CN105283460A - β-酮基膦酸及基于其的牙科材料 - Google Patents
β-酮基膦酸及基于其的牙科材料 Download PDFInfo
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- CN105283460A CN105283460A CN201480029226.2A CN201480029226A CN105283460A CN 105283460 A CN105283460 A CN 105283460A CN 201480029226 A CN201480029226 A CN 201480029226A CN 105283460 A CN105283460 A CN 105283460A
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- Prior art keywords
- dental material
- base
- beta
- dental
- phosphonic acids
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- 238000012856 packing Methods 0.000 claims description 5
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- 229920002554 vinyl polymer Polymers 0.000 claims description 3
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
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- PHNWGDTYCJFUGZ-UHFFFAOYSA-N hexyl dihydrogen phosphate Chemical compound CCCCCCOP(O)(O)=O PHNWGDTYCJFUGZ-UHFFFAOYSA-N 0.000 description 1
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- CCRIVCWOXSIYEP-UHFFFAOYSA-N methyl prop-2-enoate;hydrochloride Chemical compound Cl.COC(=O)C=C CCRIVCWOXSIYEP-UHFFFAOYSA-N 0.000 description 1
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- JVCXFJJANZMOCM-UHFFFAOYSA-N phenyl(trimethylgermyl)methanone Chemical compound C[Ge](C)(C)C(=O)C1=CC=CC=C1 JVCXFJJANZMOCM-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000005499 phosphonyl group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
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- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
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- 125000006850 spacer group Chemical group 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- PCNIYCRKELJPHT-UHFFFAOYSA-N trifluoroborane ytterbium Chemical compound [Yb].B(F)(F)F PCNIYCRKELJPHT-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
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Abstract
根据通式I的β-酮基膦酸:其中,A=脂族C1-C18基,其可以被-O-、-S-、-CO-O-或-O-CO-O-间断;n=1、2、3或4;m=1或2;X=不存在或C1-C10基,所述C1-C10基可以被-O-、-S-、-CO-O-、-O-CO-NH-或-CO-NR1-间断,其中R1是H或C1-C7烷基,和PG=可以经历自由基聚合的基团。该β-酮基膦酸特别适合用于牙科材料的制备。
Description
本发明涉及可以经历自由基聚合的β-酮基膦酸和包含这样的β-酮基膦酸的牙科材料。这些牙科材料特别适合作为粘合剂、粘固剂(cement)或涂层材料。
可以经历自由基聚合并且具有酸基团的单体经常用于制备牙科材料。一方面它们给予牙科材料自蚀刻(self-etching)性质,使得可以免除在施加该材料之前,为了蚀刻牙齿表面并除去所谓的玷污层而用酸处理牙齿表面。此外,它们通过与牙体之间的离子或共价相互作用改善在牙齿上的粘合。
单体的蚀刻能力主要由它们的酸度决定。从磺酸经由酸性磷酸盐和膦酸到羧酸酸度降低。酸性磷酸盐目前主要用于制备自蚀刻牙科粘合剂。虽然磺酸具有相对高的酸度,但是实际上只有2-丙烯酰胺基-2-甲基丙烷磺酸具有相对大的价值,这是由于磺酸的其它性质,例如它们的聚合能力和它们粘合到天然牙体的能力不是最适宜的。
EP1057468A1公开了牙科粘合剂,其包括作为含有磷酸基的酸组分单体,如甲基丙烯酰氧基癸基二氢磷酸酯(MDP)、甲基丙烯酰氧基乙基苯基氢磷酸酯(MEPP)或甲基丙烯酰氧基乙基二氢磷酸酯(MEP)。这些单体仍广泛地用于自蚀刻牙科材料的制备。
这些化合物的一个缺点是,它们在水溶液中不稳定。它们的磷酸酯键和它们的甲基丙烯酸酯键两者在水的存在下都经历水解分裂。该水解被由酸单体释放的质子加速。水经常被用作自蚀刻牙科材料中的溶剂,由于它对于在牙体的蚀刻期间发生的离子过程是必需的。
为了改善自蚀刻牙科材料的抗水解性,已经提议具有可聚合基团和酸基团之间的键的酸单体,该键对水解更稳定。
DE10018968C1公开了可聚合的丙烯酰基膦酸,其具有高的水解稳定性。在膦酸中,膦酸酯键被更不易受水解影响的碳与磷之间的直接键取代。丙烯酰基膦酸进一步特征在于,可聚合基团优选地通过醚而不是酯官能团键合。
DE10234326B3涉及丙烯酸酯膦酸,例如2,4,6-三甲基苯基-2-[4-(二羟基磷酰基)-2-氧杂丁基]丙烯酸酯,其具有特别高的水解稳定性。改善的水解稳定性归因于空间相互作用。
DE19918974A1公开了羟烷基膦酸酯的(甲基)丙烯酸酯,如2-甲基丙烯酰氧基乙烷膦酸(MAPA),据说其特征在于对牙齿基底的强且持久的粘合。然而,这些单体的水解稳定性并不令人满意。
EP1169996A1涉及牙科材料,其据说具有良好的粘合性质和高的水解稳定性。该材料包括可聚合的膦酸,例如,1-(2,5-二甲基-1,5-己二烯基)膦酸(DMHD)和4-甲基丙烯酰胺基-4-甲基戊基膦酸(MAMPA)。DMHD至少不十分适合用于自由基聚合。
本发明的目的是提供酸性可聚合单体,其特别适合用于牙科材料的制备,并且其具有与高酸度相结合的高的水解稳定性。进一步地,该单体具有牙科使用所必需的性质分布(profileofproperties)。具体地,它们易于溶解于极性溶剂和极性溶剂与水的混合物中,在自由基聚合中具有高的聚合速率,并且显示出对牙齿结构,特别是对于牙釉质的好的粘合。
根据本发明,该目的是由根据通式I的β-酮基膦酸实现的:
其中,
A=脂族C1-C18基(radical),所述脂族C1-C18基可以被-O-、-S-、-CO-O-或-O-CO-O-间断,
n=1、2、3或4,
m=1或2,
X=不存在或C1-C10基,所述C1-C10基可以被-O-、-S-、-CO-O-、-O-CO-NH-或-CO-NR1-间断,其中R1是H或C1-C6烷基,优选为H、CH3或C2H5,和
PG=可以经历自由基聚合的基团。
基团A是被基[(PG)n-X]取代m次或,如果X不存在,被PG取代n次,并且被β-酮基膦酸基取代一次的脂族基。该式只包括与化学价理论相容的那些化合物。因此,例如如果A仅包括一个碳原子,则该碳原子可以携带最多四个取代基。
基被杂原子或官能团间断的说明理解为意味着杂原子或官能团插入碳链中并且在两侧被C原子分界。一行杂原子和/或官能团并不被归入该定义。
优选地,A不被间断,或者被1至4,特别地1至2个杂原子或官能团间断,特别优选地1或2个O原子间断。
X是被PG取代n次且通过另外的键键合到A的脂族基。X优选为C1-C10亚烷基,特别是直链亚烷基。X可以被-O-、-S-、-CO-O-、-O-CO-NH-或-CO-NR1-间断,其中X优选地不被杂原子或官能团间断。
PG是可以经历自由基聚合的基团。优选的可以经历自由基聚合的基团是乙烯基、烯丙基、CH2=CR2-CO-Y-、R3O-CO-C(=CH2)-CH2-Y-,其中,Y是O或NR4或不存在,R2是H或CH3,R3和R4彼此独立地各自为H或C1-C7烷基。(甲基)丙烯酰氧基基团(CH2=CR2-CO-Y-,其中Y=O)是特别优选的,特别地(甲基)丙烯酰胺基(CH2=CR2-CO-Y-,其中Y=NR4)和R3O-CO-C(=CH2)-CH2-Y-(其中Y=优选地O);R2在每种情况下是H或CH3,R3是CH3或C2H5,并且R4是H、CH3或C2H5。
可以彼此独立地选择变量的上述优选限定。根据本发明,然而,所有变量具有一个优选的限定和特别地一个特别优选的限定的那些化合物自然是特别优选的。
其中变量如下限定的化合物因此是优选的:
A=脂族C2-C15基,所述脂族C2-C15基可以被-O-间断,优选地直链C1-C10基,所述直链C1-C10基可以被1或2个O原子间断,
n=1或2,优选地1,
m=1或2,
X=C1-C4亚烷基或不存在,优选地C1或C2基或不存在,和
PG=乙烯基、烯丙基、CH2=CR2-CO-Y-或R3O-CO-C(=CH2)-CH2-Y-,其中Y是O或NR4或不存在,R2是H或CH3,且R3和R4彼此独立地各自为H或C1-C7烷基;特别优选地CH2=CR2-CO-Y-,其中Y=O或NR4,或R3O-CO-C(=CH2)-CH2-Y-,其中Y=O;R2=H或CH3,R3=CH3或C2H5,并且R4=H、CH3或C2H5。
可以容易地制备通式I的可聚合的β-酮基膦酸。例如,OH官能化的β-酮基膦酸酯可以与COOH-烷基官能化的可聚合基反应,从而产生相应的可聚合的β-酮基膦酸酯,以及然后使用例如溴化三甲基硅烷(TMSiBr)硅烷化,并甲醇分解,从而产生通式I的可聚合的β-酮基膦酸:
具体地,例如甲基丙烯酸3-羧基丙基酯可以与5-羟基-2-氧代戊基膦酸二乙酯反应,随后释放膦酸基团:
关于这点,可以根据Arbuzov反应通过α-卤代酮与三烷基亚磷酸酯的反应(参见,例如A.K.Bhattacharya,G.Thyagarajan,Chem.Rev.81(1981)415-430),通过在化学计量的有机金属试剂的存在下,膦酸烷基酯与羧酸衍生物的酰化反应(参见,例如K.M.Maloney,J.Y.L.Chung,J.Org.Chem.74(2009)7554-7576),通过β-羟基烷基膦酸酯的氧化反应(参见,例如Koprowskietal.,Tetrahedron65(2009)4017-4024),以及通过烯烃与O2和H-膦酸酯的直接或催化氧化磷酸化反应来制备酮基膦酸酯(W.Wie,J.-X.Ji,Angew.Chem.123(2011)9263-9265)。
根据本发明的通式I的可聚合的β-酮基膦酸的优选实例是:
通式I的可聚合的β-酮基膦酸特别适合用于牙科材料的制备,特别是具有自蚀刻性质的牙科材料。它们非常易于溶解在醇,例如乙醇和异丙醇中,以及丙酮或它们的含水混合物中。与具有可比较的间隔长度的已知的可聚合的烷基膦酸相比,例如水-醇溶液惊奇地显示了显著更低的pH,即它们是显著地更酸性的,这对自蚀刻性质是有利的。此外,与常规的烷基膦酸相比,它们显示了高的牙釉质粘附。另一优点是它们与酸性磷酸酯相比改善的水解稳定性。因此,根据本发明的β-酮基膦酸将膦酸高的水解稳定性与磷酸酯高的酸度结合。
基于牙科材料的总重量,通式I的β-酮基膦酸优选地以0.1至50wt.-%,特别优选地1至40wt.-%的量和极其特别优选地以2至30wt.-%的量使用。
根据本发明的、基于通式I的可聚合的β-酮基膦酸的牙科材料可以优选地包含可以经历自由基聚合的其它单体(共聚单体),特别优选地单或多官能的(甲基)丙烯酸衍生物。单官能的单体理解为是指具有一个可以经历自由基聚合的基团的单体,而多官能的单体理解为是指具有两个或更多,优选地2至4个可以经历自由基聚合的基团的单体。在这方面的实例为(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸苄基酯、(甲基)丙烯酸四氢呋喃甲酯或(甲基)丙烯酸异冰片酯,双酚A二(甲基)丙烯酸酯、二-GMA(甲基丙烯酸与双酚A二缩水甘油醚的加成物),UDMA(甲基丙烯酸2-羟乙酯(HEMA)与2,2,4三甲基六亚甲基二异氰酸酯的加成物),二(甲基)丙烯酸二乙二醇酯,二(甲基)丙烯酸三乙二醇酯,二(甲基)丙烯酸四乙二醇酯,三羟甲基丙烷三(甲基)丙烯酸酯,季戊四醇四(甲基)丙烯酸酯和丙三醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯或1,12-十二烷二醇二(甲基)丙烯酸酯。
进一步优选的共聚单体为N-单或双取代的丙烯酰胺,如N-乙基丙烯酰胺、N,N-二甲基丙烯酰胺、N-(2-羟乙基)丙烯酰胺或N-甲基-N-(2-羟乙基)丙烯酰胺,或N-单取代的甲基丙烯酰胺,如N-乙基甲基丙烯酰胺或N-(2-羟乙基)甲基丙烯酰胺,和N-乙烯吡咯烷酮或烯丙基醚。这些单体的特征是高的水解稳定性和相对低的粘度以及因此适合用作例如稀释单体。
同样地优选地共聚单体是交联吡咯烷酮,如1,6-二(3-乙烯基-2-吡咯烷酮基)己烷,或可商业上获得的二丙烯酰胺,如亚甲基或亚乙基二丙烯酰胺,或二(甲基)丙烯酰胺,如N,N'-二乙基-1,3-二(丙烯酰胺基)丙烷、1,3-二(甲基丙烯酰胺基)丙烷、1,4-二(丙烯酰胺基)丁烷或1,4-二(丙烯酰基)哌嗪,其可以通过相应的二胺与(甲基)丙烯酰氯的反应合成。这些单体的特征也在于高的水解稳定性。它们含有两个或更多的可以经历自由基聚合的基团,并由此适合用作例如交联单体。
单官能的和交联的单体的混合物优选地用作共聚单体,其中与二-GMA、UDMA、三乙二醇二甲基丙烯酸酯和/或十二烷二醇二甲基丙烯酸酯组合的、包括甲基丙烯酸2-羟乙酯的单体混合物是特别有利的。
最后,也可以使用一种或多种上述单体与其它的粘合性单体的混合物,所述其它的粘合性单体含有酸基团并且可以经历自由基聚合。含有酸基团的适合的单体是可聚合的羧酸,如马来酸、丙烯酸、甲基丙烯酸、2-(羟甲基)丙烯酸、4-(甲基)丙烯酰氧基乙基偏苯三酸酐、10-甲基丙烯酰氧基癸基丙二酸、N-(2-羟基-3-甲基丙烯酰氧基-丙基)-N-苯基甘氨酸或4-乙烯基苯甲酸。适合的膦酸单体的实例是乙烯基膦酸、4-乙烯基苯基膦酸、4-乙烯基苄基膦酸、2-甲基丙烯酰氧基乙基膦酸、2-甲基丙烯酰胺基乙基膦酸、4-甲基丙烯酰胺基-4-甲基戊基膦酸、2-[4-(二羟基磷酰基)-2-氧杂丁基]丙烯酸或2-[4-(二羟基磷酰基)-2-氧杂丁基]丙烯酸乙酯或2,4,6-三甲基苯基酯。适合的酸性可聚合的磷酸酯的实例是2-甲基丙烯酰氧基丙基磷酸一或二氢酯、2-甲基丙烯酰氧基乙基磷酸一或二氢酯、2-甲基丙烯酰氧基乙基苯基磷酸氢酯、二季戊四醇五甲基丙烯酰氧基磷酸酯、10-甲基丙烯酰氧基癸基磷酸二氢酯、磷酸单(1-丙烯酰基哌啶-4-基)酯、6-(甲基丙烯酰胺基)己基磷酸二氢酯和1,3-二(N-丙烯酰基-N-丙胺基)丙烷-2-基磷酸二氢酯。适合的可聚合的磺酸的实例是乙烯基磺酸、4-乙烯基苯基磺酸或3-(甲基丙烯酰胺基)丙基磺酸。优选地选择含有酸基团的其它单体的总量,使得其不超过式I的酮基膦酸(或多种酮基膦酸)的量以及特别优选地低于酮基膦酸(或多种酮基膦酸)的量。
为了引发自由基聚合,根据本发明的牙科材料优选地包含自由基聚合引发剂。对于光聚合,优选地采用苯甲酮、苯偶姻及其衍生物或α-二酮或其衍生物,如9,10-菲醌、1-苯基丙烷-1,2-二酮、二乙酰或4,4'-二氯苯偶酰。优选地,使用樟脑醌和2,2-二甲氧基-2-苯基苯乙酮,特别优选地使用与作为还原剂的胺组合的α-二酮,所述胺如4-(二甲基氨基)苯甲酸酯、N,N-二甲氨基乙基甲基丙烯酸酯、N,N-二甲基-对称-二甲基苯胺或三乙醇胺。NorrishI型光引发剂也是特别适合的,尤其是酰基或二酰基膦氧化物、单酰基三烷基或二酰基二烷基锗化合物,如苯甲酰基三甲基锗、二苯甲酰基二乙基锗或二(4-甲氧基苯甲酰基)二乙基锗。各种光引发剂的混合物,如也可以使用与樟脑醌和4-二甲基氨基苯甲酸乙基酯组合的二苯甲酰基二乙基锗。
用于在室温下进行的聚合的引发剂是氧化还原引发剂的组合,例如过氧化苯甲酰与N,N-二甲基-对称-二甲基苯胺、N,N-二甲基-对-甲苯胺、N,N-二乙基-3,5-二叔丁苯胺或N,N-二乙基-对-甲苯胺的组合。另外,包含过氧化物或氢过氧化物和还原剂,例如抗坏血酸、巴比妥酸盐、硫脲或亚磺酸(sulphinicacid)的氧化还原体系也是特别适合的。
根据本发明的牙科材料优选地包含光引发剂或光引发剂和氧化还原引发剂优选地过氧化物的组合。用于双重固化的一种特别有利的引发剂组合是樟脑醌和过氧化苯甲酰的混合物,其中这些引发剂还优选地与胺组合。
此外,根据本发明采用的组合物优选地包含用于改善机械性能或用于调节粘度的有机或无机填料颗粒。用于调节机械性能的填料优选地具有10nm至10μm,优选地10nm至1.0μm的平均粒径,以及用于调节粘度的填料优选地具有10至1000nm,优选地10至200nm的平均粒径。这些填料类型优选地一起使用。除非另外说明,平均粒径是重量平均值。
优选的无机微粒填料是基于氧化物的无定形球形材料,所述氧化物诸如ZrO2和TiO2或SiO2、ZrO2和/或TiO2的混合氧化物,纳米微粒或微细填料,如火成二氧化硅或沉淀二氧化硅,和微型填料,如具有0.01至1μm的平均粒径的石英、玻璃陶瓷或玻璃粉,以及射线透不过的填料,如三氟化镱或纳米微粒氧化钽(V)或硫酸钡。优选的有机填料是基于聚(甲基)丙烯酸酯例如PMMA或纤维素衍生物例如羧甲基纤维素的填料,其在固化后被研磨至上述粒度。有机填料依次可以具有所提及的无机填料的填料含量。
含溶剂的牙科材料代表了本发明的另一优选的实施方案。特别地,本文中考虑水和极性有机溶剂,如丙酮、异丙醇,以及特别地乙醇和这些溶剂的混合物。水和极性有机溶剂的混合物,特别地水和乙醇的混合物、水和丙酮的混合物或水、乙醇和丙酮的混合物,是特别优选的。
根据本发明使用的组合物可以任选地包含其它添加剂,例如稳定剂、调味物质、着色剂、杀菌活性化合物、释放氟离子的添加剂、荧光增白剂、增塑剂和/或UV吸收剂。
根据本发明的、包含以下组分的牙科材料是优选的:
a)0.1至50wt.-%,优选地1至40wt.-%,以及特别优选地2至30wt.-%的通式I的可聚合的β-酮基膦酸,
b)0.01至10wt.-%,特别优选地0.1至3.0wt.-%的引发剂,
c)0至80wt.-%,优选地0至60wt.-%以及特别优选地5至50wt.-%的另外的单体,
d)0至80wt.-%的填料,
e)0至70wt.-%,优选地0至60wt.-%以及特别优选地0至50wt.-%的溶剂,和任选地
f)0.01至10wt.-%,优选地0.01至3wt.-%的其它添加剂。
根据本发明的牙科材料优选地包含作为另外的单体(c)的5至40wt.-%的非酸性的单或多官能单体和/或0至60wt.-%,优选地0至30wt.-%的酸性单体。
填料或多种填料(d)的量取决于目标用途。用作粘合剂的牙科材料优选地包含0至20wt.-%的填料,而用作粘固剂(cement)或填充材料(复合材料)的牙科材料优选地包含20至80wt.-%的填料。用作粘固剂或填充材料的牙科材料优选地不包含溶剂。
用作粘合剂的牙科材料优选地具有以下组成:
a)0.1至50wt.-%,优选地1至40wt.-%,以及特别优选地2至30wt.-%的通式I的可聚合的β-酮基膦酸,
b)0.01至10wt.-%,特别优选地0.1至3.0wt.-%的引发剂,
c)0至60wt.-%,优选地0至40wt.-%以及特别优选地5至40wt.-%的非酸性的单或多官能单体和/或0至60wt.-%,优选地0至30wt.-%的酸性单体,
d)0至20wt.-%的填料,
e)0至70wt.-%,优选地0至60wt.-%以及特别优选地0至50wt.-%的溶剂,优选地水或水、乙醇和/或丙酮的混合物,和任选地
f)0.01至3wt.-%的其它添加剂。
在每种情况下所有的百分数与组合物的总重量相关。
由所提及的组分组成的那些牙科材料是特别优选的。其中单独组分在每种情况下选自上述优选的和特别优选的物质的那些材料是更加优选的。
牙科材料特别适合用作粘合剂、粘固剂、填充材料或涂层材料。牙科材料主要适合用于牙医修复损坏的牙齿的口内使用(临床材料)。然而,它们也可以口外使用,例如,用于牙科修复物(技术等级材料)的生产和修理。
以下在实施例的帮助下更详细地解释本发明。
实施例
实施例1:
9-甲基丙烯酰氧基-2-氧代壬基膦酸(MOPA)的合成
a)2-氧代-9-THP-氧壬基膦酸二乙酯1的合成
将商业上可得到的(2-氧丙基)膦酸二乙酯(10.0g,51.5mmol,1.1当量)(其制备与文献(Kosobokov,M.D.;Titanyuk,I.D.;Beletskaya,I.P.MendeleevCommunications2011,21,142-143)类似)在干燥的THF(15ml)中的溶液滴加到NaH((2.27g,56.7mmol,1.2当量)在矿物油中的60%的分散体的搅拌的混合物中,该分散体已经在0℃下、于干燥THF(20ml)中使用己烷(2x20ml)预洗。反应混合物被加热到室温,搅拌1小时,然后再次冷却至0℃,滴加n-BuLi的溶液(22.5ml的2.5M己烷溶液,56.2mmol,1.2当量),溶液在0℃下搅拌30分钟。然后添加2-(6-溴己氧基)四氢-2H-呋喃(12.4g,46.8mmol)(其制备与文献(Fu,Y.;Weng,Y.;Wen-Xu,H.;Qinghai,Z.Synlett2011,6,809-812)类似)在干燥的THF(15ml)中的溶液,以及反应混合物被加热到室温并搅拌15h。然后将反应产物小心引入到冰冷却的NH4Cl水溶液(150ml)中,并用二乙醚(3x100ml)萃取水相。合并的有机相由无水Na2SO4干燥,并真空浓缩。得到的粗产品通过快速柱层析纯化(洗脱液:乙酸乙酯/己烷:75/25),并得到9.6g(25.4mmol)的膦酸酯1,其为浅黄色液体,产率:54%。
1HNMR(400MHz,CDCl3):δ=1.23-1.40(m,6H,CH2);1.35(t,3JHH=7.0Hz,6H,POCH2 CH 3 );1.46-1.63(m,8H,CH2);1.65-1.76(m,1H,CH2);1.77-1.89(m,1H,CH2);2.61(t,3JHH=7.3Hz,2H,CH2 CH 2 C=O);3.07(d,2JHP=22.8Hz,2H,CH2P);3.37(dt,2JHH=9.6Hz,3JHH=6.5Hz,1H,CH2O);3.46-3.54(m,1H,CH2O);3.72(dt,2JHH=9.6Hz,3JHH=6.9Hz,1H,CH2O);3.83-3.90(m,1H,CH2O);4.09-4.20(m,4H,POCH 2 CH3);4.54-4.59(m,1H,OCHO)。
31PNMR(162MHz,CDCl3):20.0。
13CNMR(101MHz,CDCl3):δ=16.3(d,3JCP=6.3Hz,POCH2 CH3);19.7(CH2);23.3(CH2);25.5(CH2);26.0(CH2);28.9(CH2);29.2(CH2);29.7(CH2);30.8(CH2);42.4(d,1JCP=127.3Hz,CH2P);44.0(CH2 CH2C=O);62.3(CH2O);62.4(d,2JCP=6.4Hz,POCH2CH3);67.5(CH2O);98.8(OCHO);202.1(d,2JCP=6.0Hz,C=O)。
b)9-羟基-2-氧代壬基膦酸二乙酯2
将膦酸酯1(47.2mmol)和甲苯磺酸吡啶(1.19g,4.72mmol)添加到乙醇(500ml)中,并且混合物在55℃下搅拌3h,然后真空浓缩。得到的粗产品通过快速柱层析纯化(洗脱液:乙酸乙酯/己烷:95/5),并得到11.04g(37.6mmol)的膦酸酯2,其为浅黄色液体,产率:80%。
1HNMR(400MHz,CDCl3):δ=1.26-1.40(m,6H,CH2);1.34(t,3JHH=6.9Hz,6H,POCH 2 CH3);1.51-1.64(m,4H,CH2);2.62(t,3JHH=7.4Hz,2H,CH 2 CH 2 C=O);3.07(d,2JHP=22.8Hz,2H,15CH2P);3.63(t,3JHH=6.6Hz,2H,CH2OH);4.09-4.20(m,4H,POCH 2 CH3)。
31PNMR(162MHz,CDCl3):20.0。
13CNMR(101MHz,CDCl3):δ=16.2(d,3JCP=6.2Hz,POCH2 CH3);23.2(CH2);25.5(CH2);28.8(CH2);29.0(CH2);32.7(CH2);42.3(d,1JCP=127.3Hz,CH2P);43.9(CH2 CH2C=O);62.5(d,2JCP=6.5Hz,POCH2CH3);62.7(CH2OH);202.1(d,2JCP=6.2Hz,C=O)。
c)9-甲基丙烯酰氧基-2-氧代壬基膦酸二乙酯3
在搅拌下,将甲基丙烯酸酐(6.14ml,41.2mmol,1.1当量)滴加到羟基膦酸酯2(37.5mmol)、三乙胺(5.75ml,41.2mmol,1.1当量)和4-二甲基氨基吡啶(229mg,1.9mmol,5mol.-%)在无水二氯甲烷(100ml)中的溶液中。搅拌15h后,使用蒸馏水(100ml)洗涤反应混合物,分离有机相,通过无水Na2SO4干燥,并真空浓缩。得到的粗产品通过快速柱层析纯化(洗脱液:乙酸乙酯/己烷:80/20),并得到11.53g(31.9mmol)的膦酸酯3,其为浅黄色液体,产率:85%。
1HNMR(400MHz,CDCl3):δ=1.23-1.42(m,6H,CH2);1.32(t,3JHH=7.1Hz,6H,POCH2 CH 3 );1.52-1.70(m,4H,CH2);1.93(1s,3H,CH3);2.61(t,3JHH=7.3Hz,2H,CH2 CH 2 C=O);3.05(d,2JHP=22.9Hz,2H,CH2P);4.08-4.19(m,6H,POCH 2 CH3和CH2OC=O);5.51-5.55(m,1H,CH2=C);6.08(1s,1H,CH2=C)。
31PNMR(162MHz,CDCl3):20.0。
13CNMR(101MHz,CDCl3):δ=16.3(d,3JCP=6.3Hz,POCH2 CH3);18.3(CH3);23.3(CH2);25.8(CH2);28.5(CH2);28.8(CH2);29.0(CH2);42.4(d,1JCP=127.3Hz,CH2P);44.0(CH2 CH2C=O);62.5(d,2JCP=6.4Hz,POCH2CH3);64.7(CH2OC=O);125.1(CH2=C);136.5(CH2=C);167.5(OC=O);202.0(d,2JCP=6.2Hz,PCH2C=O)。
d)9-甲基丙烯酰氧基-2-氧代壬基膦酸(MOPA)
将溴化三甲基硅烷(12.5ml,94.7mmol,3.0当量)添加到膦酸酯3(11.43ml,31.6mmol)在无水二氯甲烷(100ml)的溶液中,混合物在30℃下搅拌5小时。其后,真空浓缩反应产物,添加甲醇(100ml),混合物在室温下搅拌30分钟。添加BHT(250ppm)之后,在高真空下将溶液浓缩至恒重,并得到9.6g(31.4mmol)酮基膦酸MOPA,其为浅黄色液体,产率:99%。
1HNMR(400MHz,CDCl3):δ=1.23-1.42(m,6H,CH2);1.52-1.71(m,4H,CH2);1.94(1s,3H,CH3);2.63(t,3JHH=7.3Hz,2H,CH2 CH 2 C=O);3.19(d,2JHP=22.7Hz,2H,CH2P);4.13(t,3JHH=6.6Hz,2H,CH2OC=O);5.54-5.58(m,1H,CH2=C);6.09(1s,1H,CH2=C);10.25(1s,2H,POH)。
31PNMR(162MHz,CDCl3):22.2。
13CNMR(101MHz,CDCl3):δ=18.3(CH3);23.2(CH2);25.7(CH2);28.5(CH2);28.7(CH2);28.9(CH2);42.3(d,1JCP=131.3Hz,CH2P);44.2(CH2 CH2C=O);64.9(CH2OC=O);125.5(CH2=C);136.4(CH2=C);167.8(OC=O);204.6(d,2JCP=6.4Hz,PCH2C=O)。
实施例2
借助DSC研究9-甲基丙烯酰氧基-2-氧代壬基膦酸MOPA的光聚合
将0.1wt.-%的光引发剂二(4-甲氧基苯甲酰基)二乙基锗添加到摩尔比为8:2的交联剂N,N'-二乙基-1,3-二(丙烯酰胺基)丙烷(DEPBA)和MOPA的混合物中。混合物在具有通过LED灯(Bluephase,IvoclarVivadent)辐射的光聚合附件的差示扫描量热仪(Diamond,PerkinElmer)中于37℃下聚合2分钟。产生了与纯交联剂相比类似地高的最大聚合速率(0.078s-1)和同时发生的混合物的双键转化率(63%)。
实施例3
MOPA溶液的pH测定
测定了MOPA、10-(甲基丙烯酰氧基)癸基二氢磷酸酯(MDP)和10-(甲基丙烯酰氧基)癸基磷酸(MDPA)在水和乙醇的重量比为1:1的混合物中的20%溶液的pH。测定了对于MOPA产生的pH为1.9,而对于磷酸二氢酯MDP产生的pH为1.6,以及对于膦酸单体MDPA,pH为2.3。由此,惊讶地发现,与具有相似的C数量的间隔基团的烷基膦酸相比,研究的酮基膦酸是显著地更强酸性的。
实施例4
基于9-甲基丙烯酰氧基-2-氧代壬基膦酸MOPA的粘合剂和粘附研究
为了研究对牛科动物牙齿的牙本质和牙釉质的粘附,制备了具有表1中所显示的组合物的粘合剂。牛科动物牙齿嵌入塑料圆筒,使得牙本质或牙釉质与塑料在同一平面。使用微小的刷子刷一层上述组合物的粘合剂,在牙齿结构上摇动粘合剂大约20秒,使用风扇短暂地吹以除去溶剂,并暴露于LED灯(Bluephase,IvoclarVivadent)的光下10秒。EvoCeram复合材料(IvoclarVivadent)的圆筒在粘合剂层上聚合。
然后将测试样本于37℃下储存在水中24h,根据ISO指南"ISO2003-ISOTR11405:“牙科材料对牙齿结构的粘附的测试指南”测定剪切粘接强度:粘合剂A:牙本质:34.4MPa和牙釉质30.3MPa;粘合剂B:22.6MPa和牙釉质16.8MPa。
结果表明,基于可聚合的β-酮基膦酸的牙釉质/牙本质粘合剂给出了与牙科复合材料高的牙釉质和牙本质粘附值。
表1
粘合剂的组成(以重量计的%的数据)
组分 | 粘合剂A | 粘合剂B(比较) |
MOPA | 15.0 | - |
MDPA | - | 15.0 |
二-GMA1) | 19.0 | 19.0 |
DEPBA | 43.2 | 43.2 |
Aerosil R7092) | 1.4 | 1.4 |
光引发剂3) | 2.6 | 2.6 |
去离子水 | 14.6 | 14.6 |
异丙醇 | 4.2 | 4.2 |
1)甲基丙烯酸与双酚A二缩水甘油醚的加成物
2)平均粒度为40nm(Degussa)的甲基丙烯酰硅烷化(methacrylosilanized)的火成二氧化硅
3)樟脑醌(0.9%)、4-二甲基苯甲酸乙基酯(0.4%)和酰基膦氧化物LucerinTPO(BASF;1.3%)的混合物
Claims (15)
1.根据通式I的β-酮基膦酸:
其中
A=脂族C1-C18基,所述脂族C1-C18基可以被-O-、-S-、-CO-O-或-O-CO-O-间断,
n=1、2、3或4,
m=1或2,
X=不存在或C1-C10基,所述C1-C10基可以被-O-、-S-、-CO-O-、-O-CO-NH-或-CO-NR1-间断,其中R1是H或C1-C6烷基,和
PG=可以经历自由基聚合的基团。
2.根据权利要求1所述的β-酮基膦酸,其中,
A=脂族C2-C15基,所述脂族C2-C15基可以被-O-间断,优选地直链C1-C10基,所述直链C1-C10基可以被1或2个O原子间断,
n=1或2,优选地1,
m=1或2,
X=C1-C4亚烷基或不存在,优选地C1或C2基或不存在,和
PG=乙烯基、烯丙基、CH2=CR2-CO-Y-或R3O-CO-C(=CH2)-CH2-Y-,其中Y是O或NR4或不存在,R2是H或CH3,且R3和R4彼此独立地各自为H或C1-C7烷基。
3.根据权利要求2所述的β-酮基膦酸,其中,
A=直链脂族C1-C10基,所述直链脂族C1-C10基可以被1或2个-O-间断,
n=1,
m=1或2,
X=C1-C2基或不存在,
PG=CH2=CR2-CO-Y-,其中Y是O或NR4,或者R3O-CO-C(=CH2)-CH2-Y-,其中Y是O,以及其中R2是H或CH3,R3是CH3或C2H5,并且R4是H、CH3或C2H5。
4.牙科材料,其特征在于,其包含至少一种根据权利要求1至3中任一项所述的β-酮基膦酸。
5.根据权利要求4所述的牙科材料,所述牙科材料另外包含至少一种用于自由基聚合的引发剂。
6.根据权利要求4或5所述的牙科材料,所述牙科材料另外包含可以经历自由基聚合的其它单体。
7.根据权利要求6所述的牙科材料,所述牙科材料包含作为其它单体的一种或多种单和/或多官能的(甲基)丙烯酸衍生物和/或(甲基)丙烯酰胺衍生物。
8.根据权利要求4至7中任一项所述的牙科材料,所述牙科材料另外包含至少一种溶剂。
9.根据权利要求8所述的牙科材料,所述牙科材料包含作为溶剂的水或水和极性有机溶剂的混合物。
10.根据权利要求4至9中任一项所述的牙科材料,所述牙科材料包含:
a)0.1至50wt.-%的通式I的β-酮基膦酸,
b)0.01至10wt.-%的引发剂,
c)0至80wt.-%的其它单体,
d)0至80wt.-%的填料,
e)0至70wt.-%的溶剂。
11.根据权利要求10所述的牙科材料,其用作粘合剂,所述牙科材料包含0至20wt.-%的填料。
12.根据权利要求11所述的牙科材料,所述牙科材料包含:
a)0.1至50wt.-%,优选地1至40wt.-%,以及特别优选地2至30wt.-%的通式I的可聚合的β-酮基膦酸,
b)0.01至10wt.-%,优选地0.1至3.0wt.-%的引发剂,
c)0至60wt.-%,优选地0至40wt.-%以及特别优选地5至40wt.-%的非酸性的单或多官能单体和/或0至60wt.-%,以及优选地0至30wt.-%的酸性单体,
d)0至20wt.-%的填料,
e)0至70wt.-%,优选地0至60wt.-%以及特别优选地0至50wt.-%的溶剂。
13.根据权利要求10所述的牙科材料,其用作粘固剂或填充材料,所述牙科材料包含20至80wt.-%的填料。
14.根据权利要求4至13中任一项所述的牙科材料,用于作为粘合剂、填充材料或粘固剂口内使用。
15.权利要求4至13中任一项所述的牙科材料用于牙科修复物的口外生产或修理的用途。
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