LU502823B1 - A Functionalized High Oxygen Permeability Hydrophilic Anti-Adhesion Transparent Resin, Preparation and Application Thereof - Google Patents
A Functionalized High Oxygen Permeability Hydrophilic Anti-Adhesion Transparent Resin, Preparation and Application Thereof Download PDFInfo
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- LU502823B1 LU502823B1 LU502823A LU502823A LU502823B1 LU 502823 B1 LU502823 B1 LU 502823B1 LU 502823 A LU502823 A LU 502823A LU 502823 A LU502823 A LU 502823A LU 502823 B1 LU502823 B1 LU 502823B1
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- Prior art keywords
- acrylate
- hydrophilic
- oxygen permeability
- adhesion
- agent
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- 229920005989 resin Polymers 0.000 title claims abstract description 51
- 239000011347 resin Substances 0.000 title claims abstract description 51
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000001301 oxygen Substances 0.000 title claims abstract description 32
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 32
- 230000035699 permeability Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title description 11
- 239000000463 material Substances 0.000 claims abstract description 56
- 239000000178 monomer Substances 0.000 claims abstract description 45
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 35
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 26
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011737 fluorine Substances 0.000 claims abstract description 14
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000077 silane Inorganic materials 0.000 claims abstract description 13
- 230000010065 bacterial adhesion Effects 0.000 claims abstract description 12
- 239000012745 toughening agent Substances 0.000 claims abstract description 11
- 239000013530 defoamer Substances 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 150000003254 radicals Chemical class 0.000 claims abstract description 8
- -1 2,2,3,3-tetrafluoropropyl Chemical group 0.000 claims description 43
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 12
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- IMNBHNRXUAJVQE-UHFFFAOYSA-N (4-benzoyl-3-hydroxyphenyl) 2-methylprop-2-enoate Chemical group OC1=CC(OC(=O)C(=C)C)=CC=C1C(=O)C1=CC=CC=C1 IMNBHNRXUAJVQE-UHFFFAOYSA-N 0.000 claims description 3
- FMQPBWHSNCRVQJ-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C(F)(F)F)C(F)(F)F FMQPBWHSNCRVQJ-UHFFFAOYSA-N 0.000 claims description 3
- KQVIDCCKLYDABT-UHFFFAOYSA-N 1,3-bis(4-benzoyl-3-hydroxyphenoxy)propan-2-yl prop-2-enoate Chemical compound C=1C=C(C(=O)C=2C=CC=CC=2)C(O)=CC=1OCC(OC(=O)C=C)COC(C=C1O)=CC=C1C(=O)C1=CC=CC=C1 KQVIDCCKLYDABT-UHFFFAOYSA-N 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- VCYCUECVHJJFIQ-UHFFFAOYSA-N 2-[3-(benzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 VCYCUECVHJJFIQ-UHFFFAOYSA-N 0.000 claims description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- UVQGVNLXTFRLNL-UHFFFAOYSA-N dicyclohexyldiazene Chemical compound C1CCCCC1N=NC1CCCCC1 UVQGVNLXTFRLNL-UHFFFAOYSA-N 0.000 claims description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 3
- 150000004676 glycans Chemical class 0.000 claims description 3
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 3
- WNZQDUSMALZDQF-UHFFFAOYSA-N isobenzofuranone Natural products C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920001282 polysaccharide Polymers 0.000 claims description 3
- 239000005017 polysaccharide Substances 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims 1
- 108010010803 Gelatin Proteins 0.000 claims 1
- 229940072056 alginate Drugs 0.000 claims 1
- 235000010443 alginic acid Nutrition 0.000 claims 1
- 229920000615 alginic acid Polymers 0.000 claims 1
- 229920002678 cellulose Polymers 0.000 claims 1
- 239000001913 cellulose Substances 0.000 claims 1
- 235000010980 cellulose Nutrition 0.000 claims 1
- 229920000159 gelatin Polymers 0.000 claims 1
- 239000008273 gelatin Substances 0.000 claims 1
- 235000019322 gelatine Nutrition 0.000 claims 1
- 235000011852 gelatine desserts Nutrition 0.000 claims 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010703 silicon Substances 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 230000001988 toxicity Effects 0.000 abstract description 4
- 231100000419 toxicity Toxicity 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000007788 liquid Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 230000035484 reaction time Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000007872 degassing Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 2
- JCMFXEIQKSSNTG-UHFFFAOYSA-N 3-[[3-(2-methylprop-2-enoyloxy)propyl-bis(trimethylsilyloxy)silyl]oxy-bis(trimethylsilyloxy)silyl]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](O[Si](C)(C)C)(O[Si](C)(C)C)O[Si](O[Si](C)(C)C)(O[Si](C)(C)C)CCCOC(=O)C(C)=C JCMFXEIQKSSNTG-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention provides a functionalized hydrophilic anti-adhesion transparent resin with high oxygen permeability, which comprises fluorine monomer, silicon monomer, hydrophilic monomer, acrylate macromolecular crosslinking agent, silane crosslinking agent, free radical initiator, defoamer, toughening agent, anti-adhesion component and antibacterial agent. The macromolecular crosslinking agent can avoid the toxicity of micromolecule crosslinking agent and improve the mechanical strength and processability of resin materials. Fluorine-containing monomer and silicon monomer can effectively improve the oxygen permeability of the resin; Hydrophilic monomer endows the material with good hydrophilicity and biocompatibility; Anti-protein and bacterial adhesion components make the material have good anti-protein and bacterial adhesion ability; The antibacterial agent endows the resin with good antibacterial property.
Description
A Functionalized High Oxygen Permeability Hydrophilic Anti- ~~ 902823
Adhesion Transparent Resin, Preparation and Application Thereof
The invention relates to the technical field of resin material synthesis, in particular to a functionalized high oxygen permeability hydrophilic anti-adhesion transparent resin, its preparation and application.
Silicone resin has the advantages of hardness, transparency, insulation and high temperature resistance, and is widely used in insulating coatings, high temperature resistant adhesive, high temperature resistant coating, plastic processing, cosmetics, pressure sensitive adhesive and other fields. The fluorosilicone resin formed by introducing fluorine atoms into the polymer has excellent chemical resistance. In addition, fluorosilicone resin has the characteristics of biocompatibility, adjustable mechanical properties and stable physical and chemical properties on the surface, and it also has a good application prospect in the field of biomedical materials. Fluoroacrylate (FSA) has many functional components, such as silicon, fluorine, acrylate, hydrophilic monomer, hydrophilic and hydrophobic cross-linking agent, etc., which can effectively regulate the oxygen permeability, mechanical strength, hydrophilicity, etc. respectively, and obtain products with better comprehensive performance.
Although FSA materials have good comprehensive properties, they still have the following problems: (D Poor hydrophilicity, which can't meet the requirements of biological bodies for hydrophilic properties, and requires subsequent surface treatment; @ The oxygen permeability is low, and there is still much room for improvement for some applications that need to keep good oxygen permeability, such as wound dressings, ophthalmic products, gas separation membranes, etc. 3 The controllability of mechanical strength still needs to be further improved; @ The adhesion of various proteins and bacteria on the surface of the material is high, and at present, most of the modification technologies need secondary treatment, so the process is complicated. © Not antibacterial (especially in the biomedical field, materials are often required to have antibacterial properties to reduce the occurrence of inflammation, so it is an urgent problem to endow materials with good antibacterial ability at 1 present); © When the FSA finished product is prepared by the method of "polishing after the material is prepared (to meet the application requirements of various occasions)", the problems of oxidation yellowing, bubbles, cracks, insufficient toughness and the like of the prepared FSA material are easy to occur.
The purpose of the present invention is to overcome at least one of the shortcomings of the prior art, and provide a functionalized high oxygen permeability hydrophilic anti-adhesion transparent resin and a preparation method thereof. © According to the invention, the silicone resin material with excellent hydrophilic performance is obtained by reasonably regulating the addition amount of hydrophilic monomers, and the complex process problems of subsequent further modification of other resin materials are avoided; @ According to the invention, the high oxygen permeability of the transparent resin material is realized by reasonably regulating the reaction temperature, the reaction time, the monomer addition amount and the crosslinking agent addition amount; 3 According to the invention, the mechanical strength of the resin is improved by reasonably regulating the reaction temperature, the reaction time and the addition amount of the crosslinking agent; @ According to the invention, the resin material with the capability of resisting protein and bacteria adhesion and deposition is obtained by directly adding a certain amount of anti-protein and bacteria adhesion components in the preparation process, and compared with the prior art, the preparation method is simpler, more suitable and more efficient; © The FSA resin material with antibacterial property is obtained by adding a certain amount of antibacterial agent in the preparation process; (@ According to the invention, the problems of oxidation yellowing, bubbles, cracks, insufficient toughness and the like of FSA materials are solved by strictly controlling nitrogen ventilation mode, deoxidizing pressure and time, and adopting a certain amount of defoaming agent, toughening agent and gradient pressure control. The invention specifically adopts the following technical scheme:
On the one hand, the invention provides a functionalized high oxygen permeability hydrophilic anti-adhesion transparent resin, which comprises the following components in percentage by mass: 40%-70% of fluorine-containing monomer, 20%-40% of silicon- containing monomer, 2%-10% of hydrophilic monomer, 7%-15% of acrylate macromolecular 2 crosslinking agent and 7%-15% of silane crosslinking agent. 0.01-2% of free radical initiator LU502823 and 0.1-3% of ultraviolet absorption blocker; 0.002-0.2% of defoamer; Toughening agent 5%- 10%; 2% ~ 5% of anti-protein and bacterial adhesion components; 0. 1%~2% of antibacterial agent.
According to the invention, functional components such as macromolecular crosslinking agent, defoamer, antibacterial and anti-adhesion are added, and macromolecules formed by crosslinking the above components with various monomers are firmly combined by intermolecular forces, hydrogen bonds and covalent bonds, so that stable bonding is formed, macromolecule crystallization does not occur, light transmittance is ensured, the toxicity of micromolecule crosslinking agent can be effectively avoided, the uniformity of the material is ensured, the material is endowed with special antibacterial and anti-adhesion effects, and other micromolecule additives are not added to ensure the hydrophilicity of the material, so that the resin has a self-cleaning effect.
As mentioned above, it is further provided that the fluorine-containing monomer is 2,2,2- trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,3,3- pentafluoropropyl (meth) acrylate, one or more of 2,2,3,3,4,4-hexafluorobutyl (meth) acrylate and 1,1,1,3,3,3- hexafluoroisopropyl methacrylate, the molecule of which contains unsaturated carbon-carbon double bonds (C=C).
As mentioned above, it is further provided that the silane-containing monomer is tri (trimethylsiloxy) silylpropyl vinyl carbamate, 3-[ tri (trimethylsiloxy) silylpropyl propenyl carbamate, one or more of 3- (trimethylsilyl) propyl vinyl carbonate, TRIS and TRIS-VC, and its molecule contains unsaturated carbon-carbon double bonds (C=C).
Any of the possible implementations described above further provides an implementation, wherein the hydrophilic monomer is one or more of 2- hydroxyethyl methacrylate (HEMA),
N- vinylpyrrolidone (NVP) and methacrylic acid (MAA).
As mentioned above, an implementation is further provided, and the silane crosslinking agent is one of 1 ,3- bis (3- methacryloyloxypropyl) tetrakis (trimethylsiloxy) disiloxane, dimethyl acryloyl polydimethylsiloxane and acrylamide terminal polydimethylsiloxane. Silicone cross- linking agent can be used as both cross-linking agent and silicon monomer, which can effectively control the hardness of the whole resin material.
As mentioned above, an implementation mode is further provided, wherein the acrylate macromolecular crosslinking agent is one of neopentyl glycol dimethacrylate (NPMA) and ethylene glycol dimethacrylate; The free radical initiator is one or more of azodiisobutyl eye, azocyclohexane, phthalide peroxide and dicumyl peroxide; It can be used to increase oxygen 3 permeability and hardness, while still keeping the light transmittance of transparent resin LU502823 materials:
The ultraviolet absorption blocker is 2- hydroxy -4- (methacryloyloxy) benzophenone, 1,3- bis (4- benzoyl -3- hydroxyphenoxy) -2- propyl acrylate, one of 3-(2H- benzo [d] [1,2,3] triazol -2- yl) -4- hydroxyphenylethyl methacrylate;
The defoamer is one of dimethyl silicone oil, polydimethylsiloxane with acrylate functional group and polyether modified polydimethylsiloxane;
The toughening agent is one of acrylate rubber and MBS;
The anti-protein and bacterial adhesion components are one or more of super hydrophilic materials, polyethylene glycol (PEG) hydrophilic polymers and polysaccharides;
The antibacterial agent is one of inorganic antibacterial agent, organic antibacterial agent and natural antibacterial agent.
On the basis of the traditional transparent silicone resin, the antibacterial agent and the anti- adhesion component are introduced as functional assistants to endow the material with special functionality. The bulk blending method is adopted, that is, the antibacterial agent and the anti-adhesion component are added into the initial reaction system, and the total content of the antibacterial agent and the anti-adhesion component is controlled to be lower than 5%.
Therefore, the transparency and oxygen permeability of the resin material can be kept at a high level (the oxygen permeability coefficient is greater than 150x10- 11 (cm2/s) [mlO2/ (mlxmmHg)]), and it is different from the complex process that the functional modification of the traditional resin material requires surface treatment after the resin material is molded. The antibacterial agents of the invention are generally metal ions, metal nanoparticles, nano-oxide particles and micromolecule organic antibacterial agents. The antibacterial ingredients mentioned above do not participate in chemical reactions in the whole resin material system, but the molecular cluster structure formed after monomer cross-linking can wrap the antibacterial ingredients, ensuring the uniform dispersion of the antibacterial ingredients and ensuring the transparency of the materials.
According to the reaction characteristics and functions, the reactants are divided into two groups, namely monomer mixed solution and functional component mixed solution, and preliminary degassing operation is carried out respectively; after the two mixed solutions are mixed, fine degassing operation is carried out, and the reaction control is realized through pressure control in a reaction container isolated from air. The two-step degassing method can fully remove the reactant and the air in the reactor, and the pressure control can realize the stable reaction and improve the strength and uniformity of the material. 4
The invention has the advantages that: LU502823 1. From the point of view of material selection, fluorine-containing acrylate and silane monomer can effectively improve the oxygen permeability of resin materials, and fluorine monomer can also make up for the lipophilicity of silicone materials, which is conducive to improving hydrophilicity. The FSA material is a macromolecule with multiple branched chains, which increases the space of the network structure, thus increasing the oxygen permeability of the resin material. According to the invention, the toxicity of the micromolecule crosslinking agent is effectively avoided by using the siloxane macromolecular crosslinking agent; Moreover, the selected cross-linking agent can play the dual roles of monomer and cross-linking agent at the same time, which can effectively control the network structure and mechanical strength of resin molecules in the macromolecular structure, and can also effectively control the oxygen permeability of the material itself by controlling its addition amount. 2. From the point of view of process steps, the parameters of reaction temperature and time used in the invention are simple to set, many steps of regulation are omitted, the reaction operation is simple and convenient, the reaction conditions are mild, and the reaction process has good controllability; Compared with the reaction time of 24-48 h synthesized by the existing fluorosilicone acrylic resin material, the reaction time used in the invention is greatly shortened, the energy consumption is saved, and the preparation efficiency is greatly improved; The preparation process adopted by the invention has high repeatability. 3. From the performance point of view of the prepared FSA material, the resin material prepared by the invention has excellent hydrophilicity (< 40 degrees), which improves the problem of poor hydrophilicity (generally > 49 degrees) of the traditional fluorosilicone acrylic resin material. In addition, due to excellent hydrophilicity, the resin material prepared by the invention can effectively reduce the adhesion of protein on the surface of the material and improve the biocompatibility; The resin material prepared by the invention has better oxygen permeability. The use of toughener can effectively improve the toughness of resin materials. In the preparation process, we also introduced anti-protein and anti-bacterial adhesion components, so the resin material has excellent anti-protein and anti-bacterial adhesion ability. 4. The transparent resin material prepared by the invention contains antibacterial components, so it has excellent antibacterial ability.
5
The embodiment of the invention discloses a functionalized high oxygen permeability LU502823 hydrophilic anti-adhesion transparent resin, which comprises the following components in percentage by mass: 40%~70% of fluorine-containing monomer, 20%~40% of silicon- containing monomer, 2~10% of hydrophilic monomer, 7%~15% of acrylate macromolecular crosslinking agent, 7%~15% of silane crosslinking agent, 0.01~2% of free radical initiator and 0.1% ~ 3% of ultraviolet absorption blocker; 0.002-0.2% of defoamer; Toughening agent 5%-10%; 2% ~ 10% of anti-protein and bacterial adhesion components; 0.1%~2% of antibacterial agent.
The fluorine-containing monomer is 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3- tetrafluoropropyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, one or more of 2,2,3,3,4,4-hexafluorobutyl (meth) acrylate and 1,1,1,3,3,3- hexafluoroisopropyl methacrylate, the molecule of which contains unsaturated carbon-carbon double bonds (C=C).
The silane-containing monomer is one or more of TRIS, TRIS-VC, tri (trimethylsiloxy) silyl propyl vinyl carbamate, 3- tri (trimethylsiloxy) silyl propyl allyl carbamate and 3- (trimethylsilyl) propyl vinyl carbonate, and its molecule contains unsaturated carbon-carbon double bonds (C=C).
The hydrophilic monomer is one or more of 2- 2-hydroxyethyl methacrylate (HEMA), N- vinylpyrrolidone (NVP) and methacrylic acid (MAA).
As a specific example, the silane crosslinking agent is one of 1 ,3- bis (3- methacryloyloxypropyl) tetrakis (trimethylsiloxy) disiloxane, dimethyl acryloyl polydimethylsiloxane and acrylamide terminal polydimethylsiloxane.
Preferably, the acrylate macromolecular crosslinking agent is one of neopentyl glycol dimethacrylate (NPMA) and ethylene glycol dimethacrylate; The free radical initiator is one or more of azodiisobutyl eye, azocyclohexane, phthalide peroxide and dicumyl peroxide; The ultraviolet absorption blocker is 2- hydroxy -4- (methacryloyloxy) benzophenone, 1,3- bis (4- benzoyl -3- hydroxyphenoxy) -2- propyl acrylate, one of 3-(2H- benzo [d] [1,2,3] triazol -2- yl) -4- hydroxyphenylethyl methacrylate; The defoamer is one of dimethyl silicone oil, polydimethylsiloxane with acrylate functional group and polyether modified polydimethylsiloxane; The toughening agent is one of acrylate rubber and MBS; The anti- protein and bacterial adhesion components are one or more of super hydrophilic materials, polyethylene glycol (PEG) hydrophilic polymers and polysaccharides; The antibacterial agent is one of inorganic antibacterial agent, organic antibacterial agent and natural antibacterial agent. 6
The preparation method of the functionalized high oxygen permeability hydrophilic anti- LU502823 adhesion transparent resin comprises the following steps:
S1. Raw material formula: 40%-70% of fluorine-containing monomer, 20%-40% of silicon- containing monomer, 2%-10% of hydrophilic monomer, 7%-15% of acrylate macromolecular cross-linking agent and 7%-15% of silane cross-linking agent, 0.01-2% of free radical initiator and 0.1-3% of ultraviolet absorption blocker; 0.002-0.2% of defoamer; Toughening agent 5%-10%; 2% ~ 10% of anti-protein and bacterial adhesion components; 0.1% ~ 2% of antibacterial agent;
S2. Multiphase mixing:
Because various monomers, cross-linking agents and other functional components have different mutual solubility and affinity, which will affect the final blending effect, and all raw materials are blended in one pot, which will produce larger viscosity, thus affecting the blending uniformity, so the invention divides the above components into two batches according to their properties, and then mixes them respectively, and finally mixes them;
Firstly, the fluorine monomer, the silicon monomer and the hydrophilic monomer are put into a tetrafluoroethylene container according to the proportion, and the mixture is stirred by magnetic force for 10-50 minutes; Standing for 5-10 min; Magnetically stirring again for 10- 50 min to obtain mixed solution 1; Mixing acrylate macromolecular crosslinking agent, silane crosslinking agent, ultraviolet absorption blocker, defoamer, toughening agent, anti-protein and bacterial adhesion components and antibacterial agent in proportion in PTFE container, and stirring uniformly by magnetic force to obtain mixed solution IT;
S3. Multi-stage oxygen removal: Nitrogen gas is respectively introduced into the mixed liquid
I and the mixed liquid II obtained in step S2 for 5-20 min, and preliminary degassing is carried out; After that, further mixing the first mixed liquid and the second mixed liquid to obtain the third mixed liquid, and introducing nitrogen into the third mixed liquid and the third mixed liquid successively for 10-20 minutes to realize fine degassing; Under the protection of nitrogen, the uniformly mixed mixed liquid III is transferred to a small tetrafluoroethylene container, and then nitrogen is introduced again to prevent oxygen from staying in the mixed liquid III and oxidizing; Control the gas-liquid ratio in the small tetrafluoroethylene container to be 0.7~4, so as to prevent cracks caused by low gas-liquid ratio, bubble generation and insufficient reaction caused by high gas-liquid ratio; 7
S54. Controlling the polymerization process: putting the mixed solution 3 treated in step S3 LU502823 and a small tetrafluoroethylene container into an oven, setting the reaction temperature at 70- 90 °C and the reaction time at 4-10 h; Meanwhile, gradient pressure control is carried out;
The reaction temperature of the invention is 70-90 °C, too low can not reach the threshold value of the reaction temperature, and the sample can not be cured, while too high will increase the probability of sample oxidation and cracking; The reaction time is 4 ~ 10 h. If the reaction time is too short, the sample can't be cured, and the hardness of the obtained sample is easy to fail to reach the standard. If the reaction time is too long, the probability of oxidation and cracking of the sample will be increased.
The transparent resin material in the invention is prepared into a bulk polymerization reaction initiated by a free radical initiator, which is an exothermic reaction.
In the process of polymerization, various monomers, cross-linking agents and ultraviolet absorption blockers cross-link to form many network macromolecules, and antibacterial agents can be wrapped in these macromolecular network cavities by intermolecular van der
Waals force or hydrogen bond. In the gradient pressure control, after the sample is moved into the oven, the pressure is reduced to -0. 1~-0.01 Mpa for 10~40min to remove the gas in the reaction environment and prevent the sample from oxidizing and yellowing; Then, the atmospheric pressure environment is restored for 4~8 h to prevent bubbles from being generated in the sample; Finally, reduce the pressure again to the vacuum degree of -0. 1~- 0.01 Mpa, so as to reduce the probability of internal stress accumulation in the sample during the exothermic reaction (give enough time for the reactants and intermediate or final products to diffuse and move during the reaction) and prevent cracks. The oven atmosphere can be nitrogen or argon or carbon dioxide or air, so as to reasonably control the reaction environment of the sample and the heat exchange rate between the sample and the environment.
S5. Low-temperature demoulding: after the polymerization process reaches room temperature, in order to increase the hardness and toughness, the sample is allowed to stand at -20°C for 1h, and then taken out to obtain the functional block of high oxygen permeability hydrophilic anti-adhesion transparent resin material.
S6. After demoulding at low temperature, the functionalized high oxygen permeability hydrophilic anti-adhesion transparent resin with smooth surface is obtained by machining. 8
According to the invention, different monomers are polymerized to form a stable polymer LU502823 cross-linked structure, thus ensuring the hardness and oxygen permeability of the resin material; other functional components endow the resin material with special functionality; and by adding toughening and antibacterial components, the resin material has excellent mechanical toughness and antibacterial property, which is beneficial to processing and expanding applications. The macromolecular crosslinking agent used in the invention can avoid the toxicity of micromolecule crosslinking agent and improve the mechanical strength and processability of the transparent resin material; Fluorine-containing monomer and siloxane monomer can effectively improve the oxygen permeability of materials; The hydrophilic component endows the material with good hydrophilicity and biocompatibility;
Anti-protein and bacterial adhesion components make the resin have good anti-protein and bacterial adhesion ability; The antibacterial agent endows the resin with good antibacterial property. 9
Claims (6)
1. A functionalized hydrophilic anti-adhesion transparent resin with high oxygen LU502823 permeability is characterized in that the resin comprises the following components in percentage by mass: 40%~70% of fluorine-containing monomer, 20%~40% of silicon- containing monomer, 2~10% of hydrophilic monomer, 7%~15% of acrylate macromolecular crosslinking agent, 7%~15% of silane crosslinking agent, 0.01~2% of free radical initiator and 0.1% ~ 3% of ultraviolet absorption blocker; 0.002-0.2% of defoamer; Toughening agent 5%-10%; 2% ~ 10% of anti-protein and bacterial adhesion components; 0. 1%~2% of antibacterial agent.
2. The functionalized hydrophilic anti-adhesion transparent resin with high oxygen permeability according to claim 1 is characterized in that the fluorine-containing monomer is 2,2 2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,3,3- pentafluoropropyl (meth) acrylate, One or more of 2,2,3,3,4,4-hexafluorobutyl (meth) acrylate and 1,1,1,3,3,3- hexafluoroisopropyl methacrylate all contain unsaturated carbon-carbon double bonds (C=C) in their molecules.
3. The functionalized high oxygen permeability hydrophilic anti-adhesion transparent resin according to claim 1 is characterized in that the silane-containing monomer is TRIS, TRIS-VC, tri (trimethylsiloxy) silylpropyl vinyl carbamate, 3- tri (trimethylsiloxy) silylpropyl allyl carbamate, one or more of 3- (trimethylsilyl) propyl vinyl carbonate, all of which contain unsaturated carbon-carbon double bonds (C=C) in their molecules.
4. The functionalized high oxygen permeability hydrophilic anti-adhesion transparent resin according to claim 1 is characterized in that the hydrophilic monomer is one or more of 2- 2-hydroxyethyl methacrylate (HEMA), N- vinylpyrrolidone (NVP) and methacrylic acid (MAA).
5. The functionalized high oxygen permeability hydrophilic anti-adhesion transparent resin according to claim 1 is characterized in that the silane crosslinking agent is one of 1 ,3- bis (3- methacryloyloxypropyl) tetrakis (trimethylsiloxane) disiloxane, dimethyl acryloyl polydimethylsiloxane and acrylamide terminal polydimethylsiloxane.
6. The functionalized high oxygen permeability hydrophilic anti-adhesion transparent resin according to claim 1 is characterized in that, The acrylate macromolecular crosslinking agent is one of neopentyl glycol dimethacrylate (NPMA) and ethylene glycol dimethacrylate; The initiator is one or more of azodiisobutyl eye, azocyclohexane, phthalide peroxide and dicumyl peroxide; 10
The ultraviolet absorption blocker is 2- hydroxy -4- (methacryloyloxy) benzophenone, LU502823 1,3- bis (4- benzoyl -3- hydroxyphenoxy) -2- propyl acrylate, one of 3-(2H- benzo [d] [1,2,3] triazol -2- yl) -4- hydroxyphenylethyl methacrylate;
The defoamer is one of dimethyl silicone oil, polydimethylsiloxane with acrylate functional group and polyether modified polydimethylsiloxane;
The toughening agent is one of acrylate rubber and MBS;
The anti-protein and bacterial adhesion components are one or more of super hydrophilic materials, polyethylene glycol (PEG) hydrophilic polymers, alginate, gelatin, cellulose and other polysaccharides;
The antibacterial agent is one of inorganic antibacterial agent, organic antibacterial agent and natural antibacterial agent. 11
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| LU502823A LU502823B1 (en) | 2022-09-22 | 2022-09-22 | A Functionalized High Oxygen Permeability Hydrophilic Anti-Adhesion Transparent Resin, Preparation and Application Thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| LU502823A LU502823B1 (en) | 2022-09-22 | 2022-09-22 | A Functionalized High Oxygen Permeability Hydrophilic Anti-Adhesion Transparent Resin, Preparation and Application Thereof |
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| Publication Number | Publication Date |
|---|---|
| LU502823B1 true LU502823B1 (en) | 2024-03-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| LU502823A LU502823B1 (en) | 2022-09-22 | 2022-09-22 | A Functionalized High Oxygen Permeability Hydrophilic Anti-Adhesion Transparent Resin, Preparation and Application Thereof |
Country Status (1)
| Country | Link |
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| LU (1) | LU502823B1 (en) |
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2022
- 2022-09-22 LU LU502823A patent/LU502823B1/en active IP Right Grant
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