CN114249946A - Preparation method of ultra-low VOC polypropylene-based automobile special material - Google Patents
Preparation method of ultra-low VOC polypropylene-based automobile special material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 120
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 99
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 99
- -1 polypropylene Polymers 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 42
- 239000002893 slag Substances 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
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- 229920001971 elastomer Polymers 0.000 claims abstract description 14
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- 238000000034 method Methods 0.000 claims description 21
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- 239000000047 product Substances 0.000 claims description 12
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- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 10
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 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
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- 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
- 238000001816 cooling Methods 0.000 claims description 4
- 238000000502 dialysis Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 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
- 239000006228 supernatant Substances 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
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000001914 filtration Methods 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
- 229920005629 polypropylene homopolymer Polymers 0.000 claims 1
- 238000003915 air pollution Methods 0.000 abstract description 7
- 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 35
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 24
- 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 14
- 229910000019 calcium carbonate Inorganic materials 0.000 description 12
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- 230000036541 health Effects 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
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- 239000000126 substance Substances 0.000 description 4
- 239000013178 MIL-101(Cr) Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
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- 150000003384 small molecules Chemical class 0.000 description 2
- 206010063659 Aversion Diseases 0.000 description 1
- 229920002943 EPDM rubber Polymers 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
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- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 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
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- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 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
Abstract
The invention discloses a preparation method of an ultra-low VOC polypropylene-based automobile special material, relates to the technical field of automobile special material preparation, and mainly solves the problem of an automobile interior air pollution source. The preparation method of the ultra-low VOC polypropylene-based automobile special material comprises the following steps: (1) preparing graphite oxide; (2) preparing an MIL-101@ GO composite material; (3) the polypropylene-based automobile special material is prepared by combining an MIL-101@ GO composite material, superfine slag micro powder, a heat stabilizer and an elastomer on the basis of recycled polypropylene. Through the technical scheme, the release amount of VOC is greatly reduced from the source, the aim of ultralow VOC release of the special material for the automobile is fulfilled, and a good solution is fundamentally provided for the air pollution problem of the automobile interior trim. 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 automobile industry field is rapidly developed, the problems of energy conservation and environmental protection are gradually emphasized by people, and more energy-saving and environment-friendly materials are used on automobiles. At present, polypropylene is the most widely used material in the special automobile material, and as a general thermoplastic polymer material, the polypropylene has the advantages of light weight, excellent comprehensive performance, good processing performance, recyclability and the like, and is the mainstream material applied to the current special automobile material. In order to realize the recycling and high-efficiency utilization of polypropylene materials, the automobile industry currently utilizes a large amount of recycled polypropylene materials to be reused as special polypropylene automobile materials, but the large amount of recycled polypropylene also causes some problems:
firstly, the recycled polypropylene has a lot of small molecules due to different components and sources, and VOC (volatile organic compounds) is easily released during thermal processing and later product use; secondly, after the recycled polypropylene is subjected to multiple thermal processing, molecular chain segments are damaged or partially degraded to generate gases such as small molecules, and the low molecular compounds can cause the polypropylene material to contain a certain amount of VOC to different degrees. Thirdly, during the granulation and blending modification processes of the raw materials, the polypropylene material is degraded to a certain degree when being heated, melted and extruded, and low molecular organic matters such as straight-chain alkanes and aldehyde ketone compounds are generated as a result of the degradation; the added filler component such as talcum powder contains metal impurities which can catalyze the degradation of the polypropylene material and the heat stabilizer to generate volatile substances harmful to human bodies in the modification process. Fourthly, according to the characteristics of the molecular structure of the polypropylene material, a large number of tertiary carbon atoms exist in a molecular chain, the atoms can be aged and degraded to different degrees under the action of light, oxygen and heat to generate short carbon chains, and the carbon chains can release volatile substances such as aldehydes and ketones after being oxidized.
Therefore, the emission amount of volatile organic compounds from the polypropylene material and the recycled polypropylene material is increased due to the above-mentioned reasons, and the polypropylene material becomes an air pollution source in the vehicle, and causes a certain harm to the driver and the passenger, and is called as "invisible killer".
As a special material for automobiles, the requirement on the strength of the material is high, and with the promotion of the mandatory national VOC standard, the requirement on the VOC and the odor of a polypropylene (PP) material in the field of automobile environment-friendly materials is higher and higher, so that the research on the low-emission composite material special for automobiles becomes one of the research hotspots in the automobile interior decoration industry. In recent years, following automobile exhaust and noise pollution, automobile interior Volatile Organic Compound (VOC) pollution has received much attention.
Although there are some researches on air pollution in automobiles by some organizations in the world, the researches on the pollution in the automobiles are not carried out in many countries in the world in general, and people generally use insolation (smell scattering) or adsorptive materials (such as activated carbon) to purify the smell in the automobiles to a certain extent in daily life, but the method has little effect. The british air quality council proposed to enhance the research on the pollution suffered by automobile users, and Johnson, a chairman of the australian environmental mark association, proposed to reduce the harm of volatile organic compounds to the health of consumers, and adopted new interior trim materials and fuels of 21 st century, must be an environmental factor which needs to be given priority to automobile design. Therefore, the development of environment-friendly and healthy automobile special materials is urgent.
In recent years, Metal Organic Frameworks (MOFs) are considered to be a novel adsorbent with wide application prospects, and professor Liuyang of the university of science and technology in Huazhong prepares a novel composite adsorbing material MIL-101 (Cr)/Graphene Oxide (GO) by using a hydrothermal method (Liuyang et al, journal of chemistry, No. 78, No. 3, No. 250 and No. 255 in 2020, hereinafter referred to as "document 1"). The surface of the graphene oxide contains rich carbonyl, carboxyl and hydroxylOxygen-containing functional groups such as radical, epoxy group and the like provide coordination sites combined with MOFs, and are favorable for the adhesion of the MOFs, so that the composite adsorption material can well improve the O-resistance2The adsorption capacity of the adsorbent is significant for the fields of medical treatment, aerospace, military, chemical industry and the like.
The document 1 does not indicate whether the composite adsorbing material MIL-101 (Cr)/Graphene Oxide (GO) can solve the pollution problem of the automotive interior when being used in the field of automobile manufacturing, and based on the introduction of the document 1 to the performance characteristics of the composite adsorbing material, the composite adsorbing material is seemingly a good choice for preparing the special material for the automobile. However, tests show that the composite adsorption material cannot completely achieve the aim of ultralow VOC (volatile organic compound) release when being used for preparing automobile materials, and the special automobile material prepared from the composite adsorption material can only achieve the degree of 'having taste but not stimulating' or 'being tolerable to a certain extent' at most according to the standard grade of the smell in the automobile, and still cannot really meet the requirements of environmental protection and health of the special automobile material.
In conclusion, it is necessary to design a new process system to realize the preparation of the automobile special material with ultra-low VOC characteristic.
Disclosure of Invention
The invention aims to provide an ultra-low VOC polypropylene-based automobile special material, which is expected to greatly reduce the air pollution source of automobile interior decoration from the source.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the ultra-low VOC polypropylene-based automobile special material comprises the following steps:
(1) preparation of MIL-101@ GO composite
Dissolving equal moles of chromium nitrate and terephthalic acid in deionized water, adding graphite oxide powder with the initial mass of 5-8 wt% of the raw materials, performing ultrasonic treatment for 15-20 min, performing magnetic stirring for 20-25 min under 313K, adding 0.5-0.8 mL of hydrofluoric acid into a reaction tank, placing the reaction tank into a temperature programming furnace for hydrothermal reaction, and after the reaction is finished, sequentially performing DMF (dimethyl formamide) washing, ethanol washing and NH (NH) washing on the product4Washing the solution F with water, and centrifugingFiltering, and finally putting the product into an oven for drying for later use;
(2) uniformly mixing 3-5% of MIL-101@ GO composite material, 50-80% of polypropylene reclaimed material, 10-30% of superfine slag micropowder, 0.2-0.5% of heat stabilizer and 5-15% of elastomer according to mass ratio to obtain a mixture;
(3) and melting and blending the mixture, and then extruding and granulating to obtain the polypropylene-based automobile special material.
Further, in the step (1), the process for preparing the graphite oxide powder comprises:
(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 mixture not more than 371K, and continuing to react for 15 min;
(c) adding 333K warm water and 100mL of 30 wt% hydrogen peroxide, standing the solution until layering, and removing the supernatant;
(d) centrifugally washing with deionized water to obtain dark yellow viscous liquid;
(e) dialyzing with dialysis bag for 7 days, and spray drying to obtain brown graphite oxide powder.
Still further, the step (a) includes the steps of:
(a1) placing equal-mass graphite powder and sodium nitrate 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 potassium permanganate with the mass 6 times that of the graphite powder, controlling the temperature not to exceed 283K, after reacting for 30min, removing the ice bath, and continuing stirring at room temperature for 48h, wherein the reaction system is changed into a dark brown viscous solution.
Further, in the step (1), the set temperature-raising procedure of the hydrothermal reaction is: the solution was heated from room temperature to 493K at 5K/min for 8h, after which the solution was cooled down to 308K at a cooling rate of 0.4K/min.
Preferably, in the step (1), the product is placed in an oven and dried under 423K.
Preferably, the particle size of the superfine slag micro powder is 1.0-2.5 μm.
Preferably, in the step (3), a twin-screw extruder is used for melt blending and extrusion granulation of the mixture.
Specifically, the temperature of each section of the double-screw extruder from a feed inlet to a machine head is 160, 180, 210, 220, 200 and 205 ℃ in sequence, the rotating speed of a main machine is 500r/min, the feeding rotating speed is 18r/min, and the vacuum degree is 0.09 Mpa.
Preferably, the polypropylene is a copolymer polypropylene or a mixture of polypropylene and homopolymer polypropylene.
Preferably, the heat stabilizer is 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 any one or more of ABS, POE, LDPE, LLDPE, propenyl elastomer and EPDM.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the raw materials, the proportion, the process flow and the process parameters are redesigned, a strong acid system is combined, the novel MIL-101@ GO composite material very suitable for VOC adsorption is prepared, the material can form a special hole structure and has high porosity, and compared with an MIL-101 (Cr)/Graphene Oxide (GO) composite adsorption material in document 1, the MIL-101@ GO composite material prepared by the method remarkably improves the adsorption capacity for VOC and is more suitable for automobile materials. Meanwhile, the superfine slag powder is used as the filler of the modified PP, and the superfine slag powder is utilized, so that on one hand, the mechanical property of the special material for the automobile 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 powder used in the invention has the particle size of 1.0-2.5 microns, the smaller the particle size, the larger the specific surface area and the smaller curvature, the better the dispersion to stress, and the better the blending effect in a preparation system of a special material for an automobile, the superfine slag powder is used for a modified PP material, the physical properties of the superfine slag powder are far superior to those of calcium carbonate and talcum powder in a conventional formula system, the substitution of the calcium carbonate and the talcum powder can be realized, the environmental pollution caused by the production of the calcium carbonate and the talcum powder can be reduced, favorable conditions are provided for adsorbing VOC by an MIL-101@ GO composite material through the matching adjustment and the design of process parameters, and the adsorption performance of the MIL-101@ GO composite material is fully exerted.
Thus, by the combined action of the MIL-101@ GO composite material and the superfine slag micro powder in the system, the invention well realizes the improvement of the comprehensive performance and the ultralow VOC release of the polypropylene-based automobile special material, 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 cyclic utilization rate of the 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 the raw materials, the invention does not adopt talcum powder, but adopts superfine slag micro powder for replacement, thereby well avoiding the generation of volatile substances, and because the degradation of the heat stabilizer is well controlled, the heat stability of the PP material is enhanced, and the release of VOC in the preparation process is reduced.
(3) According to the heat treatment process for recycling the PP material, when the heat treatment temperature is increased, the heat circulating air can smoothly take organic micromolecule volatile matters on the surfaces of the waste PP particles out of the drying oven when exchanging with the outside air, so that VOC in the raw materials is further reduced, therefore, the heat treatment process is more suitable for recycling the waste PP material, the recycling and high-efficiency utilization of the waste polypropylene material are really realized, and the production cost is greatly reduced.
(4) The preparation process 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 automobile special materials, and provides a good solution for the problem of air pollution of automobile interiors from the source.
Detailed Description
The invention provides a preparation method of a polypropylene-based automobile special material, the obtained polypropylene-based automobile special material has the characteristics of good overall performance and ultralow VOC (volatile organic compound) release, and when the polypropylene-based automobile special material is applied to automobile interiors, the problem of air pollution of the automobile interiors can be well avoided, and the purposes of environmental protection and health in automobiles are realized.
The present invention is further illustrated by the following examples, which include, but are not limited to, the following examples.
Example 1
The preparation process of the ultra-low VOC polypropylene-based automobile special material provided by the embodiment comprises the following steps:
preparing graphite oxide:
first, 4g of graphite powder and 4g of sodium nitrate are weighed into a dry 1000mL three-neck flask, 220mL of 98 wt% 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 not to exceed 283K, and after 30min of reaction, the ice bath was removed and stirring was continued at room temperature for 48h, at which time the contents of the flask became a dark brown viscous solution. Then 368mL of distilled water is added, the temperature of the mixed solution is kept to be not more than 371K, the reaction is continued for 15min, and 1120mL of warm water (333K) and 100mL of 30 wt% hydrogen peroxide are added. And finally, standing the solution overnight, removing a supernatant, and centrifugally washing the obtained dark yellow viscous liquid by using deionized water. 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:
dissolving 4g of chromium nitrate and 1.64g of terephthalic acid in 48mL of deionized water, adding graphite oxide with the initial mass of 5 wt% of the raw material, performing ultrasonic treatment for 15min, performing magnetic stirring at 313K for 20min, and adding 0.5mLHF into a reaction tank. Then putting the mixture into a temperature programming furnace for hydrothermal reaction, wherein the temperature programming is as follows: the solution was heated from room temperature to 493K at 5K/min for 8h, after which the solution was cooled down to 308K at a cooling rate of 0.4K/min. After the reaction is finishedSequentially washing the product with Dimethylformamide (DMF), ethanol and NH4And washing the solution F with water, centrifuging and filtering, and finally putting the product into an oven and drying the product under the condition of 423K for later use.
The preparation method of the ultra-low VOC polypropylene-based automobile special material comprises the following steps:
the MIL-101@ GO composite material, PP, superfine slag micro powder (with the average particle size of 1 mu m), a heat stabilizer and an elastomer are uniformly mixed by a high-speed mixer according to the mass ratio of 3 to 63.7 to 18 to 0.3 to 15, and then the mixture is melted, blended and extruded in a double-screw extruder for granulation, so that the polypropylene-based automobile special material is obtained. In the embodiment, the temperature of each section of the double-screw extruder from the feed inlet to the head is 160, 180, 210 and 200 ℃ in sequence, the rotating speed of the main machine is 500r/min, the feeding rotating speed is 18r/min, and the vacuum degree is 0.09 MPa. The heat stabilizer adopts an antioxidant 1010, and the elastomer is used for enhancing the toughness of the polypropylene matrix.
Preparing the automotive interior: and (3) drying the obtained material particles for 4h at 90 ℃ in a forced air drying oven, and then performing injection molding to obtain a standard sample piece, wherein the injection molding melting temperature is 220 ℃, the injection molding pressure is 60MPa, and the molding period is 40 s.
Table 1 shows the performance test results of the polypropylene-based automotive dedicated material prepared in this example.
TABLE 1
Example 2
The thermal stabilization was performed using antioxidant 1010 and antioxidant 1076, and the remaining raw materials were the same as in example 1. The MIL-101@ GO composite material, PP, superfine slag micro powder (with the average particle size of 1.4 mu m), a heat stabilizer and an elastomer are uniformly mixed by a high-speed mixer according to the mass ratio of 3 to 63.7 to 20 to 0.3 to 13, and then the mixture is melted, blended and extruded in a double-screw extruder for granulation, so that the polypropylene-based automobile special material is obtained.
Table 2 shows the performance test results of the polypropylene-based automotive dedicated material prepared in this example.
TABLE 2
Example 3
The heat stabilizer used was antioxidant 264 and antioxidant CA, and the remaining raw materials were the same as in example 1. The MIL-101@ GO composite material, PP, superfine slag micro powder (with the average particle size of 2.3 mu m), a heat stabilizer and an elastomer are uniformly mixed by a high-speed mixer according to the mass ratio of 3 percent to 65.7 percent to 23 percent to 0.3 percent to 8 percent, and then the mixture is melted, blended and extruded in a double-screw extruder for granulation, so that the polypropylene-based automobile special material is obtained.
Table 3 shows the results of various property tests of the polypropylene-based automobile special-purpose material prepared in this example.
TABLE 3
Example 4
The heat stabilizer used was antioxidant 264 and antioxidant CA, and the remaining raw materials were the same as in example 1. The MIL-101@ GO composite material, PP, superfine slag micro powder (with the average particle size of 2.3 mu m), a heat stabilizer and an elastomer are uniformly mixed by a high-speed mixer according to the mass ratio of 3 percent to 64.7 percent to 20 percent to 0.3 percent to 12 percent, and then the mixture is melted, blended and extruded in a double-screw extruder for granulation, so that the polypropylene-based automobile special material is obtained.
Table 4 shows the performance test results of the polypropylene-based automotive dedicated material prepared in this example.
TABLE 4
Comparative example 1
The difference from the examples 1-4 is that the formula system of the comparative example 1 is not added with the MIL-101@ GO composite material, and specifically comprises the following steps: PP, superfine slag powder (with the average particle size of 2.3 microns), a heat stabilizer (antioxidant DNP and antioxidant MB) and an elastomer are uniformly mixed by a high-speed mixer according to the mass ratio of 67.7 to 20 to 0.3 to 12, and then the mixture is melted, blended and extruded in a double-screw extruder for granulation to obtain the polypropylene-based automobile special material without the MIL-101@ GO composite material.
Table 5 shows the results of various performance tests on the polypropylene-based automobile material prepared in comparative example 1.
TABLE 5
Comparative example 2
The difference from the examples 1-4 is that the formula system of the comparative example 2 is not added with superfine slag micropowder, and the concrete steps are as follows: the MIL-101@ GO composite material, PP, a heat stabilizer (an antioxidant DNP and an antioxidant MB) and an elastomer are uniformly mixed by a high-speed mixer according to the mass ratio of 3 percent to 84.7 percent to 0.3 percent to 12 percent, and then are melted, blended and extruded in a double-screw extruder for granulation to obtain the polypropylene-based automobile special material without superfine slag micropowder.
Table 6 shows the results of various property tests of the polypropylene-based automobile material prepared in comparative example 2.
TABLE 6
Comparative example 3
PP, calcium carbonate, a heat stabilizer (antioxidant 1010) and an elastomer are uniformly mixed by a high-speed mixer according to the mass ratio of 66.7 to 18 to 0.3 to 15 respectively, and then are melted, blended, extruded and granulated in a double-screw extruder to obtain the automobile material.
Table 7 shows the results of various performance tests on the automobile material prepared in comparative example 3.
TABLE 7
Comparative example 4
PP, talcum powder, a heat stabilizer (antioxidant 1010) and an elastomer are uniformly mixed by a high-speed mixer according to the mass ratio of 66.7 to 18 to 0.3 to 15 respectively, and then are melted, blended, extruded and granulated in a double-screw extruder to obtain the automobile material.
Table 8 shows the results of various performance tests on the automobile material prepared in comparative example 4.
TABLE 8
Comparative example 5
The special material for the automobile is prepared by using 100 percent of PP. Table 9 shows the results of various performance tests on the automobile material prepared in comparative example 5.
TABLE 9
VOC test conditions:
weighing 50g of prepared materials, putting the materials into a glass container, sealing a bottle opening, putting the glass container into an oven, drying the glass container at the temperature of 70 +/-2 ℃ for 24 hours, taking out the glass container, cooling the glass container to the temperature of 65 +/-5 ℃, slightly removing a seal (or a cover), and carrying out evaluation by a plurality of testers at the position 2-3 cm away from the bottle opening through noses according to the following standards:
standard 1: odor detection- -VW50180 (popular standard)
Test standards: VW 50180;
judging the grade: 6, grade;
and (4) judging the standard: 1 is odorless; 2-slightly odorous; 3-tasted but not irritating; 4, pungent smell; 5 ═ strong pungent odor; 6 ═ intolerable taste.
Standard 2: odor detection- -Q/JLY J7110538A-2012 (Jili Standard)
Judging the grade: the total number is 10 grades;
and (4) judging the standard: no odor 10; 9 ═ a little noticeable odor; 8 is an obvious odor; 7 is slightly tolerated; 6 can be tolerated; 5 ═ a bit intolerable; 4, countering; 3 is aversion; 2 is very aversive; 1 is intolerable.
The test results were averaged as shown in table 10:
watch 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 |
And (4) conclusion:
1. as can be seen from the comparison of tables 7 and 8 with table 9, the material shrinkage is reduced from 1.2% to 1.13-1.15% after the talc powder or calcium carbonate is added for filling, and the material shrinkage can be further reduced to below 1.1% after the talc powder or calcium carbonate is replaced by the ultrafine slag micropowder and the MIL-101@ GO composite material is added after the talc powder or calcium carbonate is compared with tables 1-4, which indicates that compared with the talc powder or calcium carbonate, the filling effect of the PP material can be improved by adopting the ultrafine slag micropowder and the MIL-101@ GO composite material, and the density and the melt flow rate are basically kept unchanged.
2. According to the comparison of tables 1-4 and tables 7-9, the tensile yield strength of the composite material is reduced no matter the talcum powder and the calcium carbonate are added, or the superfine slag powder and the MIL-101@ GO composite material are added, but the tensile yield strength of the composite material is still kept above 20MPa compared with that of the talcum powder or the calcium carbonate when the composite material is filled with the superfine slag powder and the MIL-101@ GO composite material, and the composite material is not too brittle or too soft, so that the characteristic is shown.
3. As can be seen from the comparison of tables 1 to 4 and tables 7 to 9, the superfine slag powder and MIL-101@ GO composite material is adopted for filling, so that the improvement is larger in bending yield strength, bending elastic modulus, pendulum impact strength and load deflection temperature compared with talcum powder or calcium carbonate, the flame retardance is better, and the flame retardance can be reduced from 23mm/min to 11 mm/min.
4. According to the comparison of tables 1-6 and 9, the PP material filled with the superfine slag micropowder or the MIL-101@ GO composite material can have different influences on various performances in the PP material, some performances are improved, and some performances are reduced; and the PP material is filled with the superfine slag micro powder and MIL-101@ GO composite material, so that various properties are well improved, and the comprehensive performance of the material is effectively improved.
5. As can be seen from Table 10, the automobile material made of the pure PP material has strong pungent odor and is difficult to tolerate; after the talcum powder or calcium carbonate is filled in the PP material, the prepared polypropylene-based automobile material still has pungent smell and cannot be tolerated to a certain extent; after the PP material is filled with superfine slag micro powder, the prepared polypropylene-based automobile material has odor which is obviously reduced compared with comparative examples 3 and 4; after the polypropylene-based automobile material is filled with the MIL-101@ GO composite material, the prepared polypropylene-based automobile material has a little odor, and the adsorption of VOC reaches a good effect; after the PP material is filled with the superfine slag micro powder and MIL-101@ GO composite material, the prepared polypropylene-based automobile material basically achieves the no-odor degree (examples 1-4), and the superfine slag micro powder and MIL-101@ GO composite material are filled in the PP material, so that the ultralow VOC (volatile organic Compounds) release of the special polypropylene-based automobile material is realized.
In conclusion, through the design of raw materials, formula proportion, process parameters and process flow, all the links are buckled and supplemented with each other, so that the comprehensive performance of the polypropylene-based automobile material is well improved, the ultralow VOC (volatile organic compound) release of the automobile material is realized from the source, the polypropylene-based automobile material is more suitable for the manufacture of automobile interior parts, and the requirements of health and environmental protection in automobiles are met.
Therefore, compared with the prior art, the invention has obvious technical progress, and has outstanding substantive characteristics and remarkable progress.
The above-mentioned 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 technical problems solved by the present invention should be consistent with the present invention, if they are not substantially modified or retouched in the spirit and concept of the present invention.
Claims (10)
1. The preparation method of the ultra-low VOC polypropylene-based automobile special material is characterized by comprising the following steps:
(1) preparation of MIL-101@ GO composite
Dissolving equal moles of chromium nitrate and terephthalic acid in deionized water, adding graphite oxide powder with the initial mass of 5-8 wt% of the raw materials, performing ultrasonic treatment for 15-20 min, performing magnetic stirring for 20-25 min under 313K, adding 0.5-0.8 mL of hydrofluoric acid into a reaction tank, placing the reaction tank into a temperature programming furnace for hydrothermal reaction, and after the reaction is finished, sequentially performing DMF (dimethyl formamide) washing, ethanol washing and NH (NH) washing on the product4Washing the solution F with water, centrifuging and filtering, and finally putting the product into an oven for drying for later use;
(2) uniformly mixing 3-5% of MIL-101@ GO composite material, 50-80% of polypropylene reclaimed material, 10-30% of superfine slag micropowder, 0.2-0.5% of heat stabilizer and 5-15% of elastomer according to mass ratio to obtain a mixture;
(3) and melting and blending the mixture, and then extruding and granulating to obtain the polypropylene-based automobile special material.
2. The method for preparing the ultra-low VOC polypropylene-based automobile special material as claimed in claim 1, wherein in the step (1), the process for preparing the graphite oxide powder comprises the following steps:
(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 mixture not more than 371K, and continuing to react for 15 min;
(c) adding 333K warm water and 100mL of 30 wt% hydrogen peroxide, standing the solution until layering, and removing the supernatant;
(d) centrifugally washing with deionized water to obtain dark yellow viscous liquid;
(e) dialyzing with dialysis bag for 7 days, and spray drying to obtain brown graphite oxide powder.
3. The method for preparing the ultra-low VOC polypropylene-based automobile special material as claimed in claim 2, wherein the step (a) comprises the following steps:
(a1) placing equal-mass graphite powder and sodium nitrate 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 potassium permanganate with the mass 6 times that of the graphite powder, controlling the temperature not to exceed 283K, after reacting for 30min, removing the ice bath, and continuing stirring at room temperature for 48h, wherein the reaction system is changed into a dark brown viscous solution.
4. The method for preparing the ultra-low VOC polypropylene-based automobile special 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 as follows: the solution was heated from room temperature to 493K at 5K/min for 8h, after which the solution was cooled down to 308K at a cooling rate of 0.4K/min.
5. The method for preparing the ultra-low VOC polypropylene-based automobile special material as claimed in claim 4, wherein in the step (1), the product is placed in an oven and dried under 423K.
6. The preparation method of the ultra-low VOC polypropylene-based automobile special material as claimed in claim 1, wherein the particle size of the superfine slag micro powder is 1.0-2.3 um.
7. The method for preparing the ultra-low VOC polypropylene-based automobile special material as claimed in claim 1, 2, 3, 5 or 6, wherein in the step (3), a twin-screw extruder is used for melt blending and extrusion granulation of the mixture.
8. The method for preparing the ultra-low VOC polypropylene-based automobile special material as claimed in claim 7, wherein the temperature of each section of the twin-screw extruder from the feed inlet to the head is 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 0.09 MPa.
9. The method for preparing the ultra-low VOC polypropylene-based automobile special material as claimed in claim 8, wherein the polypropylene is a co-polypropylene or a mixture of a co-polypropylene and a homo-polypropylene.
10. The preparation method of the ultra-low VOC polypropylene-based automobile special material as claimed in claim 9, wherein the heat stabilizer is 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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| CN103432982A (en) * | 2013-08-05 | 2013-12-11 | 华南理工大学 | Preparation method of metal organic framework-graphite oxide composite |
| 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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