CN114031727A - High-fluidity high-AN-content bulk ABS resin and preparation method thereof - Google Patents
High-fluidity high-AN-content bulk ABS resin and preparation method thereof Download PDFInfo
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- CN114031727A CN114031727A CN202111418165.7A CN202111418165A CN114031727A CN 114031727 A CN114031727 A CN 114031727A CN 202111418165 A CN202111418165 A CN 202111418165A CN 114031727 A CN114031727 A CN 114031727A
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- 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
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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
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
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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
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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Abstract
The invention discloses a high-fluidity high-AN-content bulk ABS and a preparation method thereof. One or more low-viscosity rubbers are selected, mixed and dissolved with styrene, ethylbenzene, acrylonitrile and a fourth monomer according to a certain proportion, and a rubber solution is prepared. The dissolved glue solution is continuously added into 4 plug flow reaction kettles which are connected in series according to a certain flow, and a certain proportion of initiator and chain transfer agent are added at a certain temperature and stirring speed to carry out rubber grafting and chain growth polymerization reaction. The rubber particle size, the polymer molecular weight and distribution, the proportion and content of the grafted rubber and SAN are controlled by means of adjusting the glue solution ratio, the initiator addition amount, the chain transfer agent addition amount, the styrene or acrylonitrile addition amount and addition mode, the temperatures of all regions of the reaction kettle, the stirring rotating speed and the like, and the polymer is conveyed to AN extruder with a vacuumizing device through a discharge pump for devolatilization and granulation after passing through a fourth reaction kettle, so that the bulk ABS with high fluidity and high AN content is produced.
Description
Technical Field
The invention belongs to the technical field of ABS, and particularly relates to a high-flow high-AN-content bulk ABS resin and a preparation method thereof.
Background
At present, the consumption structure of domestic ABS resin is mainly universal, accounts for 75 percent, the high-flow ABS resin accounts for 5 percent, and the functional resin with high impact resistance, high heat resistance, matte, low odor, food grade, medical grade and the like accounts for 20 percent. With the refinement of ABS application market, the requirements of terminal customers on the ABS resin performance are more and more strict, and the special material state is gradually highlighted, so that the high-flow ABS has a large application space, while the product structure of domestic production plants is mainly general, and the high-flow ABS production technology and products with the melt index exceeding 45g/10min mainly come from foreign imports, so that the development of the high-flow ABS resin is necessary.
The emulsion method for producing the ABS resin not only has complex process, long flow, high cost and large waste discharge amount, but also has high residual quantity in the product. Compared with emulsion process, the bulk ABS resin has simple process, short flow, less occupied land, low cost, almost no waste liquid discharge, wide application in the field of ABS modification and alloy due to the characteristics of high purity, good whiteness, easy coloring and the like, and has high demand for special ABS resin materials for the alloy.
The high-flow high-AN-content bulk ABS resin has high SAN content ratio, good compatibility with plastics such as Polycarbonate (PC), polyvinyl chloride (PVC), nylon (PA) and the like, and good processability, chemical resistance, oil resistance and permeability resistance; meanwhile, the rubber particle size of the high-fluidity high-AN-content bulk ABS is generally larger than that of emulsion ABS, and when the ABS is used together with PC as AN alloy, the ABS has a good toughening effect on AN alloy material while ensuring lower rubber content (the rubber content is large, and the compatibility of alloy resin can be influenced).
Disclosure of Invention
(I) technical problems to be solved by the invention
A high-fluidity high-AN-content bulk ABS and a preparation method thereof are disclosed, wherein low-viscosity rubber is adopted to carry out bulk polymerization in a plug flow reaction kettle with four serially connected kettles, and the rubber content, the graft particle size and the SAN molecular weight are controlled by a process means, so that the ABS resin has high fluidity and high AN content, can have good compatibility with other high polymer materials such as PC, PVC, PA and the like, and can meet the use requirement of AN alloy ABS material without adding other compatilizers.
(II) the technical scheme adopted by the invention
A preparation method of high-fluidity high-AN-content bulk ABS resin is characterized in that low-viscosity rubber, styrene, ethylbenzene, acrylonitrile and a fourth monomer are mixed to prepare a rubber solution, the rubber solution is continuously added into a plug flow reaction kettle with four serially connected kettles according to a certain flow, AN initiator and a chain transfer agent are added at a certain temperature and stirring speed, rubber grafting and chain growth polymerization are carried out, and the prepared ABS resin is prepared, wherein the melt index of the prepared ABS resin is not less than 35g/10min, and the impact strength of a simply supported beam is not less than 9 MPa.
The prepared ABS resin has a particle size of 200-1000 nm and an acrylonitrile content of 23-30%.
Preferably, each single reaction kettle is divided into three temperature zones, namely 12 zones, and the temperature of each zone is independently controlled.
Preferably, the low viscosity rubber is low cis-butadiene rubber and/or styrene-butadiene rubber.
Preferably, the fourth monomer is methyl acrylate, ethyl acrylate, butyl acrylate or methacrylate.
Preferably, the rubber solution comprises the following components in percentage by mass: 6-14% of low-viscosity rubber and 45-65% of styrene; 12-18% of ethylbenzene; 15-30% of acrylonitrile; 0.1-5% of a fourth monomer.
Preferably, the initiator is 1, 1-bis (t-butylperoxy) cyclohexane at a concentration of 50 to 500 ppm.
Preferably, the chain transfer agent is mercaptoethanol, dodecyl mercaptan, alpha-methylstyrene linear dimer, 2, 4-diphenyl-4-methyl-1-pentene or molecular weight regulator AMSD, at a concentration of 5-1000 ppm.
Preferably, the reaction temperature is 85-180 ℃; the rotating speed of the stirring paddle is 0.5-150 r/min.
Preferably, styrene or acrylonitrile can be supplemented in any one of the 6-10 zones in the reaction process, the proportion of the supplemented styrene is 0.5-10% of the mass of the total glue solution, and the proportion of the supplemented acrylonitrile is 0.5-10% of the mass of the total glue solution.
(III) technical effects of the invention
The invention controls the rubber particle size, the polymer molecular weight and distribution, the proportion and the content of the graft rubber and SAN in the polymer resin by means of adjusting the glue solution ratio, the adding amount of AN initiator, the adding amount of a chain transfer agent, the temperature of each area of a reaction kettle, the stirring speed and the like, and the polymer is conveyed to AN extruder with a vacuumizing device through a discharge pump for devolatilization and granulation after passing through a fourth reaction kettle to produce the bulk ABS with high fluidity and high AN content.
The ABS resin produced by the high-flow high-AN-content bulk ABS and the preparation method thereof have the characteristics of high AN content, high purity, white color and easy coloring, can be directly mixed with PC, PVC, PA and other high polymer materials to be used as alloy materials, solves the problem that a compatilizer needs to be added in the use of emulsion method alloy ABS, and also solves the problem that the domestic bulk method alloy ABS needs to be imported.
Drawings
FIG. 1 is a process flow diagram of bulk ABS of the present invention;
Detailed Description
The invention is further described with reference to the following figures and specific embodiments.
In fig. 1, a liquid preparation tank is used for preparing a liquid adhesive, a storage tank is used for storing the prepared liquid adhesive for later use, an auxiliary 1 is an initiator feeding tank, an auxiliary 2 is a first reaction kettle chain transfer agent feeding tank, an auxiliary 3 is a second reaction kettle chain transfer agent feeding tank, an auxiliary 4 is an auxiliary feeding tank of a third reaction kettle, wherein the auxiliary is a chain transfer agent, an antioxidant, an ethylbenzene solution supplemented with acrylonitrile (or styrene), an auxiliary 5 is a fourth reaction kettle ethylbenzene feeding tank, an extruder with a vacuumizing device is a devolatilization system of a polymer material, and a brace granulation device is arranged behind the extruder.
1) Rubber composition
The low cis-butyl rubber adopts Asahi-made 720AX, Dynax 97C, the butadiene styrene rubber adopts Indonesia 1322 and Asahi-made N210.
2) The initiator adopts 1, 1-bis (tert-butyl peroxy) cyclohexane
3) The chain transfer agent adopts n-dodecyl mercaptan
4) Concentration of formulation aid
The tank of the additive 1 is filled with 1 reaction additive, the ethylbenzene solution with the component of initiator has the concentration of 2.70 percent and the dosage range of 30-50 g/h, and the filling point is at the inlet of the first reaction kettle;
the auxiliary agent 2 tank is filled with 1 reaction auxiliary agent, the component is ethylbenzene solution of chain transfer agent, the concentration is 1.72%, the dosage range is 15-90 g/h, and the filling point is at the inlet of the first reaction kettle;
the auxiliary agent 3 tank is filled with a 2-reaction auxiliary agent, and the component is ethylbenzene solution of a chain transfer agent, and the concentration is 3.72%; the dosage range is 100-250 g/h, and the filling point is positioned on the pipeline between the first reaction kettle and the second reaction kettle;
3 reaction assistants are arranged in the assistant 4 tank, the components are chain transfer agent, acrylonitrile and ethylbenzene solution of antioxidant, and the respective concentrations are respectively 2.26%: 18.0%: 0.076%: the dosage range is 180 plus 280g/h, and the filling point is positioned on the pipeline between the second reaction kettle and the third reaction kettle;
the additive 5 tank is internally provided with 4 reaction additives, the component is ethylbenzene, the dosage range is 50-200 g/h, and the filling point is on the pipeline between the third reaction kettle and the fourth reaction kettle.
5) Temperature of the reaction kettle
The first to fourth reaction vessels are denoted by R1, R2, R3, R4 (the same applies hereinafter), respectively, in the order of feed.
Preheating at 70-85 deg.C before the kettle; the temperature range of R1 is 95-110 ℃; the temperature range of R2 is 100-130 ℃; the temperature range of R3 is 120-145 ℃; the temperature range of R4 was 135-165 ℃.
6) The rotating speeds of the stirring paddles of the four reaction kettles are controlled as shown in Table 1
TABLE 1 EXAMPLE 1-3 stirring speed control of four reactors
7) EXAMPLES 1-3 glue formulations
The raw materials were weighed in the weight percentages given in Table 2 to prepare the glue solutions of examples 1 to 3.
Table 2 examples 1-3 glue formulations table
8) The process flow and the control method are as follows:
the glue solutions are prepared according to the glue solution formulas of the embodiments 1 to 3 respectively, the glue solutions are continuously added into a reaction kettle according to a certain flow, and a certain proportion of initiator and chain transfer agent are added at a certain temperature and stirring speed to carry out rubber grafting and chain growth polymerization reaction. The particle size, the molecular weight and the distribution of SAN, the proportion and the content of rubber and SAN in the polymer resin are controlled by means of adjusting the glue solution ratio, the adding amount of AN initiator, the adding amount of a chain transfer agent, the temperature of each area of a reaction kettle, the stirring rotating speed and the like, and after passing through a fourth reaction kettle, the polymer is conveyed into AN extruder with a vacuumizing device through a discharge pump for devolatilization and granulation to prepare the high-flow high-AN-content ABS resin.
9) The feeding amount of glue solution: 2.665 kg/h
Example 1
1) The temperature control of each reaction zone is shown in Table 3
Table 3 example 1 control of temperature in various zones of the reactor
2) The dosage of each auxiliary agent
The dosage of the auxiliary agent 1 is 42 g/h; the dosage of the auxiliary agent 2 is 60 g/h; the dosage of the auxiliary agent 3 is 192 g/h; the dosage of the auxiliary agent 4 is 243 g/h; the amount of auxiliary 5 used was 52 g/h.
3) Rotating speed of stirring paddle of each reaction kettle
The stirring speed of R1 is 125R/min; the stirring speed of R2 is 125R/min; the stirring speed of R3 is 37R/min; the stirring speed of R4 is 12R/min.
Example 2
1) The temperature control of each reaction zone is shown in Table 4
Table 4 example 2 control of temperature in various zones of the reactor
2) The dosage of each auxiliary agent
The dosage of the auxiliary agent 1 is 42 g/h; the dosage of the auxiliary agent 2 is 55 g/h; the dosage of the auxiliary agent 3 is 192 g/h; the dosage of the auxiliary agent 4 is 207 g/h; the amount of auxiliary 5 used is 135 g/h.
3) Rotating speed of stirring paddle of each reaction kettle
The stirring speed of R1 is 125R/min; the stirring speed of R2 is 140R/min; the stirring speed of R3 is 37R/min; the stirring speed of R4 is 12R/min.
Example 3
1) The temperature control of each reaction zone is shown in Table 5
Table 5 example 3 control of temperature in various zones of the reactor
2) The dosage of each auxiliary agent
The dosage of the auxiliary agent 1 is 45 g/h; the dosage of the auxiliary agent 2 is 60 g/h; the dosage of the auxiliary agent 3 is 192 g/h; the dosage of the auxiliary agent 4 is 261 g/h; the amount of auxiliary 5 used was 52 g/h.
3) Rotating speed of stirring paddle of each reaction kettle
The stirring speed of R1 is 125R/min; the stirring speed of R2 is 125R/min; the stirring speed of R3 is 37R/min; the stirring speed of R4 is 12R/min.
The results of the structural and performance tests performed on the samples of examples 1-3 are shown in Table 6:
TABLE 6 structural and Performance index analysis
Claims (10)
1. A preparation method of high-fluidity high-AN-content bulk ABS resin is characterized in that low-viscosity rubber, styrene, ethylbenzene, acrylonitrile and a fourth monomer are mixed to prepare a rubber solution, the rubber solution is continuously added into a plug flow reaction kettle with four serially connected kettles according to a certain flow, AN initiator and a chain transfer agent are added at a certain temperature and stirring speed, rubber grafting and chain growth polymerization are carried out, and the prepared ABS resin is prepared, wherein the melt index of the prepared ABS resin is not less than 35g/10min, the impact strength of a simply supported beam is not less than 9MPa, and the acrylonitrile content is not less than 23%.
2. The method for preparing high-flow high-AN-content bulk ABS resin according to claim 1, wherein the four-kettle plug flow reactor is connected in series, each single reactor has three temperature zones, and the temperature in each zone is controlled independently, wherein the total number of the zones is 12.
3. The method of claim 1, wherein the low viscosity rubber is low cis-butadiene rubber and/or styrene butadiene rubber.
4. The method of claim 1, wherein the fourth monomer is methyl acrylate, ethyl acrylate, butyl acrylate or methacrylate.
5. The method for preparing the high-flow high-AN-content bulk ABS resin according to claim 1, wherein the rubber solution comprises the following components by mass percent: 6-14% of low-viscosity rubber and 45-65% of styrene; 12-18% of ethylbenzene; 15-30% of acrylonitrile; 0.1-5% of a fourth monomer.
6. The method of claim 1, wherein the initiator is 1.1-bis (t-butylperoxy) cyclohexane at a concentration of 50-500 ppm.
7. The method of claim 1, wherein the chain transfer agent is mercaptoethanol, n-dodecylmercaptan, linear dimer of alpha-methylstyrene, 2, 4-diphenyl-4-methyl-1-pentene, or molecular weight regulator AMSD, at a concentration of 5-1000 ppm.
8. The method of claim 1, wherein the reaction temperature is 85-180 ℃; the rotating speed of the stirring paddle is 0.5-150 r/min.
9. The method for preparing high-fluidity high-AN-content bulk ABS resin according to claim 1, wherein styrene or acrylonitrile can be supplemented in any one of the 6-10 zones in the reaction process, wherein the proportion of the supplemented styrene is 0.5-10% of the mass of the total glue solution, and the proportion of the supplemented acrylonitrile is 0.5-10% of the mass of the total glue solution.
10. A high flow high AN content bulk ABS resin characterized by being prepared by the process of any one of claims 1 to 9.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20050044174A (en) * | 2003-11-07 | 2005-05-12 | 주식회사 엘지화학 | Method for preparing acrylonitrile-butadiene-styrene resin |
| CN106699981A (en) * | 2016-12-16 | 2017-05-24 | 北方华锦化学工业集团有限公司 | Method of preparing transparent ABS resin by adopting continuous body device |
| CN110240778A (en) * | 2019-06-27 | 2019-09-17 | 北方华锦化学工业股份有限公司 | A kind of preparation method of ontology ABS resin |
| CN111057190A (en) * | 2019-12-11 | 2020-04-24 | 北方华锦化学工业股份有限公司 | Preparation method of high-gloss bulk ABS resin |
| CN111499813A (en) * | 2020-04-09 | 2020-08-07 | 北方华锦化学工业股份有限公司 | Method for preparing high-flow AES resin by adopting continuous bulk method |
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- 2021-11-26 CN CN202111418165.7A patent/CN114031727A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050044174A (en) * | 2003-11-07 | 2005-05-12 | 주식회사 엘지화학 | Method for preparing acrylonitrile-butadiene-styrene resin |
| CN106699981A (en) * | 2016-12-16 | 2017-05-24 | 北方华锦化学工业集团有限公司 | Method of preparing transparent ABS resin by adopting continuous body device |
| CN110240778A (en) * | 2019-06-27 | 2019-09-17 | 北方华锦化学工业股份有限公司 | A kind of preparation method of ontology ABS resin |
| CN111057190A (en) * | 2019-12-11 | 2020-04-24 | 北方华锦化学工业股份有限公司 | Preparation method of high-gloss bulk ABS resin |
| CN111499813A (en) * | 2020-04-09 | 2020-08-07 | 北方华锦化学工业股份有限公司 | Method for preparing high-flow AES resin by adopting continuous bulk method |
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