CN116218097A - PVC material capable of controlling temperature to foam and preparation method and application thereof - Google Patents
PVC material capable of controlling temperature to foam and preparation method and application thereof Download PDFInfo
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- CN116218097A CN116218097A CN202211088951.XA CN202211088951A CN116218097A CN 116218097 A CN116218097 A CN 116218097A CN 202211088951 A CN202211088951 A CN 202211088951A CN 116218097 A CN116218097 A CN 116218097A
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- temperature
- controllable
- pvc material
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- foaming
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- 239000000463 material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000006260 foam Substances 0.000 title abstract description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 67
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 67
- 238000005187 foaming Methods 0.000 claims abstract description 40
- 239000004088 foaming agent Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003063 flame retardant Substances 0.000 claims abstract description 8
- 239000004014 plasticizer Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 19
- AYNNSCRYTDRFCP-UHFFFAOYSA-N triazene Chemical compound NN=N AYNNSCRYTDRFCP-UHFFFAOYSA-N 0.000 claims description 17
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- 229920005990 polystyrene resin Polymers 0.000 claims description 6
- 235000012424 soybean oil Nutrition 0.000 claims description 6
- 239000003549 soybean oil Substances 0.000 claims description 6
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011162 core material Substances 0.000 claims description 4
- 238000001723 curing Methods 0.000 claims description 4
- 239000003995 emulsifying agent Substances 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- -1 phthalate diester Chemical class 0.000 claims description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 2
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000004604 Blowing Agent Substances 0.000 claims 2
- 239000005022 packaging material Substances 0.000 claims 1
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 235000010288 sodium nitrite Nutrition 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 241000208202 Linaceae Species 0.000 description 3
- 235000004431 Linum usitatissimum Nutrition 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 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 3
- 230000000694 effects Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000002649 leather substitute Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 229920006602 NBR/PVC Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 210000000497 foam cell Anatomy 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/108—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond in a heterocyclic ring containing at least one carbon atom
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/22—Expandable microspheres, e.g. Expancel®
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use 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; Derivatives of such polymers
- C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use 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 an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/06—Polystyrene
-
- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention provides a PVC material capable of controlling temperature to foam, a preparation method and application thereof. The temperature-controllable foaming PVC material comprises the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 20-40 parts of filler, 0.1-0.5 part of temperature-controllable foaming agent, 20-40 parts of plasticizer, 0.1-0.5 part of antioxidant and 5-20 parts of flame retardant. The PVC material provided by the invention is prepared by using the temperature-controllable foaming agent, has good foaming controllability, the foaming initial temperature is close to the melting point of PVC, the foaming uniformity is good, the foam holes are compact, the impact resistance of the PVC material is effectively improved, and the prepared PVC material has low density and light weight, and meanwhile, the preparation process is simple and safe, and has good industrial application prospect.
Description
Technical Field
The invention relates to the technical field of foaming material preparation, in particular to a temperature-controllable foaming PVC material and a preparation method and application thereof.
Background
Polyvinyl chloride (Polyvinyl chloride, PVC) is a polymer obtained by polymerizing vinyl chloride monomers under the action of light and heat by a radical polymerization mechanism, with an initiator such as a peroxide or an azo compound. PVC material is light, has the advantages of water resistance, moisture resistance, flame retardance, heat insulation and the like, is the universal plastic with the largest worldwide output, has very wide application, and has wide application in the aspects of building materials, industrial products, daily necessities, floor leathers, floor tiles, artificial leather, pipes, wires and cables, packaging films, bottles, foaming materials, sealing materials, fibers and the like.
At present, the worldwide automobile industry develops rapidly, and the automobile industry not only becomes the pillar industry in developed countries such as the United states and Japan, but also is the pillar industry in some developing countries including China, and the rapid development of the automobile industry drives the rapid development of the automobile foot pad industry. Currently, automobile foot pads have no unified national standard or industry standard, and various types of foot pads exist, and the existing automobile foot pads comprise chemical fiber foot pads, PVC materials, rubber foot pads, wire ring foot pads, flax foot pads, leather foot pads, wool foot pads and the like, wherein the chemical fiber foot pads are very dirty; although the flax foot pad is low in price and soft, the flax foot pad is easy to fuzzing and deform after being cleaned; the leather foot pad is convenient to clean, but has poor sound insulation effect; the rubber foot pad is convenient to clean, but is not environment-friendly and has heavier taste; the wool foot pad has high cost and is difficult to clean. At present, the development direction of the automobile foot pad is as follows: low cost, simple processing technique, injection molding, high production efficiency and no influence on the service performance.
Chinese patent CN114437428A discloses a modified NBR/PVC foam material and a preparation method thereof, which effectively improves the quality and thermal stability of the material, is nontoxic and environment-friendly, but the foaming effect and impact resistance are to be further improved. The high-elastic PVC synthetic leather disclosed in the patent application No. CN102002865A and the production method thereof utilize PVC as a resin matrix, and a foaming agent, a filler and the like are added to prepare high-grade artificial leather, however, the existence of dioctyl phthalate has certain negative effects on the environment and human bodies, and meanwhile, the existing defects are not solved: the collapse and rupture of the cells makes the mechanical properties and quality of the PVC composite less desirable.
Therefore, in order to better meet the requirements of production and practical application, it is necessary to provide a PVC material with good foaming uniformity, low density and good impact resistance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a PVC material with good foaming uniformity, low density and good shock resistance so as to meet the actual production requirements.
To achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a temperature-controllable foaming PVC material, which comprises the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 20-40 parts of filler, 0.1-0.5 part of temperature-controllable foaming agent, 20-40 parts of plasticizer, 0.1-0.5 part of antioxidant and 5-20 parts of flame retardant.
In some embodiments of the invention, the filler is one or more of talc, calcium carbonate, silica.
In some embodiments of the invention, the plasticizer is one or more combinations of epoxidized soybean oil stearate, trioctyl trimellitate, and phthalate diester.
In some embodiments of the invention, the antioxidant is any one of antioxidant 626 or antioxidant 1010.
In some embodiments of the invention, the flame retardant is brominated polystyrene resin PBS-64HW or polybrominated styrene.
In some embodiments of the present invention, the temperature controllable microsphere foaming agent comprises a package material and a core material positioned inside the package material, wherein the package material is urea formaldehyde resin, and the core material is a triazene polymer, wherein the triazene polymer is selected from the following compounds of formula I-1 and/or formula I-2:
wherein a is an integer of 1 to 7, and b is an integer of 1 to 5.
Further, the preparation method of the triazene polymer comprises the following steps:
(1) Mixing 4,4' -diaminophenyl ether with hydrochloric acid, mechanically stirring to obtain milky white turbid liquid, and then adding sodium nitrite solution under ice bath condition to obtain yellowish transparent clear solution;
(2) And (3) adjusting the pH value to 9-10, adding diamine into the product obtained in the step (1) under the ice bath condition, separating out beige solid, continuously stirring, and carrying out suction filtration to obtain the product, namely the triazene polymer.
In some embodiments of the invention, the molar ratio of 4,4' -diaminophenyl ether to diamine is from 1:1 to 1.2 (e.g., may be 1:1,1:1.11,1:1.12,1:1.13,1:1.14,1:1.15,1:1.16,1:1.17,1:1.18,1:1.19,1:1.2, or any value therein).
In the process for preparing a triazene polymer of the present invention, the concentration of said hydrochloric acid in step (1) is 40 to 60% (for example, may be 40%,42%,44%,46%,48%,50%,52%,54%,56%,58%,60% or any value thereof);
in some embodiments of the invention, the diamine in step (2) is anhydrous piperazine or 1, 6-hexamethylenediamine.
Further, the preparation method of the temperature-controllable foaming agent specifically comprises the following steps:
(1) Uniformly mixing urea and formaldehyde, and dissolving with deionized water;
(2) Heating the system and stirring to obtain a prepolymer;
(3) Adding a triazene polymer into a system, adding an emulsifier, and dispersing into a uniform and stable emulsion;
(4) Adding dilute hydrochloric acid to regulate pH to 2-3, starting polymerization, heating and curing reaction, regulating pH to 7-9 with sodium hydroxide, and removing water to obtain the final product.
In some embodiments of the invention, the molar ratio of urea to formaldehyde described in step (1) is from 1.5 to 2:1 (which may be, for example, 1.5:1,1.6:1,1.7:1,1.8:1,1.9:1,2:1 or any point therein), the mass of deionized water is 2-4 times (which may be, for example, 2-fold, 2.5-fold, 3-fold, 3.5-fold, 4-fold or any value therein) the mass sum of urea and formaldehyde.
In some embodiments of the invention, the system described in step (2) is warmed to 70-80 ℃ (e.g., may be 70 ℃,71 ℃,72 ℃,73 ℃,74 ℃,75 ℃,76 ℃,77 ℃,78 ℃,79 ℃,80 ℃, or any value therein).
In some embodiments of the invention, the mass of the triazene polymer in step (3) is 8-9 times (e.g., may be 8 times, 8.1 times, 8.2 times, 8.3 times, 8.4 times, 8.5 times, 8.6 times, 8.7 times, 8.8 times, 8.9 times, 9 times or any value therein) the mass of the package material; the emulsifier is PVA1788 or PVA1799.
Further, the preparation method of the temperature-controllable foaming PVC material comprises the following steps:
(1) Adding polyvinyl chloride resin and filler into an internal mixer, uniformly mixing, and adding a plasticizer, a temperature-controllable foaming agent, an antioxidant and a flame retardant into the internal mixer, and uniformly mixing again;
(2) And (3) adding the plasticizing material obtained in the step (1) into a foaming furnace for foaming, wherein the product is the PVC material.
In some embodiments of the invention, the foaming temperature is 220-240 ℃ (e.g., may be 220 ℃,221 ℃,222 ℃,223 ℃,224 ℃,225 ℃,226 ℃,227 ℃,228 ℃,229 ℃,230 ℃,231 ℃,232 ℃,233 ℃,234 ℃,235 ℃,236 ℃,237 ℃,238 ℃,239 ℃,240 ℃, or any value therein).
In some embodiments of the invention, the foaming time is from 2 to 3 minutes (e.g., may be 2 minutes, 2.5 minutes, 3 minutes, or any value therein).
Compared with the prior art, the invention has the following beneficial effects:
(1) The temperature-controllable foaming PVC material provided by the invention is prepared by using the temperature-controllable foaming agent, and has the advantages of good foaming controllability, good foaming initial temperature close to the melting point of PVC, good foaming uniformity and compact foam cells.
(2) The temperature-controllable foaming PVC material provided by the invention has the advantages that the used temperature-controllable foaming agent has good compatibility with the PVC material, the bubble structure is uniform and regular, the density of the PVC material is effectively reduced, and the weight is light;
(3) The PVC material capable of controlling the temperature to foam has a uniform and compact cell structure, when the material is subjected to an external load, the load is dispersed to adjacent cells along the cell wall, and at the moment, the good cell structure can passivate crack tips and tissue crack propagation, so that the impact strength of the material is effectively improved;
(4) The preparation method is simple and safe in preparation process, can be widely applied to various polymer foaming materials, and has good industrial application prospect.
Detailed Description
The invention will be described below in connection with specific embodiments. The following examples are illustrative of the present invention and are not intended to limit the present invention. Other combinations and various modifications within the spirit of the invention may be made without departing from the spirit or scope of the invention.
Preparation of triazene Polymer I
The preparation method comprises the following steps:
(1) 1mol of 4,4' -diaminodiphenyl ether is taken and dissolved in hydrochloric acid with the concentration of 50 percent, mechanical stirring is carried out for 30min to obtain milky turbid liquid, then the milky turbid liquid is placed in an ice water bath for stirring and cooling, 1mol of sodium nitrite is taken and dissolved in 5ml of water, the sodium nitrite aqueous solution is dropwise added into a reaction bottle, the reactant gradually becomes clear from turbid liquid, and finally becomes light yellow transparent clear solution;
(2) Adjusting the pH value to 9-10, dissolving 1.2mol of anhydrous piperazine in 30ml of water, then adding the water into the reactant, vigorously stirring under ice bath conditions, precipitating a large amount of beige solid, continuously stirring and reacting for 1h, filtering, washing with water, and drying to obtain brown solid, namely the triazene polymer.
Preparation of triazene Polymer II
The preparation method comprises the following steps:
(1) 1mol of 4,4' -diaminodiphenyl ether is taken and dissolved in hydrochloric acid with the concentration of 50 percent, mechanical stirring is carried out for 30min to obtain milky turbid liquid, then the milky turbid liquid is placed in an ice water bath for stirring and cooling, 1mol of sodium nitrite is taken and dissolved in 5ml of water, the sodium nitrite aqueous solution is dropwise added into a reaction bottle, the reactant gradually becomes clear from turbid liquid, and finally becomes light yellow transparent clear solution;
(2) Adjusting the pH value to 9-10, dissolving 1.2mol of 1, 6-hexamethylenediamine in 30ml of water, then adding the solution into the product of the step (1), vigorously stirring under the ice bath condition, precipitating a large amount of beige solid, continuing stirring and reacting for 1h, filtering, washing with water, and drying to obtain brown solid, namely the triazene polymer I-2-2.
Preparation of temperature-controllable foaming agent I
The preparation method comprises the following steps:
(1) Uniformly mixing 0.15mol of urea and 0.1mol of formaldehyde, and dissolving with deionized water;
(2) Heating the system to 70 ℃, and stirring to obtain a prepolymer;
(3) Adding 2mol of triazene polymer I into a system, adding PVA1799, and dispersing into uniform and stable emulsion;
(4) Adding dilute hydrochloric acid to regulate pH to 2-3, starting polymerization, heating and curing reaction, regulating pH to 7-9 with sodium hydroxide, and removing water to obtain the final product.
Preparation of temperature-controllable foaming agent II
The preparation method comprises the following steps:
(1) Uniformly mixing 0.2mol of urea and 0.1mol of formaldehyde, and dissolving with deionized water;
(2) Heating the system to 70 ℃, and stirring to obtain a prepolymer;
(3) Adding 2.4mol of triazene polymer II into the system, adding PVA1788, and dispersing into uniform and stable emulsion;
(4) Adding dilute hydrochloric acid to regulate pH to 2-3, starting polymerization, heating and curing reaction, regulating pH to 7-9 with sodium hydroxide, and removing water to obtain the final product.
Example 1
The temperature-controllable foaming PVC material comprises the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 20 parts of calcium carbonate, 0.1 part of a temperature-controllable foaming agent I, 20 parts of trioctyl trimellitate, 0.1 part of an antioxidant 1010 and 5 parts of brominated polystyrene resin PBS-64HW.
The preparation method comprises the following steps:
(1) Adding polyvinyl chloride resin and filler into an internal mixer, uniformly mixing, and adding a plasticizer, a temperature-controllable foaming agent, an antioxidant and a flame retardant into the internal mixer, and uniformly mixing again;
(2) And (3) adding the plasticizing material obtained in the step (1) into a foaming furnace for foaming, wherein the product is the PVC material.
Example 2
The temperature-controllable foaming PVC material comprises the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 25 parts of silicon dioxide, 0.3 part of a temperature-controllable foaming agent I, 25 parts of phthalic diester, 0.2 part of an antioxidant 626, and 10 parts of brominated polystyrene resin PBS-64 HW.
The preparation method is the same as in example 1.
Example 3
The temperature-controllable foaming PVC material comprises the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 30 parts of talcum powder, 0.4 part of temperature-controllable foaming agent I, 30 parts of epoxidized soybean oil stearate, 0.3 part of antioxidant 626, and 15 parts of brominated polystyrene resin PBS-64 HW.
The preparation method is the same as in example 1.
Example 4
The temperature-controllable foaming PVC material comprises the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 35 parts of talcum powder, 0.5 part of temperature-controllable foaming agent I, 35 parts of trioctyl trimellitate, 0.4 part of antioxidant 1010 and 20 parts of brominated polystyrene resin PBS-64 HW.
The preparation method is the same as in example 1.
Example 5
The temperature-controllable foaming PVC material comprises the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 40 parts of calcium carbonate, 0.1 part of a temperature-controllable foaming agent II, 40 parts of epoxidized soybean oil stearate, 0.5 part of an antioxidant 626 and 5 parts of polybrominated styrene.
The preparation method is the same as in example 1.
Example 6
The temperature-controllable foaming PVC material comprises the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 20 parts of silicon dioxide, 0.3 part of a temperature-controllable foaming agent II, 40 parts of trioctyl trimellitate, 0.5 part of an antioxidant 626 and 10 parts of polybrominated styrene.
The preparation method is the same as in example 1.
Example 7
The temperature-controllable foaming PVC material comprises the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 40 parts of talcum powder, 0.4 part of temperature-controllable foaming agent II, 20 parts of epoxidized soybean oil stearate, 0.1 part of antioxidant 1010 and 15 parts of polybrominated styrene.
The preparation method is the same as in example 1.
Example 8
The temperature-controllable foaming PVC material comprises the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 33 parts of calcium carbonate, 0.5 part of a temperature-controllable foaming agent II, 28 parts of epoxidized soybean oil stearate, 0.3 part of an antioxidant 1010 and 20 parts of polybrominated styrene.
The preparation method is the same as in example 1.
Comparative example
The difference from example 1 is that: the foaming agent is prepared by compounding sodium bicarbonate and azodicarbonamide.
The PVC materials of the examples and comparative examples were respectively selected for performance testing as follows:
(1) And (3) density detection: detection according to GB/T6343-2009;
(2) Surface microscopic morphology observation: observing the shape of the cross section bubble by using a scanning electron microscope;
(3) Impact resistance test: according to GB/T1043-2008 test.
The measurement results are shown in Table 1:
table 1 results of measurement of the index related to the temperature-controllable foamed PVC material of examples and comparative examples
As can be seen from comparison of comparative example 1 and example 1, the PVC material prepared in example 1 has uniform foaming, a higher initial foaming temperature, a melting point similar to that of PVC, and good uniformity, low density and good impact resistance. As can be seen from the comparison of the comparative examples and the examples, the PVC material provided by the invention is prepared from the foaming agent with controllable temperature, the foaming agent has good compatibility with the PVC material, the foaming temperature is nearly consistent with the melting point of the PVC material, the foaming uniformity is good, the cells are compact, the density of the PVC material is effectively reduced, and the weight is light; when the material is subjected to an external load, the load can be dispersed to adjacent cells along the cell walls, and at the moment, the good cell structure can passivate crack tips and structure crack propagation, so that the impact strength of the material is effectively improved.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement it, but not limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (10)
1. The temperature-controllable foaming PVC material is characterized by comprising the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 20-40 parts of filler, 0.1-0.5 part of temperature-controllable foaming agent, 20-40 parts of plasticizer, 0.1-0.5 part of antioxidant and 5-20 parts of flame retardant.
2. The temperature-controllable, foamed PVC material according to claim 1, wherein the filler is one or a combination of talc, calcium carbonate, silica.
3. The temperature-controllable, foamed PVC material of claim 1, wherein the plasticizer is one or more of epoxidized soybean oil stearate, trioctyl trimellitate, and a phthalate diester.
4. The temperature-controllable, foamed PVC material according to claim 1, wherein the antioxidant is an antioxidant 626 or an antioxidant 1010.
5. The temperature-controllable, foamed PVC material according to claim 1, wherein the flame retardant is brominated polystyrene resin PBS-64HW or polybrominated styrene.
6. The temperature-controllable, foamed PVC material according to claim 1, wherein the temperature-controllable microsphere foaming agent comprises a package material and a core material located inside the package material, the package material being urea formaldehyde resin, the core material being a triazene polymer, wherein the triazene polymer is selected from the group consisting of compounds of the following formulae I-1 and/or I-2:
wherein a is an integer of 1 to 7, and b is an integer of 1 to 5.
7. The temperature-controllable blowing agent of claim 1, wherein the temperature-controllable blowing agent preparation method comprises the steps of:
(1) Uniformly mixing urea and formaldehyde, and dissolving the urea and the formaldehyde by deionized water;
(2) Heating the system and stirring to obtain a prepolymer;
(3) Adding a triazene polymer into a system, adding an emulsifier, and dispersing into a uniform and stable emulsion;
(4) Adjusting the PH to 2-3, starting polymerization, heating and curing reaction, adjusting the PH to about 7-9, and removing water to obtain the temperature-controllable foaming agent.
8. The method for preparing a temperature-controllable foaming agent according to claim 7, wherein the molar ratio of urea to formaldehyde in the step (1) is 1.5-2:1, the mass of deionized water is 2-4 times of the sum of the mass of urea and formaldehyde; heating the system in the step (2) to 70-80 ℃; the mass of the triazene polymer in the step (3) is 8-9 times of that of the packaging material, and the emulsifier is PVA1788 or PVA1799.
9. The method for preparing the temperature-controllable foaming PVC material as claimed in any one of claims 1 to 8, which comprises the following steps:
(1) Adding polyvinyl chloride resin and filler into an internal mixer, uniformly mixing, and adding a plasticizer, a temperature-controllable foaming agent, an antioxidant and a flame retardant into the internal mixer, and uniformly mixing again;
(2) And (3) adding the plasticizing material obtained in the step (1) into a foaming furnace for foaming, wherein the product is the PVC material.
10. Use of a temperature controllable foamed PVC material according to any one of claims 1 to 9 for the preparation of a footpad.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB645115A (en) * | 1947-10-16 | 1950-10-25 | Us Rubber Co | Improvements in gas expanded material and method of making same |
| GB783745A (en) * | 1954-12-14 | 1957-09-25 | American Cyanamid Co | Production of cellular cured polymeric material |
| US3425963A (en) * | 1964-02-19 | 1969-02-04 | Ontario Research Foundation | Mixtures of blowing agents and foamable compositions of matter employing the same |
| US3836382A (en) * | 1971-09-21 | 1974-09-17 | Ciba Geigy Ag | Pressure-sensitive copying material |
| CN105753755A (en) * | 2016-03-21 | 2016-07-13 | 山西大同大学 | 3, 3'-dimethylthio-4, 4'-bis(2,6-dichloro-4-nitrophenyl diazoamino) biphenyl, preparation method and application |
| CN106977923A (en) * | 2017-03-31 | 2017-07-25 | 广东工业大学 | A kind of triazenes mixture and preparation method thereof |
| CN110590597A (en) * | 2019-09-25 | 2019-12-20 | 浙江工业大学 | A kind of preparation method of aryl triazene compound |
| CN110845956A (en) * | 2019-12-09 | 2020-02-28 | 杨国亭 | Wear-resistant coating for new energy automobile and preparation method thereof |
| CN112679784A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Foaming agent, PVC foaming composition prepared from foaming agent and preparation method of PVC foaming composition |
-
2022
- 2022-09-07 CN CN202211088951.XA patent/CN116218097B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB645115A (en) * | 1947-10-16 | 1950-10-25 | Us Rubber Co | Improvements in gas expanded material and method of making same |
| GB783745A (en) * | 1954-12-14 | 1957-09-25 | American Cyanamid Co | Production of cellular cured polymeric material |
| US3425963A (en) * | 1964-02-19 | 1969-02-04 | Ontario Research Foundation | Mixtures of blowing agents and foamable compositions of matter employing the same |
| US3836382A (en) * | 1971-09-21 | 1974-09-17 | Ciba Geigy Ag | Pressure-sensitive copying material |
| CN105753755A (en) * | 2016-03-21 | 2016-07-13 | 山西大同大学 | 3, 3'-dimethylthio-4, 4'-bis(2,6-dichloro-4-nitrophenyl diazoamino) biphenyl, preparation method and application |
| CN106977923A (en) * | 2017-03-31 | 2017-07-25 | 广东工业大学 | A kind of triazenes mixture and preparation method thereof |
| CN110590597A (en) * | 2019-09-25 | 2019-12-20 | 浙江工业大学 | A kind of preparation method of aryl triazene compound |
| CN112679784A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Foaming agent, PVC foaming composition prepared from foaming agent and preparation method of PVC foaming composition |
| CN110845956A (en) * | 2019-12-09 | 2020-02-28 | 杨国亭 | Wear-resistant coating for new energy automobile and preparation method thereof |
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