CN118027549A - Polypropylene composite material for flame-treatment-free low-odor low-emission automotive upholstery and preparation method thereof - Google Patents
Polypropylene composite material for flame-treatment-free low-odor low-emission automotive upholstery and preparation method thereof Download PDFInfo
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- CN118027549A CN118027549A CN202311803024.6A CN202311803024A CN118027549A CN 118027549 A CN118027549 A CN 118027549A CN 202311803024 A CN202311803024 A CN 202311803024A CN 118027549 A CN118027549 A CN 118027549A
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- -1 Polypropylene Polymers 0.000 title claims abstract description 124
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 117
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 117
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 48
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- 239000000853 adhesive Substances 0.000 claims abstract description 23
- 230000001070 adhesive effect Effects 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- 239000012745 toughening agent Substances 0.000 claims abstract description 17
- 239000004595 color masterbatch Substances 0.000 claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 15
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 9
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 229920001971 elastomer Polymers 0.000 claims abstract description 4
- 239000000806 elastomer Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000011049 filling Methods 0.000 claims abstract 2
- 238000012360 testing method Methods 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 32
- 239000003963 antioxidant agent Substances 0.000 claims description 22
- 230000003078 antioxidant effect Effects 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 20
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 14
- 239000000945 filler Substances 0.000 claims description 14
- 239000003063 flame retardant Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 239000000314 lubricant Substances 0.000 claims description 12
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 10
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 3
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 150000002193 fatty amides Chemical class 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 150000003384 small molecules Chemical class 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 23
- 238000005507 spraying Methods 0.000 abstract description 17
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- 230000000052 comparative effect Effects 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
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- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000013102 re-test Methods 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- 230000016776 visual perception Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a flame-treatment-free low-odor low-emission polypropylene composite material for automotive upholstery and a preparation method thereof, wherein the polypropylene composite material comprises the following components in percentage by weight: polypropylene: 20-40%; chlorinated polypropylene: 10-30%; toughening agent: 5-15%; and (3) filling: 15-20%; porous graphene: 5-10%; polar additive: 10-20%; and (3) a compatilizer: 0.5-5%; other auxiliary agents: 0.5-2%; 0.5-1% of color master batch. The invention has the advantages that: the chlorinated polypropylene, the polar additive and the toughening agent-thermoplastic polyurethane elastomer are selected, so that the surface tension of the material can reach more than 38mN/m, and the material can be directly coated by spraying glue or sprayed by spraying paint without the flame pretreatment process; meanwhile, by utilizing the highly ordered pore structure of the porous graphene, small molecular substances generated by decomposition of the adsorption material in the processing process can be captured, so that the material emission performance is improved, and the interface binding force with the adhesive/coating is greatly increased.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to a flame-treatment-free polypropylene composite material for low-odor and low-emission automotive upholstery and a preparation method thereof.
Background
Polypropylene is widely used for manufacturing automobile interior parts, such as instrument panels, door panels, auxiliary instrument panels and the like, due to the advantages of no toxicity, acid and alkali resistance, low water absorption, easiness in processing, good dimensional stability and the like.
At present, the automotive interior trim leather pattern piece obtained by directly injection molding the modified polypropylene material is difficult to meet the touch and visual perception requirements of consumers, and the injection molded leather pattern piece is gradually changed into a coating piece, a slush molding foaming piece, a paint spraying piece and the like. The polypropylene material has high crystallinity, a dense grain network, weak dispersion force on the surface and weak boundary layer formed on the surface in the processing process, so that the surface bonding performance is poor; it is therefore often desirable to flame treat the surface of polypropylene substrates to increase their surface polarity and thereby improve their wetting properties with paints and adhesives. However, the complicated automobile interior part structure cannot be completely matched with the flame treatment process, so that the problems of infirm coating of the adhesive or paint spraying, shrinkage cavity or non-infiltration after paint spraying and the like of the part are easy to occur; the flame treatment process has the problems of low efficiency, environmental pollution, poor safety and the like. In order to solve the problems and improve the air quality in the automobile to protect the health of consumers, a polypropylene composite material for automobile interior trim parts, which is free of flame treatment, low in odor and low in emission, is researched and developed.
Disclosure of Invention
The invention aims to meet the requirements of polypropylene materials in the automotive interior market, so that a polypropylene composite material which is free of flame treatment and has low odor and low emission is developed and is applied to the processing and preparation of automotive interior cladding parts or paint spraying parts, so that the product has good mechanical properties and also has the properties of free of flame treatment, low odor, low emission and the like.
The invention aims at providing a polypropylene composite material for a flame-treatment-free low-odor low-emission automotive interior part, which comprises the following raw materials: the composite material comprises the following components in percentage by weight:
the polypropylene composite material for the flame-treatment-free low-odor low-emission automotive upholstery and the preparation method thereof are characterized in that the polypropylene is one or a mixture of several kinds of copolymerized polypropylene with the melt flow rate of 50-100 g/10min under the test condition of 230 ℃ and 2.16 Kg;
The flame-treatment-free low-odor low-emission polypropylene composite material for the automotive upholstery and the preparation method thereof are characterized in that the chlorinated polypropylene is one or a mixture of more than 25-45% of chlorine content;
the flame-treatment-free low-odor low-emission polypropylene composite material for the automotive upholstery and the preparation method thereof are characterized in that the toughening agent is at least one of thermoplastic polyurethane elastomer or ethylene-octene copolymer with the hardness of 20D-45D;
The flame-treatment-free low-odor low-emission polypropylene composite material for the automotive upholstery and the preparation method thereof are characterized in that the filler is one or a mixture of a plurality of talcum powder, kaolin, calcium carbonate and glass beads;
The polypropylene composite material for the flame-treatment-free low-odor low-emission automotive upholstery and the preparation method thereof are characterized in that the porous graphene has the following sheet diameter: 0.5-5 mu m, specific surface area: 100-894 m 2/g, pore diameter: the porous structure of the material can capture or adsorb residual organic small molecules in the polypropylene resin matrix to achieve the requirements of improving smell and controlling VOC content, and simultaneously, the material is beneficial to the permeation of the coating/adhesive to the surface of the material, so that the interfacial binding force of the material and the coating/adhesive is increased;
The flame-treatment-free low-odor low-emission polypropylene composite material for the automotive upholstery and the preparation method thereof are characterized in that the polar additive is methacrylic acid long carbon chain ester, the chemical formula of the polar additive is methacrylic acid long carbon chain ester, and the chemical formula is: Wherein R: c nH2n+1 n is more than or equal to 8;
the flame-treatment-free low-odor low-emission polypropylene composite material for the automotive upholstery and the preparation method thereof are characterized in that the compatilizer is maleic anhydride grafted polypropylene, the grafting rate is as high as 4.0%, and the melting point is 160-170 ℃;
The flame-treatment-free low-odor low-emission polypropylene composite material for the automotive upholstery and the preparation method thereof are characterized in that the other auxiliary agents comprise one or a mixture of a dispersing agent, a lubricating agent and an antioxidant;
the polypropylene composite material for the flame-treatment-free low-odor low-emission automotive upholstery and the preparation method thereof are characterized in that the dispersing agent is one of low-relative-molecular-weight polyethylene wax, stearate and fatty amide, and the relative molecular weight is 1000-10000;
the flame-treatment-free low-odor low-emission polypropylene composite material for the automotive upholstery and the preparation method thereof are characterized in that the lubricant is one or a mixture of more of zinc stearate, calcium stearate and magnesium stearate;
The flame-treatment-free low-odor low-emission polypropylene composite material for the automotive upholstery and the preparation method thereof are characterized in that the antioxidant master batch is a compound synergistic antioxidant of a main antioxidant (phenols), an auxiliary antioxidant (phosphite esters) and epoxy resin, wherein the melting temperature of the main antioxidant DSC is 110-125 ℃, the melting temperature of the auxiliary antioxidant DSC is 180-190 ℃, and the melting temperature of the epoxy resin DSC is 120-160 ℃;
the polypropylene composite material for the flame-treatment-free low-odor low-emission automotive upholstery and the preparation method thereof are characterized in that the color master batch is an inorganic black master batch;
the polypropylene composite material for the flame-treatment-free low-odor low-emission automotive upholstery and the preparation method thereof are as follows:
Step 1: the material is prepared by weighing polypropylene, chlorinated polypropylene, a toughening agent, a filler, porous graphene, a polar additive, a compatilizer, other auxiliary agents and masterbatch according to the weight ratio;
Step 2: placing the polypropylene, the chlorinated polypropylene, the toughening agent, the filler and the porous graphene in the step 1 into a high-speed stirrer, mixing for about 10 minutes at room temperature, and adding the polar additive, the compatilizer, the other auxiliary agents, the color master batch and other components to mix for 20 minutes uniformly;
step 3: the extrusion temperatures in the screws were respectively: 180-200 ℃ in the first area, 200-225 ℃ in the second area, 200-225 ℃ in the third area, 200-215 ℃ in the fourth area, 190-210 ℃ in the fifth area, and the screw rotating speed is 350-400 r/min.
Step 4: after the twin screw is heated to the test temperature, the mixture after the mixing treatment in the step 2 is melted, blended and extruded in a twin screw extruder, then cooled by water, dried and granulated, finally enters a homogenizing and material drying system, the material drying system adopts three-tank dynamic circulation material drying, a cooling tank is added, high-temperature materials are subjected to blowing cooling circulation in an additional bin, so that odor micromolecules are fully volatilized to help odor to be lifted, and a material drying process is carried out for 4 hours at 130 ℃, so that a product is finally obtained.
The polypropylene composite material for the automotive upholstery is based on the application of flame-retardant, low-odor and low-emission polypropylene composite material; the method is characterized in that the surface tension of the polypropylene composite material reaches more than 38mN/m, the odor grade reaches 2.5-3.0 grade of the mass, the TVOC is reduced to below 20 mu gC/g, and the application requirement of the automobile interior market is met.
Detailed Description
Example 1
The polypropylene composite material for the flame-treatment-free low-odor low-emission automotive upholstery comprises the following raw materials in parts by weight: 30 parts of copolymerized polypropylene (Korean SK, brand: BX3900, melt finger 60g/10 min), 20 parts of chlorinated polypropylene (Japanese Toyobo, brand: DX-526P, viscosity: 100-200mPa x s), 8 parts of TPU (Wanhua, brand: 50975), 20 parts of talcum powder (commercially available, mesh: 10000 mesh), 5 parts of porous graphene (commercially available, pore size: 0.01-4.58 nm), 12 parts of polar additive (commercially available, long carbon chain methacrylate), 2.3 parts of compatilizer (commercially available, maleic anhydride grafted polypropylene), 0.2 parts of lubricant (commercially available, zinc stearate), 1.5 parts of antioxidant masterbatch (homemade) and 1 part of color masterbatch.
Putting the weighed polypropylene, chlorinated polypropylene, a toughening agent, a filler and porous graphene into a high-speed stirrer, mixing for about 10 minutes at room temperature, adding polar additives, compatilizers, other auxiliary agents, masterbatch and other components, mixing for 20 minutes until the components are uniform, and adding the components into a double-screw extruder, wherein the temperatures of all sections of the extruder are respectively as follows: 180 ℃ in the first region, 200 ℃ in the second region, 210 ℃ in the third region, 210 ℃ in the fourth region and 200 ℃ in the fifth region; after the twin-screw is heated to the test temperature, setting the screw rotating speed to 350r/min, carrying out melt blending on the mixture after the mixing treatment in a twin-screw extruder, carrying out water cooling after extrusion, drying and granulating, finally entering a homogenizing and material drying system, and finally obtaining the product by a material drying process at 130 ℃ for 4 hours.
And placing the product particles at normal temperature for 24 hours, then performing odor and TVOC testing, adopting injection molding machine equipment to prepare 355 x 100 x 3.2mm optical plate from polypropylene particles, then placing the sample plate at normal temperature for 24 hours, then performing surface tension and contact angle testing, simultaneously performing adhesive coating and paint spraying treatment on the optical plate respectively, and finally performing peeling force and paint adhesion (cross-cut) testing.
Example 2
The polypropylene composite material for the flame-treatment-free low-odor low-emission automotive upholstery comprises the following raw materials in parts by weight: 26 parts of copolymerized polypropylene (Korean SK, brand: BX3900, melt finger 60g/10 min), 18 parts of chlorinated polypropylene (Japanese Toyobo, brand: DX-526P, viscosity: 100-200mPa x s), 10 parts of TPU (Wanhua, brand: 50975), 20 parts of talcum powder (commercially available, mesh: 10000 mesh), 7 parts of porous graphene (commercially available, pore size: 0.01-4.58 nm), 14 parts of polar additive (commercially available, long carbon chain methacrylate), 2.3 parts of compatilizer (commercially available, maleic anhydride grafted polypropylene), 0.2 parts of lubricant (commercially available, zinc stearate), 1.5 parts of antioxidant masterbatch (homemade) and 1 part of color masterbatch.
Putting the weighed polypropylene, chlorinated polypropylene, a toughening agent, a filler and porous graphene into a high-speed stirrer, mixing for about 10 minutes at room temperature, adding polar additives, compatilizers, other auxiliary agents, masterbatch and other components, mixing for 20 minutes until the components are uniform, and adding the components into a double-screw extruder, wherein the temperatures of all sections of the extruder are respectively as follows: 180 ℃ in the first region, 200 ℃ in the second region, 210 ℃ in the third region, 210 ℃ in the fourth region and 200 ℃ in the fifth region; after the twin-screw is heated to the test temperature, setting the screw rotating speed to 350r/min, carrying out melt blending on the mixture after the mixing treatment in a twin-screw extruder, carrying out water cooling after extrusion, drying and granulating, finally entering a homogenizing and material drying system, and finally obtaining the product by a material drying process at 130 ℃ for 4 hours.
And placing the product particles at normal temperature for 24 hours, then performing odor and TVOC testing, adopting injection molding machine equipment to prepare 355 x 100 x 3.2mm optical plate from polypropylene particles, then placing the sample plate at normal temperature for 24 hours, then performing surface tension and contact angle testing, simultaneously performing adhesive coating and paint spraying treatment on the optical plate respectively, and finally performing peeling force and paint adhesion (cross-cut) testing.
Example 3
The polypropylene composite material for the flame-treatment-free low-odor low-emission automotive upholstery comprises the following raw materials in parts by weight: 28 parts of copolymerized polypropylene (Korean SK, brand: BX3900, melt finger 60g/10 min), 18 parts of chlorinated polypropylene (Japanese Toyobo, brand: DX-526P, viscosity: 100-200mPa x s), 8 parts of TPU (Wanhua, brand: 50975), 20 parts of talcum powder (commercially available, mesh: 10000 mesh), 5 parts of porous graphene (commercially available, pore size: 0.01-4.58 nm), 16 parts of polar additive (commercially available, long carbon chain methacrylate), 2.3 parts of compatilizer (commercially available, maleic anhydride grafted polypropylene), 0.2 parts of lubricant (commercially available, zinc stearate), 1.5 parts of antioxidant masterbatch (homemade) and 1 part of color masterbatch.
Putting the weighed polypropylene, chlorinated polypropylene, a toughening agent, a filler and porous graphene into a high-speed stirrer, mixing for about 10 minutes at room temperature, adding polar additives, compatilizers, other auxiliary agents, masterbatch and other components, mixing for 20 minutes until the components are uniform, and adding the components into a double-screw extruder, wherein the temperatures of all sections of the extruder are respectively as follows: 180 ℃ in the first region, 200 ℃ in the second region, 210 ℃ in the third region, 210 ℃ in the fourth region and 200 ℃ in the fifth region; after the twin-screw is heated to the test temperature, setting the screw rotating speed to 350r/min, carrying out melt blending on the mixture after the mixing treatment in a twin-screw extruder, carrying out water cooling after extrusion, drying and granulating, finally entering a homogenizing and material drying system, and finally obtaining the product by a material drying process at 130 ℃ for 4 hours.
And placing the product particles at normal temperature for 24 hours, then performing odor and TVOC testing, adopting injection molding machine equipment to prepare 355 x 100 x 3.2mm optical plate from polypropylene particles, then placing the sample plate at normal temperature for 24 hours, then performing surface tension and contact angle testing, simultaneously performing adhesive coating and paint spraying treatment on the optical plate respectively, and finally performing peeling force and paint adhesion (cross-cut) testing.
Example 4
The polypropylene composite material for the flame-treatment-free low-odor low-emission automotive upholstery comprises the following raw materials in parts by weight: 30 parts of copolymerized polypropylene (Korean SK, brand: BX3900, melt finger 60g/10 min), 20 parts of chlorinated polypropylene (Japanese Toyobo, brand: DX-526P, viscosity: 100-200mPa x s), 10 parts of TPU (Wanhua brand: 50975), 20 parts of talcum powder (commercially available, mesh: 10000 mesh), 5 parts of porous graphene (commercially available, pore size: 0.01-4.58 nm), 10 parts of polar additive (commercially available, long carbon chain methacrylate), 2.3 parts of compatilizer (commercially available, maleic anhydride grafted polypropylene), 0.2 parts of lubricant (commercially available, zinc stearate), 1.5 parts of antioxidant masterbatch (homemade) and 1 part of color masterbatch.
Putting the weighed polypropylene, chlorinated polypropylene, a toughening agent, a filler and porous graphene into a high-speed stirrer, mixing for about 10 minutes at room temperature, adding polar additives, compatilizers, other auxiliary agents, masterbatch and other components, mixing for 20 minutes until the components are uniform, and adding the components into a double-screw extruder, wherein the temperatures of all sections of the extruder are respectively as follows: 180 ℃ in the first region, 200 ℃ in the second region, 210 ℃ in the third region, 210 ℃ in the fourth region and 200 ℃ in the fifth region; after the twin-screw is heated to the test temperature, setting the screw rotating speed to 350r/min, carrying out melt blending on the mixture after the mixing treatment in a twin-screw extruder, carrying out water cooling after extrusion, drying and granulating, finally entering a homogenizing and material drying system, and finally obtaining the product by a material drying process at 130 ℃ for 4 hours.
And placing the product particles at normal temperature for 24 hours, then performing odor and TVOC testing, adopting injection molding machine equipment to prepare 355 x 100 x 3.2mm optical plate from polypropylene particles, then placing the sample plate at normal temperature for 24 hours, then performing surface tension and contact angle testing, simultaneously performing adhesive coating and paint spraying treatment on the optical plate respectively, and finally performing peeling force and paint adhesion (cross-cut) testing.
Comparative example 1
The polypropylene composite material for the flame-treatment-free low-odor low-emission automotive upholstery comprises the following raw materials in parts by weight: 69.3 parts of copolymerized polypropylene (Korean SK, brand: BX3900, melt finger 60g/10 min), 8 parts of ethylene-octene copolymer (Mobil, brand: 7467), 20 parts of talcum powder (commercially available, mesh: 10000 mesh), 0.2 part of lubricant (commercially available, zinc stearate), 1.5 parts of antioxidant master batch (homemade) and 1 part of color master batch.
Putting the weighed polypropylene, the toughening agent and the filler into a high-speed stirrer, mixing for about 10min at room temperature, adding other additives, color master batches and other components, mixing for 20min until uniformity, and adding into a double-screw extruder, wherein the temperatures of all sections of the extruder are respectively as follows: 180 ℃ in the first region, 200 ℃ in the second region, 210 ℃ in the third region, 210 ℃ in the fourth region and 200 ℃ in the fifth region; after the twin-screw is heated to the test temperature, setting the screw rotating speed to 350r/min, carrying out melt blending on the mixture after the mixing treatment in a twin-screw extruder, carrying out water cooling after extrusion, drying and granulating, finally entering a homogenizing and material drying system, and finally obtaining the product by a material drying process at 130 ℃ for 4 hours.
And placing the product particles at normal temperature for 24 hours, then performing odor and TVOC testing, adopting injection molding machine equipment to prepare 355 x 100 x 3.2mm optical plate from polypropylene particles, then placing the sample plate at normal temperature for 24 hours, then performing surface tension and contact angle testing, simultaneously performing adhesive coating and paint spraying treatment on the optical plate respectively, and finally performing peeling force and paint adhesion (cross-cut) testing.
Comparative example 2
The polypropylene composite material for the flame-treatment-free low-odor low-emission automotive upholstery comprises the following raw materials in parts by weight: 47 parts of copolymerized polypropylene (Korean SK, brand: BX3900, melt finger 60g/10 min), 20 parts of chlorinated polypropylene (Japanese Toyobo, brand: DX-526P, viscosity: 100-200 mPa. S), 8 parts of ethylene-octene copolymer (Mobil, brand: 7467), 20 parts of talcum powder (commercial, mesh: 10000 mesh), 2.3 parts of compatilizer (commercial, maleic anhydride grafted polypropylene), 0.2 part of lubricant (commercial, zinc stearate), 1.5 parts of antioxidant masterbatch (homemade) and 1 part of color masterbatch.
Placing the weighed polypropylene, chlorinated polypropylene, toughening agent and filler into a high-speed stirrer, mixing for about 10min at room temperature, adding compatilizer, other auxiliary agents, masterbatch and other components, mixing for 20min until uniformity, and adding into a double-screw extruder, wherein the temperatures of all sections of the extruder are as follows: 180 ℃ in the first region, 200 ℃ in the second region, 210 ℃ in the third region, 210 ℃ in the fourth region and 200 ℃ in the fifth region; after the twin-screw is heated to the test temperature, setting the screw rotating speed to 350r/min, carrying out melt blending on the mixture after the mixing treatment in a twin-screw extruder, carrying out water cooling after extrusion, drying and granulating, finally entering a homogenizing and material drying system, and finally obtaining the product by a material drying process at 130 ℃ for 4 hours.
And placing the product particles at normal temperature for 24 hours, then performing odor and TVOC testing, adopting injection molding machine equipment to prepare 355 x 100 x 3.2mm optical plate from polypropylene particles, then placing the sample plate at normal temperature for 24 hours, then performing surface tension and contact angle testing, simultaneously performing adhesive coating and paint spraying treatment on the optical plate respectively, and finally performing peeling force and paint adhesion (cross-cut) testing.
Comparative example 3
The polypropylene composite material for the flame-treatment-free low-odor low-emission automotive upholstery comprises the following raw materials in parts by weight: 45 parts of copolymerized polypropylene (Korean SK, brand: BX3900, melt finger 60g/10 min), 20 parts of chlorinated polypropylene (Japanese Toyobo, brand: DX-526P, viscosity: 100-200mPa, s), 10 parts of TPU (Wanhua brand: 50975), 20 parts of talcum powder (commercial, mesh: 10000 mesh), 2.3 parts of compatilizer (commercial, maleic anhydride grafted polypropylene), 0.2 part of lubricant (commercial, zinc stearate), 1.5 parts of antioxidant masterbatch (homemade) and 1 part of color masterbatch.
Placing the weighed polypropylene, chlorinated polypropylene, toughening agent and filler into a high-speed stirrer, mixing for about 10min at room temperature, adding compatilizer, other auxiliary agents, masterbatch and other components, mixing for 20min until uniformity, and adding into a double-screw extruder, wherein the temperatures of all sections of the extruder are as follows: 180 ℃ in the first region, 200 ℃ in the second region, 210 ℃ in the third region, 210 ℃ in the fourth region and 200 ℃ in the fifth region; after the twin-screw is heated to the test temperature, setting the screw rotating speed to 350r/min, carrying out melt blending on the mixture after the mixing treatment in a twin-screw extruder, carrying out water cooling after extrusion, drying and granulating, finally entering a homogenizing and material drying system, and finally obtaining the product by a material drying process at 130 ℃ for 4 hours.
And placing the product particles at normal temperature for 24 hours, then performing odor and TVOC testing, adopting injection molding machine equipment to prepare 355 x 100 x 3.2mm optical plate from polypropylene particles, then placing the sample plate at normal temperature for 24 hours, then performing surface tension and contact angle testing, simultaneously performing adhesive coating and paint spraying treatment on the optical plate respectively, and finally performing peeling force and paint adhesion (cross-cut) testing.
Comparative example 4
The polypropylene composite material for the flame-treatment-free low-odor low-emission automotive upholstery comprises the following raw materials in parts by weight: 53 parts of copolymerized polypropylene (Korean SK, brand: BX3900, melt finger 60g/10 min), 8 parts of ethylene-octene copolymer (Mobil, brand: 7467), 20 parts of talcum powder (commercial, mesh: 10000 mesh), 14 parts of polar additive (commercial, methacrylic acid long carbon chain ester), 2.3 parts of compatilizer (commercial, maleic anhydride grafted polypropylene), 0.2 part of lubricant (commercial, zinc stearate), 1.5 parts of antioxidant master batch (homemade) and 1 part of color master batch.
Placing the weighed polypropylene, chlorinated polypropylene, a toughening agent and a filler into a high-speed stirrer, mixing for about 10min at room temperature, adding polar additives, compatilizers, other auxiliary agents, color master batches and other components, mixing for 20min until uniformity, and adding into a double-screw extruder, wherein the temperatures of all sections of the extruder are respectively as follows: 180 ℃ in the first region, 200 ℃ in the second region, 210 ℃ in the third region, 210 ℃ in the fourth region and 200 ℃ in the fifth region; after the twin-screw is heated to the test temperature, setting the screw rotating speed to 350r/min, carrying out melt blending on the mixture after the mixing treatment in a twin-screw extruder, carrying out water cooling after extrusion, drying and granulating, finally entering a homogenizing and material drying system, and finally obtaining the product by a material drying process at 130 ℃ for 4 hours.
And placing the product particles at normal temperature for 24 hours, then performing odor and TVOC testing, adopting injection molding machine equipment to prepare 355 x 100 x 3.2mm optical plate from polypropylene particles, then placing the sample plate at normal temperature for 24 hours, then performing surface tension and contact angle testing, simultaneously performing adhesive coating and paint spraying treatment on the optical plate respectively, and finally performing peeling force and paint adhesion (cross-cut) testing.
Performance evaluation mode and implementation standard:
Odor: testing according to the PV3900 standard, wherein the testing conditions are 80+/-2 ℃ for 2 hours+/-10 min; putting 20g of polypropylene composite material particles into a 1L special odor bottle, putting a container into an oven at 80+/-2 ℃, storing for 2 hours+/-10 minutes, taking out, and evaluating odor after the odor bottle is cooled to 60+/-5 ℃; odorless-1; odorous but non-interfering smell-2; obvious smell, but no disturbing smell of sex gas-3; having an interfering odour-4; has strong interfering smell-5; intolerable odor-6;
TVOC performance: testing was performed according to the PV3341 standard;
Surface tension: injecting particles into 355 x 100 x 3.2mm sample plates through an injection molding machine, adopting different dyne solutions prepared by ethanol and water, dipping a certain dyne solution by using a cotton swab, coating (coating area >3cm 2) on the surface of a flat square plate, if the square plate does not shrink within 2s, and re-testing the dyne solvent with a higher standard value; if shrinkage occurs within 2 seconds and breaks into many small droplets, the number indicated by the last used dyne solvent is the surface tension of the plate.
Surface contact angle: the particles were injection molded into 355 x 100 x 3.2mm plaques by an injection molding machine, 2 μl deionized water was drawn off with a micropipette and added dropwise to the plaques, and the angle was measured after 10 s.
Peel force: injecting particles into 355 x 100 x 3.2mm sample plates through an injection molding machine, then carrying out glue spraying coating treatment, and carrying out test according to GB/T2791-1995;
paint adhesion (cross-hatch): the particles were injection molded into 355 x 100 x 3.2mm templates by an injection molding machine, then spray coated and tested according to GB/T9286-2021
Table 1-4 and comparative examples 1-4 Material formulation tables (wt.%)
Table two performance tables of examples 1 to 4 and comparative examples 1 to 4
1. Compared with the prior art, the invention has the following advantages: flame treatment is avoided, and the odor and the emission are low.
2. The invention selects methacrylic acid long carbon chain ester as a polar additive, can form a strong polar group with chlorinated polypropylene in a system, and increases the polarity of the material; meanwhile, the toughening agent selects thermoplastic polyurethane elastomer, on one hand, the polarity of the system can be increased in cooperation with the polar additive to improve the surface tension so as to enable the surface tension to reach more than 38 mN/m, and the surface contact angle is reduced from 104.9 degrees to 69.7 degrees; meanwhile, the adhesive can form stronger adhesive force with most of bi-component polyurethane adhesives/coatings, the stripping force or adhesive force of the adhesive is effectively improved, and the effect of glue spraying coating/spraying treatment after flame treatment is achieved;
2. according to the invention, the residual organic micromolecules in the polypropylene resin matrix are captured or adsorbed by utilizing the porous structure of the porous graphene so as to meet the requirements of odor promotion and VOC content control, the odor of the material can be promoted to the level of 2.5-3.0, and the TVOC is reduced to below 20 mu gC/g; meanwhile, the adhesive/coating can permeate into the material, so that the interfacial binding force between the material and the coating/adhesive is increased.
Claims (16)
1. A flame-treatment-free low-odor low-emission polypropylene composite material for automotive upholstery is characterized in that: the material comprises the following raw materials in percentage by weight: polypropylene: 20-40%; chlorinated polypropylene: 10-30%; toughening agent: 5-15%; and (3) filling: 15-20%; porous graphene: 5-10%; polar additive: 10-20%; and (3) a compatilizer: 0.5-5%; other auxiliary agents: 0.5-2%; 0.5-1% of color master batch.
2. The flame-retardant low odor low emission polypropylene composite for automotive upholstery according to claim 1, wherein: the polypropylene is one or a mixture of several kinds of copolymerized polypropylene with melt flow rate of 50-100 g/10min under the test condition of 230 ℃ and 2.16 Kg.
3. The flame-retardant low odor low emission polypropylene composite for automotive upholstery according to claim 1, wherein: the chlorinated polypropylene is one or a mixture of more than one of the chlorinated polypropylene with 25-45 percent of chlorine content.
4. The flame-retardant low odor low emission polypropylene composite for automotive upholstery according to claim 1, wherein: the toughening agent is at least one of thermoplastic polyurethane elastomer or ethylene-octene copolymer with the hardness of 20D-45D.
5. The flame-retardant low odor low emission polypropylene composite for automotive upholstery according to claim 1, wherein: the filler is one or a mixture of more of talcum powder, kaolin, calcium carbonate and glass beads.
6. The flame-retardant low odor low emission polypropylene composite for automotive upholstery according to claim 1, wherein: the sheet diameter of the porous graphene is as follows: 0.5-5 mu m, specific surface area: 100-894 m 2/g, pore diameter: the porous structure of the porous material can capture or adsorb residual organic small molecules in the polypropylene resin matrix at 0.01-4.58 nm so as to achieve the requirements of improving smell and controlling VOC content, and simultaneously facilitate the permeation of the coating/adhesive to the surface of the material, thereby increasing the interfacial binding force between the material and the coating/adhesive.
7. The flame-retardant low odor low emission polypropylene composite for automotive upholstery according to claim 1, wherein: the polar additive is methacrylic acid long carbon chain ester, and the chemical formula is as follows:
wherein R: c nH2n+1 n is more than or equal to 8.
8. The flame-retardant low odor low emission polypropylene composite for automotive upholstery according to claim 1, wherein: the compatilizer is maleic anhydride grafted polypropylene, the grafting rate is up to 4.0%, and the melting point is 160-170 ℃.
9. The flame-retardant low odor low emission polypropylene composite for automotive upholstery according to claim 1, wherein: the other auxiliary agent comprises one or a mixture of a plurality of dispersing agents, lubricating agents and antioxidant master batches.
10. The flame-retardant low odor low emission polypropylene composite for automotive upholstery according to claim 9, wherein: the dispersing agent is one of polyethylene wax, stearate and fatty amide with low relative molecular weight, and the relative molecular weight is 1000-10000.
11. The flame-retardant low odor low emission polypropylene composite for automotive upholstery according to claim 9, wherein: the lubricant is one or a mixture of more of zinc stearate, calcium stearate and magnesium stearate.
12. The flame-retardant low odor low emission polypropylene composite for automotive upholstery according to claim 9, wherein: the antioxidant master batch is a compound synergistic antioxidant of a phenolic main antioxidant, a phosphite ester auxiliary antioxidant and epoxy resin, wherein the melting temperature of the main antioxidant DSC is 110-125 ℃, the melting temperature of the auxiliary antioxidant DSC is 180-190 ℃, and the melting temperature of the epoxy resin DSC is 120-160 ℃.
13. The flame-retardant low odor low emission polypropylene composite for automotive upholstery according to claim 1, wherein: the color master batch is an inorganic black master batch.
14. The flame-retardant low odor low emission polypropylene composite material for automotive upholstery according to any one of claims 1 to 13, comprising the steps of:
Step 1: the material is prepared by weighing polypropylene, chlorinated polypropylene, a toughening agent, a filler, porous graphene, a polar additive, a compatilizer, other auxiliary agents and masterbatch according to the weight ratio;
Step 2: placing the polypropylene, the chlorinated polypropylene, the toughening agent, the filler and the porous graphene in the step 1 into a high-speed stirrer, mixing for about 10 minutes at room temperature, and adding the polar additive, the compatilizer, the other auxiliary agents, the color master batch and other components to mix for 20 minutes uniformly;
step 3: the extrusion temperatures in the screws were respectively: 180-200 ℃ in the first area, 200-225 ℃ in the second area, 200-225 ℃ in the third area, 200-215 ℃ in the fourth area, 190-210 ℃ in the fifth area, and the screw rotating speed is 350-400 r/min;
Step 4: after the twin screw is heated to the test temperature, the mixture after the mixing treatment in the step 2 is melted, blended and extruded in a twin screw extruder, then cooled by water, dried and granulated, finally enters a homogenizing and material drying system, the material drying system adopts three-tank dynamic circulation material drying, a cooling tank is added, high-temperature materials are subjected to blowing cooling circulation in an additional bin, so that odor micromolecules are fully volatilized to help odor to be lifted, and a material drying process is carried out for 4 hours at 130 ℃, so that a product is finally obtained.
15. The application of the polypropylene composite material with low odor and low emission based on flame-free treatment in the automotive interior trim parts.
16. The use according to claim 15, characterized in that: the surface tension of the polypropylene composite material reaches more than 38mN/m, the polypropylene composite material can be prevented from being directly coated or sprayed in the flame pretreatment process, and the interface binding force between the polypropylene composite material and the coating/adhesive also reaches the effect of being coated or sprayed after flame treatment; meanwhile, the odor of the material can be improved to the level of 2.5-3.0 of the public, and the TVOC is reduced to below 20 mu gC/g.
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