KR102096553B1 - Rubbery polymer, method for preparing graft copolymer comprising the rubbery polymer and thermoplastic resin composition - Google Patents

Abstract

The present invention relates to a method for producing a rubber polymer, a method for producing a graft copolymer containing the same, and a thermoplastic resin composition, and more specifically, to continuously inject isoprene and aromatic vinyl monomer at a specific point in emulsion polymerization of the rubber polymer. By copolymerizing isoprene and aromatic vinyl monomers in the main chain of the butadiene polymer, a rubber polymer having a low gel content even under a high conversion rate can be prepared, and the graft copolymer and the thermoplastic resin composition prepared therewith are glossy and It has an excellent impact strength.

Description

Method of manufacturing a rubber polymer, method of manufacturing a graft copolymer containing the same, and a thermoplastic resin composition {RUBBERY POLYMER, METHOD FOR PREPARING GRAFT COPOLYMER COMPRISING THE RUBBERY POLYMER AND THERMOPLASTIC RESIN COMPOSITION}

The present invention relates to a method for producing a rubber polymer, a method for producing a graft copolymer comprising the same, and a thermoplastic resin composition, and more specifically, a method for producing a rubber polymer having a high gel content and a low conversion rate, and It relates to a method for producing a graft copolymer having improved glossiness, impact resistance, and the like, and a thermoplastic resin composition.

The conjugated diene rubber polymer represented by polybutadiene is widely used as an impact modifier for various thermoplastic resins such as ABS (Acrylonitrile-Butadiene-Styrene) resin or MBS (Methacrylate-Butadiene-Styrene) resin due to its excellent physical properties such as impact resistance. .

In particular, ABS-based resins are widely used as materials for electrical / electronic products, automobile parts, and general office supplies due to their excellent balance of physical properties such as impact resistance, chemical resistance, and moldability.

In general, ABS-based resins are produced by an emulsion polymerization method, and specifically, in order to impart impact strength, a diene-based rubber polymer is prepared by an emulsion polymerization method, and then an aromatic vinyl monomer and a vinyl cyan monomer are added to the emulsion polymerization method. It is prepared by graft polymerization.

In order to further improve the impact resistance of the ABS-based resin, it is important to control the physical properties of the diene-based rubber polymer latex included as an impact modifier, and the gel content mainly due to the average particle diameter of the diene-based rubber polymer and the internal crosslinking of the diene-based compound. It is known to greatly affect the impact resistance, and generally, the larger the average particle size of the rubber particles and the lower the gel content, the better the impact strength.

Normally, in the emulsion polymerization of diene-based rubber latex, a method of polymerizing at high temperature to produce a large-diameter rubber latex within a short time is known, but in this case, crosslinking of diene-based monomers is promoted to increase the gel content and obtain a rubber polymer with a small particle size. It was difficult to improve the impact resistance.

Therefore, there is a need to develop a technique for producing a rubber polymer having a high polymerization conversion rate and a low gel content within a short reaction time.

Korean Registered Patent No. 10-1661399

In order to solve the problems of the prior art as described above, an object of the present invention is to provide a method for producing a rubber polymer having a low gel content even under high conversion.

In addition, the present invention aims to provide a method for producing a graft copolymer comprising a rubber polymer according to the above manufacturing method, and furthermore, by mixing the graft copolymer with a matrix resin, improved impact resistance, glossiness, etc. It is an object to provide a resin composition.

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

In order to achieve the above object, the present invention is a first polymerization in which 50 to 80 parts by weight of a butadiene monomer, 0.01 to 0.3 parts by weight of an initiator, and 0.1 to 5 parts by weight of an emulsifier are polymerized in a total amount based on 100 parts by weight of the monomers used. step; A second polymerization step of polymerization by adding 0.05 to 0.5 parts by weight of an initiator and 0.1 to 3 parts by weight of an emulsifier at a conversion time of 25 to 45% of the polymerization reaction; And a third polymerization step in which an emulsion containing 5 to 35 parts by weight of an aromatic vinyl monomer, 5 to 35 parts by weight of an isoprene monomer, and 0.1 to 2 parts by weight of an emulsifier is continuously charged at a conversion time of 50 to 70% of the polymerization reaction. It provides a method for producing a rubber polymer characterized in that it comprises a.

In addition, the present invention graft polymerizes 20 to 50% by weight of one or more monomers selected from aromatic vinyl monomers, vinyl cyanic monomers and acrylic acid ester monomers to 50 to 80% by weight (based on solid content) of the rubber polymer latex prepared above. It provides a method for producing a graft copolymer characterized in that it comprises a step.

In addition, the present invention provides a thermoplastic resin composition comprising the graft copolymer in an amount of 15 to 50% by weight.

According to the present invention, in the emulsion polymerization of a rubber polymer, isoprene and aromatic vinyl monomers are continuously added at a specific point in time to copolymerize isoprene and aromatic vinyl monomers into the main chain of a butadiene rubber polymer, and rubber having a low gel content even under high conversion. A polymer can be prepared, and the graft copolymer and the thermoplastic resin composition containing the same have excellent impact resistance properties such as impact strength and appearance properties such as glossiness.

Hereinafter, a method of manufacturing the rubber polymer of the present substrate will be described in detail.

The present inventors confirmed that a rubber polymer latex having a high conversion rate and a low gel content was produced by copolymerizing the butadiene main chain by injecting an isoprene monomer and an aromatic vinyl monomer at a specific point in time during the emulsion polymerization of the butadiene monomer and further selling it based on this. Thus, the present invention has been completed.

The rubber polymer manufacturing method of the present invention is, for example, based on 100 parts by weight of the monomers used, (A) 50 to 80 parts by weight of a butadiene monomer, 0.01 to 0.3 parts by weight of an initiator, and 0.1 to 5 parts by weight of an emulsifier to perform polymerization reaction A first polymerization step; (B) a second polymerization step of polymerization by adding 0.05 to 0.5 parts by weight of an initiator and 0.1 to 3 parts by weight of an emulsifier at a conversion time of 25 to 45% of the polymerization reaction; And (C) 5 to 35 parts by weight of an aromatic vinyl monomer, 5 to 35 parts by weight of an isoprene monomer, and 0.1 to 2 parts by weight of an emulsifier at a conversion rate of 50 to 70% of the polymerization reaction. It may be characterized in that it comprises a; three-polymerization step.

Polymerization conversion rate in the present description, after drying the latex 2g in a 150 ℃ hot air dryer for 15 minutes, by measuring the weight to obtain the total solids content (TSC) can be calculated the polymerization conversion rate by the following equation (1).

[Equation 1]

Polymerization conversion rate (%) = [Total solid content (TSC) X (total amount of injected monomers and auxiliary materials)] / [100- (total amount of added auxiliary materials other than monomer)]

Hereinafter, a method of manufacturing the rubber polymer will be described in detail for each step.

(A) First polymerization stage

The first polymerization step of the present invention is a step of forming a butadiene polymer by emulsion polymerization including a butadiene monomer, an initiator, and an emulsifier.

The butadiene monomer is, for example, 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene And it may be at least one selected from the group consisting of chloroprene, preferably containing 1,3-butadiene.

The butadiene monomer may be preferably added in an amount of 50 to 80 parts by weight, for example, based on 100 parts by weight of the total monomer added to the rubber polymer production, more preferably 55 to 75 parts by weight, most preferably 60 to 70 parts by weight It will be denied. Within this range, it is possible to manufacture a rubber polymer having excellent polymerization efficiency and high conversion and low gel content.

The initiator is not particularly limited as long as it is an initiator commonly used in the art, and a peroxy-based initiator can be preferably used. The peroxy-based initiator may be one or more selected from the group consisting of t-butyl hydroperoxide, paramethane hydroperoxide, cumene hydroperoxide, diisopropyl benzene hydroperoxide, and benzoyl peroxide as specific examples, and It contains t-butyl hydroperoxide.

The initiator may be preferably added in an amount of 0.01 to 0.3 parts by weight, 0.05 to 0.25 parts by weight, or 0.1 to 0.2 parts by weight based on 100 parts by weight of the total monomer added to the production of the rubber polymer. A rubber polymer with excellent gel content and low desired average particle diameter can be produced.

The emulsifier is not particularly limited as long as it is an emulsifier commonly used in the production of rubber polymers in the art, and preferably from the group consisting of alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, fatty acid salts and rosinates. It may be one or more selected.

The emulsifier may be used in an amount of 0.1 to 5 parts by weight, 1 to 5 parts by weight, or 1.5 to 3 parts by weight, for example, based on 100 parts by weight of the total monomer added to the production of the rubber polymer. It may be possible to prepare a rubber polymer having an average particle diameter.

The first polymerization step may further include at least one selected from an oxidation-reduction catalyst, a molecular weight modifier, and an electrolyte, and preferably include all of them.

The oxidation-reduction catalyst may include, for example, one or more selected from the group consisting of ferrous sulfide, dextrose, sodium pyrrophosphate, sodium sulfite, sodium formaldehyde sulfoxylate, and sodium ethylenediamine tetraacetate. , Preferably containing ferrous sulfide, dextrose and sodium pyrrophosphate.

The oxidation-reduction catalyst may be preferably added in an amount of 0.0001 to 0.1 parts by weight, 0.005 to 0.5 parts by weight, or 0.01 to 0.2 parts by weight based on a total of 100 parts by weight of monomers added during the preparation of the rubber polymer. The stability of the latex and the polymerization reaction is excellent, but the activity of the initiator is promoted, thereby improving the polymerization efficiency.

The molecular weight modifiers include, for example, t-dodecylmercaptan, t-tetradecylmercaptan, n-tetradecylmercaptan, n-octylmercaptan, sec-octylmercaptan, n-nonylmercaptan, n-decylmercaptan, Alkyl mercaptan compounds, such as n-dodecyl mercaptan and n-octadecyl mercaptan, can be used, Preferably it contains t-dodecyl mercaptan.

The molecular weight modifier may be added in an amount of 0.01 to 0.5 parts by weight, 0.05 to 0.3 parts by weight, or 0.1 to 0.25 parts by weight based on a total of 100 parts by weight of monomers added during rubber polymer production, and has a desired average particle diameter within this range. The rubber polymer can be easily produced.

The electrolyte is, for example, KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , NaHSO ₃ , K ₄ P ₂ O ₇ , Na ₄ P ₂ O ₇ , K ₃ PO ₄ , Na ₃ PO ₄ , K ₂ HPO ₄ and Na ₂ HPO ₄ may include one or more selected from the group consisting of, but is not limited thereto.

The electrolyte may be preferred in terms of polymerization efficiency and latex stability, for example, in an amount of 0.01 to 1 part by weight, 0.05 to 0.8 part by weight, or 0.1 to 0.5 part by weight based on a total of 100 parts by weight of monomers added during rubber polymer production.

In addition, in the first polymerization step, a butadiene monomer, an initiator, an emulsifier, and optionally an oxidation-reduction-based catalyst, a molecular weight modifier, and / or an electrolyte are collectively introduced into a reactor, and the reaction temperature is 50 to 60 ° C. or 52 for 2 to 4 hours. It can be polymerized at ~ 58 ℃, in this case, by controlling the gelation of butadiene, a rubber polymer having a low gel content under a high polymerization conversion rate can be produced.

(B) Second polymerization stage

In the second polymerization step, a polymerization reaction is performed by further adding an initiator and an emulsifier at a specific time. In this way, the initiator and the emulsifier are divided and introduced in the middle of the initial reaction and polymerization, so that a rubber polymer having a high polymerization conversion rate and a low gel content can be easily produced.

For example, in the second polymerization step, an initiator and an emulsifier may be additionally added at a conversion rate of 25 to 45% or 30 to 40%, and in this case, the polymerization efficiency is excellent, and the polymerization conversion rate of the finally obtained rubber polymer is high. It also has an effect of improving physical properties such as impact resistance due to low gel content.

The initiator of the second polymerization step is not particularly limited as long as it is an initiator commonly used in the art, preferably, a water-soluble persulfate-based initiator can be used, and in this case, the polymerization reaction efficiency is excellent and stability, but the aggregation step described later is excellent. It has the effect of improving the acid resistance properties.

As a specific example, the water-soluble persulfate-based initiator may be at least one selected from potassium persulfate, sodium persulfate, and ammonium persulfate.

The initiator in the second polymerization step may be additionally added in an amount of 0.05 to 0.5 parts by weight or 0.1 to 0.3 parts by weight, for example, the reaction efficiency may be further improved within this range, and the gel content is low while the polymerization conversion rate is high. Rubber polymers can be produced.

The emulsifier in the second polymerization step may be the same as the emulsifier in the first polymerization step, for example, and may be added in an amount of 0.1 to 3 parts by weight or 0.3 to 1 part by weight.

In addition, in the second polymerization step, it may be desirable to react with an increase in temperature after additionally adding an initiator and an emulsifier. In this case, the polymerization efficiency is improved, and thus the polymerization conversion rate of the rubber polymer finally obtained is high.

In one example, the second polymerization step may be preferably performed by raising the temperature to a temperature of 5 to 10 ° C higher than the reaction temperature of the first polymerization step.

(C) Third polymerization stage

The third polymerization step of the present invention is a step of copolymerizing the aromatic vinyl monomer and the isoprene monomer to the butadiene polymer formed through the first and second polymerization steps.

In one example, the third polymerization step may be preferably carried out by polymerization by introducing an emulsion containing an aromatic vinyl monomer, an isoprene monomer and an emulsifier at a polymerization conversion rate of 50 to 70% or 55 to 65%. A rubber polymer having high efficiency and stability, and high polymerization conversion rate and low gel content, can be obtained.

The aromatic vinyl monomer is not particularly limited as long as it is a styrene-based compound that can be copolymerized with the butadiene polymer, and is preferably a group consisting of styrene, alpha methyl styrene, para methyl styrene, ortho ethyl styrene, ortho methyl styrene, and vinyl toluene. It may be one or more selected from, and most preferably is styrene.

The aromatic vinyl monomer may be preferably added in an amount of 5 to 35 parts by weight, 10 to 30 parts by weight, or 10 to 20 parts by weight, for example, based on 100 parts by weight of the total monomer added during the production of the rubber polymer. It has the effect of improving the polymerization conversion rate of the rubber polymer, while having a low gel content, and improving the impact resistance and glossiness of the final resin composition.

In addition, the isoprene monomer may be added in an amount of 5 to 35 parts by weight, 10 to 30 parts by weight, or 20 to 30 parts by weight, as an example based on 100 parts by weight of the monomer used in the production of the rubber polymer, and the polymerization conversion rate within this range A rubber polymer having a high gel content and a low gel content can be obtained, which has the effect of improving physical properties such as impact strength and glossiness of the resin composition.

The emulsifier in the third polymerization step may be the same as the emulsifier in the first polymerization step, for example, and may preferably contain rosin acid salt. In this case, it has an advantageous effect in securing polymerization stability.

The emulsifier of the third polymerization step may be added in an amount of 0.1 to 2 parts by weight, 0.5 to 1.5 parts by weight, or 0.8 to 1.3 parts by weight based on a total of 100 parts by weight of monomers used in manufacturing a rubber polymer, for example, within this range. It has excellent stability and has excellent effect on appearance characteristics such as glossiness of the final processed product.

In addition, in the third polymerization step, if necessary, a polymerization reaction may be additionally performed by further including a molecular weight modifier, and the same molecular weight modifier as in the first polymerization step may be used as the molecular weight modifier.

When the molecular weight modifier is further included in the third polymerization step, the amount thereof may be 0.01 to 0.3 parts by weight or 0.05 to 0.15 parts by weight based on 100 parts by weight of the monomers used as an example, and the desired average particle diameter within this range may be obtained. The rubber polymer having it can be easily obtained.

In the third polymerization step, it may be desirable to continuously input an emulsion containing an aromatic vinyl monomer, an isoprene monomer, an emulsifier, and optionally a molecular weight modifier, in this case, controlling the gelation of butadiene to achieve a high polymerization conversion rate. Even a rubber polymer having a low gel content can be obtained.

In the present description, the continuous input is to include all the cases in which the material to be added to the reaction is continuously added without a rest period or is introduced by a drop-by-drop method.

The continuous input may be, for example, the emulsion (based on solids) at an amount of 5 to 10 parts / hr, 7.5 to 10 parts / hr or 5 to 8 parts / hr per hour.

In addition, the third polymerization step may be carried out within a range of a reaction temperature of, for example, 70 to 95 ° C or 75 to 90 ° C. In this range, while the polymerization efficiency is excellent, the polymerization conversion rate of the finally obtained rubber polymer is It has a high advantage.

In addition, the third polymerization step may be preferably polymerized for 6 to 8 hours at the reaction temperature. In this case, a rubber polymer having a high polymerization conversion rate and low gel content and a desired average particle diameter may be prepared. have.

The rubber polymer latex obtained from the third polymerization step may preferably have a polymerization conversion ratio of 90% or more, 93% or more, 95% or more, 95 to 99.99%, or 97 to 99.99%, for example. It has excellent productivity due to low reaction monomer content and excellent appearance characteristics such as glossiness of the final processed product.

In addition, the average particle diameter of the rubber polymer in the latex obtained after the completion of the third polymerization step may be, for example, 800 to 1,500 mm 2, preferably 900 to 1,300 mm 3, and most preferably 1,000 to 1,200 mm 3 .

When the average particle diameter of the rubber polymer in the latex obtained after the completion of polymerization is within the above range, there is an advantage in that the gel content is low and the mechanical properties such as impact strength of the final processed product are excellent.

In this substrate, the average particle diameter of the rubber polymer in the latex can be measured, for example, using a Nicomp 380 equipment by the dynamic light skating method.

(D) Coagulation step

The method for preparing a rubber polymer of the present invention may further include an aggregation step of injecting a coagulant into the rubber polymer latex obtained after the completion of the third polymerization step, thereby large-curing the rubber polymer.

The agglutination step is not particularly limited and may be appropriately selected and carried out when it is within a range usually performed in the technical field to which the present invention pertains. It can be agglomerated by adding to 3 parts by weight or 1.6 to 2.5 parts by weight.

The coagulant may be, for example, an acid coagulant such as sulfuric acid, hydrochloric acid, acetic acid, or formic acid, or one or more metal coagulants selected from aluminum sulfate, calcium chloride, and magnesium sulfate, and an acid coagulant in terms of cohesive efficiency and productivity. It may be desirable.

The agglomeration step may be preferably performed while stirring at 30 to 80 ° C. or 40 to 60 ° C. at 10 to 60 rpm, for example, in which case a rubber polymer having excellent cohesiveness and a desired average particle diameter can be obtained.

The latex aggregated by the coagulant may preferably have a gel content of 60 to 90% by weight, 60 to 85% by weight, 70 to 85% by weight, or 70 to 80% by weight, and the final resin composition within this range. It has the advantage of excellent impact resistance, such as impact strength.

The gel content in the present description can be calculated through Equation 2 below after washing the agglomerated latex as an example, drying it in a vacuum oven at 60 ° C. for 24 hours, and putting it in toluene to separate it into a sol and a gel.

[Equation 2]

Gel content (% by weight) = (weight of insoluble matter (gel) / total weight of sample) X 100

In addition, the average particle diameter of the rubber polymer in the agglomerated latex may be, for example, 3,000 to 4,000 MPa, 3,000 to 3,600 MPa or 3,100 to 3,400 MPa, and within this range, impact resistance such as impact strength of the final resin composition is excellent. There is.

(E) Base treatment step

Another example of the present invention, in order to improve the stability of the latex degraded by the acid coagulant introduced in the coagulation step, a base of a concentration of 5 to 7% by weight is based on 100 parts by weight of latex 1.4 to 2.8 parts by weight or 1 to 1 It may further include a base treatment step of adding 2.35 parts by weight.

The base may be, for example, one or more selected from potassium hydroxide, sodium hydroxide, magnesium hydroxide, and the like, and the stability of the latex may be improved by injecting it into the aggregated latex, and ultimately, productivity.

In describing the method for manufacturing the rubber polymer of the present disclosure, polymerization conditions, reaction pressure, and the like, as examples of other conditions not specifically specified, are not particularly limited and appropriately selected when they are within a range commonly practiced in the technical field to which the present invention pertains. It can be carried out.

Furthermore, the rubber polymer according to the rubber polymer manufacturing method of the present disclosure may be used in the production of a graft copolymer, and the method of manufacturing the graft copolymer containing the rubber polymer will be described below.

The graft copolymer manufacturing method of the present disclosure is, for example, 50 to 80% by weight of the rubber polymer latex (based on solid content), 20 to 50% by weight of one or more monomers selected from aromatic vinyl monomers, vinyl cyan monomers, and acrylic ester monomers. It may include a step of graft polymerization, including.

In another example, the method for preparing the graft copolymer of the present disclosure is based on 55 to 70% by weight of the rubber polymer latex (based on solid content), 25 to 25 or more monomers selected from aromatic vinyl monomers, vinyl cyan monomers, and acrylic ester monomers. It may include the step of graft polymerization, including 45% by weight.

In another example, the method for preparing the graft copolymer of the present disclosure comprises 55 to 65% by weight of the rubber polymer latex (based on solid content), one or more monomers selected from aromatic vinyl monomers, vinyl cyan monomers, and acrylic ester monomers 35 It may include a step of graft polymerization, including from 45% by weight.

As a specific example, the method of preparing the graft copolymer of the present disclosure is a monomer mixture containing 15 to 35% by weight of aromatic vinyl monomer and 5 to 25% by weight of vinyl cyan monomer in 50 to 80% by weight (based on solid content) of the rubber polymer latex. 100 parts by weight, including 0.05 to 1 part by weight of an emulsifier and 0.05 to 1 part by weight of an initiator may include graft polymerization. The thus prepared vinyl cyan monomer-rubber polymer-aromatic vinyl monomer graft copolymer has an advantage of excellent physical properties such as impact resistance, chemical resistance, and processability.

The aromatic vinyl monomer may be, for example, one or more selected from the group consisting of styrene, alphamethylstyrene, alphaethylstyrene, paramethylstyrene, orthobutylstyrene, bromostyrene, chlorostyrene, trichlorostyrene, etc., It preferably contains styrene or alphamethylstyrene.

The vinyl cyan monomer may be, for example, one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like, and preferably includes acrylonitrile.

The emulsifier and the initiator used in the production of the graft copolymer may use, for example, the same material as used in preparing the rubber polymer, and may further include an oxidation-reduction catalyst, a molecular weight modifier, and the like.

The copolymer latex obtained according to the method for preparing the graft copolymer may be obtained in powder form through, for example, conventional coagulation, aging, dehydration, washing and drying processes, and further, the graft copolymer in powder form is a matrix resin. It may be provided with a thermoplastic resin composition excellent in impact resistance and surface gloss by being mixed and processed.

In one example, the thermoplastic resin composition may include 15 to 50% by weight of the graft copolymer according to the present invention, and within this range, while maintaining high physical properties such as impact resistance and gloss inherent to the graft copolymer, processing And easy molding.

The matrix resin is, for example, an aromatic vinyl monomer such as a styrene-acrylonitrile copolymer, a vinyl cyan monomer copolymer, and a heat-resistant SAN such as an alphamethylstyrene-acrylonitrile copolymer and an N-phenylmaleimide-styrene-acrylonitrile. It may be one or more selected from the copolymers, but is not limited thereto.

As a preferred example, the thermoplastic resin composition may be prepared by kneading and extruding 15 to 50% by weight of the graft copolymer and 50 to 85% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer, and impact resistance within this range , It has excellent surface characteristics such as glossiness, and has an effect of easy processing and molding.

The kneading and extrusion may be carried out under conditions of 200 to 240 ° C and 200 to 300 rpm, or 210 to 220 ° C and 200 to 250 rpm, for example, but it is not limited thereto.

In addition, the thermoplastic resin composition according to the present disclosure may be provided as a molded article further comprising the step of injection after kneading and extrusion, the injection is 200 to 230 ℃ and 450 to 650 bar as an example, or 200 to 220 ℃ and 500 It may be carried out under the conditions of 600 bar, but is not limited thereto.

In addition, the thermoplastic resin composition according to the present disclosure may be characterized by having excellent polymerization strength and high gel strength and low gel content and excellent impact strength and surface gloss.

In one example, the thermoplastic resin composition has an excellent impact resistance as the Izod impact strength measured in accordance with ASTM D256 is 20 kgcm / cm or more or 20 to 25 kgcm / cm.

In addition, the thermoplastic resin composition may be characterized in that the glossiness measured according to ASTM D528, for example, is 101.5 or more or 101.5 to 105, and has excellent surface properties.

Hereinafter, a preferred embodiment is provided to help the understanding of the present invention, but the following examples are merely illustrative of the present invention, and it is apparent to those skilled in the art that various changes and modifications are possible within the scope and technical scope of the present invention. It is no wonder that such variations and modifications fall within the scope of the appended claims.

[Example]

Example  One

1. Preparation of rubber polymer (butadiene-styrene-isoprene)

First polymerization step: nitrogen substituted polymerization reactor 1,3-butadiene monomer 70 parts by weight, fatty acid salt 2.3 parts by weight, t-butyl hydroperoxide 0.12 parts by weight, ferrous sulfide 0.0005 parts by weight, dextrose 0.008 parts by weight Part, 0.006 parts by weight of sodium pyrrophosphate, 0.1 parts by weight of t-dodecylmercaptan, 0.3 parts by weight of sodium carbonate as an electrolyte, and 80 parts by weight of ion-exchanged water were added in batch to perform emulsion polymerization at 55 ° C.

Second polymerization step: At the time of polymerization conversion of 30 to 40%, 0.2 parts by weight of potassium persulfate and 0.5 parts by weight of fatty acid salt were added and the reaction temperature was raised to 60 ° C.

Third polymerization step: polymerization conversion rate of 55 to 65%, 10 parts by weight of styrene monomer in a separate mixing device, 20 parts by weight of isoprene monomer, 1.0 part by weight of rosin acid salt, 50 parts by weight of ion-exchanged water, 0.1 of t-dodecylmercaptan The emulsion prepared by mixing parts by weight was continuously added to the polymerization reactor for 4 hours while the polymerization temperature was raised to 80 ° C to react, and the reaction was terminated to prepare a small-diameter rubber polymer.

Aggregation and base treatment step: 100 parts by weight of the latex prepared above was added to another reaction tank to adjust the stirring speed to 60 rpm, and 1.7 parts by weight of 5 wt% acetic acid aqueous solution was gradually added for 30 minutes and stirred, followed by 1.6 wt of 7 wt% KOH aqueous solution The part was stirred and stirred for 30 minutes to stabilize it to prepare a large-diameter rubber polymer.

2. Preparation of graft copolymer

60 parts by weight of the large-diameter rubber polymer latex prepared above (based on solid content), 150 parts by weight of ion-exchanged water, 0.3 parts by weight of rosinate 11.2 parts by weight of acrylonitrile, 28.8 parts by weight of styrene, 10 parts of ion-exchanged water in a separate mixing device The emulsion prepared by mixing parts by weight, 0.12 parts by weight of t-butyl hydroperoxide, 0.2 parts by weight of rosin acid salt, and 0.3 parts by weight of t-dodecyl mercaptan was continuously added at 70 ° C for 3 hours.

At this time, 0.054 parts by weight of dextrose, 0.024 parts by weight of pyrrophosphate, and 0.006 parts by weight of ferrous sulfate were continuously added together. After the monomer emulsion was added, 0.05 parts by weight of dextrose, 0.03 parts by weight of sodium pyrrophosphate, 0.001 parts by weight of ferrous sulfate, and 0.05 parts by weight of t-butyl hydroperoxide were added to the reactor and the temperature was raised to 80 ° C. After heating over 1 hour, the reaction was terminated.

After the reaction was completed, a solution of magnesium sulfate was added to the latex to solidify, followed by dehydration, washing, and drying to obtain a graft copolymer powder.

3. Preparation of thermoplastic resin composition

23 parts by weight of the graft copolymer powder prepared above and 67 parts by weight of SAN resin (manufactured by LG Chem, product name: 81HF) in a mixer, mixed (250 rpm), and then extruder (210 ° C.) to pelletize the resin composition. After preparing, by injection (210 ℃, 550bar) to prepare a specimen for physical properties measurement.

Example  2

In the first polymerization step of Example 1, 1,3-butadiene monomer was added to 60 parts by weight, and in the third polymerization step, 20 parts by weight of styrene monomer and 20 parts by weight of isoprene monomer were added. It was carried out in the same manner as in 1.

Example  3

Example 1, except that 1,3-butadiene monomer was added at 60 parts by weight in the first polymerization step of Example 1, and 10 parts by weight of styrene monomer and 30 parts by weight of isoprene monomer were added at the third polymerization step. It was carried out in the same manner as.

Example  4

Example 1, except that 1,3-butadiene monomer was added at 60 parts by weight in the first polymerization step of Example 1, and 30 parts by weight of styrene monomer and 10 parts by weight of isoprene monomer were added at the third polymerization step. It was carried out in the same manner as.

Comparative example  One

In the third polymerization step of Example 1, it was carried out in the same manner as in Example 1, except that 30 parts by weight of 1,3-butadiene was used instead of 10 parts by weight of styrene monomer and 20 parts by weight of isoprene monomer.

Comparative example  2

In the third polymerization step of Example 1, it was carried out in the same manner as in Example 1, except that 30 parts by weight of isoprene monomer was used instead of 10 parts by weight of styrene monomer and 20 parts by weight of isoprene monomer.

Comparative example  3

In the third polymerization step of Example 1, it was carried out in the same manner as in Example 1, except that 30 parts by weight of styrene monomer was used instead of 10 parts by weight of styrene monomer and 20 parts by weight of isoprene monomer.

Comparative example  4

In the first polymerization step of Example 1, 1,3-butadiene monomer was added in 40 parts by weight instead of 70 parts by weight, and in the second polymerization step, potassium persulfate and fatty acid salt were introduced at a polymerization conversion rate of 12 to 16% at the time of polymerization. In the polymerization step at a polymerization conversion rate of 30 to 45% in the polymerization stage, 40 parts by weight of styrene monomer, 20 parts by weight of isoprene monomer, 1.0 part by weight of rosinate, 50 parts by weight of ion-exchanged water, and 0.1 weight of t-dodecylmercaptan It was carried out in the same manner as in Example 1, except that the emulsion prepared by mixing parts was continuously added for 6 hours.

Comparative example  5

In the first polymerization step of Example 1, 1,3-butadiene monomer was added in 90 parts by weight, and in the second polymerization step, potassium persulfate and fatty acid salt were introduced at a polymerization conversion rate of 12 to 16%, and the third polymerization step. At a polymerization conversion rate of 30 to 45%, 5 parts by weight of styrene monomer, 5 parts by weight of isoprene monomer, 1.0 part by weight of rosinate, 50 parts by weight of ion-exchanged water, and 0.1 parts by weight of t-dodecylmercaptan It was carried out in the same manner as in Example 1, except that the prepared emulsion was continuously added for 6 hours.

Comparative example  6

First polymerization step: a nitrogen-substituted polymerization reactor in a 1,3-butadiene monomer 70 parts by weight, styrene monomer 10 parts by weight, isoprene monomer 20 parts by weight, fatty acid salt 2.7 parts by weight, t-butyl hydroperoxide 0.12 parts by weight, 0.0005 parts by weight of ferrous sulfide, 0.008 parts by weight of dextrose, 0.006 parts by weight of sodium pyrrophosphate, 0.1 parts by weight of t-dodecyl mercaptan, 0.3 parts by weight of sodium carbonate as electrolyte, and 130 parts by weight of ion-exchanged water at 55 ° C Emulsion polymerization was performed.

Second polymerization step: At the time of polymerization conversion of 30 to 40%, 0.2 parts by weight of potassium persulfate and 0.5 parts by weight of fatty acid salt were added and the reaction temperature was raised to 60 ° C.

Third polymerization step: polymerization conversion rate of 55 to 65% without separate mixing device, 1.0 part by weight of rosin acid, 0.1 part by weight of t-dodecyl mercaptan was introduced into the polymerization reactor and the polymerization temperature was raised to 80 ° C to react. Then, the reaction was terminated to prepare a small-diameter rubber polymer.

[Test Example]

The properties of the rubber polymer latex and the specimens prepared in Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1 below.

1) Polymerization Conversion Rate (%): After drying 2 g of latex in a 150 ° C. hot air dryer for 15 minutes, the weight was measured to obtain the total solid content (TSC), and the polymerization conversion rate was calculated by Equation 1 below.

[Equation 1]

Polymerization conversion rate (%) = [Total solid content (TSC) X (total amount of injected monomers and auxiliary materials)] / [100- (total amount of added auxiliary materials other than monomer)]

2) Average particle diameter of rubber polymer: It was measured using a Nicomp 380 equipment by dynamic light scattering method.

3) Gel content (% by weight): After washing the agglomerated latex and drying it in a vacuum oven at 60 ° C. for 24 hours, chop the obtained rubber mass with scissors and put 1 g of a rubber fragment into 100 g of toluene, and at room temperature for 48 hours. After storage in the dark, it was separated into sol and gel, and the gel content was calculated by Equation 2 below.

[Equation 2]

Gel content (% by weight) = (weight of insoluble matter (gel) / total weight of sample) X 100

4) Izod impact strength (kgcm / cm): Izod impact strength was measured according to ASTM D256 using a 1/4 "thickness specimen.

5) Glossiness: The glossiness of the specimen was measured at an angle of 45 ° according to ASTM D528.

division Example Comparative example One 2 3 4 One 2 3 4 5 6 Batch input butadiene 70 60 60 60 70 70 70 40 90 70 Styrene - - - - - - - - - 10 Isoprene - - - - - - - - - 20 Continuous input Styrene 10 20 10 30 - - 30 40 5 - Isoprene 20 20 30 10 - 30 - 20 5 - butadiene - - - - 30 - - - - - Polymerization time (hours) 15 15 16 14 17 16 15 14 15 17 Polymerization conversion rate (%) 97.3 97.2 97.1 98.2 97.0 96.3 97.8 98.0 97.1 93.0 Small diameter rubber particle size 1200 1200 1300 1050 1200 1100 1000 980 1210 1300 Large diameter rubber particle size 3150 3200 3200 3100 3200 3150 3000 3100 3200 3100 Gel content (% by weight) 80 70 75 82 92 87 95 97 85 86 Impact strength (kgcm / cm) 20 22 21 19 18 17 15 16 19 19 Glossiness 102.0 102.5 101.5 103.0 100.2 98.0 101.2 102.1 100.2 98.5

As shown in Table 1, it can be seen that the rubber polymer prepared according to the embodiment of the present invention has a high polymerization conversion rate of 97% or more, but a gel content of 85% by weight or less, and a thermoplastic resin manufactured by including it. It was confirmed that the composition specimen had an impact strength of 19 kgcm / cm or more and a glossiness of 101.5 or more, and simultaneously had a high impact strength and glossiness.

On the other hand, in the case of the rubber polymer prepared using only the butadiene monomer (Comparative Example 1), it was confirmed that the polymerization conversion rate was slightly low even though the total polymerization time required was larger than in Examples, and the impact strength was low due to the high gel content. .

In addition, in the case of a rubber polymer (Comparative Example 2) produced using two types of butadiene monomer and isoprene monomer, the polymerization conversion ratio is lower than that of the example, the gel content is high, and ultimately the impact strength and gloss are lowered. I could confirm that.

In addition, in the case of the rubber polymer (Comparative Example 3) prepared using two types of butadiene monomers and styrene monomers, it was confirmed that the gelation of butadiene was considerable and the impact strength was poor.

In addition, in the case of Comparative Examples 3 and 4 in which the content and input time of each monomer deviated from the examples of the present description, the gel content was high, and the physical properties of any one of the impact strength and glossiness were lowered, resulting in poor physical property balance compared to the examples. I could confirm that.

In addition, although the same type and content of the monomer as in Example 1 was applied, in Comparative Example 6 in which the initial reaction monomer was added in batch, the polymerization conversion rate was confirmed to be the lowest despite the longer polymerization time, thereby making the gloss It was confirmed that the degree was lowered.

Claims (19)

A first polymerization step in which 50 to 80 parts by weight of a butadiene monomer, 0.01 to 0.3 parts by weight of an initiator, and 0.1 to 5 parts by weight of an emulsifier are polymerized and reacted collectively based on 100 parts by weight of the monomers used; A second polymerization step of polymerization by adding 0.05 to 0.5 parts by weight of an initiator and 0.1 to 3 parts by weight of an emulsifier at a conversion time of 25 to 45% of the polymerization reaction; And 3 to 3 parts by weight of an emulsion containing 5 to 35 parts by weight of an aromatic vinyl monomer, 5 to 35 parts by weight of an isoprene monomer, and 0.1 to 2 parts by weight of an emulsifier at a conversion rate of 50 to 70% of the polymerization reaction. Characterized by containing;
Method of manufacturing a rubber polymer. According to claim 1,
The first polymerization step is characterized in that it is carried out within a range of the reaction temperature 50 to 60 ℃
Method of manufacturing a rubber polymer. According to claim 1,
The first polymerization step is characterized in that it further comprises at least one selected from an oxidation-reduction catalyst, a molecular weight modifier, and an electrolyte.
Method of manufacturing a rubber polymer. According to claim 3,
The first polymerization step is characterized in that it comprises an oxidation-reduction catalyst 0.0001 to 0.1 parts by weight, a molecular weight modifier 0.01 to 0.5 parts by weight and an electrolyte 0.01 to 1 parts by weight
Method of manufacturing a rubber polymer. According to claim 1,
The initiator of the first polymerization step is characterized in that it comprises at least one selected from the group consisting of t-butyl hydro peroxide, paramethane hydro peroxide, cumene hydro peroxide, diisopropyl benzene hydro peroxide and benzoyl peroxide. To do
Method of manufacturing a rubber polymer. According to claim 1,
The emulsifier is characterized in that it comprises at least one selected from the group consisting of alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, fatty acid salts and rosinates.
Method of manufacturing a rubber polymer. According to claim 1,
The initiator of the second polymerization step is characterized in that the water-soluble persulfate-based compound
Method for producing rubber polymer. According to claim 1,
The third polymerization step is characterized in that it further comprises 0.01 to 0.3 parts by weight of a molecular weight modifier.
Method of manufacturing a rubber polymer. According to claim 1,
The third polymerization step is characterized in that the reaction temperature is carried out within a range of 70 to 95 ℃
Method of manufacturing a rubber polymer. According to claim 1,
After completion of the third polymerization step, the average particle diameter of the rubber polymer in the latex is 800 to 1,500 mm 2,
Method of manufacturing a rubber polymer. According to claim 1,
After the third polymerization step is completed, characterized in that it further comprises an agglomeration step to agglomerate by adding a coagulant to the rubber polymer latex obtained
Method of manufacturing a rubber polymer. The method of claim 11,
The aggregated latex has a gel content of 60 to 85% by weight.
Method of manufacturing a rubber polymer. The method of claim 11,
It characterized in that it further comprises a base treatment step of stabilizing by introducing a base (base) to the aggregated latex
Method of manufacturing a rubber polymer. The method of claim 13,
The average particle size of the rubber polymer in the base-treated latex is characterized in that 3,000 to 4,000Å
Method of manufacturing a rubber polymer. The rubber polymer latex prepared according to any one of claims 1 to 14, 50 to 80% by weight (based on solids), at least one monomer selected from aromatic vinyl monomers, vinyl cyan monomers and acrylic ester monomers 20 to 50 Characterized in that it comprises a step of graft polymerization of the weight percent
Method for producing graft copolymer. Characterized in that it comprises 15 to 50% by weight of the graft copolymer according to the production method of claim 15
Thermoplastic resin composition. The method of claim 16,
The thermoplastic resin composition is characterized in that it comprises 15 to 50% by weight of the graft copolymer and 50 to 85% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer
Thermoplastic resin composition. The method of claim 17,
The thermoplastic resin composition is characterized in that the Izod impact strength measured in accordance with ASTM D256 is 19kgcm / cm or more
Thermoplastic resin composition. The method of claim 17,
The thermoplastic resin composition is characterized in that the glossiness measured in accordance with ASTM D528 is 101.5 or more
Thermoplastic resin composition.