KR20170042941A - In situ trimodal rubber latex and preparing method thereof - Google Patents
In situ trimodal rubber latex and preparing method thereof Download PDFInfo
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- KR20170042941A KR20170042941A KR1020150142170A KR20150142170A KR20170042941A KR 20170042941 A KR20170042941 A KR 20170042941A KR 1020150142170 A KR1020150142170 A KR 1020150142170A KR 20150142170 A KR20150142170 A KR 20150142170A KR 20170042941 A KR20170042941 A KR 20170042941A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/10—Latex
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/05—Bimodal or multimodal molecular weight distribution
Abstract
More particularly, the present invention relates to an in-situ tri-modal rubber latex comprising 5 to 25% by weight of a rubber having an average particle diameter of 800 to 1500 ANGSTROM, 60 to 89% by weight of a rubber having an average particle diameter of 2500 to 3500 ANGSTROM, 5 to 30% by weight of rubber having a particle diameter of 3500 to 6000 Å and 0.05 to 3% by weight of polymer aggregates having an average particle diameter of 800 to 3000 Å, and a process for producing the same.
According to the present invention, there is provided an in-situ tridimodal rubber latex which is produced in-situ and is economical and has excellent mechanical properties and surface characteristics when applied to a thermoplastic copolymer resin, a method for producing the same, and a thermoplastic air- There is an effect of providing a cohesive resin.
Description
The present invention relates to an in situ trimodal rubber latex and a method for producing the same, and more particularly to a rubber latex having an average particle diameter of 800 to 1500 Å and a rubber having an average particle diameter of 2500 to 3500 Å, In situ trimodal rubber latex comprising 5 to 30% by weight of rubber having an average particle size of 3500 to 6000 Å and 0.05 to 3% by weight of polymer aggregates having an average particle size of 800 to 3000 Å, ≪ / RTI >
For ABS-based graft resins, which are the most common resins used in televisions, refrigerators, and automobiles, surface gloss improvement is a potentially required property of consumers because they are considered to be more advanced products.
For this purpose, although a large-diameter rubber latex was used for the ABS-based graft resin, there was a limit to the increase of the surface gloss, a decrease in reflection haze, and particularly, the impact strength was seriously deteriorated. In the case of using a small-diameter rubber latex, opposite to the case of using a large-diameter rubber latex, the large-diameter and small-diameter were used in the latex state or after polymerization and dried, respectively. However, And reflection haze were unsatisfactory, and there was a problem that physical properties greatly varied according to injection conditions.
In order to solve this problem, three kinds of particles having an average particle diameter of small diameter, large diameter and first diameter were introduced into the ABS-based graft resin. The two kinds of latexes having different average particle diameters were mainly used to polymerize the ABS resin, The latex may be mixed at the time of extrusion, or three types of latexes having different average particle sizes may be first prepared and then mixed at the time of extrusion. However, this method is disadvantageous in that it requires economical and time-consuming loss because each particle must be manufactured separately.
In order to solve the problems of the prior art as described above, the present invention aims to provide an in-situ type trimodal rubber latex.
These and other objects of the present disclosure can be achieved by all of the present invention described below.
In order to attain the above object, the present invention provides a rubber composition comprising 5 to 25% by weight of a rubber having an average particle diameter of 800 to 1500 Å, 60 to 89% by weight of rubber having an average particle diameter of 2500 to 3500 Å, a rubber having an average particle diameter of 3500 to 6000 Å, And 0.05 to 3% by weight of a polymer aggregate having an average particle diameter of 800 to 3000 ANGSTROM.
Further, the present invention relates to a method for producing a toner, comprising: (i) first polymerizing 60 to 80 parts by weight of a conjugated diene monomer; (Ii) 20 to 40 parts by weight of a conjugated diene monomer and 0.1 to 0.8 parts by weight of an emulsifier at a polymerization conversion rate of 30 to 60% during the first polymerization to carry out a second polymerization; And (iii) 0.05 to 3 parts by weight of a polymer aggregate having an average particle diameter of 800 to 3000 ANGSTROM at a polymerization conversion rate of 70 to 90% during the second polymerization, to thereby carry out a third polymerization step. And a manufacturing method thereof.
The present disclosure also provides a thermoplastic copolymer resin comprising an in situ tri-modal rubber latex.
According to the present invention, there is provided an in-situ tridimodal rubber latex which is produced in-situ and is economical and has excellent mechanical properties and surface characteristics when applied to a thermoplastic copolymer resin, a process for producing the same, and a thermoplastic copolymer There is an effect of providing a resin.
Hereinafter, the in-situ tri-modal rubber latex of the present invention and its production method and the like will be described in detail.
The inositrothymodal rubber latex of the present invention comprises 5 to 25% by weight of a rubber having an average particle diameter of 800 to 1500 ANGSTROM, 60 to 89% by weight of a rubber having an average particle diameter of 2500 to 3500 ANGSTROM, 5 to 30 wt% of a rubber having an average particle diameter of 3500 to 6000 ANGSTROM And 0.05 to 3% by weight of a polymer aggregate having an average particle diameter of 800 to 3000 ANGSTROM. Within this range, the rubber latex and the thermoplastic copolymer latex containing the latex are excellent in stability and excellent in surface gloss, reflection haze and staying gloss The impact strength is excellent.
The in situchytmodal rubber latex of the present invention refers to a trimodal rubber latex formed by polymerizing simultaneously or continuously in one reactor, not mixed with rubber latex having different average particle diameters prepared separately.
In another example, the in situ tri-modal rubber latex comprises 5 to 20% by weight of rubber having an average particle diameter of 800 to 1500 ANGSTROM, 65 to 85% by weight of rubber having an average particle diameter of 2500 to 3500 ANGSTROM, 5 to 25 And 1 to 2% by weight of a polymer aggregate having an average particle diameter of 800 to 3000 Å. Within this range, the rubber latex and the thermoplastic copolymer latex containing the latex are excellent in stability, and the surface gloss, the reflection haze, And excellent impact strength.
The rubber may be, for example, an acrylate rubber, a conjugated diene rubber or a mixture thereof.
Examples of the acrylate rubber include one or more kinds selected from the group consisting of butyl acrylate rubber, 2-ethylhexyl acrylate rubber, butyl acrylate-styrene copolymer and 2-ethylhexyl acrylate-acrylonitrile copolymer .
The conjugated diene rubber may be at least one member selected from the group consisting of a butadiene polymer, a butadiene-styrene copolymer (SBR), a butadiene-acrylonitrile copolymer (NBR), and an ethylene-propylene copolymer (EPDM) .
Examples of the polymer aggregates having an average particle diameter of 800 to 3000 ANGSTROM include an unsaturated carboxylic acid or an ester monomer thereof; And a comonomer having a functional group.
In addition, the manufacturing method of the present invention includes the steps of: (i) first polymerizing 60 to 80 parts by weight of a conjugated diene monomer; (Ii) 20 to 40 parts by weight of a conjugated diene monomer and 0.1 to 1.0 part by weight of an emulsifier at a polymerization conversion rate of 30 to 60% during the first polymerization, and then performing a second polymerization; And (iii) 0.05 to 3 parts by weight of a polymer aggregate having an average particle diameter of 800 to 3000 Å at a polymerization conversion of 70 to 90% during the second polymerization.
The conjugated diene monomer may be at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, and pyrene.
As another example, the conjugated diene monomer may further include an aromatic vinyl monomer, a vinyl cyan monomer, or a mixture thereof, and may be included in an amount of 20 parts by weight or less based on 100 parts by weight of the total monomers.
In the step (i), the first polymerization may include, for example, 1 to 3 parts by weight of an emulsifier, 0.5 to 3 parts by weight of an electrolyte, 0.1 to 0.5 parts by weight of a molecular weight adjuster and 0.1 to 0.5 parts by weight of an initiator.
In the step (ii), when the polymerization conversion is 30 to 60%, for example, the average particle size may be 2300 to 2700 Å or 2400 to 2600 Å. In this range, the balance of small diameter and large diameter particle production is excellent, The surface properties are excellent.
In the step (ii), the second polymerization may include, for example, 0.1 to 1.0 part by weight, or 0.3 to 0.8 part by weight of an emulsifier. Within this range, the minor and minor diameters generated in the secondary polymerization have an effective ratio The ratio of the small diameter, the large diameter and the initial diameter after the third polymerization is optimized.
In the step (ii), for example, 0.05 to 0.5 parts by weight of an initiator may be used as the second polymerization.
In the step (iii), for example, polymer aggregates may be introduced at a polymerization conversion of 70 to 90%, 70 to 80%, or 70 to 75%. In this case, the latex is stable and part of the small diameter is large, Some of them have excellent effect to enlarge to the first sight.
In the step (iii), the third polymerization may include, for example, 0.05 to 3 parts by weight, 0.5 to 2.5 parts by weight, or 1 to 2 parts by weight of the polymer aggregate. Within this range, the latex is stable, The aggregate is combined with a part of the small diameter and the large diameter, and a part of the small diameter becomes a large diameter, and a part of the large diameter is excellent in the effect to enlarge to the first diameter.
The first polymerization may be carried out at 65 to 70 ° C for example, the second polymerization may be carried out at 70 to 75 ° C and the third polymerization may be carried out at 80 to 85 ° C, for example, There is an effect of rising.
The polymer aggregate having an average particle diameter of 800 to 3000 ANGSTROM is, for example, an unsaturated carboxylic acid polymer or an unsaturated carboxylic acid ester polymer, and specifically includes: (a) polymerizing 10 to 20 parts by weight of an unsaturated carboxylic acid or its ester monomer; (b) adding 75 to 85 parts by weight of an unsaturated carboxylic acid or its ester monomer and 5 to 10 parts by weight of a comonomer having a functional group in a polymerization conversion ratio of 80 to 95% during the polymerization to form an emulsion; And (c) terminating the polymerization at a polymerization conversion rate of 98% or more during the polymerization.
The unsaturated carboxylic acid or its ester monomer may be, for example, an ethylenic carboxylic acid, an ester thereof, an acrylate monomer, or a mixture thereof.
The unsaturated carboxylic acid polymer may further include at least one comonomer selected from the group consisting of a conjugated double bond monomer of C 4-6 , a monovinyl aromatic hydrocarbon monomer, and a vinyl cyan monomer. In this case, It is applicable to latex and has an effect of improving mechanical properties and surface characteristics.
The ethylenically unsaturated carboxylic acid may be at least one selected from the group consisting of acrylic acid, methacrylic acid, methyl acrylic acid, itaconic acid, crotonic acid, fumaric acid and maleic acid.
The unsaturated carboxylic acid ester monomer may be, for example, an alkyl ester of the unsaturated carboxylic acid, i.e., an alkyl-unsaturated carboxylic acid ester.
The functional group may be at least one selected from the group consisting of an amide group, an alcohol group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a boric acid group. In this case, the functional group may lower the role of the emulsifier in the rubber latex, So that the particles can effectively collide with each other to enlarge the particles.
The comonomer having the functional group may be at least one selected from the group consisting of methacrylamide, acrylamide, methacrylic acid and acrylic acid.
For example, the step (a) may be performed by emulsion polymerization at 75 to 85 ° C using 0.1 to 0.5 parts by weight of an emulsifier, 0.05 to 0.02 parts by weight of an initiator, and 60 to 70 parts by weight of ion exchange water.
The step (b) may be performed by emulsion polymerization using, for example, 1 to 5 parts by weight of an emulsifier, 30 to 40 parts by weight of ion exchange water and 0.5 to 2 parts by weight of an initiator.
The emulsifying agent of the present invention is at least one selected from the group consisting of allyl aryl sulfonate, alkaline methyl alkyl sulfonate, sulfonated alkyl ester, fatty acid soap, and rosin acid alkali salt.
The initiator of the present invention may be at least one selected from the group consisting of a water-soluble polymerization initiator, a fat-soluble polymerization initiator, and an oxidation-reduction catalyst.
The water-soluble polymerization initiator may be, for example, a persulfate, and the persulfate may be at least one selected from the group consisting of potassium persulfate, sodium persulfate, and ammonium persulfate.
The oil-soluble polymerization initiator may be, for example, a peroxy compound. As another example, a cumene hydroperoxide, diisopropylbenzene hydroperoxide, azobisisobutylonitrile, tertiary butyl hydroperoxide, paramethane hydroperoxide , And benzoyl peroxide.
The oxidation-reduction catalyst may be at least one selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate, and sodium sulfite.
The electrolyte may include, for example, KCl, NaCl, KHCO 3 , NaHCO 3 , K 2 CO 3 , Na 2 CO 3 , KHSO 3 , K 2 SO 4 , NaHSO 3 , K 2 P 2 O 7 , Na 2 P 2 O 7 , K 3 PO 4 , Na 3 PO 4 , and K 2 HPO 4 .
The molecular weight regulator may be, for example, mercaptans.
Further, the present disclosure may be a thermoplastic copolymer resin polymerized including the above-mentioned in situ tridimodal rubber latex.
The thermoplastic copolymer resin may be, for example, an ABS copolymer resin in which an aromatic vinyl compound and a vinyl cyan compound are graft-polymerized to the in situ tridimodal rubber latex.
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 spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.
[Example]
Example One
≪ Production of macromolecular aggregates &
15 parts by weight of ethyl acrylate, 0.3 part by weight of an oleic acid potassium salt as an emulsifier, 0.01 part by weight of an initiator and potassium sulfate, and 65 parts by weight of ion-exchanged water were charged in a batch at 80 DEG C . 80 parts by weight of ethyl acrylate and 5 parts by weight of methacrylamide, 3 parts by weight of an oleic acid potassium salt as an emulsifier and 35 parts by weight of ion-exchanged water were added to emulsion And emulsification polymerization was carried out at 80 DEG C while charging 1 part by weight of initiator, potassium sulfate and 165 parts by weight of ion-exchanged water for 3 hours. The polymerization was terminated at a polymerization conversion rate of 98% or more during the emulsion polymerization, and the obtained polymer aggregate had an average particle size of 1970 Å.
≪ Preparation of In Situ Trimodal Rubber Latex >
60 parts by weight of ion-exchanged water, 75 parts by weight of 1,3-butadiene, 1 part by weight of potassium rosinate as an emulsifier, 0.8 parts by weight of fatty acid soap, 1.5 parts by weight of sodium sulfate as an electrolyte, 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight regulator and 0.3 part by weight of potassium persulfate (K 2 S 2 O 8 ) as initiators were polymerized at a reaction temperature of 70 ° C., , 25 parts by weight of 3-butadiene, and 0.15 part by weight of potassium persulfate were added to the mixture at a polymerization conversion of 45% and 0.8 parts by weight of an emulsifier Latemul ASK (Kao Corp., Japan) at an average particle diameter of 2300 to 2700 Å. 60%. Then, the mixture was heated to 80 DEG C to polymerize. Thereafter, 1.5 parts by weight of the polymer aggregate prepared above at a polymerization conversion rate of 75% was added and reacted. The reaction was terminated at a polymerization conversion of 97% . The pH of the final latex was adjusted to a general level of 10.7.
Capillary Hydrodynamic Fractionation (CHDF) confirmed that three types of in situ tridimodal rubber latexes with different average particle sizes were produced.
<ABS resin production>
To a nitrogen-substituted polymerization reactor were added 65 parts by weight of the above-prepared in situ tridimodal latex and 100 parts by weight of ion-exchanged water, 10 parts by weight of acrylonitrile mixed in a separate mixing apparatus, 25 parts by weight of styrene, 20 parts by weight , 0.1 part by weight of t-butyl hydroperoxide, 1.0 part by weight of potassium rosinate, and 0.3 part by weight of tertiary dodecyl mercaptan, 0.054 part by weight of dextrose, 0.004 part by weight of sodium pyrophosphate, and ferrous sulfate 0.0002 Parts by weight at 70 캜 for 3 hours. After the completion of the addition, 0.05 part by weight of dextrose, 0.03 part by weight of sodium pyrophosphate, 0.001 part by weight of ferrous sulfate and 0.005 part by weight of t-butylhydroperoxide were added to the polymerization reactor, and the mixture was heated to 80 DEG C for 1 hour And then the reaction was terminated to prepare an ABS latex. The polymerization conversion was 98%. The prepared ABS latex was agglomerated with sulfuric acid and dehydrated and dried to obtain ABS powder. The ABS latex was blended with SAN resin at a weight ratio of 26:74 and then extruded to prepare a specimen for physical property measurement.
Example 2
The procedure of Example 1 was repeated, except that 0.2 part by weight of an emulsifier Latemul ASK (Kao Corporation, Japan) was added at a polymerization conversion of 45% in the production of the in situ tridimodal rubber latex.
Comparative Example One
The experiment was carried out in the same manner as in Example 1 except that the polymer aggregate was not administered in Example 1 above.
Comparative Example 2
Example 1 was repeated except that 1.5 parts by weight of potassium carbonate was used as the electrolyte in Example 1, and the polymer aggregate and the emulsifier Latemul ASK were not administered.
Comparative Example 3
The procedure of Example 1 was repeated, except that 1.5 parts by weight of an emulsifier Latemul ASK (Kao, Japan) added at a polymerization conversion of 45% was used in the preparation of the in situ tridimodal rubber latex.
Comparative Example 4
The procedure of Example 1 was repeated except that the polymer aggregate was used in an amount of 4.0 parts by weight in Example 1.
[Test Example]
The properties of the specimens prepared in Example 1 and Comparative Examples 1 to 4 were measured by the following methods, and the results are shown in Table 1 below.
How to measure
Polymerization Conversion (%): 1.5 g of the prepared latex was dried in a hot air drier at 150 캜 for 15 minutes, and the weight was measured to determine the total solid content (TSC). The polymerization conversion ratio was calculated by the following formula 1 g of the prepared latex was diluted with 100 g of distilled water, and then measured using a light-scattering type measuring instrument (Nicomp), and the number-average particle size of the measuring instrument was recorded.
[Equation 1]
Average particle diameter (Å) and content (weight%) thereof were measured using Capillary Hydrodynamic Fractionation (CHDF, Matec Applied Science, Model 1100).
* Solidified Solids (wt%): The latex prepared by the emulsion polymerization method was passed through a 100 mesh mesh filter and dried in a hot air drier at 100 ° C. for 1 hour. As a ratio of the theoretical total amount of additive (emulsifier, etc.).
* Latex stability (weight%): The latex stability of the rubbery polymer was determined by filtering 500 g of the final polymerized latex obtained using a 100-mesh net and then allowing it to stand at 10,000 RPM in a homo-mixer (TK Robomics) for 60 minutes. The coagulated product hanging from the mesh net was recorded as a percentage by weight with respect to the theoretical total solid content. In addition, the time for solidification of the polymer was measured and recorded at 15,000 RPM for the graft copolymer and classified as stable latex for polymer over 60 minutes.
* Izod impact strength (1/4 ", kgf · cm / cm): measured according to ASTM D256.
* Measured according to ASTM D1238 under the conditions of flow index (MI; g / 10 min): 220 ° C / 10kg.
Tensile strength (kgf / cm 2 ): Measured according to ASTM D638.
Surface gloss: Measured according to ASTM D528 at a 45 ° angle.
* Gloss of stay: The pellet obtained from the extruder is placed in an injection machine and held at 250 ° C for 15 minutes to obtain a polished specimen. The polished specimen is measured at an angle of 45 ° with the specimen injected without staying at 200 ° C. Respectively. At this time, the smaller the measured value, the better the staying gloss.
* Reflection haze: Using a Rhopoint IQ device, we measured 512 diodes arranged in a straight line to profile reflected light in a large circular arc from 14 ° to 27 °. At an angle of 20 [deg.], By the following equation (2).
&Quot; (2) "
* Retention Discoloration (ΔE): L, a, and b values of the specimen before and after retention were obtained for the gloss specimen obtained by the same method as that for specifying the staying gloss, using a Suga color computer, The degree of discoloration was calculated. At this time, the smaller the measured value,
&Quot; (3) "
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The
(%)
(weight%)
(weight%)
(25% by weight)
(7 wt%))
(73% by weight)
2930
(100
weight%)
(5% by weight)
(10% by weight)
(65% by weight)
(85% by weight)
(27% by weight)
(46% by weight)
(83% by weight)
(10% by weight)
(8% by weight)
(49% by weight)
(7 wt%))
B
S
Number
G
(%)
(weight%)
As shown in Table 1, Examples 1 and 2 of the present invention have excellent mechanical properties such as tensile strength and impact strength, as well as excellent processability, thermal stability, surface gloss, and reflection haze (surface sharpness).
On the other hand, in Comparative Examples 1 (bimodal) to 2 (monomodal), mechanical properties and surface gloss, reflection haze, retention discoloration and retention gloss were both lowered. In particular, the mechanical strength and surface characteristics (surface gloss, reflection haze) are in a trade-off relationship, and it has been confirmed that the introduction of the inkschutrimodal rubber latex provides a synergistic effect in which both mechanical properties and surface characteristics are improved.
In addition, Comparative Example 3, which contained an excess amount of an emulsifier during the production of the in-situ tri-modal rubber latex, resulted in a large amount of pores and decreased surface characteristics such as impact strength, stain discoloration and retention luster, In Example 4, the stability of the gum latex was degraded and a large amount of solid coagulation was produced.
Claims (17)
Wherein the rubber is an acrylate rubber, a conjugated diene rubber or a mixture thereof.
The polymer aggregate may be an unsaturated carboxylic acid or its ester monomer; And a comonomer having a functional group. ≪ RTI ID = 0.0 > In < / RTI >
(Ii) 20 to 40 parts by weight of a conjugated diene monomer and 0.1 to 0.8 parts by weight of an emulsifier at a polymerization conversion rate of 30 to 60% during the first polymerization to carry out a second polymerization; And
(Iii) 0.05 to 3 parts by weight of polymer aggregates having an average particle diameter of 800 to 3000 ANGSTROM at a polymerization conversion of 70 to 90% during the second polymerization, and then performing a third polymerization step. (Method for manufacturing rubber latex).
Wherein the polymer aggregate having an average particle diameter of 800 to 3000 ANGSTROM comprises: (a) polymerizing 10 to 20 parts by weight of an unsaturated carboxylic acid or an ester monomer thereof; (b) adding 75 to 85 parts by weight of an unsaturated carboxylic acid or its ester monomer and 5 to 10 parts by weight of a comonomer having a functional group in a polymerization conversion ratio of 80 to 95% during the polymerization to form an emulsion; And (c) terminating the polymerization at a polymerization conversion rate of 98% or higher during the polymerization.
Wherein the step (a) comprises emulsion polymerization at 75 to 85 ° C using 0.1 to 0.5 parts by weight of an emulsifier, 0.05 to 0.02 parts by weight of an initiator, and 60 to 70 parts by weight of ion exchange water. Way.
Wherein the step (b) comprises emulsion polymerization using 1 to 5 parts by weight of an emulsifier, 30 to 40 parts by weight of ion exchange water and 0.5 to 2 parts by weight of an initiator.
Wherein the unsaturated carboxylic acid or its ester monomer is an ethylenically unsaturated carboxylic acid, an ester thereof, an acrylate monomer, or a mixture thereof.
Wherein the functional group is at least one member selected from the group consisting of an amide group, an alcohol group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a boric acid group.
Wherein the emulsifier is at least one member selected from the group consisting of allyl aryl sulfonate, alkaline methyl alkyl sulfate, sulfonated alkyl ester, fatty acid soap, and rosin acid alkali salt.
Wherein the step (ii) has an average particle diameter of 2300 to 2700 ANGSTROM when the polymerization conversion is 30 to 60%.
In the step (i), the first polymerization is conducted using 1 to 3 parts by weight of an emulsifier, 0.5 to 3 parts by weight of an electrolyte, 0.1 to 0.5 parts by weight of a molecular weight adjuster and 0.1 to 0.5 parts by weight of an initiator. Method of manufacturing latex.
Wherein in the step (ii), 0.05 to 0.5 parts by weight of an initiator is used as the second polymerization.
Wherein the first polymerization is carried out at 65 to 70 占 폚, the second polymerization is carried out at 70 to 75 占 폚, and the third polymerization is carried out at 80 to 85 占 폚.
Wherein the conjugated diene monomer is at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, and pyrylene.
Wherein the conjugated diene monomer further comprises an aromatic vinyl compound monomer, a vinyl cyan monomer, or a mixture thereof.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200005093A (en) * | 2018-07-05 | 2020-01-15 | 주식회사 엘지화학 | Method for preparing large particle sized rubber latex, and method for preparing abs graft copolymer |
| WO2020130569A1 (en) * | 2018-12-20 | 2020-06-25 | 주식회사 엘지화학 | Diene-based rubber latex, manufacturing method thereof, and core-shell structured graft copolymer comprising same |
| CN112041357A (en) * | 2018-12-20 | 2020-12-04 | 株式会社Lg化学 | Diene rubber latex, method for producing same, and graft copolymer having core-shell structure comprising same |
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| KR20010003659A (en) * | 1999-06-24 | 2001-01-15 | 유현식 | Thermoplastic resin composition with good heat resistance and elongation property |
| KR20050067838A (en) | 2003-12-29 | 2005-07-05 | 제일모직주식회사 | Method of preparing abs resin composition with good heat resistance, transparence and natural color |
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| KR20200005093A (en) * | 2018-07-05 | 2020-01-15 | 주식회사 엘지화학 | Method for preparing large particle sized rubber latex, and method for preparing abs graft copolymer |
| WO2020130569A1 (en) * | 2018-12-20 | 2020-06-25 | 주식회사 엘지화학 | Diene-based rubber latex, manufacturing method thereof, and core-shell structured graft copolymer comprising same |
| KR20200077430A (en) * | 2018-12-20 | 2020-06-30 | 주식회사 엘지화학 | Diene based rubber latex, method for preparing thereof and core-shell structured graft copolymer comprising the same |
| CN112041357A (en) * | 2018-12-20 | 2020-12-04 | 株式会社Lg化学 | Diene rubber latex, method for producing same, and graft copolymer having core-shell structure comprising same |
| JP2021518876A (en) * | 2018-12-20 | 2021-08-05 | エルジー・ケム・リミテッド | Diene rubber latex, this manufacturing method, and a graft copolymer with a core-shell structure containing it. |
| CN112041357B (en) * | 2018-12-20 | 2023-11-24 | 株式会社Lg化学 | Diene rubber latex, method for producing the same, and graft copolymer having core-shell structure comprising the same |
| US11932709B2 (en) | 2018-12-20 | 2024-03-19 | Lg Chem, Ltd. | Diene-based rubber latex, method for preparing thereof and graft copolymer with core-shell structure comprising the same |
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