THERMODYNAMICALLY MISCIBLE POLYMER COMPOSITION

Abstract: A thermodynamically miscible polymer composition con­ taining (A) a copolymer having recurring units of a C₂ to C₄ α-­ olefin and recurring units of an N-aryl substituted maleimide and (B) a copolymer of acrylonitrile with styrene or α-methyl styrene. Said copolymer (B) can be optionally grafted with rub­ ber which forms a disperse phase within the continuous phase formed by the two copolymers.

Description: This invention relates to polymer compositions. In one of its more specific aspects this invention pertains to thermodynamically miscible polymer compositions containing a copolymer of a C₂to C₄ α-olefin with an N-aryl substituted maleimide monomer and an acrylonitrile copolymer. The miscibility of polymers is generally determined using differential scanning calorimetry to measure glass transition temperature. A thermodynamically miscible polymer composition will exhibit a single glass transition temperature value which typically lies intermediate between the glass transition temperatures of the individual polymeric components. Correspondingly, a partially miscible or immiscible composition will exhibit two or more glass transition temperature values. Accordingly, two or more polymers are thermodynamically miscible when a mixture of the polymers results in a material exhibiting a single, well defined glass transition temperature. DE-A-1925996 describes a molding composition comprising (a) a copolymer of maleimide or an N-alkyl or N-cycloalkyl maleimide and (b) a rubber having a second order transition temperature below +10°C and carries examples where graft copolymers comprising styrene and acrylonitrile grafted on the polybutadiene are employed as the rubber. However, the rubber (b) is present in the composition as a dispersion of microscopic or submicroscopic particles in the copolymer (a). Quite surprisingly, it has been found that within certain proportions a copolymer of a C₂ to c₄ α-olefin with an N-aryl substituted maleimide is thermodynamically miscible with a styrene/acrylonitrile copolymer. According to this invention there is provided a polymer composition comprising (A) a copolymer having from 40 to 60 mole % of a C₂ to C₄ α-olefin and from 60 to 40 mole % of an N-aryl substituted maleimide and (B) a polymer selected from the group consisting of (1) a copolymer matrix of from 65 to 85% by weight of a vinyl aromatic monomer selected from the group consisting of styrene and α-methylstyrene and from 15 to 35% by weight acrylonitrile, and (2) a rubber grafted with a copolymer matrix of from 65 to 85% by weight of a vinyl aromatic monomer selected from the group consisting of styrene and α-methylstyrene and from 15 to 35% by weight acrylonitrile wherein the weight ratio of component (A) to the copolymer matrix or component (B) is from 99:1 to 1:99; and wherein component (A) and the copolymer matrix of (B) are thermodynamically miscible with one another such that the polymer composition exhibits a single glass transition temperature value. According to this invention, there is also provided a method of producing a molded composition which comprises forming a composition comprising (A) a copolymer having from 40 to 60 mole % of a C₂ to C₄ α-olefin and from 60 to 40% by weight of an N-aryl substituted maleimide and (B) a polymer selected from the group consisting of (1) a copolymer matrix of from 65 to 85% by weight of a vinyl aromatic monomer selected from the group consisting of styrene and α-methylstyrene and from 15 to 35% by weight acrylonitrile, and (2) a rubber grafted with a copolymer matrix of from 65 to 85% by weight of a vinyl aromatic monomer selected from the group consisting of styrene and α -methylstyrene, and from 15 to 35% by weight acrylonitrile and wherein the weight ratio of component (A) to the copolymer matrix of component (B) is from 99:1 to 1:99, and wherein component (A) and the copolymer matrix of (B) are thermodynamically miscible with one another such that the polymer composition exhibits a single glass transition temperature value, and molding the resulting composition. Also, according to this invention there is provided a molded composition comprising a single continuous phase, the single continuous phase being a polymer composition comprising (A) a copolymer having from 40 to 60 mole % of a C₂ to C₄ α -olefin and from 60 to 40 mole % of an N-aryl substituted maleimide and (B) a copolymer matrix of from 65 to 85% by weight of a vinyl aromatic monomer selected from the group consisting of styrene and α -methylstyrene and from 15 to 35% by weight acrylonitrile. According to this invention there is also provided a molded composition comprising a continuous phase and a disperse phase within the continuous phase, the continuous phase being a polymer composition comprising (A) a copolymer having from 40 to 60 mole % of a C₂ to C₄ α -olefin and from 60 to 40 mole % of an N-aryl substituted maleimide and (B) a copolymer matrix of from 65 to 85% by weight of a vinyl aromatic monomer selected from the group consisting of styrene and α -methylstyrene, and from 15 to 35% by weight acrylonitrile, the disperse phase being a rubber which is grafted with said copolymer matrix (B). When reference is made to the weight of the copolymer matrix of (B) it is to be understood that the weight of any rubber is to be excluded. As the C₂ to C₄ α -olefin component of (A) use can be made of ethylene, propylene, butene-1, butene-2, and isobutylene or mixtures thereof. Isobutylene is preferred. The N-aryl substituted maleimide of component (A) can be N-phenylmaleimide, N-tolylmaleimide, N-(chlorophenyl) maleimide, N-(bromophenyl) maleimide and the like, and their mixtures. The preferred N-aryl substituted maleimide is N-phenylmaleimide. The preferred component (A) copolymer composition is from 40 to 60 mole % isobutylene and from 60 to 40% by weight N-aryl substituted maleimide. The peak molecular weight of the component (A) copolymer as measured by gel permeation chromatography (vs a monodisperse polystyrene standard) should be within the range of from 50,000 to about 500,000. The most preferred peak molecular weight range is from about 70,000 to about 150,000. Examples of suitable component (B) materials include ABS (acrylonitrile-poly(butadiene)-styrene terpolymer), AES (acrylonitrile-EPDM-styrene terpolymer), SAN (styrene-acrylonitrile copolymer) and the like and their mixtures. The preparation of the rubber grafted (ABS or AES) polymers is well known and is incorporated in this invention by reference to U.S. Patent Nos. 3,509,237; 3,509,238; 3,851,014; 3,903,200; 4,471,092 and 4,476,283. The preferred composition of component (B) is a rubber, either polybutadiene or EPDM, grafted with a copolymer having from 72 to 80% by weight of a vinyl aromatic monomer and 20 to 28% by weight of acrylonitrile. The vinyl aromatic monomer in component (B) can be either styrene or α -methylstyrene, however, most preferred is styrene. The polymer composition of this invention will comprise from 99 to 1% by weight of component (A) and from 1 to 99% by weight of the copolymer matrix of component (B) excluding the weight of the rubber, if present. Preferably the polymer composition will comprise from 1 to 25 weight % of component (A) and from 99 to 75 weight % of the polymer matrix of component (B). If the rubber grafted with a copolymer matrix is selected as component (B), the amount of rubber utilized will be from 1 to 40 parts by weight per 100 parts of the copolymer matrix of (B), that is, the vinyl aromatic plus the acrylonitrile. The polymer composition can be prepared using any suitable method of blending such as, for example, melt mixing or reaction blending. Reaction blending involves, for example, dissolving an already formed isobutylene/N-aryl substituted maleimide copolymer in a mixture of styrene monomer and acrylonitrile monomer followed by incorporation of a free radical initiator and copolymerization of the styrene and acrylonitrile monomers. Evaluation of material properties was performed based on the following ASTM standard tests: flexural modulus (D-790), tensile strength (D-638), elongation (D-638), notched Izod (D-256) and DTUL (deflection temperature under load), 3.175mm at 1.82 x 10⁶ Pa (1/8" at 264 psi), (D-648). Glass transition temperature was determined by differential scanning calorimetry (DSC). Example 1 This example demonstrates the preparation of an α-olefin/N-aryl substituted maleimide suitable for use in the practice of this invention. A solution of about 107.4 grams of N-phenylmaleimide in 333 milliliters of methyl ethyl ketone was prepared in a mixing vessel. Next, the solution was transferred into a one liter stirred reactor at room temperature under a nitrogen atmosphere. Into the reactor were charged about 42.7 grams of isobutylene and 0.6 grams of azoisobutyronitrile (Vazo 64 initiator, E.I. DuPont) to begin the polymerization. The polymerization reaction was carried out at 60°C for about 7 hours. The excess isobutylene was vented off, and the resultant copolymer was isolated by precipitation in methanol and dried in a vacuum oven at 90°C for about 3 hours. About 125 grams of isobutylene/N-phenylmaleimide copolymer were recovered. The copolymer was tested and found to contain 80.3 weight % N-phenylmaleimide (% N-determination) with the balance being isobutylene. The copolymer was also found to possess a glass transition temperature (DSC) of 207°C and a peak molecular weight of about 110,000 as measured by gel permeation chromatography (vs a monodisperse polystyrene standard). The copolymer was also subjected to thermal gravimetric analysis in both oxygen and nitrogen atmospheres. The results of the static thermal tests are set forth in following Table I. Copolymer Weight Loss % Atmosphere 1% 5% 50% Oxygen 385°C 422°C 467°C Nitrogen 410°C 456°C 494°C Example 2 This example demonstrates the thermodynamic miscibility of a polymer composition of this invention. Equal amounts of the isobutylene/N-phenylmaleimide copolymer prepared in Example 1 and a styrene/acrylonitrile copolymer designated Lustran® SAN-31 (23.4 wt % acrylonitrile) by Monsanto Chemical Company, were combined by dissolving both copolymers in tetrahydrofuran followed by precipitation in methanol. The resulting polymer composition was dried in a vacuum oven at 120°C-until a constant weight was reached. Following Table 2 compares the individual glass transition temperatures of each above copolymer with the glass transition temperature of their composition. For the composition according to the invention (Polymer Composition), the data show a single well defined glass transition temperature intermediate between the glass transition temperatures of the copolymer components (A) and (B). Tg(°C) Isobutylene/N-phenylmaleimide copolymer (A) 207 Lustran®-SAN-31 (styrene/acrylonitrile copolymer) (B) 109 Polymer Composition (C)(50 wt% A/50 wt% B) 147 Example 3 This example demonstrates the thermodynamic miscibility of a polymer composition of this invention. Equal amounts of the isobutylene/N-phenylmaleimide copolymer prepared in Example 1 and a styrene/acrylonitrile copolymer designated Lustran® SAN-33 (32.2 wt % styrene/acrylonitrile) by Monsanto Chemical Company, were combined by dissolving both copolymers in tetrahydrofuran followed by precipitation in methanol. The resulting polymer composition was dried in a vacuum oven at 120°C--until a constant weight was reached. Following Table 3 compares the individual glass transition temperatures of each above copolymer with the glass transition temperature of their composition. For the composition according to the invention (Polymer Composition), the data show a single well defined glass transition temperature intermediate between the glass transition temperatures of the copolymer components (A) and (B). Tg(°C) Isobutylene/N-phenylmaleimide copolymer (A) 207 Lustran®-SAN-33 (styrene/acrylonitrile copolymer) (B) 109 Polymer Composition (C)(50 wt% A/50 wt% B) 146 Example 4 This example demonstrates the preparation of three polymer compositions of this invention using the isobutylene/N-phenylmaleimide prepared according to Example 1 and a rubber (polybutadiene) grafted with a styrene/acrylonitrile copolymer matrix. Substantially the method of Example 2 was used with the exception that the copolymers were individually combined in amounts to give three polymer compositions containing 10, 20 and 50 weight percent isobutylene/N-phenylmaleimide, respectively. Following Table 4, shows the glass transition temperature values of each composition as compared to the glass transition temperatures of the individual copolymer components. Composition (wt%) Isobutylene/N-phenylmaleimide copolymer -- 10 20 50 100 ABS 100 90 80 50 -- Tg(DSC) 107°C 116°C 124°C 155°C 207°C Example 5 The example demonstrates the useful physical properties, particularly heat distortion temperature, obtained from a polymer composition of this invention which contains 10 parts of an isobutylene/N-phenylmaleimide copolymer prepared following substantially the procedure of Example 1, and 100 parts of the rubber grafted styrene/acrylonitrile copolymer of Example 4. The copolymers were combined using the procedure of Example 4, extruded into pellets and the pellets injection molded into test specimens. Table 5 shows the physical properties obtained as compared to the physical properties of the molded ABS resin alone. It will be evident from the foregoing that various modifications can be made to this invention. Such, however, are considered as being within the scope of the invention.

Claims: A polymer composition comprising (A) a copolymer having from 40 to 60 mole % of a C₂ to C₄ α-olefin and from 60 to 40 mole % of an N-aryl substituted maleimide and (B) a polymer selected from the group consisting of (1) a copolymer matrix of from 65 to 85% by weight of a vinyl aromatic monomer selected from the group consisting of styrene and α-methylstyrene and from 15 to 35% by weight acrylonitrile, and (2) a rubber grafted with a copolymer matrix of from 65 to 85% by weight of a vinyl aromatic monomer selected from the group consisting of styrene and α-methylstyrene, and from 15 to 35% by weight acrylonitrile wherein the weight ratio of component (A) to the copolymer matrix of component (B) is from 99:1 to 1:99; and wherein component (A) and the copolymer matrix of (B) are thermodynamically miscible with one another The polymer composition of claim 1 in which in component (A) said N-aryl substituted maleimide is selected from the group consisting of at least one of N-phenylmaleimide, N-tolylmaleimide, N-(chlorophenyl) maleimide and N-(bromophenyl) maleimide. The polymer composition of claim 1 or claim 2 in which in component (A) said C₂ to C₄ α-olefin is selected from the group consisting of at least one of ethylene, propylene, butene-1, butene-2 and isobutylene. The polymer composition of claim 1 in which component (A) is a copolymer of recurring units of isobutylene and N-phenylmaleimide. The polymer composition of any one of claims 1 to 4 in which the component (A) copolymer has a peak molecular weight within the range of from about 50,000 to about 500,000. The polymer composition of any one of claims 1 to 5 in which the component (A) copolymer has a peak molecular weight within the range of from about 70,000 to about 150,000. The polymer composition of any one of claims 1 to 5 in which said component (B) is selected from acrylonitrile-poly(butadiene)-styrene terpolymers, acrylonitrile-EPDM-styrene terpolymers, styrene-acrylonitrile copolymers, acrylonitrile-poly(butadiene)- α-methyl-styrene terpolymers, acrylonitrile-EPDM-α-methylstyrene terpolymers, and α-methylstyrene-acrylonitrile copolymers. The polymer composition of any one of claims 1 to 7 in which the weight ratio of component (A) to the copolymer matrix of component (B) is from 25:75 to 1:99. The polymer composition Of any one of claims 1 to 8 in which in said component (B)(1) said rubber is employed in an amount within the range of from 1 to 40 parts per each 100 parts by weight of the total weight of vinyl aromatic monomer plus acrylonitrile. A method of producing a molded composition which comprises forming a composition as claimed in any one of claims 1 to 9 and molding the resulting composition. A molded composition comprising a single continuous phase, and optionally a disperse phase within the continuous phase, said continuous phase being a polymer composition comprising (A) a copolymer having from 40 to 60 mole % of a C₂ to C₄ α-olefin and from 60 to 40 mole % of an N-aryl substituted maleimide and (B) a copolymer matrix of from 65 to 85% by weight of a vinyl aromatic monomer selected from the group consisting of styrene and α-methylstyrene and from 15 to 35% by weight acrylonitrile, and said disperse phase being a rubber which is grafted with said copolymer matrix (B), and wherein the single continuous phase the weight ratio of component (A) to the copolymer matrix (B) is from 99:1 to 1:99, and component (A) and the copolymer matrix (B) are thermodinamically miscible with one another.

Inventors: LE-KHAC, BI
Applicants: ARCO CHEMICAL TECHNOLOGY, L.P.
Application year: 1986
Main classification: C08L35
IPC codes: C08L23, C08L21, C08L33, C08L35, C08L51, C08L101, C08L25, C08L55, C08L7