CN104940027A - Low-shrinkage dental restoration resin and preparation method thereof - Google Patents
Low-shrinkage dental restoration resin and preparation method thereof Download PDFInfo
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- CN104940027A CN104940027A CN201510357036.XA CN201510357036A CN104940027A CN 104940027 A CN104940027 A CN 104940027A CN 201510357036 A CN201510357036 A CN 201510357036A CN 104940027 A CN104940027 A CN 104940027A
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Abstract
The invention discloses low-shrinkage dental restoration resin and a preparation method thereof. The low-shrinkage dental restoration resin is prepared by an alkyl methacrylate ester monomer, a modified Boltorn type second-generation hyperbranched polyester monomer, a diluent and epoxy system and an initiator agent, wherein the alkyl methacrylate ester monomer accounts for 25-60 percent of the mass of a whole resin system, the modified Boltorn type second-generation hyperbranched polyester monomer accounts for 0-40 percent, the diluent and epoxy system accounts for 30-50 percent, and the initiator agent accounts for 1-5 percent. The ingredients are evenly mixed according to the proportion and then injected into a specific mold, and then photocuring molding is performed to obtain low-shrinkage dental restoration resin materials. According to the low-shrinkage dental restoration resin and the preparation method thereof, the dental restoration resin has the advantages that the low shrinkage is achieved, micro leaking is reduced and triethylene-glycol dimethacrylate is completely eradicated, and has the more ideal effect on the properties such as the double bond conversion rate and the shrinkage rate; the polymerization shrinkage of the composite resin is greatly lowered by introducing the diluent and epoxy system and the modified Boltorn type second-generation hyperbranched polyester monomer.
Description
Technical field
The invention belongs to dental prosthetic material technical field, particularly a kind of lower shrinkage dental prosthetic resin and preparation method thereof.
Technical background
Dental prosthetic material, from birth, successively experienced by the very long development course of natural materials-metal material-pottery-macromolecular material-composite.The introduction of resin-based dental composite is the leap of the important meaning in science of dental materials field.In the middle ten days in 20th century, Stereolithography technology comes into the life of people gradually, and photocuring has unique advantage: curing rate is fast, and curing efficiency is high, and mechanical performance is high, completes polymerization under room temperature, and cure sites is alternative large, no pollution etc.After the sixties in 20th century, light-cured composite is by first for dental restorative area, and light-cured composite system composition comprises resin matrix, inorganic filler and corresponding light initiation system.The preparation of light-cured composite is simple, and operate easy, color and luster is good, intensity and plasticity high, adhesive effect is good, and can sanding and polishing after solidification, and multiple advantage makes it be subject to extensive concern in Dental Erosion field.
Need meet certain requirements as during dental resin matrix: 1) photopolymerization degree is high, and the polymer after solidification is bridging property, this ensure that dummy mechanical property requirements; 2) after polymerization, cubical contraction is low, can ensure bubble-free in dummy like this, seamless.In Clinical practice, often add with certain proportion and there is dilution and the monomer of crosslinked action and bisphenol-A-dimethyl allene acid glycidyl ester (Bis-GMA) jointly form resinous substrates.Diluting monomer conventional is at present double methyl methacrylate triethylene glycol ester (TEGDMA), and its viscosity is very low, and also has methacryloxy functional groups at molecule two ends, also participates in the polymerization of system while diluted system.But TEGDMA adds the polymerization shrinkage that membership increases system.And there are some researches show, TEGDMA monomer can show certain cytotoxicity, and may cause allergy, and therefore TEGDMA addition need limit to some extent.And the generation of recurrent caries mainly comes from the oral cavity bacterium adhered between dummy and dental interface and grows after repairing, form dental plaque corrosion tooth body and repair materials makes repairing failure.
Summary of the invention
Lower shrinkage dental prosthetic resin that the object of the present invention is to provide a kind of shrinkage factor low and preparation method thereof.
The technical solution realizing the object of the invention is: a kind of lower shrinkage dental prosthetic resin, is prepared from by methacrylate-based monomer, modification Boltorn type secondary hyperbranched poly esters monomer, diluent and epoxy systems and initiator, wherein:
Methacrylate-based monomer accounts for 25 ~ 60% of whole resin system quality;
Modification Boltorn type secondary hyperbranched poly esters monomer accounts for 0 ~ 40% of whole resin system quality;
Diluent and epoxy systems account for 30 ~ 50% of whole resin system;
Initiator accounts for 1 ~ 5% of whole resin system quality.
Preferably, described methacrylate-based monomer is bisphenol-A-dimethyl allene acid glycidyl ester Bis-GMA.
Preferably, described modification Boltorn type secondary hyperbranched poly esters monomer is obtained by reacting by the secondary hyper-branched polyester of Boltorn type and modified monomer, modified containing carbon-carbon double bond and oh group.
Preferably, described diluent and epoxy systems comprise Expanding Monomer and epoxy resin, the mass ratio of Expanding Monomer and epoxy resin is (1 ~ 4): 4, its epoxy resin is 3, 4-epoxycyclohexyl-methyl-3, 4-epoxycyclohexyl formic acid esters, methyl two [2-(7-oxabicyclo [4.1.0]-3-in heptan base)-ethyl] phenyl silane or 2, 4, 6, 8-tetramethyl-2, 4, 6, 8-tetra-[2-(7-oxabicyclo [4.1.0]-3-in heptan base)-ethyl]-1, 3, 5, 7-tetra-oxa--2, 4, 6, 8-tetra-silicon Tetramethylene., Expanding Monomer is 3, 9-diethyl-3, 9-propylene oxygen methyl isophthalic acid, 5, 7, 11-tetra-oxygen spiral shell assorted [5, 5] hendecane.
Preferably, in described ternary photosensitized initiation system.
Preferably, described modified monomer is the combination of methacrylic chloride and propionyl chloride, wherein the mol ratio of methacrylic chloride and the secondary hyper-branched polyester of Boltorn type is (7 ~ 10): 1, and the mol ratio of propionyl chloride and the secondary hyper-branched polyester of Boltorn type is (6 ~ 9): 1.
Preferably, described ternary photosensitized initiation system comprises photic acid compound, visible light photosensitizer and electron donor compound group, photic acid compound is Diaryl iodonium hexafluorophosphate, triaryl sulfur hexafluorophosphate or triaryl selenium hexafluorophosphate, visible light photosensitizer is camphorquinone, benzophenone, 1-Phenylethanone., benzoin ether or thia anthraquinone, electron donor compound is N, N mono-dimethylamino methyl ethyl acrylate, dimethyl ethenyl amine benzoic acid or N, N mono-dimethyl is to vinyl aniline, wherein photic acid compound, visible light photosensitizer and electron donor compound mass ratio are (1 ~ 3): (0.1 ~ 1): 0.1.
A kind of preparation method of lower shrinkage dental prosthetic resin described above, with methacrylate-based monomer 25 ~ 60%(weight), modification Boltorn type secondary hyperbranched poly esters monomer 0 ~ 40%(weight), diluent and epoxy systems 30 ~ 50%(weight) and initiator 1 ~ 5%(weight) be batching, inject after mix homogeneously in specific mould and carry out Stereolithography, obtain lower shrinkage dental prosthetic resin material.
Compared with prior art, its remarkable advantage is in the present invention: (1) forms firm firming body under light illumination, reduces the shrinkage factor of resin for restoration, has desirable hardness simultaneously; (2) introducing of Expanding Monomer and epoxy resin, instead of the cytotoxic diluent double methyl methacrylate triethylene glycol ester (TEGDMA) of dental pulp, reduces the cytotoxicity of resin for restoration.
Detailed description of the invention
Lower shrinkage dental prosthetic resin of the present invention, is prepared from by methacrylate-based monomer, modification Boltorn type secondary hyperbranched poly esters monomer, diluent and epoxy systems and initiator, wherein:
Methacrylate-based monomer accounts for 25 ~ 60% of whole resin system quality;
Modification Boltorn type secondary hyperbranched poly esters monomer accounts for 0 ~ 40% of whole resin system quality;
Diluent and epoxy systems account for 30 ~ 50% of whole resin system;
Initiator accounts for 1 ~ 5% of whole resin system quality.
Preferably, described methacrylate-based monomer is bisphenol-A-dimethyl allene acid glycidyl ester Bis-GMA.
Preferably, described modification Boltorn type secondary hyperbranched poly esters monomer is obtained by reacting by the secondary hyper-branched polyester of Boltorn type and modified monomer, modified containing carbon-carbon double bond and oh group.Wherein the secondary hyper-branched polyester of Boltorn type is by tetramethylolmethane and two hydroxymethyl propionic acid Reactive Synthesis, acetone precipitation, sucking filtration again after dissolving, then adds modified monomer in low temperature, centrifugal, filters, washing, dry obtained modified ultra-branching polyester.Described modified monomer is the combination of methacrylic chloride and propionyl chloride, wherein the mol ratio of methacrylic chloride and the secondary hyper-branched polyester of Boltorn type is (7 ~ 10): 1, and the mol ratio of propionyl chloride and the secondary hyper-branched polyester of Boltorn type is (6 ~ 9): 1.
Above-mentioned modification Boltorn type secondary hyperbranched poly esters monomer instead of part bisphenol-A-dimethyl allene acid glycidyl ester (Bis-GMA), reduces the polymerization shrinkage of whole resin system.
Preferably, described diluent and epoxy systems comprise Expanding Monomer and epoxy resin, the mass ratio of Expanding Monomer and epoxy resin is (1 ~ 4): 4, its epoxy resin is 3, 4-epoxycyclohexyl-methyl-3, 4-epoxycyclohexyl formic acid esters, methyl two [2-(7-oxabicyclo [4.1.0]-3-in heptan base)-ethyl] phenyl silane or 2, 4, 6, 8-tetramethyl-2, 4, 6, 8-tetra-[2-(7-oxabicyclo [4.1.0]-3-in heptan base)-ethyl]-1, 3, 5, 7-tetra-oxa--2, 4, 6, 8-tetra-silicon Tetramethylene., Expanding Monomer is 3, 9-diethyl-3, 9-propylene oxygen methyl isophthalic acid, 5, 7, 11-tetra-oxygen spiral shell assorted [5, 5] hendecane.
Above-mentioned diluent and epoxy systems instead of clinical conventional double methyl methacrylate triethylene glycol ester (TEGDMA), not only reduce the shrinkage factor of whole resin for restoration, and reduce the cytotoxicity of resin for restoration.
Preferably, described initiator is ternary photosensitized initiation system.Described ternary photosensitized initiation system comprises photic acid compound, visible light photosensitizer and electron donor compound group, photic acid compound is Diaryl iodonium hexafluorophosphate, triaryl sulfur hexafluorophosphate or triaryl selenium hexafluorophosphate, visible light photosensitizer is camphorquinone, benzophenone, 1-Phenylethanone., benzoin ether or thia anthraquinone, electron donor compound is N, N mono-dimethylamino methyl ethyl acrylate, methyl ethylene amine benzoic acid or N, N mono-dimethyl is to vinyl aniline, wherein photic acid compound, visible light photosensitizer and electron donor compound mass ratio are (1 ~ 3): (0.1 ~ 1): 0.1, because the addition of each component of ternary photosensitized initiation system in whole resin system is less, if add membership successively to cause error, so in advance by its mixing and stirring, keep in Dark Place stand-by in refrigerator.
Following examples 1 give the mass ratio of resin B is-GMA and the TEGDMA of Clinical practice, and embodiment 2 ~ 16 gives the mass percent that each raw material accounts for whole resin system, wherein: methacrylate-based monomer is Bis-GMA; Modification Boltorn type secondary hyperbranched poly esters monomer is the secondary hyper-branched polyester of 7:6:1 modification Boltorn type (namely the mol ratio of methacrylic chloride, propionyl chloride, the secondary hyper-branched polyester of Boltorn type is 7:6:1); Diluent and epoxy systems epoxy resin are 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexyl formic acid esters (EE), Expanding Monomer are 3,9-diethyl-3,9-propylene oxygen methyl isophthalic acid, 5,7,11-tetra-oxygen spiral shell is mixed [5,5] hendecane (BAOM), and EE:BAOM mass ratio is 1:1; Consist of diphenyl iodine hexafluorophosphate, camphorquinone and dimethylaminoethyl methacrylate DMAEMA in ternary photosensitized initiation system, three's mass ratio is 3:1:0.1.Embodiment 17 gives the shrinkage factor of embodiment 1 ~ 16 and the testing result of double bond conversion rate.
Embodiment 1
Bis-GMA50%, TEGDMA45%, ternary photosensitized initiation system 5%
Embodiment 2
EE:BAOM is diluent and epoxy systems 30%, the secondary hyper-branched polyester 40% of Bis-GMA25%, 7:6:1 modification Boltorn type, the ternary photosensitized initiation system 5% of 1:1
Embodiment 3
EE:BAOM is diluent and epoxy systems 30%, the secondary hyper-branched polyester 30% of Bis-GMA35%, 7:6:1 modification Boltorn type, the ternary photosensitized initiation system 5% of 1:1
Embodiment 4
EE:BAOM is diluent and epoxy systems 30%, the secondary hyper-branched polyester 20% of Bis-GMA45%, 7:6:1 modification Boltorn type, the ternary photosensitized initiation system 5% of 1:1
Embodiment 5
EE:BAOM is diluent and epoxy systems 30%, the secondary hyper-branched polyester 15% of Bis-GMA50%, 7:6:1 modification Boltorn type, the ternary photosensitized initiation system 5% of 1:1
Embodiment 6
EE:BAOM is diluent and epoxy systems 30%, the secondary hyper-branched polyester 10% of Bis-GMA55%, 7:6:1 modification Boltorn type, the ternary photosensitized initiation system 5% of 1:1
Embodiment 7
EE:BAOM is diluent and epoxy systems 30%, the secondary hyper-branched polyester 5% of Bis-GMA60%, 7:6:1 modification Boltorn type, the ternary photosensitized initiation system 5% of 1:1
Embodiment 8
EE:BAOM is diluent and epoxy systems 40%, the secondary hyper-branched polyester 25% of Bis-GMA30%, 7:6:1 modification Boltorn type, the ternary photosensitized initiation system 5% of 1:1
Embodiment 9
EE:BAOM is diluent and epoxy systems 40%, the secondary hyper-branched polyester 20% of Bis-GMA35%, 7:6:1 modification Boltorn type, the ternary photosensitized initiation system 5% of 1:1
Embodiment 10
EE:BAOM is diluent and epoxy systems 40%, the secondary hyper-branched polyester 10% of Bis-GMA45%, 7:6:1 modification Boltorn type, the ternary photosensitized initiation system 5% of 1:1
Embodiment 11
EE:BAOM is diluent and epoxy systems 40%, the secondary hyper-branched polyester 5% of Bis-GMA50%, 7:6:1 modification Boltorn type, the ternary photosensitized initiation system 5% of 1:1
Embodiment 12
EE:BAOM is diluent and epoxy systems 40%, the secondary hyper-branched polyester 0% of Bis-GMA55%, 7:6:1 modification Boltorn type, the ternary photosensitized initiation system 5% of 1:1
Embodiment 13
EE:BAOM is diluent and epoxy systems 50%, the secondary hyper-branched polyester 15% of Bis-GMA30%, 7:6:1 modification Boltorn type, the ternary photosensitized initiation system 5% of 1:1
Embodiment 14
EE:BAOM is diluent and epoxy systems 50%, the secondary hyper-branched polyester 10% of Bis-GMA35%, 7:6:1 modification Boltorn type, the ternary photosensitized initiation system 5% of 1:1
Embodiment 15
EE:BAOM is diluent and epoxy systems 50%, the secondary hyper-branched polyester 5% of Bis-GMA40%, 7:6:1 modification Boltorn type, the ternary photosensitized initiation system 5% of 1:1
Embodiment 16
EE:BAOM is diluent and epoxy systems 50%, the secondary hyper-branched polyester 0% of Bis-GMA45%, 7:6:1 modification Boltorn type, the ternary photosensitized initiation system 5% of 1:1
Embodiment 17
After tested, the secondary hyper-branched polyester of Bis-GMA, 7:6:1 modification Boltorn type that embodiment 1 ~ 16 provides listed by table 1, EE:BAOM be the diluent of 1:1 and epoxy systems with different quality than the shrinkage factor after photocuring and double bond conversion rate.
Table 1
| Embodiment | Shrinkage factor/% | Double bond conversion rate/% |
| 1 | 5.8 | 49.6 |
| 2 | 2.34 | 90.55 |
| 3 | 2.73 | 89.56 |
| 4 | 3.09 | 93.23 |
| 5 | 3.27 | 96 |
| 6 | 3.66 | 90 |
| 7 | 3.77 | 89.83 |
| 8 | 1.96 | 85.75 |
| 9 | 2.16 | 86.64 |
| 10 | 2.59 | 90.24 |
| 11 | 2.96 | 92.28 |
| 12 | 3.1 | 90.07 |
| 13 | 2.1 | 76.36 |
| 14 | 2.27 | 80.3 |
| 15 | 2.46 | 81.1 |
| 16 | 2.55 | 82.64 |
Embodiment 2,8,9,13,14,15 shrinkage factor is all below 2.5% as can be seen from Table 1, except embodiment 13, the double bond conversion rate of other embodiments is all higher, by shrinkage factor and the double bond conversion rate degree of these embodiments, preferred embodiment 2,8,9, and it can thus be appreciated that, most preferred each component proportion is: the Bis-GMA amount of selecting accounts for 25 ~ 35% of whole resin system quality, diluent and the intumescent system amount of selecting account for 30 ~ 40% of whole resin system quality, and the modified ultra-branching polyester amount of selecting accounts for 20 ~ 40% of whole resin system quality.
In embodiment 18 ~ 24, take following name: modification Boltorn type secondary hyperbranched poly esters monomer is designated as A by (1), A is that 7:6:1,7:8:1,7:9:1,8:6:1,8:8:1,10:6:1 or 9:7:1 carry out reaction products therefrom by methacrylic chloride, propionyl chloride and the secondary hyper-branched polyester of Boltorn type according to mol ratio.(2) diluent and epoxy systems are designated as B, B is 1:4 by epoxy resin and Expanding Monomer according to mass ratio, 1:2, or 1:1 mix homogeneously gained, its epoxy resin is 3, 4-epoxycyclohexyl-methyl-3, 4-epoxycyclohexyl formic acid esters, methyl two [2-(7-oxabicyclo [4.1.0]-3-in heptan base)-ethyl] phenyl silane or 2, 4, 6, 8-tetramethyl-2, 4, 6, 8-tetra-[2-(7-oxabicyclo [4.1.0]-3-in heptan base)-ethyl]-1, 3, 5, 7-tetra-oxa--2, 4, 6, 8-tetra-silicon Tetramethylene. is wherein a kind of, Expanding Monomer is 3, 9-diethyl-3, 9-propylene oxygen methyl isophthalic acid, 5, 7, 11-tetra-oxygen spiral shell assorted [5, 5] hendecane (BAOM).(3) ternary photoinitiator is designated as C, C is by photic acid compound, visible light photosensitizer and electron donor compound group are 3:1:0.1 according to mass ratio, 3:0.1:0.1, 3:0.5:0.1, 1:0.1:0.1, 1:0.5:0.1 or 1:1:0.1 mix homogeneously gained, wherein photic acid compound is Diaryl iodonium Nian salt, triaryl sulfur anchor salt or the confused salt of triaryl selenium, visible light photosensitizer is camphorquinone, benzophenone, 1-Phenylethanone., benzoin ether or thia anthraquinone, electron donor compound is N, N mono-dimethylamino methyl ethyl acrylate, dimethyl ethenyl amine benzoic acid or N, N mono-dimethyl is to vinyl aniline.
Embodiment 18
Lower shrinkage dental prosthetic resin of the present invention, raw materials quality percentage ratio is followed successively by: B 30%, Bis-GMA60%, A5%, C5%.
A is that 7:6:1 carries out reaction products therefrom by methacrylic chloride, propionyl chloride and the secondary hyper-branched polyester of Boltorn type according to mol ratio.
B is that 1:4 mixs homogeneously gained by epoxy resin and Expanding Monomer according to mass ratio, its epoxy resin is 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexyl formic acid esters, Expanding Monomer is 3,9-diethyl-3,9-propylene oxygen methyl isophthalic acid, 5,7,11-tetra-oxygen spiral shell is mixed [5,5] hendecane (BAOM).
C is 3:1:0.1 mix homogeneously gained by photic acid compound, visible light photosensitizer and electron donor compound group according to mass ratio, wherein photic acid compound is Diaryl iodonium hexafluorophosphate, visible light photosensitizer is camphorquinone, electron donor compound is N, N mono-dimethylamino methyl ethyl acrylate.
Embodiment 19
Lower shrinkage dental prosthetic resin of the present invention, raw materials quality percentage ratio is followed successively by: B 30%, Bis-GMA25%, A40%, ternary light C5%.
A is that 7:8:1 carries out reaction products therefrom by methacrylic chloride, propionyl chloride and the secondary hyper-branched polyester of Boltorn type according to mol ratio.
B is that 1:4 mixs homogeneously gained by epoxy resin and Expanding Monomer according to mass ratio, its epoxy resin is methyl two [2-(7-oxabicyclo [4.1.0]-3-in heptan base)-ethyl] phenyl silane, Expanding Monomer is 3,9-diethyl-3,9-propylene oxygen methyl isophthalic acid, 5,7,11-tetra-oxygen spiral shell is mixed [5,5] hendecane (BAOM).
C is 3:0.1:0.1 mix homogeneously gained by photic acid compound, visible light photosensitizer and electron donor compound group according to mass ratio, wherein photic acid compound is triaryl sulfur hexafluorophosphate, visible light photosensitizer is benzophenone, and electron donor compound is dimethyl ethenyl amine benzoic acid.
Embodiment 20
Lower shrinkage dental prosthetic resin of the present invention, raw materials quality percentage ratio is followed successively by: B 30%, Bis-GMA37%, A30%, ternary light C3%.
A is that 7:9:1 carries out reaction products therefrom by methacrylic chloride, propionyl chloride and the secondary hyper-branched polyester of Boltorn type according to mol ratio.
B is that 1:2 mixs homogeneously gained by epoxy resin and Expanding Monomer according to mass ratio, and its epoxy resin is 2,4,6,8-tetramethyl-2,4,6,8-tetra-[2-(7-oxabicyclo [4.1.0]-3-in heptan base)-ethyl]-1,3,5,7-tetra-oxa--2,4,6,8-tetra-silicon Tetramethylene., Expanding Monomer is 3,9-diethyl-3,9-propylene oxygen methyl isophthalic acid, 5,7,11-tetra-oxygen spiral shell is mixed [5,5] hendecane (BAOM).
C is 3:0.5:0.1, mix homogeneously gained by photic acid compound, visible light photosensitizer and electron donor compound group according to mass ratio, wherein photic acid compound is Diaryl iodonium hexafluorophosphate, visible light photosensitizer is 1-Phenylethanone., electron donor compound be N, N mono-dimethyl to vinyl aniline.
Embodiment 21
Lower shrinkage dental prosthetic resin of the present invention, raw materials quality percentage ratio is followed successively by: B 40%, Bis-GMA32%, A25%, ternary light C3%.
A is that 8:6:1 carries out reaction products therefrom by methacrylic chloride, propionyl chloride and the secondary hyper-branched polyester of Boltorn type according to mol ratio.
B is that 1:2 mixs homogeneously gained by epoxy resin and Expanding Monomer according to mass ratio, its epoxy resin is methyl two [2-(7-oxabicyclo [4.1.0]-3-in heptan base)-ethyl] phenyl silane, Expanding Monomer is 3,9-diethyl-3,9-propylene oxygen methyl isophthalic acid, 5,7,11-tetra-oxygen spiral shell is mixed [5,5] hendecane (BAOM).
C is 3:0.5:0.1 mix homogeneously gained by photic acid compound, visible light photosensitizer and electron donor compound group according to mass ratio, wherein photic acid compound is triaryl sulfur hexafluorophosphate, visible light photosensitizer is benzoin ether, electron donor compound is N, N mono-dimethylamino methyl ethyl acrylate.
Embodiment 22
Lower shrinkage dental prosthetic resin of the present invention, raw materials quality percentage ratio is followed successively by: B 40%, Bis-GMA57%, A0%, ternary light C3%.
A is that 8:8:1 carries out reaction products therefrom by methacrylic chloride, propionyl chloride and the secondary hyper-branched polyester of Boltorn type according to mol ratio.
B is that 1:1 mixs homogeneously gained by epoxy resin and Expanding Monomer according to mass ratio, and its epoxy resin is 2,4,6,8-tetramethyl-2,4,6,8-tetra-[2-(7-oxabicyclo [4.1.0]-3-in heptan base)-ethyl]-1,3,5,7-tetra-oxa--2,4,6,8-tetra-silicon Tetramethylene., Expanding Monomer is 3,9-diethyl-3,9-propylene oxygen methyl isophthalic acid, 5,7,11-tetra-oxygen spiral shell is mixed [5,5] hendecane (BAOM).
C is 1:0.1:0.1 mix homogeneously gained by photic acid compound, visible light photosensitizer and electron donor compound group according to mass ratio, wherein photic acid compound is Diaryl iodonium hexafluorophosphate, visible light photosensitizer is thia anthraquinone, electron donor compound be N, N mono-dimethyl to vinyl aniline.
Embodiment 23
Lower shrinkage dental prosthetic resin of the present invention, raw materials quality percentage ratio is followed successively by: B 50%, Bis-GMA40%, A9%, ternary light C1%.
A is that 10:6:1 carries out reaction products therefrom by methacrylic chloride, propionyl chloride and the secondary hyper-branched polyester of Boltorn type according to mol ratio.
B is that 1:1 mixs homogeneously gained by epoxy resin and Expanding Monomer according to mass ratio, and its epoxy resin is 2,4,6,8-tetramethyl-2,4,6,8-tetra-[2-(7-oxabicyclo [4.1.0]-3-in heptan base)-ethyl]-1,3,5,7-tetra-oxa--2,4,6,8-tetra-silicon Tetramethylene., Expanding Monomer is 3,9-diethyl-3,9-propylene oxygen methyl isophthalic acid, 5,7,11-tetra-oxygen spiral shell is mixed [5,5] hendecane (BAOM).
C is 1:0.5:0.1 mix homogeneously gained by photic acid compound, visible light photosensitizer and electron donor compound group according to mass ratio, wherein photic acid compound is Diaryl iodonium hexafluorophosphate, visible light photosensitizer is camphorquinone, electron donor compound is N, N mono-dimethylamino methyl ethyl acrylate.
Embodiment 24
Lower shrinkage dental prosthetic resin of the present invention, raw materials quality percentage ratio is followed successively by: B 50%, Bis-GMA30%, A19%, ternary light C1%.
A is that 9:7:1 carries out reaction products therefrom by methacrylic chloride, propionyl chloride and the secondary hyper-branched polyester of Boltorn type according to mol ratio.
B is that 1:1 mixs homogeneously gained by epoxy resin and Expanding Monomer according to mass ratio, wherein 2,4,6,8-tetramethyl-2,4,6,8-tetra-[2-(7-oxabicyclo [4.1.0]-3-in heptan base)-ethyl]-1,3,5,7-tetra-oxa--2,4,6,8-tetra-silicon Tetramethylene., Expanding Monomer is 3,9-diethyl-3,9-propylene oxygen methyl isophthalic acid, 5,7,11-tetra-oxygen spiral shell is mixed [5,5] hendecane (BAOM).
C is 1:1:0.1 mix homogeneously gained by photic acid compound, visible light photosensitizer and electron donor compound group according to mass ratio, wherein photic acid compound is triaryl selenium hexafluorophosphate, visible light photosensitizer is thia anthraquinone, and electron donor compound is dimethyl ethenyl amine benzoic acid.
To sum up, the present invention forms firm firming body under light illumination, reduces the shrinkage factor of resin for restoration, has desirable hardness simultaneously; The introducing of Expanding Monomer and epoxy resin, instead of the cytotoxic diluent double methyl methacrylate triethylene glycol ester (TEGDMA) of dental pulp, reduces the cytotoxicity of resin for restoration.
Claims (8)
1. a lower shrinkage dental prosthetic resin, is characterized in that, is prepared from by methacrylate-based monomer, modification Boltorn type secondary hyperbranched poly esters monomer, diluent and epoxy systems and initiator, wherein:
Methacrylate-based monomer accounts for 25 ~ 60% of whole resin system quality;
Modification Boltorn type secondary hyperbranched poly esters monomer accounts for 0 ~ 40% of whole resin system quality;
Diluent and epoxy systems account for 30 ~ 50% of whole resin system;
Initiator accounts for 1 ~ 5% of whole resin system quality.
2. lower shrinkage dental prosthetic resin according to claim 1, is characterized in that, described methacrylate-based monomer is bisphenol-A-dimethyl allene acid glycidyl ester Bis-GMA.
3. lower shrinkage dental prosthetic resin according to claim 1, it is characterized in that, described modification Boltorn type secondary hyperbranched poly esters monomer is obtained by reacting by the secondary hyper-branched polyester of Boltorn type and modified monomer, modified containing carbon-carbon double bond and oh group.
4. lower shrinkage dental prosthetic resin according to claim 1, it is characterized in that, described diluent and epoxy systems comprise Expanding Monomer and epoxy resin, the mass ratio of Expanding Monomer and epoxy resin is (1 ~ 4): 4, its epoxy resin is 3, 4-epoxycyclohexyl-methyl-3, 4-epoxycyclohexyl formic acid esters, methyl two [2-(7-oxabicyclo [4.1.0]-3-in heptan base)-ethyl] phenyl silane or 2, 4, 6, 8-tetramethyl-2, 4, 6, 8-tetra-[2-(7-oxabicyclo [4.1.0]-3-in heptan base)-ethyl]-1, 3, 5, 7-tetra-oxa--2, 4, 6, 8-tetra-silicon Tetramethylene., Expanding Monomer is 3, 9-diethyl-3, 9-propylene oxygen methyl isophthalic acid, 5, 7, 11-tetra-oxygen spiral shell assorted [5, 5] hendecane.
5. have the lower shrinkage dental prosthetic resin asked described in 1 according to right, it is characterized in that, described initiator is ternary photosensitized initiation system.
6. lower shrinkage dental prosthetic resin according to claim 3, it is characterized in that, described modified monomer is the combination of methacrylic chloride and propionyl chloride, wherein the mol ratio of methacrylic chloride and the secondary hyper-branched polyester of Boltorn type is (7 ~ 10): 1, and the mol ratio of propionyl chloride and the secondary hyper-branched polyester of Boltorn type is (6 ~ 9): 1.
7. lower shrinkage dental prosthetic resin according to claim 5, it is characterized in that, described ternary photosensitized initiation system comprises photic acid compound, visible light photosensitizer and electron donor compound group, photic acid compound is Diaryl iodonium hexafluorophosphate, triaryl sulfur hexafluorophosphate or triaryl selenium hexafluorophosphate, visible light photosensitizer is camphorquinone, benzophenone, 1-Phenylethanone., benzoin ether or thia anthraquinone, electron donor compound is N, N mono-dimethylamino methyl ethyl acrylate, dimethyl ethenyl amine benzoic acid or N, N mono-dimethyl is to vinyl aniline, wherein photic acid compound, visible light photosensitizer and electron donor compound mass ratio are (1 ~ 3): (0.1 ~ 1): 0.1.
8. the preparation method of a lower shrinkage dental prosthetic resin as claimed in claim 1, it is characterized in that, with methacrylate-based monomer 25 ~ 60%(weight), modification Boltorn type secondary hyperbranched poly esters monomer 0 ~ 40%(weight), diluent and epoxy systems 30 ~ 50%(weight) and initiator 1 ~ 5%(weight) be batching, inject after mix homogeneously in specific mould and carry out Stereolithography, obtain lower shrinkage dental prosthetic resin material.
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| CN113121748A (en) * | 2021-03-19 | 2021-07-16 | 东华大学 | Preparation of low-shrinkage Bis-GMA-free hyperbranched polyamine-ester flow resin for dental repair |
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