CN117050441A - Special polyvinyl chloride internal plasticization antibacterial medical catheter material and preparation method thereof - Google Patents
Special polyvinyl chloride internal plasticization antibacterial medical catheter material and preparation method thereof Download PDFInfo
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- CN117050441A CN117050441A CN202311169016.0A CN202311169016A CN117050441A CN 117050441 A CN117050441 A CN 117050441A CN 202311169016 A CN202311169016 A CN 202311169016A CN 117050441 A CN117050441 A CN 117050441A
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- Prior art keywords
- nano
- particles
- polyvinyl chloride
- antibacterial
- inorganic
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- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 74
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 74
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 51
- 239000000463 material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- 239000004014 plasticizer Substances 0.000 claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 231100000252 nontoxic Toxicity 0.000 claims abstract description 11
- 230000003000 nontoxic effect Effects 0.000 claims abstract description 11
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 10
- 239000003607 modifier Substances 0.000 claims abstract description 10
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 claims abstract description 9
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 8
- 238000004898 kneading Methods 0.000 claims abstract description 6
- 239000008187 granular material Substances 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 40
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 229920001661 Chitosan Polymers 0.000 claims description 11
- 239000000314 lubricant Substances 0.000 claims description 11
- 229910010272 inorganic material Inorganic materials 0.000 claims description 9
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 229920006026 co-polymeric resin Polymers 0.000 claims description 7
- 239000012760 heat stabilizer Substances 0.000 claims description 7
- 239000011147 inorganic material Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 239000002082 metal nanoparticle Substances 0.000 claims description 5
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 239000002923 metal particle Substances 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000003549 soybean oil Substances 0.000 claims description 3
- 235000012424 soybean oil Nutrition 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 235000019486 Sunflower oil Nutrition 0.000 claims description 2
- 239000004110 Zinc silicate Substances 0.000 claims description 2
- 229940116318 copper carbonate Drugs 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 150000002484 inorganic compounds Chemical group 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000391 magnesium silicate Substances 0.000 claims description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 239000002600 sunflower oil Substances 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims 1
- DOVLHZIEMGDZIW-UHFFFAOYSA-N [Cu+3].[O-]B([O-])[O-] Chemical compound [Cu+3].[O-]B([O-])[O-] DOVLHZIEMGDZIW-UHFFFAOYSA-N 0.000 claims 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims 1
- 235000019792 magnesium silicate Nutrition 0.000 claims 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims 1
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 claims 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims 1
- 235000004416 zinc carbonate Nutrition 0.000 claims 1
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 claims 1
- 235000019352 zinc silicate Nutrition 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 6
- 230000032683 aging Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 description 11
- 239000003242 anti bacterial agent Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000004599 antimicrobial Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- -1 acrylic ester Chemical class 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012567 medical material Substances 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 210000000056 organ Anatomy 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- 238000013268 sustained release Methods 0.000 description 2
- 239000012730 sustained-release form Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- HTTJABKRGRZYRN-UHFFFAOYSA-N Heparin Chemical compound OC1C(NC(=O)C)C(O)OC(COS(O)(=O)=O)C1OC1C(OS(O)(=O)=O)C(O)C(OC2C(C(OS(O)(=O)=O)C(OC3C(C(O)C(O)C(O3)C(O)=O)OS(O)(=O)=O)C(CO)O2)NS(O)(=O)=O)C(C(O)=O)O1 HTTJABKRGRZYRN-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006084 composite stabilizer Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001631 haemodialysis Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000000322 hemodialysis Effects 0.000 description 1
- 229960002897 heparin Drugs 0.000 description 1
- 229920000669 heparin Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000002539 nanocarrier Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 235000010447 xylitol Nutrition 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/02—Applications for biomedical use
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a polyvinyl chloride internal plasticization antibacterial medical catheter special material and a preparation method thereof. The special granules for the polyvinyl chloride internal plasticization antibacterial medical catheter comprise the following components in parts by weight: 10.0 to 15.0 parts of polyvinyl chloride resin with high polymerization degree; 10.0 to 20.0 portions of polyvinyl chloride resin with ultralow polymerization degree; 15.0 to 45.0 portions of vinyl chloride-vinyl acetate copolymer resin; 0.5 to 3.0 portions of antibacterial slow release agent; 5.0 to 15.0 percent of nontoxic plasticizer; 2.0 to 8.0 portions of polyvinyl chloride toughening modifier; 2.0 to 12.0 parts of cyclodextrin and the like are prepared by granulating by a double screw extruder after special physical melt kneading modification, the special material has the advantages of smaller relative molecular mass, short plasticizing time, antibacterial property and the like, no toxic plasticizer is added in the processing process, and the problems of accelerated product aging and biosafety caused by plasticizer migration are avoided.
Description
Technical Field
The invention belongs to the field of polyvinyl chloride processing, and particularly relates to a polyvinyl chloride internal plasticization antibacterial medical catheter special material and a preparation method thereof
Background
With the increasing population aging and population increasing, the medical equipment industry is promoted to be continuously expanded, and with the increasing importance of national health and happiness satisfaction of the country, the policy and regulation of the medical care industry are also increasingly regulated, and the quality of medical equipment is particularly important. PVC has been used as medical material for many years, and according to market estimation, PVC accounts for about 25% of medical plastic products, mainly has chemical corrosion resistance, has strong resistance to oxidizing agents, reducing agents and strong acids, is wear-resistant, easy to produce and low in cost, and is widely applied to medical hemodialysis pipelines, breathing masks, oxygen inhalation hoses, blood storage devices, dialysis accessories, surgical gloves, artificial organs and the like. PVC resin has no toxicity and excellent performance, and the main factor affecting the application of the PVC resin in the medical field is a plasticizer, and in the processing system of PVC medical materials, in order to improve the plasticizing performance, ester plasticizer products are mainly added, and a series of problems are brought by adding the products, such as adding a small amount of small molecular plasticizer into hard products, and the strength of the materials is reduced; if small molecular plasticizers are added into soft products, the plasticizers migrate, the plasticizers leak and are dissolved in the liquid medicine after migrating, the internal quality of the liquid medicine is affected after long-term storage, and meanwhile, certain potential safety hazards exist for patients after long-term use. The medical authorities therefore have a fundamental requirement for medical plastics to be chemically stable and biosafety. In short, the components in the plastic material can not be separated out into liquid medicine or human body, and can not cause toxicity and damage of tissues and organs, and is nontoxic and harmless to human body. The technical innovation of the traditional PVC material is required, the technical bottleneck problem of development of the PVC material is solved, and the application field of the PVC material is expanded.
Chinese patent CN 105949669A discloses a "low-precipitation medical plastic catheter material and its preparation method". The invention discloses a low-precipitation medical plastic catheter material and a preparation method thereof, and the low-precipitation medical plastic catheter material is characterized by comprising the following components in parts by weight: 35-60 parts of polyvinyl chloride resin, 20-36 parts of polyether-ether-ketone resin, 15-22 parts of polycarbonate, 4-9 parts of succinic anhydride, 3-8 parts of glycerol methacrylate, 2-6 parts of hydroxypropyl methyl cellulose, 0.02-0.04 part of heparin, 6-11 parts of sodium bisulfite, 3-10 parts of cyclodextrin, 5-9 parts of epoxidized soybean oil, 4-10 parts of carbon black, 4-12 parts of calcium stearate, 6-11 parts of xylitol, 1-6 parts of cysteine and 3-7 parts of polyvinyl alcohol. The patent uses a large amount of auxiliary additives, the production process steps are complex, the processing temperature is higher, the production cost is high, part of the auxiliary additives are decomposed at the higher temperature to generate the pungent smoke hazard, for example, succinic anhydride is added as the auxiliary additive, and the medical plastic catheter material with low precipitation property is not added with antibacterial materials such as antibacterial agents and the like, has poor antibacterial effect and is easy to be polluted by bacteria, viruses and the like.
Disclosure of Invention
The invention aims to solve the technical problems of providing a polyvinyl chloride internal plasticization antibacterial medical catheter special material, in particular to a modified formula system consisting of a polyvinyl chloride resin with high polymerization degree, a polyvinyl chloride resin with ultralow polymerization degree, a vinyl chloride-vinyl acetate copolymer resin, a vinyl chloride-acrylic ester copolymer resin, an antibacterial slow release agent, a nontoxic plasticizer, a heat stabilizer, a polyvinyl chloride toughening modifier, a lubricant, a nano inorganic material and the like, and the special physical melt kneading modification is used for developing the PVC internal plasticization medical catheter special material.
The invention solves the technical problems by adopting the scheme that: a polyvinyl chloride internal plasticization antibacterial medical catheter special material and a preparation method thereof comprise the following components in percentage by weight: 10.0 to 15.0 parts of polyvinyl chloride resin with high polymerization degree; 10.0 to 30.0 portions of polyvinyl chloride resin with ultralow polymerization degree; 15.0 to 45.0 portions of vinyl chloride-vinyl acetate copolymer resin; 10.0 to 50.0 portions of vinyl chloride-acrylic ester copolymer resin; 0.5 to 3.0 portions of antibacterial slow release agent; 5.0 to 15.0 percent of nontoxic plasticizer; 2.0 to 7.0 portions of heat stabilizer; 2.0 to 8.0 portions of polyvinyl chloride toughening modifier; 5.0 to 30.0 portions of nanometer active inorganic material; 0.1 to 5.0 parts of lubricant; 2.0 to 12.0 portions of cyclodextrin.
Wherein, preferably, 10.0 to 15.0 parts of polyvinyl chloride resin with high polymerization degree; 15.0 to 25.0 portions of polyvinyl chloride resin with ultralow polymerization degree; 20.0 to 25.0 portions of vinyl chloride-vinyl acetate copolymer resin; 25.0 to 35.0 parts of vinyl chloride-acrylic ester copolymer; 2.0 to 3.0 portions of antibacterial slow release agent; 10.0 to 15.0 portions of nontoxic plasticizer; 3.0 to 4.5 portions of stabilizer; 3.0 to 5.0 portions of polyvinyl chloride toughening modifier; 15.0 to 25.0 portions of nano active inorganic material; 0.5 to 2.0 portions of lubricant; 3.0 to 6.0 portions of cyclodextrin.
The PVC resin with high polymerization degree is selected from loose suspension method PVC resin with narrow molecular weight distribution and average polymerization degree of 2450-2500, compared with common PVC, the PVC with high polymerization degree has the characteristics of high molecular weight, long molecular chain, high crimping property, increased entanglement points among molecular chains, higher crystallinity than the common PVC resin, enhanced acting force among the molecular chains of the PVC with high polymerization degree, difficult sliding among the molecular chains, higher tensile strength, tear strength, elongation at break, wear resistance, high temperature resistance, low temperature resistance, lower compression permanent deformation, excellent plasticizer retention property, small influence of temperature on hardness change, unique rubber-like elasticity and the like.
The average degree of polymerization of the ultra-low degree of polymerization polyvinyl chloride resin is 300-500, and the resin has the advantages of smaller relative molecular mass, high apparent density, low melting and gelation temperature, low melting viscosity, excellent compatibility with other high polymer materials and 'intramolecular plasticization' effect, and improves the processing performance of PVC products.
The average polymerization degree of the vinyl chloride-vinyl acetate copolymer resin is 350-450, preferably the content of vinyl acetate accounts for 10-15% of the mass of the vinyl chloride-vinyl acetate copolymer resin, and the chemical resistance and the thermoplastic performance can be improved.
The polymerization degree of the vinyl chloride-acrylic ester copolymer resin is below 300-600, the acrylic ester content accounts for 20% -40% of the mass fraction of the vinyl chloride-acrylic ester copolymer resin, the dosage of the small molecular plasticizer is reduced, precipitation in the using process is reduced, the compatibility of the small molecular plasticizer and modified PVC is improved, and the processability of the PVC resin is improved.
The antibacterial slow release agent is prepared from one or more than one of chitosan and modified metal organic frame material, a precipitator and inorganic nano metal particles, and the inorganic nano/high molecular porous structure material compatible with PVC base materials is synthesized by the interaction of the inorganic nano metal particles, the chitosan and the modified metal organic frame material to realize the assembly of a nano porous network structure. The formula of the antibacterial slow-release agent comprises the following components in parts by weight: 1.0 to 30.0 parts of one or more than one mixture of chitosan and modified metal organic frame material, 1.0 to 40.0 parts of inorganic metal nanometer, 1.0 to 10.0 parts of precipitant and 40.0 to 90.0 parts of water. Wherein the precipitant is an inorganic compound which can react with the inorganic nano precursor to generate water-insoluble inorganic nano particles, and is 1-3 of inorganic acid, inorganic alkali, organic acid, organic alkali and inorganic salt; the inorganic metal nano-particles are one or more of nano-gold particles, nano-silver particles, nano-platinum particles, nano-zinc carbonate particles, nano-magnesium carbonate particles, nano-copper carbonate particles, nano-zinc borate particles, nano-copper borate particles, nano-magnesium borate particles, nano-tin oxide particles, nano-zinc oxide particles, nano-magnesium oxide particles, nano-copper oxide particles, nano-magnesium bismuthate particles, nano-zinc bismuthate particles, nano-copper bismuthate particles, nano-aluminum silicate particles, nano-magnesium silicate particles and nano-zinc silicate particles.
The antibacterial slow release agent is an inorganic metal nano/high molecular porous structure material which realizes antibacterial effect by adding an antibacterial transfer carrier, and the added antibacterial transfer carrier has the advantages of ensuring the stability of the antibacterial agent in the product processing process, and if the antibacterial agent is directly used in the processing of the high molecular material, the antibacterial effect of the active materials is very limited, because the high temperature in the traditional processing technology of the polymeric high molecular material can cause a great loss of the antibacterial agent. The use of an antimicrobial delivery vehicle can effectively reduce the loss of antimicrobial agent and maintain its antimicrobial activity because the antimicrobial agent encapsulated in a microcarrier or nanocarrier will have a higher stability to the processing conditions of the polymeric material than the free-loaded active compound. The carriers can protect the active agents from severe environmental conditions, and can reduce aggregation among the antibacterial agents and the problem of too fast release, thereby greatly increasing the antibacterial effect. The inorganic metal nano-particles, the chitosan and the modified metal organic framework material interact to realize the assembly of the nano-porous network structure, the inorganic metal nano/polymer porous structure material compatible with the PVC base material is synthesized, the slow release function is realized, and the antibacterial agent can be slowly and continuously released from the pore canal to the outside through the concentration difference between the inside and outside of the microcarrier system, so that the antibacterial time can be prolonged. The added antibacterial transfer carrier has the main advantages that the inorganic metal nano/high-molecular porous structure material combined by the microcarrier has higher loading efficiency for packaging the antibacterial compound, so that the concentration of the antibacterial agent on the surface of the polyvinyl chloride internal plasticization antibacterial medical catheter product material is relatively higher, thereby improving self-cleaning activity and being beneficial to maintaining antibacterial activity.
The preparation process includes stirring chitosan and/or modified metal-organic frame material, inorganic metal nanometer particle and water at 0-150 deg.c, adding precipitant, regulating pH value of the solution, depositing one or more of chitosan and modified metal-organic frame material and inorganic nanometer particle slowly in 1-20 hr, filtering, washing, drying at 0-100 deg.c, and crushing in crusher. The antibacterial sustained release agent carrier has safe components, is harmless to human bodies, does not release toxic and harmful gases and does not irritate skin, bacteria, mold and the like do not generate drug resistance after the antibacterial sustained release agent carrier is antibacterial, the toughness and the stretching degree of the composite material can be increased, and the stability, the ageing resistance, the corrosion resistance and the like of the material are improved.
The nontoxic plasticizer is one or more than one mixture of tributyl citrate (TBC), acetyl tributyl citrate (ATBC), medical grade Epoxidized Soybean Oil (ESO) and epoxidized sunflower oil, and has the advantages of good compatibility, high plasticizing efficiency, no toxicity, difficult volatilization, strong weather resistance and good mildew resistance.
The heat stabilizer is an environment-friendly calcium-zinc composite stabilizer.
The appearance of the polyvinyl chloride toughening modifier is white powder; apparent density is more than or equal to 0.35g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Screen residue (30 mesh): less than or equal to 2.0 percent; volatiles: the polyvinyl chloride toughening modifier is a novel green toughening polymer material with impact modification effect, and the product is a toughening modification product which takes chemical modified special polyvinyl chloride resin as a main raw material, and can promote plasticizing and reinforcing polyvinyl chloride melt processingFluidity, and can impart better toughness and low temperature impact properties to PVC articles.
The cyclodextrin has a molecular structure with a slightly conical hollow cylinder three-dimensional ring structure, in the cavity structure, the outer upper end (larger opening end) is composed of secondary hydroxyl groups of C2 and C3, the lower end (smaller opening end) is composed of primary hydroxyl groups of C6, the cyclodextrin has hydrophilicity, and a hydrophobic region is formed in the cavity due to the shielding effect of C-H bonds. The PVC material has no reducing end or non-reducing end, has no reducibility, is very stable in alkaline and weak acid mediums, has better thermal stability, and can endow PVC products with better processing stability.
The lubricant is a mixture of medical grade stearic acid and polyethylene wax, and the compounding ratio of the lubricant is preferably 1:1, so that the efficiency of the lubricant is improved, and the dosage of the lubricant is reduced.
Compared with the prior art, the invention has the following beneficial effects
The polyvinyl chloride internal plasticization antibacterial medical catheter special material has the advantages of smaller relative molecular mass, low melting and gelation temperature, short plasticization time, excellent processability, antibacterial property, smooth surface, high thermal stability, good toughness and low-temperature impact resistance and the like, and no toxic plasticizer is added in the processing process, so that the problems of accelerated product aging and biosafety caused by plasticizer migration are avoided.
The specific embodiment is as follows:
the invention is further described below in connection with examples. The scope of the invention is not limited by these examples, but is set forth in the claims.
Examples 1 to 5
A. The test samples of examples 1 to 5 were sequentially measured according to the weight ratio of each part in Table 1, and then a high polymerization degree polyvinyl chloride resin, a heat stabilizer, an ultra-low polymerization degree polyvinyl chloride resin, a vinyl chloride-acrylic ester copolymer resin, and a vinyl chloride-vinyl acetate copolymer resin were put into a hot-mixing kneading modification apparatus, the hot-mixing kneading modification apparatus was started, the high-speed was started after 1 minute at a low speed in a high-mixing system, and a polyvinyl chloride toughening modifier was put at 40 to 45 ℃; dropping non-toxic plasticizer at 70-80 deg.c in 1-2 min; then adding nano active inorganic material, antibacterial slow-release agent, lubricant and cyclodextrin. The high-speed stirring and mixing temperature is 105+/-1 ℃ for 10-15 minutes, the low-speed cooling stirring and mixing speed is 400-500 rpm, the low-speed stirring and mixing temperature is 40+/-1 ℃ for 5-8 minutes, and the discharging is for standby.
B. Adding the mixed ingredients into a parallel double-screw or conical double-screw extruder for extrusion granulation, and setting the temperature of the extruder: the special granules for the polyvinyl chloride internal plasticization antibacterial medical catheter are obtained by air cooling, granulating, metering and packaging at 135-180 ℃.
Comparative example 1
A. Comparative example 1 test sample, after sequentially metering according to the weight portion ratio in table 1, putting a polyvinyl chloride resin with high polymerization degree and a heat stabilizer into a hot-mixing kneading modification device, starting the high-speed after 1 minute under the low speed of a high-mixing system, and putting a polyvinyl chloride toughening modifier at 40-45 ℃; dropping non-toxic plasticizer at 70-80 deg.c in 1-2 min; then adding nano active inorganic material, antibacterial slow-release agent, lubricant and cyclodextrin. The high-speed stirring and mixing temperature is 105+/-1 ℃ for 10-15 minutes, the low-speed cooling stirring and mixing speed is 400-500 rpm, the low-speed stirring and mixing temperature is 40+/-1 ℃ for 5-8 minutes, and the discharging is for standby.
B. Adding the mixed ingredients into a parallel double-screw or conical double-screw extruder for extrusion granulation, and setting the temperature of the extruder: the special granules for the polyvinyl chloride internal plasticization antibacterial medical catheter are obtained by air cooling, granulating, metering and packaging at 135-180 ℃.
Table 1 examples 1 to 5 proportion table of each component
The special granules for polyvinyl chloride internal plasticization antibacterial medical catheters, which are prepared by the invention, are tested by standard spline, and the performance data are shown in table 2.
TABLE 2 comparison of the specific Properties of the different Components
| Sample numbering | Maximum tensile strength, MPa | Elongation at break% | Modulus of elasticity, MPa | Simple beam notch impact, KJ/-square meter |
| Example 1 | 53.85 | 20.75 | 3348.32 | 6.14 |
| Example 2 | 44.39 | 17.01 | 4032.41 | 4.57 |
| Example 3 | 49.85 | 18.21 | 3426.02 | 5.03 |
| Example 4 | 41.96 | 14.24 | 3618.65 | 3.98 |
| Example 5 | 39.12 | 13.25 | 3934.53 | 3.12 |
| Comparative example 1 | 35.9 | 10.2 | 2925.26 | 2.08 |
Claims (7)
1. A special material for polyvinyl chloride internal plasticization antibacterial medical catheter and its preparation method, characterized in that a modified formula system composed of high polymerization degree polyvinyl chloride resin, ultra-low polymerization degree polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-acrylic ester copolymer resin, antibacterial slow release agent, nontoxic plasticizer, heat stabilizer, polyvinyl chloride toughening modifier, nano active inorganic material, lubricant and cyclodextrin is adopted, after special physical melt kneading modification, extrusion granulation is carried out by using a double screw extruder, and air cooling granulation, metering and packaging are carried out to obtain granules which are uniform for polyvinyl chloride internal plasticization antibacterial medical catheter.
2. The polyvinyl chloride internal plasticization antibacterial medical catheter special material and the preparation method thereof according to claim 1 are characterized by comprising the following components in parts by weight: 10.0 to 15.0 parts of polyvinyl chloride resin with high polymerization degree; 10.0 to 20.0 portions of polyvinyl chloride resin with ultralow polymerization degree; 15.0 to 45.0 portions of vinyl chloride-vinyl acetate copolymer resin; 10.0 to 50.0 portions of vinyl chloride-acrylic ester copolymer resin; 0.5 to 3.0 portions of antibacterial slow release agent; 5.0 to 15.0 percent of nontoxic plasticizer; 2.0 to 7.0 portions of heat stabilizer; 2.0 to 8.0 portions of polyvinyl chloride toughening modifier; 5.0 to 30.0 portions of nanometer active inorganic material; 0.1 to 5.0 parts of lubricant; 2.0 to 12.0 portions of cyclodextrin.
3. The polyvinyl chloride internal plasticization antibacterial medical catheter special material and the preparation method thereof according to claim 1, wherein the antibacterial slow release agent is prepared from one or more than one of chitosan and modified metal organic frame materials, a precipitator and inorganic nano metal particles, and the inorganic nano metal particles interact with the chitosan and the modified metal organic frame materials to realize the assembly of a nano porous network structure, so as to synthesize an inorganic metal nano/high polymer porous structure material compatible with a PVC base material; the composition comprises the following components in parts by weight: 1.0 to 30.0 parts of one or more than one mixture of chitosan and modified metal organic frame material, 1.0 to 40 parts of inorganic metal nano particles, 1.0 to 10.0 parts of precipitant and 40 to 90 parts of water.
4. The polyvinyl chloride internal plasticization antibacterial medical catheter special material and the preparation method thereof according to claims 1 and 3 are characterized in that the preparation method of the antibacterial slow release agent comprises the following steps: under the condition of 0-150 ℃, one or more than one mixture of chitosan and modified metal organic frame material, inorganic metal nano particles and water are stirred uniformly, a precipitator is added, the pH value of the solution is regulated, one or more than one mixture of chitosan and modified metal organic frame material and inorganic nano particles are slowly precipitated within 1-20 hours, the obtained precipitate is filtered and washed, and then dried at the drying temperature of 0-100 ℃, and crushed by a crusher for standby.
5. The polyvinyl chloride internal plasticization antibacterial medical catheter special material and the preparation method thereof according to claim 1 and 3, wherein the precipitator required for the preparation of the antibacterial slow-release agent is an inorganic compound which can react with an inorganic nano precursor to generate insoluble inorganic nano particles, and is 1-3 of inorganic acid, inorganic alkali, organic acid, organic alkali and inorganic salt.
6. The polyvinyl chloride internal plasticization antibacterial medical catheter special material and the preparation method thereof according to claim 1 and 3, wherein the inorganic metal nano particles required by the preparation of the antibacterial slow release agent are one or more of nano gold particles, nano silver particles, nano platinum particles, nano zinc carbonate particles, nano magnesium carbonate particles, nano copper carbonate particles, nano zinc borate particles, nano copper borate particles, nano magnesium borate particles, nano tin oxide particles, nano zinc oxide particles, nano magnesium oxide particles, nano copper oxide particles, nano magnesium bismuthate particles, nano zinc bismuthate particles, nano copper bismuthate particles, nano aluminum silicate particles, nano magnesium silicate particles and nano zinc silicate particles.
7. The polyvinyl chloride internal plasticization antibacterial medical catheter special material and the preparation method thereof according to claim 1, wherein the nontoxic plasticizer is one or more than one mixture of tributyl citrate (TBC), acetyl tributyl citrate (ATBC), medical grade Epoxidized Soybean Oil (ESO) and epoxidized sunflower oil.
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