CA1229196A - Polyimide molding compositions - Google Patents
Polyimide molding compositionsInfo
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- CA1229196A CA1229196A CA000458787A CA458787A CA1229196A CA 1229196 A CA1229196 A CA 1229196A CA 000458787 A CA000458787 A CA 000458787A CA 458787 A CA458787 A CA 458787A CA 1229196 A CA1229196 A CA 1229196A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
Abstract
POLYAMIDE MOLDING COMPOSITIONS
ABSTRACT OF THE DISCLOSURE
A molding composition is provided comprising aromatic vinyl ether and maleimide. The cured composition exhibits high heat distortion temperatures and is easily processed into finished products with or without a catalyst.
ABSTRACT OF THE DISCLOSURE
A molding composition is provided comprising aromatic vinyl ether and maleimide. The cured composition exhibits high heat distortion temperatures and is easily processed into finished products with or without a catalyst.
Description
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 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 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
RD-14,199 and monofunctional mateimide of the formula:
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 , 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 ¦ 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
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 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 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.
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 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 .....
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.
, -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) ~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 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 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
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 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 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
RD-14,199 and monofunctional mateimide of the formula:
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 , 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 ¦ 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
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 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 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.
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 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 .....
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.
, -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) ~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 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 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
O-CH=CH-CH
O-CH=CH-CH3 1.9 4 CH3-CH=CH-0 0-CH=CH-CH3 3.0
Claims (38)
1. A molding composition comprising:
(A) aromatic vinyl ether of the formula (I) and (B) maleimide having at least one chemically combined unit of the formula (II) wherein R1 is an alkylene radical of from 1 to 8 carbon atoms, R2, R3, R4, R5 and R6 are selected from the group consisting of hydrogen, halogen and alkyl radicals of from 1 to 8 carbon atoms, G is selected from the group consisting of - O - , , and mixtures thereof, A is selected from a group consisting of monovalent and polyvalent aromatic radicals of from 6 to 130 carbon atoms and n is an integer equal to 1-10 inclusive.
(A) aromatic vinyl ether of the formula (I) and (B) maleimide having at least one chemically combined unit of the formula (II) wherein R1 is an alkylene radical of from 1 to 8 carbon atoms, R2, R3, R4, R5 and R6 are selected from the group consisting of hydrogen, halogen and alkyl radicals of from 1 to 8 carbon atoms, G is selected from the group consisting of - O - , , and mixtures thereof, A is selected from a group consisting of monovalent and polyvalent aromatic radicals of from 6 to 130 carbon atoms and n is an integer equal to 1-10 inclusive.
2. A molding composition of claim 1 additionally comprising an effective amount of thermal-curing catalyst.
3. A molding composition of claim 1 additionally comprising an effective amount of photo-curing catalyst.
4. A molding composition of claim 2 wherein the thermal-curing catalyst is selected from the class consisting of organic peroxide and azo-compounds.
5. A molding composition in accordance with claim 2 wherein the thermal-curing catalyst is selected from a group of organic peroxides consisting of t-butyl perbenzoate, t-butylhydroperoxide benzopinacole, and benzoyl peroxide.
6. A photocurable composition in accordance with claim 3 wherein the photocurable catalyst is N-butylbenzoin ether.
7. A molding composition of claim 1 wherein the maleimide is bismaleimide of the following formula wherein R6 and R5 are as previously defined in claim 1 and X is selected from the group consisting of divalent hydrocarbon radicals of from 1 to 35 carbon atoms and divalent groups of the formula where Z is either a bond between the phenyl groups or is selected from the class of divalent radicals consisting of hydrocarbon radicals of from 0 to 15 carbon atoms, - S -, - O -, - SO2 -, and ; wherein R7 is a monovalent alkyl radical of from 1 to 6 carbon atoms.
8. A molding composition in accordance with claim 7 wherein the divalent radical, X, of the bismale-imide is bisphenol-A.
9. A molding composition of claim 1 wherein
9. A molding composition of claim 1 wherein
Claim 9 continued:
wherein R6 and R5 are as previously defined and both X and X' are independently selected from the group consisting of divalent hydrocarbon radicals of from 1 to 35 carbon atoms and divalent groups of the formula where Z is selected from the class of divalent radicals consisting of divalent hydrocarbon radicals of from 0 to 15 carbon atoms, - X -, - O -, - SO2 -, , and ; wherein R7 is a monovalent alkyl radical of from 1 to 6 carbon atoms and m is an integer from 1 to 10 inclusive.
wherein R6 and R5 are as previously defined and both X and X' are independently selected from the group consisting of divalent hydrocarbon radicals of from 1 to 35 carbon atoms and divalent groups of the formula where Z is selected from the class of divalent radicals consisting of divalent hydrocarbon radicals of from 0 to 15 carbon atoms, - X -, - O -, - SO2 -, , and ; wherein R7 is a monovalent alkyl radical of from 1 to 6 carbon atoms and m is an integer from 1 to 10 inclusive.
10. A molding composition in accordance with claim 1 wherein the maleimide is selected from the group consisting of N,N'-4,4'-diphenylmethane bismaleimide and N,N'-6-methyl-1,3-phenylene bismaleimide.
11. A molding composition in accordance with claim 1 wherein the aromatic radicals represented by A
of formula I are selected from the group consisting of phenylene, tolylene, xylylene, naphthylene, xenyl, anthry-lene, diaryl groups of the formula and polyvalent aromatic, radicals selected from the group consisting of wherein Q is selected from a class consisting of divalent radicals of the formulas - S -,- O -, - SO2 -, and alkylene radicals of from 1-8 carbon atoms, R7 is an alkyl radical of from 1 to 6 carbon atoms, and n' is an integer equal to 1 to 10 inclusive.
of formula I are selected from the group consisting of phenylene, tolylene, xylylene, naphthylene, xenyl, anthry-lene, diaryl groups of the formula and polyvalent aromatic, radicals selected from the group consisting of wherein Q is selected from a class consisting of divalent radicals of the formulas - S -,- O -, - SO2 -, and alkylene radicals of from 1-8 carbon atoms, R7 is an alkyl radical of from 1 to 6 carbon atoms, and n' is an integer equal to 1 to 10 inclusive.
12. A molding composition in accordance with claim 1 wherein the aromatic radical A of formula I is bisphenol-A.
13. A molding composition in accordance with claim 1 wherein the aromatic vinyl ether is selected from a group consisting of bisvinyl ethers having the formula:
and
and
14. A molding composition in accordance with claim 1 wherein a molar ratio of maleimide to aromatic vinyl ether has a value within the range of about 0.25 to about 4.
15. A molding composition comprising:
(A) 0 to 60% of one or more fillers and (s) 40 to 100% of a reactive composition comprising:
(a) aromatic vinyl ether of the formula and (b) maleimide having at least one chemically combined unit of the formula wherein R6, R2, R4 and R5 are selected from the group consisting of hydrogen, halogen, alkyl radicals of from 1 to 8 carbon atoms, R7 is an alkylene radical of from 1 to 8 carbon atoms, G is selected from the group consisting of - O -, , and mixtures thereof, A is selected from a group of monovalent and polyvalent aromatic radicals of from 6 to 130 carbon atoms and n is an integer equal to 1-10 inclusive.
(A) 0 to 60% of one or more fillers and (s) 40 to 100% of a reactive composition comprising:
(a) aromatic vinyl ether of the formula and (b) maleimide having at least one chemically combined unit of the formula wherein R6, R2, R4 and R5 are selected from the group consisting of hydrogen, halogen, alkyl radicals of from 1 to 8 carbon atoms, R7 is an alkylene radical of from 1 to 8 carbon atoms, G is selected from the group consisting of - O -, , and mixtures thereof, A is selected from a group of monovalent and polyvalent aromatic radicals of from 6 to 130 carbon atoms and n is an integer equal to 1-10 inclusive.
16. A molding composition in accordance with claim 15, wherein said filler is selected from a group consisting of clay, silica, calcium carbonate, aluminum trihydrate, carbon black, talc, calcium sulfate and wollastonite.
17. A molding composition in accordance with claim 15 wherein said filler is in the form of a fiber matrix.
18. A method of curing a film on a substrate, said film comprised of a composition of claim 3, said method comprising radiating said film with ultraviolet light.
19. A method of curing a patterned mask on a substrate, said mask comprised of a composition of claim 3, said method comprising the steps of:
(a) depositing about 2 millimeters of an uncured composition of claim 3 on said substrate, (b) exposing portions of said composition with ultraviolet light for about 30 seconds or more, and (c) removing uncured portions of said composition with a solvent.
Claims Supported by the Supplementary Disclosure
(a) depositing about 2 millimeters of an uncured composition of claim 3 on said substrate, (b) exposing portions of said composition with ultraviolet light for about 30 seconds or more, and (c) removing uncured portions of said composition with a solvent.
Claims Supported by the Supplementary Disclosure
20. A molding composition comprising:
(A) aromatic vinyl ether of the formula (Ia) and (B) maleimide having at least one chemically combined unit of the formula (IIa) wherein R1 is an alkylene radical of from 1 to 8 carbon atoms, R2 , R3 , R4 , R5 and R6 are selected from the group consisting of hydrogen, halogen and alkyl radicals of from 1 to 8 carbon atoms, G is selected from the group consisting of - O -, , and mixtures thereof, A is selected from a group consisting of monovalent and polyvalent aromatic radicals of from 6 to 130 carbon atoms, N is an integer equal to 1-10 inclusive and both aa and bb are integers having a value of 0 to 1, subject to the proviso that when bb is zero, aa is zero.
(A) aromatic vinyl ether of the formula (Ia) and (B) maleimide having at least one chemically combined unit of the formula (IIa) wherein R1 is an alkylene radical of from 1 to 8 carbon atoms, R2 , R3 , R4 , R5 and R6 are selected from the group consisting of hydrogen, halogen and alkyl radicals of from 1 to 8 carbon atoms, G is selected from the group consisting of - O -, , and mixtures thereof, A is selected from a group consisting of monovalent and polyvalent aromatic radicals of from 6 to 130 carbon atoms, N is an integer equal to 1-10 inclusive and both aa and bb are integers having a value of 0 to 1, subject to the proviso that when bb is zero, aa is zero.
21. A molding composition of claim 20 additionally comprising an effective amount of thermal-curing catalyst.
22. A molding composition of claim 20 additionally comprising an effective amount of photo-curing catalyst.
23. A molding composition of claim 21 wherein the thermal-curing catalyst is selected from the group consisting of organic peroxide and azo-compounds.
24. A molding composition in accordance with claim 21 wherein the thermal-curing catalyst is selected from a group of organic peroxides consisting of t-butyl perbenzoate, t-butylhydro-peroxide benzopinacole, and benzolyl peroxide.
25. A photocurable composition in accordance with claim 22 wherein the photocurable catalyst is n-butylbenzoin ether.
26. A molding composition of claim 20 wherein the maleimide is bismaleimide of the following formula wherein R6 and R5 are previously defined in claim 20 and X is selected from the group consisting of divalent hydrocarbon radicals of from l to 35 carbon atoms and divalent groups of the formula wherein Z is either a bond between the phenol groups or selected from the class of divalent radicals consisting of hydrocarbon radicals of from 1 to 15 carbon atoms, - S -, - O -, - SO2 -, , , and ; wherein R7 is a monovalent alkyl radical of from 1 to 6 carbon atoms.
27. A molding composition in accordance with claim 26 wherein the divalent radical, X, of the bis-maleimide is bisphenol-A.
28. A molding composition of claim 20 wherein the maleimide is of the following formula wherein R6 and R5 are as previously defined in claim 20 and both X and X' are independently selected from the group consisting of divalent hydrocarbon radicals of from 1 to 35 carbon atoms and divalent groups of the formula where Z is selected from the class of divalent radicals consisting of divalent hydrocarbon radicals from 0 to 15 carbon atoms, - X -, - O -, - SO2-, ,, and ;
wherein R7 is a monovalent alkyl radicals of from 1 to 6 carbon atoms and m is an integer from 1 to 10 inclusive.
wherein R7 is a monovalent alkyl radicals of from 1 to 6 carbon atoms and m is an integer from 1 to 10 inclusive.
29. A molding composition in accordance with claim 20 wherein the maleimide is selected from the group consisting of N,N'-4,4'-diphenylmethane bismaleimide and N,N'-6-methyl-1,3-phenylene bismaleimide.
30. A molding composition in accordance with claim 20 wherein the aromatic radicals represented by A
of formula (Ia) are selected from the group consisting of phenylene, tolylene, xylylene, naphthylene, xenyl, anthrylene, diaryl groups of the formula and polyvalent aromatic radicals selected from the group of formulas consisting of and where Q is selected from a class consisting of divalent radicals of the formulas - S -, - O -, - SO2 -, , and alkylene radicals of from 1-8 carbon atoms, R7 is an alkyl radical of from 1 to 6 carbon atoms, and n' is an integer equal to 1 to 10 inclusive.
of formula (Ia) are selected from the group consisting of phenylene, tolylene, xylylene, naphthylene, xenyl, anthrylene, diaryl groups of the formula and polyvalent aromatic radicals selected from the group of formulas consisting of and where Q is selected from a class consisting of divalent radicals of the formulas - S -, - O -, - SO2 -, , and alkylene radicals of from 1-8 carbon atoms, R7 is an alkyl radical of from 1 to 6 carbon atoms, and n' is an integer equal to 1 to 10 inclusive.
31. A molding composition in accordance with claim 20 wherein the aromatic radical A of formula (Ia) is bisphenol-A.
32. A molding composition in accordance with claim 20 wherein the aromatic vinyl ether is selected from a group consisting of bisvinyl ethers having the formulas
33. A molding composition in accordance with claim 20 wherein a molar ratio of maleimide to aromatic vinyl ether has a value within the range of about 0.25 to about 4.
34. A molding composition comprising:
(A) 0 to 60% of one or more fillers and (B) 40 to 100% of a reactive composition comprising:
(a) aromatic vinyl ether of the formula A? (G)aa-(R1)bb and (b) maleimide having at least one chemically combined unit of the formula where R6, R2 , R3 , R4 and R5 are selected from the group consisting of hydrogen, halogen and alkyl radicals of from l to 8 carbon atoms, R1 is an alkylene radical of from 1 to 8 carbon atoms, G is selected from the group consisting of - O -, , and mixtures thereof, A is selected from a group consisting of monovalent and polyvalent aromatic radicals of from 6 to 130 carbon atoms, n is an integer equal to 1-10 inclusive and both aa and bb are integers having a value of 1 to 0, subject to the proviso that when bb is zero, zz is zero.
(A) 0 to 60% of one or more fillers and (B) 40 to 100% of a reactive composition comprising:
(a) aromatic vinyl ether of the formula A? (G)aa-(R1)bb and (b) maleimide having at least one chemically combined unit of the formula where R6, R2 , R3 , R4 and R5 are selected from the group consisting of hydrogen, halogen and alkyl radicals of from l to 8 carbon atoms, R1 is an alkylene radical of from 1 to 8 carbon atoms, G is selected from the group consisting of - O -, , and mixtures thereof, A is selected from a group consisting of monovalent and polyvalent aromatic radicals of from 6 to 130 carbon atoms, n is an integer equal to 1-10 inclusive and both aa and bb are integers having a value of 1 to 0, subject to the proviso that when bb is zero, zz is zero.
35. A molding composition in accordance with claim 34 wherein said filler is selected from a group consisting of clay, silica, calcium carbonate, aluminum trihydrate, carbon black, talc, calcium sulfate and wollastonite.
36. A molding composition in accordance with claim 34, wherein said filler is in the form of a fiber matrix.
37. A method of curing a film on a substrate, said film comprised of a composition of claim 22, said method comprising radiating said film with ultraviolet light.
38. A method of curing a patterned mask on a substrate, said mask comprised of a composition of claim 22, said method comprising the steps of:
(a) depositing about 2 millimeters of an uncured composition of claim 22 on said substrate, (b) exposing portions of said composition with ultraviolet light for about 30 seconds or more, and (c) removing uncured portions owe said composition with a solvent.
(a) depositing about 2 millimeters of an uncured composition of claim 22 on said substrate, (b) exposing portions of said composition with ultraviolet light for about 30 seconds or more, and (c) removing uncured portions owe said composition with a solvent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US51472883A | 1983-07-18 | 1983-07-18 | |
| US514,728 | 1983-07-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1229196A true CA1229196A (en) | 1987-11-10 |
Family
ID=24048433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000458787A Expired CA1229196A (en) | 1983-07-18 | 1984-07-12 | Polyimide molding compositions |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS6069113A (en) |
| CA (1) | CA1229196A (en) |
| DE (1) | DE3426299A1 (en) |
| FR (1) | FR2549479B1 (en) |
| GB (1) | GB2143540B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0643471B2 (en) * | 1985-10-14 | 1994-06-08 | 住友化学工業株式会社 | Thermosetting resin composition |
| DE60109356T2 (en) * | 2000-05-18 | 2005-07-28 | National Starch And Chemical Investment Holding Corp., Wilmington | Vinyl ethers and carbamate or urea functionality containing pressure sensitive adhesives for semiconductor devices |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2094607A5 (en) * | 1970-06-26 | 1972-02-04 | Rhone Poulenc Sa | |
| CH615935A5 (en) * | 1975-06-19 | 1980-02-29 | Ciba Geigy Ag | |
| CH621811A5 (en) * | 1976-06-17 | 1981-02-27 | Ciba Geigy Ag | |
| CH621810A5 (en) * | 1976-06-17 | 1981-02-27 | Ciba Geigy Ag | |
| JPS53134087A (en) * | 1977-04-28 | 1978-11-22 | Toshiba Corp | Heat-resistant resin composition |
| JPS54100488A (en) * | 1978-01-25 | 1979-08-08 | Toshiba Corp | Heat-resistant impregnation resin composition |
| JPS581682B2 (en) * | 1979-03-24 | 1983-01-12 | 富士通株式会社 | Thermosetting flame retardant resin composition |
| EP0021019B1 (en) * | 1979-05-18 | 1984-10-17 | Ciba-Geigy Ag | Photocrosslinkable copolymers, photosensitive recording material containing them, its utilisation in the production of photographic pictures and process for the production of photographic pictures |
-
1984
- 1984-07-12 CA CA000458787A patent/CA1229196A/en not_active Expired
- 1984-07-17 DE DE19843426299 patent/DE3426299A1/en not_active Withdrawn
- 1984-07-18 JP JP14771984A patent/JPS6069113A/en active Granted
- 1984-07-18 FR FR8411361A patent/FR2549479B1/en not_active Expired
- 1984-07-18 GB GB08418313A patent/GB2143540B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0439483B2 (en) | 1992-06-29 |
| FR2549479A1 (en) | 1985-01-25 |
| GB2143540B (en) | 1987-04-23 |
| JPS6069113A (en) | 1985-04-19 |
| DE3426299A1 (en) | 1985-01-31 |
| FR2549479B1 (en) | 1986-08-01 |
| GB2143540A (en) | 1985-02-13 |
| GB8418313D0 (en) | 1984-08-22 |
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