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 System
  • 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).

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• 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)

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• 2000
  • 2000-07-26 WO PCT/US2000/020348 patent/WO2001008639A1/en not_active Application Discontinuation
  • 2000-07-26 JP JP2001513370A patent/JP2003505486A/ja active Pending
  • 2000-07-26 EP EP00950725A patent/EP1200038A1/de not_active Withdrawn

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