CN111393822B - PC/ABS alloy plastic for shell material and preparation method thereof - Google Patents
PC/ABS alloy plastic for shell material and preparation method thereof Download PDFInfo
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- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- 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
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention provides a PC/ABS alloy plastic for a shell material, which is prepared from the following components in parts by weight: 70-100 parts of PC/ABS recycled powder, 0.1-0.5 part of ultraviolet absorbent, 1-3 parts of flame retardant, 0.1-0.1 part of toughening agent KNY 010.01, 0.1-0.3 part of toughening agent 1105A, 1-2 parts of heat stabilizer and 0.5-1.5 parts of compatibilizer; the ultraviolet absorbent has a structural formula shown in a formula I; the PC/ABS alloy has the characteristics of high performance, high flame retardance, high impact resistance, cold resistance, high stability, yellowing resistance, aging resistance, static resistance and the like, can be used for preparing intelligent ammeter shells, instrument shells, fax machine shells or copier shells, can meet or exceed the material standards of the national household appliance industry in each index, has high material stability and good quality, and contributes to environmental protection, energy conservation and emission reduction of the domestic and international household appliance industry.
Description
Technical Field
The invention relates to the technical field of plastics, in particular to PC/ABS alloy plastic for a shell material and a preparation method thereof.
Background
The PC/ABS alloy is an engineering plastic alloy developed in the middle of the 60's of the 20 th century, can form complementation in performance, has the heat resistance, dimensional stability and mechanical property of PC, has the advantages of low melt viscosity, good processing fluidity and the like compared with PC, and can reduce the stress sensitivity of products and reduce the cost, so that the PC/ABS alloy can replace PC to be used in shell materials of automobiles, machinery, household appliances, computers, communication equipment, office equipment and the like. But due to the structural defects of the PC/ABS alloy, the PC/ABS alloy is easy to age and degrade during processing, storage and use, so that yellowing is generated and partial or all of mechanical properties disappear.
Along with the rapid development of science and technology and the expansion of markets, the updating speed of electronic and electrical equipment is faster and faster, wherein the requirements of novel electronic consumer products such as computers, mobile phones and the like are increased rapidly, and the service life is shorter and shorter, so that the rapid increase of electronic wastes is promoted; under the urgent situation of resources, the utilization of plastic recycling materials is more important in plastic processing enterprises, and the plastic recycling technology is still a hot spot of research in various countries. Therefore, the application of the waste reclaimed materials in plastic processing enterprises is trending.
Disclosure of Invention
The invention aims to provide a PC/ABS alloy plastic for a shell material and a preparation method thereof, and the PC/ABS alloy plastic has a good anti-aging effect.
The technical scheme of the invention is realized as follows:
the invention provides a PC/ABS alloy plastic for a shell material, which is prepared from the following components in parts by weight: 70-100 parts of PC/ABS recycled powder, 0.1-0.5 part of ultraviolet absorbent, 1-3 parts of flame retardant, 0.1-0.1 part of toughening agent KNY 010.01, 0.1-0.3 part of toughening agent 1105A, 1-2 parts of heat stabilizer and 0.5-1.5 parts of compatibilizer;
the ultraviolet absorbent has a structural formula as shown in formula I:
formula I;
the PC/ABS recovered powder is a crushed material with the particle size of less than or equal to 10mm, which is obtained by crushing a recovered PC/ABS alloy material; the recovered PC/ABS alloy material is waste electrical appliance defective material, defective material or waste material produced from raw materials.
As a further improvement of the invention, the ultraviolet absorber is prepared according to the following method: respectively dissolving 2, 4-dihydroxy benzophenone and 1,3, 5-tri (chloromethyl) -benzene in a solvent, preparing NaOH solution, dropwise adding the 1,3, 5-tri (chloromethyl) -benzene solution and the NaOH solution into the 2, 4-dihydroxy benzophenone solution while stirring, controlling the reaction temperature to be not higher than 10 ℃, reacting for 3-5 hours after the dropwise adding is finished, cooling to be lower than 0 ℃, and filtering to obtain the ultraviolet absorbent.
As a further improvement of the invention, the solvent is one or a mixture of more of acetone, acetonitrile, pyridine and tetrahydrofuran, and the preparation method of the NaOH solution is that 0.01-0.012mol of NaOH is dissolved in 10mL of water; the mass ratio of the 2, 4-dihydroxybenzophenone, the 1,3, 5-tris (chloromethyl) -benzene and the NaOH is (3-3.2): 1: (1-1.2).
As a further improvement of the invention, the flame retardant is selected from one or a mixture of more of resorcinol bis (diphenyl phosphate), melamine cyanuric acid, melamine phosphate and red phosphorus master batch.
As a further improvement of the invention, the heat stabilizer is prepared by mixing barium soap, organic phosphite ester and dihydropyridine, and the mass ratio of the barium soap to the organic phosphite ester is 1: (0.2-0.5): (0.1-0.3).
As a further improvement of the invention, the compatibilizer is one selected from polyethylene grafted maleic anhydride, acrylonitrile-styrene-butadiene copolymer grafted maleic anhydride, polypropylene grafted maleic anhydride and styrene-butadiene copolymer grafted maleic anhydride.
As a further improvement of the invention, the performance index of the recycled PC/ABS alloy material at least meets one of the following three conditions: the impact strength of the cantilever beam notch is more than or equal to 5KJ/m2The tensile strength is more than or equal to 32MPa or the elongation at break is more than or equal to 15 percent.
The invention further protects the application of the compound shown as the formula I as an ultraviolet absorbent.
The invention further protects a preparation method of the PC/ABS alloy plastic for the shell material, which specifically comprises the following steps: weighing the raw materials in proportion, putting the PC/ABS recovered powder, the toughening agent KNY01, the toughening agent 1105A, the compatibilizer, the ultraviolet absorber, the flame retardant and the heat stabilizer into a stirrer for repeatedly stirring three times, wherein the stirring time is 1-2h each time, uniformly mixing, feeding into a double-screw extruder for melting and mixing, extruding the obtained melt by the double-screw extruder, cooling by a water tank at 30-50 ℃, carrying out grain cutting operation by a grain cutting machine, and collecting grains to obtain the PC/ABS alloy plastic for the shell material.
As a further improvement of the invention, the rotating speed of the stirrer is 500-.
The invention has the following beneficial effects: according to the preparation of the PC/ABS alloy plastic, waste electrical appliance type defective materials, defective materials or waste materials are adopted to replace PC and ABS raw materials, in order to ensure that the performance of a final product is excellent, the inventor collocates proper additives according to the characteristics of the recovered PC + ABS alloy material, optimizes the dosage of each additive, and selects each additive and prepares the recovered PC + ABS alloy material by an excellent process, so that the recovered PC + ABS alloy material can also prepare the PC/ABS alloy material with excellent performance, and the PC/ABS alloy plastic contributes to national energy conservation, emission reduction and renewable resource utilization;
the ultraviolet absorbent prepared by the invention is benzophenone ultraviolet absorbent, has the advantages of low price, convenient synthesis, high yield and the like, simultaneously, the newly synthesized ultraviolet absorbent has high relative molecular mass, avoids the defects of low molecular weight, thermal instability, easy decomposition and volatilization of common benzophenone ultraviolet absorbents, is added into alloy plastic, increases the thermal stability and compatibility, has excellent yellowing resistance, and has no change of the appearance of PC/ABS alloy added with the ultraviolet absorbent after being exposed to sunlight for 5 months, and the situations of embrittlement, yellowing and the like occur when other ultraviolet absorbents are used under the same condition;
the toughening agent combination added in the invention comprises the following components: the toughening agents KNY01 and 1105A can obviously improve the mechanical properties of the alloy material, and the inventor finds that the toughening agents KNY01 can improve the toughness of the material at constant temperature, the toughening agents 1105A can improve the toughness of the material at low temperature, the two toughening agents are matched and used in PC/ABS to have synergistic effect, so that the effect of '1 +1 > 2' is well played, and the excellent properties of the PC/ABS alloy are more effectively ensured;
the PC/ABS alloy has the characteristics of high performance, high flame retardance, high impact resistance, cold resistance, high stability, yellowing resistance, aging resistance, static resistance and the like, can be used for preparing intelligent ammeter shells, instrument shells, fax machine shells or copier shells, can meet or exceed the material standards of the national household appliance industry in each index, has high material stability and good quality, and contributes to environmental protection, energy conservation and emission reduction of the domestic and international household appliance industry.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a nuclear magnetic hydrogen spectrum of an ultraviolet absorber represented by formula I.
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 preparation of UV absorbers
The preparation method comprises the following steps:
respectively dissolving 0.03mol of 2, 4-dihydroxybenzophenone and 0.01mol of 1,3, 5-tris (chloromethyl) -benzene in acetonitrile, and preparing a NaOH solution, wherein the preparation method of the NaOH solution comprises the steps of dissolving 0.01mol of NaOH in 10mL of water, dropwise adding the 1,3, 5-tris (chloromethyl) -benzene solution and the NaOH solution into the 2, 4-dihydroxybenzophenone solution while stirring, controlling the reaction temperature to be not higher than 10 ℃, reacting for 3 hours after the dropwise adding is finished, cooling to below 0 ℃, and filtering to obtain the ultraviolet absorbent, wherein the yield is 92%, and the structural formula is shown as formula I;
formula I.
Synthesis of roadmaps:
the ultraviolet absorbent shown in the formula I is characterized by infrared ray of 3455cm-1The left and right broad peaks correspond to the stretching vibration absorption peak of hydroxyl in the aromatic ring, which is 3082cm-1The absorption peak is 1632cm-1、1587cm-1、1521cm-1Is a characteristic absorption peak of an aromatic ring C-C skeleton, 1242cm-1The absorption peaks at the left and right are C-O stretching vibration absorption of the aromatic ether, which indicates that 2, 4-dihydroxy benzophenone and 1,3, 5-tri (chloromethyl) -benzene react to generate the ultraviolet absorbent shown in the formula I, and the most characteristic absorption peak is 1240cm-1And (3) stretching vibration absorption peaks of the left and right ether bonds.
FIG. 1 is a nuclear magnetic hydrogen spectrum of an ultraviolet absorber represented by the formula I, [ CDCl ]3-d 6 ,500MHz] δ7.7(m,6H),7.36~7.42(m,12H),7.05(s,3H),6.43(m,3H),6.34(s,3H),5.2(s,6H),5.0(s,3H)。
The ultraviolet absorbent prepared by the invention is benzophenone ultraviolet absorbent, has the advantages of low price, convenient synthesis, high yield and the like, simultaneously, the newly synthesized ultraviolet absorbent has high relative molecular quality, avoids the defects of low molecular weight, thermal instability, easy decomposition and volatilization of common benzophenone ultraviolet absorbents, increases the thermal stability and compatibility of the ultraviolet absorbent when being added into alloy plastics, has excellent yellowing resistance, does not change the appearance of PC/ABS alloy added with the ultraviolet absorbent after being exposed to sunlight for 5 months, and has the conditions of embrittlement, yellowing and the like when other ultraviolet absorbents are used under the same condition.
EXAMPLE 2 preparation of UV absorbers
The preparation method comprises the following steps:
respectively dissolving 0.032mol of 2, 4-dihydroxy benzophenone and 0.01mol of 1,3, 5-tris (chloromethyl) -benzene in acetone, and preparing NaOH solution, wherein the NaOH solution is prepared by dissolving 0.012mol of NaOH in 10mL of water, dropwise adding the 1,3, 5-tris (chloromethyl) -benzene solution and the NaOH solution into the 2, 4-dihydroxy benzophenone solution while stirring, controlling the reaction temperature to be not higher than 10 ℃, reacting for 5 hours after the dropwise adding is finished, cooling to below 0 ℃, and filtering to obtain the ultraviolet absorbent, wherein the yield is 95%.
EXAMPLE 3 PC/ABS alloy Plastic for housing Material
The raw materials comprise the following components in parts by weight: 70 parts of PC/ABS recovered powder, 0.1 part of ultraviolet absorbent, 1 part of resorcinol bis (diphenyl phosphate), 010.01 parts of toughening agent KNY, 0.1 part of toughening agent 1105A, 1 part of heat stabilizer and 0.5 part of polyethylene grafted maleic anhydride.
The PC/ABS recovered powder is a crushed material with the particle size of less than or equal to 10mm, which is obtained by crushing a recovered PC/ABS alloy material; the recovered PC/ABS alloy material is the waste material of waste electrical appliances made from raw materials, and the performance indexes of the recovered PC/ABS alloy material meet the following requirements: the impact strength of the cantilever beam notch is more than or equal to 5KJ/m2And the tensile strength is more than or equal to 32 MPa.
The heat stabilizer is prepared by mixing barium soap, organic phosphite ester and dihydropyridine in a mass ratio of 1: 0.2: 0.1.
the preparation method of the PC/ABS alloy plastic for the shell material specifically comprises the following steps: weighing the raw materials in proportion, putting the recovered PC/ABS powder, the toughening agent KNY01, the toughening agent 1105A, the polyethylene grafted maleic anhydride, the ultraviolet absorbent, the resorcinol bis (diphenylphosphate) and the heat stabilizer into a stirrer for repeatedly stirring three times, wherein the rotating speed of the stirrer is 500r/min, the stirring time is 1h each time, uniformly mixing, feeding the mixture into a double-screw extruder for melting and mixing, the rotating speed of the double-screw extruder is 300r/min, the melting and mixing temperature is 200 ℃, extruding the obtained melt by the double-screw extruder, cooling the melt by a water tank at 30 ℃, carrying out grain cutting operation by a grain cutter, wherein the rotating speed of the grain cutter is 300r/min, and collecting grains, namely the PC/ABS alloy plastic for the shell material.
EXAMPLE 4 PC/ABS alloy Plastic for housing Material
The raw materials comprise the following components in parts by weight: 100 parts of PC/ABS recovered powder, 0.5 part of ultraviolet absorber, 3 parts of melamine, 010.1 parts of toughening agent KNY, 0.3 part of toughening agent 1105A, 2 parts of heat stabilizer and 1.5 parts of styrene-butadiene copolymer grafted maleic anhydride.
The PC/ABS recovered powder is a crushed material with the particle size of less than or equal to 10mm, which is obtained by crushing a recovered PC/ABS alloy material; the recovered PC/ABS alloy material is a waste electrical appliance defective product material manufactured by raw materials, and the performance indexes of the recovered PC/ABS alloy material meet the following requirements: the impact strength of the cantilever beam notch is more than or equal to 5KJ/m2And the elongation at break is more than or equal to 15 percent.
The heat stabilizer is prepared by mixing barium soap, organic phosphite ester and dihydropyridine in a mass ratio of 1: 0.5: 0.3.
the preparation method of the PC/ABS alloy plastic for the shell material specifically comprises the following steps: weighing the raw materials in proportion, putting the recovered PC/ABS powder, the toughening agent KNY01, the toughening agent 1105A, the styrene-butadiene copolymer grafted maleic anhydride, the ultraviolet absorbent, the melamine and the heat stabilizer into a stirrer for repeatedly stirring three times, wherein the rotating speed of the stirrer is 1000r/min, the stirring time is 2 hours each time, uniformly mixing, sending into a double-screw extruder for melt mixing, the rotating speed of the double-screw extruder is 500r/min, the melt mixing temperature is 220 ℃, extruding the obtained melt through the double-screw extruder, cooling through a 50 ℃ water tank, carrying out grain cutting operation through a grain cutter, the rotating speed of the grain cutter is 500r/min, and collecting grains, namely the PC/ABS alloy plastic for the shell material.
EXAMPLE 5 PC/ABS alloy Plastic for housing Material
The raw materials comprise the following components in parts by weight: 85 parts of PC/ABS recovered powder, 0.3 part of ultraviolet absorber, 2 parts of melamine phosphate, 010.05 parts of toughening agent KNY, 0.2 part of toughening agent 1105A, 1.4 parts of heat stabilizer and 1.1 parts of polypropylene grafted maleic anhydride.
The PC/ABS recovered powder material is prepared by pulverizing recovered PC/ABS alloy material to obtain recovered material with particle diameter not more than10mm of crushed material; the recovered PC/ABS alloy material is a waste electrical appliance defective material made of raw materials, and the performance indexes of the recovered PC/ABS alloy material at least meet the following requirements: the impact strength of the cantilever beam notch is more than or equal to 5KJ/m2The tensile strength is more than or equal to 32MPa, and the elongation at break is more than or equal to 15 percent.
The heat stabilizer is prepared by mixing barium soap, organic phosphite ester and dihydropyridine in a mass ratio of 1: 0.35: 0.2.
the preparation method of the PC/ABS alloy plastic for the shell material specifically comprises the following steps: weighing the raw materials in proportion, putting the recovered PC/ABS powder, the toughening agent KNY01, the toughening agent 1105A, the polypropylene grafted maleic anhydride, the ultraviolet absorbent, the melamine phosphate and the heat stabilizer into a stirrer, repeatedly stirring for three times, wherein the rotating speed of the stirrer is 750r/min, the stirring time is 1.5h each time, uniformly mixing, sending into a double-screw extruder for melting and mixing, the rotating speed of the double-screw extruder is 400r/min, the melting and mixing temperature is 210 ℃, extruding the obtained melt through the double-screw extruder, cooling through a water tank at 40 ℃, carrying out grain cutting operation through a grain cutter, the rotating speed of the grain cutter is 400r/min, and collecting grains, namely the PC/ABS alloy plastic for the shell material.
Comparative example 1
Compared with example 5, the ultraviolet absorber was replaced by a UV-531 ultraviolet absorber, and other conditions were not changed.
The raw materials comprise the following components in parts by weight: 85 parts of PC/ABS recycled powder, 0.3 part of UV-531 ultraviolet absorbent, 2 parts of melamine phosphate, 0.2 part of flexibilizer KNY 010.05 parts, 0.2 part of flexibilizer 1105A, 1.4 parts of heat stabilizer and 1.1 parts of polypropylene grafted maleic anhydride.
The PC/ABS recovered powder is a crushed material with the particle size of less than or equal to 10mm, which is obtained by crushing a recovered PC/ABS alloy material; the recovered PC/ABS alloy material is a waste electrical appliance defective material made of raw materials, and the performance indexes of the recovered PC/ABS alloy material at least meet the following requirements: the impact strength of the cantilever beam notch is more than or equal to 5KJ/m2The tensile strength is more than or equal to 32MPa, and the elongation at break is more than or equal to 15 percent.
The heat stabilizer is prepared by mixing barium soap, organic phosphite ester and dihydropyridine in a mass ratio of 1: 0.35: 0.2.
the preparation method of the PC/ABS alloy plastic for the shell material specifically comprises the following steps: weighing the raw materials in proportion, putting the recovered PC/ABS powder, the toughening agent KNY01, the toughening agent 1105A, the polypropylene grafted maleic anhydride, the UV-531 ultraviolet absorbent, the melamine phosphate and the heat stabilizer into a stirrer, repeatedly stirring for three times, wherein the rotating speed of the stirrer is 750r/min, the stirring time is 1.5h each time, uniformly mixing, feeding the mixture into a double-screw extruder, carrying out melt mixing, wherein the rotating speed of the double-screw extruder is 400r/min, the melt mixing temperature is 210 ℃, extruding the obtained melt by the double-screw extruder, cooling the melt by a water tank at 40 ℃, carrying out grain cutting operation by a grain cutter, wherein the rotating speed of the grain cutter is 400r/min, and collecting grains, namely the PC/ABS alloy plastic for the shell material.
Comparative example 2
Compared with example 5, the toughening agent KNY01 was not added, and other conditions were not changed.
The raw materials comprise the following components in parts by weight: 85 parts of PC/ABS recovered powder, 0.3 part of ultraviolet absorber, 2 parts of melamine phosphate, 0.25 part of toughening agent 1105A, 1.4 parts of heat stabilizer and 1.1 parts of polypropylene grafted maleic anhydride.
The PC/ABS recovered powder is a crushed material with the particle size of less than or equal to 10mm, which is obtained by crushing a recovered PC/ABS alloy material; the recovered PC/ABS alloy material is a waste electrical appliance defective material made of raw materials, and the performance indexes of the recovered PC/ABS alloy material at least meet the following requirements: the impact strength of the cantilever beam notch is more than or equal to 5KJ/m2The tensile strength is more than or equal to 32MPa, and the elongation at break is more than or equal to 15 percent.
The heat stabilizer is prepared by mixing barium soap, organic phosphite ester and dihydropyridine, and the mass ratio of the barium soap to the organic phosphite ester is 1: 0.35: 0.2.
the preparation method of the PC/ABS alloy plastic for the shell material specifically comprises the following steps: weighing the raw materials in proportion, putting the PC/ABS recovered powder, the toughening agent 1105A, the polypropylene grafted maleic anhydride, the ultraviolet absorbent, the melamine phosphate and the heat stabilizer into a stirrer for repeatedly stirring three times, wherein the rotating speed of the stirrer is 750r/min, the stirring time of each time is 1.5h, uniformly mixing, sending the mixture into a double-screw extruder for melting and mixing, the rotating speed of the double-screw extruder is 400r/min, the melting and mixing temperature is 210 ℃, extruding the obtained melt by the double-screw extruder, cooling the melt by a water tank at 40 ℃, carrying out grain cutting operation by a grain cutter, wherein the rotating speed of the grain cutter is 400r/min, and collecting grains, namely the PC/ABS alloy plastic for the shell material.
Comparative example 3
Compared with example 5, no toughening agent 1105A was added, and other conditions were not changed.
The raw materials comprise the following components in parts by weight: 85 parts of PC/ABS recovered powder, 0.3 part of ultraviolet absorbent, 2 parts of melamine phosphate, 010.25 parts of flexibilizer KNY, 1.4 parts of heat stabilizer and 1.1 parts of polypropylene grafted maleic anhydride.
The PC/ABS recovered powder is a crushed material with the particle size of less than or equal to 10mm, which is obtained by crushing a recovered PC/ABS alloy material; the recovered PC/ABS alloy material is a waste electrical appliance defective material made of raw materials, and the performance indexes of the recovered PC/ABS alloy material at least meet the following requirements: the impact strength of the cantilever beam notch is more than or equal to 5KJ/m2The tensile strength is more than or equal to 32MPa, and the elongation at break is more than or equal to 15 percent.
The heat stabilizer is prepared by mixing barium soap, organic phosphite ester and dihydropyridine in a mass ratio of 1: 0.35: 0.2.
the preparation method of the PC/ABS alloy plastic for the shell material specifically comprises the following steps: weighing the raw materials in proportion, putting the PC/ABS recovered powder, the toughening agent KNY01, the polypropylene grafted maleic anhydride, the ultraviolet absorbent, the melamine phosphate and the heat stabilizer into a stirrer for repeatedly stirring three times, wherein the rotating speed of the stirrer is 750r/min, the stirring time of each time is 1.5h, uniformly mixing, sending the mixture into a double-screw extruder for melting and mixing, the rotating speed of the double-screw extruder is 400r/min, the melting and mixing temperature is 210 ℃, extruding the obtained melt by the double-screw extruder, cooling the melt by a water tank at 40 ℃, carrying out grain cutting operation by a grain cutter, wherein the rotating speed of the grain cutter is 400r/min, and collecting grains to obtain the PC/ABS alloy plastic for the shell material.
Comparative example 4
In comparison with example 5, the heat stabilizer consisted exclusively of organophosphites, the other conditions being unchanged.
The raw materials comprise the following components in parts by weight: 85 parts of PC/ABS recovered powder, 0.3 part of ultraviolet absorbent, 2 parts of melamine phosphate, 010.05 parts of toughening agent KNY, 0.2 part of toughening agent 1105A, 1.4 parts of organic phosphite ester and 1.1 parts of polypropylene grafted maleic anhydride.
The PC/ABS recovered powder is a crushed material with the particle size of less than or equal to 10mm, which is obtained by crushing a recovered PC/ABS alloy material; the recovered PC/ABS alloy material is a waste electrical appliance defective material made of raw materials, and the performance indexes of the recovered PC/ABS alloy material at least meet the following requirements: the impact strength of the cantilever beam notch is more than or equal to 5KJ/m2The tensile strength is more than or equal to 32MPa, and the elongation at break is more than or equal to 15 percent.
The preparation method of the PC/ABS alloy plastic for the shell material specifically comprises the following steps: weighing the raw materials in proportion, putting the recovered PC/ABS powder, the toughening agent KNY01, the toughening agent 1105A, the polypropylene grafted maleic anhydride, the ultraviolet absorbent, the melamine phosphate and the organic phosphite into a stirrer, repeatedly stirring for three times, wherein the rotating speed of the stirrer is 750r/min, the stirring time is 1.5h each time, uniformly mixing, sending into a double-screw extruder for melting and mixing, the rotating speed of the double-screw extruder is 400r/min, the melting and mixing temperature is 210 ℃, extruding the obtained melt by the double-screw extruder, cooling by a water tank at 40 ℃, carrying out grain cutting operation by a grain cutter, the rotating speed of the grain cutter is 400r/min, and collecting grains, namely the PC/ABS alloy plastic for the shell material.
Comparative example 5
In comparison with example 5, the heat stabilizer consisted of barium soap only, and the other conditions were not changed.
The raw materials comprise the following components in parts by weight: 85 parts of PC/ABS recovered powder, 0.3 part of ultraviolet absorber, 2 parts of melamine phosphate, 010.05 parts of toughening agent KNY, 0.2 part of toughening agent 1105A, 1.4 parts of barium soap and 1.1 parts of polypropylene grafted maleic anhydride.
The PC/ABS recovered powder is a crushed material with the particle size of less than or equal to 10mm, which is obtained by crushing a recovered PC/ABS alloy material; the recovered PC/ABS alloy material is a waste electrical appliance defective material made of raw materials, and the performance indexes of the recovered PC/ABS alloy material at least meet the following requirements: the impact strength of the cantilever beam notch is more than or equal to 5KJ/m2Tensile strength of not less than 32MPa, elongation at breakThe length is more than or equal to 15 percent.
The preparation method of the PC/ABS alloy plastic for the shell material specifically comprises the following steps: weighing the raw materials in proportion, putting the recovered PC/ABS powder, the toughening agent KNY01, the toughening agent 1105A, the polypropylene grafted maleic anhydride, the ultraviolet absorbent, the melamine phosphate and the barium soap into a stirrer for repeatedly stirring three times, wherein the rotating speed of the stirrer is 750r/min, the stirring time is 1.5h each time, uniformly mixing, sending into a double-screw extruder for melting and mixing, the rotating speed of the double-screw extruder is 400r/min, the melting and mixing temperature is 210 ℃, extruding the obtained melt by the double-screw extruder, cooling by a water tank at 40 ℃, carrying out grain cutting operation by a grain cutter, the rotating speed of the grain cutter is 400r/min, and collecting grains, namely the PC/ABS alloy plastic for the shell material.
Test example 1
The PC/ABS alloy plastic for housing materials prepared in the above-described examples 3 to 5 and comparative examples 1 to 5 and a commercially available PC/ABS alloy plastic (available from Primex Plastics, USA) were subjected to performance tests using the relevant standards, and the results of the measurements are shown in tables 1 and 2.
Placing the sample in a xenon lamp exposure light yellowing test box for irradiation according to a GB/T16422.2-2014 plastic laboratory light source exposure test method, and then measuring the yellow index according to a HG/T3862-2006 plastic yellow index test method to obtain the yellow index delta YI. The yellowing index delta YI is an important index for representing the photo-oxidative aging performance, and the smaller the delta YI is, the better the anti-light yellowing performance is.
Tensile strength and elongation at 23 ℃ were measured according to ASTM D638.
Specific gravity was measured according to ASTM D792.
Mold shrinkage was tested according to ASTM D955.
Flexural strength and flexural modulus were tested in accordance with ASTM D790.
Notched bar impact strength was tested according to ASTM D256.
The heat distortion temperature was measured according to ASTM D648.
Flame resistance was tested according to UL 94.
TABLE 1
| Group of | Specific gravity of | Mold shrinkage (%) | Flexural Strength (Kgf/cm)2） | Flexural modulus (Kgf/cm)2） | Notched impact strength (Kgf. cm/cm) |
| Example 3 | 1.19 | 0.2-0.3 | 1250 | 27000 | 90 |
| Example 4 | 1.21 | 0.2-0.3 | 1247 | 26880 | 92 |
| Example 5 | 1.18 | 0.2-0.3 | 1255 | 27120 | 95 |
| Comparative example 1 | 1.17 | 0.6-0.8 | 1022 | 26500 | 87 |
| Comparative example 2 | 1.16 | 0.4-0.6 | 780 | 23450 | 67 |
| Comparative example 3 | 1.17 | 0.4-0.6 | 810 | 24100 | 70 |
| Comparative example 4 | 1.19 | 0.5-0.7 | 1020 | 25700 | 85 |
| Comparative example 5 | 1.18 | 0.5-0.7 | 1095 | 26200 | 80 |
| Is commercially available | 1.21 | 0.4-0.6 | 1100 | 26800 | 75 |
TABLE 2
| Group of | Tensile Strength (Kgf/cm)2） | Elongation (%) | Temperature of Heat deformation (. degree. C.) | Flame resistance | Yellowing property |
| Example 3 | 700 | 95 | 110 | V0 | 0.05 |
| Example 4 | 702 | 94 | 108 | V0 | 0.06 |
| Example 5 | 705 | 96 | 112 | V0 | 0.04 |
| Comparative example 1 | 670 | 90 | 72 | V1 | 1.02 |
| Comparative example 2 | 520 | 75 | 102 | V0 | 0.25 |
| Comparative example 3 | 532 | 79 | 107 | V0 | 0.12 |
| Comparative example 4 | 680 | 91 | 75 | V2 | 0.39 |
| Comparative example 5 | 682 | 89 | 80 | V1 | 0.45 |
| Is commercially available | 685 | 90 | 95 | V0 | 0.18 |
As can be seen from tables 1 and 2, the PC/ABS alloy plastics for housing materials prepared in embodiments 3 to 5 of the present invention meet the requirements of the national household appliance industry for various materials, have the characteristics of high performance, high flame retardance, high impact resistance, cold resistance, high stability, yellowing resistance, aging resistance, and antistatic property, and are used for preparing housings of smart electricity meters, fax machines, and copier machines.
Comparative example 1 the ultraviolet absorbent prepared by the invention is replaced by the common UV-531 ultraviolet absorbent, the yellowing resistance is obviously reduced, and the thermal deformation temperature is obviously reduced;
compared with the example 5, the comparative examples 2 and 3 are not added with the toughening agent KNY01 or the toughening agent 1105A respectively, the mechanical property is obviously reduced, and the synergistic effect of the two toughening agents in the PC/ABS is shown; the toughening agent combination added in the invention comprises the following components: the toughening agents KNY01 and 1105A can obviously improve the mechanical properties of the alloy material, and the inventor finds that the toughening agents KNY01 can improve the toughness of the material at constant temperature, the toughening agents 1105A can improve the toughness of the material at low temperature, the two toughening agents are matched and used in PC/ABS to have synergistic effect, so that the effect of '1 +1 > 2' is well played, and the excellent properties of the PC/ABS alloy are more effectively ensured;
in comparative example 4 and comparative example 5, the heat stabilizer only has organic phosphite ester or barium soap respectively, the heat stability is reduced, the yellowing resistance is reduced, the flame resistance is reduced, as can be seen, the effect of singly using one heat stabilizer such as organic phosphite ester or barium soap is far inferior to the effect of compounding the organic phosphite ester or barium soap and the two heat stabilizers are matched and used in PC/ABS to have synergistic effect, so that the effect of '1 +1 > 2' is well played, and the excellent performance of the PC/ABS alloy is more effectively ensured.
Compared with the prior art, the preparation of the PC/ABS alloy plastic of the invention adopts waste electrical appliance type defective materials, defective materials or waste materials to replace PC and ABS raw materials, in order to ensure that the performance of the final product is excellent, the inventor collocates proper auxiliary agents aiming at the characteristics of the recovered PC + ABS alloy material, optimizes the dosage of each auxiliary agent, and selects each auxiliary agent and prepares the PC/ABS alloy material by an excellent process, so that the recovered PC + ABS alloy material can also prepare the PC/ABS alloy material with excellent performance, thereby making a contribution to national energy conservation, emission reduction and renewable resource utilization;
the PC/ABS alloy has the characteristics of high performance, high flame retardance, high impact resistance, cold resistance, high stability, yellowing resistance, aging resistance, static resistance and the like, can be used for preparing intelligent ammeter shells, instrument shells, fax machine shells or copier shells, can meet or exceed the material standards of the national household appliance industry in each index, has high material stability and good quality, and contributes to environmental protection, energy conservation and emission reduction of the domestic and international household appliance industry.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (8)
1. The PC/ABS alloy plastic for the shell material is characterized by being prepared from the following components in parts by weight: 70-100 parts of PC/ABS recycled powder, 0.1-0.5 part of ultraviolet absorbent, 1-3 parts of flame retardant, 0.1-0.1 part of toughening agent KNY 010.01, 0.1-0.3 part of toughening agent 1105A, 1-2 parts of heat stabilizer and 0.5-1.5 parts of compatibilizer; the heat stabilizer is prepared by mixing barium soap, organic phosphite ester and dihydropyridine, and the mass ratio is 1: (0.2-0.5): (0.1-0.3);
the ultraviolet absorbent has a structural formula as shown in formula I:
formula I;
the PC/ABS recovered powder is a crushed material with the particle size of less than or equal to 10mm obtained by crushing a recovered PC/ABS alloy material; the recovered PC/ABS alloy material is waste electrical appliance defective material, defective material or waste material produced from raw materials.
2. The PC/ABS alloy plastic for the shell material as claimed in claim 1, wherein the ultraviolet absorber is prepared by the following method: respectively dissolving 2, 4-dihydroxy benzophenone and 1,3, 5-tri (chloromethyl) -benzene in a solvent, preparing NaOH solution, dropwise adding the 1,3, 5-tri (chloromethyl) -benzene solution and the NaOH solution into the 2, 4-dihydroxy benzophenone solution while stirring, controlling the reaction temperature to be not higher than 10 ℃, reacting for 3-5 hours after the dropwise adding is finished, cooling to be lower than 0 ℃, and filtering to obtain the ultraviolet absorbent.
3. The PC/ABS alloy plastic for the shell material as claimed in claim 2, wherein the solvent is one or a mixture of acetone, acetonitrile, pyridine and tetrahydrofuran, and the NaOH solution is prepared by dissolving 0.01-0.012mol of NaOH in 10mL of water; the mass ratio of the 2, 4-dihydroxybenzophenone, the 1,3, 5-tris (chloromethyl) -benzene and the NaOH is (3-3.2): 1: (1-1.2).
4. The PC/ABS alloy plastic for the shell material as claimed in claim 1, wherein the flame retardant is one or more selected from resorcinol bis (diphenyl phosphate), melamine cyanuric acid, melamine phosphate and red phosphorus master batch.
5. The PC/ABS alloy plastic for the shell material as recited in claim 1, wherein the compatibilizer is one selected from polyethylene grafted maleic anhydride, acrylonitrile-styrene-butadiene copolymer grafted maleic anhydride, polypropylene grafted maleic anhydride, and styrene-butadiene copolymer grafted maleic anhydride.
6. The PC/ABS alloy plastic for shell materials as claimed in claim 1, wherein the recycled PC/ABS alloy material has at least one of the following three properties: the impact strength of the cantilever beam notch is more than or equal to 5KJ/m2The tensile strength is more than or equal to 32MPa or the elongation at break is more than or equal to 15 percent.
7. The preparation method of the PC/ABS alloy plastic for the shell material as claimed in any one of claims 1 to 6, which comprises the following steps: weighing the raw materials in proportion, putting the PC/ABS recovered powder, the toughening agent KNY01, the toughening agent 1105A, the compatibilizer, the ultraviolet absorber, the flame retardant and the heat stabilizer into a stirrer for repeatedly stirring three times, wherein the stirring time is 1-2h each time, uniformly mixing, feeding into a double-screw extruder for melting and mixing, extruding the obtained melt by the double-screw extruder, cooling by a water tank at 30-50 ℃, carrying out grain cutting operation by a grain cutting machine, and collecting grains to obtain the PC/ABS alloy plastic for the shell material.
8. The method for preparing PC/ABS alloy plastic for shell material as claimed in claim 7, wherein the rotation speed of the stirrer is 500-.
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