JPS63110205A - Heat-resistant resin - Google Patents

Abstract

PURPOSE:To obtain a linear random copolymer resin, consisting of structural units of an N-arylmethacrylamide and structural units of styrene and methyl methacrylate and having excellent heat resistance, fluidity, colorability as well as transparency. CONSTITUTION:A linear random copolymer heat-resistant resin, consisting of (A) 10-90mol% structural units of an N-arylmethacrylamide expressed by formula I (X is Cl, Br, methyl, ethyl, methoxy, ethoxy or nitro; n is 0-3), e.g. N-phenylmethacrylamide, N-4-chlorophenylmethacrylamide, N-4- methylphenylmethacrylamide, etc., (B) 90-10mol% one or more structural units of styrene and methyl methacrylate expressed by formula II or III and having 0.1-0.5 specific viscosity (etasp) (measured by using a solution in N,N- dimethylformamide solvent in 0.3% concentration at 30 deg.C). When the ratio of the units expressed by formula II in the structural units (B) is 50-100mol%, fluidity can be improved.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a heat-resistant resin having excellent heat resistance, fluidity, colorability, and transparency.

<Prior Art and Problems> Polystyrene resins and acrylonitrile-styrene copolymer resins, which are known as general-purpose resins, have excellent moldability but are poor in heat resistance. Conventionally, methods for improving heat resistance include a two-step method in which styrene is polymerized using maleic anhydride as a comonomer and then imidized (US Pat. No. 8,492,196), and methacrylic acid or α-methyl There is a method of using styrene etc. as a comonomer, but while these can improve heat resistance, the process is complicated, and the processability is significantly reduced due to the influence of the carboxyl group in the molecule. - When using methylstyrene, there are many problems such as coloring caused by acrylonitrile used to improve copolymerizability, and the heat resistance of these products is also not sufficient.

As a result of intensive research to solve these problems, we found that the specific viscosity (ηsp) is o, i ~ 0.5, N-aryl methacrylamide, styrene, or methyl methacrylate.
The copolymer resin consisting of the seed monomer and optionally other copolymerizable monomers has a Vicat softening temperature of about 110°C.
It was discovered that it has the above-mentioned high heat resistance and excellent fluidity, leading to the present invention.

<Means for solving the problem> That is, the present invention has a specific viscosity (η8F) of 0.1 to 0.5.
(However, X is a chlorine atom, a bromine atom, or a methyl group.

It represents an ethyl group, a methoxy group, an ethoxy group, or a nitro group, and n is 0, 1, 2 or 3. ) N-arylmethacrylamide structural unit (4) 10 to 90 mol% and one or two monomer structural units Q3) of styrene and methyl methacrylate 90 to 10 mol% Contains linear random copolymer heat-resistant resin.

The specific viscosity (η8F) of the copolymer resin of the present invention is 0.1 to 0.
．． It is 5. The specific viscosity (ηsp) was measured using an Ostwald viscometer using a 0.8% solution of N,N-dimethylformamide, 3
This refers to the value measured at 0°C.

If the specific viscosity (η8P) is less than 0.1, the fluidity will improve, but the molded product will become brittle, and if it is greater than 0.5, the fluidity will drop significantly, which is not preferred.

The composition ratio of N-aryl methacrylamide represented by the structural unit (4) in the copolymer resin of the present invention is 10 to 90.
It is mole%. If it is less than 10 mol %, the effect of improving heat resistance will not be exhibited so much, and if it is more than 90 mol %, heat resistance will be improved but the molded product will be brittle and fluidity will decrease.

Among N-aryl methacrylamides, preferably,
N-phenyl, 4-methylphenyl, 4-chlorophenyl methacrylamide, which have heat resistance, fluidity,
Particularly excellent in colorability and transparency.

In the present invention, styrene and methyl methacrylate, which have copolymerizability, heat resistance, and no problem with coloring, are selected as monomers to be copolymerized with N-arylmethacrylamide.
Each can be used alone or in any proportion, and the resulting copolymer [41] has excellent transparency. Although any ratio of styrene and methyl methacrylate can be used, it is preferable to increase the ratio.

Styrene as used in the present invention refers to styrene and nuclear-substituted styrenes such as parachlorostyrene, orthochlorostyrene, and paramethylstyrene.

In the present invention, other copolymerizable monomers that can be added as necessary include methacrylic acid, maleic anhydride,
Monomers such as N-phenylmaleimide, α-methylstyrene, acrylonitrile, and methacrylonitrile can be used alone or in combination.

The amount used is 0 to 15 mol% (monomer total 100%
mole%).

The method of copolymerization in the present invention is not particularly limited, and common suspension polymerization methods, emulsion polymerization methods, bulk polymerization methods, solution polymerization methods, etc. can be used. In particular, a suspension polymerization method is preferred because of its simple wastewater treatment and drying steps.

In the reaction, known initiators such as peroxides and azo compounds are suitably used, and known redox initiators can also be used. Further, in the suspension polymerization method, emulsion polymerization method, etc., known dispersants and emulsifiers can be used.

The reaction is usually carried out at a temperature of 30 to 150°C for 1 to 15 hours. In addition, for controlling the molecular weight, known chain transfer agents such as t-dodecylmercaptan and 2-mercaptoethanol, and diallyl phthalate are used.

Known polyfunctional compounds such as diethylene glycol diacrylate and ethylene glycol dimethacrylate may be used during the production of the copolymer resin.

Furthermore, known lubricants such as behenic acid, stearic acid, and liquid paraffin may be added during the production of the copolymer resin.

The copolymer resin obtained in the present invention may be used alone or in a blend with the above-mentioned lubricants, known stabilizers, colorants, flame retardants, pigments, and various other polymers. Various polymers to be blended include polyvinyl chloride resin, chlorinated vinyl chloride resin, MBS resin, chlorinated polyethylene resin, acrylic rubber resin, NBR resin, polycarbonate resin, polyarylate resin, and polyamide resin. There are known resins such as engineering plastics.

The copolymer resin of the present invention is an injection method.

Can be processed and molded using a roll or extrusion molding machine. Further, as a product form, it can be used in the fields of plastic molded products and foam molded products.

<Examples> Examples of the present invention are shown below, but these do not limit the present invention.

The composition of the copolymer resin of the present invention was determined by elemental analysis and 1H-N
Measured by MR. The heat resistance, fluidity, colorability, and transparency were measured by the following method after the resin was rolled and pressed.

Heat resistance: Vicat softening temperature (JIS-ni-7206)
5 kti/d weighted fluidity: B method flow (JIS-7210), measurement temperature 240°C 1100kq/c4 weighted transparency: JIS
Transmittance was measured according to -6714 and determined as follows.

Transmittance 85% or more 85-7070% or less Symbol ◎
○ × Coloring property: Judgment was made as follows by two-eye observation.

Almost no coloring ◎ Very light yellow coloring ○ Yellow coloring △ Examples 1 to 3, Comparative Examples 1 to 2 Pour 600 y of deionized water in which 0.3 y of polyvinyl alcohol has been dissolved in a 1 liter autoclave equipped with a stirrer. , N-phenylmethacrylamide 60f1 styrene 4 under stirring
After adding a mixture of 01 and an initiator in the ratio shown in Table 1 based on 100 parts by weight of monomers in total, the mixture was purged with nitrogen. 9
After raising the temperature to 0'C and polymerizing for 7 hours, the temperature was further increased to 120°C.
The temperature was raised to °C and polymerization was carried out for 4 hours.

After rolling and pressing the obtained copolymer resin, heat resistance, fluidity, transparency, and colorability were measured. Comparative examples were similarly polymerized using the initiators shown in Table 1, and then the physical properties were measured. The results are shown in Table 1.

Table 1 also shows the specific viscosity (ηsp) of each copolymer resin.

By comparing Margin Examples 1 to 3 and Comparative Examples 1 to 2 below, it was found that when the specific viscosity (ηsp) is smaller than 0.1, the fluidity improves, but it becomes brittle and cannot be molded; It can be seen that when it is larger, the fluidity is significantly reduced.

Examples 4 to 10, Comparative Examples 3 to 5 0.10 parts by weight of benzoyl peroxide, t-butylperoxy-8,5,5-trimethyl to 10oz 31 parts of monomers having various compositions shown in Table 2. Hexanoate 0
．． After polymerizing in the same manner as in Examples 1 to 3 using 10 parts by weight, each physical property was measured.

Comparative examples were also polymerized in the same manner using monomers having the compositions shown in Table 2, and then various physical properties were measured. The results are also listed in Table 2.

Comparative Example 6 Styrene 80V1 methacrylic acid 20g, benzoyl peroxide 0.8 parts by weight, t-butylperoxy-8,5
, 5-) Limethylhexanoate) 0.10 parts by weight of the mixed solution was placed in an autoclave, and the atmosphere was replaced with nitrogen at 90°C.
After the temperature was raised to 120°C and polymerization was carried out for 7 hours, the temperature was further raised to 120°C and polymerization was carried out for 4 hours.

The obtained copolymer resin was pulverized, rolled, and pressed, and then various physical properties were measured. The results are shown in Table 2.

From Example 2.4.5 below, as the composition ratio of N-aryl methacrylamide increases, the heat resistance can be greatly improved.
It can be seen that the above heat resistance can be improved. Also, comparative example 4
The amount of N-arylmethacrylamide used is 10 mol%
When the amount is less, the effect of improving heat resistance is small, and in Comparative Example 5, fluidity is significantly lowered and it is found to be brittle. From Example 2.6.7, it can be seen that heat resistance, transparency, and colorability are excellent regardless of the composition of monomer (6), styrene and methyl methacrylate. Among these, simple (a)
It can be seen that when the composition of styrene therein is 50 mol % or more, the fluidity can be significantly improved. From Example 8, it can be seen that heat resistance can be further improved by copolymerizing monomer (b). From Example 9.10, N-4-chlorophenylmethacrylamide as N-arylmethacrylamide.

It can be seen that the use of N-4-methylphenylmethacrylamide also has excellent heat resistance, fluidity, transparency, and colorability.

The copolymer resin of the present invention can significantly improve fluidity compared to the conventional method of improving heat resistance using methacrylic acid or the like as in Comparative Example 6 (Example 4).

Claims (6)

[Claims] (1) Formula: ▲ Numerical formula, chemical formula, table, etc. ▼ (However, X represents chlorine, bromine, methyl group, ethyl group, methoxy group, ethoxy group, or nitro group, and n is 0, 1, 2, or 3. ) 10 to 90 mol% of the structural unit (A) represented by the formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ One or two types represented by Structural unit (B) 90-1
The specific viscosity (η_S_P) (measured at 0.3% concentration of N,N-dimethylformamide solvent at 30°C) is 0.0 mol%.
A linear random copolymer heat-resistant resin having a molecular weight of 1 to 0.5. (2) The heat-resistant resin according to claim 1, wherein the proportion of ▲ showing mathematical formulas, chemical formulas, tables, etc. in 100 mol % of the monomer of the structural unit (B) is 50 to 100 mol %. (3) The heat-resistant resin according to claim 1 or 2, wherein the N-arylmethacrylamide of the structural unit (A) is N-phenylmethacrylamide. (4) The heat-resistant resin according to claim 1 or 2, wherein the N-aryl methacrylamide of the structural unit (A) is N-4 methylphenyl methacrylamide. (5) The heat-resistant resin according to claim 1 or 2, wherein the N-aryl methacrylamide of the structural unit (A) is N-4 chlorophenyl methacrylamide. (6) Claim 1 obtained by suspension polymerization method
The heat-resistant resin according to any one of items 1 to 5.