CN109535681B - Alloy material for high-fluidity thin-wall product and preparation method thereof - Google Patents

Alloy material for high-fluidity thin-wall product and preparation method thereof Download PDF

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CN109535681B
CN109535681B CN201811277083.3A CN201811277083A CN109535681B CN 109535681 B CN109535681 B CN 109535681B CN 201811277083 A CN201811277083 A CN 201811277083A CN 109535681 B CN109535681 B CN 109535681B
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alloy material
calcium carbonate
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fluidity
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郑宇航
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Guangdong Polygruimer Co ltd
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
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Abstract

The invention relates to the technical field of alloy materials, in particular to an alloy material for a high-fluidity thin-wall product and a preparation method thereof, wherein the alloy material for the high-fluidity thin-wall product comprises the following raw materials in parts by weight: 40-60 parts of PC resin, 10-15 parts of ABS resin, 20-30 parts of HDPE resin, 5-10 parts of flame retardant, 6-18 parts of flow increasing agent, 10-15 parts of impact modifier, 3-9 parts of dispersant, 2-5 parts of hydrolysis resistant agent and 1-3 parts of compatilizer; the flow increasing agent is a mixture consisting of ethylene bis stearamide and polyethylene wax; the impact modifier is a mixture composed of polyolefin elastomer, modified nano calcium carbonate and vinyl acetate-maleic anhydride graft copolymer, and when the wall thickness of the prepared alloy material product is 2mm, the impact strength is more than 44.36KJ/m2And the MFR is more than 20.14g/10min, and the preparation method is suitable for preparing thin-walled products.

Description

Alloy material for high-fluidity thin-wall product and preparation method thereof
Technical Field
The invention relates to the technical field of alloy materials, in particular to an alloy material for a high-fluidity thin-wall product and a preparation method thereof.
Background
Polycarbonate (PC) is an amorphous thermoplastic resin with excellent comprehensive performance, has excellent electrical insulation, extensibility, dimensional stability and chemical corrosion resistance, has higher strength, heat resistance and cold resistance, has the advantages of self-extinguishing flame retardance, no toxicity, colorability and the like, and is widely used engineering plastic. However, the PC alloy materials developed in the current market basically have the defects of not strong enough impact resistance (about 500J/m) and not good enough fluidity (about 17g/10min of melt index), are not suitable for manufacturing thin-wall products, can meet high impact resistance only when reaching the corresponding thickness, and are easy to have the defects of rough surface and the like during injection molding because of not good fluidity, and influence the molding production period.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide an alloy material for a high-fluidity thin-wall product, which has high fluidity and high impact resistance, and the impact strength is more than 44.36KJ/m when the wall thickness of the product is 2mm2And the MFR is more than 20.14g/10min, and the preparation method is suitable for preparing thin-walled products.
The second purpose of the invention is to provide a preparation method of the alloy material for the high-fluidity thin-wall product, so that the prepared PC-ABS alloy material has better comprehensive properties such as impact resistance, flame retardance, strength and the like, and has high fluidity and good processing stability.
The first purpose of the invention is realized by the following technical scheme: an alloy material for high-fluidity thin-wall products comprises the following raw materials in parts by weight:
Figure GDA0002781056860000021
the flow increasing agent is a mixture consisting of ethylene bis stearamide and polyethylene wax; the impact modifier is a mixture consisting of polyolefin elastomer, modified nano calcium carbonate and vinyl acetate-maleic anhydride graft copolymer.
The PC-ABS alloy material for the high-fluidity thin-wall product is prepared by adopting the raw materials in parts by weight, the prepared alloy material has high gloss, high fluidity and excellent impact resistance, the MFR value is more than 20.14g/10min, and when the wall thickness of the product is 2mm, the impact strength is more than 44.36KJ/m2The tensile strength is greater than 30.56MPa, the good balance of rigidity and toughness is realized, the flame retardant polycarbonate composite material is suitable for preparing thin-wall products, the flame retardant property is good, and the flame retardant grade can reach A level.
The PC resin has excellent electrical insulation performance, extensibility, dimensional stability and chemical corrosion resistance, has higher strength, good heat resistance and cold resistance, and also has the advantages of self-extinguishing, flame retardance, no toxicity, colorability and the like, the ABS resin has good impact resistance, scratch resistance and heat resistance, high toughness, easy processing, good processing flowability, good processing dimensional stability and good surface gloss, and the HDPE has good self-lubricating property, so that the flowability of the PC resin is improved, the impact resistance of the material is improved, and the raw material cost can be reduced by mixing the HDPE with the PC. Therefore, the PC-ABS alloy material produced by blending the PC, the ABS and the HDPE resin has the characteristics of good impact resistance, electrical insulation property, flame retardance and weather resistance, high fluidity, easy processing and good surface gloss, and is suitable for preparing thin-wall products with high fluidity and high impact resistance.
According to the invention, the composite flow increasing agent is composed of ethylene bis stearamide and polyethylene wax, so that the flow increasing modification is carried out on the PC-ABS alloy material, and the flow property and the processing stability of the PC-ABS alloy material are improved. The ethylene bis stearamide has good compatibility with the PC-ABS alloy material, and can play a role in good internal and external lubrication when added into the PC-ABS alloy material, while the polyethylene wax and the HDPE have good compatibility and can penetrate into molecular chains of the HDPE to play a role in lubrication in a molten state, so that HDPE macromolecules are easier to move, the dispersibility of other raw material components in the PC-ABS alloy material is improved to a certain extent, and the comprehensive performance of the alloy material is improved.
The PC-ABS alloy material is subjected to impact resistance modification by using the polyolefin elastomer, the modified nano calcium carbonate and the vinyl acetate-maleic anhydride graft copolymer, so that the prepared PC-ABS alloy material has excellent impact resistance.
The elastic body vinyl acetate in the vinyl acetate-maleic anhydride graft copolymer can be divided into a plurality of elastic cores which are uniformly dispersed when the elastic body vinyl acetate is impacted in the alloy material, and because the vinyl acetate has better flexibility and larger deformation capability, the impact absorption and dispersion capability can be changed by the vinyl acetate-maleic anhydride graft copolymer, so that the impact resistance of the alloy material is improved. The polyolefin elastomer and the HDPE have good compatibility, and when the polyolefin elastomer is added in parts by weight, the HDPE can be wrapped in polyolefin elastomer particles, so that the volume of an elastic rubber area in an alloy system is increased, a stress concentration area in the alloy system is enlarged, and the impact strength of the PC-ABS alloy material is improved. The modified nano calcium carbonate can improve the dispersion performance of calcium carbonate particles in an alloy material and improve the compatibility of the calcium carbonate particles and the alloy material, and the nano calcium carbonate particles are embedded in an alloy material matrix to form a stress concentration point so that cracks generated in an alloy material system are hindered and passivated, and finally, the cracks are stopped and are not developed into destructive cracks. Therefore, the impact modifier can carry out synergistic impact modification on alloy materials through the absorption and dispersion effects of the elastic deformation of the vinyl acetate-maleic anhydride graft copolymer on impact energy, the effect of the polyolefin elastomer wrapping HDPE to enlarge a rubber area and further enlarge a stress concentration area of a system and the prevention and passivation effects of nano calcium carbonate on crack propagation, so that the impact resistance of the PC-ABS alloy material is improved, and the prepared alloy material is suitable for manufacturing thin-wall products.
According to the invention, the flame retardant is added to improve the flame retardant property of the PC-ABS alloy material, and the hydrolysis resistant agent and the dispersing agent are added to improve the stability of the PC-ABS alloy material and prolong the service life of the PC-ABS alloy material. The addition of the compatilizer can further improve the compatibility between the mixed materials and improve the comprehensive performance of the mixed materials.
Wherein the weight ratio of the polyolefin elastomer to the modified nano calcium carbonate to the vinyl acetate-maleic anhydride graft copolymer is 2-3:0.5-1: 2.5-4.
According to the invention, the impact modifier prepared by adopting the weight ratio has a better impact modification effect on the PC-ABS alloy material, and is more beneficial to improving the notch impact strength of the alloy material, and when the content of the vinyl acetate-maleic anhydride graft copolymer is too large, the notch impact strength of the composite material is gradually reduced along with the increase of the vinyl acetate-maleic anhydride graft copolymer. When the content of the modified nano calcium carbonate is too much, the nano calcium carbonate is easy to polymerize in an alloy system, the phenomenon of uneven dispersion occurs, and the alloy system cannot uniformly transfer stress, so that the brittleness, the toughness and the impact strength of the alloy material are increased.
Wherein the weight ratio of the ethylene bis stearamide to the polyethylene wax is 0.5-1.5: 4.
When the ethylene bis stearamide and the polyethylene wax in the weight ratio are adopted, the prepared PC-ABS alloy material not only has high fluidity, but also has high impact resistance, high tensile strength and high bending strength, so that the prepared product can achieve good balance of toughness and rigidity, and can endow the product with good appearance and mechanical properties. Tests show that when the content of the ethylene bis stearamide is too high or too low, the impact resistance, the bending modulus, the bending strength and the elongation at break of the PC-ABS alloy material are affected, and when the content of the ethylene bis stearamide is too low, the flow property of the prepared PC-ABS alloy material is reduced, the surface gloss of a product is affected, and the processing difficulty is improved.
The flame retardant is a mixture consisting of zinc borate, organic phosphate, wood powder and polyvinylidene fluoride.
According to the invention, the flame retardant property of the PC-ABS alloy material is improved by compounding zinc borate, organic phosphate, wood powder and polyvinylidene fluoride. The compounding of the zinc borate and the organic phosphate can improve the flame retardant property of the alloy material, simultaneously reduce the heat release rate and the smoke release rate, and cooperate with the wood powder to improve the thermal stability and the char yield of the alloy material, and the polyvinylidene fluoride improves the anti-dripping property of the alloy material, so that the fire is not easy to spread.
Wherein the organic phosphate can be at least one of hydroquinone bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate) and bisphenol A (diphenyl phosphate).
The organic phosphate has high phosphorus content and good compatibility with alloy materials, has the advantages of difficult volatilization, migration resistance and lasting flame retardant effect, and is more favorable for improving the flame retardant property of the alloy materials.
The preparation method of the modified nano calcium carbonate comprises the following steps:
(1) stirring and mixing an aluminate coupling agent absolute ethyl alcohol solution with the mass concentration of 25-30% and nano calcium carbonate for 5-12min, carrying out ultrasonic treatment for 10-12min, then adding a silane coupling agent absolute ethyl alcohol solution with the mass concentration of 10-25% and mixing for 10-20min, carrying out ultrasonic treatment for 6-8min, and carrying out vacuum drying and ethanol recovery to obtain coupling agent modified nano calcium carbonate;
(2) adding the coupling agent modified nano calcium carbonate prepared in the step (1) into deionized water, adding sodium dodecyl sulfate, and performing ultrasonic dispersion for 5-15min to obtain emulsion;
(3) and (3) heating the emulsion prepared in the step (2) to 50-65 ℃ under the condition of stirring, adding ammonium persulfate under the condition of introducing nitrogen, dropwise adding a butyl acrylate monomer when the temperature is raised to 75-80 ℃, after dropwise adding, carrying out heat preservation reaction for 1.5-2 hours, filtering, washing with acetone, drying, and crushing to prepare the modified nano calcium carbonate.
According to the invention, butyl acrylate monomer is grafted on the surface of the nano calcium carbonate particles by adopting the method, so that the modified nano calcium carbonate with stable property and good compatibility with the alloy material is prepared, can be uniformly dispersed in an alloy material system, and is beneficial to improving the comprehensive performance of the alloy material. And the organic layer grafted on the surface of the nano calcium carbonate and the alloy material form an elastic transition region, when the alloy material is impacted, the grafted layer deforms to trigger the alloy material to generate silver lines and deformation, so that the impact energy is absorbed, and therefore, the butyl acrylate monomer grafted on the surface of the nano calcium carbonate has a synergistic toughening effect.
Wherein the weight ratio of the aluminate coupling agent to the nano calcium carbonate to the silane coupling agent is 0.5-1.0:60-75: 2-3; the weight ratio of the coupling agent modified nano calcium carbonate to the deionized water to the sodium dodecyl sulfate to the ammonium persulfate to the butyl acrylate monomer is 2-3:80-90:0.3-0.6:5-6: 15-20.
The modified nano calcium carbonate prepared by adopting the reagents with the weight ratio has higher grafting rate and more stable property, and the butyl acrylate monomer grafted on the surface of the nano calcium carbonate is not easy to be separated from the nano calcium carbonate, thereby being more beneficial to toughening and modifying the composite material and improving the shock resistance of the alloy material.
Preferably, the aluminate coupling agent is NDZ-201, and the silane coupling agent is KH-550.
The compatilizer is at least one of methyl methacrylate-butadiene-styrene copolymer, maleic anhydride grafted ethylene-octene copolymer and maleic anhydride grafted acrylonitrile-butadiene-styrene terpolymer.
The compatilizer can be matched with other raw materials for reaction and synergistic reaction, so that the interfacial tension between molecules when the PC, ABS and DHPE resins react with other raw materials is effectively reduced, the interfacial bonding force is further improved, the dispersed phase and the continuous phase are uniform, a stable structure is formed, the mutual matching reaction of the raw materials of the PC-ABS alloy material is promoted, the mechanical properties such as the tensile strength, the impact strength and the like of the PC-ABS alloy material are improved, the good balance of toughness and rigidity of the PC-ABS alloy material is realized, the fluidity and the processing rheological property are improved, and the surface smoothness is improved. The methyl methacrylate-butadiene-styrene copolymer has good compatibility with PC and ABS, has the functions of compatibilization and toughening, and can obviously improve the impact resistance and the flow property of a PC-ABS alloy system.
Wherein the dispersant is at least one of triethyl hexyl phosphoric acid, sodium dodecyl sulfate, methyl amyl alcohol, polyacrylamide, Guel gum and fatty acid polyglycol ester; the hydrolysis resisting agent is at least one of bis (2, 6-diisopropylbenzene) carbodiimide, sodium dihydrogen phosphate, hexamethylenetetramine and phosphite.
By adopting the dispersing agent, the dispersing stability of the PC-ABS alloy material can be effectively improved, the granular substances in the PC-ABS alloy material system are not easy to polymerize to generate precipitation, the leveling effect is good, and the prepared PC-ABS alloy material has high glossiness and high fluidity, excellent impact resistance and flame retardant property and good mechanical property.
The hydrolysis resistant agent is added into a PC-ABS alloy system, so that the weather resistance of the PC-ABS alloy system can be effectively improved, the autocatalytic degradation reaction of each raw material component in the preparation process is prevented, the stability of the PC-ABS alloy material is improved, and the service life of the PC-ABS alloy material is prolonged.
Preferably, the hydrolysis resistant agent is a mixture of sodium dihydrogen phosphate, hexamethylenetetramine and phosphite according to the weight ratio of 23-40:30-40: 0.01-0.03.
When the components and the hydrolysis resistant agent in the weight ratio are compounded, the ester exchange reaction of the PC can be effectively inhibited, the color of the PC is improved, and the thermal stability and the hydrolysis stability of a PC-ABS alloy system are improved.
Wherein the particle size of the nano calcium carbonate in the step (1) is 50-100 nm.
By adopting the nano calcium carbonate with the particle size, on one hand, the dispersibility of the modified nano calcium carbonate in a PC-ABS alloy system is favorably improved, the compatibility of the alloy system is improved, and the prepared PC-ABS alloy material has excellent impact resistance; on the other hand, the nano calcium carbonate with the particle size can effectively improve the hydrolysis resistance of a PC-ABS system, and does not influence the toughness of the PC-ABS alloy material.
Wherein the grain size of the wood powder is 20-150 μm.
When the grain size of wood flour is too big, the roughness on the surface of wood flour is high, the structure is loose, the compatibility between the non-polar HDPE resin and the polar wood flour is poor, the PE melt is not easy to permeate into the wood flour, so that the wood flour is easy to form a cavity defect, the alloy material is easy to form stress concentration at the defect position when bearing larger stretching force, so that the material is easy to break, therefore, when the grain size of the wood flour is too big, the tensile strength of the alloy material is reduced, and when the grain size of the wood flour is too small, the bending property, the impact property and the tensile strength of the alloy material can be influenced.
The second purpose of the invention is realized by the following technical scheme: the preparation method of the alloy material for the high-fluidity thin-wall product comprises the following steps:
s1, mixing and uniformly stirring the HDPE resin, the dispersing agent, the impact modifier and the flame retardant according to the weight ratio, and then putting the mixture into an extrusion device for mixing, extruding and granulating to obtain a master batch A;
and S2, mixing the master batch A prepared in the step S1 with ABS resin, PC resin, a flow increasing agent, an anti-hydrolysis agent and a compatilizer according to a weight ratio, uniformly stirring, and then putting the mixture into an extrusion device for mixing, extruding and granulating to obtain the high-fluidity alloy material for the thin-wall product.
The compatibility of the HDPE resin and the polyolefin elastomer of the impact modifier is better than that of PC and ABS resin, the HDPE resin, the impact modifier, the dispersant and the flame retardant are mixed and extruded and granulated in an extrusion device, so that the HDPE resin is wrapped in the polyolefin elastomer, the impact resistance of the PC-ABS alloy material is favorably improved, the HDPE resin and the flame retardant are uniformly mixed under the action of the dispersant, and then the master batch A prepared by melt extrusion and the rest raw materials are subjected to secondary extrusion and granulation, so that the dispersibility of the impact modifier, the flow increasing agent and the flame retardant in the composite material is favorably improved, and the comprehensive performance of the prepared PC-ABS alloy material is better. The use of the secondary extrusion method strengthens the dispersion uniformity of the impact modifier in the PC-ABS alloy matrix, so that the prepared PC-ABS alloy material has better comprehensive properties such as impact resistance, flame retardance, strength and the like, high fluidity and good processing stability.
Wherein the barrel temperature of the extrusion equipment in the step S1 is 200-300 ℃, and the screw rotation speed of the extrusion equipment in the step S1 is 180-200 r/min; the barrel temperature of the extrusion equipment in the step S2 is 290-310 ℃, and the screw rotation speed of the extrusion equipment in the step S2 is 220-250 r/min.
According to the invention, through strictly controlling the rotation speed of the two times of mixing and stirring of the raw materials and the temperature of extrusion granulation, all the raw material components can be fully mixed into the mixing system of the PC-ABS alloy material, so that the prepared PC-ABS alloy material has excellent comprehensive properties such as electrical insulation property, impact resistance, rigidity, flame retardance and the like, and achieves good balance of toughness and rigidity, good forming property, good processing property and high fluidity.
When the screw rotating speed of the step S1 or S2 is too high, the polyolefin elastomer wrapped outside the HDPE resin is easily separated from the HDPE particles by the shearing force generated in the stirring process, and the grafting groups of raw material reagents in the impact modifier are easily damaged, so that the compatibility of the impact modifier and a PC-ABS composite system is reduced, the impact resistance is reduced, the mechanical property of the prepared PC-ABS alloy material is reduced, the flow property of the product is influenced by the reagents which are not uniformly dispersed in the alloy material system, and the appearance defects such as surface cavities or different color points and the like are easily generated in the prepared finished product. When the screw rotation speed is too high, the components are not uniformly mixed, and an alloy material with high impact resistance, high fluidity and excellent flame retardant property cannot be obtained.
The invention has the beneficial effects that:
1. the PC/ABS alloy material for the high-fluidity thin-wall product prepared by the invention has the tensile strength of more than 30.56MPa and the impact strength of more than 44.36KJ/m when the wall thickness is 2mm2The good balance of rigidity and toughness is realized, the PC-ABS alloy material is suitable for manufacturing thin-wall products, the MFR is more than 20.14g/10min, the PC-ABS alloy material has good flow property and good processing stability, and the flame retardant is added into the alloy material to ensure that the prepared PC-ABS alloy material reaches the flame retardant A level;
2. the PC-ABS alloy material for the high-fluidity thin-wall product strengthens the dispersion uniformity of the impact modifier in the PC-ABS alloy matrix by using the secondary extrusion method, so that the prepared PC-ABS alloy material has better comprehensive performances of impact resistance, flame retardance, strength and the like, and has high fluidity and good processing stability.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
An alloy material for high-fluidity thin-wall products comprises the following raw materials in parts by weight:
Figure GDA0002781056860000111
Figure GDA0002781056860000121
the flow increasing agent is a mixture of ethylene bis stearamide and polyethylene wax in a weight ratio of 0.5: 4; the impact modifier is a mixture of polyolefin elastomer, modified nano calcium carbonate and vinyl acetate-maleic anhydride graft copolymer in a weight ratio of 2:0.5: 2.5.
The flame retardant is a mixture of zinc borate, hydroquinone bis (diphenyl phosphate), wood powder and polyvinylidene fluoride according to the weight ratio of 2:4.5:6: 1.
The preparation method of the modified nano calcium carbonate comprises the following steps:
(1) mixing an NDZ-201 aluminate coupling agent absolute ethyl alcohol solution with the mass concentration of 25% with nano calcium carbonate by stirring for 5min, carrying out ultrasonic treatment for 10min, then adding a KH-550 silane coupling agent absolute ethyl alcohol solution with the mass concentration of 10% to mix for 10min, carrying out ultrasonic treatment for 6min, and carrying out vacuum drying and ethanol recovery to obtain coupling agent modified nano calcium carbonate;
(2) adding the coupling agent modified nano calcium carbonate prepared in the step (1) into deionized water, adding sodium dodecyl sulfate, and performing ultrasonic dispersion for 5min to obtain emulsion;
(3) and (3) heating the emulsion prepared in the step (2) to 50 ℃ under the condition of stirring, adding ammonium persulfate under the condition of introducing nitrogen, dropwise adding a butyl acrylate monomer when the temperature is raised to 75 ℃, after dropwise adding, carrying out heat preservation reaction for 1.5 hours, filtering, washing with acetone, drying, and crushing to prepare the modified nano calcium carbonate.
Wherein the weight ratio of the NDZ-201 aluminate coupling agent to the nano calcium carbonate to the KH-550 silane coupling agent is 0.5:60: 2; the weight ratio of the coupling agent modified nano calcium carbonate to the deionized water to the sodium dodecyl sulfate to the ammonium persulfate to the butyl acrylate monomer is 2:80:0.3:5: 15.
Wherein the compatilizer is methyl methacrylate-butadiene-styrene copolymer, the dispersant is triethylhexylphosphoric acid, and the hydrolysis-resistant agent is bis (2, 6-diisopropylbenzene) carbodiimide.
Wherein the grain diameter of the nano calcium carbonate in the step (1) is 50nm, and the grain diameter of the wood powder is 20 mu m.
The preparation method of the alloy material for the high-fluidity thin-wall product comprises the following steps:
s1, mixing and uniformly stirring the HDPE resin, the dispersant, the impact modifier and the flame retardant according to the weight ratio, then putting the mixture into an extrusion device for mixing, extruding and granulating,
preparing a master batch A;
and S2, mixing the master batch A prepared in the step S1 with ABS resin, PC resin, a flow increasing agent, an anti-hydrolysis agent and a compatilizer according to a weight ratio, uniformly stirring, and then putting the mixture into an extrusion device for mixing, extruding and granulating to obtain the high-fluidity alloy material for the thin-wall product.
Wherein the barrel temperature of the extrusion equipment in the step S1 is 200 ℃, and the screw rotation speed of the extrusion equipment in the step S1 is 180 r/min; the barrel temperature of the extrusion apparatus in step S2 was 290 ℃ and the screw rotation speed of the extrusion apparatus in step S2 was 220 r/min.
Example 2
An alloy material for high-fluidity thin-wall products comprises the following raw materials in parts by weight:
Figure GDA0002781056860000141
wherein the flow increasing agent is a mixture of ethylene bis stearamide and polyethylene wax in a weight ratio of 1: 4; the impact modifier is a mixture of polyolefin elastomer, modified nano calcium carbonate and vinyl acetate-maleic anhydride graft copolymer according to the weight ratio of 2.5:0.75: 3.25; the flame retardant is a mixture of zinc borate, resorcinol bis (diphenyl phosphate), wood flour and polyvinylidene fluoride according to the weight ratio of 2:4.5:6: 1.
The preparation method of the modified nano calcium carbonate comprises the following steps:
(1) mixing NDZ-201 aluminate coupling agent absolute ethyl alcohol solution with the mass concentration of 27.5% and nano calcium carbonate by stirring for 8.5min, performing ultrasonic treatment for 11min, then adding KH-550 silane coupling agent absolute ethyl alcohol solution with the mass concentration of 17.5% to mix for 15min, performing ultrasonic treatment for 7min, and performing vacuum drying and ethanol recovery to obtain coupling agent modified nano calcium carbonate;
(2) adding the coupling agent modified nano calcium carbonate prepared in the step (1) into deionized water, adding sodium dodecyl sulfate, and performing ultrasonic dispersion for 10min to obtain emulsion;
(3) and (3) heating the emulsion prepared in the step (2) to 57.5 ℃ under the condition of stirring, adding ammonium persulfate under the condition of introducing nitrogen, dropwise adding a butyl acrylate monomer when the temperature is raised to 77.5 ℃, after dropwise adding, carrying out heat preservation reaction for 1.75 hours, filtering, washing with acetone, drying, and crushing to prepare the modified nano calcium carbonate.
Wherein the weight ratio of the NDZ-201 aluminate coupling agent to the nano calcium carbonate to the KH-550 silane coupling agent is 0.75:67.5: 2.5; the weight ratio of the coupling agent modified nano calcium carbonate to the deionized water to the sodium dodecyl sulfate to the ammonium persulfate to the butyl acrylate monomer is 2.5:85:0.45:5.5: 17.5.
Wherein the compatilizer is maleic anhydride grafted ethylene-octene copolymer, the dispersant is sodium dodecyl sulfate, and the hydrolysis resistant agent is sodium dihydrogen phosphate.
Wherein the grain diameter of the nano calcium carbonate in the step (1) is 75nm, and the grain diameter of the wood powder is 85 μm.
The preparation method of the alloy material for the high-fluidity thin-wall product comprises the following steps:
s1, mixing and uniformly stirring the HDPE resin, the dispersant, the impact modifier and the flame retardant according to the weight ratio, then putting the mixture into an extrusion device for mixing, extruding and granulating,
preparing a master batch A;
and S2, mixing the master batch A prepared in the step S1 with ABS resin, PC resin, a flow increasing agent, an anti-hydrolysis agent and a compatilizer according to a weight ratio, uniformly stirring, and then putting the mixture into an extrusion device for mixing, extruding and granulating to obtain the high-fluidity alloy material for the thin-wall product.
Wherein the barrel temperature of the extrusion equipment in the step S1 is 250 ℃, and the screw rotation speed of the extrusion equipment in the step S1 is 190 r/min; the barrel temperature of the extrusion apparatus in step S2 was 300 ℃ and the screw rotation speed of the extrusion apparatus in step S2 was 235 r/min.
Example 3
An alloy material for high-fluidity thin-wall products comprises the following raw materials in parts by weight:
Figure GDA0002781056860000161
wherein the flow increasing agent is a mixture of ethylene bis stearamide and polyethylene wax according to the weight ratio of 1.5: 4; the impact modifier is a mixture of polyolefin elastomer, modified nano calcium carbonate and vinyl acetate-maleic anhydride graft copolymer in a weight ratio of 3:1: 4; the flame retardant is a mixture of zinc borate, bisphenol A (diphenyl phosphate), wood powder and polyvinylidene fluoride according to the weight ratio of 2:4.5:6: 1.
The preparation method of the modified nano calcium carbonate comprises the following steps:
(1) mixing 30% NDZ-201 aluminate coupling agent absolute ethyl alcohol solution and nano calcium carbonate for 12min by stirring, carrying out ultrasonic treatment for 12min, then adding 25% KH-550 silane coupling agent absolute ethyl alcohol solution for mixing for 20min, carrying out ultrasonic treatment for 8min, and carrying out vacuum drying and ethanol recovery to obtain coupling agent modified nano calcium carbonate;
(2) adding the coupling agent modified nano calcium carbonate prepared in the step (1) into deionized water, adding sodium dodecyl sulfate, and performing ultrasonic dispersion for 15min to obtain emulsion;
(3) and (3) heating the emulsion prepared in the step (2) to 65 ℃ under the condition of stirring, adding ammonium persulfate under the condition of introducing nitrogen, dropwise adding a butyl acrylate monomer when the temperature is raised to 80 ℃, after dropwise adding, carrying out heat preservation reaction for 2 hours, filtering, washing with acetone, drying, and crushing to prepare the modified nano calcium carbonate.
Wherein the weight ratio of the NDZ-201 aluminate coupling agent to the nano calcium carbonate to the KH-550 silane coupling agent is 1.0:75: 3; the weight ratio of the coupling agent modified nano calcium carbonate to the deionized water to the sodium dodecyl sulfate to the ammonium persulfate to the butyl acrylate monomer is 3:90:0.6:6: 20.
Wherein the compatilizer is maleic anhydride grafted acrylonitrile-butadiene-styrene terpolymer, the dispersing agent is methyl amyl alcohol, and the hydrolysis resistant agent is a mixture of hexamethylenetetramine and sodium phosphite according to a weight ratio of 99: 1.
Wherein the grain diameter of the nano calcium carbonate in the step (1) is 100nm, and the grain diameter of the wood powder is 150 mu m.
The preparation method of the alloy material for the high-fluidity thin-wall product comprises the following steps:
s1, mixing and uniformly stirring the HDPE resin, the dispersant, the impact modifier and the flame retardant according to the weight ratio, then putting the mixture into an extrusion device for mixing, extruding and granulating,
preparing a master batch A;
and S2, mixing the master batch A prepared in the step S1 with ABS resin, PC resin, a flow increasing agent, an anti-hydrolysis agent and a compatilizer according to a weight ratio, uniformly stirring, and then putting the mixture into an extrusion device for mixing, extruding and granulating to obtain the high-fluidity alloy material for the thin-wall product.
Wherein the barrel temperature of the extrusion equipment in the step S1 is 300 ℃, and the screw rotation speed of the extrusion equipment in the step S1 is 200 r/min; the barrel temperature of the extrusion apparatus in step S2 was 310 ℃ and the screw rotation speed of the extrusion apparatus in step S2 was 250 r/min.
Example 4
An alloy material for high-fluidity thin-wall products is characterized in that: the feed comprises the following raw materials in parts by weight:
Figure GDA0002781056860000181
wherein the flow increasing agent is a mixture of ethylene bis stearamide and polyethylene wax in a weight ratio of 1: 4; the impact modifier is a mixture of polyolefin elastomer, modified nano calcium carbonate and vinyl acetate-maleic anhydride graft copolymer according to the weight ratio of 2.5:0.75: 3.25; the flame retardant is a mixture of zinc borate, resorcinol bis (diphenyl phosphate), wood flour and polyvinylidene fluoride according to the weight ratio of 2:4.5:6: 1.
The preparation method of the modified nano calcium carbonate comprises the following steps:
(1) mixing NDZ-201 aluminate coupling agent absolute ethyl alcohol solution with the mass concentration of 27.5% and nano calcium carbonate by stirring for 8.5min, performing ultrasonic treatment for 11min, then adding KH-550 silane coupling agent absolute ethyl alcohol solution with the mass concentration of 17.5% to mix for 15min, performing ultrasonic treatment for 7min, and performing vacuum drying and ethanol recovery to obtain coupling agent modified nano calcium carbonate;
(2) adding the coupling agent modified nano calcium carbonate prepared in the step (1) into deionized water, adding sodium dodecyl sulfate, and performing ultrasonic dispersion for 10min to obtain emulsion;
(3) and (3) heating the emulsion prepared in the step (2) to 57.5 ℃ under the condition of stirring, adding ammonium persulfate under the condition of introducing nitrogen, dropwise adding a butyl acrylate monomer when the temperature is raised to 77.5 ℃, after dropwise adding, carrying out heat preservation reaction for 1.75 hours, filtering, washing with acetone, drying, and crushing to prepare the modified nano calcium carbonate.
Wherein the weight ratio of the NDZ-201 aluminate coupling agent to the nano calcium carbonate to the KH-550 silane coupling agent is 0.75:67.5: 2.5; the weight ratio of the coupling agent modified nano calcium carbonate to the deionized water to the sodium dodecyl sulfate to the ammonium persulfate to the butyl acrylate monomer is 2.5:85:0.45:5.5: 17.5.
The compatilizer is a mixture of maleic anhydride grafted ethylene-octene copolymer and maleic anhydride grafted acrylonitrile-butadiene-styrene terpolymer according to a weight ratio of 1:2, the dispersant is a mixture of gulf gum and fatty acid polyethylene glycol ester according to a weight ratio of 1:1, and the hydrolysis resisting agent is a mixture of sodium dihydrogen phosphate, hexamethylenetetramine and sodium phosphite according to a weight ratio of 31.5:35: 0.02.
Wherein the grain diameter of the nano calcium carbonate in the step (1) is 75nm, and the grain diameter of the wood powder is 85 μm.
The preparation method of the alloy material for the high-fluidity thin-wall product comprises the following steps:
s1, mixing and uniformly stirring the HDPE resin, the dispersant, the impact modifier and the flame retardant according to the weight ratio, then putting the mixture into an extrusion device for mixing, extruding and granulating,
preparing a master batch A;
and S2, mixing the master batch A prepared in the step S1 with ABS resin, PC resin, a flow increasing agent, an anti-hydrolysis agent and a compatilizer according to a weight ratio, uniformly stirring, and then putting the mixture into an extrusion device for mixing, extruding and granulating to obtain the high-fluidity alloy material for the thin-wall product.
Wherein the barrel temperature of the extrusion equipment in the step S1 is 250 ℃, and the screw rotation speed of the extrusion equipment in the step S1 is 190 r/min; the barrel temperature of the extrusion apparatus in step S2 was 300 ℃ and the screw rotation speed of the extrusion apparatus in step S2 was 235 r/min.
Comparative example 1
Comparative example 1 differs from example 2 in that comparative example 1 does not add HDPE resin.
Comparative example 2
Comparative example 2 differs from example 2 in that no modified nanocalcium carbonate was added to the impact modifier of comparative example 2.
Comparative example 3
Comparative example 3 differs from example 2 in that no polyethylene wax is added to the flow enhancer of comparative example 3.
Performance testing
The PC-ABS alloy materials prepared in the above examples 1 to 4 and comparative examples 1 to 3 were tested for Melt Flow Rate (MFR), tensile strength, elongation at break and flame retardant rating according to the relevant test standards, and the PC-ABS alloy materials prepared in the examples 1 to 4 and comparative examples 1 to 3 were injection molded to prepare samples having a size of 100 mm.100 mm.2 mm and to perform impact strength tests on the samples, and the test results are summarized in Table 1.
Wherein, the MFR test is carried out according to GB/T3682-83, the impact strength test is carried out according to GB/T1843-96, and the tensile strength and the elongation at break test are carried out according to GB/T1040-92.
TABLE 1 summary of the results of the performance tests of the PC-ABS alloy materials of examples 1-3 and comparative examples 1-4
Figure GDA0002781056860000211
Figure GDA0002781056860000221
As can be seen from the observation of the appearance of the sample of the PC-ABS alloy material prepared in the embodiments 1-4, the PC/ABS alloy material for the high-fluidity thin-wall product prepared by the invention has the advantages of smooth surface, uniform material surface color, high gloss, no abnormal color points or cavities and good appearance.
The PC/ABS alloy material for the high-fluidity thin-wall product prepared by the invention has the tensile strength of more than 30.56MPa and the impact strength of more than 44.36KJ/m when the wall thickness is 2mm2The good balance of rigidity and toughness is realized, the MFR is more than 20.14g/10min, the PC-ABS alloy material has good flow property and good processing stability, and the flame retardant is added into the alloy material to ensure that the prepared PC-ABS alloy material reaches the flame retardant A level.
As is clear from comparison of comparative example 1 with example 2, example 2 has higher MFR and higher impact strength than comparative example 1. According to the invention, the HDPE resin is compounded with the PC resin and the ABS resin, so that the compounded HDPE resin effectively improves the flow property of the PC-ABS alloy material, and the prepared PC-ABS alloy material has excellent processing fluidity. On the other hand, after the HDPE resin is compounded with the PC-ABS alloy material, because the HDPE resin and the polyolefin elastomer have good compatibility, the HDPE can be wrapped in polyolefin elastomer particles in the system, so that the volume of an elastic rubber area in the alloy system is increased, the stress concentration area in the alloy system is enlarged, and the impact strength of the PC-ABS alloy material is improved.
Compared with the embodiment 2, the impact strength of the embodiment 2 is higher than that of the embodiment 2, the impact modifier disclosed by the invention can be used for carrying out synergistic impact modification on an alloy material through the absorption and dispersion effects of the elastic deformation of the vinyl acetate-maleic anhydride graft copolymer on impact energy, the effect of wrapping HDPE by the polyolefin elastomer to increase a rubber area so as to increase a stress concentration area of a system and the prevention and passivation effects of nano calcium carbonate on crack propagation, so that the impact resistance of the PC-ABS alloy material is improved, and the prepared alloy material is suitable for manufacturing thin-wall products.
Compared with the example 2, the comparative example 3 shows that the MFR value of the PC-ABS alloy material is larger than that of the comparative example 3, because the ethylene bis stearamide and the polyethylene wax form the composite flow increasing agent, the PC-ABS alloy material can be lubricated internally and externally under the synergistic action, the PC-ABS alloy material is subjected to synergistic flow increasing modification, the effect is better and more remarkable compared with the effect of singly using the ethylene bis stearamide or the polyethylene wax, the processing flow property of the PC-ABS alloy material is improved, and meanwhile, the tensile strength and the bending strength of the alloy material are improved.
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 (9)

1. An alloy material for high-fluidity thin-wall products is characterized in that: the feed comprises the following raw materials in parts by weight:
Figure FDA0002781056850000011
the flow increasing agent is a mixture consisting of ethylene bis stearamide and polyethylene wax; the impact modifier is a mixture consisting of a polyolefin elastomer, modified nano calcium carbonate and a vinyl acetate-maleic anhydride graft copolymer;
the preparation method of the modified nano calcium carbonate comprises the following steps:
(1) stirring and mixing an aluminate coupling agent absolute ethyl alcohol solution with the mass concentration of 25-30% and nano calcium carbonate for 5-12min, carrying out ultrasonic treatment for 10-12min, then adding a silane coupling agent absolute ethyl alcohol solution with the mass concentration of 10-25% and mixing for 10-20min, carrying out ultrasonic treatment for 6-8min, and carrying out vacuum drying and ethanol recovery to obtain coupling agent modified nano calcium carbonate;
(2) adding the coupling agent modified nano calcium carbonate prepared in the step (1) into deionized water, adding sodium dodecyl sulfate, and performing ultrasonic dispersion for 5-15min to obtain emulsion;
(3) and (3) heating the emulsion prepared in the step (2) to 50-65 ℃ under the condition of stirring, adding ammonium persulfate under the condition of introducing nitrogen, dropwise adding a butyl acrylate monomer when the temperature is raised to 75-80 ℃, after dropwise adding, carrying out heat preservation reaction for 1.5-2 hours, filtering, washing with acetone, drying, and crushing to prepare the modified nano calcium carbonate.
2. The alloy material for high-fluidity thin-walled products according to claim 1, wherein: the weight ratio of the polyolefin elastomer to the modified nano calcium carbonate to the vinyl acetate-maleic anhydride graft copolymer is 2-3:0.5-1: 2.5-4.
3. The alloy material for high-fluidity thin-walled products according to claim 1, wherein: the weight ratio of the ethylene bis stearamide to the polyethylene wax is 0.5-1.5: 4.
4. The alloy material for high-fluidity thin-walled products according to claim 1, wherein: the flame retardant is a mixture consisting of zinc borate, organic phosphate, wood powder and polyvinylidene fluoride.
5. The alloy material for high-fluidity thin-walled products according to claim 1, wherein: the compatilizer is at least one of methyl methacrylate-butadiene-styrene copolymer, maleic anhydride grafted ethylene-octene copolymer and maleic anhydride grafted acrylonitrile-butadiene-styrene terpolymer.
6. The alloy material for high-fluidity thin-walled products according to claim 1, wherein: the dispersing agent is at least one of triethyl hexyl phosphoric acid, sodium dodecyl sulfate, methyl amyl alcohol, polyacrylamide, Guel gum and fatty acid polyglycol ester; the hydrolysis resisting agent is at least one of bis (2, 6-diisopropylbenzene) carbodiimide, sodium dihydrogen phosphate, hexamethylenetetramine and phosphite.
7. The alloy material for high-fluidity thin-walled products according to claim 1, wherein: the particle size of the nano calcium carbonate in the step (1) is 50-100 nm.
8. The alloy material for high-fluidity thin-walled products according to claim 4, wherein: the grain size of the wood powder is 20-150 mu m.
9. The method for producing an alloy material for high-fluidity thin-walled products, according to any one of claims 1 to 8, wherein: the method comprises the following steps:
s1, mixing and uniformly stirring the HDPE resin, the dispersing agent, the impact modifier and the flame retardant according to the weight ratio, and then putting the mixture into an extrusion device for mixing, extruding and granulating to obtain a master batch A;
and S2, mixing the master batch A prepared in the step S1 with ABS resin, PC resin, a flow increasing agent, an anti-hydrolysis agent and a compatilizer according to a weight ratio, uniformly stirring, and then putting the mixture into an extrusion device for mixing, extruding and granulating to obtain the high-fluidity alloy material for the thin-wall product.
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