Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
  • C08L23/0869—Acids or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/24—Homopolymers or copolymers of amides or imides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/10—Homopolymers or copolymers of methacrylic acid esters

Definitions

• the present invention relates to a thermoplastic resin composition
• a thermoplastic resin composition comprising a methacrylimide group-containing polymer and a thermoplastic resin, and having superior heat resistance, mechanical properties, and processability.
• Methacrylimide group-containing polymers are excellent in heat resistance, clarity, heat distortion temperature, stiffness, surface hardness, and processability. However, they are poor in mechanical properties represented by impact strength. Therefore, they are limited in their application as a molding material by themselves.
• thermoplastic resins such as ethylene-ethyl acrylate copolymer, polyamide-imide, polyether-ether ketone, and polyether sulfone are superior in mechanical properties such as tensile strength, bending strength, and impact strength, and thermal properties such as heat distortion temperature and thermal decomposition temperature. They are expected to find use in broad application areas as injection moldings, extrusion moldings, and engineering plastics. Unfortunately, however, they have such a high heat distortion temperature that they need a high molding temperature and hence they are required to be improved in processability.
• thermoplastic resins As a result of studies for improving low mechanical strength which is a disadvantage of the methacrylimide group-containing polymers and also for improving poor processability which is a disadvantage of the thermoplastic resins, it has been found that the objects are achieved by blending the thermoplastic resins with a methacrylimide group-containing polymer.
• the present invention is to provide a thermoplastic resin composition
• a thermoplastic resin composition comprising:
• thermoplastic resin selected from the group consisting of ethylene-ethyl acrylate copolymer, polyamide-imide, polyether-ether ketone, and polyether sulfone, (with the total amount of (A) and (B) being 100 parts by weight).
• thermoplastic resin (B') selected from the group consisting of styrene-maleimide copolymer, polyphenylene ether-polystyrene blend polymer, polyaryl ester (all aromatic polyester), and polyether imide may be used in place of the thermoplastic resin (B).
• the component (A) used in the present invention is a methacrylimide group-containing polymer containing the methacrylimide unit represented by the formula (I) above. It may be a homopolymer or a copolymer. Methacrylimide group-containing polymers having any chemical structure may achieve the purpose of the present invention so long as they have the methacrylimide unit represented by the formula (I). Generally, a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, or phenyl group is preferably used as R in the formula (I).
• the methacrylimide group-containing polymer used in the present invention may be produced in any known processes. It may be produced by, for example, reacting a methacrylic resin (such as polymethyl methacrylate) with ammonia or a primary amine (such as methylamine and ethylamine) in a proper solvent (such as aromatic hydrocarbons including benzene, toluene, and xylene, and alcohols including methanol, ethanol, and propanol, alone or in combination) at 170°-350° C., preferably 200°-300° C., in an autoclave, thereby forming the methacrylimide ring.
• a methacrylic resin such as polymethyl methacrylate
• ammonia or a primary amine such as methylamine and ethylamine
• a proper solvent such as aromatic hydrocarbons including benzene, toluene, and xylene, and alcohols including methanol, ethanol, and propanol,
• the methacrylimide group-containing polymer used in the present invention should contain at least 10% by weight, preferably more than 20% by weight of the methacrylimide unit. With a content less than 10% by weight, the polymer does not exhibit its inherent heat resistance.
• the methacrylimide group-containing polymer used to make the thermoplastic resin composition of the present invention may contain the above-mentioned by-product in the form of acid functional group and/or acid anhydride functional group in an amount in excess of 0.4 milliequivalents for the polymer. With an amount less than 0.4 milliequivalents, the methacrylimide group-containing polymer tends to be hardly readily miscible with the above-mentioned thermoplastic resin and hence it may not contribute to the improvement of processability of the thermoplastic resins. (The reason for this is not elucidated yet.) Upper limit of the amount of the acid functional group and/or acid anhydride functional group is preferably 1.2 milliequivalents so that the resin composition of the present invention keeps its water resistance intact.
• the component (B) used in the present invention is one or more than one kind of thermoplastic resin selected from the group consisting of ethyleneethyl acrylate copolymer, polyamide-imide, polyetherether ketone, and polyether sulfone.
• thermoplastic resin selected from the group consisting of ethyleneethyl acrylate copolymer, polyamide-imide, polyetherether ketone, and polyether sulfone.
• High impact polystyrene, styrene-maleimide copolymer, polyphenylene ether and polyaryl ester can be used as the component B or additional component.
• the polyamide-imide includes, for example, one which is obtained by reacting trimellitic anhydride with an aromatic or aliphatic diamine.
• the polyetherether ketone includes, for example, "Victrex PEEK” available from I.C.I.
• the polyether sulfone includes, for example, “Polyether sulfone 420P" available from I.C.I.
• thermoplastic resin composition of the present invention is composed of 1-99 parts by weight of said methacrylimide group-containing polymer (A) and 1-99 parts by weight of at least one kind of said thermoplastic resin (B), with the total amount of (A) and (B) being 100 parts by weight.
• the amount of component (A) should preferably be 20-80 parts by weight and the amount of component (B) should preferably be 20-80 parts by weight, so that the resulting thermoplastic resin composition exhibits the superior processability inherent in the methacrylimide group-containing polymer (A) and the superior mechanical properties inherent in the thermoplastic resin (B).
• the methacrylimide group-containing polymer (A) and the thermoplastic resin (B) may be mixed with each other by melt-mixing them in the shape of granules, powder, or chips using a V-blender, supermixer, or kneader.
• thermoplastic resin (B') selected from the group consisting of styrene-maleimide copolymer, polyphenylene ether-polystyrene blend polymer, polyaryl ester (all aromatic polyester), and polyether imide may be used in place of the thermoplastic resin (B).
• thermoplastic resin composition of the present invention may be incorporated with a heat stabilizer, antioxidant, and UV ray absorber to improve heat resistance, oxidation resistance, and light resistance, respectively. It may also be incorporated with a plasticizer, pigment, and lubricant. In addition, it may be reinforced with a fibrous material such as glass fibers and carbon fibers.
• thermoplastic resin composition of the present invention may be formed into a variety of moldings by the known plastic molding process such as press molding, injection molding, and extrusion molding.
• thermoplastic resin composition of the present invention may be given improved mechanical properties represented by impact strength when it is incorporated with an impact resistant resin and a rubbery polymer as an impact modifier, the former including acrylonitrile-butadiene-styrene terpolymer (ABS resin), methyl methacrylate-butadiene-styrene terpolymer (MBS resin), ethylene-propylene-diene rubber (EPDM), and acrylonitrile-styrene graft copolymer (AES resin), and the latter including ethylene ionomer resin, modified polyethylene containing glycidyl ester groups, polyether ester, polyether ester amide, and polyether amide.
• ABS resin acrylonitrile-butadiene-styrene terpolymer
• MVS resin methyl methacrylate-butadiene-styrene terpolymer
• EPDM ethylene-propylene-diene rubber
• AES resin acrylon
• thermoplastic resins such as styrene-acrylonitrile copolymer (SAN resin), styrene-methyl methacrylateacrylonitrile copolymer, and ⁇ -methylstyrene-styreneacrylonitrile copolymer.
• SAN resin styrene-acrylonitrile copolymer
• styrene-methyl methacrylateacrylonitrile copolymer styrene-methyl methacrylateacrylonitrile copolymer
• ⁇ -methylstyrene-styreneacrylonitrile copolymer styrene-acrylonitrile copolymer
• Imide content (mol %) in the methacrylimide group-containing polymer was measured by the nitrogen content by the elementary analysis by CHN corder (Model MT-3, made by Yanagimoto Seisakusho), and the proton NMR JNM-FX-100 (JEOL) spectrometer at 100 MHz.
• Intrinsic viscosity of the polymer was calculated from the relative viscosity ( ⁇ rel ) of the polymer according to the formula below. ##EQU1## wherein C denotes the amount in gram of the polymer in 100 ml of solvent.)
• the relative viscosity of the polymer is obtained from t s /t o , where ts is the time required for a 0.5% by weight chloroform solution of the polymer sample to flow through a Deereax-Bishoff viscometer at 25 ⁇ 0.1° C., and t o is the time required for chloroform to flow through the viscometer at the same temperature.
• Samples of the methacrylimide group-containing polymer were prepared by the following methods.
• a 10-liter reactor equipped with a paddle spiral stirrer, pressure gauge, sample charger, and jacketed heater was charged with 100 parts of sufficiently dried methyl methacrylate polymer (having an intrinsic viscosity of 0.51), 90 parts of toluene, and 10 parts of methanol. With the atmosphere in the reactor sufficiently replaced with nitrogen, the contents were heated to 200° C. and stirred for dissolution. To the reactor was added 21.7 parts (0.7 mol) of methylamine from the sample-injecting device. Reaction was carried out for 3 hours at an internal pressure of 60 kg/cm 2 G. Upon completion of the reaction, there was obtained a methacrylimide group-containing polymer (designated as A-1). The polymer was dried and pulverized for use as a sample.
• a sample of methacrylimide group-containing polymer (designated as A-2) was prepared in the same manner as in the method for Sample polymer A-1, except that the methyl methacrylate polymer was replaced by methyl methacrylate-methacrylic acid (90:10) copolymer (having an intrinsic viscosity of 0.60).
• a sample of methacrylimide group-containing polymer (designated as A-3) was prepared in the same manner as in the method for Sample polymer A-1, except that the methylamine was replaced by 0.7 mol of ammonia.
• a sample of methacrylimide group-containing polymer (designated as A-4) was prepared in the same manner as in the method for Sample polymer A-2, except that the methylamine was replaced by 0.7 mol of ammonia.
• the sample (A-1) of methacrylimide group-containing polymer obtained in the method for Sample polymer A-1 was dissolved in tetrahydrofuran and the resulting solution was bubbled with diazomethane gas for the alkylation of the acid component and the acid anhydride component.
• Thermoplastic resins B are Thermoplastic resins B
• thermoplastic resins (B) used in Examples were made ready as follows:
• thermoplastic resins than the thermoplastic resin (B) were made ready as follows:
• ABS resin obtained by polymerizing 22.5 parts of styrene and 7.5 parts of acrylonitrile in the presence of 70 parts of polybutadiene rubber.
• C-2 Polyether ester obtained by polycondensing 91.5 parts of dimethyl terephthalate, 41.5 parts of dimethyl isophthalate, 38.5 parts of poly(tetramethyleneoxide) glycol, and 94.5 parts of 1,4-butanediol by the aid of 0.1 parts of titanium butoxide catalyst.
• the resin composition composed of the methacrylimide group-containing polymer (A-1) and one of the thermoplastic resins (B-1 to B-6) can be molded at molding temperatures which are 50°-60° C. lower than those of the thermoplastic resins used alone.
• Resin compositions were prepared from the methacrylimide group-containing polymers (A-1 to A-5) obtained and the thermoplastic resin (B-1 ⁇ in the mixing ratio shown in Table 3.
• Each of the resin compositions was made into test pieces by injection molding (at a cylinder temperature of 320° C. and a mold temperature of 120° C.). The test pieces were tested for physical properties. The results are shown in Table 3. Examples 7 to 15 are Referential examples.
• Resin compositions were prepared from the methacrylimide group-containing polymer (A-1), the thermoplastic resin (B-3), and other thermoplastic resins (C-1 or C-2) in the mixing ratio shown in Table 4. Each of the resin compositions was made into test pieces by injection molding and they were tested for physical properties in the same manner as in Example 1. The results are shown in Table 4. Examples 16 to 20 are Referential examples.
• a resin composition was prepared from 70 parts of the methacrylimide group-containing polymer (A-1) and 30 parts of a polyphenylene ether-polystyrene blend resin ("Noryl 731J", made by General Electric Co., Ltd.). This resin composition was made into a test piece by injection molding and tested to find the heat distortion temperature of 148° C.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Applications Claiming Priority (4)

Publications (1)

Family

ID=26508756

Family Applications (1)

Country Status (2)

Families Citing this family (2)

Citations (4)

Family Cites Families (2)

• 1989
  • 1989-07-18 US US07/381,478 patent/USH1004H/en not_active Abandoned
  • 1989-07-25 EP EP19890113682 patent/EP0354407A3/de not_active Withdrawn

Patent Citations (4)

Also Published As

Similar Documents

Legal Events