CN113736028B - Preparation method of industrial ASA resin emulsion - Google Patents
Preparation method of industrial ASA resin emulsion Download PDFInfo
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- CN113736028B CN113736028B CN202110922462.9A CN202110922462A CN113736028B CN 113736028 B CN113736028 B CN 113736028B CN 202110922462 A CN202110922462 A CN 202110922462A CN 113736028 B CN113736028 B CN 113736028B
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- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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Abstract
The invention discloses a preparation method of an industrial ASA resin emulsion, which comprises a seed emulsion preparation process, a PBA emulsion synthesis process and an ASA resin emulsion synthesis process. The seed emulsion outlet is connected with the seed emulsion standing kettle inlet, the seed emulsion standing kettle is connected with the PBA emulsion synthesis kettle inlet, the PBA emulsion synthesis kettle outlet is connected with the ASA emulsion synthesis kettle inlet, qualified ASA resin emulsion is extracted from the ASA emulsion synthesis kettle and finally subjected to a separation process, and large-scale and industrial production of high-performance ASA resin emulsion is realized through the process flow.
Description
Technical Field
The invention relates to the field of new material preparation, and particularly relates to a preparation method of an industrial ASA resin emulsion.
Background
ASA resin is a short name for butyl acrylate-styrene-acrylonitrile graft copolymer. After the raw materials of butyl acrylate, styrene and acrylonitrile are prepared into ASA resin emulsion, the ASA resin particles are finally obtained through the processes of demulsification, centrifugation, drying and the like. ASA is a new material with excellent performance, has the advantages of excellent weather resistance, oxidation resistance, good mechanical property, coloring performance, higher electrical insulation, corrosion resistance, oil resistance and the like, is widely applied to the fields of automobiles, building materials, electronic products and the like, and has huge market potential. At present, domestic industrial production ASA process devices mainly adopt foreign technologies, and technical disclosure related to ASA resin industrial process flow is not available.
Disclosure of Invention
The invention provides a preparation method of an industrial ASA resin emulsion, which can realize large-scale and industrial production of high-performance ASA resin emulsion.
The invention relates to a preparation method of an industrial ASA resin emulsion, which comprises the following steps:
adding deionized water, butyl acrylate, a cross-linking agent, an emulsifier and an initiator into a seed emulsion preparation kettle, and heating and stirring for reaction to obtain seed emulsion, wherein the reaction temperature is 20-200 ℃, the reaction pressure is-0.1-1 MpaG, and the stirring speed is 40-400 r/min;
introducing the seed emulsion into a seed emulsion standing kettle, and standing for 1-72 hours to obtain standing seed emulsion, wherein 2-24 seed emulsion standing kettles are arranged;
step (3) introducing the seed emulsion after standing, an emulsifier, styrene, an acrylonitrile monomer, a reducing agent and deionized water into a PBA synthesis kettle, and reacting in an inert atmosphere to obtain PBA emulsion, wherein the reaction temperature is 20-200 ℃, the reaction time is 1-16 h, the reaction pressure is-0.1-1 MpaG, and the stirring speed is 40-400 r/min;
and (4) introducing the PBA emulsion, styrene, an acrylonitrile monomer and a reducing agent into an ASA synthesis kettle, and reacting to obtain the ASA emulsion, wherein the reaction temperature is 20-200 ℃, the reaction time is 1-16 h, the reaction pressure is 0-1 MpaG, and the stirring speed is 40-400 r/min.
Preferably, in the step (1), the weight ratio of the deionized water, the butyl acrylate, the cross-linking agent, the emulsifier and the initiator is 50-100.
Preferably, in the step (3), the weight ratio of the seed emulsion, the emulsifier, the styrene, the acrylonitrile monomer, the reducing agent and the deionized water is 40-100.
Preferably, in the step (4), the weight ratio of the PBA emulsion to the styrene to the acrylonitrile monomer to the reducing agent is 40-100: 10-50: 1-10.
Preferably, the cross-linking agent is one or a mixture of more of ethylene glycol diacrylate, butylene glycol diacrylate, hexanediol diacrylate, methyl methacrylate and propyl methacrylate.
Preferably, the initiator is any one or a mixture of more of hydrogen peroxide, sodium persulfate, cumene hydroperoxide, dicumyl peroxide, lauroyl peroxide and tert-butyl peroxybenzoate.
Preferably, the emulsifier is any one or a mixture of several of sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride and octadecyl trimethyl ammonium chloride.
Preferably, the reducing agent is any one or a mixture of several of ferrous sulfate, ferrous chloride, sodium thiosulfate, sodium sulfite, sodium borohydride and lithium borohydride.
The invention provides a preparation method of an industrial ASA resin emulsion, which comprises a seed emulsion preparation process, a PBA emulsion synthesis process and an ASA resin emulsion synthesis process. The seed emulsion outlet is connected with the seed emulsion standing kettle inlet, the seed emulsion standing kettle is connected with the PBA emulsion synthesis kettle inlet, the PBA emulsion synthesis kettle outlet is connected with the ASA emulsion synthesis kettle inlet, qualified ASA resin emulsion is extracted from the ASA emulsion synthesis kettle and finally subjected to a separation process, and large-scale and industrial production of high-performance ASA resin emulsion is realized through the process flow.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a process flow diagram of the preparation method of the industrial ASA resin emulsion of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Referring to fig. 1, an embodiment 1 of the present invention provides a method for preparing an industrial ASA resin emulsion, including the following steps:
(1) Adding deionized water, butyl acrylate, ethylene glycol diacrylate, sodium dodecyl sulfate and hydrogen peroxide into a seed emulsion preparation kettle according to a weight ratio of 70;
(2) Introducing the seed emulsion into a seed emulsion standing kettle, standing for 6 hours to obtain standing seed emulsion, wherein the number of the seed emulsion standing kettles is 3, incoming materials are received in the first seed emulsion standing kettle, the number of the seed emulsion standing kettles is two, and the number of the seed emulsion standing kettles is three, and downstream feeding is carried out in the third seed emulsion standing kettle;
(3) Pumping the seed emulsion after standing, sodium dodecyl sulfate, styrene, an acrylonitrile monomer, ferrous sulfate and deionized water into a PBA synthesis kettle according to a weight ratio of 70;
(4) Introducing the PBA emulsion, styrene, an acrylonitrile monomer and ferrous sulfate into an ASA synthesis kettle according to a weight ratio of 70:30: 7:2, keeping the temperature for reaction for 2 hours, reacting to obtain an ASA emulsion, wherein the reaction temperature is 50 ℃, the reaction pressure is 0.05MpaG, the stirring speed is 100r/min, extracting the prepared ASA emulsion from the ASA synthesis kettle, and performing separation processes such as demulsification, centrifugation, drying and the like to finally obtain ASA resin particles.
Example 2
Referring to fig. 1, embodiment 2 of the present invention provides a method for preparing an industrial ASA resin emulsion, including the following steps:
(1) Adding deionized water, butyl acrylate, methyl methacrylate, sodium dodecyl sulfate and sodium persulfate into a seed emulsion preparation kettle according to a weight ratio of 60;
(2) Introducing the seed emulsion into a seed emulsion standing kettle, standing for 6 hours to obtain standing seed emulsion, wherein the number of the seed emulsion standing kettles is 3, incoming materials are received in the first seed emulsion standing kettle, the number of the seed emulsion standing kettles is two, and the number of the seed emulsion standing kettles is three, and downstream feeding is carried out in the third seed emulsion standing kettle;
(3) Pumping the seed emulsion after standing, sodium dodecyl sulfate, styrene, an acrylonitrile monomer, ferrous sulfate and deionized water into a PBA synthesis kettle according to a weight ratio of 70;
(4) Introducing the PBA emulsion, styrene, an acrylonitrile monomer and ferrous sulfate into an ASA synthesis kettle according to a weight ratio of 70:30: 7:2, keeping the temperature for reaction for 2 hours, reacting to obtain an ASA emulsion, wherein the reaction temperature is 50 ℃, the reaction pressure is 0.05MpaG, the stirring speed is 100r/min, extracting the prepared ASA emulsion from the ASA synthesis kettle, and performing separation processes such as demulsification, centrifugation, drying and the like to finally obtain ASA resin particles.
Example 3
Referring to fig. 1, embodiment 3 of the present invention provides a method for preparing an industrial ASA resin emulsion, including the following steps:
(1) Adding deionized water, butyl acrylate, ethylene glycol diacrylate, sodium dodecyl sulfate and hydrogen peroxide into a seed emulsion preparation kettle according to a weight ratio of 70;
(2) Introducing the seed emulsion into a seed emulsion standing kettle, standing for 12h to obtain standing seed emulsion, wherein the number of the seed emulsion standing kettles is 3, incoming materials are received in the first seed emulsion standing kettle, the number of the seed emulsion standing kettles is two, and the number of the seed emulsion standing kettles is three for downstream feeding;
(3) Pumping the seed emulsion after standing, sodium dodecyl sulfate, styrene, an acrylonitrile monomer, ferrous sulfate and deionized water into a PBA synthesis kettle according to a weight ratio of 70;
(4) Introducing the PBA emulsion, styrene, an acrylonitrile monomer and ferrous sulfate into an ASA synthesis kettle according to a weight ratio of 70:30: 7:2, keeping the temperature for reaction for 2 hours, reacting to obtain an ASA emulsion, wherein the reaction temperature is 60 ℃, the reaction pressure is 0.10MpaG, the stirring speed is 150r/min, extracting the prepared ASA emulsion from the ASA synthesis kettle, and performing separation processes such as demulsification, centrifugation, drying and the like to finally obtain ASA resin particles.
Example 4
Referring to fig. 1, embodiment 4 of the present invention provides a method for preparing an industrial ASA resin emulsion, including the following steps:
(1) Adding deionized water, butyl acrylate, ethylene glycol diacrylate, sodium dodecyl sulfate and hydrogen peroxide into a seed emulsion preparation kettle according to a weight ratio of (80);
(2) Introducing the seed emulsion into a seed emulsion standing kettle, standing for 6 hours to obtain standing seed emulsion, wherein the number of the seed emulsion standing kettles is 3, incoming materials are received in the first seed emulsion standing kettle, the number of the seed emulsion standing kettles is two, and the number of the seed emulsion standing kettles is three, and downstream feeding is carried out in the third seed emulsion standing kettle;
(3) Pumping the seed emulsion after standing, sodium dodecyl sulfate, styrene, an acrylonitrile monomer, ferrous sulfate and deionized water into a PBA synthesis kettle according to a weight ratio of (75);
(4) Introducing the PBA emulsion, styrene, an acrylonitrile monomer and ferrous sulfate into an ASA synthesis kettle according to a weight ratio of 80: 25: 5:3, keeping the temperature for reaction for 2 hours, reacting to obtain an ASA emulsion, wherein the reaction temperature is 50 ℃, the reaction pressure is 0.05MpaG, the stirring speed is 100r/min, extracting the prepared ASA emulsion from the ASA synthesis kettle, and performing separation processes such as demulsification, centrifugation, drying and the like to finally obtain ASA resin particles.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (5)
1. A preparation method of industrial ASA resin emulsion is characterized by comprising a seed emulsion preparation process, a PBA emulsion synthesis process and an ASA resin emulsion synthesis process, wherein a seed emulsion outlet is connected with a seed emulsion standing kettle inlet, the seed emulsion standing kettle is connected with a PBA emulsion synthesis kettle inlet, the PBA emulsion synthesis kettle outlet is connected with an ASA emulsion synthesis kettle inlet, and qualified ASA resin emulsion is extracted from the ASA emulsion synthesis kettle and finally subjected to a separation process;
the method specifically comprises the following steps:
adding deionized water, butyl acrylate, a cross-linking agent, an emulsifier and an initiator into a seed emulsion preparation kettle, and heating and stirring for reaction to obtain seed emulsion, wherein the reaction temperature is 20-200 ℃, the reaction pressure is-0.1-1 MpaG, and the stirring speed is 40-400 r/min; the weight ratio of the deionized water to the butyl acrylate to the crosslinking agent to the emulsifier to the initiator is (50-100);
introducing the seed emulsion into a seed emulsion standing kettle, and standing for 1-72 hours to obtain standing seed emulsion, wherein the number of the seed emulsion standing kettles is 3, the incoming material is received by the first seed emulsion standing kettle, the second seed emulsion standing kettle is used for standing, and the third seed emulsion standing kettle is used for feeding at the downstream;
step (3) introducing the seed emulsion after standing, an emulsifier, styrene, an acrylonitrile monomer, a reducing agent and deionized water into a PBA synthesis kettle, and reacting in an inert atmosphere to obtain PBA emulsion, wherein the reaction temperature is 20-200 ℃, the reaction time is 1-16 h, the reaction pressure is-0.1-1 MpaG, and the stirring speed is 40-400 r/min; the weight ratio of the seed emulsion to the emulsifier to the styrene to the acrylonitrile monomer to the reducing agent to the deionized water is (40-100);
introducing the PBA emulsion, styrene, an acrylonitrile monomer and a reducing agent into an ASA synthesis kettle, and reacting to obtain an ASA emulsion, wherein the reaction temperature is 20-200 ℃, the reaction time is 1-16 h, the reaction pressure is 0-1 MpaG, and the stirring speed is 40-400 r/min;
the weight ratio of the PBA emulsion, the styrene, the acrylonitrile monomer and the reducing agent is 40-100: 10-50: 1-10.
2. The method of claim 1, wherein the cross-linking agent is selected from the group consisting of ethylene glycol diacrylate, butylene glycol diacrylate, hexylene glycol diacrylate, methyl methacrylate, and propyl methacrylate.
3. The method for preparing an industrial ASA resin emulsion as claimed in claim 1, wherein the initiator is selected from one or more of hydrogen peroxide, sodium persulfate, cumene hydroperoxide, dicumyl peroxide, lauroyl peroxide, and tert-butyl peroxybenzoate.
4. The method of claim 1, wherein the emulsifier is selected from the group consisting of sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, and octadecyl trimethyl ammonium chloride.
5. The method for preparing an industrial ASA resin emulsion as claimed in claim 1, wherein the reducing agent is selected from one or more of ferrous sulfate, ferrous chloride, sodium thiosulfate, sodium sulfite, sodium borohydride and lithium borohydride.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6077903A (en) * | 1998-05-12 | 2000-06-20 | The Goodyear Tire Rubber Company | Continuous process for producing rubbery polymer |
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| KR101223295B1 (en) * | 2010-07-06 | 2013-01-16 | 주식회사 엘지화학 | Ｍｅｔｈｏｄ ｏｆ ｒｕｂｂｅｒｙ ｐｏｌｙｍｅｒ ａｎｄ ｒｕｂｂｅｒ ｒｅｉｎｆｏｒｃｅｄ ｔｈｅｒｍｏｐｌａｓｔｉｃｓ ｕｓｉｎｇ ｔｈｅ ｓａｍｅ |
| CN103254365B (en) * | 2013-05-17 | 2015-03-25 | 合肥工业大学 | Method for preparing ASA (Acrylonitrile-Styrene-Acrylate) copolymer latex by using water-solubility redox initiator at low temperature |
| CN105273142B (en) * | 2014-12-12 | 2018-08-21 | 东海昊桦新材料科技有限公司 | A kind of preparation method and its device of AAS weatherabilities resin |
| CN105647047B (en) * | 2016-01-21 | 2018-01-16 | 天津中财型材有限责任公司 | Chemical modification asa resin and its preparation method and application |
| KR102207173B1 (en) * | 2018-08-08 | 2021-01-25 | 주식회사 엘지화학 | Method for preparing graft copolymer, graft copolymer and thermoplastic resin products |
| CN109627387A (en) * | 2018-12-04 | 2019-04-16 | 重庆云天化瀚恩新材料开发有限公司 | Acrylate-styrene bipolymer-acrylonitrile core-shell graft copolymer preparation method |
| CN110845670A (en) * | 2019-12-11 | 2020-02-28 | 临朐齐力催化剂有限公司 | ASA resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6077903A (en) * | 1998-05-12 | 2000-06-20 | The Goodyear Tire Rubber Company | Continuous process for producing rubbery polymer |
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