KR20140146783A - Manufacturing method of ABS resin - Google Patents
Manufacturing method of ABS resin Download PDFInfo
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- KR20140146783A KR20140146783A KR20130069503A KR20130069503A KR20140146783A KR 20140146783 A KR20140146783 A KR 20140146783A KR 20130069503 A KR20130069503 A KR 20130069503A KR 20130069503 A KR20130069503 A KR 20130069503A KR 20140146783 A KR20140146783 A KR 20140146783A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C1/00—Treatment of rubber latex
- C08C1/02—Chemical or physical treatment of rubber latex before or during concentration
- C08C1/065—Increasing the size of dispersed rubber particles
- C08C1/07—Increasing the size of dispersed rubber particles characterised by the agglomerating agents used
-
- 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
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
- C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
Abstract
Description
More particularly, the present invention relates to an ABS resin aged with an aging agent, a process for producing the ABS resin, and a process for producing a thermoplastic resin by mixing the obtained ABS resin with a flow control resin and having excellent moldability and impact resistance But also has excellent thermal stability, gloss and whiteness.
Generally, acrylonitrile-butadiene-styrene (ABS) resin is prepared by emulsion polymerization or bulk polymerization method. The emulsion polymerization method is easy to exhibit excellent impact strength and gloss characteristics, but has limitations such as whiteness and thermal stability due to the use of an emulsifier. In addition, when coloring with black, excellent glossiness and high blackness There is a limit to the expression. On the other hand, the ABS resin produced by the bulk polymerization method does not contain an emulsifier and has excellent whiteness and thermal stability. However, the ABS resin has poor surface gloss, impact resistance and moldability.
As a result of intensive studies to solve the problems of the prior art as described above, it has been found that when an ABS resin is manufactured, an optimal aging process is applied to produce a resin composition having excellent impact resistance, moldability, heat stability, gloss, whiteness, It is possible to produce an ABS resin having a low content. Thus, the present invention has been completed.
An object of the present invention is to provide a thermoplastic resin which is excellent in molding processability and impact resistance, but also excellent in heat stability, gloss and whiteness.
The above object of the present invention can be achieved by the present invention described below.
The ABS resin according to the present invention is obtained by adding 0.1 to 10 parts by weight of an aging agent based on 100 parts by weight of an ABS-based graft copolymer latex, followed by aging.
The method for producing an ABS resin according to the present invention comprises the steps of: (1) preparing an ABS-based graft copolymer latex; And (2) 0.1 to 10 parts by weight of an aging agent based on 100 parts by weight of the ABS-based graft copolymer latex, followed by aging.
In addition, the thermoplastic resin according to the present invention is characterized in that 10 to 50% by weight of the ABS resin obtained is mixed with a flow control resin as the balance.
According to the present invention, there is provided an ABS resin aged with an aging agent and a process for producing the ABS resin, and the obtained ABS resin and the flowability-regulating resin are mixed to form a thermoplastic resin having excellent moldability and impact resistance, There is an effect of providing a resin. In addition, as an effect of the present invention, it is possible to produce a resin having a low content of volatile components.
The ABS resin according to the present invention is obtained by graft-polymerizing an aromatic vinyl monomer and a vinyl cyan monomer to a diene rubber polymer, adding an aging agent to the ABS-based graft copolymer latex thus obtained, aging, , And is characterized in that it is dried to obtain an ABS resin in powder form. Then, the obtained ABS resin is mixed with the flowability-regulating resin so that the ABS resin can be manufactured from a thermoplastic resin composition having excellent moldability and impact resistance and excellent thermal stability, gloss and whiteness. Further, the ABS resin and the flowability- And can be produced into a molded article excellent in impact resistance and excellent in heat stability, gloss and whiteness.
Hereinafter, the configuration of the present invention will be described in detail.
The ABS resin according to the present invention is obtained by adding 0.1 to 10 parts by weight of an aging agent based on 100 parts by weight of an ABS-based graft copolymer latex, followed by aging.
The ABS-based graft copolymer latex of the present invention is a suspension in which the copolymer is suspended in an amount of 50 to 60% by weight.
The ABS-based graft copolymer latex is obtained by graft-polymerizing an aromatic vinyl monomer and a vinyl cyan monomer to a diene rubber polymer, and can be understood by those skilled in the art. Preferably, the diene rubber polymer may be a homopolymer of a diene monomer, a copolymer of a diene monomer and an aromatic vinyl monomer, or a copolymer of a diene monomer and a vinyl cyan monomer. The diene monomer may be selected from the group consisting of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene and mixtures of two or more thereof.
The copolymer of the diene monomer and the aromatic vinyl monomer is obtained by copolymerizing an aromatic vinyl monomer with the diene monomer, wherein the aromatic vinyl monomer is used in an amount of 1 to 30 It is preferable to use the polymer in an amount of 10 to 20% by weight, preferably 10 to 20% by weight, and most preferably 12 to 18% by weight in order to improve the impact strength. The aromatic vinyl monomer may be selected from the group consisting of styrene,? -Methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, vinyltoluene and mixtures of two or more thereof. But the present invention is not limited thereto.
The copolymer of the diene monomer and the vinyl cyan monomer is obtained by copolymerizing a vinyl cyan monomer with the diene monomer, wherein the vinyl cyan monomer is used in an amount of from 1 to 30, based on the total weight of the mixture of the diene monomer and the vinyl cyan monomer, It is preferable to use the polymer in an amount of 10 to 20% by weight, preferably 10 to 20% by weight, and most preferably 12 to 18% by weight in order to improve the impact strength. The vinyl cyan monomer may be selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and mixtures of two or more thereof. Specifically, acrylonitrile is used. However, It is not.
The diene rubber polymer may be synthesized by emulsion polymerization. As the emulsifier added during emulsion polymerization, a compound selected from the group consisting of an alkali salt of fatty acid, an alkali salt of rosin acid, an alkali salt of oleic acid, and a mixture of two or more thereof It is possible. The polymerization initiator may be selected from the group consisting of sodium persulfate, potassium persulfate, cumene hydroperoxide, diisopropylbenzene hydroperoxide, and mixtures of two or more thereof.
The ABS-based graft copolymer latex is obtained by copolymerizing 12 to 48 parts by weight of an aromatic vinyl monomer in 45 to 70 parts by weight, preferably 50 to 60 parts by weight, and most preferably 52 to 58 parts by weight of the obtained diene rubber polymer, Preferably 20 to 45 parts by weight, most preferably 35 to 43 parts by weight, and vinyl cyan monomer 7 to 18 parts by weight, preferably 9 to 16 parts by weight, and most preferably 11 to 14 parts by weight, Polymerized by polymerization. It is preferable that the aromatic vinyl monomer is used within a range of 12 to 48 parts by weight based on the total weight of the diene rubber polymer in order to improve the impact strength.
Also, it is preferable that the vinyl cyan monomer is used within a range of 7 to 18 parts by weight based on the total weight of the diene rubber polymer.
The graft polymerization of the diene rubber polymer, the aromatic vinyl monomer and the vinyl cyan monomer may be synthesized by emulsion polymerization. Examples of the emulsifier added during emulsion polymerization include alkali salts of fatty acids, alkali salts of rosin acid, alkali salts of oleic acid And a mixture of two or more thereof. As the polymerization initiator, those selected from the group consisting of sodium persulfate, potassium persulfate, cumene hydroperoxide, diisopropylbenzene hydroperoxide and mixtures of two or more thereof can be used. Molecular weight control agents may also be added. The selection and use amount of the emulsifier, the polymerization initiator, the molecular weight regulator and the like are well known to those skilled in the art without requiring much experimentation. The ABS-based graft copolymer latex to be obtained or the ABS The physical properties of the resin, and other instructions of the supplier of the raw material.
In the present invention, in producing the ABS resin from the ABS-based graft copolymer latex obtained according to the above-mentioned process, an aging agent is added to the ABS-based graft copolymer latex so that the ABS-based graft copolymer latex , 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, and most preferably 0.3 to 1 part by weight of the aging agent based on 100 parts by weight of the acrylic resin It is characteristic of point. The aging agent is preferably selected from the group consisting of alkali metal oxides, alkaline earth metal oxides, and mixtures of two or more thereof.
The aging agent may preferably be selected from the group consisting of sodium oxide, calcium oxide, magnesium oxide, and mixtures thereof.
By the addition of the aging agent, neutralization occurs during aging to adjust the pH of the ABS-based graft copolymer latex.
The aging after addition of the aging agent can be carried out at a temperature of 70 to 110 캜, preferably 80 to 100 캜, and most preferably 85 to 95 캜.
The aging may be performed before or after the agglomeration of the ABS-based graft copolymer latex. It is preferable that the aging is carried out after agglomeration of the ABS-based graft copolymer latex. The flocculation is carried out by adding an flocculant, and it is preferable that an acid is used as the flocculant. The acid may be selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, acetic acid, and a mixture of two or more thereof. The acid may be preferably used in the form of an aqueous acid solution, and most preferably an aqueous sulfuric acid solution . The type and amount of coagulant used in the coagulant are well known to those skilled in the art without requiring much experimentation and the ABS copolymer graft copolymer latex to be obtained or the ABS resin And may be understood as being known to the extent that it can be selected and used by the enemy on the basis of the instruction manual of the other raw material supplier.
The agglomeration can be carried out at a temperature of 60 to 80 캜, preferably 70 to 78 캜, most preferably 73 to 76 캜. The ABS resin according to the present invention has a volatile content of 2.0 g or less, preferably 1.8 g or less, and most preferably 1.5 g or less. The volatile component content is measured by heating the sample at 250 ° C for 30 minutes. The volatile component content is a value obtained by subtracting the total amount of the sample after heating from the total amount of the sample before heating.
The method for producing an ABS resin according to the present invention comprises the steps of: (1) preparing an ABS-based graft copolymer latex; And (2) 0.1 to 10 parts by weight of an aging agent based on 100 parts by weight of the ABS-based graft copolymer latex, followed by aging.
The ABS-based graft copolymer latex, which is one of raw materials used in the production of the ABS resin according to the present invention, is the same as or similar to the previously described ABS latex copolymer latex, And the description thereof will be omitted.
The aging may be performed by adding 0.1 to 10 parts by weight of an aging agent based on 100 parts by weight of the ABS-based graft copolymer latex. The aging agent and the aging condition are the same as or similar to those described above, and repeated explanation is omitted.
An agglomeration step may be further included between the synthesis step and the aging step.
The coagulation step is a step of agglomerating the solid content of the ABS-based graft copolymer latex obtained in the synthesis step to increase the solid content, thereby facilitating subsequent processes such as dehydration, washing and drying, The ABS resin according to the invention can be obtained in the form of a powder. Alternatively, the agglomeration step may be performed after the aging step. The agglomeration in the agglomeration step is the same as or similar to that described above, and repeated explanation is omitted.
Preferably, the agglomeration step is preferably carried out before the aging step, that is, between the synthesis step and the aging step .
According to the above, an ABS resin according to the present invention is obtained, and the ABS resin has characteristics of excellent thermal stability, gloss and whiteness. It will be appreciated that the ABS resin may include other conventional additives known in the art to control the physical properties. Such additives may include additives that function to control, assist, or improve the physical properties of the resin such as inorganic fillers, ultraviolet absorbers, lubricants, and antioxidants. It will be understood that the present invention is well known to those skilled in the art without undue experimentation.
The thermoplastic resin according to the present invention is characterized in that the ABS resin is mixed with the flowability-regulating resin in an amount of 10 to 50% by weight, preferably 20 to 40% by weight, and most preferably 25 to 35% by weight. If the content of the ABS resin is less than 10% by weight based on the total weight of the thermoplastic resin according to the present invention, there may be a problem that the physical properties, particularly impact resistance, are lowered. On the other hand, The flowability of the resulting thermoplastic resin becomes too high or too low, which makes it difficult to control the flowability and thus the moldability may be deteriorated.
The flow control resin functions to control the flowability of the thermoplastic resin according to the present invention, and can control the moldability of the thermoplastic resin thereby to facilitate processing such as extrusion molding. Said flow control resin may preferably be an SA resin or an ASA resin prepared by bulk polymerization, but these are merely illustrative and the present invention is not intended to be limited thereto, It will be understood by those skilled in the art that the physical properties of the thermoplastic resin obtained by blending with the ABS resin, particularly the use of any other resins used to control the molding, such as molding, by controlling the flowability. Sa-based resin or ASA-based resin as the flow control resin is well-known and can be purchased and used by those skilled in the art from a number of domestic and overseas manufacturers. The SA-based resin is a commercially available resin comprising a styrene-acrylonitrile copolymer produced by the bulk polymerization method, and the thermoplastic resin obtained according to the present invention is a typical resin functioning to have high fluidity. The ASA-based resin The resin is also a commercially available resin comprising an acrylonitrile-styrene-acrylonitrile copolymer produced by bulk polymerization, and the thermoplastic resin obtained according to the present invention is a typical resin functioning to have low fluidity.
Therefore, by mixing the ABS resin obtained according to the present invention with the flow control resin, it is possible to control the physical properties of the resin, particularly the fluidity, for molding processability, particularly extrusion molding. It should be appreciated that the thermoplastic resin may include other conventional additives known in the art to control the physical properties. Such additives may include additives that function to control, assist, or improve the physical properties of the resin such as inorganic fillers, ultraviolet absorbers, lubricants, and antioxidants. It will be understood that the present invention is well known to those skilled in the art without undue experimentation.
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 1
75 parts by weight of ion-exchanged water, 80 parts by weight of 1,3-butadiene as a monomer, 20 parts by weight of styrene and 2.5 parts by weight of a potassium salt of rosin as an emulsifier were gradually added to the mixture, Sulfates were added and polymerized to prepare an ABS-based graft copolymer latex.
55 parts by weight of the prepared ABS-based graft copolymer latex and 65 parts by weight of ion-exchanged water were added to the polymerization reactor, and the temperature of the reactor was raised to 70 캜. A mixed emulsion of cumene hydroperoxide as a polymerization initiator was added to the separate tank in an amount of 1.5 parts by weight of a rosin potassium salt emulsifier, 42 parts by weight of styrene, 13 parts by weight of acrylonitrile, and the mixture was continuously introduced for 4 hours. To prepare a copolymer.
Next, the latex was coagulated at a coagulation temperature of 75 캜 by adding 1.0 part by weight of a 5% aqueous solution of sulfuric acid, and the mixture was aged and treated with 0.5 part by weight of magnesium oxide while heating to 90 캜, followed by dehydration, washing and drying to obtain a powder .
Finally, a small amount of a lubricant and an antioxidant were added to 30 parts by weight of the graft copolymer prepared by the above method and 70 parts by weight of a styrene-acrylonitrile copolymer (Grade: 80HF) prepared by bulk polymerization, The pellet was obtained.
Example 2
Pellets were obtained in the same manner as in Example 1, except that 0.5 part by weight of sodium oxide was used instead of magnesium oxide in the aging tank in Example 1.
Example 3
Example 1 was repeated except that an alpha methyl styrene-acrylonitrile copolymer (Grade: 98 UHM) was used instead of the styrene-acrylonitrile copolymer produced by the bulk polymerization to be subjected to the extrusion process in Example 1 above. Pellets were obtained in the same manufacturing process.
Comparative Example 1
Pellets were obtained in the same manner as in Example 1 except that 20% calcium chloride solution was used instead of 5% sulfuric acid aqueous solution as the coagulant in Example 1.
Comparative Example 2
The pellets were obtained in the same manner as in Example 1 except that the magnesium oxide was not aged in the aging tank.
Comparative Example 3
Pellets were obtained in the same manner as in Example 3 except that the aging process was not carried out in the aging tank in Example 3.
[Test Example]
The physical property evaluation conditions used in the invention are as follows, and the main characteristics of the resin prepared in Examples and Comparative Examples are shown in Table 1.
Extrusion conditions: The temperature of the extruder was set at 180 to 230 占 폚 and extruded in a twin-screw extruder.
* Injection condition: The injection temperature was set at 200 to 230 ° C, and the specimen was injected into an ASTM standard mold.
* Moldability: Evaluated by ASTM D1238 flow index
* Impact resistance: Evaluated by Notched Izod impact strength according to ASTM D256 method.
* Thermal Stability: The color change was compared after exposure for 2 hours in 190 ℃ oven. The more color change, the lower the quality (○: Excellent, Δ: Medium X: Inferior).
* Gloss: Evaluates surface gloss according to ASTM D2457 method.
Whiteness: Whiteness index is evaluated according to CIE Lab method.
* Volatile content: The sample is measured by heating at 250 ° C for 30 minutes. The volatile content is expressed as the heating loss by subtracting the total amount of the sample after heating from the total amount of the sample before heating.
The thermoplastic resins according to Examples 1 to 3 of the present invention are superior to those of Comparative Examples 1 to 3 in moldability, impact resistance, thermal stability, gloss and whiteness. It is also possible to produce a resin having a low content of volatile components.
Claims (20)
Wherein the ABS-based graft copolymer latex is obtained by graft-polymerizing an aromatic vinyl monomer and a vinyl cyan monomer to a diene rubber polymer.
Wherein the diene rubber polymer is selected from the group consisting of a homopolymer of a diene monomer, a copolymer of a diene monomer and an aromatic vinyl monomer, or a copolymer of a diene monomer and a vinyl cyan monomer.
Wherein the diene monomer is selected from the group consisting of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene and mixtures of two or more thereof. ABS resin.
Wherein the copolymer of the diene monomer and the aromatic vinyl monomer is obtained by copolymerizing the aromatic vinyl monomer with the diene monomer, wherein the aromatic vinyl monomer is present in an amount of from 1 to 30, based on the total weight of the mixture of the diene monomer and the aromatic vinyl monomer By weight based on the weight of the ABS resin.
Wherein the aromatic vinyl monomer is selected from the group consisting of styrene,? -Methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, vinyltoluene and mixtures of two or more thereof.
Wherein the copolymer of the diene monomer and the vinyl cyan monomer is obtained by copolymerizing the vinyl cyan monomer with the diene monomer, wherein the vinyl cyan monomer is present in an amount of from 1 to 30, based on the total weight of the mixture of the diene monomer and the vinyl cyan monomer, By weight based on the weight of the ABS resin.
Wherein said vinyl cyan monomer is selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and mixtures of two or more thereof.
Wherein the ABS-based graft copolymer latex is obtained by mixing 12 to 48 parts by weight of an aromatic vinyl monomer with 45 to 70 parts by weight of the diene rubber polymer and graft-polymerizing the same.
Wherein the aging agent is selected from the group consisting of an alkali metal oxide, an alkaline earth metal oxide, and a mixture of two or more thereof.
Wherein the aging agent is selected from the group consisting of sodium oxide, calcium oxide, magnesium oxide, and mixtures thereof.
The aging after addition of the aging agent is carried out at a temperature of 70 to 110 ° C
Wherein the aging is carried out after agglomeration of the ABS-based graft copolymer latex, and the agglomeration is carried out by adding an aggregating agent.
Wherein the flocculant is selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, acetic acid, and mixtures of two or more thereof.
Wherein the ABS resin has a volatile content of 2.0 g or less.
(2) a latex aging step of adding 0.1 to 10 parts by weight of an aging agent based on 100 parts by weight of the ABS-based graft copolymer latex, followed by aging;
The method of claim 1,
Wherein the agglomeration step further comprises an agglomeration step between the synthesis step and the aging step.
Wherein the agglomeration step further comprises an agglomeration step between the synthesis step and the aging step.
Wherein the flow control resin is an SA-based resin or an ASA-based resin.
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| KR20130069503A KR20140146783A (en) | 2013-06-18 | 2013-06-18 | Manufacturing method of ABS resin |
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| KR20130069503A KR20140146783A (en) | 2013-06-18 | 2013-06-18 | Manufacturing method of ABS resin |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180067800A (en) * | 2016-12-13 | 2018-06-21 | 주식회사 엘지화학 | Method for preparing thermoplastic resin |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180067800A (en) * | 2016-12-13 | 2018-06-21 | 주식회사 엘지화학 | Method for preparing thermoplastic resin |
| US11326047B2 (en) | 2016-12-13 | 2022-05-10 | Lg Chem, Ltd. | Method of preparing thermoplastic resin |
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