CN1209821A - 基于环氧化物的可聚合组合物 - Google Patents
基于环氧化物的可聚合组合物 Download PDFInfo
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- CN1209821A CN1209821A CN97191799A CN97191799A CN1209821A CN 1209821 A CN1209821 A CN 1209821A CN 97191799 A CN97191799 A CN 97191799A CN 97191799 A CN97191799 A CN 97191799A CN 1209821 A CN1209821 A CN 1209821A
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- glyceryl
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Classifications
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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- A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- A61K6/896—Polyorganosilicon compounds
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- 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
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- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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- C08G59/24—Di-epoxy compounds carbocyclic
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Abstract
本发明涉及可聚合组合物,含有:(a)3—80wt%的以下通式的环氧化物或环氧化物混合物:(b)0—80wt%与(a)不同的环氧化物或它们的混合物,(c)3—85wt%填料,(d)0.01—25wt%的引发剂、阻滞剂和/或加速剂,(e)0—25wt%的助剂,其中各百分含量均基于组合物的总重量。该新可聚合组合物特别适合作为牙科组合物。
Description
本发明涉及基于环氧化物的可聚合组合物,新的环脂族环氧化物及其用途。
迄今为止,在可聚合牙科组合物中主要使用甲基丙烯酸酯和丙烯酸酯单体。特别值得注意的是Bowen描述的2,2-双〔4,1-亚苯氧基(2-羟基-3,1-丙二基)-甲基丙烯酸酯〕-亚丙基(双-GMA)〔US-A-3066112〕。该甲基丙烯酸酯与二甲基丙烯酸三甘醇酯的混合物至今还用作牙科塑性直接填充材料的标准配方。二次甲酰化的双-(羟甲基)三环〔5.2.1.02,6〕-癸烷的甲基丙烯酸衍生物也可证明是牙科复合材料的适合单体。〔W.Gruber等人,DE-A-27 14 538;W.Schmitt等人,DE-C-28 16 823;J.Reiners等人,EP-A-0 261 520〕。已知可聚合牙科组合物的一个很大的缺点是例如在用作填充材料时由于形成边缘缝隙而引起二次龋齿的聚合收缩。此外,在基于丙烯酸酯的牙科组合物中,由氧引起的聚合抑制会导致形成所谓的润滑层,后者例如在填充中是不希望的,甚至是有害的。最后,基于丙烯酸酯的牙科组合物对牙基体的粘附性小。
尽管对环氧化物和环脂族环氧化物已有广泛的认识(US-A-2716 123,US-A-2 750 395,US-A-2 863 881,US-A-3 187018),但这样的单体和由其配制的具有牙科应用必须性质的阳离子可聚合组合物以往任何时候还未能购得。
双官能环脂族环氧化物的制备已在50年代的专利中有述(US-A-2 750 395,US-A-900 506,US-A-907 149,US-A-2745 847,US-A-2 853 499,US-A-3 187 018,US-A-2 863881,US-A-2 853 498)。含硅的环脂族环氧化物由Crivello等人公开于各种出版物中(EP-A-0 449 027;J.Polymer Sci.(聚合物科学杂志),Part A:Polym.Chem.(聚合物化学),28(1990)479;ibid.31(1993)2563;ibid.31(1993)2729;ibid.31(1993)3109;ibid.31(1993)3121;ibid.33(1995)2463)。已知的环脂族环氧化物基本上是低分子量单体,而且有稍微降低的聚合收缩〔J.Adhes.Sci.Technol.9(10)1995,1343:DE-A-4 340 949〕,但由于其高的官能密度而不满足牙科应用的要求(加工,物理性能)。
对牙科应用的可阳离子固化的环氧组合物还知之甚少:专利US-A-5 556 896描述的含环氧化物的组合物必须含有作为收缩补偿单体的螺原碳酸酯。Ciba公司于1958年在专利AT-A-204 687中公开了基于双酚A的环氧化物牙科组合物,它借助于路易斯酸催化剂而固化。这种制备物中存在的问题是固化时间长,机械强度低和贮存稳定性低。Minnesota Mining和Manufacturing Company及Wictorin等公司在专利(WO96/13538和WO95/30402)中公开了可阳离子固化的环氧混合物,优选含有3,4-环氧基环己基-甲基-3,4-环氧基环己烷羧酸酯或双(3,4-环氧基环己基己二酸酯)。该类型的环氧化物是高度有毒的并在体外试验中表明这些单体有在牙科应用中不希望有的突变性质。
本发明的任务是提供一种可聚合的组合物,它同已知的组合物相比具有较高的反应活性和必需的机械性能以及小的体积收缩并且没有突变性和仅有很小的细胞毒性。
根据本发明,该任务可由一种可聚合组合物解决,该组合物包括:
当n=2时
Z是有1-22,优选1-18个碳原子的环脂族或芳族基团或这些基团的混合物,其中一个或多个碳原子可被O,C=O,-O(C=O)-,SiR2和/或NR代替,或是有0-22,优选1-18个碳原子的脂族基团,其中一个或多个碳原子可被O,C=O,-O(C=O)-,NR或SiR2代替,其中至少一个碳原子必须被SiR2代替,和R是有1-7个碳原子的脂族基,其中一个或多个碳原子可被O,C=O和/或-O(C=O)-代替,
当n>2时,
Z是有0-22,优选0-18个碳原子的脂族、环脂族或芳族基团或这些基团的混合体,其中一个或多个碳原子可被O、C=O、-O(C=O)、SiR2和/或NR代替和R是有1-7个碳原子的脂族基团,其中一个或多个碳原子可被O、C=O和/或-O-(C=O)代替,
而其中对于B型来说:
Z是有0-22,优选1-18个碳原子的脂族、环脂族或芳族基团或这些基团的混合体,其中一个或多个碳原子可被O、C=O、-O(C=O)、SiR2和/或NR代替和R是有1-7个碳原子的脂族基团,其中一个或多个碳原子可被O、C=O和/或-O(C=O)代替,
其中对于A型和B型来说:
A是有1-18,优选1-15个碳原子的脂族、环脂族或芳族基团或这些基团的混合体,其中一个或多个碳原子可被O、C=O、-O(C=O)、SiR2和/或NR代替和R是有1-7个碳原子的脂族基团,其中一个或多个碳原子可被O、C=O和/或-O(C=O)代替,
B1,B2,D,E相互独立是氢原子或有1-9,优选1-7个碳原子的脂族基团,其中一个或多个碳原子可被O、C=O、-O(C=O)-、SiR2和/或NR代替和R是有1-7个碳原子的脂族基团,其中一个或多个碳原子可被O、C=O和/或-O(C=O)代替,
n是2-7,优选2-5,特别是2-4,
m是1-10,优选1-7,特别是1-5,
p是1-5,优选1-4,特别是1或2,
q是1-5,优选1-4,特别是1或2,
X是CH2,S或O(b)0-80,优选0-70wt%与(a)不同的环氧化物或它们的混合物,(c)3-85,优选5-75wt%填料,(d)0.01-25,优选0.01-20wt%的引发剂、阻滞剂和/或加速剂,(e)0-25,优选0-20wt%的助剂,其中各百分含量均基于组合物的总重量。
本发明优选的组合物含有:一种或多种下述的环氧化物作为组分(a):ⅰ)2,2-双〔4,1-亚苯氧基-3,1-丙二基-3,4-环氧基-环己基羧酸酯〕亚丙基ⅱ)2,2-双〔4,1-亚苯氧基-3,1-丙二基-氧基-亚甲基-3,4-环氧基-环己基〕亚丙基ⅲ)2,2-双〔3,4-环氧基-环己基亚甲基(4,1-亚苯氧基-3,1-丙基羧酸酯)〕亚丙基ⅳ)2,2-双〔4,1-亚苯氧基-3,1-丙二基-1,1,3,3-四甲基二硅氧烷基-1,2-乙二基-3,4-环氧基环己基〕亚丙基ⅴ)2,2-双〔4,1-亚苯氧基-3,1-丙二基-3-氧杂三环[3.2.1.02,4]辛基-6-羧基〕亚丙基ⅵ)2,2-双〔4,1-亚苯氧基-3,1-丙二基-3,8-二氧杂三环[3.2.1.02,4]辛基-6-羧基〕亚丙基ⅶ)2,2-双{4,1-亚苯氧基-3,1-丙二基-[3,5,7-三(乙二基-3,4-环氧基环己基)-1,3,5,7-四甲基环四硅氧烷基]}亚丙基ⅷ)双〔亚甲基-氧基-3,1-丙二基-3,4-环氧基环己基羧酸酯〕三环[5.2.1.02,6]癸烷ⅸ)双〔亚甲基-氧基-3,1-丙二基-氧基-亚甲基-3,4-环氧基环己基〕三环[5.2.1.02,6]癸烷ⅹ)双〔3,4-环氧基环己基亚甲基-丙烷羧酸-1-氧基-亚甲基〕三环[5.2.1.02,6]癸烷ⅹⅰ)双〔亚甲基-氧基-3,1-丙二基-1,1,3,3-四甲基二硅氧烷二基-1,2-乙二基-3,4-环氧基环己基〕三环[5.2.1.02,6]癸烷ⅹⅱ)双{亚甲基-氧基-3,1-丙二基-3-氧杂三环[3.2.1.02,6]辛基-6-羧基}三环[5.2.1.02,6]-癸烷ⅹⅲ)双{亚甲基-氧基-3,1-丙二基-3,8-二氧杂三环[3.2.1.02,6]辛基-6-羧基}三环[5.2.1.02,6]癸烷ⅹⅳ)双(亚甲基-氧基-(3-丙二基-3,5,7-三(2,1-乙二基-3,4-环氧基环己基)-1,3,5,7-四甲基环四硅氧烷基)-三环[5.2.1.02,6]癸烷ⅹⅴ) 1,1,1-三〔亚甲基-氧基-亚甲基-3,4-环氧基环己基〕丙烷ⅹⅵ)1,1,1-三〔亚甲基-氧基-1,3-丙二基-1,1,3,3-四甲基二硅氧烷二基-1,2-乙二基-3,4-环氧基环己基〕丙烷ⅹⅶ)1,1,1-三{亚甲基-3-氧杂三环[3.2.1.02,4]辛基-6-羧基}丙烷ⅹⅷ)1,1,1-三{亚甲基-3,8-二氧杂三环[3.2.1.02,4]-辛基-6-羧基}丙烷ⅹⅸ)1,1,1-三〔亚甲基-氧基-3,1-丙二基-3,5,7-三(2,1-乙二基-3,4-环氧基环己基)-1,3,5,7-四甲基环四硅氧烷基〕丙烷ⅹⅹ)1,1,1-三〔亚甲基-氧基-双(乙二基氧基)-3,4-环氧基环己基羧酸酯〕丙烷ⅹⅹⅰ)1,1,1-三〔亚甲基-氧基-双(乙二基氧基)-亚甲基-3,4-环氧基环己基〕丙烷ⅹⅹⅱ)1,1,1-三〔亚甲基-氧基-双(乙二基氧基)-丙二基-1,1,3,3-四甲基二硅氧烷基-1,2-乙二基-3,4-环氧基环己基〕丙烷ⅹⅹⅲ)1,1,1-三{亚甲基-氧基-双(乙二基氧基)-3-氧杂三环[3.2.1.02,4]辛基-6-羧基}丙烷ⅹⅹⅳ)1,1,1-三{亚甲基-氧基-双(乙二基氧基)-3,8-二氧杂三环[3.2.1.02,4]辛基-6-羧基}丙烷ⅹⅹⅴ)1,1,1-三〔亚甲基-氧基-双(乙二基氧基)-丙二基-3,5,7-三(2,1-乙二基-3,4-环氧基环己基)-1,3,5,7-四甲基环四硅氧烷基〕丙烷ⅹⅹⅵ)α,ω)-双〔3,4-环氧基环己基乙二基-1,1,3,3-四甲基二硅氧烷基-3,1-丙二基〕聚四氢呋喃ⅹⅹⅶ)α,ω-双{3-氧杂三环[3.2.1.02,4]辛基-6-羧基}聚四氢呋喃ⅹⅹⅷ)α,ω-双{3,8-二氧杂三环[3.2.1.02,4]辛基-6-羧基}聚四氢呋喃ⅩⅩⅸ)α,ω-双(3-丙二基-3,5,7-三(2,1-乙二基-3,4-环氧基环己基)-1,3,5,7-四甲基环四硅氧烷基)聚四氢呋
本发明还涉及上述分别列出的新环脂族环氧化物本身。
环氧化物可以简单的方式制备。为了制备无硅氧烷基单元的A型环氧化物,将由二-、三-或多醇与环己烯羧酸或环己烯基甲醇进行常规醚化或酯化得到的环脂链烯烃用过苯甲酸在适合的溶剂中优选在乙醚中进行环氧化。反应结束后用苛性钠溶液多次洗涤并用硫酸镁干燥。真空蒸出挥发性组分。
带有硅氧烷基单元的A型环氧化物的制备可由常规的两步氢化硅烷化反应达到:向溶于合适溶剂(如己烷)中的过量的带有至少两个活性氢原子的硅氧烷和催化量的H2PtCl6中加入带有二、三或多个末端链烯官能团的化合物。反应结束后除去混合物中沉淀的铂,用水洗一次和经硫酸镁干燥。在第二个氢化硅烷化反应中将得到的含有二、三或聚硅氧烷的化合物溶于合适的溶剂例如甲苯或烷烃中,并与H2PtCl6和乙烯基环己烯环氧化物一起加热。除去混合物中沉淀的铂并水洗一次。通过真空蒸出挥发性组分而得到产物。
为了制备带有3-氧杂三环[3.2.1.02.4]辛基单元末端的B型环氧化物,将二、三或聚(甲基)丙烯酸酯与取代(或未取代)单体环戊二烯、噻吩或呋喃在路易斯酸催化下(如ZnCl2或AlCl3)在标准压力或在高压釜中反应形成相应的狄尔斯-阿德耳产物。桥环双键的环氧化是用过苯甲酸在合适的溶剂优选乙醚中进行。反应结束后用苛性钠溶液洗涤多次和经硫酸镁干燥。真空蒸去挥发性组分。
本发明可聚合组合物可含有本发明的环氧化物及其它低粘度环氧化物作为组分(b)。按(b)的低粘度环氧化物例如是:3,4-环氧基环己基甲基-3,4-环氧基环己烷羧酸酯(US-A-2 716 123),3,4-环氧基-6-甲基环己基-3,4-环氧基-6-甲基环己烷羧酸酯(US-A-2 716 123)或有关的环氧化物,乙烯基环己烯二环氧化物(US-A-2 948 688),二环戊二烯二氧化物(US-A-2 985 667),双(3,4-环氧基环己基甲基)己二酸酯(US-A-2 750 395,US-A-2 863 881,US-A-3 187 018),下式的1,3,5,7-四(2,1-乙二基-3,4-环氧基环己基)-1,3,5,7-四甲基环四硅氧烷:
下式的1,3,5,7,9-五(2,1-乙二基-3,4-环氧基环己基)-1,3,5,7,9-五甲基环五硅氧烷(US-A-5 085124):和用环脂族环氧化物官能化的低分子量硅氧烷,例如下式的1,1,3,3-四甲基-1,3-双(乙二基-3,4-环氧基环己基)二硅氧烷(EP-A 0 449 027,EP-A-0 574 265):
按组分(b)的低粘度环氧化物的存在浓度为0-80wt%,优选5-75wt%,均以组合物总重量计算。
按组分(c)的无机填料可以常用的牙科填料,例如石英,磨细的任选X光不透明的、任选活性的玻璃、难溶的氟化物,如CaF2、YF3(EP-B-0 238 025),硅胶以及焦化硅酸或其颗粒。同样地,组合物可以含有作为供给氟化物的组分的一种或多种通式为AnMFm的水溶性无机络合氟化物,其中A为一价或多价阳离子,M为第Ⅲ、Ⅳ或Ⅴ主族或副族金属,n为1-3的整数,m为4-6的整数(DE-A-4 445266)。它在牙科组合物中的浓度为3-85wt%,优选5-75wt%和尤其是30-75wt%。为了更好地引入到聚合物基体中,有利的是,使填料以及必要时X光不透明添加物如YF3疏水化。常用疏水剂是硅烷,如三甲氧基缩水甘油基硅烷。无机填料的最大粒度优选20μm,特别是12μm。特别优选使用平均粒度<7μm的填料。
按本发明组合物的组分(d)的引发剂可以是:路易斯或布朗斯台德酸或释放引发聚合的酸的化合物,例如BF3或其醚加合物(BF3·THF,BF3·Et2O等),AlCl3,FeCl3,HPF6,HAsF6,HSbF6,HBF4或者用紫外光或可见光辐照后或用热和/或压力引发聚合的物质,如六氟磷酸(eta-6-枯烯)(eta-5-环戊二烯基)铁,四氟硼酸(eta-6-枯烯)(eta-5-环戊二烯基)铁,六氧锑酸(eta-6-枯烯)(eta-5-环戊二烯基)铁,取代的二芳基碘鎓盐和三芳基锍盐。用作加速剂可以是过酸酯型、二酰基过氧化物型、过二碳酸盐型和氢过氧化物型的过氧化合物。优选使用氢过氧化物,特别优选使用的加速剂是以约70-90%浓度的枯烯溶液的氢过氧化枯烯。光引发剂与氢过氧化枯烯的比值可在很宽的界限1∶0.001-1∶10变化,但优选比值为1∶0.1-1∶6,特别优选1∶0.5-1∶4。同样地可以使用配合剂,如草酸,8-羟基喹啉,乙二胺四乙酸和芳族多羟基化合物。可以加入的阻滞剂是碱,典型地为叔胺。组分(d)在本发明组合物中的用量为0.01-25wt%,优选0.01-20wt%,基于组合物总重量计算、
按组分(e)的合适助剂可以是例如常用于牙科领域的稳定剂、颜料或稀释剂。
本发明含环氧化物的可聚合组合物特别适合作为用于牙科目的材料,例如用于制备人造牙齿或临时替代物,用作涂料,用于粘结基体以及作为牙科填料。
本发明可聚合组合物在牙科应用中有一个特别的优点。本发明组合物的体积收缩远远低于基于甲基丙烯酸酯单体的已知组合物的收缩。从而,例如可大大避免作为填料时的边缘空隙问题。同样,本发明环氧化物和由其制备的可聚合组合物的尺寸稳定性和贮存稳定在作为精确模型材料中也是很有好处的。
基于丙烯酸酯的牙科组合物与基于环氧化物的组合物相比有很短的凝固时间和因而有瞬间的固化,相反,本发明的组合物显示经例如10-240秒均匀进行的固化。从而可避免生成聚合物内部的应力,因此,本发明的组合物在达到最终的硬化前,还有一段最佳的加工时间。
本发明可聚合组合物除了有高的抗压强度和抗弯强度外,还有意外的高的抗冲击性,这对于牙科应用有重要意义。
此外,本发明的牙科填料对牙齿基质显示极好的粘附性。另外,本发明的环氧化物不会突变并且在毒性上是可接受的。
本发明单体的合成实施例
1.制备2,2-双〔4,1-亚苯氧基-3,1-丙二基-3,4-环氧基环己基羧酸酯〕亚丙基:
100g 2,2-双(4-氧基丙基羧基苯基)丙烷与85g4-环己烯羧酸在甲苯中回流6小时。蒸出溶剂和过量的4-环己烯羧酸。留下161g 2,2-双〔4-氧基丙基苯基-3-环己烯基羧酸酯)丙烷,将其加入在500ml乙醚中的过苯甲酸中,反应8小时后,用10%的苛性钠溶液洗涤多次并以硫酸镁干燥。真空蒸去挥发性成分。
2.制备双(3,4-环氧基环己基乙基-四甲基二硅氧烷基丙氧基甲基)-三环[5.2.1.02,6]癸烷。
174g四甲基二硅氧烷先加入800ml己烷中并加入120mgH2PtCl6。向其中加入80g三环[5.2.1.02,6]癸烷二烯丙醚并将混合物在85℃(沸点)加热3小时。从混合物中除去沉淀的铂,用水洗涤一次并将混合物以硫酸镁干燥。真空蒸出己烷和挥发性成分。得到的双(四甲基二硅氧烷基丙氧基甲基)-三环[5.2.1.02,6]癸烷溶于200ml己烷中并加入120mgH2PtCl6和71g乙烯基-3,4-环己烯环氧化物,将混合物在85℃加热3小时。从混合物中除去沉淀的铂,用水洗涤一次并经硫酸镁干燥。真空中浓缩反应混合物后得到202g双(3,4-环氧基环己基乙基-四甲基二硅氧烷基丙氧甲基)-三环[5.2.1.02,6]癸烷。
3.制备α,ω-双(3-丙二基-3,5,7-三(2,1-乙二基-3,4-环氧基环己基)-1,3,5,7-四甲基环四硅氧烷基)-聚四氢呋喃。
126g α,ω-聚四氢呋喃-600-二烯丙基醚加入在700ml己烷中的151g 1,3,5,7-四甲基环四硅氧烷和110mg H2PtCl6中。在85℃反应3小时后分离出沉淀的铂并真空蒸出所有挥发性成分。剩下α,ω-双〔3,5,7-三(3,4-环氧基环己基乙基)-3-丙基-1,3,5,7-四甲基环四硅氧烷基〕-聚四氢呋喃,将其与179g乙烯基环己烯环氧化物和130mg H2PtCl6在800ml甲苯中于120℃加热3小时。分离出沉淀的铂并直空蒸出所有挥性性成分。剩下339gα,ω-双〔3,5,7-三(3,4-环氧基环己基乙基)-3-丙基-1,3,5,7-四甲基-环四硅氧烷基〕-聚四氢呋喃。
4.制备α,ω-双(6-甲基-二氧杂三环[3.2.1.02,4]辛基-6-羧基)聚乙二醇
85gα,ω-聚乙二醇-600-二甲基丙烯酸酯与19g呋喃在300ml甲苯中于高压釜中在10巴和120℃加热4小时。真空蒸发挥发性成分。剩下α,ω-双(3-甲基-7-氧杂双环[2.2.1]庚基-3-羧基)聚乙二醇,将其滴加入31g过苯甲酸与300ml乙醚形成的溶液中。反应8小时后用10%的苛性钠溶液洗涤多次并经硫酸镁干燥。真空蒸发挥发性成分。
5.制备1,1,1-三〔亚甲基-氧基-双(乙二基-氧基)-亚甲基-3,4-双氧基环己基〕丙烷
168g 1,1,1-三〔亚甲基-羟基-双(乙二基氧基)丙烷先放于600ml四氢呋喃中。分批加入178g叔丁醇钾并在30℃搅拌1小时。接着滴加溶于300ml四氢呋喃中的277g3-环己烯基溴甲烷。反应混合物在75℃加热24小时。蒸去溶剂,混合物悬浮在甲基叔丁醚中,滤去沉淀。水萃取后剩下249g 1,1,1-三〔亚甲基-氧基-双(乙二基氧基)-亚甲基-3-环己烯基〕丙烷,将其溶于500ml乙醚中。溶液加入在400ml乙醚中的61g过苯甲酸中,反应8小时后用10%苛性钠溶液洗涤多次。混合物经硫酸镁干燥,真空蒸去挥发性成分。
可聚合组合物的实施例
1.可聚合组合物的一般制备
1.1 光或UV固化的单组分体系
本发明可聚合单组分组合物的制备是两步法,其中在第一步将除光引发剂外的所有组分进行均匀预混合。在第二步,将光引发剂在避光条件下均匀地捏合入糊料中。所得可加工的本发明环氧树脂在完全混合后装入不透光容器中。
1.2 双组分体系
本发明可聚合双组分组合物的制备是首先制备由环氧化物单体、部分填料、阻滞剂、加速剂和助剂组成的均匀混合的组分A。另外,制备由引发剂、稀释剂和另一部分填料组成的均匀混合的组分B。将组分A和B例如装入双筒系统。通过双筒系统中静态混合器,双组分组合物可直接加工。
2.应用实施例
实施例1
组分A:由17.6重量份α,ω-双(3-丙二基-3,5,7-三(2,1-乙二基-3,4-环氧基环己基)-1,3,5,7-四甲基环四硅氧烷基)-二四氢呋喃、17.6重量份3,4-环氧基环己基甲基-3,4-环氧基环己烷羧酸酯和64.7重量份硅烷化的着色石英捏合成糊料。另一组分B由32.8重量份聚乙二醇、4.7重量份BF3·OEt2和62.5重量份硅烷化的着色石英组成。糊料A和B以2∶1的比例经一静态混合器混合。组合物在两分钟内完全固化。
实施例2
由18重量份双(亚甲基-氧基-3,1-丙二基-3,4-环氧基环己基羧酸酯)-三环[5.2.1.0.2,6]癸烷、10重量份1,1,3,3-四甲基-1,3-双(乙二基-3,4-环氧基环己基)二硅氧烷、68.9重量份硅烷化的着色石英、1.2重量份六氟磷酸(eta-6-枯烯)(eta-5-环戊二烯基)铁和1.8重量份氢过氧化枯烯捏合成糊料,用一灯(发光仪EliparⅡ,ESPE Dental-Medizin GmbH & Co.KG,德国)辐照在约40秒内使糊料完全固化。
实施例3
将16.7重量份1,1,1-三〔亚甲基-氧基-1,3-丙二基-1,1,3,3-四甲基二硅氧烷二基-1,2-乙二基-3,4-环氧基环己基〕丙烷、4.5重量份3,4-环氧基环己基甲基-3,4-环氧基环己烷羧酸酯、5.2重量份1,3,5,7-四(2,1-乙二基-3,4-环氧基环己基)-1,3,5,7-四甲基环四硅氧烷、70.5重量份硅烷化的着色石英、1.2重量份六氟磷酸(etc-6-枯烯)(eta-5-环戊二烯基)铁和1.9重量份氢过氧化枯烯捏合成糊料,用一灯(发光仪EliparⅡ,ESPEDental-Medizin GmbH & Co.KG.德国)辐照在约40秒内完全固化。
实施例4
将18重量份2,2-双〔4,1-亚苯氧基-3,1-丙二基-3,4-环氧基环己基羧酸酯〕亚丙基、13重量份3,4-环氧基环己基甲基-3,4-环氧基环己烷羧酸酯、65.4重量份硅烷化的着色石英、1.5重量份六氟磷酸(eta-6-枯烯)(eta-5-环戊二烯基)铁和2.1重量份氢过氧化枯烯捏合成糊料,用一灯(发光仪EliparⅡ,ESPE Dentanl-Medizin GmbH & Co.KG,德国)辐照在约40秒内完全固化。
实施例5对比糊料,购得的牙科组合物
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5(对比) | |
抗压强度〔MPa〕 | 388 | 331 | 361 | 355 | 385 |
抗弯强度〔MPa〕(ISO 4049) | 151 | 131 | 121 | 141 | 118 |
体积收缩〔%〕 | 1.3 | 0.8 | 0.7 | 1.0 | 2.2 |
Claims (11)
其中对于A型来说:
当n=2时
Z是有1-22,优选1-18个碳原子的环脂族或芳族基团或这些基团的混合物,其中一个或多个碳原子可被O,C=O,-O(C=O)-,SiR2和/或NR代替,或是有0-22,优选1-18个碳原子的脂族基团,其中一个或多个碳原子可被O,C=O,-O(C=O)-,NR或SiR2代替,其中至少一个碳原子必须被SiR2代替,和R是有1-7个碳原子的脂族基,其中一个或多个碳原子可被O,C=O和/或-O(C=O)-代替,
当n>2时,
Z是有0-22,优选0-18个碳原子的脂族、环脂族或芳族基团或这些基团的混合体,其中一个或多个碳原子可被O、C=O、-O(C=O)、SiR2和/或NR代替和R是有1-7个碳原子的脂族基团,其中一个或多个碳原子可被O、C=O和/或-O-(C=O)代替,
而其中对于B型来说:
Z是有0-22,优选1-18个碳原子的脂族、环脂族或芳族基团或这些基团的混合体,其中一个或多个碳原子可被O、C=O、-O(C=O)、SiR2和/或NR代替和R是有1-7个碳原子的脂族基团,其中一个或多个碳原子可被O、C=O和/或-O(C=O)代替,
其中对于A型和B型来说:
A是有1-18个碳原子的脂族、环脂族或芳族基团或这些基团的混合体,其中一个或多个碳原子可被O、C=O、-O(C=O)、SiR2和/或NR代替和R是有1-7个碳原子的脂族基团,其中一个或多个碳原子可被O、C=O和/或-O(C=O)代替,
B1,B2,D,E相互独立是氢原子或有1-9个碳原子的脂族基团,其中一个或多个碳原子或被O、C=O、-O(C=O)-、SiR2和/或NR代替和R是有1-7个碳原子的脂族基团,其中一个或多个碳原子可被O、C=O和/或-O(C=O)代替,
n是2-7,
m是1-10,
p是1-5,
q是1-5,
X是CH2,S或O(b)0-80wt%与(a)不同的环氧化物或它们的混合物,(c)3-85wt%填料,(d)0.01-25wt%的引发剂、阻滞剂和/或加速剂,(e)0-25wt%的助剂,其中各百分含量均基于组合物的总重量。
2.按权利要求1的可聚合组合物,其特征是,它含有作为组分(a)的一种或多种下列的环氧化物:ⅰ)2,2-双〔4,1-亚苯氧基-3,1-丙二基-3,4-环氧基-环己基羧酸酯〕亚丙基ⅱ)2,2-双〔4,1-亚苯氧基-3,1-丙二基-氧基-亚甲基-3,4-环氧基-环己基〕亚丙基ⅲ)2,2-双〔3,4-环氧基-环己基亚甲基(4,1-亚苯氧基-3,1-丙基羧酸酯)〕亚丙基ⅳ)2,2-双〔4,1-亚苯氧基-3,1-丙二基-1,1,3,3-四甲基二硅氧烷基-1,2-乙二基-3,4-环氧基环己基〕亚丙基ⅴ)2,2-双〔4,1-亚苯氧基-3,1-丙二基-3-氧杂三环[3.2.1.02,4]辛基-6-羧基〕亚丙基ⅵ)2,2-双〔4,1-亚苯氧基-3,1-丙二基-3,8-二氧杂三环[3.2.1.02,4]辛基-6-羧基〕亚丙基ⅶ)2,2-双{4,1-亚苯氧基-3,1-丙二基-[3,5,7-三(乙二基-3,4-环氧基环己基)-1,3,5,7-四甲基环四硅氧烷基]}亚丙基ⅷ)双〔亚甲基-氧基-3,1-丙二基-3,4-环氧基环己基羧酸酯〕三环[5.2.1.02,6]癸烷ⅸ)双〔亚甲基-氧基-3,1-丙二基-氧基-亚甲基-3,4-环氧基环己基〕三环[5.2.1.02,6]癸烷ⅹ)双〔3,4-环氧基环己基亚甲基-丙烷羧酸-1-氧基-亚甲基〕三环[5.2.1.02,6]癸烷ⅹⅰ)双〔亚甲基-氧基-3,1-丙二基-1,1,3,3-四甲基二硅氧烷二基-1,2-乙二基-3,4-环氧基环己基〕三环[5.2.1.02,6]癸烷ⅹⅱ)双{亚甲基-氧基-3,1-丙二基-3-氧杂三环[3.2.1.02,6]辛基-6-羧基}三环[5.2.1.02,6]-癸烷ⅹⅲ)双{亚甲基-氧基-3,1-丙二基-3,8-二氧杂三环[3.2.1.02,6]辛基-6-羧基}三环[5.2.1.02,6]癸烷ⅹⅳ)双(亚甲基-氧基-(3-丙二基-3,5,7-三(2,1-乙二基-3,4-环氧基环己基)-1,3,5,7-四甲基环四硅氧烷基)-三环[5.2.1.02,6]癸烷ⅹⅴ)1,1,1-三〔亚甲基-氧基-亚甲基-3,4-环氧基环己基〕丙烷ⅹⅵ)1,1,1-三〔亚甲基-氧基-1,3-丙二基-1,1,3,3-四甲基二硅氧烷二基-1,2-乙二基-3,4-环氧基环己基〕丙烷ⅹⅶ)1,1,1-三{亚甲基-3-氧杂三环[3.2.1.02,4]辛基-6-羧基}丙烷ⅹⅷ)1,1,1-三{亚甲基-3,8-二氧杂三环[3.2.1.02,4]-辛基-6-羧基}丙烷ⅹⅸ)1,1,1-三〔亚甲基-氧基-3,1-丙二基-3,5,7-三(2,1-乙二基-3,4-环氧基环己基)-1,3,5,7-四甲基环四硅氧烷基〕丙烷ⅹⅹ)1,1,1-三〔亚甲基-氧基-双(乙二基氧基)-3,4-环氧基环己基羧酸酯〕丙烷ⅹⅹⅰ)1,1,1-三〔亚甲基-氧基-双(乙二基氧基)-亚甲基-3,4-环氧基环己基〕丙烷ⅹⅹⅱ)1,1,1-三〔亚甲基-氧基-双(乙二基氧基)-丙二基-1,1,3,3-四甲基二硅氧烷基-1,2-乙二基-3,4-环氧基环己基〕丙烷ⅹⅹⅲ)1,1,1-三{亚甲基-氧基-双(乙二基氧基)-3-氧杂三环[3.2.1.02,4]辛基-6-羧基}丙烷ⅹⅹⅳ )1,1,1-三{亚甲基-氧基-双(乙二基氧基)-3,8-二氧杂三环[3.2.1.02,4]辛基-6-羧基}丙烷ⅹⅹⅴ)1,1,1-三〔亚甲基-氧基-双(乙二基氧基)-丙二基-3,5,7-三(2,1-乙二基-3,4-环氧基环己基)-1,3,5,7-四甲基环四硅氧烷基〕丙烷ⅹⅹⅵ)α,ω-双〔3,4-环氧基环己基乙二基-1,1,3,3-四甲基二硅氧烷基-3,1-丙二基〕聚四氢呋喃ⅹⅹⅶ)α,ω-双{3-氧杂三环[3.2.1.02,4]辛基-6-羧基}聚四氢呋喃ⅹⅹⅷ)α,ω-双{3,8-二氧杂三环[3.2.1.02,4]辛基-6-羧基}聚四氢呋喃ⅹⅹⅸ)α,ω-双(3-丙二基-3,5,7-三(2,1-乙二基-3,4-环氧基环己基)-1,3,5,7-四甲基环四硅氧烷基)聚四氢呋喃
3.按权利要求1或2的可聚合组合物,其特征是,含有作为按(b)的低粘度环氧化物的3,4-环氧基环己基甲基-3,4-环氧基环己烷羧酸酯,3,4-环氧基-6-甲基环己基-3,4-环氧基-6-甲基环己烷羧酸酯,二环戊二烯二氧化物,双(3,4-环氧基环己基甲基)己二酸酯,1,3,5,7-四(2,1-乙二基-3,4-环氧基环己基)-1,3,5,7-四甲基环四硅氧烷,1,3,5,7,9-五(2,1-乙二基-3,4-环氧基环己基)-1,3,5,7,9-五甲基环五硅氧烷,1,1,3,3-四甲基-1,3-双(乙二基-3,4-环氧基环己基)二硅氧烷和/或用环脂族环氧化物官能化的低分子量硅氧烷。
4.按权利要求1-3至少一项的可聚合组合物,其特征为,含有作为按c)的填料的石英,磨碎的玻璃、硅胶或硅酸或其颗粒物。
5.按权利要求1-4至少一项的可聚合组合物,其特征为,含有作为阻滞剂、加速剂和/或引发剂的路易斯酸或布朗斯台德酸或通过用紫外光或可见光辐照,通过热和/或压力生成这类酸的化合物。
6.按权利要求1-5至少一项的可聚合组合物,其特征为,含有作为助剂的二醇、稀释剂、稳定剂、抑制剂和/或颜料。
7.按权利要求1-6至少一项的可聚合组合物,由以下物质组成:A 一种催化剂糊料,含有组分(a)和(b)的环氧化物、组分(c)的部分或全部填料、任选的按组分(d)的阻滞剂或加速剂和任选的按组分(e)的助剂;以及空间上与其分开的B 一种催化剂糊料,含有按组分(d)的引发剂、任选的按组分(c)的部分填料和任选的按组分(e)的助剂。
8.环氧化物,是以下物质:
ⅰ)2,2-双〔4,1-亚苯氧基-3,1-丙二基-3,4-环氧基-环己基羧酸酯〕亚丙基ⅱ)2,2-双〔4,1-亚苯氧基-3,1-丙二基-氧基-亚甲基-3,4-环氧基-环己基〕亚丙基ⅲ)2,2-双〔3,4-环氧基-环己基亚甲基(4,1-亚苯氧基-3,1-丙基羧酸酯)〕亚丙基ⅳ )2,2-双〔4,1-亚苯氧基-3,1-丙二基-1,1,3,3-四甲基二硅氧烷基-1,2-乙二基-3,4-环氧基环己基〕亚丙基ⅴ)2,2-双〔4,1-亚苯氧基-3,1-丙二基-3-氧杂三环[3.2.1.02,4]辛基-6-羧基〕亚丙基ⅵ)2,2-双〔4,1-亚苯氧基-3,1-丙二基-3,8-二氧杂三环[3.2.1.02,4]辛基-6-羧基〕亚丙基ⅶ)2,2-双{4,1-亚苯氧基-3,1-丙二基-[3,5,7-三(乙二基-3,4-环氧基环己基)-1,3,5,7-四甲基环四硅氧烷基]}亚丙基ⅷ)双〔亚甲基-氧基-3,1-丙二基-3,4-环氧基环己基羧酸酯〕三环[5.2.1.02,6]癸烷ⅸ)双〔亚甲基-氧基-3,1-丙二基-氧基-亚甲基-3,4-环氧基环己基〕三环[5.2.1.02,6]癸烷ⅹ)双〔3,4-环氧基环己基亚甲基-丙烷羧酸-1-氧基-亚甲基〕三环[5.2.1.02,6]癸烷ⅹⅰ)双〔亚甲基-氧基-3,1-丙二基-1,1,3,3-四甲基二硅氧烷二基-1,2-乙二基-3,4-环氧基环己基〕三环[5.2.1.02,6]癸烷ⅹⅱ)双{亚甲基-氧基-3,1-丙二基-3-氧杂三环[3.2.1.02,6]辛基-6-羧基}三环[5.2.1.02,6]-癸烷ⅹⅲ)双{亚甲基-氧基-3,1-丙二基-3,8-二氧杂三环[3.2.1.02,6]辛基-6-羧基}三环[5.2.1.02,6]癸烷ⅹⅳ )双(亚甲基-氧基-(3-丙二基-3,5,7-三(2,1-乙二基-3,4-环氧基环己基)-1,3,5,7-四甲基环四硅氧烷基)-三环[5.2.1.02,6]癸烷ⅹⅴ)1,1,1-三〔亚甲基-氧基-亚甲基-3,4-环氧基环己基〕丙烷ⅹⅵ)1,1,1-三〔亚甲基-氧基-1,3-丙二基-1,1,3,3-四甲基二硅氧烷二基-1,2-乙二基-3,4-环氧基环己基〕丙烷ⅹⅶ)1,1,1-三{亚甲基-3-氧杂三环[3.2.1.02,4]辛基-6-羧基}丙烷ⅹⅷ)1,1,1-三{亚甲基-3,8-二氧杂三环[3.2.1.02,4]-辛基-6-羧基}丙烷ⅹⅸ)1,1,1-三〔亚甲基-氧基-3,1-丙二基-3,5,7-三(2,1-乙二基-3,4-环氧基环己基)-1,3,5,7-四甲基环四硅氧烷基〕丙烷ⅹⅹ)1,1,1-三〔亚甲基-氧基-双(乙二基氧基)-3,4-环氧基环己基羧酸酯〕丙烷ⅹⅹⅰ)1,1,1-三〔亚甲基-氧基-双(乙二基氧基)-亚甲基-3,4-环氧基环己基〕丙烷ⅹⅹⅱ)1,1,1-三〔亚甲基-氧基-双(乙二基氧基)-丙二基-1,1,3,3-四甲基二硅氧烷基-1,2-乙二基-3,4-环氧基环己基〕丙烷ⅹⅹⅲ)1,1,1-三{亚甲基-氧基-双(乙二基氧基)-3-氧杂三环[3.2.1.02,4]辛基-6-羧基}丙烷ⅹⅹⅳ )1,1,1-三{亚甲基-氧基-双(乙二基氧基)-3,8-二氧杂三环[3.2.1.02,4]辛基-6-羧基}丙烷ⅹⅹⅴ)1,1,1-三〔亚甲基-氧基-双(乙二基氧基)-丙二基-3,5,7-三(2,1-乙二基-3,4-环氧基环己基)-1,3,5,7-四甲基环四硅氧烷基〕丙烷ⅹⅹⅵ)α,ω-双〔3,4-环氧基环己基乙二基-1,1,3,3-四甲基二硅氧烷基-3,1-丙二基〕聚四氢呋喃ⅹⅹⅶ)α,ω-双{3-氧杂三环[3.2.1.02,4]辛基-6-羧基}聚四氢呋喃ⅹⅹⅴⅲ)α,ω-双{3,8-二氧杂三环[3.2.1.02,4]辛基-6-羧基}聚四氢呋喃ⅩⅩⅸ)α,ω-双(3-丙二基-3,5,7-三(2,1-乙二基,3,4-环氧基环己基)-1,3,5,7-四甲基环四硅氧烷基)聚四氢呋
9.按权利要求1-7至少一项的可聚合组合物或按权利要求8的环脂族环氧化物作为涂料组合物的用途。
10.按权利要求1-7至少一项的可聚合组合物或按权利要求8的环脂族环氧化物用于粘附基体的用途。
11.按权利要求1-7至少一项的可聚合组合物或按权利要求8的环脂族环氧化物作为牙科组合物的用途。
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- 1996-11-21 DE DE19648283A patent/DE19648283A1/de not_active Withdrawn
-
1997
- 1997-11-21 AU AU54849/98A patent/AU719390B2/en not_active Ceased
- 1997-11-21 EP EP97951256A patent/EP0879257B1/de not_active Expired - Lifetime
- 1997-11-21 DE DE59706867T patent/DE59706867D1/de not_active Expired - Lifetime
- 1997-11-21 CN CN97191799A patent/CN1106417C/zh not_active Expired - Fee Related
- 1997-11-21 WO PCT/EP1997/006504 patent/WO1998022521A1/de active IP Right Grant
- 1997-11-21 JP JP52322698A patent/JP4001352B2/ja not_active Expired - Fee Related
- 1997-11-21 CA CA002246163A patent/CA2246163A1/en not_active Abandoned
- 1997-11-21 AT AT97951256T patent/ATE215575T1/de not_active IP Right Cessation
- 1997-11-21 US US09/101,867 patent/US6245828B1/en not_active Expired - Lifetime
-
2001
- 2001-01-16 US US09/759,455 patent/US20020002212A1/en not_active Abandoned
-
2003
- 2003-03-18 US US10/389,814 patent/US6908953B2/en not_active Expired - Fee Related
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CN100584301C (zh) * | 2006-10-04 | 2010-01-27 | 中国科学院长春应用化学研究所 | 一种可见光固化纳米复合树脂牙体修复材料及制备方法 |
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DE59706867D1 (de) | 2002-05-08 |
ATE215575T1 (de) | 2002-04-15 |
CA2246163A1 (en) | 1998-05-28 |
US6908953B2 (en) | 2005-06-21 |
WO1998022521A1 (de) | 1998-05-28 |
JP4001352B2 (ja) | 2007-10-31 |
AU5484998A (en) | 1998-06-10 |
CN1106417C (zh) | 2003-04-23 |
US20040024113A1 (en) | 2004-02-05 |
US20020002212A1 (en) | 2002-01-03 |
JP2001513117A (ja) | 2001-08-28 |
AU719390B2 (en) | 2000-05-11 |
EP0879257A1 (de) | 1998-11-25 |
US6245828B1 (en) | 2001-06-12 |
DE19648283A1 (de) | 1998-05-28 |
EP0879257B1 (de) | 2002-04-03 |
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