阅读说明：本技术 一种纤维增强聚合物义齿垫片材料及其制备方法 (Fiber-reinforced polymer denture gasket material and preparation method thereof ) 是由 张良俊 李燕燕 张良芬 于 2020-03-23 设计创作，主要内容包括：本发明提供了一种纤维增强聚合物义齿垫片材料及其制备方法。一般情况下在义齿佩戴的时候,建议在义齿与牙床之间配上义齿垫片,能提高义齿与牙床之间的密合度,缓冲咀嚼时的压力,提高佩戴者的舒适度。口腔环境是一个白天有氧,晚上无氧交替的环境,同时有唾液,还可能有食物残渣的情况。义齿垫片在这样的一个环境,对材料的吸水率及耐唾液方面的性能有较高的要求。义齿垫片还要承受反复咀嚼过程中的压力,对材料的耐疲劳性要求较高。本发明充分考虑义齿垫片的使用环境和对材料性能的要求,在室温固化硅橡胶中加入纤维。本发明所提供的纤维增强聚合物义齿垫片材料制备方法简便,同时具有弹性好,膜片边缘断裂率低,撕裂强度大,拉伸性能好等优点,弹性回复率达到99.6%以上,在实际应用中制成的义齿垫片性能优异。(The invention provides a fiber reinforced polymer denture gasket material and a preparation method thereof. Generally, when the denture is worn, a denture gasket is arranged between the denture and the dental bed, so that the fit between the denture and the dental bed can be improved, the pressure during chewing can be buffered, and the comfort level of a wearer can be improved. The oral environment is an environment with oxygen in the daytime and without oxygen at night, and saliva and food residues are possibly in the meantime. The denture pad has high requirements on the water absorption and saliva resistance of the material in such an environment. The denture pad also needs to bear the pressure in the repeated chewing process, and has higher requirement on the fatigue resistance of the material. The invention fully considers the using environment of the denture pad and the requirement on the material performance, and adds the fiber into the room temperature curing silicon rubber. The fiber reinforced polymer denture gasket material provided by the invention is simple and convenient in preparation method, and has the advantages of good elasticity, low breakage rate of the edge of the diaphragm, high tearing strength, good tensile property and the like, the elastic recovery rate reaches more than 99.6%, and the denture gasket prepared in practical application has excellent performance.)

1. A fiber reinforced polymer denture spacer material characterized by the principal components comprising: polysiloxanes blocked at the end of the molecular chain by hydroxyl, polysiloxanes having one or two groups containing alkoxysiloxy groups per molecular chain, siloxanes containing hydrolysable groups, chopped fibres, reinforcing materials, nanofillers, consistency regulators and other auxiliaries.

2. A fiber reinforced polymer denture spacer material according to claim 1, wherein the components are used in the following amounts, calculated in parts by mass: 23-56 parts of polysiloxane with molecular chain ends blocked by hydroxyl, 36-52 parts of polysiloxane with one or two groups containing alkoxy siloxane groups on each molecular chain, 5-25 parts of siloxane containing hydrolyzable groups, 2.8-16 parts of chopped fibers, 5.6-13.5 parts of reinforcing materials, 3.5-32 parts of nano fillers, 0-26 parts of consistency regulator and 0-5 parts of other auxiliary agents.

3. The fiber-reinforced polymer denture spacer material according to claim 1, wherein the polysiloxane blocked with hydroxyl groups at the molecular chain ends has a viscosity of 1000 to 650000 mPa-s at room temperature and has a structure represented by formula i;

structural formula I

In the formula I, R₁、R₂Is an alkyl radical having from 1 to 15 carbon atoms, R₃Is a monovalent hydrocarbon radical of 1 to 15 carbon atoms, n having a value of between 50 and 500 depending on the viscosity; r₁、R₂Alkyl groups of (a) include methyl, ethyl, propyl, butyl, pentyl, hexyl, and similar alkyl groups; r₃Including methyl, ethyl, propyl, butyl, pentyl, hexyl, and similar alkyl groups; vinyl, allyl, butenyl, pentenyl, hexenyl, and similar alkenyl groups; also included are phenyl, tolyl, xylyl, and similar aryl groups.

4. The fiber-reinforced polymer denture spacer material according to claim 1, wherein the polysiloxane having one or two alkoxysilyl group-containing groups per molecular chain has a viscosity of 1000 to 650000 mPa-s at room temperature, and the structure thereof is represented by formula ii;

structural formula II

In the formula II R₁Are the same or different monovalent hydrocarbon groups free of aliphatic unsaturation including methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and similar alkyl groups; r₂Is an alkyl group including methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl andsimilar alkyl groups, here preferably methyl, ethyl and propyl; r₃Are the same or different monovalent hydrocarbon radicals including methyl, ethyl, propyl, butyl, pentyl, hexyl and similar alkyl radicals; vinyl, allyl, butenyl, pentenyl, hexenyl, and similar alkenyl groups; also included are phenyl, tolyl, xylyl, and similar aryl groups; n is₀N1 is an integer from 0 to 2, depending on the need to control viscosity, and is an integer from 1 to 100.

5. A fiber reinforced polymer denture spacer material according to claim 1, wherein the siloxane of hydrolyzable groups has two, three or four silicon-bonded hydrolyzable groups and is of the structure of formula iii;

structural formula III

In the formula III, R₁Monovalent hydrocarbon groups having 1 to 10 carbon atoms including methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and similar alkyl groups; r₂Is a hydrolyzable group, x has a value of 0 or 1; r₂Including methoxy, ethoxy, and similar alkoxy groups; acetoxy and similar acyloxy groups; n-butylalkyl and similar alkylamino groups; n-methyl acetamide groups and similar amide groups; acryloxy and similar alkyleneoxy N-methylacetamido groups and similar amide groups; among these, preferred are: triacetoxysilane, ethyltriacetoxysilane, vinyltrioximosilane, tetraketoximosilane, trioximosilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, or a mixture of more than one thereof.

6. A fiber reinforced polymer denture spacer material according to claim 1, wherein the chopped fibers include, but are not limited to, glass fibers, carbon nanofibers, the fibers having a length between 40nm and 500 nm.

7. The fiber reinforced polymer denture spacer material according to claim 1, wherein the reinforcing agent comprises, but is not limited to, MQ resin, fumed silica, talc, mica powder, wherein the fumed silica, talc, mica powder have a specific surface area of 1000 mesh or more.

8. A fiber reinforced polymer denture spacer material according to claim 1, wherein the nanofiller includes, but is not limited to, calcium carbonate, kaolin, quartz powder, and has a specific surface area of 1000 mesh or more.

9. A fiber reinforced polymer denture spacer material according to claim 1, prepared by the method comprising:

① adding polysiloxane with the molecular chain end blocked by hydroxyl and polysiloxane with one or two groups containing alkoxy siloxane group on each molecular chain into a planetary mixer, and mixing uniformly, wherein the rotation speed of the planetary mixer is 20-70 r/min;

② adding the chopped fibers into the mixture, and stirring for 30-70 minutes at the rotation speed of the planetary mixer of 20-70 r/min;

③ adding reinforcing materials, nano fillers and other auxiliary agents, and stirring for 30-70 minutes at the rotation speed of the planetary mixer of 20-70 r/min;

④ adding siloxane containing hydrolyzable group, mixing, and adding appropriate amount of consistency regulator according to consistency;

⑤ adding the mixture into a die with a groove having a pressing piece, compacting and solidifying the pressing piece to obtain polymer film with corresponding thickness of 0.3-10 mm, preferably 0.3mm, 0.5mm, 0.8mm, 1mm, 1.5mm, 2mm, 2.5mm, 3.0 mm.

Technical Field

The invention belongs to the field of medical high polymer materials, and relates to a fiber reinforced polymer denture gasket material and a preparation method thereof.

Background

The denture is what is commonly referred to as a "denture", which means that the "denture" means the "artificial leg" of the human being. The medical science is a general term for restorations made after partial or all teeth of the upper and lower jaws are lost. The complete denture can maintain the beauty, the language and the chewing function of the face of the patient and avoid the pain of the patient caused by tooth missing. However, the denture has some problems in the wearing process, firstly, the denture is difficult to contact with the alveolar bone to achieve the ideal state, and the wearer often feels pain. Secondly, gaps between the false tooth and the dental bed and between the false tooth and the upper jaw cannot be closed, and food is embedded between the false tooth and the dental bed during chewing to cause discomfort and easily cause gingivitis and periodontitis. At this time, the denture gasket is arranged between the denture and the dental bed, so that the tightness between the denture and the dental bed can be improved, the pressure during chewing can be buffered, and the comfort level of a wearer can be improved.

Room temperature vulcanizing silicone Rubber (RTVPS) is a new silicone elastomer that has been introduced in the sixties, and silicone rubbers containing hydroxyl (or acetoxy) groups at the end groups are generally viscous fluids with relatively low molecular weights. The room temperature curing silicon rubber is a semi-inorganic polymer synthetic material with a main chain of a silicon-oxygen bond and a side chain of an organic group. The silicon-oxygen bond structure of the main chain determines that the polymer has a wide use temperature range (-60 to +250 ℃). The most remarkable characteristic of the rubber is that the rubber can be cured at room temperature without heating and pressurizing, and the use is very convenient.

An ideal denture pad should have high elasticity when chewed and then exhibit stickiness to take on occlusal forces and relieve pain. Dynamic viscoelasticity test research shows that the room temperature silicone rubber shows elastic behavior, so that the room temperature silicone rubber has better capability of buffering chewing pressure and is an ideal denture gasket material.

The oral environment is an environment with oxygen in the daytime and without oxygen at night, and saliva and food residues are possibly in the meantime. The denture pad has high requirements on the water absorption agent and the saliva resistance of the material in such an environment. The denture pad also needs to bear the pressure in the repeated chewing process, and has higher requirement on the fatigue resistance of the material. False tooth gaskets prepared by common room temperature curing silica gel are often excellent in initial performance, and have the conditions of no elasticity, no cracking, no deformation and the like along with the prolonging of time. The characteristics of the use environment of the denture gasket and the requirements on the material performance are fully considered, and the fibers are added into the room-temperature curing silicone rubber, so that the tear resistance and the elastic recovery rate of the room-temperature curing silicone rubber are improved; the risk of decomposition and fracture of the denture pad is reduced, and the comfort and biological safety of the denture wearer during use are improved.

Disclosure of Invention

The invention aims to provide a medical high polymer material, in particular to a fiber reinforced polymer denture cushion material and a preparation method thereof.

The fiber reinforced polymer denture gasket material mainly comprises the following components: polysiloxanes blocked at the end of the molecular chain by hydroxyl, polysiloxanes having one or two groups containing alkoxysiloxy groups per molecular chain, siloxanes containing hydrolysable groups, chopped fibres, reinforcing materials, nanofillers, consistency regulators and other auxiliaries.

The dosage of each component is as follows according to the mass portion: 23-56 parts of polysiloxane with molecular chain ends blocked by hydroxyl, 36-52 parts of polysiloxane with one or two groups containing alkoxy siloxane groups on each molecular chain, 5-25 parts of siloxane containing hydrolyzable groups, 2.8-16 parts of chopped fibers, 5.6-13.5 parts of reinforcing materials, 3.5-32 parts of nano fillers, 0-26 parts of consistency regulator and 0-5 parts of other auxiliary agents.

The viscosity of the polysiloxane with the molecular chain end being blocked by hydroxyl at room temperature is 1000-650000 mPas, and the structure of the polysiloxane is shown as a structural formula I.

Structural formula I

In the formula I, R₁、R₂Is an alkyl radical having from 1 to 15 carbon atoms, R₃Is a monovalent hydrocarbon group of 1 to 15 carbon atoms, and n has a value of 50 to 500 depending on the viscosity. R₁、R₂The alkyl group of (b) includes methyl, ethyl, propyl, butyl, pentyl, hexyl and the like. R₃Including methyl, ethyl, propyl, butyl, pentyl, hexyl, and similar alkyl groups; vinyl, allyl, butenyl, pentenyl, hexenyl, and similar alkenyl groups; also comprises phenyl,Tolyl, xylyl, and similar aryl groups.

The viscosity of the polysiloxane with one or two alkoxy siloxane group-containing groups on each molecular chain at room temperature is 1000-650000 mPas, and the structure is shown as a structural formula II.

Structural formula II

In the formula II R₁Are identical or different monovalent hydrocarbon groups free of aliphatic unsaturation including methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and similar alkyl groups. R₂Are alkyl groups including methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and similar alkyl groups, with methyl, ethyl and propyl groups being preferred herein. R₃Are the same or different monovalent hydrocarbon radicals including methyl, ethyl, propyl, butyl, pentyl, hexyl and similar alkyl radicals; vinyl, allyl, butenyl, pentenyl, hexenyl, and similar alkenyl groups; also included are phenyl, tolyl, xylyl, and similar aryl groups. n is₀N1 is an integer from 0 to 2, depending on the need to control viscosity, and is an integer from 1 to 100.

The above hydrolyzable group siloxanes have two, three or four silicon-bonded hydrolyzable groups and are structurally represented by formula III.

Structural formula III

In the formula III, R₁Is a monovalent hydrocarbon group having 1 to 10 carbon atoms and includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and similar alkyl groups. R₂Is a hydrolyzable group, x has a value of 0 or 1. R₂Including methoxy, ethoxy, and similar alkoxy groups; acetoxy and similar acyloxy groups; n-butylalkyl and similar alkylamino groups; n-methyl acetamide groups and similar amide groups; propenyloxy and like alkenyloxy N-methyl acetamido groupsGroups and similar amide groups. Among these, preferred are: triacetoxysilane, ethyltriacetoxysilane, vinyltrioximosilane, tetraketoximosilane, trioximosilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, or a mixture of more than one thereof.

The chopped fibers include, but are not limited to, glass fibers and nano carbon fibers, and the length of the fibers is 40nm to 500 nm.

The reinforcing agent comprises, but is not limited to, MQ resin, fumed silica, talcum powder and mica powder, wherein the specific surface area of the fumed silica, the talcum powder and the mica powder is more than 1000 meshes.

The nano filler includes, but is not limited to, calcium carbonate, kaolin and quartz powder, and the specific surface area of the nano filler is more than 1000 meshes.

The consistency regulator includes, but is not limited to, dimethicone and liquid paraffin.

The other auxiliary agents are proper amount of essence, color paste, coupling agent, pseudo preparation and the like.

The fiber-reinforced polymer denture spacer material of the present invention may further contain various additives known for use in fiber-reinforced polymer denture spacers within the range not prejudicial to the object of the present invention. These additives include, but are not limited to, inorganic fillers, organic solvents, mold inhibitors, flame retardants, heat stabilizers, plasticizers, and thixotropic agents.

The preparation method of the fiber reinforced polymer denture gasket material is as follows.

1) Polysiloxane with molecular chain end blocked by hydroxyl and polysiloxane with one or two groups containing alkoxy siloxane group on each molecular chain are added into a planetary mixer and mixed evenly. The rotation speed of the planetary mixer is 20-70 rpm.

2) And adding the chopped fibers into the mixture, and stirring for 30-70 minutes at the rotation speed of 20-70 revolutions per minute of the planetary mixer.

3) Adding a reinforcing material, a nano filler and other auxiliary agents, and stirring for 30-70 minutes at the rotation speed of the planetary mixer of 20-70 revolutions per minute.

4) Adding siloxane containing hydrolyzable group, mixing uniformly, and adding proper amount of consistency regulator according to consistency.

5) Adding the mixture into a mold with a groove, wherein the groove is provided with a pressing sheet, and compacting and solidifying the pressing sheet to prepare the polymer film with the corresponding thickness. The polymer film has a thickness of 0.3 to 10mm, preferably: 0.3mm, 0.5mm, 0.8mm, 1mm, 1.5mm, 2mm, 2.5mm, 3.0 mm.

All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The fiber reinforced polymer denture gasket material provided by the invention is simple and convenient in preparation method, and has the advantages of good elasticity, low gasket edge fracture rate, high tearing strength, good tensile property and the like, the elastic recovery rate reaches more than 99.6%, and the denture gasket prepared in practical application has excellent performance.

The invention is further illustrated by the following specific examples

Example 1

① at room temperature, 5600g of a polysiloxane having a viscosity of 450000mPa.s and blocked at the molecular chain end by a hydroxyl group, 3600g of a polysiloxane having one or two alkoxysiloxy-group-containing groups per molecular chain and having a viscosity of 20000mPa.s was fed into a planetary mixer and rotated at a rotation speed of 50 rpm for 40 minutes, 1500g of a chopped glass fiber having a length of 65nm was fed and rotated at a rotation speed of 50 rpm for 40 minutes.

500g of calcium carbonate and 500g of fumed silica are weighed out and stirred together with the mixture, and the mixture is rotated at a speed of 50 rpm for 60 minutes. 2100g of vinyltrioximinosilane and 400g of 3-methacryloxypropyltrimethoxysilane were added and the mixture was rotated at 50 rpm for 30 minutes.

② adding the mixture into a mould with a groove, compacting and solidifying the mould, controlling the thickness of the film to be 1mm, and controlling the elastic recovery rate of the film to be 99.7%.