CN117304671A - High-adhesion renewable PC-ABS material for automobiles and preparation method thereof - Google Patents
High-adhesion renewable PC-ABS material for automobiles and preparation method thereof Download PDFInfo
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- CN117304671A CN117304671A CN202311337328.8A CN202311337328A CN117304671A CN 117304671 A CN117304671 A CN 117304671A CN 202311337328 A CN202311337328 A CN 202311337328A CN 117304671 A CN117304671 A CN 117304671A
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- 239000000463 material Substances 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims description 16
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 101
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims abstract description 99
- 239000004417 polycarbonate Substances 0.000 claims abstract description 52
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 50
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 33
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 33
- 239000003607 modifier Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 229920001577 copolymer Polymers 0.000 claims description 20
- 239000000155 melt Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- 239000000853 adhesive Substances 0.000 claims description 10
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 claims description 4
- 229920001897 terpolymer Polymers 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 239000003973 paint Substances 0.000 abstract description 23
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 230000003993 interaction Effects 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 12
- 229920003023 plastic Polymers 0.000 description 10
- 239000004033 plastic Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000011161 development Methods 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 238000004064 recycling Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000258971 Brachiopoda Species 0.000 description 1
- 229920001875 Ebonite Polymers 0.000 description 1
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- -1 recyclables Polymers 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- 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
- C08L2205/02—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a high-adhesion renewable PC-ABS material for automobiles, which is prepared from the following raw materials: 5-70 parts by weight of polycarbonate; 0 to 60 parts by weight of recyclable material; 20-40 parts by weight of acrylonitrile-butadiene-styrene copolymer; 0.1 to 8 parts by weight of a compatilizer; 0-10 parts by weight of an adhesion modifier; 0.3 to 1.6 parts by weight of antioxidant; 0.5 to 2 parts by weight of black matrix. Compared with the prior art, the high-adhesion renewable PC-ABS material for the automobile provided by the invention adopts specific components with specific contents to realize better overall interaction, and the obtained high-adhesion renewable PC-ABS material for the automobile has good paint adhesion on the basis of better and stable mechanical properties; meanwhile, the recyclable materials are adopted, so that the carbon emission can be reduced, the resource utilization rate is improved, and the method has a wide application prospect.
Description
Technical Field
The invention relates to the technical field of renewable materials, in particular to a high-adhesion renewable PC-ABS material for an automobile and a preparation method thereof.
Background
The PC-ABS material is an alloy material prepared by melt blending PC (polycarbonate) and ABS (acrylonitrile-butadiene-styrene terpolymer), has the characteristics of high rigidity, high toughness, high heat resistance, easiness in processing, easiness in spraying, easiness in recycling and the like, is one of the most widely used materials in the high polymer materials for the vehicle, and is widely applied to parts such as radiator grids, column plates, tail gates, fog lamp covers, tail lamp shells and the like.
With the development of industry, the global demand for polymer materials is rapidly increased in recent years, and the problems of energy, safety, environment and the like brought to society are also increased, especially the problem of processing waste plastic parts after use, and how to recycle the waste plastic parts by natural decomposition is a mainstream solution at present, so that the problem of environmental pollution of plastic can be solved, and the use of chemical raw materials can be reduced, thereby reducing the exploitation of petroleum. Therefore, the development of renewable materials is one of the important ways to achieve sustainable development of economy.
However, the PC-ABS material for automobiles in the prior art has a technical problem that paint adhesion is to be improved, thereby limiting development and application of the green material.
Disclosure of Invention
Therefore, the invention aims to improve the paint adhesion of the renewable materials, solve the problems that the original adhesion of the surface of the injection molded part is reduced and the surface paint spraying effect is affected, so that the product qualification rate is reduced, the plastic is not easy to degrade, the carbon emission is high, the environmental pollution is large and the like due to the fact that the recycling source of the low-carbon renewable materials is complex, and impurities or sundries which cannot be treated by a physical method are contained in the modified renewable materials, such as dust, label fragments, untreated paint and the like, and provide the high-adhesion renewable PC-ABS material for the automobile under the condition that the mechanical physical property of the renewable materials is guaranteed to be comparable to that of new materials.
The invention provides a high-adhesion renewable PC-ABS material for automobiles, which is prepared from the following raw materials:
5-70 parts by weight of polycarbonate;
0 to 60 parts by weight of recyclable material;
20-40 parts by weight of acrylonitrile-butadiene-styrene copolymer;
0.1 to 8 parts by weight of a compatilizer;
0-10 parts by weight of an adhesion modifier;
0.3 to 1.6 parts by weight of antioxidant;
0.5 to 2 parts by weight of black matrix.
Preferably, the polycarbonate is bisphenol A type polycarbonate, the molecular weight is 15000 g/mol-45000 g/mol, and the melt index under the condition of 300 ℃ and 1.2kg is 10g/10 min-15 g/10min.
Preferably, the recyclable material is recyclable polycarbonate with GRS authentication, the molecular weight is 15000 g/mol-45000 g/mol, and the melt index under the conditions of 300 ℃ and 1.2kg is 16g/10 min-20 g/10min.
Preferably, the weight percentage content of butadiene in the acrylonitrile-butadiene-styrene copolymer is 20% -40%, and the melt index under the conditions of 220 ℃ and 10kg is 15g/10 min-25 g/10min.
Preferably, the compatilizer is selected from one or more of methyl methacrylate-butadiene-styrene terpolymer, styrene-acrylate copolymer and ethylene-butyl acrylate-glycidyl methacrylate copolymer.
Preferably, the adhesion modifier is an ABS grafted maleic anhydride copolymer and/or a polyolefin polymer.
Preferably, the antioxidant comprises the following components in percentage by mass: the hindered phenol antioxidant and the phosphite antioxidant in the (1-2) are compounded.
The invention also provides a preparation method of the high-adhesion renewable PC-ABS material for the automobile, which is characterized by comprising the following steps of:
the polycarbonate, the recyclable material, the acrylonitrile-butadiene-styrene copolymer, the compatilizer, the adhesive force modifier, the antioxidant and the black matrix are mixed, and the high-adhesive force renewable PC-ABS material for the automobile is obtained through melt blending, extrusion, cooling and granulation in sequence.
Preferably, the mixing process is carried out by a high-speed mixer, the rotating speed is 800 r/min-1000 r/min, and the time is 3 min-6 min;
the melt blending process is carried out by adopting a double screw extruder, and the temperature is 200-250 ℃.
Preferably, before the mixing, the method further comprises:
drying the polycarbonate, the recyclable material and the acrylonitrile-butadiene-styrene copolymer;
the drying process is carried out by adopting an oven, the temperature is 80-100 ℃, and the time is 3-5 h.
The invention provides a high-adhesion renewable PC-ABS material for automobiles, which is prepared from the following raw materials: 5-70 parts by weight of polycarbonate; 0 to 60 parts by weight of recyclable material; 20-40 parts by weight of acrylonitrile-butadiene-styrene copolymer; 0.1 to 8 parts by weight of a compatilizer; 0-10 parts by weight of an adhesion modifier; 0.3 to 1.6 parts by weight of antioxidant; 0.5 to 2 parts by weight of black matrix. Compared with the prior art, the high-adhesion renewable PC-ABS material for the automobile provided by the invention adopts specific components with specific contents to realize better overall interaction, and the obtained high-adhesion renewable PC-ABS material for the automobile has good paint adhesion on the basis of better and stable mechanical properties; meanwhile, the recyclable materials are adopted, so that the carbon emission can be reduced, the resource utilization rate is improved, and the method has a wide application prospect.
In addition, the preparation method provided by the invention has the advantages of simple process, mild and easily controlled conditions, suitability for large-scale production and great potential for further application and development.
Drawings
FIG. 1 is a graph showing the effect of paint adhesion of the high adhesion renewable PC-ABS material for automobiles provided in example 1;
FIG. 2 is a graph showing the effect of paint adhesion of the high adhesion renewable PC-ABS material for automobiles provided in example 2;
FIG. 3 is a graph showing the effect of paint adhesion of the high adhesion renewable PC-ABS material for automobiles provided in example 3;
FIG. 4 is a graph showing the effect of the paint adhesion of the high adhesion renewable PC-ABS material for automobiles provided in example 4;
FIG. 5 is a graph showing the effect of paint adhesion of the high adhesion renewable PC-ABS material for automobiles provided in example 5;
FIG. 6 is a graph showing the effect of paint adhesion of the high adhesion renewable PC-ABS material for automobiles provided in example 6;
fig. 7 is a graph showing the effect of paint adhesion of the high-adhesion renewable PC-ABS material for automobiles provided in example 7.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a high-adhesion renewable PC-ABS material for automobiles, which is prepared from the following raw materials:
5-70 parts by weight of polycarbonate;
0 to 60 parts by weight of recyclable material;
20-40 parts by weight of acrylonitrile-butadiene-styrene copolymer;
0.1 to 8 parts by weight of a compatilizer;
0-10 parts by weight of an adhesion modifier;
0.3 to 1.6 parts by weight of antioxidant;
0.5 to 2 parts by weight of black matrix.
In the invention, the high-adhesion renewable PC-ABS material for the automobile is prepared from raw materials comprising polycarbonate, recyclable materials, acrylonitrile-butadiene-styrene copolymer, compatilizer, adhesion modifier, antioxidant and black matrix, and is preferably prepared from polycarbonate, recyclable materials, acrylonitrile-butadiene-styrene copolymer, compatilizer, adhesion modifier, antioxidant and black matrix.
In the present invention, the polycarbonate is preferably bisphenol A type polycarbonate, and the molecular weight is preferably 15000g/mol to 45000g/mol, more preferably 35000g/mol to 39000g/mol, and the melt index under the condition of 1.2kg at 300℃is preferably 10g/10min to 15g/10min, more preferably 12g/10min to 13g/10min. The source of the polycarbonate is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the high adhesion renewable PC-ABS material for automobiles comprises 5 to 70 parts by weight of polycarbonate, preferably 6 to 65 parts by weight.
In the present invention, the recyclable material is preferably a recyclable polycarbonate having GRS certification, and the molecular weight is preferably 15000g/mol to 45000g/mol, more preferably 40000g/mol to 45000g/mol, and the melt index under 1.2kg conditions at 300℃is preferably 16g/10min to 20g/10min, more preferably 18g/10min to 19g/10min. In the present invention, the GRS authentication: global recovery standard (Global recycling standards); on this basis, the present invention is not particularly limited as to the source of the recyclable polycarbonate with GRS authentication.
In the present invention, the high adhesion renewable PC-ABS material for automobiles comprises 0 to 60 parts by weight of a recyclable material, preferably 30 to 50 parts by weight.
In the present invention, the butadiene content of the acrylonitrile-butadiene-styrene copolymer is preferably 20% to 40%, more preferably 25% to 30%, and the melt index at 220 ℃ under 10kg conditions is preferably 15g/10min to 25g/10min, more preferably 18g/10min to 19g/10min. The source of the acrylonitrile-butadiene-styrene copolymer is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the high adhesion renewable PC-ABS material for automobiles comprises 20 to 40 parts by weight of acrylonitrile-butadiene-styrene copolymer, preferably 25 to 35 parts by weight.
In the present invention, the compatibilizer is preferably one or more selected from the group consisting of methyl methacrylate-butadiene-styrene terpolymer, styrene-acrylate copolymer, ethylene-butyl acrylate-glycidyl methacrylate copolymer, more preferably methyl methacrylate-butadiene-styrene copolymer. The source of the compatibilizing agent is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the high adhesion renewable PC-ABS material for automobiles comprises 0.1 to 8 parts by weight of a compatibilizer, preferably 4 to 6 parts by weight.
In the present invention, the adhesion modifier is preferably an ABS grafted maleic anhydride copolymer and/or a polyolefin polymer, more preferably an ABS grafted maleic anhydride copolymer. In a preferred embodiment of the invention, the adhesion modifier is an ABS grafted maleic anhydride copolymer with 15-25% anhydride content. The source of the adhesion modifier is not particularly limited and commercially available products known to those skilled in the art may be used.
In the present invention, the high adhesion renewable PC-ABS material for automobiles includes 0 to 10 parts by weight of an adhesion modifier, preferably 3 to 9 parts by weight.
In the invention, the antioxidant is preferably prepared from the following components in percentage by mass: the hindered phenol antioxidant and the phosphite antioxidant in the following (1-2) are compounded, and more preferably the mass ratio is 1:1 and phosphite ester antioxidant. The source of the antioxidant is not particularly limited and commercially available products known to those skilled in the art may be used.
In the invention, the high-adhesion renewable PC-ABS material for automobiles comprises 0.3 to 1.6 parts by weight of antioxidant, preferably 0.5 to 1.5 parts by weight.
In the present invention, the black matrix is preferably a black matrix of a PE carrier; the present invention is not particularly limited as long as it is commercially available as known to those skilled in the art.
In the present invention, the high adhesion renewable PC-ABS material for automobiles includes 0.5 to 2 parts by weight of black matrix, preferably 1 part by weight.
The high-adhesion renewable PC-ABS material for the automobile provided by the invention adopts specific components with specific content, realizes overall better interaction, can improve the paint adhesion of the renewable material, and has good paint adhesion on the basis of better and stable mechanical properties; meanwhile, the recyclable materials are adopted, so that the carbon emission can be reduced, the resource utilization rate is improved, and the method has a wide application prospect.
The invention also provides a preparation method of the high-adhesion renewable PC-ABS material for the automobile, which is characterized by comprising the following steps of:
the polycarbonate, the recyclable material, the acrylonitrile-butadiene-styrene copolymer, the compatilizer, the adhesive force modifier, the antioxidant and the black matrix are mixed, and the high-adhesive force renewable PC-ABS material for the automobile is obtained through melt blending, extrusion, cooling and granulation in sequence.
In the present invention, the polycarbonate, the recyclable material, the acrylonitrile-butadiene-styrene copolymer, the compatibilizer, the adhesion modifier, the antioxidant and the black matrix are the same as those described in the above technical scheme, and are not described herein again.
In the present invention, before the mixing, it is preferable to further include:
the polycarbonate, recyclables, acrylonitrile-butadiene-styrene copolymer are dried.
In the present invention, the drying process is preferably performed by using an oven, and the temperature is preferably 80 to 100 ℃, more preferably 90 ℃, and the time is preferably 3 to 5 hours, more preferably 4 hours.
In the invention, the mixing process is preferably carried out by a high-speed mixer, the rotating speed is preferably 800-1000 r/min, and the time is preferably 3-6 min.
In the invention, the melt blending process is preferably performed by a twin-screw extruder, and the temperature is preferably 200-250 ℃, more preferably 220-250 ℃; the invention is not particularly limited in the subsequent extrusion, cooling and pelletization processes, and can be implemented by adopting a technical scheme which is known to those skilled in the art and is implemented by adopting a double screw extruder.
The preparation method provided by the invention has the advantages of simple process, mild and easily controlled conditions, suitability for large-scale production and great potential for further application and development.
The invention provides a high-adhesion renewable PC-ABS material for automobiles, which is prepared from the following raw materials: 5-70 parts by weight of polycarbonate; 0 to 60 parts by weight of recyclable material; 20-40 parts by weight of acrylonitrile-butadiene-styrene copolymer; 0.1 to 8 parts by weight of a compatilizer; 0-10 parts by weight of an adhesion modifier; 0.3 to 1.6 parts by weight of antioxidant; 0.5 to 2 parts by weight of black matrix. Compared with the prior art, the high-adhesion renewable PC-ABS material for the automobile provided by the invention adopts specific components with specific contents to realize better overall interaction, and the obtained high-adhesion renewable PC-ABS material for the automobile has good paint adhesion on the basis of better and stable mechanical properties; meanwhile, the recyclable materials are adopted, so that the carbon emission can be reduced, the resource utilization rate is improved, and the method has a wide application prospect.
In addition, the preparation method provided by the invention has the advantages of simple process, mild and easily controlled conditions, suitability for large-scale production and great potential for further application and development.
In order to further illustrate the present invention, the following examples are provided. The raw materials used in the following examples of the invention are all common raw materials in the field, are commercially available sources, and the adopted methods are all conventional methods in the field without special description; in the following examples, the polycarbonate was bisphenol A type polycarbonate having a molecular weight of 38000g/mol, a melt index of 12g/10min at 300℃under 1.2kg and a density of 1.19g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The recoverable polycarbonate is a recoverable polycarbonate with GRS certification, has a molecular weight of 40000g/mol, a melt index of 19g/10min at 300 ℃ under 1.2kg conditions, and a density of 1.19g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index of the acrylonitrile-butadiene-styrene copolymer at 220 ℃ and 10kg is 19g/10min, and the density is 1.142/cm 3 The weight percentage of butadiene is 28%; the compatilizer is methyl methacrylate-butadiene-styrene terpolymer, preferably MBS EM500; the adhesive force modifier is an ABS grafted maleic anhydride copolymer with an anhydride content of 21 percent; antioxidant is basf 1010 and 168 according to 1:1 weight ratio; black colorThe color master is black master of the cabot PE carrier.
Example 1
(1) The polycarbonate, the recyclable polycarbonate and the acrylonitrile-butadiene-styrene copolymer are placed in an oven for drying at 90 ℃ for 4 hours and then placed in a sealed bag for standby.
(2) The raw materials and other auxiliary agents (65 parts by weight of polycarbonate, 30 parts by weight of acrylonitrile-butadiene-styrene copolymer, 5 parts by weight of methyl methacrylate-butadiene-styrene copolymer, 1 part by weight of antioxidant and 1 part by weight of black master batch) in the step (1) are weighed according to the weight proportion, and are placed into a high-speed mixer to be mixed, the rotating speed is 900r/min, and the time is 5min, so that a mixture is obtained.
(3) Pouring the mixture obtained in the step (2) into a charging barrel in a double-screw extruder, extruding, cooling and granulating after the mixture is melted and mixed at 220-250 ℃ by the double-screw extruder, thus obtaining the high-adhesion renewable PC-ABS material for automobiles.
Performance test:
the high-adhesion renewable PC-ABS material for automobiles obtained in the example 1 is molded by an injection molding machine (the temperature of the injection molding machine is set to 220-260 ℃, the pressure maintaining time is 3-6 s, the injection pressure is 60-90 MPa, and the injection speed is 50-70 mm/s), and then test bars and test pieces to be sprayed are obtained; wherein, the test piece to be sprayed is sprayed and cured according to the part spray painting process of PC-ABS material.
Test bars and paint test pieces were prepared according to GB standard and tested, mechanical and thermal properties were tested by a universal tester, an impact tester and a Vicat-heat distortion temperature tester, paint adhesion was tested according to GB/T9286 standard by cross-hatch method, and the main performance data are shown in Table 1.
Example 2
The preparation method provided in example 1 was used, with the difference that: 35 parts of polycarbonate, 30 parts of recyclable polycarbonate, 30 parts of acrylonitrile-butadiene-styrene copolymer, 5 parts of methyl methacrylate-butadiene-styrene copolymer, 1 part of antioxidant and 1 part of black master batch by weight to obtain the high-adhesion renewable PC-ABS material for automobiles.
Performance test see example 1.
Example 3
The preparation method provided in example 1 was used, with the difference that: 62 parts of polycarbonate, 30 parts of acrylonitrile-butadiene-styrene copolymer, 5 parts of methyl methacrylate-butadiene-styrene copolymer, 3 parts of ABS grafted maleic anhydride, 1 part of antioxidant and 1 part of black matrix; the high-adhesion renewable PC-ABS material for the automobile is obtained.
Performance test see example 1.
Example 4
The preparation method provided in example 1 was used, with the difference that: 32 parts of polycarbonate, 30 parts of recyclable polycarbonate, 30 parts of acrylonitrile-butadiene-styrene copolymer, 5 parts of methyl methacrylate-butadiene-styrene copolymer, 3 parts of ABS grafted maleic anhydride, 1 part of antioxidant and 1 part of black matrix; the high-adhesion renewable PC-ABS material for the automobile is obtained.
Performance test see example 1.
Example 5
The preparation method provided in example 1 was used, with the difference that: 29 parts of polycarbonate, 30 parts of recyclable polycarbonate, 30 parts of acrylonitrile-butadiene-styrene copolymer, 5 parts of methyl methacrylate-butadiene-styrene copolymer, 6 parts of ABS grafted maleic anhydride, 1 part of antioxidant and 1 part of black matrix; the high-adhesion renewable PC-ABS material for the automobile is obtained.
Performance test see example 1.
Example 6
The preparation method provided in example 1 was used, with the difference that: 9 parts of polycarbonate, 50 parts of recyclable polycarbonate, 30 parts of acrylonitrile-butadiene-styrene copolymer, 5 parts of methyl methacrylate-butadiene-styrene copolymer, 6 parts of ABS grafted maleic anhydride, 1 part of antioxidant and 1 part of black matrix; the high-adhesion renewable PC-ABS material for the automobile is obtained.
Performance test see example 1.
Example 7
The preparation method provided in example 1 was used, with the difference that: 6 parts of polycarbonate, 50 parts of recyclable polycarbonate, 30 parts of acrylonitrile-butadiene-styrene copolymer, 5 parts of methyl methacrylate-butadiene-styrene copolymer, 9 parts of ABS grafted maleic anhydride, 1 part of antioxidant and 1 part of black matrix; the high-adhesion renewable PC-ABS material for the automobile is obtained.
Performance test see example 1.
TABLE 1 Performance data of renewable PC-ABS materials for automobiles
The test criteria are as follows:
sample preparation standard: GB/T2918 plastic sample state adjustment and experimental standard environment;
tensile strength test standard: determination of GB/T1040.2 Plastic tensile Properties part 2: test conditions for molding and extrusion;
flexural Strength and flexural modulus test criteria: GB/T9341 plastics bending property determination;
notched impact strength test criteria: measuring the impact strength of the GB/T1843 plastic cantilever beam;
1.8MPa heat distortion test Standard: determination of GB/T1634.2 Plastic deformation under load part 2: plastics, hard rubber and long fiber reinforced composites;
paint adhesion test criteria: GB/T9286 color paint and varnish cross-hatch experiments.
According to the results shown in Table 1, the difference in material properties after the reclaimed materials were added in examples 1 to 2 was not too large, but the paint adhesion was deteriorated, the paint adhesion on the reclaimed materials surface of comparative examples 1 to 5 was decreased by increasing the reclaimed material proportion and the property change was not too large, but the adhesion was significantly improved as the proportion of the adhesion modifier was increased more, and the material was not greatly affected. Therefore, the application of the paint adhesion modifier in the technical scheme of the application improves the material adhesion, has little influence on the material performance, and simultaneously adopts the recyclable polycarbonate material after GRS authentication, thereby promoting the application of the recyclable polycarbonate in an industrial chain, reducing the carbon emission and improving the resource utilization rate.
In summary, the high-adhesion renewable PC-ABS material for the automobile provided by the invention has the following beneficial effects:
(1) The recyclable polycarbonate material with GRS authentication is adopted, and then the PC new material, the ABS resin, the compatilizer, the adhesive force modifier, the antioxidant and the black matrix are combined, so that the PC-ABS material with performance comparable to that of the new material modification can be obtained, the recycling application of the recycled polycarbonate material in an industrial chain can be promoted, the carbon emission is reduced, and the resource utilization rate is improved.
(2) The adhesive force modifier is added into the high-adhesive force renewable PC-ABS material, so that the compatibility between the material and impurities is improved by increasing the polarity in the material, the yield of product coating is improved, and the material is suitable for industrial production and application.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The high-adhesion renewable PC-ABS material for the automobile is characterized by being prepared from the following raw materials:
5-70 parts by weight of polycarbonate;
0 to 60 parts by weight of recyclable material;
20-40 parts by weight of acrylonitrile-butadiene-styrene copolymer;
0.1 to 8 parts by weight of a compatilizer;
0-10 parts by weight of an adhesion modifier;
0.3 to 1.6 parts by weight of antioxidant;
0.5 to 2 parts by weight of black matrix.
2. The high adhesion renewable PC-ABS material for automobiles according to claim 1, wherein the polycarbonate is bisphenol a type polycarbonate having a molecular weight of 15000g/mol to 45000g/mol and a melt index of 10g/10min to 15g/10min at 300 ℃ under 1.2 kg.
3. The high adhesion renewable PC-ABS material for automobiles according to claim 1, wherein the recyclable material is a recyclable polycarbonate with GRS certification, has a molecular weight of 15000g/mol to 45000g/mol, and has a melt index of 16g/10min to 20g/10min at 300 ℃ under 1.2kg conditions.
4. The high adhesion renewable PC-ABS material for automobiles according to claim 1, wherein the weight percentage of butadiene in the acrylonitrile-butadiene-styrene copolymer is 20% to 40%, and the melt index under 10kg conditions at 220 ℃ is 15g/10min to 25g/10min.
5. The high adhesion renewable PC-ABS material for automobiles according to claim 1 wherein the compatibilizer is selected from one or more of methyl methacrylate-butadiene-styrene terpolymer, styrene-acrylate copolymer, ethylene-butyl acrylate-glycidyl methacrylate copolymer.
6. The high adhesion renewable PC-ABS material for automobiles according to claim 1, wherein the adhesion modifier is ABS grafted maleic anhydride copolymer and/or polyolefin polymer.
7. The high adhesion renewable PC-ABS material for automobiles according to claim 1, wherein the antioxidant consists of the following components in mass ratio 1: the hindered phenol antioxidant and the phosphite antioxidant in the (1-2) are compounded.
8. A method for preparing the high-adhesion renewable PC-ABS material for automobiles according to any one of claims 1 to 7, characterized by comprising the steps of:
the polycarbonate, the recyclable material, the acrylonitrile-butadiene-styrene copolymer, the compatilizer, the adhesive force modifier, the antioxidant and the black matrix are mixed, and the high-adhesive force renewable PC-ABS material for the automobile is obtained through melt blending, extrusion, cooling and granulation in sequence.
9. The preparation method according to claim 8, wherein the mixing process is performed by a high-speed mixer at a rotation speed of 800-1000 r/min for 3-6 min;
the melt blending process is carried out by adopting a double screw extruder, and the temperature is 200-250 ℃.
10. The method according to any one of claims 8 to 9, characterized in that before the mixing, further comprising:
drying the polycarbonate, the recyclable material and the acrylonitrile-butadiene-styrene copolymer;
the drying process is carried out by adopting an oven, the temperature is 80-100 ℃, and the time is 3-5 h.
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