CN114395075B - 一种牙科用零填料渗透树脂及其制备方法 - Google Patents
一种牙科用零填料渗透树脂及其制备方法 Download PDFInfo
- Publication number
- CN114395075B CN114395075B CN202210067840.4A CN202210067840A CN114395075B CN 114395075 B CN114395075 B CN 114395075B CN 202210067840 A CN202210067840 A CN 202210067840A CN 114395075 B CN114395075 B CN 114395075B
- Authority
- CN
- China
- Prior art keywords
- resin
- isosorbide
- dental
- zero
- filler
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011347 resin Substances 0.000 title claims abstract description 90
- 229920005989 resin Polymers 0.000 title claims abstract description 90
- 239000000945 filler Substances 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 7
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims abstract description 32
- 229960002479 isosorbide Drugs 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 238000000016 photochemical curing Methods 0.000 claims abstract description 14
- 239000003112 inhibitor Substances 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 3
- 230000000149 penetrating effect Effects 0.000 claims description 36
- 229930006711 bornane-2,3-dione Natural products 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 10
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 8
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 claims description 6
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 5
- UKRQMDIFLKHCRO-UHFFFAOYSA-N 2,4,6-trimethylbenzoyl chloride Chemical compound CC1=CC(C)=C(C(Cl)=O)C(C)=C1 UKRQMDIFLKHCRO-UHFFFAOYSA-N 0.000 claims description 4
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 claims description 4
- 125000002362 bornane-2,3-dione group Chemical group 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 238000005115 demineralization Methods 0.000 abstract description 12
- ZSZRUEAFVQITHH-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 2-(trimethylazaniumyl)ethyl phosphate Chemical compound CC(=C)C(=O)OCCOP([O-])(=O)OCC[N+](C)(C)C ZSZRUEAFVQITHH-UHFFFAOYSA-N 0.000 abstract description 11
- 230000003902 lesion Effects 0.000 abstract description 11
- 230000001580 bacterial effect Effects 0.000 abstract description 7
- 230000003204 osmotic effect Effects 0.000 abstract description 5
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 231100000433 cytotoxic Toxicity 0.000 abstract description 3
- 230000001472 cytotoxic effect Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 210000003298 dental enamel Anatomy 0.000 description 18
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 12
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 230000002328 demineralizing effect Effects 0.000 description 12
- 241000283690 Bos taurus Species 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 229920006267 polyester film Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HMLSBRLVTDLLOI-UHFFFAOYSA-N 1-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)C(C)OC(=O)C(C)=C HMLSBRLVTDLLOI-UHFFFAOYSA-N 0.000 description 4
- 241001521783 Streptococcus mutans UA159 Species 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000022972 amelogenesis Effects 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 208000006558 Dental Calculus Diseases 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 206010044029 Tooth deposit Diseases 0.000 description 3
- 230000003833 cell viability Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000006059 cover glass Substances 0.000 description 3
- 208000002925 dental caries Diseases 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 3
- 210000004283 incisor Anatomy 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 3
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- CAEWJEXPFKNBQL-UHFFFAOYSA-N prop-2-enyl carbonochloridate Chemical compound ClC(=O)OCC=C CAEWJEXPFKNBQL-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 230000003214 anti-biofilm Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 231100000135 cytotoxicity Toxicity 0.000 description 2
- 230000003013 cytotoxicity Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- UEKHZPDUBLCUHN-UHFFFAOYSA-N 2-[[3,5,5-trimethyl-6-[2-(2-methylprop-2-enoyloxy)ethoxycarbonylamino]hexyl]carbamoyloxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC(=O)NCCC(C)CC(C)(C)CNC(=O)OCCOC(=O)C(C)=C UEKHZPDUBLCUHN-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 102400000888 Cholecystokinin-8 Human genes 0.000 description 1
- 101800005151 Cholecystokinin-8 Proteins 0.000 description 1
- 239000006144 Dulbecco’s modified Eagle's medium Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 206010016818 Fluorosis Diseases 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 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
- 229920002472 Starch Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000032770 biofilm formation Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 208000004042 dental fluorosis Diseases 0.000 description 1
- 210000005258 dental pulp stem cell Anatomy 0.000 description 1
- 239000004851 dental resin Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 201000010840 enamel caries Diseases 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000010069 protein adhesion Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- IZTQOLKUZKXIRV-YRVFCXMDSA-N sincalide Chemical compound C([C@@H](C(=O)N[C@@H](CCSC)C(=O)NCC(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CC(O)=O)C(=O)N[C@@H](CC=1C=CC=CC=1)C(N)=O)NC(=O)[C@@H](N)CC(O)=O)C1=CC=C(OS(O)(=O)=O)C=C1 IZTQOLKUZKXIRV-YRVFCXMDSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
- A61K6/62—Photochemical radical initiators
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Biophysics (AREA)
- Plastic & Reconstructive Surgery (AREA)
- Dental Preparations (AREA)
Abstract
本发明提供一种牙科用零填料渗透树脂及其制备方法，所述渗透树脂按质量分数包括：低粘度异山梨醇基光固化单体91.5％‑98％；2‑甲基丙烯酰氧乙基磷酰胆碱0.5％‑6％；光引发剂1％‑2％；阻聚剂0.5％。本发明公开的新型渗透树脂的主成分为具有良好生物相容性的异山梨醇基光固化单体，能有效规避传统渗透树脂所引起的明显细胞毒反应，并且异山梨醇基光固化单体的双五环结构也赋予了其更优异的机械性能，实现了高生物安全性及良好的机械性能的统一；同时还引入了一种具有抗菌斑生物膜黏附作用的两性离子化合物MPC，这有助于提高渗透树脂的抗菌性能，从而降低病损治疗区再脱矿发生的风险。
Description
技术领域
本发明涉及医用树脂技术领域，尤其涉及一种牙科用零填料渗透树脂。
背景技术
渗透树脂是以低粘度、高渗透系数的三缩四乙二醇二甲基丙烯酸酯(TEGDMA)光固化单体为主要成分的一种树脂材料，现有的商用产品为ICON。它主要适用于无光泽的白垩色釉质病损区，如早期釉质龋，特别是正畸治疗后托槽周围的釉质白斑，氟牙症或釉质发育不全等。低粘度渗透树脂通过毛细作用力渗入羟基磷灰石晶体微孔之中，填充间隙，形成树脂-多孔羟基磷灰石复合体。微孔中的空气或水被树脂所取代，孔隙和釉质之间折光率的差异减小使得原本呈现白垩色的病变恢复接近正常牙釉质的色泽，获得美学的改善。应用渗透树脂能避免钻磨轻度病变的牙体，以最大程度保留自身牙体组织，属于微创治疗的范畴，这也吸引了一众学者对其材料性能及功能改善等开展研究。
当前的牙科用渗透树脂材料产品单一，存在诸多不足。一方面相较Bis-GMA，UDMA等单体，TEGDMA分子质量小且含有环氧乙烷长链，易发生化学降解反应、更易从基质中释放导致细胞毒反应。现有研究发现固化后ICON树脂的浸出液培养牙髓干细胞48h后呈现中度的细胞毒性。复合树脂或流动树脂等材料中作为稀释剂的TEGDMA含量较少，而在渗透树脂中其占比大于70％，具有较大的潜在生物学风险。考虑到渗透树脂的应用人群多为儿童及青少年，我们要特别关注该材料的生物安全性能。另一方面由于主成分为长链状TEGDMA单体，ICON固化后机械强度不足，耐磨性不如流体树脂和树脂封闭剂等，并且其中缺乏抗菌成分，长期口腔环境下病损治疗区再脱矿发生的风险不容忽视。
针对上述问题，我们尝试研制新型的牙科用渗透树脂，考虑利用异山梨醇这一原料合成其中的主要成分-低粘度光固化单体。异山梨醇是一种由葡萄糖衍生而来的无毒、可生物降解的二元醇，它可以从包括纤维素和淀粉在内的生物质材料的解聚中广泛获得。现有的基于异山梨醇合成的光固化单体均表现出良好的生物安全性，其中部分结构具备与TEGDMA类似的低粘性，提示此类单体有用于渗透性树脂改性的可能，并且异山梨醇中的双五环结构理论上能赋予其衍生单体良好的机械性能。同时新型渗透树脂中还尝试加入2-甲基丙烯酰氧乙基磷酰胆碱(MPC)成分，它是可参与光固化反应的两性离子化合物，生物相容性好，具有抗蛋白附着、减少菌斑生物膜形成的性能。已有研究将其作为抗菌成分加入复合树脂或粘结剂中。
发明内容
本发明的目的在于，提供一种具有良好的机械性能及抗菌性的、含有低粘度异山梨醇基光固化单体及2-甲基丙烯酰氧乙基磷酰胆碱(MPC)的新型牙科用零填料渗透树脂。
为了实现上述目的，本发明提供了一种牙科用零填料渗透树脂，所述渗透树脂按质量分数包括：
作为一个优选方案，所述异山梨醇基光固化单体为异山梨醇二甲基丙烯酸酯(IBM)或异山梨醇二烯丙基碳酸酯(IBAC)中的至少一种。
作为一个优选方案，所述渗透树脂按质量分数包括：
作为一个优选方案，所述光引发剂为樟脑醌(CQ)，以及甲基丙烯酸N,N-二甲氨基乙酯(DEAEMA)或(2,4,6-三甲基苯甲酰氯)二苯基氧化膦(TPO)中的至少一种。即光引发剂为樟脑醌(CQ)及甲基丙烯酸N,N-二甲氨基乙酯(DEAEMA)的组合，或者樟脑醌(CQ)及(2,4,6-三甲基苯甲酰氯)二苯基氧化膦(TPO)的组合，或者樟脑醌(CQ)、甲基丙烯酸N,N-二甲氨基乙酯(DEAEMA)及(2,4,6-三甲基苯甲酰氯)二苯基氧化膦(TPO)的组合。
作为一个优选方案，所述阻聚剂为2,6-二叔丁基对甲酚(BHT)或4-甲氧基苯酚(MEHQ)中的至少一种。
本发明的另一方面，提供了牙科用零填料渗透树脂的制备方法，所述制备方法包括以下步骤：将各组分避光条件下磁力搅拌充分混匀，转速为800-1000r/min，静置后即得。
首先利用异山梨醇和甲基丙烯酰氯或氯甲酸烯丙基酯反应，生成具有低粘度的异山梨醇基光固化单体，即异山梨醇二甲基丙烯酸酯(IBM)或异山梨醇二烯丙基碳酸酯(IBAC)，后按一定质量比将各组分避光条件下充分磁力搅拌混匀，静置后即得。
应用时，釉质白垩色病损区经酸蚀处理2min后，冲洗吹干，并用乙醇润湿酸蚀面30s后吹干，将制备的新型渗透树脂足量涂布5min，多余材料用棉卷去除，光固化灯照射40s，固化后打磨抛光表面即可。
本发明优选所述异山梨醇二甲基丙烯酸酯(IBM)的制备方法为将异山梨醇，三乙胺以及4-二甲氨基吡啶(DMAP)加入预置磁子的250mL三颈瓶中，无水CH2Cl2搅拌溶解。将反应瓶置于冰水浴中，缓慢滴加甲基丙烯酰氯。滴加结束后反应温度自然回升至室温，反应过夜。加水淬灭反应，分出有机相，CH2Cl2萃取水相一次。合并有机相，无水Na2SO4干燥后旋干，硅胶柱层析后得到透明无色液体产物。
本发明优选所述异山梨醇二烯丙基碳酸酯(IBAC)的制备方法：将异山梨醇，三乙胺以及4-二甲氨基吡啶(DMAP)加入预置磁子的250mL三颈瓶中，无水CH2Cl2搅拌溶解。将反应瓶置于冰水浴中，缓慢加入氯甲酸烯丙基酯。加入完毕后反应温度自然回升至室温，搅拌过夜。加水淬灭反应，分出有机相，CH2Cl2萃取水相一次。合并有机相，无水Na2SO4干燥后旋干，硅胶柱层析后得到透明无色液体产物。低粘度单体易产生毛细管虹吸作用，填充脱矿区的羟基磷灰石微孔结构，产生改善光泽的效果，并且阻止病变发展。
本发明的优点在于，本发明公开的新型渗透树脂的主成分为具有良好生物相容性的异山梨醇基光固化单体，能有效规避传统渗透树脂所引起的明显细胞毒反应，并且异山梨醇基光固化单体的双五环结构也赋予了其更优异的机械性能，实现了高生物安全性及良好的机械性能的统一；同时还引入了一种具有抗菌斑生物膜黏附作用的两性离子化合物MPC，这有助于提高渗透树脂的抗菌性能，从而降低病损治疗区再脱矿发生的风险。
附图说明
图1是新型牙科用渗透树脂A与ICON渗透树脂的粘度比较；
图2是新型牙科用渗透树脂A与ICON渗透树脂在牛牙釉质表面的接触角比较；
图3是新型牙科用渗透树脂A与ICON渗透树脂固化试件的维氏表面显微硬度的比较；
图4是新型牙科用渗透树脂A在牛牙釉质脱矿表面的色泽改善效果；
图5是新型牙科用渗透树脂A在牛牙釉质脱矿区作用后的表面形貌变化；
图6是新型牙科用渗透树脂A,B,C固化试件浸提液的细胞毒性；
图7是新型牙科用渗透树脂A,B,C固化试件表面的变形链球菌UA159生物膜形成情况的扫描电镜图；
图8是渗透树脂D,E在牛牙釉质表面的接触角；
图9是渗透树脂D,E固化试件表面的变形链球菌UA159生物膜形成情况的扫描电镜图。
具体实施方式
下面结合具体实施例，进一步阐述本发明。下述实施例中所使用的实验方法如无特殊说明，均为常规方法。下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。显然，所描述的实施例仅为本发明的一部分应用，而并非全部。应理解，这些实施例仅用于说明本发明的特性而并非用于限制本发明的范围。本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明的保护范围。
异山梨醇二甲基丙烯酸酯(IBM)的制备：
将异山梨醇(5.01g,0.034mol)，三乙胺(14.56g,0.144mol)以及DMAP(0.42g,3.4mmol)加入预置磁子的250mL三颈瓶中，30mL无水CH2Cl2搅拌溶解。将反应瓶置于0℃冰水浴中，缓慢滴加甲基丙烯酰氯(11.92g,0.114mol)。滴加结束后反应温度自然回升至室温，反应过夜。加水淬灭反应，分出有机相，CH2Cl2萃取水相一次。合并有机相，无水Na2SO4干燥后旋干，硅胶柱层析(淋洗剂：正己烷/二氯甲烷/甲醇(v/v/v＝100/300/5))后得到5.14g透明无色液体产物异山梨醇二甲基丙烯酸酯(IBM)，产率53.55％。
异山梨醇二烯丙基碳酸酯(IBAC)的制备：
将异山梨醇(5.00g,0.034mol)，三乙胺(14.56g,0.144mol)以及DMAP(0.42g,3.4mmol)加入预置磁子的250mL三颈瓶中，30mL无水CH2Cl2搅拌溶解。将反应瓶置于0℃冰水浴中，缓慢加入氯甲酸烯丙基酯(10.31g,0.0855mol)。加入完毕后反应温度自然回升至室温，搅拌过夜。加水淬灭反应，分出有机相，CH2Cl2萃取水相一次。合并有机相，无水Na2SO4干燥后旋干，硅胶柱层析得到透明无色液体产物异山梨醇二烯丙基碳酸酯(IBAC)。
实施例1.
IBM,MPC,CQ,DMAEMA,BHT各自按质量占比97％,1％,0.5％,1％,0.5％取样，充分混匀，采用磁力搅拌器避光搅拌30min，转速设置为800r-1000r/min，静置后即得新型渗透树脂A，避光保存待用。
实施例2.
IBM,IBAC,MPC,CQ,DMAEMA,BHT各自按质量占比78％,18％,2％,0.5％,1％,0.5％取样，充分混匀，采用磁力搅拌器避光搅拌30min，转速设置为800r-1000r/min，静置后即得新型渗透树脂B，避光保存待用。
实施例3.
IBM,IBAC,MPC,CQ,DMAEMA,BHT各自按质量占比75％,20％,3％,0.5％,1％,0.5％取样，充分混匀，采用磁力搅拌器避光搅拌30min，转速设置为800r-1000r/min，静置后即得新型渗透树脂C，避光保存待用。
新型渗透树脂的性能测定
粘度：
37度恒温条件下流变仪检测剪切速率1-10s-1范围内新型渗透树脂A与ICON商用树脂的粘度，如图1所示两者粘度相仿。
接触角：
选取形态完整，釉质发育正常，无龋坏，隐裂和缺损的牛切牙，除去牙结石及色素，经硬组织切割机制备长宽约6mm，厚度约3-4mm的牙釉质本质块。SiC砂纸600目，1200目，3000目依次表面打磨平整。各取新型渗透树脂A与ICON树脂1滴滴在平整的釉质表面，DSA接触角测量仪拍照并分析角度，如图2显示两者接触角相仿。
表面硬度：
取适量新型渗透树脂A与ICON树脂于直径*高为4mm*6mm的不锈钢模具中，聚酯薄膜覆盖并用盖玻片压平，光固化灯照射表面及底面各40s，获得相应的固化试样(n＝5)。按照50g,10s的加载条件测得每个试样的维氏表面显微硬度值并计算平均值，如图3所示新型渗透树脂A的表面硬度优于ICON树脂。
色泽改善：
选取形态完整，釉质发育正常，无龋坏，隐裂和缺损的牛切牙，除去牙结石及色素，在牙颈部将牙横向切断去除牙根。每颗牙牙冠的唇面保留一区域(3mm*4mm)作为脱矿区，保留区以外涂布两层防酸指甲油，干燥24h。按部分饱和酸缓冲系统配制人工脱矿液：0.01mmol/l NaF，2.2mmol/l CaCl2,2.2mmol/l KH2PO4及50mmol/l醋酸，调定pH至4.5。
将处理后的牛牙浸泡在人工脱矿液中，置于37度恒温箱内3周，每2日更换新鲜脱矿液。最终获得的脱矿区牙面光泽消失、粗糙，形成明显的白垩色斑，冲洗擦干备用。
脱矿病损区经酸蚀处理2min后，冲洗吹干，并用乙醇润湿酸蚀面30s后吹干，将新型渗透树脂A或ICON树脂足量涂布5min，多余材料用棉卷去除，光固化灯照射40s，固化后打磨抛光表面。观察治疗前后的釉质病损区的色泽变化并拍照记录，如图4所示新型渗透树脂A作用后白垩色病损区的色泽改善效果明显。
脱矿区牛牙釉质表面的粗糙形貌改善：
将表面包含渗透树脂A治疗区，ICON树脂治疗区，脱矿未治疗区及正常釉质区的牛牙脱水干燥，表面镀金，进行扫描电镜检测，电压5kV，放大率20000倍。结果如图5所示新型渗透树脂A能有效改善脱矿区牛牙釉质表面的粗糙形貌。
细胞存活率比较：
分别取适量新型渗透树脂A,B,C与ICON于直径*高为4mm*6mm的不锈钢模具中，聚酯薄膜覆盖并用盖玻片压平，光固化灯照射表面及底面各40s，获得相应的固化试样。固化的树脂试件消毒后依照0.2g/1ml的浸提比例，37度恒温条件下浸泡在DMEM细胞培养液中24h，获得各自的条件培养液。取处于对数期生长的L929细胞进行96孔板铺板，待细胞贴壁生长良好后去除旧培养基，加入相应条件培养液培养24h，最终采用CCK8法检测细胞活率。如图6所示新型渗透树脂A,B,C组的细胞存活率明显优于ICON组。
抗生物膜黏附性能比较：
分别取适量新型渗透树脂A,B,C与ICON于直径*高为4mm*6mm的不锈钢模具中，聚酯薄膜覆盖并用盖玻片压平，光固化灯照射表面及底面各40s，获得相应的固化试样。固化的树脂试件消毒后放入无菌24孔板中，每孔加入2ml左右含浓度106CFU/ml变形链球菌UA159菌液的BHI培养液(1％蔗糖)，37度厌氧培养24h后取出进行后续检测。各组样品采用戊二醛固定，后行梯度酒精脱水，喷金后扫描电镜下观察材料试件表面的菌斑生物膜的黏附情况,电压5kV，放大率5000倍。图7显示新型渗透树脂A,B,C均表现出优于ICON的抗生物膜黏附的性能，其中以渗透树脂C效果最佳。
对比例1.
IBM,MPC,CQ,DMAEMA,BHT各自按质量占比90％,8％,0.5％,1％,0.5％取样，充分混匀，采用磁力搅拌器避光搅拌30min，转速设置为800r-1000r/min，静置后即得渗透树脂D，避光保存待用。
对比例2.
IBM,MPC,CQ,DMAEMA,BHT各自按质量占比88％,10％,0.5％,1％,0.5％取样，充分混匀，采用磁力搅拌器避光搅拌30min，转速设置为800r-1000r/min，静置后即得渗透树脂E，避光保存待用。
对比例的性能测试
选取形态完整，釉质发育正常，无龋坏，隐裂和缺损的牛切牙，除去牙结石及色素，经硬组织切割机制备长宽约6mm，厚度约3-4mm的牙釉质本质块。SiC砂纸600目，1200目，3000目依次表面打磨平整。各取渗透树脂D,E 1滴滴在釉质表面，DSA接触角测量仪拍照并分析角度(图8)，与图2对比显示渗透树脂D,E的接触角明显大于ICON树脂，提示我们渗透树脂D，E不易在釉质病损微孔区形成良好的渗透效果。
分别取适量渗透树脂D,E树脂于直径*高为4mm*6mm的不锈钢模具中，聚酯薄膜覆盖并用盖玻片压平，光固化灯照射表面及底面各40s，获得相应的固化试样。固化的树脂试件消毒后放入无菌24孔板中，每孔加入2ml左右含浓度106CFU/ml变形链球菌UA159菌液的BHI培养液(1％蔗糖)，37度厌氧培养24h后取出进行后续检测。各组样品采用戊二醛固定，后行梯度酒精脱水，喷金后扫描电镜下观察材料试件表面的菌斑生物膜的黏附情况,电压5kV，放大率2000倍。图9显示渗透树脂D,E虽具有良好的抗生物膜黏附的性能，但是两者固化后表面结构完整性差，不适合应用于牙釉质微创治疗。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (5)
1.一种牙科用零填料渗透树脂，其特征在于，所述渗透树脂按质量分数包括：
所述异山梨醇基光固化单体为异山梨醇二甲基丙烯酸酯或异山梨醇二烯丙基碳酸酯中的至少一种。
2.根据权利要求1所述的一种牙科用零填料渗透树脂，其特征在于，所述渗透树脂按质量分数包括：
3.根据权利要求1或2所述的一种牙科用零填料渗透树脂，其特征在于，所述光引发剂为樟脑醌，以及甲基丙烯酸N,N-二甲氨基乙酯或(2,4,6-三甲基苯甲酰氯)二苯基氧化膦中的至少一种。
4.根据权利要求1或2所述的一种牙科用零填料渗透树脂，其特征在于，所述阻聚剂为2,6-二叔丁基对甲酚或4-甲氧基苯酚中的至少一种。
5.权利要求1—2任一所述牙科用零填料渗透树脂的制备方法，其特征在于，所述制备方法包括以下步骤：将各组分避光条件下磁力搅拌充分混匀，转速为800-1000r/min，静置后即得。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210067840.4A CN114395075B (zh) | 2022-01-20 | 2022-01-20 | 一种牙科用零填料渗透树脂及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210067840.4A CN114395075B (zh) | 2022-01-20 | 2022-01-20 | 一种牙科用零填料渗透树脂及其制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114395075A CN114395075A (zh) | 2022-04-26 |
| CN114395075B true CN114395075B (zh) | 2023-02-28 |
Family
ID=81231990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210067840.4A Active CN114395075B (zh) | 2022-01-20 | 2022-01-20 | 一种牙科用零填料渗透树脂及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114395075B (zh) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2295030B1 (en) * | 2009-09-10 | 2019-11-20 | Cognis IP Management GmbH | Use of isosorbide ethers in detergents and cleaners |
| KR101549294B1 (ko) * | 2009-10-19 | 2015-09-01 | 간사이 페인트 가부시키가이샤 | 활성 에너지선 경화성 조성물 |
| SG11201706827WA (en) * | 2015-02-26 | 2017-09-28 | Basf Se | Method for producing isosorbide ethoxylate dimethacrylate |
| WO2019202038A2 (en) * | 2018-04-19 | 2019-10-24 | University Of Tartu | Synthesis and polymerization of isosorbide-based monomethacrylates |
| CN109602615A (zh) * | 2019-01-07 | 2019-04-12 | 四川大学 | 一种树脂及其制备方法和用途 |
| CN111557855B (zh) * | 2020-06-10 | 2021-06-18 | 山东大学 | 低收缩牙科复合树脂及其制备方法 |
-
2022
- 2022-01-20 CN CN202210067840.4A patent/CN114395075B/zh active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114395075A (zh) | 2022-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tanumiharja et al. | Microtensile bond strengths of glass ionomer (polyalkenoate) cements to dentine using four conditioners | |
| Fang et al. | Biomodification to dentin by a natural crosslinker improved the resin–dentin bonds | |
| Willershausen et al. | The influence of oral bacteria on the surfaces of resin‐based dental restorative materials‐an in vitro study | |
| He et al. | Incorporation of an antibacterial and radiopaque monomer in to dental resin system | |
| Moussa et al. | Hydrophobic and antimicrobial dentin: A peptide-based 2-tier protective system for dental resin composite restorations | |
| Thomé et al. | In vitro analysis of inhibitory effects of the antibacterial monomer MDPB-containing restorations on the progression of secondary root caries | |
| CH618951A5 (en) | Process for the preparation of a sintered ceramic | |
| Gungormus et al. | Peptide-assisted pre-bonding remineralization of dentin to improve bonding | |
| Luque-Martinez et al. | EDTA Conditioning Increases the Long-term Microtensile Bond Strength to Sclerotic Dentin Mediated by Self-etch Adhesives. | |
| CN114395075B (zh) | 一种牙科用零填料渗透树脂及其制备方法 | |
| Hashimoto et al. | Crystal growth by fluoridated adhesive resins | |
| US8956629B2 (en) | Dental composition containing organic nanotube | |
| AlSahafi et al. | Novel antibacterial low-shrinkage-stress resin-based cement | |
| Skartveit et al. | Effect of TiF4 solutions on bacterial growth in vitro and on tooth surfaces | |
| Guigand et al. | An ultrastructural study of root canal walls in contact with endodontic biomaterials | |
| Bilic-Prcic et al. | Mechanical Properties of Glass Ionomer Cements after Incorporation of Marine Derived Porous Cuttlefish Bone Hydroxyapatite. | |
| Saba et al. | In vitro assessment of water sorption, solubility and surface roughness of compomer and giomer materials after immersion in different beverages | |
| Abdulkader et al. | Shear bond strength of nano-hydroxyapatite incorporated self adhesive resin cement to zirconia ceramic | |
| Garcia et al. | Physicochemical effects of niobic acid addition into dental adhesives | |
| CN112315815B (zh) | 一种含纳米氟化钙的生物活性材料的制备方法及应用 | |
| Wang et al. | Evaluation of cytotoxicity of dental restorative nanometer hydroxyapatite composite resin in vitro by dentin barrier method | |
| Abdulkader et al. | Shear bond strength of nano‐hydroxyapatite incorporated self adhesive resin cement to lithium disilicate | |
| Paul et al. | Comparative evaluation of shear bond strength and failure pattern of three different dentin adhesive systems-An In Vitro Study | |
| Isolan et al. | Bonding effectiveness of experimental one-step self-etch adhesives to sound and caries-affected dentin | |
| Tekce et al. | Does Double-layer Application of a Universal Adhesive Affect Its Bonding to Different Tooth Substrates? |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231220 Address after: 201816 No. 461 Tanghang Village, Huating Town, Jiading District, Shanghai Patentee after: SHANGHAI NEW CENTURY DENTAL MATERIAL Co.,Ltd. Address before: 200011 No. 639, manufacturing Bureau Road, Shanghai, Huangpu District Patentee before: SHANGHAI NINTH PEOPLE'S HOSPITAL SHANGHAI JIAOTONG University SCHOOL OF MEDICINE |