CN115141321A - Preparation method of continuous bulk ABS resin - Google Patents
Preparation method of continuous bulk ABS resin Download PDFInfo
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- CN115141321A CN115141321A CN202210735490.4A CN202210735490A CN115141321A CN 115141321 A CN115141321 A CN 115141321A CN 202210735490 A CN202210735490 A CN 202210735490A CN 115141321 A CN115141321 A CN 115141321A
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- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003292 glue Substances 0.000 claims abstract description 72
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 30
- 229920001971 elastomer Polymers 0.000 claims abstract description 29
- 239000005060 rubber Substances 0.000 claims abstract description 29
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 26
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 12
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 238000002834 transmittance Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 10
- 239000012986 chain transfer agent Substances 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 230000003068 static effect Effects 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229920002857 polybutadiene Polymers 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- 239000005064 Low cis polybutadiene Substances 0.000 claims description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 3
- -1 1, 1-di-tert-butyl cyclohexane peroxide Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 15
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- 238000011161 development Methods 0.000 description 6
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- 238000009776 industrial production Methods 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
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- 238000012827 research and development Methods 0.000 description 2
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000012780 transparent material Substances 0.000 description 2
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
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- 230000003287 optical effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
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- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
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Classifications
-
- 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
-
- 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
-
- 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
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
Abstract
The invention discloses a preparation method of continuous body transparent ABS resin, which comprises the following steps: the rubber is cut up and dissolved in solution of styrene, acrylonitrile, methyl methacrylate, butyl acrylate and ethylbenzene to prepare a glue solution, the glue solution is filtered and preheated and then is continuously added into a polymerization reaction system in two ways to carry out polymerization reaction, the first glue solution is added at the inlet of a first reactor, and the second glue solution is added at the inlet of a third reactor. And (3) allowing the material to enter a secondary devolatilization system after rubber grafting reaction, phase transition reaction and post polymerization reaction, removing the solvent and unreacted monomers, and finally extruding and granulating through a die head to obtain the continuous bulk transparent ABS resin. The transparent ABS resin rubber prepared by the invention has bimodal distribution of particle size, light transmittance of more than 88 percent, haze of less than 5 percent, good mechanical property, good melt flowability and excellent comprehensive performance. Compared with the emulsion production process, the invention has the advantages of low production investment, energy conservation, environmental protection and the like.
Description
Technical Field
The invention belongs to the technical field of synthesis and preparation of organic polymer materials, and particularly relates to a preparation method of continuous bulk transparent ABS resin.
Background
The ABS resin is a copolymer of butadiene (B), styrene (S), acrylonitrile (A) and the like, wherein rubber serving as the main component of the ABS mainly plays a toughening role, and particularly the low-temperature toughening effect is obvious; styrene mainly endows ABS resin with glossiness, rigidity and processing fluidity; acrylonitrile has good heat resistance and chemical resistance. The ABS resin is a fifth general synthetic resin behind PP, PE, PVC and PS, and has wide application.
The current industrial production of ABS is dominated by emulsion polymerization. The emulsion ABS relates to the working procedures of latex synthesis and agglomeration, latex grafting, agglomeration, dehydration and drying, SAN synthesis, blending extrusion granulation and the like, and has the advantages of long process flow, high energy consumption and more three wastes. With the development of society, people have higher and higher requirements on environmental protection, and the ABS resin prepared by the bulk method is gradually paid attention to and is the most important direction for the future development of the synthesis of the ABS resin.
The transparent ABS resin is a special resin developed on the basis of common ABS resin, has excellent mechanical property and good melt flowability, and can meet the requirement of light transmission property, so that the ABS resin is more colorful at present when the demand of transparent materials is increasingly growing.
ABS is a typical representative of rubber toughening resins, belongs to a two-phase multi-component polymer blending system, and has the defect of poor light transmission, which is mainly caused by a light scattering effect caused at the interface of two phases due to light irradiation on the surface of the ABS resin. There are two ways for ABS resins to obtain light transmission: firstly, the refractive index of a rubber dispersed phase and a matrix resin phase is matched, so that the light scattering effect is reduced and the transparent ABS resin is transparent; secondly, the rubber particle size is smaller than the visible light wavelength, the dispersion and continuous two phases are nearly uniform in optics, and the ABS resin can also be transparent.
Although high light transmittance ABS can be obtained by reducing the size of rubber particles, the mechanical properties of ABS resin are lost. Therefore, the method for preparing the transparent ABS is generally selected to adjust the refractive indexes of two phases of the dispersed phase and the continuous phase, in the two phases, the refractive index of the SAN resin is 1.569, the refractive index of the butadiene rubber is lower, the butadiene rubber is generally not used independently, and the refractive index of the butadiene styrene rubber is higher than 1.534-1.535, so that the transparent ABS is more suitable to be used as a rubber raw material of the transparent ABS resin. In order to reduce the refractive index of SAN resin phase, polymethyl methacrylate (1.492) and polybutyl acrylate (1.524) with lower refractive index can be introduced as the regulator of the refractive index for regulation, the difference of the refractive index of the final dispersed phase and the continuous phase is less than 0.009, and the ABS resin can realize transparency.
Different from other transparent materials such as PS (polystyrene), the material has low mechanical property and poor heat resistance, PMMA (polymethyl methacrylate) is brittle and easy to crack, the product has low hardness, scratch resistance and easy gloss removal, PC (polycarbonate) has high cost and high price, and the material has obvious disadvantages and limited application. Transparent ABS resins are not limited to specific fields due to their good comprehensive properties, and now have become an indispensable new polymer material in human daily life, such as transparent elements: light emitting diodes, optical disks, optical fibers, etc., household appliances: refrigerator, refrigerator-freezer food dish, TV protect screen, cold and warm light lamp shade etc. industry class: automotive interiors, commodity packaging, ornaments and the like, medical: a transparent medical tool such as a syringe. In the future, the profit of the transparent ABS resin is still considerable, the market cannot be saturated in a short time, and the research, development and production of the continuous body transparent ABS resin are close to the blank, so that the continuous body transparent ABS resin needs to be vigorously developed, and the application prospect is very wide.
The related reports of the continuous bulk transparent ABS resin are less, and the invention patent of northern Hua Jin chemical industry Co., ltd. "a method for preparing the transparent ABS resin by adopting a continuous bulk device" (the authorization publication No. CN 106699981B) mainly comprises the following steps: the invention relates to a method for preparing transparent ABS resin by adopting a continuous body device, which comprises three parts of the dissolution of butadiene styrene rubber, the body polymerization reaction of styrene, acrylonitrile and methyl methacrylate monomers and the devolatilization and granulation of the transparent ABS resin. The continuous body device adopts a two-stage series-connection tubular plug flow reactor connected in parallel to carry out continuous body polymerization, and comprises a raw material preparation system, a tubular plug flow reactor, an auxiliary agent tank system and a vacuum devolatilization extrusion granulation system. The method for preparing the transparent ABS resin by adopting the process is simple and convenient, has good stability, and can ensure that materials stay in the system for a long time, so that all monomers can fully react in the system to prepare the ABS resin with both mechanical strength and transparency. "
The above invention has the following disadvantages: the devolatilization system adopts an extruder for devolatilization, and the extruder has poor devolatilization capacity and poor devolatilization effect, so that the problems of poor product quality, high reject ratio and the like are easily caused; the polymerization system of the invention is four plug flow reactors, and has the problems of large production investment, high equipment energy consumption and the like.
At present, the research and development and production of domestic continuous transparent ABS resin are still in the initial stage. The continuous transparent ABS resin with high light transmittance, low haze, good melt flowability and mechanical properties is still in the blank stage at present at home due to high development difficulty, high process control requirement and the like. In order to break through foreign technical blockade and realize the localization of the high-performance continuous body transparent ABS resin, the invention has important strategic significance for the development of the continuous body transparent ABS industry in China and has extraordinary significance for promoting and developing the production and manufacturing technology of the continuous body transparent ABS resin in China. The invention provides a theoretical basis for the production of the continuous body transparent ABS resin and guides the industrial production of the continuous body transparent ABS resin.
Disclosure of Invention
The invention aims to provide a preparation method of continuous body transparent ABS resin, and the prepared transparent ABS resin has the advantages of high light transmittance, low haze, excellent mechanical property, good melt flowability, low investment, low cost, energy conservation, environmental protection and the like.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of continuous bulk transparent ABS resin comprises the following steps:
s1: cutting rubber, dissolving the cut rubber in solution of styrene, acrylonitrile, methyl methacrylate, butyl acrylate, ethylbenzene and the like according to a certain proportion to form glue solution, filtering and preheating the glue solution, continuously adding the glue solution into a polymerization reaction system in two paths for reaction, wherein the polymerization system is formed by connecting three plug flow reactors R1, R2 and R3 and a reactor R4 with a high-efficiency static mixing structure in series;
s2: after the polymerization reaction is finished, the materials are subjected to two-stage devolatilization to remove the solvent and unreacted monomers, and are extruded and granulated to obtain the continuous bulk transparent ABS resin.
Furthermore, the first reactor R1, the second reactor R2 and the third reactor R3 adopt a plug flow reactor with three temperature control areas, a multi-layer heat exchange coil and a paddle stirrer structure, and the fourth reactor R4 adopts a tubular reactor with three temperature control areas and a static mixing structure.
Furthermore, the selected rubber is styrene butadiene rubber and/or low cis-polybutadiene rubber, the rubber accounts for 5-20% of the total amount of the glue solution, the styrene accounts for 15-30% of the total amount of the glue solution, the acrylonitrile accounts for 5-15% of the total amount of the glue solution, the methyl methacrylate accounts for 30-50% of the total amount of the glue solution, the butyl acrylate accounts for 0-3% of the total amount of the glue solution, and the ethylbenzene accounts for 15-35% of the total amount of the glue solution.
Furthermore, 1-di-tert-butyl cyclohexane peroxide is selected as an initiator, the amount of the initiator is 0.01-0.05% of the total amount of the glue solution, n-dodecyl mercaptan is selected as a chain transfer agent, the amount of the chain transfer agent is 0.04-0.50% of the total amount of the glue solution, and an antioxidant 1076 is selected as an antioxidant, and the amount of the antioxidant is 0.1-0.3% of the total amount of the glue solution.
Furthermore, the preheating temperature is 80-85 ℃, the temperature range of the first reactor R1 is 90-130 ℃, the temperature range of the second reactor R2 is 110-140 ℃, the temperature range of the third reactor R3 is 120-160 ℃, and the temperature range of the fourth reactor R4 is 140-180 ℃.
Furthermore, the glue solution is continuously added into the polymerization system in two strands, wherein the first strand of glue solution is added at the inlet of the first reactor, the second strand of glue solution is added at the inlet of the third reactor, the adding amount of the first strand of glue solution accounts for 70-100% of the total adding amount of the glue solution, and the adding amount of the second strand of glue solution accounts for 0-30% of the total adding amount of the glue solution.
Further, the transparent ABS resin has a light transmittance of more than 88% and a haze of less than 5%.
The beneficial effects of the invention are:
1. at present, the research and development and production of the domestic continuous transparent ABS resin are in a starting stage, the invention aims to break through the technical blockade of international patents, develop the continuous transparent ABS resin which has excellent performances such as high mechanical property, good melt flowability, high light transmittance, low haze and the like and has independent intellectual property rights, has very important strategic significance for realizing the domestic production of the high-performance continuous transparent ABS resin, and has extraordinary significance for promoting and developing the industrialized production and manufacturing technology of the continuous transparent ABS resin with the independent intellectual property rights in China. The invention provides a theoretical basis for the industrial production of the continuous body transparent ABS resin and guides the future industrial development direction of the continuous body transparent ABS resin.
2. The invention provides a preparation method of continuous bulk transparent ABS resin.A polymerization system consists of three plug flow reactors with three temperature control areas, a plurality of layers of heat exchange coil pipes and a flat paddle stirring structure and a tubular reactor with three temperature control areas and a high-efficiency static mixing structure. Compared with the traditional production process that a polymerization system adopts a kettle type reactor, the plug flow reactor selected by the invention has the advantages of excellent heat exchange efficiency, high rubber grafting efficiency and the like; the shutdown cleaning equipment of the plug flow reactor has long period and small influence on the productivity; the plug flow reactor has the advantages of no wall material hanging phenomenon, no influence of variegated acrylonitrile oligomer on the color of the product, no influence of acrylonitrile steam on the gas-liquid phase balance and liquid phase component change in the reactor and the like. The invention has the advantages of high production efficiency, good product quality and the like.
3. Compared with the traditional polymerization process that all reactors adopt plug flow reactors, the fourth reactor adopts a tubular reactor with a high-efficiency static mixing structure, and the preparation method of the continuous bulk transparent ABS resin has the advantages of low manufacturing cost, low maintenance cost, low energy consumption in the using process and the like.
4. According to the preparation method of the continuous body transparent ABS resin, provided by the invention, a polymerization system mode that glue solution is continuously added into two strands is adopted, the performance of the prepared transparent ABS resin is obviously superior to that of the traditional polymerization process, the rubber particle size is in bimodal distribution, the impact strength of the product is high, and the color degree is good.
Drawings
FIG. 1 is a process diagram of the continuous transparent ABS resin.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
The embodiment of the invention provides a preparation method of continuous body transparent ABS resin, which comprises the following steps:
the first step is as follows: cutting a certain amount of rubber into pieces, dissolving the rubber pieces into solutions of styrene, acrylonitrile, methyl methacrylate, butyl acrylate, ethylbenzene and the like according to a proportion to form a glue solution, filtering and preheating the glue solution, and then continuously adding the glue solution into a polymerization system in two paths, wherein the polymerization system is formed by connecting three plug flow reactors R1, R2 and R3 and a fourth reactor R4 with a high-efficiency static mixing structure in series; wherein the rubber is selected from styrene butadiene rubber and/or low cis-polybutadiene rubber, the rubber accounts for 5-20% of the total amount of the glue solution, the styrene accounts for 15-30% of the total amount of the glue solution, the acrylonitrile accounts for 5-15% of the total amount of the glue solution, the methyl methacrylate accounts for 30-50% of the total amount of the glue solution, the butyl acrylate accounts for 0-3% of the total amount of the glue solution, and the ethylbenzene accounts for 15-30% of the total amount of the glue solution; wherein the preheating temperature is 80-85 ℃, the temperature range of the first reactor R1 is 90-130 ℃, the temperature range of the second reactor R2 is 110-140 ℃, the temperature range of the third reactor R3 is 120-160 ℃, and the temperature range of the fourth reactor R4 is 140-180 ℃;
the second step is that: adding a first strand of glue solution at an inlet of a first reactor R1, adding a second strand of glue solution at an inlet of a third reactor R3, wherein the adding amount of the first strand of glue solution accounts for 70-100% of the adding total amount of the two strands of glue solutions, and the adding amount of the second strand of glue solution accounts for 0-30% of the adding total amount of the two strands of glue solutions; wherein, 1-di-tert-butyl cyclohexane peroxide is selected as an initiator, the dosage of the initiator is 0.01-0.05% of the total amount of the glue solution, n-dodecyl mercaptan is selected as a chain transfer agent, the dosage of the chain transfer agent is 0.04-0.50% of the total amount of the glue solution, an antioxidant 1076 is selected as an antioxidant, and the dosage of the antioxidant is 0.1-0.3% of the total amount of the glue solution;
the third step: after the polymerization reaction is finished, the materials are subjected to two-stage devolatilization to remove the solvent and unreacted monomers, and are extruded and granulated to obtain the transparent ABS resin, wherein the two-stage devolatilization devices are D1 and D2 in the attached drawing 1.
Referring to fig. 1, in the first step, the first reactor R1, the second reactor R2, and the third reactor R3 are plug flow reactors having three temperature control regions, a multi-layer heat exchange coil, and a flat-blade stirrer structure, and the fourth reactor R4 is a tubular reactor having three temperature control regions, a high-efficiency static mixing structure; in the figure 1, a first strand of glue solution, an initiator, a chain transfer agent and the like are added into a first reactor R1 together for polymerization reaction; and the second strand of glue solution and the effluent material of the second reactor R2 sequentially enter a third reactor R3 and a fourth reactor R4 for polymerization reaction.
In order to further explain the invention better, the following examples illustrate the advantages of the invention, but the invention is not limited thereto.
Example 1:
the glue solution is added into a polymerization system without splitting, the transparent ABS resin is prepared from methyl methacrylate with different dosages, and other unexplained parameters are carried out according to conventional conditions or parameters recommended by manufacturers.
Wherein the polymerization system is formed by connecting three plug flow reactors and a tubular reactor in series; the other devices comprise a gel cutting device, a sol device, a solution storage tank, a devolatilization device, an extrusion device, a granulation device and the like.
The raw materials comprise styrene, acrylonitrile, styrene butadiene rubber, methyl methacrylate and butyl acrylate, and the solvent is ethylbenzene. The sol solution comprises the following raw materials in proportion: 27% of styrene, 9% of rubber, 9% of acrylonitrile, 29.8% of methyl methacrylate, 0.2% of butyl acrylate and 25% of ethylbenzene.
The amount of each auxiliary agent (accounting for the percentage content of the glue solution) is as follows: the dosage of the initiator is 0.02 percent, the dosage of the chain transfer agent is 0.2 percent, and the dosage of the antioxidant is 0.2 percent.
The method comprises the following specific steps:
the method comprises the following steps: cutting rubber, dissolving the rubber in monomer such as styrene, acrylonitrile, methyl methacrylate, butyl acrylate and the like and solvent ethylbenzene prepared according to a certain proportion to form a rubber solution, filtering and preheating the rubber solution to a specific temperature (the temperature of a preheater is 85 +/-1 ℃), adding the rubber solution into a first plug flow reactor R1 from the top through a speed regulating gear pump, an initiator, a chain transfer agent and other auxiliaries to perform rubber grafting reaction, wherein the reaction temperature of each upper region, the reaction temperature of each middle region and the reaction temperature of each lower region of the R1 are respectively 110.3 ℃, 115.5 ℃, 119.9 ℃, and the stirring speed is 28 rpm;
step two: the material flows out from the bottom of the first reactor R1 and then enters the second plug flow reactor R2 from the top to carry out phase transition reaction, the reaction temperature of each zone above, in the middle and below the R2 is respectively 122.2 ℃,127.3 ℃, 132.2 ℃, and the stirring speed is 26 rpm;
the material flows out from the bottom of the second reactor R2 and then enters a third plug flow reactor R3 from the top for polymerization reaction, the reaction temperature of each zone above, in the middle and below the R3 is 136.8 ℃, 142.2 ℃ and 147.5 ℃, and the stirring speed is 15 rpm;
the material flows out from the bottom of the third reactor R3 and then enters the tubular reactor R4 from the top to continue the post-polymerization reaction, and the reaction temperature of each zone of the R4 is 151.7 ℃,157.1 ℃ and 162.1 ℃;
step three: and after the reaction is finished, performing secondary devolatilization and granulation on the materials to obtain the transparent ABS resin.
The performance of the transparent ABS resin obtained in example 1 was measured, and the results were as follows:
example 2:
the glue solution was divided into two streams and added to the polymerization system, the first stream of glue solution accounted for 80% of the total amount of glue solution, the second stream of glue solution accounted for 20% of the total amount of glue solution, and the rest conditions were the same as in example 1. Other unspecified parameters were performed according to conventional conditions or using the manufacturer's recommended parameters.
The performance of the transparent ABS resin obtained in example 2 was measured, and the results were as follows:
therefore, the performance of the transparent ABS resin prepared by adding the glue solution in two strands is obviously superior to that of the transparent ABS resin prepared by adding the glue solution in two strands.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (7)
1. A preparation method of continuous bulk transparent ABS resin comprises the following steps:
s1: adding the cut rubber into solutions of styrene, acrylonitrile, methyl methacrylate, butyl acrylate, ethylbenzene and the like according to a formula ratio, stirring and dissolving completely to form a glue solution, filtering and preheating the glue solution, and continuously adding the glue solution into a polymerization reaction system for polymerization reaction, wherein the polymerization system is formed by connecting three plug flow reactors R1, R2 and R3 and a tubular reactor R4 with a high-efficiency static mixing structure in series;
s2: after the polymerization reaction is finished, the materials are subjected to two-stage devolatilization to remove the solvent and the unreacted monomer, and the transparent ABS resin is obtained through granulation.
2. The method for preparing continuous bulk transparent ABS resin according to claim 1, wherein the first reactor R1, the second reactor R2 and the third reactor R3 are plug flow reactors having three temperature control regions, a multi-layer heat exchange coil and a flat paddle stirring structure, and the fourth reactor R4 is a tubular reactor having three temperature control regions and a high-efficiency static mixing structure.
3. The preparation method of the continuous transparent ABS resin, according to claim 1, wherein the selected rubber is styrene butadiene rubber and/or low cis-polybutadiene rubber, the rubber accounts for 5% -20% of the total amount of the glue solution, the styrene accounts for 15% -30% of the total amount of the glue solution, the acrylonitrile accounts for 5% -15% of the total amount of the glue solution, the methyl methacrylate accounts for 30% -50% of the total amount of the glue solution, the butyl acrylate accounts for 0-3% of the total amount of the glue solution, and the ethylbenzene accounts for 15% -35% of the total amount of the glue solution.
4. The method for preparing continuous transparent ABS resin according to claim 1, wherein 1, 1-di-tert-butyl cyclohexane peroxide is used as the initiator, the amount of the initiator is 0.01% -0.05% of the total amount of the glue solution, n-dodecyl mercaptan is used as the chain transfer agent, the amount of the chain transfer agent is 0.04% -0.50% of the total amount of the glue solution, antioxidant 1076 is used as the antioxidant, and the amount of the antioxidant is 0.1% -0.3% of the total amount of the glue solution.
5. The method for preparing a continuous bulk transparent ABS resin according to claim 1, wherein the preheating temperature range is 80-85 ℃, the temperature range of the first reactor R1 is 90-130 ℃, the temperature range of the second reactor R2 is 110-140 ℃, the temperature range of the third reactor R3 is 120-160 ℃, and the temperature range of the fourth reactor R4 is 140-180 ℃.
6. The method according to claim 1, wherein the first and second glue solutions are continuously added to the polymerization system, the first glue solution is added at the inlet of the first reactor, the second glue solution is added at the inlet of the third reactor, the first glue solution accounts for 70-100% of the total glue solution, and the second glue solution accounts for 0-30% of the total glue solution.
7. The method of claim 1, wherein the transparent ABS resin has a light transmittance of more than 88% and a haze of less than 5%.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130610A (en) * | 2006-08-23 | 2008-02-27 | 中国石油天然气集团公司 | Toughness reinforcing phenylethylene resin composition of transparent rubber and method for preparing the same |
| WO2009012900A1 (en) * | 2007-07-20 | 2009-01-29 | Polimeri Europa S.P.A. | Process for the preparation of transparent, impact-resistant, vinyl aromatic copolymers |
| US20090143532A1 (en) * | 2006-08-16 | 2009-06-04 | Cheil Industries Inc. | Transparent Rubber Modified Styrene Resin and Method for Preparing the Same by Continuous Bulk Polymerization |
| KR20100062417A (en) * | 2008-12-02 | 2010-06-10 | 주식회사 엘지화학 | Transparent resin having excellent heat resistance and impact resistance and method for preparing the same |
| CN104250417A (en) * | 2013-06-28 | 2014-12-31 | 第一毛织株式会社 | Transparent thermoplastic resin composition having improved whitening resistance at low temperature and excellent impact strength |
| CN113583186A (en) * | 2021-09-09 | 2021-11-02 | 科元控股集团有限公司 | Production method of continuous bulk ABS resin |
-
2022
- 2022-06-27 CN CN202210735490.4A patent/CN115141321A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090143532A1 (en) * | 2006-08-16 | 2009-06-04 | Cheil Industries Inc. | Transparent Rubber Modified Styrene Resin and Method for Preparing the Same by Continuous Bulk Polymerization |
| CN101130610A (en) * | 2006-08-23 | 2008-02-27 | 中国石油天然气集团公司 | Toughness reinforcing phenylethylene resin composition of transparent rubber and method for preparing the same |
| WO2009012900A1 (en) * | 2007-07-20 | 2009-01-29 | Polimeri Europa S.P.A. | Process for the preparation of transparent, impact-resistant, vinyl aromatic copolymers |
| KR20100062417A (en) * | 2008-12-02 | 2010-06-10 | 주식회사 엘지화학 | Transparent resin having excellent heat resistance and impact resistance and method for preparing the same |
| CN104250417A (en) * | 2013-06-28 | 2014-12-31 | 第一毛织株式会社 | Transparent thermoplastic resin composition having improved whitening resistance at low temperature and excellent impact strength |
| CN113583186A (en) * | 2021-09-09 | 2021-11-02 | 科元控股集团有限公司 | Production method of continuous bulk ABS resin |
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