CN116640391A - Preparation method of environment-friendly flame-retardant anti-skid composite material applied to automobile foot pad - Google Patents
Preparation method of environment-friendly flame-retardant anti-skid composite material applied to automobile foot pad Download PDFInfo
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- CN116640391A CN116640391A CN202310364747.4A CN202310364747A CN116640391A CN 116640391 A CN116640391 A CN 116640391A CN 202310364747 A CN202310364747 A CN 202310364747A CN 116640391 A CN116640391 A CN 116640391A
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- 239000002131 composite material Substances 0.000 title claims abstract description 87
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000003063 flame retardant Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000853 adhesive Substances 0.000 claims abstract description 44
- 230000001070 adhesive effect Effects 0.000 claims abstract description 44
- 239000003292 glue Substances 0.000 claims abstract description 41
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 27
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000003381 stabilizer Substances 0.000 claims abstract description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 11
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 11
- 239000000314 lubricant Substances 0.000 claims abstract description 11
- 239000004609 Impact Modifier Substances 0.000 claims abstract description 9
- 239000004014 plasticizer Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 55
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000007864 aqueous solution Substances 0.000 claims description 40
- 108010073771 Soybean Proteins Proteins 0.000 claims description 34
- 235000019710 soybean protein Nutrition 0.000 claims description 32
- 238000004821 distillation Methods 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 15
- 229940126062 Compound A Drugs 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 9
- 239000005750 Copper hydroxide Substances 0.000 claims description 9
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 5
- -1 tin carboxylate Chemical class 0.000 claims description 5
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 claims description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 2
- LQLQDKBJAIILIQ-UHFFFAOYSA-N Dibutyl terephthalate Chemical compound CCCCOC(=O)C1=CC=C(C(=O)OCCCC)C=C1 LQLQDKBJAIILIQ-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 2
- LQKWPGAPADIOSS-UHFFFAOYSA-N bis(2-methylpropyl) benzene-1,4-dicarboxylate Chemical compound CC(C)COC(=O)C1=CC=C(C(=O)OCC(C)C)C=C1 LQKWPGAPADIOSS-UHFFFAOYSA-N 0.000 claims description 2
- 239000006084 composite stabilizer Substances 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 229940037312 stearamide Drugs 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 8
- 238000012545 processing Methods 0.000 abstract description 6
- 229940071440 soy protein isolate Drugs 0.000 abstract description 6
- 239000000047 product Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 29
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005299 abrasion Methods 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 9
- 239000004033 plastic Substances 0.000 description 9
- 239000004801 Chlorinated PVC Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 6
- 230000035882 stress Effects 0.000 description 4
- 238000007385 chemical modification Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 150000004053 quinones Chemical class 0.000 description 2
- 125000004151 quinonyl group Chemical group 0.000 description 2
- 229940001941 soy protein Drugs 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
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- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- YAHBZWSDRFSFOO-UHFFFAOYSA-L dimethyltin(2+);2-(2-ethylhexoxy)-2-oxoethanethiolate Chemical compound CCCCC(CC)COC(=O)CS[Sn](C)(C)SCC(=O)OCC(CC)CCCC YAHBZWSDRFSFOO-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 102220040412 rs587778307 Human genes 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 238000012546 transfer Methods 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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2248—Oxides; Hydroxides of metals of copper
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of an environment-friendly flame-retardant anti-skid composite material applied to an automobile foot pad, which comprises the following components: polyvinyl chloride resin, plasticizer, lubricant, impact modifier, modified composite glue, processing aid and stabilizer; the modified composite adhesive is prepared by connecting dopamine hydrochloride and lignocellulose to obtain a grafted compound, and then combining epoxy chloropropane and ammonia water to further generate viscous liquid in an alkaline environmentThe bulk, viscous liquid and grafted compound are further crosslinked with soy protein isolate and with Cu 2+ Chelating to obtain the final product. Compared with the prior art, the environment-friendly flame-retardant anti-skid composite material prepared by the method has the advantages of good mechanical property, high wear resistance, excellent flame retardant property, simple and environment-friendly processing process and stable product quality, and is suitable for being used as a production raw material of an automobile foot pad.
Description
Technical Field
The invention relates to the technical field of polymer material processing, in particular to a preparation method of an environment-friendly flame-retardant anti-slip composite material applied to an automobile foot pad.
Background
The plastic prepared by processing the PVC resin has good electrical insulation, wear resistance, ageing resistance and chemical stability, and is widely applied to the aspects of floor leather, pipes, wires and cables, packaging films and the like. However, in the automotive field, the wear-resistant and anti-skid properties are further enhanced, and the flame retardant properties of the materials should be increased, which are critical to the safety problem of automobiles.
The modification method of polyvinyl chloride mainly comprises two chemical modification and physical modification. The purpose of the modification is generally to improve impact toughness, heat stability and heat resistance. The chemical modification is to change the structure of PVC molecular chain through copolymerization, substitution, grafting, crosslinking and other chemical reactions to achieve the modification purpose. However, chemical modification is prone to produce polluting emissions and the quality uniformity of the product is poor. The physical modification is that the modifier is mixed with PVC in a physical mode, so that chemical change does not occur, and the PVC performance is improved. The physical modification of PVC mainly comprises: blending modification, in-situ modification and the like. The physical modification is not ideal enough and generally reduces the advantageous properties of PVC resins. Therefore, the preparation method which is environment-friendly and has obvious effect is of great significance for preparing the PVC composite material.
Chinese patent No. CN105175963B discloses a chlorinated polyvinyl chloride modified material, which is prepared from the following components in parts by weight: 100 parts of chlorinated polyvinyl chloride resin, 1-5 parts of composite lubricant, 5-10 parts of composite heat stabilizer, 5-15 parts of filler, 5-20 parts of toughening agent, 3-10 parts of processing aid and 0.5-3 parts of pigment. The preparation method comprises the following steps: weighing the components according to a formula for standby; firstly, pouring chlorinated polyvinyl chloride resin into a high-speed mixer for mixing, then pouring a composite heat stabilizer, finally pouring a composite lubricant, a filler, a toughening agent, a processing aid and pigment for mixing to 105-120 ℃, discharging and cooling; and (3) carrying out melt extrusion and hot cutting on the cooled mixture to obtain the chlorinated polyvinyl chloride modified material. The chlorinated polyvinyl chloride modification of the invention overcomes the problems of high melt viscosity and difficult molding and processing, and the obtained product has high impact strength, good surface smoothness and high thermal stability. However, the wear resistance of the chlorinated polyvinyl chloride modified material prepared by the method is poor, the flame retardant property is not improved, and the production process is not environment-friendly.
Disclosure of Invention
In view of the defects of poor wear resistance, low mechanical property and flame retardance and non-environmental protection of the polyvinyl chloride material in the prior art, the technical problem to be solved by the invention is to provide the environment-friendly flame-retardant anti-slip composite material with good mechanical property, high wear resistance and high flame retardance.
In order to achieve the above object, the present invention adopts the following technical scheme:
the invention relates to a preparation method of an environment-friendly flame-retardant anti-slip composite material applied to an automobile foot pad, which comprises the following components: polyvinyl chloride resin, plasticizer, lubricant, impact modifier, modified composite glue, processing aid and stabilizer.
Preferably, the preparation method of the environment-friendly flame-retardant anti-slip composite material applied to the automobile foot pad comprises the following components in percentage by weight: 50 to 65 percent of polyvinyl chloride resin, 25 to 40 percent of plasticizer, 0.1 to 0.5 percent of lubricant, 2 to 4 percent of impact modifier, 5 to 10 percent of modified composite adhesive, 1 to 3 percent of processing aid and 0.1 to 1 percent of stabilizer.
Preferably, the plasticizer is at least one of acetyl tributyl citrate, epoxidized soybean oil, dioctyl phthalate, dibutyl terephthalate and diisobutyl terephthalate.
Preferably, the stabilizer is at least one of a calcium-zinc composite stabilizer, an organic tin mercaptide stabilizer and an organic tin carboxylate stabilizer.
Preferably, the processing aid is a polyacrylate compound.
Preferably, the lubricant is at least one of calcium stearate, butyl stearate, stearamide, paraffin wax or polyethylene wax.
Preferably, the impact modifier is at least one of chlorinated polyethylene, methyl methacrylate, and acrylate.
Preferably, the modified composite adhesive is prepared by the following method, and the parts by weight are as follows:
s1, adding 0.5-2 parts of lignocellulose into 90-100 parts of water, uniformly stirring, adding 0.1-1 part of 5-15 mmol/L of tris (hydroxymethyl) aminomethane aqueous solution and 0.1-1 part of 0.5-2 g/L of dopamine hydrochloride aqueous solution, regulating the pH to 7-8 by adopting 1-3 wt% of sodium hydroxide aqueous solution, stirring and reacting for 20-30 h at 50-70 ℃ after solute is completely dissolved, filtering, collecting solid, washing for 2-3 times by using 40-70 wt% of ethanol aqueous solution, and drying for 30-40 h at 40-60 ℃ to obtain grafted compound;
s2, adding 3-8 parts of epichlorohydrin and 0.5-2 parts of 25-28 wt% ammonia water into a reaction kettle, stirring, then adding 0.01-0.3 part of 0.1-1 wt% ammonium fluoride aqueous solution, reacting for 40-50 hours at 20-30 ℃, then heating for 1-5 hours at 30-50 ℃, and then obtaining a compound A by reduced pressure distillation, wherein the reduced pressure distillation pressure is 1-5 kPa, the temperature is 70-90 ℃ and the time is 1-5 hours; then cooling the compound A to 10-25 ℃, adding 0.2-0.8 part of 40-50 wt% sodium hydroxide aqueous solution, sealing and reacting for 1-3 hours, and distilling under reduced pressure until the solid content is 80-92%, thus obtaining viscous liquid;
s3, adding 3-8 parts of soybean protein isolate into 90-100 parts of water, stirring at a constant speed of 600-1000 r/min for 10-30 min to obtain soybean protein glue, adding 1-5 parts of viscous liquid prepared in the step S2 into the soybean protein glue, stirring uniformly to obtain mixed glue, adding 0.1-1 part of grafting compound prepared in the step S1 into the mixed glue, stirring uniformly to obtain an adhesive, and finally, adding 0.5-2 parts of copper hydroxide into the adhesive, stirring and reacting for 10-30 min at a stirring speed of 200-500 r/min to obtain the modified composite glue.
An environment-friendly flame-retardant anti-slip composite material applied to an automobile foot pad is prepared by the following steps:
step 1, according to the mass percentage, polyvinyl chloride resin, plasticizer, lubricant, impact modifier, filler, processing aid and stabilizer are put into a mixer to be mixed for 2-4 hours, taken out and dried, and a premix is obtained;
step 2, putting the premix obtained in the step 1 into a grinding device, and grinding for 10-15 min at a grinding speed of 1000-2000 r/min to obtain a blend;
step 3, the blend obtained in the step 2 is sent into an internal mixer to be internally mixed for 20-25 min at 130-140 ℃ to obtain an internal mixed material;
and step 4, putting the banburying material prepared in the step 3 into a double-screw extruder, extruding the banburying material in the double-screw extruder after the residence time is 2-5 min to obtain a reaction product, and granulating and drying the reaction product to obtain the environment-friendly flame-retardant anti-skid composite material.
Preferably, the parameters of the double-screw extruder are that the barrel temperature of the activation section is 200-230 ℃, the temperature of the mixing section is 200-230 ℃, the temperature of the discharging section is 200-210 ℃, the temperature of the machine head is 200-220 ℃, and the rotating speed of the double-screw extruder is 200-500 rpm.
According to the invention, dopamine hydrochloride is successfully connected with lignocellulose through hydrogen bonds to obtain a grafted compound, epichlorohydrin and ammonia water are combined to further generate viscous liquid in an alkaline environment, epoxy groups and quinone groups of the viscous liquid can be crosslinked with soybean protein isolate through covalent bonds, a crosslinked structure is constructed, catechol groups of the grafted compound interact with active groups of the soybean protein isolate to form hydrogen bonds, and carboxyl groups of the soybean protein isolate interact with Cu 2+ Chelate forms ionic bonds, and is constructed into a network structure with energy dissipation, so that the internal conformation of the soybean protein is changed. The cross-linked structure constructed by the viscous liquid and the soybean protein isolate has gaps, is easy to break under stress, enhances the physical structure after being combined with the grafted compound, forms a reinforced concrete-like structure, and a plurality of catechol groups interact with amino groups and carboxyl groups of the soybean protein isolate to form more hydrogen bonds as stress sacrificial bonds, so that the energy dissipation in the breaking process is increased, and the mechanical property of the modified composite adhesive is improved. And due to Cu 2+ Chelating catechol group in modified compound glue to form ionic bond and constructing organic-inorganic hybridized structure. The ionic bond is used as an energy consumption bond in the tensile deformation, so that the toughness of the modified composite adhesive is further improved. Furthermore, cu as part of the organic-inorganic hybrid structure 2+ As hard phase, hard and soft structure is formed in the adhesive, catechol group enhances Cu 2+ Interfacial bonding force with the modified composite adhesive matrix to generate forceIs used for the transfer and dissipation of (a). In the process of granulating by double screw extrusion, the modified composite adhesive and the polyvinyl chloride resin are mutually compounded and permeated, so that the connection between polyvinyl chloride resin matrixes is enhanced, and the toughness and strength of the environment-friendly flame-retardant anti-skid composite material are improved.
The grafting of dopamine hydrochloride blocks the directional aggregation of lignocellulose, thereby reducing crystallinity. The catechol group of the obtained grafted compound is oxidized to generate quinone compounds, and is covalently crosslinked with active groups of soy protein isolate to form a crosslinked structure, and Cu is added after copper hydroxide is added 2+ Chelating carboxyl groups of the isolated soy protein forms ionic bonds. And finally, the obtained modified composite adhesive system is in composite connection with the polyvinyl chloride resin matrix to construct a multi-bond structure comprising covalent bonds, hydrogen bonds and ionic bonds. The multi-key structure increases the energy dissipation in the friction process and improves the wear resistance of the environment-friendly flame-retardant anti-skid composite material.
The modified composite adhesive system and the polyvinyl chloride resin matrix are in composite connection to form a compact network structure, and the modified composite adhesive forms an organic-inorganic hybrid structure on the basis of the compact network structure, and inorganic copper hydroxide is heated and decomposed to absorb part of heat released by combustion, so that the continuation of the combustion process is effectively reduced, the environment-friendly flame-retardant anti-slip composite material is more compact, and a carbon layer is formed for protection, so that the flame retardance of the environment-friendly flame-retardant anti-slip composite material is improved.
Compared with the prior art, the invention has the beneficial effects that:
1) The environment-friendly flame-retardant anti-skid composite material for automobile foot pad is prepared through the steps of firstly, successfully connecting dopamine hydrochloride with lignocellulose through hydrogen bond to obtain a grafted compound, then combining epichlorohydrin with ammonia water to further generate viscous liquid in alkaline environment, and further crosslinking the viscous liquid and the grafted compound with soy protein isolate through covalent bond and Cu 2+ The modified composite adhesive is prepared by chelation, and is mutually compounded and permeated with polyvinyl chloride resin, so that the strength and the wear resistance of the environment-friendly flame-retardant anti-skid composite material are improved, and the flame retardant property is endowed;
2) The environment-friendly flame-retardant anti-slip composite material applied to the automobile foot pad is prepared by adopting a scientific proportioning and preparation method, the processing process is simple and environment-friendly, the product quality is stable, and the environment-friendly flame-retardant anti-slip composite material is suitable for being used as a production raw material of the automobile foot pad.
Detailed Description
The technical scheme of the present invention will be described in detail by means of specific examples, which should be explicitly set forth for illustration, but should not be construed as limiting the scope of the present invention.
The parameters of partial raw materials in the embodiment of the invention are as follows:
lignocellulose, model number of new material of vibration plastics limited in su zhou: T30S.
Polyvinyl chloride resin, model number of Rong Ren chemical industry Co., ltd., changzhou: p-440, solids content: 99.98%.
Chlorinated polyethylene, shijia Runzhuang plastic new material science and technology Co., ltd., brand: 135A, processing grade: injection molding grade, grade: and (5) a quality product.
Polyacrylate, shandong national chemical Co., ltd., molecular weight: 59.11, CAS number: 107-10-8.
Soy protein isolate, shanghai vision biosciences, content: 99%, appearance: powder, color: light yellow.
Example 1
An environment-friendly flame-retardant anti-slip composite material applied to an automobile foot pad is prepared by the following steps:
step 1, adding 56kg of polyvinyl chloride resin, 30kg of acetyl tributyl citrate, 0.3kg of calcium stearate, 3kg of chlorinated polyethylene, 8kg of modified composite glue, 2kg of polyacrylate and 0.7 kg of methyl tin mercaptide into a mixer, mixing for 3 hours, taking out and drying to obtain a premix;
step 2, putting the premix obtained in the step 1 into a grinding device, and grinding for 12min at a grinding speed of 1500r/min to obtain a blend;
step 3, feeding the blend obtained in the step 2 into an internal mixer, and banburying for 25min at 135 ℃ to obtain a banburying material;
and 4, putting the banburying material prepared in the step 3 into a double-screw extruder, standing for 4min in the double-screw extruder, extruding, wherein the parameters of the double-screw extruder are that the barrel temperature of an activation section is 210 ℃, the temperature of a mixing section is 220 ℃, the temperature of a discharging section is 205 ℃, the temperature of a machine head is 210 ℃, the rotating speed of the double-screw extruder is 300rpm, so as to obtain a reaction product, and granulating and drying the reaction product to obtain the environment-friendly flame-retardant anti-slip composite material applied to the automobile foot pad.
The modified composite adhesive is prepared by the following method:
s1, adding 1kg of lignocellulose into 99kg of water, uniformly stirring, adding 0.5kg of 10mmol/L of tris (hydroxymethyl) aminomethane aqueous solution and 0.5kg of 1g/L of dopamine hydrochloride aqueous solution, regulating the pH to 7.5 by adopting 2wt% of sodium hydroxide aqueous solution, stirring and reacting for 24 hours at 60 ℃ after the solute is completely dissolved, filtering, collecting solid, washing 3 times by using 50wt% of ethanol aqueous solution, and drying for 36 hours at 50 ℃ to obtain a grafted compound;
s2, adding 5kg of epichlorohydrin and 1kg of 25wt% ammonia water into a reaction kettle, stirring, then adding 0.1kg of 0.5wt% ammonium fluoride aqueous solution, reacting for 48 hours at 23 ℃, then heating for 3 hours at 40 ℃, and then obtaining a compound A by reduced pressure distillation, wherein the reduced pressure distillation pressure is 3kPa, the temperature is 80 ℃ and the time is 3 hours; then cooling the compound A to 20 ℃, adding 0.5kg of 50wt% sodium hydroxide aqueous solution, performing closed reaction for 2 hours, and performing reduced pressure distillation until the solid content is 90%, thus obtaining viscous liquid;
s3, adding 5kg of soybean protein isolate into 95kg of water, stirring for 20min at a constant speed of 800r/min by using a cantilever type electric stirring paddle to obtain soybean protein glue, adding 3kg of viscous liquid prepared in the step S2 into the soybean protein glue, stirring uniformly to obtain mixed glue, adding 0.5kg of grafted compound prepared in the step S1 into the mixed glue, stirring uniformly to obtain an adhesive, and finally, adding 1kg of copper hydroxide into the adhesive, and stirring for reacting for 20min at a stirring speed of 300r/min to obtain the modified composite glue.
Example 2
The preparation method of the environment-friendly flame-retardant anti-slip composite material applied to the automobile foot pad is basically the same as that of the embodiment 1, and the only difference is that: the preparation methods of the modified composite adhesive are different.
The modified composite adhesive is prepared by the following method:
s1, adding 1kg of lignocellulose into 99kg of water, uniformly stirring, adding 0.5kg of 10mmol/L of tris (hydroxymethyl) aminomethane aqueous solution, adopting 2wt% of sodium hydroxide aqueous solution to adjust the pH to 7.5, stirring and reacting for 24 hours at 60 ℃ after the solute is completely dissolved, filtering, collecting the solid, washing for 3 times with 50wt% of ethanol aqueous solution, and drying for 36 hours at 50 ℃ to obtain a grafted compound;
s2, adding 5kg of epichlorohydrin and 1kg of 25wt% ammonia water into a reaction kettle, stirring, then adding 0.1kg of 0.5wt% ammonium fluoride aqueous solution, reacting for 48 hours at 23 ℃, then heating for 3 hours at 40 ℃, and then obtaining a compound A by reduced pressure distillation, wherein the reduced pressure distillation pressure is 3kPa, the temperature is 80 ℃ and the time is 3 hours; then cooling the compound A to 20 ℃, adding 0.5kg of 50wt% sodium hydroxide aqueous solution, performing closed reaction for 2 hours, and performing reduced pressure distillation until the solid content is 90%, thus obtaining viscous liquid;
s3, adding 5kg of soybean protein isolate into 95kg of water, stirring for 20min at a constant speed of 800r/min by using a cantilever type electric stirring paddle to obtain soybean protein glue, adding 3kg of viscous liquid prepared in the step S2 into the soybean protein glue, stirring uniformly to obtain mixed glue, adding 0.5kg of grafted compound prepared in the step S1 into the mixed glue, stirring uniformly to obtain an adhesive, and finally, adding 1kg of copper hydroxide into the adhesive, and stirring for reacting for 20min at a stirring speed of 300r/min to obtain the modified composite glue.
Example 3
The preparation method of the environment-friendly flame-retardant anti-slip composite material applied to the automobile foot pad is basically the same as that of the embodiment 1, and the only difference is that: the preparation methods of the modified composite adhesive are different.
The modified composite adhesive is prepared by the following method:
s1, adding 1kg of lignocellulose into 99kg of water, uniformly stirring, adding 0.5kg of 10mmol/L of tris (hydroxymethyl) aminomethane aqueous solution and 0.5kg of 1g/L of dopamine hydrochloride aqueous solution, regulating the pH to 7.5 by adopting 2wt% of sodium hydroxide aqueous solution, stirring and reacting for 24 hours at 60 ℃ after the solute is completely dissolved, filtering, collecting solid, washing 3 times by using 50wt% of ethanol aqueous solution, and drying for 36 hours at 50 ℃ to obtain a grafted compound;
s2, adding 1kg of 25wt% ammonia water into a reaction kettle, then adding 0.1kg of 0.5wt% ammonium fluoride aqueous solution, reacting for 48 hours at 23 ℃, then heating for 3 hours at 40 ℃, and then obtaining a compound A by reduced pressure distillation, wherein the reduced pressure distillation pressure is 3kPa, the temperature is 80 ℃ and the time is 3 hours; then cooling the compound A to 20 ℃, adding 0.5kg of 50wt% sodium hydroxide aqueous solution, performing closed reaction for 2 hours, and performing reduced pressure distillation until the solid content is 90%, thus obtaining viscous liquid;
s3, adding 5kg of soybean protein isolate into 95kg of water, stirring for 20min at a constant speed of 800r/min by using a cantilever type electric stirring paddle to obtain soybean protein glue, adding 3kg of viscous liquid prepared in the step S2 into the soybean protein glue, stirring uniformly to obtain mixed glue, adding 0.5kg of grafted compound prepared in the step S1 into the mixed glue, stirring uniformly to obtain an adhesive, and finally, adding 1kg of copper hydroxide into the adhesive, and stirring for reacting for 20min at a stirring speed of 300r/min to obtain the modified composite glue.
Example 4
The preparation method of the environment-friendly flame-retardant anti-slip composite material applied to the automobile foot pad is basically the same as that of the embodiment 1, and the only difference is that: and replacing the modified composite adhesive with an adhesive.
The adhesive is prepared by the following method:
s1, adding 1kg of lignocellulose into 99kg of water, uniformly stirring, adding 0.5kg of 10mmol/L of tris (hydroxymethyl) aminomethane aqueous solution and 0.5kg of 1g/L of dopamine hydrochloride aqueous solution, regulating the pH to 7.5 by adopting 2wt% of sodium hydroxide aqueous solution, stirring and reacting for 24 hours at 60 ℃ after the solute is completely dissolved, filtering, collecting solid, washing 3 times by using 50wt% of ethanol aqueous solution, and drying for 36 hours at 50 ℃ to obtain a grafted compound;
s2, adding 5kg of epichlorohydrin and 1kg of 25wt% ammonia water into a reaction kettle, stirring, then adding 0.1kg of 0.5wt% ammonium fluoride aqueous solution, reacting for 48 hours at 23 ℃, then heating for 3 hours at 40 ℃, and then obtaining a compound A by reduced pressure distillation, wherein the reduced pressure distillation pressure is 3kPa, the temperature is 80 ℃ and the time is 3 hours; then cooling the compound A to 20 ℃, adding 0.5kg of 50wt% sodium hydroxide aqueous solution, performing closed reaction for 2 hours, and performing reduced pressure distillation until the solid content is 90%, thus obtaining viscous liquid;
s3, adding 5kg of soybean protein isolate into 95kg of water, stirring for 20min at a constant speed of 800r/min by using a cantilever type electric stirring paddle to obtain soybean protein glue, adding 3kg of viscous liquid prepared in the step S2 into the soybean protein glue, stirring uniformly to obtain mixed glue, adding 0.5kg of grafted compound prepared in the step S1 into the mixed glue, and stirring uniformly to obtain the adhesive.
Comparative example 1
The preparation method of the environment-friendly flame-retardant anti-slip composite material applied to the automobile foot pad is basically the same as that of the embodiment 1, and the only difference is that: and replacing the modified composite adhesive with an adhesive.
The adhesive is prepared by the following method:
s1, adding 1kg of lignocellulose into 99kg of water, uniformly stirring, adding 0.5kg of 10mmol/L of tris (hydroxymethyl) aminomethane aqueous solution, adopting 2wt% of sodium hydroxide aqueous solution to adjust the pH to 7.5, stirring and reacting for 24 hours at 60 ℃ after the solute is completely dissolved, filtering, collecting the solid, washing for 3 times with 50wt% of ethanol aqueous solution, and drying for 36 hours at 50 ℃ to obtain a grafted compound;
s2, adding 1kg of 25wt% ammonia water into a reaction kettle, then adding 0.1kg of 0.5wt% ammonium fluoride aqueous solution, reacting for 48 hours at 23 ℃, then heating for 3 hours at 40 ℃, and then obtaining a compound A by reduced pressure distillation, wherein the reduced pressure distillation pressure is 3kPa, the temperature is 80 ℃ and the time is 3 hours; then cooling the compound A to 20 ℃, adding 0.5kg of 50wt% sodium hydroxide aqueous solution, performing closed reaction for 2 hours, and performing reduced pressure distillation until the solid content is 90%, thus obtaining viscous liquid;
s3, adding 5kg of soybean protein isolate into 95kg of water, stirring for 20min at a constant speed of 800r/min by using a cantilever type electric stirring paddle to obtain soybean protein glue, adding 3kg of viscous liquid prepared in the step S2 into the soybean protein glue, stirring uniformly to obtain mixed glue, adding 0.5kg of grafted compound prepared in the step S1 into the mixed glue, and stirring uniformly to obtain the adhesive.
Comparative example 2
The preparation method of the environment-friendly flame-retardant anti-slip composite material applied to the automobile foot pad is basically the same as that of the embodiment 1, and the only difference is that: the preparation method of the environment-friendly flame-retardant anti-slip composite material applied to the automobile foot pad is free of adding modified composite glue.
Test example 1
Mechanical property test
Determination of tensile Properties of plastics section 3, see GB/T1040.3-2006: test strips of thin plastic and thin sheet were subjected to mechanical property test, and samples of examples and comparative examples were injection molded into standard bars according to national standards at a test speed of 10mm/min.
The bending performance test was performed with reference to GB/T9341-2008 "determination of Plastic bending Performance", and samples of examples and comparative examples were injection molded into standard bars according to national standards at a test speed of 1mm/min.
Each sample was tested three times and averaged and the test results are shown in table 1.
Table 1: mechanical property test results
As can be seen from the test results of Table 1, the mechanical properties of example 1 are best, probably because the invention successfully connects dopamine hydrochloride with lignocellulose through hydrogen bond to obtain a grafted compound, combines epichlorohydrin with ammonia water to further generate viscous liquid in alkaline environment, the epoxy group and the quinone group of the viscous liquid can be crosslinked with soybean protein isolate through covalent bond formation to construct a crosslinked structure, the catechol group of the grafted compound interacts with the active group of the soybean protein isolate to form hydrogen bond, and the carboxyl group of the soybean protein isolate interacts with Cu 2+ Chelate forms ionic bonds, and is constructed into a network structure with energy dissipation, so that the internal conformation of the soybean protein is changed. Viscous liquid and soy protein isolate constructionThe cross-linked structure is easy to break under stress, after the grafting compound is combined, the physical structure is enhanced, a reinforced concrete-like structure is formed, and a plurality of catechol groups interact with amino groups and carboxyl groups of the soybean protein isolate to form more hydrogen bonds as stress sacrificial bonds, so that the energy dissipation in the breaking process is increased, and the mechanical property of the modified composite adhesive is improved. And due to Cu 2+ Chelating catechol group in modified compound glue to form ionic bond and constructing organic-inorganic hybridized structure. The ionic bond is used as an energy consumption bond in the tensile deformation, so that the toughness of the modified composite adhesive is further improved. Furthermore, cu as part of the organic-inorganic hybrid structure 2+ As hard phase, hard and soft structure is formed in the adhesive, catechol group enhances Cu 2+ The interfacial bonding force with the modified composite glue matrix generates force transmission and dissipation. In the process of granulating by double screw extrusion, the modified composite adhesive and the polyvinyl chloride resin are mutually compounded and permeated, so that the connection between polyvinyl chloride resin matrixes is enhanced, and the toughness and strength of the environment-friendly flame-retardant anti-skid composite material are improved.
Test example 2
Friction performance test
The example and comparative materials were prepared as standard samples of 22mm by 14mm by 2mm size. The friction performance test is carried out according to GB/T3960-2016 plastic sliding friction wear test method, and the test temperature is 23+/-5 ℃ and the relative humidity is 50+/-5%. The test parameters are as follows: and loading 196N, rotating the test ring at 200rpm, and testing for 2 hours.
The mass m of the sample to be measured is firstly weighed before the test 1 After testing, the sample is washed by acetone and then dried, and the mass m of the sampled sample is called 2 The quality difference before and after abrasion is the quality abrasion loss, the quality abrasion loss is used as an index for evaluating the abrasion resistance of the sample, the larger the quality abrasion loss is, the worse the abrasion resistance of the sample is, each sample is subjected to 3 tests, and the average value is obtained. The abrasion loss was calculated according to formula 1.
Mass wear was calculated as per 1: m=m 1 -m 2 …………………………1
Wherein: m mass abrasion loss in grams (g);
m 1 the mass of the sample before the test is expressed in grams (g);
m 2 the mass of the test specimen is given in grams (g).
The test results are shown in Table 2.
Table 2: results of Friction Performance test
| Test protocol | Mass abrasion loss (g) |
| Example 1 | 0.09 |
| Example 2 | 0.21 |
| Example 3 | 0.22 |
| Example 4 | 0.24 |
| Comparative example 1 | 0.31 |
| Comparative example 2 | 0.33 |
As can be seen from the test results in Table 2, the friction performance test results of example 1 are best, probably because the grafting of dopamine hydrochloride in the present invention blocks the directional aggregation of lignocellulose,thereby reducing crystallinity. The catechol group of the obtained grafted compound is oxidized to generate quinone compounds, and is covalently crosslinked with active groups of soy protein isolate to form a crosslinked structure, and Cu is added after copper hydroxide is added 2+ Chelating carboxyl groups of the isolated soy protein forms ionic bonds. And finally, the obtained modified composite adhesive system is in composite connection with the polyvinyl chloride resin matrix to construct a multi-bond structure comprising covalent bonds, hydrogen bonds and ionic bonds. The multi-key structure increases the energy dissipation in the friction process and improves the wear resistance of the environment-friendly flame-retardant anti-skid composite material.
Test example 3
Flame retardant Performance test
The Limiting Oxygen Index (LOI) of plastics refers to the volume percent of the lowest oxygen required for a sample to maintain a balanced combustion under standard conditions, the greater the value of the gas composition in a mixture of nitrogen and oxygen, the better the flame resistance. Combustion behaviour measured according to GB/T2406.2-2009 "oxygen index for plastics", part 2: room temperature test oxygen index test the materials of the examples and comparative examples of the present invention were prepared as standard bars with the dimensions: 100mm by 10mm by 4mm. Each group was tested three times and averaged. The test results are shown in Table 3.
Table 3: flame retardant Property test results
| Test protocol | Limiting Oxygen Index (LOI)% |
| Example 1 | 30.3 |
| Example 2 | 26.4 |
| Example 3 | 25.8 |
| Example 4 | 23.1 |
| Comparative example 1 | 22.6 |
| Comparative example 2 | 21.5 |
As can be seen from the test results in table 3, the flame retardant performance of example 1 is best, probably because the modified composite adhesive system and the polyvinyl chloride resin matrix form a compact network structure after being in composite connection, and the modified composite adhesive forms an organic-inorganic hybrid structure on the basis of the compact network structure, and the inorganic copper hydroxide is heated and decomposed to absorb part of heat released by combustion, so that the duration of the combustion process is effectively reduced, the environment-friendly flame retardant and skid-resistant composite material is more compact, and carbon layer protection is formed, so that the flame retardant performance of the environment-friendly flame retardant and skid-resistant composite material is improved.
Claims (10)
1. The preparation method of the environment-friendly flame-retardant anti-slip composite material applied to the automobile foot pad is characterized by comprising the following components: polyvinyl chloride resin, plasticizer, lubricant, impact modifier, modified composite glue, processing aid and stabilizer.
2. The method for preparing the environment-friendly flame-retardant anti-slip composite material applied to the automobile foot pad as claimed in claim 1, which is characterized by comprising the following components in percentage by weight: 50 to 65 percent of polyvinyl chloride resin, 25 to 40 percent of plasticizer, 0.1 to 0.5 percent of lubricant, 2 to 4 percent of impact modifier, 5 to 10 percent of modified composite adhesive, 1 to 3 percent of processing aid and 0.1 to 1 percent of stabilizer.
3. The method for preparing the environment-friendly flame-retardant anti-slip composite material applied to the automobile foot pad according to claim 1 or 2, which is characterized by comprising the following steps: the plasticizer is at least one of acetyl tributyl citrate, epoxidized soybean oil, dioctyl phthalate, dibutyl terephthalate and diisobutyl terephthalate.
4. The method for preparing the environment-friendly flame-retardant anti-slip composite material applied to the automobile foot pad according to claim 1 or 2, which is characterized by comprising the following steps: the stabilizer is at least one of a calcium-zinc composite stabilizer, an organic tin mercaptide stabilizer and an organic tin carboxylate stabilizer.
5. The method for preparing the environment-friendly flame-retardant anti-slip composite material applied to the automobile foot pad according to claim 1 or 2, which is characterized by comprising the following steps: the processing aid is a polyacrylate compound.
6. The method for preparing the environment-friendly flame-retardant anti-slip composite material applied to the automobile foot pad according to claim 1 or 2, which is characterized by comprising the following steps: the lubricant is at least one of calcium stearate, butyl stearate, stearamide, paraffin wax or polyethylene wax.
7. The method for preparing the environment-friendly flame-retardant anti-slip composite material applied to the automobile foot pad according to claim 1 or 2, which is characterized by comprising the following steps: the impact modifier is at least one of chlorinated polyethylene, methyl methacrylate and acrylic ester.
8. The preparation method of the environment-friendly flame-retardant anti-slip composite material applied to the automobile foot pad as claimed in claim 1 or 2, wherein the modified composite adhesive is prepared by the following steps of:
s1, adding 0.5-2 parts of lignocellulose into 90-100 parts of water, uniformly stirring, adding 0.1-1 part of 5-15 mmol/L of tris (hydroxymethyl) aminomethane aqueous solution and 0.1-1 part of 0.5-2 g/L of dopamine hydrochloride aqueous solution, regulating the pH to 7-8 by adopting 1-3 wt% of sodium hydroxide aqueous solution, stirring and reacting for 20-30 h at 50-70 ℃ after solute is completely dissolved, filtering, collecting solid, washing for 2-3 times by using 40-70 wt% of ethanol aqueous solution, and drying for 30-40 h at 40-60 ℃ to obtain grafted compound;
s2, adding 3-8 parts of epichlorohydrin and 0.5-2 parts of 25-28 wt% ammonia water into a reaction kettle, stirring, then adding 0.01-0.3 part of 0.1-1 wt% ammonium fluoride aqueous solution, reacting for 40-50 hours at 20-30 ℃, then heating for 1-5 hours at 30-50 ℃, and then obtaining a compound A by reduced pressure distillation, wherein the reduced pressure distillation pressure is 1-5 kPa, the temperature is 70-90 ℃ and the time is 1-5 hours; then cooling the compound A to 10-25 ℃, adding 0.2-0.8 part of 40-50 wt% sodium hydroxide aqueous solution, sealing and reacting for 1-3 hours, and distilling under reduced pressure until the solid content is 80-92%, thus obtaining viscous liquid;
s3, adding 3-8 parts of soybean protein isolate into 90-100 parts of water, stirring at a constant speed of 600-1000 r/min for 10-30 min to obtain soybean protein glue, adding 1-5 parts of viscous liquid prepared in the step S2 into the soybean protein glue, stirring uniformly to obtain mixed glue, adding 0.1-1 part of grafting compound prepared in the step S1 into the mixed glue, stirring uniformly to obtain an adhesive, and finally, adding 0.5-2 parts of copper hydroxide into the adhesive, stirring and reacting for 10-30 min at a stirring speed of 200-500 r/min to obtain the modified composite glue.
9. The method for preparing the environment-friendly flame-retardant anti-slip composite material applied to the automobile foot pad according to any one of claims 1 to 8, which is characterized by comprising the following steps:
step 1, according to the mass percentage, polyvinyl chloride resin, plasticizer, lubricant, impact modifier, filler, processing aid and stabilizer are put into a mixer to be mixed for 2-4 hours, taken out and dried, and a premix is obtained;
step 2, putting the premix obtained in the step 1 into a grinding device, and grinding for 10-15 min at a grinding speed of 1000-2000 r/min to obtain a blend;
step 3, the blend obtained in the step 2 is sent into an internal mixer to be internally mixed for 20-25 min at 130-140 ℃ to obtain an internal mixed material;
and step 4, putting the banburying material prepared in the step 3 into a double-screw extruder, extruding the banburying material in the double-screw extruder after the residence time is 2-5 min to obtain a reaction product, and granulating and drying the reaction product to obtain the environment-friendly flame-retardant anti-skid composite material.
10. The method for preparing the environment-friendly flame-retardant anti-slip composite material applied to the automobile foot pad as claimed in claim 9, which is characterized in that: the parameters of the double-screw extruder are that the temperature of a machine barrel of an activation section is 200-230 ℃, the temperature of a mixing section is 200-230 ℃, the temperature of a discharging section is 200-210 ℃, the temperature of a machine head is 200-220 ℃, and the rotating speed of the double-screw extruder is 200-500 rpm.
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| CN103059470A (en) * | 2012-12-25 | 2013-04-24 | 东莞市祺龙电业有限公司 | High-abrasion-resistant and environment-friendly polyvinyl chloride (PVC) modified materials and preparation method thereof |
| CN112831137A (en) * | 2021-01-09 | 2021-05-25 | 杭州恒冠塑业有限公司 | PVC (polyvinyl chloride) plate and preparation method thereof |
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| CN103059470A (en) * | 2012-12-25 | 2013-04-24 | 东莞市祺龙电业有限公司 | High-abrasion-resistant and environment-friendly polyvinyl chloride (PVC) modified materials and preparation method thereof |
| CN112831137A (en) * | 2021-01-09 | 2021-05-25 | 杭州恒冠塑业有限公司 | PVC (polyvinyl chloride) plate and preparation method thereof |
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