JPS6069148A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a thermoplastic resin compsn. having a high heat distortion temp. and excellent thermal stability and processability, by mixing a copolymer rubber with an imidated compd. of a specified arom. vinyl monomer/maleic anhydride copolymer. CONSTITUTION:An arom. vinyl monomer (e.g. styrene) is prepd. whose polymer soln. obtd. by dispersing 1g of its polymer in 100ml of methyl ethyl ketone at 30 deg.C has a reduced viscosity of 0.3 or above. A copolymer composed of 50- 80wt% said monomer, 5-40wt% maleic anhydride and 0-30wt% copolymerizable vinyl monomer such as acrylonitrile is prepd. and at least 90mol% of the acid anhydride groups thereof is imidated. The resulting copolymer is mixed with at least one member selected from among a styrene/acrylonitrile copolymer, an ABS resin and a methyl methacrylate/butadiene/styrene copolymer to obtain the desired thermoplastic resin compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a thermoplastic resin composition with significantly improved heat stability and processability, and more specifically, an aromatic vinyl monomer, maleic anhydride, and vinyl copolymerizable with these. A thermoplastic resin in which 90 mol% or more of the acid anhydride groups are imidized by reacting with ammonia and/or a primary amine in the presence of a tertiary amine when imidizing a copolymer consisting of monomers. and at least one of SAN resin, MuBEI resin, and MB8 resin as a main component.

Various copolymers of aromatic vinyl monomers, maleic anhydride, and other vinyl monomers have been known. (Special Publication No. 15829, Special Publication No. 15829, Special Publication No. 15829, Special Publication No. 15829, Special Publication No. 15829)
No. 51955, Special Publication No. 49-10156).

These polymers copolymerized with maleic anhydride have a high heat distortion temperature, but due to the presence of acid anhydride groups derived from maleic anhydride in the copolymer chain, they are resistant to water at high temperatures. It easily undergoes chemical changes and decomposes when exposed to heat, and is subject to significant restrictions when injection or extrusion processing is performed, and when the processed product is brought into contact with water or steam or exposed to high temperatures. It has the disadvantage of causing a decrease in mechanical properties, especially impact strength.

One purpose of the present invention is to solve these drawbacks, and the present invention aims to solve these drawbacks by using an aromatic vinyl monomer having a specific reduced viscosity,
A copolymer consisting of maleic anhydride and other vinyl monomers is reacted with ammonia and/or a primary amine in the presence of a tertiary amine, and 90% or more of the acid anhydride groups in the copolymer are A thermoplastic resin stable to water and heat was obtained while maintaining the heat distortion temperature of the copolymer, and this was mixed with at least one of EIAN resin, AB8 resin, and MB8 resin. The present invention provides thermoplastic resins.

1.5% of the polymer was added to 100% of a methyl ethyl ketone solution at a temperature of 30°C. Of reduced viscosity ya of gold-containing polymer solution
p10) Aromatic vinyl monomer which is 0.3 50-8
When imidizing a copolymer consisting of 0% by weight, 5% to 40% by weight of maleic anhydride, and 0% to 30% by weight of a vinyl monomer copolymerizable with these, in the presence of a tertiary amine, the copolymer is By reacting the polymer with ammonia and/or primary amine at a temperature of 80 to 350°C, 90 mol% or more of acid anhydride groups can be converted into imide groups.

The present invention will be explained in more detail below.

Generally, aromatic vinyl monomer and maleic anhydride are
Mutual copolymerizability is strong, and in polymerization under normal radical polymerization conditions, the molar ratio of aromatic vinyl and maleic anhydride is 1 = 1.
An alternating copolymer with the composition is formed. For this reason, it is preferable to carry out radical polymerization while adding maleic anhydride at a rate substantially lower than the polymerization rate of the aromatic vinyl monomer.

The copolymer of an aromatic vinyl monomer, maleic anhydride, and a monomer copolymerizable with these used in the present invention (hereinafter referred to as an aromatic vinyl-maleic acid copolymer) has a reduced viscosity of α3 The above value is preferably 0.33 or more.

In the present invention, reduced viscosity means 1.0 mm of polymer in 100 mm of methyl ethyl ketone solution at a temperature of 30°C. Of is the viscosity of the gold-containing polymer solution.

In the present invention, the composition and reduced viscosity of the aromatic vinyl-maleic acid copolymer are particularly important; 0 to 30 vinyl monomers copolymerizable with this
% is because the copolymer maintains high heat deformation temperature and mechanical strength, and the reason why the reduced viscosity is 0.3 or more is because it is a copolymer that maintains a high heat distortion temperature and mechanical strength. This is because imidized polymers have poor mechanical properties when molded.

In the aromatic vinyl-maleic acid copolymer used in the present invention, the aromatic vinyl monomers include styrene, α-methylstyrene, vinyltoluene, t-butylstyrene,
Styrene monomers such as chlorostyrene and substituted monomers thereof, among which monomers such as medium styrene and α-methylstyrene are particularly preferred.

Vinyl monomers that can be copolymerized with these include vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, and acrylic acids such as methyl acrylate, ethyl acrylate, and butyl acrylate. Ester monomers, methacrylic acid ester monomers such as methyl methacrylic acid ester and ethyl methacrylic acid ester, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylamide, methacrylic acidamide, acenaphthylene and N-vinyl Carbazole and the like, among which monomers such as acrylonitrile, acrylic esters and methacrylic esters are 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 specific examples of primary amines include methylamine, ethylamine, n-propyA/7 Mi7 Examples include alkyl amines such as 1eo-propylamine, butylamine, pentylamine, and cyclohexylamine, aromatic amines such as aniline, tolylamine, and naphthylamine, and halogen-substituted aromatic amines such as chloro- or bromo-substituted aniline. The amount used is at least the molar equivalent of maleic acid in the aromatic vinyl-maleic acid copolymer. Preferably, the molar equivalent is 1 to 1.3 times the molar equivalent of maleic acid.

In the present invention, the aromatic vinyl-maleic anhydride copolymer as described above is reacted with ammonia and/or a primary amine in the presence of a 6th-class amine, but in the absence of a tertiary amine. The conversion reaction requires a long time and it is difficult to increase the imidization rate to 90 mol% or more. 3rd part
The amount of the class amine added is preferably at least 1 molar equivalent of o,00 to the maleic anhydride group of the copolymer.

Further, although an imidized polymer having an imidization rate of 90 mol % or less is superior to a non-imidized maleic anhydride copolymer, it is still undesirable because its stability against water and heat is insufficient.

In the present invention, the imidization reaction of the maleic anhydride copolymer is carried out in the form of a lump, in a solution, and in a suspended state in a non-aqueous solution, but when carried out in a solution state or a suspended state in a non-aqueous medium, It is preferable to use an ordinary reaction vessel, such as an autoclave, but if the reaction is carried out in a bulk molten state, an extruder equipped with a devolatilization device may be used.

In addition, in the present invention, the imidization is shown by the following reaction formula, but the ring-closing reaction of reaction formula (I) and the ring-closing reaction of 1) can be performed in separate apparatuses. It may be carried out continuously using the following equipment.

The reaction temperature for imidization is about 80 to 550°C, preferably 100 to 300°C. If the temperature is 80° C. or lower, the reaction rate is slow and the reaction takes a long time, which is not practical. On the other hand 3
If the temperature is 50°C or higher, the physical properties will deteriorate due to thermal decomposition of the polymer.

Tertiary amines include trimethylamine, triethylamine, tripropylamine, tributylamine, N, H
-dimethylaniline, N,N-diethylaniline, etc.

Examples of the solvent for imidizing the maleic anhydride copolymer in a solution state include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, tetrahydrofuran, and dimethyl formamide, among which methyl ethyl ketone is particularly preferred.

When imidizing in a suspended state in a non-aqueous medium, the non-aqueous medium includes pentane, hexane, heptane, octane, 2-
There are aliphatic hydrocarbons such as methylpentane, cyclopentane, and cyclohexane.

The imidized maleic anhydride copolymer produced by the method described above maintains a high heat distortion temperature, has a high degree of stability against water and heat, and has other mechanical properties. It also has excellent properties. This imidized polymer has good compatibility with styrene-acrylonitrile copolymer (RAM resin), ABEI resin, MBEI resin, etc., and can be mixed with these in any proportion by a conventional method. Depending on the ratio, it is possible to obtain a resin composition that takes advantage of the characteristics of each resin.

It is also possible to further add stabilizers, plasticizers, lubricants, fillers, colorants, etc. to the resin composition of the present invention.

The present invention will be explained below with reference to manufacturing examples of resins used in the examples and examples. Note that all parts in the production examples and examples are expressed in parts by weight.

1) Production of aromatic vinyl-maleic anhydride copolymer (a) Styrene 7 was placed in an autoclave equipped with a stirrer.
After charging 5 parts and purging the inside of the system with nitrogen gas, it was heated to a temperature of 80°C. A solution prepared by dissolving 25 parts of maleic anhydride and 3 parts of benzoyl peroxide A in 50 parts of methyl ethyl ketone was added to the mixture over 10 hours. For another 2 hours after addition,
The temperature was maintained at 80°C. A portion of the viscous reaction solution was sampled and unreacted monomer was quantified by gas chromatography to calculate the polymerization rate and the content of maleic anhydride in the polymer. 150 parts of methyl ether ketone was added to the remaining reaction solution, cooled to room temperature, poured into 800 parts of methanol with vigorous stirring, separated by v and dried to obtain a white powdery polymer. The reduced viscosity η5p10 of the polymer is determined by the polymer concentration C=1. Of/100-methyl ethyl ketone,
Measured at 30°C.

In addition, various aromatic vinyl-maleic anhydride copolymers were produced in the same manner as described above except that the blending ratio of the monomers was varied ('b) to (fl), and the reduced viscosity These conditions and results are shown in Table 1.

(Note) In Table 1, monomers are abbreviated as follows.

(1) st-, styrene (2) α-MBt-...α-methylstyrene (3)
MAH--maleic anhydride (4) AIJ--acrylonitrile (5) 30 parts of maleic anhydride copolymer obtained from MMA□methyl methacrylate (a), triethylamine a
3 parts were dissolved in 70 parts of methyl ethyl ketone in an autoclave, and 68 parts of aniline in an amount equivalent to 1.05 times the molar amount of the maleic anhydride group was added thereto, followed by reaction at 130°C for 7 hours. The reaction solution was cooled to room temperature, poured into 300 parts of vigorously stirred methanol, split and dried to obtain an imidized polymer.

According to 0-15 NMR analysis, the conversion rate of sialic acid anhydride groups to imide groups was 99%. The imidized polymer with 30. φ
It was extruded into pellets using a screw extruder equipped with a devolatilization device. The performance of this polymer is shown in Table 2.

3) Production of imidized polymer The same operation as in Example 1 was performed except that 50 parts of each of the maleic anhydride copolymers obtained in (b) to +fl of Example 1 were used. Note that aniline was used in an amount of 1.05 times the molar equivalent of each maleic anhydride group. The performance of these imidized polymers is shown in Table 2.

For comparison, the same operation as in Example 1 was performed on the maleic anhydride copolymer obtained in Example 1 (al and (C)) except that no tertiary amine was used as a catalyst. Its performance was measured and the results are shown in Table 2, Experiment A7 and Cliff 8.

In a stirred autoclave, 30 parts of the maleic anhydride copolymer powder obtained in Example 1 (a) and 0.2 parts of trimethylamine were suspended in 70 parts of n-hexane. 2.9 parts of methylamine was added to this and the reaction was carried out at 130°C for 7 hours. After cooling the reaction suspension to room temperature, it was filtered and dried to obtain an imidized polymer. These results are shown in Table 2 Experiment 1
69.

Table 2 The measured values in Table 2 were determined by the following method.

(1) Imidization rate --- O-13 parts MRK.

(2) Thermal stability - Nitrogen flow 50 Co/m
Temperature when the weight loss of the polymer is 1% in thermobalance analysis under the conditions of temperature increase rate of 10°C/in x.

(3) Vicat softening temperature ---Mu STM D 152
5 (5 kg load) (4) Impact strength: Notched Izot impact strength ASTM D 256 A1130 parts, 5t70 parts, sodium stearate 2.5
0.6 parts of t-dodecylmercaptan and 250 parts of water were heated to 70°C, and 0.5 parts of potassium persulfate Q 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 raised to 75°C.
The temperature was raised to 1 and kept for 3 hours to complete polymerization.

The polymerization rates reached 5t97% and Al18%, respectively. The obtained latex was coagulated with calcium chloride, washed with water, and dried to obtain a white powder copolymer, which was designated as BAN-1.

Preparation of copolymer (AB8 resin) 70 parts of polybutadiene latex (solid content 50%, average particle size (1.35μ, gel content 89%), 1 part of sodium stearate, 0.5 parts of sodium formaldehyde sulfoxylate. 1 part, 0.03 part of tetrasodium ethylene diamine tetraacetic acid, 0.1103 part of ferrous sulfate, and 200 parts of water were heated to 65°C, and to this was added a monomer mixture of 30% AN and 8t exceeding 70%. 35 parts of t-dodecyl mercaptan, 0.14 parts of t-dodecyl mercaptan, Cume 77, and Ido 6 peroxide were added continuously for 154 hours, and then polymerized for 1.5 hours at 65° C. The polymerization rate was 5t97% for each. , AN was 97%.After adding an antioxidant to the obtained latex, it was coagulated with calcium chloride, washed with water, dried, and then mixed with a white powder to obtain a graft copolymer, which was designated as ABS-1. .

Examples-1 to 8 and Comparative Examples-1 to 3 3) Imidized copolymer C (experiment 43) obtained in the production of the imidized copolymer and BAN resin BAN-1 and W or A
BEI Resin Resin Mura 8 was blended in the ratio shown in Table 3, and this blend was extruded through a 30 mm diameter screw extruder equipped with a devolatilization device to pelletize it. After each of these pellets was injection molded, the Vicat softening temperature and Izod impact strength were measured, and the results are shown in Table 3 and 1:2.
Shown in the figure.

As can be seen from Table 3, Figures 1 and 2, imidized resin and 5B8 resin or EIAM resin can be mixed well at any ratio, and the characteristics of each resin can be utilized depending on the mixing ratio. It can be seen that a resin mixture can be obtained. Therefore, according to the present invention, it is possible to obtain a resin mixture according to product design at any time.

Example 9 Imidized copolymer e (Experiment 165) obtained in the production of the imidized copolymer in 3) and ``Estyrene A3-20'' (
RAM resin (manufactured by Nippon Steel Chemical Co., Ltd.) were blended in an amount of 50 parts each, pelletized in the same manner as in Example-1, and the physical properties thereof were measured. As a result, the Vicat softening temperature was 123℃,
The Izod impact strength was 2.2 kl·cw'am.

Example-10 3) A is 50 parts each of the imidized copolymer e (Experiment 5) obtained in the production of the doped copolymer and Cycolac TI (manufactured by Ube Cycon Co., Ltd., ABS resin). The mixture was blended and pelletized in the same manner as in Example-1, and its physical properties were measured. As a result, the Vicat softening temperature was 127°C and the Izod impact strength was 10k17.(2) False.

[Brief explanation of drawings]

Figure 1 shows the changes in Vicat softening temperature and Izot impact strength depending on the mixing ratio of each component of the imidized resin and AB8 resin mixture of the present invention, and Figure 2 shows the changes in Vicat softening temperature and Izot impact strength depending on the mixing ratio of the imidized resin and EIAI. FIG. 3 is a diagram showing changes in temperature and Izod impact strength. Patent applicant Denki Kagaku Kogyo Co., Ltd. Agent Hirodo Nakamoto Shodo Inoue Katsura Yoshimine Figure 1

Claims (1)

[Scope of Claims] 1. Polymer in 1.0% of methyl ether ketone solution at 30°C. Aromatic vinyl monomer 50 whose reduced viscosity 1θp10 〉0.3 of the contained polymer solution
-80% by weight of maleic anhydride, 5-40% by weight of maleic anhydride, and 0-30% by weight of a vinyl monomer copolymerizable with these, in which 90 mol% or more of the acid anhydride groups are imidized. A thermoplastic resin composition containing as a main component a mixture of a styrene-acrylonitrile copolymer, an acrylonitrile-butadiene-styrene copolymer, and a methyl methacrylate-butadiene-styrene copolymer. 2. The aromatic vinyl monomer is styrene> and/or α
- The composition according to claim 1, which uses an imidized copolymer of methylstyrene. 5. The composition according to claim 1, wherein the copolymerizable vinyl monomer is an imidized copolymer of one or more selected from acrylonitrile, acrylic esters, and methacrylic esters.