CN102816089A - Quaternary ammonium salt and carbamate structure containing antibacterial methyl acrylate monomer, its preparation method and application thereof - Google Patents
Quaternary ammonium salt and carbamate structure containing antibacterial methyl acrylate monomer, its 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
And its production and application
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 that contain quaternary ammonium salt structure.
Background technology
The dental caries disease is chronic, the carrying out property destruction of dental hard tissue that is caused by multiple factor; As if forming cavity and in time being repaired, pathology can develop to deep layer, causes complication such as dental pulp inflammation, periapical infection; Cause disorganization and cause violent pain, even influence whole body health.Therefore it is very necessary carious tooth to be carried out the effective for repairing treatment.
Dental material is a most active research field in the modern Prosthodontics, has merged Materials science, life science, polymer chemistry and stomatology, and development in the last few years rapidly.And the monomer that contains the methyl acrylic ester structure is that the photocuring teeth repairing material is requisite.Wherein the disclosed a kind of methyl acrylic ester monomers B is-GMA that contains structure of bisphenol A of patent US3066112 and US6030606 has been widely used in the teeth repairing material at present; Compare with other repair materials, it has lower polymerization volumetric shrinkage, high-adhesion and excellent characteristics such as mechanical property.Nowadays, business-like methacrylate based repair materials contains Bis-GMA, polyurethanes methacrylic ester (UDMA) and dimethacrylate triethylene Glycol monomers such as (TEGDMA) usually.
Compare with traditional pottery repair materials; The no antibiotic activity of methacrylate resin itself; The surface forms bacterial plaque easily; After repairing the operation completion; Bacterium and microorganism are more prone to accumulate in methacrylic ester repair materials surface or the percolation zone bonding interface gap; Cause secondary caries, even cause that dummy comes off.Therefore, the methacrylate based dental prosthetic material of exploitation with anti-microbial activity will become the prevention secondary caries one of bonding persistent effective way will take place, improves.
Preparation has an approach of the methyl acrylic ester dental prosthetic material of anti-microbial activity and introduces the methyl acrylic ester monomer with anti-microbial activity group (like quaternary ammonium salt structure) exactly.Imazato and a kind of dental prosthetic material of team's synthetic thereof of patent US5733949 report just belong to this antiseptic-germicide with methacrylic ester quaternary ammonium salt monomer methacryloxypropyl dodecyl bromopyridine (MDPB); This monomeric repair materials not only can effectively reduce streptococcus mutans and microorganism in its surperficial gathering; And can with oral cavity macromolecular material generation Chemical bond, by the dental prosthetic material successfully listing at present of MDPB preparation.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 has long lasting anti-microbial activity by the dental prosthetic material of its preparation.
Yet; Only contain a metacrylic acid ester structure in the molecular structure of MDPB and DMAE-CB; Crosslinking rate is limited during with the resinous substrates monomer polymerization; It is influenced that too high levels can cause the performance of material in material; Uncrosslinked germ resistance monomer also might ooze out from resin-based materials; Be unfavorable for oral Health, and there are difficult problem such as mix in these two kinds of monomers and dental prosthetic material hydrophobicity double methyl methacrylate monomer commonly used such as TEGDMA.
Summary of the invention
The objective of the invention is to the no germ resistance of existing its existence of dental prosthetic material and existing antibiotic methacrylate monomer and dental prosthetic material with methacrylate based body difficulty mix, problem such as crosslinking rate is low; A series of quaternary ammonium salt structure and carboxylamine ester structures of containing are provided, and with existing dental prosthetic material with methacrylate monomer consistency good novel many methacrylic esters antibacterial monomer and method for making and application.
Above-mentioned purpose of the present invention is achieved through following scheme:
Containing quaternary ammonium antibacterial urethane structure and methacrylate monomers of the formula the formula (I)? Below:
R in the structural formula (I)
1Get any one of structural formula (II).
N is any one numerical value in 1 to 19 in the structural formula (II).
X gets any one in the structural formula (III) in the structural formula (I).
R in the structural formula (I)
2Get in the structure formula IV any one.
M in the structure formula IV is any one numerical value in 0 to 27.
Contain the carboxylamine ester structure in the said formula (I).Contain quaternary ammonium salt structure in the said formula (I).
The said preparation method who contains the germ resistance methacrylate monomer of quaternary ammonium salt and carboxylamine ester structure comprises the steps:
Step 1: N, the preparation of N-dialkyl group diethanolamine quaternary ammonium salt
, the three-necked bottle of magneton adds N methyldiethanol amine and haloalkane in being housed; Add certain amount of solvent; 40 ~ 90 ℃ of refluxed stirring reactions 5-30 hour; Be cooled to room temperature; Filter; And with filter cake in 25-50 ℃ of following vacuum-drying 24-72 hour, obtain N, N-dialkyl group diethanolamine quaternary ammonium salt (Q).
Step 2: the preparation of germ resistance methacrylate monomer
, the three-necked bottle of magneton adds isoflurane chalcone diisocyanate (IPDI) or toluene di-isocyanate(TDI) (TDI) in being housed; Under stirring, constantly add N by constant pressure funnel; N- dialkyl group diethanol amine quaternary ammonium salt (Q) and catalyst; Add certain amount of solvent and reduce system viscosity; Reacted 0.5～24 hour down at 5 ~ 65 ℃; In the isocyanates system-NCO percentage is near theoretical value; Water-bath adjusts the temperature to 15 ~ 90 ℃; In reactor, add methacrylic acid hydroxyl alkyl esters compound or 2- hydroxyl-1 by constant pressure funnel then; 3- dimethyl allene acyloxy propane; Add catalyst and polymerization inhibitor simultaneously; And use the eluent solvent constant pressure funnel; In 2 ~ 18 hours reaction time, then product is carried out 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 a reactant total mass; Stopper is 0.1% ~ 0.6% of a reactant total mass.
Said solvent is selected from ether, methylene dichloride, trichloromethane, ethyl acetate, 1,2-ethylene dichloride, benzene, toluene, acetone, butanone, cyclohexanone or N, the above mixture of one or more of dinethylformamide.
Catalyzer is selected from triethylamine, triethylenediamine, tetramethyl butane diamine, N, one or more the above mixtures in N-dimethyl benzylamine, dibutyl tin dilaurate, the 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, the 2-Tert. Butyl Hydroquinone etc.
N; Alkyl in the 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 (be that raw material reacts with isoflurane chalcone diisocyanate, Rocryl 400, N methyldiethanol amine, bromo n-hexadecane be example) is as follows.
Another object of the present invention provides the above-mentioned application of germ resistance methacrylate monomer in dental prosthetic material that contains quaternary ammonium salt and carboxylamine ester structure.Have broad-spectrum efficient antibacterial properties after the novel methyl acrylate monomer of the present invention polymerization, can be separately when specifically using or cooperate with other monomers and to be used to prepare dental prosthetic material.
Compared with prior art, the present invention has following beneficial effect:
The remarkable advantage of the novel methyl acrylate monomer of the present invention preparation is that to have a broad-spectrum high efficacy antibiotic, both can cooperate with other monomers and be used for dental prosthetic material, also can be used for matrix resin separately.Therefore, the big monomer of germ resistance novel methyl acrylate that contains quaternary ammonium salt structure and carboxylamine ester structure of the present invention's preparation has the potential of the dental prosthetic material that is developed to the treatment carious tooth.
Description of drawings
Fig. 1 is AB in the instance
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 description further, but specific embodiment is not done any qualification to the present invention.
Embodiment 1 AB
1IL
10Monomer
Present embodiment AB
1IL
10Monomeric preparation method comprises the steps:
Step 1: in the three-necked bottle of magneton is housed, add 5.95g N methyldiethanol amine and 15.55g 1-bromo-dodecane; The methylene dichloride that adds 100ml; 60 ℃ of refluxed stirring reactions 15 hours; Be cooled to room temperature; Filter; And with filter cake in 50 ℃ of following vacuum-dryings 72 hours, obtain N-methyl-N-dodecyl diethanolamine bromine.
Step 2: the methylene dichloride that in the 250ml three-necked bottle of magneton is housed, adds 4.44g isoflurane chalcone diisocyanate and 100ml; Under whipped state, constantly add 3.67g N-methyl-N-dodecyl diethanolamine bromine and 0.002g dibutyl tin dilaurate after 70 ℃ of oil baths are reacted 8 hours down; Add 2.60g Rocryl 400 and 0.0107g Resorcinol and continue reaction after 20 hours down for 75 ℃, then reaction product is carried out purification processes in oil bath.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
Present embodiment AB
1IL
12Monomeric preparation method comprises the steps:
Step 1: in the three-necked bottle of magneton is housed, add 5.95g N methyldiethanol amine and 14.56g 1-bromo-tetradecane; The methylene dichloride that adds 100ml; 80 ℃ of refluxed stirring reactions 5 hours; Be cooled to room temperature; Filter; And with filter cake in 50 ℃ of following vacuum-dryings 72 hours, obtain N-methyl-N-tetradecyl diethanolamine bromine.
Step 2: the methylene dichloride that in the 250ml three-necked bottle of magneton is housed, adds 4.44g isoflurane chalcone diisocyanate and 100ml; Under whipped state, constantly add 3.95g N-methyl-N-tetradecyl diethanolamine bromine and 0.11g dibutyl tin dilaurate after 70 ℃ of oil baths are reacted 8.5 hours down; Add 2.60g Rocryl 400 and 0.066g Resorcinol and continue reaction after 22 hours down for 75 ℃, then reaction product is carried out purification processes in oil bath.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
Present embodiment AB
1IL
14Monomeric preparation method comprises the steps:
Step 1: in the three-necked bottle of magneton is housed, add 5.95g N methyldiethanol amine and 15.27g 1-bromine n-Hexadecane; The methylene dichloride that adds 100ml; 70 ℃ of refluxed stirring reactions 9 hours; Be cooled to room temperature; Filter; And with filter cake in 50 ℃ of following vacuum-dryings 72 hours, obtain N-methyl-N-hexadecyl diethanolamine bromine.
Step 2: the methylene dichloride that in the 250ml three-necked bottle of magneton is housed, adds 4.44g isoflurane chalcone diisocyanate and 100ml; Under whipped state, constantly add 4.26g N-methyl-N-hexadecyl diethanolamine bromine and 0.057g dibutyl tin dilaurate after 75 ℃ of oil baths are reacted 9 hours down; Add 2.70g Rocryl 400 and 0.0342g Resorcinol and continue reaction after 24 hours down for 80 ℃, then reaction product is carried out purification processes in oil bath.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
Present embodiment AB
1IL
16Monomeric preparation method comprises the steps:
Step 1: in the three-necked bottle of magneton is housed, add 5.95g N methyldiethanol amine and 16.66g 1-bromo-octadecane; The methylene dichloride that adds 100ml; 90 ℃ of refluxed stirring reactions 4 hours; Be cooled to room temperature; Filter; And with filter cake in 50 ℃ of following vacuum-dryings 72 hours, obtain N-methyl-N-octadecyldiethanol amine bromine.
Step 2: the methylene dichloride that in the 250ml three-necked bottle of magneton is housed, adds 4.44g isoflurane chalcone diisocyanate and 100ml; Under whipped state, constantly add 4.51g N-methyl-N-octadecyldiethanol amine bromine and 0.0116g dibutyl tin dilaurate after 75 ℃ of oil baths are reacted 10 hours down; Add 2.70g Rocryl 400 and 0.0699g Resorcinol and continue reaction after 24 hours down for 85 ℃, then reaction product is carried out purification processes in oil bath.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 contains AB
1IL
10, AB
1IL
12, AB
1IL
14And AB
1IL
16The mechanical property of monomer dental resin and double bond conversion rate
Present embodiment is with AB
1IL
10, AB
1IL
12, AB
1IL
14And AB
1IL
16Monomer mixes respectively at dental prosthetic material thinner TEGDMA commonly used, the mechanical property behind the resin solidification of institute's preparation.Its resin formula is following:
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 shown in table 1 and table 2.
Can know by table 1, add the synthetic AB of institute in resin system at dental prosthetic material
1IL
10, AB
1IL
12, AB
1IL
14And AB
1IL
16Monomer can be given its favorable mechanical performance.
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 contains AB
1IL
10, AB
1IL
12, AB
1IL
14And AB
1IL
16The germ resistance of monomer dental resin.
Present embodiment is with AB
1IL
10, AB
1IL
12, AB
1IL
14And AB
1IL
16Monomer mixes respectively at dental prosthetic material thinner TEGDMA commonly used, and the common cariogenic bacteria streptococcus mutans in oral cavity carries out the germ resistance test behind the resin solidification of institute's preparation.Its resin formula is following:
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.
Can know by Fig. 1, add the synthetic AB of institute in resin system at 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 (10)
1. the germ resistance methacrylate monomer that contains quaternary ammonium salt and carboxylamine ester structure, its structural formula is suc as formula shown in (I):
R in the structural formula (I)
1Get any one of structural formula (II):
N is any one numerical value in 1 to 19 in the structural formula (II);
X gets any one in the structural formula (III) in the structural formula (I):
R in the structural formula (I)
2Get in the structure formula IV any one;
M in the structure formula IV is any one numerical value in 0 to 27.
2. the germ resistance methacrylate monomer that contains quaternary ammonium salt and carboxylamine ester structure according to claim 1 is characterized in that containing carboxylamine ester structure and quaternary ammonium salt structure in the said formula (I).
3. the said preparation method who contains the germ resistance methacrylate monomer of quaternary ammonium salt and carboxylamine ester structure of 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
, the three-necked bottle of magneton adds N methyldiethanol amine and haloalkane in being housed; Add solvent cut; 40 ~ 90 ℃ of refluxed stirring reactions 5-30 hour; Be cooled to room temperature; Filter; And with filter cake in 25-50 ℃ of following vacuum-drying 24-72 hour, obtain N, N-dialkyl group diethanolamine quaternary ammonium salt (Q);
Step 2: the preparation of germ resistance methacrylate monomer
, the three-necked bottle of magneton adds isoflurane chalcone diisocyanate (IPDI) or toluene di-isocyanate(TDI) (TDI) in being housed; Under stirring, constantly add N by constant pressure funnel; N- dialkyl group diethanol amine quaternary ammonium salt (Q) and catalyst; Add solvent and reduce system viscosity; 5 ~ 65 ℃ down reaction in the isocyanates system-NCO percentage is near theoretical value; Water-bath adjusts the temperature to 15 ~ 90 ℃; In reactor, add methacrylic acid hydroxyl alkyl esters compound or 2- hydroxyl-1 by constant pressure funnel then; 3- dimethyl allene acyloxy propane; Add catalyst and polymerization inhibitor simultaneously; And use the eluent solvent constant pressure funnel; In 2 ~ 18 hours reaction time, then product is carried out purification processes.
4. preparation method according to claim 3 is characterized in that said is 0.5～24 hour 5 ~ 65 ℃ of times of reacting down.
5. preparation method according to claim 3 is characterized in that in the step 1, and the mol ratio of N methyldiethanol amine and haloalkane is 1:1.05-1.10.
6. according to the said preparation method of claim 3, it is characterized in that in the said step 2, 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 a reactant total mass; Stopper is 0.1% ~ 0.6% of a reactant total mass.
7. preparation method according to claim 3; It is characterized in that in the step 1, two; Said solvent is selected from ether, methylene dichloride, trichloromethane; Ethyl acetate, 1; 2-ethylene dichloride, benzene, toluene, acetone, butanone, cyclohexanone or N, the above mixture of one or more of dinethylformamide; Catalyzer is selected from triethylamine, triethylenediamine, tetramethyl butane diamine, N, one or more the above mixtures in N-dimethyl benzylamine, dibutyl tin dilaurate, the 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, the 2-Tert. Butyl Hydroquinone etc.; Stopper is selected from one or more the above mixtures in Resorcinol, para benzoquinone, toluhydroquinone, MEHQ, 2,5 di tert butyl hydroquinone, the 2-Tert. Butyl Hydroquinone etc.
8. preparation method according to claim 3; It is characterized in that in the said step; N, the alkyl in the 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.
9. preparation method according to claim 3; It is characterized in that in the said step that the alkyl in the 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.
10. the said application that contains germ resistance methacrylate monomer matrix resin in of quaternary ammonium salt and carboxylamine ester structure of claim 1 as dental prosthetic material.
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| CN113233995A (en) * | 2021-04-13 | 2021-08-10 | 华南理工大学 | Antibacterial styrene-acrylic emulsion containing biquaternary ammonium salt structure and preparation method and application thereof |
| CN113876595A (en) * | 2021-10-18 | 2022-01-04 | 东华大学 | Birch alcohol-based quaternary ammonium salt antibacterial organic monomer, application of composite resin of birch alcohol-based quaternary ammonium salt antibacterial organic monomer and preparation method of composite resin of birch alcohol-based quaternary ammonium salt antibacterial organic monomer |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3066112A (en) * | 1959-01-30 | 1962-11-27 | Rafael L Bowen | Dental filling material comprising vinyl silane treated fused silica and a binder consisting of the reaction product of bis phenol and glycidyl acrylate |
| US5733949A (en) * | 1994-10-07 | 1998-03-31 | Kuraray Co., Ltd. | Antimicrobial adhesive composition for dental uses |
| US6030606A (en) * | 1998-06-22 | 2000-02-29 | 3M Innovative Properties Company | Dental restoratives comprising Bis-EMA6 |
| US20040005515A1 (en) * | 2002-06-24 | 2004-01-08 | Konica Corporation | Light sensitive planographic printing plate precursor and its processing method |
| CN101199449A (en) * | 2007-11-20 | 2008-06-18 | 中国人民解放军第四军医大学 | Application of hyamine antibiont on dentistry antibacterial replacement material |
| CN102079713A (en) * | 2009-12-01 | 2011-06-01 | 南京理工大学 | Cross-linked polyquaternary ammonium salt type antibiosis monomer, preparation method of cross-linked polyquaternary ammonium salt type antibiosis monomer and application of cross-linked polyquaternary ammonium salt type antibiosis monomer in dentistry repairing materials |
-
2012
- 2012-07-06 CN CN201210234867.4A patent/CN102816089B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3066112A (en) * | 1959-01-30 | 1962-11-27 | Rafael L Bowen | Dental filling material comprising vinyl silane treated fused silica and a binder consisting of the reaction product of bis phenol and glycidyl acrylate |
| US5733949A (en) * | 1994-10-07 | 1998-03-31 | Kuraray Co., Ltd. | Antimicrobial adhesive composition for dental uses |
| US6030606A (en) * | 1998-06-22 | 2000-02-29 | 3M Innovative Properties Company | Dental restoratives comprising Bis-EMA6 |
| US20040005515A1 (en) * | 2002-06-24 | 2004-01-08 | Konica Corporation | Light sensitive planographic printing plate precursor and its processing method |
| CN101199449A (en) * | 2007-11-20 | 2008-06-18 | 中国人民解放军第四军医大学 | Application of hyamine antibiont on dentistry antibacterial replacement material |
| CN102079713A (en) * | 2009-12-01 | 2011-06-01 | 南京理工大学 | Cross-linked polyquaternary ammonium salt type antibiosis monomer, preparation method of cross-linked polyquaternary ammonium salt type antibiosis monomer and application of cross-linked polyquaternary ammonium salt type antibiosis monomer in dentistry repairing materials |
Non-Patent Citations (3)
| Title |
|---|
| CHETAN A KHATRI等: "Synthesis, characterization and evaluation of urethane derivatives of Bis-GMA", 《DENTAL MATERIALS》, vol. 19, no. 7, 30 November 2003 (2003-11-30) * |
| NORBERT MOSZNER等: "Synthesis and polymerisation of new multifunctional urethane methacrylates", 《DIE ANGEWANDTE MAKROMOLEKULARE CHEMIE》, vol. 265, no. 1, 31 March 1999 (1999-03-31), pages 31 - 35, XP000804979, DOI: doi:10.1002/(SICI)1522-9505(19990301)265:1<31::AID-APMC31>3.3.CO;2-S * |
| 祁玲玲: "新型可聚合季铵盐及其在牙科抗菌高分子材料中的应用研究", 《中国优秀硕士学位论文 工程科技Ⅰ辑》, no. 8, 15 August 2010 (2010-08-15) * |
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