CN110591348B - Toughened PA/ABS alloy material and preparation method thereof - Google Patents
Toughened PA/ABS alloy material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of polymer alloy materials, in particular to a toughened PA/ABS alloy material and a preparation method thereof. The toughened PA/ABS alloy material comprises the following raw materials: polyamide, ABS high rubber powder, compatilizer and antioxidant; the compatilizer is an epoxy type compatilizer with a long side chain structure. The toughening PA/ABS alloy material can simultaneously enhance the tensile strength, the bending strength and the toughening, and realizes the toughening.
Description
Technical Field
The invention relates to the technical field of polymer alloy materials, in particular to a toughened PA/ABS alloy material and a preparation method thereof.
Background
PA (also called nylon, polyamide) and ABS are two important plastic products, wherein nylon has excellent mechanical property, heat resistance, abrasion resistance, chemical resistance and self-lubricity, has low friction coefficient, certain flame retardance and easy processing, is suitable for being filled with glass fiber and other fillers for reinforcing and modifying, improves the performance and expands the application range; ABS is a thermoplastic high polymer material with high strength, good toughness and easy processing and molding, can be suitable for the field of various plastic products according to different proportions of three monomers, has the main advantage of low price, and can obtain a novel product with excellent performance by preparing two plastics into alloy.
However, the compatibility of nylon and ABS is poor, and a compatilizer is often required to be added into the nylon and ABS to improve the toughness of the PA/ABS alloy material; the butadiene chain segment in the ABS inevitably causes the reduction of the tensile strength of the PA/ABS alloy material, but the existing compatilizer cannot solve the problem, so how to realize strengthening and toughening is a great difficulty when preparing the PA/ABS alloy material.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a toughening PA/ABS alloy material which can simultaneously enhance the tensile strength, the bending strength and the toughening and realize the toughening.
The invention also aims to provide a preparation method of the toughened PA/ABS alloy material, which has the advantages of simple operation, convenient control, high production efficiency and low production cost and can be used for large-scale production.
The purpose of the invention is realized by the following technical scheme: a toughened PA/ABS alloy material comprises the following raw materials in parts by weight:
the compatilizer is an epoxy type compatilizer with a long side chain structure.
The toughened PA/ABS alloy material takes polyamide and ABS high-rubber powder as main resin, and antioxidant is added to improve the aging resistance of the PA/ABS alloy material; the epoxy type compatilizer with a long side chain structure is added, so that gaps between PA phases and ABS phases can be effectively filled in the process of melt blending, the interface strength is improved, the reinforcing effect is achieved, and the tensile strength and the bending strength of the toughened PA/ABS alloy material can be enhanced; meanwhile, due to the high glue content of the ABS high glue powder, the epoxy group of the epoxy compatilizer enables the ABS high glue powder to have excellent compatibility, the compatibility of the polyamide and the ABS high glue powder is improved under the action of the epoxy compatilizer, the toughness of the toughened PA/ABS alloy material can be greatly improved, the effects of simultaneously enhancing the tensile strength, the bending strength and the toughening are achieved, and the toughening is realized; in addition, 0.3-0.8 part by weight of epoxy type compatilizer with a long side chain structure is added to play roles of compatibilization, toughening and reinforcement, so that the addition amount of an auxiliary agent in the toughened PA/ABS alloy material is greatly reduced, and the characteristics of the PA/ABS are greatly reserved.
Preferably, the polyamide is at least one of PA6, PA66, PA11, PA12, PA46, PA610, PA612, PAl010, PA7, PA9, and PA 13.
The polyamide has excellent mechanical performance, mechanical strength, toughness, self-lubricating property, friction resistance, heat resistance, electric insulation performance and weather resistance. From the viewpoints of easiness of obtaining industrial application, various characteristics, economy and the like, PA6 is preferable in the present invention because of the high cost performance of PA6, environmental friendliness, simple production process and the like. The PA6 is preferably, but not limited to, japanese space division 1030B.
Preferably, the rubber content of the ABS high rubber powder is 50-70 wt%, and the acrylonitrile content of the ABS high rubber powder is 20-35 wt%. The ABS high rubber powder is preferably but not limited to Korea HR 181.
By adopting the technical scheme, the rubber content of the high rubber powder is controlled to be 50-70 wt%, the toughness of the material can be greatly improved, when the toughened PA/ABS alloy material is subjected to impact fracture, the fracture energy can be effectively absorbed, the impact performance of the alloy material is improved, the thermal deformation temperature of the material can be improved, and a stress network structure can be formed, so that the impact performance of the toughened PA/ABS alloy material is improved; the acrylonitrile content of the ABS high rubber powder is controlled to be 20-35 wt%, the ABS high rubber powder has strong polarity, is easy to color, has good chemical resistance and strong rigidity, improves the glossiness, and improves the heat resistance and the chemical resistance of the toughened PA/ABS alloy material.
Preferably, the preparation method of the compatilizer comprises the following steps:
(A1) uniformly mixing 10-30 parts by weight of aromatic vinyl monomer, 2-10 parts by weight of long-alkyl methacrylate monomer and 2-10 parts by weight of epoxy unsaturated hydrocarbon to obtain a mixed monomer;
(A2) and (C) adding 30-40 parts of dispersant-water solution into the mixed monomer obtained in the step (A1), then adding 0.1-0.3 part of initiator under the condition of continuous stirring, heating to 70-85 ℃ for reaction for 6-8h, and then centrifuging, washing and drying to obtain the compatilizer.
The compatilizer prepared by the preparation method introduces phenyl, epoxy and long alkyl with long side chains, inhibits the degradation of PA/ABS, improves the grafting rate of aromatic vinyl monomers, and improves the grafting rate of epoxy unsaturated hydrocarbon, so that the compatilizer of the invention obtains epoxy with higher content, can improve the compatibility of toughening PA/ABS alloy materials, and in the process of melt blending, the long alkyl with long side chains can effectively fill gaps between PA phase and ABS phase, improve the interface strength and play a role in strengthening. In the step (A1), the aromatic vinyl monomer, the long alkyl methacrylate monomer and the epoxy unsaturated hydrocarbon are firstly mixed into a mixed monomer to prepare an oil phase system, and then the dispersant-water solution is mixed into the step (A2), so that the monomer can be uniformly dispersed in the water phase and can be always kept in a stable dispersion state, a suspension environment can be created, the monomer polymerization is promoted, and the yield of the compatilizer is improved; the dosage of the initiator is controlled to be 0.1 to 0.3 weight part, if the dosage of the initiator is too high, although the free radicals generated in unit time are relatively increased and the reaction speed is accelerated, the reaction heat can not be dredged in time, so that particles are generated in a reactant system instantaneously, the molecular weight of the compatilizer is rapidly reduced, the phenyl content is reduced, and the heat resistance is deteriorated; if the dosage of the initiator is too low, the initiation reaction is too slow, the production efficiency is too low, and the time cost is wasted. Compared with emulsion polymerization, the method has the advantages that the free radical copolymerization is carried out by using a suspension polymerization mode, the process is simpler, the production cost is lower, and the product is easier to separate and dry.
Preferably, the aromatic vinyl monomer is at least one of styrene, methyl styrene, ethyl styrene, butyl styrene, chlorinated styrene and brominated styrene; the epoxy unsaturated hydrocarbon is at least one of glycidyl acrylate, glycidyl methacrylate and glycidyl diacrylate; the structural general formula of the long alkyl methacrylate monomer is
Wherein n is 3-18, and n is an integer.
By adopting the aromatic vinyl monomer, the phenyl content of the compatilizer is increased, and the compatilizer is added into a toughened PA/ABS alloy material to greatly improve the heat resistance of the PA/ABS alloy material; more preferably, the aromatic vinyl monomer is styrene, and the content of phenyl groups is higher. The epoxy unsaturated hydrocarbon is adopted to improve the grafting ratio of the epoxy unsaturated hydrocarbon, so that the compatilizer of the invention obtains epoxy groups with higher content. The long-alkyl methacrylate monomer can improve the compatibility of toughened PA/ABS alloy materials, and in the process of melt blending, the long-alkyl methacrylate monomer with a long side chain can effectively fill gaps between the PA phase and the ABS phase to play a role in reinforcement, and more preferably, n is 3 (namely n-butyl methacrylate), n is 7 (namely n-octyl methacrylate), n is 11 (namely lauryl methacrylate), n is 15 (cetyl methacrylate), and n is 17 (namely octadecyl methacrylate), so that the long-alkyl methacrylate monomer is more easily obtained from the market and has relatively low cost.
Preferably, the initiator is at least one of benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate.
The invention has good initiating effect by strictly controlling the type, compounding and proportion of the initiator, promotes the free radical polymerization of the mixed monomer in the step (A1), improves the polymerization rate and improves the production efficiency. More preferably, the initiator is a mixture of benzoyl peroxide, dicumyl peroxide and azobisisobutyronitrile in a weight ratio of 1:0.5-1.5: 1.5-2.5.
Preferably, the dispersant-water solution is prepared by mixing a dispersant and water in a weight ratio of 0.1-0.2: 4-6, and the dispersant is at least one of calcium hydroxy phosphate, polyethylene glycol, calcium chloride, vinyl bis stearamide, zinc stearate and polyvinyl alcohol.
By adopting the technical scheme, the phenomenon that the reaction efficiency and the yield of the compatilizer are reduced due to the coagulation of liquid drops in the process of constructing the suspension environment is avoided. More preferably, the dispersant is a mixture of calcium hydroxy phosphate, polyethylene glycol and calcium chloride in a weight ratio of 2: 1-3: 1-2 are compounded.
Preferably, the antioxidant is formed by mixing a hindered phenol main antioxidant and a thioether auxiliary antioxidant in a weight ratio of 2-5: 0-1.
By adopting the technical scheme, the oxidation process of the toughened PA/ABS alloy material can be delayed or inhibited, so that the aging of the PA/ABS alloy material is prevented and the service life of the PA/ABS alloy material is prolonged; the hindered phenol main antioxidant and the thioether auxiliary antioxidant have synergistic effect, effectively capture peroxide free radicals to terminate the oxidation process in the aging process of the toughened PA/ABS alloy material, thereby achieving the antioxidation effect, having good antioxidation effect at high temperature and being not easy to hydrolyze in a high-humidity state; compared with amine antioxidants, the antioxidant is not easy to separate out under the conditions of high temperature and high humidity, so that the lasting anti-aging effect is kept; compared with the synergy of the hindered phenol main antioxidant and the phosphite ester auxiliary antioxidant, the hindered phenol main antioxidant and the thioether auxiliary antioxidant are mixed according to the weight ratio of 2-5:0-1, although the antioxidant effect is not better than that of the synergy of the hindered phenol main antioxidant and the phosphite ester auxiliary antioxidant in a short time, the phosphite ester auxiliary antioxidant is easy to hydrolyze, and the antioxidant is not easy to hydrolyze, so that the antioxidant can maintain the anti-aging effect for a long time, and is more favorable for playing the antioxidant effect under the conditions of high temperature and high humidity.
Preferably, the hindered phenol main antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2' -methylenebis (4-methyl-6-tert-butylphenol), n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, at least one of 2, 6-di-tert-butyl-p-cresol, 1, 3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene and 2, 2-methylenebis- (4-ethyl-6-tert-butylphenol); the thioether auxiliary antioxidant is at least one of dilauryl thiodipropionate, 2, 4-di (n-octyl thiomethylene) -6-methylphenol and octadecyl thiodipropionate.
By adopting the technical scheme, the function of capturing free radicals can be better exerted, so that the free radicals do not participate in oxidation circulation any more, and the strengthening and toughening PA/ABS alloy material is prevented from carrying out automatic oxidation reaction. More preferably, the hindered phenol main antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 2,2' -methylenebis (4-methyl-6-tert-butylphenol) in a weight ratio of 5: 1-3, mixing; the thioether auxiliary antioxidant is dilauryl thiodipropionate and 2, 4-di (n-octyl thiomethylene) -6-methylphenol according to the weight ratio of 1-3: 1 are mixed.
The other purpose of the invention is realized by the following technical scheme: the preparation method of the toughened PA/ABS alloy material comprises the following steps:
(S1), weighing polyamide, ABS high-rubber powder, a compatilizer and an antioxidant according to the parts by weight for later use;
(S2) uniformly mixing the polyamide, the ABS high-rubber powder, the compatilizer and the antioxidant in a high-speed mixer, and then extruding and granulating through a double-screw extruder to obtain the toughened PA/ABS alloy material.
The preparation method disclosed by the invention is simple to operate, convenient to control, high in production efficiency and low in production cost, and can be used for large-scale production. In the step (S2), the polyamide, the ABS high-rubber powder, the compatilizer and the antioxidant are uniformly mixed in a high-speed mixer, so that the uniformity and the stability of the material in the extrusion process are facilitated.
Further, the processing temperature of each section of the double-screw extruder from the feeding section is respectively as follows: 200-. According to the invention, the temperature of each zone in the double-screw extruder is controlled, so that the prepared toughened PA/ABS alloy material has excellent mechanical properties, no foaming, smooth surface and high glossiness. When the temperature in each zone is too high, the heat resistance of the antioxidant is not so high that the effect of the antioxidant is easily lowered, so that the processing temperature is controlled to be lower than 245 ℃.
The invention has the beneficial effects that: the toughened PA/ABS alloy material takes polyamide and ABS high-rubber powder as main resin, and antioxidant is added to improve the aging resistance of the PA/ABS alloy material; the epoxy type compatilizer with a long side chain structure is added, so that gaps between PA phases and ABS phases can be effectively filled in the process of melt blending, the interface strength is improved, the reinforcing effect is achieved, and the tensile strength and the bending strength of the toughened PA/ABS alloy material can be enhanced; meanwhile, due to the high glue content of the ABS high glue powder and the excellent compatibility of the epoxy group of the epoxy compatilizer, the compatibility of the polyamide and the ABS high glue powder is improved under the action of the epoxy compatilizer, the toughness of the toughened PA/ABS alloy material can be greatly improved, the effects of simultaneously enhancing the tensile strength, the bending strength and the toughening are achieved, and the toughening is realized.
The preparation method of the toughened PA/ABS alloy material has the advantages of simple operation, convenient control, high production efficiency and low production cost, and can be used for large-scale production.
Drawings
FIG. 1 is a schematic synthesis of example 1 of the present invention.
Detailed Description
For the understanding of those skilled in the art, the present invention will be further described with reference to the following examples and drawings, which are not intended to limit the present invention.
Example 1
A toughened PA/ABS alloy material comprises the following raw materials in parts by weight:
the compatilizer is an epoxy type compatilizer with a long side chain structure.
The polyamide is PA 6.
The rubber content of the ABS high rubber powder is 60 wt%, and the acrylonitrile content of the ABS high rubber powder is 28 wt%.
As shown in fig. 1, the preparation method of the compatibilizer comprises the following steps:
(A1) uniformly mixing 20 parts by weight of aromatic vinyl monomer, 6 parts by weight of long-alkyl methacrylate monomer and 6 parts by weight of epoxy unsaturated hydrocarbon to obtain a mixed monomer;
(A2) and (C) adding 35 parts of dispersant-water solution into the mixed monomer obtained in the step (A1), then adding 0.2 part of initiator under the condition of continuous stirring, heating to 78 ℃ for reaction for 7 hours, and then centrifuging, washing and drying to obtain the compatilizer.
The aromatic vinyl monomer is styrene; the epoxy unsaturated hydrocarbon is glycidyl methacrylate; the structural general formula of the long alkyl methacrylate monomer is
Wherein n-11, lauryl methacrylate.
The initiator is a mixture of benzoyl peroxide, dicumyl peroxide and azobisisobutyronitrile in a weight ratio of 1:1: 2.
The dispersant-water solution is prepared by mixing a dispersant and water in a weight ratio of 0.15: 5, the dispersing agent is prepared by mixing calcium hydroxy phosphate, polyethylene glycol and calcium chloride according to the weight ratio of 2: 2: 1.5 is prepared by compounding.
The antioxidant is hindered phenol main antioxidant.
The hindered phenol main antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
The preparation method of the toughened PA/ABS alloy material comprises the following steps:
(S1), weighing polyamide, ABS high-rubber powder, a compatilizer and an antioxidant according to the parts by weight for later use;
(S2) uniformly mixing the polyamide, the ABS high-rubber powder, the compatilizer and the antioxidant in a high-speed mixer, and then extruding and granulating through a double-screw extruder to obtain the toughened PA/ABS alloy material.
The processing temperature of each section of the double-screw extruder from the feeding section is respectively as follows: 224 ℃, 232 ℃, 236 ℃, 231 ℃, 239 ℃, 240 ℃, 237 ℃ and 238 ℃, wherein the die head temperature of the double-screw extruder is 242 ℃, and the screw rotating speed of the double-screw extruder is 360 r/min.
Example 2
A toughened PA/ABS alloy material comprises the following raw materials in parts by weight:
the compatilizer is an epoxy type compatilizer with a long side chain structure.
The polyamide is PA66 and PA11 according to the weight ratio of 1:1 are mixed.
The rubber content of the ABS high rubber powder is 50 wt%, and the acrylonitrile content of the ABS high rubber powder is 20 wt%.
The preparation method of the compatilizer comprises the following steps:
(A1) uniformly mixing 10 parts by weight of aromatic vinyl monomer, 2 parts by weight of long-alkyl methacrylate monomer and 2 parts by weight of epoxy unsaturated hydrocarbon to obtain a mixed monomer;
(A2) and (C) adding 30 parts of dispersant-water solution into the mixed monomer obtained in the step (A1), then adding 0.1 part of initiator under the condition of continuous stirring, heating to 70 ℃ for reaction for 6 hours, and then centrifuging, washing and drying to obtain the compatilizer.
The aromatic vinyl monomer is methyl styrene and ethyl styrene according to the weight ratio of 2: 1, mixing; the long alkyl methacrylate monomer is n-butyl methacrylate; the epoxy unsaturated hydrocarbon is glycidyl acrylate.
The initiator is azobisisobutyronitrile.
The dispersant-water solution is prepared by mixing a dispersant and water in a weight ratio of 0.1: 4, the dispersing agent is prepared by mixing calcium hydroxy phosphate, polyethylene glycol and calcium chloride according to the weight ratio of 2: 1:1 is prepared by compounding.
The antioxidant is formed by mixing a hindered phenol main antioxidant and a thioether auxiliary antioxidant according to the weight ratio of 2: 0.5.
The hindered phenol main antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 2,2' -methylenebis (4-methyl-6-tert-butylphenol) according to the weight ratio of 5:1, mixing; the thioether auxiliary antioxidant is dilauryl thiodipropionate and 2, 4-di (n-octyl thiomethylene) -6-methylphenol according to the weight ratio of 1:1 are mixed.
The preparation method of the toughened PA/ABS alloy material comprises the following steps:
(S1), weighing polyamide, ABS high-rubber powder, a compatilizer and an antioxidant according to the parts by weight for later use;
(S2) uniformly mixing the polyamide, the ABS high-rubber powder, the compatilizer and the antioxidant in a high-speed mixer, and then extruding and granulating through a double-screw extruder to obtain the toughened PA/ABS alloy material.
The processing temperature of each section of the double-screw extruder from the feeding section is respectively as follows: 200 ℃, 230 ℃, 235 ℃, the die head temperature of the double-screw extruder is 240 ℃, and the screw rotating speed of the double-screw extruder is 320 r/min.
Example 3
A toughened PA/ABS alloy material comprises the following raw materials in parts by weight:
the compatilizer is an epoxy type compatilizer with a long side chain structure.
The polyamide is PA46 and PA7 according to the weight ratio of 1:1 are mixed.
The rubber content of the ABS high-rubber powder is 70 wt%, and the acrylonitrile content of the ABS high-rubber powder is 35 wt%.
The preparation method of the compatilizer comprises the following steps:
(A1) uniformly mixing 30 parts by weight of aromatic vinyl monomer, 10 parts by weight of long-alkyl methacrylate monomer and 10 parts by weight of epoxy unsaturated hydrocarbon to obtain a mixed monomer;
(A2) and (C) adding 40 parts of dispersant-water solution into the mixed monomer obtained in the step (A1), then adding 0.3 part of initiator under the condition of continuous stirring, heating to 85 ℃ for reaction for 8 hours, and then centrifuging, washing and drying to obtain the compatilizer.
The aromatic vinyl monomer is butyl styrene, chlorinated styrene and brominated styrene according to the weight ratio of 5: 1:1, mixing; the long-alkyl methacrylate monomer is n-butyl methacrylate and lauryl methacrylate according to the weight ratio of 1: 3, mixing; the epoxy unsaturated hydrocarbon is glycidyl acrylate and glycidyl methacrylate, and the weight ratio of the epoxy unsaturated hydrocarbon to the glycidyl acrylate is 1: 4, and mixing.
The initiator is a mixture of benzoyl peroxide, dicumyl peroxide and azobisisobutyronitrile in a weight ratio of 1:1.5: 2.5.
The dispersant-water solution is prepared by mixing a dispersant and water in a weight ratio of 0.2: 6, the dispersing agent is prepared by mixing calcium hydroxy phosphate, polyethylene glycol and calcium chloride according to the weight ratio of 2: 3: 2 is prepared by compounding.
The antioxidant is formed by mixing hindered phenol main antioxidant and thioether auxiliary antioxidant according to the weight ratio of 5:1.
The hindered phenol main antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 2,2' -methylenebis (4-methyl-6-tert-butylphenol) according to the weight ratio of 5: 3, mixing; the thioether auxiliary antioxidant is dilauryl thiodipropionate and 2, 4-di (n-octyl thiomethylene) -6-methylphenol according to the weight ratio of 3: 1 are mixed.
The preparation method of the toughened PA/ABS alloy material comprises the following steps:
(S1), weighing polyamide, ABS high-rubber powder, a compatilizer and an antioxidant according to the parts by weight for later use;
(S2) uniformly mixing the polyamide, the ABS high-rubber powder, the compatilizer and the antioxidant in a high-speed mixer, and then extruding and granulating through a double-screw extruder to obtain the toughened PA/ABS alloy material.
The processing temperature of each section of the double-screw extruder from the feeding section is respectively as follows: 230 ℃, 235 ℃, 240 ℃, 245 ℃ of a die head of the double-screw extruder, and 400r/min of screw rotating speed of the double-screw extruder.
Example 4
A toughened PA/ABS alloy material comprises the following raw materials in parts by weight:
the compatilizer is an epoxy type compatilizer with a long side chain structure.
The polyamide is PA 6.
The rubber content of the ABS high rubber powder is 52 wt%, and the acrylonitrile content of the ABS high rubber powder is 33 wt%.
The preparation method of the compatilizer comprises the following steps:
(A1) uniformly mixing 12 parts by weight of aromatic vinyl monomer, 7 parts by weight of long-alkyl methacrylate monomer and 6 parts by weight of epoxy unsaturated hydrocarbon to obtain a mixed monomer;
(A2) and (C) adding 32 parts of dispersant-water solution into the mixed monomer obtained in the step (A1), then adding 0.12 part of initiator under the condition of continuous stirring, heating to 74 ℃, reacting for 6.5h, and then centrifuging, washing and drying to obtain the compatilizer.
The aromatic vinyl monomer is styrene; the long-alkyl methacrylate monomer is octadecyl methacrylate; the epoxy unsaturated hydrocarbon is glycidyl methacrylate.
The initiator is a mixture of benzoyl peroxide, dicumyl peroxide and azobisisobutyronitrile in a weight ratio of 1:0.5: 1.5.
The dispersant-water solution is prepared by mixing a dispersant and water in a weight ratio of 0.12: 4.5, the dispersant is prepared by mixing calcium hydroxy phosphate, polyethylene glycol and calcium chloride according to the weight ratio of 2: 1.5:1.5 is prepared by compounding.
The antioxidant is formed by mixing a hindered phenol main antioxidant and a thioether auxiliary antioxidant according to the weight ratio of 2.5: 0.5.
The hindered phenol main antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 2,2' -methylenebis (4-methyl-6-tert-butylphenol) according to the weight ratio of 5:2, mixing; the thioether auxiliary antioxidant is dilauryl thiodipropionate and 2, 4-di (n-octyl thiomethylene) -6-methylphenol according to the weight ratio of 2: 1 are mixed.
The preparation method of the toughened PA/ABS alloy material comprises the following steps:
(S1), weighing polyamide, ABS high-rubber powder, a compatilizer and an antioxidant according to the parts by weight for later use;
(S2) uniformly mixing the polyamide, the ABS high-rubber powder, the compatilizer and the antioxidant in a high-speed mixer, and then extruding and granulating through a double-screw extruder to obtain the toughened PA/ABS alloy material.
The processing temperature of each section of the double-screw extruder from the feeding section is respectively as follows: 215 ℃, 232 ℃, 238 ℃, 235 ℃, 233 ℃, 238 ℃, 237 ℃, the die head temperature of the double-screw extruder is 243 ℃, and the screw rotating speed of the double-screw extruder is 380 r/min.
Example 5
A toughened PA/ABS alloy material comprises the following raw materials in parts by weight:
the compatilizer is an epoxy type compatilizer with a long side chain structure.
The polyamide is PA 13.
The rubber content of the ABS high rubber powder is 67 wt%, and the acrylonitrile content of the ABS high rubber powder is 22 wt%.
The preparation method of the compatilizer comprises the following steps:
(A1) uniformly mixing 27 parts by weight of aromatic vinyl monomer, 4 parts by weight of long-alkyl methacrylate monomer and 2 parts by weight of epoxy unsaturated hydrocarbon to obtain a mixed monomer;
(A2) and (C) adding 38 parts of dispersant-water solution into the mixed monomer obtained in the step (A1), then adding 0.28 part of initiator under the condition of continuous stirring, heating to 83 ℃, reacting for 7.8h, centrifuging, washing and drying to obtain the compatilizer.
The aromatic vinyl monomer is methyl styrene; the long-alkyl methacrylate monomer is lauryl methacrylate and hexadecyl methacrylate according to the weight ratio of 3: 1, mixing; the epoxy unsaturated hydrocarbon is glycidyl diacrylate.
The initiator is a mixture of benzoyl peroxide, dicumyl peroxide and azobisisobutyronitrile in a weight ratio of 1:0.8: 2.2.
The dispersant-water solution is prepared by mixing a dispersant and water in a weight ratio of 0.17: 5.7, wherein the dispersant is a mixture of hydroxyl vinyl bis stearamide, zinc stearate and polyvinyl alcohol according to a weight ratio of 1: 3: 1 is prepared by compounding.
The antioxidant is formed by mixing a hindered phenol main antioxidant and a thioether auxiliary antioxidant according to the weight ratio of 3: 0.3.
The hindered phenol main antioxidant is 2, 6-di-tert-butyl-p-cresol; the thioether auxiliary antioxidant is dilauryl thiodipropionate.
The preparation method of the toughened PA/ABS alloy material comprises the following steps:
(S1), weighing polyamide, ABS high-rubber powder, a compatilizer and an antioxidant according to the parts by weight for later use;
(S2) uniformly mixing the polyamide, the ABS high-rubber powder, the compatilizer and the antioxidant in a high-speed mixer, and then extruding and granulating through a double-screw extruder to obtain the toughened PA/ABS alloy material.
The processing temperature of each section of the double-screw extruder from the feeding section is respectively as follows: 217 ℃, 234 ℃, 236 ℃, 237 ℃, 233 ℃, 236 ℃, 237 ℃, 238 ℃, 239 ℃, the die head temperature of the double-screw extruder is 244 ℃, and the screw rotating speed of the double-screw extruder is 330 r/min.
Comparative example 1
This comparative example differs from example 1 in that: the toughened PA/ABS alloy material does not contain a compatilizer.
Comparative example 2
This comparative example differs from example 1 in that: the compatilizer is commercially available compatilizer SAG-001 (Hipposhu molecular New materials science and technology Co., Ltd., Nantong).
Comparative example 3
This comparative example differs from example 1 in that: the amount of the compatibilizer was 3 parts by weight, and the compatibilizer was commercially available as SAG-001 (advanced molecular materials science and technology ltd, south tomayi).
Example 6
The toughened PA/ABS alloy materials of examples 1-5 and comparative examples 1-3 are respectively subjected to impact strength, tensile strength, elongation at break, flexural strength and flexural modulus tests, and the test methods are as follows:
and (3) testing impact strength: the notched impact strength was determined according to GB/T1043.1-2008, specimen size: (80X 10X 4) mm, notch type: type A, the test environment is 23 +/-2 ℃, and the unit is kJ/m2。
And (3) testing tensile strength: measured according to GB/T1040.2-2006, test speed: 50mm/min in MPa.
Elongation at break test: measured according to GB/T1040.2-2006, test speed: 50mm/min in%.
And (3) testing the bending strength: measured according to GB/T9341-2008, the units are MPa.
Flexural modulus test: measured according to GB/T9341-2008, the units are MPa.
The test results are shown in table 1 below:
TABLE 1
| Notched impact strength | Tensile strength | Elongation at break | Bending strength | Flexural modulus | |
| Example 1 | 70.5 | 44.5 | 153 | 51.2 | 1230 |
| Example 2 | 70.1 | 43.8 | 150 | 49.5 | 1130 |
| Example 3 | 71.4 | 45.2 | 155 | 53.3 | 1380 |
| Example 4 | 70.6 | 44.3 | 153 | 52.4 | 1275 |
| Example 5 | 70.5 | 44.8 | 151 | 51.8 | 1190 |
| Comparative example 1 | 30.1 | 39.0 | 130 | 34.0 | 660 |
| Comparative example 2 | 41.8 | 38.7 | 131 | 34.9 | 685 |
| Comparative example 3 | 71.2 | 38.2 | 135 | 36.5 | 720 |
As can be seen from the above table 1, the notch impact strength, the tensile strength, the elongation at break, the bending strength and the bending modulus of the toughened PA/ABS alloy material prepared by the epoxy type compatilizer with the long side chain structure in the embodiments 1 to 5 of the invention are all significantly improved compared with the comparative example 1 without adding the compatilizer, which indicates that the compatilizer of the invention can greatly improve the toughness of the toughened PA/ABS alloy material, and achieve the effects of simultaneously enhancing the tensile strength, the bending strength and the toughening, thereby realizing the toughening.
Comparative example 2, in comparison with example 1, in which the epoxy type compatibilizer having a long side chain structure was replaced with the commercially available compatibilizer SAG-001, even though the notched impact strength was improved, it failed to improve the tensile strength and the effect of improving the notched impact strength was lower than that of example 1.
In comparative example 3, compared to example 1, when the epoxy type compatibilizer having a long side chain structure was replaced with the commercially available compatibilizer SAG-001 and the amount of the commercially available compatibilizer SAG-001 was increased to 3 parts by weight, the notched impact strength was significantly improved, but the tensile strength was not yet enhanced, and the flexural strength was not significantly enhanced, and only the toughening effect was achieved.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (7)
1. A toughened PA/ABS alloy material is characterized in that: the feed comprises the following raw materials in parts by weight:
the rubber content of the ABS high-rubber powder is 50-70 wt%, and the acrylonitrile content of the ABS high-rubber powder is 20-35 wt%;
the preparation method of the compatilizer comprises the following steps:
(A1) uniformly mixing 10-30 parts by weight of aromatic vinyl monomer, 2-10 parts by weight of long-alkyl methacrylate monomer and 2-10 parts by weight of epoxy unsaturated hydrocarbon to obtain a mixed monomer;
(A2) adding 30-40 parts of dispersant-water solution into the mixed monomer obtained in the step (A1), then adding 0.1-0.3 part of initiator under the condition of continuous stirring, heating to 70-85 ℃ for reaction for 6-8h, and then centrifuging, washing and drying to obtain the compatilizer;
the aromatic vinyl monomer is at least one of styrene, methyl styrene, ethyl styrene, butyl styrene, chlorinated styrene and brominated styrene; the epoxy unsaturated hydrocarbon is at least one of glycidyl acrylate, glycidyl methacrylate and glycidyl diacrylate; the structural general formula of the long alkyl methacrylate monomer is
Wherein n is 3-18, and n is an integer.
2. The toughened PA/ABS alloy material as claimed in claim 1, wherein: the polyamide is at least one of PA6, PA66, PA11, PA12, PA46, PA610, PA612, PAl010, PA7, PA9 and PA 13.
3. The toughened PA/ABS alloy material as claimed in claim 1, wherein: the initiator is at least one of benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate.
4. The toughened PA/ABS alloy material as claimed in claim 1, wherein: the dispersant-water solution is prepared by mixing a dispersant and water in a weight ratio of 0.1-0.2: 4-6, and the dispersant is at least one of calcium hydroxy phosphate, polyethylene glycol, calcium chloride, vinyl bis stearamide, zinc stearate and polyvinyl alcohol.
5. The toughened PA/ABS alloy material as claimed in claim 1, wherein: the antioxidant is formed by mixing a hindered phenol main antioxidant and a thioether auxiliary antioxidant in a weight ratio of 2-5: 0-1.
6. The toughened PA/ABS alloy material as claimed in claim 5, wherein: the hindered phenol main antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2' -methylenebis (4-methyl-6-tert-butylphenol), n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, at least one of 2, 6-di-tert-butyl-p-cresol, 1, 3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene and 2, 2-methylenebis- (4-ethyl-6-tert-butylphenol); the thioether auxiliary antioxidant is at least one of dilauryl thiodipropionate, 2, 4-di (n-octyl thiomethylene) -6-methylphenol and octadecyl thiodipropionate.
7. A method for preparing a toughened PA/ABS alloy material as claimed in any of claims 1 to 6, characterized in that: the method comprises the following steps:
(S1), weighing polyamide, ABS high-rubber powder, a compatilizer and an antioxidant according to the parts by weight for later use;
(S2) uniformly mixing the polyamide, the ABS high-rubber powder, the compatilizer and the antioxidant in a high-speed mixer, and then extruding and granulating through a double-screw extruder to obtain the toughened PA/ABS alloy material.
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