CN102816088A - Tertiary amine structure containing methacrylate macromonomer without bisphenol A structure, preparation method and application thereof - Google Patents
Tertiary amine structure containing methacrylate macromonomer without bisphenol A structure, preparation method and application thereof Download PDFInfo
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- CN102816088A CN102816088A CN2012102348513A CN201210234851A CN102816088A CN 102816088 A CN102816088 A CN 102816088A CN 2012102348513 A CN2012102348513 A CN 2012102348513A CN 201210234851 A CN201210234851 A CN 201210234851A CN 102816088 A CN102816088 A CN 102816088A
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Abstract
The invention discloses a trtiary amine structure containing methacrylate macromonomer without bisphenol A structure, a preparation method and an application thereof. The trtiary amine structure containing methacrylate macromonomer without the bisphenol A structure can be used as an organic monomer component of a dental prosthetic material. The macromonomer has large molecular weight and large molecular volume, contains the tertiary amine structure, but contains no bisphenol A structure. Therefore, the macromonomer can be used as a coinitiator for light initiated polymerization. In addition, the macromonomer has low polymerization volume shrinkage during the polymerization process, and a polymerization product has good mechanical properties.
Description
Technical field
The present invention relates to can be used as the big monomer of methacrylic ester of light initiation polymerization system, be specifically related to a series of big monomer of methacrylic ester and method for making and application that the tertiary amine structure does not contain structure of bisphenol A that contain.
Background technology
Carious tooth and dental pulp periapical disease are frequently-occurring disease and the common diseases in the clinical oral; Wherein to be classified as by the World Health Organization be one of human three big diseases to carious tooth, shows that according to " national for the third time oral health epidemiological report of survey " China's deciduous teeth and permanent teeth trouble caries incidence are respectively up to 66% and 28%; If can not get timely treatment; Will continue to develop into the dental pulp periapical disease, even can cause alveolar bone and inflammation of jaws, have a strong impact on patient's quality of life.Therefore, carious tooth and dental pulp periapical disease are carried out very necessity of effective for repairing treatment.
The monomer that contains metacrylic acid ester structure is the indispensable organic constituent of photocuring dental prosthetic material.Utilizing at present the monomer that contains metacrylic acid ester structure to prepare the photocuring dental prosthetic material not only has a large amount of research reports, and existing manyly in clinical, is applied.The disclosed a kind of methyl acrylic ester monomers B is-GMA that contains structure of bisphenol A of patent US3066112 and US6030606 is the matrix resin of at present the most frequently used clinically methyl acrylic ester dental prosthetic material.Though being compared to small molecular weight monomer such as TEB 3K, Bis-GMA has lower polymerization shrinkage, clinically because the treatment that its polymerization shrinkage caused failure is still inevitable.
In order to solve the polymerization shrinkage problem of methyl acrylic ester dental prosthetic; The research of synthesizing the methacrylate monomers with macromolecule and macromole volume is quite active; For example Junhao Ge etc. has synthesized two kinds of molecular weight and has been respectively 777 on the basis of structure of bisphenol A; 889 big monomer M tBDMA of novel methyl propenoate and DtBDMA, experimental result shows that these two kinds of macromolecules and big volume monomer can effectively reduce polymerization shrinkage.Joong-Gon Ki etc. are with 1; 1,1-three phenylor ethane, dimethylaminoethyl methacrylate; Double methyl methacrylate triethylene glycol esters etc. have synthesized the big monomer of methyl acrylic ester of a series of three-functionality-degrees for raw material; Big monomeric shrinkage ratio Bis-GMA is much lower for this series, water-absorbent simultaneously, and performances such as water-soluble and double bond conversion rate are also better.Chan-Moon Chung etc. utilizes Bis-GMA, Tetra hydro Phthalic anhydride to synthesize to have the new monomer of three benzene ring structures, finds that this monomeric polymerization shrinkage (2.13%) is littler than the shrinking percentage (2.74%) of Bis-GMA, and its water-soluble (1.27 μ g/mm
3) be starkly lower than water-soluble (the 2.10 μ g/mm that contain the Bis-GMA material
3).
Though above macromolecule and big volume monomer can reduce the polymerization shrinkage of methyl acrylic ester dental prosthetic material, these monomers all belong to the verivate of Bis-GMA, all contain the dihydroxyphenyl propane group in their structure.And in recent years the security of the goods of structure of bisphenol A is suffered the query of more and more national; Think that the goods that contain structure of bisphenol A may cause that a lot of diseases comprise the cancer relevant with hormone, even may influence the problem of securities such as infant growth growth.Therefore, the methyl acrylic ester dental prosthetic material that contains the dihydroxyphenyl propane structure of clinical use suffers the query of security equally.
Since the potentially dangerous property of dihydroxyphenyl propane structure, synthetic non-structure of bisphenol A, the low big monomer of methacrylic ester that shrinks, and use it for the focus that dental prosthetic material becomes research gradually.Mohammad Atai etc. are with 3-isocyanic ester methylene-3; 5,5-3-methyl cyclohexanol based isocyanate (IPDI), PEG 400 (PEG400); And Rocryl 400 (HEMA) for raw material has synthesized a kind of amido-containing acid ester structure and do not contain the big monomer of novel methyl propenoate of dihydroxyphenyl propane structure; Research shows that the resin monomer Bis-GMA of big monomer of this kind and clinical usefulness compares, and has higher double bond conversion rate and lower polymerization shrinkage.
Summary of the invention
The objective of the invention is to big and contain the defective of the methacrylate monomers etc. of structure of bisphenol A with genotoxic potential to existing dental prosthetic material polymerization shrinkage; A series of structure of bisphenol A that do not contain are provided, have the big monomer of many methacrylic esters and the method for making and the application of tertiary amine structure.
Another object of the present invention provides the application of the big monomer of above-mentioned novel methyl propenoate in dental prosthetic material.
Above-mentioned purpose of the present invention is achieved through following scheme:
Contain the big monomer of methacrylic ester that the tertiary amine structure does not contain structure of bisphenol A, its structural formula is shown in formula I:
R in the structural formula (I)
1Get any one of structural formula (II).
M is any numerical value in 1 to 19 in the structural formula (II).
R in the structural formula (I)
2Get in the structural formula (III) any one.
N in the structural formula (III) is any numerical value in 0 to 27.
Of the present inventionly contain the big monomeric preparation method of methacrylic ester that the tertiary amine structure does not contain structure of bisphenol A, comprise the steps:
, the three-necked bottle of magneton adds IPDI (3-isocyanic ester methylene-3,5,5-3-methyl cyclohexanol based isocyanate) or TDI (2 in being housed; The 4-toluene-2,4-diisocyanate), under whipped state, constantly adds N-alkyl diethylolamine or trolamine, with certain amount of solvent drip washing constant pressure funnel through constant pressure funnel; Reacted 0.5～10 hour down at 5 ~ 80 ℃; In the vulcabond system-the amount consumption of NCO is near theoretical value, and water-bath adjusts the temperature to 15 ~ 90 ℃, in reactor drum, adds hydroxyalkyl methacrylate compounds or 2-hydroxyl-1 through constant pressure funnel then; 3-dimethyl allene acyloxy propane, catalyzer and a certain amount of stopper; And use the eluent solvent constant pressure funnel, in 2 ~ 18 hours reaction times, then reaction product is carried out purification processes.
Wherein N-alkyl diethylolamine comprises N methyldiethanol amine; The N-ethyldiethanolamine; N-propyl group diethylolamine; N butyl diethanol amine; N-amyl group diethylolamine; N-hexyl diethylolamine; N-heptyl diethylolamine; N-octyl group diethylolamine; N-nonyl diethylolamine; N-decyl diethylolamine; N-undecyl diethylolamine; N-dodecyl diethylolamine; N-tridecyl diethylolamine; N-tetradecyl diethylolamine; N-pentadecyl diethylolamine; N-hexadecyl diethylolamine; N-heptadecyl diethylolamine; The N-octadecyldiethanol amine; N-nonadecyl diethylolamine; N-eicosyl diethylolamine; N-heneicosyl diethylolamine; N-docosyl diethylolamine; N-tricosyl diethylolamine; N-tetracosyl diethylolamine; N-pentacosyl diethylolamine; N-cerylic diethylolamine; N-heptacosyl diethylolamine; N-octacosyl diethylolamine; N-nonacosyl diethylolamine.
The hydroxyalkyl methacrylate compounds comprises the methylacrylic acid hydroxyethyl ester; Hydroxypropyl methacrylate; The hydroxyethyl methacrylate butyl ester; Hydroxyethyl methacrylate amyl group ester; The hydroxyethyl methacrylate polyhexamethylene; Hydroxyethyl methacrylate heptyl ester; Hydroxyethyl methacrylate octyl group ester; Hydroxyethyl methacrylate nonyl ester; The hydroxyethyl methacrylate decyl ester; Hydroxyethyl methacrylate undecyl ester; The hydroxyethyl methacrylate dodecyl ester; Hydroxyethyl methacrylate tridecyl ester; Hydroxyethyl methacrylate tetradecyl ester; Hydroxyethyl methacrylate pentadecyl ester; The hydroxyethyl methacrylate cetyl ester; Hydroxyethyl methacrylate heptadecyl ester; The hydroxyethyl methacrylate stearyl; Hydroxyethyl methacrylate nonadecyl ester; Hydroxyethyl methacrylate eicosyl ester.
Solvent comprises methylene dichloride, trichloromethane, ETHYLE ACETATE, 1,2-ethylene dichloride, benzene, toluene, acetone, butanone, cyclohexanone or N, the above mixture of one or more of dinethylformamide.
Catalyzer comprises triethylamine, triethylenediamine, tetramethyl butane diamine, N, one or more the above mixtures in N-dimethyl benzylamine, dibutyl tin dilaurate, the stannous octoate etc.
Stopper comprises one or more the above mixtures in Resorcinol, para benzoquinone, toluhydroquinone, MEHQ, 2,5 di tert butyl hydroquinone, the 2-Tert. Butyl Hydroquinone etc.
The chemical equation of above-mentioned steps (be that raw material reacts with IPDI, N methyldiethanol amine, HEMA be example) is as follows.
The present invention preparation do not contain structure of bisphenol A, contain the big monomer of novel methyl propenoate of tertiary amine structure, can be used as the organic monomer component of photocuring dental prosthetic material.Such big monomer have contain tertiary amine and carboxylamine ester structure, molecular weight is big and the bigger characteristics of molecular volume, so such big monomer can promote light initiating polymerizing reaction and reduce characteristics such as oxygen inhibition effect, and the polymerization volumetric shrinkage during polymerization is less.
Prior art is compared, and the present invention has following beneficial effect:
The big monomeric remarkable advantage of novel methyl propenoate of the present invention preparation be do not contain structure of bisphenol A, have the light initiation polymerization of promotion function, polymerization shrinkage is low in the time of can reducing oxygen inhibition effect, polymerization, double bond conversion rate is high, the polymerisate mechanical property is good.Therefore, the present invention preparation do not contain structure of bisphenol A, contain the potential of the big monomer tool of novel methyl propenoate of tertiary amine structure as photocuring dental prosthetic material matrix resin.
Embodiment
Below in conjunction with specific embodiment description is further done in enforcement of the present invention, but enforcement of the present invention and protection domain are not limited thereto.
Embodiment 1 MDEA-IPDI-HEMA (AC
1G) big monomer
Present embodiment MDEA-IPDI-HEMA (AC
1G) big monomeric preparation method comprises the steps:
In the 250ml three-necked bottle of magneton is housed, add 22.23g IPDI, under whipped state, constantly add 5.96g N methyldiethanol amine (MDEA), with the eluent solvent constant pressure funnel of 2g through constant pressure funnel; Reacted 0.5 hour down at 60 ℃; In the vulcabond system-the amount consumption of NCO is near theoretical value, and water-bath adjusts the temperature to 90 ℃, in reactor drum, adds 21.69g Rocryl 400 (HEMA), 0.010g catalyzer and 0.299g stopper through constant pressure funnel then and reacts; Add material and use the eluent solvent constant pressure funnel; Reacted 2 hours, and then reaction product was carried out purification processes, productive rate 83%.FT-IR:?ν?(cm-1)?3335,?3063,?2955,?2926,?2850,?1714,?1638,?1242；?
1H-NMR（400?MHz,?DMSO）：δ?6.15?(s,?2H),?δ?5.60?(s,?2H),?δ?4.82?(s,?4H),?δ?4.21-4.32?(m,?12H),?δ?3.77-3.87?(m,?2H),?δ?2.45-2.93?(m,?8H),?δ?2.17?(s,?3H),?δ?1.96?(s,?6H),?δ?0.87-1.73?(m,?30H)。
Embodiment 2 MDEA-IPDI-HEMA (AC
1G) big monomer
Present embodiment MDEA-IPDI-HEMA (AE
1G) big monomeric preparation method comprises the steps:
In the 250ml three-necked bottle of magneton is housed, add 22.23g TDI, under whipped state, constantly add 5.96g N methyldiethanol amine (MDEA), with the eluent solvent constant pressure funnel of 2g through constant pressure funnel; Reacted 5 hours down at 40 ℃; In the vulcabond system-the amount consumption of NCO is near theoretical value, and water-bath adjusts the temperature to 60 ℃, in reactor drum, adds 21.69g Rocryl 400 (HEMA), 0.010g catalyzer and 0.05g stopper through constant pressure funnel then and reacts; Add material and use the eluent solvent constant pressure funnel; Reacted 12 hours, and then reaction product was carried out purification processes, productive rate 91%.FT-IR:?ν?(cm-1)?3335,?3063,?2955,?2926,?2850,?1714,?1638,?1242；?
1H-NMR（400?MHz,?DMSO）：δ?6.15?(s,?2H),?δ?5.60?(s,?2H),?δ?4.82?(s,?4H),?δ?4.21-4.32?(m,?12H),?δ?3.77-3.87?(m,?2H),?δ?2.45-2.93?(m,?8H),?δ?2.17?(s,?3H),?δ?1.96?(s,?6H),?δ?0.87-1.73?(m,?30H)。
Embodiment 3 MDEA-IPDI-HEMA (AC
1G) big monomer
Present embodiment MDEA-IPDI-HEMA (AC
1G) big monomeric preparation method comprises the steps:
In the 250ml three-necked bottle of magneton is housed, add 22.23g IPDI, under whipped state, constantly add 5.96g N methyldiethanol amine (MDEA), with the eluent solvent constant pressure funnel of 2g through constant pressure funnel; Reacted 10 hours down at 20 ℃; The amount consumption of a NCO in the vulcabond system is near theoretical value, and water-bath adjusts the temperature to 40 ℃, in reactor drum, adds 21.69g Rocryl 400 (HEMA), 0.4988g catalyzer and the reaction of 0.05g stopper through constant pressure funnel then; Add material and use the eluent solvent constant pressure funnel; Reacted 24 hours, and then reaction product was carried out purification processes, productive rate 87%.FT-IR:?ν?(cm-1)?3335,?3063,?2955,?2926,?2850,?1714,?1638,?1242；?
1H-NMR（400?MHz,?DMSO）：δ?6.15?(s,?2H),?δ?5.60?(s,?2H),?δ?4.82?(s,?4H),?δ?4.21-4.32?(m,?12H),?δ?3.77-3.87?(m,?2H),?δ?2.45-2.93?(m,?8H),?δ?2.17?(s,?3H),?δ?1.96?(s,?6H),?δ?0.87-1.73?(m,?30H)。
Embodiment 4 MDEA-IPDI-HEMA (AC
1G) big monomeric light-initiated promoter action
Present embodiment contains the big monomer (AC of novel methyl propenoate of tertiary amine structure not contain structure of bisphenol A
1G) substitute clinical light-initiated promotor dimethylaminoethyl methacrylate (DMAEMA) commonly used as light-initiated promotor, it is joined (it is as shown in table 1 to fill a prescription) in the Bis-GMA/TEGDMA resin system by different ratios, test AC with infrared spectroscopy
1The content of G is to the influence of resin system double bond conversion rate, and compares with the resin system that contains DMAEMA, and its result is as shown in table 2.
Table 1 AC
1G is as the resin system of light-initiated promotor and the compositing formula of reference resin system
Table 2 AC
1G is as the resin system of light-initiated promotor and the double bond conversion rate of reference resin system
Visible by table 2, AC
1G has light-initiated promoter action, and along with AC
1The increase of G content, its light-initiated promoter action is more and more obvious.
Embodiment 5 MDEA-IPDI-HEMA (AC
1G) big monomer prepares the performance of dental prosthetic material with resin matrix as matrix resin
Present embodiment contains the big monomer (AC of novel methyl propenoate of tertiary amine structure not contain structure of bisphenol A
1G) part substitutes or replacing whole dihydroxyphenyl propane class dimethacrylate Bis-GMA commonly used clinically and active dilution dimethacrylate triglycol ester (TEGDMA); Light trigger camphorquinone CQ; Light-initiated promotor dimethylaminoethyl methacrylate (DMAEMA) is joined (it is as shown in table 3 to fill a prescription) preparation dental prosthetic mutually and is used resin matrix
Table 3 AC
1G is as the resin system of matrix resin and the compositing formula of reference resin system
Double bond conversion rate when studying this resin system polymerization, the mechanical property of polymerization shrinkage and polymerisate, and compare with business-like Bis-GMA/TEGDMA resin system.Its result is as shown in table 4.
Table 4 AC
1G is as the resin system of matrix resin and double bond conversion rate, polymerization shrinkage and the mechanical property of reference resin system
Visible by table 4, for Bis-GMA, contain AC
1G has higher double bond conversion rate as resin system, lower polymerization shrinkage and mechanical property preferably.
Claims (10)
1. contain the big monomer of methacrylic ester that the tertiary amine structure does not contain structure of bisphenol A, it is characterized in that said big monomeric structural formula does
R wherein
1Get following structural formula C
m, D, E
m, among the F any:
Wherein m is any numerical value in 1 to 19;
R among the structural formula A
2Get following structural formula G, H
m, among the I any one,
Wherein n is any numerical value in 0 to 27.
2. contain the big monomer of methacrylic ester that the tertiary amine structure does not contain structure of bisphenol A according to claim 1 is said, it is characterized in that containing the carboxylamine ester structure among said structural formula A or the B.
3. claim 1 is said contains the big monomeric preparation method of methacrylic ester that the tertiary amine structure does not contain structure of bisphenol A, it is characterized in that comprising the steps:
, the three-necked bottle of magneton adds IPDI or TDI in being housed; Under whipped state, constantly add N-alkyl diethylolamine or trolamine, use the eluent solvent constant pressure funnel through constant pressure funnel, 5 ~ 60 ℃ down reaction in the vulcabond system-NCO per-cent is near theoretical value; Water-bath adjusts the temperature to 15 ~ 90 ℃; In reactor drum, add hydroxyalkyl methacrylate compounds or 2-hydroxyl-1 through constant pressure funnel then, 3-dimethyl allene acyloxy propane, catalyzer and stopper, and use the eluent solvent constant pressure funnel; In 2 ~ 18 hours reaction times, then reaction product is carried out purification processes.
4. preparation method according to claim 3 is characterized in that said is 0.5～10 hour 5 ~ 60 ℃ of times of reacting down.
5. preparation method according to claim 4 is characterized in that the mol ratio of said IPDI or TDI and N-alkyl diethylolamine is 2:1; With the mol ratio of trolamine (TEA) be 3:1; Hydroxyalkyl methacrylate compounds or 2-hydroxyl-1, the mol ratio of 3-dimethyl allene acyloxy propane and N-alkyl diethylolamine (MDEA) or trolamine (TEA) is 1:1; Catalyst levels be the reactant total mass 0.02% ~ 1%; Stopper is 0.1% ~ 0.6% of a reactant total mass.
6. preparation method according to claim 5; It is characterized in that in the said step that the alkyl in the N-alkyl diethylolamine 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, cerylic, heptacosyl, octacosyl, nonacosyl or cyclohexyl.
7. preparation method according to claim 5; It is characterized in that in the said step, the alkyl in the hydroxyalkyl methacrylate compounds 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. preparation method according to claim 5; It is characterized in that said solvent comprises methylene dichloride, trichloromethane; ETHYLE ACETATE, 1,2-ethylene dichloride, benzene, toluene, acetone, butanone, cyclohexanone or N, the above mixture of one or more of dinethylformamide; Said catalyzer comprises triethylamine, triethylenediamine, tetramethyl butane diamine, N, one or more the above mixtures in N-dimethyl benzylamine, dibutyl tin dilaurate, the stannous octoate etc.; Said stopper comprises one or more the above mixtures in Resorcinol, para benzoquinone, toluhydroquinone, MEHQ, 2,5 di tert butyl hydroquinone, the 2-Tert. Butyl Hydroquinone etc.
9. claim 1 is said contains the application as light-initiated promotor in as dental prosthetic material of the big monomer of methacrylic ester that the tertiary amine structure do not contain structure of bisphenol A.
10. the said tertiary amine structure that contains of claim 1 does not contain the application of the big monomer of methacrylic ester of structure of bisphenol A as matrix resin in the dental prosthetic material.
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| CN103450243A (en) * | 2013-08-21 | 2013-12-18 | 华南理工大学 | Low-polymeric volume shrinkage (methyl) acrylate monomer without bisphenol A structure, and preparation method and application thereof |
| CN103896869A (en) * | 2014-03-06 | 2014-07-02 | 华南理工大学 | Antibacterial metacrylic acid ester monomer with thiazole ring structure as well as preparation method and application thereof |
| CN105017083A (en) * | 2015-05-29 | 2015-11-04 | 华南理工大学 | Methacrylate macromonomer containing fluorine structure but not containing bisphenol A structure, preparation method therefor and application thereof |
| CN109678761A (en) * | 2018-12-19 | 2019-04-26 | 上海维凯光电新材料有限公司 | A kind of high-modulus fluorochemical urethane acrylate and preparation method thereof |
| CN110591020A (en) * | 2019-09-06 | 2019-12-20 | 重庆云天化瀚恩新材料开发有限公司 | ASA high-rubber powder with excellent weather resistance, preparation method and application thereof |
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| CN103450243B (en) * | 2013-08-21 | 2016-10-05 | 华南理工大学 | (methyl) acrylate monomer of oligomerization cubical contraction without structure of bisphenol A and its preparation method and application |
| CN103896869A (en) * | 2014-03-06 | 2014-07-02 | 华南理工大学 | Antibacterial metacrylic acid ester monomer with thiazole ring structure as well as preparation method and application thereof |
| CN105017083A (en) * | 2015-05-29 | 2015-11-04 | 华南理工大学 | Methacrylate macromonomer containing fluorine structure but not containing bisphenol A structure, preparation method therefor and application thereof |
| CN105017083B (en) * | 2015-05-29 | 2017-06-06 | 华南理工大学 | The methacrylate macromer without structure of bisphenol A and its preparation method and application containing fluorine structure |
| CN109678761A (en) * | 2018-12-19 | 2019-04-26 | 上海维凯光电新材料有限公司 | A kind of high-modulus fluorochemical urethane acrylate and preparation method thereof |
| CN110591020A (en) * | 2019-09-06 | 2019-12-20 | 重庆云天化瀚恩新材料开发有限公司 | ASA high-rubber powder with excellent weather resistance, preparation method and application thereof |
| CN110591020B (en) * | 2019-09-06 | 2022-05-20 | 重庆云天化瀚恩新材料开发有限公司 | ASA high-rubber powder with excellent weather resistance, preparation method and application thereof |
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