JPS6031514A - Heat and impact-resistant resin and its production - Google Patents

Abstract

PURPOSE:To produce the titled resin excellent in impact and heat resistance, by polymerizing a vinyl aromatic monomer with an unsaturated dicarboxylic acid anhydride in the presence of a diene elastomer and polymerizing the product with a layered block elastomer. CONSTITUTION:A copolymer matrix (A) comprising 75-95wt% vinyl aromatic monomer, 5-25wt% unsaturated dicarboxylic acid anhydride, and 0-20wt% monomer copolymerizable therewith (e.g., methyl methacrylate) is polymerized at 50-180 deg.C in the presence of a diene elastomer (B) (e.g., polybutadiene) of a particle diameter of 0.05-10mu. After phase transition of the elastomer, a layered elastomer (C) having a MI of 1.0-20.0g/10min and a long period of 100-1,000Angstrom is added in such an amount that the total of components B and C is 10-25wt% and the rate of component C is 5-40wt%, based on the total elastomer, and the mixture is polymerized to obtain a heat and impact-resistant resin containing component C in the form of an onion-like recurring structure and/or a lamella.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a heat-resistant needle gfj impact resin reinforced with an elastomer made of a copolymer of a vinyl aromatic monomer and an unsaturated dicarboxylic anhydride having a special microstructure, and a method for producing the same.

Copolymer resins of vinyl aromatic monomers and unsaturated dicarboxylic acid anhydrides have recently begun to attract attention because they have a higher heat deformation temperature than vinyl aromatic homopolymers (eg, polystyrene).

However, since the copolymer resin has low impact resistance and is insufficient as a molding material, a method of reinforcing it with an elastomer has been proposed, for example, in Japanese Patent Publication No. 7849/1983. That is, Japanese Patent Publication No. 55-7849 discloses that an elastomer is dispersed in a matrix resin with a particle size of 0.02 to 50μ, and that the elastomer has non-equimolar moles of a vinyl aromatic monomer and an unsaturated dicarboxylic anhydride. Although a method for producing a resin containing an adsorbed random copolymer has been disclosed, the improvement in the embrittlement of the copolymer resin is still insufficient.

The present inventors aimed to improve the above-mentioned drawbacks (as a result of studies, it was found that a copolymer matrix resin (A) consisting of a vinyl aromatic monomer, an unsaturated dicarboxylic acid anhydride, and a monomer that can be copolymerized with these) was found. The inventors have discovered that a thermal impact resistant resin with excellent performance can be obtained by incorporating a layered block elastomer (OJ) into the diene elastomer +Bj, and the present invention has been completed.

That is, the present invention comprises (a) 75 to 95% by weight of a vinyl aromatic monomer, 5 to 25% by weight of an unsaturated dicarboxylic anhydride, and 20 to 20% by weight of a monomer that can be copolymerized with these; b) Diene elastomer (B) and 100-1
Layered block elastomer with long period of 000A<
A layered block elastomer (030 proportion is 5 to 40% by weight of the total elastomer, vinyl aromatic monomer, unsaturated A copolymer matrix consisting of a dicarboxylic acid anhydride and a monomer that can be copolymerized with these (diene elastomer (B) is dispersed in N, and at least most of the diene elastomer particles encapsulate the copolymer matrix resin) In addition to the copolymer matrix resin, some of the diene-based elastomer particles contain a layered block elastomer (07) having a long period of 100 to 1000 A (incorporating 07 in an onion-like repeating structure or/and lamella shape). This relates to a heat-resistant and impact-resistant resin characterized by: 75 to 95% by weight of vinyl aromatic monomer, 5 to 25% by weight of unsaturated dicarboxylic acid anhydride, and these. A monomeric diene elastomer (B) containing 0 to 20% by weight of copolymerizable monomers and 100 to 100% by weight
Layered block elastomer (0) with a long period of 0A
In the graft copolymerization in the presence of , the vinyl aromatic monomer and the unsaturated dicarboxylic acid anhydride are first polymerized in the presence of the diene elastomer, and after phase inversion of the elastomer in the polymerization system, the above The layered block elastomer is added to the polymerization system and subjected to a polymerization reaction, and the total of the above two types of elastomers is 10 to 25% by weight in the resulting graft copolymer, and the proportion of the J-shaped block elastomer is 95 to 40% by weight of the total elastomer. % by weight.

In the present invention, vinyl aromatic monomers include styrene, α-methylstyrene, p-merstyrene, vinyltoluene, halostyrenes (for example, 0-
chlorstyrene, p-chlorostyrene, etc.) and mixtures thereof.

Styrene is preferred. Examples of unsaturated dicarboxylic anhydrides include maleic anhydride, chloromaleic anhydride, dichlorotetramaleic anhydride, citraconic anhydride, itaconic anhydride, phenylmaleic anhydride, Acoela) ff Examples include anhydrides and mixtures thereof. Maleic anhydride is preferred.

In the present invention, the ratio of the vinyl aromatic monomer to the unsaturated dicarboxylic acid anhydride is preferably in the range of 75 to 95% by weight of the former and 5 to 25% by weight of the latter. If the amount of unsaturated dicarboxylic anhydride is less than 5% by weight, a sufficient effect of improving heat resistance cannot be expected. If the amount is more than 25 polymers, the resulting copolymer will be insoluble in the polymerization system and will precipitate, making it impossible to carry out homogeneous polymerization, lowering the molecular cap, considerably lowering water resistance, and lowering melt fluidity. This is inconvenient because it has many disadvantages as a plastic product, such as confusion.

When copolymerizing a vinyl aromatic monomer and an unsaturated dicarboxylic acid anhydride, use a composition in which the former is more than equimolar;
In addition, since both have strong alternating copolymerizability and the consumption rate of the latter is fast, it is also possible to adopt a method of adding unsaturated dicarboxylic acid anhydride to the polymerization system one after another to make the copolymerization composition uniform.

In carrying out the present invention, 10,000 parts by weight of the vinyl aromatic monomer and other monomers that can be copolymerized with the unsaturated dicarbonyl IIR anhydride are mixed in a ratio of 0 to 20 parts by weight, either singly or It is also possible to perform multicomponent copolymerization using two or more types. Examples of such other monomers include methyl methacrylate/I/acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-human n-xyethyl methacrylate, glycidyl methacrylate, allyl methacrylate, acrylic acid, methacrylic acid, etc. These include acrylic compounds, unsaturated nitrile compounds such as acrylonitrile and methacrylnitrile, and monomers capable of vinyl polymerization such as olefins, diolefins, vinyl chloride, vinylidene chloride, and vinyl acetate.

Examples of diene-based didistomers used in the present invention (BJ include polybutadiene, styrene-butadiene random copolymers, etc., and layered block elastomers (C) having a long period of 100 to 1000 A include vinyl aromatic monomers and There are block polymers such as block elastomers of conjugated diene, and preferably the conjugated diene content is 50%.
It is a multi-branch elastomer of a vinyl aromatic monomer (eg, styrene) and a conjugated diene (eg, butadiene, isoprene) in an amount of less than 5% by weight (preferably 5 to 45% by weight). Here, the layered morphology having a long period of 100 to 100 DA means that when observed under a transmission electron microscope after staining with the known osmic acid staining method, the diene component, which is a component to be dyed in the elastomer, is as shown in Figure 1. This refers to a form in which the stripes exhibit a striped pattern, and are arranged at intervals of 100 to 1000 A with a long repetition period d. The melt flow index of such a layered PRODIC copolymer is 200 on a melt indexer.
7:, 1.0-20.0I under measurement conditions of 5 to 11 loads
i/10 minutes.

The total amount of (B) and (OJ) used is preferably 10 to 25 parts by weight. If it is less than 10 parts by weight, a sufficient impact resistance improvement effect cannot be expected, while if it is more than 25 parts by weight, the resulting resin It becomes too flexible (the effect of improving the heat deformation temperature by the unsaturated dicarboxylic anhydride is impaired).Also, the proportion of (03) in the total amount of (B) and (Ct) used is preferably 5 to 40% by weight.

(If 1 is less than the 5-tiered % of the elastomer consensus, the effect of improving the impact resistance of the present invention cannot be expected, and if it is more than 40i%, the total diene content in the elastomer is too small (too much and the impact strength On the contrary, the particle size of the diene elastomer is preferably 0.05 to 10 μm.

If it is smaller than 0.05μ, the impact resistance force zp will be reduced.

On the other hand, if it is larger than 10μ, the number of rubber particles dispersed in the matrix resin decreases, and impact resistance is similarly impaired.

In the method for producing a heat-resistant and impact-resistant resin of the present invention, for example, in a batch polymerization method, a diene elastomer (B
J is added at the beginning of the reaction, and after the polymerization reaction has progressed and phase inversion of the polymer 2 stomer has occurred (this is confirmed by phenomena such as the polymerization system changing from a transparent state to a cloudy state). Add the layered plastic elastomer (0) to the polymerization system. This method of addition involves adding the diene elastomer (BJ) to the polymerization system.

It is possible to select a method in which the layered block elastomer CO) is added continuously immediately after the phase inversion, a method in which the layered block elastomer CO) is added in several parts at time intervals, and a method in which the layered block elastomer CO) is added at a certain period after the phase inversion. However, if the polymerization rate is 4 of the final polymerization rate (setting)
It is desirable to complete the addition of all the entomers used by the time J# reaches 75, otherwise the dispersibility of the entomers added to the polymerization system in the final stage of the polymerization into the yarn will be significantly worse. There is a fear.

For example, in a continuous polymerization method, a diene elastomer (BJ) is continuously added to the first tank, and a layered block elastomer (O) is continuously added to the second tank and thereafter.This addition method A method of continuously adding to 6 tanks after the 2nd tank, a method of continuously adding only to one or more selected tanks after the 2nd WI, or a method of adding continuously to a continuous horizontal reaction tank showing piston flow or A method of continuously adding at multiple points or the like may be adopted.

In the production method of the present invention, the temperature of the polymerization reaction is 50C to 1
A range of 80C is appropriate; below that, the polymerization rate is too slow and the reaction takes too long; above that, the polymerization rate is too fast, and a runaway reaction is likely to occur (dangerous). At high temperatures of 1,000°C or higher, so-called thermal graft polymerization can be carried out without a catalyst by thermal radical initiation of styrene, but benzoyl peroxide, lauroyl peroxide,
It is of course possible to carry out conventional radical graft polymerization using an ij4 oxide catalyst such as dicumyl peroxide or a radical A/initiator such as azoisobutyronitrile.

The graft polymerization reaction can be carried out in bulk without a bath agent,
Benzene, toluene, xylene, methyl ethyl ketone,
Solution polymerization using a suitable solvent such as furan, dioxane, chloroform or carbon tetrachloride for tetrahydrogen is also possible, and there is no particular restriction on the polymerization method. Further, as necessary, additives such as an antioxidant, an ultraviolet absorber, a lubricant, a desensitizing agent, and a coloring agent can be added as appropriate before, during, or after the polymerization.

According to the present invention, in particular, by blending a layered block elastomer (CtJ) having a long period of 100 to 1000 A (as in the present invention), a copolymer matrix (AJ's rigid polymer chains can cause significant stiffness). The embrittlement property can be significantly improved.The heat-resistant and impact-resistant III resin of the present invention is a diene-based elastomer containing a matrix-forming copolymer resin (A) (KM is further incorporated into BJ). layered 1
Its characteristic lies in the fact that the μ-tsuku elastomer (0) is encapsulated in an onion-like &9-shaped structure or/and in a lamellar shape. Furthermore, a form in which a part of the layered block elastomer (C) is dispersed in a layered manner in a copolymer matrix (gradient) to reinforce the matrix is also included in the present invention. A transmission electron microphotograph of a heat-resistant and impact-resistant resin of the present invention having a copolymer resin (AJ) and a layered polymer having a long period of 100 to 1000 A and a Tsuque elastomer (q) is exemplified.

In the heat-resistant and impact-resistant resin of the present invention, a layered block elastomer (cutting material) comprising a vinyl aromatic monomer as a matrix compatibilizing functional group and a conjugated diene as an impact-absorbing and absorbing compatibilizing functional group is used. Diene elastomer which is a shock absorbing layer (incorporated into BJ, diene elastomer/*
(By connecting 87 with buttons, it is assumed that the impact absorption power is synergistically greatly increased. In particular, as shown in Figure 2, diene elastomer (BJ and matrix (A) The effect can be further enhanced by placing a layered block elastomer (GJ) near the interface with the material.

Regarding the rubber reinforcement mechanism, as described in "1-Aas Resin" 88 members (published by the Society of Polymer Science and Technology) (generally, the rubber reinforcement mechanism is
There is a crack theory and a craze theory, but if the interfacial adhesion between the matrix resin phase and the rubber phase is weak, voids will easily form at the interface as crazes occur, resulting in cracks and destruction, but if the interfacial adhesion is strong This is said to be caused by the occurrence of cracks in the early stages of craze formation.

In the present invention, by arranging the no-shaped block elastomer (0) having a matrix compatibilizing functional group and an impact-absorbing layer compatibilizing functional group as described above, the graft chain with the entomer developed at the polymerization site can be It is presumed that the adhesive strength can be further increased and the elastomer reinforcing effect can be synergistically involved.

The production method of the present invention involves adding a diene elastomer (BJ at the beginning of the reaction, and forming a layered block elastomer (0).
It is characterized by post-adding during polymerization, and in a continuous polymerization method, for example, as shown in Comparative Example 3, when layered Prutsk elastomer (0) is added to the first tank together with diene elastomer (87), , the impact resistance improvement effect is diminished. In this case, the layered block elastomer <C) becomes a diene elastomer (in the form of a nebula-like extremely dispersed structure around the BJ. Also, as shown in Comparative Example 4) As shown in FIG. 3, a layered block elastomer (CJ
If only the materials are melt-blended, the characteristics of the present invention as shown in FIG. 2 will not be achieved, and the impact resistance will actually decrease. Therefore, it is necessary for the layered block elastomer to exhibit a unique non-repetitive GL rigid structure in order to have higher impact resistance than conventional structures.

The resin material obtained by the method of the present invention has excellent impact resistance, heat resistance, moldability, and other properties required for reliability, so it can be molded by injection molding, extrusion molding, or other heat forming methods. It can be advantageously used as a material for manufacturing plastic molded products.

The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 A solution of 10 parts of polybutadiene (Asahi Kasei Kogyo Co., Ltd. M; Diene NF35A) dissolved in 90 parts of styrene monomer and 15 parts of maleic anhydride monomer were dissolved in 8 parts of styrene monomer.
A solution dissolved in 7 parts by weight of styrene monomer was continuously charged at a rate of 17 kg/hr and 4.4'k)/hr into the first polymerization camp located in a 250-storey building where the internal temperature was kept at 160C. . This first Arashi godan is a complete mixing tank with 3 paddles, and the contents of the 1M godan are uniformly mixed. The reaction mixture is continuously taken out from the first polymerization tank so that the filling rate of the first polymerization camp is a constant value of about 4°0%,
The mixture is supplied to a second polymerization tank having a capacity of 180 mm and maintained at an internal temperature of 130C. On the other hand, in the second polymerization tank, butadiene and styrene with long period d = 35 OA layered Prutsk elastomer (Asahi Kasei Co., Ltd.!!: Asaflex 810, temperature 2
00C, the bath melt flow index at load M 5 ki is 5.017
For 10 minutes, a solution of 17 parts by weight of bound styrene (70%) dissolved in 83 parts of styrene monomer and a styrene monomer solution of the maleic anhydride monomer were each mixed at 5.0 kl/M.

Continuously feed at a rate of 5.5 kg/hr. The second polymerization tank is a complete mixing tank equipped with a double helical ribbon, and the second polymerization tank is uniformly mixed and stirred at SO rpm, and the second polymerization tank is heated so that the filling rate of the second polymerization tank is a constant value of about 75%. Continuously remove the reaction mixture from the tank and
Continuously feed the demonomer maintained at 6
．． It is heated to a temperature of 250 to 260C to devolatilize it, and is taken out as a strand and cut to make a pellet.

On the other hand, about 10.9 g of the reaction mixture in the first polymerization tank and the second polymerization tank were taken out, dissolved in 100++ J of methyl ethyl ketone, reprecipitated in 100 m of methanol, filtered and dried, weighed, and solidified. When the type fraction was determined, the solid fraction in the first polymerization camp was 40.7% by weight, and the solid fraction in the second polymerization tank was 56.5% by weight. The enstomer content in the pellet was 14.1% by weight.

Furthermore, after dissolving and dispersing 0.5I of the pellets in 50 grams of methyl ethyl ketone, titration was performed with a 0.1 weight concentration methanol solution of sodium hydroxide, and the weight of anhydrous maleic in the total polymer was determined to be 6.9% by weight. - Molded products for physical property evaluation were molded using an injection molding machine, and the Izot impact strength and heat distortion temperature were measured. The results are shown in Table-1.

Further, the molded article was stained using a known osmic acid staining method, and then observed using a transparent, type 4 electron microscope, and the photograph shown in FIG. 2 was obtained.

Example 2 Which internal temperature of the first polymerization tank and the second polymerization tank is 4120C?
The charging speed of the polybutadiene styrene monomer solution and the maleic anhydride styrene monomer solution of Example 1 into the first polymerization tank was 9.2 k1!, respectively. /
hr, 2.4 kll/hr, Example 1
The charging rate of the 0-layer block elastomer styrene monomer solution and the maleic anhydride styrene monomer solution to the second polymerization tank was 2.7 kg/hr, respectively.
The same experiment as Example 1 was repeated, except that , 3.0 kg/hr. The results are shown in Table-1.

Example 3 15.5 kg of the polybutadiene styrene monomer solution of Example 1 was charged into a double helical helical reboiler JI47:) with a capacity of 404, and the temperature was raised to 130C without stirring. After heating up, the internal temperature is 150C, 3
While maintaining the stirring speed at 0 rpm, the styrene monomer solution of maleic anhydride of Example 1 was mixed with B for the first 2 hours.
, at a rate of 759/hr, 780 every 2 hours
J/hr.

It was supplied at a rate of 79,511/hr and 7,101/hr. On the other hand, the interior of the polymerization tank was observed 2 hours after the completion of the temperature rise, and the reaction mixture changed from transparent to opaque, confirming phase inversion of the elastomer. Therefore, 1.8 kl of a solution dissolved in 75 parts by weight of the layered block elastomer 25 heavy JHR 1 styrene monomer described in Example 1 was gradually fed into the same polymerization tank over a period of 3 hours and 50 minutes to 4 hours after the completion of heating. did.

After 8 hours from the completion of temperature rise, about 10 times of the reaction mixture in the polymerization tank was sampled for analysis, and 65J of 4,4'-thiobis(6-t-butyl-
3 methylphenol) and continued stirring for an additional 5 minutes, the reaction mixture was charged into a demonomer machine and 5 To
rr, and was devolatilized at 250C to form a pellet.

The sample of the reaction mixture and pellets were analyzed, molded and measured by the method shown in Example 1, and the results are shown in Table 1.

Comparative Example 1 The internal temperature of the first polymerization tank and the second M combination tank are both 120C.
The charging speed of the maleic anhydride styrene monomer solution of Example 1 and the 10.7 wt% polybutadiene styrene monomer solution into the first polymerization tank was 2, respectively.
．． 3kl/hr.

8.1 kg/hr, and a styrene monomer solution of polybutadiene (concentration 12.5% by weight) was charged into the second polymerization tank in place of the styrene monomer solution of maleic anhydride and the layered block polymer of Example 1. The speed is 5.1 kjJ/hr, respectively.

The same experiment as Example 1 was repeated except at 5.5 kIP/hr. The morphology of the rubber is similar to that seen in high-impact polystyrene (AX-PS) resin, showing a salami structure containing a matrix resin. After staining, it was observed with a transmission electron microscope, and the third
I got a picture of the figure.

Comparative Example 2 The internal temperature of the first polymerization tank and the second polymerization tank is 0120C.
' and the concentration of polybutadiene rubber d! The charging rates of the 11.6 wt% styrene monomer bath solution and the maleic anhydride styrene monomer solution of Example 1 to the s1 polymerization were 11, 7 kg/hr, and 2.6 k, respectively.
g/hr, and no styrene monomer solution of the layered block elastomer of Example 10 was fed to any polymerization tank, and only the maleic anhydride styrene monomer solution of Example 1 was fed to the second polymerization tank. 1 kg/h
The same experiment as in Example 1 was repeated except feeding at a feed rate of r. The results are shown in Table-1.

Comparative Example 3 A solution in which 3.8% by weight of layered block elastomer and 86% polybutadiene were combined and dissolved in styrene monomer and a mono-styrene solution of maleic anhydride in Example 1 were charged at a rate of 25A kll each
The same experiment as in Example 1 was repeated except that only the styrene monomer solution of maleic anhydride from Example 1 was charged into the second polymerization tank at a rate of 5.4 kIP/hr. The results are shown in Table-1.

Comparative Example 4 Belem) 5kp obtained by the method of Comparative Example 1 and the layered plastic elas)-r-7911 used in Example 1 were mixed in a tumbler.
After mixing in a mold mixer, the mixture was melt-blended in an extruder at 2400 ml. The obtained pellets were evaluated by the method of Example 1, and the results are shown in Table 1.

[Brief explanation of the drawing]

Fig. 1 is a long-period transmission electron microscopy model of the layered block elastomer used in the present invention, and Fig. 2 is a transmission electron microscopy model of the sample of Example 1 by Kaoru Furuya, the applicant's representative. 2 Figure 3

Claims (1)

[Scope of Claims] t (a) 75 to 95% by weight of a vinyl aromatic monomer, 5 to 25% by weight of an unsaturated dicarboxylic acid anhydride, and 0 to 20% by weight of a monomer copolymerizable with these; , (b) Diene elastomer (BJ Akibini 100-1
Laminar gastrointestinal 2-stomer with a long cycle of 000A (
A graft copolymer in which the total amount of GJ is 10 to 25% by weight, a layered block elastomer (the proportion of q is 5 to 40% by weight in the total elastomer, and a vinyl aromatic monomer) , a diene elastomer (B) is dispersed in a copolymer matrix (A) consisting of an unsaturated dicarboxylic acid anhydride and a monomer copolymerizable with these, and at least most of the diene elastomer particles are copolymerized. In addition to the copolymer matrix resin, a part of the diene-based elastomer particles contains a layered block elastomer (0) having a long circumference of 100 to 1000 people in an onion-like repeated S structure or/and A heat-resistant and impact-resistant resin characterized by lamellar encapsulation. 2. 75 to 95% by weight of vinyl aromatic monomer, 5 to 25% by weight of unsaturated dicarboxylic acid anhydride, and can be copolymerized with these. In graft copolymerizing monomers in a proportion of 0 to 20% by weight in the presence of a diene elastomer fB) and a layered block elastomer (CJ) having a long period of 100 to 1000 A, first a vinyl aromatic monomer is mer and an unsaturated dicarboxylic acid anhydride in the presence of the diene elastomer, and after phase inversion of the elastomer lying in the polymerization system, the layered bootque elastomer is added to the polymerization system to cause a polymerization reaction, The total amount of the above two elastomers is 10-25% in the resulting graft copolymer, and the proportion of the layered block elastomer is 5-25% in the total elastomer.
A method for producing a heat-resistant and impact-resistant resin, characterized in that the resin has a content of 40%.