CN105906664A - Quaternary phosphonium salt-type antibacterial monomer and preparation method thereof - Google Patents
Quaternary phosphonium salt-type antibacterial monomer and preparation method thereof Download PDFInfo
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- CN105906664A CN105906664A CN201610073376.4A CN201610073376A CN105906664A CN 105906664 A CN105906664 A CN 105906664A CN 201610073376 A CN201610073376 A CN 201610073376A CN 105906664 A CN105906664 A CN 105906664A
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- phosphonium salt
- monomer
- season
- alkyl
- antibacterial monomer
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- 0 *C(C(O*[P+](*)(*)N)=*)=C Chemical compound *C(C(O*[P+](*)(*)N)=*)=C 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5407—Acyclic saturated phosphonium compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F30/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
Abstract
The invention relates to a quaternary phosphonium salt-type antibacterial monomer shown in the formula and a preparation method thereof. One end of the monomer is an antibacterial group which is a quaternary phosphonium salt group, the other end of the monomer is a polymerizable group which is an acrylate group and the middle chain of the monomer is an alkyl chain segment. Through the polymerizable group, the monomer can be bonded to a dental restoration material through a chemical reaction so that the dental restoration material has long-term antibacterial properties. The invention also relates to a polymer prepared from the quaternary phosphonium salt-type antibacterial monomer as a polymerization monomer and also relates a dental restorative material containing the polymer.
Description
Technical field
The present invention relates to the season phosphonium salt type antibacterial monomer and preparation method thereof for dental prosthetic material.The invention still further relates to use the polymeric material that this phosphonium salt antibacterial monomer is polymerized as polymerization monomer in season, and comprise the dental prosthetic material of this polymeric material.
Background technology
Macromolecular material is widely used in stomatology with its good chemical property, physical and mechanical properties, biocompatibility and ease for operation etc..Wherein, composite resin, bonding agent and base etc. are widely used in prevention of caries, repair tooth body defect of dentition and improve color of teeth and outward appearance.But, the resin base oral cavity material after solidification cannot be avoided internal containing a small amount of unconverted monomer, the volatilization of residual monomer or dissolution cause material surface coarse, have micropore.Therefore, resin base oral cavity material, compared with other repair materials, is more easy to be infected by bacterial, causes repairing failure, and other the most denture stomatitis of oral disease etc. even occur.
The anti-microbial property improving resin base oral cavity material is always the emphasis of scholar's research, by introducing antibiotic substance in the material so that the inactivation of bacteria adhered to, can prevent antibacterial from infecting.At present antibiotic substance is broadly divided into three classes: antibacterials, inorganic antiseptic and organic antibacterial agent.
Such as, Chinese patent CN103285028 describes the antibacterials such as employing chlorhexidine acetate, chlorhexidine gluconate, polyhexamethylene guanidine or benzalkonium bromide.But, the dissolution of antibacterials makes the structure of material be destroyed, and causes chemical property, physical and mechanical properties to be remarkably decreased, and the dissolution of antibacterials has " burst effect ", and Durability of antimicrobial effect is not enough.
Inorganic antiseptic is mainly metal and compound thereof, and wherein silver-series antibacterial agent such as zeolite with carrying silver is widely used in stomatologic tissue conditioning agents, acrylic resin and collutory etc. with its good anti-microbial property and biological safety.The life active compound making microorganism by being bonded or replace the modes such as metal ion prothetic group with active group such as sulfydryl inactivates and plays antibacterial action.Record according to Chinese patent CN1977787, by adding nanometer silver, to antibiotic rates such as staphylococcus aureus, escherichia coli, candida albicanses all more than 99%.Chinese patent CN101239024 with the addition of nanometer silver the most in a binder and plays antibacterial effect.But, silver base inorganic antibacterial agent dispersibility is poor, it is difficult to be uniformly added in oral cavity material, and color stability also needs to be improved further.And there are some researches show, although argentiferous aluminosilicate has good antibacterial effect to oral cavity common bacteria, but does not show good anti-microbial property after adding in resin material.
Cationic nitrogenous type organic antibacterial agent such as alkyl quaternary ammonium salts, pyridiniujm and imidazole salts etc. have the antibacterial functions of wide spectrum, mainly combine with the anion of antibacterial and the surface of cell membrane of mycete, or react with sulfydryl, destroy protein and the synthesis system of cell membrane, thus suppress the breeding of antibacterial and mycete.The feature of this type of antibacterial is physical antibacterial, has the advantage such as persistency and restorability.The antibiotic property methacrylate monomer of preparation in Chinese patent CN102807510, containing quaternary ammonium salt structure and carbamate structures, can be as the antibacterial components in dental prosthetic material.This monomer has methacrylic acid ester group and quaternary ammonium salt structure, and therefore this monomer not only itself has antibacterial activity, it is also possible to give with polymerizate during other monomer copolymerization with antibiotic property.Chinese patent CN101199449 discloses the class quaternary antibacterial monomer application at dental antibacterial repair materials, is to be bonded in dental resin sill by a class quaternary antibacterial monomer, gives dental resin sill with anti-microbial property.Polymer-based group-methacrylic acid ester group that in its general structure, one end is common in being monomeric bisphenol A-glycidyl methacrylate, carbamate double methyl methacrylate or diluting monomer double methyl methacrylate triethylene glycol ester molecular structure, the other end is the functional group with antibacterial action, including the N+ of lotus positive electricity be positioned at the phenyl ring of side chain, m-chloro phenyl ring or chain alkyl, such as methylacryoyloxyethyl-benzyl-dimethyl ammonium chloride, methylacryoyloxyethyl-n-hexadecyl-alkyl dimethyl ammonium chloride etc..But also studies have found that some antibacterial has Drug resistance to azonia type organic antibacterial agent.
In addition to quaternary ammonium salt organic antibacterial agent, season phosphonium salt be also one of the new direction of antibacterial research.Chemically from the point of view of structure, phosphorus atoms is bigger than the ionic radius of nitrogen-atoms, polarization is strong so that season phosphonium salt be easier to adsorb electronegative thalline, simultaneously because P elements is positioned at the lower section of nitrogen element in the periodic table of elements, phosphorus has more weak electronegativity than nitrogen.Additionally, season phosphonium salt molecular structure more stable, be all not susceptible to reaction with general Oxidizing and Reducing Agents and acid, alkali, can use in the range of the acid-base value of pH=2～12, and quaternary ammonium salt only when about pH=9, effect is just most preferably.But, relative to quaternary ammonium salt, season phosphonium salt research at present also in the starting stage.
Summary of the invention
It is an object of the invention to overcome the defect of prior art, it is provided that a kind of season phosphonium salt antibacterial monomer and preparation method thereof for dental prosthetic material.
On the one hand, the present invention provides one season phosphonium salt antibacterial monomer, and its chemical constitution is as follows:
In this structure, one end is antibacterial group season phosphonium salt group, and the other end is polymerizable groups acrylate group, and middle segment is alkyl segment.
In the season according to the present invention in phosphonium salt antibacterial monomer, R2、R3、R4Can be that identical group can also be for different groups, the most identical group.
According to the present invention season phosphonium salt antibacterial monomer a kind of preferred embodiment, R1Selected from hydrogen and alkyl, preferably C1To C6Straight chain or branched-alkyl, more preferably methyl.
According to the present invention season phosphonium salt antibacterial monomer a kind of preferred embodiment, R2、R3、R4It is independently from each other hydrogen, alkyl and benzyl, preferably C1To C6Straight chain or branched-alkyl, more preferably normal-butyl.
According to the present invention season phosphonium salt antibacterial monomer a kind of preferred embodiment, middle alkyl segment is the alkyl segment of n=2～16, preferably n=6～14, more preferably n=8～12.
According to the present invention season phosphonium salt antibacterial monomer a kind of preferred embodiment, X be selected from Cl, Br and I, preferably Cl and Br, more preferably Br.
On the other hand, the present invention provide a kind of following formula season phosphonium salt antibacterial monomer preparation method,
The method includes making many alkylphosphines and acrylic acid halogen ester react under inert gas shielding, and reaction equation is as follows:
A kind of preferred embodiment of preparation in accordance with the present invention, the method comprises the following steps: equipped with thermometer, agitator four-hole bottle in add solvent, many alkylphosphines, acrylic acid halogen ester, be heated under inert gas shielding backflow；Reactant solvent such as ethers is dissolved dispersion, and then crystallization and recrystallization, obtain product.
In preparation in accordance with the present invention, the consumption mol ratio of many alkylphosphines and acrylic acid halogen ester can be 1:0.8～1.2, preferably 1:1.
In preparation in accordance with the present invention, R2、R3、R4Can be that identical group can also be for different groups, the most identical group.
A kind of preferred embodiment of preparation in accordance with the present invention, R2、R3、R4It is independently from each other hydrogen, alkyl and benzyl, preferably C1To C6Straight chain or branched-alkyl, more preferably normal-butyl.
A kind of preferred embodiment of preparation in accordance with the present invention, R1For hydrogen or alkyl, preferably C1To C6Straight chain or branched-alkyl, more preferably methyl.
A kind of preferred embodiment of preparation in accordance with the present invention, in acrylic acid halogen ester, halogen is selected from Cl, Br and I, preferably Cl and Br, more preferably Br.
A kind of preferred embodiment of preparation in accordance with the present invention, middle alkyl segment is the alkyl segment of n=2～16, preferably n=6～14, more preferably n=8～12.
On the other hand, the present invention provides a kind of polymeric material, and it uses the season phosphonium salt antibacterial monomer of the present invention to be polymerized as polymerization monomer.This polymeric material can be homopolymer or copolymer, can comprise the monomer in addition to phosphonium salt antibacterial monomer of the season except the present invention.The preparation of this polymeric material can use the typical polymerization methods of polymer arts.
On the other hand, the present invention provides a kind of dental prosthetic material, and it comprises the polymeric material according to the present invention.
Compared with prior art, the season phosphonium salt antibacterial monomer of the present invention has the advantage that
1) can be attached in dental materials by the way of chemical crosslinking, chemistry injury will not be produced because of the dissolution in saliva and lose antibacterial activity；
2) phosphonium salt 2 orders of magnitude higher than the anti-microbial property of ammonium salt；
3) phosphonium salt molecular structure is more stable, can use in the range of the acid-base value of pH=2～12, and quaternary ammonium salt only when about pH=9 effect just optimal.
Accompanying drawing explanation
Fig. 1 is the nmr spectrum of the methacryloxypropyl dodecyl bromide tributylphosphine of embodiment 1 preparation.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1 methacryloxypropyl dodecyl bromide tributylphosphine (monomer 1)
1) 22g 12 bromohydrin is joined in 1000ml single port flask, add 250ml dichloropropane and the triethylamine of 16.5g, the lower dropping 14.76g methacrylic chloride of stirring.After dropping, continue stirring 3 hours.After reaction terminates, system is respectively with water and saturated sodium carbonate and saturated aqueous common salt washing.Organic facies anhydrous sodium sulfate is dried, and concentrates, chromatography.Obtain methacrylic acid ten dibromo alcohol ester 19.5g, productivity 73%.
2) methacrylic acid ten dibromo alcohol ester 7.6g is joined in 250ml single port flask, add 100ml acetonitrile and 2.3g tributylphosphine, stirred at reflux 5 hours.After reaction terminates, system concentrates, chromatography.Obtain salt 3.631g, productivity 59.2%.
3) nuclear magnetic spectrogram is as shown in Figure 1.
1H-NMR (500MHz, d6-DMSO): δ 0.92 (t, J=8.0Hz, 9H), 1.26-1.29 (m, 15H), 1.36-1.50 (m, 15H), 1.57-1.63 (m, 2H), 1.88 (s, 3H), 2.16-2.24 (m, 8H), 4.08 (t, J=8.0Hz, 2H), 5.67 (t, J=2.0Hz, 1H), 6.01 (s, 1H).
Embodiment 2 methacryloxypropyl eight alkyl bromide tributylphosphine (monomer 2)
1) 20g eight bromohydrin is joined in 1000ml single port flask, add 250ml dichloropropane and the triethylamine of 17.7g, the lower dropping 16.65g methacrylic chloride of stirring.After dropping, continue stirring 5 hours.After reaction terminates, system is respectively with water and saturated sodium carbonate and saturated aqueous common salt washing.Organic facies anhydrous sodium sulfate is dried, and concentrates, chromatography.Obtain methacrylic acid eight bromohydrin ester 18.4g, productivity 76%.
2) methacrylic acid eight bromohydrin ester 6.9g is joined in 250ml single port flask, add 100ml acetonitrile and 2.4g tributylphosphine, stirred at reflux 3 hours.After reaction terminates, system concentrates, chromatography.Obtain salt 4.654g, productivity 62.7%.
Embodiment 3 methacryloxypropyl ten alkyl chloride tripropyl phosphine (monomer 3)
1) 23g ten chloropharin is joined in 1000ml single port flask, add 250ml dichloropropane and the triethylamine of 15.9g, the lower dropping 18.76g methacrylic chloride of stirring.After dropping, continue stirring 4 hours.After reaction terminates, system is respectively with water and saturated sodium carbonate and saturated aqueous common salt washing.Organic facies anhydrous sodium sulfate is dried, and concentrates, chromatography.Obtain methacrylic acid ten chloropharin ester 17.9g, productivity 68%.
2) methacrylic acid ten chloropharin ester 6.5g is joined in 250ml single port flask, add 100ml acetonitrile and 2.1g tripropyl phosphine, stirred at reflux 3 hours.After reaction terminates, system concentrates, chromatography.Obtain salt 3.724g, productivity 60.1%.
Embodiment 4 three kinds season the phosphonium salt monomer antibacterial activity test to common oral pathogenic bacterium
Streptococcus mutans and Candida albicans is used to carry out anti-microbial property evaluation.Choose the reason of both antibacterials: (a) mainly comprising and pathogenic bacterium as oral biological film, representative；B () utilizes both antibacterials to carry out easy and simple to handle, the technology maturation of material anti-microbial property evaluation.
As a example by methacryloxypropyl dodecyl bromide tributylphosphine, minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) test process of antibacterial monomer are as follows:
With brain-heart infusion medium (BHI) as solvent, prepare certain density antibacterial monomer solution.Initial concentration is defined as 1.0mg/ml, and continuous doubling dilution is standby.Bacterial concentration is adjusted to 1 × 10 after experimental strain cultivation overnight7CFU/mL.Each test tube adds antibacterial monomer solution lml, bacterium solution 100 μ l.Streptococcus mutans culture tube is placed in 37 DEG C, 5%CO2, 5%N2Incubator is cultivated 24～48h.Candida albicans culture tube is placed in 37 DEG C of air jet flow casees cultivation 18～24h.The minimum inhibitory concentration that antibacterial monomer least concentration is this antibacterial monomer (MIC) that examination liquid in pipe is limpid.Culture in the limpid test tube of inoculating loop picking, streak inoculation, on BHI agar plate, hatches 48h, without the minimum bactericidal concentration (MBC) that minimum antibacterial monomer concentration is this antibacterial monomer of bacterial growth.
Being comparison with the methacryloxypropyl dodecyl bromopyridine (Methacryloyloxydodecylpyridinium bromide, MDPB) of commercialization at present, the anti-microbial property of several monomers is as shown in table 1:
The minimum inhibitory concentration (MIC) of table 1 monomer and minimum bactericidal concentration (MBC)
Claims (10)
1. a season phosphonium salt antibacterial monomer, its general structure is as follows:
In this structure, one end is antibacterial group season phosphonium salt group, and the other end is polymerizable groups third
Enoate group, middle segment is alkyl segment.
Season the most according to claim 1 phosphonium salt antibacterial monomer, it is characterised in that R1Selected from hydrogen and alkyl,
Preferably C1To C6Straight chain or branched-alkyl, more preferably methyl.
Season the most according to claim 1 phosphonium salt antibacterial monomer, it is characterised in that R2、R3、R4For phase
Same group or different groups.
Season the most according to claim 1 phosphonium salt antibacterial monomer, it is characterised in that R2、R3、R4Each other
Independently selected from hydrogen, alkyl and benzyl, preferably C1To C6Straight chain or branched-alkyl, more preferably positive fourth
Base.
Season the most according to claim 1 phosphonium salt antibacterial monomer, it is characterised in that X selected from Cl, Br and
I, preferably Cl and Br, more preferably Br.
Season the most according to claim 1 phosphonium salt antibacterial monomer, it is characterised in that n=2～16, preferably
N=6～14, more preferably n=8～12.
7. one of claim 1 to 6 season phosphonium salt antibacterial monomer preparation method, it is characterised in that make many alkane
Base phosphine and acrylic acid halogen ester react under inert gas shielding, and reaction equation is as follows:
Preparation method the most according to claim 7, it is characterised in that equipped with thermometer, agitator
Four-hole bottle adds solvent, many alkylphosphines, acrylic acid halogen ester, is heated to back under inert gas shielding
Stream；Reactant solvent such as ethers is dissolved dispersion, and then crystallization and recrystallization, obtain product；Wherein
The consumption mol ratio of many alkylphosphines and acrylic acid halogen ester is 1:0.8～1.2, preferably 1:1.
9. a polymeric material, it uses the season phosphonium salt antibacterial monomer conduct of one of claim 1 to 6
Polymerization monomer is polymerized.
10. a dental prosthetic material, it comprises the polymeric material of claim 9.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107674093A (en) * | 2017-10-18 | 2018-02-09 | 南京大学（苏州）高新技术研究院 | A kind of unsaturated chain alkyl quaternary phosphonium salt ionic liquid self-assembled materials |
| CN110256617A (en) * | 2019-02-26 | 2019-09-20 | 华南理工大学 | Poly- (methyl) acrylate antibacterial agent of Han quaternary alkylphosphonium salt structure and preparation method thereof and application in the plastic |
| CN114394995A (en) * | 2022-01-24 | 2022-04-26 | 洛阳冠银生物科技有限公司 | Preparation method and application of polymerizable organic acid tetrakis (hydroxymethyl) phosphonium |
| CN115340627A (en) * | 2022-07-26 | 2022-11-15 | 华南理工大学 | Polyacrylic acid emulsion containing quaternary phosphonium salt and having antibacterial function, and preparation method and application thereof |
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| CN1253767A (en) * | 1998-08-20 | 2000-05-24 | 可乐丽股份有限公司 | Adhesive compound for tooth |
| JP2012046468A (en) * | 2010-08-30 | 2012-03-08 | Kuraray Medical Inc | Dental kit |
| CN103739786A (en) * | 2013-12-31 | 2014-04-23 | 河南金誉包装科技股份有限公司 | High polymer quaternary phosphonium salt antibacterial material and preparation method thereof |
| JP2014231493A (en) * | 2013-05-29 | 2014-12-11 | 株式会社トクヤマデンタル | Dental restoration kit |
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2016
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1253767A (en) * | 1998-08-20 | 2000-05-24 | 可乐丽股份有限公司 | Adhesive compound for tooth |
| JP2012046468A (en) * | 2010-08-30 | 2012-03-08 | Kuraray Medical Inc | Dental kit |
| JP2014231493A (en) * | 2013-05-29 | 2014-12-11 | 株式会社トクヤマデンタル | Dental restoration kit |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107674093A (en) * | 2017-10-18 | 2018-02-09 | 南京大学（苏州）高新技术研究院 | A kind of unsaturated chain alkyl quaternary phosphonium salt ionic liquid self-assembled materials |
| CN107674093B (en) * | 2017-10-18 | 2019-12-31 | 南京大学（苏州）高新技术研究院 | Unsaturated long-chain alkyl quaternary phosphonium salt ionic liquid self-assembly material |
| CN110256617A (en) * | 2019-02-26 | 2019-09-20 | 华南理工大学 | Poly- (methyl) acrylate antibacterial agent of Han quaternary alkylphosphonium salt structure and preparation method thereof and application in the plastic |
| CN114394995A (en) * | 2022-01-24 | 2022-04-26 | 洛阳冠银生物科技有限公司 | Preparation method and application of polymerizable organic acid tetrakis (hydroxymethyl) phosphonium |
| CN115340627A (en) * | 2022-07-26 | 2022-11-15 | 华南理工大学 | Polyacrylic acid emulsion containing quaternary phosphonium salt and having antibacterial function, and preparation method and application thereof |
| CN115340627B (en) * | 2022-07-26 | 2023-12-26 | 华南理工大学 | Quaternary phosphonium salt-containing polyacrylic emulsion with antibacterial function and preparation method and application thereof |
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Application publication date: 20160831 |