CN117304571B - Nanoparticle modified PVC heat stabilizer and preparation method thereof - Google Patents
Nanoparticle modified PVC heat stabilizer and preparation method thereof Download PDFInfo
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- CN117304571B CN117304571B CN202311621193.8A CN202311621193A CN117304571B CN 117304571 B CN117304571 B CN 117304571B CN 202311621193 A CN202311621193 A CN 202311621193A CN 117304571 B CN117304571 B CN 117304571B
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- titanium dioxide
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- 239000012760 heat stabilizer Substances 0.000 title claims abstract description 48
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003381 stabilizer Substances 0.000 claims abstract description 49
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 26
- 229920005862 polyol Polymers 0.000 claims abstract description 24
- 150000003077 polyols Chemical class 0.000 claims abstract description 24
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 22
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims abstract description 22
- 235000013539 calcium stearate Nutrition 0.000 claims abstract description 22
- 239000008116 calcium stearate Substances 0.000 claims abstract description 22
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002480 mineral oil Substances 0.000 claims abstract description 18
- 235000010446 mineral oil Nutrition 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 16
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- 239000007822 coupling agent Substances 0.000 claims description 18
- 239000004408 titanium dioxide Substances 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000002041 carbon nanotube Substances 0.000 claims description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 7
- 239000002079 double walled nanotube Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 15
- 230000007774 longterm Effects 0.000 abstract description 6
- 239000004800 polyvinyl chloride Substances 0.000 description 76
- 229920000915 polyvinyl chloride Polymers 0.000 description 76
- 230000000052 comparative effect Effects 0.000 description 16
- 239000011701 zinc Substances 0.000 description 7
- 239000011575 calcium Substances 0.000 description 6
- 239000006084 composite stabilizer Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 241000282326 Felis catus Species 0.000 description 5
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- XKORCTIIRYKLLG-ARJAWSKDSA-N methyl (z)-3-aminobut-2-enoate Chemical compound COC(=O)\C=C(\C)N XKORCTIIRYKLLG-ARJAWSKDSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- JNMGZPCAABLYPO-UHFFFAOYSA-N 1,2,2,3-tetramethylcyclohexan-1-ol Chemical compound CC1CCCC(C)(O)C1(C)C JNMGZPCAABLYPO-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical group ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- -1 salt compound Chemical class 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
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- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D333/40—Thiophene-2-carboxylic acid
-
- 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
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- 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
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- 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
- C08K5/07—Aldehydes; Ketones
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- 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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- 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
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
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- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- 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
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- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
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- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a nanoparticle modified PVC heat stabilizer and a preparation method thereof, and belongs to the technical field of PVC heat stabilizers, wherein the nanoparticle modified PVC heat stabilizer comprises the following raw materials in parts by weight: 6-10 parts of calcium stearate, 12-17 parts of zinc stearate, 20-25 parts of auxiliary stabilizer, 7-16 parts of polyol, 1-3 parts of beta-methyl aminocrotonate, 5-10 parts of beta-diketone, 3-8 parts of bisphenol A diglycidyl ether, 2-5 parts of antioxidant, 4-8 parts of modified titanium dioxide and 4-9 parts of mineral oil; the invention also provides a preparation method of the auxiliary stabilizer and the modified titanium dioxide. The nanoparticle modified PVC heat stabilizer provided by the invention can improve the long-term heat stability of PVC materials, can improve the mechanical properties of PVC, and solves the problem that the transparency of PVC products is not high after the existing heat stabilizer is added.
Description
Technical Field
The invention belongs to the technical field of PVC heat stabilizers, and particularly relates to a nanoparticle modified PVC heat stabilizer and a preparation method thereof.
Background
Polyvinyl chloride plastic is polymerized from vinyl chloride monomer, is one of common thermoplastic plastics, and has the commodity name of chlorine plastic, and is abbreviated as PVC. As one of the most productive general plastics in the world, PVC is very widely used, and is widely used in 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.
PVC is widely used as a protective panel in engineering and equipment fields for the following reasons: chemical resistance: PVC has excellent corrosion resistance and good resistance to various chemicals such as acids, bases, salts, etc. Therefore, the PVC protection plate can effectively protect equipment from corrosion, and prolong the service life of the equipment. Insulation properties: PVC is a good insulating material that can prevent the flow of electricity. In some equipment needing electrical insulation protection, the occurrence of electrical accidents can be reduced by using PVC protection plates. Abrasion resistance: the PVC protection plate has smooth surface and certain hardness, and can effectively resist friction and abrasion. This is important in situations where the device needs to be constantly in contact, movement or friction, and can protect the device surface from scratches or abrasion. And (3) light weight: compared with other materials, the PVC protection plate has lighter weight, so that the installation is more convenient. Meanwhile, the flexible plastic composite material also has certain flexibility, can be bent or cut according to the needs, and is suitable for equipment with different shapes. Economical and practical: PVC is a relatively economical material with lower costs than other panel materials. This makes PVC shields a widely used option.
The PVC plastic has the advantages of nonflammability, strong corrosion resistance to chemical agents, difficult abrasion and good electrical insulation, and besides, the PVC plastic has mature production process, low price and easy processing and forming. Pure polyvinyl chloride resins are rigid thermoplastic materials whose inherent molecular structure determines the instability due to the presence of defective structures on the PVC molecular chain, such as allyl chloride groups, end groups, oxygen-containing groups, head-to-head structures, etc. Therefore, in order to prevent the PVC article from deteriorating and discoloring during use, a heat stabilizer is added to make it more stable. PVC decomposition temperature is very close to plasticizing temperature, and degradation easily occurs in the heating process, so that severe color change and mechanical property degradation occur on the surface of PVC materials, and therefore, thermal degradation of PVC must be inhibited by adding a proper heat stabilizer. Common PVC heat stabilizers are lead salt composite stabilizers, organic tin stabilizers and calcium-zinc composite stabilizers. However, lead salt compound stabilizer and organic tin stabilizer have certain toxicity, while calcium-zinc compound stabilizer is a good nontoxic stabilizer, and the thermal stabilization effect of the calcium-zinc compound stabilizer is equivalent to that of lead salt stabilizer, so that the calcium-zinc compound stabilizer is widely applied.
Disclosure of Invention
The invention aims to provide a nanoparticle modified PVC heat stabilizer and a preparation method thereof, wherein the nanoparticle modified PVC heat stabilizer can improve the long-term heat stability of PVC materials, improve the mechanical properties of PVC, and solve the problem that the transparency of PVC products is not high after the existing heat stabilizer is added.
In order to achieve the above object, the present invention provides the following technical solutions:
the nanoparticle modified PVC heat stabilizer comprises the following raw materials in parts by weight: 6-10 parts of calcium stearate, 12-17 parts of zinc stearate, 20-25 parts of auxiliary stabilizer, 7-16 parts of polyol, 1-3 parts of beta-methyl aminocrotonate, 5-10 parts of beta-diketone, 3-8 parts of bisphenol A diglycidyl ether, 2-5 parts of antioxidant, 4-8 parts of modified titanium dioxide and 4-9 parts of mineral oil; the auxiliary stabilizer has the following structural formula:
。
beta-aminocrotonate methyl ester, CAS:14205-39-1.
Bisphenol A diglycidyl ether, CAS 1675-54-3.
Mineral oil, CAS:8042-47-5.
Further, the preparation method of the auxiliary stabilizer comprises the following steps: in terms of the weight portions of the components,
(1) Mixing 1 part of 3-sulfonylamino methyl acetate-2-thiophenecarboxylic acid methyl ester (CAS: 106820-63-7) and 30-35 parts of 2.5-3mol/L NaOH aqueous solution, reacting for 2 hours at 65-70 ℃, cooling to room temperature, standing for 15-20 hours at-20 ℃, adjusting the pH of the solution to 2, filtering and drying to obtain a product A;
(2) Mixing 1 part of the product A with 10-12 parts of phosphorus trichloride, carrying out reflux reaction for 6-7h, and carrying out reduced pressure distillation to obtain a product B;
(3) Reflux-reacting 1 part of product B with 20-30 parts of isopropanol at 85-90 ℃ for 15-20h, cooling to room temperature, distilling under reduced pressure, and adopting a silica gel column according to the volume ratio of 1:2, petroleum ether/ethyl acetate is eluted to obtain the auxiliary stabilizer.
Further, the reflux temperature in the step (2) is 70-75 ℃.
Further, the mass ratio of the auxiliary stabilizer to the polyol to the beta-methyl aminocrotonate to the beta-diketone to the bisphenol A diglycidyl ether is 4-5:2-3:0.2-0.4:1-2:1.
PVC is often used as equipment guard plate, and PVC decomposition temperature is very close with plasticizing temperature, and plasticizing temperature can lead to PVC decomposition temperature in the mould in-process, usually adds the heat stabilizer, and calcium zinc heat stabilizer is because nontoxic safety, and Ca/Zn complex heat stabilizer is the most widely used PVC heat stabilizer at present, but zinc chloride that zinc salt produced in the use can catalyze the degradation of PVC, takes place "zinc burn" phenomenon, makes its long-term heat stabilization effect relatively poor. Because PVC equipment guard plate generally needs to shape according to different equipment, and the time of being heated is long in the shaping process repeatedly, current Ca/Zn complex heat stabilizer adds in the PVC back, bears the time of heating and can't satisfy the shaping time requirement of PVC guard plate, can appear blackening phenomenon. The self-made auxiliary stabilizer is added to be compounded with a plurality of common auxiliary stabilizers on the market, so that the Ca/Zn composite stabilizer has excellent synergistic effect, and the long-term heat stability effect of the Ca/Zn composite stabilizer can be greatly improved. And the inventors have unexpectedly found that when the mass ratio of the self-made auxiliary stabilizer, the polyol, the beta-methyl aminocrotonate, the beta-diketone and the bisphenol A diglycidyl ether of the present invention is 4-5:2-3:0.2-0.4:1-2: when 1, the PVC is added into PVC, so that the mechanical property of the PVC is improved.
Further, the preparation method of the modified titanium dioxide comprises the following steps: according to the weight parts, (1) 100 parts of titanium dioxide, 8-10 parts of gamma-glycidoxypropyl trimethoxysilane and 1-2 parts of calcium stearate are mixed, and stirred for 30-35min at 85 ℃; (2) Heating to 120 ℃, continuously adding 5-7 parts of titanate coupling agent, 2-3 parts of lanthanum oxide, 4-5 parts of glass powder and 1-3 parts of carbon nano tube, and stirring for 30-40min to obtain the modified titanium dioxide.
Further, the carbon nanotubes are double-walled carbon nanotubes, diameter: 2-4 nm, length: 0.5-2 μm, and specific surface area of 350-450m 2 And/g. Purchased from qinfeng nano.
The equipment guard board has higher transparency requirement, is attractive, and can accurately monitor equipment, and the inventor finds that the compound heat stabilizer has better heat stabilization effect, but the prepared PVC product has low transparency and cannot be used in PVC soft products with higher transparency requirement. The compatibility of the commercial titanium dioxide and the self-made stabilizer provided by the invention is poor, and the transparency improving effect is not obvious after the addition. According to the invention, the transparency of the PVC product added with the stabilizer is improved by adding the modified titanium dioxide, so that the quality of the product is greatly improved. After the modified titanium dioxide is added, the compatibility of the raw materials and the PVC matrix in the system is improved, and the transparency of the product is further improved.
The titanate coupling agent is a titanate coupling agent NXH-401. Purchased from nanjing pavilion, new materials technology limited.
The average particle size of the glass frit was 7 μm, purchased from amp Mi Wei na, cat: t801.
The particle size of the titanium dioxide is 10-15 mu m, and the titanium dioxide is purchased from Shanghai river-jumping titanium dioxide chemical products Co.
Further, the polyol is selected from one or more of pentaerythritol, dipentaerythritol, polyvinyl alcohol, tetramethyl cyclohexanol, and ditrimethylolpropane.
Further, the antioxidant is selected from one or more of antioxidant 1076, antioxidant 1031, and antioxidant 1010.
The invention also provides a preparation method of the nanoparticle modified PVC heat stabilizer, which comprises the following steps: mixing the calcium stearate, the zinc stearate, the auxiliary stabilizer, the mineral oil, the antioxidant and the modified titanium dioxide, stirring and refluxing for 40min at 100 ℃, then sequentially adding the polyol, the beta-methyl aminocrotonate, the beta-diketone and the bisphenol A diglycidyl ether, stirring and refluxing for 20min at 110 ℃, and cooling to room temperature to obtain the nanoparticle modified PVC heat stabilizer.
Compared with the prior art, the invention has the advantages that:
1. the invention provides a nanoparticle modified PVC heat stabilizer and a preparation method thereof, and the prepared heat stabilizer can improve the heat stability and mechanical properties of PVC materials and simultaneously improve the problem of low transparency of PVC products after the existing heat stabilizer is added.
2. The Ca/Zn composite stabilizer is compounded with a plurality of auxiliary stabilizers which are common in the market by adding the self-made auxiliary stabilizers, has excellent synergistic effect, and can greatly improve the long-term heat stability effect of the Ca/Zn composite stabilizer.
3. When the self-made auxiliary stabilizer, the polyol, the beta-methyl aminocrotonate, the beta-diketone and the bisphenol A diglycidyl ether are prepared according to the mass ratio of 4-5:2-3:0.2-0.4:1-2:1, the mechanical properties of the PVC are improved.
4. According to the invention, the transparency of the PVC product added with the stabilizer is improved by adding the modified titanium dioxide, so that the quality of the product is greatly improved. After the modified titanium dioxide is added, the compatibility of the raw materials of the system and the PVC matrix is improved, and the transparency of the product is improved.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The raw materials of the invention are purchased from the following manufacturers, and the other raw materials are all commercially available unless otherwise specified:
beta-aminocrotonic acid methyl ester: purchased from aladine, cat No.: A102015.
bisphenol a diglycidyl ether, available from aladine, cat: and B131786.
Mineral oil, available from aladine, cat No.: m274343.
Methyl 3-sulfonylamino acetate-2-thiophenecarboxylate, available from Jiangsu Pu Le Si Biotech Co.
Pentaerythritol, available from merck, cat: 236241.
the carbon nanotubes are double-walled carbon nanotubes with diameters: 2-4 nm, length: 0.5-2 μm, and specific surface area of 350-450m 2 And/g. Purchased from qinfeng nano.
The titanate coupling agent is a titanate coupling agent NXH-401. Purchased from nanjing pavilion, new materials technology limited.
The average particle size of the glass frit was 7 μm, purchased from amp Mi Wei na, cat: t801.
The particle size of the titanium dioxide is 10-15 mu m, and the titanium dioxide is purchased from Shanghai river-jumping titanium dioxide chemical products Co.
Gamma-glycidoxypropyl trimethoxysilane, available from merck, cat: 440167.
antioxidant 1076, available from new materials technologies, inc.
Dibenzoyl peroxide, available from new materials technologies, inc.
2-acrylamido-2-methylpropanesulfonic acid, available from new materials technologies, inc. of Jewelry, qingdao.
The alumina had an average particle size of 10 μm and was purchased from Tianjin Gao Ke New Material technology Co., ltd.
The average particle size of the diatomite is 20 mu m, and the diatomite is purchased from Tianjin Gaokui New Material technology Co., ltd.
Example 1
The embodiment provides a nanoparticle modified PVC heat stabilizer, which comprises the following raw materials in parts by weight: 8 parts of calcium stearate, 15 parts of zinc stearate, 22 parts of auxiliary stabilizer, 12 parts of polyol, 1.5 parts of beta-methyl aminocrotonate, 8 parts of beta-diketone, 5 parts of bisphenol A diglycidyl ether, 3 parts of antioxidant, 6 parts of modified titanium dioxide and 7 parts of mineral oil; the auxiliary stabilizer has the following structural formula:
。
the preparation method of the auxiliary stabilizer comprises the following steps: in terms of the weight portions of the components,
(1) Mixing 1 part of 3-sulfonylamino methyl acetate-2-thiophenecarboxylic acid methyl ester with 32 parts of 2.5mol/L NaOH aqueous solution, reacting at 67 ℃ for 2 hours, cooling to room temperature, standing at-20 ℃ for 18 hours, adjusting the pH of the solution to 2, and carrying out suction filtration and drying to obtain a product A;
(2) Mixing 1 part of product A with 11 parts of phosphorus trichloride, carrying out reflux reaction for 6.5 hours at 72 ℃, and carrying out reduced pressure distillation to obtain a product B;
(3) Reflux-reacting 1 part of product B with 25 parts of isopropanol at 87 ℃ for 17 hours, cooling to room temperature, distilling under reduced pressure, and adopting a silica gel column according to the volume ratio of 1:2, petroleum ether/ethyl acetate is eluted to obtain the auxiliary stabilizer.
The preparation method of the modified titanium dioxide comprises the following steps: mixing 100 parts of titanium dioxide, 9 parts of gamma-glycidoxypropyl trimethoxysilane and 1.5 parts of calcium stearate according to parts by weight, and stirring for 30min at 85 ℃; (2) Heating to 120 ℃, continuously adding 6 parts of titanate coupling agent, 3 parts of lanthanum oxide, 4 parts of glass powder and 2 parts of carbon nano tube, and stirring for 35min to obtain the modified titanium dioxide.
The carbon nanotubes are double-wall carbon nanotubes with the diameter: 2-4 nm, length: 0.5-2 mu m, and a specific surface area of 350-450m 2 /g。
The titanate coupling agent is a titanate coupling agent NXH-401.
The average particle diameter of the glass frit was 7. Mu.m.
The particle size of the titanium dioxide is 10-15 mu m.
The polyol is pentaerythritol.
The antioxidant is selected from antioxidants 1076.CAS:2082-79-3.
The invention also provides a preparation method of the nanoparticle modified PVC heat stabilizer, which comprises the following steps: mixing the calcium stearate, the zinc stearate, the auxiliary stabilizer, the mineral oil, the antioxidant and the modified titanium dioxide, stirring and refluxing for 40min at 100 ℃, then sequentially adding the polyol, the beta-methyl aminocrotonate, the beta-diketone and the bisphenol A diglycidyl ether, stirring and refluxing for 20min at 110 ℃, and cooling to room temperature to obtain the nanoparticle modified PVC heat stabilizer.
Example 2
The embodiment provides a nanoparticle modified PVC heat stabilizer, which comprises the following raw materials in parts by weight: 7 parts of calcium stearate, 17 parts of zinc stearate, 20 parts of auxiliary stabilizer, 8 parts of polyol, 1 part of beta-methyl aminocrotonate, 7 parts of beta-diketone, 4 parts of bisphenol A diglycidyl ether, 3 parts of antioxidant, 8 parts of modified titanium dioxide and 9 parts of mineral oil; the auxiliary stabilizer has the following structural formula:
。
the preparation method of the auxiliary stabilizer comprises the following steps: in terms of the weight portions of the components,
(1) Mixing 1 part of 3-sulfonylamino methyl acetate-2-thiophenecarboxylic acid methyl ester with 32 parts of 2.5mol/L NaOH aqueous solution, reacting at 67 ℃ for 2 hours, cooling to room temperature, standing at-20 ℃ for 18 hours, adjusting the pH of the solution to 2, and carrying out suction filtration and drying to obtain a product A;
(2) Mixing 1 part of product A with 11 parts of phosphorus trichloride, carrying out reflux reaction for 6.5 hours at 72 ℃, and carrying out reduced pressure distillation to obtain a product B;
(3) Reflux-reacting 1 part of product B with 25 parts of isopropanol at 87 ℃ for 17 hours, cooling to room temperature, distilling under reduced pressure, and adopting a silica gel column according to the volume ratio of 1:2, petroleum ether/ethyl acetate is eluted to obtain the auxiliary stabilizer.
The preparation method of the modified titanium dioxide comprises the following steps: mixing 100 parts of titanium dioxide, 9 parts of gamma-glycidoxypropyl trimethoxysilane and 1.5 parts of calcium stearate according to parts by weight, and stirring for 30min at 85 ℃; (2) Heating to 120 ℃, continuously adding 6 parts of titanate coupling agent, 3 parts of lanthanum oxide, 4 parts of glass powder and 2 parts of carbon nano tube, and stirring for 35min to obtain the modified titanium dioxide.
The carbon nanotubes are double-wall carbon nanotubes with the diameter: 2-4 nm, length: 0.5-2 mu m, and a specific surface area of 350-450m 2 /g。
The titanate coupling agent is a titanate coupling agent NXH-401.
The average particle diameter of the glass frit was 7. Mu.m.
The particle size of the titanium dioxide is 10-15 mu m.
The polyol is pentaerythritol.
The antioxidant is selected from antioxidants 1076.CAS:2082-79-3.
The invention also provides a preparation method of the nanoparticle modified PVC heat stabilizer, which comprises the following steps: mixing the calcium stearate, the zinc stearate, the auxiliary stabilizer, the mineral oil, the antioxidant and the modified titanium dioxide, stirring and refluxing for 40min at 100 ℃, then sequentially adding the polyol, the beta-methyl aminocrotonate, the beta-diketone and the bisphenol A diglycidyl ether, stirring and refluxing for 20min at 110 ℃, and cooling to room temperature to obtain the nanoparticle modified PVC heat stabilizer.
Example 3
The embodiment provides a nanoparticle modified PVC heat stabilizer, which comprises the following raw materials in parts by weight: 9 parts of calcium stearate, 13 parts of zinc stearate, 24 parts of auxiliary stabilizer, 15 parts of polyol, 2.2 parts of beta-methyl aminocrotonate, 6 parts of beta-diketone, 7 parts of bisphenol A diglycidyl ether, 2 parts of antioxidant, 7 parts of modified titanium dioxide and 8 parts of mineral oil; the auxiliary stabilizer has the following structural formula:
。
the preparation method of the auxiliary stabilizer comprises the following steps: in terms of the weight portions of the components,
(1) Mixing 1 part of 3-sulfonylamino methyl acetate-2-thiophenecarboxylic acid methyl ester with 32 parts of 2.7mol/L NaOH aqueous solution, reacting at 67 ℃ for 2 hours, cooling to room temperature, standing at-20 ℃ for 18 hours, adjusting the pH of the solution to 2, and carrying out suction filtration and drying to obtain a product A;
(2) Mixing 1 part of product A with 12 parts of phosphorus trichloride, carrying out reflux reaction for 6.5 hours at 72 ℃, and carrying out reduced pressure distillation to obtain a product B;
(3) Reflux-reacting 1 part of product B with 24 parts of isopropanol at 87 ℃ for 17 hours, cooling to room temperature, distilling under reduced pressure, and adopting a silica gel column according to the volume ratio of 1:2, petroleum ether/ethyl acetate is eluted to obtain the auxiliary stabilizer.
The preparation method of the modified titanium dioxide comprises the following steps: mixing 100 parts of titanium dioxide, 98 parts of gamma-glycidoxypropyl trimethoxysilane and 2 parts of calcium stearate according to parts by weight, and stirring for 35min at 85 ℃; (2) Heating to 120 ℃, continuously adding 7 parts of titanate coupling agent, 32 parts of lanthanum oxide, 4.5 parts of glass powder and 2.7 parts of carbon nano tube, and stirring for 35min to obtain the modified titanium dioxide.
The carbon nanotubes are double-wall carbon nanotubes with the diameter: 2-4 nm, length: 0.5-2 mu m, and a specific surface area of 350-450m 2 /g。
The titanate coupling agent is a titanate coupling agent NXH-401.
The average particle diameter of the glass frit was 7. Mu.m.
The particle size of the titanium dioxide is 10-15 mu m.
The polyol is pentaerythritol.
The antioxidant is selected from antioxidants 1076.CAS:2082-79-3.
The invention also provides a preparation method of the nanoparticle modified PVC heat stabilizer, which comprises the following steps: mixing the calcium stearate, the zinc stearate, the auxiliary stabilizer, the mineral oil, the antioxidant and the modified titanium dioxide, stirring and refluxing for 40min at 100 ℃, then sequentially adding the polyol, the beta-methyl aminocrotonate, the beta-diketone and the bisphenol A diglycidyl ether, stirring and refluxing for 20min at 110 ℃, and cooling to room temperature to obtain the nanoparticle modified PVC heat stabilizer.
Comparative example 1
The difference between this comparative example and example 1 is: the nanoparticle modified PVC heat stabilizer comprises the following raw materials in parts by weight: 15 parts of calcium stearate, 8 parts of zinc stearate, 15 parts of auxiliary stabilizer, 4 parts of polyol, 9 parts of beta-methyl aminocrotonate, 14 parts of beta-diketone, 1 part of bisphenol A diglycidyl ether, 4 parts of antioxidant, 3 parts of modified titanium dioxide and 6 parts of mineral oil.
Comparative example 2
The difference between this comparative example and example 1 is: the nanoparticle modified PVC heat stabilizer comprises the following raw materials in parts by weight: 9 parts of calcium stearate, 14 parts of zinc stearate, 25 parts of auxiliary stabilizer, 7 parts of polyol, 3 parts of beta-methyl aminocrotonate, 5 parts of beta-diketone, 8 parts of bisphenol A diglycidyl ether, 3 parts of antioxidant, 5 parts of modified titanium dioxide and 6 parts of mineral oil.
Comparative example 3
The difference between this comparative example and example 1 is: the nanoparticle modified PVC heat stabilizer comprises the following raw materials in parts by weight: 7 parts of calcium stearate, 15 parts of zinc stearate, 22 parts of auxiliary stabilizer, 10 parts of polyol, 2 parts of epoxidized soybean oil, 7 parts of phosphite ester, 5 parts of bisphenol A diglycidyl ether, 3 parts of antioxidant, 5 parts of modified titanium dioxide and 7 parts of mineral oil.
Comparative example 4
The difference between this comparative example and example 1 is: the embodiment provides a nanoparticle modified PVC heat stabilizer, which comprises the following raw materials in parts by weight: 8 parts of calcium stearate, 15 parts of zinc stearate, 10 parts of auxiliary stabilizer, 18 parts of polyol, 6 parts of beta-methyl aminocrotonate, 2 parts of beta-diketone, 3 parts of antioxidant, 6 parts of modified titanium dioxide and 7 parts of mineral oil.
Comparative example 5
The difference between this comparative example and example 1 is: the embodiment provides a nanoparticle modified PVC heat stabilizer, which comprises the following raw materials in parts by weight: 8 parts of calcium stearate, 15 parts of zinc stearate, 14 parts of polyol, 1.5 parts of beta-aminocrotonic acid methyl ester, 18 parts of beta-diketone, 15 parts of bisphenol A diglycidyl ether, 3 parts of antioxidant, 6 parts of modified titanium dioxide and 7 parts of mineral oil.
Comparative example 6
The difference between this comparative example and example 1 is: the preparation method of the modified titanium dioxide comprises the following steps: 15 parts of titanium dioxide, 100 parts of acetone, 4 parts of dibenzoyl peroxide and 2 parts of 2-acrylamido-2-methylpropanesulfonic acid are mixed, reacted for 5 hours at 60 ℃, filtered and dried for 8-10 hours in an oven at 80 ℃ to obtain the modified titanium dioxide.
Comparative example 7
The difference between this comparative example and example 1 is: the preparation method of the modified titanium dioxide comprises the following steps: mixing 100 parts of titanium dioxide, 9 parts of gamma-glycidoxypropyl trimethoxysilane and 1 part of calcium stearate according to parts by weight, and stirring for 30min at 85 ℃; (2) Heating to 120 ℃, adding 6 parts of titanate coupling agent, continuously adding 2 parts of aluminum oxide and 4 parts of diatomite, and stirring for 35min to obtain the modified titanium dioxide. The average particle diameter of the alumina was 10. Mu.m, and the average particle diameter of the diatomaceous earth was 20. Mu.m.
Performance testing
PVC purchased from Shaanxi northwest metachemical group Co., ltd (SG-7) and nanoparticle-modified PVC heat stabilizer prepared in examples 1-2 and comparative examples 1-7 were mixed in a mass ratio of 100:4, blending and pressing to obtain a PVC sheet with the thickness of 1mm, placing the PVC sheet into a constant temperature ageing oven, controlling the temperature of the constant temperature ageing oven to be 190 ℃, observing the color of the PVC sheet every 10min, and recording the complete blackening time of the sample sheet. And (3) scanning the light transmittance of each wave band of the PVC sample in the wavelength range of 400-800nm by using a near infrared/visible/ultraviolet spectrophotometer, and measuring the light transmittance of the PVC sample. With reference to GB/T1040-2006, tensile strength and elongation at break are determined. The results are shown in Table 1.
TABLE 1 Performance test results
。
As can be seen from examples 1-3, the PVC heat stabilizer prepared by the invention has excellent long-term heat stability, and the PVC with the heat stabilizer has high light transmittance and excellent mechanical property. As is clear from comparative examples 1 to 7, the heat stabilizer was reduced in performance to various degrees by changing the composition of the raw materials and the preparation method.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (1)
1. The nanoparticle modified PVC heat stabilizer is characterized by comprising the following raw materials in parts by weight: 8 parts of calcium stearate, 15 parts of zinc stearate, 22 parts of auxiliary stabilizer, 12 parts of polyol, 1.5 parts of beta-methyl aminocrotonate, 8 parts of beta-diketone, 5 parts of bisphenol A diglycidyl ether, 3 parts of antioxidant, 6 parts of modified titanium dioxide and 7 parts of mineral oil; the auxiliary stabilizer has the following structural formula:；
the preparation method of the auxiliary stabilizer comprises the following steps: in terms of the weight portions of the components,
(1) Mixing 1 part of 3-sulfonylamino methyl acetate-2-thiophenecarboxylic acid methyl ester with 32 parts of 2.5mol/L NaOH aqueous solution, reacting at 67 ℃ for 2 hours, cooling to room temperature, standing at-20 ℃ for 18 hours, adjusting the pH of the solution to 2, and carrying out suction filtration and drying to obtain a product A;
(2) Mixing 1 part of product A with 11 parts of phosphorus trichloride, carrying out reflux reaction for 6.5 hours at 72 ℃, and carrying out reduced pressure distillation to obtain a product B;
(3) Reflux-reacting 1 part of product B with 25 parts of isopropanol at 87 ℃ for 17 hours, cooling to room temperature, distilling under reduced pressure, and adopting a silica gel column according to the volume ratio of 1:2, petroleum ether/ethyl acetate is eluted to obtain an auxiliary stabilizer;
the preparation method of the modified titanium dioxide comprises the following steps: mixing 100 parts of titanium dioxide, 9 parts of gamma-glycidoxypropyl trimethoxysilane and 1.5 parts of calcium stearate according to parts by weight, and stirring for 30min at 85 ℃; (2) Heating to 120 ℃, continuously adding 6 parts of titanate coupling agent, 3 parts of lanthanum oxide, 4 parts of glass powder and 2 parts of carbon nano tubes, and stirring for 35min to obtain modified titanium dioxide;
the carbon nanotubes are double-wall carbon nanotubes with the diameter: 2-4 nm, length: 0.5-2 mu m, and a specific surface area of 350-450m 2 /g；
The titanate coupling agent is a titanate coupling agent NXH-401;
the average particle diameter of the glass powder is 7 mu m;
the particle size of the titanium dioxide is 10-15 mu m;
the polyol is pentaerythritol;
the antioxidant is selected from antioxidants 1076;
the preparation method of the nanoparticle modified PVC heat stabilizer comprises the following steps: mixing the calcium stearate, the zinc stearate, the auxiliary stabilizer, the mineral oil, the antioxidant and the modified titanium dioxide, stirring and refluxing for 40min at 100 ℃, then sequentially adding the polyol, the beta-methyl aminocrotonate, the beta-diketone and the bisphenol A diglycidyl ether, stirring and refluxing for 20min at 110 ℃, and cooling to room temperature to obtain the nanoparticle modified PVC heat stabilizer.
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| WO2013137688A1 (en) * | 2012-03-16 | 2013-09-19 | Lg Hausys, Ltd. | Synthetic resin composition for pvc nontoxci windows, and nontoxic pvc windows |
| CN109096648A (en) * | 2018-08-08 | 2018-12-28 | 蚌埠市鑫晟新材料科技有限公司 | A kind of fretting map injection molding PVC buckle and its processing method |
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