A denture base composite material and its preparation process

Abstract

The present invention relates to the field of material technology, and discloses a denture base composite material and a preparation process thereof. This composite material is prepared by carrying out a free radical copolymerization reaction with methyl methacrylate as the main raw material, modified tourmaline and a functional polymer monomer. By carrying out in-situ polymerization of methyl methacrylate and the functional polymer monomer on the surface of acetylene gas, tourmaline exists in the composite material in the form of chemical bonds. On the one hand, it can play a role in transmitting and dispersing stress loads and enhance the mechanical strength of the composite material. On the other hand, chemical bonding is conducive to the uniform dispersion of tourmaline. Utilizing the characteristic that tourmaline can release negative ions, it can regulate the balance of oral functions. The presence of the functional polymer monomer can make the composite material have a hydrophobic and oleophobic surface, making the composite material easy to clean.

Description

Technical Field

[0001] The present invention relates to the field of material technology, and particularly to a composite material for denture base and its preparation process. Background Art

[0002] In the broad field of stomatology, dentures (false teeth), as an important means to restore the function of missing teeth, improve facial morphology and enhance the quality of life of patients, the selection and development of their manufacturing materials have always been one of the key factors driving the progress of oral restoration technology. The denture base, as the supporting structure of the denture, not only undertakes the important mission of restoring physiological functions such as chewing and pronunciation, but also directly affects the comfort, aesthetics and durability of the denture. Therefore, it needs to have good biocompatibility, mechanical strength, stability, processing performance and certain aesthetics. According to the different material properties, denture base materials can be roughly divided into several categories such as traditional plastic base materials, metal base materials, ceramic base materials and new composite materials. Among them, plastic base materials are mainly made of polymethyl methacrylate as raw materials. Its advantages lie in good processing performance, easy to shape, polish and buff, and relatively low cost, which is suitable for the economic affordability of most patients. In addition, PMMA base materials have stable color and are not easy to discolor, which can meet the basic aesthetic requirements, so they have a wide range of applications.

[0003] However, polymethyl methacrylate itself has poor toughness and mechanical properties, and often breaks during occlusion, which in turn causes the fracture of the base, resulting in dysbacteriosis and even denture stomatitis. Its defects are obvious in practical applications. In addition, there are often food residues in the oral cavity, and these food residues will adhere to the gaps between teeth and are not easy to clean. Therefore, preparing a polymethyl methacrylate composite material with easy cleaning and excellent mechanical properties is of great significance for the further development of the denture industry. Summary of the Invention

[0004] In order to solve the problems mentioned in the background art, the purpose of the present invention is to provide a composite material for denture base and its preparation process.

[0005] The purpose of the present invention can be achieved by the following technical solutions:

[0006] A preparation process of a composite material for denture base, the composite material is made of raw materials including the following weight parts:

[0007]

[0008] The preparation process includes the following steps:

[0009] First step, weigh each raw material according to the weight parts and set aside;

[0010] Step 2: Add the modified tourmaline into purified water. After ultrasonic dispersion until uniform, add the activator, and then carry out ultrasonic treatment at an ultrasonic frequency of 80 - 100 kHz for 10 - 30 min. Then, start heating, control the temperature at 70 - 75 °C, add methyl methacrylate, functional polymer monomer and initiator under stirring conditions. After adding, raise the temperature to 78 - 82 °C, keep the temperature for 8 - 16 h, then stop heating. After the material cools down, filter and separate to collect the product, and the composite material can be obtained.

[0011] As a further scheme of the present invention, the preparation method of the functional polymer monomer is as follows:

[0012] Step S1: Add curcumin and anhydrous toluene into a reactor filled with nitrogen. After adding, start stirring. After mixing evenly, it is recorded as the first mixed solution. Add allyldichloro(methyl)silane into anhydrous toluene, and mechanically stir to mix evenly, which is recorded as the second mixed solution.

[0013] Step S2: Add the second mixed solution into the first mixed solution at a stirring rate of 1000 - 1500 r / min to form a reaction solution. Add an acid-binding agent to the reaction solution. After adding, gradually raise the temperature to 60 - 65 °C, and keep stirring at this temperature for 8 - 12 h. Then, evaporate to remove the solvent, cool down and discharge the material, and the functional polymer monomer can be obtained.

[0014] As a further scheme of the present invention, in Step S2, the molar ratio of curcumin to allyldichloro(methyl)silane in the reaction solution is 1 - 1.2:1.

[0015] As a further scheme of the present invention, in Step S2, the acid-binding agent is pyridine or triethylamine.

[0016] In the above technical scheme, using curcumin and allyldichloro(methyl)silane as reactants, under the action of an acid-binding agent, the active hydroxyl substituents and silicon-chlorine groups in their structures can undergo continuous substitution to form a block-type macromolecular substance connected by silicon-oxygen bonds. A large number of unsaturated alkenyl substituents are contained in the structure of this macromolecular substance, which can participate in subsequent free radical copolymerization reactions.

[0017] As a further scheme of the present invention, the preparation method of the modified tourmaline is as follows:

[0018] Mix tourmaline with 1,4-dioxane, and carry out ultrasonic dispersion until a uniform dispersion liquid is formed. Then, add a surface functionalization modification reagent to the dispersion liquid. After adding, introduce nitrogen to discharge air, start heating, raise the temperature to 40 - 50 °C, keep the temperature for 3 - 6 h, then cool down and discharge the material. Centrifuge to obtain solid materials, and after washing and vacuum drying processes, the modified tourmaline can be obtained.

[0019] As a further solution of the present invention, the mass ratio of tourmaline to the surface functionalized modification reagent is 1:2 - 3.5.

[0020] As a further solution of the present invention, the surface functionalized modification reagent is diallylcarbamyl chloride.

[0021] In the above technical solution, the surface of tourmaline contains active hydroxyl groups. By using diallylcarbamyl chloride as the surface functionalized modification reagent, the surface of tourmaline is modified with vinyl functional groups, and tourmaline with a large number of unsaturated vinyl functional groups on the surface is obtained, that is, modified tourmaline.

[0022] As a further solution of the present invention, the activator is sodium dodecylbenzenesulfonate or sodium dodecyl sulfate.

[0023] As a further solution of the present invention, the initiator is azobisisobutyronitrile or azobisisoheptonitrile.

[0024] A denture base composite material is prepared by using the above preparation process.

[0025] Advantages of the present invention:

[0026] The present invention adopts suspension polymerization to carry out in-situ polymerization of methyl methacrylate and functional polymer monomers on the surface of acetylene gas, and a denture base composite material is prepared. First of all, tourmaline exists in the composite material in the form of chemical bonds. On the one hand, it can play a role in transmitting and dispersing stress loads, enhancing the mechanical strength of the composite material. On the other hand, chemical bonding is conducive to the uniform dispersion of tourmaline. By utilizing the characteristic that tourmaline can release negative ions, the balance of oral functions is adjusted.

[0027] A large number of silicon-oxygen bonds are contained in the structure of the functional polymer monomer. These silicon-oxygen bonds show strong hydrophobicity, which can endow the composite material with hydrophobic and oleophobic effects, reducing the adhesion of food residues on the tooth surface. In addition, a large amount of curcumin contained in its structure has a broad-spectrum antibacterial effect, which can eliminate oral bacteria and improve the oral microbial environment.

[0028] Of course, it is not necessary for any product implementing the present invention to achieve all the above-mentioned advantages simultaneously. Description of the drawings

[0029] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for describing the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0030] Figure 1Infrared analysis test chart of the functional polymer monomer. Detailed implementation mode

[0031] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0032] Preparation example 1

[0033] Preparation of the functional polymer monomer:

[0034] Step S1: Add 1.2 g of curcumin and 100 mL of anhydrous toluene to a reactor filled with nitrogen. After adding, start stirring. After mixing evenly, it is recorded as the first mixed solution. Add 0.45 g of allyldichloro(methyl)silane to 100 mL of anhydrous toluene and mechanically stir to mix evenly, which is recorded as the second mixed solution;

[0035] Step S2: Add the second mixed solution to the first mixed solution at a stirring rate of 1500 r / min to form a reaction solution. Add 0.1 g of pyridine to the reaction solution. After adding, then gradually raise the temperature to 65 °C. Keep stirring at this temperature for 9 h, then evaporate to remove the solvent, cool down and discharge to obtain the functional polymer monomer.

[0036] The functional polymer monomer is made into a potassium bromide tablet for infrared analysis test. The results are shown in Figure 1 , where the absorption peak at 3211 cm -1 is the characteristic absorption peak of the hydroxyl group, and the absorption peaks at 3092 cm -1 and 3067 cm -1 are the carbon-hydrogen absorption peaks on the benzene ring skeleton of curcumin. The absorption peak at 3008 cm -1 is the characteristic absorption peak of the carbon-hydrogen on the unsaturated carbon-carbon double bond. The absorption peak at 1000 - 1100 cm -1 is the characteristic absorption peak of the overlapping ether bond and siloxane bond.

[0037] Preparation example 2

[0038] Preparation of the modified tourmaline:

[0039] Mix 2.4 g of tourmaline with 1,4-dioxane, and ultrasonically disperse it until a uniform dispersion is formed. Then, add 6 g of diallylcarbamyl chloride to the dispersion. After adding, introduce nitrogen to expel air, turn on the heating, raise the temperature to 50 °C, keep the temperature for 4 h, then cool down and discharge the material. Centrifuge to obtain the solid material, and after washing and vacuum drying, the modified tourmaline can be obtained through the post-treatment process.

[0040] Example 1

[0041] A denture base composite material is made from the following raw materials by weight:

[0042]

[0043] The preparation process of the composite material includes the following steps:

[0044] First step: Weigh each raw material according to the weight parts and set aside.

[0045] Second step: Add the modified tourmaline to purified water, ultrasonically disperse it evenly, then add sodium dodecylbenzenesulfonate, and ultrasonically treat it for 30 min at an ultrasonic frequency of 80 kHz. Then, turn on the heating, control the temperature at 70 °C, and add methyl methacrylate, functional polymer monomer, and azobisisobutyronitrile under stirring conditions. After adding, raise the temperature to 78 °C, keep the temperature for 16 h, then stop heating. After the material cools down, filter and separate to collect the product, and the composite material can be obtained.

[0046] The preparation method of the functional polymer monomer can be found in Preparation Example 1, and the preparation method of the modified tourmaline can be found in Preparation Example 2, and the same applies hereinafter.

[0047] Example 2

[0048] A denture base composite material is made from the following raw materials by weight:

[0049]

[0050]

[0051] The preparation process of the composite material includes the following steps:

[0052] First step: Weigh each raw material according to the weight parts and set aside.

[0053] Step 2: Add the modified tourmaline into purified water. After ultrasonic dispersion until uniform, add sodium dodecyl sulfate. Then, under the ultrasonic frequency of 100 kHz, ultrasonic for 20 min, turn on the heating, control the temperature at 75 °C, add methyl methacrylate, functional polymer monomer and azodiisobutyronitrile under stirring conditions. After adding, raise the temperature to 80 °C, keep warm for 12 h, then stop heating. After the material cools down, filter and separate to collect the product, and the composite material can be obtained.

[0054] Example 3

[0055] A denture base composite material is made from raw materials including the following parts by weight:

[0056]

[0057] The preparation process of the composite material includes the following steps:

[0058] Step 1: Weigh each raw material according to the parts by weight and set aside.

[0059] Step 2: Add the modified tourmaline into purified water. After ultrasonic dispersion until uniform, add sodium dodecylbenzene sulfonate. Then, under the ultrasonic frequency of 100 kHz, ultrasonic for 10 min, turn on the heating, control the temperature at 75 °C, add methyl methacrylate, functional polymer monomer and azodiisobutyronitrile under stirring conditions. After adding, raise the temperature to 82 °C, keep warm for 8 h, then stop heating. After the material cools down, filter and separate to collect the product, and the composite material can be obtained.

[0060] Comparative Example 1

[0061] A denture base composite material is made from raw materials including the following parts by weight:

[0062]

[0063] The preparation process of the composite material includes the following steps:

[0064] Step 1: Weigh each raw material according to the parts by weight and set aside.

[0065] Step 2: Add the modified tourmaline into purified water. After ultrasonic dispersion until uniform, add sodium dodecyl sulfate. Then, under the ultrasonic frequency of 100 kHz, ultrasonic for 20 min, turn on the heating, control the temperature at 75 °C, add methyl methacrylate and azodiisobutyronitrile under stirring conditions. After adding, raise the temperature to 80 °C, keep warm for 12 h, then stop heating. After the material cools down, filter and separate to collect the product, and the composite material can be obtained.

[0066] Comparative Example 2

[0067] A denture base composite material is made from raw materials including the following parts by weight:

[0068]

[0069] The preparation process of the composite material includes the following steps:

[0070] First step: Weigh each raw material according to the parts by weight and set aside.

[0071] Second step: Add tourmaline into purified water. After ultrasonic dispersion evenly, add sodium dodecyl sulfate. Under the ultrasonic frequency of 100 kHz, ultrasonic for 20 min, then turn on the heating, control the temperature at 75 °C, and add methyl methacrylate, functional polymer monomer and azobisisobutyronitrile under stirring conditions. After adding, raise the temperature to 80 °C, keep warm for 12 h, then stop heating. After the material cools, filter and separate to collect the product, and the composite material can be obtained.

[0072] Test example

[0073] Make the composite materials in the examples and comparative examples into standard test samples and conduct comprehensive performance tests. The test results are recorded in Table 1:

[0074] Table 1 - Test results

[0075]

[0076] Note: The test method for tensile strength refers to the standard GB / T 1040 - 1992;

[0077] The test method for flexural strength refers to the standard GB / T 9341 - 2008;

[0078] The test method for impact strength refers to the standard GB / T 1843 - 2008;

[0079] The test method for antibacterial rate refers to the standard QB / T 2591 - 2003.

[0080] The water contact angle is tested by a water contact angle measuring instrument.

[0081] It can be analyzed from the test results that the composite material prepared from modified tourmaline and functional polymer monomer as raw materials has excellent mechanical properties and antibacterial properties, and the water contact angle exceeds 150°, showing superhydrophobicity and having an easy-to-clean effect.

[0082] After removing the functional polymer monomer, it can be clearly seen that the composite material no longer has the superhydrophobic effect, but due to the presence of tourmaline, it can still show a certain antibacterial property.

[0083] After replacing the modified tourmaline with tourmaline, due to the interface problem between tourmaline and polymethyl methacrylate, its enhancement advantage cannot be effectively exerted, resulting in a significant decline in the mechanical properties of the composite material.

[0084] In this article, specific examples are used to illustrate the principle and implementation mode of the present invention. The description of the above embodiments is only used to help understand the method and its core idea of the present invention, including the best mode, and also enables any person skilled in the art to practice the present invention, including manufacturing and using any device or system, and implementing any combined method. It should be noted that for those of ordinary skill in the art in the technical field, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention. The protection scope of the present invention patent is defined by the claims and may include other embodiments that can be conceived by those skilled in the art. If these other embodiments have structural elements similar to the literal description of the claims, or if they include equivalent structural elements that have no substantial difference from the literal description of the claims, then these other embodiments should also be included within the scope of the claims.

[0085] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features; and these modifications or replacements will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A preparation process of a denture base composite material, characterized in that, The composite material is made from raw materials including the following parts by weight: 46 - 53 parts of methyl methacrylate; 3 - 4.5 parts of functional polymerizable monomer; 2 - 3 parts of modified tourmaline; 0.5 - 1 part of activator; 0.5 - 1 part of initiator; 200 - 240 parts of purified water; The preparation process includes the following steps: First step: Weigh each raw material according to the parts by weight and set aside. Second step: Add the modified tourmaline into the purified water. After ultrasonic dispersion until uniform, add the activator, and under the ultrasonic frequency of 80 - 100 kHz, ultrasonic for 10 - 30 min, then turn on the heating, control the temperature at 70 - 75 °C, and add methyl methacrylate, functional polymerizable monomer and initiator under stirring conditions. After adding, raise the temperature to 78 - 82 °C, keep warm for 8 - 16 h, then stop heating. After the material cools, filter and separate to collect the product, thus obtaining the composite material. The functional polymerizable monomer is prepared by using curcumin and allyldichloro(methyl)silane as reactants, and under the action of an acid acceptor, continuous substitution reactions occur between the active hydroxyl substituents and silicon chlorine groups in their structures. The modified tourmaline is prepared by using diallylcarbamyl chloride as a surface functionalization modification reagent to carry out surface alkenyl functionalization modification on tourmaline.

2. The preparation process of a denture base composite material according to claim 1, characterized in that, The preparation method of the functional polymerizable monomer is as follows: Step S1: Add curcumin and anhydrous toluene into a reactor filled with nitrogen. After adding, turn on the stirring. After mixing evenly, record it as the first mixed solution. Add allyldichloro(methyl)silane into anhydrous toluene and mechanically stir to mix evenly, record it as the second mixed solution. Step S2: Under the stirring rate of 1000 - 1500 r / min, add the second mixed solution into the first mixed solution to form a reaction solution. Add an acid acceptor to the reaction solution. After adding, then gradually raise the temperature to 60 - 65 °C. Keep stirring at this temperature for 8 - 12 h, then evaporate to remove the solvent, cool down and discharge, thus obtaining the functional polymerizable monomer.

3. The preparation process of a denture base composite material according to claim 2, characterized in that, In step S2, the molar ratio of curcumin to allyldichloro(methyl)silane in the reaction solution is 1 - 1.2:

1.

4. The preparation process of a denture base composite material according to claim 2, characterized in that, In step S2, the acid acceptor is pyridine or triethylamine.

5. The preparation process of a denture base composite material according to claim 1, characterized in that, The preparation method of the modified tourmaline is as follows: Mix tourmaline with 1,4 - dioxane and ultrasonic disperse until a uniform dispersion is formed. Then add the surface functionalization modification reagent to the dispersion. After adding, introduce nitrogen to discharge air, turn on the heating, raise the temperature to 40 - 50 °C, keep warm for 3 - 6 h, then cool down and discharge. Centrifuge to obtain the solid material, and after washing and vacuum drying, the modified tourmaline can be obtained through the post - treatment process.

6. The preparation process of a denture base composite material according to claim 5, characterized in that, The mass ratio of the tourmaline to the surface functionalization modification reagent is 1:2 - 3.

5.

7. The preparation process of a denture base composite material according to claim 1, characterized in that, The activator is sodium dodecylbenzenesulfonate or sodium dodecyl sulfate.

8. The preparation process of a denture base composite material according to claim 1, characterized in that, The initiator is azobisisobutyronitrile or azobisisoheptonitrile.

9. A denture base composite material, characterized in that, Prepared by using the preparation process according to any one of claims 1 - 8.

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