CN119219892A - A preparation method of medical hydrophilic polyurethane sponge - Google Patents
A preparation method of medical hydrophilic polyurethane sponge Download PDFInfo
- Publication number
- CN119219892A CN119219892A CN202411416449.6A CN202411416449A CN119219892A CN 119219892 A CN119219892 A CN 119219892A CN 202411416449 A CN202411416449 A CN 202411416449A CN 119219892 A CN119219892 A CN 119219892A
- Authority
- CN
- China
- Prior art keywords
- stirring
- polyurethane sponge
- hydrophilic polyurethane
- mixture
- ciprofloxacin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004814 polyurethane Substances 0.000 title claims abstract description 58
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 81
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical class C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims abstract description 56
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 27
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000006260 foam Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 11
- 229920000570 polyether Polymers 0.000 claims abstract description 11
- 229920005862 polyol Polymers 0.000 claims abstract description 11
- 150000003077 polyols Chemical class 0.000 claims abstract description 11
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 10
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 10
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 8
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000005187 foaming Methods 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 35
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 229960003405 ciprofloxacin Drugs 0.000 claims description 14
- 239000003381 stabilizer Substances 0.000 claims description 14
- 229920001661 Chitosan Polymers 0.000 claims description 11
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 7
- BAZVFQBTJPBRTJ-UHFFFAOYSA-N 2-chloro-5-nitropyridine Chemical compound [O-][N+](=O)C1=CC=C(Cl)N=C1 BAZVFQBTJPBRTJ-UHFFFAOYSA-N 0.000 claims description 7
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 28
- 230000008569 process Effects 0.000 abstract description 8
- 238000001514 detection method Methods 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000003814 drug Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- 239000000725 suspension Substances 0.000 description 5
- 230000001580 bacterial effect Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011496 polyurethane foam Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920001817 Agar Polymers 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 108020000946 Bacterial DNA Proteins 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 206010052428 Wound Diseases 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- -1 silver ions Chemical class 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 108010041052 DNA Topoisomerase IV Proteins 0.000 description 1
- 102000003844 DNA helicases Human genes 0.000 description 1
- 230000004543 DNA replication Effects 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Chemical group COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000013518 transcription Methods 0.000 description 1
- 230000035897 transcription Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen 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
- C07D213/72—Nitrogen atoms
- C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
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- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
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- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The invention discloses a preparation method of medical hydrophilic polyurethane sponge, which belongs to the technical field of polyurethane sponge and comprises the following steps of stirring and mixing polyether polyol, polyester polyol, pure water, a foam homogenizing agent 9205, stannous octoate, a propylene glycol solution of triethylene diamine with the mass fraction of 33% and a nano silver antibacterial agent, adding polyisocyanate into the mixture, stirring and mixing the mixture, adding modified ciprofloxacin into the mixture, stirring and mixing the mixture to obtain a mixed material, pouring the mixed material into a mould, standing the mould, foaming the mixed material, solidifying the mixed material, and demoulding the mixed material to obtain the medical hydrophilic polyurethane sponge. The invention provides a method for preparing polyurethane sponge by utilizing a one-step foaming process, which realizes comprehensive improvement of hydrophilicity and antibacterial property of polyurethane sponge by introducing self-made nano silver antibacterial agent and modified ciprofloxacin, and finally prepares medical hydrophilic polyurethane sponge with excellent hydrophilicity, antibacterial property and antibacterial stability through detection.
Description
Technical Field
The invention belongs to the technical field of polyurethane sponge, and particularly relates to a preparation method of medical hydrophilic polyurethane sponge.
Background
Polyurethane sponge shows great application potential in the field of wound care in a unique three-dimensional porous structure. However, the polyurethane sponge itself has insufficient hydrophilicity, which limits its application in the medical field, for which the hydrophilicity of the polyurethane sponge is improved in the prior art:
the invention discloses a medical hydrophilic polyurethane sponge and a preparation method thereof, wherein polyethylene glycol and polyacrylamide are introduced into a polyurethane sponge system, and the hydrophilic polyurethane sponge is prepared by a two-step method.
The above-mentioned prior art can show the hydrophilicity that improves polyurethane sponge, but because the high risk of bacterial infection in the hospital environment, polyurethane itself does not possess antibacterial property moreover, consequently, develops a hydrophilic polyurethane sponge that has antibacterial function, is crucial to satisfying medical clinical demand, consequently needs to improve current polyurethane sponge.
Disclosure of Invention
The invention provides a preparation method of polyurethane sponge, which further improves the antibacterial performance of polyurethane foam materials on the basis of improving the hydrophilicity of the polyurethane foam materials and meets the clinical requirements of medical treatment.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the medical hydrophilic polyurethane sponge comprises the following steps:
And stirring and mixing polyether polyol, polyester polyol, pure water, a foam stabilizer 9205, stannous octoate, a propylene glycol solution of triethylene diamine with the mass fraction of 33% and a nano silver antibacterial agent, adding polyisocyanate into the mixture, stirring and mixing the mixture, adding modified ciprofloxacin into the mixture, stirring and mixing the mixture to obtain a mixed material, pouring the mixed material into a mould, standing, foaming and solidifying the mixed material for 40-50 min, and demoulding the mixed material to obtain the medical hydrophilic polyurethane sponge.
Further, the dosage ratio of the polyether polyol, the polyester polyol, the pure water, the foam stabilizer 9205, the stannous octoate, the propylene glycol solution of the triethylene diamine with the mass fraction of 33%, the nano silver antibacterial agent, the polyisocyanate and the modified ciprofloxacin is 75 g:25 g:3 g:1.0~1.5 g:0.15~0.20 g:0.3~0.5 g:1.2-1.5 g:45~50 g:20 g.
Further, the polyisocyanate is one of isophorone diisocyanate, 4' -diphenylmethane diisocyanate and hexamethylene diisocyanate.
Further, the nano silver antibacterial agent is prepared by the following steps:
And adding carboxymethyl chitosan into deionized water under stirring, adding sodium hydroxide into the deionized water under stirring to adjust the pH of the system to 10.0-10.5, adding nano silver into the system under stirring, and stirring at constant temperature for 2-3 h to obtain the nano silver antibacterial agent.
Further, the dosage ratio of the deionized water, the carboxymethyl chitosan and the nano silver is 100 mL:0.2~0.3 g:0.1g.
Further, the modified ciprofloxacin is prepared by the following steps:
adding ciprofloxacin, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide into dichloromethane under stirring, stirring and mixing at room temperature for 1h, adding an amino-terminated monomer into the mixture under stirring, heating to 35-40 ℃, stirring and reacting for 12-h, cooling to room temperature after the reaction is finished, and removing dichloromethane by rotary evaporation to obtain modified ciprofloxacin, wherein the preparation process of the modified ciprofloxacin is as follows:
。
Further, the dosage ratio of the methylene dichloride, the ciprofloxacin, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, the N-hydroxysuccinimide and the amino-terminated monomer is 100 mL:0.1 mol:14~15 g:9~10 g:21~22 g.
Further, the amino-terminated monomer is prepared by the steps of:
s1, adding tris (hydroxymethyl) aminomethane and triethylamine into dimethyl sulfoxide, stirring for 30 min, charging nitrogen, adding 2-chloro-5-nitropyridine into the mixture, heating to 85-90 ℃, stirring for reacting for 5-6 hours, cooling to room temperature after the reaction is finished, and removing the dimethyl sulfoxide by rotary evaporation to obtain an intermediate, wherein the preparation process of the intermediate is as follows:
。
S2, adding absolute ethyl alcohol, 18% hydrochloric acid aqueous solution and iron powder into deionized water, heating to 80-90 ℃, stirring for 30min, cooling to room temperature, adding an intermediate into the mixture, stirring at a constant temperature to 80-90 ℃, stirring at a constant temperature for 5-6 h, cooling to room temperature after the completion of the stirring, filtering, adding ammonia water into filtrate to adjust the pH of the system to 8.5-9.0, standing for 12h at room temperature, and carrying out suction filtration, washing and drying to obtain an amino-terminated monomer, wherein the preparation process of the amino-terminated monomer is as follows:
。
Further, the dosage ratio of dimethyl sulfoxide, tris (hydroxymethyl) aminomethane, triethylamine and 2-chloro-5-nitropyridine in S1 is 100 mL:0.11~0.12 mol:10~11 g:0.1 mol.
Further, the dosage ratio of the deionized water, the absolute ethyl alcohol, the hydrochloric acid aqueous solution with the mass fraction of 18 percent, the iron powder and the intermediate in the S2 is 100 mL:20 mL:6~8 mL:20 g:40~45 g.
The invention has the beneficial effects that:
The invention provides a method for preparing polyurethane sponge by utilizing a one-step foaming process, which realizes comprehensive improvement of hydrophilicity and antibacterial property of polyurethane sponge by introducing self-made nano silver antibacterial agent and modified ciprofloxacin, and finally prepares medical hydrophilic polyurethane sponge with excellent hydrophilicity, antibacterial property and antibacterial stability through detection, thereby meeting the clinical requirements of medical treatment.
Firstly, the nano silver antibacterial agent is added in the polyurethane sponge, the nano silver antibacterial agent is prepared by carrying nano silver on carboxymethyl chitosan, the invention utilizes the broad spectrum and high-efficiency antibacterial property of nano silver to realize effective antibacterial property. Meanwhile, when the hydrophilic polyurethane sponge is subjected to liquid adsorption and extrusion discharge for many times, the nano silver powder on the polyurethane sponge is easy to fall off and run off, so that the stability of the antibacterial performance of the polyurethane sponge is poor, and the fallen nano silver is easy to cause damage to the health of a human body through skin or wounds, therefore, the invention utilizes rich carboxyl groups on carboxymethyl chitosan to chelate with the nano silver, the adhesive stability of the nano silver on the polyurethane sponge is improved, the carboxymethyl chitosan also has better antibacterial property, the hydrophilic carboxyl on the carboxymethyl chitosan can assist in improving the hydrophilic property of the polyurethane sponge, and finally, the antibacterial property and the stability of the polyurethane sponge can be obviously improved by introducing the nano silver antibacterial agent.
Then, the modified ciprofloxacin is added into the polyurethane sponge, the modified ciprofloxacin is prepared by amidation reaction of carboxyl on the ciprofloxacin and terminal amino of terminal amino monomers, the ciprofloxacin has broad-spectrum antibacterial property, the ciprofloxacin mainly inhibits bacterial DNA helicase and topoisomerase IV to interfere bacterial DNA replication, repair and transcription processes, the nano silver destroys cell walls and cell membranes of bacteria by releasing silver ions to interfere metabolism and propagation of the bacteria, the action mechanisms of the two are different, the two mechanisms can complement each other, the antibacterial effect is enhanced, and meanwhile, the combined use of the ciprofloxacin and the nano silver can reduce the use concentration of a single drug, reduce the selection pressure of drug-resistant strains and delay the generation of drug resistance. Through antibacterial property detection, ciprofloxacin and nano silver have a synergistic effect.
Then, the modified ciprofloxacin has amide (-CONH-) groups, the amide groups have excellent hydrophilicity, the introduction of the modified ciprofloxacin can improve the hydrophilicity of the polyurethane sponge, and meanwhile, the amino-terminated monomer contains abundant hydroxyl groups, so that the hydrophilicity of the polyurethane sponge can be further improved.
Finally, the modified ciprofloxacin contains rich nitrogen-containing structures, such as a nitrogen-containing ring structure (piperazine ring, quinoline ring and pyridine ring), an amide group and an amino group (-NH-), and a coordination bond can be formed between a nitrogen atom in the nitrogen-containing structure and silver in the nano silver antibacterial agent, so that the stability of the antibacterial performance of the polyurethane sponge is further improved, and the antibacterial performance of the polyurethane sponge is comprehensively improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, 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.
Example 1
Preparing a nano silver antibacterial agent:
100 mL of deionized water is taken, carboxymethyl chitosan with the substitution degree of 0.2 g (the substitution degree is more than or equal to 80 percent, the chemical reagent is purchased from the national medicine group chemical reagent Co., ltd.) is added into the deionized water, sodium hydroxide is added into the deionized water to adjust the pH of the system to 10.0, nano silver with the pH of 0.1 g (99.9 percent, 20-40 nm, the chemical reagent is purchased from the national medicine group Co., ltd.) is added into the deionized water, and the nano silver antibacterial agent is obtained by stirring the mixture at constant temperature for 2 h.
Example 2
Preparing a nano silver antibacterial agent:
100 mL deionized water is taken, carboxymethyl chitosan (with substitution degree more than or equal to 80 percent and purchased from national pharmaceutical group chemical reagent Co., ltd.) of 0.28 g is added into the deionized water under stirring, sodium hydroxide is added into the deionized water under stirring to adjust the pH of the system to 10.5, nano silver (99.9 percent, 20-40 nm and purchased from national pharmaceutical group chemical reagent Co., ltd.) of 0.1 g is added into the system under stirring, and the antibacterial agent is obtained under constant temperature stirring for 3 h.
Example 3
Preparing a nano silver antibacterial agent:
100 mL of deionized water is taken, carboxymethyl chitosan with the substitution degree of 0.3 g (the substitution degree is more than or equal to 80 percent, the chemical reagent is purchased from the national medicine group chemical reagent Co., ltd.) is added into the deionized water, sodium hydroxide is added into the deionized water to adjust the pH of the system to 10.5, nano silver with the pH of 0.1 g (99.9 percent, 20-40 nm, the chemical reagent is purchased from the national medicine group Co., ltd.) is added into the deionized water, and the nano silver antibacterial agent is obtained by stirring the mixture at constant temperature for 3 h.
Example 4
Preparation of amino-terminated monomers:
s1, taking dimethyl sulfoxide 100mL, adding 0.11 mol of tris (hydroxymethyl) aminomethane (AR; purchased from national pharmaceutical systems and chemicals Co., ltd.) and 10 g of triethylamine (AR; purchased from national pharmaceutical systems and chemicals Co., ltd.), stirring for 30 min, charging nitrogen, adding 0.1 mol of 2-chloro-5-nitropyridine (98; purchased from national pharmaceutical systems and chemicals Co., ltd.) into the mixture, heating to 85 ℃, stirring for reacting for 5h, cooling to room temperature after the reaction is finished, and removing the dimethyl sulfoxide by rotary evaporation to obtain an intermediate;
S2, taking 100 mL deionized water, adding 20 mL absolute ethyl alcohol, 6 mL hydrochloric acid aqueous solution with the mass fraction of 18% and 20 g iron powder (with the particle size of 3 mu m, purchased from national medicine group chemical reagent Co., ltd.) into the deionized water, heating to 80 ℃, stirring the mixture to 30 min, cooling to room temperature, stirring the mixture to 40g intermediate, heating to 80 ℃, stirring the mixture at constant temperature to 5 h, cooling to room temperature, filtering, adding ammonia water into the filtrate to adjust the pH of the system to 8.5, standing the mixture at room temperature for 12 h, carrying out suction filtration, washing and drying to obtain the amino-terminated monomer.
Example 5
Preparation of amino-terminated monomers:
S1, taking dimethyl sulfoxide 100mL, adding 0.12 mol of tris (hydroxymethyl) aminomethane (AR; purchased from national pharmaceutical systems and chemicals Co., ltd.) and 10.5 g of triethylamine (AR; purchased from national pharmaceutical systems and chemicals Co., ltd.), stirring for 30min, charging nitrogen, adding 0.1 mol of 2-chloro-5-nitropyridine (98; purchased from national pharmaceutical systems and chemicals Co., ltd.) into the mixture, heating to 90 ℃, stirring for reacting for 6 h, cooling to room temperature after the reaction is finished, and removing dimethyl sulfoxide by rotary evaporation to obtain an intermediate;
S2, taking 100 mL deionized water, adding 20 mL absolute ethyl alcohol, 7 mL hydrochloric acid aqueous solution with the mass fraction of 18% and 20 g iron powder (with the particle size of 3 mu m, purchased from national medicine group chemical reagent Co., ltd.) into the deionized water, heating to 90 ℃, stirring the mixture to 30 min, cooling to room temperature, stirring the mixture to 44 g intermediate, heating to 90 ℃, stirring the mixture at constant temperature to 6h, cooling to room temperature, filtering, adding ammonia water into the filtrate to adjust the pH of the system to 9.0, standing the mixture at room temperature for 12 h, carrying out suction filtration, washing and drying to obtain the amino-terminated monomer.
Example 6
Preparation of amino-terminated monomers:
S1, taking dimethyl sulfoxide 100mL, adding 0.12 mol of tris (hydroxymethyl) aminomethane (AR; purchased from national pharmaceutical systems and chemicals Co., ltd.) and 11g of triethylamine (AR; purchased from national pharmaceutical systems and chemicals Co., ltd.), stirring for 30 min, charging nitrogen, adding 0.1 mol of 2-chloro-5-nitropyridine (98; purchased from national pharmaceutical systems and chemicals Co., ltd.) into the mixture, heating to 90 ℃, stirring for reacting for 6h, cooling to room temperature after the reaction is finished, and removing the dimethyl sulfoxide by rotary evaporation to obtain an intermediate;
S2, taking 100 mL deionized water, adding 20 mL absolute ethyl alcohol, 8 mL hydrochloric acid aqueous solution with the mass fraction of 18% and 20 g iron powder (with the particle size of 3 mu m, purchased from national medicine group chemical reagent Co., ltd.) into the deionized water, heating to 90 ℃, stirring the mixture to 30 min, cooling to room temperature, stirring the mixture to 45 g intermediate, heating to 90 ℃, stirring the mixture at constant temperature to 6h, cooling to room temperature, filtering, adding ammonia water into the filtrate to adjust the pH of the system to 9.0, standing the mixture at room temperature for 12 h, carrying out suction filtration, washing and drying to obtain the amino-terminated monomer.
Example 7
Preparation of modified ciprofloxacin:
100. 100 mL of methylene chloride was taken, 0.1 mol of ciprofloxacin (98%; available from Shanghai Meilin Biotechnology Co., ltd.), 14 g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (98%; available from Shanghai Meilin Biotechnology Co., ltd.) and 9 g of N-hydroxysuccinimide (98%; available from Shanghai Meilin Biotechnology Co., ltd.) were added thereto with stirring, 1h was mixed at room temperature with stirring, and then 21 g of the amino-terminated monomer prepared in example 4 was added thereto with stirring, the temperature was raised to 35℃and reacted with stirring at 12 h, after completion of which the reaction, the reaction was cooled to room temperature, and the methylene chloride was removed by rotary evaporation to obtain modified ciprofloxacin.
Example 8
Preparation of modified ciprofloxacin:
100. 100 mL of methylene chloride was taken, 0.1 mol of ciprofloxacin (98%; available from Shanghai Meilin Biotechnology Co., ltd.), 14.5. 14.5 g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (98%; available from Shanghai Meilin Biotechnology Co., ltd.) and 10 g of N-hydroxysuccinimide (98%; available from Shanghai Meilin Biotechnology Co., ltd.) were added thereto with stirring, 1 h was mixed at room temperature with stirring, and then 22 g of the amino-terminated monomer prepared in example 5 was added thereto with stirring, and the temperature was raised to 40℃with stirring to react 12 h, and after completion, the reaction was cooled to room temperature, the methylene chloride was removed by spin evaporation to obtain modified ciprofloxacin.
Example 9
Preparation of modified ciprofloxacin:
100 mL of methylene chloride was taken, 0.1 mol of ciprofloxacin (98%; available from Shanghai Meilin Biochemical Co., ltd.), 15 g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (98%; available from Shanghai Meilin Biochemical Co., ltd.) and 10 g of N-hydroxysuccinimide (98%; available from Shanghai Meilin Biochemical Co., ltd.) were added thereto with stirring, 1h was mixed at room temperature with stirring, and then 22 g of the amino-terminated monomer prepared in example 6 was added thereto with stirring, and the temperature was raised to 40℃and reacted with stirring to 12 h, after completion, the mixture was cooled to room temperature, and the methylene chloride was removed by spin evaporation to obtain a modified ciprofloxacin.
Example 10
Preparing medical hydrophilic polyurethane sponge:
75 g of polyether polyol (elastomer polyether polyol; average Mn2000; from Shanghai Seikovia Biotech Co., ltd.), 25 g of polyester polyol (VANTHANOL ® WHP-204; from Wanhua chemical Co., ltd.), 3 g of pure water, 1.0 g of foam stabilizer 9205 (from Zhang Kong Tobo electronics Co., ltd.), 0.15 g of stannous octoate (analytically pure; from Guogon Chemie Co., ltd.), 0.3 g of propylene glycol solution of triethylene diamine with a mass fraction of 33% (from Santhylene diamine Co., ltd.), 1.2 g of nano silver antibacterial agent prepared in example 1, stirring and mixing 20 min, adding 45 g of polyisocyanate isophorone diisocyanate, 4' -diphenylmethane diisocyanate and hexamethylene diisocyanate (analytically pure; from Guogon Chemie Co., ltd.), stirring and mixing min, adding 20 of modified polypropylene glycol solution of triethylene diamine with a mass fraction of 1.3 g to prepare a foam, stirring and mixing the mixture by pouring the mixture into a foam stabilizer of 388, and solidifying the foam stabilizer into a foam mold of min.
Example 11
Preparing medical hydrophilic polyurethane sponge:
75 g of polyether polyol (elastomer polyether polyol; average Mn2000; from Shanghai Seikovia Biotech Co., ltd.), 25 g of polyester polyol (VANTHANOL ® WHP-204; from Wanhua chemical group Co., ltd.), 3g of pure water, 1.4 g of foam stabilizer 9205 (from Zhang Kong Tobo electronics Co., ltd.), 0.20 g of stannous octoate (analytically pure; from Guogon Chemie Co., ltd.), 0.45 g of propylene glycol solution of triethylene diamine with a mass fraction of 33% (from Santhylene diamine Co., ltd.), 1.5. g of nano silver antibacterial agent prepared in example 2, 30min of stirring, 50g of polyisocyanate isophorone diisocyanate, 4' -diphenylmethane diisocyanate and hexamethylene diisocyanate (analytically pure; from Guogon Chemie Co., ltd.), min of stirring, 20 of stirring, 38 of stirring for mixing, 8 of modified polypropylene diamine with a foam stabilizer prepared in example 3.5.37, and 38 of foam stabilizer, and curing.
Example 12
Preparing medical hydrophilic polyurethane sponge:
75 g of polyether polyol (elastomer polyether polyol; average Mn2000; from Shanghai Seikovia Biotech Co., ltd.), 25g of polyester polyol (VANTHANOL ® WHP-204; from Wanhua chemical group Co., ltd.), 3 g of pure water, 1.5 g of foam stabilizer 9205 (from Zhang Kong Tobo electronics Co., ltd.), 0.20 g of stannous octoate (analytically pure; from Guogon Chemie Co., ltd.), 0.5 g of propylene glycol solution of triethylene diamine with a mass fraction of 33% (from Santhylene diamine Co., ltd.), 1.5 g of nano silver antibacterial agent prepared in example 3, 30min of stirring, 50g of polyisocyanate isophorone diisocyanate, 4' -diphenylmethane diisocyanate and hexamethylene diisocyanate (analytically pure; from Guogon Chemie Co., ltd.), min of stirring, 20 of stirring for curing, and min of foam stabilizer, and 38 of modified polyurethane foam stabilizer prepared in example 3, and 38 of sponge foam stabilizer were prepared by pouring into a foam mold.
Comparative example 1
Comparative example 1 is a control group of example 11, the nano silver antibacterial agent prepared in example 2 of 1.5 g in example 11 was removed, and the rest raw materials, the raw material usage and the preparation method were kept unchanged, to finally obtain the medical hydrophilic polyurethane sponge.
Comparative example 2
Comparative example 2 is a control group of example 11, the modified ciprofloxacin prepared in example 8 of 20 g in example 11 is replaced by ciprofloxacin of 20 g, and the rest raw materials, the raw material consumption and the preparation method are kept unchanged, so as to finally obtain the medical hydrophilic polyurethane sponge.
Comparative example 3
Comparative example 2 is a control group of example 11, the modified ciprofloxacin prepared in example 8 of 20g in example 11 was removed, and the remaining raw materials, the raw material usage and the preparation method were kept unchanged, to finally obtain a medical hydrophilic polyurethane sponge.
Test example 1
The medical hydrophilic polyurethane sponges (hereinafter referred to as "sponges") prepared in examples 10 to 12 and comparative examples 1 to 3 were subjected to performance tests as follows, and the following test procedures were carried out in the same manner with respect to the individual examples, and the specific test results are shown in the following table 1:
Hydrophilicity the wettability of the sponge surface was characterized by using an FCA2000A4R contact angle measuring instrument, specifically, the water contact angle was measured by observing a 4.5 μl drop of water onto the sponge surface, and the average was taken from multiple measurements (10 measurements in this test example).
Antibacterial Properties 10 mg sponge was mixed with 1. 1 mL E.coli/Staphylococcus aureus suspension (hereinafter abbreviated as bacterial suspension) at 10. 10 7 CFU/mL on a 37℃constant temperature shaking table, and then cultured in a co-mixed manner at 200 r/min at 12 h, and the resultant was designated as an experimental group, while the bacterial suspension without sponge was used as a control group. After 12 h was co-cultured, the co-cultured experimental group/control group bacterial suspensions were diluted to 10 5 CFU/mL with PBS phosphate buffer (0.05 mol/L; ph7.0; containing 0.05M NaCl; purchased from shanghai-source biotechnology limited), 100 μl of the diluted experimental group/control group bacterial suspensions were coated on the surface of an agar plate, the agar plate was placed in a shaking incubator at 37 ℃ for 24h, and after the culture, the colony count was recorded by a plate colony count method, and the antibacterial ratio was calculated by referring to the following formula, wherein N 0 is the colony count of the control group and N 1 is the colony count of the experimental group.
Antibacterial ratio= (N 0-N1）×100%/N0.
Antibacterial stability, namely immersing the sponge into pure water fully, taking out and extruding until no liquid drops exist, repeating the water absorption-extrusion process for 100 times, drying the sponge at normal temperature in a drying oven until the weight is constant after the sponge is extruded for the last time, and calculating the antibacterial rate by referring to the detection process of the antibacterial performance.
TABLE 1 Performance test results
As can be seen from Table 1, the addition of the nano silver antibacterial agent and the modified ciprofloxacin prepared by the invention can remarkably improve the hydrophilicity and antibacterial property of the polyurethane sponge, and meanwhile, the nano silver antibacterial agent and the modified ciprofloxacin have a synergistic effect on the antibacterial property, and finally, the modification process of the ciprofloxacin and the modified ciprofloxacin have remarkable influence on the stability of the antibacterial property of the polyurethane sponge.
It should be noted that in this document, terms such as "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (10)
1. A preparation method of medical hydrophilic polyurethane sponge is characterized by comprising the following steps of stirring and mixing polyether polyol, polyester polyol, pure water, a foam stabilizer 9205, stannous octoate, a propylene glycol solution of triethylene diamine with the mass fraction of 33% and a nano silver antibacterial agent, adding polyisocyanate into the mixture, stirring and mixing the mixture, adding modified ciprofloxacin into the mixture, stirring and mixing the mixture to obtain a mixed material, pouring the mixed material into a mould, standing the mixed material, foaming and solidifying the mixed material, and demoulding the mixed material after 40-50 minutes to obtain the medical hydrophilic polyurethane sponge.
2. The method for preparing the medical hydrophilic polyurethane sponge according to claim 1, wherein the dosage ratio of polyether polyol, polyester polyol, pure water, foam stabilizer 9205, stannous octoate, propylene glycol solution of triethylene diamine with the mass fraction of 33%, nano silver antibacterial agent, polyisocyanate and modified ciprofloxacin is 75 g:25 g:3 g:1.0~1.5 g:0.15~0.20 g:0.3~0.5 g:1.2-1.5 g:45~50 g:20 g.
3. The method for preparing a medical hydrophilic polyurethane sponge according to claim 1, wherein the polyisocyanate is one of isophorone diisocyanate, 4' -diphenylmethane diisocyanate and hexamethylene diisocyanate.
4. The preparation method of the medical hydrophilic polyurethane sponge according to claim 1, wherein the nano silver antibacterial agent is prepared by adding carboxymethyl chitosan into deionized water under stirring, adding sodium hydroxide into the deionized water under stirring to adjust the pH of a system to 10.0-10.5, adding nano silver into the system under stirring, and stirring at a constant temperature for 2-3 hours to obtain the nano silver antibacterial agent.
5. The method for preparing a medical hydrophilic polyurethane sponge according to claim 4, wherein the dosage ratio of deionized water, carboxymethyl chitosan and nano silver is 100 mL:0.2~0.3 g:0.1g.
6. The preparation method of the medical hydrophilic polyurethane sponge according to claim 1 is characterized in that the modified ciprofloxacin is prepared by adding ciprofloxacin, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide into dichloromethane under stirring, stirring and mixing at room temperature for 1h, adding amino-terminated monomers into the mixture under stirring, heating to 35-40 ℃, stirring and reacting for 12-h, cooling to room temperature after the completion of stirring, and removing dichloromethane by rotary evaporation to obtain the modified ciprofloxacin.
7. The method for preparing a medical hydrophilic polyurethane sponge according to claim 6, wherein the dosage ratio of dichloromethane, ciprofloxacin, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide and amino-terminated monomer is 100 mL:0.1 mol:14~15 g:9~10 g:21~22 g.
8. The method for preparing a medical hydrophilic polyurethane sponge according to claim 6, wherein the amino-terminated monomer is prepared by the following steps:
S1, adding tris (hydroxymethyl) aminomethane and triethylamine into dimethyl sulfoxide, stirring for 30min, charging nitrogen, adding 2-chloro-5-nitropyridine into the mixture, heating to 85-90 ℃, stirring for reacting for 5-6 hours, cooling to room temperature after the reaction is finished, and removing the dimethyl sulfoxide by rotary evaporation to obtain an intermediate;
S2, adding absolute ethyl alcohol, a hydrochloric acid aqueous solution with the mass fraction of 18% and iron powder into deionized water, heating to 80-90 ℃, stirring for 30-min, cooling to room temperature, stirring and adding an intermediate into the mixture, heating to 80-90 ℃, stirring at constant temperature for 5-6 hours, cooling to room temperature after the completion of the stirring, filtering, adding ammonia water into the filtrate to adjust the pH of the system to 8.5-9.0, standing for 12-h at room temperature, and carrying out suction filtration, washing and drying to obtain the amino-terminated monomer.
9. The method for preparing a medical hydrophilic polyurethane sponge according to claim 8, wherein the dosage ratio of dimethyl sulfoxide, tris (hydroxymethyl) aminomethane, triethylamine and 2-chloro-5-nitropyridine in S1 is 100 mL:0.11~0.12 mol:10~11 g:0.1 mol.
10. The method for preparing the medical hydrophilic polyurethane sponge according to claim 8, wherein the dosage ratio of deionized water, absolute ethyl alcohol, 18% hydrochloric acid aqueous solution by mass fraction, iron powder and intermediate in S2 is 100 mL:20 mL:6~8 mL:20 g:40~45 g.
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|---|---|---|---|---|
| US20070179210A1 (en) * | 2006-01-31 | 2007-08-02 | Tyco Healthcare Group Lp | Super soft foams |
| CN101223887B (en) * | 2008-01-31 | 2011-09-14 | 吴继贤 | Nano silver antimicrobial solution and preparing method thereof |
| CN102245214A (en) * | 2008-10-10 | 2011-11-16 | 仿生耳研究所 | Biodegradable polymer - bioactive moiety conjugates |
| CN104927348A (en) * | 2014-03-20 | 2015-09-23 | 北京化工大学 | Antibacterial and anticoagulant polymer material, preparation method and application thereof |
| CN113563558A (en) * | 2021-08-06 | 2021-10-29 | 南京金栖化工集团有限公司 | Preparation method of nano-silver antibacterial polyurethane slow-resilience sponge |
-
2024
- 2024-10-11 CN CN202411416449.6A patent/CN119219892B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070179210A1 (en) * | 2006-01-31 | 2007-08-02 | Tyco Healthcare Group Lp | Super soft foams |
| CN101223887B (en) * | 2008-01-31 | 2011-09-14 | 吴继贤 | Nano silver antimicrobial solution and preparing method thereof |
| CN102245214A (en) * | 2008-10-10 | 2011-11-16 | 仿生耳研究所 | Biodegradable polymer - bioactive moiety conjugates |
| CN104927348A (en) * | 2014-03-20 | 2015-09-23 | 北京化工大学 | Antibacterial and anticoagulant polymer material, preparation method and application thereof |
| CN113563558A (en) * | 2021-08-06 | 2021-10-29 | 南京金栖化工集团有限公司 | Preparation method of nano-silver antibacterial polyurethane slow-resilience sponge |
Non-Patent Citations (3)
| Title |
|---|
| CHANG JM等: "Poly(N-Acryloyl Ciprofloxacin-Co-Acrylic Acid)-Incorporated Waterborne Polyurethane Leather Coating with Long-lasting Antimicrobial Property", 《JOURNAL OF THE AMERICAN LEATHER CHEMISTS ASSOCIATION》, vol. 112, no. 1, 31 January 2017 (2017-01-31), pages 15 - 22 * |
| KOWALCZUK等: "Characterization of Ciprofloxacin-Bismuth-Loaded Antibacterial Wound Dressing", 《MOLECULES》, vol. 25, no. 21, 30 November 2020 (2020-11-30), pages 5096 * |
| 常金明 等: "持效抗菌型聚氨酯的制备及其性能研究", 《2016第十一届全国皮革化学品学术交流会暨中国皮革协会技术委员会第21届年会摘要集》, 27 July 2016 (2016-07-27), pages 98 * |
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