CN103450243B - (methyl) acrylate monomer of oligomerization cubical contraction without structure of bisphenol A and its preparation method and application - Google Patents
(methyl) acrylate monomer of oligomerization cubical contraction without structure of bisphenol A and its preparation method and application Download PDFInfo
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- CN103450243B CN103450243B CN201310368256.3A CN201310368256A CN103450243B CN 103450243 B CN103450243 B CN 103450243B CN 201310368256 A CN201310368256 A CN 201310368256A CN 103450243 B CN103450243 B CN 103450243B
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- 0 CCC(CCC1C*2OC2CC1)C(C)O*(C)(C)CCC1CC2OC2CC1 Chemical compound CCC(CCC1C*2OC2CC1)C(C)O*(C)(C)CCC1CC2OC2CC1 0.000 description 4
- KRYSJALHNMHKTK-UHFFFAOYSA-N CC(C(OC(CC(CC[Si](C)(C)NC)CC1)C1O)=O)=C Chemical compound CC(C(OC(CC(CC[Si](C)(C)NC)CC1)C1O)=O)=C KRYSJALHNMHKTK-UHFFFAOYSA-N 0.000 description 1
- BQKIIPDZFJXVEC-UHFFFAOYSA-N CCCCC(CC1)CC(C)C1O Chemical compound CCCCC(CC1)CC(C)C1O BQKIIPDZFJXVEC-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses (methyl) acrylate monomer of oligomerization cubical contraction without structure of bisphenol A and preparation method thereof and application.(methyl) acrylate polymeric monomer without structure of bisphenol A prepared by the present invention, can be as the organic monomer component of dental prosthetic material.This polymeric monomer has that molecular weight is big, molecular volume big, without features such as structure of bisphenol A, therefore, this polymeric monomer polymerization cubical contraction when polymerization is less, and the potential hazard that human body is existed by the dental materials that can reduce structure of bisphenol A.
Description
Technical field
The present invention relates to a series of monomer that can be used as light initiation polymerization system, be specifically related to (methyl) acrylate monomer of a series of oligomerization cubical contraction without structure of bisphenol A and preparation method thereof and application.
Background technology
In 19 end of the centurys, American Dental doctor Miller, in its works " microorganism in Human Oral Cavity ", proposes the antibacterial mechanism that dental caries occurs for the first time, i.e. produces acid due to bacterial fermentation sugar, cause enamel decalcification cariogenic.Dental caries occur after tooth itself can not self-healing, can only by dental operation excise lesion portion, then use certain repair materials filling.Owing to the space applied widely, easy to use, cheap, modified of composite resin base repair materials is big；Simultaneously because composite resin directly can bond with tooth, therefore can retain the dental tissue of health more, be dummy material the most promising, that development is the swiftest and the most violent.
Although having had multiple different monomers to use in resin for restoration now, three kinds of monomers occupy main market: Bis-GMA(glycidyl Methacrylate), UDMA(methacrylate urethane ester) and TEGDMA(TEGDMA), almost other monomers are all to be changed on their architecture basics.The greatest problem of resin is polymerization cubical contraction, forms covalent bond due to monomer in the course of the polymerization process, can inevitably result in the volume contraction of resin when connecting tightr to each other.Polymerization volume contraction can cause being formed between filler and tooth microgap, makes bonding interface there is Micro blazed-grating and nano leakage, becomes the passage that antibacterial invades, again forms dental caries ring, i.e. recurrent caries, cause Endodontic failure.
For solving the polymerization shrinkage problem of composite resin, the research that synthesis has macromolecule and macromole volume monomer is the most active, Bis-GMA and 5 kinds of isocyanates have been synthesized 5 kinds of novel methacrylate macromer (structure such as formula IV) by such as Chetan A.Khatri etc., test result indicate that these 5 kinds of polymeric monomer can effectively reduce polymerization shrinkage.
Although macromolecule mentioned above and large volume methacrylate monomer can effectively reduce the polymerization volume contraction of dental prosthetic resin, but these monomers are all to improve on the basis of Bis-GMA, all contain structure of bisphenol A in molecular structure.And some results of study show, bisphenol-A can play the effect of estrogen, therefore the safety to the goods of structure of bisphenol A is queried by more and more national, think that the goods containing structure of bisphenol A may cause a lot of disease to include the cancer relevant to hormone, in some instances it may even be possible to the problem that the safeties such as infant growth growth can be affected.Therefore, bisphenol-A has been listed in noxious substance list and has prohibitted the use of by the countries such as the methyl acrylic ester dentistry composite resin containing structure of bisphenol A of Clinical practice is also subjected to the query of safety, Canada.
Due to the potential hazard of structure of bisphenol A, synthesis is without structure of bisphenol A, (methyl) acrylate polymeric monomer of oligomerization volume contraction, and uses it for being increasingly becoming in dentistry composite resin the focus of research.Jingwei He etc. are with 5,5 '-two (4-hydroxy phenyl)-hexahydro-4,7-benzofulvene (5,5 '-BPHM), epoxychloropropane, and methacrylic acid is a kind of fatty ring double methyl methacrylate structure of Material synthesis and without the novel methacrylate macromer 5 of structure of bisphenol A, 5 '-BHMPHM, research shows, this polymeric monomer is compared with clinical resin monomer Bis-GMA, has higher double bond conversion rate and relatively low polymerization cubical contraction.
Summary of the invention
Present invention aims to the defect of existing dental prosthetic material polymerization volume contraction (methyl) acrylate monomer etc. greatly and containing the structure of bisphenol A with genotoxic potential, it is provided that (methyl) acrylate polymeric monomer of a series of oligomerization cubical contractions without structure of bisphenol A and preparation method thereof and application.
The above-mentioned purpose of the present invention is achieved by following scheme:
(methyl) acrylate monomer of oligomerization cubical contraction without structure of bisphenol A, its structural formula is as follows:
In structure formula (I), A1, A2, A3 such as are at inseparable isomers of productivity, are referred to as A；
R in structure formula (I)1Take in structural formula B or C any one:
R in structure formula (I)2Take in following structural formula D～Q any one:
Any one numerical value during wherein m is 1 to 19.
The preparation method of (methyl) acrylate monomer of the described oligomerization cubical contraction without structure of bisphenol A, comprises the steps:
Step one:
1 is added in the three-necked bottle equipped with magneton (magnetic stir bar), double [the 2-(3 of 3-, 4-epoxide ring hex-1-yl) ethyl] tetramethyl disiloxane, it is simultaneously introduced methacrylic acid or acrylic acid, adds catalyst, polymerization inhibitor and solvent, at 40～90 DEG C, return stirring reacts 5-30 hour, it is cooled to room temperature, filters, then product is purified process, obtaining the monomer of structure ACD or ABD, wherein the implication of A, B, C, D and structural relation are as hereinbefore；
Step 2:
Methacrylic acid isocyanate-yl alkyl ester or acyl chloride compound is added in equipped with the three-necked bottle of magneton, it is simultaneously introduced the product of step one, adds catalyst, polymerization inhibitor and solvent, react 0.5～18 hour at 25～65 DEG C, then product is purified process, obtains product.
Optimize further, in described step one, 1,3-double [2-(3,4-epoxide ring hex-1-yl) ethyl] tetramethyl disiloxane and methacrylic acid or acrylic acid mol ratio be 1:2.02-2.10, catalyst amount is the 0.02%～1% of reactant gross mass；Polymerization inhibitor is the 0.1%～0.6% of reactant gross mass.
Optimizing further, in described step 2, the mol ratio of the product of methacrylic acid isocyanate-yl alkyl ester or acyl chlorides and step one is 2:1；Catalyst amount is the 0.02%～1% of reactant gross mass；Polymerization inhibitor is the 0.1%～0.6% of reactant gross mass.
Optimize further, described step one, in two, described solvent is selected from ether, dichloromethane, chloroform, ethyl acetate, 1, one or more things mixed above or solvent-free of 2-dichloroethanes, benzene, toluene, acetone, butanone, cyclohexanone or DMF.
Optimizing further, in step one, described catalyst is selected from triethylamine, triethylenediamine, tetramethyl butane diamine, N, one or more things mixed above in N-dimethyl benzylamine；In step 2, described catalyst is selected from triethylamine, triethylenediamine, tetramethyl butane diamine, N, one or more things mixed above in N-dimethyl benzylamine, dibutyl tin dilaurate, stannous octoate.
Optimize further, described step one, in two, polymerization inhibitor selected from hydroquinone, 1,4-benzoquinone, methylnaphthohydroquinone, MEHQ, 2, one or more things mixed above in 5-di-tert-butyl hydroquinone, 2-tert-butyl hydroquinone etc..
Optimize further, in described step 2, the alkyl in methacrylic acid isocyanate-yl alkyl ester type compound includes: ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl or eicosyl.
nullOptimize further，In described step 2，Acyl chloride compound includes: acryloyl chloride、Methacrylic chloride、Chloroacetic chloride、Propionyl chloride、Butyl chloride、Valeric chloride、Caproyl chloride、Oenanthyl chloro、Caprylyl chloride、Pelargonyl chloride、Decanoyl chloride、Undecyl acyl chlorides、Dodecyl acyl chlorides、Tridecyl acyl chlorides、Myristyl acyl chlorides、Pentadecyl acyl chlorides、Cetyl acyl chlorides、Heptadecyl acyl chlorides、Octadecyl chloride、Nonadecyl acyl chlorides、Eicosyl acyl chlorides、Cyclopropyl acyl chlorides、Cyclopenta acyl chlorides、Cyclohexyl acyl chlorides、Isobutyryl chloride、Isoveryl chloride、Cinnamoyl chloride、Furoyl chloride、Benzenecarbonyl chloride.、Phenyllacetyl chloride、Phenylpropyl alcohol acyl chlorides、Benzene butyl chloride、Benzene valeric chloride、Benzene caproyl chloride、Benzene oenanthyl chloro、Benzene caprylyl chloride、Benzene pelargonyl chloride、Benzene decanoyl chloride、Benzene undecyl acyl chlorides、Benzene dodecyl acyl chlorides、Benzene tridecyl acyl chlorides、Benzene myristyl acyl chlorides、Benzene pentadecyl acyl chlorides、Benzene cetyl acyl chlorides、Benzene heptadecyl acyl chlorides、Benzene octadecyl chloride、Benzene nonadecyl acyl chlorides or benzene eicosyl acyl chlorides.
(methyl) acrylate monomer of oligomerization cubical contraction without structure of bisphenol A prepared by the present invention, individually or can coordinate with other monomers during concrete application and be used for preparing dental prosthetic material, as the application of matrix resin in dental prosthetic material.
The chemical equation (being as a example by raw material reacts by double [2-(the 3,4-epoxide ring hex-1-yl) ethyl] tetramethyl disiloxane of 1,3-, methacrylic acid, isocyanatoethyl methacrylate) of above-mentioned steps is as follows.
Compared with prior art, there is advantages that
The remarkable advantage of novel (methyl) acrylate monomer prepared by the present invention is free from structure of bisphenol A, cubical contraction is little, double bond conversion rate is high, polymerizate mechanical property is good in polymerization, both can coordinate with other monomers for dental prosthetic material, it is possible to be individually used for matrix resin.Therefore, novel (methyl) the acrylate polymeric monomer of the oligomerization cubical contraction without structure of bisphenol A that prepared by the present invention has the potential being developed to photocuring dental prosthetic material.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further described through, but protection scope of the present invention is not done any restriction by specific embodiment.
Embodiment 1 ACD monomer
The present embodiment ACD monomer preparation method comprise the steps:
Step one: add 9.276g1 in equipped with the round-bottomed flask of magneton, double [the 2-(3 of 3-, 4-epoxide ring hex-1-yl) ethyl] tetramethyl disiloxane and 4.275g methacrylic acid, add the dichloromethane of 100ml, 0.050g N, N-dimethyl benzylamine, 0.06g hydroquinone return stirring at 90 DEG C reacts 24 hours, it is cooled to room temperature, then product is carried out acid solution washing alkali liquid washing purification process.
Product characterizes with infrared and nuclear-magnetism:
1H-NMR(400MHz, CCl3D): δ 6.14 (s, 2H), δ 5.60 (s, 2H), δ 3.95-3.15 (m, 4H), δ 2.01 (s, 6H), δ 1.90-1.45 (m, 14H), δ 1.45-1.20 (m, 8H), 0.50 (t, 12H).
FT-IR: ν (cm-1) 3648-3134,2920,2854,1720,1637,1253,1173,795,650.
The embodiment 2 polymerization cubical contraction containing ACD monomer dental resin
The diluent TEGDMA that ACD monomer and dental prosthetic material are conventional mix by the present embodiment, with the conventional resin system Bis-GMA/TEGDMA of dental prosthetic material as matched group, resin prepared by institute solidify after polymerization cubical contraction.
Its resin formula and polymerization volume shrinkage results are as shown in table 1 to table 2.
The table 1 resin composition containing ACD monomer
Table 2 is containing ACD monomer resin system and the polymerization cubical contraction of reference resin system
Visible, for Bis-GMA, ACD content of monomer be 51.2% resin system there is minimum polymerization shrinkage.
Producing of polymerization shrinkage changes caused mainly due to intermolecular distance before and after methacrylate resin polymerization.Double bond content in the size of polymerization shrinkage and system, molecular volume, molecular weight etc. are closely related.Compared with Bis-GMA, monomer ACD molecular weight is 554, higher than the 512 of Bis-GMA, under conditions of double bond number is identical, increases molecular weight and i.e. reduces double bond content, can effectively reduce polymerization shrinkage.By result above it could be speculated that the methacrylate derivative of this monomer also will have relatively low polymerization shrinkage.
The embodiment 3 mechanical performance containing ACD monomer dental resin
Resin system prepared by embodiment 3, on the basis of embodiment 3, is studied the mechanical performance after its solidification by the present embodiment.
Measuring mechanical property result is as shown in table 3.
Table 3 is containing ACD monomer resin system and the mechanical performance of reference resin system
Visible, for Bis-GMA, the mechanical performance containing the resin system of ACD monomer has declined, but still conforms to the application standard of dental prosthetic resin.
The polymerization shrinkage of the embodiment 4 composite containing ACD monomer
The present embodiment is according to the result of embodiment 2, the resin system that i.e. ACD content of monomer is 51.2% selecting polymerization cubical contraction minimum carries out preparation and the performance study thereof of corresponding composite, it is embodied as follows: ACD monomer, powder body conventional with dental prosthetic material for diluent TEGDMA are mixed, with business-like dental prosthetic material GC-A3(hereinafter referred to as GC) as matched group, the polymerization shrinkage of composite prepared by institute.Its resin formula and mechanical properties results are as shown in table 4 to table 5.
The table 4 composite composition containing ACD monomer
Table 5 is containing ACD monomer resin system and the polymerization shrinkage of reference resin system
Visible, for GC, powder content is that the polymerization shrinkage of the composite of 72% significantly lowers, the 61.5% of only GC.
The mechanical performance of the embodiment 5 composite containing ACD monomer
The present embodiment is on the basis of embodiment 3, composite containing ACD monomer prepared by embodiment 3, with business-like dental prosthetic material GC-A3(hereinafter referred to as GC) as matched group, composite prepared by institute is 35 DEG C of mechanical performances soaked before and after 7 days in 30mL distilled water.Its resin formula and mechanical properties results are as shown in table 6.
Table 6 contains composite and the mechanical performance of reference resin system of ACD monomer
Visible, for GC, powder content be the composite of 72% soaked before and after mechanical performance be most preferably.
The water absorption rate of the embodiment 6 composite containing ACD monomer and dissolution rate
The present embodiment is on the basis of embodiment 3, composite containing ACD monomer prepared by embodiment 3, with business-like dental prosthetic material GC-A3(hereinafter referred to as GC) as matched group, composite prepared by institute in 30mL distilled water 35 DEG C soak the water absorption rate after 7 days and dissolution rate.Its resin formula and test result are as shown in table 7.
Composite containing ACD monomer of table 7 and the water absorption rate of reference resin system and dissolution rate
Visible, for GC, powder content is that the water absorption rate of the composite of 72% is greatly lowered, only 0.88%；But its dissolution rate is that whole system is the highest.
Claims (8)
1. (methyl) acrylate list of the oligomerization cubical contraction without structure of bisphenol A
The preparation method of body, (methyl) of the described oligomerization cubical contraction without structure of bisphenol A
Acrylate monomer, its structural formula is as follows:
In structure formula (I), A1, A2, A3 such as are at inseparable isomers of productivity,
It is referred to as A；
R in structure formula (I)1Take in structural formula B or C any one:
R in structure formula (I)2Take in following structural formula D～Q any one:
Any one numerical value during wherein m is 1 to 19；
It is characterized in that preparation method comprises the steps:
Step one:
Double [2-(the 3,4-epoxide ring hex-1-yl) ethyl] four of 1,3-is added in equipped with the three-necked bottle of magneton
Tetramethyldisiloxane, is simultaneously introduced methacrylic acid or acrylic acid, adds catalyst, polymerization inhibitor
And solvent, at 40～90 DEG C, return stirring reacts 5-30 hour, is cooled to room temperature, filters,
Then product is purified process, obtains the monomer of structure ACD or ABD；
Step 2:
Methacrylic acid isocyanate-yl alkyl ester or acyl is added in equipped with the three-necked bottle of magneton
Chlorine compounds, is simultaneously introduced the product of step one, adds catalyst, polymerization inhibitor and solvent,
React 0.5～18 hour at 25～65 DEG C, then product is purified process,
To product.
Preparation method the most according to claim 1, it is characterised in that in described step one, 1,3-
Double [2-(3,4-epoxide ring hex-1-yl) ethyl] tetramethyl disiloxane and methacrylic acid or propylene
The mol ratio of acid is 1:2.02-2.10, and catalyst amount is reactant gross mass
0.02%～1%；Polymerization inhibitor is the 0.1%～0.6% of reactant gross mass.
Preparation method the most according to claim 1, it is characterised in that in described step 2, first
Base acrylic acid isocyanate-yl alkyl ester or acyl chlorides with the mol ratio of the product of step one are
2:1；Catalyst amount is the 0.02%～1% of reactant gross mass；Polymerization inhibitor is the total matter of reactant
The 0.1%～0.6% of amount.
Preparation method the most according to claim 1, it is characterised in that described step one, in two,
Described solvent is selected from ether, dichloromethane, chloroform, ethyl acetate, 1,2-dichloroethanes,
One or more of benzene, toluene, acetone, butanone, cyclohexanone or N,N-dimethylformamide with
Upper mixture or solvent-free.
Preparation method the most according to claim 1, it is characterised in that in step one, described in urge
Agent is selected from triethylamine, triethylenediamine, tetramethyl butane diamine, N, in N-dimethyl benzylamine
One or more things mixed above；In step 2, described catalyst is selected from triethylamine, Sanya
Ethyldiamine, tetramethyl butane diamine, N, N-dimethyl benzylamine, dibutyl tin dilaurate, pungent
One or more things mixed above in acid stannous.
Preparation method the most according to claim 1, it is characterised in that described step one, in two,
Polymerization inhibitor is selected from hydroquinone, 1,4-benzoquinone, methylnaphthohydroquinone, MEHQ, 2,5-bis-
One or more things mixed above in tert-butyl hydroquinone, 2-tert-butyl hydroquinone.
Preparation method the most according to claim 1, it is characterised in that in described step 2,
Alkyl in methacrylic acid isocyanate-yl alkyl ester type compound includes: ethyl, propyl group,
Butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, 12
Alkyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl,
Octadecyl, nonadecyl or eicosyl.
Preparation method the most according to claim 2, it is characterised in that in described step 2,
Acyl chloride compound includes: acryloyl chloride, methacrylic chloride, chloroacetic chloride, propionyl chloride,
Butyl chloride, valeric chloride, caproyl chloride, oenanthyl chloro, caprylyl chloride, pelargonyl chloride, decanoyl chloride,
Undecyl acyl chlorides, dodecyl acyl chlorides, tridecyl acyl chlorides, myristyl acyl chlorides,
Pentadecyl acyl chlorides, cetyl acyl chlorides, heptadecyl acyl chlorides, octadecyl chloride,
Nonadecyl acyl chlorides, eicosyl acyl chlorides, cyclopropyl acyl chlorides, cyclopenta acyl chlorides, hexamethylene
Base acyl chlorides, isobutyryl chloride, isoveryl chloride, cinnamoyl chloride, furoyl chloride, Benzenecarbonyl chloride.,
Phenyllacetyl chloride, phenylpropyl alcohol acyl chlorides, benzene butyl chloride, benzene valeric chloride, benzene caproyl chloride, benzene oenanthyl
Chlorine, benzene caprylyl chloride, benzene pelargonyl chloride, benzene decanoyl chloride, benzene undecyl acyl chlorides, benzene 12
Alkyl acyl chloride, benzene tridecyl acyl chlorides, benzene myristyl acyl chlorides, benzene pentadecyl acyl chlorides,
Benzene cetyl acyl chlorides, benzene heptadecyl acyl chlorides, benzene octadecyl chloride, benzene nonadecane
Base acyl chlorides or benzene eicosyl acyl chlorides.
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| CN102584883A (en) * | 2011-10-20 | 2012-07-18 | 湖北固润科技股份有限公司 | Multi-silicon methacrylate and acrylate monomer and synthetic method |
| CN102816088A (en) * | 2012-07-06 | 2012-12-12 | 华南理工大学 | Tertiary amine structure containing methacrylate macromonomer without bisphenol A structure, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102584883A (en) * | 2011-10-20 | 2012-07-18 | 湖北固润科技股份有限公司 | Multi-silicon methacrylate and acrylate monomer and synthetic method |
| CN102816088A (en) * | 2012-07-06 | 2012-12-12 | 华南理工大学 | Tertiary amine structure containing methacrylate macromonomer without bisphenol A structure, preparation method and application thereof |
Non-Patent Citations (2)
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| Organosilicon dental composite restoratives based on 1,3-bis[(p-acryloxymethyl) phenethyl] tetramethyldisiloxane;J.H. Lai et al.;《Dental Materials》;20040630;第20卷(第6期);第44-46页 * |
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