CN101167684A - Method for preparing fluorine-silica rubber artificial tooth soft lining material - Google Patents
Method for preparing fluorine-silica rubber artificial tooth soft lining material Download PDFInfo
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Abstract
The invention belongs to the technology field of biological medical high polymer materials, and concretely relates to a process for preparing soft lining material of fluorosilicone rubber false toot. The concrete steps comprise charging modified silicone oil which is made from acrylic mixing monomer to nonmonomerd hydroxyl silicone oil, and charging silane cross linking agent, ethylene glycol dimethacrylate, and white carbon black, by which modified silicone oil with a certain degree of polymerization and cross linking is made, charging the fluorosilicone rubber on the sealing end of the hydroxyl group, by which the fluorosilicone rubber is made. The silicon sulfide rubber with the room temperature is made by the mixing and reaction of the two kinds of rubber. The invention has the advantages of reasonable preparing line, easily available raw materials, relatively low cost, simple synthetic technology and has significant values of popularizing and using.
Description
Technical field
The invention belongs to the biological medical polymer material technical field, be specifically related to a kind of preparation method of fluorine-silica rubber artificial tooth soft lining material.
Background technology
The oral cavity biomaterial is a big branch of biomaterial, also is the important component part of bio-medical material.Soft liner materials for denture is an ingredient of oral cavity biomaterial, claims the flexible denture gasket material again.
The comparison of rising about the research of soft liner materials for denture early.At the beginning of the forties, along with the beginning that acrylics is used on dental prosthetic, people just begin to expect adopting flexible plastic making base or rubber blanket in duroplasts base tissue surface, and the patient may be more comfortable after wearing artificial tooth like this.1945, Matthews used plastifying gel polyvinyl chloride first, but owing to solidification temperature up to 160 ℃ and the unendurable shortcoming of elasticity be eliminated.Occurred plastifying acrylic compounds and silicone rubber soft lining material subsequently in succession, the soft lining material that grows up after the sixties also has hydrogel class, polyurethane etc.
What soft liner materials for denture research at present was maximum, most widely used is esters of acrylic acid and silicone rubber kinds.
The esters of acrylic acid soft liner materials for denture is divided into heat-curing type and self-solidifying type two classes.This type of soft lining material dissolves each other easily at bonding interface, can form good binding with polymethyl methacrylate (PMMA) base.Include monomerics, slowly from material, separate out when meeting water or saliva, material is followed the string and hardening.
The silicone rubber soft lining material can be divided into four kinds, i.e. thermohardening type silicone rubber soft lining material, one-component silicone rubber denture liner material, condensed type silicone rubber denture liner material and addition-type silicon rubber denture liner material.This type of soft lining material good biocompatibility, good springiness, technology is simple but mycete is easily grown in existence, and adhesive property is poor, and curing rate waits shortcoming slowly.
Poly-phosphazine fluoroelastomer class soft lining material is that Gettleman released in 1984, and the adhesive strength that the flexibility of this type of material reaches artificial tooth all makes moderate progress.The clinical practice of this kind product is less, at present unique clinical commodity Novus by name that is applied to.Discoveries such as Kawano are compared with other soft lining materials, and the adhesive property of it and basal seat area is the highest, and viscoelasticity is higher, and its dissolubility is also lower.
At present external soft lining material development relatively lags behind, and external soft lining material has the product of a lot of brands, but pluses and minuses are all respectively arranged based on silicone rubber kinds and plastifying esters of acrylic acid material, does not still have a kind of product of high comprehensive performance.The soft lining material of domestic marketization still belongs to blank.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of fluorine-silica rubber artificial tooth soft lining material.
The preparation method of the fluorine-silica rubber artificial tooth soft lining material that the present invention proposes, concrete steps are as follows:
(1) organic solvent and hydroxy silicon oil are placed there-necked flask, the addition of organic solvent is 0.5-2 a times of hydroxy silicon oil volume, and there-necked flask is furnished with motor stirrer, condensing tube and thermometer, mix homogeneously, again the acrylic compounds mix monomer is packed in the Dropping funnel, place on the there-necked flask, at N
2Protection down, under catalyst action, under 50-100 ℃ of bath temperature, polymerization reaction take place, dropwise addition of acrylic acid class mix monomer during the reaction beginning, after treating that the acrylic compounds mix monomer dropwises, add organic solvent again, the addition of organic solvent is 0.5-2 a times of hydroxy silicon oil volume, polymerization reaction time is 1-5 hour, promptly get modified silicon oil, wherein, acrylic compounds mix monomer addition is the 2%-28% of hydroxy silicon oil weight;
(2) modified silicon oil with step (1) gained joins in the unmodified hydroxy silicon oil, the addition of modified silicon oil is 0.1-0.3 a times of hydroxy silicon oil volume, under nitrogen atmosphere, under the silane crosslinker effect, reaction is 0.5-2 hour under 30-80 ℃ of temperature, and the silane crosslinker addition is 0.1-0.3 a times of hydroxy silicon oil volume; Then add Ethylene glycol dimethacrylate (EDMA), continue reaction 0.5-2 hour, the Ethylene glycol dimethacrylate addition is 10% of a hydroxy silicon oil volume; And then adding white carbon through coupling agent treatment, the addition of white carbon is the 5%-24% of hydroxy silicon oil volume, continues reaction 2-4h, add silane crosslinker again, reacted 0.5-2 hour, the silane crosslinker addition is 0.1-0.3 a times of hydroxy silicon oil volume, promptly gets modified silicon rubber;
(3) hydroxy-end capped fluorosioloxane rubber is joined in the three-necked bottle of the nitrogen of having friendly relations, and the white carbon of adding coupling agent treatment, behind the mix homogeneously, add coupling agent, reacted 0.5-2 hour, promptly get and have certain degree of polymerization and crosslinked fluorosioloxane rubber, the coupling agent addition is the 20%-50% of hydroxy-end capped fluorosioloxane rubber weight, and the addition of white carbon is the 5%-15% of coupling agent volume;
(4) the treated fluorosioloxane rubber hybrid reaction of the modified silicon rubber of step (2) gained and step (3) gained after 0.5-2 hour, is dripped dibutyl tin laurate and di-n-butylamine, reacted 0.5-2 hour, promptly get room temperature vulcanized silicone rubber; The dibutyl tin laurate addition is the 15-50% of modified silicon rubber quality, and the addition of di-n-butylamine is the 15-50% of modified silicon rubber quality; Treated fluorosioloxane rubber addition is the 5-30% of modified silicon rubber quality;
(5) with behind step (4) the gained room temperature vulcanized silicone rubber moulding, place vacuum drying oven, under 30-80 ℃ of temperature, took out bubble 1-3 hour, place constant temperature oven then, under 50-100 ℃ of temperature, post vulcanization 2-6 hour, promptly get required product.
Among the present invention, organic solvent described in the step (1) is in toluene, dimethylbenzene, vinylacetate or the butyl acetate etc. one to two kind.
Among the present invention, acrylic compounds mix monomer described in the step (1) is in butyl acrylate, methyl methacrylate, methacrylic acid or the senecioate-hydroxypropyl acrylate etc. one to two kind.
Among the present invention, catalyst described in the step (1) is in azodiisobutyronitrile, p-methyl benzenesulfonic acid or the dibenzoyl peroxide etc. one to two kind, and the catalyst addition is the 0.5-2% of mixed solution gross mass.
Among the present invention, silane crosslinker described in the step (2) be in methyl tributanoximo silane, vinyl tributanoximo silane, MTMS, MTES or the methyl triacetoxysilane etc. any.
Among the present invention, the modified silicon rubber structure of step (2) gained is as follows:
Among the present invention, the fluorosioloxane rubber structural formula is as follows described in the step (3):
Among the present invention, coupling agent described in the step (3) be in KH-550, KH-560, KH-570, NDZ-201, NDZ-311, NDZ-401 or Nanjing University-42 (anilinomethyl triethoxysilane) etc. any.
The present invention be have that good mechanical property particularly bonds and the silicone rubber basis of hot strength on, add the fluorine silicon rubber components, it is good and have than high bond strength with base PMMA and have the fluorine-containing modified silicon rubber soft lining material of excellent antibacterial effect to develop in oral environment medium-resistance.
The present invention is in basic maintenance silicone rubber soft lining material mechanical property, adding fluorosioloxane rubber component has improved the resistance to medium of material itself, reduced water absorption rate, dissolution rate, and significantly improved anti-microbial property, its comprehensive physical and mechanical properties satisfies clinical requirement substantially.In the oral cavity material field wide application prospect is arranged.Its preparation circuit is reasonable, raw material is easy to get, and the relatively cheap synthesis technique of price is simple, has important promotion and application and is worth.
Soft lining material of the present invention compare with the ordinary silicon elastomeric material basic keep silicone rubber soft lining material mechanical property in, improved soft lining material itself medium-resistance, reduced water absorption rate, dissolution rate.
Description of drawings
Fig. 1 is the SEM collection of illustrative plates of embodiment 1.
Fig. 2 is the AFM collection of illustrative plates of embodiment 2.
Fig. 3 is the SEM collection of illustrative plates of embodiment 3.
Fig. 4 is the AFM collection of illustrative plates of embodiment 4.
Fig. 5 is the SEM collection of illustrative plates of embodiment 6.
The specific embodiment
Further specify the present invention below by embodiment.
Embodiment 1
1, acrylic compounds mix monomer modified silicon rubber:
1: 1 mixed solvent of 100ml toluene and vinylacetate is mixed with the 100ml hydroxy silicon oil, the mix homogeneously in the Dropping funnel of again 28ml butyl acrylate, 8ml methyl methacrylate, 2ml methacrylic acid, 2ml senecioate-hydroxypropyl acrylate being packed into, and install to be furnished with motor stirrer, on the there-necked flask of condensing tube, thermometer, put in the water-bath and heat, feed N
2Protection; When the mixed solution temperature reaches 70 ℃, add refined azodiisobutyronitrile 1g and p-methyl benzenesulfonic acid 1g, beginning dropwise addition of acrylic acid class mix monomer, polyreaction is carried out about 70 ℃; The acrylic compounds mix monomer adds 1: 1 mixed solvent of 100ml toluene and vinylacetate after dripping and becoming fully again, and dropwise reaction 3h promptly gets modified silicon oil altogether.
2, fluorosioloxane rubber and modified silicon rubber co-vulcanization:
The modified silicon oil of 15ml is joined in the unmodified hydroxy silicon oil of 100ml, in the three-necked bottle of nitrogen of having friendly relations, add 10ml methyl tributanoximo silane cross-linking agent, under 50 ℃ of environment, react 1h, after adding Ethylene glycol dimethacrylate (EDMA) 10ml, continue reaction 1h, add the white carbon 21% that Nanjing University-42 handles, after continuing reaction 4h, add methyl tributanoximo silane cross-linking agent 10ml again, response time 0.5h promptly gets modified silicon rubber;
The hydroxy-end capped fluorosioloxane rubber of 15ml is joined in the three-necked bottle of the nitrogen of having friendly relations, and add the white carbon that Nanjing University-42 handles.Behind the mix homogeneously, add Nanjing University-425ml, reaction 1h obtains having certain degree of polymerization and crosslinked fluorosioloxane rubber;
With 15ml modified silicon rubber and the treated two kinds of rubber mix of fluorosioloxane rubber of 1ml, after continuing to react 1h, drip dibutyl tin laurate and di-n-butylamine 5ml, reaction 1h stopped reaction is made room temperature vulcanized silicone rubber; Behind the room temperature vulcanized silicone rubber moulding of making, put into 50 ℃ of vacuum drying ovens and take out bubble 2h; Put into 80 ℃ of post vulcanization 4h of constant temperature oven, obtain product.
The agglutinating hot strength of products obtained therefrom and PMMA is 1.03MPa, and water absorption rate is 0.23%, and dissolution rate is 0.10%, Shao Shi (A type) hardness number 37, and bacteriostasis rate 60%, Fig. 1 are scanning electron microscope (SEM) photo after the tension failure.
Embodiment 2
1, acrylic compounds mix monomer modified silicon rubber:
1: 1 mixed solvent of 150ml dimethylbenzene and butyl acetate is mixed with the 100ml hydroxy silicon oil, the mix homogeneously in the Dropping funnel of again 28ml butyl acrylate, 8ml methyl methacrylate, 2ml methacrylic acid, 2ml senecioate-hydroxypropyl acrylate being packed into, and install to be furnished with motor stirrer, on the there-necked flask of condensing tube, thermometer, put in the water-bath and heat, feed N
2Protection; When the mixed solution temperature reaches 50 ℃, add refined azodiisobutyronitrile 2g, beginning dropwise addition of acrylic acid class mix monomer, polyreaction is carried out about 50 ℃; The acrylic compounds mix monomer drips complete Cheng Houzai and adds 150ml toluene and 1: 1 mixed solvent of vinyl acetate, and dropwise reaction 5h promptly gets modified silicon oil altogether.
2, fluorosioloxane rubber and modified silicon rubber co-vulcanization:
The modified silicon oil of 5ml is joined in the unmodified hydroxy silicon oil of 100ml, in the three-necked bottle of nitrogen of having friendly relations, add 10ml methyl tributanoximo silane cross-linking agent, under 800 ℃ of environment, react 0.5h, after adding Ethylene glycol dimethacrylate (EDMA) 10ml, continue reaction 0.5h, add the white carbon 15% that KH550 handles, after continuing reaction 2h, add vinyl tributanoximo silane cross-linking agent 20ml again, response time 1h promptly gets modified silicon rubber;
The hydroxy-end capped fluorosioloxane rubber of 5ml is joined in the three-necked bottle of the nitrogen of having friendly relations, and add the white carbon that KH550 handles.Behind the mix homogeneously, add KH5501ml, reaction 0.5h; Obtain having certain degree of polymerization and crosslinked fluorosioloxane rubber;
With 15ml modified silicon rubber and the treated two kinds of rubber mix of fluorosioloxane rubber of 4ml, continue to drip dibutyl tin laurate and di-n-butylamine 7.5ml behind the reaction 0.5h, reaction 0.5h stopped reaction is made room temperature vulcanized silicone rubber; Take out bubble 3h with putting into 30 ℃ of vacuum drying ovens behind the room temperature vulcanized silicone rubber moulding of making; Put into 50 ℃ of post vulcanization 6h of constant temperature oven, obtain product.
The agglutinating hot strength of products obtained therefrom and PMMA is 1.03MPa, and water absorption rate is 0.24%%, and dissolution rate is 0.10%, Shao Shi (A type) hardness number 43, and bacteriostasis rate 20%, Fig. 2 are the atomic force microscope photo.
Embodiment 3
1, acrylic compounds mix monomer modified silicon rubber:
1: 1 mixed solvent of 100ml toluene and butyl acetate is mixed with the 100ml hydroxy silicon oil, the mix homogeneously in the Dropping funnel of again 20ml butyl acrylate, 6ml methyl methacrylate, 4ml methacrylic acid, 4ml senecioate-hydroxypropyl acrylate being packed into, and install to be furnished with motor stirrer, on the there-necked flask of condensing tube, thermometer, put in the water-bath and heat, feed N
2Protection; When the mixed solution temperature reaches 60 ℃, add refined azodiisobutyronitrile 1g and p-methyl benzenesulfonic acid 1g, beginning dropwise addition of acrylic acid class mix monomer, polyreaction is carried out about 60 ℃; The acrylic compounds mix monomer drips complete Cheng Houzai and adds 100ml toluene and 1: 1 mixed solvent of butyl acetate, and dropwise reaction 2h promptly gets modified silicon oil altogether.
2, fluorosioloxane rubber and modified silicon rubber co-vulcanization:
The modified silicon oil of 10ml is joined in the unmodified hydroxy silicon oil of 100ml, in the three-necked bottle of nitrogen of having friendly relations, add 10ml methyl tributanoximo silane cross-linking agent, under 30 ℃ of environment, react 2h, after adding Ethylene glycol dimethacrylate (EDMA) 10ml, continue reaction 0.5h and add the white carbon 5% that KH570 handles, after continuing reaction 2h, add methyl tributanoximo silane cross-linking agent 30ml again; Response time 2h promptly gets modified silicon rubber;
The hydroxy-end capped fluorosioloxane rubber of 10ml is joined in the three-necked bottle of the nitrogen of having friendly relations, and add the white carbon that KH570 handles.Behind the mix homogeneously, add KH5705ml, reaction 0.5h; Obtain having certain degree of polymerization and crosslinked fluorosioloxane rubber;
With 10ml modified silicon rubber and the treated two kinds of rubber mix of fluorosioloxane rubber of 2ml, continue to drip dibutyl tin laurate and di-n-butylamine 1.5ml behind the reaction 2h, reaction 0.5h stopped reaction is made room temperature vulcanized silicone rubber; Take out bubble 2h with putting into 30 ℃ of vacuum drying ovens behind the room temperature vulcanized silicone rubber moulding of making; Put into 100 ℃ of post vulcanization 6h of constant temperature oven, obtain product.
The agglutinating hot strength of products obtained therefrom and PMMA is 0.92MPa, and Fig. 3 is the stereoscan photograph after the tension failure; Water absorption rate is 0.22%, and dissolution rate is 0.08%, Shao Shi (A type) hardness number 32, bacteriostasis rate 40%.
Embodiment 4
1, acrylic compounds mix monomer modified silicon rubber:
200ml dimethylbenzene is mixed with the 100ml hydroxy silicon oil, the mix homogeneously in the Dropping funnel of again 24ml butyl acrylate, 10ml methyl methacrylate, 4ml methacrylic acid, 2ml senecioate-hydroxypropyl acrylate being packed into, and install to be furnished with motor stirrer, on the there-necked flask of condensing tube, thermometer, put in the water-bath and heat, feed N
2Protection; When the mixed solution temperature reaches 50 ℃, add refined azodiisobutyronitrile 0.5g and dibenzoyl peroxide 0.5g, beginning dropwise addition of acrylic acid class mix monomer, polyreaction is carried out about 50 ℃; The acrylic compounds mix monomer drips complete Cheng Houzai and adds 100ml toluene and 1: 1 mixed solvent of vinyl acetate, and dropwise reaction 4h promptly gets modified silicon oil altogether.
2, fluorosioloxane rubber and modified silicon rubber co-vulcanization:
The modified silicon oil of 5ml is joined in the unmodified hydroxy silicon oil of 100ml, in the three-necked bottle of nitrogen of having friendly relations, add 10ml methyl tributanoximo silane cross-linking agent, under 30 ℃ of environment, react 2h, after adding Ethylene glycol dimethacrylate (EDMA) 10ml, continue reaction 2h and add the white carbon 24% that NDZ-311 handles, continue to add methyl triacetoxysilane cross-linking agent 20ml again behind the reaction 6h; Response time 1h promptly gets modified silicon rubber;
The hydroxy-end capped fluorosioloxane rubber of 5ml is joined in the three-necked bottle of the nitrogen of having friendly relations, and add the white carbon that NDZ-311 handles.Behind the mix homogeneously, add NDZ-3111ml, reaction 3h; Obtain having certain degree of polymerization and crosslinked fluorosioloxane rubber;
With 15ml modified silicon rubber and the treated two kinds of rubber mix of fluorosioloxane rubber of 3ml, continue to drip dibutyl tin laurate and di-n-butylamine 5ml behind the reaction 2h, reaction 2h stopped reaction is made room temperature vulcanized silicone rubber; Take out bubble 1h with putting into 70 ℃ of vacuum drying ovens behind the room temperature vulcanized silicone rubber moulding of making; Put into 100 ℃ of post vulcanization 2h of constant temperature oven and obtain product.
The agglutinating hot strength of products obtained therefrom and PMMA is 0.82MPa, and water absorption rate is 0.32%, and dissolution rate is 0.14%, Shao Shi (A type) hardness number 31, and bacteriostasis rate 10%, Fig. 4 are the atomic force microscope photo.
Embodiment 5
1, acrylic compounds mix monomer modified silicon rubber:
1: 1 mixed solvent of 150ml toluene and butyl acetate is mixed with the 100ml hydroxy silicon oil, the mix homogeneously in the Dropping funnel of again 28ml butyl acrylate, 8ml methyl methacrylate, 2ml methacrylic acid, 2ml senecioate-hydroxypropyl acrylate being packed into, and install to be furnished with motor stirrer, on the there-necked flask of condensing tube, thermometer, put in the water-bath and heat, feed N
2Protection; When the mixed solution temperature reaches 70 ℃, add refined p-methyl benzenesulfonic acid 2g, beginning dropwise addition of acrylic acid class mix monomer, polyreaction is carried out about 70 ℃; The acrylic compounds mix monomer drips complete Cheng Houzai and adds 100 toluene and 1: 1 mixed solvent of vinyl acetate, and dropwise reaction 3h promptly gets modified silicon oil altogether.
2, fluorosioloxane rubber and modified silicon rubber co-vulcanization:
The modified silicon oil of 15ml is joined in the unmodified hydroxy silicon oil of 100ml, in the three-necked bottle of nitrogen of having friendly relations, add 10ml methyl tributanoximo silane cross-linking agent, under 50 ℃ of environment, react 1h, after adding Ethylene glycol dimethacrylate (EDMA) 10ml, continue reaction 1h and add the white carbon 15% that NDZ-201 handles, continue to add methyl tributanoximo silane cross-linking agent 10ml again behind the reaction 4h; Response time 2h promptly gets modified silicon rubber;
The hydroxy-end capped fluorosioloxane rubber of 15ml is joined in the three-necked bottle of the nitrogen of having friendly relations, and add the white carbon that NDZ-201 handles.Behind the mix homogeneously, add NDZ-2013ml, reaction 0.5-2h; Obtain having certain degree of polymerization and crosslinked fluorosioloxane rubber;
With 15ml modified silicon rubber and the treated two kinds of rubber mix of fluorosioloxane rubber of 2ml, continue to drip dibutyl tin laurate and di-n-butylamine 3ml behind the reaction 1h, reaction 1h stopped reaction is made room temperature vulcanized silicone rubber; Take out bubble 1-3h with putting into 50 ℃ of vacuum drying ovens behind the room temperature vulcanized silicone rubber moulding of making; Put into 80 ℃ of post vulcanization 4h of constant temperature oven and obtain product.
The agglutinating hot strength of products obtained therefrom and PMMA is 1.01MPa, and water absorption rate is 0.29%, and dissolution rate is 0.11% Shao Shi (A type) hardness number 41, bacteriostasis rate 60%.
Embodiment 6
1, acrylic compounds mix monomer modified silicon rubber:
1: 1 mixed solvent of 100ml toluene and butyl acetate is mixed with the 100ml hydroxy silicon oil, the mix homogeneously in the Dropping funnel of again 28ml butyl acrylate, 8ml methyl methacrylate, 2ml methacrylic acid, 2ml senecioate-hydroxypropyl acrylate being packed into, and install to be furnished with motor stirrer, on the there-necked flask of condensing tube, thermometer, put in the water-bath and heat, feed N
2Protection; When the mixed solution temperature reaches 70 ℃, add refined azodiisobutyronitrile 1g and p-methyl benzenesulfonic acid 1g, beginning dropwise addition of acrylic acid class mix monomer, polyreaction is carried out about 70 ℃; The acrylic compounds mix monomer drips complete Cheng Houzai and adds 100 toluene and 1: 1 mixed solvent of vinyl acetate, and dropwise reaction 3h promptly gets modified silicon oil altogether.
2, fluorosioloxane rubber and modified silicon rubber co-vulcanization:
The modified silicon oil of 15ml is joined in the unmodified hydroxy silicon oil of 100ml, in the three-necked bottle of nitrogen of having friendly relations, add 10ml methyl tributanoximo silane cross-linking agent, under 50 ℃ of environment, react 1h, after adding Ethylene glycol dimethacrylate (EDMA) 10ml, continue reaction 1h and add the white carbon 21% that NDZ-401 handles, continue to add methyl tributanoximo silane cross-linking agent 20ml again behind the reaction 4h; Response time 0.5h promptly gets modified silicon rubber;
The hydroxy-end capped fluorosioloxane rubber of 15ml is joined in the three-necked bottle of the nitrogen of having friendly relations, and add the white carbon that NDZ-401 handles.Behind the mix homogeneously, add NDZ-4015ml, reaction 0.5-2h;
With 15ml modified silicon rubber and the treated two kinds of rubber mix of fluorosioloxane rubber of 2ml, continue to drip dibutyl tin laurate and di-n-butylamine 5ml behind the reaction 1h, reaction 1h stopped reaction is made room temperature vulcanized silicone rubber; Take out bubble 1-3h with putting into 50 ℃ of vacuum drying ovens behind the room temperature vulcanized silicone rubber moulding of making; Put into 80 ℃ of post vulcanization 4h of constant temperature oven and obtain product.
The agglutinating hot strength of products obtained therefrom and PMMA is 0.97MPa, and water absorption rate is 0.31%, and dissolution rate is 0.10%, Shao Shi (A type) hardness number 39, and bacteriostasis rate 60%, Fig. 5 are scanning electron microscope (SEM) photo after the tension failure.
Claims (8)
1. the preparation method of a fluorine-silica rubber artificial tooth soft lining material is characterized in that concrete steps are as follows:
(1) organic solvent and hydroxy silicon oil are placed there-necked flask, the addition of organic solvent is 0.5-2 a times of hydroxy silicon oil volume, and there-necked flask is furnished with motor stirrer, condensing tube and thermometer, mix homogeneously, again the acrylic compounds mix monomer is packed in the Dropping funnel, place on the there-necked flask, at N
2Protection down, under catalyst action, under 50-100 ℃ of bath temperature, polymerization reaction take place, dropwise addition of acrylic acid class mix monomer during the reaction beginning, after treating that the acrylic compounds mix monomer dropwises, add organic solvent again, the addition of organic solvent is 0.5-2 a times of hydroxy silicon oil volume, polymerization reaction time is 1-5 hour, promptly get modified silicon oil, wherein, acrylic compounds mix monomer addition is the 2%-28% of hydroxy silicon oil weight;
(2) modified silicon oil with step (1) gained joins in the unmodified hydroxy silicon oil, the addition of modified silicon oil is 0.1-0.3 a times of hydroxy silicon oil volume, under nitrogen atmosphere, under the silane crosslinker effect, reaction is 0.5-2 hour under 30-80 ℃ of temperature, and the silane crosslinker addition is 0.1-0.3 a times of hydroxy silicon oil volume; Then add Ethylene glycol dimethacrylate, continue reaction 0.5-2 hour, the Ethylene glycol dimethacrylate addition is 10% of a hydroxy silicon oil volume; And then adding white carbon through coupling agent treatment, the addition of white carbon is the 5%-24% of hydroxy silicon oil volume, continues reaction 2-4h, add silane crosslinker again, reacted 0.5-2 hour, the silane crosslinker addition is 0.1-0.3 a times of hydroxy silicon oil volume, promptly gets modified silicon rubber;
(3) hydroxy-end capped fluorosioloxane rubber is joined in the three-necked bottle of the nitrogen of having friendly relations, and the white carbon of adding coupling agent treatment, behind the mix homogeneously, add coupling agent, reacted 0.5-2 hour, promptly get and have certain degree of polymerization and crosslinked fluorosioloxane rubber, the coupling agent addition is the 20%-50% of hydroxy-end capped fluorosioloxane rubber weight, and the addition of white carbon is the 5%-15% of coupling agent volume;
(4) the treated fluorosioloxane rubber hybrid reaction of the modified silicon rubber of step (2) gained and step (3) gained after 0.5-2 hour, is dripped dibutyl tin laurate and di-n-butylamine, reacted 0.5-2 hour, promptly get room temperature vulcanized silicone rubber; The dibutyl tin laurate addition is the 15-50% of modified silicon rubber quality, and the addition of di-n-butylamine is the 15-50% of modified silicon rubber quality; Treated fluorosioloxane rubber addition is the 5-30% of modified silicon rubber quality;
(5) with behind step (4) the gained room temperature vulcanized silicone rubber moulding, place vacuum drying oven, under 30-80 ℃ of temperature, took out bubble 1-3 hour, place constant temperature oven then, under 50-100 ℃ of temperature, post vulcanization 2-6 hour, promptly get required product.
2. the preparation method of fluorine-silica rubber artificial tooth soft lining material according to claim 1 is characterized in that organic solvent described in the step (1) is in toluene, dimethylbenzene, vinylacetate or the butyl acetate one to two kind.
3. the preparation method of fluorine-silica rubber artificial tooth soft lining material according to claim 1, it is characterized in that acrylic compounds mix monomer described in the step (1) is in butyl acrylate, methyl methacrylate, methacrylic acid or the senecioate-hydroxypropyl acrylate one to two kind, the catalyst addition is the 0.5-2% of mixed solution gross mass.
4. the preparation method of fluorine-silica rubber artificial tooth soft lining material according to claim 1 is characterized in that catalyst described in the step (1) is in azodiisobutyronitrile, p-methyl benzenesulfonic acid or the dibenzoyl peroxide one to two kind.
5. the preparation method of fluorine-silica rubber artificial tooth soft lining material according to claim 1, it is characterized in that silane crosslinker described in the step (2) be in methyl tributanoximo silane, vinyl tributanoximo silane, MTMS, MTES or the methyl triacetoxysilane any.
6. the preparation method of fluorine-silica rubber artificial tooth soft lining material according to claim 1 is characterized in that the modified silicon rubber structure of step (2) gained is as follows:
7. the preparation method of fluorine-silica rubber artificial tooth soft lining material according to claim 1 is characterized in that the fluorosioloxane rubber structural formula is as follows described in the step (3):
8. the preparation method of fluorine-silica rubber artificial tooth soft lining material according to claim 1, it is characterized in that coupling agent described in the step (3) be in KH-550, KH-560, KH-570, NDZ-201, NDZ-311, NDZ-401 or the anilinomethyl triethoxysilane any.
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| CN101653985B (en) * | 2009-09-17 | 2011-05-25 | 陈友金 | Method for preparing lining fluorine-silicon silica gel hose for connecting supercharger |
| CN106137774A (en) * | 2016-08-08 | 2016-11-23 | 浙江大学 | Pit and fissure sealant based on Tooth surface hydrophobization theory |
| CN106176250A (en) * | 2016-08-03 | 2016-12-07 | 浙江大学 | Tooth bonding agent system based on hydrophobic bonding new concept |
| CN106519529A (en) * | 2016-11-01 | 2017-03-22 | 金福兴 | Medical biomaterial with high toughness and high surface hardness, and preparation method thereof |
| CN111437203A (en) * | 2020-03-27 | 2020-07-24 | 点铂医疗科技（常州）有限公司 | Fluorine modified false tooth soft lining material and preparation method thereof |
| CN112521755A (en) * | 2020-12-04 | 2021-03-19 | 南通大学 | Preparation method of modified nano-silica toughened silicone rubber |
-
2007
- 2007-10-18 CN CNA2007100471870A patent/CN101167684A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101653985B (en) * | 2009-09-17 | 2011-05-25 | 陈友金 | Method for preparing lining fluorine-silicon silica gel hose for connecting supercharger |
| CN106176250A (en) * | 2016-08-03 | 2016-12-07 | 浙江大学 | Tooth bonding agent system based on hydrophobic bonding new concept |
| CN106176250B (en) * | 2016-08-03 | 2020-06-23 | 浙江大学 | Tooth adhesive system based on new hydrophobic adhesion concept |
| CN106137774A (en) * | 2016-08-08 | 2016-11-23 | 浙江大学 | Pit and fissure sealant based on Tooth surface hydrophobization theory |
| CN106137774B (en) * | 2016-08-08 | 2020-04-17 | 浙江大学 | Pit and fissure sealant based on tooth surface hydrophobization concept |
| CN106519529A (en) * | 2016-11-01 | 2017-03-22 | 金福兴 | Medical biomaterial with high toughness and high surface hardness, and preparation method thereof |
| CN111437203A (en) * | 2020-03-27 | 2020-07-24 | 点铂医疗科技（常州）有限公司 | Fluorine modified false tooth soft lining material and preparation method thereof |
| CN112521755A (en) * | 2020-12-04 | 2021-03-19 | 南通大学 | Preparation method of modified nano-silica toughened silicone rubber |
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