CN103622836B - Poly-2-acrylamide-2-methylpro panesulfonic acid-methyl methacrylate-galapectite denture base material and preparation method - Google Patents
Poly-2-acrylamide-2-methylpro panesulfonic acid-methyl methacrylate-galapectite denture base material and preparation method Download PDFInfo
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- CN103622836B CN103622836B CN201310636380.3A CN201310636380A CN103622836B CN 103622836 B CN103622836 B CN 103622836B CN 201310636380 A CN201310636380 A CN 201310636380A CN 103622836 B CN103622836 B CN 103622836B
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- acrylamide
- methyl methacrylate
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- panesulfonic acid
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- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 38
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 26
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 21
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- 238000009998 heat setting Methods 0.000 claims abstract description 17
- 239000002071 nanotube Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
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- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 7
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- 239000000843 powder Substances 0.000 claims description 24
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- 238000011049 filling Methods 0.000 claims description 19
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- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 claims description 9
- -1 2-ethyl Chemical group 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
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- 230000000977 initiatory effect Effects 0.000 claims description 6
- 229910052756 noble gas Inorganic materials 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 4
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 4
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- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 3
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- 239000001506 calcium phosphate Substances 0.000 claims description 3
- CADZRPOVAQTAME-UHFFFAOYSA-L calcium;hydroxy phosphate Chemical compound [Ca+2].OOP([O-])([O-])=O CADZRPOVAQTAME-UHFFFAOYSA-L 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- OABYVIYXWMZFFJ-ZUHYDKSRSA-M sodium glycocholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(=O)NCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 OABYVIYXWMZFFJ-ZUHYDKSRSA-M 0.000 claims description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 3
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 3
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 3
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- DMYOHQBLOZMDLP-UHFFFAOYSA-N 1-[2-(2-hydroxy-3-piperidin-1-ylpropoxy)phenyl]-3-phenylpropan-1-one Chemical compound C1CCCCN1CC(O)COC1=CC=CC=C1C(=O)CCC1=CC=CC=C1 DMYOHQBLOZMDLP-UHFFFAOYSA-N 0.000 description 1
- 208000006819 Denture Stomatitis Diseases 0.000 description 1
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Landscapes
- Dental Preparations (AREA)
- Dental Prosthetics (AREA)
Abstract
The invention discloses a kind of poly-2-acrylamide-2-methylpro panesulfonic acid-methyl methacrylate-halloysite nanotubes denture base material and preparation method thereof, regulate and control with the polymeric matrix charge environment of second comonomer 2-acrylamide-2-methylpro panesulfonic acid to the first monomers methyl methacrylate, two monomers carry out copolymerization by suspension polymerisation mode, interpolation nanotube galapectite and copolymerization product realize compound, copolymerization product is mixed post-heating with heat setting type dental base acrylic resin liquid and solidifies.The present invention take methyl methacrylate as base material, the method of in-situ suspension polymerization is adopted to prepare nano composite material, realize regulating and controlling the charge environment of matrix, and add the nano-filled thing of galapectite and be polymerized, purer PMMA resin, bending strength and hot strength are all greatly improved, and successfully improve galapectite dispersibility in the base, solve PMMA denture base material particularly Problems existing in bending strength in mechanical strength.
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, it is particularly matrix with PMMA, regulation and control matrix charge environment, filled with nanotubes galapectite (HNTs), preparation PMMA based nano composite material.
Background technology
Along with progress and the growth in the living standard of society, people are increasingly strong to the requirement of aesthetic reparation, and also more and more higher to the requirement of oral cavity material, meanwhile, retaining of tooth makes the spectrum of disease in oral cavity there occurs change.According to interrelated data measuring and calculating, China's population morbidity of dental caries is 37%, and on average everyone has dental caries 2.47, and by 1,200,000,000 populations, nearly 500,000,000 people of national eurodonticus, dental caries sum is more than 1,000,000,000.In adult, patients with periodontal disease about 80%, this all can cause very a high proportion of dentition defect.The average agomphosis of over-65s elderly population 11.These all need to use dental prosthetic material to repair, and the market of visible China dental prosthetic material is very wide.
Adopt the natural and application of artificial material making basal seat area in prosthetic dentistry field, existing long history.Hardwood, animal bone, Dens Elephatis etc. is adopted to make embedding base decoration the earliest, within 1885, adopt thiorubber., nineteen thirty-seven, KulZer company of Germany released heat-curing type PMMA denture base material " Paladan " first, start new era of prosthetic dentistry, due to its superior performance, easy and simple to handle, bio-compatible performance good, so far still as the first-selection of clinical practice.But, due to the existence of 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, cause artificial tooth easily vertical folding in clinical repair, during occlusion, 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, the arrangement of artificial tooth 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 dysbacteriosis to cause denture stomatitis.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, with methyl methacrylate (PMMA) for base material, adopt the method for in-situ suspension polymerization to prepare PMMA nano composite material, object is the dental prosthetic material obtaining excellent performance.Be electropositive based on halloysite nanotubes (HNTs) inner surface electric charge, with charged monomer 2-acrylamide-2-methylpro panesulfonic acid (AMPS) and MMA copolymerization, realize regulating and controlling the charge environment of matrix, and add the nano-filled thing of HNTs and be polymerized, 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:
Poly-2-acrylamide-2-methylpro panesulfonic acid-methyl methacrylate-galapectite denture base material and preparation method, regulate and control with the polymeric matrix charge environment of second comonomer 2-acrylamide-2-methylpro panesulfonic acid to the first monomers methyl methacrylate, two monomers carry out copolymerization by suspension polymerisation mode, described 2-acrylamide-2-methylpro panesulfonic acid and methyl methacrylate two kinds of monomer composition oil phases, the consumption of 2-acrylamide-2-methylpro panesulfonic acid is the 1-10wt% of oil phase quality, the consumption of methyl methacrylate monomer is the 90-99wt% of oil phase quality, add oil phase quality lwt%-10wt% halloysite nanotubes (HNTs) and realize 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 lwt%-5wt% of oil phase quality
Specifically carry out according to following step:
Step 1, with 2-acrylamide-2-methylpro panesulfonic acid and methyl methacrylate for comonomer, obtained by suspension polymerisation, in suspension polymerization system, the volume ratio of aqueous phase and oil phase is 1 ~ 5, described oil phase is made up of 2-acrylamide-2-methylpro panesulfonic acid and methyl methacrylate two kinds of monomers, and the consumption of 2-acrylamide-2-methylpro panesulfonic acid is the 1-10wt% of oil phase quality, and the consumption of methyl methacrylate monomer is the 90-99wt% of oil phase quality; Described aqueous phase is made up 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%;
Step 2, its quality lwt%-10wt% nanotube galapectite is added in oil phase, suspension is obtained after ultrasonic disperse, this suspension and aqueous phase are added in reactor, stir, pass into noble gas to be in course of reaction in inert gas atmosphere to remain on whole reactor, on the initiation temperature being warming up to initiator, add initiator with initiated polymerization simultaneously, obtain 2-acrylamide-2-methylpro panesulfonic acid-methylmethacrylate copolymer A, the consumption of described initiator be two kinds of monomer masses and 0.5-2wt%;
Step 3, copolymer A step 2 prepared carries out filtering and washing, and obtains copolymer powder B after oven dry;
Step 4, by copolymer powder B and heat setting type dental base acrylic resin liquid according to mass ratio (1 ~ 2): 1, carries out mix homogeneously;
Step 5, treats that the mixture of step 4 mix homogeneously enters dough after date and taken out, and in a mold, pressure is 2-4MPa in filling;
Step 6, is heating and curing to the mould after filling, heats 1.5-3.5h, then be warming up to 90-100 DEG C in the water of 70-80 DEG C, leaves standstill cooling, die sinking after keeping 1-3h.
In suspension polymerization system of the present invention, described dispersant is the one in basic magnesium carbonate, calcium hydroxy phosphate (HAP), hydroxyethyl-cellulose (HEC) or tricalcium phosphate, preferred hydroxyethyl-cellulose (HEC); The volume ratio of described aqueous phase and oil phase is preferably 3; Described surfactant is the one in dodecylbenzene sodium sulfonate (SDBS), sodium lauryl sulphate (SDS) or sodium glycocholate, is preferably dodecylbenzene sodium sulfonate (SDBS); Described initiator is the one in azodiisobutyronitrile (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN), benzoyl peroxide (BPO) or peroxy dicarbonate two (2-ethyl) own ester (EHP), preferred azodiisobutyronitrile (AIBN) or benzoyl peroxide (BPO); Described noble gas is the one in nitrogen, helium or hydrogen; Time on the initiation temperature being heated to initiator, according to reactant number need the polyreaction sufficiently long time, to ensure that two kinds of monomers realize higher conversion ratio when copolymerization, the preferred reaction time is 3-10 hour.The consumption of described dispersant and surfactant can be exchanged, and meets the Particle size requirements of denture base material with the small bead polymer meeting 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 DEG C, heat 1.5h, then be warming up to 100 DEG C, leave standstill cooling after keeping 1, die sinking.
In many denture base materials, small bead polymer (the pearl PMMA powder be made up through suspension polymerisation of methyl methacrylate (MMA) monomer, i.e. 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 μm, transmittance is more than 90%, and density is about 1.19g/cm
3.Pearl PMMA powder prepared by monomer polymerization exists a lot of not enough in mechanical property.For research HNTs surface charge property and the electrostatic interaction between polymer matrices and HNTs, with the surperficial Zeta potential of the original HNTs of ZetaPALS type high-resolution Zeta potential test analysis of U.S. Brookhaven, composite nano-microsphere and copolymerization microsphere.Various particle dispersion to be measured is carried out ultrasonic disperse in deionized water, then fluid sample is joined in test ware and test.Show according to surface potential detection, 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 selects electronegative monomer 2-acrylamide-2-methylpro panesulfonic acid (AMPS) and MMA copolymerization, realize regulating and controlling the charge environment of matrix, to realize the better dispersion of HNTs in polymeric matrix, i.e. unmodified HNTs inner surface belt positive charge, added to the suspension copolymerization system situ compound tense of MMA and AMPS, AMPS can by electrostatic interaction enter into HNTs pipe in and with MMA copolymerization, inorganic filler and polymer are formed and runs through network, strengthen interface cohesion.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, after toner is made into standard specimen, purer PMMA resin, bending strength and hot strength are all greatly improved, successfully improve HNTs dispersibility in the base, solve PMMA denture base material particularly Problems existing in bending strength in mechanical strength.
Detailed description of the invention
Technical scheme of the present invention is further illustrated below in conjunction with specific embodiment.
What the HNTs used 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/D1.54 |
The heat setting type dental base acrylic resin liquid that embodiment is selected is the artificial tooth base resin (drum) of Dentistry Material Plant, Shanghai Medical Machinery Co., Ltd., and composition is as shown in the table:
Embodiment 1
(1) (monomer total amount is 60mL) in there-necked flask is added after being mixed by 1.8gAMPS and 58.2gMMA monomer, add 3gHNTs, suspension after ultrasonic disperse, in 150mL deionized water, add 1.5g hydroxyethyl-cellulose (HEC) and 0.075g dodecylbenzene sodium sulfonate (SDBS) simultaneously, be poured into after preliminary stirring in there-necked flask, continue stirring at low speed.Logical N
2after protection 40min, be warming up to 90 DEG C, and continue to keep inert atmosphere, add 0.4g initiator B PO initiated polymerization.Reaction 9h, by reaction system cold filtration, repeatedly use deionized water wash filtration product, at 60 DEG C, vacuum drying is to constant weight, obtains P (MMA-co-AMPS)/HNTs nano-complex;
(2) mixed homogeneously according to the mass ratio of 1:1 with heat setting type dental base acrylic resin liquid by P (MMA-AMPS)/HNTs copolymerization product (powder), thing to be mixed enters dough after date and is taken out, and in a mold, pressure is 4Mpa in filling;
(3) mould after filling is heating and curing, in the water of 70 DEG C, heats 1.5h, then be warming up to 100 DEG C, after keeping 1h, leave standstill cooling, die sinking.
Embodiment 2
(1) (monomer total amount is 60mL) in there-necked flask is added after being mixed by 3gAMPS and 57gMMA monomer, add 0.6gHNTs, suspension after ultrasonic disperse, in 150mL deionized water, add 1.8g hydroxyethyl-cellulose (HEC) and 0.067g dodecylbenzene sodium sulfonate (SDBS) simultaneously, be poured into after preliminary stirring in there-necked flask, continue stirring at low speed.Logical N
2after protection 40min, be warming up to 90 DEG C, and continue to keep inert atmosphere, add 0.4g initiator B PO initiated polymerization.Reaction 9h, by reaction system cold filtration, repeatedly use deionized water wash filtration product, at 60 DEG C, vacuum drying is to constant weight, obtains P (MMA-co-AMPS)/HNTs nano-complex;
(2) mixed homogeneously according to the mass ratio of 1:1 with heat setting type dental base acrylic resin liquid by P (MMA-AMPS)/HNTs copolymerization product (powder), thing to be mixed enters dough after date and is taken out, and in a mold, pressure is 4Mpa in filling;
(3) mould after filling is heating and curing, in the water of 70 DEG C, heats 1.5h, then be warming up to 100 DEG C, after keeping 1h, leave standstill cooling, die sinking.
Embodiment 3
(1) (monomer total amount is 60mL) in there-necked flask is added after being mixed by 6gAMPS and 54gMMA monomer, add 0.9gHNTs, suspension after ultrasonic disperse, in 150mL deionized water, add 1.6g hydroxyethyl-cellulose (HEC) and 0.075g dodecylbenzene sodium sulfonate (SDBS) simultaneously, be poured into after preliminary stirring in there-necked flask, continue stirring at low speed.Logical N
2after protection 40min, be warming up to 90 DEG C, and continue to keep inert atmosphere, add 0.6g initiator B PO initiated polymerization.Reaction 9h, by reaction system cold filtration, repeatedly use deionized water wash filtration product, at 60 DEG C, vacuum drying is to constant weight, obtains P (MMA-co-AMPS)/HNTs nano-complex;
(2) mixed homogeneously according to the mass ratio of 1:1 with heat setting type dental base acrylic resin liquid by P (MMA-AMPS)/HNTs copolymerization product (powder), thing to be mixed enters dough after date and is taken out, and in a mold, pressure is 4Mpa in filling;
(3) mould after filling is heating and curing, in the water of 70 DEG C, heats 1.5h, then be warming up to 100 DEG C, after keeping 1h, leave standstill cooling, die sinking.
Embodiment 4
(1) (monomer total amount is 60mL) in there-necked flask is added after being mixed by 6gAMPS and 54gMMA monomer, add 6gHNTs, suspension after ultrasonic disperse, in 150mL deionized water, add 1.8g hydroxyethyl-cellulose (HEC) and 0.072g dodecylbenzene sodium sulfonate (SDBS) simultaneously, be poured into after preliminary stirring in there-necked flask, continue stirring at low speed.After logical N2 protects 40min, be warming up to 90 DEG C, and continue to keep inert atmosphere, add 0.6g initiator B PO initiated polymerization.Reaction 9h, by reaction system cold filtration, repeatedly use deionized water wash filtration product, at 60 DEG C, vacuum drying is to constant weight, obtains P (MMA-co-AMPS)/HNTs nano-complex;
(2) mixed homogeneously according to the mass ratio of 1:1 with heat setting type dental base acrylic resin liquid by P (MMA-AMPS)/HNTs copolymerization product (powder), thing to be mixed enters dough after date and is taken out, and in a mold, pressure is 4Mpa in filling;
(3) mould after filling is heating and curing, in the water of 70 DEG C, heats 1.5h, then be warming up to 100 DEG C, after keeping 1h, leave standstill cooling, 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, be poured into after preliminary stirring in there-necked flask, continue stirring at low speed.Logical N
2after protection 10min, be warming up to 100 DEG C, 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) mixed homogeneously according to the mass ratio of 1:1 with heat setting type dental base acrylic resin liquid by PMMA artificial tooth base resin powder, thing to be mixed enters dough after date and is taken out, and in a mold, pressure is 4Mpa in filling;
(3) mould after filling is heating and curing, in the water of 70 DEG C, heats 1.5h, then be warming up to 100 DEG C, after keeping 1h, leave standstill cooling, die sinking.
P (MMA-co-AMPS)/HNTs artificial tooth base resin that the present invention obtains can carry out bending property, the tensile property that mechanical performance evaluates copolymer resins in the following ways
Prepared by standard specimen
1. model preparation: the wax shape test piece of making 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 the model forming band chamber, and in gypsum surface, be coated with separating medium for subsequent use.
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, and liquid is crossed and shunk greatly at most.After both mixing, stir gently immediately and make powder liquid mix homogeneously, vibrate gently to get rid of bubble simultaneously.
3. leave standstill swelling: powder liquid has following change after being in harmonious proportion in time: damp sand phase, pasty state phase, haircuts phase, dough period, firmly admittedly phase.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, fully integrate with hands, with further mix homogeneously, then insert and prepare in the mould of sample.
4. filling: all filling operation should complete in dough period.Pressure testing one twice, finished edge removes unnecessary resin, pressure 2-4MPa.
5. be heating and curing: in the water of 70 DEG C, heat 1.5h, then be rapidly heated to 100 DEG C, leave standstill cooling after keeping 1h, die sinking, polishes smooth sample by No. 280, No. 400, No. 800, No. 1200 and No. 2000 sand paper successively,
Measuring mechanical property
1. bending property test: utilize omnipotent mechanics machine to load obtained standard mechanics of bending sample, until sample fracture, test fulcrum span is 50mm, and loading velocity is 5mm/min.
2. tensile property test: utilize omnipotent mechanics machine to carry out extension test to obtained standard tensile mechanics sample, rate of extension is 2mm/min.
Measuring mechanical property carries out to the omnipotent mechanics machine of M350-20KN type of Testometric company of embodiment 1-4 product utilization Britain as follows:
1. bending property test: For Three Points Bending Specimen size 64 × 10 × 3.3mm, loads until sample fracture, and test fulcrum span is 50mm, and 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 (HNTs and two kind of monomer mass and percent) of PMMA copolymer resin during different HNTs content
Above to invention has been exemplary description; should be noted that; when not departing from core of the present invention, any simple distortion, amendment or other those skilled in the art can not spend the equivalent replacement of creative work all to fall into protection scope of the present invention.
Claims (10)
1. poly-2-acrylamide-2-methylpro panesulfonic acid-methyl methacrylate-galapectite denture base material, it is characterized in that, regulate and control with the polymeric matrix charge environment of second comonomer 2-acrylamide-2-methylpro panesulfonic acid to the first monomers methyl methacrylate, two monomers carry out copolymerization by suspension polymerisation mode, described 2-acrylamide-2-methylpro panesulfonic acid and methyl methacrylate two kinds of monomer composition oil phases, the consumption of 2-acrylamide-2-methylpro panesulfonic acid is the 1-10wt% of oil phase quality, the consumption of methyl methacrylate monomer is the 90-99wt% of oil phase quality, interpolation oil phase quality lwt%-10wt% halloysite nanotubes and copolymerization product realize compound, then copolymerization product is mixed homogeneously with heat setting type dental base acrylic resin liquid, be heating and curing,
Carry out according to following step:
Step 1, with 2-acrylamide-2-methylpro panesulfonic acid and methyl methacrylate for comonomer, obtained by suspension polymerisation, in suspension polymerization system, the volume ratio of aqueous phase and oil phase is 1 ~ 5, described oil phase is made up of 2-acrylamide-2-methylpro panesulfonic acid and methyl methacrylate two kinds of monomers, and the consumption of 2-acrylamide-2-methylpro panesulfonic acid is the 1-10wt% of oil phase quality, and the consumption of methyl methacrylate monomer is the 90-99wt% of oil phase quality; Described aqueous phase is made up 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%;
Step 2, its quality lwt%-10wt% nanotube galapectite is added in oil phase, suspension is obtained after ultrasonic disperse, this suspension and aqueous phase are added in reactor, stir, pass into noble gas to be in course of reaction in inert gas atmosphere to remain on whole reactor, on the initiation temperature being warming up to initiator, add initiator with initiated polymerization simultaneously, obtain 2-acrylamide-2-methylpro panesulfonic acid-methylmethacrylate copolymer A, the consumption of described initiator be two kinds of monomer masses and 0.5-2wt%;
Step 3, copolymer A step 2 prepared carries out filtering and washing, and obtains copolymer powder B after oven dry;
Step 4, by copolymer powder B and heat setting type dental base acrylic resin liquid according to mass ratio (1 ~ 2): 1, carries out mix homogeneously;
Step 5, treats that the mixture of step 4 mix homogeneously enters dough after date and taken out, and in a mold, pressure is 2-4MPa in filling;
Step 6, is heating and curing to the mould after filling, heats 1.5-3.5h, then be warming up to 90-100 DEG C in the water of 70-80 DEG C, leaves standstill cooling, die sinking after keeping 1-3h.
2. poly-2-acrylamide-2-methylpro panesulfonic acid-methyl methacrylate-galapectite denture base material according to claim 1, it is characterized in that, the consumption of described nanotube galapectite is the lwt%-5wt% of oil phase quality.
3. poly-2-acrylamide-2-methylpro panesulfonic acid-methyl methacrylate-galapectite denture base material according to claim 1, it is characterized in that, described dispersant is the one in basic magnesium carbonate, calcium hydroxy phosphate, hydroxyethyl-cellulose or tricalcium phosphate; The volume ratio of described aqueous phase and oil phase is 3; Described surfactant is the one in dodecylbenzene sodium sulfonate, sodium lauryl sulphate or sodium glycocholate; Described initiator is the one in azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide or peroxy dicarbonate two (2-ethyl) own ester; Described noble gas is the one in nitrogen, helium or hydrogen.
4. poly-2-acrylamide-2-methylpro panesulfonic acid-methyl methacrylate-galapectite denture base material according to claim 1, it is characterized in that, time on the initiation temperature being heated to initiator, the response time is 3-10 hour.
5. poly-2-acrylamide-2-methylpro panesulfonic acid-methyl methacrylate-galapectite denture base material according to claim 1, is characterized in that, in described step 4, copolymer powder B and heat setting type dental base acrylic resin liquid are 1.5:1 according to mass ratio; In described step 5, pressure is 3Mpa; In described step 6, in the water of 70 DEG C, heat 1.5h, then be warming up to 100 DEG C, after keeping 1h, leave standstill cooling, die sinking.
6. the preparation method of poly-2-acrylamide-2-methylpro panesulfonic acid-methyl methacrylate-galapectite denture base material, it is characterized in that, regulate and control with the polymeric matrix charge environment of second comonomer 2-acrylamide-2-methylpro panesulfonic acid to the first monomers methyl methacrylate, two monomers carry out copolymerization by suspension polymerisation mode, described 2-acrylamide-2-methylpro panesulfonic acid and methyl methacrylate two kinds of monomer composition oil phases, the consumption of 2-acrylamide-2-methylpro panesulfonic acid is the 1-10wt% of oil phase quality, the consumption of methyl methacrylate monomer is the 90-99wt% of oil phase quality, interpolation oil phase quality lwt%-10wt% halloysite nanotubes and copolymerization product realize compound, then copolymerization product is mixed homogeneously with heat setting type dental base acrylic resin liquid, be heating and curing,
Carry out according to following step:
Step 1, with 2-acrylamide-2-methylpro panesulfonic acid and methyl methacrylate for comonomer, obtained by suspension polymerisation, in suspension polymerization system, the volume ratio of aqueous phase and oil phase is 1 ~ 5, described oil phase is made up of 2-acrylamide-2-methylpro panesulfonic acid and methyl methacrylate two kinds of monomers, and the consumption of 2-acrylamide-2-methylpro panesulfonic acid is the 1-10wt% of oil phase quality, and the consumption of methyl methacrylate monomer is the 90-99wt% of oil phase quality; Described aqueous phase is made up 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%;
Step 2, its quality lwt%-10wt% nanotube galapectite is added in oil phase, suspension is obtained after ultrasonic disperse, this suspension and aqueous phase are added in reactor, stir, pass into noble gas to be in course of reaction in inert gas atmosphere to remain on whole reactor, on the initiation temperature being warming up to initiator, add initiator with initiated polymerization simultaneously, obtain 2-acrylamide-2-methylpro panesulfonic acid-methylmethacrylate copolymer A, the consumption of described initiator be two kinds of monomer masses and 0.5-2wt%;
Step 3, copolymer A step 2 prepared carries out filtering and washing, and obtains copolymer powder B after oven dry;
Step 4, by copolymer powder B and heat setting type dental base acrylic resin liquid according to mass ratio (1 ~ 2): 1, carries out mix homogeneously;
Step 5, treats that the mixture of step 4 mix homogeneously enters dough after date and taken out, and in a mold, pressure is 2-4MPa in filling;
Step 6, is heating and curing to the mould after filling, heats 1.5-3.5h, then be warming up to 90-100 DEG C in the water of 70-80 DEG C, leaves standstill cooling, die sinking after keeping 1-3h.
7. the preparation method of poly-2-acrylamide-2-methylpro panesulfonic acid-methyl methacrylate-galapectite denture base material according to claim 6, it is characterized in that, the consumption of described nanotube galapectite is the lwt%-5wt% of oil phase quality; Described dispersant is the one in basic magnesium carbonate, calcium hydroxy phosphate, hydroxyethyl-cellulose or tricalcium phosphate; The volume ratio of described aqueous phase and oil phase is 3; Described surfactant is the one in dodecylbenzene sodium sulfonate, sodium lauryl sulphate or sodium glycocholate; Described initiator is the one in azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide or peroxy dicarbonate two (2-ethyl) own ester; Described noble gas is the one in nitrogen, helium or hydrogen.
8. the preparation method of poly-2-acrylamide-2-methylpro panesulfonic acid-methyl methacrylate-galapectite denture base material according to claim 6, it is characterized in that, time on the initiation temperature being heated to initiator, the response time is 3-10 hour.
9. the preparation method of poly-2-acrylamide-2-methylpro panesulfonic acid-methyl methacrylate-galapectite denture base material according to claim 6, it is characterized in that, in described step 4, copolymer powder B and heat setting type dental base acrylic resin liquid are 1.5:1 according to mass ratio; In described step 5, pressure is 3Mpa; In described step 6, in the water of 70 DEG C, heat 1.5h, then be warming up to 100 DEG C, after keeping 1h, leave standstill cooling, die sinking.
10. the poly-2-acrylamide-2-methylpro panesulfonic acid-methyl methacrylate-galapectite denture base material as described in one of claim 1-5 is in the application in denture base material.
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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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| Title |
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| "可乳化共聚单体AMPS用于超声无皂乳液聚合的研究";王艳丽;谭德新;徐初阳;闵凡飞;;《化学世界》;20091231;第15-18页 * |
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