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
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- alkyl
- antibacterial monomer
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 64
- 239000000178 monomer Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 125000005496 phosphonium group Chemical class 0.000 title abstract 3
- 150000004714 phosphonium salts Chemical group 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 25
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- -1 acrylic acid halogen ester Chemical class 0.000 claims description 19
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- QPMJENKZJUFOON-PLNGDYQASA-N ethyl (z)-3-chloro-2-cyano-4,4,4-trifluorobut-2-enoate Chemical group CCOC(=O)C(\C#N)=C(/Cl)C(F)(F)F QPMJENKZJUFOON-PLNGDYQASA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 230000000845 anti-microbial effect Effects 0.000 description 9
- 239000002585 base Substances 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 239000003242 anti bacterial agent Substances 0.000 description 6
- 229940088710 antibiotic agent Drugs 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 6
- 235000002639 sodium chloride Nutrition 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000003115 biocidal effect Effects 0.000 description 5
- 210000000214 mouth Anatomy 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000011797 cavity material Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 3
- 241000222122 Candida albicans Species 0.000 description 3
- 208000035126 Facies Diseases 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 241000194019 Streptococcus mutans Species 0.000 description 2
- 230000002421 anti-septic effect Effects 0.000 description 2
- 244000052616 bacterial pathogen Species 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229940095731 candida albicans Drugs 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000004851 dental resin Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 2
- SDEVOFCZKAPFID-UHFFFAOYSA-M (1-dodecylpyridin-1-ium-2-yl) 2-methylprop-2-enoate;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+]1=CC=CC=C1OC(=O)C(C)=C SDEVOFCZKAPFID-UHFFFAOYSA-M 0.000 description 1
- 0 *C(C(O*[P+](*)(*)N)=*)=C Chemical compound *C(C(O*[P+](*)(*)N)=*)=C 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- YGYQHTPQUJUSLI-UHFFFAOYSA-N 3-(2-bromo-3-dodecylpyridin-4-yl)propyl 2-methylprop-2-enoate Chemical compound C(C(=C)C)(=O)OCCCC1=C(C(=NC=C1)Br)CCCCCCCCCCCC YGYQHTPQUJUSLI-UHFFFAOYSA-N 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 208000006819 Denture Stomatitis Diseases 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 208000025157 Oral disease Diseases 0.000 description 1
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical compound C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001347 alkyl bromides Chemical class 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229960002233 benzalkonium bromide Drugs 0.000 description 1
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229960002152 chlorhexidine acetate Drugs 0.000 description 1
- 229960003333 chlorhexidine gluconate Drugs 0.000 description 1
- YZIYKJHYYHPJIB-UUPCJSQJSA-N chlorhexidine gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O.C1=CC(Cl)=CC=C1NC(=N)NC(=N)NCCCCCCNC(=N)NC(=N)NC1=CC=C(Cl)C=C1 YZIYKJHYYHPJIB-UUPCJSQJSA-N 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 210000004513 dentition Anatomy 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 208000030194 mouth disease Diseases 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- MCSINKKTEDDPNK-UHFFFAOYSA-N propyl propionate Chemical compound CCCOC(=O)CC MCSINKKTEDDPNK-UHFFFAOYSA-N 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 210000003296 saliva Anatomy 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000036346 tooth eruption Effects 0.000 description 1
- KCTAHLRCZMOTKM-UHFFFAOYSA-N tripropylphosphane Chemical compound CCCP(CCC)CCC KCTAHLRCZMOTKM-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 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 Table
- 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
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- General Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Polymers & Plastics (AREA)
- Biochemistry (AREA)
- Plastic & Reconstructive Surgery (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
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 |
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| 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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| 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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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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| 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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