aid in the practice of this invention and are not
intended to limit this invention.
To produce N,N'-4,4'-diphenylmethane bismaleimide,
4,~'-diaminodiphenylmethane and 0.5 mole malefic android were
added to 1 liter of acetone. Rapid reaction occurred to form a
14
I
RD-14,199
bismaleamic acid precipitate. Then 0.5 mole triethylamine,
0~02 mole nickel acetate and 2.5 moles of acetic android
were added. After refluxing the mixture for 2.5 hours, all
of the bismaleamic acid had dissolved and the reaction mixture
s was poured into an equal volume of water. The product which
separated as an oil, was allowed to crystallize in an ice
bath and was purified by two recrystallization from Tulane.
The yield prior to recrystallization was 65-80X theory.
To Produce the divinely ether of the following formula
SHEA
CH2=CH-O-cH2-cH2- -CH2-CH2 O-CH=CH~,
SHEA
bisphenol-A t68~5 9.), Tulane (500 ml) and 24 g Noah dissolved
in 100 ml water were added to a 1000 ml flask. The flask was
equipped with a paddle stirrer, reflex condenser, Dean Stark
trap, and a nitrogen inlet. The reaction mixture was heated to
reflex and the water which was formed was collected on the trap
and removed from the reaction. Reflex was continued until no
more water was being collected, than the trap was replaced with
a special Dean Stark trap containing activated molecular sieves.
Reflex was continued overnight to fully dry the system. The
20 reaction mixture was then filtered and the bisphenol-A-
disodium salt collected. The above salt was transferred to a
2000 ml flask and one liter dim ethyl sulfoxide was added. This
reaction mixture was heated to approximately 60C and 65 g 2-
chloroethyl vinyl ether was added slowly. The reaction mixture
was then stirred at 60C for 1 hour, cooled and stirred at
room temperature for an additional 5 hours, then poured into
1000 ml 50% Noah. An oil separated and was removed. The
oil was washed three additional times with 50% aqueous Noah to
remove unrequited bisphenol-A. The wash solutions were
extracted with ether and the extractions added to the oil.
On evaporation of the ether, a 77 g yield of the divinely
ether was obtained (69.8X yield).
I
~q~9~6
. ROY
To produce the aromatic divinely ether of the formula:
CH3-CH=CH-O-CH2-CH2- ~-CH2-CH2-o-cH=cH-cH3
A reaction mixture of 632.76 g ( 2 moles bisethoxylated bus-
phenol-A (Donnelly, AWAKES Comma, 300 ml Tulane, and 45902 g
( 6 moles) allylchloride was stirred until the bisethoxylated
bisphenol-A had dissolved. Then 240 9 (6 moles) solid
Noah was added and stirring continued for 0.5 hour. Next,
32 9 (0.1 mole) tetrabuty1ammonium bromide was added and the
stirring continued for 0.5 hour. The temperature of the
reaction mixture was slowly raised to 50 then the reaction
temperature rose to 100C as exothermic reaction took place.
The reaction mixture temperature was brought to 75C with a
water bath and stirred overnight (16 hours). The product
was isolated by pouring the reaction mixture into 2 liters of
distilled water and isolating the organic layer by means of
a separator funnel. After washing the organic layer with
three 500 ml portions of water, it was dried over solid sodium
sulfate and the Tulane removed under vacuum to yield 690 g
(86' theory) of bisallyl ether product.
To the bisallyl ether of ethoxylated bisphenol A,
3g6.5 9 (1 molejwere added 0.96 g (1 x 10-3 mole) RuCl2(PPh3)3.
The reaction mixture was brought slowly to lZOC with a silicone
oil bath and maintained at this temperature for 1.5 hour.
After cooling, the product was examined by nuclear magnetic
resonance and found to have isomerized completely to the bus-
propenyl ether. The product was a mixture of three isometric
bispropenyl ethers swishes cisterns, transitoriness).
The examples below are Provided to illustrate embodiments of
this invention-and are not intended to limit this invention.
All parts are by weight unless otherwise specified.
2Z9~9G
RD-14,199
Example I
The following example demonstrates the preparation and
method of curing an embodiment of this invention.
The following materials were heated and mixed
together at 80C until homogeneous.
CHz=CH-O-CH2-CH2-O 0-CHz-CH2-O-CH=~H2 46 parts
N OH No>\ 44.8 oats
t-butylperbenzoate 2 parts
The mixture was allowed to cool and harden. Then it was
pulverized and dry blended with 100 Darts silica (Combustion
Engineering, OHM 42I~. This mixture was further mixed on a 2-roll
mill at 80C and allowed to harden. The solid molding compound
was transfer molded in a 12 ton Hull transfer molding press at
600 psi and 160C for 2 minutes. Test bars were obtained having a
heat distortion temperature at 264 psi of greater than 200C.
The mechanical properties are illustrated in Table I.
TABLE I
Flexural Flexural Tensile Tensile
Tempt ~C) Strength Modulus _ Strength Modulus
8.843 2.02 x 106 2.554 7.04 x 105
150 8.843 2.02 x lo 2.027 7.04 x 105
180 8.843 2.02 106 2.077 7.5 x 105
17
.....
3~L~6
RD-14,199
Example II
This example demonstrates a method of preparing and
outing an embodiment of this invention.
Into a large beaker there were placed
CH3-CH=CH-O-cH2-cH2-o -CH2-CH2-0-CH=CH-CH3 ~9.5 parts
N Ho _ N S\ ~4.8 parts
t-butylperbenzoate 1 nary
The mixture was heated and stirred at 80C until homogeneous,
then 120 parts silica (OHM 42I) were added and mixing continued
until a homogeneous blend was obtained. A molding compound with
a dough-like consistency was obtained which was transfer molded
as described in the previous example Bars and discs were
obtained having a heat distortion temperature of 180C.
Example IT
This example demonstrates another method of curing an
embodiment of this invention.
Example I was repeated omitting the silica filler.
After the mixture was made homogeneous by stirring at 80C,
it was used to impregnate glass cloth. The impregnated cloth
was then cut into 6" x 6" squares and 7 of the squares stacked
together to make a prepreg. After pressing the prepreg in a
Carver press for 2 minutes a 160C and 500 psi, a cured laminate
resulted.
Example IV
This example demonstrates a method for preparing an
curing an embodiment of this invention.
Using the procedure of Example r, the following
components were mixed at 80C.
18
, -
I
RD-14,199
SHEA
CH2=CH-0-CH2-CH-0 0-cH2-cH2-o-cH=cH2 I parts
SHEA
SHEA o
I \ 35.3 parts
t-butylperbenzoate I part
Subsequently, thy mixture was powder blended with 120 parts
silica (OHM 42I) and then mill rolled at 80C. The hardened
molding compound was then transfer molded as described in
Example 4 to give molded parts with a heat distortion temperature
of greater than 200C.
Example V
This example demonstrates the effect different radical
initiators have on the resin gel time.
. Equimolar amounts of the following materiels were heated
and mixed together at 150C using I by weight of various radical
initiators;
CH2=CH-0-CH2-CH2-0 0-CH7-CHz-~-CH=CH2 (.01 moles)
OH N ~.01 moles)
19
~2,Z9~.9G
RD-14,199
The gel times for five different mixtures utilizing the radical
initiators listed in Table II were measured with a Sunshine
Gel meter equipped with a constant temperature bath maintained
at 150C. The gel time measurements and half-life of the initiators
S are indicated in Table II._ __ __ 7_.
9~L~316
RD-14,199
YE o Lo O
I
J E
Lo_
_ I
o o o o
a: o o
T _ _ I _ _
CRY:
O et O I
C. . r-
_ C_ I O Us
I_ I_
Z
w x a
I: _ O
I_ r C o
C I
I X a O
I_ O O
Z TV
r-
at O O
Jo MU
at N a a l I
cc a
Lo
~Z;2~6
RD-14,1g9
Example VI
This example demonstrates a method of photo-curing an
embodim nut of this invention.
To 3.58 9 (0.01 mole) N,N'-bismaleimide-4,4'-d;phenyl
methane and 3.10 9 (0.01 mole) bisphenol A-bispropenyl
ether there was added 0.13 9 (3% by weight) N-butylbenzoin
ether (Bunsen n-butyl ether). The mixture was warmed
slightly to produce a homogeneous solution and then spread
as a 2 mix film onto a glass plate using a drubber. The
lo film was irradiated for 30 seconds at a distance of 6 inches
from a medium pressure mercury arc lamp to produce a cross-
linked insoluble film. Where a mask was placed over the film
prior to irradiation, a negative image of the mask was
obtained on washing the film with acetone after irradiation.
Although the above examples have shown various
modifications of the present invention, it should be under-
stood that further modifications by one skilled in the art are
possible in light of the above teachings without departing from
the spirit and scope of this invention.
~9~916 ROD 14,199
SUPPLEMENTARY DISCLOSURE
It has been found the aromatic vinyl ether
that may be used with -the present invention may have
the formula
R3
A -awry )bb~ C, C on Formula It
R R
wherein R2, R3 and R4 are selected from the group con-
sitting of hydrogen, halogen and alkyd radicals of from
1 to 8 carbon atoms, Al is an alkaline radical of from
1 to carbon atoms, G is selected from the group
o
consisting of -O-, -C-O- and mixtures thereof, A is
selected from a group of monovalent and polyvalent
aromatic radicals having 6 to 130 carbon atoms, n is an
integer equal to 1-10 inclusive and both a and by are
integers having a value of 0 or 1 subject to the proviso
that where by is zero a is zero. ,R3
Thus the vinyl ether groups -O-C I may be
R R
bonded directly to the aromatic group A or be separated
by a diva lent radical Al with or without the functional
group G.
Thus specific examples of formula It include
the examples given in the original texts for Formula I
as well as the following:
CH3-CH=CH-O CH3-CH=CH-O O-CH=CH-CH3
O-CH=CH-CH3
_ 23 -
Jo .
.
ROD 14,199
SHEA OH Of 1 'cH=cH-cH3
CH=CH-CH3 CH=CH-CH3
CH3-CH=CH-o~CH2~3-o-CH=CH-CH3 rev
CH3-CH=CH-O- -CH=CH-CH3
CH3-CH=CH-0 0-CH=CH-CH3
CN3-CH=CH-0 2 C-C}I=CH-CH3
CH3-CH=CH-0 5 -CH=CH-CH3
CH3-CH=CH-0 -CH=CH-CH3
CH3-CH=CH-0 -CH=CH-CH3
-24 -
I`'
I 9 ROD 14,199
wherein n is an integer of from l to 10 inclusive.
The following example demonstrates methods for
preparing and curing embodiments of this invention:
Example VII
To 0.01 mole of each of the aromatic vinyl
ethers shown in Table III were added and blended 0.01 g
t-butylperbenzoate and 0.01 mole (3.58 g) of N,N'-4,4'-
diphenylmethane bismaleimide having the formula
N SHEA N
O O
lo to form a dry paste. Each of the samples were placed in
a Sunshine Gel timer and the vet times measured at 130C.
The gel times for each sample appear in Table III.
TABLE III
; Gel times for various Aromatic Vinyl Ethers
Sample No. Aromatic Vinyl Ether Gel Time (min.)
0-CH=CH-CH3 1.7
O-CH=CH=CH3
2 CH3-CH=CH-O-CH2 - CH2-0-CH=C~I-CH3 1.
O-CH=CH-CH
O-CH=CH-CH3 1.9
4 CH3-CH=CH-0 0-CH=CH-CH3 3.0
-25 -
