US 3,998,907 AGrant
Rubber-Modified Dicarboxylic Acid Imide Copolymers
Issue Date:1976-12-21
•4 Claims
Abstract
Rubber-modified copolymers comprising 5 to 40 weight percent of an elastomer and 95 to 60 weight percent of a copolymer containing 1 to 50 mole percent of an imide derivative of an ethylenically unsaturated dicarboxylic acid monomer and 99 to 50 mole percent of one or more monomers copolymerizable therewith are prepared by the reaction of aqueous ammonia or amines with an aqueous suspension of a rubber-modified copolymer of the copolymerizable monomers and an ethylenically unsaturated dicarboxylic acid, anhydride, or half acid derivative. The reaction is carried out at a temperature between 125.degree. and 200.degree. C. at autogenous pressure for between 0.5 and 48 hours. The imide products can be recovered in the form of discrete particles, such as beads or pellets, if desired.
Metadata
Assignee
- Arco Polymers, Inc.
Inventor
- Adolph V. DiGiulio
Application Information
Application Number:US 5102669
Filing Date:1974-09-30
Priority Date:1972-08-29
Art Unit:144
Classifications
IPC:
C08G 1883
Field of Search:
26078 UA;78.5 T;879;887;857 U;857 D;857 L;857 G;876 R
Patent Drawings
This patent does not have any drawings.
Description
Background of the Disclosure
This invention relates to the chemical conversion of dicarboxylic acid, anhydride, or half acid groups into cyclic imide groups by the reaction of aqueous ammonia or an aqueous amine solution on copolymers containing the reactive groups.
A wide variety of imide copolymers should be preparable, with modified properties and functionalities, depending on the amine utilized. By varying the substituent on the imide nitrogen, copolymers with markedly improved properties, such as heat distortion temperature, solvent resistance, flexibility, and flow characteristics may be prepared.
Thus, the imide or N-phenylimide copolymers have higher glass transition temperatures than the corresponding dicarboxylic acid or anhydride containing copolymers, the glass temperature increasing with increasing imide content. This enhanced glass temperature is a very useful and desirable property for thermoplastic polymers.
Copolymers with imides of ethylenically unsaturated dicarboxylic acids, such as maleimide, can be prepared by direct copolymerization of the monomers. However, the imides are expensive and relatively unavailable. Although, the preparation of these copolymers by direct polymerization usually yields the 1:1 alternating copolymer, special techniques have been developed to prepare non-equimolar copolymers. Methods have been developed to convert anhydride containing copolymers to the corresponding imide copolymers by reacting the copolymers with anhydrous ammonia or with anhydrous amines in organic solvents. However, these methods involve the necessity of either handling anhydrous gases or using the two step process of preparing a solid half acid amide salt with subsequent cyclization of the salt to the desired imide product.
Brief Summary of the Invention
It has now been found that rubber-modified copolymers containing an imide derivative of an ethylenically unsaturated dicarboxylic acid monomer can be prepared directly by reacting aqueous ammonia or amines at 125.degree. - 200.degree. C. and under autogenous pressures of between 60 and 150 psi. for 0.5 to 48 hours with a rubber-modified copolymer containing an ethylenically unsaturated dicarboxylic acid, its anhydride, or a half acid derivative of the dicarboxylic acid. The process eliminates the need for using anhydrous ammonia or amines. An advantage herein lies in the fact that many amines are normally available commercially in aqueous solution. Thus, methylamine is available as a 40% solution in water. Ammonia is commonly sold in 28-30% solution in water as ammonium hydroxide. Another advantage of the method is that it eliminates the need to prepare the imide, or N-substituted imide prior to polymerization with the other monomer.
Detailed Description of the Invention
The starting copolymers for the present invention comprise any of the known copolymers of ethylenically unsaturated dicarboxylic acids, or their derivatives, with one or more copolymerizable monomers. The copolymerizable monomers may be vinyl aryl monomers, such as styrene, alphamethylstyrene, nuclear methylstyrenes, ethylstyrene, isopropylstyrene, tert-butylstyrene, chlorostyrenes, dichlorostyrenes, vinyl naphthalene and the like; aliphatic alpha-monoolefins, such as ethylene, propylene, isobutylene, 1-butene, and 1-hexene; alkyl vinyl ethers, such as butyl vinyl ether, ethyl vinyl ether and 2-ethylhexyl vinyl ether; conjugated diolefins, such as butadiene, isoprene, and 2,3-dimethylbutadiene; unsaturated nitriles, such as acrylonitrile and methacrylonitrile; and acrylic monomers, such as acrylic acid, methacrylic acid, methyl acrylate and methyl methacrylate. Mixtures of two or more of these copolymerizable monomers may be used if desired.
For the rubber-modified copolymers, the starting copolymers may be any of the above copolymers into which 5 to 40 percent by weight of one of the known elastomers has been incorporated. The elastomers may be incorporated into the anhydride copolymers by blending, mixing, or copolymerizing the monomers in the presence of the rubber.
Suitable rubbers, or elastomers, include conjugated 1,3-diene rubbers, styrene-diene copolymer rubbers, acrylonitrile-diene copolymer rubbers, ethylene-propylene-diene terpolymer rubbers, acrylate-diene copolymer rubbers, and mixtures thereof.
Preferred rubbers are diene rubbers such as homopolymers of conjugated dienes such as butadiene, isoprene, chloroprene, and piperylene and copolymers of such dienes with up to 50 mole percent of one or more copolymerizable mono-ethylenically unsaturated monomers, such as styrene, substituted styrenes, acrylonitrile, methacrylonitrile and isobutylene.
The acid moiety may be an ethylenically unsaturated dicarboxylic acid, its anhydride, or a half acid derivative of such a dicarboxylic acid or mixtures thereof. Suitable acids and their derivatives useful in the present invention are maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, ethyl maleic acid, methyl itaconic acid, chloromaleic acid, dichloromaleic acid, bromomaleic acid, dibromomaleic acid and the like, the anhydrides of these acids, the acid amide derivatives, or the half esters of these with suitable alcohols. The alcohols used may be the primary and secondary alkanols containing up to 6 carbon atoms, such as, methyl alcohol, ethyl alcohol, n-propyl alcohol, n-butyl alcohol, secbutyl alcohol, and n-pentyl alcohol; halogenated alkanols having up to 6 carbon atoms, such as 2,3-dichloro-1-propanol, and 2-bromo-1-propanol; arylalkyl alcohols, such as benzyl alcohol; cyclic alcohols having up to 6 carbon atoms, such as cyclopentanol, cyclohexanol and tetrahydrofurfuryl alcohol; ether alcohols, such as 2-butoxyethanol and the ethyl ether of diethylene glycol, and the like.
The starting copolymers may be either the alternating copolymers containing ratios of dicarboxylic acid monomer to copolymerizable monomer of about 1:1, or the non-equimolar copolymers containing less than about 50 mole percent of the dicarboxylic acid monomer.
The non-equimolar copolymers are comprised of a minor amount, that is less than 50 mole percent, of an ethylenically unsaturated dicarboxylic acid moiety and a major amount, that is greater than about 50 mole percent, of one or more monomers copolymerizable therewith.
Non-equimolar starting copolymers may be prepared by any of the several methods available for the preparation of non-equimolar copolymers, Thus, these copolymers may be prepared by solution polymerization directly from the respective monomers by the incremental addition of the reactive monomer as taught by U.S. Pat. No. 2,971,939; by a continuous recycle polymerization process such as described in U.S. Patents Nos. 2,769,804 and 1,989,517; or by the suspension polymerization process described in my U.S. Pat. No. 3,509,110.
The copolymers of the present invention are prepared by reacting the starting copolymers with aqueous ammonia or amines. Suitable amines are the alkyl amines having 1 to 4 carbon atoms, such as methylamine, ethylamine, propylamine, isopropylamine and butylamine; ethanolamine; aniline, benzylamine; allylamine and the like.
Also suitable are the water soluble .alpha.,.omega.-alkylenediamines having 2 to 6 carbon atoms in the alkylene group, such as ethylenediamine, and hexamethylenediamine. Arylene diamines, such as the phenylene diamines and benzidines may also be used. The diamines are useful for preparing copolymers having varying degrees of crosslinking. These diamines may be used alone or in combination with other monoamines to vary the degree of crosslinking.
The ammonia or amines may be used in stoichiometric amounts based on the dicarboxylic acid moiety in the copolymer. However, it is preferred to use an excess of the stoichiometric amount to ensure complete conversion of the dicarboxylic acid moiety to the desired imide or N-substituted imide. Use of less than stoichiometric amounts of the amine make it possible to prepare terpolymers containing both the uncyclized dicarboxylic acid function and the imide function. Further heating in the open will completely cyclize the acid function to form the terpolymers containing the anhydride and the imide groups.
The reaction is preferably carried out at temperatures of between 125.degree. C. and 200.degree. C. At temperatures below 125.degree. C., for example 80.degree.-100.degree. C., the product upon separation contains uncyclized species which when heated more strongly cyclize to both the anhydride and the desired imide moiety. If discrete particulate product is desired, the upper limit of temperature will vary depending on the dicarboxylic functionality content of the copolymer. The lower the functionality (anhydride, half acid, or imide) content, the greater the tendency for agglomeration at a given temperature. Further, the use of a suspending agent, such as for example polyvinyl alcohol, during the heating, will raise the temperature which can be reached without agglomeration. Thus, a copolymer containing about 7 mole percent imide, heated without the use of a suspending agent, might agglomerate at 140.degree.-145.degree. C. However, the use of suspending agent will effectively raise the temperature attainable without agglomeration to about 160.degree. C.
The reaction is carried out at autogenous pressure. The pressures reached will normally vary between 60 and 150 psi depending on the concentration and volatility of the particular amine being used and the temperature of the reaction. If carried out at atmospheric pressure, the product of the reaction of aqueous amines with the dicarboxylic acid moiety can be shown to be the amine salt of the carboxylic acid or perhaps the carboxamic acid derivatives. The reaction must therefore be effected in a closed system but the pressure will vary with the reaction system employed.
The reaction may be carried out for times varying between about 0.5 and 48 hours depending upon the degree of conversion of the dicarboxylic acid moiety desired, upon the temperature employed, upon the type and concentration of reagents used, and upon the physical form of the starting copolymer. Thus, if small particle size beads are used, the time of reaction may be less than if larger pellets are utilized. Higher temperatures of reaction allow shorter times of reaction for any particular system of reactants. Shorter times also may be used if one wishes to prepare an interpolymer containing the non-functional monomer, the anhydride, the imide, and uncyclized dicarboxylic functionality. These interpolymers can be completely cyclized to terpolymers of the non-functional monomer, anhydride, and imide if so desired. The cyclization may be easily carried out by heating the product containing the uncyclized moleties to a temperature of 200.degree.-225.degree.C., for 0.5-1.0 hour preferably under vacuum. Longer times may be used if desired. Much shorter times are needed if the heating is done in a devolatilizing extruder.
The desired product may be recovered by any of the known methods of separating solids from a liquid medium. These include filtration, decantation and centrifugation. The product so separated is then washed with water, or dilute acid followed by water, to remove impurities, and dried in air, or preferably in a circulating oven at about 50.degree.-80.degree. C. for 24-48 hours. The temperature useful in this drying step may be higher if desired, depending on the particular copolymers to be dried. Since the imide containing copolymers have higher glass transition temperatures than the corresponding anhydride containing copolymers, higher temperatures of drying can be used without causing the discrete particles of copolymer to melt and fuse together.
The products are desirable and useful polymers because of their enhanced glass transition temperatures. Thus, polystyrene has a glass temperature of 100.degree. C. A copolymer of styrene and 10 mole-% N-methylmaleimide has a glass temperature of 122.degree. C. and a copolymer of styrene and 9 mole-% maleimide has a glass temmperature of 133.degree. C. Increasing the maleimide content of a styrene copolymer to 18.1 mole-% raised the glass temperature to 151.degree. C. Similarly, a copolymer of styrene with 7 mole-% N-n-butylmaleimide has a Tg of 108.degree. C., and one containing 7 mole-% N-(betahydroxyethyl) maleimide has a Tg of 114.degree. C. Copolymers of styrene with the imide comonomers, such as maleimide, itaconimide, etc., also are useful as chemically reactive intermediates. The imide group can be further reacted with, for example, formaldehyde to give an N-methylol derivative useful for further reaction, such as crosslinking by condensation with bisphenols, diisocyanates and the like. These and other reactions dependent upon the reactive hydrogen on the imide group can be utilized in many ways by one skilled in the art.
Although the present invention relates primarily to copolymers containing dicarboxylic acids or their derivaties, it should be obvious to one skilled in the art that the reaction could be applicable to copolymers containing monocarboxylic acids in close enough spatial configuration so that cyclic imides having 5-8 membered rings could be formed. Examples of such copolymers are those containing acrylic acid, methacrylic acid, crotonic acid, of cinnamic acid wherein two or more carboxyl containing monomers ar in close proximity to each other.
The following examples are given to illustrate further the invention but are not intended to be all inclusive. All percentages are weight percent unless otherwise indicated.
Example I
To a 1 liter bench type Parr autoclave was added 10 g. of pellets of a copolymer of styrene and maleic anhydride containing 10.9 mole percent anhydride, 390 ml. water, and 60 ml. of a 28-30% aqueous ammonium hydroxide solution. The reactor was closed and heated to 139.degree.-147.degree. C. for about 12 hours during which time the pressure varied between 63 and 86 psi. The reactor was cooled down, the pressure released, and the polymer pellets separated from the aqueous layer by filtration. The pellets were washed with water, and dried in air at room temperature. The product was in the form of opaque pellets, which analyzed by infared to have about 2.0 mole percent maleic anhydride groups and 8.9 mole percent maleimide groups. The glass transition temperature measured by differential thermal analysis was 129.degree. C. on the crude pellets and 132.degree. C. on polymer reprecipiated by methanol from methyl ethyl ketone and dried at about 38.degree. C. Further heating of the crude pellets at 230.degree. C. for 0.5-1.0 hour did not cause any change in the anhydride or imide content of the polymer. Thus, it may be seen that the treatment of the anhydride copolymer with aqueous ammonia gave directly, the desired imide copolymer.
Example Ii
To a 12 ounce glass bottle was added 80g. of a styrene-maleic anhydride copolymer pellets containing 10.9 mole percent of anhydride, 142 ml. water, 1.33 ml. of 5% polyvinyl alcohol solution in water, and 36.3 ml. of 40% aqueous solution of methylamine. The bottle was sealed, heated to a temperature of 137.degree. C. for about 12.5 hours. On cooling the product was recovered in the form of opaque pellets which analyzed by infrared as having about 1.0 mole percent anhydride and 9.9 mole percent N-methylmaleimide groups. The terpolymer has a glass transition temperature of 122.degree. C. as measured by differential thermal analysis. The product was then fused at 200.degree. C. under 1 mm. pressure for 3 hours to remove traces of moisture and to complete cyclization of possibly uncyclized species. Examination of the infrared spectra of the unfused and fused products showed them to be essentially identical.
Example Iii
To each of a series of 12 ounce bottles was added 80g. of styrene-maleic anhydride copolymer containing the mole percent of maleic anhydride indicated in the Table I, water and ammonium hydroxide as indicated, and 1.6 ml. of 5% aqueous polyvinyl alcohol solution. The bottles were capped and raised to the temperature indicated in the table for the length of time indicated. In all cases, after the product has been separated from the water and dried in air at 60.degree. C. for about 24 hours, the copolymers were found to have been converted essentially quantitatively to the styrene-maleimide copolymers.
The sample from bottle No. 5 which contained 18.1 mole % maleimide had a glass temperature, Tg, measured by differential thermal analysis of 151.degree. C., compared to a styrene-maleic anhydride copolymer containing 18.1 mole % anhydride which has a Tg of 128.degree. C.
Example Iv
To illustrate the effect of temperature of reaction upon the cyclization reaction, several experiments were conducted in sealed glass tubes. Three different copolymers were used as follows:
Copolymer A was a styrene-methyl hydrogen maleate copolymer containing 4.1 mole-% maleate; copolymer B was a styrene-n-butyl hydrogen maleate copolymer containing 7.2 mole-% maleate; and copolymer C was a styrene-maleic acid-maleic anhydride terpolymer containing 4.7 mole-% acid and 3.1 mole-% anhydride. The copolymers in bead form, the amine, and water were sealed in the glass tubes and heated to varying temperatures for varying times. The products were then separated from the water, dried and heated at 225.degree. C. for 40 to 60 minutes to ensure complete cyclization of the products. The results are given in Table II.
As may be seen from run numbers 1 and 6, a temperature of from 80.degree. to 100.degree. C. gave predominantly the anhydride product rather than the desired imide. As between the 130.degree. C. temperature and the 150.degree. C. temperature, little difference could be seen when using butylamine, methylamine, or ethanolamine, but the higher temperature with aqueous ammonia gave greater percentages of the desired imide than obtained at 130.degree. C. as shown by comparing run 7 with run 11 and 13 with run 17.
Infrared data on samples from runs 2-5, 7-10, and 13-16 prior to the final heating at 225.degree. C., indicated that the products made at 130.degree. contained some uncyclized derivatives of the imides. The heating step then completed the cyclization to the desired imide structures. Similar analysis of the products of runs 11, 12 and 17-20 indicated that the products made at 150.degree. C. were essentially all cyclized even prior to the final heating step.
Example V
To each of two 1 liter Parr bench type autoclaves were added 25g. of a styrene-n-butyl hydrogen maleate copolymer containing 7.2 mole-% maleate in bead form, 400 ml. water and 43.3 g. of 40% aqueous methylamine solution. One of the autoclaves was heated to 146.degree.-9.degree. C. for 3-4 hours at a pressure of 75 psi. The product was in the form of beads and contained substantial amounts of imide and some uncyclized moieties. This product, when heated at 225.degree. C. for 45 minutes was completely cyclized and analyzed at 6.2 mole-% N-methylmaleimide and about 1.0 mole-% maleic anhydride.
The other autoclave was heated to 146.degree.-157.degree. C. for 16 hours at a pressure of 90-100 psi. The product was agglomerated but contained only the desired N-methylmaleimide structure, with no need for further heating. The agglomeration of the beads was probably due to the fact that the system was heated above the softening point of the polymer beads.
Example Vi
To a 3 liter resin kettle equipped with stirrer, thermometer, reflux condenser and a nitrogen atmosphere was added 1700 ml. of deionized water, 20 ml. of 5% polyvinyl alcohol solution and 145 ml. of aniline. The mixture was heated to reflux temperature and 400 g. of styrenemaleic anhydride copolymer pellets containing 18.1 mole per cent maleic anhydride and 21 ml. additional polyvinyl alcohol solution were added. The stirred mixture was refluxed for 45 minutes. Then 45 ml. of aniline was added over 24 minutes, and the stirred mixture refluxed an additional 45 minutes. An additional 362 g. of the copolymer and 14 ml. of aniline were added over 20 minutes and the entire mixture was refluxed for 80 minutes and the mixture cooled. The purpose of this preliminary procedure was to ensure intimate mixing of the copolymer and the aniline without agglomeration of the copolymer pellets.
The mixture was then transferred to 12 oz. bottles, each bottle containing approximately 80 g. of wet pellets and about 125-135 g. of liquid. The bottles were purged with nitrogen, capped, and heated at 140.degree. C. for 12 hours while rotating in an oil bath. The discrete opaque pellets were filtered, washed and dried. A portion of these pellets was analyzed by infrared and by non-aqueous titration with sodium methoxide solution. The infrared analysis showed the product to be predominantly styrene-N-phenylmaleimide, with a small amount of unreacted anhydride and some acidic species. After heating at 215.degree. C. under vacuum, the product was shown to contain 15.9 mole per cent N-phenylmaleimide and 2.2 mole per cent of maleic anhydride moieties in the copolymer.
A second lot of pellets, about 80 g. was added to a bottle containing 165 ml. of water, 8 ml. of aniline, and 4 ml. of polyvinyl alcohol solution, capped, and heated for an additional 12 hours at 140.degree. C. Analysis of this product by infrared and by titration showed that essentially all of the remaining anhydride moieties had been converted to the N-phenylmaleimide derivative. Analysis of this product, and a sample heated at 215.degree. C. under vacuum showed both products to be essentially identical, each containing 0.5 mole per cent of anhydride and 17.6 mole per cent N-phenylmaleimide moieties.
Example Vii
A sealed 12 oz. bottle containing 80 g. of a styrene-maleic anhydride copolymer pellets having 18.1 mole per cent anhydride, 142 ml. water, 1.67 ml. of 5% aqueous polyvinyl alcohol solution, and 18.5 ml. allylamine was heated at 140.degree. C. for 12 hours. The product was analyzed by infrared and by non-aqueous titration and found to be a copolymer of styrene with 0.2 mole per cent maleic anhydride and 17.9 mole per cent N-allylmaleimide. This copolymer has a Tg of 123.degree. C. compared to 128.degree. C. for the starting anhydride copolymer.
Example Viii
To illustrate the use of diamines, a sealed 12 oz. bottle containing 40 g. of styrene-maleic anhydride copolymer having 20.6 mole per cent anhydride, 75 ml. of water, 1.0 ml. of 5% aqueous polyvinyl alcohol solution and 5.0 g. of ethylene diamine was heated at 140.degree. C. for about 12 hours. The resulting discrete pellets were washed and dried, and then they were digested in chloroform. Analysis of the product showed that 25% of the product was insoluble, crosslinked polymer, while 75% remained as soluble, un-crosslinked polymer.
Similar experiments with varying concentrations of benzidine or hexamethylenediamine gave partially insoluble products. Often the pellets crosslinked on the surface, since treatment with a solvent for the initial anhydride copolymer, such as methyl ethyl ketone, gave hollow particles of insoluble polymer. The amount of cross-linking obtained can be controlled either by increasing the diamine concentration or by changing the reaction time, or both. The amount of cross-linking obtained is also dependent upon the particle size and shape of the initial copolymer; the smaller particles giving greater cross-linking.
Example Ix
A sealed 12 oz. bottle containing 80 g. of pellets of a copolymer of styrene (90%) and maleic anhydride (10%) modified with 15% by weight of a rubber consisting of a copolymer of butadiene (90%) and styrene (10%) prepared by solution polymerization in a stereospecific system, 149.5 ml. water, 1.67 ml. of 5% aqueous polyvinyl alcohol solution, and 28.8 ml. of 28-30% ammonium hydroxide was heated at 140.degree. C. for 12 hours. The product was separated in discrete particulate form from the aqueous medium, washed with water, and dried in air at room temperature. The anhydride portion of the product was shown by infrared and by non-aqueous titration to be at least 90% converted from the anhydride to the imide derivative. This rubber-modified anhydrideimide copolymer has a Tg. of 123.degree.-5.degree. C., compared to 114.5.degree. C. for the anhydride-containing starting copolymer.
This example illustrates that rubber modified copolymers containing anhydride groups can also be converted directly to the imide by the instant process.
Example X
Into a 12 oz. bottle were placed 100 g. of pellets of a copolymer of styrene (92%) and maleic anhydride (8%) modified with 10% by weight of a rubber consisting of a copolymer of butadiene (90%) and styrene (10%) prepared by solution polymerization in a stereospecific system. Also added to the bottle were 145 ml. water, 3.2 ml. of 5% aqueous polyvinyl alcohol solution, and 36 ml. of 40% aqueous methylamine solution. The bottle was sealed, heated to 140.degree. C. for 6 hours with agitation by rotation, and the discrete, opaque pellets recovered, washed and dried. The final product contained 0.5% of maleic anhydride, 6.7% of N-methylmaleimade, 82.8% styrene and 10% of the above rubber. The rubber-modified terpolymer had a Tg. of 119.degree. C. compared to a Tg. of 117.degree. C. for the anhydride starting copolymer.
Similar reaction replacing the aqueous methylamine with aqueous aniline gave a product with 1.5% maleic anhydride and 5.7% N-phenylmaleimide having a Tg. of 117.degree. C. compared to a Tg of 112.degree. C. for the rubber-modified anhydride starting material.
Example Xi
The procedure of Example IX was repeated six times, except that the copolymer pellets were replaced with pellets consisting of
A. a copolymer of styrene (92%) and maleic anhydride (8%) modified with 10% by weight of a rubber consisting of a copolymer of butadiene (90%) and styrene (10%) prepared by a solution polymerization in a stereospecific system;
B. a copolymer of styrene (92%) and maleic anhydride (8%) modified with 10% of a stereospecific polybutadiene rubber prepared by solution polymerization using an alkyllithium catalyst;
C. a copolymer of styrene (92%) and maleic anhydride (8%) modified with 10% by weight of a cold rubber consisting of butadiene (95%) and styrene (5%) prepared in emulsion;
D. a copolymer of styrene (90%) and maleic anhydride (10%) modified with 15% by weight of a high cis 1,4-polybutadiene rubber (98% cis) prepared by a Ziegler Natta catalyst process;
E. a terpolymer of styrene (81.2%) acrylonitrile (9.0%) and maleic anhydride (9.8%) modified with 15% by weight of a rubber consisting of copolymer of butadiene (90%) and styrene (10%) prepared by a solution polymerization in a stereospecific system; and
F. a copolymer of styrene (83%) and maleic anhydride (17%) modified with 10% by weight of the rubber used in run E.
after reaction with ammonia and separation of the pellets the products were analyzed and all found to have greater than 90% of the anhydride groups converted to imide groups. The Tg's of the six products were (A) 119.degree. C., (B) 126.5.degree. C., (C) 121.5.degree. C., (D) 125.degree. C., (E) 132.degree. C., and (F) 154.degree. C., compared to the Tg of the starting anhydride polymers of 112.degree. C., 110.5.degree. C., 113.degree. C., 110.degree. C., 123.degree. C., and 134.degree. C., respectively.
Example Xii
Into a closed reactor equipped with a stirrer was placed 100 parts of pellets of a copolymer of styrene (92%) and maleic anhydride (8%) modified with 10% by weight of a rubber consisting of a copolymer of butadiene (90%) and styrene (10%) prepared by solution polymerization in a stereospecific system, 36 parts of 28-30% aqueous ammonium hydroxide, 114 parts of distilled water, and 1.25 parts of magnesium carbonate. The mixture was suspended by agitation and heated at 145.degree. C. for 4 hours. The product contained at least 5.7% maleimide and less than 1.5% maleic anhydride. A sample withdrawn from the reactor at the end of 1 hour at the 145.degree. C. was analyzed to have the same composition as the final product. This indicates that at the higher temperatures, less time is required to convert the anhydride group into the imide derivative.
Claims
What is claimed is:
1. A process for preparing a rubber-modified copolymer comprising (a) 5 to 40 weight percent of an elastomer and (b) 95 to 60 weight percent of a copolymer containing from 1 to 50 mole percent of an imide derivative of an ethylenically unsaturated dicarboxylic acid and 99 to 50 mole percent of one or more monomers copolymerizable therewith, said process comprising: a. forming an aqueous suspension of (1) a rubbermodified copolymer comprising (a) 5 to 40 weight percent of an elastomer selected from the group consisting of homopolymers of conjugated 1,3-dienes, copolymers of said 1,3-dienes with up to 50 mole percent of one or more monoolefinically unsaturated monomers copolymerizable therewith, ethylenepropylene-diene terpolymer rubbers, acrylate-diene copolymer rubbers, and mixtures thereof, and (b) 95 to 60 weight percent of a copolymer in discrete particulate form containing 1 to 50 mole percent of a dicarboxylic moiety selected from the group consisting of an ethylenically unsaturated dicarboxylic acid, an ethylenically unsaturated dicarboxylic anhydride and an ethylenically unsaturated dicarboxylic acid half acid derivative, and mixtures thereof and 99-50 mole percent of one or more monomers copolymerizable therewith selected from the group consisting of a vinyl aryl monomer, an aliphatic alpha-monoolefin, an alkyl vinyl ether, a conjugated diolefin, an unsaturated nitrile, an acrylic monomer and mixtures thereof and (2) aqueous ammonia or an aqueous amine selected from the group consisting of alkyl amines having 1 to 4 carbon atoms in the alkyl group, allyl amine, ethanolamine, aniline, benzylamine, .alpha.,.omega.-alkylene diamines having 2 to 6 carbon atoms in the alkylene group, and arylene diamines in an amount sufficient to react stoichiometrically with the dicarboxylic moiety; b. heating said suspension with agitation in a closed system at a temperature of between 125.degree. and 200.degree. C. at autogenous pressure for 0.5 to 48 hours to allow reaction between the ammonia or amine and the dicarboxylic moiety; and c. separating the rubber-modified copolymer in discrete particulate form from the aqueous medium.
2. A process for preparing a rubber-modified copolymer comprising (a) 5 to 40 weight percent of an elastomer, and (b) 95 to 60 weight percent of a non-equimolar copolymer in discrete particulate form containing a major amount of vinyl aryl monomer and a minor amount of an imide derivative of an ethylenically unsaturated dicarboxylic acid monomer comprising: a. forming an aqueous suspension of (1) a rubber-modified copolymer comprising (a) 5 to 40 weight percent of an elastomer selected from the group consisting of homopolymers of 1,3-dienes, copolymers of said 1,3-dienes with up to 50 mole percent of one or more monoolefinically unsaturated monomers copolymerizable therewith, ethylene-propylene-diene terpolymer rubbers, acrylate-diene copolymer rubbers, and mixture thereof, and (b) 95 to 60 weight percent of a copolymer in discrete particulate form containing a major amount of said vinyl aryl monomer and a minor amount of a monomer selected from the group consisting of an ethylenically unsaturated dicarboxylic acid, an ethylenically unsaturated dicarboxylic anhydride, and an ethylenically unsaturated dicarboxylic acid half acid derivative and mixtures thereof and (2) aqueous ammonia or an aqueous amine selected from the group consisting of alkyl amines having 1 to 4 carbon atoms in the alkyl group, allyl amine, ethanolamine, aniline, benzylamine, .alpha.,.omega.-alkylenediamines having 2 to 6 carbon atoms in the alkylene group, and arylene diamines in an amount sufficient to react stoichiometrically with the dicarboxylic monomer; b. heating said suspension with agitation in a closed system at a temperature of between 125.degree. and 200.degree. C. at autogenous pressure for 0.5 to 48 hours; and c. separating the rubber-modified copolymer in discrete particulate form from the aqueous medium.
3. The process of claim 2 wherein said copolymer is selected from the group consisting of styrene-maleic anhydride, styrene-methyl acid maleate, styrene-n-butyl acid maleate, styrene-maleic acid-maleic anhydride, and styrene-butadiene-maleic anhydride.
4. A composition when made by the process of claim 1, wherein said rubber-modified copolymer is prepared by polymerizing a mixture of said dicarboxylic moiety and said one or more monomers in the presence of said elastomer, comprising (a) 5 to 40 weight percent of an elastomer selected from the group consisting of homopolymers of conjugated dienes such as butadiene, isoprene, chloroprene and piperylene; copolymers of such conjugated dienes with up to 50 percent by weight of one or more monoolefinically unsaturated monomers such as styrene, substituted styrenes, acrylonitrile, methacrylonitrile, and isobutylene; ethylene-propylene-diene terpolymer rubbers; acrylate-diene copolymer rubbers; and mixtures thereof and (b) 95 to 60 weight percent of a copolymer containing 1 to 50 mole percent of an imide derivative of an ethylenically unsaturated dicarboxylic acid monomer, and 99 to 50 mole percent of at least one monomer copolymerizable therewith selected from the group consisting of a vinyl aryl monomer, an aliphatic alpha-monoolefin, an alkyl vinyl ether, a conjugated diolefin, an unsaturated nitrile, and acrylic monomer, and mixtures thereof; said imide derivative being selected from the group consisting of ethylenically unsaturated dicarboxylic imides and their N-substituted imides wherein the N-substituent is selected from the group consisting of alkyl having from 1 to 4 carbon atoms, hydroxyethyl, benzyl, phenyl, allyl, aminophenyl, aminobiphenyl, and .omega.-aminoalkyl having 2 to 6 carbon atoms in the alkyl group.
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