1. Mixed crystal phase TiO₂The grafted polymethyl methacrylate denture base resin is characterized in that: the mixed crystal phase TiO₂Grafted polymethacrylic acidThe preparation method of the methyl ester denture base resin comprises the following steps:

(1) dissolving tetrabutyl titanate in absolute ethyl alcohol, dissolving titanium tetrachloride in deionized water, mixing the two solutions, adjusting the pH value to 2-5, adding hexadecyl trimethyl ammonium bromide, stirring for reaction, placing the obtained gel in a hydrothermal reaction kettle, performing hydrothermal crystallization at the temperature of 130-170 ℃, washing, separating, drying in vacuum, calcining at the temperature of 400-450 ℃ for 2-4h to obtain mixed crystal phase nano TiO₂；

(2) Mixing crystal phase nano TiO₂Adding the mixture and 2, 4-toluene diisocyanate into an acetone solvent, carrying out ultrasonic treatment for 3-6h in the nitrogen atmosphere, carrying out centrifugal washing and vacuum drying to obtain isocyanated mixed crystal phase nano TiO₂；

(3) Adding methyl methacrylate and dibenzyl trithiocarbonate into a tetrahydrofuran solvent under the nitrogen atmosphere, then dropwise adding azodiisobutyronitrile, heating for reaction, then adding n-butylamine, stirring for reaction, precipitating, washing, filtering and drying in vacuum to obtain mercapto-terminated polymethyl methacrylate;

(4) the end-mercapto polymethyl methacrylate and mixed crystal phase nano TiO are mixed₂Adding the mixed crystal phase into a toluene solvent, performing ultrasonic dispersion, adding triethylamine, stirring for reaction, precipitating, filtering, washing and drying in vacuum to obtain mixed crystal phase nano TiO₂Grafting polymethyl methacrylate antibacterial material;

(5) mixing crystal phase nano TiO₂Uniformly mixing the grafted polymethyl methacrylate antibacterial material and benzoyl peroxide, adding denture water prepared from N, N-dimethylaniline and methyl methacrylate, and curing in a mold to obtain mixed crystal phase TiO₂Grafted polymethyl methacrylate denture base resin.

2. The mixed crystal phase TiO of claim 1₂The grafted polymethyl methacrylate denture base resin is characterized in that: the mixed crystal phase nano TiO in the step (2)₂The mass ratio of the isocyanate to the 2, 4-toluene diisocyanate is 100: 80-120.

3. The mixed crystal phase TiO of claim 1₂The grafted polymethyl methacrylate denture base resin is characterized in that: the mass ratio of the methyl methacrylate, the dibenzyl trithiocarbonate and the azobisisobutyronitrile in the step (3) is 100:200-260: 40-50.

4. The mixed crystal phase TiO of claim 1₂The grafted polymethyl methacrylate denture base resin is characterized in that: the temperature for heating and reacting in the step (3) is 55-75 ℃, and the reaction time is 14-20 h.

5. The mixed crystal phase TiO of claim 1₂The grafted polymethyl methacrylate denture base resin is characterized in that: the temperature of the stirring reaction in the step (3) is 20-40 ℃, and the reaction time is 20-30 h.

6. The mixed crystal phase TiO of claim 1₂The grafted polymethyl methacrylate denture base resin is characterized in that: in the step (4), the end-mercapto-polymethyl methacrylate and the mixed crystal phase nano TiO₂The mass ratio of (A) to (B) is 100: 1-4.

7. The mixed crystal phase TiO of claim 1₂The grafted polymethyl methacrylate denture base resin is characterized in that: the temperature for stirring and reacting in the step (4) is 20-40 ℃, and the reaction time is 30-60 min.

8. The mixed crystal phase TiO of claim 1₂The grafted polymethyl methacrylate denture base resin is characterized in that: the mixed crystal phase nano TiO in the step (5)₂The mass ratio of the grafted polymethyl methacrylate antibacterial material to the benzoyl peroxide to the N, N-dimethylaniline to the methyl methacrylate is 100:0.8-1.2:0.4-0.6: 40-60.

9. The mixed crystal phase TiO of claim 1₂The grafted polymethyl methacrylate denture base resin is characterized in that: the curing temperature in the step (5) is 20-50 ℃, and the curing time is 15-60 min.

Background

With the development of society and the increasing living standard of people, various high-sugar diets such as: milky tea, cola, ice lolly, cake, etc., are foods which people like to eat, under the continuous impact of sweet food, the teeth of people become more fragile, more and more people have to perform tooth filling or use false teeth to perform normal chewing food with the corrosion of years, while the false tooth base is a bracket for connecting the artificial teeth and the alveolar ridge of the missing teeth to disperse the pressure caused by chewing, is an important component of the false tooth, is usually made of metal or resin, and polymethyl methacrylate is a main material of the false tooth base resin.

Because the denture base needs to be in the oral cavity for a long time, residual food can provide nutrition for microorganisms such as bacteria and fungi to form dental plaque, the service life of the denture can be shortened, and the denture is easy to be infected by inflammation for users, particularly the old people, the denture is required to have certain antibacterial performance, polymethyl methacrylate is used as a main material of the denture base resin denture powder, does not have the antibacterial performance per se, and therefore needs to be subjected to antibacterial modification, and TiO with good photocatalytic antibacterial activity₂The artificial tooth is a good antibacterial material and can effectively kill common bacteria in oral cavities such as candida albicans and the like, but because the artificial tooth usually works under the condition of dark light, the artificial tooth needs to have good antibacterial performance under the condition of weak light, and TiO with wide forbidden band is needed₂Certain modification is carried out to ensure that the antibacterial agent has better light utilization rate, and meanwhile, the antibacterial agent is difficult to maintain long-term stable antibacterial performance due to physical mixing and needs to be solved by a chemical grafting mode.

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides mixed crystal phase TiO₂The grafted polymethyl methacrylate denture base resin and the preparation method solve the problem of simple physical addition of TiO₂Poor long-term stability of the antibacterial, and ordinary TiO₂Poor antibacterial performance under the condition of weak light.

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme: mixed crystal phase TiO₂The preparation method of the grafted polymethyl methacrylate denture base resin comprises the following steps:

(1) dissolving tetrabutyl titanate in absolute ethyl alcohol, dissolving titanium tetrachloride in deionized water, mixing the two solutions, adjusting the pH value to 2-5, adding hexadecyl trimethyl ammonium bromide, stirring for reaction, placing the obtained gel in a hydrothermal reaction kettle, performing hydrothermal crystallization at the temperature of 130-170 ℃, washing, separating, drying in vacuum, calcining at the temperature of 400-450 ℃ for 2-4h to obtain mixed crystal phase nano TiO₂；

(2) Will be mixed withCrystalline phase nano TiO₂Adding the mixture and 2, 4-toluene diisocyanate into an acetone solvent, carrying out ultrasonic treatment for 3-6h in the nitrogen atmosphere, carrying out centrifugal washing and vacuum drying to obtain isocyanated mixed crystal phase nano TiO₂；

(3) Adding methyl methacrylate and dibenzyl trithiocarbonate into a tetrahydrofuran solvent under the nitrogen atmosphere, then dropwise adding azodiisobutyronitrile, heating for reaction, then adding n-butylamine, stirring for reaction, precipitating, washing, filtering and drying in vacuum to obtain mercapto-terminated polymethyl methacrylate;

(4) the end-mercapto polymethyl methacrylate and mixed crystal phase nano TiO are mixed₂Adding the mixed crystal phase into a toluene solvent, performing ultrasonic dispersion, adding triethylamine, stirring for reaction, precipitating, filtering, washing and drying in vacuum to obtain mixed crystal phase nano TiO₂Grafting polymethyl methacrylate antibacterial material;

(5) mixing crystal phase nano TiO₂Uniformly mixing the grafted polymethyl methacrylate antibacterial material and benzoyl peroxide, adding denture water prepared from N, N-dimethylaniline and methyl methacrylate, and curing in a mold to obtain mixed crystal phase TiO₂Grafted polymethyl methacrylate denture base resin.

Preferably, the mixed crystal phase nano TiO in the step (2)₂The mass ratio of the isocyanate to the 2, 4-toluene diisocyanate is 100: 80-120.

Preferably, the mass ratio of the methyl methacrylate, the dibenzyl trithiocarbonate and the azobisisobutyronitrile in the step (3) is 100:200-260: 40-50.

Preferably, the heating in the step (3) is carried out at the temperature of 55-75 ℃ for 14-20 h.

Preferably, the stirring reaction in the step (3) is carried out at the temperature of 20-40 ℃ for 20-30 h.

Preferably, in the step (4), the end-mercapto-polymethyl methacrylate and the mixed crystal phase nano TiO are adopted₂The mass ratio of (A) to (B) is 100: 1-4.

Preferably, the temperature for stirring to carry out the reaction in the step (4) is 20-40 ℃, and the reaction time is 30-60 min.

Preferably, the mixed crystal phase nano TiO in the step (5)₂The mass ratio of the grafted polymethyl methacrylate antibacterial material to the benzoyl peroxide to the N, N-dimethylaniline to the methyl methacrylate is 100:0.8-1.2:0.4-0.6: 40-60.

Preferably, the curing temperature in the step (5) is 20-50 ℃, and the curing time is 15-60 min.

(III) advantageous technical effects

Compared with the prior art, the invention has the following experimental principles and beneficial technical effects:

the mixed crystal phase TiO₂Grafted polymethyl methacrylate denture base resin is prepared by using two different titanium sources of tetrabutyl titanate and titanium tetrachloride to obtain mixed crystal phase nano TiO₂And obtaining isocyanated mixed crystal phase nano TiO by processing 2, 4-toluene diisocyanate₂The methacrylic acid monomer initiates reversible addition-fragmentation chain transfer polymerization on dibenzyl trithiocarbonate through azodiisobutyronitrile initiator, then n-butylamine is added to ammonolyze trithiocarbonate to obtain mercapto-terminated polymethyl methacrylate, and the mercapto-terminated polymethyl methacrylate and isocyanated mixed crystal phase nano TiO are further mixed with₂Carrying out sulfydryl-isocyanate click reaction under the catalysis of triethylamine to obtain mixed crystal phase nano TiO₂Grafting polymethyl methacrylate antibacterial material, mixing the grafted polymethyl methacrylate antibacterial material with benzoyl peroxide to obtain denture powder, preparing denture water from N, N-dimethylaniline and methyl methacrylate, mixing and curing to obtain mixed crystal phase nano TiO₂Grafted polymethyl methacrylate denture base resin, and TiO obtained by sol-gel-hydrothermal method and calcination₂Has a ternary crystal phase structure of anatase phase, brookite phase and rutile phase to form an out-of-phase structure, so that not only can TiO be enabled to be₂The band structure of the material is crossed, the separation of electron-hole pairs is promoted, and TiO can be reduced₂The forbidden band width improves the utilization rate of light energy, so that the photocatalyst antibacterial material still has better photocatalytic antibacterial activity in an environment with weaker light energy, and the generated active holes, hydroxyl free radicals and the like can damage the structures of candida albicans, staphylococcus aureus and other bacteria to achieve the aim ofThe purpose of anti-bacterial, thereby protecting the denture base, prolonging the service life and reducing the possibility of inflammation caused by using the denture.

The mixed crystal phase TiO₂The grafted polymethyl methacrylate denture base resin is uniformly grafted in a polymethyl methacrylate matrix in a covalent bond grafting mode, has better dispersibility compared with physical mixing, and simultaneously enables TiO to exist due to the existence of chemical bonds₂Can be firmly combined with polymethyl methacrylate matrix, thereby achieving the long-lasting antibacterial effect, good antibacterial stability, good dispersibility and good antibacterial effect through being combined with TiO₂The chemical bonding mode reduces the problem of mechanical property reduction caused by doping, thereby prolonging the service life of the denture, protecting denture base resin with good dispersibility in an all-round way and inhibiting the breeding of bacteria at corners.

Detailed Description

In order to achieve the purpose, the invention provides the following technical scheme: the mixed crystal phase TiO₂The preparation method of the grafted polymethyl methacrylate denture base resin comprises the following steps:

(1) dissolving tetrabutyl titanate in absolute ethyl alcohol, dissolving titanium tetrachloride in deionized water, mixing the two solutions, adjusting the pH value to 2-5, adding hexadecyl trimethyl ammonium bromide, stirring for reaction, placing the obtained gel in a hydrothermal reaction kettle, performing hydrothermal crystallization at the temperature of 130-170 ℃, washing, separating, drying in vacuum, calcining at the temperature of 400-450 ℃ for 2-4h to obtain mixed crystal phase nano TiO₂；

(2) Mixing crystal phase nano TiO₂Adding the mixed crystal phase and 2, 4-toluene diisocyanate into an acetone solvent, wherein the mixed crystal phase is nano TiO₂The mass ratio of the isocyanate to 2, 4-toluene diisocyanate is 100:80-120, ultrasonic treatment is carried out for 3-6h under the atmosphere of nitrogen, centrifugal washing and vacuum drying are carried out, and the isocyanated mixed crystal phase nano TiO is obtained₂；

(3) Adding methyl methacrylate and dibenzyl trithiocarbonate into a tetrahydrofuran solvent under the nitrogen atmosphere, then dropwise adding azobisisobutyronitrile, wherein the mass ratio of the methyl methacrylate to the dibenzyl trithiocarbonate to the azobisisobutyronitrile is 100:200: 260:40-50, heating for reaction at the temperature of 55-75 ℃ for 14-20h, adding n-butylamine, stirring for reaction at the temperature of 20-40 ℃ for 20-30h, precipitating, washing, filtering and drying in vacuum to obtain mercapto-terminated polymethyl methacrylate;

(4) the end-mercapto polymethyl methacrylate and mixed crystal phase nano TiO are mixed₂Adding the mixture into a toluene solvent, wherein the end-mercapto polymethyl methacrylate and the mixed crystal phase nano TiO₂The mass ratio of the components is 100:1-4, ultrasonic dispersion is carried out, triethylamine is added, stirring is carried out for reaction, the reaction temperature is 20-40 ℃, the reaction time is 30-60min, precipitation, filtration, washing and vacuum drying are carried out, and mixed crystal phase nano TiO is obtained₂Grafting polymethyl methacrylate antibacterial material;

(5) mixing crystal phase nano TiO₂Uniformly mixing the grafted polymethyl methacrylate antibacterial material and benzoyl peroxide, and then adding denture water prepared from N, N-dimethylaniline and methyl methacrylate, wherein the mixed crystal phase is nano TiO₂The graft polymethyl methacrylate antibacterial material, the benzoyl peroxide, the N, N-dimethylaniline and the methyl methacrylate are solidified in a mould at the temperature of 20-50 ℃ for 15-60min according to the mass ratio of 100:0.8-1.2:0.4-0.6:40-60 to obtain mixed crystal phase TiO₂Grafted polymethyl methacrylate denture base resin.

Example 1

(1) Dissolving tetrabutyl titanate in absolute ethyl alcohol, dissolving titanium tetrachloride in deionized water, mixing the two solutions, adjusting the pH to 2, adding hexadecyl trimethyl ammonium bromide, stirring for reaction, placing the obtained gel in a hydrothermal reaction kettle, performing hydrothermal crystallization at 130 ℃, washing, separating, vacuum drying, and calcining at 400 ℃ for 2 hours to obtain mixed crystal phase nano TiO₂；

(2) Mixing crystal phase nano TiO₂Adding the mixed crystal phase and 2, 4-toluene diisocyanate into an acetone solvent, wherein the mixed crystal phase is nano TiO₂The mass ratio of the 2, 4-toluene diisocyanate to the water is 100:80, ultrasonic treatment is carried out for 3 hours in the nitrogen atmosphere, and centrifugal washing is carried outVacuum drying to obtain isocyanated mixed crystal phase nano TiO₂；

(3) Adding methyl methacrylate and dibenzyl trithiocarbonate into a tetrahydrofuran solvent under the nitrogen atmosphere, then dropwise adding azobisisobutyronitrile, wherein the mass ratio of the methyl methacrylate to the dibenzyl trithiocarbonate to the azobisisobutyronitrile is 100:200:40, heating to react at the temperature of 55 ℃ for 14h, adding n-butylamine, stirring to react at the temperature of 20 ℃ for 20h, and carrying out precipitation washing, filtering and vacuum drying to obtain the mercapto-terminated polymethyl methacrylate;

(4) the end-mercapto polymethyl methacrylate and mixed crystal phase nano TiO are mixed₂Adding the mixture into a toluene solvent, wherein the end-mercapto polymethyl methacrylate and the mixed crystal phase nano TiO₂The mass ratio of the components is 100:1, ultrasonic dispersion is carried out, triethylamine is added, stirring is carried out for reaction, the reaction temperature is 20 ℃, the reaction time is 30min, precipitation, filtration, washing and vacuum drying are carried out, and mixed crystal phase nano TiO is obtained₂Grafting polymethyl methacrylate antibacterial material;

(5) mixing crystal phase nano TiO₂Uniformly mixing the grafted polymethyl methacrylate antibacterial material and benzoyl peroxide, and then adding denture water prepared from N, N-dimethylaniline and methyl methacrylate, wherein the mixed crystal phase is nano TiO₂The grafted polymethyl methacrylate antibacterial material, the benzoyl peroxide, the N, N-dimethylaniline and the methyl methacrylate are solidified in a mould at the solidification temperature of 20 ℃ for 15min according to the mass ratio of 100:0.8:0.4:40 to obtain mixed crystal phase TiO₂Grafted polymethyl methacrylate denture base resin.

Example 2

(1) Dissolving tetrabutyl titanate in absolute ethyl alcohol, dissolving titanium tetrachloride in deionized water, mixing the two solutions, adjusting the pH value to 3, adding hexadecyl trimethyl ammonium bromide, stirring for reaction, placing the obtained gel in a hydrothermal reaction kettle, performing hydrothermal crystallization at 140 ℃, washing, separating, vacuum drying, and calcining at 420 ℃ for 3 hours to obtain mixed crystal phase nano TiO₂；

(2) Mixing crystal phase nano TiO₂Adding the mixed crystal phase and 2, 4-toluene diisocyanate into an acetone solvent, wherein the mixed crystal phase is nano TiO₂The mass ratio of the isocyanate to 2, 4-toluene diisocyanate is 100:90, ultrasonic treatment is carried out for 4 hours in the nitrogen atmosphere, centrifugal washing and vacuum drying are carried out, and the isocyanated mixed crystal phase nano TiO is obtained₂；

(3) Adding methyl methacrylate and dibenzyl trithiocarbonate into a tetrahydrofuran solvent under the nitrogen atmosphere, then dropwise adding azobisisobutyronitrile, wherein the mass ratio of the methyl methacrylate to the dibenzyl trithiocarbonate to the azobisisobutyronitrile is 100:220:45, heating to react at the temperature of 60 ℃ for 16h, adding n-butylamine, stirring to react at the temperature of 30 ℃ for 24h, and carrying out precipitation washing, filtering and vacuum drying to obtain the mercapto-terminated polymethyl methacrylate;

(4) the end-mercapto polymethyl methacrylate and mixed crystal phase nano TiO are mixed₂Adding the mixture into a toluene solvent, wherein the end-mercapto polymethyl methacrylate and the mixed crystal phase nano TiO₂The mass ratio of the mixed crystal phase nano TiO is 100:2, ultrasonic dispersion is carried out, triethylamine is added, stirring is carried out for reaction, the reaction temperature is 30 ℃, the reaction time is 40min, precipitation, filtration, washing and vacuum drying are carried out, and the mixed crystal phase nano TiO is obtained₂Grafting polymethyl methacrylate antibacterial material;

(5) mixing crystal phase nano TiO₂Uniformly mixing the grafted polymethyl methacrylate antibacterial material and benzoyl peroxide, and then adding denture water prepared from N, N-dimethylaniline and methyl methacrylate, wherein the mixed crystal phase is nano TiO₂The grafted polymethyl methacrylate antibacterial material, the benzoyl peroxide, the N, N-dimethylaniline and the methyl methacrylate are solidified in a mould at the solidification temperature of 30 ℃ for 30min according to the mass ratio of 100:0.9:0.45:45 to obtain mixed crystal phase TiO₂Grafted polymethyl methacrylate denture base resin.

Example 3

(1) Dissolving tetrabutyl titanate in anhydrous ethanol, dissolving titanium tetrachloride in deionized waterMixing the two solutions in water, adjusting pH to 4, adding cetyl trimethyl ammonium bromide, stirring for reaction, placing the obtained gel in a hydrothermal reaction kettle, performing hydrothermal crystallization at 160 deg.C, washing for separation, vacuum drying, and calcining at 440 deg.C for 3 hr to obtain mixed crystal phase nanometer TiO₂；

(2) Mixing crystal phase nano TiO₂Adding the mixed crystal phase and 2, 4-toluene diisocyanate into an acetone solvent, wherein the mixed crystal phase is nano TiO₂The mass ratio of the isocyanate to 2, 4-toluene diisocyanate is 100:100, ultrasonic treatment is carried out for 5 hours in the nitrogen atmosphere, centrifugal washing and vacuum drying are carried out, and the isocyanated mixed crystal phase nano TiO is obtained₂；

(3) Adding methyl methacrylate and dibenzyl trithiocarbonate into a tetrahydrofuran solvent under the nitrogen atmosphere, then dropwise adding azobisisobutyronitrile, wherein the mass ratio of the methyl methacrylate to the dibenzyl trithiocarbonate to the azobisisobutyronitrile is 100:240:46, heating to react at the temperature of 65 ℃ for 18 hours, adding n-butylamine, stirring to react at the temperature of 35 ℃ for 26 hours, and carrying out precipitation washing, filtering and vacuum drying to obtain the mercapto-terminated polymethyl methacrylate;

(4) the end-mercapto polymethyl methacrylate and mixed crystal phase nano TiO are mixed₂Adding the mixture into a toluene solvent, wherein the end-mercapto polymethyl methacrylate and the mixed crystal phase nano TiO₂The mass ratio of the components is 100:3, ultrasonic dispersion is carried out, triethylamine is added, stirring is carried out for reaction, the reaction temperature is 30 ℃, the reaction time is 50min, precipitation, filtration, washing and vacuum drying are carried out, and mixed crystal phase nano TiO is obtained₂Grafting polymethyl methacrylate antibacterial material;

(5) mixing crystal phase nano TiO₂Uniformly mixing the grafted polymethyl methacrylate antibacterial material and benzoyl peroxide, and then adding denture water prepared from N, N-dimethylaniline and methyl methacrylate, wherein the mixed crystal phase is nano TiO₂The mass ratio of the grafted polymethyl methacrylate antibacterial material to the benzoyl peroxide to the N, N-dimethylaniline to the methyl methacrylate is 100:1:0.5:50, and the grafted polymethyl methacrylate antibacterial material is cured in a mould at the curing temperature of 40 DEG CCuring for 45min to obtain mixed crystal phase TiO₂Grafted polymethyl methacrylate denture base resin.

Example 4

(1) Dissolving tetrabutyl titanate in absolute ethyl alcohol, dissolving titanium tetrachloride in deionized water, mixing the two solutions, adjusting the pH value to 5, adding hexadecyl trimethyl ammonium bromide, stirring for reaction, placing the obtained gel in a hydrothermal reaction kettle, performing hydrothermal crystallization at 170 ℃, washing, separating, vacuum drying, and calcining at 450 ℃ for 4 hours to obtain mixed crystal phase nano TiO₂；

(2) Mixing crystal phase nano TiO₂Adding the mixed crystal phase and 2, 4-toluene diisocyanate into an acetone solvent, wherein the mixed crystal phase is nano TiO₂The mass ratio of the isocyanate to 2, 4-toluene diisocyanate is 100:120, ultrasonic treatment is carried out for 6 hours in the nitrogen atmosphere, centrifugal washing and vacuum drying are carried out, and the isocyanated mixed crystal phase nano TiO is obtained₂；

(3) Adding methyl methacrylate and dibenzyl trithiocarbonate into a tetrahydrofuran solvent under the nitrogen atmosphere, then dropwise adding azobisisobutyronitrile, wherein the mass ratio of the methyl methacrylate to the dibenzyl trithiocarbonate to the azobisisobutyronitrile is 100:260:50, heating to react at the temperature of 75 ℃ for 20 hours, adding n-butylamine, stirring to react at the temperature of 40 ℃ for 30 hours, and carrying out precipitation washing, filtering and vacuum drying to obtain the mercapto-terminated polymethyl methacrylate;

(4) the end-mercapto polymethyl methacrylate and mixed crystal phase nano TiO are mixed₂Adding the mixture into a toluene solvent, wherein the end-mercapto polymethyl methacrylate and the mixed crystal phase nano TiO₂The mass ratio of the components is 100:4, ultrasonic dispersion is carried out, triethylamine is added, stirring is carried out for reaction, the reaction temperature is 40 ℃, the reaction time is 60min, precipitation, filtration, washing and vacuum drying are carried out, and mixed crystal phase nano TiO is obtained₂Grafting polymethyl methacrylate antibacterial material;

(5) mixing crystal phase nano TiO₂Uniformly mixing the grafted polymethyl methacrylate antibacterial material and benzoyl peroxide, and then adding N, N-dimethylaniline and methylDenture base water prepared from methyl acrylate, wherein mixed crystal phase is nanometer TiO₂The grafted polymethyl methacrylate antibacterial material, the benzoyl peroxide, the N, N-dimethylaniline and the methyl methacrylate are solidified in a mould at the solidification temperature of 50 ℃ for 60min at the mass ratio of 100:1.2:0.6:60 to obtain mixed crystal phase TiO₂Grafted polymethyl methacrylate denture base resin.

Comparative example 1

(1) Dissolving tetrabutyl titanate in absolute ethyl alcohol, dissolving titanium tetrachloride in deionized water, mixing the two solutions, adjusting the pH to 2, adding hexadecyl trimethyl ammonium bromide, stirring for reaction, placing the obtained gel in a hydrothermal reaction kettle, performing hydrothermal crystallization at 130 ℃, washing, separating, vacuum drying, and calcining at 400 ℃ for 2 hours to obtain mixed crystal phase nano TiO₂；

(2) Mixing crystal phase nano TiO₂Adding the mixed crystal phase and 2, 4-toluene diisocyanate into an acetone solvent, wherein the mixed crystal phase is nano TiO₂The mass ratio of the isocyanate to 2, 4-toluene diisocyanate is 100:60, ultrasonic treatment is carried out for 3 hours in the nitrogen atmosphere, centrifugal washing and vacuum drying are carried out, and the isocyanated mixed crystal phase nano TiO is obtained₂；

(3) Adding methyl methacrylate and dibenzyl trithiocarbonate into a tetrahydrofuran solvent under the nitrogen atmosphere, then dropwise adding azobisisobutyronitrile, wherein the mass ratio of the methyl methacrylate to the dibenzyl trithiocarbonate to the azobisisobutyronitrile is 100:160:30, heating to react at the temperature of 55 ℃ for 14h, adding n-butylamine, stirring to react at the temperature of 20 ℃ for 20h, and carrying out precipitation washing, filtering and vacuum drying to obtain the mercapto-terminated polymethyl methacrylate;

(4) the end-mercapto polymethyl methacrylate and mixed crystal phase nano TiO are mixed₂Adding the mixture into a toluene solvent, wherein the end-mercapto polymethyl methacrylate and the mixed crystal phase nano TiO₂The mass ratio of the components is 100:0.6, ultrasonic dispersion is carried out, triethylamine is added, stirring is carried out for reaction, the reaction temperature is 20 ℃, the reaction time is 30min, precipitation, filtration, washing and vacuum drying are carried outTo obtain mixed crystal phase nano TiO₂Grafting polymethyl methacrylate antibacterial material;

(5) mixing crystal phase nano TiO₂Uniformly mixing the grafted polymethyl methacrylate antibacterial material and benzoyl peroxide, and then adding denture water prepared from N, N-dimethylaniline and methyl methacrylate, wherein the mixed crystal phase is nano TiO₂The grafted polymethyl methacrylate antibacterial material, the benzoyl peroxide, the N, N-dimethylaniline and the methyl methacrylate are solidified in a mould at the solidification temperature of 30 ℃ for 30min according to the mass ratio of 100:0.8:0.4:40 to obtain mixed crystal phase TiO₂Grafted polymethyl methacrylate denture base resin.

Comparative example 2

(1) Dissolving tetrabutyl titanate in absolute ethyl alcohol, dissolving titanium tetrachloride in deionized water, mixing the two solutions, adjusting the pH to 2, adding hexadecyl trimethyl ammonium bromide, stirring for reaction, placing the obtained gel in a hydrothermal reaction kettle, performing hydrothermal crystallization at 130 ℃, washing, separating, vacuum drying, and calcining at 400 ℃ for 2 hours to obtain mixed crystal phase nano TiO₂；

(2) Mixing crystal phase nano TiO₂Adding the mixed crystal phase and 2, 4-toluene diisocyanate into an acetone solvent, wherein the mixed crystal phase is nano TiO₂The mass ratio of the isocyanate to 2, 4-toluene diisocyanate is 100:70, ultrasonic treatment is carried out for 3 hours in the nitrogen atmosphere, centrifugal washing and vacuum drying are carried out, and the isocyanated mixed crystal phase nano TiO is obtained₂；

(3) Adding methyl methacrylate and dibenzyl trithiocarbonate into a tetrahydrofuran solvent under the nitrogen atmosphere, then dropwise adding azobisisobutyronitrile, wherein the mass ratio of the methyl methacrylate to the dibenzyl trithiocarbonate to the azobisisobutyronitrile is 100:180:35, heating to react at the temperature of 55 ℃ for 14 hours, adding n-butylamine, stirring to react at the temperature of 20 ℃ for 20 hours, and precipitating, washing, filtering and vacuum drying to obtain the mercapto-terminated polymethyl methacrylate;

(4) the end-mercapto polymethyl methacrylate and mixed crystal phase nano TiO are mixed₂Adding the mixture into a toluene solvent, wherein the end-mercapto polymethyl methacrylate and the mixed crystal phase nano TiO₂The mass ratio of the components is 100:0.3, ultrasonic dispersion is carried out, triethylamine is added, stirring is carried out for reaction, the reaction temperature is 20 ℃, the reaction time is 30min, precipitation, filtration, washing and vacuum drying are carried out, and mixed crystal phase nano TiO is obtained₂Grafting polymethyl methacrylate antibacterial material;

(5) mixing crystal phase nano TiO₂Uniformly mixing the grafted polymethyl methacrylate antibacterial material and benzoyl peroxide, and then adding denture water prepared from N, N-dimethylaniline and methyl methacrylate, wherein the mixed crystal phase is nano TiO₂The grafted polymethyl methacrylate antibacterial material, the benzoyl peroxide, the N, N-dimethylaniline and the methyl methacrylate are solidified in a mould at the solidification temperature of 20 ℃ for 40min according to the mass ratio of 100:0.8:0.4:40 to obtain mixed crystal phase TiO₂Grafted polymethyl methacrylate denture base resin.

0.8g of the antibacterial denture base resin of the embodiment and the comparative example is soaked in artificial saliva for 1 month, sterilized, ground into powder, added into a conical flask, numbered one by one, then respectively added with 75ml of buffer solution and 5ml of cultured candida albicans, fully vibrated for 18 hours at room temperature in a dark environment, and taken with 1ml of the contacted bacterial suspension without the antibacterial denture base as a blank control, diluted and cultured for 24 hours again, the colony count is counted and the antibacterial rate is calculated, and the test standard is GB/T20944.3-2008.