阅读说明：本技术 一种氟改性义齿软衬材料及其制备方法 (Fluorine modified false tooth soft lining material and preparation method thereof ) 是由 张良俊 李燕燕 于 2020-03-27 设计创作，主要内容包括：一种氟改性义齿软衬材料及其制备方法属于医用改性高分子聚合物材料领域。义齿软衬材料在口腔领域的应用已有上百年历史,软衬材料具有提高义齿组织面与牙槽嵴之间的密合度,封闭剂义齿边缘,缓冲冲击性咬合力,减轻或消除压痛等优点。本发明制备了含氟硅橡胶改性剂,在室温硅橡胶中引入含氟树脂,制备出含氟改性硅橡胶义齿软衬材料。本发明所提供的氟改性义齿软衬材料制备方法简便,同时具有弹性回复好,撕裂强度大,口内溶解率低,拉伸性能好等优点。伸长率达到150%,弹性回复达到99.8%,是一种性能优异的齿科软衬材料。(A fluorine modified false tooth soft lining material and a preparation method thereof, belonging to the field of medical modified high polymer materials. The application of the false tooth soft lining material in the oral cavity field has been for a hundred years, and the soft lining material has the advantages of improving the fit between a false tooth tissue surface and an alveolar ridge, sealing the false tooth edge, buffering the impact occlusal force, reducing or eliminating the pressure pain and the like. The invention prepares the fluorine-containing silicon rubber modifier, introduces fluorine-containing resin into the room temperature silicon rubber, and prepares the fluorine-containing modified silicon rubber false tooth soft lining material. The fluorine modified denture soft lining material provided by the invention has the advantages of simple and convenient preparation method, good elastic recovery, high tearing strength, low intraoral dissolution rate, good tensile property and the like. The elongation rate reaches 150 percent, the elastic recovery reaches 99.8 percent, and the dental soft lining material has excellent performance.)

1. A fluorine modified denture soft lining material is characterized by comprising the following components: the modifier comprises a fluorine-containing silicon rubber modifier, one or more than one polysiloxane containing two vinyl groups per molecule, one or more than one polysiloxane containing three or more than three Si-H groups per molecule, a nano filler, a reinforcing agent, a catalyst and other auxiliary agents; the dosage of each component is calculated according to the mass parts as follows: 5-15 parts of a fluorine-containing silicon rubber modifier and 45-80 parts of vinyl polysiloxane; 2-9 parts of polysiloxane with Si-H group; 5-20 parts of nano filler; 1-10 parts of a reinforcing agent; 0.5 to 5 portions of catalyst and 0 to 2 portions of other auxiliary agents.

2. The fluorine-modified denture upholstery material as claimed in claim 1, wherein the vinyl silicone is a linear or branched vinyl silicone oil having vinyl groups, at least two vinyl groups, a viscosity in the range of 100-7000pa.s, and a formula of formula ii:

structural formula II

Wherein R is C_nH_2n－1。

3. The fluorine-modified denture soft liner material according to claim 1, wherein the polysiloxane containing Si-H groups is a hydrogen-containing silicone oil having a viscosity of 100-:

structural formula III

Wherein R is CnH2 n-1.

4. The fluorine-modified denture upholstery material as claimed in 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.

5. The fluorine-modified denture soft liner 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 has a specific surface area of more than 1000 mesh.

6. The fluorine-modified denture soft liner material according to claim 1, wherein the catalyst is a complex of chloroplatinic acid and a vinyl polysiloxane, wherein the vinyl polysiloxane contains one or more vinyl groups.

7. The fluorine-modified denture soft liner material according to claim 1, wherein the fluorine-containing silicone rubber modifier has the following structural formula I,

structural formula I

N =0,1,2,3 in the structural formula

R₁is-CH₃、—CH₂CH₃、—CH（CH₃）_2、—（CH₂）₂CH₃、—（CH₂）₃CH₃、

—（CH₂）₄CH₃、—CHCH₂CH₃or-CH₂C（CH₃）₃；

R₂is-CH₃、—CH₂CH₃、—CH（CH₃）_2、—（CH₂）₂CH₃、—（CH₂）₃CH₃、

—（CH₂）₄CH₃、—CHCH₂CH₃or-CH₂C（CH₃）₃。

8. The method for preparing a fluorine-containing silicone rubber modifier according to claim 7, comprising the steps of:

①, adding trifluoropropyl methyl cyclotrisiloxane, vinyl trialkoxysiloxane and tetramethyl disiloxane into a normal-pressure reaction kettle at room temperature, starting a stirrer, stirring at the speed of 15-30 r/min, and stirring for 20-40 minutes;

② introducing nitrogen for protection, heating to 60-90 ℃, stirring, dripping the silane crosslinking agent, controlling the dripping time to be 1-2 hours, and stirring at the speed of 15-30 r/min, after finishing dripping, heating to 100-150 ℃, and reacting for 3-5 hours;

③ removing low molecular products under vacuum degree of-0.02-0.05 MPa until no effluent liquid exists, removing vacuum, cooling to below 60 deg.C, and discharging to obtain the fluorine-containing silicone rubber modifier.

9. The fluorine-containing silicone rubber modifier according to claim 7, wherein the components comprise, by mass, 18.8 to 46.0 parts of trifluoropropylmethylcyclotrisiloxane, 16.0 to 42.0 parts of vinyltrialkoxysiloxane, 9.4 to 20.8 parts of tetramethyldisiloxane and 2.0 to 7.5 parts of a silane crosslinking agent; the vinyl trialkoxysiloxane is one or a composition of more than one of vinyl triethoxysilane, vinyl trimethoxy siloxane and vinyl tripropoxy siloxane; the silane cross-linking agent is one or a composition of more than one of vinyl tributyrinoxime silane, methyl trimethoxy silane, methyl triethoxy silane or methyl triacetoxy silane.

10. The fluorine-modified denture soft lining material according to claim 1, characterized in that the preparation method is as follows:

① preparing fluorine-containing silicon rubber modifier for later use;

② adding the liquid components into the normal pressure reaction kettle according to a certain proportion, and stirring and mixing uniformly at a stirring speed of 20-65 r/m;

③ adding a certain amount of powder components into the liquid components, stirring at 20-35 r/m for 1.5-2.5 hr;

④, adding the mixture into a kneader from a normal pressure reaction kettle, adding other auxiliary agents, and kneading uniformly;

the speed of the roller of the kneader is 20-35 r/min, and the kneading time is 1.5-3 hours;

⑤ adding the mixture into a mixer, adding catalyst, mixing and solidifying at room temperature to obtain the final product.

Technical Field

The invention belongs to the field of medical modified high-molecular polymer materials, and particularly relates to a fluorine modified denture soft lining 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 false tooth soft lining material is also called elastic false tooth soft lining material, and is a lining material applied to the false tooth base tissue surface. Denture upholstery material has been used in the field of dental prosthetics for over a hundred years. The soft lining material can improve the tightness between the denture tissue surface and the alveolar ridge, seal the denture edge, buffer the impact occlusal force, relieve or eliminate the pressure pain, improve the denture retention and the like, can obviously improve the comfort level and the satisfaction degree of a patient, and is widely applied clinically.

Research on denture upholstery materials has been rising relatively early. In the early 40 s, with the advent of acrylic applications for dental restorations, it became apparent that soft plastic could be used to form a base or rubber pad on a hard plastic base tissue surface, which could be more comfortable for the patient to wear a denture. The upholstery material is classified into two major types, permanent or semi-permanent denture upholstery material and temporary denture upholstery material, which are also called short-term upholstery material, tissue conditioner, functional impression material, according to the period in which the upholstery is used.

Ideally the material of the soft liner should have a high elasticity when chewed and then exhibit a viscosity to take up bite and relieve pain. Viscoelasticity imparts the ability of the upholstery material to disperse and absorb chewing pressure. In 1945 Matthews used plasticized polyvinyl chloride gels for the first time, but were rejected due to the disadvantage that curing temperature and elasticity could not be maintained. Subsequently plasticized acrylic and silicone rubber upholstery materials, also hydrogels, polyurethanes, etc. developed after the 60 s have been presented in succession.

Dynamic viscoelasticity test research shows that the acrylic soft lining material shows viscoelasticity behavior, while the silicon rubber shows elasticity behavior, so that the acrylic soft lining material has better capacity of buffering chewing pressure. Room temperature vulcanizing silicone Rubber (RTVPS) refers to a type of silicone rubber that can be vulcanized at room temperature without heating. Room temperature vulcanizing silicone rubber is a silicone rubber whose terminal groups contain hydroxyl (or acetoxy) groups, and is a relatively low molecular weight, usually viscous fluid. The rubber is added with a proper amount of reinforcing filler, vulcanizing agent and catalyst (or under the action of moisture in the air), and then the rubber can be vulcanized at room temperature to form an elastomer. After the vulcanization is completed, the rubber composition is good in heat resistance, cold resistance, dielectric property and the like, and can be used for casting and coating rubber materials if the mechanical strength is lower.

As is well known, fluorine has large electronegativity, small atomic radius, short C-F bond and large bond energy, so that the fluorocarbon polymer has the advantages of weather resistance, high temperature resistance, corrosion resistance and the like. The invention introduces fluorine-containing resin into the room temperature silicon rubber to prepare the fluorine-containing modified silicon rubber false tooth soft lining material. The denture soft lining material prepared by the invention has good performance, and meanwhile, the denture soft lining material has increased durability in the oral environment and can have good compatibility with denture base materials.

Disclosure of Invention

The invention aims to provide a medical fluorine modified high molecular polymer material, in particular to a fluorine modified denture soft lining material and a preparation method thereof.

The fluorine modified denture soft lining material mainly comprises the following components: the modifier comprises a fluorine-containing silicon rubber modifier, one or more than one polysiloxane containing two vinyl groups per molecule, one or more than one polysiloxane containing three or more than three Si-H groups per molecule, a nano filler, a reinforcing agent, a catalyst and other auxiliary agents.

The fluorine modified denture soft lining material comprises the following components in parts by weight: 5-15 parts of a fluorine-containing silicon rubber modifier and 45-80 parts of vinyl polysiloxane; 2-9 parts of polysiloxane with Si-H group; 5-20 parts of nano filler; 1-10 parts of a reinforcing agent; 0.5 to 5 portions of catalyst and 0 to 2 portions of other auxiliary agents.

The structural formula of the fluorine-containing silicon rubber modifier is shown as the following structural formula I,

structural formula I

N =0,1,2,3 in the structural formula

R₁is-CH₃、—CH₂CH₃、—CH（CH₃）_2、—（CH₂）₂CH₃、—（CH₂）₃CH₃、

—（CH₂）₄CH₃、—CHCH₂CH₃or-CH₂C（CH₃）₃。

R₂is-CH₃、—CH₂CH₃、—CH（CH₃）_2、—（CH₂）₂CH₃、—（CH₂）₃CH₃、

—（CH₂）₄CH₃、—CHCH₂CH₃or-CH₂C（CH₃）₃。

The preparation method of the fluorine-containing silicone rubber modifier comprises the following steps:

① at room temperature, adding trifluoropropylmethyl cyclotrisiloxane, vinyl trialkoxysiloxane and tetramethyl disiloxane into a normal pressure reaction kettle, starting a stirrer, stirring at the speed of 15-30 r/min, and stirring for 20-40 minutes.

② introducing nitrogen for protection, heating to 60-90 ℃, stirring, dripping the silane crosslinking agent, controlling the dripping time to be 1-2 hours, stirring at a speed of 15-30 r/min, finishing the dripping, heating to 100-150 ℃, and reacting for 3-5 hours.

③ removing low molecular products under the vacuum degree of-0.02 to-0.05 MPa until no effluent liquid exists, removing vacuum, cooling to below 60 ℃, discharging to obtain the fluorine-containing silicon rubber modifier.

The composite material is prepared from 18.8-46.0 parts of trifluoropropylmethyl cyclotrisiloxane, 16.0-42.0 parts of vinyl trialkoxysiloxane, 9.4-20.8 parts of tetramethyl disiloxane and 2.0-7.5 parts of silane cross-linking agent by mass.

The vinyl trialkoxysiloxane is one or a composition of more than one of vinyl triethoxysilane, vinyl trimethoxy siloxane and vinyl tripropoxy siloxane.

The silane cross-linking agent is one or a composition of more than one of vinyl tributyrinoxime silane, methyl trimethoxy silane, methyl triethoxy silane or methyl triacetoxy silane. The vinyl polysiloxane is linear or branched vinyl silicone oil with vinyl, at least has two vinyl groups, the viscosity is between 100-7000Pa.s, and the molecular formula is shown as a structural formula II:

structural formula II

Wherein R is C_nH_2n－1

The polysiloxane containing Si-H groups is hydrogen-containing silicone oil with the viscosity of 100-6500Pa.s and the content of Si-H bonds of 0.1-1.5. The molecular formula is shown as structural formula III:

structural formula III

Wherein R is CnH2 n-1

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 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 catalyst is a complex of chloroplatinic acid and vinyl polysiloxane, and the vinyl polysiloxane contains one or more vinyl groups.

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

The denture material according to the present invention may further contain various additives known for use in denture material compositions 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 fluorine modified denture soft lining material is as follows.

① preparing the modifier for fluorine-containing silicon rubber.

② the liquid components are weighed according to a certain proportion and added into a normal pressure reaction kettle, and the mixture is stirred and mixed evenly with the stirring speed of 20 to 65 r/m.

③ adding a certain amount of powder into the liquid component, and stirring at 20-35 rpm for 1.5-2.5 hr.

④ the mixture is added into a kneader from a normal pressure reaction kettle, other auxiliary agents are added, and the mixture is kneaded evenly, the speed of a roller of the kneader is 20-35 r/min, and the kneading time is 1.5-3 hours.

⑤ adding the above mixture into a mixer, adding catalyst, mixing and curing at room temperature to obtain the final product.

The method of making the fluorine-modified denture liner material described herein does not represent the only form in which the present invention may be made or utilized. Unless defined otherwise, 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 fluorine modified denture soft lining material provided by the invention has the advantages of simple and convenient preparation method, good elastic recovery, high tearing strength, low intraoral dissolution rate, good tensile property and the like. The elongation rate reaches 150 percent, the elastic recovery reaches 99.8 percent, and the dental soft lining material has excellent performance.

The invention is further illustrated by the following specific examples

Example 1

① at room temperature, 350g of trifluoropropylmethyl cyclotrisiloxane, 320g of vinyl triethoxy siloxane and 285g of tetramethyl disiloxane are weighed and added into a normal pressure reaction kettle, a stirrer is started, the stirring speed is 20 r/min, the stirring is carried out for 20 minutes, nitrogen is introduced for protection, the temperature is raised to 70 ℃, 42g of methyl triacetoxysilane is added dropwise while stirring, the adding time is controlled to be 1.5 hours, the stirring speed is 30 r/min, the dropwise addition is finished, the temperature is raised to 120 ℃, the reaction is carried out for 4 hours, low molecular weight products are removed under the vacuum degree of-0.02 to-0.05 MPa, the vacuum is removed, the temperature is reduced to below 60 ℃, and the fluorine-containing silicon rubber modifier is obtained for later use.

② g of vinyl-terminated polydimethylsiloxane oil with the viscosity of 150Pa.s and the viscosity of 120 Pa.s, 30g of polysiloxane containing Si-H groups with the viscosity of 2000Pa.s and 80g of fluorine-containing silicon rubber modifier are added into a reaction kettle and stirred evenly at the stirring speed of 25 r/min.

50g of calcium carbonate, 50g of fumed silica and the liquid mixture were weighed out and added to a kneader, and kneaded for 2.5 hours with the roll speed of the kneader being controlled to 20 to 35 rpm. 15g of catalyst is added into a mixing mill, and the mixture is mixed and cured to prepare the film-shaped denture soft lining material.