CN118515847B - Antibacterial, waterproof and breathable TPU for producing band-aids, preparation method and application thereof - Google Patents
Antibacterial, waterproof and breathable TPU for producing band-aids, preparation method and application thereof Download PDFInfo
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- CN118515847B CN118515847B CN202410988157.3A CN202410988157A CN118515847B CN 118515847 B CN118515847 B CN 118515847B CN 202410988157 A CN202410988157 A CN 202410988157A CN 118515847 B CN118515847 B CN 118515847B
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- antibacterial
- band
- tpu
- waterproof
- aid
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 52
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002033 PVDF binder Substances 0.000 claims abstract description 26
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 26
- 238000009987 spinning Methods 0.000 claims abstract description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 10
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 10
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 10
- 239000004970 Chain extender Substances 0.000 claims abstract description 8
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000012948 isocyanate Substances 0.000 claims abstract description 8
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 46
- 239000000463 material Substances 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 10
- 230000003385 bacteriostatic effect Effects 0.000 claims description 8
- WBYWAXJHAXSJNI-VOTSOKGWSA-N trans-cinnamic acid Chemical compound OC(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-N 0.000 claims description 8
- 239000000314 lubricant Substances 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- RNSLCHIAOHUARI-UHFFFAOYSA-N butane-1,4-diol;hexanedioic acid Chemical compound OCCCCO.OC(=O)CCCCC(O)=O RNSLCHIAOHUARI-UHFFFAOYSA-N 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000011206 ternary composite Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- FZWBABZIGXEXES-UHFFFAOYSA-N ethane-1,2-diol;hexanedioic acid Chemical compound OCCO.OC(=O)CCCCC(O)=O FZWBABZIGXEXES-UHFFFAOYSA-N 0.000 claims description 2
- 238000010559 graft polymerization reaction Methods 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 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 description 2
- 239000006096 absorbing agent Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 2
- 229920003225 polyurethane elastomer Polymers 0.000 abstract description 2
- 239000012046 mixed solvent Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 230000035699 permeability Effects 0.000 description 15
- 239000012528 membrane Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002121 nanofiber Substances 0.000 description 6
- 206010052428 Wound Diseases 0.000 description 5
- 208000027418 Wounds and injury Diseases 0.000 description 5
- 235000006708 antioxidants Nutrition 0.000 description 5
- 238000010835 comparative analysis Methods 0.000 description 5
- 230000002745 absorbent Effects 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000002706 hydrostatic effect Effects 0.000 description 2
- 239000012170 montan wax Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 238000007655 standard test method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 230000008952 bacterial invasion Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 230000023597 hemostasis Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002068 microbial inoculum Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/02—Adhesive bandages or dressings
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Vascular Medicine (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Heart & Thoracic Surgery (AREA)
- Biomedical Technology (AREA)
- Artificial Filaments (AREA)
Abstract
本发明公开了一种用于生产创可贴的抑菌防水透湿型TPU、制备方法及其应用，属于聚氨酯弹性体技术领域。其技术方案为：包括原料聚酯多元醇、异氰酸酯、扩链剂、加工助剂、催化剂、改性聚偏氟乙烯和抗菌剂；所述抑菌防水透湿型TPU基材的制备方法为：DMF和乙酸乙酯混合得到专用溶剂，将TPU颗粒分散到混合溶剂中得到纺丝液并进行静电纺丝，得到抑菌防水透湿型TPU基材。与现有技术相比，本发明制备的溶剂使得TPU溶解的质量分数可达25%，因而纺丝的产量相对比传统DMF体系得到极大的提高。同时，本发明制备的TPU基材还具有抑菌、防水、透湿、高回弹等特点，极大地提高了其在创可贴生产领域的适用性。The present invention discloses an antibacterial, waterproof and breathable TPU for producing band-aids, a preparation method and an application thereof, and belongs to the technical field of polyurethane elastomers. The technical scheme thereof is as follows: comprising raw materials of polyester polyol, isocyanate, chain extender, processing aid, catalyst, modified polyvinylidene fluoride and antibacterial agent; the preparation method of the antibacterial, waterproof and breathable TPU substrate is as follows: DMF and ethyl acetate are mixed to obtain a special solvent, TPU particles are dispersed in the mixed solvent to obtain a spinning solution and electrostatic spinning is performed to obtain an antibacterial, waterproof and breathable TPU substrate. Compared with the prior art, the solvent prepared by the present invention allows the mass fraction of TPU dissolved to reach 25%, so the spinning yield is greatly improved compared with the traditional DMF system. At the same time, the TPU substrate prepared by the present invention also has the characteristics of antibacterial, waterproof, breathable, high resilience, etc., which greatly improves its applicability in the field of band-aid production.
Description
Technical Field
The invention belongs to the technical field of polyurethane elastomers, and particularly relates to a bacteriostatic waterproof moisture-permeable TPU for producing a band-aid, a preparation method and application thereof.
Background
The band-aid is a surgical article most commonly used in our life and mainly consists of a dry adhesive plaster, a medicated absorption pad and a separation permeable membrane. In the band-aid, the drug-containing absorption pad is in direct contact with the wound, and the main function of the band-aid is hemostasis and wound protection. The dry adhesive tape is mainly used for fixing the band-aid, and the absorbent pad containing the medicine is ensured to continuously act on the wound. The isolating permeable membrane has the main functions of inhibiting bacterial invasion, isolating water-impregnated wounds, and guaranteeing the ventilation and dryness of the wounds, so that the infection risk is reduced.
The nanofiber membrane obtained by electrostatic spinning has soft hand feeling due to superfine fiber diameter, and is formed by splitting and drafting high polymer solution into jet flow in an electric field by utilizing high-voltage static electricity, and finally depositing the jet flow on the surface of a receiving device along with volatilization of a solvent. The nanofiber membrane has a large specific surface area, so that the coverage, warmth retention and bulkiness of the nanofiber membrane are better than those of other types of fibers, the high porosity of the nanofiber membrane can improve the moisture permeability, and the invasion of harmful gas, dust and bacteria can be effectively prevented. The electrostatic spinning nanofiber membrane also has higher elongation at break and elastic deformation, so that the electrostatic spinning nanofiber membrane has wide application prospect in the field of waterproof and moisture permeable materials.
The film prepared from polyurethane is cheap and easy to obtain, simple to prepare, has good mechanical property and chemical stability, and has waterproofness and breathability, so that the film is widely applied to the waterproof and moisture permeable field. With the development of electrostatic spinning technology, polyurethane and other polymers, natural polymer materials and the like are subjected to blending spinning, so that the performance of the polyurethane material is improved, and the application field of the polyurethane material can be wider. Research shows that the introduction of fluorine element into the membrane material can improve the hydrophobicity of the material. The polyvinylidene fluoride has small surface energy, strong hydrophobicity, good chemical stability, heat resistance and mechanical property, and is a polymer film material with excellent performance.
The solutions for electrostatic spinning TPU are mostly N, N-Dimethylformamide (DMF) or Dimethylacetamide (DMAC), the dispersion capacity of the two solutions to TPU is low, generally between 8% and 12%, the increase of the concentration of the solutions can increase the spinning yield, but simultaneously the spinning liquid is sticky, the Taylor cone diameter under an electric field in the spinning process is reduced, the contact between a filament body and air is reduced, the volatilization of a spinning solvent is incomplete in the spinning process, and the phenomenon that the solvent breaks down a film is caused, so that the quality of spinning is greatly influenced.
The analysis shows that the TPU product prepared by the industrial electrostatic spinning at the present stage has the problems of low yield, bacteriostasis, water resistance and difficult compatibility of the moisture permeability.
Disclosure of Invention
The invention provides a bacteriostatic waterproof moisture-permeable TPU for producing a band-aid, which has good dispersibility and solubility in spinning solution. The invention also provides a preparation method and application of the TPU, which are used for producing the isolation permeable membrane in the band-aid structure, and the TPU substrate has outstanding performance and is mainly characterized by bacteriostasis, water resistance, moisture permeability, high rebound, large yield and the like.
The technical scheme of the invention is as follows:
in a first aspect, the antibacterial waterproof moisture-permeable TPU for producing the band-aid comprises the following raw materials in parts by mass:
60-80 parts of polyester polyol;
17-33 parts of isocyanate;
3-7 parts of chain extender;
0.8-1.2 parts of processing aid;
0.01-0.02 part of catalyst;
10-20 parts of modified polyvinylidene fluoride;
1-2 parts of antibacterial agent.
Preferably, the polyester polyol is one of poly (1, 4-butylene glycol adipate) diol, poly (ethylene glycol adipate) diol and poly (1, 4-butylene glycol adipate) diol, and the number average molecular weight of the polyester polyol is 1000-2000.
Preferably, the isocyanate is 4,4' -diphenylmethane diisocyanate (MDI-100).
Preferably, the chain extender is one or more of dipropylene glycol, 1, 4-butanediol, and neopentyl glycol.
Preferably, the processing aid is an antioxidant, a lubricant and an ultraviolet absorber; the antioxidants are hindered phenol antioxidants 1010 and phosphite antioxidants 626; the lubricants are amide WAX type lubricants WAX-C and montan WAX type lubricants WAX-E; the ultraviolet absorbent is methyl ether ultraviolet absorbent UV-1 and hindered ammonia ultraviolet absorbent 770; the catalyst is one of stannous octoate, triethylene diamine and butyl titanate.
Preferably, the preparation method of the modified polyvinylidene fluoride comprises the following steps: and (3) taking Benzoyl Peroxide (BPO) as an initiator, taking 3-phenylacrylic acid (CA) as a monomer, and initiating graft polymerization in an N, N-dimethylformamide solution dissolved with polyvinylidene fluoride (PVDF) to prepare the polyvinylidene fluoride grafted with 3-phenylacrylic acid, namely the modified polyvinylidene fluoride.
Preferably, the antibacterial agent is a reduced graphene oxide-titanium dioxide-nano silver ternary composite antibacterial material, wherein the mass ratio of the reduced graphene oxide to the titanium dioxide to the nano silver is 1:1 (1-3).
In a second aspect, the preparation method of the antibacterial waterproof moisture-permeable TPU for producing the band-aid is disclosed, and comprises the following steps: simultaneously injecting polyester polyol dissolved with a processing aid, a chain extender and isocyanate into a double-screw extruder, adding modified polyvinylidene fluoride and an antibacterial agent into the double-screw extruder, and then injecting a catalyst into the double-screw extruder; the mixed materials are reacted and plasticized in a screw rod, and are granulated by an underwater cutting system, so that the antibacterial waterproof moisture-permeable TPU used for producing the band-aid is obtained.
Preferably, the extrusion temperature of the double-screw extruder is 130-220 ℃, and the screw rotating speed is 170-230r/min.
The third aspect discloses an application of the antibacterial waterproof moisture-permeable TPU in producing a antibacterial waterproof moisture-permeable TPU substrate of a band-aid, and the preparation method comprises the following steps: and mixing N, N-dimethylformamide and ethyl acetate according to the mass ratio of 1 (1-2) to obtain a mixed solution, dispersing the antibacterial waterproof moisture-permeable TPU for producing the band-aid into the mixed solution to obtain a spinning solution, and carrying out electrostatic spinning to obtain the antibacterial waterproof moisture-permeable TPU base material for producing the band-aid.
Compared with the prior art, the invention has the following beneficial effects:
1. the mixed solution of the solvent N, N-dimethylformamide and ethyl acetate prepared by the method ensures that the mass fraction of the TPU dissolved in the spinning solution can reach 25%, so that the spinning yield is greatly improved compared with the traditional DMF system. Meanwhile, the TPU substrate prepared by the method has the characteristics of bacteriostasis, water resistance, moisture permeability, high resilience and the like, and the applicability of the TPU substrate in the field of band-aid production is greatly improved.
2. According to the invention, the waterproof and moisture permeability of the TPU is greatly improved by adding the modified polyvinylidene fluoride in the process of preparing the TPU; the polyvinylidene fluoride has small surface energy, strong hydrophobicity, good chemical stability, heat resistance and mechanical property, is a polymer film material with excellent performance, can participate in the reaction process of TPU by modification, and improves the waterproof and moisture permeability of TPU on the premise of not affecting the mechanical property of TPU.
3. According to the invention, the antibacterial agent is added in the process of preparing the TPU, so that the antibacterial effect of the TPU is greatly improved.
Detailed Description
In order to better understand the technical solutions of the present invention, the following description will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments.
Hindered phenolic antioxidant 1010, available from basf, germany;
phosphite antioxidant 626, available from basf, germany;
amide WAX lubricant WAX-C, available from Cortain, germany;
montan WAX lubricant WAX-E, available from Cortain, germany;
the methyl ether ultraviolet absorber UV-1, available from Basff, germany;
Hindered amine ultraviolet absorber 770 available from basf, germany;
4,4' -diphenylmethane diisocyanate MDI-100, commercially available from Basoff, germany;
reduced graphene oxide, available from ala Ding Shiji inc.
The specific preparation method of the modified polyvinylidene fluoride in the examples and the comparative examples comprises the following steps: 10g of 3-phenylacrylic acid was dissolved in 100mL of N, N-Dimethylformamide (DMF), and the mixture was stirred well and transferred to a constant pressure dropping funnel for use. 200mL of DMF was added to a four-necked flask equipped with a stirrer, a condenser and an air-guide tube, and 50g of polyvinylidene fluoride (PVDF) powder was added to the four-necked flask, and the mixture was heated to 50℃and stirred at constant temperature for 30 minutes to sufficiently disperse the powder. The flask was sealed, then high-purity nitrogen was introduced to remove air from the system while maintaining constant stirring to allow the system to mix uniformly, then the temperature of the system was raised to 70 ℃,10 g of terephthaloyl peroxide (BPO) as an initiator was added, and after 30 minutes under nitrogen protection, a DMF solution of 3-phenylacrylic acid was added dropwise, the dropping speed was controlled at 0.15mL/min, and polymerization was carried out, and the reaction was completed for 8 hours. Taking out the flask from the water bath, cooling at room temperature, adding absolute ethyl alcohol to precipitate the modified polyvinylidene fluoride, removing 3-phenyl acrylic acid homopolymer and impurities, repeating for three times, and then vacuum drying the obtained product to constant weight at 50 ℃ to obtain grafted polyvinylidene fluoride PVDF-g-P (CA), namely the modified polyvinylidene fluoride.
The antibacterial agent (the reduced graphene oxide-titanium dioxide-nano silver ternary composite antibacterial material) in the examples and the comparative example is synthesized by adopting a one-pot method, and the specific preparation method is as follows: taking a silver nitrate aqueous solution with the concentration of 30% in a beaker, adding reduced graphene oxide and titanium dioxide into the silver nitrate aqueous solution, wherein the mass ratio of the reduced graphene oxide to the titanium dioxide to the nano silver is 1:1 (1-3), and placing the mixed solution in ultrasonic equipment for fully and uniformly mixing; adding excessive L-ascorbic acid as a reducing agent, closing the reaction kettle, then introducing high-purity nitrogen to remove air in the system, keeping continuous stirring in the reaction kettle to ensure that the system is uniformly mixed, keeping the temperature of the system at 80 ℃, and finishing the reaction for 12 hours. The closed reaction kettle is heated and stirred, and cooled at room temperature. Filtering the substances in the reaction kettle by a suction filter, and continuously flushing with distilled water in the suction filtration process. And after the suction filtration is finished, vacuum drying the precipitate at 70 ℃ to constant weight, thus obtaining the reduced graphene oxide-titanium oxide-nano silver ternary composite antibacterial material.
The parts by weight of each raw material, extrusion temperature and screw speed in examples and comparative examples are shown in Table 1.
Table 1 weight parts of each raw material, extrusion temperature and screw rotation speed in examples and comparative examples
The preparation methods of the antibacterial waterproof moisture-permeable TPU substrates used for producing the band-aid in examples 1 to 4 and comparative examples 1 to 4 are as follows:
The polyester polyol dissolved with the processing aid, the chain extender and the isocyanate are respectively injected into the double-screw extruder from three inlets of the double-screw extruder at the same time, the modified polyvinylidene fluoride and the antibacterial agent are added into the double-screw extruder, and then the catalyst is injected into the double-screw extruder. The mixed materials are reacted and plasticized in a screw rod, and are granulated by an underwater cutting system, so that the antibacterial waterproof moisture-permeable TPU used for producing the band-aid is obtained.
Dispersing antibacterial waterproof moisture-permeable TPU particles for producing the band-aid into a spinning solution formed by a solvent to be dissolved until a transparent spinning solution is formed, and carrying out electrostatic spinning on the transparent spinning solution under the conditions of room temperature (25 ℃) and relative humidity of 50%, so as to obtain the antibacterial waterproof moisture-permeable TPU substrate for producing the band-aid.
The TPU substrates prepared in the examples and comparative examples were tested as follows:
(1) Hardness testing: the test was carried out according to the method specified in ASTM D2240 Standard test method for rubber Properties.
(2) Tensile strength test: the test was performed according to the method specified in the Standard ASTM D412 method for tensile testing of vulcanized rubbers and thermoplastic elastomers.
(3) Elastic recovery test: and (3) bonding each group of TPU base materials (keeping the thickness of the materials to be the same) onto elastic woven fabrics in the same specification and pattern through a hot pressing process, cutting the bonded woven fabrics into standard sample strips, and testing on a servo tension machine (high-speed rail detection instrument Co., ltd.). The testing method comprises the following steps: the stretching is kept at 300% for 5min, the release is carried out for 5min, and the distance change between spline stretching detection points is measured.
(4) Hydrostatic pressure resistance test: according to the standard AATCC 127 Water resistance: the test was performed by the method specified in hydrostatic test.
(5) Air permeability test: the test was performed according to the method specified in standard test method for determining the water vapor permeability of materials by astm e 96. And testing the air permeability of the material by adopting a full-automatic air permeability meter.
(6) Moisture permeability test: referring to the test method for the water vapor permeability of the ASTME 96/E96M 16 material, a water vapor permeability tester is used for measuring the moisture permeability of the material.
(7) Antibacterial performance test: the test was carried out according to the method specified in Standard GB/T31402-2015 test method for antibacterial Property of Plastic surface. Antibacterial tests were performed on staphylococcus aureus and escherichia coli.
The test results of the TPU substrate prepared in the examples and comparative examples are shown in Table 2.
Table 2 test results for TPU substrates prepared in examples and comparative examples
From comparative analysis of the various performance test data of examples 1-4 and comparative examples 1-4, it can be seen that:
(1) As can be seen from the data of comparative analysis example 1 and comparative example 1, whether modified polyvinylidene fluoride is added to the material under the same hardness condition affects the waterproof performance of the material, and the addition of modified polyvinylidene fluoride makes the waterproof performance of the material better.
(2) The data of comparative analysis example 1 and comparative example 2 show that the addition of the antimicrobial agent can improve the bacteriostatic properties of the materials under the same hardness condition.
(3) Comparing the data of analysis example 1 and comparative example 3, it is clear that the solvent adapted by the invention can make the mass fraction of TPU in the spinning solution reach 25%, and the spinning yield of the invention is greatly improved compared with that of the traditional DMF system.
(4) As can be seen from the data of comparative analysis examples 2 and 3, the type of the antimicrobial additive directly affects the antibacterial performance of the material, and in the three comparative antimicrobial compositions of the present invention, the reduced graphene oxide: titanium dioxide: nanosilver=1:1:3 resistance: the microbial inoculum performs optimally.
(5) Comparing the data of analysis example 4 with comparative example 4, it is known that the solvent type affects the amount of TPU dissolved, and the spinning yield of the present invention is greatly improved over the conventional ethyl acetate system.
(6) The data of comparative analysis example 1 and comparative example 4 show that the higher the hardness of the material under different hardness conditions, the better the waterproof performance and the poorer the corresponding air permeability.
(7) Comparing the data of example 1 with the data of example 3 shows that the higher the hardness of the material under different hardness conditions, the poorer the elastic recovery performance.
Claims (7)
1. The antibacterial waterproof moisture-permeable TPU used for producing the band-aid is characterized by comprising the following raw materials in parts by mass:
60-80 parts of polyester polyol;
17-33 parts of isocyanate;
3-7 parts of chain extender;
0.8-1.2 parts of processing aid;
0.01-0.02 part of catalyst;
10-20 parts of modified polyvinylidene fluoride;
1-2 parts of an antibacterial agent;
the isocyanate is 4,4' -diphenylmethane diisocyanate;
The preparation method of the modified polyvinylidene fluoride comprises the following steps: initiating graft polymerization in N, N-dimethylformamide solution dissolved with polyvinylidene fluoride by taking terephthaloyl peroxide as an initiator and 3-phenylacrylic acid as a monomer to prepare polyvinylidene fluoride grafted with 3-phenylacrylic acid, namely modified polyvinylidene fluoride;
The antibacterial agent is a reduced graphene oxide-titanium dioxide-nano silver ternary composite antibacterial material, wherein the mass ratio of the reduced graphene oxide to the titanium dioxide to the nano silver is 1:1:3.
2. The bacteriostatic, waterproof and moisture-permeable TPU for use in the production of a band aid according to claim 1, wherein said polyester polyol is one of poly (1, 4-butylene glycol adipate) diol, poly (ethylene glycol adipate) diol and poly (1, 4-butylene glycol adipate) diol, and the number average molecular weight of the polyester polyol is 1000-2000.
3. The bacteriostatic, waterproof and moisture-permeable TPU for use in the manufacture of a band-aid of claim 1, wherein said chain extender is one of dipropylene glycol, 1, 4-butanediol and neopentyl glycol.
4. The bacteriostatic, waterproof, moisture-permeable TPU for use in the production of a band-aid of claim 1, wherein said processing aids are antioxidants, lubricants and uv absorbers; the catalyst is one of stannous octoate, triethylene diamine and butyl titanate.
5. A process for the preparation of a bacteriostatic, waterproof, moisture-permeable TPU for the production of a band-aid according to any one of claims 1 to 4, comprising the steps of: simultaneously injecting polyester polyol dissolved with a processing aid, a chain extender and isocyanate into a double-screw extruder, adding modified polyvinylidene fluoride and an antibacterial agent into the double-screw extruder, and then injecting a catalyst into the double-screw extruder; the mixed materials are reacted and plasticized in a screw rod, and are granulated by an underwater cutting system, so that the antibacterial waterproof moisture-permeable TPU used for producing the band-aid is obtained.
6. The method for preparing the antibacterial waterproof moisture-permeable TPU for producing the band-aid according to claim 5, wherein the extrusion temperature of the double-screw extruder is 130-220 ℃ and the screw rotating speed is 170-230r/min.
7. Use of a bacteriostatic waterproof moisture-permeable TPU for the production of a band-aid according to any one of claims 1-4, characterized in that it is prepared by the following method: mixing N, N-dimethylformamide and ethyl acetate according to the mass ratio of 1 (1-2) to obtain a mixed solution, dispersing the antibacterial waterproof moisture-permeable TPU (thermoplastic polyurethane) for producing the band-aid obtained in any one of claims 1-4 into the mixed solution to obtain a spinning solution, and carrying out electrostatic spinning to obtain the antibacterial waterproof moisture-permeable TPU substrate for producing the band-aid.
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