KR910008298B1 - Incombustible styren resin - Google Patents

Abstract

A fire retardant styrene resin is produced by the polymn. of 5-60 wt.% rubber latex of 0.1-0.5μm particle dia., 5-30 wt.% aromatic vinyl hydrocarbon, 5-30 wt.% unsatd. nitrile and 2-20 wt.% promostyrene cpd. of formula (I) [x= 1-5 , the polymn. of 5- 30 wt.% aromatic vinyl hydrocarbon, 5-30 wt.% unsatd. nitrile and 5-30 wt.% cpd. (I), and the polymn. of 0.5-10 wt.% aromatic vinyl hydrocarbon and 0.5-8 wt.% unsatd. nitrile. The resin is pref. acrylonitrile butadiene styrene (ABS) or acrylonitrile styrene (SAN).

Description

Method for manufacturing styrene flame retardant resin

The present invention is a method for producing a flame retardant resin having excellent flame retardancy, more specifically acrylonitrile-butadiene-styrene (hereinafter referred to as ABS) and acrylonitrile- containing a bromosterene compound represented by the following general formula: A method for producing a styrene (hereinafter referred to as SAN) resin.

Wherein x is an integer of 1-5.

ABS resins are rapidly increasing in application to ultra precision industries such as various home appliances and computer monitor housings.In the case of flame retardant ABS, high flame retardancy is required as the thickness of the injection molded product becomes thinner. .

In general, as a method of imparting flame retardancy to ABS resins, a method of obtaining a flame retardant effect by adding at least one component selected from a flame retardant containing polyvinyl chloride or a halide and an inorganic compound such as antimony trioxide into the ABS resin is known. have. The flame retardant ABS obtained in this way has problems such as satisfactory heat resistance, weather resistance, impact resistance, processability, or blooming when the color of the injection molding is dark, depending on the type of flame retardant.

In the present invention, as a result of solving the problems of the conventional flame-retardant ABS resin as described above to produce a reaction-type flame-retardant ABS resin other than the additional flame-retardant ABS that is excellent in heat resistance, weather resistance, impact resistance, no blooming phenomenon, butadiene Bromosterene compound, acrylonitrile, and styrene in rubber are prepared by three-step emulsion polymerization method or mixed with ordinary ABS or SAN, which is excellent in heat resistance, weather resistance, and impact resistance, and has no lasting flame retardancy. It has been found that ABS resins can be obtained and the present invention has been completed.

When styrene and acrylonitrile are polymerized at once in the butadiene rubber, which is a general method for producing ABS containing the bromostyrene compound of the present invention, the reaction rate of the bromostyrene compound is fast and no random copolymer is obtained. , Latex stability and physical properties and thermal stability is lowered, pollution problems due to residual monomers of the bromostyrene compound is raised. However, in the present invention, by performing a three-step polymerization process to produce a reactive flame-retardant ABS resin, the above problems can be eliminated. In the first step, a small amount of bromostyrene compound is added to the polymer to reduce the styrene and acryl. The arrangement of ronitrile and bromostyrene compound becomes random and at the same time maintains latex stability from a sudden reaction. In the second step, the bromostyrene compound is added in excess of the monomer to form a random copolymer as a whole. In the third step, a small amount of styrene and acrylonitrile is added to remove residual monomers of the bromostyrene compound.

In the method of the present invention, in the first step, 5-60% by weight of rubber latex, 5-30% by weight of aromatic vinyl hydrocarbon, 5-30% by weight of unsaturated nitrile, and 2-20% by weight of bromostyrene compound are polymerized. In the two-stage reaction, 5-30% of aromatic vinyl hydrocarbons, 5-30% by weight of unsaturated nitrile, and 5-30% by weight of bromostyrene compound are polymerized. In the third step, 0.5-10% by weight of aromatic vinyl hydrocarbon and unsaturated nitrile. It is characterized by polymerizing 0.5-8% by weight.

Hereinafter, the present invention will be described in detail.

In the first step to protect the latex stability, 50-85% by weight of gel-containing and 5-60% by weight of rubber latex having a particle size of 0.1-0.5 μm are placed in a reactor and stirring is carried out to emulsifier and ion-exchanged water for emulsification. 5-30% by weight of aromatic vinyl hydrocarbon, 5-30% by weight of unsaturated nitrile, 2-20% by weight of bromostyrene compound, and a chain transfer agent, and then the temperature was increased to reach 40-80 ° C. The initiator is placed in a reactor and polymerized for about 1 hour.

When the gel content of the rubber latex used herein is less than 50% by weight and 80% by weight or more, the impact strength is lowered, and even when the average particle diameter is less than 0.1 µm and 0.5 µm or more, the impact strength is lowered. Rubbery latexes used include conjugated 1.3-diene polymers or copolymers with one or more polymerizable monoethylenically unsaturated monomers, which include aromatic vinyl hydrocarbons (e.g. styrene, alkylstyrene, alkylstyrene vinyl). Naphthalene, etc.) acrylonitrile, methacrylonitrile, alkyl vinyl acrylate, vinylidene halide, and the like.

Emulsifiers for emulsification are sodium lauryl sulfate, potassium oleate, sodium oleate, sodium or potassium fatty acid, sodium rosin or potassium rosin acid polymer alkyl or alkyl di-sulfate and sulfonate alkali metal salts or ammonium. Aromatic vinyl hydrocarbons include styrene, α-methylstyrene, α-methylvinyl toluene, vinyltoluene, O-ethylstyrene, and P-ethylstyrene. Examples of unsaturated nitriles include acrylonitrile, methacrylonitrile, ethacrylonitrile or mixtures of two or more. Initiators include benzoyl peroxide, t-butylhydro peroxide, acetyl peroxide, cumene hydroperoxide, sodium persulfate, ammonium persulfate, calcium persulfate and the like.

The addition of a small amount of bromostyrene compound in comparison to the monomer in the one-step polymerization is intended to protect the latex stability from the rapid reaction of the bromostyrene compound, and also for the randomization of the polymer as a whole. The bromostyrene compound has a fast reaction rate, but if the residual amount is left, it is necessary to polymerize all the bromostyrene compounds since pollution problems may occur during the post-polymerization post-treatment process. In order to remove the monomer of the unreacted bromostyrene compound, the reaction proceeds by adding only aromatic vinyl hydrocarbon, unsaturated hydrogen and unsaturated nitrile in the three stage polymerization. In the two-stage polymerization, an emulsifier, ionized water, polymerization initiator, chain transfer agent, aromatic vinyl hydrocarbon 5-30% by weight, unsaturated nitrile 5-30% by weight, bromostyrene compound 5-30% by weight, a container capable of stirring all It is injected into the reactor continuously for 2 hours with stirring at. The ratio of the injected amount of the first step and the second step of the bromostyrene compound is preferably 1: 9-5: 5.

As a method of injecting the monomer into the reactor, there is a method of adding a monomer compound, an emulsifier, ionized water, an initiator, etc. all at once, a method of dividingly adding a constant amount, and a method of continuously adding a predetermined amount. The method is preferred.

Examples of the bromostyrene compound used in steps 1 and 2 include bromostyrene, dibromostyrene, tribromostyrene, tetrabromostyrene, and pentabromostyrene.

In the third stage polymerization, emulsifier, ion-exchanged water, polymerization initiator, chain transfer agent, 0.5-10% of aromatic vinyl hydrocarbon, and 0.5-5% of unsaturated nitrile are continuously injected into the reactor for 2 hours with stirring in a vessel capable of stirring. After three stages of polymerization, the polymerization is continued for 2 hours.

It relates to an ABS resin method containing a bromostyrene compound which is the first object of the present invention mentioned above.

Since the production method of the SAN resin containing the bromostyrene compound, which is the second object of the present invention, is the same except for adding rubbery latex, the detailed description thereof will be omitted.

Hereinafter, the embodiment will be described in detail.

Example 1

The one-stage polymerization is 100 parts of ionized water, 80% gel content, 25 parts of polybutadiene rubbery latex with an average particle diameter of 0.3 μm, 1 part of sodium lauryl sulfate, 12 parts of styrene, 7 parts of dibromostyrene, 10 parts of acrylonitrile and 0.2 parts of t-dodecyl mercaptan is placed in a reactor and the temperature inside the reactor is raised while stirring. When the temperature inside the reactor reaches 60 ℃, 0.3 parts of initiator potassium persulfate was injected and polymerized for 1 hour. In the two-stage polymerization reaction, 100 parts of ion-exchanged water, 1 part of sodium lauryl sulfate, 15 parts of styrene, 13 parts of dibromostyrene, 12 parts of acrylonitrile and 0.2 parts of t-dodecylmercaptan were added. The part is injected, stirred to make an emulsion, and then continuously added to the reactor over 2 hours. In the three-stage polymerization reaction, 50 parts of ion-exchanged water, 0.1 part of sodium lauryl sulfate, 4 parts of styrene, 2 parts of acrylonitrile, and 0.05 parts of potassium persulfate were added to the vessel, where the mixture was stirred to form an emulsion. Continuously into the reactor. The polymerization reaction was continued for another 2 hours to produce a reactive flame retardant ABS. The prepared latex was mixed with 8 parts of antimony trioxide, 1.0 part of calcium stearate, and 1.0 part of diphenylisooctyl phosphite, extruded in an extruder, and the physical properties of the specimen were injected to measure physical properties. Its measurement results are shown in Table 1.

Example 2

In Example 1, the physical properties were measured in the same manner as in Example 1 except that 15 parts of styrene and 13 parts of dibromostyrene were used instead of 13 parts of dibromostyrene. Its measurement results are shown in Table 1.

Example 3

The physical properties were measured in the same manner as in Example 1 except that the same amount of tribrotostyrene was used instead of the dibromostyrene used in Example 1. Its measurement results are shown in Table 1.

Example 4

The physical properties were measured in the same manner as in Example 3 except that 15 parts of styrene and 15 parts of tribromostyrene were used in place of 13 parts of styrene and 13 parts of tribromostyrene in Example 3. Its measurement results are shown in Table 1.

Comparative Example 1

250 parts of ion-exchanged water, 25 parts of polybutadiene rubber latex, 2.1 parts of sodium lauryl sulfate, 31 parts of styrene, 20 parts of dibromostyrene, 24 parts of acrylonitrile, 0.4 part of t-dodecyl mercaptan into the reactor and stirring Raise the temperature inside the reactor. When the temperature inside the reactor reaches 60 ℃, 0.5 parts of potassium persulfate is injected to polymerize for 5 hours to produce a reactive flame retardant ABS. Physical properties were measured in the same manner as in Example. Its measurement results are shown in Table 1.

Example 5

In the first stage polymerization, 100 parts of ion-exchanged water, 1 part of sodium lauryl sulfate, 20 parts of styrene, 15 parts of dibromostyrene, 10 parts of acrylonitrile, and 0.2 parts of t-dodecyl mercaptan were added to the reactor and stirred. Raise the temperature.

When the temperature inside the reactor reaches 60 ℃, 0.3 parts of potassium persulfate was injected and polymerized for 1 hour. In the two stage polymerization reaction, 100 parts of ion-exchanged water, 1 part of sodium lauryl sulfate, 15 parts of styrene, 25 parts of dibromostyrene, 10 parts of acrylonitrile, 0.2 parts of t-dodecylmercaptan and potassium persulfate 0.3 parts are injected, stirred to make an emulsion, and then continuously added to the reactor over 2 hours. In the third stage polymerization reaction, 50 parts of ion-exchanged water, 0.1 parts of sodium lauryl sulfate, 3 parts of styrene, 2 parts of acrylonitrile, and 0.005 parts of potassium persulfate are added to the vessel, which can be stirred, and stirred to form an emulsion for 2 hours. Continuous feeding into the reactor. The polymerization reaction was continued for another 2 hours to produce a reactive flame retardant SAN resin. 50 parts of resin (50 parts of ABS (A) (butadiene rubber, 33 parts of styrene, 17 parts of AN, 0.3 parts of t-dodecyl mercaptan) made of powdered latex by coagulation and drying process, antimony trioxide Eight parts, 1.0 part of calcium stearate, 1.0 part of diphenylisooctyl phosphite were mixed and extruded in an extruder, and then a physical property specimen was injected to measure physical properties. Its measurement results are shown in Table 1.

Example 6

The physical properties were measured in the same manner as in Example 5 except that the same amount of tribromostyrene was used instead of the dibromostyrene used in Example 5. Its measurement results are shown in Table 1.

Comparative Example 2

50 parts of ABS (A), 30 parts of SAN (Lucky 90HR), 20 parts of 1, 2-bis (2, 4, 6-tribromophenoxy) -ethane, 8 parts of antimony trioxide, 1.0 part of calcium stearate, diphenyl 1.0 parts of isooctyl phosphite were mixed and extruded in an extruder, and then the physical property pieces were injected to measure physical properties. Its measurement results are shown in Table 1.

Comparative Example 3

The same procedure as in Comparative Example 2 was carried out except that the same amount of decabromodiphenyl oxide was used instead of 1, 2-bis (2, 4, 6-tribromophenoxy) -ethane used in Comparative Example 2. Physical properties were measured. Its measurement results are shown in Table 1.

TABLE 1

How to measure

* 1: ASTM D 648

* 2: ASTM D 256

* 3: After 300 hours of irradiation in weather-O-meter

* 4: Visually judge the black specimen after 1 month test at 70 ℃ oven

In the table, O: no blooming phenomenon,

X: Blooming phenomenon.

Claims (7)

Gel content of 50-80% by weight, 5-60% by weight of rubbery latex having an average particle diameter of 0.1-0.5㎛, 5-30% by weight of aromatic vinyl hydrocarbons, 5-30% by weight of unsaturated nitrile, First reaction step to polymerize 2-20% by weight of the styrene compound, second reaction to polymerize 5-30% by weight of aromatic vinyl hydrocarbon, 5-30% by weight of unsaturated nitrile, and 5-30% by weight of bromostyrene compound And a third reaction step of removing unreacted monomer by polymerizing 0.5-10% by weight of aromatic vinyl hydrocarbon and 0.5-8% by weight of unsaturated nitrile.

Wherein x is an integer from 1 to 5. The method of claim 1 or 2, wherein the rubber latex is a conjugated 1, 3-diene polymer or a copolymer with at least one polymerizable monoethylenically unsaturated monomer. The method of claim 1, wherein the aromatic vinyl hydrocarbon is styrene, α-methylstyrene, α-methylvinyltoluene, vinyltoluene, O-ethylstyrene, P-ethylstyrene. The method of claim 1, wherein the unsaturated nitrile is acrylonitrile, methacrylonitrile, ethacrylonitrile or a mixture of two or more. The method of claim 1, wherein the bromostyrene is bromostyrene, dibromostyrene, tribromostyrene, tetrabromostyrene, or pentabromostyrene. The method of claim 1, wherein the ratio of the injected amount of the first and second reactions of bromostyrene is 1: 9-5: 5. 5-30% by weight of aromatic vinyl hydrocarbon, 5-30% of unsaturated nitrile, the first reaction step to polymerize 2-20% by weight of bromostyrene compound represented by the following general formula, 5-30% by weight of aromatic vinyl hydrocarbon, unsaturated A second reaction step of polymerizing 5-30% by weight of nitrile, 5-30% by weight of bromostyrene compound, 0.5-10% by weight of aromatic vinyl hydrocarbon, 0.5-8% by weight of unsaturated nitrile to remove unreacted monomer Method for producing a styrenic flame-retardant resin, characterized in that consisting of a third reaction step.

Wherein x is an integer from 1 to 5.