KR100604087B1 - Continuous Process of Preparing High-Flow and High-Gloss Rubber-Modified Styrenic Resin - Google Patents

Abstract

The continuous manufacturing method of the high flow, high gloss rubber modified styrene resin according to the present invention is a liquid feed material composition containing low seed poly butadiene and high seed poly butadiene dissolved in styrene monomer to the first reactor to the point before the phase transition Reaction to form a first polymer of rubber continuous polymer having a monomer conversion of 5 to 15%, and the first polymer is continuously introduced into a second reactor, which is a phase transfer reactor, so that the monomer has a conversion of 15 to 30% and a polystyrene resin is continuous. A second polymer having a rubber-dispersed phase grafted thereon is formed, the second polymer is continuously introduced into a third reactor to produce a third polymer having a monomer conversion of 30 to 60%, and the third polymer is Continuously fed to the reactor to produce a fourth polymer having a monomer conversion of 60 to 90%, and Water-volatile matter input to the canceller and is characterized in that comprising the step of removing the residual volatile matter and unreacted monomer.

Rubber modified styrenic resins, high seas and low seas polybutadiene.

Description

Continuous Process of Preparing High-Flow, High-Gloss Rubber-Modified Styrene-based Resins {Continuous Process of Preparing High-Flow and High-Gloss Rubber-Modified Styrenic Resin}             

1 is a schematic diagram of a continuous polymerization apparatus of a rubber-modified styrene resin according to the present invention.

Field of invention

The present invention relates to a continuous polymerization method of a rubber modified styrene resin. More specifically, the present invention uses a mixture of High Cis Polybutadiene Rubber and Low Cis Polybutadiene Rubber to provide high fluidity and appearance gloss and have high impact resistance. A continuous polymerization production method for effectively producing a modified styrene resin.

Background of the Invention

Styrene-based resins have been produced commercially a lot of excellent transparency, thermal stability, processability. In particular, rubber modified polystyrene resins having enhanced impact resistance have been developed by introducing rubber particles into styrene resins. Such rubber-modified styrene-based resins have a low vinyl transition temperature (T _g ) in monovinylidene aromatic compounds such as styrene, alpha-methyl styrene, and ring-substituted styrene, in particular polybutadiene particles in a matrix of styrene polymers. It is dispersed to enhance impact resistance.

In particular, in recent years, as consumer's tendency to prefer large products and products with beautiful appearance increases, consumer electronics companies are increasing the output of large products, and at the same time, measures to improve molding processability and appearance glossiness of large products. This is being tried. It is essential to improve the fluidity in forming large products. As the fluidity is improved, the molding process can be facilitated and the appearance of the product can be improved. However, when the fluidity is increased, the impact resistance of the product is relatively lowered, and there is a problem that a crack occurs in the appearance of the molded product even with a small impact. The impact resistance and fluidity of the rubber-modified styrene-based resin show the opposite relationship. As the impact resistance increases, the fluidity decreases, and when the flowability increases, the impact resistance decreases. Therefore, resin manufacturers are properly adjusting impact resistance and fluidity according to consumers' preferences, and resin manufacturers are focusing on researching and developing excellent products having high flow, high gloss and impact resistance at the same time.

Therefore, in the present invention, in order to overcome the above problems, by using a mixture of high seed polybutadiene (1,4 Cis content of 95% or more) and low seed polybutadiene (1,4 Cis content of 25-40%), The method of preparing a rubber modified styrene resin having both high gloss and impact resistance properties has been completed.

An object of the present invention is to provide a continuous production method of a rubber-modified styrenic resin using a high Seeds poly butadiene rubber and a low Seeds poly butadiene rubber with very excellent fluidity and glossiness and excellent impact resistance.

The above and other objects of the present invention can be achieved by the present invention described below.

In order to manufacture a rubber modified styrene resin having high flowability, high gloss, and impact resistance simultaneously according to the present invention, the glass transition temperature is lower than that of low seed polybutadiene rubber (high cis polybutadiene (1,4 Cis content of 95% or more) ) To complement the impact resistance properties of rubber modified styrene resins. The lower the glass transition temperature, the higher the flexibility of the resin at room temperature and the production of rubber modified styrene resins resistant to external impacts. In particular, the increased impact resistance property can be applied to improve the fluidity by increasing the ability to improve the fluidity on the physical property balance. In addition, the appearance glossiness of the molded article is improved by using a mixture of high seed polybutadiene rubber and low seed polybutadiene (1,4 Cis content of 25 to 40%) rubber.

The continuous manufacturing method of the high flow, high gloss rubber modified styrene resin according to the present invention is a liquid feed material composition containing low seed poly butadiene and high seed poly butadiene dissolved in styrene monomer to the first reactor to the point before the phase transition Reaction to form a first polymer of rubber continuous polymer having a monomer conversion of 5 to 15%, and the first polymer is continuously introduced into a second reactor, which is a phase transfer reactor, so that the monomer has a conversion of 15 to 30% and a polystyrene resin is continuous. A second polymer having a rubber-dispersed phase grafted thereon is formed, the second polymer is continuously introduced into a third reactor to produce a third polymer having a monomer conversion of 30 to 60%, and the third polymer is Continuously fed to the reactor to produce a fourth polymer having a monomer conversion of 60 to 90%, and Water-volatile matter input to the canceller and is characterized in that comprising the step of removing the residual volatile matter and unreacted monomer.

A detailed description of each of these steps follows.

Preparation of First Polymer

In the method for producing a rubber-modified styrene resin according to the present invention, first, the styrene monomer, the high seed poly butadiene and the low seed poly butadiene are dissolved in a dissolution tank, and then transferred to a first full charge reactor.

The styrene monomers are styrene, α-methyl styrene, α-ethyl styrene, p-methyl styrene, and the like, and may be mixed with unsaturated nitrile monomers and / or alkyl acrylate monomers as monomers other than styrene. Acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, acrylonitrile and the like.

The polybutadiene is in the form of a synthetic polymer such as rubber, and can be used alone, respectively, and the composition ratio of the mixed use is not particularly limited. It is also possible to use mixed with styrene butadiene copolymer (Styrene-Rubber Copolymer).

In addition, as the solvent used in the present invention, aromatic compounds such as ethyl benzene (Ethyl Benzene), benzene, toluene, methyl ethyl ketone, and the like can be used.

The first reactor of the present invention is a full charge type in which the polymerization mixture is fed to the bottom of the reactor in a continuous flow stirred reactor (CSTR) and the reactant is discharged upwards to the reactor. The polymerization proceeds at 100 to 130 ° C. for 1 to 2 hours. In this case, the conversion rate is 5 to 15% and the reaction is transferred to the second polymerization reactor after the phase change reaction.

In the first reactor, additives such as an initiator and a molecular weight regulator are used, and tertiary butyl peroxyacetate, tertiary butyl peroxybenzoate, and the like are used as the initiator. As the molecular weight modifier, α-methyl styrene dimer, mercaptan, halide, terpene and the like are used.

The product of the first polymerization reactor is a polystyrene polymerized in a continuous rubber phase in the dispersed phase.

Preparation of Second Polymer

The first polymer is continuously introduced into a second reactor, which is a phase transfer reactor, to prepare a second polymer having a monomer conversion of 15 to 30%.

The second reactor of the present invention is a continuous flow stirred reactor as a phase transfer reactor.

The polymerization proceeds at 110 to 135 ° C. for 1 to 2 hours, with a conversion of 15 to 35%.

The second polymerization reactor of the present invention is a phase transfer reactor that serves to disperse rubber particles on continuous polystyrene. The reactants of the first polymerization reactor are dispersed in the polystyrene phase on the continuous rubber, but the volume volume of the polystyrene produced by the polymerization through the second polymerization reactor is equal to the volume volume of the initially charged rubber (including polystyrene grafted to the rubber). Phase transition starts at and the rubber dispersed phase is formed in the polystyrene continuous phase.

The particle diameter and distribution of the rubber particles produced through the phase transition process, and the polystyrene form occluded in the rubber particles are important factors for determining the physical properties of the rubber-modified styrene resin.

Preparation of Third Polymer

The second polymer is continuously introduced into a third reactor to prepare a third polymer having a monomer conversion of 30 to 60%.

The third reactor is a horizontal reactor, which makes a plug flow stream of a reactant and reacts for 0.5 to 1.5 hours at a reaction temperature of 140 to 155 ° C., with a conversion rate of 30 to 60%.

In the third polymerization reactor, additives such as molecular weight regulators and plasticizers are used, and α-methyl styrene dimers, mercaptans, halides and terpenes are used as the molecular weight regulators. As a plasticizer, the carbon number of mineral oil is used differently.

Preparation of the fourth polymer

The third polymer is continuously added to the fourth reactor to prepare a fourth polymer having a monomer conversion of 60 to 90%.

The fourth reactor is polymerized at a conversion rate of 60 to 90% at a temperature of 150 to 180 ° C. as a final reactor of the polymerization step.

The fourth reactor of the present invention is divided into four zones from the inlet to the outlet, and is a full-charged flow flow type reactor capable of temperature control and easy control of reaction heat generated by polymerization. The polymer having a conversion rate of 60 to 90% through the fourth reactor is transferred to a devolatilizer to remove unreacted monomers and solvents, thereby preparing a final rubber-modified styrene resin.

The rubber modified styrene resin prepared according to the present invention may also be used as a compounding composition to improve the fluidity of the rubber modified styrene resin.

By molding the rubber-modified styrene resin prepared according to the present invention can be used in large products having excellent gloss and impact resistance, such a molding method can be easily carried out by those skilled in the art to which the present invention belongs. Can be.

The present invention will be further illustrated by the following examples, which are merely illustrative of the present invention and are not intended to limit or limit the scope of the present invention.

Example 1

Styrene monomer 88.4 parts, 5 parts styrene monomer solution 5.3 parts by weight of high seas polybutadiene rubber with a viscosity of 60 cps, 5% styrene monomer solution 1.3 parts by weight of low-seas polybutadiene rubber with a viscosity of 45 cps and 5.0 parts by weight of ethyl benzene in a solvent After dissolving, a reaction raw material solution was prepared and fed to a full-charge continuous flow stirred reactor (Full-Charge CSTR) which is a first reactor. In the first reactor, in the presence of 280 ppm of tertiary buffy peroxy acetate, the reaction was performed at 101 ° C. and 110 RPM for 1 hour. The reaction product passed through the first reactor was 1.6 hour in a continuous flow stirred reactor, which was the second reactor at 114 ° C. and 80 RPM. After the reaction, the reactor was introduced into a horizontal reactor, which is a third reactor. In the third reactor, the reaction mixture is a fourth flow reactor, a flow-flow pulley, after reacting 0.8 ppm at 145 ° C. and 21 RPM under 100 ppm of a molecular weight modifier tert-dodecyl mercaptan and 1.2 parts by weight (phr) of mineral oil. Transfer to azi reactor. In the fourth reactor, the reaction temperature was increased step by step, and the reaction temperature was reacted at 169 ° C, 175 ° C, 180 ° C, and 189 ° C. The polymers passed through the four reactors were removed by pellets after removal of unreacted monomers and solvents through a volatilization tank, thereby preparing a final polymer. Resin characteristic analysis and physical property analysis of the injection molded product were performed on the final polymerized product, and the results are shown in Table 1.

Example 2

The polymerization conditions of the second reactor were changed to 115 ° C. and the stirring rate was 70 RPM. The other conditions were the same as those of Example 1 to prepare a final polymerization product. Resin characteristic analysis and physical property analysis of the injection molded product were performed on the final polymerized product, and the results are shown in Table 1.

Comparative Example 1

Under the same reaction conditions as in Example 1, 88.5 parts by weight of a styrene monomer as a reaction raw material, 6.6 parts by weight of a High Seas polybutadiene rubber having a viscosity of 150 cps, and 5.0 parts by weight of ethyl benzene in a solvent were dissolved in a complete mixing tank. The solution was prepared to prepare the final polymerized product. Resin characteristic analysis and physical property analysis of the injection molded product were performed on the final polymerized product, and the results are shown in Table 1.

Comparative Example 2

Under the same reaction conditions as in Comparative Example 1, 88.5 parts by weight of styrene monomer as a reaction raw material, 6.6 parts by weight of low-sea polybutadiene rubber having a viscosity of 170 cps of 5% styrene monomer solution, and 5.0 parts by weight of ethyl benzene in a solvent were dissolved in a complete mixing tank. The final polymer was prepared by preparing a raw material solution. Resin characteristic analysis and physical property analysis of the injection molded product were performed on the final polymerized product, and the results are shown in Table 1.

Comparative Example 3

The polymerization conditions of the second reactor were changed to 115 ° C. and the stirring speed was 60 RPM. The other conditions were 88.5 parts by weight of styrene monomer and 5% styrene monomer solution at 60 cps under the same reaction conditions as those of Comparative Example 1. 6.6 parts by weight of High Seas polybutadiene rubber and 5.0 parts by weight of ethyl benzene in a solvent were dissolved in a complete mixing bath to prepare a reaction raw material solution to prepare a final polymerized product. Resin characteristic analysis and physical property analysis of the injection molded product were performed on the final polymerized product, and the results are shown in Table 1.

Izod impact strength in the Examples and Comparative Examples of the present invention was measured by ASTM D-256, fluidity ASTM D-1238, glossiness ASTM D-523.

Example Comparative Example One 2 One 2 3 First reactor % Conversion 5.0 4.9 4.7 4.6 5.0 Reaction temperature (℃) 101 101 101 101 100 Stirring Speed (RPM) 110 110 110 110 110 Retention time (hr) One One One One One Initiator (ppm) 280 280 280 280 280 Second reactor % Conversion 25.3 26.6 23.1 22.4 25.3 Reaction temperature (℃) 114 115 114 114 115 Stirring Speed (RPM) 80 70 80 80 60 Retention time (hr) 1.6 1.6 1.7 1.8 1.6 Third reactor % Conversion 52.1 52.9 53.2 51.1 52.7 Reaction temperature (℃) 145 145 145 145 145 Retention time (hr) 0.8 0.8 1.1 1.0 0.8 Molecular Weight Modifier (ppm) 100 100 100 100 100 Mineral oil (phr) 1.2 1.2 1.2 1.2 1.2 Fourth reactor % Conversion 78.1 78.3 75.7 76.4 77.5 Properties Impact Strength (kgfcm / cm) 9.7 10.1 14.5 13.1 12.1 Fluidity (g / 10min, 5kg, 200 ℃) 11.6 11.2 5.3 6.8 9.7 Glossiness (%, 60˚) 98.0 91.6 51.2 61.2 72.3

As shown in Table 1, it can be seen that when high cis polybutadiene rubber and low cis poly butadiene rubber are used under given reaction conditions, rubber modified styrene resins having high flow, high gloss, and high impact characteristics can be prepared. Can be.

The present invention has the effect of providing a continuous production method of a rubber-modified styrene resin having excellent fluidity and glossiness and excellent impact resistance by using a high seas poly butadiene rubber and a low seas poly butadiene rubber.

Simple modifications and variations of the present invention can be readily used by those skilled in the art, and all such variations or modifications can be considered to be included within the scope of the present invention.

Claims (6)

The liquid feed material composition in which the high seed poly butadiene and the low seed poly butadiene are dissolved in the styrene monomer and the solvent are reacted in the first reactor at 100 to 130 ° C. for 1 to 2 hours to the point before the phase transition and the conversion of the monomer is 5 to 15%. Producing a first polymer; Continuously introducing the first polymer into a second reactor to polymerize at 110 to 135 ° C. for 1 to 2 hours to produce a second polymer having a monomer conversion of 15 to 30%; Continuously adding the second polymer to the third reactor and reacting at 140 to 155 ° C. for 0.5 to 1.5 hours to produce a third polymer having a monomer conversion of 30 to 60%; Continuously adding the third polymer to the fourth reactor and reacting in a range of 150 to 190 ° C. to produce a fourth polymer having a monomer conversion of 60 to 90%; And Adding the fourth polymer to a volatile remover to remove unreacted monomers and solvents; The first reactor is a full charge continuous stirred tank reactor; The second reactor is a continuous stirred tank type reactor as a phase transfer reactor; The third reactor is a horizontal reactor for producing a flux flow type of reactant; The fourth reactor is divided into four zones from the inlet to the outlet, each of which is a flow-flow full charge reactor capable of temperature control and easy control of reaction heat generated by polymerization. Continuous production method of rubber modified styrene resin. The method of claim 1, wherein the styrene monomer is a styrene monomer alone or a mixture with an unsaturated nitrile monomer and / or an alkyl acrylate monomer. The method of claim 1, wherein the high seed poly butadiene has a 1,4-cis content of 95% or more and a styrene solution viscosity of 30 to 90 cps, the low seed poly butadiene has a 1,4-cis content of 25 to 40% And a styrene solution viscosity of 30 to 70 cps. delete Compounding composition comprising a rubber-modified styrene resin prepared by the method of any one of claims 1 to 3. A molded article manufactured by molding a rubber-modified styrene resin produced by the method of any one of claims 1 to 3.

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