CN109206540B - 具有硅烷基转移试剂的聚合物材料 - Google Patents
具有硅烷基转移试剂的聚合物材料 Download PDFInfo
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- CN109206540B CN109206540B CN201810725114.0A CN201810725114A CN109206540B CN 109206540 B CN109206540 B CN 109206540B CN 201810725114 A CN201810725114 A CN 201810725114A CN 109206540 B CN109206540 B CN 109206540B
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- dental material
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- 239000000463 material Substances 0.000 title claims description 41
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims description 32
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- 238000012546 transfer Methods 0.000 title description 15
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 22
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 13
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
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- 239000005548 dental material Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
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- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical group CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
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- NZEDMAWEJPYWCD-UHFFFAOYSA-N 3-prop-2-enylsulfonylprop-1-ene Chemical compound C=CCS(=O)(=O)CC=C NZEDMAWEJPYWCD-UHFFFAOYSA-N 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
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Classifications
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- C07F7/1804—Compounds having Si-O-C linkages
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- 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
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- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
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- 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
- A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- A61K6/896—Polyorganosilicon compounds
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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- 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
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- 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
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- 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
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- 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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- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- 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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- C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3081—Treatment with organo-silicon compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
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Abstract
根据通式I的可自由基聚合的硅烷,基于其的缩聚物和用其表面改性的填料:其中R1是直链或支链的脂族C1‑C9烷基、苯基或烷基化苯基,R2、R3在每种情况下彼此独立地不存在,或者是可被S或O原子中断的直链或支链脂族C1‑C20亚烷基,R4、R5、R6在每种情况下各自独立地为‑Cl、‑O‑CH3、‑O‑C2H5、‑CH3或‑C2H5,X是CH2或O,Y不存在,或为O或NR',其中R'为H或C1‑5烷基,并且Z不存在,或为O、NR”、‑CO‑O‑、‑CO‑NR”‑、‑O‑CO‑O‑、‑O‑CO‑NR”‑或‑NR”‑CO‑NR”‑,其中R”是H或C1‑5烷基,并且其中基团R2和R3不能同时不存在,并且如果R2或R3不存在,则Z不存在。
Description
技术领域
本发明涉及可自由基聚合的硅烷,其本身、以聚硅氧烷缩合物形式或以填料结合形式适合作为链转移剂,用于监测和控制自由基聚合中的网络结构。
背景技术
自由基聚合物是通过一种(均聚物)或多种(共聚物)可自由基聚合的单体的自由基聚合形成的。根据聚合的单体的官能度,获得直链(在单官能单体的情况下)或交联的(在双官能或多官能单体的情况下)聚合物。自由基聚合的一大优点是,一方面,许多技术上相关的单体(尤其是乙烯,乙烯基单体,如苯乙烯、氯乙烯、丙烯腈和乙酸乙烯酯,二烯,(甲基)丙烯酸酯和(甲基)丙烯酰胺)可以自由基聚合,并且另一方面,自由基聚合可以在本体(本体聚合)、溶液、悬浮液或乳液中进行。为了引发聚合,添加形成自由基的引发剂,其通过热解、光解或氧化还原反应形成自由基。
自由基聚合根据链增长机理进行,其中由引发剂形成的引发聚合的初级自由基被加成到单体的双键。以此方式形成的引发剂自由基在快速增长反应中与许多其他单体分子加成,直到通过结合或歧化终止聚合物自由基的增长并形成最终的大分子。
通过添加链转移剂,所谓的调节剂,可以以有针对性的方式调节形成的聚合物的数均摩尔质量(参见H.G.Elias,Makromoleküle[Macromolecules],第1卷,第6版,Wiley-VCH,Weinheim等,199,299-352)。已知的链转移剂包括例如形成含硫自由基(thiylradical)的硫醇,其随后通过氢原子转移引发新的聚合链。
根据自由基加成-断裂链转移(AFCT)机理反应的含双键的试剂已被证明作为链转移剂特别有用。作为AFCT试剂,硫化合物如烯丙基硫醚、烯丙基砜、二硫代酯、二硫代氨基甲酸酯、黄原酸酯和三硫代碳酸酯是特别有效的,并且被充分研究(Moad等,Polymer 49,1079-1131(2008))。此外,从受控自由基聚合已知可逆的AFCT试剂(RAFT试剂),例如,二硫代酯、二硫代氨基甲酸酯,三硫代碳酸酯或黄原酸酯(参见例如Moad等,上述引文)。
US2,694,699描述了α-磺酰氧基丙烯酸酯的均聚和共聚。烷基硫醇可作为链调节剂添加。
US5,932,675公开了一种用于通过自由基聚合制备低分子量聚合物的方法,其中通过添加例如α-(叔丁硫基甲基)苯乙烯作为链转移试剂控制分子量。
EP2965741A1公开了含有烯丙基砜作为链转移试剂的可自由基聚合的牙科材料。这些材料的特征在于低聚合收缩应力。
EP3090722A1涉及含有乙烯基磺酸酯作为AFCT试剂的可自由基聚合的牙科材料。这些材料具有窄的玻璃化转变范围并形成均匀的聚合物网络。
已知的AFCT试剂通常是在不完全聚合的情况下可以从固化的材料泄漏出来的低分子量化合物。特别地,它们可以被唾液从固化的牙科材料洗出,从毒理学观点看这是不希望的。
发明内容
本发明的目的是提供适合作为用于自由基反应的链转移试剂的物质,其在聚合后不从固化的材料泄漏出来,并且其特别是不被唾液洗出。
根据本发明,该目的通过通式I的硅烷、通过可以通过这些硅烷的水解缩合获得的聚硅氧烷缩合物、或通过用通式I的硅烷表面改性的填料来实现:
其中
R1是直链或支链的脂族C1-C9烷基、苯基或烷基化苯基,
R2、R3在每种情况下彼此独立地不存在或者是可以被S或O原子中断的直链或支链的脂族C1-C20亚烷基,
R4、R5、R6在每种情况下各自独立地为-Cl、-O-CH3、-O-C2H5、-CH3或-C2H5,
X是CH2或O,
Y不存在,或为O或NR',其中R'为H或C1-5烷基,并且
Z不存在,或为O、NR”、-CO-O-、-CO-NR”-、-O-CO-O-、-O-CO-NR”-或-NR”-CO-NR”-,其中R”是H或C1-5烷基。
基团R2和R3不能同时不存在,并且如果R2或R3不存在,则Z优选也不存在。
烷基化苯基意指被1至5个烷基,优选被1个烷基取代的苯基。C1-10烷基是优选的,且特别是C1-5烷基。
其中变量具有以下含义的式I的化合物是优选的:
R1是-CH3、-C2H5、苯基或甲苯基(H3C-Ph-),特别是对甲苯基,
R2、R3在每种情况下彼此独立地不存在,或为可以被O原子中断的直链脂族C1-C10亚烷基,
R4、R5、R6在每种情况下彼此独立地为-O-CH3或-O-C2H5,
X为CH2或O,
Y不存在或为O,并且
Z不存在,或为O、-CO-O-、-CO-NH-、-O-CO-O-或-O-CO-NH-。
其中变量具有以下含义的式I的硅烷是特别优选的:
R1是-CH3、-C2H5、苯基或甲苯基(H3C-Ph-),特别是对甲苯基,
R2是可以被O原子中断的直链脂族C2-C8亚烷基,
R3不存在或为直链脂族C1-C6亚烷基,
R4、R5、R6在每种情况下彼此独立地为-O-CH3或-O-C2H5,
X是CH2或O,
Y是O,并且
Z不存在,或为-CO-NH-或-O-CO-NH-。
基团R4、R5、R6在所有情况下优选具有相同的含义。
式I仅延伸到与化学价理论相容的那些化合物。基团被一个或多个O原子或S原子中断的指示应理解为意指这些原子在每种情况下都插入基团的碳链中。这些原子因此在两侧均与C原子邻接并且不能在末端。C1自由基不能被中断。
式I的化合物本身在自由基聚合中作为链转移剂是有活性的,并且其作为链调节剂的用途同样也是本发明的主题。它们优选以缩聚物的形式或以填料结合的形式使用。因此当在下文中提及式I的化合物时,也意指聚硅氧烷缩合物和与填料结合的硅烷。
一些式I的聚合转移活性Si化合物是已知的,并且可以根据已知的合成方法容易地制备。因此,含烯丙基砜基团的衍生物(X=CH2)可以通过将碘化合物加成到不饱和衍生物(A)和随后的HI裂解(B)来制备。随后,然后可以通过与合适的硅烷的反应(C)获得根据本发明的式I的聚合转移活性Si化合物,其中保护基团技术任选地应用在初始阶段或中间阶段(Z'=O或NR):
一个具体的实例是:
含有乙烯基砜酯基团的衍生物(X=O)可通过使丙酮酸衍生物与磺酰卤在碱性条件下反应来制备。例如从含有受保护的(G)OH基-OG(G为例如四氢-2H-吡喃:THP)的丙酮酸酯开始(A),在乙烯基砜酯合成之后,保护基团可被裂解掉(cleave off)(B),并且通过与合适的硅烷的进一步反应(C),获得根据本发明的式I的聚合转移活性Si化合物(Z'=O或NR):
一个具体的实例是:
根据本发明的式I的聚合转移活性Si化合物的优选实例是:
可以根据由溶胶-凝胶化学已知的方法,由根据本发明的式I的聚合转移活性Si化合物制备聚硅氧烷缩合物(参见专著:Sol-Gel-Science,C.J.Brinker,G.W.Scherer,Academic Press Inc.,Boston等,1990),其在水中几乎不具有溶解性。缩合物优选通过水解缩合来制备。
在水解缩合中,将一种或多种式I的硅烷,优选一种式I的硅烷,以本体或优选作为有机溶剂中的溶液与化学计量量或过量的水(优选>每摩尔可水解硅烷基团1至10摩尔水)混合,并且使其反应。优选的溶剂是丙酮、乙醇、甲醇、异丙醇、乙酸乙酯、甲基异丁基酮、DMF、THF、二噁烷或其混合物。在溶液中,硅烷优选用0.1至5倍体积的溶剂稀释。水的添加以一批或分批进行,其中水优选在添加之前用有机溶剂稀释。之前提及的溶剂同样优选用于此目的。
水解缩合优选在0至30℃或在所用溶剂的沸点(优选30至140℃)下进行。根据该方法的优选实施方案,反应分两步进行。为此目的,首先将这些组分在0至30℃,优选在室温(20℃)下混合,然后升温至较高温度,优选至30至140℃,以完成反应。然后,优选在20至140℃下将反应混合物进一步搅拌优选1至120小时的时间。在烷氧基硅烷的情况下,甲氧基硅烷的反应比乙氧基硅烷的反应更快地进行。
为加速反应,可以有利地添加合适的催化剂,如酸,例如乙酸或盐酸,或碱,例如氨、胺、NaOH、甲基咪唑或氟化铵。催化剂优选以基于硅烷的量0.001至3.0重量%的量使用。
反应完成后,将溶剂和挥发性组分除去,优选通过真空蒸发除去。溶剂和挥发性组分优选首先在水喷射真空中蒸发掉大部分,然后将残余物进一步在油泵真空中干燥。
可以借助29Si NMR光谱测定除去溶剂和挥发性组分后得到的有机官能聚硅氧烷的缩合度。根据根据本发明的硅烷的缩合度和结构,获得液体或固体缩聚物。基团R4至R6决定所形成的缩合物的结构。因此,在可水解基团(-Cl、-O-CH3和-O-C2H5)与不可水解基团(-CH3和-C2H5)之间造成区别。如果所有的基团R4至R6都是可水解的,则在完全转化时得到交联的缩合物(聚硅氧烷),其可由下式描述:
如果只有两个基团,例如R4和R5是可水解的,则得到可通过下式描述的聚硅氧烷:
这些是直链缩合物。
如果只有一个基团,例如R4是可水解的,则得到根据下式的二硅氧烷:
除了制备聚硅氧烷之外,含有至少一个可水解基团R4至R6的根据本发明的式I的Si化合物还适合用于填料的表面改性。填料的改性可以以本身已知的方式进行(参见例如专著:Silane Coupling Agents,E.P.Pluedemann,第2版,Plenum Press,New York-London1991)。
无机颗粒填料,如优选平均粒度为0.01-15μm的石英和不透射线的钡或锶铝硅酸盐玻璃的粉末,或不透X射线的填料如三氟化镱优选适合作为填料。优选的无机颗粒填料还有基于氧化物的无定形球形纳米颗粒填料,诸如气相二氧化硅、沉淀二氧化硅、ZrO2、ZnO、TiO2,或由SiO2、ZrO2和/或TiO2制成的混合氧化物,优选地具有10至1000纳米的平均粒度。此外,优选的填料是颗粒状的,优选纳米颗粒状氧化钽(V)或硫酸钡以及SiO2与氧化镱(III)或氧化钽(V)的混合氧化物。另外,也可使用纤维填料如纳米纤维、玻璃纤维、聚酰胺或碳纤维。特别优选的填料是钡或锶铝硅酸盐玻璃、由SiO2和ZrO2制成的混合氧化物、氟化镱。
具有至少一个可水解基团R4至R6的式I的硅烷经由其硅烷基与氧化填料表面上的OH基团反应,并因此结合到填料。为了获得最佳的表面改性,优选将填料分散在与一种或多种式I的硅烷,优选地与一种式I的硅烷和水(优选地基于所用硅烷的量1-10摩尔),并且优选还与催化剂(优选地基于所用硅烷的量0.001-2摩尔%)混合并搅拌的有机溶剂中,所述有机溶剂特别优选乙醇、丙酮、异丙醇、甲醇、乙酸乙酯、THF或其混合物。反应优选在0℃至100℃的温度下进行,例如在0℃至室温(20℃)或在升高的温度(30至100℃)下进行。与制备缩合物类似,优选在添加之前用溶剂稀释水,其中为此目的优选上述提及的溶剂。优选的催化剂是酸,例如乙酸或盐酸,碱,例如氨或胺或氟化铵。搅拌反应混合物直至反应完成,优选搅拌1至20小时,例如过夜(约15小时)。随后将表面改性的填料分离出来,优选过滤出来,然后优选用纯溶剂洗涤,随后干燥至恒重。表面改性的程度可以由炽灼残渣或元素碳分析确定。
式I的硅烷、由其获得的聚硅氧烷缩合物和用其表面改性的填料具有有聚合转移活性的烯丙基砜或乙烯基砜酯基团,并且可用于可自由基聚合的单体,且特别是多官能(甲基)丙烯酸酯、其混合物、或多官能(甲基)丙烯酸酯与单(甲基)丙烯酸酯的混合物的聚合,用于监测和控制网络结构。
根据本发明发现,即使式I的硅烷与填料结合或作为缩合物存在,其也能有效地控制聚合。这是令人惊讶的,因为调节分子在反应介质中的移动性通过将它们结合成更大的单元而受到很大限制。
式I的化合物中的聚合转移活性基团产生具有更窄玻璃化转变,即玻璃化转变发生在更窄的温度范围内的聚合物。此外,获得了更均匀的聚合物网络,即其特征在于它们在交联点之间具有更窄的摩尔质量分布的网络。这具有可以通过弛豫(relaxation)过程更好地缓解链张力的优点。相应地,聚合收缩应力也可以在材料固化期间降低,这对于牙科应用,例如,作为填充材料是很大的优点。
式I的硅烷具有可自由基聚合的双键,式I的硅烷可通过该可自由基聚合的双键与可自由基聚合的单体反应,结果它们在固化期间结合到聚合物网络中。而且,缩合物和表面改性的填料实际上不溶于水,结果它们不会例如被唾液从固化材料洗出。
式I的硅烷优选以其缩合物的形式和以填料结合形式使用。然而,它们也可以本身用于制备可自由基聚合的材料。在这种情况下,硅烷基团使得与存在的填料原位结合成为可能。
根据本发明的硅烷、缩合物和填料适合用于制备例如用于技术应用,用于生产例如用于手术或眼科学,和特别用于制备牙科材料的医疗装置的聚合物、塑料、热固性塑料和复合材料/复合物。
为了此目的,式I的硅烷,且特别是其缩合物或用其表面改性的填料可以与不同类型的可自由基聚合的单体组合。特别优选的是含有至少一种单官能或多官能(甲基)丙烯酸酯作为可自由基聚合单体的材料。单官能(甲基)丙烯酸酯意指具有一个可自由基聚合基团的化合物,多官能(甲基)丙烯酸酯意指具有两个或更多个,优选2至4个可自由基聚合基团的化合物。根据非常特别优选的实施方案,根据本发明的组合物含有至少一种二甲基丙烯酸酯或单甲基丙烯酸酯和二甲基丙烯酸酯的混合物。含有单官能和多官能(甲基)丙烯酸酯作为可自由基聚合单体的材料特别适合作为牙科材料,其中对于口腔内固化的材料,甲基丙烯酸酯是优选的。
特别合适的单官能或多官能(甲基)丙烯酸酯的实例是(甲基)丙烯酸甲酯,(甲基)丙烯酸乙酯,(甲基)丙烯酸2-羟乙酯,(甲基)丙烯酸丁酯,(甲基)丙烯酸苄酯,(甲基)丙烯酸四氢糠酯或(甲基)丙烯酸异冰片酯,对枯基苯氧基乙二醇甲基丙烯酸酯(CMP-1E),双酚A二(甲基)丙烯酸酯,双-G(M)A((甲基)丙烯酸和双酚A二缩水甘油醚的加成产物),乙氧基化或丙氧基化的双酚A二(甲基)丙烯酸酯,例如具有3个乙氧基的双酚A二甲基丙烯酸酯SR-348c(Sartomer)或2,2-双[4-(2-(甲基)丙烯酰氧基丙氧基)苯基]丙烷,UD(M)A((甲基)丙烯酸2-羟乙酯和2,2,4-三甲基六亚甲基二异氰酸酯的加成产物),二-、三-或四甘醇二(甲基)丙烯酸酯,三羟甲基丙烷三(甲基)丙烯酸酯,季戊四醇四(甲基)丙烯酸酯,以及甘油二-和三(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(D3MA)或1,12-十二烷二醇二(甲基)丙烯酸酯。
另外,根据本发明的材料优选还含有至少一种用于自由基聚合的引发剂。为了引发自由基光聚合反应,优选使用二苯甲酮、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。樟脑醌(CQ)和2,2-二甲氧基-2-苯基-苯乙酮是特别优选使用的,并且非常特别优选使用α-二酮与作为还原剂的胺的组合,所述胺诸如4-(二甲基氨基)-苯甲酸乙酯(EDMAB)、甲基丙烯酸N,N-二甲基氨基乙酯、N,N-二甲基-间二甲苯胺(N,N-dimethyl-sym.-xylidine)或三乙醇胺。Norrish I型光引发剂也是合适的,优选双酰基氧化膦、单酰基三烷基锗化合物或二酰基二烷基锗化合物,例如苯甲酰基三甲基锗、二苯甲酰基二乙基锗或双(4-甲氧基苯甲酰基)二乙基锗(MBDEGe)的酰基。也可以有利地使用不同光引发剂的混合物,例如,双(4-甲氧基苯甲酰基)二乙基锗与樟脑醌和4-二甲基氨基苯甲酸乙酯的组合。
为了引发自由基聚合,偶氮化合物如2,2'-偶氮双(异丁腈)(AIBN)或偶氮双(4-氰基戊酸),或过氧化物如过氧化二苯甲酰、过氧化二月桂酰、过辛酸叔丁酯、过苯甲酸叔丁酯或二(叔丁基)过氧化物是特别合适的。为了借助过氧化物加速引发,也可以使用与芳族胺的组合。优选的氧化还原体系是过氧化苯甲酰与胺,如N,N-二甲基-对甲苯胺、N,N-二羟乙基-对甲苯胺、对-二甲基氨基苯甲酸乙酯或结构相关体系的组合。另外,由过氧化物和还原剂,如抗坏血酸、巴比妥酸盐或亚磺酸组成的氧化还原体系,或者氢过氧化物与还原剂和催化金属离子的组合,例如氢过氧化枯烯、硫脲衍生物和乙酰丙酮铜(II)的混合物也适合用于双重固化。
根据优选的实施方案,根据本发明的材料另外含有有机颗粒填料或优选含有无机颗粒填料,特别优选含有一种或多种无机颗粒填料。含有单体和填料的混合物被称为复合材料。
粒度为0.010至15μm的基于氧化物,如SiO2、ZrO2和TiO2,或由SiO2、ZrO2、ZnO和/或TiO2制成的混合氧化物的填料,粒度为10至300纳米的纳米颗粒或微细填料,如气相二氧化硅或沉淀二氧化硅,以及粒度为0.01-15μm,优选0.2至1.5μm的玻璃粉末,如石英、玻璃陶瓷或例如钡或锶铝硅酸盐玻璃的不透X射线的玻璃粉末,以及粒度为0.2至5μm的不透X射线的填料,如三氟化镱、氧化钽(V)、硫酸钡或SiO2与氧化镱(III)或氧化钽(V)的混合氧化物是特别合适的。也可以使用纤维填料,如纳米纤维或晶须。
除非另有说明,否则本文中的所有粒度均为重均粒度。
根据粒度将填料分成大填料(macrofiller)和微填料(microfiller)。通过研磨石英、不透X射线的玻璃、硼硅酸盐或陶瓷获得大填料,其具有纯无机性质,并且主要由碎片状颗粒组成。平均粒度为0.2至10微米的大填料是优选的。气相SiO2或沉淀二氧化硅优选用作微填料,或者也可以用混合氧化物,例如SiO2-ZrO2,其可以通过金属醇盐的水解共缩合获得。微填料优选具有约5至100nm的平均粒度。
为了改善填料颗粒与交联聚合基质之间的结合,可以用(甲基)丙烯酸酯官能化的硅烷对SiO2基填料进行表面改性。这种硅烷的实例是3-(甲基)丙烯酰氧基丙基三甲氧基硅烷。为了表面改性非硅酸盐填料,例如ZrO2或TiO2的非硅酸盐填料,也可以使用官能化的酸性磷酸酯,例如10-(甲基)丙烯酰氧基癸基磷酸二氢酯。
任选地,根据本发明使用的组合物可以含有其他添加剂,尤其是稳定剂、染料、杀微生物活性成分、释放氟离子的添加剂、膨胀剂、光亮剂、增塑剂或UV吸收剂。
根据本发明的材料优选包含以下组分:
(a)1至50重量%,优选2至40重量%,且特别优选3至30重量%的至少一种式I的硅烷,优选至少一种通式(I)的一种或多种硅烷的缩合物和/或至少一种用至少一种式I的硅烷表面改性的填料,
(b)0.01-5重量%,优选0.1-5重量%,且特别优选1.0-3.0重量%的至少一种用于自由基聚合的引发剂,
(c)5至80重量%,优选10至60重量%,且特别优选10至50重量%的至少一种可自由基聚合的单体。
另外,材料优选还包含
(d)1-80重量%的至少一种与组分(a)不同的填料。
填充水平符合材料的期望的预期用途。填充复合材料优选具有50-80重量%的填料含量和10-70重量%的复合粘固剂。当式(I)的填料结合的硅烷用作组分(a)时,这些量涉及(a)和(d)的总量。
另外,这些材料可以有利地包含
(e)0至5重量%,优选0至3重量%,且特别优选0.2至3重量%的(多种)添加剂。
除非另有说明,否则本文中的所有量均与材料的总质量有关。在每种情况下可以分别选择优选的量范围。
特别优选由提及的组分组成的材料。此外,优选其中各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。此外,特别优选除了式I的硅烷、基于其的缩合物或用其表面改性的填料之外不包含其他链调节剂的材料。
根据本发明的材料特别适合作为牙科材料,特别是作为牙科粘固剂、填充复合材料和饰面材料以及用于制造假牙、义齿、嵌体、高嵌体、齿冠和齿桥的材料。它们的特征在于,在固化之后,式I的硅烷一方面通过可自由基聚合的基团结合到聚合物网络中,并且另一方面通过硅烷基团结合到填料或整合到缩合物中,结果硅烷不会从固化的材料泄漏出来,并且特别是在与唾液接触时不被洗出。另外,该材料具有降低的聚合收缩应力(PSS)和改善的冲击强度。
牙科材料主要适合用于由牙科医生口腔内施用以修复损坏的牙齿,即用于治疗性应用,例如作为牙科粘固剂、填充复合材料和饰面材料。然而,它们也可以在口外使用,例如用于制备或修复牙科修复体,如假牙、义齿、嵌体、高嵌体、齿冠和齿桥。
本发明的另一主题是可通过根据本发明的牙科材料的聚合获得的均聚物和共聚物。例如,可以使用切割工艺来加工这种类型的聚合物,以形成假牙或义齿。它们优选以圆柱形或盘形坯料形式获得。
此外,根据本发明的材料还适合添加用于制备成型体,所述成型体可以例如通过铸造、压缩成型或3D打印制备。改善的冲击强度特别地使这些材料达到与普通热塑性塑料相同的水平。另外,固化中的小延迟对于3D打印是有利的。因此,根据本发明的材料可以通过立体光固化成型或3D打印非常好地加工。
此外,本发明涉及式I的硅烷、其缩合物和用其表面改性的填料作为自由基聚合中的链转移剂,或用于监测或控制自由基聚合,特别是(甲基)丙烯酸酯的自由基聚合中的网络结构的用途。
下面参照实施例更详细地解释本发明。
具体实施方式
实施例1:
硅烷2-(甲苯-4-磺酰氧基)-丙烯酸2-[N-(3-三乙氧基甲硅烷基)-丙基氨基甲酰
氧基乙基]酯的合成
第一阶段:丙酮酸2-(四氢吡喃-2-基氧基)-乙酯
将丙酮酸(17.61g,0.20mol)、2-(四氢-2H-吡喃-2-基氧基)乙醇(29.24g,0.20mol)和N,N-二甲基氨基吡啶(0.60g,5.0mmol)的二氯甲烷(200ml)溶液在-5℃下分批与N,N'-二环己基碳二亚胺(45.39g,0.22mol)混合。在-5℃下搅拌悬浮液2小时,然后在环境温度下搅拌。20小时后,用正庚烷(200ml)稀释反应混合物并通过硅胶过滤。在旋转蒸发器中浓缩滤液,并借助柱色谱(SiO2,正庚烷/乙酸乙酯2:1)纯化粗产物。得到32.78g(0.152mol;76%)的淡黄色液体。
1H-NMR(CDCl3,400MHz):δ=1.47–1.65(m,4H;CH2-CH2-CH2),1.66–1.87(m,2H;CH2-CH2-CH2),2.48(s,3H;CH3),3.48–3.56(m,1H;O-CH2),3.70–3.78(m,1H;O-CH2),3.81–3.89(m,1H;O-CH2),3.95–4.02(m,1H;O-CH2),4.38–4.49(m,2H;COO-CH2),4.66(t,1H;J=3.3Hz;O-CH-O)。
13C-NMR(CDCl3,100.6MHz):δ=19.0(CH2),25.2(CH2),26.6(CH3),30.2(CH2),61.9(O-CH2),64.4(O-CH2),65.2(O-CH2),98.5(O-CH-O),160.6(C=O),191.4(C=O)。
IR(纯):2943(w),2872(w),1730(vs),1442(w),1385(w),1357(w),1299(m),1202(w),1184(w),1124(vs),1077(s),1033(s),1020(s),907(w),894(w),871(m),813(m),718(w)cm-1。
C10H16O5分析计算值:C,55.55;H,7.46。实测值:C,55.89;H,7.25。
第二阶段:2-(甲苯-4-磺酰氧基)-丙烯酸2-(四氢吡喃-2-基氧基)-乙酯
向丙酮酸2-(四氢吡喃-2-基氧基)-乙酯(32.58g,0.151mol)、对甲苯磺酰氯(28.72g,0.151mol)和N,N-二甲基氨基吡啶(0.90g,7.5mmol)的二氯甲烷(250ml)溶液滴加三乙胺(27.45g,0.271mol)。将反应混合物在环境温度下搅拌20小时,用水(3×100ml)和饱和NaCl水溶液(100ml)洗涤,用无水硫酸钠干燥,过滤并在旋转蒸发器中浓缩。借助柱色谱法(SiO2,正庚烷/乙酸乙酯4:1)纯化粗产物。得到24.26g(65.5mmol;43%)的淡黄色油状物。
1H-NMR(CDCl3,400MHz):δ=1.47–1.86(m,6H;CH2-CH2-CH2),2.46(s,3H;CH3),3.48–3.55(m,1H;O-CH2),3.59–3.65(m,1H;O-CH2),3.83–3.91(m,2H;O-CH2),4.22–4.33(m,2H;O-CH2),4.63(t,1H;J=3.3Hz;O-CH-O),5.64(d,1H;J=2.2Hz;=CH),6.16(d,1H;J=2.2Hz;=CH),7.36(d,2H;J=8.2Hz;Ar-H),8.85(d,2H;J=8.2Hz;Ar-H)。
13C-NMR(CDCl3,100.6MHz):δ=19.1(CH2),21.6(CH3),25.2(CH2),30.3(CH2),61.9(O-CH2),64.5(O-CH2),64.9(O-CH2),98.6(O-CH-O),117.0(=CH2),128.5(Ar-CH),129.6(Ar-CH),132.4(Ar-C),142.9(=C),145.5(Ar-C),160.8(C=O)。
IR(纯):2943(w),2871(w),1736(m),1639(w),1597(w),1494(w),1453(w),1378(m),1295(m),1194(s),1179(s),1151(s),1125(vs),1091(s),1078(s),1035(m),1019(m),985(m),958(s),905(m),872(m),814(s),780(m),711(vs),696(s),661(s)cm-1。
C17H22O7S分析计算值:C,55.12;H,5.99;S,8.66。实测值:C,55.73;H,6.06;S,8.39。
第三阶段:2-(甲苯-4-磺酰氧基)-丙烯酸2-羟乙酯
将2-(甲苯-4-磺酰氧基)-丙烯酸2-(四氢吡喃-2-基氧基)-乙酯(24.16g,65.2mmol)的甲醇(250ml)溶液与15氢型(10.0g)混合,并在环境温度下搅拌。20小时后,过滤反应混合物并在旋转蒸发器中浓缩滤液。借助柱色谱法(SiO2,二氯甲烷/乙酸乙酯4:1)纯化粗产物。得到10.57g(36.9mmol;57%)的淡黄色油状物。
1H-NMR(CDCl3,400MHz):δ=2.46(s,3H;CH3),2.76(t,1H;J=6.5Hz;OH),3.78–3.84(m,2H;O-CH2),4.25–4.30(m,2H;O-CH2),5.50(d,1H;J=2.3Hz;=CH),6.18(d,1H;J=2.3Hz;=CH),7.37(d,2H;J=8.2Hz;Ar-H),8.83(d,2H;J=8.2Hz;Ar-H)。
13C-NMR(CDCl3,100.6MHz):δ=21.6(CH3),60.3(O-CH2),67.4(O-CH2),117.5(=CH2),128.3(Ar-CH),129.8(Ar-CH),132.0(Ar-C),142.9(=C),145.8(Ar-C),161.0(C=O)。
IR(纯):3545(br w),1735(s),1639(m),1596(m),1494(w),1373(s),1294(s),1194(s),1178(s),1144(vs),1089(s),1018(w),956(s),918(m),877(m),815(s),781(s)710(vs),695(s),660(s)cm-1。
C12H14O6S分析计算值:C,50.34;H,4.93;S,11.20。实测值:C,50.37;H,4.97;S,11.09。
第4阶段:2-(甲苯-4-磺酰氧基)-丙烯酸2-[N-(3-三乙氧基甲硅烷基)-丙基氨基甲酰氧基乙基]酯
向2-(甲苯-4-磺酰氧基)-丙烯酸2-羟乙酯(10.47g,36.6mmol)和二月桂酸二丁基锡(0.13g,0.2mmol)的丙酮(20ml)溶液滴加3-(三乙氧基甲硅烷基)丙基异氰酸酯(9.04g,36.6mmol)。将反应溶液在环境温度下搅拌,并且在24小时后,在旋转蒸发器中浓缩。借助柱色谱法(SiO2,正庚烷/乙酸乙酯1:1)纯化粗产物。得到11.56g(21.1mmol;58%)的淡黄色油状物。
1H-NMR(CDCl3,400MHz):δ=0.58–0.68(m,2H;Si-CH2),1.22(t,9H;J=7.0Hz;CH2-CH 3),1.57–1.68(m,2H;CH2-CH 2-CH2),2.46(s,3H;CH3),3.11–3.22(m,2H;O-CH2),3.82(q,6H;J=7.0Hz;CH 2-CH3),4.17–4.24(m,2H;O-CH2),4.25–4.32(m,2H;O-CH2),5.15–5.30(m,1H;NH),5.65(d,1H;J=2.5Hz;=CH),6.15(d,1H;J=2.5Hz;=CH),7.37(d,2H;J=8.4Hz;Ar-H),8.84(d,2H;J=8.4Hz;Ar-H)。
13C-NMR(CDCl3,100.6MHz):δ=7.4(Si-CH2),18.0(CH3),21.5(CH3),23.0(CH2),43.2(CH2),58.2(O-CH2),61.6(O-CH2),63.9(O-CH2),117.3(=CH2),128.3(Ar-CH),129.6(Ar-CH),132.3(Ar-C),142.6(=C),145.5(Ar-C),155.8(C=O),160.5(C=O)。
29Si-NMR(CDCl3,79.5MHz):δ=-45.7。
IR(纯):3339(br w),2974(w),2928(w),2887(w),2928(w),1727(s),1639(w),1597(w),1524(w),1444(w),1380(m),1296(m),1241(m),1180(s),1195(s),1156(s),1076(vs),957(s),815(m),779(m),713(m),696(w),663(w)cm-1。
C22H35NO10SSi分析计算值:C,49.51;H,6.61;N,2.62;S,6.01。实测值:C,50.44;H,6.72;N,2.95;S,5.80。
实施例2:
2-(甲苯-4-磺酰氧基)-丙烯酸2-[N-(3-三乙氧基甲硅烷基)-丙基氨基甲酰氧基
乙基]酯的水解缩合
将2-(甲苯-4-磺酰氧基)-丙烯酸2-[N-(3-三乙氧基甲硅烷基)-丙基氨基甲酰氧基乙基]酯(5.34g,10.0mmol)的乙醇(48.0g)溶液与盐酸(0.5M,0.54g,55.8mmol)混合,并在室温下搅拌72小时。除去溶剂并将残余物在60℃下在高真空下干燥。得到4.09g(9.6mmol;96%)不溶于水的高度粘稠的淡黄色油状物。
1H-NMR(CDCl3,400MHz):δ=0.50–0.77(m,2H;Si-CH2),1.50–1.73(m,2H;CH2-CH 2-CH2),2.45(s,3H;CH3),3.03–3.24(m,2H;O-CH2),4.15–4.38(m,4H;O-CH2),5.49–5.54(m,1H;=CH),6.06-6.18(m,1H;=CH),7.34(d,2H;J=7.8Hz;Ar-H),7.82(d,2H;J=7.8Hz;Ar-H)。
实施例3:
硅烷3-(三乙氧基甲硅烷基)-丙基-2-(甲苯磺酰基甲基)丙烯酸酯的合成
在氮气下,将二异丙基乙胺(23.4ml,0.134mol)滴加到2-(甲苯磺酰基甲基)丙烯酸(29.36g,0.122mol)和(3-碘丙基)三乙氧基硅烷(40.60g,0.122mol)的无水乙腈(200ml)溶液。将反应混合物在80℃下搅拌24小时,然后真空浓缩。加入乙醚(200ml)后,盐析出,将其滤出。将剩余的滤液减压浓缩,并借助柱色谱法(洗脱剂=乙酸乙酯/庚烷:1/1)纯化残余物。得到34.04g(产率63%)的无色油状物。
1H NMR(CDCl3,400MHz):δ=0.53-0.62(m,2H,CH2Si);1.21(t,3JHH=7.0Hz,9H,OCH2 CH 3);1.61-1.71(m,2H,CH 2CH2Si);2.42(s,3H,CArCH3);3.80(q,3JHH=7.0Hz,6H,OCH 2CH3);3.92(t,3JHH=6.9Hz,2H,CH2OCO);4.11(s,2H,CH2S);5.87(s,1H,C=CH2);6.47(s,1H,C=CH2);7.28-7.33(m,2H,CHAr);7.68-7.73(m,2H,CHAr)。13C NMR(CDCl3,101MHz):δ=6.5(CH2Si);18.3(OCH2 CH3);21.6(CAr CH3);22.0(CH2CH2Si);57.5(CH2S);58.4(OCH2CH3);67.5(CH2OCO);128.7(CHAr);129.2(C=CH2);129.6(CHAr);133.1(C=CH2);135.5(CAr);144.9(CAr);164.8(C=O)。29Si NMR(CDCl3,79MHz):-46.2。
实施例4:
3-(三乙氧基甲硅烷基)-丙基-2-(甲苯磺酰基甲基)丙烯酸酯的水解缩合
将3-(三乙氧基甲硅烷基)-丙基-2-(甲苯磺酰基甲基)丙烯酸酯(8.91g,20.0mmol)的乙醇(110ml)溶液与盐酸(0.55M,1.07g,60mmol)混合并在环境温度下搅拌72小时。除去溶剂并将残余物在60℃下在高真空下干燥。得到6.35g(95%产率)不溶于水的高度粘稠的淡黄色油状物。
1H-NMR(CDCl3,400MHz):δ=0.68–0.77(m,2H;Si-CH2),1.61–1.74(m,2H;CH2-CH 2-CH2),2.43(s,3H;CH3),3.79–3.82(m,2H;O-CH2),4.04–4.12(m,4H;SO2-O-CH2),5.73–5.83(m,1H;=CH),6.46(s,1H;=CH),7.32(d,2H;Ar-H),7.72(d,2H;Ar-H)。
实施例5:
用来自实施例3的硅烷3-(三乙氧基甲硅烷基)-丙基-2-(甲苯磺酰基甲基)丙烯酸
酯对气相二氧化硅进行硅烷化
向10.0g气相二氧化硅(比表面积35-65m2/g,OX50,Evonik)的100ml环己烷悬浮液缓慢滴加2.31g(5.20mmol)的3-(三乙氧基甲硅烷基)-丙基-2-(甲苯磺酰基甲基)丙烯酸酯,然后缓慢滴加0.332g(5.61mmol)正丙胺。将悬浮液在20℃下搅拌24小时,然后以3000rpm离心。倾析出环己烷后,将沉淀再用环己烷洗涤两次,并在每种情况下进行离心。所得的固体在旋转蒸发器中在40℃/0.1mbar下干燥48小时,然后过筛(90μm)。得到7.08g不溶于水的白色粉末(灼烧残渣:90.6%,空白值OX50:99.1%)。
实施例6:
具有来自实施例2的缩合物的甲基丙烯酸酯树脂的制备和光聚合
制备氨基甲酸酯二甲基丙烯酸酯RM-3(2mol甲基丙烯酸2-羟乙酯和1mol 2,2,4-三甲基六亚甲基二异氰酸酯的加成产物)与三乙二醇二甲基丙烯酸酯(TEGDMA)的重量比为1:2的混合物。向其加入0.3重量%的(双(4-甲氧基苯甲酰基)二乙基锗,Ivoclar Vivadent AG)和5.0重量%的AFCT试剂作为光引发剂。使用来自实施例2的缩合物作为AFCT试剂,并且使用2-(甲苯-4-磺酰氧基)丙烯酸乙酯TSAEE作为参照乙烯基砜酯。由光聚合树脂制备相应的测试片,其用牙科光源(Ivoclar Vivadent AG)照射2次,持续3分钟,并由此固化。在将测试片储存在水中24小时后根据ISO标准ISO-4049(牙科-基于聚合物的填充、修复和粘结材料)进行挠曲强度和挠曲弹性模量的测定。当使用作为缩合物的AFCT试剂时,显示出机械性能的改善(参见表1)。
表1:光聚合物性质
光聚合物 | 挠曲强度(MPa) | 挠曲弹性模量(GPa) |
A(不含AFCT试剂)* | 81.0 | 1.82 |
B(含实施例2的缩合物) | 91.5 | 2.07 |
C(含TSAEE)* | 83.9 | 1.91 |
*对比例
另外,将测试片在研钵中研磨,并将粉末形式的聚合物分散在乙醇水溶液(50体积%乙醇)中。搅拌72小时后,分离出固体部分,并借助HPLC检验液体残余物。结果表明,部分AFCT试剂TSAEE可以从参照聚合物C洗出,而在样品B的洗脱液中不能检测到AFCT试剂。
实施例7:
具有来自实施例4的缩合物的甲基丙烯酸酯树脂的制备和光聚合
制备重量比为1:2的氨基甲酸酯二甲基丙烯酸酯RM-3和TEGDMA的混合物。向其加入0.3重量%的和5重量%的AFCT试剂作为光引发剂。使用来自实施例4的缩合物作为AFCT试剂,并且使用2-(甲苯-4-磺酰基甲基)丙烯酸乙酯TSMAEE作为参照烯丙基砜。由光聚合树脂制备相应的测试片,其用牙科光源(Ivoclar Vivadent AG)照射2次,持续3分钟并由此固化。在将测试件储存在水中24小时后根据ISO标准ISO-4049(牙科-基于聚合物的填充、修复和粘结材料)进行挠曲强度和挠曲弹性模量的测定。
表2:光聚合物性质
光聚合物 | 挠曲强度(MPa) | 挠曲弹性模量(GPa) |
D(不含AFCT试剂)* | 81.0 | 1.82 |
E(含实施例4的缩合物) | 84.7 | 1.90 |
F(含TSMAEE)* | 73.0 | 1.68 |
*对比例
这里同样地,当使用作为缩合物的AFCT试剂时,显示出机械性能的改善(参见表2)。
另外,将测试片在研钵中研磨,并将粉末形式的聚合物分散在乙醇水溶液(50体积%乙醇)中。搅拌72小时后,分离出固体部分并借助HPLC检验液体残余物。结果表明,部分AFCT试剂TSAEE可以从参照聚合物F洗出,而在样品E的洗脱液中不能检测到AFCT试剂。
Claims (32)
1.一种根据通式I的可自由基聚合的硅烷:
其中:
R1是直链或支链的脂族C1-C9烷基、苯基或烷基化苯基,
R2、R3在每种情况下彼此独立地不存在,或者是可被S或O原子中断的直链或支链的脂族C1-C20亚烷基,
R4、R5、R6在每种情况下彼此独立地为-Cl、-O-CH3、-O-C2H5、-CH3或-C2H5,并且R4、R5和R6的至少一个是可水解基团,
X是CH2或O,
Y不存在,或为O或NR',其中R'为H或C1-5烷基,并且
Z不存在,或为O、NR”、-CO-O-、-CO-NR”-、-O-CO-O-、-O-CO-NR”-或-NR”-CO-NR”-,其中R”是H或C1-5烷基,
并且其中基团R2和R3不能同时不存在,并且如果R2或R3不存在,则Z不存在。
2.根据权利要求1所述的可自由基聚合的硅烷,其中
R1是-CH3、-C2H5、苯基或甲苯基,
R2、R3在每种情况下彼此独立地不存在,或为可被O原子中断的直链脂族C1-C10亚烷基,
R4、R5、R6在每种情况下彼此独立地为-O-CH3或-O-C2H5,
X为CH2或O,
Y不存在或为O,并且
Z不存在或为O、-CO-O-、-CO-NH-、-O-CO-O-或-O-CO-NH-。
3.根据权利要求1所述的可自由基聚合的硅烷,其中
R1是-CH3、-C2H5、苯基或甲苯基,
R2是可被O原子中断的直链脂族C2-C8亚烷基,
R3不存在或为直链脂族C1-C6亚烷基,
R4、R5、R6在每种情况下彼此独立地为-O-CH3或-O-C2H5,
X是CH2或O,
Y是O,并且
Z不存在,或为-CO-NH-或-O-CO-NH-。
4.一种用于制备聚硅氧烷缩合物的方法,其中将至少一种根据权利要求1至3中一项所述的硅烷与化学计量量或过量的水混合,然后使混合物反应。
5.根据权利要求4所述的方法,其中首先将所述硅烷溶于有机溶剂中,然后将溶液与水或水和有机溶剂的混合物混合,然后使混合物在范围为0℃至140℃的温度下反应,随后除去溶剂和挥发性组分。
6.根据权利要求4或5所述的方法,其中将所述混合物另外与催化剂混合。
7.根据权利要求6所述的方法,其中所述催化剂为酸。
8.根据权利要求7所述的方法,其中所述酸为乙酸或盐酸。
9.根据权利要求6所述的方法,其中所述催化剂为碱。
10.根据权利要求9所述的方法,其中所述碱为氨、胺、NaOH或氟化铵。
11.根据权利要求9所述的方法,其中所述碱为甲基咪唑。
12.一种用于制备表面改性填料的方法,其中将填料分散在有机溶剂中,将分散体与至少一种根据权利要求1至3中一项所述的硅烷、水和任选的催化剂混合并搅拌,随后将填料与溶剂分离。
13.根据权利要求12所述的方法,其中将以下用作填料:无机颗粒填料;不透X射线的填料;基于氧化物的无定形球形填料;颗粒状氧化钽(V),硫酸钡,或SiO2与氧化镱(III)或氧化钽(V)的混合氧化物;纤维填料。
14.根据权利要求13所述的方法,其中所述无机颗粒填料为石英粉末、钡或锶铝硅酸盐玻璃粉末。
15.根据权利要求13所述的方法,其中所述不透X射线的填料为三氟化镱。
16.根据权利要求13所述的方法,其中所述基于氧化物的无定形球形填料为气相二氧化硅,沉淀二氧化硅,ZrO2,ZnO,TiO2,或SiO2、ZrO2和/或TiO2的混合氧化物。
17.根据权利要求13所述的方法,其中所述纤维填料为纳米纤维、玻璃纤维、聚酰胺或碳纤维。
18.根据权利要求12至17中任一项所述的方法,其中将混合物在范围为0至100℃的温度下搅拌1至20小时。
19.一种聚硅氧烷缩合物,其根据权利要求4至11中任一项所述的方法获得。
20.一种表面改性填料,其根据权利要求12至18中任一项所述的方法获得。
21.一种牙科材料,其特征在于其包含根据权利要求1至3中任一项所述的硅烷、根据权利要求19所述的聚硅氧烷缩合物和/或根据权利要求20所述的表面改性填料。
22.根据权利要求21所述的牙科材料,其在每种情况下基于所述材料的总质量包含:
(a)1至50重量%的至少一种式I的硅烷;至少一种根据权利要求19所述的聚硅氧烷缩合物和/或至少一种根据权利要求20所述的表面改性填料,
(b)0.01至5重量%的至少一种用于自由基聚合的引发剂,和
(c)5至80重量%的至少一种可自由基聚合的单体。
23.根据权利要求22所述的牙科材料,其在每种情况下基于所述材料的总质量包含2至40重量%的至少一种式I的硅烷。
24.根据权利要求22所述的牙科材料,其在每种情况下基于所述材料的总质量包含3至30重量%的至少一种式I的硅烷。
25.根据权利要求22所述的牙科材料,其在每种情况下基于所述材料的总质量包含0.1至5重量%的至少一种用于自由基聚合的引发剂。
26.根据权利要求22所述的牙科材料,其在每种情况下基于所述材料的总质量包含1.0至3.0重量%的至少一种用于自由基聚合的引发剂。
27.根据权利要求22所述的牙科材料,其在每种情况下基于所述材料的总质量包含10至60重量%的至少一种可自由基聚合的单体。
28.根据权利要求22所述的牙科材料,其在每种情况下基于所述材料的总质量包含10至50重量%的至少一种可自由基聚合的单体。
29.根据权利要求22至28中任一项所述的牙科材料,其另外包含:
(d)1-80重量%的填料。
30.根据权利要求22至28中任一项所述的牙科材料,其另外包含:
(d)10-70重量%的填料。
31.根据权利要求22至28中任一项所述的牙科材料,其另外包含:
(d)50-80重量%的填料。
32.根据权利要求1至3中一项所述的硅烷、根据权利要求19所述的聚硅氧烷缩合物或根据权利要求20所述的表面改性填料用于制备牙科材料的用途。
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WO2016005540A1 (de) * | 2014-07-11 | 2016-01-14 | Ivoclar Vivadent Ag | Dentalmaterialien mit debonding-on-demand eigenschaften |
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EP3424983B1 (de) | 2019-10-23 |
JP2019014887A (ja) | 2019-01-31 |
JP7094165B2 (ja) | 2022-07-01 |
US20190010172A1 (en) | 2019-01-10 |
CN109206540A (zh) | 2019-01-15 |
EP3424983A1 (de) | 2019-01-09 |
ES2767850T3 (es) | 2020-06-18 |
US10781223B2 (en) | 2020-09-22 |
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