CN102488623B - Preparation method of polymethyl methacrylate (PMMA)-silicon nanotube (SNT) composite denture base material - Google Patents
Preparation method of polymethyl methacrylate (PMMA)-silicon nanotube (SNT) composite denture base material Download PDFInfo
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Abstract
The invention discloses a polymethyl methacrylate (PMMA)-silicon nanotube (SNT) composite denture base material and a preparation method and an application thereof. The preparation method comprises the following steps of: suspending and polymerizing 100 parts by weight of methyl methacrylate monomers and 1-10 parts by weight of silicon nanotubes, uniformly mixing a product with a thermal coagulation dental base acrylic resin liquid; and heating and curing. In the invention, a PMMA/SNTs nano-composite material is prepared by adopting an in-situ suspension polymerization method, SNTs are taken as fillers, the performance of the PMMA is improved by performing SNTs in-situ filling, so that bending strength and tensile strength are improved greatly in comparison to pure PMMA resin, problems existing on the aspect of mechanical strength, in particular on the aspect of tensile strength of the PMMA denture base material are solved, and an oral rehabilitation material with excellent performance is obtained.
Description
Technical field
The invention belongs to the 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, utilize nano-tube to fill, 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 are also more and more higher to the requirement of oral cavity material, and simultaneously, retaining of tooth makes the spectrum of disease in oral cavity that change occur.According to the 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, the dental caries sum is more than 1,000,000,000.In the adult, patients with periodontal disease is about 80%, and 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 the embedding base decorates, adopted thiorubber. in 1885, nineteen thirty-seven, Germany Kulzer company released heat-curing type PMMA denture base material " Paladan " first, started new era of prosthetic dentistry, because its superior performance, easy and simple to handle, the bio-compatible performance is good, so far still as the first-selection of clinical practice.But, because 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, artificial tooth is indulged folding easily on causing in clinical repair, the phenomenon of rupture of base often occurs during interlock, therefore the mechanical performance of PMMA can not satisfy the requirement of Oral Repair fully, even if best clinical experience is arranged, the selection of indication, artificial tooth's arrangement and the most rational operating process, still there is the problem of mechanical strength aspect in the PMMA base material, particularly impact strength is relatively poor, often causes fractureing of base, and causes that dysbacteriosis causes denture stomatitis.
After nineteen ninety-five Nakamura team found Silica Nanotube (SNTs) first, increasing scientist had made a large amount of research to the function of its synthetic method, base attribute, various potential application.SNTs compares SiO
2Nano-powder has more superior physicochemical property, and is stable such as nanotube, is difficult for occuring and can hindering agglomeration etc., therefore, great for Research Significances such as the feature of SNTs and application.Applied research for SNTs deepens continuously in recent years, and is a lot of about the report of CNT and macromolecule formation composite, but then relatively less about the research of SNTs in composite.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, obtain the dental prosthetic material of excellent performance, adopt the method for in-situ suspension polymerization to prepare the PMMA/SNTs nano composite material, use nano-tube as implant, utilize the SNTs filling in situ to improve the properties of PMMA, realize compound on polymeric matrix and the inorganic decentralized photo nanoscale.
The present invention is achieved by following technical proposals:
A kind of polymethyl methacrylate-nano-tube composite denture base material, made through suspension polymerisation by following component, 100 parts by weight of methylmethacrylate monomers, 1～10 weight portion nano-tube, product and the solidifying type dental base acrylic resin liquid mix homogeneously of heat are heating and curing.
Described nano-tube adopts the ammonium tartrate template to be prepared the preferred 1-5 weight portion of its consumption.
A kind of polymethyl methacrylate-nano-tube composite denture base material, make with following method:
(1) with methyl methacrylate (MMA) as monomer, make by suspension polymerisation, in suspension polymerization system, the volume ratio of water and oil phase is 1～5, described oil phase is comprised of methyl methacrylate monomer, described water is comprised of water, dispersant and surfactant, and wherein the consumption of dispersant is 2～3.5wt% of monomer mass, and the consumption of surfactant is 0.1～0.2wt% of monomer mass
(2) 1-10 weight portion nano-tube (SNTs) and 100 weight portion MMA monomers are mixed, suspension behind the ultra-sonic dispersion and water add in the reactor, stir, passing into noble gas is in the inert gas atmosphere in course of reaction to remain on whole reactor, be warming up on the initiation temperature of initiator, add simultaneously initiator with initiated polymerization, obtain methyl methacrylate-silica polymer A, the consumption of described initiator is 0.5～2wt% of MMA monomer mass
(3) polymer A of step (2) preparation is filtered and washed, obtain polymer powder B after the oven dry
(4) with polymer powder B and the solidifying type dental base acrylic resin liquid of heat according to mass ratio (1～2): 1, carry out mix homogeneously
(5) mixture for the treatment of step (4) mix homogeneously enters the dough after date and is taken out, and is filled in the mould, and pressure is 2～4MPa
(6) mould after the filling is heating and curing, in 70～80 ℃ water, heats 1.5～3.5h, be warming up to again 90～100 ℃, keep leaving standstill cooling, die sinking behind 1～3h.
In the 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 the tricalcium phosphate, preferred 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 the 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) the own ester (EHP), preferred azodiisobutyronitrile (AIBN) or benzoyl peroxide (BPO); Described noble gas is a kind of in nitrogen, helium or the argon; In the time of on being heated to the initiation temperature of initiator, according to what of reactant, realize higher conversion ratio and meet the requirements of molecular weight that the preferred reaction time is 3-10 hour to guarantee monomer when the copolymerization sufficiently long time of needs polyreaction.The consumption of described dispersant and surfactant can be changed, and meets the particle diameter requirement of denture base material with the small bead polymer that satisfies final preparation.
In the preparation method of the present invention, in the described step (4), copolymer powder B is preferably 1.5: 1 with the solidifying type dental base acrylic resin liquid of heat according to mass ratio; In the described step (5), the preferred 3Mpa of pressure; In the described step (6), preferably in 70 ℃ water, heat 1.5h, be warming up to again 100 ℃, leave standstill cooling, die sinking after the maintenance 1.
The preparation of Silica Nanotube can be adopted the ammonium tartrate template among the present invention, as take by weighing quantitative D, L-TARTARIC ACID joins in the beaker of 500ml, add 250ml dehydrated alcohol and 3ml deionized water, ultrasonic to fully dissolving, then add the 36.5g ethyl orthosilicate under the room temperature condition, in 30 ℃ of waters bath with thermostatic control, leave standstill 30min after stirring.At last, add 112ml ammonia, under 30 ℃, continue to leave standstill 1h.The gained white gels with a large amount of deionized water cyclic washings until in the standard screen pH of solution be that neutrality stops.The gained white product namely obtains Silica Nanotube (SNTs) in 80 ℃ of lower freeze-day with constant temperature in the sieve, the preferred 1-5 weight portion of its consumption in preparation process (2).
The present invention utilizes Silica Nanotube that MMA is carried out modification, and except the structure that tubulose is arranged, some spherical silicon dioxide granule exists among the SNTs, and these tubuloses and spherical silicon dioxide granule disperse uniformly.When MMA and SNTs were compound, spherical particle can rotate effect with the SNTs of tubulose, has promoted SNTs to disperse in the MMA matrix, so the dispersibility of SNTs in the MMA matrix can be better.In addition, because the tubular structure among the SNTs is opening, so understand in the tube chamber that the strand of some MMA molecule enters into SNTs, this has also played certain crosslinked and potentiation.The pattern of SNTs is shown in Figure of description 1: SNTs is the square long straight tube of both ends open, and diameter is 200-300nm, about length 50 μ m.
In many denture base materials, small bead polymer (the pearl PMMA powder of being made by the process suspension polymerisation of methyl methacrylate (MMA) monomer, be dental base acrylic resin powder) be the main component of denture base material, weight average molecular weight is 60～1,000,000, particle diameter is 40～70 μ m, transmittance is more than 90%, and density is about 1.19g/cm
3The pearl PMMA powder of monomer polymerization preparation exists a lot of not enough in mechanical property.Technical scheme of the present invention satisfies the basic demand (such as particle diameter, weight average molecular weight) of denture base material through the small bead polymer of PMMA/SNTs for preparing after the suspension polymerisation, after toner is made into standard specimen, purer PMMA resin, bending strength and hot strength all are greatly improved, and have solved the problem that the PMMA denture base material particularly exists aspect hot strength aspect mechanical strength.
Description of drawings
Fig. 1 is the scanning electron microscope diagram (SEM) of the Silica Nanotube that makes with the ammonium tartrate template.
The specific embodiment
The present invention is further illustrated below in conjunction with specific embodiment.Further specify technical scheme of the present invention below in conjunction with specific embodiment.The solidifying type dental base acrylic resin liquid of the heat that embodiment selects is the artificial tooth base resin (I type) of Dentistry Material Plant, Shanghai Medical Machinery Co., Ltd., and composition is as shown in the table:
The preparation of the Silica Nanotube that uses can be adopted the ammonium tartrate template: take by weighing quantitative D, L-TARTARIC ACID joins in the beaker of 500ml, add 250ml dehydrated alcohol and 3ml deionized water, ultrasonic to fully dissolving, then add the 36.5g ethyl orthosilicate under the room temperature condition, in 30 ℃ of waters bath with thermostatic control, leave standstill 30min after stirring.At last, add 112ml ammonia, under 30 ℃, continue to leave standstill 1h.The gained white gels with a large amount of deionized water cyclic washings until in the standard screen pH of solution be that neutrality stops.The gained white product namely obtains Silica Nanotube (SNTs) in 80 ℃ of lower freeze-day with constant temperature in the sieve.
Embodiment 1
(1) 1.8g nano-tube (SNTs) and 60g MMA monomer (the monomer total amount is 60mL) are mixed, suspension behind the ultra-sonic dispersion adds in the there-necked flask, in the 170ml deionized water, add simultaneously 1.5g hydroxyethyl-cellulose (HEC) and 0.074g dodecylbenzene sodium sulfonate (SDBS), be poured in the there-necked flask after preliminary the stirring, continue stirring at low speed.Logical N
2Behind the protection 40min, be warming up to 90 ℃, and continue to keep inert atmosphere, add 0.4g initiator B PO initiated polymerization.Reaction 9h, with the reaction system cold filtration, the cyclic washing filtration product, vacuum drying obtains the PMMA/SNTs nano-complex to constant weight under 60 ℃ of conditions, is designated as PMMA/SNTs;
(2) PMMA/SNTs (powder) and the solidifying type dental base acrylic resin liquid of heat are carried out mix homogeneously according to 1: 1 mass ratio, thing to be mixed enters the dough after date and is taken out, and is filled in the mould, and pressure is 4Mpa;
(3) mould after the filling is heating and curing, in 70 ℃ water, heats 1.5h, be warming up to again 100 ℃, keep leaving standstill cooling, die sinking behind the 1h.
Embodiment 2
(1) 0.6g nano-tube (SNTs) and 60g MMA monomer (the monomer total amount is 60mL) are mixed, suspension behind the ultra-sonic dispersion adds in the there-necked flask, in the 150ml deionized water, add simultaneously 1.8g hydroxyethyl-cellulose (HEC) and 0.075g dodecylbenzene sodium sulfonate (SDBS), be poured in the there-necked flask after preliminary the stirring, continue stirring at low speed.Logical N
2Behind the protection 40min, be warming up to 90 ℃, and continue to keep inert atmosphere, add 0.5g initiator B PO initiated polymerization.Reaction 9h, with the reaction system cold filtration, the cyclic washing filtration product, vacuum drying obtains the PMMA/SNTs nano-complex to constant weight under 60 ℃ of conditions, is designated as PMMA/SNTs;
(2) PMMA/SNTs (powder) and the solidifying type dental base acrylic resin liquid of heat are carried out mix homogeneously according to 1: 1 mass ratio, thing to be mixed enters the dough after date and is taken out, and is filled in the mould, and pressure is 4Mpa;
(3) mould after the filling is heating and curing, in 70 ℃ water, heats 1.5h, be warming up to again 100 ℃, keep leaving standstill cooling, die sinking behind the 1h.
Embodiment 3
(1) 3g nano-tube (SNTs) and 60g MMA monomer (the monomer total amount is 60mL) are mixed, suspension behind the ultra-sonic dispersion adds in the there-necked flask, in the 150ml deionized water, add simultaneously 1.6g hydroxyethyl-cellulose (HEC) and 0.069g dodecylbenzene sodium sulfonate (SDBS), be poured in the there-necked flask after preliminary the stirring, continue stirring at low speed.Logical N
2Behind the protection 40min, be warming up to 90 ℃, and continue to keep inert atmosphere, add 0.5g initiator B PO initiated polymerization.Reaction 9h, with the reaction system cold filtration, the cyclic washing filtration product, vacuum drying obtains the PMMA/SNTs nano-complex to constant weight under 60 ℃ of conditions, is designated as PMMA/SNTs;
(2) PMMA/SNTs (powder) and the solidifying type dental base acrylic resin liquid of heat are carried out mix homogeneously according to 1: 1 mass ratio, thing to be mixed enters the dough after date and is taken out, and is filled in the mould, and pressure is 4Mpa;
(3) mould after the filling is heating and curing, in 70 ℃ water, heats 1.5h, be warming up to again 100 ℃, keep leaving standstill cooling, die sinking behind the 1h.
Embodiment 4
(1) 6g nano-tube (SNTs) and 60g MMA monomer (the monomer total amount is 60mL) are mixed, suspension behind the ultra-sonic dispersion adds in the there-necked flask, in the 150ml deionized water, add simultaneously 1.8g hydroxyethyl-cellulose (HEC) and 0.072g dodecylbenzene sodium sulfonate (SDBS), be poured in the there-necked flask after preliminary the stirring, continue stirring at low speed.Logical N
2Behind the protection 40min, be warming up to 90 ℃, and continue to keep inert atmosphere, add 0.5g initiator B PO initiated polymerization.Reaction 9h, with the reaction system cold filtration, the cyclic washing filtration product, vacuum drying obtains the PMMA/SNTs nano-complex to constant weight under 60 ℃ of conditions, is designated as PMMA/SNTs;
(2) PMMA/SNTs (powder) and the solidifying type dental base acrylic resin liquid of heat are carried out mix homogeneously according to 1: 1 mass ratio, thing to be mixed enters the dough after date and is taken out, and is filled in the mould, and pressure is 4Mpa;
(3) mould after the filling is heating and curing, in 70 ℃ water, heats 1.5h, be warming up to again 100 ℃, keep leaving standstill cooling, die sinking behind the 1h.
Comparative Examples
(1) 60mL MMA monomer is added in the there-necked flask, in the 180ml deionized water, add simultaneously 1.9g hydroxyethyl-cellulose (HEC) and 0.075g dodecylbenzene sodium sulfonate (SDBS), be poured in the there-necked flask after preliminary the stirring, continue stirring at low speed.Logical N
2Behind the protection 10min, be warming up to 100 ℃, add 0.5g initiator B PO initiated polymerization.10h is with the reaction system cold filtration in reaction, the cyclic washing filtration product.Vacuum drying obtains PMMA artificial tooth base resin powder to constant weight.
(2) PMMA artificial tooth base resin powder and the solidifying type dental base acrylic resin liquid of heat are carried out mix homogeneously according to 1.5: 1 mass ratio, thing to be mixed enters the dough after date and is taken out, and is filled in the mould, and pressure is 2Mpa;
(3) mould after the filling is heating and curing, in 70 ℃ water, heats 1.5h, be warming up to again 100 ℃, keep leaving standstill cooling, die sinking behind the 2h.
The PMMA/SNTs artificial tooth base resin that the present invention obtains can carry out the mechanical performance evaluation in the following ways
The standard specimen preparation
1, model preparation: with the wax shape test piece that rde wax flakes (2mm is thick) is made the standard specimen size, select dental flask, with Gypsum Fibrosum artificial tooth wax shape is embedded in the flask, after gypsum sets, with boiling water the wax fusing is washed down, make it to form the model with the chamber, and it is for subsequent use to be coated with separating medium in gypsum surface.
2, powder liquid is in harmonious proportion: gained copolymerization powder and the hot type dental base acrylic resin liquid of coagulating are mixed in mass ratio at 1.5: 1, and powder too much easily produces bubble, and liquid is crossed at most contraction greatly.After both mix, stir gently immediately and make powder liquid mix homogeneously, vibrate gently to get rid of simultaneously bubble.
3, leave standstill swelling: following variation is arranged after powder liquid is in harmonious proportion in time: 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 apparatus.Treat that concoction enters dough period, take out concoction, fully integrate with hands, with further mix homogeneously, then insert in the mould of preparation sample.
4, filling: all filling operation should be finished in dough period.Pressure testing one twice, finished edge is removed unnecessary resin, pressure 2～4MPa.
5, be heating and curing: heat 1.5h in 70 ℃ water, be rapidly heated to 100 ℃ again, keep leaving standstill cooling behind the 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 that the standard mechanics of bending sample that makes is loaded, until sample fracture, test fulcrum span is 50mm, and loading velocity is 5mm/min.
2, tensile property test: utilize omnipotent mechanical test machine that the standard tensile mechanics sample that makes is carried out extension test, rate of extension is 2mm/min.
It is as follows to utilize the omnipotent mechanical test machine of M350-20KN type of Britain Testometric company to carry out measuring mechanical property to embodiment 1-4 and Comparative Examples:
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 (the nano-tube consumption accounts for the mass percent of MMA monomer consumption) of PMMA resin during different SNTs content
More than the present invention has been done exemplary description; should be noted that; in the situation that does not break away 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 (6)
1. the preparation method of polymethyl methacrylate-nano-tube composite denture base material is characterized in that, prepares according to following step:
(1) with methyl methacrylate as monomer, make by suspension polymerisation, in suspension polymerization system, the volume ratio of water and oil phase is 1～5, described oil phase is comprised of methyl methacrylate monomer, described water is comprised of water, dispersant and surfactant, and wherein the consumption of dispersant is 2～3.5wt% of monomer mass, and the consumption of surfactant is 0.1～0.2wt% of monomer mass;
(2) 1-10 weight portion nano-tube and 100 weight portion MMA monomers are mixed, suspension behind the ultra-sonic dispersion and water add in the reactor, stir, passing into noble gas is in the inert gas atmosphere in course of reaction to remain on whole reactor, be warming up on the initiation temperature of initiator, add simultaneously initiator with initiated polymerization, obtain methyl methacrylate-silica polymer A, the consumption of described initiator is 0.5～2wt% of MMA monomer mass;
(3) polymer A of step (2) preparation is filtered and washed, obtain polymer powder B after the oven dry;
(4) with polymer powder B and the solidifying type dental base acrylic resin liquid of heat according to mass ratio (1～2): 1, carry out mix homogeneously;
(5) mixture for the treatment of step (4) mix homogeneously enters the dough after date and is taken out, and is filled in the mould, and pressure is 2～4MPa;
(6) mould after the filling is heating and curing, in 70～80 ℃ water, heats 1.5～3.5h, be warming up to again 90～100 ℃, keep leaving standstill cooling, die sinking behind 1～3h.
2. the preparation method of a kind of polymethyl methacrylate according to claim 1-nano-tube composite denture base material is characterized in that, described dispersant is a kind of in basic magnesium carbonate, calcium hydroxy phosphate, hydroxyethyl-cellulose or the tricalcium phosphate; 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 the sodium glycocholate; 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); Described noble gas is a kind of in nitrogen, helium or the argon.
3. the preparation method of a kind of polymethyl methacrylate according to claim 1-nano-tube composite denture base material is characterized in that, described dispersant is hydroxyethyl-cellulose; Described surfactant is dodecylbenzene sodium sulfonate; Described initiator is azodiisobutyronitrile or benzoyl peroxide.
4. the preparation method of a kind of polymethyl methacrylate according to claim 1-nano-tube composite denture base material is characterized in that, described nano-tube adopts the ammonium tartrate template to be prepared the preferred 1-5 weight portion of its consumption.
5. the preparation method of a kind of polymethyl methacrylate according to claim 1-nano-tube composite denture base material is characterized in that, reacts being heated on the initiation temperature of initiator, and the response time is 3-10 hour.
6. the preparation method of a kind of polymethyl methacrylate according to claim 1-nano-tube composite denture base material is characterized in that, in the described step (4), polymer powder B is preferably 1.5: 1 with the solidifying type dental base acrylic resin liquid of heat according to mass ratio; In the described step (5), the preferred 3Mpa of pressure; In the described step (6), preferably in 70 ℃ water, heat 1.5h, be warming up to again 100 ℃, keep leaving standstill cooling, die sinking behind the 1h.
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| 纳米管/纳米粒子杂化海藻酸凝胶固定化醇脱氢酶;陆杨;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20070715(第1期);B014-53 * |
| 陆杨.纳米管/纳米粒子杂化海藻酸凝胶固定化醇脱氢酶.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2007,(第1期),B014-53. |
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