CN114249946B - Preparation method of ultralow VOC polypropylene-based automobile special material - Google Patents
Preparation method of ultralow VOC polypropylene-based automobile special material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 113
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 92
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 92
- -1 polypropylene Polymers 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 40
- 239000013177 MIL-101 Substances 0.000 claims abstract description 28
- 239000002893 slag Substances 0.000 claims abstract description 26
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920001971 elastomer Polymers 0.000 claims abstract description 14
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- 238000002156 mixing Methods 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
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- 238000000034 method Methods 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
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- 230000003078 antioxidant effect Effects 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 6
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
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- 239000005457 ice water Substances 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 239000004317 sodium nitrate Substances 0.000 claims description 5
- 235000010344 sodium nitrate Nutrition 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 4
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 claims description 4
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 claims description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
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- 239000011259 mixed solution Substances 0.000 claims description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 2
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 claims description 2
- 238000003915 air pollution Methods 0.000 abstract description 8
- 229910002804 graphite Inorganic materials 0.000 abstract description 4
- 239000010439 graphite Substances 0.000 abstract description 4
- 239000012855 volatile organic compound Substances 0.000 description 30
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 18
- 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 description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 description 11
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- 238000001179 sorption measurement Methods 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 9
- 238000011056 performance test Methods 0.000 description 9
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- 239000002910 solid waste Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
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- 239000013178 MIL-101(Cr) Substances 0.000 description 2
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- 239000002440 industrial waste Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010063659 Aversion Diseases 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
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- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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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 discloses a preparation method of an ultralow VOC polypropylene-based automobile special material, relates to the technical field of automobile special material preparation, and mainly solves the problem of an air pollution source of automobile interior trim. The preparation method of the ultralow VOC polypropylene-based automobile special material comprises the following steps: (1) preparing graphite oxide; (2) preparing MIL-101@GO composite material; (3) Based on recycled polypropylene, the MIL-101@GO composite material, superfine slag micropowder, heat stabilizer and elastomer are combined to prepare the polypropylene-based automobile special material. Through the technical scheme, the invention greatly reduces the release amount of VOC from the source, achieves the aim of ultralow VOC release of the special material for the automobile, and provides a good solution for the problem of air pollution of the interior trim of the automobile from the source. Therefore, the invention is very suitable for large-scale popularization and application.
Description
Technical Field
The invention relates to the technical field of preparation of automobile special materials, in particular to a preparation method of an ultralow VOC polypropylene-based automobile special material.
Background
While the field of automobile industry is rapidly developing, energy saving and environmental protection problems are gradually emphasized, and more energy saving and environmental protection materials are used on automobiles. At present, polypropylene is the most widely used material in the automobile special material, and is a general thermoplastic polymer material, which has the advantages of light weight, excellent comprehensive performance, good processing performance, recycling and the like, and is the main stream material for the application of the current automobile special material. In order to realize the recycling and recycling of polypropylene materials, the current automobile industry utilizes a large amount of recycled polypropylene materials to be reused as a polypropylene special material for automobiles, but a large amount of recycled polypropylene also causes some problems:
firstly, the recycled polypropylene has a plurality of small molecules due to different components and sources, and VOC (volatile gas) is easy to release during thermal processing and later product use; secondly, after the recycled polypropylene is subjected to multiple thermal processing, molecular chain segments are destroyed and even locally degraded, and gases such as small molecules are generated, and the low-molecular compounds can cause the polypropylene material to contain a certain amount of VOC to different degrees. Thirdly, in the process of granulating and blending modification of the raw materials, the polypropylene material is degraded to a certain extent when heated and melted and extruded, and low molecular organic matters such as linear alkane and aldehyde ketone compounds are produced as a result of the degradation; and the filler component such as talcum powder contains metal impurities which can catalyze the degradation of the polypropylene material and the heat stabilizer in the modification process to generate volatile matters harmful to human bodies. Fourth, according to the characteristics of the molecular structure of the polypropylene material, a large number of tertiary carbon atoms exist in the molecular chain, and the atoms are subjected to aging degradation to different degrees under the action of light, oxygen and heat to generate short carbon chains, and the carbon chains are oxidized to release volatile substances of aldehyde ketones.
Therefore, the above causes that the amount of volatile organic compounds discharged from the polypropylene material and the recovered polypropylene material increases, and the polypropylene material becomes a source of air pollution in the vehicle, and causes a certain hazard to the driver and the passengers, which is called as a "concealed killer".
As the special material for the automobile, the requirement on the strength of the material is very high, and along with the push-out of the national VOC mandatory standard, the requirement on the VOC and the smell of the polypropylene (PP) material in the field of the environment-friendly material for the automobile is also higher and higher, so that the research of the special composite material for the automobile with low emission becomes one of research hotspots in the automobile interior industry. In recent years, following pollution of automobile exhaust and noise, pollution of Volatile Organic Compounds (VOC) of automobile interiors has received a great deal of attention.
Although there are some institutions in the world to study the air pollution in the automobile, in general, the study on the air pollution in the automobile in countries in the world is not much, and at present, in life, people generally adopt insolation (smell scattering) or materials with adsorptivity (such as activated carbon) to purify the smell in the automobile to a certain extent, but the effect is very little. The british air quality agency recommends strengthening the research on pollution to automobile users, and the Australian environmental sign society chairman Johnson also proposes that reducing the harm of volatile organic compounds to the health of consumers, adopting 21 st century new in-car decoration materials and fuels, must be an environmental factor that the design of automobiles needs priority. Therefore, development of environmentally friendly and healthy automobile special materials has been eager.
In recent years, metal Organic Frameworks (MOFs) are considered to be a novel adsorbent with wide application prospects, and Liu Yang of the university of Huazhong science and technology teaches that a novel composite adsorption material MIL-101 (Cr)/Graphene Oxide (GO) is prepared by a hydrothermal method (Liu Yang et al, journal of chemistry, volume 78, 3 rd, pages 250-255, hereinafter referred to as "document 1"). The graphene oxide surface contains rich carbonyl, carboxyl, hydroxyl, epoxy and other oxygen-containing functional groups, so that coordination points combined with MOFs are provided, adhesion of the MOFs is facilitated, and the composite adsorption material can well improve the reaction rate of the oxygen-containing functional groups on O 2 Is significant for the fields of medical treatment, aerospace, military, chemical industry and the like.
Document 1 does not indicate whether the pollution problem of automobile interior trim can be solved by using the composite adsorption material MIL-101 (Cr)/Graphene Oxide (GO) in the automobile manufacturing field, but based on the description of the performance characteristics of the composite adsorption material in document 1, the application of the composite adsorption material in preparing automobile special materials seems to be a good choice. However, experiments show that the composite adsorption material can not completely realize the aim of ultra-low VOC release when being used for preparing automobile materials, and the automobile special material prepared by the composite adsorption material can only achieve the degree of ' tastiness ', but not stimulation ' or ' tolerance to a certain extent ' at most according to the standard grade of the odor in the automobile, and still can not really meet the requirements of environmental protection and health of the automobile special material.
In summary, it is necessary to design a new process system to realize the preparation of the special automobile material with the characteristic of ultra-low VOC.
Disclosure of Invention
The invention aims to provide an ultralow VOC polypropylene-based automobile special material, which aims to greatly reduce the air pollution source of automobile interior trim from the source.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the ultralow VOC polypropylene-based automobile special material comprises the following steps:
(1) Preparation of MIL-101@GO composite material
Dissolving equimolar chromium nitrate and terephthalic acid in deionized water, adding graphite oxide powder with the initial mass of 5-8 wt% of the raw materials, carrying out ultrasonic treatment for 15-20 min, magnetically stirring for 20-25 min under 313K, adding 0.5-0.8 mL of hydrofluoric acid into a reaction tank, putting the reaction tank into a temperature programming furnace for hydrothermal reaction, and after the reaction is finished, sequentially carrying out DMF washing, ethanol washing and NH on the product 4 F, centrifugally filtering after washing the solution and water, and finally, putting the product into a baking oven for baking for later use;
(2) Uniformly mixing MIL-101@GO composite material, polypropylene reclaimed material, superfine slag micropowder, heat stabilizer and elastomer according to the mass ratio of 3-5% to 50-80% to 10-30% to 0.2-0.5% to 5-15% respectively to obtain a mixture;
(3) And (3) melting and blending the mixture, and extruding and granulating to obtain the polypropylene-based special material for the automobiles.
Further, in the step (1), the process of preparing graphite oxide powder is as follows:
(a) Mixing graphite powder, sodium nitrate, concentrated sulfuric acid and potassium permanganate in an ice water bath reaction system to obtain a viscous solution;
(b) Adding distilled water, keeping the temperature of the mixed solution at 371K, and continuing to react for 15min;
(c) Adding 333K warm water and 100mL of 30wt% hydrogen peroxide, standing the solution until layering, and discarding the supernatant;
(d) Centrifugal washing with deionized water to obtain dark yellow viscous liquid;
(e) Dialyzing with dialysis bag for 7 days, and spray drying to obtain tan graphite oxide powder.
Still further, the step (a) includes the steps of:
(a1) Placing graphite powder and sodium nitrate with equal mass into a reaction container, slowly adding concentrated sulfuric acid under the reaction condition of ice-water bath, stirring for 10-15 min, and uniformly mixing;
(a2) Adding 6 times of potassium permanganate, controlling the temperature to be less than 283K, reacting for 30min, removing the ice bath, and continuously stirring for 48h at room temperature, wherein the reaction system becomes dark brown viscous solution.
Further, in the step (1), the set temperature-raising program of the hydrothermal reaction is: the solution was heated from room temperature to 493K at 5K/min and held for 8 hours, after which the solution was cooled to 308K at a cooling rate of 0.4K/min.
Preferably, in the step (1), the product is put into an oven and dried under 423K.
Preferably, the ultrafine slag powder has a particle diameter of 1.0 to 2.5. Mu.m.
Preferably, in the step (3), the mixture is melt blended and extrusion pelletized using a twin screw extruder.
Specifically, the temperatures of the sections from the feed inlet to the machine head of the double-screw extruder are 160, 180, 210, 220, 200 and 205 ℃ in sequence, the rotating speed of the main machine is 500r/min, the feeding rotating speed is 18r/min, and the vacuum degree is 0.09Mpa.
Preferably, the polypropylene is a copolymer polypropylene or a mixture of polypropylene and homo-polypropylene.
Preferably, the heat stabilizer is any one or more of antioxidant 1010, antioxidant 1076, antioxidant 264, antioxidant CA, antioxidant 164, antioxidant DNP, antioxidant DLTP, antioxidant TNP, antioxidant TPP and antioxidant MB.
Preferably, the elastomer is one or more of ABS, POE, LDPE, LLDPE, propylene-based elastomer and EPDM.
Compared with the prior art, the invention has the following advantages:
(1) According to the invention, raw materials, proportions, technological processes and technological parameters are redesigned, and a novel MIL-101@GO composite material very suitable for VOC adsorption is prepared by combining a strong acid system, and the material can form a special hole structure and has very high porosity. Meanwhile, the superfine slag micropowder is used as the filler of the modified PP, so that on one hand, the mechanical property of the special automobile material can be improved, the environmental pollution caused by solid waste accumulation is reduced, and the recycling of solid waste and industrial waste heat resources is realized; on the other hand, the superfine slag micropowder with the particle size of 1.0-2.5 microns is smaller, has larger specific surface area and smaller curvature, is better in stress dispersion, has better blending effect in an automobile special material preparation system, has physical properties far superior to those of calcium carbonate and talcum powder in a conventional formula system, can realize the replacement of the calcium carbonate and talcum powder, can reduce the environmental pollution caused by the production of the calcium carbonate and the talcum powder, and provides favorable conditions for adsorbing VOC (volatile organic compounds) of the MIL-101@GO composite material by virtue of the design of proportioning adjustment and technological parameters, and fully exerts the adsorption performance of the MIL-101@GO composite material.
Therefore, through the combined action of MIL-101@GO composite material and superfine slag micropowder in the system, the invention well realizes the improvement of the comprehensive performance of the polypropylene-based automobile special material and the ultralow VOC release, not only provides an environment-friendly and healthy automobile special material, but also protects the environment from the source, realizes the reutilization of solid waste and industrial waste heat resources, improves the recycling rate of resources, reduces the energy consumption and solid waste accumulation, and realizes the purposes of improving the product performance and reducing the production cost.
(2) In the process of granulating and blending modification of raw materials, talcum powder is not adopted, but superfine slag micropowder is adopted for substitution, so that volatile matters are well avoided, and the thermal stability of the PP material is enhanced and the release of VOC in the preparation process is reduced because the degradation of the heat stabilizer is well controlled.
(3) According to the heat treatment process for the recycled PP material, when the heat treatment temperature is increased, the heat circulation air can smoothly bring the organic micromolecular volatile matters on the surfaces of the waste PP particles out of the oven when exchanging with the outside air, so that VOC in the raw materials is further reduced, and therefore, the heat treatment process is more suitable for recycling the waste PP material, really realizes recycling and high-efficiency utilization of the waste polypropylene material, and greatly reduces the production cost.
(4) The preparation process of the invention reduces the release amount of VOC from multiple dimensions (raw materials, system proportion and preparation process), further effectively controls the release of VOC from the source, realizes the aim of ultralow VOC release of the special material for automobiles, and provides a good solution for the air pollution problem of automobile interiors from the source.
Detailed Description
The invention provides a preparation method of a polypropylene-based automobile special material, and the obtained polypropylene-based automobile special material has the characteristics of good overall performance and ultralow VOC release, and can well avoid the problem of air pollution of automobile interiors when being applied to the automobile interiors, thereby realizing the purposes of environmental protection and health in the automobile.
The invention is further illustrated below with reference to examples, examples of which are included in the practice of the invention but are not limited thereto.
Example 1
The preparation process of the ultralow VOC polypropylene-based automobile special material provided by the embodiment comprises the following steps:
preparation of graphite oxide:
firstly, 4g of graphite powder and 4g of sodium nitrate are weighed into a dry 1000mL three-necked flask, 220mL of 98wt% concentrated sulfuric acid is slowly added under the conditions of ice-water bath and stirring, and the mixture is stirred for 15min and uniformly mixed. Then, 24g of potassium permanganate was added, the temperature was controlled to be not more than 283K, and after 30 minutes of reaction, the ice bath was removed and stirring was continued at room temperature for 48 hours, at which time the reaction mass in the flask became a dark brown viscous solution. Then 368mL of distilled water is added, the temperature of the mixed solution is kept not to exceed 371K, the reaction is continued for 15min, and 1120mL of warm water (333K) and 100mL of 30wt% hydrogen peroxide are added. And finally, standing the solution overnight, discarding the supernatant, and centrifugally washing the supernatant with deionized water to obtain dark yellow viscous liquid. And dialyzing for about one week by using a dialysis bag, and finally performing spray drying to obtain a tan Graphite Oxide (GO) powder sample.
Preparation of MIL-101@GO composite material:
4g of chromium nitrate and 1.64g of terephthalic acid are dissolved in 48mL of deionized water, graphite oxide accounting for 5wt% of the initial mass of the raw material is added, after ultrasonic treatment is carried out for 15min, magnetic stirring is carried out for 20min at 313K, and 0.5mLHF is added into a reaction tank. Then placing the mixture into a temperature programming furnace for hydrothermal reaction, and setting a temperature programming program as follows: the solution was heated from room temperature to 493K at 5K/min and held for 8 hours, after which the solution was cooled to 308K at a cooling rate of 0.4K/min. After the reaction is finished, the product is sequentially washed by Dimethylformamide (DMF), ethanol and NH 4 And F, centrifugally filtering after washing the solution and water, and finally putting the product into an oven and drying the product under the condition of 423K for standby.
Preparation of ultra-low VOC polypropylene-based automobile special material:
mixing MIL-101@GO composite material, PP, superfine slag micropowder (average particle size 1 mu m), heat stabilizer and elastomer according to the mass ratio of 3 to 63.7 to 18 to 0.3 to 15 respectively by a high-speed stirrer, and then carrying out melt blending and extrusion granulation in a double-screw extruder to obtain the polypropylene-based automobile special material. In the present embodiment of the present invention, the temperature of each section of the double-screw extruder from the feed inlet to the machine head is 160 percent 180, 210, 200 c, the rotation speed of the main machine is 500r/min, the feeding rotation speed is 18r/min, and the vacuum degree is 0.09MPa. The heat stabilizer adopts antioxidant 1010, and the elastomer is used for enhancing the toughness of the polypropylene matrix.
Preparation of an automotive interior part: and (3) drying the obtained granules in a blast drying oven for 4 hours at 90 ℃, and then performing injection molding to obtain a standard sample, wherein the injection molding melting temperature is 220 ℃, the injection molding pressure is 60MPa, and the molding period is 40s.
Table 1 shows the results of various performance tests of the polypropylene-based automobile special material prepared in this example.
TABLE 1
Example 2
The heat stabilization was carried out using antioxidant 1010 and antioxidant 1076, and the other raw materials were the same as in example 1. Mixing MIL-101@GO composite material, PP, superfine slag micropowder (average particle diameter of 1.4 mu m), heat stabilizer and elastomer according to the mass ratio of 3 to 63.7 to 20 to 0.3 to 13 percent by a high-speed stirrer uniformly, and then carrying out melt blending and extrusion granulation in a double-screw extruder to obtain the polypropylene-based automobile special material.
Table 2 shows the results of various performance tests of the polypropylene-based automobile special material prepared in this example.
TABLE 2
Example 3
The heat stabilizer was antioxidant 264 and antioxidant CA, and the rest of the raw materials were the same as in example 1. Mixing MIL-101@GO composite material, PP, superfine slag micropowder (average particle diameter of 2.3 mu m), heat stabilizer and elastomer according to the mass ratio of 3 to 65.7 to 23 to 0.3 to 8 respectively, uniformly stirring by a high-speed stirrer, and then carrying out melt blending and extrusion granulation in a double-screw extruder to obtain the polypropylene-based automobile special material.
Table 3 shows the results of various performance tests of the polypropylene-based automobile special material prepared in this example.
TABLE 3 Table 3
Example 4
The heat stabilizer was antioxidant 264 and antioxidant CA, and the rest of the raw materials were the same as in example 1. Mixing MIL-101@GO composite material, PP, superfine slag micropowder (average particle diameter of 2.3 mu m), heat stabilizer and elastomer according to the mass ratio of 3 to 64.7 to 20 to 0.3 to 12 percent respectively, uniformly stirring by a high-speed stirrer, and then carrying out melt blending and extrusion granulation in a double-screw extruder to obtain the polypropylene-based automobile special material.
Table 4 shows the results of various performance tests of the polypropylene-based automobile special material prepared in this example.
TABLE 4 Table 4
Comparative example 1
The difference from examples 1 to 4 is that MIL-101@GO composite material is not added into the formula system of comparative example 1, and specifically: uniformly mixing PP, superfine slag micropowder (average grain diameter 2.3 mu m), heat stabilizer (antioxidant DNP and antioxidant MB) and elastomer according to the mass ratio of 67.7 to 20 to 0.3 to 12 percent by a high-speed stirrer, and then carrying out melt blending and extrusion granulation in a double-screw extruder to obtain the polypropylene-based automobile special material without MIL-101@GO composite material.
Table 5 shows the results of various performance tests of the polypropylene-based automobile materials prepared in comparative example 1.
TABLE 5
Comparative example 2
The difference from examples 1 to 4 is that no ultrafine slag micropowder is added to the formulation system of comparative example 2, specifically: mixing MIL-101@GO composite material, PP, heat stabilizer (antioxidant DNP and antioxidant MB) and elastomer in the mass ratio of 3 to 84.7 to 0.3 to 12 respectively by a high-speed stirrer uniformly, and then carrying out melt blending and extrusion granulation in a double-screw extruder to obtain the polypropylene-based automobile special material without superfine slag micropowder.
Table 6 shows the results of various performance tests of the polypropylene-based automobile materials prepared in comparative example 2.
TABLE 6
Comparative example 3
Uniformly mixing PP, calcium carbonate, a heat stabilizer (antioxidant 1010) and an elastomer according to the mass ratio of 66.7 to 18 to 0.3 to 15 respectively by a high-speed mixer, and then carrying out melt blending and extrusion granulation in a double-screw extruder to obtain the automobile material.
Table 7 shows the results of various performance tests of the automobile materials prepared in comparative example 3.
TABLE 7
Comparative example 4
The PP, the talcum powder, the heat stabilizer (antioxidant 1010) and the elastomer are uniformly mixed by a high-speed mixer according to the mass ratio of 66.7 percent to 18 percent to 0.3 percent to 15 percent respectively, and then are subjected to melt blending and extrusion granulation in a double-screw extruder to obtain the automobile material.
Table 8 shows the results of various performance tests of the automobile materials prepared in comparative example 4.
TABLE 8
Comparative example 5
100% PP is utilized to prepare the special material for the automobile. Table 9 shows the results of various performance tests of the automobile materials prepared in comparative example 5.
TABLE 9
VOC test conditions:
weighing 50g of prepared materials, placing the materials into a glass container, sealing a bottle mouth, placing the glass container into an oven, baking the glass container for 24 hours at 70+/-2 ℃, taking out the glass container, slightly removing a seal (or a cover) after the glass container is cooled to 65+/-5 ℃, and evaluating the glass container according to the following standard by a plurality of testers at a position 2-3 cm away from the bottle mouth:
standard 1: smell detection- -VW50180 (popular Standard)
Test standard: VW50180;
evaluation grade: stage 6;
evaluation criteria: 1 = no off-flavor; 2 = slightly odorous; 3 = tasty, but not irritating; 4 = having a pungent odor; 5 = strong pungent odor; 6 = intolerable taste.
Standard 2: odor detection- -Q/JLY J7110538A-2012 (Jili Standard)
Evaluation grade: totally divided into 10 grades;
evaluation criteria: 10 =odorless; 9 = a little noticeable odor; 8 = noticeable odor; 7 = slightly tolerated; 6 = tolerable; 5 = somewhat intolerable; 4 = dislike; 3 = aversion; 2 = very aversive; 1 = intolerable.
The test results were averaged as shown in table 10:
table 10
| Test product | Public standard | Jili standard |
| Example 1 | 1.2 | 9.9 |
| Example 2 | 1.1 | 9.8 |
| Example 3 | 1.0 | 10.0 |
| Example 4 | 1.1 | 10 |
| Comparative example 1 | 3.0 | 8.8 |
| Comparative example 2 | 2.2 | 9.2 |
| Comparative example 3 | 4.3 | 5.7 |
| Comparative example 4 | 4.2 | 5.9 |
| Comparative example 5 | 5.3 | 4.5 |
Conclusion:
1. as can be seen from comparison of tables 7 and 8 with Table 9, after the talcum powder or the calcium carbonate is added for filling, the shrinkage rate of the material is reduced from 1.2% to 1.13-1.15%, while comparison of tables 1-4 shows that after the talcum powder or the calcium carbonate is replaced by superfine slag micropowder and MIL-101@GO composite material is added, the shrinkage rate of the material can be further reduced to below 1.1%, which indicates that compared with the talcum powder or the calcium carbonate, the filling effect of the PP material can be improved by adopting the superfine slag micropowder and MIL-101@GO composite material, and the density and the melt flow rate are basically kept unchanged.
2. As can be seen from the comparison of tables 1 to 4 and tables 7 to 9, the tensile yield strength of the composite material is reduced no matter talcum powder, calcium carbonate or superfine slag micropowder+MIL-101@GO composite material is added, but the composite material is filled with superfine slag micropowder+MIL-101@GO composite material, the tensile yield strength of the composite material can still be maintained above 20MPa compared with talcum powder or calcium carbonate, and the composite material is neither too brittle nor too soft, and has moderate characteristics.
3. As can be seen from the comparison of tables 1-4 and tables 7-9, the filling with the superfine slag micropowder + MIL-101@GO composite material has the advantages of greater improvement in bending yield strength, bending elastic modulus, pendulum impact strength and load deflection temperature, better flame retardance and capability of being reduced from 23mm/min to 11mm/min compared with talcum powder or calcium carbonate.
4. As can be seen from the comparison of tables 1 to 6 and 9, the PP material is filled with ultrafine slag powder or MIL-101@GO composite material alone, which has different effects on the properties in the tables, some properties are improved, and some properties are reduced; and the PP material is filled with superfine slag micropowder and MIL-101@GO composite material, so that all properties are improved well, and the comprehensive properties of the material are improved effectively.
5. As can be seen from table 10, the automobile materials made of pure PP materials have strong pungent odor and are intolerable; after the PP material is filled with talcum powder or calcium carbonate, the prepared polypropylene-based automobile material still has pungent smell and is slightly intolerable; after the PP material is filled with superfine slag micropowder, the prepared polypropylene-based automobile material has smell which is obviously reduced compared with comparative examples 3 and 4; after the PP material is filled with the MIL-101@GO composite material, the prepared polypropylene-based automobile material has slight odor, which shows that the adsorption of VOC achieves a better effect; and after the PP material is filled with the superfine slag micropowder and MIL-101@GO composite material, the prepared polypropylene-based automobile material basically reaches the degree of no peculiar smell (examples 1-4), which shows that the ultra-low VOC release of the polypropylene-based automobile special material is realized by filling the PP material with the superfine slag micropowder and MIL-101@GO composite material.
In conclusion, through the design of raw materials, formula proportion, process parameters and process flow, all links are mutually buckled and complemented, the comprehensive performance of the polypropylene-based automobile material is well improved, the ultralow VOC release of the automobile material is realized from the source, the automobile material is more suitable for being applied to the manufacture of automobile interior trim parts, and the requirements of health and environmental protection in an automobile are met.
Therefore, compared with the prior art, the invention has obvious technical progress and outstanding substantive characteristics and obvious progress.
The above embodiment is only one of the preferred embodiments of the present invention, and should not be used to limit the scope of the present invention, and all the modifications or color changes that are not significant in the spirit and scope of the main body design of the present invention are still consistent with the present invention.
Claims (9)
1. The preparation method of the ultralow VOC polypropylene-based automobile special material is characterized by comprising the following steps:
(1) Preparation of MIL-101@GO composite material
Dissolving equimolar chromium nitrate and terephthalic acid in deionized water, adding graphite oxide powder with the initial mass of 5-8 wt% of the raw materials, carrying out ultrasonic treatment for 15-20 min, magnetically stirring for 20-25 min under 313K, adding 0.5-0.8 mL of hydrofluoric acid into a reaction tank, putting the reaction tank into a temperature programming furnace for hydrothermal reaction, and after the reaction is finished, sequentially carrying out DMF washing, ethanol washing and NH on the product 4 F, centrifugally filtering after washing the solution and water, and finally, putting the product into a baking oven for baking for later use;
(2) Uniformly mixing MIL-101@GO composite material, polypropylene reclaimed material, superfine slag micropowder, heat stabilizer and elastomer according to the mass ratio of 3-5% to 50-80% to 10-30% to 0.2-0.5% to 5-15% respectively to obtain a mixture; the grain diameter of the superfine slag micropowder is 1.0-2.3 um;
(3) And (3) melting and blending the mixture, and extruding and granulating to obtain the polypropylene-based special material for the automobiles.
2. The method for preparing the ultra-low VOC polypropylene-based automotive special material according to claim 1, wherein in the step (1), the process for preparing the graphite oxide powder is as follows:
(a) Mixing graphite powder, sodium nitrate, concentrated sulfuric acid and potassium permanganate in an ice water bath reaction system to obtain a viscous solution;
(b) Adding distilled water, keeping the temperature of the mixed solution at 371K, and continuing to react for 15min;
(c) Adding 333K warm water and 100mL of 30wt% hydrogen peroxide, standing the solution until layering, and discarding the supernatant;
(d) Centrifugal washing with deionized water to obtain dark yellow viscous liquid;
(e) Dialyzing with dialysis bag for 7 days, and spray drying to obtain tan graphite oxide powder.
3. The method for preparing the ultra-low VOC polypropylene-based automotive vehicle material according to claim 2, wherein the step (a) comprises the steps of:
(a1) Placing graphite powder and sodium nitrate with equal mass into a reaction container, slowly adding concentrated sulfuric acid under the reaction condition of ice-water bath, stirring for 10-15 min, and uniformly mixing;
(a2) Adding 6 times of potassium permanganate, controlling the temperature to be less than 283K, reacting for 30min, removing the ice bath, and continuously stirring for 48h at room temperature, wherein the reaction system becomes dark brown viscous solution.
4. The method for preparing an ultralow VOC polypropylene-based automotive material according to any one of claims 1 to 3, wherein in the step (1), the set temperature-raising program of the hydrothermal reaction is: the solution was heated from room temperature to 493K at 5K/min and held for 8 hours, after which the solution was cooled to 308K at a cooling rate of 0.4K/min.
5. The method for preparing the ultra-low VOC polypropylene-based automotive special material according to claim 4, wherein in the step (1), the product is put into an oven and dried under 423K.
6. The method for preparing the ultra-low VOC polypropylene-based automobile special material according to claim 1, 2, 3 or 5, wherein in the step (3), the mixture is melted, blended and extruded to be granulated by a twin-screw extruder.
7. The method for preparing the ultra-low VOC polypropylene-based automobile special material according to claim 6, wherein the temperatures of the sections from the feed inlet to the machine head of the double-screw extruder are 160, 180, 210, 220, 200, 205 ℃ in sequence, the rotating speed of the main engine is 500r/min, the feeding rotating speed is 18r/min, and the vacuum degree is 0.09Mpa.
8. The method for preparing the ultra-low VOC polypropylene-based automotive special material according to claim 7, wherein the polypropylene is a copolymer polypropylene or a mixture of copolymer polypropylene and homo-polypropylene.
9. The preparation method of the ultralow VOC polypropylene-based automobile special material according to claim 8, wherein the heat stabilizer is any one or more of antioxidant 1010, antioxidant 1076, antioxidant 264, antioxidant CA, antioxidant 164, antioxidant DNP, antioxidant DLTP, antioxidant TNP, antioxidant TPP and antioxidant MB.
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| CN103432997A (en) * | 2013-08-30 | 2013-12-11 | 华南理工大学 | Cu-based organic skeleton-graphene oxide composite porous material and preparation method thereof |
| CN109749247A (en) * | 2017-11-01 | 2019-05-14 | 现代自动车株式会社 | Polypropylene composite materials resin combination with fibrous texture |
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