CN108034235B - PA/ASA alloy material and preparation method thereof - Google Patents

PA/ASA alloy material and preparation method thereof Download PDF

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CN108034235B
CN108034235B CN201810002010.7A CN201810002010A CN108034235B CN 108034235 B CN108034235 B CN 108034235B CN 201810002010 A CN201810002010 A CN 201810002010A CN 108034235 B CN108034235 B CN 108034235B
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asa
asa alloy
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viscosity
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CN108034235A (en
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刘春艳
丁婉琦
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Shanghai Zhonglei New Material Science Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
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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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

Abstract

The invention provides a PA/ASA alloy material and a preparation method thereof, wherein the PA/ASA alloy material comprises the following components in parts by weight: 30-80 parts of PA resin, 20-70 parts of ASA resin, 1-15 parts of wear-resistant filler, 0.1-1 part of filler pretreating agent, 1-20 parts of compatibilization toughening agent and 0.1-1 part of antioxidant; the PA/ASA alloy material prepared by the preparation method disclosed by the invention has the advantages of high strength, good toughness, excellent thermal property, excellent mechanical property, good spraying-free matte effect, surface wear resistance comparable to that of a spray paint product, and good application prospect.

Description

PA/ASA alloy material and preparation method thereof
Technical Field
The invention belongs to the field of high polymer materials, and relates to a PA/ASA alloy material and a preparation method thereof.
Background
Polyamide (PA for short) has excellent mechanical property, electrical property, wear resistance, self-lubricating property, chemical resistance, excellent barrier property and processing fluidity, and is one of engineering plastics widely applied in industry and daily life. However, the modified products are often used for industrial purposes because of their disadvantages such as high water absorption, poor dimensional stability, high molding shrinkage, and low notch impact. The PA and engineering plastic (graft copolymer of acrylate rubber, acrylonitrile and styrene, and ASA in English) alloy makes up the defects of the PA, has the advantages of the PA and the ASA, and simultaneously obtains the characteristics that the PA and the ASA do not have, such as various advantages of weather resistance, wear resistance, good chemical resistance, noise reduction, shock absorption, matte and the like. PA/ASA belongs to a thermodynamic incompatible system, and the PA/ASA and the thermodynamic incompatible system are simply physically blended to obtain an alloy with poor mechanical properties. Meanwhile, as a spraying-free product, compared with a paint spraying product replaced by the PA/ASA product, the PA/ASA product on the market at present has insufficient wear resistance and limited application range.
CN106751775A discloses the invention provides a wear-resistant PA/ASA alloy and a preparation method thereof. The wear-resistant PA/ASA alloy comprises the following components in parts by weight: 40-60 parts of PA, 20-40 parts of ASA, 10-15 parts of compatilizer, 5-10 parts of reinforcing substance and 0.5-1.5 parts of lubricant, wherein the interface compatibility and the wear resistance of the PA/ASA alloy are respectively improved by adding maleic anhydride graft compatilizer and organic montmorillonite/wollastonite, but the wear resistance, the heat resistance and the toughness of the wear-resistant PA/ASA still have defects and need to be further improved; CN101407630A discloses a PA/ASA alloy material and a preparation method thereof, which comprises the following components and contents of PA30-75 wt%; ASA20-45 wt%; SAN0-30 wt%; 1-10 wt% of compatilizer; 0-5 wt% of nano montmorillonite; 0.1-0.7 wt% of lubricant; 0.1-1 wt% of antioxidant. The mechanical property, the thermal property and the barrier property of the alloy are improved by adding the nano montmorillonite, but the wear resistance and the heat resistance of the alloy are not obviously enhanced; CN102337025A discloses a high notch impact PA/ASA alloy material and a preparation method thereof, which comprises the following components and contents: PA30-90 parts; 20-80 parts of ASA; 3-15 parts of a compatilizer; 3-20 parts of a toughening agent; 0.2-0.5 part of lubricant; 0.2-1 part of antioxidant, and the impact toughness of the alloy is improved by adding the grafted POE/grafted EPDM toughening agent and the maleic anhydride graft compatilizer, but the wear resistance and heat resistance of the alloy are not improved. CN105273400A discloses a weather-resistant PA/ASA alloy material, which comprises the following raw materials in parts by weight: 45-65 parts of polyamide; 15-25 parts of acrylonitrile-styrene copolymer; 0-15 parts of minerals; 5-10 parts of a compatilizer; 8-12 parts of a toughening agent; 0.5-1 part of processing aid, and acrylonitrile-styrene copolymer with better rigidity and acrylonitrile-styrene-acrylate terpolymer with better toughness are compounded to prepare the high-impact and high-weather-resistant PA/ASA alloy, but the wear resistance and heat resistance of the alloy are not improved.
Therefore, the development of new PA/ASA alloy with enhanced wear, heat and impact resistance is needed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a PA/ASA alloy material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
on one hand, the invention provides a PA/ASA alloy material, which comprises the following components in parts by weight:
Figure BDA0001537131680000021
in the invention, the wear-resistant filler pretreated by the filler pretreatment agent and the compatibilization toughening agent have synergistic effect in the PA/ASA blend compounded by low-viscosity and high-viscosity nylon, and the PA/ASA alloy material is obtained through shear blending, reactive compatibilization and toughening, and has the advantages of high strength, good toughness, excellent thermal property, excellent mechanical property, good spray-free matte effect, surface wear resistance comparable to that of a spray-painted product, and good application prospect.
In the invention, the weight part of the PA resin in the PA/ASA alloy material is 30-80 parts, and can be 30 parts, 40 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts or 80 parts, for example.
Preferably, the PA resin is PA6 and/or PA 66.
Preferably, the PA resin has a relative viscosity of 2.3 to 3.2, and may be, for example, 2.3, 2.5, 2.7, 2.9, 3.0, or 3.2.
Preferably, the PA resin is a combination of low viscosity PA and high viscosity PA.
Preferably, the low viscosity PA has a relative viscosity of 2.3 to 2.7.
Preferably low, the high viscosity PA has a relative viscosity of 2.8 to 3.2.
In the invention, the low-viscosity PA and the high-viscosity PA are compounded, the different viscosities are compounded at different toughening ratios, the PA compounding ratios are different, the mechanical property and the wear resistance are higher, and the wear-resistant filler and the toughening agent are easier to disperse.
In the invention, the weight part of the ASA resin in the PA/ASA alloy material is 20-70 parts, and can be, for example, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts or 70 parts.
Preferably, the acrylonitrile content of the ASA resin is 20% to 40%, and may be, for example, 20%, 25%, 30%, 35% or 40%.
In the invention, the weight part of the wear-resistant filler in the PA/ASA alloy material is 1-15 parts, and can be 1 part, 3 parts, 5 parts, 6 parts, 8 parts, 10 parts, 12 parts or 15 parts, for example.
Preferably, the wear-resistant filler is one or a combination of at least two of talcum powder, nano calcium carbonate, nano barium sulfate or nano molybdenum disulfide; preferably a combination of talc, nano barium sulfate and molybdenum disulfide.
In the invention, if the wear-resistant filler is added excessively, the PA/ASA alloy material becomes brittle, the performance is poor, and the appearance is poor. The flaky talcum powder, the spherical nano barium sulfate and the molybdenum disulfide solid lubricant are compounded and uniformly dispersed in a matrix after pretreatment, so that the interfacial bonding property of the inorganic filler and a polymer matrix is effectively improved, the surface hardness of the PA/ASA alloy is improved, the surface friction coefficient is reduced, the influence on the appearance of a product due to poor bonding property of the inorganic filler and the matrix is avoided, and the wear resistance, the mechanical property and the thermal property of the product are effectively improved.
In the invention, the filler pretreatment agent is 0.1-1 part by weight in the PA/ASA alloy material, and can be 0.1 part, 0.3 part, 0.5 part, 0.6 part, 0.8 part or 1 part by weight.
Preferably, the filler pretreating agent is a combination of a silane coupling agent and a higher fatty acid or a combination of a silane coupling agent and a higher fatty acid salt; preferably a combination of the silane coupling agent KH560 and calcium stearate.
In the invention, the silane coupling agent KH560 and calcium stearate are used together, so that the dispersibility is improved.
In the invention, the antioxidant is 0.1-1 part by weight in the PA/ASA alloy material, and can be 0.1 part, 0.4 part, 0.5 part, 0.6 part, 0.8 part or 1 part by weight.
Preferably, the antioxidant comprises a primary antioxidant and a secondary antioxidant.
Preferably, the primary antioxidant comprises any one of antioxidant 1076, antioxidant 1098F or antioxidant 245, and the secondary antioxidant comprises any one of antioxidant 168, antioxidant 126 or antioxidant P-EPQ.
Preferably, the antioxidant is a compound of antioxidant 1076 and antioxidant 126.
Preferably, the compounding ratio of the antioxidant 1076 to the antioxidant 126 is 1: 4-4: 1, for example, 1:1, 1:2, 1:3, 1:4, 2:1, 3:1 or 4:1, preferably 2: 1.
In the invention, the weight part of the compatibilization toughening agent in the PA/ASA alloy material is 1-20 parts, and can be 1 part, 5 parts, 8 parts, 10 parts, 13 parts, 15 parts, 18 parts or 20 parts, for example.
Preferably, the compatibilized toughening agent is a maleic anhydride-type graft copolymer and/or an acrylic acid-type graft copolymer.
Preferably, the maleic anhydride type graft copolymer is one or a combination of at least two of ASA grafted maleic anhydride (ASA-g-MAH), styrene-acrylonitrile copolymer grafted maleic anhydride (SAN-g-MAH) or polyolefin elastomer grafted maleic anhydride (POE-g-MAH), wherein the SAN content in the ASA-g-MAH and SAN-g-MAH is consistent with the SAN content in the matrix ASA.
Preferably, the acrylic acid type graft copolymer is one or a combination of at least two of ethylene-butyl acrylate-glycidyl methacrylate copolymer (PTW), ethylene-glycidyl methacrylate copolymer (EGMA), or polyolefin elastomer grafted glycidyl methacrylate (POE-g-GMA).
In the invention, if the addition amount of the compatibilization toughening agent is too high, the appearance of the PA/ASA alloy material is influenced, and if the compatibilization toughening agent is not added, the strength is reduced, so that the appearance is slightly changed. In addition, reactive compatibilization toughening agents such as ASA-g-MAH, SAN-g-MAH, POE-g-MAH or PTW, EGMA, POE-g-GMA are compounded, active functional groups in the MAH and the GMA react with PA terminal amino or terminal carboxyl, so that a good reactive compatibilization effect is achieved, a rubber phase is more easily dispersed into a proper size in a matrix, a good toughening effect is achieved, the mechanical property of the PA/ASA alloy material is effectively improved, the influence of wear-resistant fillers on impact resistance is compensated, and the purpose of reactive compatibilization toughening is achieved.
As a preferable technical scheme, the PA/ASA alloy material comprises the following components in parts by weight:
Figure BDA0001537131680000051
on the other hand, the invention provides a preparation method of the PA/ASA alloy material, which comprises the following steps:
(1) mixing and heating the wear-resistant filler and the filler pretreating agent for pretreatment;
(2) sequentially adding and blending the PA resin, the ASA resin and the compatibilizer and toughener;
(3) and (3) extruding and granulating the blend obtained in the step (1) and the step (2) to obtain the PA/ASA alloy material.
Preferably, the mixing in step (1) is carried out in a high speed mixer.
Preferably, the temperature of said mixing in step (1) is 80-120 ℃, for example 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃.
Preferably, the mixing time in step (1) is 30-60min, for example, 30min, 35min, 40min, 45min, 50min, 55min or 60 min.
Preferably, the blending in step (2) is carried out in a high speed mixer.
Preferably, the blending time in step (2) is 3-15min, for example, 3min, 5min, 8min, 10min, 12min, 13min or 15 min.
Preferably, the temperature of the blending in step (2) is 20 to 60 ℃, and may be, for example, 20 ℃, 30 ℃, 40 ℃, 50 ℃ or 60 ℃.
Preferably, the mixing sequence in the step (2) is that the PA is firstly mixed with the ASA uniformly or the PA is firstly mixed with the compatibilization toughening agent uniformly and then blended with other components, preferably the PA is firstly mixed with the compatibilization toughening agent.
Preferably, the extrusion in step (3) is performed in a twin screw extruder, the blend of step (1) is added to a side level and the blend of step (2) is added to a main level.
Preferably, the extrusion method in step (3) is that the blend is extruded by main feeding and side feeding double-scale blanking in an extruder;
preferably, the rotation speed of the motor at the side feeding port is 200-.
Preferably, the rotation speed of the motor of the main feeding port is 300-700r/min, such as 300r/min, 400r/min, 500r/min, 600r/min or 700 r/min.
Preferably, the extrusion temperature in step (3) is 230-260 ℃, and may be, for example, 230 ℃, 240 ℃, 250 ℃ or 260 ℃.
Preferably, the extrusion method in the step (3) is to extrude the blend in an extruder by using main feeding and side feeding double-scale blanking, and obtain the PA/ASA alloy material through drawing, cooling and dicing.
Compared with the prior art, the invention has the following beneficial effects:
the PA/ASA alloy material provided by the invention is prepared by the synergistic effect of the wear-resistant filler pretreated by the filler pretreatment agent and the compatibilization toughening agent in the PA/ASA blend compounded by low-viscosity and high-viscosity nylon, and the PA/ASA alloy material is obtained by shear blending, reactive compatibilization and toughening, and has the advantages of high strength, good toughness, excellent thermal property, excellent mechanical property, good spray-free matte effect and surface wear resistance comparable to that of a spray-painted product.
In the invention, the low-viscosity PA and the high-viscosity PA are compounded, so that the wear-resistant composite material has higher mechanical property and wear resistance, and is easier to disperse wear-resistant filler and toughening agent; the wear-resistant filler is uniformly dispersed in the matrix after pretreatment, so that the interfacial bonding property of the inorganic filler and the polymer matrix is effectively improved, the surface hardness of the PA/ASA alloy is improved, the surface friction coefficient is reduced, the influence on the appearance of the product due to poor bonding property of the inorganic filler and the matrix is avoided, and the wear resistance, the mechanical property and the thermal property of the product are effectively improved; the active functional group in the reactive compatibilization toughening agent reacts with the PA terminal amino group or the PA terminal carboxyl group to achieve a good reactive compatibilization effect, so that a rubber phase is more easily dispersed into a proper size in a matrix, a good toughening effect is obtained, the mechanical property of the PA/ASA alloy material is effectively improved, the influence of the wear-resistant filler on the impact resistance is compensated, the purpose of reactive compatibilization toughening is achieved, and the reactive compatibilization toughening agent has a good application prospect.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The PA/ASA alloy material prepared by the embodiment comprises the following components in parts by weight:
Figure BDA0001537131680000081
mixing and heating talcum powder, nano barium sulfate, molybdenum disulfide, a silane coupling agent KH560 and calcium stearate in a high-speed mixer for pretreatment; then SAN-g-MAH, POE-g-MAH and PA6 are mixed in a high-speed mixer, and ASA, antioxidant 1076 and antioxidant 126 are added and mixed; and finally, carrying out main feeding and side feeding double-scale blanking extrusion granulation by using an extruder, and carrying out traction, cooling and grain cutting to obtain the PA/ASA alloy material.
Wherein, PA6 is the compound of low viscosity PA (viscosity 2.5) and high viscosity PA (viscosity 3.0), the compound ratio is 3: 7.
example 2
The PA/ASA alloy material prepared by the embodiment comprises the following components in parts by weight:
Figure BDA0001537131680000082
Figure BDA0001537131680000091
mixing and heating talcum powder, nano barium sulfate, a silane coupling agent KH560 and calcium stearate in a high-speed mixer for pretreatment; then mixing the PTW and the PA6 in a high-speed mixer, and then adding the ASA resin, the antioxidant 245 and the antioxidant 126 for mixing; and finally, carrying out main feeding and side feeding double-scale blanking extrusion granulation by using an extruder, and carrying out traction, cooling and grain cutting to obtain the PA/ASA alloy material.
Wherein, PA6 is the compound of low viscosity PA (viscosity 2.4) and high viscosity PA (viscosity 2.8), the compound ratio is 3: 7.
example 3
The PA/ASA alloy material prepared by the embodiment comprises the following components in parts by weight:
Figure BDA0001537131680000092
Figure BDA0001537131680000101
mixing and heating molybdenum disulfide, nano barium sulfate, a silane coupling agent KH560 and calcium stearate in a high-speed mixer for pretreatment; then mixing EGMA and PA6 in a high-speed mixer, adding ASA resin, antioxidant 1098F and antioxidant P-EPQ, and mixing; and finally, carrying out main feeding and side feeding double-scale blanking extrusion granulation by using an extruder, and carrying out traction, cooling and grain cutting to obtain the PA/ASA alloy material.
Wherein, PA6 is the compound of low viscosity PA (viscosity 2.4) and high viscosity PA (viscosity 2.9), the compound ratio is 3: 7.
example 4
The PA/ASA alloy material prepared by the embodiment comprises the following components in parts by weight:
Figure BDA0001537131680000102
mixing talcum powder, a silane coupling agent KH560 and calcium stearate in a high-speed mixer, heating and pretreating; then SAN-g-MAH and PA6 are mixed in a high-speed mixer, and then ASA resin, antioxidant 1076 and antioxidant 168 are added and mixed; and finally, carrying out main feeding and side feeding double-scale blanking extrusion granulation by using an extruder, and carrying out traction, cooling and grain cutting to obtain the PA/ASA alloy material.
Wherein, PA6 is the compound of low viscosity PA (viscosity 2.7) and high viscosity PA (viscosity 3.2), the compound ratio is 3: 7.
example 5
The PA/ASA alloy material prepared by the embodiment comprises the following components in parts by weight:
Figure BDA0001537131680000111
mixing and heating talcum powder, nano calcium carbonate, molybdenum disulfide, a silane coupling agent KH560 and calcium stearate in a high-speed mixer for pretreatment; then SAN-g-MAH, POE-g-MAH and PA6 are mixed in a high-speed mixer, and then ASA resin, antioxidant 245 and antioxidant P-EPQ are added and mixed; and finally, carrying out main feeding and side feeding double-scale blanking extrusion granulation by using an extruder, and carrying out traction, cooling and grain cutting to obtain the PA/ASA alloy material.
Wherein, PA6 is the compound of low viscosity PA (viscosity 2.3) and high viscosity PA (viscosity 2.8), the compound ratio is 3: 7.
example 6
The PA/ASA alloy material prepared by the embodiment comprises the following components in parts by weight:
Figure BDA0001537131680000112
Figure BDA0001537131680000121
mixing and heating talcum powder, nano calcium carbonate, molybdenum disulfide, a silane coupling agent KH560 and calcium stearate in a high-speed mixer for pretreatment; then mixing ASA-g-MAH, POE-g-MAH and PA6 in a high-speed mixer, adding ASA resin, antioxidant 1098F and antioxidant 168, and mixing; and finally, carrying out main feeding and side feeding double-scale blanking extrusion granulation by using an extruder, and carrying out traction, cooling and grain cutting to obtain the PA/ASA alloy material.
Wherein, PA6 is the compound of low viscosity PA (viscosity 2.3) and high viscosity PA (viscosity 2.9), the compound ratio is 3: 7.
example 7
The PA/ASA alloy material prepared by the embodiment comprises the following components in parts by weight:
Figure BDA0001537131680000122
Figure BDA0001537131680000131
mixing and heating talcum powder, nano calcium carbonate, a silane coupling agent KH560 and calcium stearate in a high-speed mixer for pretreatment; then PTW and POE-g-GMA are mixed with PA6 and PA66 in a high-speed mixer, and then ASA resin, antioxidant 1076 and antioxidant 126 are added and mixed; and finally, carrying out main feeding and side feeding double-scale blanking extrusion granulation by using an extruder, and carrying out traction, cooling and grain cutting to obtain the PA/ASA alloy material.
Wherein, the viscosity of PA6 is 2.3, and the viscosity of PA66 is 3.0.
Example 8
The PA/ASA alloy material prepared by the embodiment comprises the following components in parts by weight:
Figure BDA0001537131680000132
Figure BDA0001537131680000141
mixing and heating talcum powder, nano calcium carbonate, molybdenum disulfide, a silane coupling agent KH560 and calcium stearate in a high-speed mixer for pretreatment; then SAN-g-MAH, POE-g-MAH and PA6 are mixed in a high-speed mixer, and ASA resin is added and mixed; and finally, carrying out main feeding and side feeding double-scale blanking extrusion granulation by using an extruder, and carrying out traction, cooling and grain cutting to obtain the PA/ASA alloy material.
Wherein, PA6 is the compound of low viscosity PA (viscosity 2.5) and high viscosity PA (viscosity 2.9), the compound ratio is 3: 7.
comparative example 1
The only difference between the comparative example and the example 1 is that the comparative example does not comprise a filler pretreating agent (a silane coupling agent KH560 and calcium stearate), and the rest components, parts by weight and preparation method are the same as those of the example 1, so that the PA/ASA alloy material is prepared.
Comparative example 2
The difference between the comparative example and the example 1 is that the comparative example does not include filler pretreatment agents (silane coupling agents KH560 and calcium stearate) and wear-resistant fillers (talcum powder, nano calcium carbonate and molybdenum disulfide), and the rest components, the parts by weight and the preparation method are the same as those of the example 1, so that the PA/ASA alloy material is prepared.
Comparative example 3
The difference between the comparative example and the example 1 is that in the wear-resistant filler in the comparative example, 8 parts by weight of talcum powder, 8 parts by weight of nano barium sulfate and 8 parts by weight of molybdenum disulfide are used, and the rest components, the parts by weight and the preparation method are the same as those in the example 1, so that the PA/ASA alloy material is prepared.
Comparative example 4
The difference between the comparative example and the example 1 is that 15 parts by weight of the compatibilization toughening agent SAN-g-MAH, 15 parts by weight of the POE-g-MAH, and the rest components, the parts by weight and the preparation method are the same as those in the example 1, so that the PA/ASA alloy material is prepared.
Comparative example 5
The difference between the comparative example and the example 1 is that the comparative example does not include a compatibilization toughening agent, and the other components, the weight parts and the preparation method are the same as those of the example 1, so that the PA/ASA alloy material is prepared.
Comparative example 6
The difference between the comparative example and the example 1 is that the PA/ASA alloy material is prepared by using the low-viscosity PA6 with the same viscosity, but not by using the low-viscosity PA6 for compounding, and the rest components, the parts by weight and the preparation method are the same as the example 1.
The PA/ASA alloy materials prepared in the examples 1-8 and the comparative examples 1-6 are subjected to mechanical test, apparent property test, heat resistance test, scratch resistance test and impact resistance test, and the specific test results are shown in the following table 1:
TABLE 1
Figure BDA0001537131680000151
Figure BDA0001537131680000161
As can be seen from comparison between examples 1-8 and comparative examples 1-2, the wear-resistant filler and the filler pretreating agent are reasonably matched for use, so that the impact strength of the material can be improved, and particularly, the wear resistance, the mechanical property, the thermal property and the apparent property of the material are greatly improved by compounding the talcum powder, the nano barium sulfate and the molybdenum disulfide in example 1;
as can be seen from the comparison between examples 1 to 8 and comparative example 3, the addition amount of the wear-resistant filler is too large, the notch impact strength of the material is greatly reduced, the material becomes brittle, and the appearance is poor;
as can be seen from the comparison between examples 1-8 and comparative examples 4-5, the strength of the material is reduced and the wear resistance is deteriorated due to excessive addition of the compatibilization toughening agent in the material; if the compatibilizer and toughening agent is not added, the impact strength of the material is reduced, the appearance is poor, and the performance is influenced.
As can be seen from the comparison between examples 1-8 and comparative example 6, the mechanical properties and mechanical properties of the material are reduced when PA with the same viscosity is compounded;
according to the scratch resistance test result, the material which does not contain the filler pretreatment agent and the wear-resistant filler and the material prepared by compounding the PA with the same viscosity have the worst scratch resistance.
In conclusion, the alloy material provided by the invention has the advantages of high strength, good toughness, thermal property and wear resistance, and higher value.
The applicant states that the present invention is illustrated by the above examples to a PA/ASA alloy material and a method for preparing the same, but the present invention is not limited to the above detailed methods, i.e., it is not meant that the present invention must rely on the above detailed methods to be practiced. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (27)

1. The PA/ASA alloy material is characterized by comprising the following components in parts by weight:
Figure FDA0003068767350000011
the PA resin is a compound of low-viscosity PA and high-viscosity PA, the relative viscosity of the low-viscosity PA is 2.3-2.7, and the relative viscosity of the high-viscosity PA is 2.8-3.2; the PA resin is PA6 and/or PA 66; the compound ratio of the low-viscosity PA to the high-viscosity PA is 3:7 or 2: 1;
the content of acrylonitrile in the ASA resin is 20-40%;
the filler pretreating agent is a combination of a silane coupling agent and higher fatty acid or a combination of the silane coupling agent and higher fatty acid salt;
the wear-resistant filler is one or the combination of at least two of talcum powder, nano calcium carbonate, nano barium sulfate or nano molybdenum disulfide.
2. The PA/ASA alloy material according to claim 1, wherein the wear-resistant filler is a combination of talc, nano barium sulfate and molybdenum disulfide.
3. The PA/ASA alloy material according to claim 1, wherein the filler pre-treatment agent is a combination of a silane coupling agent KH560 and calcium stearate.
4. The PA/ASA alloy material of claim 1, wherein the antioxidants comprise primary antioxidants and secondary antioxidants.
5. The PA/ASA alloy material according to claim 4, wherein the primary antioxidant comprises any one of antioxidant 1076, antioxidant 1098F or antioxidant 245, and the secondary antioxidant comprises any one of antioxidant 168, antioxidant 126 or antioxidant P-EPQ.
6. The PA/ASA alloy material of claim 5, wherein the antioxidant is a combination of antioxidant 1076 and antioxidant 126.
7. The PA/ASA alloy material of claim 6, wherein the compounding ratio of the antioxidant 1076 to the antioxidant 126 is 1: 4-4: 1.
8. The PA/ASA alloy material of claim 7, wherein the compounding ratio of the antioxidant 1076 to the antioxidant 126 is 2: 1.
9. The PA/ASA alloy material according to claim 1, wherein the compatibilized toughening agent is a maleic anhydride-type graft copolymer and/or an acrylic acid-type graft copolymer.
10. The PA/ASA alloy material of claim 9, wherein the maleic anhydride-based graft copolymer is one or a combination of at least two of ASA grafted maleic anhydride, styrene-acrylonitrile copolymer grafted maleic anhydride, or polyolefin elastomer grafted maleic anhydride.
11. The PA/ASA alloy material according to claim 9, wherein the acrylic-based graft copolymer is one or a combination of at least two of an ethylene-butyl acrylate-glycidyl methacrylate copolymer, an ethylene-glycidyl methacrylate copolymer, or a polyolefin elastomer grafted glycidyl methacrylate.
12. The PA/ASA alloy material according to any of claims 1-11, wherein the PA/ASA alloy material comprises the following components in parts by weight:
Figure FDA0003068767350000021
Figure FDA0003068767350000031
the PA resin is a compound of low-viscosity PA and high-viscosity PA, the relative viscosity of the low-viscosity PA is 2.3-2.7, and the relative viscosity of the high-viscosity PA is 2.8-3.2; the PA resin is PA6 and/or PA 66; the compound ratio of the low-viscosity PA to the high-viscosity PA is 3:7 or 2: 1;
the content of acrylonitrile in the ASA resin is 20-40%;
the filler pretreating agent is a combination of a silane coupling agent and higher fatty acid or a combination of the silane coupling agent and higher fatty acid salt;
the wear-resistant filler is one or the combination of at least two of talcum powder, nano calcium carbonate, nano barium sulfate or nano molybdenum disulfide.
13. The method for preparing a PA/ASA alloy material according to any one of claims 1-12, characterized in that it comprises the steps of:
(1) mixing and heating the wear-resistant filler and the filler pretreating agent for pretreatment;
(2) blending the PA resin, the ASA resin, the compatibilizer and the toughening agent and the antioxidant in sequence;
(3) and (3) extruding and granulating the blend obtained in the step (1) and the step (2) to obtain the PA/ASA alloy material.
14. The method for preparing PA/ASA alloy material according to claim 13, wherein the mixing in step (1) is performed in a high-speed mixer.
15. The method for preparing PA/ASA alloy material according to claim 13, wherein the temperature of the mixing in step (1) is 80-120 ℃.
16. The method for preparing PA/ASA alloy material according to claim 13, wherein the mixing time in step (1) is 30-60 min.
17. The method for preparing PA/ASA alloy material according to claim 13, wherein the blending in step (2) is performed in a high-speed mixer.
18. The method for preparing PA/ASA alloy material according to claim 13, wherein the blending time in step (2) is 3-15 min.
19. The method for preparing PA/ASA alloy material according to claim 13, wherein the blending temperature in step (2) is 20-60 ℃.
20. The method for preparing the PA/ASA alloy material according to claim 13, wherein the mixing sequence in the step (2) is that PA is uniformly mixed with ASA or PA is uniformly mixed with the compatibilizer and toughener and then is blended with other components.
21. The method for preparing PA/ASA alloy material according to claim 20, wherein the mixing sequence in step (2) is that PA is mixed with the compatibilizer/toughening agent first.
22. The method for preparing PA/ASA alloy material according to claim 13, wherein the extrusion in step (3) is performed in a twin-screw extruder, the treatment in step (1) is added to a side level, and the blend in step (2) is added to a main level.
23. The method for preparing PA/ASA alloy material according to claim 13, wherein the extrusion method in step (3) is main-feed and side-feed two-scale blanking extrusion of the blend in an extruder.
24. The method for preparing PA/ASA alloy material according to claim 23, wherein the motor speed of the side feeding port is 200-400 rpm.
25. The method for preparing PA/ASA alloy material according to claim 23, wherein the motor speed of the main feeding port is 300-700 r/min.
26. The method for preparing PA/ASA alloy material according to claim 13, wherein the extrusion temperature in step (3) is 230-260 ℃.
27. The method of any one of claims 13 to 26, wherein the method comprises the steps of:
(1) high-speed blending the wear-resistant filler and the filler pretreating agent in a high-speed mixer at the temperature of 80-120 ℃ for 30-60min, and adding the mixture into a side feeder of a double-screw extruder;
(2) sequentially blending PA resin, ASA resin, compatibilization toughening agent and antioxidant in a high-speed mixer at a high speed of 20-60 ℃ for 3-15min, and then adding the mixture into a main feeder of a double-screw extruder;
(3) controlling the motor speed of a main feeding port of the double-screw extruder to be 300-400 r/min and the motor speed of a side feeding port to be 200-400r/min, extruding and granulating, wherein the extrusion temperature is 230-260 ℃, and after extruding, drawing, cooling and granulating the material to obtain the PA/ASA alloy material.
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