CN113968945A - Antibacterial polyurethane composite resin and preparation method and application thereof - Google Patents
Antibacterial polyurethane composite resin and preparation method and application thereof Download PDFInfo
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- CN113968945A CN113968945A CN202111532603.2A CN202111532603A CN113968945A CN 113968945 A CN113968945 A CN 113968945A CN 202111532603 A CN202111532603 A CN 202111532603A CN 113968945 A CN113968945 A CN 113968945A
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- antibacterial
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- composite resin
- polyurethane
- polyurethane composite
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 119
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 87
- 239000004814 polyurethane Substances 0.000 title claims abstract description 87
- 239000000805 composite resin Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 53
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 51
- 239000003085 diluting agent Substances 0.000 claims abstract description 42
- 238000000016 photochemical curing Methods 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 34
- 239000004970 Chain extender Substances 0.000 claims abstract description 31
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 31
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 27
- 229920000570 polyether Polymers 0.000 claims abstract description 27
- 238000007639 printing Methods 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 229920000728 polyester Polymers 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims description 53
- 239000011347 resin Substances 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 238000001029 thermal curing Methods 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 3
- 230000000845 anti-microbial effect Effects 0.000 claims 2
- 238000003756 stirring Methods 0.000 description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- -1 dihydric alcohol Chemical class 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 230000002829 reductive effect Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 10
- 229910052709 silver Inorganic materials 0.000 description 10
- 239000004332 silver Substances 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- 238000010146 3D printing Methods 0.000 description 8
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 229920005862 polyol Polymers 0.000 description 8
- 150000003077 polyols Chemical class 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 7
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 7
- 229940119545 isobornyl methacrylate Drugs 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 239000004599 antimicrobial Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000036541 health Effects 0.000 description 5
- 238000013007 heat curing Methods 0.000 description 5
- 235000019260 propionic acid Nutrition 0.000 description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 5
- 238000007605 air drying Methods 0.000 description 4
- 238000009395 breeding Methods 0.000 description 4
- 230000001488 breeding effect Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 210000002421 cell wall Anatomy 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000001243 protein synthesis Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000014616 translation Effects 0.000 description 2
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- DPAVORBDLHTGCY-UHFFFAOYSA-N 1,2-dichlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(Cl)C(Cl)=CC=C3SC2=C1 DPAVORBDLHTGCY-UHFFFAOYSA-N 0.000 description 1
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 1
- UYEDESPZQLZMCL-UHFFFAOYSA-N 1,2-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(C)C(C)=CC=C3SC2=C1 UYEDESPZQLZMCL-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- FODCFYIWOJIZQL-UHFFFAOYSA-N 1-methylsulfanyl-3,5-bis(trifluoromethyl)benzene Chemical compound CSC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 FODCFYIWOJIZQL-UHFFFAOYSA-N 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- HRPUANCEDYZMFT-UHFFFAOYSA-N 2-(1-hydroxycyclohexyl)-1-phenylethanone Chemical compound C=1C=CC=CC=1C(=O)CC1(O)CCCCC1 HRPUANCEDYZMFT-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- MSFSPUZXLOGKHJ-UHFFFAOYSA-N Muraminsaeure Natural products OC(=O)C(C)OC1C(N)C(O)OC(CO)C1O MSFSPUZXLOGKHJ-UHFFFAOYSA-N 0.000 description 1
- 108010013639 Peptidoglycan Proteins 0.000 description 1
- 230000006819 RNA synthesis Effects 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical group [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- ZCZFEIZSYJAXKS-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COC(=O)C=C ZCZFEIZSYJAXKS-UHFFFAOYSA-N 0.000 description 1
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical compound C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GTNGBHWYALUTBM-UHFFFAOYSA-N diphenylmethanone;hydrochloride Chemical compound Cl.C=1C=CC=CC=1C(=O)C1=CC=CC=C1 GTNGBHWYALUTBM-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000002068 genetic effect Effects 0.000 description 1
- 150000004676 glycans Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 108020004999 messenger RNA Proteins 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000001668 nucleic acid synthesis Methods 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- JRWNODXPDGNUPO-UHFFFAOYSA-N oxolane;prop-2-enoic acid Chemical compound C1CCOC1.OC(=O)C=C JRWNODXPDGNUPO-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 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 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000004260 plant-type cell wall biogenesis Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 150000004804 polysaccharides Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- FZYDVDRIQZXXIW-UHFFFAOYSA-N propanoic acid;prop-2-enoic acid Chemical compound CCC(O)=O.OC(=O)C=C FZYDVDRIQZXXIW-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000013518 transcription Methods 0.000 description 1
- 230000035897 transcription Effects 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- 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
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention provides an antibacterial polyurethane composite resin and a preparation method and application thereof. The preparation raw materials of the antibacterial polyurethane composite tree comprise, by mass: 53.5 to 55.5 parts of polyurethane prepolymer, 0.2 to 0.4 part of inorganic antibacterial agent, 29.5 to 31 parts of diluent, 4 to 5 parts of cross-linking agent, 1 to 2 parts of photoinitiator and 9 to 9.5 parts of chain extender; wherein the polyurethane prepolymer is at least one of polyester prepolymer and polyether prepolymer. The antibacterial polyurethane composite resin has excellent antibacterial property, can maintain good mechanical property, and can still maintain high antibacterial property when being subjected to long-time continuous photocuring printing.
Description
Technical Field
The invention relates to the technical field of polymer composite materials, in particular to an antibacterial polyurethane composite resin and a preparation method and application thereof.
Background
3D prints and belongs to one kind of rapid prototyping manufacturing technology, is one kind and increases the material by layer and pile up the quick material increase manufacturing technology that the material produced three-dimensional entity, has not only overcome the loss that traditional material reduction made and has produced, makes product manufacturing more intelligent, accurate and high-efficient moreover, wherein, prints the material and is the material basis that 3D printed. With the rapid development of polymer material industry, polyurethane is widely applied to various fields such as food processing, packaging industry, medical treatment and the like with excellent performance and low price, and also becomes a main printing material to prepare various polyurethane products.
However, the conventional polyurethane material is very prone to grow and propagate bacteria during use and storage, and the polyurethane is often used for preparing articles which are in close contact with human bodies for a long time, such as steering wheel sheaths, vehicle door armrests, steering control lever skins and the like, so that the conventional polyurethane material is not beneficial to human health. In the traditional technology, the antibacterial property of the high polymer material is mainly realized by two modes of forming an organic antibacterial group through organic reaction or adding an inorganic antibacterial agent. For example, the polyurethane with antibacterial property is synthesized by combining organic antibacterial agent and polyurethane through reaction, wherein organic antibacterial monomer is connected with polyurethane long chain, so that permanent antibacterial property can be achieved, but because the formula of the photocuring polyurethane is complex, photoreactive property needs to be considered, the addition of the organic antibacterial agent can generate adverse effect on the photoreactive property, and the addition of the inorganic antibacterial agent can generate adverse effect on the mechanical property of the polyurethane
Therefore, the prior art still remains to be developed.
Disclosure of Invention
Based on the antibacterial polyurethane composite resin, the invention provides the antibacterial polyurethane composite resin with excellent antibacterial property and mechanical property, and a preparation method and application thereof.
The technical scheme of the invention is as follows.
The invention provides an antibacterial polyurethane composite resin, which is prepared from the following raw materials in parts by mass: 53.5 to 55.5 parts of polyurethane prepolymer, 0.2 to 0.4 part of inorganic antibacterial agent, 29.5 to 31 parts of diluent, 4 to 5 parts of cross-linking agent, 1 to 2 parts of photoinitiator and 9 to 9.5 parts of chain extender;
wherein the polyurethane prepolymer is at least one selected from polyester polyurethane prepolymer and polyether polyurethane prepolymer.
In some embodiments, the raw materials for preparing the antibacterial polyurethane composite resin comprise: 54.5 to 55.5 portions of polyurethane prepolymer, 0.2 to 0.4 portion of inorganic antibacterial agent, 29.5 to 30.7 portions of diluent, 4 to 5 portions of cross-linking agent, 1.5 to 2 portions of photoinitiator and 9 to 9.2 portions of chain extender.
In some embodiments, the raw materials for preparing the antibacterial polyurethane composite resin comprise: 54.5 parts of polyurethane prepolymer, 0.4 part of inorganic antibacterial agent, 29.5 parts of diluent, 4.5 parts of cross-linking agent, 2 parts of photoinitiator and 9.1 parts of chain extender.
In some embodiments, the polyurethane prepolymer is a polyether polyurethane prepolymer; and/or
The viscosity of the polyurethane prepolymer is 130000 cps-1500000 cps.
In some embodiments, the percentage of isocyanate groups in the polyurethane prepolymer is between 4% and 5%.
In some of these embodiments, the inorganic antimicrobial agent is a ZnO/Ag composite antimicrobial agent.
In some of these embodiments, the chain extender includes 2-methyl-2-propenoic acid-2- (2-methoxyethoxy) ethyl ester and polyethylene glycol dimethacrylate.
In another aspect of the present invention, there is provided a method for preparing an antibacterial polyurethane composite resin, comprising the steps of:
providing the raw materials for preparing the antibacterial polyurethane composite resin;
mixing the polyurethane prepolymer, the inorganic antibacterial agent, the diluent, the crosslinking agent and the photoinitiator, and then carrying out defoaming treatment to obtain a resin precursor;
and mixing the resin precursor with the chain extender, and defoaming to obtain the antibacterial polyurethane composite resin.
In still another aspect of the present invention, there is provided an antibacterial photo-curable resin article whose raw material includes the antibacterial polyurethane composite resin as described above.
In some embodiments, the raw material is subjected to a photo-curing printing process and a thermal curing process in sequence to obtain the antibacterial photo-curing resin product.
In some of these embodiments, the face velocity of the photocuring printing process is greater than 50 mm/h.
In another aspect of the present invention, a 3D printing method is provided, including the steps of:
the antibacterial polyurethane composite resin is used as photosensitive resin to perform 3D photocuring printing.
The raw materials for preparing the antibacterial polyurethane composite resin comprise the polyurethane prepolymer, the inorganic antibacterial agent, the diluent, the cross-linking agent, the photoinitiator and the chain extender in a specific ratio, and all the components coordinate to make the antibacterial polyurethane composite resin have excellent antibacterial property, and simultaneously can keep good mechanical property, and can still keep high antibacterial property when being subjected to long-time continuous photocuring printing treatment. When the polyurethane prepolymer is used for preparing an antibacterial photo-curing resin product, the breeding of bacteria on the surface of the product can be reduced, so that the human health can be protected, and the polyurethane prepolymer has good mechanical properties, and further the service life of the product is prolonged.
In the preparation method of the antibacterial polyurethane composite resin, the preparation raw materials comprise the polyurethane prepolymer, the inorganic antibacterial agent, the diluent, the cross-linking agent, the photoinitiator and the chain extender in a specific ratio, and the components coordinate with each other, so that the prepared antibacterial polyurethane composite resin has excellent antibacterial property and can keep good mechanical property.
The raw material of the antibacterial light-cured resin product of the present invention includes the antibacterial polyurethane composite resin described above. The antibacterial photo-curing resin product has excellent mechanical properties, and can relieve the breeding of bacteria and protect the health of human bodies. Further, the preparation method of the antibacterial photo-curing resin product comprises the following steps: and (3) carrying out photocuring printing treatment and thermocuring treatment on the raw material in sequence, and matching with the antibacterial photocuring resin. The raw material comprises the antibacterial polyurethane composite resin, and the inorganic antibacterial agent and other components are coordinated to ensure that the antibacterial polyurethane composite resin has excellent antibacterial property, the inorganic antibacterial agent does not influence the photocuring performance of the antibacterial polyurethane composite resin, the photocuring speed is high, and the antibacterial polyurethane composite resin can be cured smoothly under the condition that the surface speed of photocuring printing treatment is greater than 50 mm/h.
In the 3D printing method, the antibacterial polyurethane composite resin is used as photosensitive resin for 3D photocuring printing, and the inorganic antibacterial agent and other components coordinate to achieve excellent antibacterial property of the antibacterial polyurethane composite resin, so that the inorganic antibacterial agent does not affect the photocuring performance of the antibacterial polyurethane composite resin, the photocuring speed is high, and the prepared product has excellent mechanical properties and antibacterial properties.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
One embodiment of the present invention provides an antibacterial polyurethane composite resin, which is prepared from the following raw materials in parts by mass: 53.5 to 55.5 parts of polyurethane prepolymer, 0.2 to 0.4 part of inorganic antibacterial agent, 29.5 to 31 parts of diluent, 4 to 5 parts of cross-linking agent, 1 to 2 parts of photoinitiator and 9 to 9.5 parts of chain extender;
wherein the polyurethane prepolymer is at least one selected from polyester polyurethane prepolymer and polyether polyurethane prepolymer.
The raw materials for preparing the antibacterial polyurethane composite resin comprise polyurethane prepolymer, inorganic antibacterial agent, diluent, cross-linking agent, photoinitiator and chain extender in a specific proportion, and all the components coordinate to make the antibacterial polyurethane composite resin have excellent antibacterial property, and simultaneously can keep good mechanical property, and can still keep high antibacterial property when being subjected to long-time continuous photocuring printing treatment. When the polyurethane prepolymer is used for preparing an antibacterial photo-curing resin product, the breeding of bacteria on the surface of the product can be reduced, so that the human health can be protected, and the polyurethane prepolymer has good mechanical properties, and further the service life of the product is prolonged.
The polyester prepolymer and the polyether prepolymer are distinguished mainly by aiming at the types of polyols in the preparation of the polyurethane prepolymer, when the polyol in the preparation of the polyurethane prepolymer is mainly polyether polyol, the polyether prepolymer is prepared, and in the molecular structure of the polyether polyol, the ether bond cohesive energy is low and the polyether polyol is easy to rotate, so that the polyurethane material prepared from the polyether prepolymer has low-temperature flexibility and excellent hydrolysis resistance; when the polyol in the preparation of the polyurethane prepolymer is mainly polyester polyol, the polyester polyol is polyester prepolymer, and the polyester polyol refers to a polymer obtained by polycondensation reaction of polycarboxylic acid such as dicarboxylic acid and the like and polyol such as dihydric alcohol, and can be broadly referred to as: polyol polymers containing ester groups (COO) or carbonate groups (OCOO). The polyester type polyurethane prepared from the polyester type prepolymer has excellent mechanical properties.
In some embodiments, the polyurethane prepolymer is selected from polyether polyurethane prepolymers.
The polyether type polyurethane prepolymer has low viscosity of the raw material system, is easy to be mutually soluble with isocyanate and other additives, and has excellent processing performance.
In some of these embodiments, the viscosity of the polyurethane prepolymer is 130000cps to 1500000 cps.
The above viscosity means a viscosity at a temperature of 60 ℃ under normal pressure.
In some embodiments, the percentage of isocyanate groups in the polyurethane prepolymer is 4% to 5%.
Preferably, the raw materials for preparing the antibacterial polyurethane composite resin comprise: 54.5 to 55.5 portions of polyurethane prepolymer, 0.2 to 0.4 portion of inorganic antibacterial agent, 29.5 to 30.7 portions of diluent, 4 to 5 portions of cross-linking agent, 1.5 to 2 portions of photoinitiator and 9 to 9.2 portions of chain extender.
Further preferably, the raw materials for preparing the antibacterial polyurethane composite resin comprise: 54.5 parts of polyurethane prepolymer, 0.4 part of inorganic antibacterial agent, 29.5 parts of diluent, 4.5 parts of cross-linking agent, 2 parts of photoinitiator and 9.1 parts of chain extender.
In some of these embodiments, the inorganic antimicrobial agent is an inorganic silver antimicrobial agent.
The inorganic silver antibacterial agent has stable physical and chemical properties, can keep excellent antibacterial property in the processing process and the using process, can achieve good antibacterial effect at low concentration, and has excellent antibacterial property while keeping good mechanical property by adding the inorganic silver antibacterial agent with specific weight.
The action mechanism of the inorganic silver antibacterial agent has the following aspects:
1) silver ions interfere with cell wall synthesis. The important component of the bacterial cell wall is peptidoglycan, the interference effect of the inorganic silver antibacterial agent on the cell wall mainly inhibits the connection of a polysaccharide chain and tetrapeptide crosslinking, so that the integrity of the cell wall is lost, the protection effect on osmotic pressure is lost, and the thallus is damaged to die.
2) Silver ions can damage cell membranes, which are an important component of the vital activities of bacterial cells. Therefore, if the cell membrane is damaged or destroyed, the bacteria will die.
3) Silver ions inhibit protein synthesis, and alter and stop the protein synthesis process, thereby killing bacteria.
4) Silver ions interfere with nucleic acid synthesis, thereby preventing the replication of genetic information, including DNA, RNA synthesis, and mRNA transcription from DNA templates, among others.
In some of these embodiments, the inorganic silver antimicrobial agent is a silver ion antimicrobial agent.
Preferably, the inorganic antibacterial agent is a ZnO/Ag composite antibacterial agent.
The ZnO/Ag composite antibacterial agent has excellent antibacterial performance, and can ensure that the antibacterial polyurethane composite resin can keep excellent antibacterial performance in continuous photocuring printing.
In some preferred embodiments, the chain extender comprises 2-methyl-2-propenoic acid-2- (2-methoxyethoxy) ethyl ester and polyethylene glycol dimethacrylate in a mass ratio.
In some of the embodiments, the mass ratio of 2- (2-methoxyethoxy) ethyl 2-methyl-2-acrylate to polyethylene glycol dimethacrylate is (5-6) to (2-4).
Further, the mass ratio of 2-methyl-2-propenoic acid-2- (2-methoxyethoxy) ethyl ester to polyethylene glycol dimethacrylate was 5.7: 3.4.
The mechanical property of the prepared antibacterial polyurethane composite resin can be further improved by regulating and controlling the type and the proportion of the chain extender.
The above-mentioned diluent may be any one commonly used in the art, including but not limited to: at least one of styrene, acrylate diluent, vinyl ether diluent and cyclohexane diluent.
Preferably, the above diluent is selected from the olefinic acid ester diluents.
The gadoleic acid ester diluent has good compatibility with the polyurethane prepolymer, so that when the antibacterial polyurethane composite resin is prepared, the components such as the inorganic antibacterial agent and the like can be uniformly mixed, and the antibacterial property of the antibacterial polyurethane composite resin is improved.
In some of these embodiments, the acrylate diluent is selected from at least one of methyl methacrylate, 1, 6-hexanediol diacrylate, isobornyl acrylate, tetrahydrofuran acrylate, tripropylene glycol diacrylate, hexanediol diacrylate, bisphenol a diacrylate, trimethylolpropane triacrylate, pentaerythritol acrylate, isobornyl methacrylate, and cyclic trimethylolpropane formal acrylate.
Preferably, the diluent is isobornyl methacrylate.
The above-mentioned photoinitiator may be one commonly used in the art.
In some of these embodiments, the photoinitiator is selected from: diphenyl- (4-phenylsulfur) phenylsulfonium hexafluoroantimonate, diphenyl- (4-phenylsulfur) phenylsulfonium hexafluorophosphate, 4-octyloxybenzoylium hexafluoroantimonate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, diphenyliodonium hexafluorophosphate, 4-isopropyl-4' -methyldiphenyliodonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium tetrafluoroborate, tri-p-tolylsulfonium hexafluorophosphate, 1-hydroxy-cyclohexyl-acetophenone, α -dimethyl- α -hydroxyacetophenone, p-isopropylphenyl-2-hydroxydimethylacetone-1, benzophenone chloride, acrylated benzophenone, 4-phenylbenzophenone, 2-thiochromanone chloride, benzoylated benzophenone, 4-phenylbenzophenone, and mixtures thereof, At least one of isopropyl thioxanthone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, dimethyl thioxanthone, diethyl thioxanthone, dichlorothioxanthone, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinylbenzyl-phenyl) butanone and 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide.
In some of these embodiments, the photoinitiator is selected from 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide.
2,4, 6-trimethylbenzoyl-diphenylphosphine oxide can be activated by exposure to a light source with a wavelength of 405nm, facilitating photocured printing.
In some of these embodiments, the crosslinking agent is selected from acrylate based crosslinking agents. Specifically, the crosslinking agent is trimethyl acrylate propionate.
An embodiment of the present invention also provides a method for preparing an antibacterial polyurethane composite resin, including the following steps S100 to S300.
Step S100, providing the raw materials for preparing the antibacterial polyurethane composite resin.
The preparation raw materials comprise: 53.5 to 55.5 portions of polyurethane prepolymer, 0.2 to 0.4 portion of inorganic antibacterial agent, 29.5 to 31 portions of diluent, 4 to 5 portions of cross-linking agent, 1 to 2 portions of photoinitiator and 9 to 9.5 portions of chain extender.
And step S200, mixing and stirring the polyurethane prepolymer, the inorganic antibacterial agent, the diluent, the cross-linking agent and the photoinitiator, and then carrying out defoaming treatment to obtain a resin precursor.
Further, the mixing and stirring steps protect the following steps:
mixing and stirring the photoinitiator and the diluent at the temperature of between 60 and 70 ℃ for 40 to 50 minutes to obtain a first mixture.
At this time the photoinitiator was dissolved in the diluent to form a homogeneous resulting mixture.
And then mixing and stirring the polyurethane prepolymer, the cross-linking agent and the first mixture for 40-60 min at the temperature of 25-35 ℃ in the nitrogen atmosphere to obtain a second mixture.
And then mixing and stirring the inorganic antibacterial agent and the second mixture for 30-50 min at 25-35 ℃ in a nitrogen atmosphere.
Thus, the inorganic antibacterial agent can be uniformly mixed with other components, and the effects of uniform dispersion, lasting release, no agglomeration and no precipitation are achieved.
And step S300, mixing the resin precursor with a chain extender, and performing defoaming treatment to obtain the antibacterial polyurethane composite resin. In some of these embodiments, the mixing is in a blender or high mixer.
It will be appreciated that the mixing process described above may also be carried out in other mixing devices, as long as adequate mixing of the materials is achieved.
In some embodiments, the method further comprises the step of pretreating the polyurethane prepolymer:
the polyurethane prepolymer is dried for 1 to 2 hours at the temperature of 60 ℃, so that the viscosity of the polyurethane prepolymer can be reduced, and the generation of bubbles can be reduced.
In the preparation method of the antibacterial polyurethane composite resin, the preparation raw materials comprise the polyurethane prepolymer, the inorganic antibacterial agent, the diluent, the cross-linking agent, the photoinitiator and the chain extender in a specific ratio, and the components coordinate with each other, so that the prepared antibacterial polyurethane composite resin has excellent antibacterial property and can keep good mechanical property.
An embodiment of the present invention also provides an antibacterial photo-curable resin product, the material of which includes the antibacterial polyurethane composite resin described above.
The raw material of the antibacterial light-cured resin product comprises the antibacterial polyurethane composite resin. The antibacterial photo-curing resin product has excellent mechanical properties, and can relieve the breeding of bacteria and protect the health of human bodies.
In some embodiments, the step of preparing the antibacterial photo-curable resin article includes the following step S400.
And S400, sequentially carrying out photocuring printing treatment and thermocuring treatment on the raw material to obtain the antibacterial photocuring resin product.
In some of these embodiments, the face velocity of the photocuring printing process is greater than 50 mm/h.
The raw material comprises the antibacterial polyurethane composite resin, and the inorganic antibacterial agent and other components are coordinated to ensure that the antibacterial polyurethane composite resin has excellent antibacterial property, the inorganic antibacterial agent does not influence the photocuring performance of the antibacterial polyurethane composite resin, the photocuring speed is high, and the antibacterial polyurethane composite resin can be cured smoothly under the condition that the surface speed of photocuring printing treatment is more than 50 mm/h.
In some of these embodiments, the light power of the photocuring printing process is 3.8mw/cm2。
Furthermore, the temperature of the heat curing treatment is 115-125 ℃, and the time is 6-8 h.
It is understood that the above-mentioned antibacterial photo-curable resin article includes, but is not limited to: steering wheel sheath, door handrail, steering control pole covering, electron protective housing such as cell-phone apron etc..
The invention further provides a 3D printing method, which includes the following step S500.
And step S500, performing 3D photocuring printing by using the antibacterial polyurethane composite resin as photosensitive resin.
In the 3D printing method, the antibacterial polyurethane composite resin is used as photosensitive resin for 3D photocuring printing, and the inorganic antibacterial agent and other components coordinate to achieve excellent antibacterial property of the antibacterial polyurethane composite resin, so that the inorganic antibacterial agent does not affect the photocuring performance of the antibacterial polyurethane composite resin, the photocuring speed is high, and the prepared product has excellent mechanical properties and antibacterial properties.
While the present invention will be described with respect to particular embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover by the appended claims the scope of the invention, and that certain changes in the embodiments of the invention will be suggested to those skilled in the art and are intended to be covered by the appended claims.
The following are specific examples.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
(1) Providing raw materials: polyether type prepolymer YJM 10454.5 parts, ZnO/Ag composite antibacterial agent 0.4 parts, diluent isobornyl methacrylate 29.5 parts, cross-linking agent propionic acid trimethyl acrylate 4.5 parts, photoinitiator TPO 2.0 parts, chain extender 2-methyl-2-acrylic acid-2- (2-methoxy ethoxy) ethyl ester 5.7 parts, and polyethylene glycol dimethacrylate 3.4 parts.
(2) And sealing the polyether prepolymer in an oven at 60 ℃ for 1h, wherein the dried viscosity is 135000 cps.
Adding an initiator into a three-necked bottle, adding a diluent, placing the three-necked bottle on an electromagnetic heating stirring heating platform, heating and stirring at 60 ℃ for 40min, dissolving the initiator into the diluent, sequentially adding a polyether type prepolymer and a crosslinking agent, connecting a mechanical stirring device, stirring at room temperature of 25 ℃ for 45min under the protection of nitrogen, adding an antibacterial agent, and continuously stirring for 30min under the protection of nitrogen. And after stirring, putting the three-mouth bottle into a hot oven connected with an oil pump, defoaming in a vacuum state, observing resin, closing a vacuum valve immediately to eliminate bubbles if the resin overflows from the edge of the bottle mouth, opening the vacuum valve again until the pressure is reduced to 0.1MPa, and timing for 30min in the whole defoaming process to obtain a resin precursor.
(3) Placing the chain extender 2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester, polyethylene glycol dimethacrylate and the resin precursor into a three-necked bottle, and mechanically stirring for 30min at room temperature under nitrogen. And after stirring, putting the mixture into a hot oven connected with an oil pump until the pressure is reduced to 0.1MPa, so that the resin does not overflow any more, and timing the whole defoaming process for 30 min. And then 3D printing is carried out, and the speed is as follows: 75mm/h, optical power: 3.8mw/cm2Bottom layer 4 layers, the bottom layer was cured for 30 seconds each. Cleaning after printing, and then performing heat curing treatment: and (3) curing for 8 hours at the temperature of 120 ℃ in a constant-temperature air drying oven to obtain the antibacterial polyurethane composite resin.
Example 2
(1) Providing raw materials: polyether type prepolymer YJM 10354.5 parts, ZnO/Ag composite antibacterial agent 0.2 parts, diluent isobornyl methacrylate 30.7 parts, cross-linking agent propionic acid trimethyl acrylate 4.5 parts, photoinitiator TPO 2.0 parts, chain extender 2-methyl-2-acrylic acid-2- (2-methoxy ethoxy) ethyl ester 5.7 parts, and polyethylene glycol dimethacrylate 3.4 parts.
(2) And sealing the polyether type prepolymer in a 60 ℃ oven for 1h, wherein the dried viscosity is 140000 cps.
Adding an initiator into a three-necked bottle, adding a diluent, placing the three-necked bottle on an electromagnetic heating stirring heating platform, heating and stirring at 60 ℃ for 40min, dissolving the initiator into the diluent, directly and sequentially adding a polyether type prepolymer and a crosslinking agent, connecting a mechanical stirring device, stirring at room temperature of 25 ℃ for 45min under the protection of nitrogen, adding an antibacterial agent, and continuously stirring for 30min under the protection of nitrogen. And after stirring, putting the three-mouth bottle into a hot oven connected with an oil pump, and defoaming in a vacuum state. Observing the resin, if the resin emerges at the edge of the bottle mouth, immediately closing the vacuum valve to eliminate bubbles, then opening the vacuum valve until the pressure is reduced to 0.1MPa, so that the resin does not emerge, and timing for 30min in the whole defoaming process to obtain a resin precursor.
(3) Placing the chain extender 2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester, polyethylene glycol dimethacrylate and the resin precursor into a three-necked bottle, and mechanically stirring for 30min at room temperature under nitrogen. And after stirring, putting the mixture into a hot oven connected with an oil pump until the pressure is reduced to 0.1MPa, so that the resin does not overflow any more, and timing the whole defoaming process for 30 min. And then 3D printing is carried out, and the speed is as follows: 75mm/h, optical power: 3.8mw/cm2Bottom layer 4 layers, the bottom layer was cured for 30 seconds each. Cleaning after printing, and then performing heat curing treatment: and (3) curing for 8 hours at the temperature of 120 ℃ in a constant-temperature air drying oven to obtain the antibacterial polyurethane composite resin.
Example 3
(1) Providing raw materials: polyether type prepolymer YJM 10854 parts, ZnO/Ag composite antibacterial agent 0.4 parts, diluent isobornyl methacrylate 29.5 parts, cross-linking agent propionic acid trimethyl acrylate 4.5 parts, photoinitiator TPO 2.0 parts, chain extender 2-methyl-2-acrylic acid-2- (2-methoxy ethoxy) ethyl ester 6 parts, and polyethylene glycol dimethacrylate 3.6 parts.
(2) And sealing the polyether type prepolymer in a 60 ℃ oven for 1h, wherein the dried viscosity is 120000 cps.
Adding an initiator into a three-mouth bottle, adding a diluent, placing the three-mouth bottle on an electromagnetic heating stirring heating platform, heating and stirring for 40min at 60 ℃, dissolving the initiator into the diluent, directly and sequentially adding a polyether type prepolymer and a crosslinking agent, connecting a mechanical stirring device, stirring for 45min at room temperature under the protection of nitrogen, adding an antibacterial agent, continuously stirring for 30min under the protection of nitrogen, placing the three-mouth bottle into a hot oven connected with an oil pump after stirring is finished, and defoaming under a vacuum state: observing the resin, if the resin emerges at the edge of the bottle mouth, immediately closing the vacuum valve to eliminate bubbles, then opening the vacuum valve until the pressure is reduced to 0.1MPa, so that the resin does not emerge, and timing for 30min in the whole defoaming process to obtain a resin precursor.
(3) Placing the chain extender 2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester, polyethylene glycol dimethacrylate and the resin precursor into a three-necked bottle, and mechanically stirring for 30min at room temperature under nitrogen. After the stirring is finished, the mixture is put into a hot oven connected with an oil pump until the stirring is finishedWhen the pressure is reduced to 0.1MPa, the resin does not overflow any more, and the time is kept for deaeration for 30 min. And then 3D printing is carried out, and the speed is as follows: 75mm/h, optical power: 3.8mw/cm2Bottom layer 4 layers, the bottom layer was cured for 30 seconds each. Cleaning after printing, and then performing heat curing treatment: and (3) curing for 8 hours at the temperature of 120 ℃ in a constant-temperature air drying oven to obtain the antibacterial polyurethane composite resin.
Example 4
(1) Providing raw materials: polyether type prepolymer YJM 1124.5 parts, ZnO/Ag composite antibacterial agent 0.4 parts, diluent isobornyl methacrylate 29.5 parts, cross-linking agent propionic acid trimethyl acrylate 4.5 parts, photoinitiator TPO 2.0 parts, and chain extender 2-methyl-2-acrylic acid-2- (2-methoxy ethoxy) ethyl ester 9.2 parts.
(2) And sealing the polyether type prepolymer in a 60 ℃ oven for 1h, wherein the dried viscosity is 145000 cps.
And adding an initiator into a three-necked bottle, adding a diluent, placing the three-necked bottle on an electromagnetic heating stirring heating platform, heating and stirring for 40min at 60 ℃, dissolving the initiator into the diluent, directly and sequentially adding a polyether type prepolymer and a crosslinking agent, connecting a mechanical stirring device, stirring for 45min at room temperature under the protection of nitrogen, adding an antibacterial agent, and continuously stirring for 30min under the protection of nitrogen. And after stirring, putting the three-mouth bottle into a hot oven connected with an oil pump, and defoaming in a vacuum state. Observing the resin, if the resin is extruded out of the edge of the bottle mouth, immediately closing the vacuum valve to eliminate bubbles, then opening the vacuum valve until the pressure is reduced to 0.1MPa, so that the resin is not extruded out, and timing the whole defoaming process for 30 min. Obtaining the resin precursor.
(3) Placing the chain extender 2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester and the resin precursor into a three-necked bottle, and mechanically stirring for 30min at room temperature under nitrogen. And after stirring, putting the mixture into a hot oven connected with an oil pump until the pressure is reduced to 0.1MPa, and defoaming the mixture for 30min in timing until the resin does not overflow. And then 3D printing is carried out, and the speed is as follows: 75mm/h, optical power: 3.8mw/cm2Bottom layer 4 layers, the bottom layer was cured for 30 seconds each. Cleaning after printing, and then performing heat curing treatment: and (3) curing for 8 hours at the temperature of 120 ℃ in a constant-temperature air drying oven to obtain the antibacterial polyurethane composite resin.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that: step (1) providing raw materials: polyether type prepolymer YJM 10456 parts, ZnO/Ag composite antibacterial agent 0.4 parts, diluent isobornyl methacrylate 30.5 parts, cross-linking agent propionic acid trimethyl acrylate 5 parts, photoinitiator TPO 2.0 parts, chain extender 2-methyl-2-acrylic acid-2- (2-methoxy ethoxy) ethyl ester 5.7 parts, and polyethylene glycol dimethacrylate 3.4 parts.
Other steps and conditions were the same as in example 1.
Performance testing
The antibacterial polyurethane composite resins prepared in examples 1 to 4 and comparative example 1 were subjected to performance tests, specifically as follows:
1) the antibacterial rate of the antibacterial polyurethane composite resin against staphylococcus aureus was tested according to standard GB4789.10-2016, and the test results are shown in table 1.
2) The tensile strength of the antibacterial polyurethane composite resin was tested according to standard GB/T528-2009, with the results shown in table 1.
3) The elongation at break of the antibacterial polyurethane composite resin was tested according to standard GB/T528-.
4) The tear strength of the antibacterial polyurethane composite resin was tested according to the standard GB/T529 and 2008, and the results are shown in Table 1.
TABLE 1
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above examples only show some embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (12)
1. The antibacterial polyurethane composite resin is characterized by comprising the following raw materials in parts by mass: 53.5 to 55.5 parts of polyurethane prepolymer, 0.2 to 0.4 part of inorganic antibacterial agent, 29.5 to 31 parts of diluent, 4 to 5 parts of cross-linking agent, 1 to 2 parts of photoinitiator and 9 to 9.5 parts of chain extender;
wherein the polyurethane prepolymer is at least one selected from polyester polyurethane prepolymer and polyether polyurethane prepolymer.
2. The antibacterial polyurethane composite resin according to claim 1, wherein the antibacterial polyurethane composite resin is prepared from the following raw materials: 54.5 to 55.5 portions of polyurethane prepolymer, 0.2 to 0.4 portion of inorganic antibacterial agent, 29.5 to 30.7 portions of diluent, 4 to 5 portions of cross-linking agent, 1.5 to 2 portions of photoinitiator and 9 to 9.2 portions of chain extender.
3. The antibacterial polyurethane composite resin according to claim 1, wherein the antibacterial polyurethane composite resin is prepared from the following raw materials: 54.5 parts of polyurethane prepolymer, 0.4 part of inorganic antibacterial agent, 29.5 parts of diluent, 4.5 parts of cross-linking agent, 2 parts of photoinitiator and 9.1 parts of chain extender.
4. The antibacterial polyurethane composite resin according to any one of claims 1 to 3, wherein the polyurethane prepolymer is a polyether polyurethane prepolymer; and/or
The viscosity of the polyurethane prepolymer is 130000 cps-1500000 cps.
5. The antibacterial polyurethane composite resin as claimed in any one of claims 1 to 3, wherein the percentage content of isocyanate groups in the polyurethane prepolymer is 4% to 5%.
6. The antibacterial polyurethane composite resin according to any one of claims 1 to 3, wherein the inorganic antibacterial agent is a ZnO/Ag composite antibacterial agent.
7. The antibacterial polyurethane composite resin according to any one of claims 1 to 3, wherein the chain extender includes 2-methyl-2-propenoic acid-2- (2-methoxyethoxy) ethyl ester and polyethylene glycol dimethacrylate.
8. The preparation method of the antibacterial polyurethane composite resin is characterized by comprising the following steps of:
providing a raw material for preparing the antibacterial polyurethane composite resin according to any one of claims 1 to 7;
mixing the polyurethane prepolymer, the inorganic antibacterial agent, the diluent, the crosslinking agent and the photoinitiator, and then carrying out defoaming treatment to obtain a resin precursor;
and mixing the resin precursor with the chain extender, and defoaming to obtain the antibacterial polyurethane composite resin.
9. An antibacterial photo-curable resin product characterized in that a raw material of the antibacterial photo-curable resin product comprises the antibacterial polyurethane composite resin according to any one of 1 to 7.
10. The antimicrobial photocurable resin article according to claim 9 wherein said step of preparing said article comprises the steps of:
and carrying out photocuring printing treatment and thermocuring treatment on the raw material in sequence to obtain the antibacterial photocuring resin product.
11. The antimicrobial photocurable resin article of claim 10 wherein said photocurable printing process has a face velocity greater than 50 mm/h.
12. A3D printing method is characterized by comprising the following steps:
3D photocuring printing is performed with the antibacterial polyurethane composite resin according to any one of claims 1 to 7 as a photosensitive resin.
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