CN116082760B - Modified PVC granules for explosion-proof hot water bag and preparation method thereof - Google Patents
Modified PVC granules for explosion-proof hot water bag and preparation method thereof Download PDFInfo
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- CN116082760B CN116082760B CN202211472235.1A CN202211472235A CN116082760B CN 116082760 B CN116082760 B CN 116082760B CN 202211472235 A CN202211472235 A CN 202211472235A CN 116082760 B CN116082760 B CN 116082760B
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- 239000008187 granular material Substances 0.000 title claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title description 9
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 83
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 83
- 239000004014 plasticizer Substances 0.000 claims abstract description 19
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000006084 composite stabilizer Substances 0.000 claims abstract description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 14
- 239000000314 lubricant Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims description 26
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 16
- 150000002148 esters Chemical class 0.000 claims description 15
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical group C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 claims description 14
- 125000004122 cyclic group Chemical group 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 229920006395 saturated elastomer Polymers 0.000 claims description 14
- 235000012424 soybean oil Nutrition 0.000 claims description 14
- 239000003549 soybean oil Substances 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 13
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 12
- 239000008158 vegetable oil Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 150000001412 amines Chemical group 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 239000008188 pellet Substances 0.000 claims description 8
- 150000008301 phosphite esters Chemical class 0.000 claims description 7
- QEDNBHNWMHJNAB-UHFFFAOYSA-N tris(8-methylnonyl) phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OCCCCCCCC(C)C QEDNBHNWMHJNAB-UHFFFAOYSA-N 0.000 claims description 7
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 235000021388 linseed oil Nutrition 0.000 claims description 3
- 239000000944 linseed oil Substances 0.000 claims description 3
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 230000032683 aging Effects 0.000 description 11
- -1 polyol ester Chemical class 0.000 description 10
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 7
- 239000008116 calcium stearate Substances 0.000 description 7
- 235000013539 calcium stearate Nutrition 0.000 description 7
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- GAWWVVGZMLGEIW-GNNYBVKZSA-L zinc ricinoleate Chemical compound [Zn+2].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O.CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O GAWWVVGZMLGEIW-GNNYBVKZSA-L 0.000 description 5
- 229940100530 zinc ricinoleate Drugs 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 4
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- FJRUWRJAJNEIKD-UHFFFAOYSA-N 2,3-dihydro-1,4-benzodioxine-6,7-diamine Chemical compound O1CCOC2=C1C=C(N)C(N)=C2 FJRUWRJAJNEIKD-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical group CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000009982 effect on human Effects 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ZIUHCEIEPOPBCK-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;hexanedioic acid;octadecanoic acid Chemical compound OCC(CO)(CO)CO.OC(=O)CCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O ZIUHCEIEPOPBCK-UHFFFAOYSA-N 0.000 description 1
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 description 1
- YEQHNTCMAVPEKP-UHFFFAOYSA-N 6-methylheptyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCC(C)C)OC1=CC=CC=C1 YEQHNTCMAVPEKP-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical group ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- RWPICVVBGZBXNA-BGYRXZFFSA-N Bis(2-ethylhexyl) terephthalate Natural products CCCC[C@H](CC)COC(=O)C1=CC=C(C(=O)OC[C@H](CC)CCCC)C=C1 RWPICVVBGZBXNA-BGYRXZFFSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004807 Di(2-ethylhexyl)terephthalate 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
- LQLQDKBJAIILIQ-UHFFFAOYSA-N Dibutyl terephthalate Chemical compound CCCCOC(=O)C1=CC=C(C(=O)OCCCC)C=C1 LQLQDKBJAIILIQ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- RWPICVVBGZBXNA-UHFFFAOYSA-N bis(2-ethylhexyl) benzene-1,4-dicarboxylate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C=C1 RWPICVVBGZBXNA-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical group CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- LQKWPGAPADIOSS-UHFFFAOYSA-N bis(2-methylpropyl) benzene-1,4-dicarboxylate Chemical compound CC(C)COC(=O)C1=CC=C(C(=O)OCC(C)C)C=C1 LQKWPGAPADIOSS-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- HIAAVKYLDRCDFQ-UHFFFAOYSA-L calcium;dodecanoate Chemical compound [Ca+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O HIAAVKYLDRCDFQ-UHFFFAOYSA-L 0.000 description 1
- ZCZLQYAECBEUBH-UHFFFAOYSA-L calcium;octadec-9-enoate Chemical compound [Ca+2].CCCCCCCCC=CCCCCCCCC([O-])=O.CCCCCCCCC=CCCCCCCCC([O-])=O ZCZLQYAECBEUBH-UHFFFAOYSA-L 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- BJAJDJDODCWPNS-UHFFFAOYSA-N dotp Chemical compound O=C1N2CCOC2=NC2=C1SC=C2 BJAJDJDODCWPNS-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229940075529 glyceryl stearate Drugs 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000004209 oxidized polyethylene wax Substances 0.000 description 1
- 235000013873 oxidized polyethylene wax Nutrition 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 1
- DECPGQLXYYCNEZ-UHFFFAOYSA-N tris(6-methylheptyl) phosphite Chemical compound CC(C)CCCCCOP(OCCCCCC(C)C)OCCCCCC(C)C DECPGQLXYYCNEZ-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- 229940057977 zinc stearate Drugs 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application provides a modified PVC granule for an explosion-proof hot water bag, which comprises 50-58% of polyvinyl chloride, 40-48% of non-o-benzene plasticizer, 0.1-0.5% of lubricant, 0.5-1.2% of calcium-zinc composite stabilizer and 0.5-1.2% of auxiliary agent by the total weight, wherein the prepared PVC granule has excellent compatibility, tensile strength and stability by utilizing the synergistic effect of the components, and the prepared hot water bag has higher explosion-proof performance.
Description
Technical Field
The invention relates to the field of C08L23/08, in particular to modified PVC granules for an explosion-proof hot water bag and a preparation method thereof.
Background
The quality of the hot water bags on the market is good and bad at present, and accidents of scalding or disfiguring caused by explosion of the hot water bags often occur; the reason is mainly that the material of the hot water bag is aged, the mechanical strength is rapidly reduced, and the internal high-pressure impact is not resisted; the invention is mainly based on the problems of insufficient mechanical property, low ageing resistance, hard yellowing of the surface after use, serious influence on the use experience, large use risk and the like of the traditional PVC hot water bag, and the following research is carried out.
In order to solve the problems, chinese patent CN109486061a discloses an anti-aging PVC granulation formulation, comprising the following components: PVC, stearic acid, calcium stearate, ACR, CPE, DOTP, an antioxidant, a surfactant and a stabilizer, wherein the technical scheme adopts different plasticizers to improve the plasticity of the PVC, and the antioxidant and the stabilizer are added to improve the ageing resistance of the PVC, but the mechanical property and the pressure resistance of PVC granules are still low, so that the PVC granules are not suitable for being used as hot water bag materials; chinese patent CN109096658A discloses a modified PVC pellet and a preparation method thereof, wherein a plasticizer and an anti-aging agent are added in the preparation process of the PVC pellet, so that the high temperature resistant effect of PVC is further improved, but the plasticizer is dioctyl phthalate, has carcinogenic action on human bodies, possibly has the risk of later overflow, especially has increased risk of dissolution at higher temperature, and is not suitable for being used in hot water bags.
Therefore, the existing PVC granules have the defects of low mechanical strength, material dissolution risk, low ageing resistance, adverse effect on human body and the like, and are not suitable for hot water bags.
Disclosure of Invention
In order to solve the technical problems, the invention firstly provides the modified PVC granules for the explosion-proof hot water bag, and the stability and the mechanical strength of a PVC molecular chain are improved through the synergistic effect of the components, so that the phenomena of thermal decomposition, long-term aging discoloration and mechanical strength reduction of the PVC granules in the processing process can be effectively resisted.
Further, the raw materials of the modified PVC granules comprise 50-58% of polyvinyl chloride, 40-48% of non-o-benzene plasticizer, 0.1-0.5% of lubricant, 0.5-1.2% of calcium-zinc composite stabilizer and 0.5-1.2% of auxiliary agent by total weight.
Preferably, the raw materials of the modified PVC granules comprise, by weight, 52-55% of polyvinyl chloride, 40-45% of non-o-benzene plasticizers, 0.1-0.3% of lubricants, 0.6-0.9% of calcium-zinc composite stabilizers and 0.5-1.0% of auxiliary agents.
Further, the polymerization degree of the polyvinyl chloride is 1000-2000, and the content of residual vinyl chloride is less than or equal to 10 mug/g.
In a preferred embodiment, the polyvinyl chloride has a degree of polymerization of 1000 to 1300 and a residual vinyl chloride content of 10. Mu.g/g or less.
Further, the non-o-benzene plasticizer is selected from at least one or a combination of a plurality of dibasic esters of saturated aliphatic hydrocarbon, polyhydric alcohol esters, C12-C26 esters containing a cyclic structure and epoxy vegetable oil.
Further, the non-o-benzene plasticizer is C12-C26 ester and/or epoxy vegetable oil containing a cyclic structure.
In a preferred embodiment, when the non-o-benzene plasticizer is a combination of a C12-C26 ester having a cyclic structure and an epoxidized vegetable oil, the mass ratio is (35-50): in the step (1-5), the prepared PVC granules have excellent mechanical properties and good thermal stability; according to the application, C12-C26 ester containing a cyclic structure is inserted between molecular chains of polyvinyl chloride, so that on one hand, the distance between the molecular chains of the polyvinyl chloride is increased, on the other hand, the cyclic structure can act with polar molecules of the polyvinyl chloride to weaken the chemical acting force between the cyclic structure and adjacent polyvinyl chloride, so that entanglement between the molecular chains of the polyvinyl chloride is reduced, the plasticity of the polyvinyl chloride is increased, and when the content of the C12-C26 ester containing the cyclic structure is too high, the precipitation risk exists in a polyvinyl chloride system, and the ageing performance of PVC granules is reduced; the epoxy vegetable oil mainly relies on the fracture of epoxy bonds and the replacement of active hydrogen and chlorine in polyvinyl chloride molecular chains to modify the polyvinyl chloride, but when the molecular chain of C12-C26 ester with a cyclic structure is too long or the epoxy value of the epoxy vegetable oil is too high, the crosslinking effect in the system is too strong, and the tensile strength and the elongation at break of the prepared PVC granules are reduced.
Further preferably, the mass ratio of the C12-C26 ester containing a cyclic structure to the epoxidized vegetable oil is (39-45): (1-3).
Preferably, the dibasic ester of a saturated aliphatic hydrocarbon is di (2-ethylhexyl) adipate (DEHA).
Further, the polyol ester is selected from tributyl citrate and/or acetyl tributyl citrate.
Further, the C12-C26 ester containing a cyclic structure is at least one selected from the group consisting of di (2-ethylhexyl) terephthalate, diethylene glycol dibenzoate, dibutyl terephthalate and diisobutyl terephthalate.
Preferably, the C12-C26 ester containing a cyclic structure is diethylene glycol dibenzoate.
Further, the epoxidized vegetable oil includes, but is not limited to, at least one or a combination of more from epoxidized soybean oil, epoxidized linseed oil, epoxidized rapeseed oil, epoxidized palm oil, epoxidized corn oil.
Further, the epoxy value of the epoxy vegetable oil is more than or equal to 6.0mg KOH/g, and the iodine value is less than or equal to 3.0%.
Preferably, the epoxidized vegetable oil is epoxidized soybean oil and/or epoxidized linseed oil.
Further, the lubricant is at least one selected from polyethylene wax, oxidized polyethylene wax, stearamide, ricinoleic acid amide, fischer-Tropsch wax, liquid paraffin, monoglyceride, pentaerythritol adipic acid stearic acid complex ester, stearic acid ester, stearic acid glyceride and stearate.
Further, the lubricant is at least one selected from polyethylene wax, stearic acid and glyceryl stearate.
Further, the mass ratio of the organic calcium salt to the organic zinc salt in the calcium-zinc composite stabilizer is (0.5-3): (1-2).
Further, the calcium source in the calcium-zinc composite stabilizer is at least one of calcium stearate, calcium laurate and calcium oleate, and the zinc source is at least one of zinc stearate, zinc ricinoleate and zinc laurate.
In a preferred embodiment, the calcium-zinc composite stabilizer is a combination of calcium stearate and zinc ricinoleate, and the mass ratio is 1:1.
Further, the auxiliary agent is amine substance with at least two benzene rings and phosphite ester substance with C24-C40 saturated straight chain.
The application surprisingly discovers that when the mass ratio of the amine substance with at least two benzene rings to the phosphite ester substance with C24-C40 saturated straight chain is (1-5): 1, the mechanical strength and the thermal stability of the prepared PVC can be further improved, the color change phenomenon of PVC granules can be inhibited, and the volatilization amount of the heated odor of the PVC granules can be reduced; the reason is presumed to be that: the PVC product is easy to be oxidized in the processing process and the storage at a later higher temperature to break molecular chains, and generated oxygen free radicals can further promote oxidation, amine substances with at least two benzene rings are adopted to capture the oxygen free radicals and inhibit further oxidative degradation of the molecular chains, in addition, phosphite substances with C24-C40 saturated straight chains are adopted to replace unstable allyl chloride atoms in PVC, the PVC molecules are prevented from generating chain reaction to generate hydrogen chloride and autocatalytic degradation reaction at a high temperature, the breaking of the PVC chains and the generation of double bond structures are inhibited, but grafting of the molecular chains of phosphite substances with C24-C40 saturated straight chains on the PVC chains can further increase the crosslinking of the system, when polar groups on the molecular chains of the phosphite substances are too many, the intermolecular acting force of the system is too large, the fluidity is weakened, and the thermal stability is also reduced; in addition, phosphite ester substances with C24-C40 saturated straight chains can also cooperate with a calcium-zinc composite stabilizer to capture harmful metal ions and chlorine in a system; the relative content of the two is controlled, so that amine substances with at least two benzene rings, phosphite ester substances with C24-C40 saturated straight chains and a calcium-zinc composite stabilizer can play a synergistic role, the compatibility, ageing resistance and thermal stability of a PVC system are improved, and the precipitation of harmful substances or the dissolution of effective components is avoided.
Further, the amine substance having at least two benzene rings is selected from one or two of N, N-bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine and N, N' -bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine.
In a preferred embodiment, the amine having at least two benzene rings is N, N-bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine.
Further, the phosphite substance having a C24-C40 saturated straight chain is at least one selected from triisooctyl phosphite, triisodecyl phosphite, trilauryl phosphite, and tridecyl phosphite.
In a preferred embodiment, the phosphite having a C24-C40 saturated straight chain is triisodecyl phosphite.
Further, the modified PVC granules of the invention can also comprise ultraviolet light stabilizer, deodorant, pigment, flame retardant, matting agent and other components, and can be properly adjusted according to the requirements.
Secondly, the invention also provides a preparation method of the modified PVC granules for the explosion-proof hot water bag, which comprises the following steps:
S1, mixing and stirring the raw materials by a high-speed mixer, keeping the mixing temperature at 180-220 ℃, and then reducing the temperature of the mixed materials to 40-50 ℃ by a cold mixer;
s2, adopting a double-screw extrusion process to melt and extrude the mixed materials, keeping the screw rotation speed at 200-360r/min, wherein the melt extrusion temperatures are respectively as follows: zone I105-110 ℃, zone II 110-115 ℃, zone III 115-120 ℃, zone IV 120-125 ℃; die temperature: 120-130 ℃;
S3, granulating.
Advantageous effects
The application aims at the defects of low mechanical strength, material dissolution risk, low ageing resistance, adverse effect on human body and the like of the existing PVC granules for hot water bags, modifies and optimizes the system of the PVC granules, improves the stability of the molecular chain of polyvinyl chloride in PVC and the structural strength of the system by adopting the combination of C12-C26 ester containing a cyclic structure and epoxy vegetable oil, and provides the mass ratio of (1-5) by utilizing amine substances with at least two benzene rings and phosphite substances with saturated straight chains of C24-C40: 1, the PVC granules have good high-temperature stability and ageing resistance, the overflow risk of bad smell of the PVC granules at a higher temperature is reduced, and the prepared PVC granules have excellent compatibility, tensile strength, thermal stability and ageing resistance by utilizing the synergistic effect of the components, the calcium-zinc composite stabilizer, the lubricant and the like, so that the explosion-proof performance and the safety to human bodies of the prepared hot water bag are further improved.
Detailed Description
Examples
Example 1
The embodiment provides modified PVC granules for an explosion-proof hot water bag, wherein the raw materials of the modified PVC granules comprise, by total weight, 54.3% of polyvinyl chloride, 44% of non-o-benzene plasticizers, 0.2% of lubricants, 0.7% of calcium-zinc composite stabilizers and 0.8% of auxiliary agents; the polymerization degree of the polyvinyl chloride is 1300, the content of residual vinyl chloride is 10 mug/g, and the polyvinyl chloride is purchased from Ningbo table plastic; the non-o-benzene plasticizer consists of diethylene glycol dibenzoate (DEDB, iget chemical Co., st.) and epoxidized soybean oil, and the mass ratio is 43:1, the epoxy value of the epoxidized soybean oil is 6.0mg KOH/g, the iodine value is 3.0%, and the epoxidized soybean oil is purchased from Jiangxi Xin and chemical industry Co., ltd; the lubricant is polyethylene wax, and is purchased from Honeywell, model AC 629; the calcium-zinc composite stabilizer consists of calcium stearate and zinc ricinoleate, and the mass ratio is 1:1, a step of; the auxiliary agent is a combination of N, N-bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine (CHEMNOX 1098) and triisodecyl phosphite (AO 1610) with the mass ratio of 3:1, a step of;
The preparation method of the modified PVC granules comprises the following steps:
S1, mixing and stirring the raw materials by a high-speed mixer, keeping the mixing temperature at 200 ℃, and then reducing the temperature of the mixed materials to 45 ℃ by a cold mixer;
s2, adopting a double-screw extrusion process to melt and extrude the mixed materials, keeping the screw rotation speed to be 280r/min, wherein the melt extrusion temperatures are respectively as follows: zone I108 ℃, zone II 113 ℃, zone III 118 ℃, zone IV 123 ℃; die temperature: 128 ℃;
S3, granulating.
Example 2
The embodiment provides modified PVC granules for an explosion-proof hot water bag, wherein the raw materials of the modified PVC granules comprise 50% of polyvinyl chloride, 48% of non-o-benzene plasticizers, 0.1% of lubricants, 0.9% of calcium-zinc composite stabilizers and 1.0% of auxiliary agents by total weight; the polymerization degree of the polyvinyl chloride is 1000, the content of residual vinyl chloride is 8.5 mug/g, and the polyvinyl chloride is purchased from Ningbo table plastic; the non-o-benzene plasticizer consists of diethylene glycol dibenzoate (DEDB, iget chemical Co., st.) and epoxidized soybean oil, wherein the mass ratio is 45:3, the epoxy value of the epoxidized soybean oil is 6.0mg KOH/g, the iodine value is 3.0%, and the epoxidized soybean oil is purchased from Jiangxi Xin and chemical industry Co., ltd; the lubricant is polyethylene wax, and is purchased from Honeywell, model AC 629; the calcium-zinc composite stabilizer consists of calcium stearate and zinc ricinoleate, and the mass ratio is 1:4, a step of; the auxiliary agent is a combination of N, N-bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine (CHEMNOX 1098) and triisodecyl phosphite (AO 1610) with the mass ratio of 1:1, a step of;
The preparation method of the modified PVC granules comprises the following steps:
s1, mixing and stirring the raw materials by a high-speed mixer, keeping the mixing temperature at 220 ℃, and then reducing the temperature of the mixed materials to 50 ℃ by a cold mixer;
S2, adopting a double-screw extrusion process to melt and extrude the mixed materials, keeping the screw rotation speed at 200-360r/min, wherein the melt extrusion temperatures are respectively as follows: zone I110 ℃, zone II 115 ℃, zone III 120 ℃, zone IV 125 ℃; die temperature: 130 ℃;
S3, granulating.
Example 3
The embodiment provides modified PVC granules for an explosion-proof hot water bag, wherein the raw materials of the modified PVC granules comprise, by total weight, 58% of polyvinyl chloride, 40% of non-o-benzene plasticizers, 0.3% of lubricants, 0.8% of calcium-zinc composite stabilizers and 0.9% of auxiliary agents; the polymerization degree of the polyvinyl chloride is 1300, the content of residual vinyl chloride is 10 mug/g, and the polyvinyl chloride is purchased from Ningbo table plastic; the non-o-benzene plasticizer consists of diethylene glycol dibenzoate (DEDB, iget chemical Co., st.) and epoxidized soybean oil, and the mass ratio is 39:1, the epoxy value of the epoxidized soybean oil is 6.0mg KOH/g, the iodine value is 3.0%, and the epoxidized soybean oil is purchased from Jiangxi Xin and chemical industry Co., ltd; the lubricant is polyethylene wax, and is purchased from Honeywell, model AC 629; the calcium-zinc composite stabilizer consists of calcium stearate and zinc ricinoleate, and the mass ratio is 3:1, a step of; the auxiliary agent is a combination of N, N-bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine (CHEMNOX 1098) and triisodecyl phosphite (AO 1610) with the mass ratio of 5:1, a step of;
The preparation method of the modified PVC granules comprises the following steps:
S1, mixing and stirring the raw materials by a high-speed mixer, keeping the mixing temperature at 180 ℃, and then reducing the temperature of the mixed materials to 40 ℃ by a cold mixer;
s2, adopting a double-screw extrusion process to melt and extrude the mixed materials, keeping the screw rotation speed at 200-360r/min, wherein the melt extrusion temperatures are respectively as follows: zone I105 ℃, zone II 110 ℃, zone III 115 ℃, zone IV 120 ℃; die temperature: 125 ℃;
S3, granulating.
Example 4
Substantially identical to example 1, except that: the non-o-benzene plasticizer consists of diethylene glycol dibenzoate and epoxidized soybean oil, and the mass ratio is 48:2.
Example 5
Substantially identical to example 1, except that: the non-o-benzene plasticizer consists of adipic acid di (2-ethylhexyl) ester (DEHA) and epoxidized soybean oil, and the mass ratio is 43:1.
Example 6
Substantially identical to example 1, except that: the auxiliary agent is a combination of N, N-bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine (CHEMNOX 1098) and triisodecyl phosphite (AO 1610) with the mass ratio of 8:1.
Example 7
Substantially identical to example 1, except that: the auxiliary agent is a combination of N, N-bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine (CHEMNOX 1098) and diphenyl monoisooctyl phosphite (PDOP, purchased from DOW) with the mass ratio of 3:1.
Example 8
Substantially identical to example 1, except that: the calcium-zinc composite stabilizer consists of calcium stearate and zinc stearate.
The performance test method comprises the following steps:
1. mechanical strength: the modified PVC pellets of the examples were tested for elongation at break and tensile strength according to GB/T1040;
2. Ageing resistance: preparing samples with the length of 15mm, the width of 5mm and the height of 2mm from the modified PVC granules in the embodiment, placing the samples for 168 hours at the temperature of 85 ℃ and the RH of 85%, taking out the samples, testing the yellowness index YI of the samples by using a color difference meter, and calculating the yellowness index change value delta YI of the granules before and after the test; the rate of change of the mechanical strength of the pellets after aging was measured again.
3. Thermal stability: according to the national standard GB/T2917.1-2002, the test paper color-changing time is used for judging the heat stability, and the longer the time is, the higher the heat stability is. Performance test results:
TABLE 1
Claims (5)
1. The modified PVC granules for the explosion-proof hot water bag are characterized in that the raw materials of the modified PVC granules comprise, by weight, 50-58% of polyvinyl chloride, 40-48% of non-o-benzene plasticizers, 0.1-0.5% of lubricants, 0.5-1.2% of calcium-zinc composite stabilizers and 0.5-1.2% of auxiliary agents;
the non-o-benzene plasticizer is a combination of C12-C26 ester containing a cyclic structure and epoxy vegetable oil, and the mass ratio is (35-50): (1-5); the C12-C26 ester containing a cyclic structure is diethylene glycol dibenzoate;
The auxiliary agent is amine substances with at least two benzene rings and phosphite ester substances with C24-C40 saturated straight chains; the amine substance with at least two benzene rings is N, N-bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine; the phosphite ester substance with C24-C40 saturated straight chain is triisodecyl phosphite ester;
The mass ratio of the amine substance with at least two benzene rings to the phosphite ester substance with C24-C40 saturated straight chain is (1-5): 1.
2. A modified PVC pellet as in claim 1, wherein the epoxidized vegetable oil is epoxidized soybean oil and/or epoxidized linseed oil.
3. A modified PVC pellet as in claim 1, wherein the mass ratio of organic calcium salt to organic zinc salt in the calcium zinc composite stabilizer is (0.5-3): (1-2).
4. A modified PVC pellet as in claim 1, wherein the polyvinyl chloride has a degree of polymerization of 1000 to 2000 and a residual vinyl chloride content of 10 μg/g or less.
5. The method for producing a modified PVC pellet according to any one of claims 1 to 4, comprising:
s1, mixing and stirring raw materials by a high-speed mixer, keeping the mixing temperature at 180-220 ℃, and then reducing the temperature of the mixed materials to 40-50 ℃ by a cold mixer;
s2, adopting a double-screw extrusion process to melt and extrude the mixed materials, keeping the screw rotation speed at 200-360r/min, wherein the melt extrusion temperatures are respectively as follows: zone I105-110 ℃, zone II 110-115 ℃, zone III 115-120 ℃, zone IV 120-125 ℃; die temperature: 120-130 ℃;
S3, granulating.
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CN102807717A (en) * | 2011-05-30 | 2012-12-05 | 贝恩医疗设备(广州)有限公司 | Special non-o-benzene polyvinyl chloride plastic for blood transfusion, and preparation process thereof |
CN103012483A (en) * | 2012-12-04 | 2013-04-03 | 浙江海普顿新材料股份有限公司 | Phenol-free phosphite ester, as well as preparation method and application thereof |
CN112812472B (en) * | 2021-01-26 | 2023-11-14 | 浙江天原医用材料有限公司 | Environment-friendly low-precipitation soft PVC material and preparation method thereof |
CN114525000A (en) * | 2022-03-14 | 2022-05-24 | 云南锡业锡化工材料有限责任公司 | Flame-retardant polyvinyl chloride cable material and preparation method thereof |
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CN101215398A (en) * | 2007-12-28 | 2008-07-09 | 上海新上化高分子材料有限公司 | Non-ortho-benzene medical soft polyvinyl chloride plastic and preparation method thereof |
CN102827437A (en) * | 2012-09-20 | 2012-12-19 | 山东威高集团医用高分子制品股份有限公司 | Medical radiation-resistant polyvinyl chloride resin |
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