CN102552045B - Polymethylmethacrylate-silica composite denture base material as well as preparation method and application thereof - Google Patents

Polymethylmethacrylate-silica composite denture base material as well as preparation method and application thereof Download PDF

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CN102552045B
CN102552045B CN 201110425364 CN201110425364A CN102552045B CN 102552045 B CN102552045 B CN 102552045B CN 201110425364 CN201110425364 CN 201110425364 CN 201110425364 A CN201110425364 A CN 201110425364A CN 102552045 B CN102552045 B CN 102552045B
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base material
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CN102552045A (en
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郑俊萍
王佩佩
苏强
单佳慧
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Tianjin University
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Abstract

The invention discloses a polymethylmethacrylate-silica composite denture base material as well as a preparation method and application thereof. The polymethylmethacrylate-silica composite denture base material is prepared by through the following steps: suspending and gathering the following components in parts by weight: 100 parts of polymethylmethacrylate monomer and 1 to 10 parts of modified nano silica particles; uniformly mixing a suspended gathered product and thermally condensed denture water; and heating and solidifying. Nano SiO2 surface charge environment is used for modulation and control, and SiO2 is subjected to surface chemical modification by use of a coupling agent, namely gamma-methacryloyl-chloride-oxygroup-propyl-trimethoxy-silane (KH570). According to the SiO2 particles modified by using the method, the surfaces of the SiO2 particles are provided with unsaturated double-bond organic matters, so that the dispersion property of the SiO2 particles in a high-molecule base body is improved; and when the SiO2 particles are added into a high-polymer gathering system, the properties of the high-molecule base body can be improved greatly.

Description

The preparation method of a kind of polymethyl methacrylate-silicon dioxide composite denture base material
Technical field
The invention belongs to field of nanocomposite materials, more particularly, relate to a kind of nano silicon (SiO based on charge environment regulation and control modification 2) application of particle in PMMA, particularly take PMMA as matrix, utilize the charge environment regulation and control to fill nanometer SiO 2Particle, preparation PMMA based nano composite material.
Background technology
Nanometer SiO 2It is one of extremely important high-tech ultra-fine inorganic new material, owing to have quantum size effect, small-size effect, macro quanta tunnel effect and surface-interface effect, be presented as on the macroscopic view that specific surface area is large, surface energy is large, surface adsorption power is strong, and chemical purity is high, possess excellent performance at aspects such as resistance, thermal resistances, with its superior reinforcement, stability, thixotropy and thickening property, in numerous subjects and field, show unique characteristics, have the status of not replacing.Nanometer SiO 2Be commonly called as white carbon, be widely used in the every profession and trade as catalyst carrier, additive, delustering agent, depigmenting agent, rubber reinforcing filler, printing ink thickening agent, plastics filler, insulation and thermal insulation filler, the soft buffing compound of metal, high-grade daily-use cosmetics filler etc.
Nanometer SiO 2Molecularity is tridimensional network or claims three-dimensional chain structure, is amorphous white powder, and is the same with other nanoparticle, the surface all has hydroxyl and the unsaturated residual bond of different bond styles, the silica structure of stable state has been departed from the surface, but just because of this, nanometer SiO 2Particle is the very high activity of tool, has numerous characteristics, such as nanometer SiO 2Have anti-ultraviolet optical property, can reinforced filling, also have in addition the adsorpting pigment ion with the effect that reduces the pigment decay etc.Nanometer SiO 2Three kinds of dissimilar hydroxyls of the main existence in the surface of particle: the isolation hydroxyl, adjacent hydroxyl and two hydroxyl, the isolation hydroxyl mainly is present in the SiO that removes moisture 2The surface; Adjacent hydroxyl is present on the adjacent silicon atom, and is of crucial importance to the adsorption of polar substances; Two hydroxyls refer to be connected with simultaneously two hydroxyls on a silicon atom.Because the existence of surface hydroxyl causes nanometer SiO 2The particle surface effect is strong, easily reunites, and normally the form with secondary aggregate exists, thereby has limited nanometer SiO 2The performance of ultra-fine effect is difficult to disperse and infiltrate in polymeric matrix, and it can't normally be used in some field.Therefore must be to nanometer SiO 2Carry out surface modification, purpose is to change nanometer SiO 2The physico-chemical property on surface, the adhesion and the compatibility that improve itself and polymeric matrix improve its processing technique.Surface modification refers to adopt the methods such as chemistry, physics according to using needs particle surface to be modified, the physico-chemical property that the change particle surface of target is arranged, such as the activity that improves particle surface, improve dispersibility and the durability of particle, and add new physical and chemical performance and other characteristic etc. at particle surface.Because nanometer SiO 2Morphology of particles characteristics and surface characteristic, it must carry out surface modification as polymer filler or when being used for polymer modification, and the purpose of modification is to improve nanometer SiO 2The interface compatibility of particle and polymeric matrix, thus good interface binding power obtained.
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, take PMMA as base material, adopt the method for in-situ suspension polymerization to prepare PMMA/SiO 2Nano composite material is based on SiO 2The regulation and control of surface charge environment are to SiO 2Nano-filled thing carries out modification, changes polymeric reaction condition, and the adding of inorganic filler is on the impact of PMMA suspension polymerization system, composite property after the lower modification of research charge environment regulation and control.
Purpose of the present invention is achieved by following technical proposals:
A kind of polymethyl methacrylate-silica nanometer composite denture base material, made through suspension polymerisation by following component, 100 parts by weight of methylmethacrylate monomers, 1～10 weight portion are through the nano-silicon dioxide particle after the modification, with the solidifying type dental base acrylic resin liquid mix homogeneously of suspension polymerisation product and heat, be heating and curing again.
Nano-silicon dioxide particle after the modification of described process carries out according to following step:
Take by weighing 100 weight portion nanometer SiO 2Join in the xylene solution of the four n-octyl bromination ammoniums (TOAB) that contain the 0.1-0.5 weight portion, the silane coupler that fully adds the 0.1-3 weight portion after the dispersed with stirring, behind the ultra-sonic dispersion isothermal reaction under fluidized state of scattered suspension (can be selected at least 4 hours, preferred 4h-10h), question response carries out subsequent treatment after finishing, and obtains the lower silane coupler modified nanometer SiO of charge environment regulation and control 2
Above-mentioned subsequent treatment of carrying out can adopt following methods: the inorganic particulate suspension buchner funnel sucking filtration after will processing, again take acetone as solvent, behind the extracting 24h-48h, vacuum drying obtains the lower silane coupler modified nanometer SiO of charge environment regulation and control in apparatus,Soxhlet's 2
Described silane coupler is silane coupler KH570.
The consumption of described silane coupler is the 0.1-1 weight portion, preferred 0.1-0.3 weight portion.
Can adopt following scheme specifically: with 5g SiO 2Join in the dimethylbenzene of 150ml with 0.75gTOAB, add 1.5ml KH570 ultra-sonic dispersion after the dispersed with stirring, scattered suspension is poured in the there-necked flask, stir, heat up isothermal reaction 8h under fluidized state.With the inorganic particulate suspension buchner funnel sucking filtration after processing, again take acetone as solvent, behind the extracting 48h, vacuum drying obtains the nanometer SiO that charge environment is regulated and control lower KH-570 modification in apparatus,Soxhlet's 2, be designated as SiO 2-KH570 (TOAB).
Show unmodified nanometer SiO according to surface potential detection 2Particle surface shows elecrtonegativity, utilizes at nanometer SiO 2On the basis of surface charge environment conditioning, finish SiO 2The organic modification of surface of particle.Nanometer SiO 2The principle of adjustment and control of surface charge environment as shown in Figure 1, to SiO 2Particle carries out before the organic modification of surface, adds four n-octyl bromination ammoniums (TOAB) in oil-based solvent, treats can produce TOA after the TOAB dissolving +Ion, TOA +Contain four long alkyl chains in the structure, can in oil-based solvent, obtain good dispersibility, simultaneously again with positive charge.As nanometer SiO 2Particle joins when carrying out organic modification in the oil-based solvent, the surface elecrtonegativity make its can with TOA +In positive charge stronger electrostatic interaction occurs, make SiO 2The protective layer on surface changes to lipophile from hydrophilic, can impel SiO 2Particle is stable dispersion in oil-based solvent, and TOAB plays the effect of consisting of phase-transferring agent in system; While TOA +And SiO 2The electrostatic interaction on surface is to different-grain diameter SiO 2Action effect different, the SiO little to particle diameter 2Thereby can produce larger hydrophobic force it is entered in the modified system, and the SiO larger to particle diameter 2The hydrophobic force that produces is less to be difficult to make it to enter modified system, thereby just possesses the SiO that pair different-grain diameter is arranged 2Selection, and then confirm to enter SiO 2The surface modification system in objective subject be not SiO 2Aggregate, but the less dispersion of particle diameter nanometer SiO preferably 2
For the characterization of surfaces charge environment is regulated and control SiO 2The impact of modified effect, adopt U.S. Nicolet-5DX type infrared spectrometer to modification SiO 2Carry out FT-IR and analyze resolution 4cm -1, frequency range 4000-400cm -1Accompanying drawing 2 is original SiO 2, SiO 2-KH570 and SiO 2The FT-IR spectrogram of-KH570 (TOAB).From spectrogram, can see original SiO 2Spectral line a at 1150cm -1, 800cm -1Near absworption peak is arranged, corresponding SiO respectively 2The characteristic absorption peak of the asymmetric and symmetrical stretching vibration of middle Si-O, 3450cm -1Be surface hydroxyl stretching vibration absworption peak, original nanometer SiO is described 2Particle surface has a large amount of hydroxyls to exist.Through the corresponding SiO after the modification 2-KH570 and SiO 2Spectral line b, the c of-KH570 (TOAB) are all at 2950cm -1Near increased the flexible absworption peak of saturated C-H, at 1470cm -1Near methylene-CH has appearred 2-bending vibration absworption peak, and simultaneously at 1720cm -1Near carbonyl C=O stretching vibration peak has appearred.SiO 2After surface modification, all weaken to some extent corresponding to the stretching vibration absworption peak peak shape of surface hydroxyl, especially with SiO 2The peak shape of-KH570 (TOAB) is more weak, surface modification is described after, SiO 2The adsorbed hydroxyl content significantly reduces, and the amplitude that the modification of carrying out after the charge environment regulation and control reduces the adsorbed hydroxyl content is more obvious, illustrates that the regulation and control of charge environment are to nanometer SiO 2Modification play positive role.Before infrared spectrum detected, each sample had all passed through extracting in 48 hours, may be to detecting noisy impurity to remove.It can be said that bright, the organic group among the KH-570 and SiO 2Surface hydroxyl generation bonding reaction.
The preparation method of a kind of polymethyl methacrylate-silica nanometer composite denture base material, carry out according to following step:
(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) with the nanometer SiO of 1-10 weight portion based on charge environment regulation and control modification 2Particle and 100 weight portion MMA monomers mix, 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 the 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, to satisfy the PMMA/SiO of final preparation 2Small bead polymer meets the particle diameter requirement of denture base material.Described nanometer SiO based on charge environment regulation and control modification 2The consumption of particle is preferably the 1-5 weight portion.
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.
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.The PMMA/SiO of technical scheme of the present invention through preparing after the suspension polymerisation 2Small bead polymer satisfies the basic demand (such as particle diameter, weight average molecular weight) of denture base material, after toner is made into standard specimen, and purer PMMA resin, bending strength and hot strength all are greatly improved, and have successfully improved SiO 2Dispersibility in matrix has solved the problem that the PMMA denture base material particularly exists aspect bending strength aspect mechanical strength.
Description of drawings
Fig. 1 is nanometer SiO 2Surface charge environment conditioning sketch map.
Fig. 2 is original SiO 2With SiO after the modification 2The infrared spectrum spectrogram (adopt silane coupler KH570, a is original SiO 2, b is SiO 2-KH570, c are SiO 2-KH570 (TOAB)).
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:
Figure BDA0000121081480000051
Adopt following scheme: with 5g SiO 2Join in the dimethylbenzene of 150ml with 0.75gTOAB, add 1.5ml KH570 ultra-sonic dispersion after the dispersed with stirring, scattered suspension is poured in the there-necked flask, stir, heat up isothermal reaction 8h under fluidized state.With the inorganic particulate suspension buchner funnel sucking filtration after processing, again take acetone as solvent, behind the extracting 48h, vacuum drying obtains the nanometer SiO that charge environment is regulated and control lower KH-570 modification in apparatus,Soxhlet's 2, be designated as SiO 2-KH570 (TOAB) is carrying out following Preparation Example.
Embodiment 1
(1) with the nanometer SiO of 1.8g after based on charge environment regulation and control modification 2Particle and 60gMMA monomer (the monomer total amount is about 60mL) mix, 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 0.078g 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 polymethyl methacrylate-silicon dioxide nanocomposite to constant weight under 60 ℃ of conditions, is designated as PMMA/SiO 2-KH570 (TOAB);
(2) with PMMA/SiO 2The solidifying type dental base acrylic resin liquid of-KH570 (TOAB) (powder) and heat is carried out mix homogeneously according to 1: 1 mass ratio, and thing to be mixed enters the dough after date and 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) with the nanometer SiO of 0.6g after based on charge environment regulation and control modification 2Particle and 60g MMA monomer (the monomer total amount is 60mL) mix, suspension behind the ultra-sonic dispersion adds in the there-necked flask, in the 170ml deionized water, add simultaneously 1.8g 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 0.5g initiator B PO initiated polymerization.Reaction 9h, with the reaction system cold filtration, the cyclic washing filtration product, vacuum drying obtains polymethyl methacrylate-silicon dioxide nanocomposite to constant weight under 60 ℃ of conditions, is designated as PMMA/SiO 2-KH570 (TOAB);
(2) with PMMA/SiO 2The solidifying type dental base acrylic resin liquid of-KH570 (TOAB) (powder) and heat is carried out mix homogeneously according to 1: 1 mass ratio, and thing to be mixed enters the dough after date and 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) with the nanometer SiO of 3g after based on charge environment regulation and control modification 2Particle and 60g MMA monomer (the monomer total amount is 60mL) mix, suspension behind the ultra-sonic dispersion adds in the there-necked flask, in the 160ml deionized water, add simultaneously 1.82g hydroxyethyl-cellulose (HEC) and 0.073g 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 0.6g initiator B PO initiated polymerization.Reaction 9h, with the reaction system cold filtration, the cyclic washing filtration product, vacuum drying obtains polymethyl methacrylate-silicon dioxide nanocomposite to constant weight under 60 ℃ of conditions, is designated as PMMA/SiO 2-KH570 (TOAB);
(2) with PMMA/SiO 2The solidifying type dental base acrylic resin liquid of-KH570 (TOAB) (powder) and heat is carried out mix homogeneously according to 1: 1 mass ratio, and thing to be mixed enters the dough after date and 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) with the nanometer SiO of 6g after based on charge environment regulation and control modification 2Particle and 60g MMA monomer (the monomer total amount is 60mL) mix, suspension behind the ultra-sonic dispersion adds in the there-necked flask, in the 180ml deionized water, add simultaneously 1.6g 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 polymethyl methacrylate-silicon dioxide nanocomposite to constant weight under 60 ℃ of conditions, is designated as PMMA/SiO 2-KH570 (TOAB);
(2) with PMMA/SiO 2The solidifying type dental base acrylic resin liquid of-KH570 (TOAB) (powder) and heat is carried out mix homogeneously according to 1: 1 mass ratio, and thing to be mixed enters the dough after date and 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/SiO that the present invention obtains 2Artificial tooth base resin can carry out mechanical performance evaluation, the i.e. bending property of copolymer resins, tensile property 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 that the omnipotent mechanical test machine of M350-20KN type of embodiment 1-4 product utilization Britain Testometric company is carried out measuring mechanical property:
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.
Different SiO 2The mechanical performance (mass percent of improved silica and MMA monomer) of PMMA resin during-KH570 (TOAB) content
Figure BDA0000121081480000091
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-silica nanometer composite denture base material is characterized in that, is prepared 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) with the nanometer SiO of 1-10 weight portion based on charge environment regulation and control modification 2Particle and 100 weight portion MMA monomers mix, 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 the 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;
Wherein said nanometer SiO based on charge environment regulation and control modification 2Particle carries out according to following step:
Take by weighing 100 weight portion nanometer SiO 2Join in the xylene solution of the four n-octyl bromination ammoniums that contain the 0.1-0.5 weight portion, the silane coupler that fully adds the 0.1-3 weight portion after the dispersed with stirring, behind the ultra-sonic dispersion with the isothermal reaction under fluidized state of scattered suspension, question response carries out subsequent treatment after finishing, and obtains the lower silane coupler modified nanometer SiO of charge environment regulation and control 2
2. the preparation method of a kind of polymethyl methacrylate according to claim 1-silica nanometer composite denture base material, it is characterized in that described dispersant is a kind of in basic magnesium carbonate, calcium hydroxy phosphate, hydroxyethyl-cellulose (HEC) 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-silica nanometer composite denture base material is characterized in that, polymerization reaction time is 3-10 hour.
4. the preparation method of a kind of polymethyl methacrylate according to claim 1-silica nanometer composite denture base material is characterized in that, described nanometer SiO based on charge environment regulation and control modification 2The consumption of particle is preferably the 1-5 weight portion.
5. the preparation method of a kind of polymethyl methacrylate according to claim 1-silica nanometer composite denture base material, it 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.
6. the preparation method of a kind of polymethyl methacrylate according to claim 1-silica nanometer composite denture base material is characterized in that, the consumption of described silane coupler is the 0.1-1 weight portion.
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