CN115894808A - Low-crystal-point plate-grade ABS material and preparation method thereof - Google Patents
Low-crystal-point plate-grade ABS material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003292 glue Substances 0.000 claims abstract description 11
- 238000012662 bulk polymerization Methods 0.000 claims abstract description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000003999 initiator Substances 0.000 claims abstract description 6
- 239000005064 Low cis polybutadiene Substances 0.000 claims abstract description 5
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 5
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 13
- 238000001125 extrusion Methods 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical group CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical group CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 4
- 229920002313 fluoropolymer Polymers 0.000 claims description 3
- 239000004811 fluoropolymer Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000010094 polymer processing Methods 0.000 abstract description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 36
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 27
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 26
- 239000013078 crystal Substances 0.000 description 11
- 229920001971 elastomer Polymers 0.000 description 7
- 239000005060 rubber Substances 0.000 description 7
- 239000010408 film Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Landscapes
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of polymer composite materials, and discloses a method for preparing a low-crystal-point plate-grade ABS material by a bulk method, which specifically comprises the following steps: s1: dissolving 8-9 parts by mass of low cis-polybutadiene rubber, 13-15 parts by mass of ethylbenzene, 50-60 parts by mass of styrene and 15-25 parts by mass of acrylonitrile, filtering by a filter screen, and preheating to obtain a raw glue solution; s2: respectively conveying the raw glue solution, the initiator, the chain transfer agent and the auxiliary agent to a four-stage reaction kettle for continuous bulk polymerization, wherein each stage reaction kettle is provided with three temperature zones; s3: feeding the polymerized material into a devolatilization device, and performing primary devolatilization and secondary devolatilization to obtain a devolatilized material; s4: and adding a fluorine-containing polymer processing aid PPA accounting for 4-6% of the mass of the devolatilized material into the devolatilized material, and granulating in an extruder to obtain the low-crystalline-point plate-grade ABS material. The obtained product has the characteristics of low gloss and low gel, and the ground color is pure white, so that the ABS material has good impact strength and tensile strength.
Description
Technical Field
The invention relates to the technical field of polymer composite materials, and discloses a preparation method of a low-crystalline-point plate-grade ABS material.
Background
The ABS resin is an acrylonitrile-butadiene-styrene terpolymer, has good impact resistance, high glossiness and processability, is widely applied to the fields of automobiles, household appliances, toys and the like, and is one of the most widely used polymer materials with the largest output at present.
The plate-grade ABS resin is the ABS resin with the largest domestic consumption and higher technical content, but most of the plate-grade ABS resins depend on import. Many ABS manufacturers have completed the development of plate-grade ABS series products and have a certain market. With the continuous development of high-end products in marketing, beautiful appearance is required besides excellent performance of the products, and the products prepared from the low-crystal-point plate-grade ABS material have good appearance.
Generally, the thinner the ABS material plate is, the more obvious the crystal point is, so the crystal point problem directly restricts the application field of the plate-grade ABS resin. At present, the method for reducing the crystal point in the material mainly depends on the subsequent processing process, and the low-crystal-point plate-grade ABS material is difficult to directly synthesize and prepare.
Disclosure of Invention
The invention has the conception that the low-crystal-point plate-grade ABS material is prepared by utilizing a bulk polymerization method and selecting proper rubber and adjusting the content and process parameters of each component of the raw materials.
In a first aspect, the invention provides a method for preparing a low-crystalline-point plate-grade ABS material by a bulk method, which specifically comprises the following steps:
s1: dissolving 8-9 parts by mass of low cis-polybutadiene rubber, 13-15 parts by mass of ethylbenzene, 50-60 parts by mass of styrene and 15-25 parts by mass of acrylonitrile, filtering by a filter screen, and preheating to obtain a raw glue solution;
s2: mixing the raw glue solution obtained in the step S1 according to the following mass part ratio: 100 parts by mass of a raw glue solution, 0.5-1 part by mass of an initiator, 0.5-1 part by mass of a chain transfer agent, 0.5-1 part by mass of an antioxidant and 1-3 parts by mass of silicone oil; conveying the uniformly mixed solution to a four-stage reaction kettle for continuous bulk polymerization, wherein each stage reaction kettle is provided with three temperature zones;
s3: feeding the polymerized material into a devolatilizer, and performing primary devolatilization and secondary devolatilization to obtain a devolatilized material;
s4: and adding a fluoropolymer processing aid PPA accounting for 4-6% of the mass of the devolatilized material into the devolatilized material, and granulating in an extruder to obtain the low-crystalline-point plate-grade ABS material.
Preferably, in the step S2, the initiator is 1, 1-bis (tert-butylperoxy) cyclohexane, the chain transfer agent is n-dodecyl mercaptan, and the antioxidant is antioxidant 168 or 1010.
Preferably, the low cis polybutadiene rubber is one or a mixture of two of 55AE and 255T.
Preferably, the filter screen in the step S1 is 100-120 meshes, and the preheating temperature is 50-80 ℃.
Preferably, the temperatures of the upper temperature zone, the middle temperature zone and the lower temperature zone of the fourth reaction kettle are 135-150 ℃, 145-155 ℃ and 150-160 ℃ respectively.
Preferably, the temperatures of the upper temperature zone, the middle temperature zone and the lower temperature zone of the first reaction kettle, the second reaction kettle and the third reaction kettle in the four-stage reaction kettle are 95-130 ℃.
Preferably, in the step S3, the temperature of the first stage devolatilization is 180 ℃ to 220 ℃, and the temperature of the second stage devolatilization is 240 ℃ to 260 ℃, so as to reduce crosslinking by increasing the devolatilization temperature.
Preferably, in the step S4, a twin-screw extruder is used for granulation, the twin-screw extruder has five temperature zones, and the temperature parameters of each temperature zone are as follows: the temperature of the first-section temperature zone is 170-300 ℃, the temperature of the second-section temperature zone is 170-270 ℃, the temperature of the third-section temperature zone is 130-280 ℃, the temperature of the fourth-section temperature zone is 170-270 ℃, and the temperature of the fifth-section temperature zone is 130-270 ℃; the number of screw extrusion revolutions is not more than 140r/min.
Further, the low-crystalline-point plate-grade ABS material is drawn by a drawing roll to form an ABS film, the heating temperature of the drawing roll is 30-100 ℃, the gap of an outlet of a die head is 0.5-10 mm, the interval of the outermost side of the drawing roll is 0.5-10 mm, the speed of the drawing roll is not more than 45m/min, the air outlet angle of an air knife is not more than 70 degrees, and the air volume pressure is not more than 2MPa.
The low-crystalline-point plate-grade ABS resin prepared by the method in the first aspect has the melt index of 4-7 g/10min, the impact strength of 20-25 kJ/m, the tensile strength of 38-46 MPa and the melt strength of more than or equal to 380Nm.
The invention has the following beneficial effects:
the low-crystal-point plate-grade ABS material prepared by the invention has the characteristics of low gloss and low gel, has pure white ground color, is an ABS material with good impact strength and tensile strength, and can be widely applied to refrigerators, air conditioners and luggage cases.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following examples.
It should be noted that the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Dissolving 55AE rubber, ethylbenzene, styrene and acrylonitrile at a certain temperature, filtering by a filter screen, and preheating to obtain a raw glue solution; respectively conveying the raw rubber solution, the initiator, the chain transfer agent and other auxiliary agents to each reaction kettle for continuous bulk polymerization; and the polymerized material enters a first-stage devolatilization and devolatilization device and then enters an extruder for granulation. The bulk ABS product was tested for melt index, impact strength, tensile strength and melt strength.
The prepared bulk ABS resin is extruded in a double-screw extruder to obtain an ABS molten flaky material, the ABS molten flaky material is pulled by a traction roller to form an ABS film, and the number of crystal points is measured by using a crystal point scanner.
Examples
Dissolving 8.8% (mass fraction, the same below) 55AE rubber, 14% ethylbenzene, 54.2% styrene and 23% acrylonitrile at a certain temperature, filtering with a 120-mesh filter screen, and preheating at 75 ℃ to obtain a raw glue solution; conveying the crude rubber solution and 0.5% of 1, 1-bis (tert-butylperoxy) cyclohexane, 0.5% of n-dodecyl mercaptan, 0.5% of antioxidant 168 and 1% of silicone oil to a four-stage reaction kettle for continuous bulk polymerization, wherein the temperatures of an upper temperature zone, a middle temperature zone and a lower temperature zone of a first reaction kettle, a second reaction kettle and a third reaction kettle in the four-stage reaction kettle are 95-130 ℃, and the temperatures of the upper temperature zone, the middle temperature zone and the lower temperature zone of a fourth reaction kettle are 146 ℃, 150 ℃ and 159 ℃ respectively; and (3) feeding the polymerized material into a first-stage devolatilization device and a second-stage devolatilization device, wherein the temperature of the first-stage devolatilization device is 195 ℃, the temperature of the second-stage devolatilization device is 245 ℃, and then feeding the materials into an extruder for granulation. The prepared ABS resin is extruded in a double-screw extruder to obtain an ABS molten flaky material, the double-screw extruder has five temperature zones, and the temperature parameters of each temperature zone are as follows: the temperature of the first-stage temperature zone is 200 ℃, the temperature of the second-stage temperature zone is 230 ℃, the temperature of the third-stage temperature zone is 250 ℃, the temperature of the fourth-stage temperature zone is 260 ℃, the temperature of the fifth-stage temperature zone is 270 ℃, the screw extrusion revolution is 120r/min, and a fluoropolymer processing aid PPA with 5 mass percent of devolatilization materials is added in the melt extrusion process; and (3) dragging the ABS molten sheet material through a dragging roller to form an ABS film, wherein the heating temperature of the dragging roller is 370 ℃, the gap of a die head outlet is 55mm, the outermost side interval of the dragging roller is 5mm, the speed of the dragging roller is 45m/min, the air outlet angle of an air knife is 70 degrees, the air volume pressure is 2MPa, and the crystal point quantity of the ABS film is measured by using a crystal point scanner.
Comparative example
Dissolving 8.8% (mass fraction, the same below) 55AE rubber, 14% ethylbenzene, 59.2% styrene and 18% acrylonitrile at a certain temperature, filtering with a 120-mesh filter screen, and preheating at 75 ℃ to obtain a raw glue solution; respectively conveying 0.5% of 1, 1-bis (tert-butylperoxy) cyclohexane, 0.5% of n-dodecyl mercaptan, 0.5% of antioxidant 168 and 1% of silicone oil in the crude rubber solution to a four-stage reaction kettle for continuous bulk polymerization, wherein the temperatures of an upper temperature zone, a middle temperature zone and a lower temperature zone of a first reaction kettle, a second reaction kettle and a third reaction kettle in the four-stage reaction kettle are 95-130 ℃, and the temperatures of the upper temperature zone, the middle temperature zone and the lower temperature zone of a fourth reaction kettle are 151 ℃, 160 ℃ and 169 ℃; after the polymerized material enters a first-stage devolatilization device and a second-stage devolatilization device, wherein the temperature of a first-stage devolatilization device is 185 ℃, the temperature of a second-stage devolatilization device is 235 ℃, and then the polymerized material enters an ABS resin prepared by granulation of an extruder to be extruded in a double-screw extruder to obtain an ABS molten flaky material, wherein the double-screw extruder has five temperature zones, and the temperature parameters of each temperature zone are as follows: the first-stage temperature zone is 200 ℃, the second-stage temperature zone is 230 ℃, the third-stage temperature zone is 250 ℃, the fourth-stage temperature zone is 260 ℃, the fifth-stage temperature zone is 270 ℃, and the screw extrusion revolution is 120r/min; and (3) dragging the ABS molten sheet material through a dragging roller to form an ABS film, wherein the heating temperature of the dragging roller is 370 ℃, the gap of a die head outlet is 55mm, the outermost side interval of the dragging roller is 5mm, the speed of the dragging roller is 45m/min, the air outlet angle of an air knife is 70 degrees, the air volume pressure is 2MPa, and the crystal point quantity of the ABS film is measured by using a crystal point scanner.
Testing the effects
The examples and comparative examples were subjected to melt index (g/10 min), impact strength (kJ/m), tensile strength (MPa), melt strength (Nm) and number of crystal points, respectively, and the results are shown in Table 1:
TABLE 1 test results of examples and comparative examples
According to the test results, the number of crystal points of the product can be obviously reduced, the melt strength of the product is increased, and the low-crystal-point plate-grade ABS material is obtained by changing the process parameters such as monomer content, polymerization temperature, devolatilization temperature and the like and adding the fluorine-containing polymer processing aid PPA in the process of preparing the thin film by melt extrusion.
Claims (10)
1. A method for preparing a low-crystal-point plate-grade ABS material by a bulk method is characterized by comprising the following steps:
s1: dissolving 8-9 parts by mass of low cis-polybutadiene rubber, 13-15 parts by mass of ethylbenzene, 50-60 parts by mass of styrene and 15-25 parts by mass of acrylonitrile, filtering by a filter screen, and preheating to obtain a raw glue solution;
s2: mixing the raw glue solution obtained in the step S1 according to the following mass part ratio: 100 parts by mass of a raw glue solution, 0.5-1 part by mass of an initiator, 0.5-1 part by mass of a chain transfer agent, 0.5-1 part by mass of an antioxidant and 1-3 parts by mass of silicone oil; conveying the uniformly mixed solution to a four-stage reaction kettle for continuous bulk polymerization, wherein each stage reaction kettle is provided with three temperature zones;
s3: feeding the polymerized material into a devolatilizer, and performing primary devolatilization and secondary devolatilization to obtain a devolatilized material;
s4: and adding a fluoropolymer processing aid PPA accounting for 4-6% of the mass of the devolatilized material into the devolatilized material, and granulating in an extruder to obtain the low-crystalline-point plate-grade ABS material.
2. The bulk process for preparing a low-crystalline-point plate-grade ABS material according to claim 1, wherein the initiator is 1, 1-bis (t-butylperoxy) cyclohexane, the chain transfer agent is n-dodecylmercaptan, and the antioxidant is 168 or 1010.
3. The method for preparing the low-crystalline-point plate-grade ABS material by the bulk process according to claim 1, wherein the low-cis polybutadiene rubber is one or a mixture of 55AE and 255T.
4. The method for preparing the low-crystal-point plate-grade ABS material according to the bulk method of claim 1, wherein the filter screen in the step S1 is 100-120 meshes, and the preheating temperature is 50-80 ℃.
5. The method for preparing the low-crystalline-point plate-grade ABS material by the bulk process according to claim 1, wherein the temperatures of the upper, middle and lower temperature regions of the fourth reaction kettle in the fourth-stage reaction kettle are 135-150 ℃, 145-155 ℃ and 150-160 ℃ respectively.
6. The method for preparing the low-crystalline-point plate-grade ABS material by the bulk method according to claim 5, wherein the temperatures of the upper, middle and lower temperature regions of the first, second and third reaction kettles in the four-stage reaction kettle are 95-130 ℃.
7. The method for preparing the low-crystalline-point plate-grade ABS material according to the bulk method of claim 1, wherein in the step S3, the temperature of the first-stage devolatilization is 180-220 ℃, and the temperature of the second-stage devolatilization is 240-260 ℃.
8. The method for preparing the low-crystalline-point plate-grade ABS material by the bulk method according to claim 1, wherein a double-screw extruder is used for granulation in the step S4, the double-screw extruder has five temperature zones, and the temperature parameters of each temperature zone are as follows: the temperature of the first-section temperature zone is 170-300 ℃, the temperature of the second-section temperature zone is 170-270 ℃, the temperature of the third-section temperature zone is 130-280 ℃, the temperature of the fourth-section temperature zone is 170-270 ℃, and the temperature of the fifth-section temperature zone is 130-270 ℃; the screw extrusion revolution is not more than 140r/min.
9. The method for preparing the low-crystalline-point plate-grade ABS material by the bulk process according to any one of claims 1 to 8, wherein the low-crystalline-point plate-grade ABS material is drawn by a drawing roll to form an ABS film, the heating temperature of the drawing roll is 30-100 ℃, the gap of a die head outlet is 0.5-10 mm, the outermost interval of the drawing roll is 0.5-10 mm, the speed of the drawing roll is not more than 45m/min, the air outlet angle of an air knife is not more than 70 degrees, and the air pressure is not more than 2MPa.
10. The ABS material prepared according to any of claims 1 to 9, wherein the ABS material has a melt index of 4 to 7g/10min, an impact strength of 20 to 25kJ/m, a tensile strength of 38 to 46MPa, and a melt strength of 380Nm or more.
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| HU, YM等: "Synthesis and impact properties of in situ bulk made ABS resins toughened by high cis-1, 4 polybuadiene", 《MATERIALS SCIENCE AND ENGINEERING:A》, vol. 528, no. 22, 3 June 2011 (2011-06-03), pages 6667 - 6672 * |
| 徐璐: "本体透明ABS树脂结构控制及其性能的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ι辑》, no. 01, 15 January 2021 (2021-01-15), pages 016 - 720 * |
| 李秀悌等: "改性纳米碱式氯化镁晶须填充ABS/PP复合材料的力学性能", 材料科学与工程学报, vol. 29, no. 05, 20 October 2011 (2011-10-20), pages 11 - 15 * |
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