CN102816089B - Quaternary ammonium salt and carbamate structure containing antibacterial methyl acrylate monomer, preparation method and application thereof - Google Patents
Quaternary ammonium salt and carbamate structure containing antibacterial methyl acrylate monomer, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a quaternary ammonium salt and carbamate structure containing antibacterial methyl acrylate monomer, its preparation method and an application thereof. The quaternary ammonium salt and carbamate structure containing antibacterial methyl acrylate monomer prepared in the invention can be used as an antibacterial ingredient in a dental prosthetic material. The monomer has quaternary ammonium salt and carbamate structure. Therefore, dental cured resin containing the monomer has a certain antibacterial property and toughness.
Description
Technical field
The present invention relates to can be used as the monomer of light initiation polymerization system, be specifically related to a series of germ resistance methacrylate monomer and method for making and application containing quaternary ammonium salt structure.
Background technology
Dental caries disease is that the dental hard tissue being caused by many factors is chronic, carrying out property destruction, if form cavity and repaired in time, pathology can be to Deep Development, causes the complication such as dental pulp inflammation, periapical infection, cause disorganization and cause violent pain, even affect whole body health.Therefore carious tooth is carried out to effective repairing and treating very necessary.
Dental material is most active research field in modern Prosthodontics, has merged Materials science, life science, polymer chemistry and stomatology, and development in the last few years rapidly.And be that photocuring teeth repairing material is requisite containing the monomer of methyl acrylic ester structure.The disclosed a kind of methyl acrylic ester monomers B is-GMA that contains structure of bisphenol A of its Patent US3066112 and US6030606 has now been widely used in teeth repairing material, compared with other repair materials, it has the features such as lower polymerization volumetric shrinkage, high-adhesion and excellent mechanical property.Nowadays, business-like methacrylate based repair materials contains the monomers such as Bis-GMA, polyurethanes methacrylic ester (UDMA) and dimethacrylate triethylene Glycol (TEGDMA) conventionally.
Compared with traditional pottery repair materials, methacrylate resin itself is without anti-microbial activity, surface easily forms bacterial plaque, after reparation has operated, bacterium and microorganism are more prone to be gathered in methacrylic ester repair materials surface or percolation zone bonding interface gap, cause secondary caries, even cause that dummy comes off.Therefore the methacrylate based dental prosthetic material that, exploitation has an anti-microbial activity will become preventing secondary carious tooth one of bonding persistent effective way will occur, improves.
Preparation has an approach of the methyl acrylic ester dental prosthetic material of anti-microbial activity and introduces exactly the methyl acrylic ester monomer with anti-microbial activity group (as quaternary ammonium salt structure).The synthetic a kind of dental prosthetic material of the Imazato of patent US5733949 report and team thereof just belongs to this antiseptic-germicide with methacrylic ester quaternary ammonium salt monomer methacryloxypropyl dodecyl bromopyridine (MDPB), the repair materials of this monomer not only can effectively reduce the gathering on its surface of streptococcus mutans and microorganism, and can with oral cavity macromolecular material generation Chemical bond, the dental prosthetic material of being prepared by MDPB at present successfully listing.And a kind of monomethacrylates quaternary ammonium salt DMAE-CB of the Chen Jihua of The Fourth Military Medical University professor team develops also shows the excellent germ resistance to oral cavity pathogen, and dental prosthetic material prepared therefrom has long-acting anti-microbial activity.
But, in the molecular structure of MDPB and DMAE-CB, only contain a metacrylic acid ester structure, during with resinous substrates monomer polymerization, crosslinking rate is limited, it is influenced that in material, too high levels can cause the performance of material, uncrosslinked germ resistance monomer also likely oozes out from resin-based materials, be unfavorable for oral Health, and these two kinds of monomers hydrophobicity double methyl methacrylate monomer conventional with dental prosthetic material as TEGDMA exists the difficult problem such as mix.
Summary of the invention
The object of the invention is to for existing its existence of dental prosthetic material without germ resistance and existing antibacterial methacrylate monomer and the methacrylate based body of dental prosthetic material difficultly mix, the problem such as crosslinking rate is low, provide a series of containing quaternary ammonium salt structure and carboxylamine ester structures, and novel many methacrylic ester antibacterial monomer and method for making and the application good with existing dental prosthetic material use methacrylate monomer consistency.
Above-mentioned purpose of the present invention is achieved by following scheme:
Containing a germ resistance methacrylate monomer for quaternary ammonium salt and carboxylamine ester structure, its structural formula as shown in the formula (I):
R in structural formula (I)
1get any one of structural formula (II).
In structural formula (II), n is any one numerical value in 1 to 19.
In structural formula (I), X gets any one in structural formula (III).
R in structural formula (I)
2get any one in structure formula IV.
M in structure formula IV is any one numerical value in 0 to 27.
In described formula (I), contain carboxylamine ester structure.In described formula (I), contain quaternary ammonium salt structure.
The preparation method of the described germ resistance methacrylate monomer containing quaternary ammonium salt and carboxylamine ester structure, comprises the steps:
Step 1: N, the preparation of N-dialkyl group diethanolamine quaternary ammonium salt
In the three-necked bottle that magneton is housed, add N methyldiethanol amine and haloalkane, add a certain amount of solvent, stirring reaction 5-30 hour refluxes at 40 ~ 90 ℃, be cooled to room temperature, filter, and by filter cake vacuum-drying 24-72 hour at 25-50 ℃, obtain N, N-dialkyl group diethanolamine quaternary ammonium salt (Q).
Step 2: the preparation of germ resistance methacrylate monomer
In the three-necked bottle that magneton is housed, add isoflurane chalcone diisocyanate (IPDI) or tolylene diisocyanate (TDI), under whipped state, constantly add N by constant pressure funnel, N-dialkyl group diethanolamine quaternary ammonium salt (Q) and catalyzer, add a certain amount of solvent to reduce system viscosity, at 5 ~ 65 ℃, react 0.5～24 hour, until in isocyanic ester system-NCO per-cent approaches theoretical value, water-bath adjusts the temperature to 15 ~ 90 ℃, then in reactor, add methacrylic acid hydroxyl alkyl esters compound or 2-hydroxyl-1 by constant pressure funnel, 3-dimethyl allene acyloxy propane, add catalyzer and stopper simultaneously, and use eluent solvent constant pressure funnel, 2 ~ 18 hours reaction times, then reaction product is carried out to purification processes.
Wherein the mol ratio of N methyldiethanol amine and haloalkane is 1:1.05-1.10.
Isoflurane chalcone diisocyanate (IPDI) or tolylene diisocyanate (TDI) and N, the mol ratio of N-dialkyl group diethanolamine quaternary ammonium salt is 2:1; Methacrylic acid hydroxyl alkyl esters compound or 2-hydroxyl-1,3-dimethyl allene acyloxy propane and N, the mol ratio of N-dialkyl group diethanolamine quaternary ammonium salt is 2:1; Catalyst levels is 0.02% ~ 1% of reactant total mass; Stopper is 0.1% ~ 0.6% of reactant total mass.
Described solvent is selected from ether, methylene dichloride, trichloromethane, ethyl acetate, 1, one or more above mixtures of 2-ethylene dichloride, benzene, toluene, acetone, butanone, cyclohexanone or DMF.
Catalyzer is selected from triethylamine, triethylenediamine, tetramethyl butane diamine, N, one or more the above mixtures in N-dimethyl benzylamine, dibutyl tin dilaurate, stannous octoate etc.
Stopper is selected from one or more the above mixtures in Resorcinol, para benzoquinone, toluhydroquinone, MEHQ, 2,5 di tert butyl hydroquinone, 2-Tert. Butyl Hydroquinone etc.
N, alkyl in N-dialkyl group diethanolamine quaternary ammonium salt comprises: methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, ceryl, heptacosyl, octacosyl, nonacosyl, cyclohexyl.
Methacrylic acid hydroxyl alkyl ester base class compound comprises methacrylic acid hydroxyl ethyl ester, methacrylic acid hydroxyl propyl diester, methacrylic acid hydroxyl butyl ester, methacrylic acid hydroxyl amyl group ester, methacrylic acid hydroxyl polyhexamethylene, methacrylic acid hydroxyl heptyl ester, methacrylic acid hydroxyl octyl group ester, methacrylic acid hydroxyl nonyl ester, methacrylic acid hydroxyl decyl ester, methacrylic acid hydroxyl undecyl ester, methacrylic acid hydroxyl dodecyl ester, methacrylic acid hydroxyl tridecyl ester, methacrylic acid hydroxyl tetradecyl ester, methacrylic acid hydroxyl pentadecyl ester, methacrylic acid hydroxyl cetyl ester, methacrylic acid hydroxyl heptadecyl ester, methacrylic acid hydroxyl stearyl, methacrylic acid hydroxyl nonadecyl ester, methacrylic acid hydroxyl eicosyl ester.
The chemical equation of above-mentioned steps (reacting as example take isoflurane chalcone diisocyanate, hydroxyethyl methylacrylate, N methyldiethanol amine, bromo n-hexadecane as raw material) is as follows.
Another object of the present invention is to provide the application of the above-mentioned germ resistance methacrylate monomer containing quaternary ammonium salt and carboxylamine ester structure in dental prosthetic material.After novel methacrylate monomer polymerization of the present invention, there is broad-spectrum efficient antibacterial properties, while specifically application, can coordinate for the preparation of dental prosthetic material separately or with other monomers.
Compared with prior art, the present invention has following beneficial effect:
The remarkable advantage of novel methacrylate monomer prepared by the present invention is that to have broad-spectrum high efficacy antibacterial, both can coordinate with other monomers for dental prosthetic material, also can be separately for matrix resin.The large monomer of the novel methacrylic ester of germ resistance that what therefore, prepared by the present invention contain quaternary ammonium salt structure and carboxylamine ester structure has the potential of the dental prosthetic material that is developed to treatment carious tooth.
Accompanying drawing explanation
Fig. 1 is AB in example
1iL
n(n=10,12,14,16) is as the resin system of matrix resin and the anti-microbial property comparison diagram of reference resin system.
Embodiment
Below in conjunction with specific embodiment, the present invention is done further and described, but specific embodiment does not do any restriction to the present invention.
Embodiment 1 AB
1iL
10monomer
The present embodiment AB
1iL
10monomer preparation method comprise the steps:
Step 1: add 5.95g N methyldiethanol amine and 15.55g 1-bromo-dodecane in the three-necked bottle that magneton is housed, add the methylene dichloride of 100ml, stirring reaction 15 hours refluxes at 60 ℃, be cooled to room temperature, filter, and by filter cake vacuum-drying 72 hours at 50 ℃, obtain N-methyl-N-dodecyl diethanolamine bromine.
Step 2: the methylene dichloride that adds 4.44g isoflurane chalcone diisocyanate and 100ml in the 250ml three-necked bottle that magneton is housed, under whipped state, constantly add 3.67g N-methyl-N-dodecyl diethanolamine bromine and 0.002g dibutyl tin dilaurate to react after 8 hours at 70 ℃ of oil baths, add 2.60g hydroxyethyl methylacrylate and 0.0107g Resorcinol at 75 ℃ of oil baths, to continue reaction after 20 hours, then reaction product is carried out to purification processes.Product characterizes with infrared and nuclear-magnetism:
FT-IR: ν(cm
-1) 3324(-NH), 2955(-CH
3), 2927(-CH
2-), 2856(-CH
2-), 1717(-C=O), 1639(-C=CH
2), 1463(-CH
3), 1241(-COO-), 1166(-C-O-C-), 815(-C=CH
2), 722(-(CH2)
n-).
1H-NMR (CDCl
3, 400MHz): δ 6.85[4H, s], 6.20[2H, s], 5.60[2H,s], 4.56[4H, m], 4.29-4.32[8H, m], 3.87-3.94[4H, m], 3.75[2H, m], 3.58[2H, m], 3.45[3H, m], 2.92[4H, m], 1.95[6H, s], 1.67-1.72[6H, m], 1.18-1.35[26H, m], 1.05[12H, j], 0.93[6H, m], 0.86-0.90[3H,t].
Embodiment 2 AB
1iL
12monomer
The present embodiment AB
1iL
12monomer preparation method comprise the steps:
Step 1: add 5.95g N methyldiethanol amine and 14.56g 1-bromo-tetradecane in the three-necked bottle that magneton is housed, add the methylene dichloride of 100ml, stirring reaction 5 hours refluxes at 80 ℃, be cooled to room temperature, filter, and by filter cake vacuum-drying 72 hours at 50 ℃, obtain N-methyl-N-tetradecyl diethanolamine bromine.
Step 2: the methylene dichloride that adds 4.44g isoflurane chalcone diisocyanate and 100ml in the 250ml three-necked bottle that magneton is housed, under whipped state, constantly add 3.95g N-methyl-N-tetradecyl diethanolamine bromine and 0.11g dibutyl tin dilaurate to react after 8.5 hours at 70 ℃ of oil baths, add 2.60g hydroxyethyl methylacrylate and 0.066g Resorcinol at 75 ℃ of oil baths, to continue reaction after 22 hours, then reaction product is carried out to purification processes.Product characterizes with infrared and nuclear-magnetism:
FT-IR: ν(cm
-1) 3331(-NH), 2954(-CH
3), 2926(-CH
2-), 2855(-CH
2-), 1714(-C=O), 1639(-C=CH
2), 1463(-CH
3), 1245(-COO-), 1171(-C-O-C-), 816(-C=CH
2), 722(-(CH2)
n-).
1H-NMR (CDCl
3, 400MHz): δ 6.76[4H, s], 6.14[2H, s], 5.60[2H, s], 4.56[4H, m], 4.32[8H, m], 3.95[4H, m], 3.74[2H, m], 3.58[2H, m], 3.44-3.45[3H, m], 2.93[4H, m], 1.95[6H, s], 1.67-1.72[6H,m], 1.18-1.36[36H,m], 1.06[12H, m], 0.94[6H, m], 0.86-0.90[3H,t].
Embodiment 3 AB
1iL
14monomer
The present embodiment AB
1iL
14monomer preparation method comprise the steps:
Step 1: add 5.95g N methyldiethanol amine and 15.27g 1-bromine n-Hexadecane in the three-necked bottle that magneton is housed, add the methylene dichloride of 100ml, stirring reaction 9 hours refluxes at 70 ℃, be cooled to room temperature, filter, and by filter cake vacuum-drying 72 hours at 50 ℃, obtain N-methyl-N-hexadecyl diethanolamine bromine.
Step 2: the methylene dichloride that adds 4.44g isoflurane chalcone diisocyanate and 100ml in the 250ml three-necked bottle that magneton is housed, under whipped state, constantly add 4.26g N-methyl-N-hexadecyl diethanolamine bromine and 0.057g dibutyl tin dilaurate to react after 9 hours at 75 ℃ of oil baths, add 2.70g hydroxyethyl methylacrylate and 0.0342g Resorcinol at 80 ℃ of oil baths, to continue reaction after 24 hours, then reaction product is carried out to purification processes.Product characterizes with infrared and nuclear-magnetism:
FT-IR: ν(cm
-1) 3336(-NH), 2952(-CH
3), 2926(-CH
2-), 2856(-CH
2-), 1719(-C=O), 1641(-C=CH
2), 1460(-CH
3), 1245(-COO-), 1169(-C-O-C-), 818(-C=CH
2), 719(-(CH2)
n-).
1H-NMR (CDCl
3, 400MHz): δ 6.72[4H, s], 6.14[2H,s], 5.60[2H, s], 4.56[4H, m], 4.32[8H, m], 3.88-3.94[4H, m], 3.75[2H, m], 3.58[2H, m], 3.45[3H, m], 2.92-3.94[4H, m], 1.95[6H, s], 1.67-1.74[6H, m], 1.18-1.36[40H, m], 1.06[12H, j], 0.93[6H, m], 0.86-0.90[3H, t].
Embodiment 4 AB
1iL
16monomer
The present embodiment AB
1iL
16monomer preparation method comprise the steps:
Step 1: add 5.95g N methyldiethanol amine and 16.66g 1-bromo-octadecane in the three-necked bottle that magneton is housed, add the methylene dichloride of 100ml, stirring reaction 4 hours refluxes at 90 ℃, be cooled to room temperature, filter, and by filter cake vacuum-drying 72 hours at 50 ℃, obtain N-methyl-N-octadecyldiethanol amine bromine.
Step 2: the methylene dichloride that adds 4.44g isoflurane chalcone diisocyanate and 100ml in the 250ml three-necked bottle that magneton is housed, under whipped state, constantly add 4.51g N-methyl-N-octadecyldiethanol amine bromine and 0.0116g dibutyl tin dilaurate to react after 10 hours at 75 ℃ of oil baths, add 2.70g hydroxyethyl methylacrylate and 0.0699g Resorcinol at 85 ℃ of oil baths, to continue reaction after 24 hours, then reaction product is carried out to purification processes.Product characterizes with infrared and nuclear-magnetism:
FT-IR: ν(cm-1) 3326-NH), 2954(-CH3), 2925(-CH2-), 2854(-CH2-), 1714(-C=O), 1638(-C=CH2), 1461(-CH3), 1242(-COO-), 1169(-C-O-C-), 815(-C=CH2), 722(-(CH2)n-). 1H-NMR (CDCl3, 400MHz): δ 6.73[4H, s], 6.12[2H, s], 5.59[2H, s], 4.54[4H, m], 4.31[8H, m], 3.86-3.92[4H, m], 3.73[2H, m], 3.55[2H, m], 3.41[3H,m], 2.63-3.90[4H, m], 1.94[6H, s], 1.62-1.70[6H, m], 1.17-1.34[44H, m], 1.04[12H, m], 0.92[6H, m], 0.85-0.88[3H, t].
Embodiment 5 is containing AB
1iL
10, AB
1iL
12, AB
1iL
14and AB
1iL
16the mechanical property of monomer dental resin and double bond conversion rate
The present embodiment is by AB
1iL
10, AB
1iL
12, AB
1iL
14and AB
1iL
16monomer mixes respectively at the conventional thinner TEGDMA of dental prosthetic material, the mechanical property after the standby resin solidification of institute system.Its resin formula is as follows:
AB
1FI
n:TEMDA:CQ:DMAEMA=49.3:49.3:0.7:0.7 (n=10、12、14、16）。Machinery result and double bond conversion rate are as shown in table 1 and table 2.
As shown in Table 1, at the AB that adds synthesized in resin system for dental prosthetic material
1iL
10, AB
1iL
12, AB
1iL
14and AB
1iL
16monomer can be given its good mechanical property.
Table 1 AB
1iL
nas the resin system of matrix resin and the mechanical property of reference resin system
Table 2 AB
1iL
nas the resin system of matrix resin and the double bond conversion rate of reference resin system
Embodiment 6 is containing AB
1iL
10, AB
1iL
12, AB
1iL
14and AB
1iL
16the germ resistance of monomer dental resin.
The present embodiment is by AB
1iL
10, AB
1iL
12, AB
1iL
14and AB
1iL
16monomer mixes respectively at the conventional thinner TEGDMA of dental prosthetic material, and after the standby resin solidification of institute system, the common cariogenic bacteria streptococcus mutans in oral cavity carries out germ resistance test.Its resin formula is as follows:
AB
1FI
n:TEMDA:CQ:DMAEMA=49.3:49.3:0.7:0.7 (n=10、12、14、16）。Its result as shown in Figure 1.
As shown in Figure 1, at the AB that adds synthesized in resin system for dental prosthetic material
1iL
10, AB
1iL
12, AB
1iL
14and AB
1iL
16monomer has good antimicrobial property to streptococcus mutans, wherein AB
1iL
10germ resistance best.
Claims (8)
1. containing the germ resistance methacrylate monomer of quaternary ammonium salt and carboxylamine ester structure, its structural formula as shown in the formula (I):
R in structural formula (I)
1get any one of structural formula (II):
In structural formula (II), n is any one numerical value in 1 to 19;
In structural formula (I), X gets any one in structural formula (III):
X=F, Cl, Br or I
R in structural formula (I)
2get any one in structure formula IV:
R
2=CH
3or
or
M in structure formula IV is any one numerical value in 0 to 27.
2. the preparation method who contains the germ resistance methacrylate monomer of quaternary ammonium salt and carboxylamine ester structure described in claim 1, is characterized in that this preparation method comprises the steps:
Step 1: N, the preparation of N-dialkyl group diethanolamine quaternary ammonium salt
In the three-necked bottle that magneton is housed, add N methyldiethanol amine and haloalkane, add solvent cut, stirring reaction 5-30 hour refluxes at 40～90 ℃, be cooled to room temperature, filter, and by filter cake vacuum-drying 24-72 hour at 25-50 ℃, obtain N, N-dialkyl group diethanolamine quaternary ammonium salt (Q);
Step 2: the preparation of germ resistance methacrylate monomer
In the three-necked bottle that magneton is housed, add isoflurane chalcone diisocyanate (IPDI), under whipped state, constantly add N by constant pressure funnel, N-dialkyl group diethanolamine quaternary ammonium salt (Q) and catalyzer, add solvent to reduce system viscosity, reaction at 5～65 ℃ until in isocyanic ester system-NCO per-cent approaches theoretical value, water-bath adjusts the temperature to 15～90 ℃, then in reactor, add methacrylic acid hydroxyl alkyl esters compound or 2-hydroxyl-1 by constant pressure funnel, 3-dimethyl allene acyloxy propane, add catalyzer and stopper simultaneously, and use eluent solvent constant pressure funnel, 2～18 hours reaction times, then reaction product is carried out to purification processes,
Described solvent is selected from ether, methylene dichloride, trichloromethane, ethyl acetate, 1, one or more above mixtures of 2-ethylene dichloride, benzene, toluene, acetone, butanone, cyclohexanone or DMF; Catalyzer is selected from triethylamine, triethylenediamine, tetramethyl butane diamine, N, one or more the above mixtures in N-dimethyl benzylamine, dibutyl tin dilaurate, stannous octoate; Stopper is selected from one or more the above mixtures in Resorcinol, para benzoquinone, toluhydroquinone, MEHQ, 2,5 di tert butyl hydroquinone, 2-Tert. Butyl Hydroquinone.
3. preparation method according to claim 2, is characterized in that the time of described reaction at 5～65 ℃ is 0.5～24 hour.
4. preparation method according to claim 2, is characterized in that in step 1, and the mol ratio of N methyldiethanol amine and haloalkane is 1:1.05-1.10.
5. preparation method according to claim 2, is characterized in that in described step 2, isoflurane chalcone diisocyanate (IPDI) and N, and the mol ratio of N-dialkyl group diethanolamine quaternary ammonium salt is 2:1; Methacrylic acid hydroxyl alkyl esters compound or 2-hydroxyl-1,3-dimethyl allene acyloxy propane and N, the mol ratio of N-dialkyl group diethanolamine quaternary ammonium salt is 2:1; Catalyst levels is 0.02%～1% of reactant total mass; Stopper is 0.1%～0.6% of reactant total mass.
6. preparation method according to claim 2, it is characterized in that in described step, N, alkyl in N-dialkyl group diethanolamine quaternary ammonium salt comprises: methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, ceryl, heptacosyl, octacosyl, nonacosyl or cyclohexyl.
7. preparation method according to claim 2, it is characterized in that in described step, the alkyl in methacrylic acid hydroxyl alkyl esters compound comprises: ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or eicosyl.
8. described in claim 1, contain the application of germ resistance methacrylate monomer matrix resin in as dental prosthetic material of quaternary ammonium salt and carboxylamine ester structure.
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