JPH0262585B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a thermoplastic resin composition with excellent thermal stability, impact resistance, and hot water resistance, and more specifically, a copolymer obtained by graft polymerizing an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride to a rubbery polymer. The present invention relates to a thermoplastic resin composition containing as an essential component a mixture of a rubber-modified imidized polymer having imide groups and a rubber-modified aromatic vinyl copolymer, which are combined and reacted with ammonia and/or a primary amine. Conventionally, aromatic vinyl monomers, rubber-like polymers,
Copolymers obtained by graft polymerization of mixtures of unsaturated dicarboxylic anhydrides and other monomers, and blends of these with rubber-modified copolymers are known (Japanese Patent Laid-Open No. 48-42091, Unexamined Japanese Patent Publication 1973
−96555). Copolymers made by copolymerizing these unsaturated dicarboxylic anhydrides have high heat distortion temperatures, but this is due to the presence of acid anhydride groups resulting from the unsaturated dicarboxylic anhydrides in the copolymer chain. Not only can it be exposed to water at high temperatures, but it also tends to undergo chemical changes and decompose when exposed to heat, creating significant restrictions when performing injection or extrusion processing. If the material is exposed to Further, US Pat. No. 3,642,949 discloses a composition obtained by blending so-called ABS with a copolymer of an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride or its imide. However, in the case of such a composition, even if an unsaturated dicarboxylic acid anhydride is used, or an imide made of an unsaturated dicarboxylic acid is used, the impact strength is low and insufficient. The present invention relates to a rubber-modified imidized copolymer obtained by imidizing the acid anhydride group of a polymer obtained by graft copolymerizing an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride to a rubber-like polymer; By blending a polymer with a rubber-modified aromatic vinyl copolymer obtained by graft copolymerizing aromatic vinyl and vinyl cyanide monomers, etc., significantly improved impact resistance and This is the first success in obtaining a thermoplastic resin composition that has a high heat distortion temperature and improved hot water resistance. That is, the present invention consists of Component A: 3 to 40% by weight of a rubbery polymer, 50% to less than 60% by weight of an aromatic vinyl monomer, and more than 40% by weight of an unsaturated dicarboxylic anhydride to 50% by weight of an unsaturated dicarboxylic anhydride.
Monomer mixture consisting of 60-97% by weight or less
10 to 90 parts by weight of a rubber-modified imidized polymer having imide groups obtained by reacting a copolymer obtained by graft polymerization with ammonia and/or a primary amine, and component B: 3 to 80 parts by weight of a rubber-like polymer. 20 to 90% by weight of an aromatic vinyl monomer, 0 to 40% by weight of a vinyl cyanide monomer, and 0 to 50% by weight of a vinyl monomer copolymerizable with these. 10 to 90 parts by weight of a graft copolymer copolymerized with 97% by weight, component C: 40 to 100% by weight of aromatic vinyl monomer, 0 to 40% by weight of vinyl cyanide monomer, and copolymerized with these. The present invention provides a thermoplastic resin composition containing 0 to 80 parts by weight of a polymer obtained by polymerizing 0 to 40% by weight of a vinyl monomer. The present invention consists of component A, component B, and optionally C.
It is a composition formed by blending the components, and the A component, B component
It is important that both components contain a rubbery polymer; if either of these components does not contain a rubbery polymer, the impact resistance will decrease. The thermoplastic resin composition of the present invention may consist of only components A and B, but it may further contain up to 80% by weight of an aromatic vinyl homopolymer or a copolymer of this with vinyl cyanide, etc. Even if mixed within this range, the excellent properties of the thermoplastic resin composition of the present invention will not deteriorate, so it has the advantage that a fairly large amount of an inexpensive aromatic vinyl polymer can be blended. First, the A component polymer and its manufacturing method will be explained. A component polymer is 3 to 40% by weight, preferably 5% by weight.
Contains ~30% by weight of rubbery polymer. Rubbery polymers include butadiene homopolymers, copolymers of butadiene and vinyl monomers copolymerizable, ethylene-propylene copolymers, ethylene-propylene-diene copolymers, and butadiene and aromatic vinyl copolymers. Block copolymers, acrylic ester polymers, and copolymers of acrylic esters and vinyl monomers copolymerizable therewith are used. A
If the rubber component in the component polymer is less than 3% by weight, the impact resistance of the component A polymer and the composition containing it will be poor, and if it exceeds 40% by weight, the heat resistance and moldability will be poor. . In addition, the monomers to be grafted onto these are composed of aromatic vinyl monomers of 50% to less than 60% by weight, and unsaturated dicarboxylic acid anhydrides of more than 40% to 50% by weight. If the content is less than 50% by weight, the characteristics of the aromatic vinyl compound, especially in the case of styrene, the moldability and dimensional stability of the component A polymer and the composition containing it will be lost, and unsaturated If the amount of dicarboxylic acid anhydride exceeds 50% by weight, the copolymer becomes brittle and its moldability deteriorates significantly. The aromatic vinyl monomers constituting component A include styrene monomers and their substituted monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene; Styrene and α-methylstyrene are particularly preferred. Examples of the unsaturated dicarboxylic anhydride include anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid, with maleic anhydride being particularly preferred. The ammonia and primary amine used in the imidization reaction of the present invention may be in either an anhydrous or aqueous solution state, and examples of primary amines include methylamine, ethylamine, n-propylamine,
Alkylamines such as iso-propylamine, butylamine, pentylamine, cyclohexylamine, and aromatic amines such as chloro- or bromo-substituted alkylamines, aniline, tolylamine, naphthylamine, and halogen-substituted aromatic amines such as chloro- or bromo-substituted aniline. can be given. In the present invention, the rubbery polymer - aromatic vinyl -
A catalyst may be present when the unsaturated dicarboxylic acid anhydride copolymer is imidized with ammonia and/or a primary amine. Tertiary amines are usually used. When the imidization reaction is carried out in a solution or suspension state, it is preferable to use a conventional reaction vessel such as an autoclave, and when it is carried out in a bulk molten state, an extruder equipped with a devolatilization device may be used. The temperature of the imidization reaction is about 80-350°C, preferably 100-300°C. If the temperature is lower than 80°C, the reaction rate is slow and the reaction takes a long time, making it impractical. On the other hand, if the temperature exceeds 350°C, the physical properties will deteriorate due to thermal decomposition of the polymer. When imidizing the rubbery polymer-aromatic vinyl-unsaturated dicarboxylic acid anhydride copolymer in a solution state, solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone,
Examples include cyclohexanone, tetrahydrofuran, toluene, xylene, and chlorobenzene. When imidizing in a suspended state, heptane,
There are aliphatic hydrocarbons such as hexane, pentane, octane, 2-methylpentane, cyclopentane, and cyclohexane. Next, component B and its manufacturing method will be explained.
The rubbery polymer used in component B is a polymer consisting of a vinyl monomer copolymerizable with butadiene alone, an ethylene-propylene-diene copolymer, or an acrylic ester alone or a vinyl monomer copolymerizable with this. There are polymers made of polymers. The aromatic vinyl monomer of component B includes styrene, α-methylstyrene, vinyltoluene, t-
These include styrene monomers such as butylstyrene and chlorostyrene, and substituted monomers thereof, and among these, monomers such as styrene and α-methylstyrene are particularly preferred. Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, with acrylonitrile being particularly preferred. Vinyl monomers that can be copolymerized with these include acrylic esters such as methyl acrylic ester, ethyl acrylic ester, and butyl acrylic ester, methyl methacrylic ester,
Examples include methacrylic acid ester monomers such as ethyl methacrylic acid ester, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylamide, methacrylic acid amide, acenaphthylene, and N-vinylcarbazole. Among these, methyl methacrylate, acrylic acid, and methacrylic acid are particularly preferred. The method for producing the graft copolymer of component B is to add 40 to 80% by weight of an aromatic vinyl monomer in the presence of 3 to 80% by weight of a rubbery polymer.
Obtained by graft copolymerizing 20 to 97% by weight of a monomer mixture consisting of 90% by weight, 0 to 40% by weight of vinyl cyanide monomer, and 0 to 50% by weight of vinyl monomer copolymerizable with these monomers. . Any known polymerization technique may be employed for the polymerization, including suspension polymerization, aqueous heterogeneous polymerization such as emulsion polymerization, bulk polymerization, solution polymerization, and precipitation polymerization of the resulting polymer in a nonsolvent. Next, component C and its manufacturing method will be explained.
As the aromatic vinyl monomer of component C, styrene,
These include styrene monomers such as α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene, and substituted monomers thereof, and among these, styrene and α-methylstyrene are particularly preferred. Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, with acrylonitrile being particularly preferred. Vinyl monomers that can be copolymerized with these include acrylic ester monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate,
Methacrylic acid ester monomers such as ethyl methacrylic acid ester, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylamide, methacrylic acid amide, acenaphthylene, N-vinylcarbazole, N-alkyl-substituted maleimide, N-
Examples include aromatic substituted maleimides. The composition of the present invention is a mixture of the above-mentioned component A, component B, and optionally component C, but there are no particular restrictions on the mixing method, and known means can be used. Examples of such means include a Banbury mixer, a Henshil mixer, a tumbler mixer, a mixing roll, and a single-screw or twin-screw extruder. Mixing methods include conventional melt mixing, step-by-step melt kneading using master pellets, etc., solution blending, solution latex blending, and graft polymerization in the presence of a thermoplastic copolymer containing aromatic vinyl as an essential component. There are methods for obtaining a composition. The ratio of blending each component of component A, component B, and component C is 10 to 90% by weight for component A and 10 to 90% by weight for component B.
90% by weight, C component is 0-80% by weight, preferably 0-80% by weight
50% by weight. The reason for limiting the blend ratio in this way is to maintain the excellent heat resistance and hot water resistance of component A, prevent deterioration in moldability, further improve impact resistance, and maintain a good balance of other physical properties. It is necessary to blend component B and component C in an appropriate blending ratio. The composition of the present invention may further include stabilizers, flame retardants,
It is also possible to add plasticizers, lubricants, fillers such as glass fiber and calcium carbonate, colorants, ultraviolet absorbers, and the like. The composition of the present invention is used in applications requiring thermal stability and impact resistance, and can be preferably used, for example, in automobile parts, electric/electronic parts, home appliances, office equipment, and the like. Furthermore, because it has excellent hot water resistance, it can also be used for kitchen utensils, food and drink containers, bathroom parts, medical equipment, etc. The present invention will be explained below with reference to Examples. Note that all parts and percentages in the examples are expressed on a weight basis. Examples 1 to 12 Experimental Examples (1) Production of a copolymer in which aromatic vinyl and maleic anhydride are grafted to a rubbery polymer. In an autoclave equipped with a stirrer, 57 parts of styrene (hereinafter referred to as "st"), 100 parts of methyl ethyl ketone (hereinafter referred to as MEK) and 7 parts of polybutadiene cut into small pieces were charged, and after replacing the inside of the system with nitrogen gas, the mixture was stirred at room temperature all day and night to dissolve the rubber. After setting the temperature to 85℃, maleic anhydride (hereinafter MAH)
A solution of 43 parts of 150 parts of MEK and 0.2 parts of benzoyl peroxide was added continuously over 6 hours. The temperature was maintained at 85° C. for an additional 4 hours after the addition. A portion of the viscous reaction solution was sampled and the amount of unreacted monomer was determined using gas chromatography to determine the polymerization rate and the amount of unreacted monomer in the polymer excluding the rubber content.
MAH content was calculated. to the remaining reaction solution
150 parts of MEK was added and poured into 1500 parts of vigorously stirred methanol to precipitate, separate and dry to obtain a white powdery polymer. This was designated as Experiment No. 1. In addition, as shown in Table 1, graft copolymers were obtained in the same manner as Experiment No. 1 except that the types of raw materials and the amounts charged were changed, and Experiments No. 2 to No. 8 were obtained.

【table】

[Table] Experimental example (2) Production of rubber-modified imidized copolymer (component A) 30 parts of the copolymer obtained in Experiment No. 1 of Experimental example (1) was dissolved in 70 parts of MEK in an autoclave. To this was added 11.65 parts of aniline, which was 1.02 times the molar equivalent to the maleic anhydride group, and the mixture was reacted at 140°C for 6 hours. The reaction solution was cooled, poured into 300 parts of vigorously stirred methanol, precipitated, separated, dried, and imidized polymer (A
component) was obtained. C-13 NMR analysis showed that the conversion rate of acid anhydride groups to imide groups was approximately 100%. Similarly, the copolymers obtained in Experiment Nos. 2 to 8 of Experimental Example (1) were also subjected to an imidization reaction. In all cases, the conversion rate of acid anhydride groups to imide groups was 99% or more. The respective codes of these rubber-modified imidized copolymers correspond to Nos. 1 to 8 of Experimental Example (1).
It is expressed as Experimental example (3) Production experiment of rubber modified copolymer (component B) No. 9 80 parts of polybutadiene latex (solid content 50%,
Average particle size 0.35μ, gel content 90%), 1 part sodium stearate, 0.1 part sodium formaldehyde sulfoxylate, 0.03 part tetrasodium ethylenediamine tetraacetate acid, ferrous sulfate.
Heat 0.003 parts and 200 parts of water to 65℃, add 30% acrylonitrile (hereinafter referred to as AN) and
60 parts of a monomer mixture consisting of 70% st, 0.3 part of t-dodecyl mercaptan, and 0.2 part of kyumene hydroperoxide were continuously added over a period of 4 hours, and after the addition was completed, polymerization was carried out at 65°C for 2 hours. The polymerization rate reached 96.5%. After adding an antioxidant to the obtained latex, it was coagulated with calcium chloride, washed with water, and dried to obtain a graft copolymer as a white powder. Experiment No. 9
And so. Experiment No.10 130 parts of polybutadiene latex and 25% AN,
st60% and methyl methacrylate (below)
A graft copolymer was obtained in the same manner as in Experiment No. 9, except that 35 parts of a monomer mixture consisting of 15% (referred to as MMA) was used, and it was designated as Experiment No. 10. Experimental example (4) Production experimental example of a thermoplastic copolymer (component C) containing aromatic vinyl as an essential component No. 11 25 parts of AN, 75 parts of st, 2.5 parts of sodium stearate,
70 parts of t-dodecyl mercaptan and 250 parts of water
The mixture was heated to ℃ and 0.05 part of potassium persulfate was added thereto to initiate polymerization. 5 hours after the start of polymerization, 0.03 part of potassium persulfate was added and the temperature was lowered to 75%.
The temperature was raised to .degree. C. and maintained for 3 hours to complete polymerization. The polymerization rate reached 97%. The obtained latex was coagulated with calcium chloride, washed with water, and dried to obtain a copolymer as a white powder, which was designated as Experiment No. 11. Experiment No. 12 A copolymer was obtained in the same manner as Experiment No. 11 except that 28 parts of AN and 72 parts of αMS were used as raw materials.
It was set to 12. Experimental example (5) Blending of A component, B component, and C component A component, B component, and C component were blended in the quantitative ratio shown in Table 2, and this blend was extruded using a screw extruder equipped with a 30 mmφ devolatilization device. , pelletized. Each blend contained 0.2 parts of octadecyl 3-(3,5-dithyabutyl-4-hydroxyphenyl)-propionate (an antioxidant). The physical properties of the composition thus obtained are shown in Table 2. The numbers surrounded by circles are experiment numbers indicating production examples of any of component A, component B, and component C. Comparative Example 1 50 parts of the unimidized rubber-modified maleic anhydride copolymer (hereinafter referred to as P) obtained in Experiment No. 1 of Experimental Example (1), 35 parts of the rubber-modified copolymer obtained in Experiment No. 9 and 15 parts of the aromatic vinyl-based copolymer obtained in Experiment No. 11 for the production of component C in Experimental Example (4) were used in the experiment. Example (5)
The physical properties of the resulting composition were measured and shown in Table 2. Comparative example 2 Experimental example (1) except that polybutadiene is not present
The st-MAH copolymer obtained in the same manner as in Experimental Example (2)
An imidized copolymer was obtained in the same manner as above. The conversion rate of acid anhydride groups to imide groups was approximately 100%.
50 parts of this imidized copolymer (hereinafter referred to as Q), 35 parts of the rubber-modified copolymer obtained in Experiment No. 9 for the production of component B in Experimental Example (3), and 15 parts of the copolymer mainly composed of aromatic vinyl obtained in Production Experiment No. 11 was blended by the method shown in Experimental Example (5), and the physical properties of the resulting composition were measured and shown in Table 2. It was shown to.

Table 2 shows that the composition of the present invention exhibits significant improvements in impact strength, thermal stability, and hot water resistance without deteriorating conventional processability. The physical properties were measured as follows. (1) Thermal stability…Nitrogen flow 50c.c./min, heating rate 10
The temperature is shown when the weight loss of the polymer in thermobalance analysis is 1% under conditions of °C/min. (2) Vikatsu softening point...Load 5Kg, ASTM D-
According to 1525. (3) Impact strength: Izotsu with notches. ASTM D
-256. (4) Melt flow index: temperature 250°C, load 5kg, according to ASTM D-1238. (5) Hot water resistance...A notched Izot test piece according to ASTM D-256 was immersed in hot water at 100°C for 24 hours, and the retention rate for the impact value measured in (3) is shown.

Claims (1)

[Claims] 1 Component A: 3 to 40% by weight of the rubbery polymer,
A copolymer obtained by graft polymerization of 60 to 97% by weight of a monomer mixture consisting of 50% by weight or more and less than 60% by weight of an aromatic vinyl monomer and more than 40% by weight and less than 50% by weight of an unsaturated dicarboxylic anhydride. 10 to 90 parts by weight of a rubber-modified imidized polymer having imide groups reacted with ammonia and/or a primary amine, and component B: 3 to 80 parts by weight of the rubbery polymer, aromatic vinyl monomer. Graft copolymerized with 20-97% by weight of a monomer mixture consisting of 40-90% by weight, 0-40% by weight of vinyl cyanide monomer, and 0-50% by weight of vinyl monomer copolymerizable with these. 10 to 90 parts by weight of copolymer, component C: 40 to 100 weight % aromatic vinyl monomer, 0 to 40 weight % vinyl cyanide monomer, and 0 to 40 weight % vinyl monomer copolymerizable with these. A thermoplastic resin composition containing 0 to 80 parts by weight of a polymer obtained by polymerizing % by weight.