CN110903595A - High-temperature-resistant and corrosion-resistant ABS (acrylonitrile butadiene styrene) particles and preparation method thereof - Google Patents
High-temperature-resistant and corrosion-resistant ABS (acrylonitrile butadiene styrene) particles and preparation method thereof Download PDFInfo
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- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims abstract description 89
- 239000002245 particle Substances 0.000 title claims abstract description 43
- 230000007797 corrosion Effects 0.000 title claims abstract description 25
- 238000005260 corrosion Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 title abstract description 43
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 title abstract description 42
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 20
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229940088417 precipitated calcium carbonate Drugs 0.000 claims abstract description 20
- -1 polypropylene Polymers 0.000 claims abstract description 19
- 239000004743 Polypropylene Substances 0.000 claims abstract description 18
- 229920001155 polypropylene Polymers 0.000 claims abstract description 18
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 12
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 12
- 239000000314 lubricant Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 35
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 20
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 claims description 14
- 239000011812 mixed powder Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000007664 blowing Methods 0.000 claims description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000000861 blow drying Methods 0.000 claims description 8
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000000498 cooling water Substances 0.000 claims description 7
- 229940078494 nickel acetate Drugs 0.000 claims description 7
- 239000012188 paraffin wax Substances 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- KQOIBXZRCYFZSO-UHFFFAOYSA-N 3,5-difluoroaniline Chemical compound NC1=CC(F)=CC(F)=C1 KQOIBXZRCYFZSO-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a high-temperature-resistant and corrosion-resistant ABS (acrylonitrile-butadiene-styrene) particle and a preparation method thereof, wherein the ABS particle is prepared from the following raw materials in parts by weight: 8-10 parts of precipitated calcium carbonate, 8-10 parts of calcined argil, 8-10 parts of talcum powder, 30-40 parts of styrene, 30-40 parts of modified heat-resistant agent, 3-4 parts of benzoyl peroxide, 80-100 parts of ABS resin, 20-25 parts of polypropylene and 5-8 parts of lubricant; according to the invention, polypropylene and ABS resin are blended in the preparation process, so that the corrosion resistance of the ABS resin is enhanced, and the modified heat-resistant agent is prepared, wherein the molecule of the modified heat-resistant agent has a plurality of five-membered ring structures, each five-membered ring structure is connected with a benzene ring, and the five-membered ring and the benzene ring are both groups with strong rigidity and can well block the internal rotation of a chain segment, so that the self rigidity of the high-molecular polymer is improved, and the heat resistance of the high-molecular polymer is further increased.
Description
Technical Field
The invention belongs to the field of plastic preparation, and particularly relates to high-temperature-resistant and corrosion-resistant ABS (acrylonitrile butadiene styrene) particles and a preparation method thereof.
Background
ABS plastic is a terpolymer of acrylonitrile-butadiene-styrene. The ABS plastic is a thermoplastic plastic with good comprehensive performance of 'hard mass, tough property and high rigidity', but the actual use discovers that products made of the ABS material are not resistant to corrosion of sulfuric acid, can be crushed and broken when meeting sulfuric acid, and can be broken when being used at the temperature higher than 100 ℃, so that the application range of the ABS material is seriously influenced;
the Chinese invention patent CN107573635A discloses a high-performance flame-retardant ABS material and a preparation method thereof, wherein the ABS material is prepared from the following raw materials in parts by weight: 50-100 parts of ABS resin, 5-10 parts of transition metal compound, 1-10 parts of auxiliary flame retardant and 1-20 parts of lubricant, the ABS material prepared by the invention has good flame retardant effect and excellent mechanical property, but the ABS material has poor corrosion resistance and can be subjected to crushing fracture when meeting sulfuric acid, and the ABS material is damaged under the high-temperature condition and is not beneficial to the multi-field use of the ABS material.
Disclosure of Invention
The invention aims to provide a high-temperature-resistant and corrosion-resistant ABS particle and a preparation method thereof, aiming at improving the defects of the conventional ABS resin, a modified heat-resistant agent is prepared in the process of preparing the ABS particle, molecules of the modified heat-resistant agent have a plurality of five-membered ring structures, each five-membered ring structure is connected with a benzene ring, and the five-membered ring and the benzene rings are both strong rigid groups and can well block the internal rotation of a chain segment, so that the self rigidity of a high-molecular polymer is improved, the heat resistance of the high-molecular polymer is further improved, and polypropylene is blended with the ABS resin, so that the corrosion resistance of the ABS resin is enhanced.
The technical problems to be solved by the invention are as follows:
1. the ABS resin is a terpolymer of acrylonitrile, butadiene and styrene, the copolymer belongs to an amorphous polymer, and the rigid group in a macromolecular chain is less, so that the heat resistance of the ABS resin is poor, and a product made of the ABS resin is easy to damage under the condition that the temperature is higher than 100 ℃;
2. common ABS resin has better corrosion resistance, but the ABS resin is not resistant to sulfuric acid corrosion, and when the surface of a product made of the ABS resin is contacted with sulfuric acid, the product is crushed and cracked, so that the use of the product made of the ABS resin is seriously influenced.
The purpose of the invention can be realized by the following technical scheme:
the ABS particle is prepared from the following raw materials in parts by weight: 8-10 parts of precipitated calcium carbonate, 8-10 parts of calcined argil, 8-10 parts of talcum powder, 30-40 parts of styrene, 30-40 parts of modified heat-resistant agent, 3-4 parts of benzoyl peroxide, 80-100 parts of ABS resin, 20-25 parts of polypropylene and 5-8 parts of lubricant;
the ABS particle is prepared by the following steps:
step S1: respectively adding the precipitated calcium carbonate, the calcined argil and the talcum powder into a crusher for crushing, sieving by a 1250-mesh sieve, adding the sieved precipitated calcium carbonate, the calcined argil, the talcum powder and the nano-silica into a mixer, and stirring for 20-30min under the condition that the rotating speed is 600-750r/min to obtain mixed powder;
step S2: adding styrene, a modified heat-resistant agent and benzoyl peroxide into a four-neck flask, stirring and heating to 80-85 ℃ under the condition that the rotating speed is 450-;
step S3: adding ABS resin into an internal mixer, stirring for 10-15min under the conditions that the rotating speed is 30-40r/min and the temperature is 180-200 ℃, adding polypropylene and the solid particles prepared in the step S2 after the ABS resin is completely molten, continuing to mix for 30-50min, adding the mixed powder prepared in the step S1 and the lubricant, and continuing to mix for 2-3h to prepare a premix;
step S4: and (4) adding the premix prepared in the step S3 into a co-rotating double-screw extruder, extruding at the temperature of 200-210 ℃, adding the extruded premix into a cooling water tank for cooling, blowing the cooled premix into a blow-drying machine for drying for 15-30min, adding into a granulator, and granulating to obtain the ABS particles.
Further, the lubricant is one of paraffin, butyl stearate and ethylene bis stearamide.
The modified heat-resistant agent is prepared by the following steps:
a: adding 4-bromoaniline and acetone into a beaker, stirring for 5-10min to completely dissolve 4-bromoaniline under the condition that the rotation speed is 100-200r/min to prepare 4-bromoaniline mixed solution, adding maleic anhydride and acetone into a three-neck flask, stirring for 5-10min to completely dissolve maleic anhydride under the condition that the rotation speed is 150-300r/min, dropwise adding the 4-bromoaniline mixed solution under the conditions that the rotation speed is 150-300r/min and the temperature is 5-8 ℃, reacting for 10-20min, raising the temperature to 60-65 ℃, carrying out reflux reaction for 30-50min, adding triethylamine, acetic anhydride and nickel acetate, and continuing the reflux reaction for 2-3h to prepare an intermediate 1;
the reaction process is as follows:
b: adding maleic anhydride, N-dimethylformamide and toluene into a beaker, stirring for 5-10min under the conditions of the rotation speed of 100-200r/min and the temperature of 15-20 ℃ until the maleic anhydride is completely dissolved, adding 3, 5-difluoroaniline, reacting for 1.5-2h under the condition of the temperature of 15-20 ℃ to prepare an intermediate 2, adding the intermediate 2, p-toluenesulfonic acid and p-tert-butylcatechol into a three-neck flask, and reacting for 2-2.5h under the condition of the temperature of 110-115 ℃ to prepare an intermediate 3;
the reaction process is as follows:
c: and (3) adding the intermediate 1 prepared in the step (A), the intermediate 3 prepared in the step (B) and copper powder into a reaction kettle, and reacting for 5-8h at the temperature of 200-230 ℃ to prepare the modified heat-resistant agent.
The reaction process is as follows:
further, the dosage ratio of the maleic anhydride and the 4-bromoaniline in the step A is 5 g: 4g, wherein the dosage ratio of the nickel acetate to the maleic anhydride is 3 g: 5g, the dosage ratio of triethylamine, acetic anhydride and nickel acetate is 4 mL: 10mL of: 3g of the total weight.
Further, the dosage ratio of the maleic anhydride to the N, N-dimethylformamide in the step B is 1 g: 3mL, wherein the dosage ratio of the N, N-dimethylformamide to the toluene is 1 mL: 5mL, the dosage ratio of maleic anhydride to 3, 5-difluoroaniline is 1.5 mol: 1mol, the dosage ratio of the intermediate 2 to the p-toluenesulfonic acid is 20 g: 1g of the total weight of the composition.
The invention has the beneficial effects that: the invention blends polypropylene and ABS resin in the process of preparing a high-temperature-resistant and corrosion-resistant ABS particle, the polypropylene has good corrosion resistance, so that the corrosion resistance of the ABS particle is enhanced, meanwhile, a modified heat-resistant agent is prepared in the preparation process, molecules of the modified heat-resistant agent have a plurality of five-membered ring structures, each five-membered ring structure is connected with a benzene ring, the five-membered ring and the benzene rings are both strong rigid groups and can well block the internal rotation of a chain segment, the modified heat-resistant agent molecules and styrene are subjected to solution polymerization, and then the copolymer and the ABS resin are subjected to melt blending, so that the ratio of single bonds capable of rotating in an ABS molecular chain is relatively reduced, the internal rotation resistance of the molecular chain is increased to reduce the activity capability of the sub-chain, thereby improving the self rigidity of a high molecular polymer and further increasing the heat resistance of the high.
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
A high-temperature-resistant and corrosion-resistant ABS particle is prepared from the following raw materials in parts by weight: 8 parts of precipitated calcium carbonate, 8 parts of calcined argil, 8 parts of talcum powder, 30 parts of styrene, 30 parts of modified heat-resistant agent, 3 parts of benzoyl peroxide, 80 parts of ABS resin, 20 parts of polypropylene and 5 parts of paraffin;
the ABS particle is prepared by the following steps:
step S1: respectively adding the precipitated calcium carbonate, the calcined argil and the talcum powder into a grinder for grinding, sieving by a 1250-mesh sieve, adding the sieved precipitated calcium carbonate, the calcined argil, the talcum powder and the nano-silica into a mixer, and stirring for 20min under the condition that the rotating speed of a stirring blade is 600r/min to obtain mixed powder;
step S2: adding styrene, a modified heat-resistant agent and benzoyl peroxide into a four-neck flask, stirring and heating to 80 ℃ under the condition that the rotating speed is 450r/min until reaction liquid is white and turbid, continuously stirring for 4 hours, and filtering to remove filtrate to obtain solid particles;
step S3: adding ABS resin into an internal mixer, stirring for 10min at the rotation speed of 30r/min and the temperature of 180 ℃, adding polypropylene and the solid particles prepared in the step S2 after the ABS resin is completely melted, mixing for 30min at the rotation speed of 30r/min and the temperature of 180 ℃, adding the mixed powder and paraffin prepared in the step S1, and continuously mixing for 2h to prepare a premix;
step S4: and (4) adding the premix prepared in the step (S3) into a co-rotating twin-screw extruder, extruding at the temperature of 200 ℃, adding the extruded premix into a cooling water tank for cooling, blowing the cooled premix into a blow-drying machine for blowing for 15min, adding into a granulator, and granulating to obtain the ABS particles.
The modified heat-resistant agent is prepared by the following steps:
a: adding 4-bromoaniline and diethyl ether into a beaker, stirring for 5min to completely dissolve 4-bromoaniline under the condition that the rotation speed is 100r/min to obtain a 4-bromoaniline mixed solution, adding half of maleic anhydride and acetone into a three-neck flask, stirring for 5min to completely dissolve maleic anhydride under the condition that the rotation speed is 150r/min, dropwise adding the 4-bromoaniline mixed solution under the conditions that the rotation speed is 150r/min and the temperature is 5 ℃, reacting for 10min, raising the temperature to 60 ℃, carrying out reflux reaction for 30min, adding triethylamine, acetic anhydride and nickel acetate, and continuing the reflux reaction for 2h to obtain an intermediate 1;
b: adding the other half of maleic anhydride, N-dimethylformamide and toluene into a beaker, stirring for 5min at the rotation speed of 100r/min and at the temperature of 15 ℃ until the maleic anhydride is completely dissolved, adding 3, 5-difluoroaniline, reacting for 1.5h at the temperature of 15 ℃ to obtain an intermediate 2, adding the intermediate 2, p-toluenesulfonic acid and p-tert-butylcatechol into a three-neck flask, and reacting for 2h at the temperature of 110 ℃ to obtain an intermediate 3;
c: and (4) adding the intermediate 1 prepared in the step (A), the intermediate 3 prepared in the step (B) and copper powder into a reaction kettle, and reacting for 5 hours at the temperature of 200 ℃ to prepare the modified heat-resistant agent.
Example 2
The high-temperature-resistant and corrosion-resistant ABS particle is prepared from the following raw materials in parts by weight: 8-10 parts of precipitated calcium carbonate, 8-10 parts of calcined argil, 8-10 parts of talcum powder, 30-40 parts of styrene, 30-40 parts of modified heat-resistant agent, 3-4 parts of benzoyl peroxide, 80-100 parts of ABS resin, 20-25 parts of polypropylene and 5-8 parts of lubricant;
step S1: respectively adding the precipitated calcium carbonate, the calcined argil and the talcum powder into a grinder to be ground, sieving by a 1250-mesh sieve, adding the sieved precipitated calcium carbonate, calcined argil, talcum powder and nano-silica into a mixer, and stirring for 25min under the condition that the rotating speed is 700r/min to obtain mixed powder;
step S2: adding styrene, a modified heat-resistant agent and benzoyl peroxide into a four-mouth flask, stirring and heating to 83 ℃ under the condition that the rotating speed is 475r/min until reaction liquid is white and turbid, continuously stirring for 4.5h, and filtering to remove filtrate to obtain solid particles;
step S3: adding ABS resin into an internal mixer, stirring for 13min under the conditions that the rotating speed is 35r/min and the temperature is 190 ℃, adding polypropylene and the solid particles prepared in the step S2 after the ABS resin is completely melted, continuing to mix for 40min, adding the mixed powder prepared in the step S1 and the lubricant, and continuing to mix for 2.5h to prepare a premix;
step S4: and (4) adding the premix prepared in the step (S3) into a co-rotating double-screw extruder, extruding at the temperature of 205 ℃, adding the extruded premix into a cooling water tank for cooling, blowing the cooled premix into a blow-drying machine for blowing for 17min, adding into a granulator, and granulating to obtain the ABS particles.
Example 3
A high-temperature-resistant and corrosion-resistant ABS particle is prepared from the following raw materials in parts by weight: 10 parts of precipitated calcium carbonate, 10 parts of calcined argil, 10 parts of talcum powder, 40 parts of styrene, 40 parts of modified heat-resistant agent, 4 parts of benzoyl peroxide, 100 parts of ABS resin, 25 parts of polypropylene and 8 parts of paraffin;
the ABS particle is prepared by the following steps:
step S1: respectively adding the precipitated calcium carbonate, the calcined argil and the talcum powder into a grinder to be ground, sieving by a 1250-mesh sieve, adding the sieved precipitated calcium carbonate, the calcined argil, the talcum powder and the nano-silica into a mixer, and stirring for 30min under the condition that the rotating speed of a stirring blade is 750r/min to obtain mixed powder;
step S2: adding styrene, a modified heat-resistant agent and benzoyl peroxide into a four-neck flask, stirring and heating to 85 ℃ under the condition that the rotating speed is 500r/min until reaction liquid is white and turbid, continuing stirring for 5 hours, and filtering to remove filtrate to obtain solid particles;
step S3: adding ABS resin into an internal mixer, stirring for 15min at the rotation speed of 40r/min and the temperature of 200 ℃ until the ABS resin is completely melted, adding polypropylene and the solid particles prepared in the step S2, mixing for 50min at the rotation speed of 40r/min and the temperature of 200 ℃, adding the mixed powder and paraffin prepared in the step S1, and continuously mixing for 3h to prepare a premix;
step S4: and (4) adding the premix prepared in the step (S3) into a co-rotating twin-screw extruder, extruding at the temperature of 210 ℃, adding the extruded premix into a cooling water tank for cooling, blowing the cooled premix into a blow-drying machine for blow-drying for 30min, adding into a granulator, and granulating to obtain the ABS particles.
Comparative example 1
In the comparison of the embodiment 1, the method does not add the modified heat-resistant agent and comprises the following specific steps:
step S1: respectively adding the precipitated calcium carbonate, the calcined argil and the talcum powder into a grinder for grinding, sieving by a 1250-mesh sieve, adding the sieved precipitated calcium carbonate, the calcined argil, the talcum powder and the nano-silica into a mixer, and stirring for 20min under the condition that the rotating speed of a stirring blade is 600r/min to obtain mixed powder;
step S2: adding ABS resin into an internal mixer, stirring for 10min at the rotation speed of 30r/min and the temperature of 180 ℃ until the ABS resin is completely melted, adding polypropylene, mixing for 30min at the rotation speed of 30r/min and the temperature of 180 ℃, adding the mixed powder and paraffin prepared in the step S1, and continuously mixing for 2h to prepare a premix;
step S3: and (4) adding the premix prepared in the step (S2) into a co-rotating twin-screw extruder, extruding at the temperature of 200 ℃, adding the extruded premix into a cooling water tank for cooling, blowing the cooled premix into a blow-drying machine for blowing for 15min, adding into a granulator, and granulating to obtain the ABS particles.
Comparative example 2
This comparative example is an N-phenylmaleimide copolymer modified ABS particle.
Comparative example 3
This comparative example is a commercially available ABS pellet.
The ABS particles prepared in examples 1-3 and comparative examples 1-3 were tested for their properties, and the results are shown in Table 1 below;
heat resistance: according to the GB/T9352-, the surface of the sample contacted with the base is flat, the component is placed in a heating device, a stirrer is started, after 5min, a press needle is in a static position, sufficient weights are added on a load plate, so that the total thrust applied to the sample is 10N +/-0.2N, the reading of the dial indicator is recorded, the temperature of the heating device is uniformly increased at the speed of 50 ℃/h +/-5 ℃/h, when the depth of the needle pressing head penetrating into the sample exceeds 1mm +/-0.01 of the initial position before heating, recording the oil bath temperature measured by the sensor, namely the Vicat softening temperature of the sample.
Corrosion resistance: the ABS pellets prepared in examples 1-3 and comparative examples 1-3 were prepared into corresponding samples according to the GB/T11547-2008 standard, and the samples were tested according to the GB/T11547-2008 standard, wherein the samples were prepared from 99.5% by mass of acetic acid, 50% by mass of sulfuric acid, and 100% by mass of dichlorobenzene, and were soaked at 20 deg.C, 60 deg.C, 100 deg.C for 90 days, and the change grade of appearance was observed.
TABLE 1
As shown in the table 1, the heat resistance of the ABS particles prepared in the embodiments 1-3 is higher than that of the ABS particles prepared in the comparative examples 1-3, the corrosion resistance of the prepared ABS particles is greatly improved by blending polypropylene and ABS resin, the molecular chain mobility of ABS is reduced by using the modified heat-resistant agent, and the self-rigidity is enhanced, so that the self-heat resistance is improved.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (6)
1. A high temperature resistant, corrosion resistant ABS granule which characterized in that: the feed is prepared from the following raw materials in parts by weight: 8-10 parts of precipitated calcium carbonate, 8-10 parts of calcined argil, 8-10 parts of talcum powder, 30-40 parts of styrene, 30-40 parts of modified heat-resistant agent, 3-4 parts of benzoyl peroxide, 80-100 parts of ABS resin, 20-25 parts of polypropylene and 5-8 parts of lubricant;
the ABS particle is prepared by the following steps:
step S1: respectively adding the precipitated calcium carbonate, the calcined argil and the talcum powder into a crusher for crushing, sieving by a 1250-mesh sieve, adding the sieved precipitated calcium carbonate, the calcined argil, the talcum powder and the nano-silica into a mixer, and stirring for 20-30min under the condition that the rotating speed is 600-750r/min to obtain mixed powder;
step S2: adding styrene, a modified heat-resistant agent and benzoyl peroxide into a four-neck flask, stirring and heating to 80-85 ℃ under the condition that the rotating speed is 450-;
step S3: adding ABS resin into an internal mixer, stirring for 10-15min under the conditions that the rotating speed is 30-40r/min and the temperature is 180-200 ℃, adding polypropylene and the solid particles prepared in the step S2 after the ABS resin is completely molten, continuing to mix for 30-50min, adding the mixed powder prepared in the step S1 and the lubricant, and continuing to mix for 2-3h to prepare a premix;
step S4: and (4) adding the premix prepared in the step S3 into a co-rotating double-screw extruder, extruding at the temperature of 200-210 ℃, adding the extruded premix into a cooling water tank for cooling, blowing the cooled premix into a blow-drying machine for drying for 15-30min, adding into a granulator, and granulating to obtain the ABS particles.
2. The high temperature and corrosion resistant ABS particle and its preparation method of claim 1, wherein: the lubricant is one of paraffin, butyl stearate and ethylene bis stearamide.
3. The high temperature and corrosion resistant ABS particle and its preparation method of claim 1, wherein: the modified heat-resistant agent is prepared by the following steps:
a: adding 4-bromoaniline and acetone into a beaker, stirring for 5-10min to completely dissolve 4-bromoaniline under the condition that the rotation speed is 100-200r/min to prepare 4-bromoaniline mixed solution, adding maleic anhydride and acetone into a three-neck flask, stirring for 5-10min to completely dissolve maleic anhydride under the condition that the rotation speed is 150-300r/min, dropwise adding the 4-bromoaniline mixed solution under the conditions that the rotation speed is 150-300r/min and the temperature is 5-8 ℃, reacting for 10-20min, raising the temperature to 60-65 ℃, carrying out reflux reaction for 30-50min, adding triethylamine, acetic anhydride and nickel acetate, and continuing the reflux reaction for 2-3h to prepare an intermediate 1;
b: adding maleic anhydride, N-dimethylformamide and toluene into a beaker, stirring for 5-10min under the conditions of the rotation speed of 100-200r/min and the temperature of 15-20 ℃ until the maleic anhydride is completely dissolved, adding 3, 5-difluoroaniline, reacting for 1.5-2h under the condition of the temperature of 15-20 ℃ to prepare an intermediate 2, adding the intermediate 2, p-toluenesulfonic acid and p-tert-butylcatechol into a three-neck flask, and reacting for 2-2.5h under the condition of the temperature of 110-115 ℃ to prepare an intermediate 3;
c: and (3) adding the intermediate 1 prepared in the step (A), the intermediate 3 prepared in the step (B) and copper powder into a reaction kettle, and reacting for 5-8h at the temperature of 200-230 ℃ to prepare the modified heat-resistant agent.
4. The high temperature and corrosion resistant ABS particle and its preparation method of claim 3, wherein: the dosage ratio of the maleic anhydride and the 4-bromoaniline in the step A is 5 g: 4g, wherein the dosage ratio of the nickel acetate to the maleic anhydride is 3 g: 5g, the dosage ratio of triethylamine, acetic anhydride and nickel acetate is 4 mL: 10mL of: 3g of the total weight.
5. The high temperature and corrosion resistant ABS particle and its preparation method of claim 3, wherein: the dosage ratio of the maleic anhydride to the N, N-dimethylformamide in the step B is 1 g: 3mL, wherein the dosage ratio of the N, N-dimethylformamide to the toluene is 1 mL: 5mL, the dosage ratio of maleic anhydride to 3, 5-difluoroaniline is 1.5 mol: 1mol, the dosage ratio of the intermediate 2 to the p-toluenesulfonic acid is 20 g: 1g of the total weight of the composition.
6. A method for preparing high temperature and corrosion resistant ABS particles suitable for use in claim 1, characterized by: the method comprises the following steps:
step S1: respectively adding the precipitated calcium carbonate, the calcined argil and the talcum powder into a crusher for crushing, sieving by a 1250-mesh sieve, adding the sieved precipitated calcium carbonate, the calcined argil, the talcum powder and the nano-silica into a mixer, and stirring for 20-30min under the condition that the rotating speed is 600-750r/min to obtain mixed powder;
step S2: adding styrene, a modified heat-resistant agent and benzoyl peroxide into a four-neck flask, stirring and heating to 80-85 ℃ under the condition that the rotating speed is 450-;
step S3: adding ABS resin into an internal mixer, stirring for 10-15min under the conditions that the rotating speed is 30-40r/min and the temperature is 180-200 ℃, adding polypropylene and the solid particles prepared in the step S2 after the ABS resin is completely molten, continuing to mix for 30-50min, adding the mixed powder prepared in the step S1 and the lubricant, and continuing to mix for 2-3h to prepare a premix;
step S4: and (4) adding the premix prepared in the step S3 into a co-rotating double-screw extruder, extruding at the temperature of 200-210 ℃, adding the extruded premix into a cooling water tank for cooling, blowing the cooled premix into a blow-drying machine for drying for 15-30min, adding into a granulator, and granulating to obtain the ABS particles.
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