CN117069912B - Preparation method of antibacterial medical polymer material - Google Patents
Preparation method of antibacterial medical polymer material Download PDFInfo
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- CN117069912B CN117069912B CN202311033177.7A CN202311033177A CN117069912B CN 117069912 B CN117069912 B CN 117069912B CN 202311033177 A CN202311033177 A CN 202311033177A CN 117069912 B CN117069912 B CN 117069912B
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- antibacterial
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- medical polymer
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 76
- 239000002861 polymer material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 41
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 27
- 239000010703 silicon Substances 0.000 claims abstract description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 23
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 13
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 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 abstract description 13
- 229920000570 polyether Polymers 0.000 claims abstract description 13
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 49
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000011159 matrix material Substances 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 29
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- -1 polydimethylsiloxane Polymers 0.000 claims description 20
- 238000002390 rotary evaporation Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 claims description 16
- 238000010907 mechanical stirring Methods 0.000 claims description 16
- 150000003512 tertiary amines Chemical class 0.000 claims description 16
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 15
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 15
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 14
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000003112 inhibitor Substances 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 10
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000002274 desiccant Substances 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 229940050176 methyl chloride Drugs 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 abstract description 9
- 229920002635 polyurethane Polymers 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 8
- 239000003242 anti bacterial agent Substances 0.000 abstract description 6
- 230000014759 maintenance of location Effects 0.000 abstract description 6
- 125000000217 alkyl group Chemical group 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 abstract description 2
- 238000010025 steaming Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 238000007792 addition Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 208000015181 infectious disease Diseases 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 3
- 244000052616 bacterial pathogen Species 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000012650 click reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000005956 quaternization reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000002627 tracheal intubation Methods 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 208000002193 Pain Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- HXELDDLUAGVKCK-UHFFFAOYSA-N [N]=O.[S] Chemical group [N]=O.[S] HXELDDLUAGVKCK-UHFFFAOYSA-N 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001647 drug administration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002550 fecal effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000036737 immune function Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000000474 nursing effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000002485 urinary effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- 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
- C08G18/753—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
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/04—Macromolecular materials
- A61L29/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/61—Polysiloxanes
-
- 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
- C08G18/6666—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
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention relates to a preparation method of an antibacterial medical polymer material, and belongs to the technical field of antibacterial materials. The high polymer material is prepared by polycondensation of isophorone diisocyanate, polyether glycol, silicon-based antibacterial monomer and 1, 4-butanediol; after the silicon-based antibacterial monomer participates in polyurethane polycondensation, introducing a quaternary ammonium structure with an alkyl long chain into the main chain of the polymer, so that the polymer is endowed with good antibacterial effect, and compared with an externally added antibacterial agent or a coating antibacterial material, the antibacterial component is not easy to migrate and fall off, so that the polymer has higher safety and long-acting antibacterial property; the introduced organosilicon chain is modified, and the prepared material has good softness and shape retention capacity, and the surface wettability, and is suitable for medical catheters.
Description
Technical Field
The invention belongs to the technical field of antibacterial materials, and particularly relates to a preparation method of an antibacterial medical polymer material.
Background
The medical catheter is a passage connected with the inside and the outside of a human body, can realize medical means such as drug administration, drainage, cleaning and the like at diseased positions, and the dosage of the medical catheter occupies more than 40% of medical instruments, but the number of cases of body infection caused by the intervention catheter is not small each year, and the safety of the medical catheter directly influences the treatment result.
The polyurethane catheter is mainly made of polyurethane and silica gel, wherein the polyurethane catheter has good tolerance, stable mechanical property and high medical safety, but has poor surface wettability, strong stinging property in the intervention and withdrawal processes of the catheter, can be only used for short-term detection, and has high application limitation; the silica gel catheter is soft, high in biocompatibility and easy to infiltrate on the surface, but poor in shape retention capability and easy to deform, so that medium conveying is blocked, regular monitoring and maintenance are needed, and the working strength of medical care is increased. In addition, the external intervention polymer material has no immune function, and the surface of the external intervention polymer material can not be identified and cleaned by organisms in time after germs are adhered to the surface of the external intervention polymer material, so that germs are bred, and medical infection is caused. Such as a fecal drainage tube and a catheter, the educed excrement contains a large amount of germs, and the tube generally needs long-time intervention, if the tube cannot be cleaned in time, the tube is extremely easy to cause infection; according to the report of the prior art, the prior art means mainly comprises the steps of adding an antibacterial agent, endowing a catheter material with certain antibacterial property, and reducing the infection risk, wherein the doping method of the antibacterial agent mainly comprises two modes of blending introduction and coating introduction, and the problem of damage to the organism and the problem of deterioration of the antibacterial effect caused by falling of the antibacterial agent cannot be avoided in any mode; therefore, the application is based on the medical catheter application background, and the polymer material with the antibacterial effect is developed.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention aims to provide a preparation method of an antibacterial medical polymer material.
The aim of the invention can be achieved by the following technical scheme:
an antibacterial medical polymer material comprises the following raw materials:
isophorone diisocyanate, polyether glycol, silicon-based antibacterial monomer and 1, 4-butanediol;
the silicon-based antibacterial monomer is prepared by the following method:
step A1: uniformly mixing 1-chlorohexane, triethylamine and benzene, introducing nitrogen for protection, heating to 65-75 ℃, applying 120-180rpm for mechanical stirring, intermittently adding diallylamine, controlling the total adding reaction time to be 3-4h, reducing pressure after the reaction is finished, steaming to remove benzene and excessive 1-chlorohexane, washing a steaming substrate with water, and drying to obtain a tertiary amine matrix;
further, the dosage ratio of diallylamine, 1-chlorohexane, triethylamine and benzene was 0.1mol:0.14 to 0.18mol:6-8mL: the secondary amine structure substitution reaction in 35-45mL, 1-chlorohexane and diallylamine, the introduction of alkyl long chain, the specific reaction process can be expressed as follows:
step A2: uniformly mixing a tertiary amine matrix, a polymerization inhibitor, sodium carbonate and dioxane, introducing nitrogen for protection, preheating to 80 ℃, introducing methyl chloride for pressurizing to 4-5bar, then continuously heating to 95-105 ℃, carrying out reflux reaction for 2-2.5h, decompressing and removing excessive methyl chloride after the reaction, and maintaining rotary evaporation under vacuum to remove dioxane to obtain a quaternized matrix;
further, the amount ratio of the tertiary amine base, the polymerization inhibitor, sodium carbonate and dioxane was 0.1mol:5-8mg:0.15-0.2g:50-60mL, and the specific reaction process can be expressed as follows:
step A3: mixing quaternized matrix, thioglycollic acid, dimethylphenylphosphine and dimethylacetamide, introducing nitrogen for protection, heating to 80-90deg.C, mechanically stirring at 240-360rpm with 300-400W/m 2 Ultraviolet radiationPerforming irradiation, reacting for 1.2-1.6h, repeatedly adding deionized water after the reaction is finished, performing reduced pressure rotary evaporation, and removing dimethylacetamide to obtain a modified monomer;
further, the amount ratio of quaternized matrix, thioglycolic acid, dimethylphenylphosphine and dimethylacetamide was 0.1mol:0.2mol:10-15mg:85-100mL, thioglycollic acid and quaternized matrix click reaction, introducing carboxyl end group modification, the specific reaction process can be expressed as follows:
step A4: uniformly mixing a modified monomer, aminopropyl double-end-capped polydimethylsiloxane, thionyl chloride and dimethylformamide, heating to 70-80 ℃, applying mechanical stirring at 120-180rpm, adding a molecular sieve drying agent, carrying out constant-temperature reflux reaction for 1.6-2.2h, filtering after the reaction is finished, decompressing and steaming filtrate to remove excessive thionyl chloride, washing a steaming substrate with water to separate liquid, and removing dimethylformamide to obtain a silicon-based antibacterial monomer;
further, the molar ratio of carboxyl to amino of the modified monomer and the aminopropyl double-end-capped polydimethylsiloxane is 1:1.15-1.2, the number average molecular weight of the aminopropyl double-end-capped polydimethylsiloxane is 1000, and the modified monomer and the aminopropyl double-end-capped polydimethylsiloxane are subjected to amidation reaction to form a silicon chain-containing block oligomer, wherein the specific reaction process can be expressed as follows:
the preparation method of the antibacterial medical polymer material comprises the following steps:
step S1: uniformly mixing isophorone diisocyanate and polyether glycol under the protection of nitrogen, heating to 85-100 ℃, applying mechanical stirring at 80-100rpm, slowly adding a silicon-based antibacterial monomer, controlling the total adding reaction time to be 2.4-2.8h, discharging, detecting the content of isocyanate groups, and obtaining a prepolymer;
step S2: adding the prepolymerization material and the 1, 4-butanediol into a vacuum kettle for mixing, keeping the vacuum degree below 1kPa, heating to 120-130 ℃, stirring at 55-70rpm, reacting for 1.5-2h, and extruding and granulating after the reaction is finished to obtain the antibacterial medical polymer material.
Further, the molar ratio of isocyanate groups of the isophorone diisocyanate, hydroxyl groups of the polyether glycol, and amino groups of the silicon-based antibacterial monomer is 1:0.68-0.75:0.1-0.17.
Further, the molar ratio of isocyanate groups of the prepolymer to hydroxyl groups of 1, 4-butanediol was 1:1.
the invention has the beneficial effects that:
the invention takes part in the block copolymerization of polyurethane through the autonomous development of silicon-based antibacterial monomer, obtain the macromolecule material with stable antibacterial effect, this silicon-based antibacterial monomer takes 1-chlorohexane and diallylamine substitution reaction, make tertiary amine basal body with long chain alkyl, then carry on quaternization reaction with chloromethane under high temperature and high pressure, click reaction by thioglycollic acid and quaternization basal body, introduce the carboxyl modification of end, finally copolymerize with little excessive amine propyl double-end-capped polydimethylsiloxane, form the block oligomer containing silicon chain and end amino, it takes part in after polyurethane polycondensation, introduce the quaternary ammonium structure with long chain alkyl to the main chain of the polymer, give the polymer good antibacterial efficacy, compared with adding antibacterial agent or coating antibacterial material, antibacterial ingredient is difficult to migrate and drop, have higher security and long-term antibacterial property, and sulfur nitrogen oxide structure in the silicon-based antibacterial monomer structure can form the multi-site chelation with metal ion, have far-reaching application prospect in the metal-based antibacterial agent compound application fields such as silver system, zinc system, etc.; the silicone-based antibacterial monomer introduces an organic silicon chain into a polyurethane polymer chain, so that the polyurethane polymer chain has higher flexibility compared with polyurethane materials, has good shape retention capacity compared with silica gel materials, is particularly applied to pipes, is not easy to deform, and keeps a stable drainage effect; in addition, the quaternized structure and the amide structure in the polymer chain have good hydrophilicity, so that the material has a lower contact angle with water, is more easily infiltrated, and is easier to perform intubation operation than a pure silica gel tube.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the antibacterial medical polymer material comprises the following specific implementation processes:
1) Preparation of silicon-based antibacterial monomer
1.1, taking 1-chlorohexane, triethylamine and benzene, uniformly mixing, introducing nitrogen for protection, heating to 75 ℃, applying 180rpm mechanical stirring, taking diallylamine equivalent to be divided into three parts, adding intermittently for 30min, continuing constant-temperature stirring reaction after complete addition, and controlling the adding reaction time of diallylamine to be 3h, wherein the dosage ratio of diallylamine, 1-chlorohexane, triethylamine and benzene is 0.1mol:0.18mol:8mL:45mL, removing benzene and excessive 1-chlorohexane by reduced pressure rotary evaporation after the reaction is finished, washing a rotary evaporation substrate, removing a water phase, and drying to obtain the tertiary amine matrix.
1.2, taking a tertiary amine matrix, a polymerization inhibitor (ZM-701 polymerization inhibitor is adopted in the embodiment), sodium carbonate and dioxane are added and mixed uniformly, introducing nitrogen for protection, pre-heating to 80 ℃, introducing methyl chloride for pressurizing to 5bar, then continuously heating to 105 ℃, and carrying out reflux reaction for 2 hours, wherein the dosage ratio of the tertiary amine matrix, the polymerization inhibitor, the sodium carbonate and the dioxane is 0.1mol:8mg:0.2g:60mL, after the reaction, the excess chloromethane is pumped out under reduced pressure, and the dioxane is removed by rotary evaporation under vacuum to prepare the quaternized matrix.
1.3, taking quaternized matrix, thioglycollic acid, dimethyl phenyl phosphine and dimethylacetamide, mixing evenly, introducing nitrogen for protection, heating to 90 ℃, applying mechanical stirring at 360rpm and assisting with 400W/m 2 Ultraviolet irradiation, reacting for 1.2 hours, wherein in the reaction, the dosage ratio of quaternized matrix, thioglycollic acid, dimethylphenylphosphine and dimethylacetamide is 0.1mol:0.2mol:15mg:100mL, reaction completion scoreAnd adding deionized water with the mass 1.6 times of that of the substrate for four times, and removing the dimethylacetamide by reduced pressure rotary evaporation to prepare the modified monomer.
1.4, taking modified monomer and aminopropyl double-end-blocked polydimethylsiloxane (in the examples, products with the number average molecular weight of 1000 are adopted and are provided by chemical industry Co., ltd. Of Beijing Hua Weirui) according to the molar ratio of carboxyl to amino of 1:1.2, mixing evenly, adding thionyl chloride with the mass of 0.8 times and dimethylformamide with the mass of 0.2 times, heating to 80 ℃, applying mechanical stirring at 180rpm, adding molecular sieve drying agent with the mass of 1% of the mixed liquor (in the embodiment, zeolite type molecular sieve provided by the Tenglong water treatment materials Co., ltd.) for 1.6 hours by constant temperature reflux reaction, filtering to remove the molecular sieve drying agent after the reaction, decompressing and steaming the filtrate to remove excessive thionyl chloride, washing and separating the distilled substrate with water, and removing dimethylformamide to obtain the silicon-based antibacterial monomer.
2) Preparation of antibacterial medical polymer material
2.1, taking isophorone diisocyanate, polyether glycol (PPG-200 is adopted in the embodiment) and silicon-based antibacterial monomer, wherein the molar ratio of isocyanate group, hydroxyl group and amino group is 1:0.75:0.1, uniformly mixing isophorone diisocyanate and polyether glycol under the protection of nitrogen, heating to 100 ℃, applying mechanical stirring at 100rpm, slowly adding a silicon-based antibacterial monomer within 1h, continuously stirring at constant temperature for reaction after complete addition, controlling the total addition reaction time to be 2.4h, discharging, and detecting the content of isocyanate groups to prepare a prepolymer;
2.2, taking a prepolymer, adding 1, 4-butanediol according to the equimolar amount of hydroxyl and isocyanate groups in the prepolymer, vacuumizing until the pressure is lower than 1kPa, mixing at a constant pressure, heating to 130 ℃, stirring at 70rpm, reacting for 1.5 hours, and extruding and granulating after the reaction is finished to obtain the antibacterial medical polymer material.
Example 2
The preparation method of the antibacterial medical polymer material comprises the following specific implementation processes:
1) Preparation of silicon-based antibacterial monomer
1.1, taking 1-chlorohexane, triethylamine and benzene, uniformly mixing, introducing nitrogen for protection, heating to 65 ℃, applying mechanical stirring at 120rpm, taking the equivalent of diallylamine into three parts, adding intermittently for 40min, continuing constant-temperature stirring reaction after complete addition, and controlling the adding reaction time of diallylamine to be 4h, wherein the dosage ratio of diallylamine, 1-chlorohexane, triethylamine and benzene is 0.1mol:0.14mol:6mL:35mL, the reaction is finished, benzene and excessive 1-chlorohexane are removed by reduced pressure rotary evaporation, the rotary evaporation substrate is washed by water, the water phase is removed, and the tertiary amine matrix is prepared by drying.
1.2, taking a tertiary amine matrix, a polymerization inhibitor, sodium carbonate and dioxane, uniformly mixing, introducing nitrogen for protection, preheating to 80 ℃, introducing methyl chloride for pressurizing to 4bar, then continuously heating to 95 ℃, and carrying out reflux reaction for 2.5h, wherein the dosage ratio of the tertiary amine matrix, the polymerization inhibitor, the sodium carbonate and the dioxane is 0.1mol:5mg:0.15g: and (5) 50mL, after the reaction is finished, decompressing and pumping out excessive chloromethane, and maintaining the vacuum to remove dioxane by rotary evaporation to prepare the quaternized matrix.
1.3, taking quaternized matrix, thioglycollic acid, dimethyl phenyl phosphine and dimethylacetamide, mixing evenly, introducing nitrogen for protection, heating to 80 ℃, applying mechanical stirring at 240rpm and assisting with 300W/m 2 Ultraviolet irradiation, reacting for 1.6 hours, wherein in the reaction, the dosage ratio of quaternized matrix, thioglycollic acid, dimethylphenylphosphine and dimethylacetamide is 0.1mol:0.2mol:10mg:85mL, adding deionized water with the mass 1.2 times of the substrate for three times after the reaction is finished, and removing dimethylacetamide by vacuum rotary evaporation to prepare the modified monomer.
1.4, taking a modified monomer and aminopropyl double-end-capped polydimethylsiloxane, wherein the molar ratio of carboxyl to amino is 1:1.15, adding thionyl chloride with the mass of 0.8 times and dimethylformamide with the mass of 0.2 times into the mixture, uniformly mixing, heating to 70 ℃, applying mechanical stirring at 120rpm, adding molecular sieve drying agent with the mass of 1% of the mixed solution, carrying out constant temperature reflux reaction for 2.2 hours, filtering to remove the molecular sieve drying agent after the reaction, decompressing and steaming the filtrate to remove excessive thionyl chloride, washing and separating the steaming substrate with water, and removing dimethylformamide to obtain the silicon-based antibacterial monomer.
2) Preparation of antibacterial medical polymer material
2.1, taking isophorone diisocyanate, polyether glycol and silicon-based antibacterial monomer, wherein the molar ratio of isocyanate groups, hydroxyl groups and amino groups is 1:0.68:0.17, uniformly mixing isophorone diisocyanate and polyether glycol under the protection of nitrogen, heating to 85 ℃, applying mechanical stirring at 80rpm, slowly adding a silicon-based antibacterial monomer within 1.5h, continuously stirring at constant temperature for reaction after complete addition, controlling the total addition reaction time to be 2.8h, discharging, and detecting the content of isocyanate groups to prepare a prepolymer;
2.2, taking a prepolymer, adding 1, 4-butanediol according to the equimolar amount of hydroxyl and isocyanate groups in the prepolymer, vacuumizing until the pressure is lower than 1kPa, mixing at a constant pressure, heating to 120 ℃, stirring at 55rpm, reacting for 2 hours, and extruding and granulating after the reaction is finished to obtain the antibacterial medical polymer material.
Example 3
The preparation method of the antibacterial medical polymer material comprises the following specific implementation processes:
1) Preparation of silicon-based antibacterial monomer
1.1, taking 1-chlorohexane, triethylamine and benzene, uniformly mixing, introducing nitrogen for protection, heating to 72 ℃, applying 180rpm mechanical stirring, taking the equivalent of diallylamine into three parts, adding intermittently for 40min, continuing constant-temperature stirring reaction after complete addition, controlling the adding reaction time of diallylamine to be 3.6h, and controlling the dosage ratio of diallylamine, 1-chlorohexane, triethylamine and benzene to be 0.1mol in the reaction: 0.15mol:7mL:45mL, removing benzene and excessive 1-chlorohexane by reduced pressure rotary evaporation after the reaction is finished, washing a rotary evaporation substrate, removing a water phase, and drying to obtain the tertiary amine matrix.
1.2, taking a tertiary amine matrix, a polymerization inhibitor, sodium carbonate and dioxane, uniformly mixing, introducing nitrogen for protection, preheating to 80 ℃, introducing methyl chloride for pressurizing to 4bar, then continuously heating to 100 ℃, and carrying out reflux reaction for 2.2h, wherein the dosage ratio of the tertiary amine matrix, the polymerization inhibitor, the sodium carbonate and the dioxane is 0.1mol:6mg:0.18g:55mL, after the reaction, the excess chloromethane is pumped out under reduced pressure, and the dioxane is removed by rotary evaporation under vacuum to prepare the quaternized matrix.
1.3 collecting quaternized matrix, thioglycolic acid, dimethylphenylphosphine and dimethylacetamideAmine is added and mixed evenly, nitrogen is introduced for protection, the temperature is raised to 85 ℃, mechanical stirring at 300rpm is applied, 340W/m is added as an auxiliary 2 Ultraviolet irradiation, reacting for 1.5h, wherein in the reaction, the dosage ratio of quaternized matrix, thioglycollic acid, dimethylphenylphosphine and dimethylacetamide is 0.1mol:0.2mol:12mg:95mL, adding deionized water with the mass 1.5 times of the substrate for three times after the reaction is finished, and removing dimethylacetamide by vacuum rotary evaporation to prepare the modified monomer.
1.4, taking a modified monomer and aminopropyl double-end-capped polydimethylsiloxane, wherein the molar ratio of carboxyl to amino is 1:1.18, adding thionyl chloride with the mass of 0.8 times and dimethylformamide with the mass of 0.2 times, uniformly mixing, heating to 75 ℃, applying 180rpm mechanical stirring, adding molecular sieve drying agent with the mass of 1% of the mixed solution, carrying out constant temperature reflux reaction for 2 hours, filtering to remove the molecular sieve drying agent after the reaction, decompressing and steaming filtrate to remove excessive thionyl chloride, washing and separating a steaming substrate with water, and removing dimethylformamide to obtain the silicon-based antibacterial monomer.
2) Preparation of antibacterial medical polymer material
2.1, taking isophorone diisocyanate, polyether glycol and silicon-based antibacterial monomer, wherein the molar ratio of isocyanate groups, hydroxyl groups and amino groups is 1:0.72:0.13, uniformly mixing isophorone diisocyanate and polyether glycol under the protection of nitrogen, heating to 95 ℃, applying 100rpm mechanical stirring, slowly adding a silicon-based antibacterial monomer within 1.2h, continuously stirring at constant temperature for reaction after complete addition, controlling the total addition reaction time to be 2.6h, discharging, and detecting the content of isocyanate groups to prepare a prepolymer;
2.2, taking a prepolymer, adding 1, 4-butanediol according to the equimolar amount of hydroxyl and isocyanate groups in the prepolymer, vacuumizing until the pressure is lower than 1kPa, mixing at a constant pressure, heating to 120 ℃, stirring at 60rpm, reacting for 1.8 hours, and extruding and granulating after the reaction is finished to obtain the antibacterial medical polymer material.
In order to facilitate the detection of the related performance of the material, the antibacterial medical polymer material prepared in the embodiment is placed in a flat vulcanizing machine, and the parameters are set as follows: preheating at 120deg.C, molding at 150deg.C, pressing under 0.8MPa for 2min, and cooling to obtain sample;
comparative example 1
This comparative example was cut from a commercially available disposable ultra-smooth antimicrobial urinary catheter (Guangdong instrument standard 20152660473).
Referring to YY0325-2016 and "sterilization Specification", the above products were tested by the inhibition ring test method, using Staphylococcus aureus (ATCC 25923) and Escherichia coli (ATCC 25922) as test strains, the incubator temperature was 40 ℃, the humidity was 60%, and the incubation periods were 1d, 2d, 3d and 5d, and the specific test data are shown in Table 1:
TABLE 1
| Example 1 | Example 2 | Example 3 | Comparative example | |
| Diameter of 1d inhibition ring/mm | 21.2 | 26.7 | 25.3 | 24.9 |
| Diameter of 2d bacteriostasis ring/mm | 22.6 | 26.1 | 24.3 | 23.5 |
| Diameter/mm of 3d bacteriostasis ring | 19.3 | 21.5 | 23.0 | 17.4 |
| Diameter of 5d bacteriostasis ring/mm | 17.9 | 20.7 | 21.3 | 15.8 |
As can be seen from the data in Table 1, the material prepared in the examples has good antibacterial and bacteriostatic effects compared with the existing antibacterial materials, and can meet the short-term antibacterial demands.
To verify the antimicrobial durability of the above products, the above test specimens were repeatedly rinsed, and the specific method was: soaking the sample in 5% sodium chloride solution for 6h, rinsing in 75% medical alcohol for 1h, repeating 20 times, and performing antibacterial ring experiment again, wherein the test period is 1d, and specific test data are shown in table 2:
TABLE 2
As can be seen from the data in table 2, after rinsing, the antibacterial effect of the comparative example was drastically deteriorated, and the antibacterial effect was drastically deteriorated, and the antibacterial ring was only slightly lowered after rinsing for 20 times, and the product prepared in the example was used for at least one week according to the nursing standard.
In order to detect the use experience of the product prepared by the invention applied to medical tubing, a JC-2000A contact angle measuring instrument is adopted, and a surface contact angle test is carried out by a liquid drop method; measuring surface friction performance by using an MXD-02 type friction coefficient instrument; the specific test data are shown in table 3:
TABLE 3 Table 3
| Example 1 | Example 2 | Example 3 | Comparative example | |
| Contact angle/° | 61.4 | 53.2 | 56.0 | 52.6 |
| Kinetic friction force/N | 1.358 | 1.054 | 1.179 | 1.216 |
As can be seen from the data in Table 3, the contact of the materials prepared in the examples is far lower than 90 degrees, the dynamic friction force is similar to that of the comparative examples, and the materials have good lubricity and are more convenient for intubation operation compared with the silica gel catheter.
To verify the shape retention capability of the product prepared by the invention, a sample is cut into a strip-shaped sample strip with the specification of 50X 10mm, the sample strip is placed in a 70 ℃ oven for softening for 10min, then the sample strip is wound on a glass rod to form a temporary shape, then the sample strip is placed in a 0 ℃ ice water bath for 2min to fix the temporary shape, finally, the sample strip with the spiral shape is placed in a 40 ℃ water bath for standing for 12h, the recovery rate is measured according to the ratio of the recovered length of the sample strip to the original length, and specific test data are shown in table 4:
TABLE 4 Table 4
| Example 1 | Example 2 | Example 3 | Comparative example | |
| Recovery/% | 87.5 | 81.3 | 84.9 | 64.2 |
As can be seen from the data in Table 4, the recovery rate of the material prepared in the examples reaches more than 80%, the material has good shape retention capacity, and after the material is prepared into a catheter, the shape retention is easier to recover under the action of external force, so that the material is beneficial to stable diversion.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (8)
1. An antibacterial medical polymer material is characterized by being formed by polycondensation of isophorone diisocyanate, polyether glycol, a silicon-based antibacterial monomer and 1, 4-butanediol;
the silicon-based antibacterial monomer is prepared by the following method:
step A1: uniformly mixing 1-chlorohexane, triethylamine and benzene, introducing nitrogen for protection, heating to 65-75 ℃, stirring, intermittently adding diallylamine, controlling the total adding reaction time to be 3-4h, performing reduced pressure rotary evaporation after the reaction is finished, washing a rotary evaporation substrate, and drying to obtain a tertiary amine matrix;
step A2: uniformly mixing a tertiary amine matrix, a polymerization inhibitor, sodium carbonate and dioxane, introducing nitrogen for protection, preheating to 80 ℃, introducing methyl chloride for pressurizing to 4-5bar, then continuously heating to 95-105 ℃, carrying out reflux reaction for 2-2.5h, and carrying out reduced pressure rotary evaporation after the reaction is finished to obtain a quaternized matrix;
step A3: mixing quaternized matrix, thioglycollic acid, dimethylphenylphosphine and dimethylacetamide, introducing nitrogen for protection, heating to 80-90deg.C, stirring with 300-400W/m 2 Ultraviolet irradiation, reacting for 1.2-1.6h, repeatedly adding deionized water after the reaction is finished, and performing reduced pressure rotary evaporation to obtain a modified monomer;
step A4: uniformly mixing the modified monomer, the amine propyl double-end-capped polydimethylsiloxane, the sulfoxide chloride and the dimethylformamide, heating to 70-80 ℃, stirring, intermittently adding a molecular sieve drying agent, carrying out constant-temperature reflux reaction for 1.6-2.2h, carrying out reduced pressure rotary evaporation after the reaction is finished, and washing and separating a rotary evaporation substrate to obtain the silicon-based antibacterial monomer.
2. The antibacterial medical polymer material according to claim 1, wherein the dosage ratio of diallylamine, 1-chlorohexane, triethylamine and benzene is 0.1mol:0.14 to 0.18mol:6-8mL:35-45mL.
3. The antibacterial medical polymer material according to claim 2, wherein the usage ratio of the tertiary amine matrix, the polymerization inhibitor, the sodium carbonate and the dioxane is 0.1mol:5-8mg:0.15-0.2g:50-60mL.
4. An antibacterial medical polymer material according to claim 3, wherein the amount ratio of quaternized matrix, thioglycollic acid, dimethylphenylphosphine and dimethylacetamide is 0.1mol:0.2mol:10-15mg:85-100mL.
5. The antibacterial medical polymer material according to claim 4, wherein the molar ratio of carboxyl to amino of the modified monomer and the aminopropyl double-end-capped polydimethylsiloxane is 1:1.15-1.2, and the number average molecular weight of the aminopropyl double-end-capped polydimethylsiloxane is 1000.
6. The method for preparing the antibacterial medical polymer material according to claim 5, which is characterized by comprising the following steps:
step S1: uniformly mixing isophorone diisocyanate and polyether glycol under the protection of nitrogen, heating to 85-100 ℃, applying mechanical stirring at 80-100rpm, slowly adding a silicon-based antibacterial monomer, controlling the total adding reaction time to be 2.4-2.8h, discharging, detecting the content of isocyanate groups, and obtaining a prepolymer;
step S2: adding the prepolymerization material and the 1, 4-butanediol into a vacuum kettle for mixing, keeping the vacuum degree below 1kPa, heating to 120-130 ℃, stirring at 55-70rpm, reacting for 1.5-2h, and extruding and granulating after the reaction is finished to obtain the antibacterial medical polymer material.
7. The method for preparing the antibacterial medical polymer material according to claim 6, wherein the molar ratio of the isocyanate group of isophorone diisocyanate, the hydroxyl group of polyether glycol and the amino group of silicon-based antibacterial monomer is 1:0.68-0.75:0.1-0.17.
8. The method for preparing the antibacterial medical polymer material according to claim 7, wherein the molar ratio of isocyanate groups of the prepolymer to hydroxyl groups of 1, 4-butanediol is 1:1.
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| CN114016155A (en) * | 2021-11-25 | 2022-02-08 | 界首市金吴再生资源利用有限公司 | Antibacterial regenerated polyester fiber and preparation method thereof |
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| CN114016155A (en) * | 2021-11-25 | 2022-02-08 | 界首市金吴再生资源利用有限公司 | Antibacterial regenerated polyester fiber and preparation method thereof |
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