CN109223579B - Dental restoration material and preparation method thereof - Google Patents
Dental restoration material and preparation method thereof Download PDFInfo
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- CN109223579B CN109223579B CN201811111502.6A CN201811111502A CN109223579B CN 109223579 B CN109223579 B CN 109223579B CN 201811111502 A CN201811111502 A CN 201811111502A CN 109223579 B CN109223579 B CN 109223579B
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- 239000000463 material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 229920000642 polymer Polymers 0.000 claims abstract description 49
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 48
- 239000010936 titanium Substances 0.000 claims abstract description 48
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000009833 condensation Methods 0.000 claims abstract description 26
- 230000005494 condensation Effects 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 10
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 10
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 124
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 61
- 238000006243 chemical reaction Methods 0.000 claims description 55
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 40
- 235000019441 ethanol Nutrition 0.000 claims description 39
- 238000001291 vacuum drying Methods 0.000 claims description 28
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 23
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 18
- 239000013067 intermediate product Substances 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 14
- 238000001125 extrusion Methods 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 9
- ARMZYJYJGIRLRX-UHFFFAOYSA-N 2-[[(2-hydroxyphenyl)methylamino]methyl]phenol Chemical compound OC1=CC=CC=C1CNCC1=CC=CC=C1O ARMZYJYJGIRLRX-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 9
- 239000000661 sodium alginate Substances 0.000 claims description 9
- 235000010413 sodium alginate Nutrition 0.000 claims description 9
- 229940005550 sodium alginate Drugs 0.000 claims description 9
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 9
- -1 2,2, 2-trifluoro-1-hydroxyethyl Chemical group 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 239000012074 organic phase Substances 0.000 claims description 7
- 229920002620 polyvinyl fluoride Polymers 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 5
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- ZVRKPNJLSIJXPF-UHFFFAOYSA-N 1-diethoxyphosphoryl-2,2,2-trifluoroethanol Chemical compound CCOP(=O)(OCC)C(O)C(F)(F)F ZVRKPNJLSIJXPF-UHFFFAOYSA-N 0.000 claims description 2
- FTUSRXADIDGMRM-UHFFFAOYSA-N [F].P(O)(O)=O Chemical compound [F].P(O)(O)=O FTUSRXADIDGMRM-UHFFFAOYSA-N 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 abstract description 8
- 239000011737 fluorine Substances 0.000 abstract description 8
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 abstract description 7
- 210000003296 saliva Anatomy 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000010998 test method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 150000004781 alginic acids Chemical class 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 210000000056 organ Anatomy 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000938605 Crocodylia Species 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/15—Compositions characterised by their physical properties
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
- A61K6/74—Fillers comprising phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
Landscapes
- Health & Medical Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Plastic & Reconstructive Surgery (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dental Preparations (AREA)
Abstract
The invention discloses a dental restoration material which is prepared from the following raw material components in parts by weight: 40-50 parts of titanium-based ionic condensation polymer with a fluorine-containing phosphonate grafted main chain, 20-30 parts of polyurethane prepolymer with isocyanate groups at two ends, 1-3 parts of bismuth acetate and 10-15 parts of surface-modified Zr-O-P. The invention also discloses a preparation method of the dental prosthetic material. The dental prosthetic material disclosed by the invention has excellent biocompatibility, higher strength, hardness, toughness and wear resistance, and remarkable antibacterial effect, and can resist the corrosion of oral saliva.
Description
Technical Field
The invention relates to the technical field of medical materials, in particular to a dental prosthetic material and a preparation method thereof.
Background
Teeth are an organ for humans, amphibians, reptiles, birds and higher mammals to chew food, and are mainly used to tear and grind food, help sound, and make the face aesthetic. Teeth have become one of the important signs for measuring body beauty. Therefore, there is a strong need for a method of restoring damaged teeth.
Tooth restoration is to prepare teeth according to the principles of retention, resistance and protection of pulp-dentin organs on the basis of removing damaged or seriously weakened tooth tissues; finally, the specific material recovers the inherent shape and function through a certain procedure. One material essential in the performance of dental restorative procedures is dental restorative material, which is required not only to be implanted in the mouth but also to function stably in the specific environment of the mouth for a long period of time.
At present, common dental restorative materials mainly include resins, full porcelains and porcelain porcelains. The all-ceramic repair material needs computer all-ceramic auxiliary involvement and machining systems, and the process is complex. The porcelain repairing material has large grinding amount to the related adjacent tooth bodies in the mouth, has certain manufacturing difficulty, and is easy to cause the injury of the abutment and the mucous membrane tissue to a patient. Resin type repairing materials are the mainstream dental repairing materials at present, teeth are vivid, minimally invasive and high in strength after filling, but the preparation process is complex and the price is high, and bacteria can grow at the repairing position in the process of repairing the teeth or using false teeth, so that the discomfort of the teeth is caused or a new infection problem is caused. The addition of an antibacterial agent to make a resin repair material have a certain antibacterial property is a common improvement method, but the antibacterial agent added in the method is easy to seep out, can generate great potential safety hazards to human bodies, at least can destroy the ecosystem of oral flora, and has the problem of being durable for a short time.
Therefore, there is a need for a dental restorative material having good biocompatibility, resistance to erosion by oral saliva, excellent mechanical properties, and antibacterial properties.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a dental prosthetic material and a preparation method thereof, wherein the preparation method is simple and easy to implement, the raw materials are easy to obtain, the preparation cost is low, and the dental prosthetic material is suitable for large-scale production; the prepared dental prosthetic material has excellent biocompatibility, higher strength, hardness, toughness and wear resistance, and remarkable antibacterial effect, and can resist the corrosion of oral saliva.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: the dental restoration material is prepared from the following raw material components in parts by weight: 40-50 parts of titanium-based ionic condensation polymer with a fluorine-containing phosphonate grafted main chain, 20-30 parts of polyurethane prepolymer with isocyanate groups at two ends, 1-3 parts of bismuth acetate and 10-15 parts of surface-modified Zr-O-P.
Preferably, the preparation method of the fluorinated phosphonate grafted backbone titanium-based ionic polycondensate comprises the following steps:
i, adding bis (4-chlorophenol-KO) bis (H5-2, 4-cyclopentadien-1-yl) -titanium, 2' - [ iminodi (methylene) ] bisphenol and an alkaline catalyst into a three-mouth bottle connected with a water separator, then adding high boiling point solvent and toluene, heating the reaction system to 90-100 ℃, stirring and reacting for 6-8 hours under the protection of nitrogen or inert gas, removing water and toluene generated in the reaction process through a water separator, slowly raising the reaction temperature to 150-, precipitating in water, washing the precipitated polymer with ethanol for 3-5 times, and drying in vacuum drying oven at 80-90 deg.C to constant weight to obtain main chain titanium-based polycondensate;
II, adding (2,2, 2-trifluoro-1-hydroxyethyl) diethyl phosphonate, epichlorohydrin and sodium carbonate into an organic solvent, stirring and reacting for 6-8 hours at the temperature of 80-90 ℃, adding water after the reaction, layering, taking an organic phase, absorbing water by using anhydrous magnesium sulfate, filtering, and removing the organic solvent to obtain an intermediate product;
III, dissolving the main chain titanium-based polycondensate prepared in the step I and the intermediate product prepared in the step II in dimethyl sulfoxide, stirring and reacting at 60-80 ℃ for 10-12 hours, then precipitating in ethanol, and drying the precipitated polymer in a vacuum drying oven at 80-90 ℃ to constant weight to obtain an ionic polycondensate;
and IV, soaking the ionic condensation polymer prepared in the step III in a sodium alginate aqueous solution with the mass fraction of 10-20% at 50-60 ℃ for 20-30 hours, taking out, washing with water for 3-5 times, and drying in a vacuum drying oven at 80-90 ℃ to constant weight to obtain the fluorinated phosphonate grafted backbone titanium-based ionic condensation polymer.
Preferably, the mass ratio of the bis (4-chlorophenol-KO) bis (H5-2, 4-cyclopentadien-1-yl) -titanium, the 2,2' - [ iminobis (methylene) ] bisphenol, the alkaline catalyst, the high boiling point solvent and the toluene in the step I is 1.8:1 (0.4-0.6): 10-15: 5-8.
Preferably, the basic catalyst is selected from at least one of cesium carbonate, sodium carbonate, potassium carbonate.
Preferably, the high boiling point solvent is selected from one or more of dimethyl sulfoxide, N-methyl pyrrolidone and N, N-dimethylformamide; the inert gas is selected from helium, neon and argon.
Preferably, the mass ratio of the diethyl (2,2, 2-trifluoro-1-hydroxyethyl) phosphonate, the epichlorohydrin, the sodium carbonate and the organic solvent in the step II is 2.5:1 (0.6-0.8) to (15-20).
Preferably, the organic solvent is selected from one or more of acetonitrile, chloroform and acetone.
Preferably, the mass ratio of the main chain titanium-based polycondensate, the intermediate product and the dimethyl sulfoxide in the step III is (3-5) to 1 (20-25).
Preferably, the mass ratio of the ionic polycondensate to the sodium alginate aqueous solution in the step IV is 1 (15-25).
Preferably, the preparation method of the surface modified Zr-O-P comprises the following steps:
step S1: adding zirconium chloride and phosphorus trichloride into a beaker filled with ethanol, stirring for 1-2 hours, transferring the solution into a hydrothermal reaction kettle with a polyvinyl fluoride lining, and reacting for 15-18 hours at 220 ℃; taking out the reaction kettle, respectively washing with deionized water and absolute ethyl alcohol for 3-5 times after the reaction system is cooled, finally drying in a vacuum drying oven at the temperature of 100-plus-110 ℃ to constant weight, cooling to room temperature, grinding, and sieving with a 200-plus-300-mesh sieve to obtain Zr-O-P;
step S2: and (4) dispersing the Zr-O-P prepared in the step (S1) in ethanol, adding a silane coupling agent, stirring and reacting for 5-7 hours at the temperature of 60-80 ℃, and then removing the ethanol by rotary evaporation to obtain the surface modified Zr-O-P.
Preferably, the mass ratio of the zirconium chloride to the phosphorus trichloride to the ethanol in the step S1 is 5:0.5 (30-50).
Preferably, the mass ratio of the Zr-O-P, the ethanol and the silane coupling agent in the step S2 is 1:10: 0.2.
Preferably, the silane coupling agent is at least one selected from the group consisting of a silane coupling agent KH550, a silane coupling agent KH560, and a silane coupling agent KH 570.
Preferably, the polyurethane prepolymer with two isocyanate groups at two ends is prepared in advance by the following preparation method: panguanjun, etc., preparation and performance of polyurethane graft modified epoxy resin, science and engineering of high molecular materials, volume 24, phase 12.
Preferably, the preparation method of the dental prosthetic material comprises the following steps: the dental restoration material is prepared by uniformly mixing the raw material components to form a mixture, and then adding the mixture into a double-screw extruder for extrusion molding.
Preferably, the extrusion temperature of the double-screw extruder is 240-250 ℃, and the screw rotating speed is 1100-1300 r/min.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
1) the dental prosthetic material provided by the invention has the advantages of mild preparation conditions, simple process, cheap raw materials and clinical application value.
2) The dental restoration material provided by the invention has the advantages that the components have synergistic effect, so that the material has excellent biocompatibility, higher strength, hardness, toughness and wear resistance, and an obvious antibacterial effect, and can resist the corrosion of oral saliva.
3) According to the dental restoration material provided by the invention, the surface modification Zr-O-P is added, so that on one hand, the mechanical property of the material is improved, on the other hand, the biocompatibility, the wear resistance and the bionic property of the material are improved through phosphorus doping, and the compatibility and the self-dispersibility of the material and a polymer are improved through surface modification.
4) The dental restoration material provided by the invention combines excellent mechanical properties and weather resistance of polyurethane and polyphenyl ether, good biocompatibility of polyurethane and alginic acid and biocompatibility and structural stability of polycondensate with a titanium-containing main chain, introduces a fluorine structure, provides fluorine element, and is beneficial to the stability of material performance; an ion structure is introduced, and an alginic acid structure is introduced through ion exchange, so that the comprehensive performance, the antibacterial property and the biocompatibility are further improved; isocyanate groups at two ends of the polyurethane are easy to generate crosslinking curing reaction with hydroxyl groups on a macromolecular chain, so that the comprehensiveness of the material is improved.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
The isocyanate-based polyurethane prepolymer with two ends is prepared in advance in the following embodiments of the invention, and the preparation method is as follows: panguanjun and the like, the preparation and performance of polyurethane graft modified epoxy resin, the science and engineering of high polymer materials, volume 24, stage 12, and other raw materials from Mobei (Shanghai) Biotech limited.
Example 1
The dental restoration material is prepared from the following raw material components in parts by weight: 40 parts of titanium-based ionic condensation polymer with a fluorine-containing phosphonate grafted main chain, 20 parts of polyurethane prepolymer with isocyanate groups at two ends, 1 part of bismuth acetate and 10 parts of surface-modified Zr-O-P.
The preparation method of the fluorinated phosphonate grafted backbone titanium-based ionic polycondensate comprises the following steps:
adding 180g of bis (4-chlorophenol-KO) bis (H5-2, 4-cyclopentadien-1-yl) -titanium, 100g of 2,2' - [ iminodi (methylene) ] bisphenol and 40g of cesium carbonate into a three-neck flask connected with a water separator, adding 1000g of dimethyl sulfoxide and 500g of toluene, heating a reaction system to 90 ℃, stirring and reacting for 6 hours under the protection of nitrogen, removing water and toluene generated in the reaction process through the water separator, slowly raising the reaction temperature to 150 ℃ after water is removed, continuously refluxing and stirring for reacting for 18 hours, cooling the reaction system to room temperature after the reaction is finished, separating out the reaction system in water, washing the separated polymer for 3 times by using ethanol, and then placing the washed polymer in a vacuum drying oven at 80 ℃ to be dried to constant weight to obtain a main chain titanium-based polycondensate;
II, adding 250g of (2,2, 2-trifluoro-1-hydroxyethyl) diethyl phosphonate, 100g of epoxy chloropropane and 60g of sodium carbonate into 1500g of acetonitrile, stirring and reacting at 80 ℃ for 6 hours, adding water after the reaction, layering, taking an organic phase, absorbing water by using anhydrous magnesium sulfate, filtering, and removing the acetonitrile to obtain an intermediate product;
III, dissolving 150g of the main chain titanium-based condensation polymer prepared in the step I and 50g of the intermediate product prepared in the step II in 1000g of dimethyl sulfoxide, stirring and reacting at 60 ℃ for 10 hours, then precipitating in ethanol, and drying the precipitated polymer in a vacuum drying oven at 80 ℃ to constant weight to obtain an ionic condensation polymer;
and IV, soaking 100g of the ionic condensation polymer prepared in the step III in 1500g of sodium alginate aqueous solution with the mass fraction of 10% at 50 ℃ for 20 hours, taking out, washing with water for 3 times, and drying in a vacuum drying oven at 80 ℃ to constant weight to obtain the fluorinated phosphonate grafted backbone titanium-based ionic condensation polymer.
The preparation method of the surface modified Zr-O-P comprises the following steps:
step S1: adding 50g of zirconium chloride and 5g of phosphorus trichloride into a beaker filled with 300g of ethanol, stirring for 1 hour, transferring the solution into a hydrothermal reaction kettle with a polyvinyl fluoride lining, and reacting for 15 hours at 200 ℃; taking out the reaction kettle, respectively washing with deionized water and absolute ethyl alcohol for 3 times after the reaction system is cooled, finally drying in a vacuum drying oven at 100 ℃ to constant weight, cooling to room temperature, grinding, and sieving with a 200-mesh sieve to obtain Zr-O-P;
step S2: and (3) dispersing 20g of Zr-O-P prepared in the step S1 in 200g of ethanol, adding a silane coupling agent KH5504g, stirring and reacting at 60 ℃ for 5 hours, and then performing rotary evaporation to remove the ethanol to obtain the surface modified Zr-O-P.
The preparation method of the dental prosthetic material comprises the following steps: uniformly mixing the raw material components to form a mixture, adding the mixture into a double-screw extruder, and carrying out extrusion molding to obtain the dental restoration material; the extrusion temperature of the double-screw extruder is 240 ℃, and the screw rotating speed is 1100 r/min.
Example 2
The dental restoration material is prepared from the following raw material components in parts by weight: 43 parts of titanium-based ionic polycondensate with a fluorine-containing phosphonate grafted main chain, 22 parts of polyurethane prepolymer with isocyanate groups at two ends, 2 parts of bismuth acetate and 11 parts of surface-modified Zr-O-P.
The preparation method of the fluorinated phosphonate grafted backbone titanium-based ionic polycondensate comprises the following steps:
adding 180g of bis (4-chlorophenol-KO) bis (H5-2, 4-cyclopentadien-1-yl) -titanium, 100g of 2,2' - [ iminodi (methylene) ] bisphenol and 45g of sodium carbonate into a three-neck flask connected with a water separator, adding 1150g of N-methylpyrrolidone and 600g of toluene, heating the reaction system to 92 ℃, stirring and reacting for 6.5 hours under the protection of helium, removing water and toluene generated in the reaction process through the water separator, slowly raising the reaction temperature to 152 ℃ after water is removed, continuously refluxing and stirring and reacting for 19 hours, cooling the reaction system to room temperature after the reaction is finished, separating out the polymer in water, washing the separated out polymer for 4 times with ethanol, and then placing the polymer in a vacuum drying oven at 82 ℃ to dry to constant weight to obtain a titanium-based main chain condensation polymer;
II, adding 250g of (2,2, 2-trifluoro-1-hydroxyethyl) diethyl phosphonate, 100g of epoxy chloropropane and 65g of sodium carbonate into 1650g of chloroform, stirring and reacting for 6.5 hours at 82 ℃, adding water after the reaction, layering, taking an organic phase, absorbing water by using anhydrous magnesium sulfate, filtering, and removing chloroform to obtain an intermediate product;
III, dissolving 175g of the main chain titanium-based polycondensate prepared in the step I and 50g of the intermediate product prepared in the step II in 1050g of dimethyl sulfoxide, stirring and reacting at 65 ℃ for 10.5 hours, then precipitating in ethanol, and drying the precipitated polymer in a vacuum drying oven at 83 ℃ to constant weight to obtain an ionic polycondensate;
IV, soaking 100g of the ionic condensation polymer prepared in the step III in 1650g of sodium alginate aqueous solution with mass fraction of 13% at 53 ℃ for 23 hours, taking out, washing with water for 4 times, and drying in a vacuum drying oven at 82 ℃ to constant weight to obtain the fluorinated phosphonate grafted backbone titanium-based ionic condensation polymer.
The preparation method of the surface modified Zr-O-P comprises the following steps:
step S1: adding 50g of zirconium chloride and 5g of phosphorus trichloride into a beaker filled with 350g of ethanol, stirring for 1.2 hours, transferring the solution into a hydrothermal reaction kettle with a polyvinyl fluoride lining, and reacting for 16 hours at 205 ℃; taking out the reaction kettle, respectively washing with deionized water and absolute ethyl alcohol for 4 times after the reaction system is cooled, finally drying in a vacuum drying oven at 103 ℃ to constant weight, cooling to room temperature, grinding, and sieving with a 220-mesh sieve to obtain Zr-O-P;
step S2: and (3) dispersing 20g of Zr-O-P prepared in the step S1 in 200g of ethanol, adding a silane coupling agent KH560 5604g, stirring and reacting at 65 ℃ for 5.5 hours, and then performing rotary evaporation to remove the ethanol to obtain the surface modified Zr-O-P.
The preparation method of the dental prosthetic material comprises the following steps: uniformly mixing the raw material components to form a mixture, adding the mixture into a double-screw extruder, and carrying out extrusion molding to obtain the dental restoration material; the extrusion temperature of the double-screw extruder is 243 ℃, and the screw rotating speed is 1150 r/min.
Example 3
The dental restoration material is prepared from the following raw material components in parts by weight: 45 parts of titanium-based ionic polycondensate with a fluorine-containing phosphonate grafted main chain, 25 parts of polyurethane prepolymer with isocyanate groups at two ends, 2 parts of bismuth acetate and 13 parts of surface-modified Zr-O-P.
The preparation method of the fluorinated phosphonate grafted backbone titanium-based ionic polycondensate comprises the following steps:
adding 180g of bis (4-chlorophenol-KO) bis (H5-2, 4-cyclopentadien-1-yl) -titanium, 100g of 2,2' - [ iminodi (methylene) ] bisphenol and 50g of potassium carbonate into a three-neck flask connected with a water separator, adding 1300g of N, N-dimethylformamide and 650g of toluene, heating the reaction system to 95 ℃, stirring and reacting for 7 hours under the protection of neon gas, removing water and toluene generated in the reaction process through the water separator, slowly raising the reaction temperature to 156 ℃ after water is removed, continuously refluxing and stirring and reacting for 20 hours, cooling the reaction system to room temperature after the reaction is finished, separating out the polymer in water, washing the separated out polymer for 5 times with ethanol, and then placing the polymer in a vacuum drying oven at 85 ℃ to dry to constant weight to obtain a titanium-based main chain polycondensate;
II, adding 250g of (2,2, 2-trifluoro-1-hydroxyethyl) diethyl phosphonate, 100g of epoxy chloropropane and 70g of sodium carbonate into 1800g of acetone, stirring and reacting at 85 ℃ for 7 hours, adding water after the reaction, layering, taking an organic phase, absorbing water by using anhydrous magnesium sulfate, filtering, and removing acetone to obtain an intermediate product;
III, dissolving 200g of the main chain titanium-based condensation polymer prepared in the step I and 50g of the intermediate product prepared in the step II in 1190g of dimethyl sulfoxide, stirring and reacting at 70 ℃ for 11 hours, then precipitating in ethanol, and drying the precipitated polymer in a vacuum drying oven at 85 ℃ to constant weight to obtain an ionic condensation polymer;
IV, soaking 100g of the ionic condensation polymer prepared in the step III in 1950g of sodium alginate aqueous solution with the mass fraction of 15% at 55 ℃ for 26 hours, taking out, washing with water for 4 times, and drying in a vacuum drying oven at 86 ℃ to constant weight to obtain the fluorinated phosphonate grafted backbone titanium-based ionic condensation polymer.
The preparation method of the surface modified Zr-O-P comprises the following steps:
step S1: adding 50g of zirconium chloride and 5g of phosphorus trichloride into a beaker filled with 420g of ethanol, stirring for 1.6 hours, transferring the solution into a hydrothermal reaction kettle with a polyvinyl fluoride lining, and reacting for 16.5 hours at 212 ℃; taking out the reaction kettle, respectively washing with deionized water and absolute ethyl alcohol for 4 times after the reaction system is cooled, finally drying in a vacuum drying oven at 106 ℃ to constant weight, cooling to room temperature, grinding, and sieving with a 260-mesh sieve to obtain Zr-O-P;
step S2: and (3) dispersing the Zr-O-P20g prepared in the step S1 in 200g of ethanol, adding a silane coupling agent KH5704g, stirring and reacting at 70 ℃ for 6 hours, and then performing rotary evaporation to remove the ethanol to obtain the surface modified Zr-O-P.
The preparation method of the dental prosthetic material comprises the following steps: uniformly mixing the raw material components to form a mixture, adding the mixture into a double-screw extruder, and carrying out extrusion molding to obtain the dental restoration material; the extrusion temperature of the double-screw extruder is 246 ℃, and the screw rotating speed is 1200 r/min.
Example 4
The dental restoration material is prepared from the following raw material components in parts by weight: 48 parts of titanium-based ionic polycondensate with a fluorine-containing phosphonate grafted main chain, 28 parts of polyurethane prepolymer with isocyanate groups at two ends, 3 parts of bismuth acetate and 14 parts of surface-modified Zr-O-P.
The preparation method of the fluorinated phosphonate grafted backbone titanium-based ionic polycondensate comprises the following steps:
adding 180g of bis (4-chlorophenol-KO) bis (H5-2, 4-cyclopentadien-1-yl) -titanium, 100g of 2,2' - [ iminodi (methylene) ] bisphenol and 58g of an alkaline catalyst into a three-neck flask connected with a water separator, adding 1450g of a high-boiling-point solvent and 750g of toluene, heating the reaction system to 98 ℃, stirring and reacting for 7.5 hours under the protection of argon, removing water and toluene generated in the reaction process through the water separator, slowly raising the reaction temperature to 158 ℃ after water is removed, continuously refluxing and stirring and reacting for 21 hours, cooling the reaction system to room temperature after the reaction is finished, separating out the reaction product in water, washing the separated out polymer for 5 times by using ethanol, and then placing the washed polymer in a vacuum drying oven at 88 ℃ to dry to constant weight to obtain a main chain titanium-based polycondensate; the alkaline catalyst is a mixture formed by mixing cesium carbonate, sodium carbonate and potassium carbonate according to the mass ratio of 2:3: 1; the high-boiling-point solvent is a mixture formed by mixing dimethyl sulfoxide, N-methyl pyrrolidone and N, N-dimethylformamide according to the mass ratio of 3:4: 2;
II, adding 250g of (2,2, 2-trifluoro-1-hydroxyethyl) diethyl phosphonate, 100g of epoxy chloropropane and 78g of sodium carbonate into 1900g of organic solvent, stirring and reacting for 7.8 hours at 88 ℃, adding water after the reaction, layering, taking an organic phase, absorbing water by using anhydrous magnesium sulfate, filtering, and removing the organic solvent to obtain an intermediate product; the organic solvent is a mixture formed by mixing acetonitrile, chloroform and acetone according to the mass ratio of 1:3: 2;
III, dissolving 230g of the main chain titanium-based polycondensate prepared in the step I and 50g of the intermediate product prepared in the step II in 1200g of dimethyl sulfoxide, stirring and reacting at 78 ℃ for 11.5 hours, then precipitating in ethanol, and drying the precipitated polymer in a vacuum drying oven at 88 ℃ to constant weight to obtain an ionic polycondensate;
IV, soaking 100g of the ionic condensation polymer prepared in the step III in 2400g of sodium alginate aqueous solution with the mass fraction of 18% at 58 ℃ for 29 hours, taking out, washing with water for 5 times, and drying in a vacuum drying oven at 89 ℃ to constant weight to obtain the fluorinated phosphonate grafted backbone titanium-based ionic condensation polymer.
The preparation method of the surface modified Zr-O-P comprises the following steps:
step S1: adding 50g of zirconium chloride and 5g of phosphorus trichloride into a beaker filled with 480g of ethanol, stirring for 1.9 hours, transferring the solution into a hydrothermal reaction kettle with a polyvinyl fluoride lining, and reacting for 17.5 hours at 217 ℃; taking out the reaction kettle, respectively washing with deionized water and absolute ethyl alcohol for 5 times after the reaction system is cooled, finally drying in a vacuum drying oven at 108 ℃ to constant weight, cooling to room temperature, grinding, and sieving with a 280-mesh sieve to obtain Zr-O-P;
step S2: dispersing 20g of Zr-O-P prepared in the step S1 in 200g of ethanol, adding 4g of silane coupling agent, stirring and reacting at 79 ℃ for 6.8 hours, and then removing the ethanol by rotary evaporation to obtain surface-modified Zr-O-P; the silane coupling agent is a mixture formed by mixing a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH570 according to a mass ratio of 1:3: 1.
The preparation method of the dental prosthetic material comprises the following steps: uniformly mixing the raw material components to form a mixture, adding the mixture into a double-screw extruder, and carrying out extrusion molding to obtain the dental restoration material; the extrusion temperature of the double-screw extruder is 249 ℃, and the screw rotating speed is 1250 r/min.
Example 5
The dental restoration material is prepared from the following raw material components in parts by weight: 50 parts of titanium-based ionic polycondensate with a fluorine-containing phosphonate grafted main chain, 30 parts of polyurethane prepolymer with isocyanate groups at two ends, 3 parts of bismuth acetate and 15 parts of surface-modified Zr-O-P.
The preparation method of the fluorinated phosphonate grafted backbone titanium-based ionic polycondensate comprises the following steps:
adding 180g of bis (4-chlorophenol-KO) bis (H5-2, 4-cyclopentadien-1-yl) -titanium, 100g of 2,2' - [ iminodi (methylene) ] bisphenol and 60g of cesium carbonate into a three-neck flask connected with a water separator, adding 1500g of N, N-dimethylformamide and 800g of toluene, heating the reaction system to 100 ℃, stirring and reacting for 8 hours under the protection of nitrogen, removing water and toluene generated in the reaction process through the water separator, slowly raising the reaction temperature to 160 ℃ after water is removed, continuously refluxing and stirring and reacting for 22 hours, cooling the reaction system to room temperature after the reaction is finished, separating out the polymer in water, washing the separated out polymer for 5 times with ethanol, and then placing the polymer in a vacuum drying oven at 90 ℃ to dry to constant weight to obtain a titanium-based main chain condensation polymer;
II, adding 250g of (2,2, 2-trifluoro-1-hydroxyethyl) diethyl phosphonate, 100g of epoxy chloropropane and 80g of sodium carbonate into 2000g of chloroform, stirring at 90 ℃ for reaction for 8 hours, adding water after the reaction, layering, taking an organic phase, absorbing water by using anhydrous magnesium sulfate, filtering, and removing chloroform to obtain an intermediate product;
III, dissolving 250g of the main chain titanium-based condensation polymer prepared in the step I and 50g of the intermediate product prepared in the step II in 1250g of dimethyl sulfoxide, stirring and reacting at 80 ℃ for 12 hours, then precipitating in ethanol, and drying the precipitated polymer in a vacuum drying oven at 90 ℃ to constant weight to obtain an ionic condensation polymer;
and IV, soaking 100g of the ionic condensation polymer prepared in the step III in 2500g of sodium alginate aqueous solution with the mass fraction of 20% at the temperature of 60 ℃ for 30 hours, taking out, washing with water for 5 times, and drying in a vacuum drying oven at the temperature of 90 ℃ to constant weight to obtain the fluorinated phosphonate grafted backbone titanium-based ionic condensation polymer.
The preparation method of the surface modified Zr-O-P comprises the following steps:
step S1: adding 50g of zirconium chloride and 5g of phosphorus trichloride into a beaker filled with 500g of ethanol, stirring for 2 hours, transferring the solution into a hydrothermal reaction kettle with a polyvinyl fluoride lining, and reacting for 18 hours at 220 ℃; taking out the reaction kettle, respectively washing with deionized water and absolute ethyl alcohol for 5 times after the reaction system is cooled, finally drying in a vacuum drying oven at 110 ℃ to constant weight, cooling to room temperature, grinding, and sieving with a 300-mesh sieve to obtain Zr-O-P;
step S2: and (3) dispersing 20g of Zr-O-P prepared in the step S1 in 200g of ethanol, adding a silane coupling agent KH5504g, stirring and reacting at 80 ℃ for 7 hours, and then removing the ethanol by rotary evaporation to obtain the surface modified Zr-O-P.
The preparation method of the dental prosthetic material comprises the following steps: uniformly mixing the raw material components to form a mixture, adding the mixture into a double-screw extruder, and carrying out extrusion molding to obtain the dental restoration material; the extrusion temperature of the double-screw extruder is 250 ℃, and the screw rotating speed is 1300 r/min.
Comparative example
Common polymethylmethacrylate based dental restorative materials are commercially available.
The dental restorative materials prepared in examples 1-5 and comparative example were subjected to performance tests, the test results are shown in table 1, and the test methods are as follows:
(1) flexural modulus, flexural strength: testing according to the test method of GB/T9341-2000;
(2) coefficient of friction: testing according to the test method of GB 10006-88;
(3) biocompatibility: testing according to the test method of GB/T16886.
(4) And (3) antibacterial property: according to ISO 22196-2007 measurement of the antibacterial activity of the plastic surface.
TABLE 1
As can be seen from table 1, the dental restorative material disclosed in the embodiments of the present invention has more excellent mechanical properties, biocompatibility, wear resistance, and antibacterial properties.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. The dental restoration material is characterized by being prepared from the following raw material components in parts by weight: 40-50 parts of titanium-based ionic condensation polymer containing fluorine phosphonate grafted backbone, 20-30 parts of polyurethane prepolymer with isocyanate groups at two ends, 1-3 parts of bismuth acetate and 10-15 parts of surface-modified Zr-O-P;
the preparation method of the fluorinated phosphonate grafted backbone titanium-based ionic polycondensate comprises the following steps:
i, adding bis (4-chlorophenol-KO) bis (H5-2, 4-cyclopentadien-1-yl) -titanium, 2' - [ iminodi (methylene) ] bisphenol and an alkaline catalyst into a three-mouth bottle connected with a water separator, then adding high boiling point solvent and toluene, heating the reaction system to 90-100 ℃, stirring and reacting for 6-8 hours under the protection of nitrogen or inert gas, removing water and toluene generated in the reaction process through a water separator, slowly raising the reaction temperature to 150-, precipitating in water, washing the precipitated polymer with ethanol for 3-5 times, and drying in vacuum drying oven at 80-90 deg.C to constant weight to obtain main chain titanium-based polycondensate;
II, adding (2,2, 2-trifluoro-1-hydroxyethyl) diethyl phosphonate, epichlorohydrin and sodium carbonate into an organic solvent, stirring and reacting for 6-8 hours at the temperature of 80-90 ℃, adding water after the reaction, layering, taking an organic phase, absorbing water by using anhydrous magnesium sulfate, filtering, and removing the organic solvent to obtain an intermediate product;
III, dissolving the main chain titanium-based polycondensate prepared in the step I and the intermediate product prepared in the step II in dimethyl sulfoxide, stirring and reacting at 60-80 ℃ for 10-12 hours, then precipitating in ethanol, and drying the precipitated polymer in a vacuum drying oven at 80-90 ℃ to constant weight to obtain an ionic polycondensate;
and IV, soaking the ionic condensation polymer prepared in the step III in a sodium alginate aqueous solution with the mass fraction of 10-20% at 50-60 ℃ for 20-30 hours, taking out, washing with water for 3-5 times, and drying in a vacuum drying oven at 80-90 ℃ to constant weight to obtain the fluorinated phosphonate grafted backbone titanium-based ionic condensation polymer.
2. The dental restorative material of claim 1, wherein the mass ratio of bis (4-chlorophenol-KO) bis (H5-2, 4-cyclopentadien-1-yl) -titanium, 2' - [ iminobis (methylene) ] bisphenol, basic catalyst, high boiling point solvent, and toluene in step I is 1.8:1 (0.4-0.6): (10-15): (5-8).
3. Dental restorative material according to claim 1, wherein the basic catalyst is selected from at least one of cesium carbonate, sodium carbonate, potassium carbonate; the high boiling point solvent is selected from one or more of dimethyl sulfoxide, N-methyl pyrrolidone and N, N-dimethylformamide; the inert gas is selected from helium, neon and argon.
4. The dental restorative material of claim 1, wherein the mass ratio of the diethyl (2,2, 2-trifluoro-1-hydroxyethyl) phosphonate, epichlorohydrin, sodium carbonate and organic solvent in step II is 2.5:1 (0.6-0.8) to (15-20); the organic solvent is selected from one or more of acetonitrile, chloroform and acetone.
5. Dental restorative material according to claim 1, wherein the backbone titanium-based polycondensate, the intermediate product and the dimethyl sulfoxide in step III are in a mass ratio of (3-5: 1 (20-25); and the mass ratio of the ionic polycondensate to the sodium alginate aqueous solution in the step IV is 1 (15-25).
6. Dental restorative material according to claim 1, characterized in that the preparation method of the surface-modified Zr-O-P comprises the following steps:
step S1: adding zirconium chloride and phosphorus trichloride into a beaker filled with ethanol, stirring for 1-2 hours, transferring the solution into a hydrothermal reaction kettle with a polyvinyl fluoride lining, and reacting for 15-18 hours at 220 ℃; taking out the reaction kettle, respectively washing with deionized water and absolute ethyl alcohol for 3-5 times after the reaction system is cooled, finally drying in a vacuum drying oven at the temperature of 100-plus-110 ℃ to constant weight, cooling to room temperature, grinding, and sieving with a 200-plus-300-mesh sieve to obtain Zr-O-P;
step S2: and (4) dispersing the Zr-O-P prepared in the step (S1) in ethanol, adding a silane coupling agent, stirring and reacting for 5-7 hours at the temperature of 60-80 ℃, and then removing the ethanol by rotary evaporation to obtain the surface modified Zr-O-P.
7. The dental restorative material of claim 6, wherein the mass ratio of zirconium chloride to phosphorus trichloride to ethanol in step S1 is 5:0.5 (30-50); in the step S2, the mass ratio of the Zr-O-P, the ethanol and the silane coupling agent is 1:10: 0.2; the silane coupling agent is at least one selected from a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH 570.
8. Dental restorative material according to any of claims 1-7, characterized in that the method of preparation of the dental restorative material comprises the steps of: the dental restoration material is prepared by uniformly mixing the raw material components to form a mixture, and then adding the mixture into a double-screw extruder for extrusion molding.
9. The dental restorative material as defined in claim 8, wherein the extrusion temperature of the twin-screw extruder is 240-250 ℃, and the screw rotation speed is 1100-1300 r/min.
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