CN103622835A - DMC-MMA (methyl methacrylate)-halloysite copolymerized denture base material and preparation method thereof - Google Patents
DMC-MMA (methyl methacrylate)-halloysite copolymerized denture base material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a DMC-MMA (methyl methacrylate)-halloysite copolymerized denture base material and a preparation method thereof. According to the invention, the charge environment of the polymeric substrate of the first monomer MMA is regulated and controlled through the second monomer DMC, and the two monomers are copolymerized through the suspension polymerization method, HNTs is added and compounded with the copolymerized product, and after the copolymerized product is mixed with thermosetting type dental base acrylic resin liquid, the mixture is heated and cured. According to the invention, the MMA is used as a base material, and the nanocomposite is prepared by adopting the in situ suspension polymerization method to regulate and control the charge environment of the substrate, and the halloysite nano filler is added for polymerization, so that the relatively pure PMMA resin is obtained, and the bending strength and the tensile strength of the denture base material are greatly improved to a great extent, the dispersity of halloysite in the substrate is successfully improved, and the problem about the mechanical strength, particularly the bending strength of the PMMA denture base material, is solved.
Description
Technical field
The invention belongs to oral cavity technical field of biological material, more particularly, relate to a kind of polymethyl methacrylate (PMMA) denture base material, particularly take PMMA as matrix, regulation and control matrix charge environment, filled with nanotubes galapectite (HNTs), preparation PMMA based nano composite material.
Background technology
Along with social progress and growth in the living standard, people are increasingly strong to the requirement of aesthetic reparation, also more and more higher to the requirement of oral cavity material, and meanwhile, retaining of tooth makes the spectrum of disease in oral cavity that change occur.According to interrelated data measuring and calculating, China's population morbidity of dental caries is 37%, and on average everyone has 2.47 of dental caries, by 1,200,000,000 populations, and nearly 500,000,000 people of national eurodonticus, dental caries sum is more than 1,000,000,000.In adult, patients with periodontal disease approximately 80%, this all can cause very a high proportion of dentition defect.11 of the average agomphosis of over-65s elderly population.These all need to use dental prosthetic material reparation, and the market of visible China dental prosthetic material is very wide.
Adopt natural and artificial material to make basal seat area in the application in prosthetic dentistry field, existing long history.Adopting the earliest hardwood, animal bone, Dens Elephatis etc. to do embedding base decorates, within 1885, adopt thiorubber., nineteen thirty-seven, Germany KulZer company released heat-curing type PMMA denture base material " Paladan " first, started new era of prosthetic dentistry, due to its superior performance, easy and simple to handle, bio-compatible performance is good, so far still as the first-selection of clinical practice.But, existence due to internal stress in the not good enough and solidification process of the intensity of PMMA resin own, the toughness of resin material and intensity are all lower, on causing in clinical repair, artificial tooth is easily indulged folding, during interlock, the phenomenon of rupture of base often occurs, therefore the mechanical performance of PMMA can not meet the requirement of Oral Repair completely, even if there is best clinical experience, the selection of indication, artificial tooth's arrangement and the most rational operating process, still there is the problem of mechanical strength aspect in PMMA base material, particularly impact strength is poor, often cause fractureing of base, and cause that dysbacteriosis causes denture stomatitis.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, the methyl methacrylate (PMMA) of take is base material, adopts the method for in-situ suspension polymerization to prepare PMMA nano composite material, and object is the dental prosthetic material that obtains excellent performance.Based on HNTs surface charge, be elecrtonegativity, with charged monomer MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC) and MMA copolymerization, realization regulates and controls the charge environment of matrix, and add the nano-filled thing of HNTs to carry out polymerization, the impact of research charge environment regulation and control on PMMA suspension polymerization system, composite property.
Object of the present invention is achieved by following technical proposals:
A kind of polymethyl acyl-oxygen ethyl-trimethyl salmiac-methyl methacrylate-halloysite nanotubes denture base material, with the second monomer MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, the polymeric matrix charge environment of the first monomers methyl methacrylate is regulated and controled, two monomers carry out copolymerization by suspension polymerisation mode, two kinds of monomer composition oil phases of described MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and methyl methacrylate, the consumption of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride is the 1-10wt% of oil phase quality, the consumption of methyl methacrylate monomer is the 90-99wt% of oil phase quality, adding oil phase quality 1wt%-10wt% halloysite nanotubes (HNTs) realizes compound with copolymerization product, then copolymerization product is mixed homogeneously with heat setting type dental base acrylic resin liquid, be heating and curing.
The consumption of described nanotube galapectite is preferably the 1wt%-5wt% of oil phase quality.
A preparation method for polymethyl acyl-oxygen ethyl-trimethyl salmiac-methyl methacrylate-halloysite nanotubes denture base material, according to following step, carry out:
(1) take MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and methyl methacrylate as comonomer, by suspension polymerisation, make, in suspension polymerization system, the volume ratio of water and oil phase is 1～5, described oil phase is by MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and two kinds of monomer compositions of methyl methacrylate, the consumption of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride is the 1-10wt% of oil phase quality, and the consumption of methyl methacrylate monomer is the 90-99wt% of oil phase quality; Described water is comprised of water, dispersant and surfactant, wherein the consumption of dispersant be two kinds of monomer masses and 2-3.5wt%, the consumption of surfactant be two kinds of monomer masses and 0.1-0.2wt%;
(2) in oil phase, add its quality 1wt%-10wt% nanotube galapectite, after ultrasonic dispersion, obtain suspension, this suspension and water are added in reactor, stir, pass into noble gas with remain on whole reactor in course of reaction in inert gas atmosphere, be warming up on the initiation temperature of initiator, add initiator with initiated polymerization simultaneously, obtain MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-methylmethacrylate copolymer A, the consumption of described initiator be two kinds of monomer masses and 0.5-2wt%;
(3) copolymer A of being prepared by step (2) is filtered and is washed, and obtains copolymer powder B after oven dry;
(4) by copolymer powder B and heat setting type dental base acrylic resin liquid according to mass ratio (1～2): 1, carry out mix homogeneously;
(5) mixture for the treatment of step (4) mix homogeneously enters dough after date and is taken out, and is filled in mould, and pressure is 2-4MPa;
(6) mould after filling is heating and curing, in the water of 70-80 ℃, heats 1.5-3.5h, then be warming up to 90-100 ℃, standing cooling after maintenance 1-3h, die sinking.
In suspension polymerization system of the present invention, described dispersant is a kind of in basic magnesium carbonate, calcium hydroxy phosphate (HAP), hydroxyethyl-cellulose (HEC) or tricalcium phosphate, preferably hydroxyethyl-cellulose (HEC); The volume ratio of described water and oil phase is preferably 3; Described surfactant is a kind of in dodecylbenzene sodium sulfonate (SDBS), sodium lauryl sulphate (SDS) or sodium glycocholate, is preferably dodecylbenzene sodium sulfonate (SDBS); Described initiator is a kind of in azodiisobutyronitrile (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN), benzoyl peroxide (BPO) or peroxy dicarbonate two (2-ethyl) own ester (EHP), preferably azodiisobutyronitrile (AIBN) or benzoyl peroxide (BPO); Described noble gas is a kind of in nitrogen, helium or hydrogen; In the time of on being heated to the initiation temperature of initiator, according to reactant number need the sufficiently long time of polyreaction, to guarantee that two kinds of monomers realize higher conversion ratio when the copolymerization, the preferred reaction time is 3-10 hour.The consumption of described dispersant and surfactant can be changed, and meets the particle diameter requirement of denture base material to meet the small bead polymer of final preparation.
In preparation method of the present invention, in described step (4), copolymer powder B and heat setting type dental base acrylic resin liquid are preferably 1.5:1 according to mass ratio; In described step (5), the preferred 3Mpa of pressure; In described step (6), preferably in the water of 70 ℃, heat 1.5h, then be warming up to 100 ℃, keep 1 rear standing cooling, die sinking.
In many denture base materials, small bead polymer (the pearl PMMA powder of being made through suspension polymerisation by methyl methacrylate (MMA) monomer, be dental base acrylic resin powder) be the main component of denture base material, weight average molecular weight is at 60-100 ten thousand, particle diameter is 40-70 μ m, transmittance is more than 90%, the about 1.19g/cm of density
3.Pearl PMMA powder prepared by monomer polymerization exists a lot of not enough in mechanical property.For studying the surperficial Zeta potential of the original HNTs of ZetaPALS type high-resolution Zeta potential test analysis, composite nano-microsphere and the copolymerization microsphere of the electrostatic interaction ，Yong U.S. Brookhaven between HNTs surface charge property and polymer matrices and HNTs.Various particles to be measured are scattered in deionized water and carry out ultrasonic dispersion, then fluid sample is joined in test ware and test.According to surface potential detection, show, when pH value is 6-7, unmodified nanotube galapectite inner surface shows electropositive, the micro-weak elecrtonegativity of pipe outer wall.Technical solution of the present invention is selected positively charged monomer MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC) and MMA copolymerization, realization regulates and controls the charge environment of matrix, to realize the better dispersion of HNTs in polymeric matrix, due to unmodified HNTs outer surface belt negative charge, added to the suspension copolymerization system situ compound tense of MMA and DMC, HNTs can be adsorbed on positively charged PMMA strand by electrostatic interaction, strand to positively charged has played Stabilization, the HNTs being simultaneously adsorbed can be distributed in polymeric matrix along with the random motion of strand equably, and due to the existence of electrostatic interaction strengthened and polymeric matrix between interface binding power.The small pearl copolymerized polymer that technical scheme of the present invention is prepared after suspension polymerisation meets the basic demand (as particle diameter, weight average molecular weight) of denture base material, toner is made into after standard specimen, purer PMMA resin, bending strength and hot strength are all greatly improved, successfully improve the dispersibility of HNTs in matrix, solved the problem that PMMA denture base material particularly exists aspect mechanical strength aspect bending strength.
The specific embodiment
Below in conjunction with specific embodiment, further illustrate technical scheme of the present invention.
What the HNTs using in experimental work adopted is the commercial product that Sigma-Aldrich company provides, and specifications parameter is as shown in the table.
| Character | Powder |
| Color | Hunter whiteness 75～96 |
| Chemical constituent | Al 2Si 2O 5(OH) 4·2H 2O |
| Pore volume | 1.26～1.34mL/g |
| Diameter | 30～70nm |
| Length | 1～3μm |
| Surface area | 64m 2/g |
| Cation exchange capacity | 8.0meq/g |
| True density | 2.53g/cm 3 |
| Index of refraction | n20/D?1.54 |
The heat setting type dental base acrylic resin liquid that embodiment selects is the artificial tooth base resin (work type) of Dentistry Material Plant, Shanghai Medical Machinery Co., Ltd., and composition is as shown in the table:
Embodiment 1
(1) after being mixed with 58.2gMMA monomer, 1.8gDMC adds (monomer total amount is 60mL) in there-necked flask, add 3gHNTs, suspension after ultrasonic dispersion, in 150mL deionized water, add 1.5g hydroxyethyl-cellulose (HEC) and 0.075g dodecylbenzene sodium sulfonate (SDBS) simultaneously, after preliminary stirring, be poured in there-necked flask, continue stirring at low speed.Logical N
2after protection 40min, be warming up to 90 ℃, and continue to keep inert atmosphere, add 0.4g initiator B PO initiated polymerization.Reaction 9h, by reaction system cold filtration, uses deionized water washing and filtering product repeatedly, and at 60 ℃, vacuum drying, to constant weight, obtains P (MMA-co-DMC)/HNTs nano-complex;
(2) P (MMA-DMC)/HNTs copolymerization product (powder) is mixed homogeneously according to the mass ratio of 1:1 with heat setting type dental base acrylic resin liquid, thing to be mixed enters dough after date and is taken out, and is filled in mould, and pressure is 4Mpa;
(3) mould after filling is heating and curing, in the water of 70 ℃, heats 1.5h, then be warming up to 100 ℃, standing cooling after maintenance 1h, die sinking.
Embodiment 2
(1) after being mixed with 57gMMA monomer, 3gDMC adds (monomer total amount is 60mL) in there-necked flask, add 0.6gHNTs, suspension after ultrasonic dispersion, in 150mL deionized water, add 1.8g hydroxyethyl-cellulose (HEC) and 0.067g dodecylbenzene sodium sulfonate (SDBS) simultaneously, after preliminary stirring, be poured in there-necked flask, continue stirring at low speed.Logical N
2after protection 40min, be warming up to 90 ℃, and continue to keep inert atmosphere, add 0.4g initiator B PO initiated polymerization.Reaction 9h, by reaction system cold filtration, uses deionized water washing and filtering product repeatedly, and at 60 ℃, vacuum drying, to constant weight, obtains P (MMA-co-DMC)/HNTs nano-complex;
(2) P (MMA-DMC)/HNTs copolymerization product (powder) is mixed homogeneously according to the mass ratio of 1:1 with heat setting type dental base acrylic resin liquid, thing to be mixed enters dough after date and is taken out, and is filled in mould, and pressure is 4Mpa;
(3) mould after filling is heating and curing, in the water of 70 ℃, heats 1.5h, then be warming up to 100 ℃, standing cooling after maintenance 1h, die sinking.
Embodiment 3
(1) after being mixed with 54gMMA monomer, 6gDMC adds (monomer total amount is 60mL) in there-necked flask, add 0.9gHNTs, suspension after ultrasonic dispersion, in 150mL deionized water, add 1.6g hydroxyethyl-cellulose (HEC) and 0.075g dodecylbenzene sodium sulfonate (SDBS) simultaneously, after preliminary stirring, be poured in there-necked flask, continue stirring at low speed.Logical N
2after protection 40min, be warming up to 90 ℃, and continue to keep inert atmosphere, add 0.6g initiator B PO initiated polymerization.Reaction 9h, by reaction system cold filtration, uses deionized water washing and filtering product repeatedly, and at 60 ℃, vacuum drying, to constant weight, obtains P (MMA-co-DMC)/HNTs nano-complex;
(2) P (MMA-DMC)/HNTs copolymerization product (powder) is mixed homogeneously according to the mass ratio of 1:1 with heat setting type dental base acrylic resin liquid, thing to be mixed enters dough after date and is taken out, and is filled in mould, and pressure is 4Mpa;
(3) mould after filling is heating and curing, in the water of 70 ℃, heats 1.5h, then be warming up to 100 ℃, standing cooling after maintenance 1h, die sinking.
Embodiment 4
(1) after being mixed with 54gMMA monomer, 6gDMC adds (monomer total amount is 60mL) in there-necked flask, add 6gHNTs, suspension after ultrasonic dispersion, in 150mL deionized water, add 1.8g hydroxyethyl-cellulose (HEC) and 0.072g dodecylbenzene sodium sulfonate (SDBS) simultaneously, after preliminary stirring, be poured in there-necked flask, continue stirring at low speed.Logical N
2after protection 40min, be warming up to 90 ℃, and continue to keep inert atmosphere, add 0.6g initiator B PO initiated polymerization.Reaction 9h, by reaction system cold filtration, uses deionized water washing and filtering product repeatedly, and at 60 ℃, vacuum drying, to constant weight, obtains P (MMA-co-DMC)/HNTs nano-complex;
(2) P (MMA-DMC)/HNTs copolymerization product (powder) is mixed homogeneously according to the mass ratio of 1:1 with heat setting type dental base acrylic resin liquid, thing to be mixed enters dough after date and is taken out, and is filled in mould, and pressure is 4Mpa;
(3) mould after filling is heating and curing, in the water of 70 ℃, heats 1.5h, then be warming up to 100 ℃, standing cooling after maintenance 1h, die sinking.
Comparative example
(1) 60mLMMA monomer is added in there-necked flask, in 180mL deionized water, add 1.9g hydroxyethyl-cellulose (HEC) and 0.075g dodecylbenzene sodium sulfonate (SDBS) simultaneously, after preliminary stirring, be poured in there-necked flask, continue stirring at low speed.Logical N
2after protection 10min, be warming up to 100 ℃, add 0.5g initiator B PO initiated polymerization.10h is by reaction system cold filtration in reaction, cyclic washing filtration product.Vacuum drying, to constant weight, obtains PMMA artificial tooth base resin powder.
(2) PMMA artificial tooth base resin powder is mixed homogeneously according to the mass ratio of 1:1 with heat setting type dental base acrylic resin liquid, thing to be mixed enters dough after date and is taken out, and is filled in mould, and pressure is 4Mpa;
(3) mould after filling is heating and curing, in the water of 70 ℃, heats 1.5h, then be warming up to 100 ℃, standing cooling after maintenance 1h, die sinking.
The P that the present invention obtains (MMA-co-DMC)/HNTs artificial tooth base resin can carry out bending property, the tensile property that mechanical performance is evaluated copolymer resins in the following ways
Standard specimen preparation
1. model preparation: make the wax shape test piece of standard specimen size with rde wax flakes (2mm is thick), select dental flask, with Gypsum Fibrosum, artificial tooth wax shape is embedded in flask, after gypsum sets, with boiling water, wax fusing is washed down, make it to form the model with chamber, and it is standby in gypsum surface, to be coated with separating medium.
2. powder liquid is in harmonious proportion: by gained copolymerization powder and heat setting type dental base acrylic resin liquid in mass ratio 1.5:1 mix, powder too much easily produces bubble, liquid is crossed at most and is shunk greatly.After both mix, stir and make powder liquid mix homogeneously gently immediately, vibrate gently to get rid of bubble simultaneously.
3. standing swelling: powder liquid has following variation in time after being in harmonious proportion: damp sand phase, pasty state phase, haircuts phase, dough period, phase firmly admittedly.Wherein dough period is the most soft plastic, not the best filling phase of sticking device tool.Treat that concoction enters dough period, take out concoction, with hands, fully integrate, with further mix homogeneously, then insert in the mould of preparing sample.
4. filling: all filling operation should complete in dough period.Pressure testing one twice, finished edge is removed unnecessary resin, pressure 2-4MPa.
5. be heating and curing: in the water of 70 ℃, heat 1.5h, then be rapidly heated to 100 ℃, keep standing cooling after 1h, die sinking, polishes smooth sample with No. 280, No. 400, No. 800, No. 1200 and No. 2000 sand paper successively,
Measuring mechanical property
1. bending property test: utilize omnipotent mechanical test machine to load the standard mechanics of bending sample making, until sample fracture, test fulcrum span is 50mm, and loading velocity is 5mm/min.
2. tensile property test: utilize omnipotent mechanical test machine to carry out extension test to the standard tensile mechanics sample making, rate of extension is 2mm/min.
The omnipotent mechanical test machine of M350-20KN type of embodiment 1-4 product utilization Britain Testometric company is carried out to measuring mechanical property as follows:
1. bending property test: For Three Points Bending Specimen size 64 * 10 * 3.3mm, load until sample fracture, test fulcrum span is 50mm, loading velocity is 5mm/min.
2. tensile property test: mechanical stretch specimen size 50 * 7 * 2mm, rate of extension is 2mm/min.
The mechanical performance of PMMA copolymer resin during different HNTs content (HNTs and two kinds of monomer masses and percent)
Above the present invention has been done to exemplary description; should be noted that; in the situation that not departing from core of the present invention, the replacement that is equal to that any simple distortion, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (10)
1. polymethyl acyl-oxygen ethyl-trimethyl salmiac-methyl methacrylate-galapectite denture base material, it is characterized in that, with the second monomer MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, the polymeric matrix charge environment of the first monomers methyl methacrylate is regulated and controled, two monomers carry out copolymerization by suspension polymerisation mode, two kinds of monomer composition oil phases of described MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and methyl methacrylate, the consumption of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride is the 1-10wt% of oil phase quality, the consumption of methyl methacrylate monomer is the 90-99wt% of oil phase quality, adding oil phase quality 1wt%-10wt% halloysite nanotubes and copolymerization product realizes compound, then copolymerization product is mixed homogeneously with heat setting type dental base acrylic resin liquid, be heating and curing, according to following step, carry out:
(1) take MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and methyl methacrylate as comonomer, by suspension polymerisation, make, in suspension polymerization system, the volume ratio of water and oil phase is 1～5, described oil phase is by MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and two kinds of monomer compositions of methyl methacrylate, the consumption of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride is the 1-10wt% of oil phase quality, and the consumption of methyl methacrylate monomer is the 90-99wt% of oil phase quality; Described water is comprised of water, dispersant and surfactant, wherein the consumption of dispersant be two kinds of monomer masses and 2-3.5wt%, the consumption of surfactant be two kinds of monomer masses and 0.1-0.2wt%;
(2) in oil phase, add its quality 1wt%-10wt% nanotube galapectite, after ultrasonic dispersion, obtain suspension, this suspension and water are added in reactor, stir, pass into noble gas with remain on whole reactor in course of reaction in inert gas atmosphere, be warming up on the initiation temperature of initiator, add initiator with initiated polymerization simultaneously, obtain MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-methylmethacrylate copolymer A, the consumption of described initiator be two kinds of monomer masses and 0.5-2wt%;
(3) copolymer A of being prepared by step (2) is filtered and is washed, and obtains copolymer powder B after oven dry;
(4) by copolymer powder B and heat setting type dental base acrylic resin liquid according to mass ratio (1～2): 1, carry out mix homogeneously;
(5) mixture for the treatment of step (4) mix homogeneously enters dough after date and is taken out, and is filled in mould, and pressure is 2-4MPa;
(6) mould after filling is heating and curing, in the water of 70-80 ℃, heats 1.5-3.5h, then be warming up to 90-100 ℃, standing cooling after maintenance 1-3h, die sinking.
2. polymethyl acyl-oxygen ethyl-trimethyl salmiac-methyl methacrylate-galapectite denture base material according to claim 1, is characterized in that, the consumption of described nanotube galapectite is preferably the 1wt%-5wt% of oil phase quality.
3. polymethyl acyl-oxygen ethyl-trimethyl salmiac-methyl methacrylate-galapectite denture base material according to claim 1, is characterized in that, in the time of on being heated to the initiation temperature of initiator, the preferred reaction time is 3-10 hour.
4. polymethyl acyl-oxygen ethyl-trimethyl salmiac-methyl methacrylate-galapectite denture base material according to claim 1, it is characterized in that, described dispersant is a kind of in basic magnesium carbonate, calcium hydroxy phosphate, hydroxyethyl-cellulose or tricalcium phosphate, preferably hydroxyethyl-cellulose; The volume ratio of described water and oil phase is preferably 3; Described surfactant is a kind of in dodecylbenzene sodium sulfonate, sodium lauryl sulphate or sodium glycocholate, is preferably dodecylbenzene sodium sulfonate; Described initiator is a kind of in the own ester of azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide or peroxy dicarbonate two (2-ethyl), preferably azodiisobutyronitrile or benzoyl peroxide; Described noble gas is a kind of in nitrogen, helium or hydrogen.
5. polymethyl acyl-oxygen ethyl-trimethyl salmiac-methyl methacrylate-galapectite denture base material according to claim 1, it is characterized in that, in described step (4), copolymer powder B and heat setting type dental base acrylic resin liquid are preferably 1.5:1 according to mass ratio; In described step (5), the preferred 3Mpa of pressure; In described step (6), preferably in the water of 70 ℃, heat 1.5h, then be warming up to 100 ℃, keep 1 rear standing cooling, die sinking.
6. the preparation method of polymethyl acyl-oxygen ethyl-trimethyl salmiac-methyl methacrylate-galapectite denture base material, it is characterized in that, with the second monomer MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, the polymeric matrix charge environment of the first monomers methyl methacrylate is regulated and controled, two monomers carry out copolymerization by suspension polymerisation mode, two kinds of monomer composition oil phases of described MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and methyl methacrylate, the consumption of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride is the 1-10wt% of oil phase quality, the consumption of methyl methacrylate monomer is the 90-99wt% of oil phase quality, adding oil phase quality 1wt%-10wt% halloysite nanotubes and copolymerization product realizes compound, then copolymerization product is mixed homogeneously with heat setting type dental base acrylic resin liquid, be heating and curing, according to following step, carry out:
(1) take MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and methyl methacrylate as comonomer, by suspension polymerisation, make, in suspension polymerization system, the volume ratio of water and oil phase is 1～5, described oil phase is by MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and two kinds of monomer compositions of methyl methacrylate, the consumption of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride is the 1-10wt% of oil phase quality, and the consumption of methyl methacrylate monomer is the 90-99wt% of oil phase quality; Described water is comprised of water, dispersant and surfactant, wherein the consumption of dispersant be two kinds of monomer masses and 2-3.5wt%, the consumption of surfactant be two kinds of monomer masses and 0.1-0.2wt%;
(2) in oil phase, add its quality 1wt%-10wt% nanotube galapectite, after ultrasonic dispersion, obtain suspension, this suspension and water are added in reactor, stir, pass into noble gas with remain on whole reactor in course of reaction in inert gas atmosphere, be warming up on the initiation temperature of initiator, add initiator with initiated polymerization simultaneously, obtain MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-methylmethacrylate copolymer A, the consumption of described initiator be two kinds of monomer masses and 0.5-2wt%;
(3) copolymer A of being prepared by step (2) is filtered and is washed, and obtains copolymer powder B after oven dry;
(4) by copolymer powder B and heat setting type dental base acrylic resin liquid according to mass ratio (1～2): 1, carry out mix homogeneously;
(5) mixture for the treatment of step (4) mix homogeneously enters dough after date and is taken out, and is filled in mould, and pressure is 2-4MPa;
(6) mould after filling is heating and curing, in the water of 70-80 ℃, heats 1.5-3.5h, then be warming up to 90-100 ℃, standing cooling after maintenance 1-3h, die sinking.
7. the preparation method of polymethyl acyl-oxygen ethyl-trimethyl salmiac-methyl methacrylate-galapectite denture base material according to claim 6, is characterized in that, the consumption of described nanotube galapectite is preferably the 1wt%-5wt% of oil phase quality; Described dispersant is a kind of in basic magnesium carbonate, calcium hydroxy phosphate, hydroxyethyl-cellulose or tricalcium phosphate, preferably hydroxyethyl-cellulose; The volume ratio of described water and oil phase is preferably 3; Described surfactant is a kind of in dodecylbenzene sodium sulfonate, sodium lauryl sulphate or sodium glycocholate, is preferably dodecylbenzene sodium sulfonate; Described initiator is a kind of in the own ester of azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide or peroxy dicarbonate two (2-ethyl), preferably azodiisobutyronitrile or benzoyl peroxide; Described noble gas is a kind of in nitrogen, helium or hydrogen.
8. the preparation method of polymethyl acyl-oxygen ethyl-trimethyl salmiac-methyl methacrylate-galapectite denture base material according to claim 6, it is characterized in that, in the time of on being heated to the initiation temperature of initiator, the preferred reaction time is 3-10 hour.
9. the preparation method of polymethyl acyl-oxygen ethyl-trimethyl salmiac-methyl methacrylate-galapectite denture base material according to claim 6, it is characterized in that, it is characterized in that, in described step (4), copolymer powder B and heat setting type dental base acrylic resin liquid are preferably 1.5:1 according to mass ratio; In described step (5), the preferred 3Mpa of pressure; In described step (6), preferably in the water of 70 ℃, heat 1.5h, then be warming up to 100 ℃, keep 1 rear standing cooling, die sinking.
10. the application of the polymethyl acyl-oxygen ethyl-trimethyl salmiac-methyl methacrylate-galapectite denture base material as described in one of claim 1-5 in denture base material.
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Cited By (7)
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| CN104945557A (en) * | 2015-06-26 | 2015-09-30 | 安徽师范大学 | Macroporous resin microsphere as well as preparation method and application thereof |
| CN105985602A (en) * | 2015-01-30 | 2016-10-05 | 天津大学 | Polymethyl methacrylate-carbon nanotube composite based on charge effect and preparation method thereof |
| CN105985601A (en) * | 2015-01-30 | 2016-10-05 | 天津大学 | Polymethyl methacrylate-carboxylated carbon nanotube composite based on charge conjugation synergism and preparation method thereof |
| CN106699955A (en) * | 2015-11-17 | 2017-05-24 | 天津大学 | Application for methacryloyloxyethylhexyldimethyl ammonium bromide in disperse silicon dioxide, composite material of methacryloyloxyethylhexyldimethyl ammonium bromide, and preparation method of composite material |
| CN106726627A (en) * | 2016-12-09 | 2017-05-31 | 苏州纳贝通环境科技有限公司 | Seamless tooth filling material and its preparation technology |
| CN110330258A (en) * | 2019-07-02 | 2019-10-15 | 安徽海螺新材料科技有限公司 | A kind of vertical mill grinding slag activity excitation type grinding aid |
| CN113499270A (en) * | 2021-07-13 | 2021-10-15 | 杭州佳杰齿科有限公司 | Denture base resin and preparation method thereof |
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| CN1746216A (en) * | 2005-06-24 | 2006-03-15 | 华南理工大学 | Preparation of polymer composite material from halloysite nanometer tube |
| CN102525828A (en) * | 2011-12-16 | 2012-07-04 | 天津大学 | Poly methyl acrylyl oxygen ethyl trimethyl ammonium chloride-methyl methacrylate-silica denture base material and preparation method thereof |
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| CN105985602B (en) * | 2015-01-30 | 2018-01-23 | 天津大学 | Polymethyl methacrylate-carbon nano tube compound material based on charge effect and preparation method thereof |
| CN105985602A (en) * | 2015-01-30 | 2016-10-05 | 天津大学 | Polymethyl methacrylate-carbon nanotube composite based on charge effect and preparation method thereof |
| CN105985601A (en) * | 2015-01-30 | 2016-10-05 | 天津大学 | Polymethyl methacrylate-carboxylated carbon nanotube composite based on charge conjugation synergism and preparation method thereof |
| CN105985601B (en) * | 2015-01-30 | 2018-01-23 | 天津大学 | Polymethyl methacrylate-carboxylation carbon nano tube compound material based on charge conjugation synergy and preparation method thereof |
| CN104945557A (en) * | 2015-06-26 | 2015-09-30 | 安徽师范大学 | Macroporous resin microsphere as well as preparation method and application thereof |
| CN104945557B (en) * | 2015-06-26 | 2017-10-17 | 安徽师范大学 | A kind of macroporous resin microspheres and its preparation method and application |
| CN106699955A (en) * | 2015-11-17 | 2017-05-24 | 天津大学 | Application for methacryloyloxyethylhexyldimethyl ammonium bromide in disperse silicon dioxide, composite material of methacryloyloxyethylhexyldimethyl ammonium bromide, and preparation method of composite material |
| CN106699955B (en) * | 2015-11-17 | 2019-08-09 | 天津大学 | Application and its composite material and preparation method of the methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide in dispersed silicon dioxide |
| CN106726627A (en) * | 2016-12-09 | 2017-05-31 | 苏州纳贝通环境科技有限公司 | Seamless tooth filling material and its preparation technology |
| CN110330258A (en) * | 2019-07-02 | 2019-10-15 | 安徽海螺新材料科技有限公司 | A kind of vertical mill grinding slag activity excitation type grinding aid |
| CN110330258B (en) * | 2019-07-02 | 2021-05-18 | 安徽海螺新材料科技有限公司 | Active excitation type grinding aid for grinding slag in vertical mill |
| CN113499270A (en) * | 2021-07-13 | 2021-10-15 | 杭州佳杰齿科有限公司 | Denture base resin and preparation method thereof |
| CN113499270B (en) * | 2021-07-13 | 2023-03-24 | 杭州佳杰齿科有限公司 | Denture base resin and preparation method thereof |
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Application publication date: 20140312 |