EP1200038A1 - Siloxanhaltige makromonomere sowie dentalzusammensetzungen daraus - Google Patents

Siloxanhaltige makromonomere sowie dentalzusammensetzungen daraus

Info

Publication number
EP1200038A1
EP1200038A1 EP00950725A EP00950725A EP1200038A1 EP 1200038 A1 EP1200038 A1 EP 1200038A1 EP 00950725 A EP00950725 A EP 00950725A EP 00950725 A EP00950725 A EP 00950725A EP 1200038 A1 EP1200038 A1 EP 1200038A1
Authority
EP
European Patent Office
Prior art keywords
substituted
unsubstituted
macromonomer
group
macromonomers
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.)
Withdrawn
Application number
EP00950725A
Other languages
English (en)
French (fr)
Inventor
Joachim E. Klee
Uwe Walz
Jürgen Fiedler
Rolf Mülhaupt
Holger Frey
Ekkehardt MÜH
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dentsply Sirona Inc
Original Assignee
Dentsply International Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dentsply International Inc filed Critical Dentsply International Inc
Publication of EP1200038A1 publication Critical patent/EP1200038A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • 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
    • 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
    • A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A61K6/896—Polyorganosilicon compounds

Definitions

  • volumetric shrinkage is influenced by two different effects firstly, during polymerization the van der Waals distance of the monomers are replaced by covalent bonds and secondly, the packing density of the polymers increases in comparison to that of the monomers There are several possibilities to reduce the volumetric shrinkage
  • An aim of the invention was to reduce shrinkage by partial or complete replacement of low-molecular polymenzable monomers by the novel siloxane comprising macromonomers.
  • the invention concerns macromonomers of a molecular weight of at least M 500 g/mol containing at least one siloxane group that are described by the following generally formula wherein
  • A is a polymenzable moiety, preferably an olefinic double bond, most preferably acrylate or methacrylate
  • R is an C, to C 18 oxyalkyl, a C 5 to C 18 oxycycloalkyl or a C 5 to C 15 oxyaryiene
  • C, to C 18 alkyl, a C 5 to C 18 cycloalkyl or a C 5 to C 15 arylor heteroaryl X is N or a substituted or unsubstituted C, to C 18 alkylene, a C, to C 18 oxyalkylene or C, to C 18 carboxyalkylene Y is an C 1 to C 18 alkylene, C-, to C 18 oxyalkylene or an urethane -O-CO-NH- linking moiety
  • Z is an d to C 18 alkylene, a C 5 to C 18 cycloalkylene or a C 5 to C 15 arylene or heteroarylene, n is an integer.
  • the dental/medical composite is usable as a dental restorative material for filling and restoring teeth, making inlays and onlays, as core buildup materials, for artificial teeth, for sealing and coating materials, usable as temporary crown and bridge material
  • R is a residue derived from a diepoxide, notably a residue of the following formula
  • X is C(CH 3 ) 2 , -CH 2 -, -0-, -S-, -CO-, -S0 2 -
  • R denotes hydrogen or a substituted or unsubstituted C, to C 18 alkyl, C 5 to C 18 substituted or unsubstituted cycloalkyl, substituted or unsubstituted C 5 to C 18 aryl or heteroaryl,
  • R 2 is a difunctional substituted or unsubstituted C, to C 18 alkylene, C 2 to C 12 alkenyl, C 5 to C 18 substituted or unsubstituted cycloalkylene, C 5 to C 18 arylene or heteroarylene,
  • R 3 denotes a substituted or unsubstituted C to C 18 alkyl, C 2 to C 12 alkenyl, C 5 to C 18 substituted or unsubstituted cycloalkyl, C 6 to C 12 aryl or C 7 to C 12 aralkyl, or a siloxane moiety I, II or III
  • R 5 is a difunctional substituted or unsubstituted C, to C 18 alkylene, C 2 to C, 2 alkenyl, C 5 to C 18 substituted or unsubstituted cycloalkylene, C 5 to C 18 arylene or heteroaryiene, preferably CH 2 CH 2 CH 2 ,
  • R 6 denotes a substituted or unsubstituted C, to C 18 alkyl, C 2 to C 12 alkenyl, substituted or unsubstituted C, to C 18 alkylenoxy, C 5 to C 18 substituted or unsubstituted cycloalkyl, C 6 to C 12 aryl or C 7 to C 12 aralkyl,
  • R 4 is a substituted or unsubstituted C 6 to C 12 arylene, such as wherein X is C(CH 3 ) 2 , -CH 2 -, -0-, -S-, -CO-, -S0 2 -,
  • M is a siloxane moiety I, II or III or it is a protection groups forhydroxylic moieties such as an ether, an ester or an urethane group,
  • A is an ether, an ester or an urethane linking group
  • R 5 is a difunctional substituted or unsubstituted C, to C 18 alkylene, C 2 to C 12 alkenyl, C 5 to C 18 substituted or unsubstituted cycloalkylene, C 5 to C 18 arylene or heteroaryiene,
  • R 6 denotes a substituted or unsubstituted C, to C 18 alkyl, C 2 to C 12 alkenyl, substituted or unsubstituted C, to C 18 alkylenoxy, C 5 to C 18 substituted or unsubstituted cycloalkyl, C 6 to C 12 aryl or C 7 to C 12 aralkylene, and n is an integer
  • macromonomers 1 to 3 and 6 to 8 are synthesized in presence of catalysts in substance or in solvents such as THF, toluene, tnethyleneglycole bismethacrylate at temperatures between 60 and 100°C
  • a dental/medical composition comprise a macromonomer that is characterized by the following formulas:
  • the polymerizable monomer of the dental/medical compositions is a mono- and polyfunctional (meth)-acrylate, such as a polyalkylenoxide di- and poly-(meth)acryiate, an urethane di- and poly(meth) acrylate, a vinyl-, vinylen- or vinyliden-, acrylate- or methacrylate; preferably were used diethyleneglycol dimethacrylate, thethyleneglycol dimethacrylate, 3,(4), 8,(9)- dimethacryloyloxymethyltricyclodecane, dioxolan bismethacrylate, glycerol trimethacrylate, furfuryl methacrylate in a content of 5 to 80 wt-%.
  • Dental/medical compositions contains a polymerization initiator is a thermal initiator, a redox-initiator or a photo initiator
  • a dental/medical composition contains a filler that preferably is an inorganic filler and/or an organic filler in an amount of 20 to 85 % (w/w)
  • a dental/medical composition contains a stabilizer, that preferably is a radical absorbing monomer such as hydrochinon monomethylether, hydrochinon dimethylether, BHT, phenothiazine
  • a second polymerization reaction occurs using an organic or inorganic acid as a catalyst
  • organic acids p-toluene sulfonic acid and ascorbic acid are used
  • the preferred inorganic acids are sulfunc acid or phosphoric acid or organic derivatives of them
  • pentaerythrol t ⁇ acrylate monophosphate and dipentaerythol pentaacrylate monophosphate are used
  • the macromonomers are usable for filler surface mod ⁇ f ⁇ cat ⁇ on[CW6]
  • the surface modification of the glass is carried out in an organic solvent such as acetone, THF or toluene or in the absence of any solvents
  • the surface modification is catalyzed by amines such as primary amines, primary tertiary amines primary secondary amines, secondary amines or tertiary amines or mixtures thereof
  • amines such as primary amines, primary tertiary amines primary secondary amines, secondary amines or tertiary amines or mixtures thereof
  • amines such as primary amines, primary tertiary amines primary secondary amines, secondary amines or tertiary amines or mixtures thereof
  • 2-am ⁇ noethyl aminopropyl tnethoxysilane or triethyiamine are used
  • the new macromonomers are useable as precursors for siloxane condensation products, too These condensation products containing siloxane linkages and active polymerizable moieties are usable as monomers for dental materials Furthermore, the new hybrid monomers are usable as precursor for the preparation of nanoparticles containing active polymenzable moieties
  • the invented ⁇ , ⁇ -methacrylate terminated macromonomers 1 to 9 - 15 or the obtained gels can polymerized using photochemical and radical initiated polymerization
  • the obtained networks show good mechanical properties, a good adhesion to surfaces of metals, glass and ceramics Furthermore they show a relative low water absorption.
  • Advantageously is the relative low shrinkage during the polymerization.
  • Modified inorganic glass filler (3.0 %):
  • an barium alumo silicate glass having a particle size of 0.9 - 1.5 ⁇ m is dispersed in 250 ml of acetone.
  • 1.5 g of the adduct of 3- aminopropyl-methyl-diethoxysiiane/EGAMA is added, 2.0 g of diethylamine and 1.0 g of water are added to the dispersion.
  • the dispersion is stirred at 60° for 6 h.
  • the solvent is evaporated.
  • the remaining solid is stored at 1 15° for 15 - 18 h under reduced pressure (20 mbar) and sieved through a 220 ⁇ m sieve.
  • the obtained modified glass filler is used in dental/medical composite.
  • the obtained resin is used directly for the preparation of a dental/medical composite.
  • 240 g activated resin as described above are mixed with 760 g of modified inorganic glass filler as described above by the use of an planetary mixer under exclusion of daylight
  • the glass is successively added in five steps of 400 g, 150 g, 100, 50 g and 50 g
  • After getting a homogeneous paste the mixture is evaporated at a pressure of 180 - 220 mbar.
  • For conditioning the paste is stored under exclusion of daylight for additional 24 h at 40°C.
  • Dental/medical composites obtained according the method described above were tested on their mechanical properties on a standard testing machine (Zwick Z 010) The compressive strength was measured according to the ISO standard 9917, 1991 (dental water based cements), the flexural strength was measured according to ISO 4049, 1988 (dental composite materials)
  • the consistency of the composites were measured as following: To portion 0,5 ml of the composite it is filled into a cylindrical hole of a diameter of 0,7 ml and a height of 1 ,3 mm The composite is dosed on a surface of a polyetherketone foil and load with a weight of 575 g over a period of 30 sec Afterwards the diameter of the obtained composite circle is measured in mm and noted as the consistency of the material
  • the volumetric shrinkage is measured in two different ways According to the Archimedes method by measuring the change of the density as a result of the polymerization reaction and by measuring the linear dimensional change after the polymerization The linear dimensional change was afterwards calculated to a volumetric shrinkage (ZH-method). All results are shown in the table below
  • the composite shows a compressive strength of 291.3 MPa a flexural strength of 53 MPa and an E-modulus of 3830 MPa.
  • the volumetric shrinkage is 1.79 % at an degree of conversion of 0.86 (measured by using of DSC).

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Epidemiology (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Dental Preparations (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
EP00950725A 1999-07-28 2000-07-26 Siloxanhaltige makromonomere sowie dentalzusammensetzungen daraus Withdrawn EP1200038A1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US14609399P 1999-07-28 1999-07-28
US146093P 1999-07-28
US62620000A 2000-07-26 2000-07-26
US626200 2000-07-26
PCT/US2000/020348 WO2001008639A1 (en) 1999-07-28 2000-07-26 Siloxane containing macromonomers and dental composites thereof

Publications (1)

Publication Number Publication Date
EP1200038A1 true EP1200038A1 (de) 2002-05-02

Family

ID=26843566

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00950725A Withdrawn EP1200038A1 (de) 1999-07-28 2000-07-26 Siloxanhaltige makromonomere sowie dentalzusammensetzungen daraus

Country Status (3)

Country Link
EP (1) EP1200038A1 (de)
JP (1) JP2003505486A (de)
WO (1) WO2001008639A1 (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10101537A1 (de) * 2001-01-15 2002-08-08 Dentsply Detrey Gmbh Verfahren zur Herstellung einer polymerisierbaren Dentalzusammensetzung
DE10206451A1 (de) * 2002-02-15 2003-08-28 Dentsply Detrey Gmbh Dentalkleber-Zusammensetzung
WO2005121200A1 (fr) * 2004-05-13 2005-12-22 Rhodia Chimie Composition dentaire reticulable/polymerisable par voie cationique stable et a haute teneur en charge
FR2872408B1 (fr) * 2004-06-30 2006-09-08 Rhodia Chimie Sa Composition dentaire reticulable/polymerisable par voie cationique stable et a haute teneur en charge
DE102005018351B4 (de) * 2005-04-20 2008-05-29 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verwendung widerstandsfähiger, langlebiger Komposite im Dentalbereich
JP2014240372A (ja) * 2013-06-12 2014-12-25 三菱レイヨン株式会社 シラン化合物、シルセスキオキサン化合物とその製造方法、硬化性組成物、硬化物、透明フィルムおよび積層体
JPWO2018008580A1 (ja) * 2016-07-06 2019-04-25 セメダイン株式会社 硬化性組成物、及び製品
CN111149058B (zh) * 2017-09-22 2024-03-08 东丽株式会社 透明感光性树脂组合物及其应用、光刻间隔物和液晶显示装置及其制造方法
CN111565700B (zh) * 2017-12-21 2023-06-09 3M创新有限公司 包括硅烷处理过的表面的无机牙科用填充剂
CN109431817A (zh) * 2018-12-20 2019-03-08 四川华柚医疗器械有限公司 一种新型树脂牙及其制作方法
EP4389105A1 (de) 2022-12-20 2024-06-26 Dentsply DeTrey GmbH Dentalzusammensetzung mit einem polymerisationsschrumpfungsvermittler

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US3963771A (en) * 1970-09-02 1976-06-15 Union Carbide Corporation Amine acrylate addition reaction products
US3746738A (en) * 1972-03-28 1973-07-17 Union Carbide Corp Silicon containing polyazimides
DE4011044A1 (de) * 1990-04-05 1991-10-10 Fraunhofer Ges Forschung Silane, verfahren zu ihrer herstellung und ihre verwendung zur herstellung von polymerisaten und polykondensaten
DE4310733A1 (de) * 1993-04-01 1994-10-06 Fraunhofer Ges Forschung Selbsthärtende Systeme
RU2084456C1 (ru) * 1994-03-31 1997-07-20 Владимир Александрович Ковязин Способ получения 3-[n,n-бис (2-гидрокси-3-метакрилоксипропил)амино] пропил(триэтокси)силана
DE4416857C1 (de) * 1994-05-13 1995-06-29 Fraunhofer Ges Forschung Hydrolysierbare und polymerisierbare Silane, Verfahren zu deren Herstellung sowie deren Verwendung
DE19619046A1 (de) * 1996-05-02 1997-11-06 Ivoclar Ag Verwendung einer Zusammensetzung als Dentalmaterial und Dentalmaterial
WO1998028307A1 (en) * 1996-12-23 1998-07-02 Sartomer Company, Inc. Free radically polymerizable silane monomers and oligomers and the method for making them
DE19714320A1 (de) * 1997-03-25 1998-10-01 Ivoclar Ag Hydrolysierbare und polymerisierbare Vinylcyclopropansilane
DE19903177C5 (de) * 1999-01-21 2010-09-16 Ivoclar Vivadent Ag Verwendung von Materialien auf der Basis von Polysiloxanen als Dentalmaterialien

Non-Patent Citations (1)

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Title
See references of WO0108639A1 *

Also Published As

Publication number Publication date
WO2001008639A8 (en) 2001-06-14
WO2001008639A9 (en) 2002-09-12
JP2003505486A (ja) 2003-02-12
WO2001008639A1 (en) 2001-02-08

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