KR20130087664A - Method of preparing rubbery polymer latex and method of abs graft copolymer comprising the same - Google Patents
Method of preparing rubbery polymer latex and method of abs graft copolymer comprising the same Download PDFInfo
- Publication number
- KR20130087664A KR20130087664A KR20120008684A KR20120008684A KR20130087664A KR 20130087664 A KR20130087664 A KR 20130087664A KR 20120008684 A KR20120008684 A KR 20120008684A KR 20120008684 A KR20120008684 A KR 20120008684A KR 20130087664 A KR20130087664 A KR 20130087664A
- Authority
- KR
- South Korea
- Prior art keywords
- weight
- parts
- polymer latex
- dimethacrylate
- rubbery polymer
- Prior art date
Links
Landscapes
- Graft Or Block Polymers (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
The present invention relates to a method for producing a rubbery polymer latex and a method for producing an ABS-based graft copolymer comprising the same, and more particularly, by introducing a long-chain crosslinking agent to the shell / through the cross-linked structure of the rubbery polymer latex and ABS graft control It is possible to secure impact resistance by strengthening the shell / matrix interface, and it is possible to combine more reactive emulsifiers and to improve appearance quality such as thermal stability and gloss with minimal emulsifier. It is to provide a production method and a production method of the ABS graft copolymer.
Acrylonitrile-butadiene-styrene (ABS) copolymer resins have good mechanical properties such as impact resistance, as well as physical properties such as moldability and glossiness, so that they can be used for electrical parts, electronic parts, office equipment or automobiles. It is widely used in parts and the like.
ABS resin produced by the emulsion polymerization method has the advantage of showing a relatively good physical balance and excellent gloss. Therefore, ABS resin is mainly produced by emulsion polymerization method than bulk polymerization method. ABS resin produced by the emulsion polymerization process is mixed with styrene-acrylonitrile (SAN) copolymer to maximize the characteristics of the composition of the SAN resin can be diversified products and create high added value.
By the way, the most useful emulsion polymerization method of the ABS resin is causing environmental problems due to the remaining unreacted monomer or the remaining emulsifier, and gas is generated by the unreacted monomer and various added additives in the process of resin injection. Various environmental problems are raised by this gas. In addition, due to these impurities, the physical properties of the resin and the thermal stability are deteriorated. In order to improve this problem, the reactive emulsifier is used to prepare the graft copolymer by the emulsion polymerization method. It is possible to reduce the amount of gas generated.
However, since the reaction efficiency of the reactive emulsifier is inferior to the particles, there is a problem that affects the properties of the graft copolymer due to the unreacted emulsifier by using a large amount.
An object of the present invention is to solve the problems of the prior art, to provide a method for producing a rubbery polymer latex that can ensure impact resistance by strengthening the interface of the shell and the matrix.
In addition, another object of the present invention is to provide a method for producing an ABS graft copolymer that can achieve the appearance quality improvement such as thermal stability, gloss, etc. with a minimum amount of emulsifier.
The above and other objects of the present invention can be achieved by the present invention described below.
In order to achieve the object of the present invention, in the preparation method of the rubbery polymer latex, 100 parts by weight of the conjugated diene monomer, 0.05 to 1 parts by weight of the reactive emulsifier and 0.05 to 1 parts by weight of the long-chain crosslinking agent based on 100 parts by weight of the monomer It provides a process for producing a rubbery polymer latex, characterized in that the polymerization by batch or continuous administration.
In addition, the present invention comprises a) 100 parts by weight of a conjugated diene monomer, 0.05 to 1 part by weight of the reactive emulsifier and 0.05 to 1 part by weight of the long-chain crosslinking agent based on 100 parts by weight of the batch or continuous polymerization Preparing a rubbery polymer latex; And b) a monomer mixture comprising 15 to 35 parts by weight of an aromatic vinyl monomer, and 10 to 25 parts by weight of a vinyl cyan monomer, 0.05 to 1 part by weight of a reactive emulsifier and 0.05 to 1 part by weight of a long-chain crosslinking agent. It provides a method for producing an ABS-based graft copolymer comprising a; graft polymerization of the portion.
As described above, according to the present invention, it is possible to secure impact resistance by reinforcing the shell / matrix interface through the crosslinked structure of the rubbery polymer latex and ABS graft control. In addition, by combining more reactive emulsifiers there is an effect that can be achieved by improving the appearance quality, such as thermal stability and gloss of the ABS graft copolymer by using a minimum of emulsifiers.
Since there is a double bond in the polybutadiene during the polymerization step of the polybutadiene latex, a crosslinking agent is not added. By adding a reactive emulsifier and a crosslinking agent at the same time, it is possible to suppress unreacted reaction by using many reactive emulsifiers that do not adhere well to the core. The reaction efficiency was increased.
Allyl methacrylate (AMA) and divinylbenzene (DVB), which are commonly used crosslinking agents, have short chain lengths, which are ineffective in improving the swelling index of the manufactured rubber particles. Not suitable for In other words, the long chain crosslinking agent herein does not particularly limit the length of the chain. However, the long chain crosslinking agent is effective in that the length of the chain is longer than that of AMA or DVB, which is a general crosslinking agent for controlling the crosslinking structure and graft by improving the swelling index.
When the reactive emulsifier alone is used without the crosslinking agent, the efficiency of particle bonding is reduced. Therefore, a long chain crosslinking agent is introduced to control the polybutadiene latex crosslinking structure and maximize the reactive emulsifier bonding.
By introducing a long-chain crosslinking agent, it is possible to secure impact resistance by strengthening the shell / matrix interface through polybutadiene latex crosslinking structure and ABS graft control, and by introducing a long-chain crosslinking agent to bind more reactive emulsifier emulsifiers, thereby minimizing emulsifiers. It was confirmed that the improvement of the appearance quality such as thermal stability, gloss, etc. can be achieved, and completed the present invention.
Preparation of Rubbery Polymer Latex
The present invention is a method for producing a rubbery polymer latex, 100 parts by weight of the conjugated diene monomer, 0.05 to 1 parts by weight of the reactive emulsifier and 0.05 to 1 parts by weight of the long-chain crosslinking agent based on 100 parts by weight of the polymerized batch or continuous It is characterized by. That is, in the polybutadiene latex polymerization step, 0.05 to 1 part by weight of the reactive emulsifier and 0.05 to 1 part by weight of the long chain crosslinking agent relative to 100 parts by weight of the monomer are collectively or continuously administered.
If the content of the reactive emulsifier is less than 0.05 parts by weight, the latex stability is not good coagulation occurs, when the content exceeds 1 part by weight is contrary to the purpose of improving the appearance quality, such as thermal stability and gloss through reducing the emulsifier. In addition, when the amount of the long chain crosslinking agent is less than 0.05 parts by weight, the effect is insignificant, and the efficiency of particle bonding is low, due to the crosslinked structure of the rubbery polymer latex through the introduction of the long chain crosslinking agent and the shell / mattress interface strengthening through the ABS graft control. Impact resistance cannot be expected. In addition, when the amount of use exceeds 1 part by weight, the degree of crosslinking is excessively increased to break the overall balance of physical properties.
Reactive emulsifier used in the invention is sodium dodecyl allyl sulfosuccinate (sodiumdodecyl allylsulfosuccinate, TREM LF-40 ), styrene and sodium dodecyl allyl sulfosuccinate of the copolymer, C 16 -18 alkenyl succinyl Nick Acid di-potassium salt (C 16 -18 alkenyl succinic acid di -potassium salt, Latemul ASK series), sodium meta-allyl sulfonate (sodium methallyl sulfonate, SMAS), polyoxyethylene alkyl phenyl is written ammonium sulfate (polyoxyethylene alkylphenylether ammonium sulfate , HITENOL BC Series), polyoxyethylenealkylether sulfate ester ammonium salt (HITENOL KH Series) and the like. In the case of using such a reactive emulsifier, unlike the conventional adsorptive emulsifiers, by participating in the polymerization reaction, it has electrostatic stability by ions and at the same time, it is possible to simultaneously give three-dimensional stability by the emulsifier. It can have the advantage of reducing the usage.
As the long-chain crosslinking agent used in the present invention, ethylene glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethyleneglycol dimethacrylate, triethylene glycol dimethacrylate ( triethyleneglycol dimethacrylate), 1,3-butylene glycol methacrylate (1,3-buthyleneglycolmethacrylate), 1,3-butylene glycol diacrylate, bisphenyl ethylene oxide dimethacrylate Rubber particles have high molecular weight and glycol structure such as bisphenol A ethyleneoxide, cyclohexane dimethylethylene oxide dimethacrylate and trimethylopropane triacrylate (TMPTA). Increasing the swelling index by controlling the internal crosslinking structure Lee is
Preferably ethylene glycol diacrylate or trimethyllopropane triacrylate is used.
The conjugated diene monomer is selected from the group consisting of 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene and chloroprene.
ABS system Graft Preparation of Copolymer
In addition, the production method of the ABS graft copolymer according to the present invention a) 100 parts by weight of the conjugated diene monomer, 0.05 to 1 part by weight of the reactive emulsifier and 0.05 to 1 part by weight of the long-chain crosslinking agent based on 100 parts by weight of the polymerized polymer composition comprising the step of polymerizing step; And b) a monomer mixture comprising from 15 to 25 parts by weight of an aromatic vinyl monomer and from 10 to 25 parts by weight of a vinyl cyan monomer, from 0.05 to 1 part by weight of a reactive emulsifier and from 0.05 to 1 part by weight of a long-chain crosslinking agent. Graft polymerization of the portion; characterized in that comprises a.
When the content of the reactive emulsifier is less than 0.05 parts by weight, the effect of improving the latex stability is inadequate, and when used in excess of 1 part by weight is contrary to the purpose of improving the appearance quality, such as thermal stability and gloss through reducing the emulsifier. In addition, when the amount of the long chain crosslinking agent is less than 0.05 parts by weight, the effect of the long chain crosslinking agent is insignificant and impact resistance due to the shell / matrix interface enhancement through the ABS graft control cannot be expected. In addition, when the amount of use exceeds 1 part by weight, the degree of crosslinking is excessively increased to break the overall balance of physical properties.
In addition, when using a weight part other than the above ranges of the rubbery polymer latex, aromatic vinyl monomer and vinyl cyan monomer, the balance of chemical resistance and processability, which are inherent in the ABS graft copolymer, is broken.
The aromatic vinyl monomers include styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, o-t-butylstyrene, bromostyrene, chlorostyrene, trichlorostyrene, and the like, of which styrene is preferable.
Acrylonitrile, methacrylonitrile, etc. are mentioned as said vinyl cyan monomer, Among these, acrylonitrile is used preferably.
That is, in the ABS-based graft polymerization step, 0.05 to 1 part by weight of the reactive emulsifier and 0.01 to 1 part by weight of the long chain crosslinking agent are collectively or continuously administered to 100 parts by weight of the total monomers.
The reactive emulsifier and the long chain crosslinking agent used in the ABS based graft polymerization step are the same as those used in the polymerization step of the rubbery polymer.
It is preferable that the average particle diameter of the said rubbery polymer latex is 2600-5000 Pa, and gel content is 60-95 weight%.
In addition, the monomer mixture may further include a monomer selected from the group consisting of alkyl acrylate, alkyl methacrylate, and mixtures thereof. It is preferred to use 1 to 15 parts by weight of the alkyl acrylate, alkyl methacrylate or a mixture thereof.
The alkyl acrylate and alkyl methacrylate are methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, t-butyl acrylate, n-butyl acrylate, n-octyl acrylate, 2-ethylhexyl Acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, n-butyl methacrylate, n-octyl methacrylate or 2-ethylhexyl meta Acrylate and the like, and methyl acrylate or methyl methacrylate is preferably used.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Changes and modifications may fall within the scope of the appended claims.
[Example]
Example A1: rubbery polymer latex A1
60 parts by weight of ion-exchanged water, 75 parts by weight of 1,3-butadiene as monomer, 1.2 parts by weight of potassium oleate salt as emulsifier, 0.6 parts by weight of Na 2 CO 3 as electrolyte, potassium hydrogen carbonate (KHCO 3 ) 0.7 parts by weight, 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as the molecular weight modifier, 0.3 parts by weight of potassium persulfate as the initiator, and the polymerization was carried out at a reaction temperature of 65 ℃, the remainder at the polymerization conversion rate of 30 to 40% 25 parts by weight of a conjugated diene compound monomer, 0.3 parts by weight of Latemul ASK, a reactive emulsifier, 0.05 parts by weight of a long-chain crosslinking agent, TMPTA, and 0.05 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight regulator, and tertiary butyl hydroperoxide 0.1 as an initiator. The polymerization was completed in 21 hours with a polymerization conversion rate of 97.3% by 21 parts by weight together with 0.001 parts by weight of reducing agent (based on FeSO 4 ) and 0.001 parts by weight of ferrous sulfide. The gel content of the rubbery polymer latex obtained at this time was 87%.
Example A2: rubbery polymer latex A2
The polymerization was carried out in the same manner as the rubbery polymer latex A1, but the polymerization was completed at a polymerization conversion rate of 97.1% by administering 0.3 parts by weight of KH-10 and 0.05 parts by weight of the long-chain crosslinking agent TMPTA at 30% to 40% of the polymerization conversion rate. The gel content of the rubbery polymer latex obtained at this time was 88%.
Comparative example B1: rubbery polymer latex B1
In the same manner as the rubbery polymer latex A1, 0.3 parts by weight of Latemul ASK was added as a reactive emulsifier at a polymerization conversion rate of 30 to 40%, but the polymerization was completed at 97.1% without using a long-chain crosslinking agent, TMPTA. The gel content of the obtained rubbery polymer latex was 85%.
Comparative example B2: rubbery polymer latex B2
The same procedure as in the rubbery polymer latex A1 was carried out, except that 0.3 parts by weight of KH-10 was used as a reactive emulsifier at a polymerization conversion rate of 30 to 40%, but polymerization was completed at 97.0% without using a long-chain crosslinking agent, TMPTA. . The gel content of the obtained rubbery polymer latex was 85%.
Comparative example B3: rubbery polymer latex B3
The rubbery polymer latex A1 was carried out in the same manner, but instead of the reactive emulsifier at the polymerization conversion rate of 30 to 40%, 1.2 parts by weight of potassium oleate salt, which is an existing adsorptive emulsifier, was used and the polymerization conversion rate was 97.0% without using a long-chain crosslinking agent. The polymerization was completed. The gel content of the obtained rubbery polymer latex was 85%.
[Test Example]
The physical properties of the rubber latex prepared in Examples A1 to A2 and Comparative Examples B1 to B3 were measured by the following method, and the results are shown in Table 1 below.
1) Gel content: The rubber latex is solidified with dilute acid or metal salt, washed, dried in a vacuum oven at 60 ° C for 24 hours, and then chopped into pieces of rubber by scissors, and then 1 g of rubber sections is put into 100 g of toluene. After storage for 48 hours in the dark at room temperature separated into sol and gel, the gel content was measured by the following equation (1).
[Equation 1]
Gel content (%) = weight of insoluble gel / weight of sample X 100
2) Swelling index: After swelling the insoluble gel obtained by measuring the gel content in toluene for 12 hours and swelling, to obtain the swelling index by the following formula (2).
&Quot; (2) "
Swelling index (%) = weight of insoluble content (gel) after swelling (g) / weight of insoluble content (gel) before swelling (g) X 100
3) Particle diameter and particle size distribution: It was measured using a Nicomp 370HPL instrument (Nicomp, USA) by the dynamic laser light scattering method.
4) Polymerization Conversion Rate: Measured by solid content measurement method in latex.
5) Stability of latex: Solid coagulation content (%) was determined by the following equation (3).
&Quot; (3) "
Solid coagulation (%) = {weight of coagulum produced in the reactor (g) / weight of total rubber and monomers (g)} X 100
(30-40% conversion rate)
1.2 parts by weight of potassium salt
1.2 parts by weight of potassium salt
1.2 parts by weight of potassium salt
1.2 parts by weight of potassium salt
1.2 parts by weight of potassium salt
0.3 parts by weight
0.3 parts by weight
0.3 parts by weight
0.3 parts by weight
1.2 parts by weight of potassium salt
Example C1 : Acrylonitrile Butadiene-styrene Graft Copolymer C1
60 parts by weight of rubber latex prepared in Example A1, 7.5 parts by weight of styrene and 2.5 parts by weight of acrylonitrile were added to the reactor, and then 7.5 parts by weight of acrylonitrile, 22.5 parts by weight of styrene and ion-exchanged water in a separate mixing device. 10 parts by weight, cumene hydroperoxide 0.12 parts by weight, 0.3 parts by weight of potassium oleate salt was mixed to make an emulsion, which was continuously added to the reactor for 2 hours at 70 ℃. At this time, 0.054 parts by weight of dextrose, 0.004 parts by weight of sodium pyrolate and 0.002 parts by weight of ferrous sulfate were continuously added together.
After the addition of the emulsion, 0.05 part by weight of dextrose, 0.03 part by weight of sodium pyrolate, 0.001 part by weight of ferrous sulfate and 0.05 part by weight of t-butyl hydroperoxide were collectively added to the reactor, and the temperature was maintained for 1 hour. The temperature was raised to 80 ° C. over and the reaction was terminated. The polymerization conversion rate of the ABS graft copolymer latex obtained at this time was 98.3%.
Example C2 : Acrylonitrile Butadiene-styrene Graft Copolymer C2
60 parts by weight of the rubber latex prepared in Example A1 was added thereto, and the polymerization was performed in the same manner, but without using a long-chain crosslinking agent, ethylene glycol diacrylate, at a polymerization conversion rate of 98.2%.
Example C3 : Acrylonitrile Butadiene-styrene Graft Copolymer C3
60 parts by weight of the rubber latex prepared in Example A2 was added thereto, and the polymerization was carried out in the same manner, but without using a long-chain crosslinking agent, ethylene glycol diacrylate, at a polymerization conversion rate of 98.2%.
Comparative example D1 : Acrylonitrile Butadiene-styrene Graft Copolymer D1
60 parts by weight of the rubber latex prepared in Comparative Example B1 was added thereto, and the polymerization was carried out in the same manner, but without using a long-chain crosslinking agent, ethylene glycol diacrylate, at a polymerization conversion rate of 98.2%.
Comparative example D2 : Acrylonitrile Butadiene-styrene Graft Copolymer D2
60 parts by weight of the rubber latex prepared in Comparative Example B2 was added thereto, and the polymerization was carried out in the same manner, but without using a long-chain crosslinking agent, ethylene glycol diacrylate, at a polymerization conversion rate of 98.2%.
Comparative example D3 : Acrylonitrile Butadiene-styrene Graft Copolymer D3
60 parts by weight of rubber latex prepared in Comparative Example B3 was added thereto, and the polymerization was carried out in the same manner, but without using a long-chain crosslinking agent, ethylene glycol diacrylate, at a polymerization conversion rate of 98.2%.
Comparative example D4 : Acrylonitrile Butadiene-styrene Graft Copolymer D4
60 parts by weight of the rubber latex prepared in Comparative Example B3 was added thereto, and the polymerization was carried out in the same manner, using 0.1 parts by weight of ethylene glycol dimethacrylate, which is a long-chain crosslinking agent, at a polymerization conversion rate of 98.1%.
The acrylonitrile-butadiene-styrene graft copolymer latex prepared above was added to 450 parts by weight of water and 3.0 parts by weight of calcium chloride in a coagulation bath capable of a rapid temperature increase to 100 ° C, and then maintained at 84 ° C. 100 parts by weight of the prepared organic latex was continuously added.
After the first agglomeration of the injected latex, the temperature was raised to 95 ° C. over 10 minutes, and then the temperature was stopped and aged for 30 minutes. At the time of completion of ripening, the temperature was 92 ° C., and after maturation, the sample was dried through mother liquor separation to prepare powder.
Thus, 75 parts by weight of a copolymer resin (LG San 92HR) having a weight average molecular weight of 120,000 including 25 parts by weight of powder, 73 parts by weight of styrene, and 27 parts by weight of acrylonitrile was melt mixed and pelletized at 190 ° C. using an extruder. The test piece was created in the injection molding machine, and the physical property was evaluated.
[Test Example]
The properties of the ABS-based physical specimens prepared in Examples C1 to C3 and Comparative Examples D1 to D4 were measured by the following method, and the results are shown in Table 2 below.
1) Izod impact strength: The specimen was measured by ASTM 256 method with 1/4 "thickness.
2) Surface gloss: measured by ASTM D528 method at a 45 ° angle.
3) Retention gloss (△ G): The pellet obtained in the extruder was put in the injection molding machine and held for 15 minutes at 250 ℃ conditions to obtain a gloss specimen, measured 45 ° gloss like the specimen injected without staying at 200 ℃, The deviation value for was calculated. At this time, the smaller the deviation value, the better the retention gloss.
4) Graft Efficiency
After stirring 2 grams of powder with 100 milliliters of acetone for 24 hours to dissolve the grafted styrene copolymer in the rubber component, the gel and the sol were separated by ultracentrifugation to obtain the graft efficiency by the following equation (4).
&Quot; (4) "
Graft efficiency = weight of grafted monomer (g) / weight of monomer (g) X 100
Recoledia
0.1 weight part of acrylate
Recoledia
0.1 weight part of acrylate
efficiency(%)
(△ G)
Referring to Table 2, the acrylonitrile-butadiene-styrene graft copolymers according to Examples C1 to C3 show better impact strength, glossiness, and retention gloss than those of Comparative Examples D1 to D4. From this, it is possible to secure impact resistance by strengthening the shell / matrix interface through the crosslinked structure of the rubbery polymer latex and ABS graft control, and by combining the reactive emulsifier more, it is possible to heat the ABS graft copolymer with minimal emulsifier. It can be seen that the appearance quality such as stability and gloss is improved.
Claims (9)
100 parts by weight of the conjugated diene monomer, 0.05 to 1 part by weight of the reactive emulsifier and 0.05 to 1 part by weight of the long-chain crosslinking agent based on 100 parts by weight of the polymerization method for producing a rubbery polymer latex, characterized in that the polymerization.
The reactive emulsifier is sodium dodecyl allyl sulfosuccinate (sodiumdodecyl allylsulfosuccinate), styrene and sodium dodecyl copolymer, succinyl Nick Acid Di alkenyl C 16 -18 at the time of allyl sulfosuccinic carbonate-potassium salt (C 16 - 18 alkenyl succinic acid di-potassium salt, sodium methallyl sulfonate (SMAS), polyoxyethylene alkylphenylether ammonium sulfate and polyoxyethylenealkylethersulfate ester ammonium salt ester ammonium salt) is a method for producing a rubbery polymer latex, characterized in that at least one selected from the group consisting of.
The long chain crosslinking agent is ethylene glycol dimethacrylate (ethyleneglycol dimethacrylate), ethylene glycol diacrylate (ethyleneglycol diacrylate), diethyleneglycol dimethacrylate (diethyleneglycol dimethacrylate), triethylene glycol dimethacrylate (triethyleneglycol dimethacrylate), 1 , 3-butylene glycol methacrylate (1,3-buthyleneglycolmethacrylate), 1,3-butylene glycol diacrylate, bisphenyl A ethylene oxide dimethacrylate (bisphenol A ethyleneoxide) Cyclohexane dimethylethylene oxide dimethacrylate (cyclohexane dimethylethylene oxide dimethacrylate) and trimethylopropane triacrylate (trimethylopropane triacrylate, TMPTA) A method for producing a rubbery polymer latex, characterized in that selected from the group consisting of.
The conjugated diene monomer is a method for producing a rubbery polymer latex, characterized in that at least one selected from the group consisting of 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene and chloroprene.
b) a monomer mixture comprising 15 to 35 parts by weight of an aromatic vinyl monomer, 10 to 25 parts by weight of vinyl cyan monomer, 0.05 to 1 part by weight of a reactive emulsifier and 0.05 to 1 part by weight of a long-chain crosslinking agent Step of graft polymerization; Method of producing an ABS-based graft copolymer comprising a.
The reactive emulsifier is sodium dodecyl allyl sulfosuccinate (sodiumdodecyl allylsulfosuccinate), styrene and sodium dodecyl copolymer, succinyl Nick Acid Di alkenyl C 16 -18 at the time of allyl sulfosuccinic carbonate-potassium salt (C 16 - 18 alkenyl succinic acid di-potassium salt, sodium methallyl sulfonate (SMAS), polyoxyethylene alkylphenylether ammonium sulfate and polyoxyethylenealkylethersulfate ester ammonium salt ester ammonium salt) method of producing an ABS-based graft copolymer, characterized in that at least one selected from the group consisting of.
The long chain crosslinking agent is divinyl benzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, ethyleneglycol diacrylate, diethyleneglycol dimethacrylate, triethylene glycol dimetha Triethyleneglycol dimethacrylate, 1,3-butylene glycol methacrylate (1,3-buthyleneglycolmethacrylate), allyl methacrylate (allylmethacrylate), 1,3-butylene glycol diacrylate (1,3-buthyleneglycol diacrylate) ), Bisphenol A ethylene oxide, cyclohexane dimethylethylene oxide dimethacrylate and trimethylopropane triacrylate (TMPTA) from the group consisting of 1 ABS graft copolymers characterized in that at least one species selected Manufacturing method.
The average particle diameter of the rubbery polymer latex is 2600 to 5000 kPa, the gel content is 60 to 95% by weight of the production method of the ABS graft copolymer.
The monomer mixture is a method for producing an ABS-based graft copolymer, characterized in that further comprises a monomer selected from the group consisting of alkyl acrylate, alkyl methacrylate and mixtures thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020120008684A KR101515266B1 (en) | 2012-01-30 | 2012-01-30 | Method of preparing rubbery polymer latex and method of ABS graft copolymer comprising the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020120008684A KR101515266B1 (en) | 2012-01-30 | 2012-01-30 | Method of preparing rubbery polymer latex and method of ABS graft copolymer comprising the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20130087664A true KR20130087664A (en) | 2013-08-07 |
| KR101515266B1 KR101515266B1 (en) | 2015-04-27 |
Family
ID=49214284
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020120008684A KR101515266B1 (en) | 2012-01-30 | 2012-01-30 | Method of preparing rubbery polymer latex and method of ABS graft copolymer comprising the same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101515266B1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015047026A1 (en) * | 2013-09-30 | 2015-04-02 | (주) 엘지화학 | Rubber polymer, graft copolymer, preparation methods therefor, and impact resistant and heat resistant resin composition |
| KR20150037518A (en) * | 2013-09-30 | 2015-04-08 | 주식회사 엘지화학 | Rubbery polymer, graft copolymer, method of preparing the same, resistant impact and resistant heat resin composition |
| CN112004839A (en) * | 2018-09-18 | 2020-11-27 | 株式会社Lg化学 | Method for producing conjugated diene polymer and method for producing graft copolymer comprising same |
-
2012
- 2012-01-30 KR KR1020120008684A patent/KR101515266B1/en active IP Right Grant
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015047026A1 (en) * | 2013-09-30 | 2015-04-02 | (주) 엘지화학 | Rubber polymer, graft copolymer, preparation methods therefor, and impact resistant and heat resistant resin composition |
| KR20150037518A (en) * | 2013-09-30 | 2015-04-08 | 주식회사 엘지화학 | Rubbery polymer, graft copolymer, method of preparing the same, resistant impact and resistant heat resin composition |
| CN105121481A (en) * | 2013-09-30 | 2015-12-02 | Lg化学株式会社 | Rubber polymer, graft copolymer, preparation methods therefor, and impact resistant and heat resistant resin composition |
| US9951168B2 (en) | 2013-09-30 | 2018-04-24 | Lg Chem, Ltd. | Rubber polymer, graft copolymer, preparation methods therefor, and impact resistant and heat resistant resin composition |
| US10640596B2 (en) | 2013-09-30 | 2020-05-05 | Lg Chem, Ltd. | Rubber polymer, graft copolymer, preparation methods therefor, and impact resistant and heat resistant resin composition |
| CN112004839A (en) * | 2018-09-18 | 2020-11-27 | 株式会社Lg化学 | Method for producing conjugated diene polymer and method for producing graft copolymer comprising same |
| CN112004839B (en) * | 2018-09-18 | 2023-06-06 | 株式会社Lg化学 | Process for producing conjugated diene polymer and process for producing graft copolymer containing the same |
| US12037435B2 (en) | 2018-09-18 | 2024-07-16 | Lg Chem, Ltd. | Method for preparing conjugated diene-based polymer and method for preparing graft copolymer comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101515266B1 (en) | 2015-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101690381B1 (en) | Method for preparing of acrylonitrile-butadiene-styrene graft copolymer and acrylonitrile-butadiene-styrene thermoplastic resin comprising the same | |
| KR101223295B1 (en) | Ｍｅｔｈｏｄ ｏｆ ｒｕｂｂｅｒｙ ｐｏｌｙｍｅｒ ａｎｄ ｒｕｂｂｅｒ ｒｅｉｎｆｏｒｃｅｄ ｔｈｅｒｍｏｐｌａｓｔｉｃｓ ｕｓｉｎｇ ｔｈｅ ｓａｍｅ | |
| KR101534378B1 (en) | Thermalstabilizer free thermoplastic resin compositions, and a method for preparing thereof | |
| KR101692106B1 (en) | Acrylic impact modifier with core-shell structure and composition of acrylic resin comprising thereof | |
| KR101391048B1 (en) | MBS Graft Copolymer, Method For Preparing The Same And PVC Composition Containing The Same | |
| KR101530150B1 (en) | Method for preparing resin reinforced theremopastic resin using them | |
| KR20100038611A (en) | Core-shell structure butadiene impact modifier and thermoplastic resin composition thereof | |
| CN105008406A (en) | Transparent ABS resin and transparent ABS resin composition | |
| KR101566073B1 (en) | Impact reinforce agent for PVC, a method for preparing the same, and a resin composition containing the same | |
| KR101638240B1 (en) | Rubbery polymer, graft copolymer, method of preparing the same, resistant impact and resistant heat resin composition | |
| JP2008528756A (en) | Impact reinforcing agent for PVC resin and method for producing the same | |
| KR101896751B1 (en) | Thermoplastic resin, method for preparing the resin and thermoplastic resin composition comprising the resin | |
| KR20130087664A (en) | Method of preparing rubbery polymer latex and method of abs graft copolymer comprising the same | |
| KR100806123B1 (en) | Thermoplastic Resin Composition Using Reactive Surfactant, and Method for Preparing the Same | |
| KR101748479B1 (en) | Graft copolymer and molded article prepared therefrom | |
| JP2019108534A (en) | Method for producing core-shell copolymer, core-shell copolymer and resin composition including the same | |
| KR20140019101A (en) | Rubber reinforced graft copolymer and thermoplastic resin composition for reducing tvocs | |
| KR101602531B1 (en) | Manufacturing method of transparent thermoplastic resin having no mold deposit | |
| KR101633173B1 (en) | Method for Preparing Rubber-Reinforced Graft Copolymer and Rubber-Reinforced Graft Copolymer Prepared Therefrom | |
| KR101725599B1 (en) | Method of large paticle sized rubbery polymer and rubber reinforced thermoplastics using the same | |
| KR101540542B1 (en) | Methylmethacrylate-butadiene-styrene impact modifier and polycarbonate resin composition comprising the same | |
| KR102009313B1 (en) | Graft copolymer, method for preparing the copolymer and thermoplastic resin composition comprising the copolymer | |
| KR101452030B1 (en) | Composition for rubber polymer latex, a method for preparing large particle sized rubber polymer latex, and abs graft copolymer having improved impact strength | |
| KR20130082221A (en) | Transparent thermoplastic resin and method of preparing the same | |
| KR102232439B1 (en) | Copolymer composition, method for preparing the same and thermoplastic resin composition comprising the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20180403 Year of fee payment: 4 |
|
| FPAY | Annual fee payment |
Payment date: 20190401 Year of fee payment: 5 |