US20020143108A1 - Polymerizable compounds and compositions - Google Patents
Polymerizable compounds and compositions Download PDFInfo
- Publication number
- US20020143108A1 US20020143108A1 US10/054,360 US5436002A US2002143108A1 US 20020143108 A1 US20020143108 A1 US 20020143108A1 US 5436002 A US5436002 A US 5436002A US 2002143108 A1 US2002143108 A1 US 2002143108A1
- Authority
- US
- United States
- Prior art keywords
- macromonomer
- carbon atoms
- percent
- weight
- esterified
- 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.)
- Abandoned
Links
- 0 CC.[1*]C(=C)C(C)=O Chemical compound CC.[1*]C(=C)C(C)=O 0.000 description 18
- RCVZRCYJYCIBFL-UHFFFAOYSA-N C=C(C)C(=O)OCC(COC1=CC=C(C(C)(C)C2=CC=C(OCC(COC(=O)C(=C)C)OC(=O)CCC(=O)O)C=C2)C=C1)OC(=O)CCC(=O)O Chemical compound C=C(C)C(=O)OCC(COC1=CC=C(C(C)(C)C2=CC=C(OCC(COC(=O)C(=C)C)OC(=O)CCC(=O)O)C=C2)C=C1)OC(=O)CCC(=O)O RCVZRCYJYCIBFL-UHFFFAOYSA-N 0.000 description 2
- NOCHOUYLQGBASK-UHFFFAOYSA-N C.C.CN(C)C1=CC=CC=C1.COC(=O)C1CC=CCC1C(=O)OC.COCCCCOC Chemical compound C.C.CN(C)C1=CC=CC=C1.COC(=O)C1CC=CCC1C(=O)OC.COCCCCOC NOCHOUYLQGBASK-UHFFFAOYSA-N 0.000 description 1
- AIACXWOETVLBIA-UHFFFAOYSA-N COC(C(CCCC1)C1C(OC)=O)=O Chemical compound COC(C(CCCC1)C1C(OC)=O)=O AIACXWOETVLBIA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
- C08L67/07—Unsaturated polyesters having terminal carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/20—Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
-
- 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
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
-
- 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
- A61K6/893—Polyurethanes
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/061—Polyesters; Polycarbonates
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/064—Polymers containing more than one epoxy group per molecule
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
- C08G18/834—Chemically modified polymers by compounds containing a thiol group
- C08G18/835—Unsaturated polymers modified by compounds containing a thiol group
-
- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/10—Polycondensates containing more than one epoxy group per molecule of polyamines with epihalohydrins or precursors thereof
-
- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/12—Polycondensates containing more than one epoxy group per molecule of polycarboxylic acids with epihalohydrins or precursors thereof
-
- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
-
- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1494—Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
-
- 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
- C08G59/40—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 curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4292—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with monocarboxylic acids
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- 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
- C08G2270/00—Compositions for creating interpenetrating networks
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/922—Polyepoxide polymer having been reacted to yield terminal ethylenic unsaturation
Definitions
- the invention relates to polymerizable macromonomers and dental and medical compositions containing polymerizable macromonomers.
- the invention provides macromonomers for dental compositions and a process for preparing them.
- Dental/medical compositions which include macromonomers of the invention have a high adhesion to hard dental tissue and low volumetric shrinkage.
- R 1 is hydrogen or a substituted or unsubstituted alkyl having from 1 to 12 carbon atoms, oxyalkyl having from 1 to 12 carbon atoms, alkenyl having from 2 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, aryl having from 6 to 12 carbon atoms or aralkyl having from 7 to 12 carbon atoms.
- Each E independently is a hydroxyl group, an organic ester moiety or an inorganic ester moiety and at least one E is a ester containing moiety.
- n and m each independently is an integer from 2 to 12.
- the number of the acid moieties is chosen such that a polymer obtained by polymerizing said monomers has an adhesive strength to dentine of at least 2 MPa.
- Prior Art dental/medical compositions such as cements are either water-based ionic cements or resin based materials.
- the water-based cements have the advantage of a modest adhesion to hard tooth tissues and of a high fluoride ion release from inorganic filler material. They have the disadvantage of high water solubility, low abrasion resistance and an excessive opacity.
- the resin-based materials have the advantage of excellent mechanical properties, a suitable opacity and low water solubility. They have the disadvantage of a lack of adhesion, a very poor release of fluoride ions from an inorganic filler and a high volumetric shrinkage.
- R 1 is hydrogen or a substituted or unsubstituted alkyl having from 1 to 12 carbon atoms, oxyalkyl having from 1 to 12 carbon atoms, alkenyl having from 2 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, aryl having from 6 to 12 carbon atoms or aralkyl having from 7 to 12 carbon atoms.
- Each E independently is a hydroxyl group, an organic ester moiety, or an inorganic ester moiety. At least one E is an ester moiety.
- n and m each independently is an integer from 2 to 12.
- the esterified macromonomer is obtainable by esterification of at least a portion of the —OH groups of a macromonomer having at least one terminal double bond with at least one derivative of an inorganic or organic acid which introduces pendant groups exhibiting at least one acid moiety selected from the group of consisting of —COOH, —PO 3 H 2 , —SO 3 H, —BO 2 H or salts thereof.
- the number of the acid moieties is chosen such that a polymer obtained by polymerizing those monomers has an adhesive strength to dentine of at least 2 MPa.
- the invention provides macromonomers esterfied, with organic acids or inorganic acids or derivatives thereof.
- the esterified macromonomers are useful in composition with or without water, such as water free self-adhesive dental/medical composite.
- the dental/medical composite comprises a modified macromonomer, and/or di-or poly(methacrylates) containing phosphoric acid ester groups or salts thereof, polymerizable monomers, acid-reactive and/or reactive and/or non-reactive fillers, diluents, polymerization initiators and stabilizers.
- Composition in accordance with the invention include polymerization initiators, such as thermal initiators, redox initiators and/or photoinitiators.
- the new adhesive dental composite develops adhesion to dentine of about 4 MPa. Fillers of high X-ray absorbence provide radio-opacity values greater than that of the same thickness of aluminium.
- Macromonomers in accordance with the invention are produced by chemical modification of macromonomers containing hydroxyl groups.
- Macromonomer containing hydroxyl groups useful for making esterified macromonomer in accordance with the invention are described for example in Polym. Bull. 27 (1992) 511-517, Acta Polym. 42 (1991) 17-20 and DE 4217761.8 incorporated herein by reference.
- Preferred polymerizable compounds for use in compositions in accordance with the invention are within the scope of general formulas M1-M12 as follows:
- each E independently is a hydroxyl group, an organic ester moiety or an inorganic ester moiety
- At least one E is an ester moiety
- R is a diether or a diester containing moiety or tertiary amine
- R 1 is hydrogen or a substituted or unsubstituted alkyl having from 1 to 12 carbon atoms, oxyalkyl having from 1 to 12 carbon atoms, alkenyl having from 2 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, aryl having from 6 to 12 carbon atoms or aralkyl having from 7 to 12 carbon atoms,
- R 2 is a difunctional substituted or unsubstituted alkyl group having from 1 to 12 carbon atoms, alkenyl group having from 2 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, aryl having from 6 to 12 carbon atoms or aralkyl having from 7 to 12 carbon atoms,
- R 3 is hydrogen or a substituted or unsubstituted alkyl group having from 1 to 12 carbon atoms, alkenyl group having from 2 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, aryl having from 6 to 12 carbon atoms or aralkyl having from 7 to 12 carbon atoms,
- R 4 is a substituted or unsubstituted aryl having from 6 to 12 carbon atoms
- n is an integer of at least 1.
- R is a moiety within the scope of the general formulas:
- X is C(CH 3 ) 2 , —CH 2 —, —O—, —S—, —CO—, or —SO 2 —.
- R 4 is a moiety within the scope of the general formulas:
- X is C(CH 3 ) 2 , —CH 2 —, —O—, —S—, —CO—, —SO 2 —.
- E is a hydroxyl group, an ester moiety, a boric acid moiety, a sulfuric acid moiety or a phosphoric acid moiety.
- Macromonomers within the scope of general formula M-1 are synthesized in two steps. At first an oligomer mixture is obtained by reaction of an ⁇ , ⁇ -unsaturated acids with excessive amounts of a diepoxide, such as bisphenol-A diglycidyl ether (DGEBA), bisphenol-F diglycidyl ether (DGEBF), butanediol diglycidyl ether (BDODGE), tetrahydro terephtalic acid diglycidyl ether or diglycidyl aniline. This mixture contains the bis-ester of the diepoxicle along with the mono-ester and unreacted diepoxide as governed by the ratio of the diepoxide and the unsaturated acid. The formation of macromonomers follows in a second reaction of the previous reacted oligomers with dicarboxylic acids to M-1 (DE 4217761.8).
- a diepoxide such as bisphenol-A diglycidyl ether (DGEBA), bis
- macromonomers M-1, M-2, M-3 and M-6 wherein each E is hydrogen contain both types of molecules having primary and/or secondary alcohol units.
- the resulting macromonomers are viscous liquids or solids which are soluble in THF, CHCl 3 and DMF. Their glass transition temperatures are relatively low (between 0 and 50° C.) depending on the nature of the comonomer and the molecular mass of the macromonomers.
- Macromonomers M-5 wherein each E is hydrogen are prepared by one-step reaction of the diepoxides, disecondary diamines and 2,3-epoxypropyl-(meth)acrylate according to the following equation:
- a second route to obtain macromonomers M-5 wherein each E is hydrogen is a two-step reaction.
- the diepoxide is reacted with the disecondary diamine to an ⁇ , ⁇ -terminated prepolymer.
- the obtained prepolymer is reacted with 2,3-epoxypropyl-(meth) acrylate (DD 277689, J. Klee, H.-H. Hörhold, H. Schütz, Acta Polym. 42 (1991)17-20).
- Macromonomers M-9 wherein each E is hydrogen are prepared by reaction of diepoxides, dicarboxylic acids and aminoalkyl (meth)acrylates according to the following equation:
- succinic acid anhydride maleic acid anhydride, dichloromaleic acid anhydride, dimethyl maleic acid anhydride, malonic acid anhydride, aconit acid anhydride, adipic acid anhydride, 3,3-tetramethylen glutaric acid anhydride, cyclohexen-1,2 acid anhydride, nadinic acid anhydride, phthalic acid anhydride, trimellitic acid anhydride, 2-sulfo-benzoic acid anhydride, 2-sulfo succinic acid anhydride, phthalic acid anhydride p-(O-phosphat), phthaloylchloride, succinic acid dimethyl ester.
- derivatives of inorganic acids preferably were used phosphorous penta chloride, phosphorous trichloride, phosphorous oxychloride, sulfuryl chloride, thionyl chloride, phosphor thionyl chloride, boric acid anhydride, boron trichloride.
- the esterification of the macromonomer hydroxyl groups is carried out in pure substance or in diluted solutions.
- solvents such as tetrahydro furane, dioxane, or polymerizable monomers such as triethylenglycol bismethacrylate, diethylenglycol bismethacrylate, dioxolan bismethacrylate, vinyl-, vinylen- or vinyliden-, acrylate- or methacrylate substituted spiroorthoesters and 2,2-Bis[p-(acryloxyethoxy)phenyl]propane are present during esterification of the macromonomers.
- the temperature is in the preferred range of 60° C. to 120° C.
- a dental/medical composite, a dental/medical sealant, a dental/medical adhesive and a dental/medical primer have been developed comprising a modified ⁇ , ⁇ -(meth) acryloyl terminated macromonomer notably a di- or poly(meth)acrylate monomer having phosphorous ester groups or salts thereof, polymerizable monomers, fillers, polymerization initiators and stabilizers.
- di- or poly(meth)acrylate monomer having phosphorous ester groups and salts thereof are employed pentaerythrit triacrylate monophosphate, dipentaerythrit penta-acrylate monophosphate, glycerol di(meth)acrylate monophosphate, triethylenglycol (meth)acrylate monophosphate.
- organic polymerizable monomers mono- and polyfunctional (meth)acrylates, such as polyalylenoxide di- and poly(meth)acrylates, urethane di- and poly(meth)acrylates, vinyl-, vinylen- or vinyliden-, acrylate- or methacrylate substituted spiroorthoesters, spiroorthocarbonates or bicyloorthoesters.
- mono- and polyfunctional (meth)acrylates such as polyalylenoxide di- and poly(meth)acrylates, urethane di- and poly(meth)acrylates, vinyl-, vinylen- or vinyliden-, acrylate- or methacrylate substituted spiroorthoesters, spiroorthocarbonates or bicyloorthoesters.
- diethylenglycol dimethacrylate triethylenglycol dimethacrylate, 3,(4),8,(9)-dimethacryloyloxymethyltricyclodecane, dioxolan bismethacrylate, glycerol trimethacrylate, furfuryl methacrylate in a content of 5 to 80 wt-%.
- thermal initiators thermal initiators, redox initiators and/or photo initiators in a content of 0.001 to 3 wt-%.
- Thermal initiators are initiators such as peroxides, peresters, perketals, peroxy carbonates, hydroxyperoxides, persulfates and azo compounds preferably dibenzoyl peroxide, cumol hydroperoxide, diisopropyl peroxycarbonate, dipotassium persulfate, azobisisobutylonitril.
- Preferred redox initiator systems for use in compositions in accordance with the invention are peroxide/amine systems, such as peracid/amine, perester/amine, perketal/amine, peroxycarbonate/amine and hydroxyperoxide/amine systems; peroxide/metal ion salts, such as ascorbic acid/peroxide/metal ion compounds, (thio)barbituric acid/peroxide/metal ion compounds, metal ion compounds/sulfinates, metal ion compounds/(thio)barbituric acid; transition metal carbonyl compounds and halogenids of organic compounds; boralkyl compounds, peroxysulfates and thiols.
- redox-initiators are benzoylperoxide/N,N-bis-( ⁇ -hydroxyethyl)-p-toluidine, benzoylperoxide/N,N-bis-( ⁇ -hydroxyethyl)-p-benzoic acid ethylester, benzoylperoxide/tributylamine, cumol hydroperoxide/N,N-bis-( ⁇ -hydroxyethyl)-p-toluidine, diisopropyl peroxycarbonate/dimethylbenzylamine.
- Preferred photoinitiators for use in polymerizable compositions in accordance with the invention which include macromonomers with the scope of general formulas M-1 through M-12 are camphorquinone, benzophenone and 2,2-dimethylbenzylketal.
- Preferred fillers for use in compositions in accordance with the invention include inorganic compounds, such as La 2 O 3 , ZrO 2 , BiPO 4 , CaWO 4 , BaWO 4 , SrF 2 , Bi 2 O 3 , glasses and/or organic fillers, such as polymer granulate.
- Dental/medical composite compositions of the invention preferably include filler in an amount from about 50 to about 85 percent by weight.
- Dental/medical adhesive compositions of the invention preferably include filler in an amount from about 50 to about 65 percent by weight.
- Dental/medical sealant compositions of the invention preferably include filler in an amount from about 10 to about 50 percent by weight.
- Dental/medical composite compositions, adhesives and sealant of the invention include one-component and two-component paste/paste and powder/liquid-material which is to be mixed immediately before use.
- Shrinkage of composite compositions of the invention is preferably less than 4.5 and more preferably less than 1.5 percent by volume.
- Adhesive dental composite compositions of the invention containing radio-opaque fillers preferably provide a radio-opacity of at least 1.5 mm/mm Al, more preferably at least 3 to 7 mm/mm Al, and most preferably at least 7 mm/mmAl.
- the self-adhesive dental/medical composites compositions in accordance with a preferred embodiment of the invention have a fluoride release of at least 1 ⁇ g/cm 2 , more preferably at least 1-3 ⁇ g/cm 2 , and most preferably at least 3-10 ⁇ g/cm 2 .
- Self-adhesive dental/medical composites compositions in accordance with a preferred embodiment of the invention have an opacity of at least 40%, more preferably at least 20-40%, and most preferably at least 5-20%.
- the setting time of the adhesive dental/medical adhesive compositions in accordance with a preferred embodiment of the invention at 37° C. is between 1 minute and 60 minutes, more preferably between 5 and 30 minutes and most preferably between 2 and 5 minutes.
- the setting time of adhesive compositions in accordance with a preferred embodiment of the invention at 23° C. is preferably between 10 minutes and 300 minutes more, preferably between 5 and 100 minutes and most preferably between 5 and 20 minutes.
- bond strength to dentin is measured using extracted human teeth.
- the teeth used for the shear bond strength test are treated in 1% sodium hypochlorite for one hour and then stored in distilled water in a refrigerator at about 4° C. until needed.
- the teeth are washed with water, mechanically sanded with 320 grit carborundum paper until a flat dentin surface is exposed.
- the teeth are then individually blown dry with compressed dry air to ensure the dentin surface is free from noticeable moisture.
- a small plastic straw with 5 mm inner diameter and 2 to 3 mm in length is filled with the polymerizable composition being tested and seated on the dentin so as to form a post without pressure.
- the upper open end of the straw is covered with a thin film and cured.
- the specimens are then stored in distilled water at 37° C. for 24 hours.
- the teeth are then vertically mounted in a 7 cm ring using gypsum to provide a base for testing with the post at right angles thereto.
- the mounted specimens are then loaded in shear in an Zwick device model number 1455 manufactured by Zwick GmbH for measurement of adhesion of the post to dentin at 1 mm/minute crosshead speed.
- the load is applied parallel to the prepared tooth surface and at right angles to the post until fracture occurred.
- the shear bond strength is then calculated.
- Fluoride Release is measured by making three 1 ⁇ 20 mm (diameter) discs of each material. Each disc is placed in 25 ml water stored for a week at 37° C. Using an ion selective electrode, the fluoride concentration in mg F ⁇ /cm 2 is determined for each disc. The average value of the three discs is recorded.
- compressive strength is measured according to ISO 9917, EN 29917; flexural strength is measured according to ISO 4049, EN 24049; elastic modulus is measured according to ISO 4049, EN 24049; opacity is measured according to ISO 9912, EN 29912; IR spectra are measured using a Fourier transformation Infra Red spectrometer at 23° C.
- the macromonomer of formula M-1 wherein n is 1, R is —OC 6 H 4 —C(CH 3 ) 2 —C 6 H 4 O—, R 1 is —CH 3 , R 2 is —(CH 2 ) 4 — is referred to hereinafter as macromonomer M-1A and is prepared by reacting 150.000 g (0.441 mol) bisphenol-A diglycidyl ether, 32.200 g (0.220 mol) adipic acid and 2.000 g triethylbenzylammoniumchloride for four hours at 80° C. while stirring.
- the obtained methacrylate terminated macromonomer is soluble in organic solvents such as chloroform, DMF and THF. No absorption of epoxide groups at 915 and 3050 cm ⁇ 1 is observed in the IR-spectrum. Absorption of ester groups were found at 1720 cm ⁇ 1 .
- the obtained methacrylate terminated macromonomer is soluble in organic solvents such as chloroform, DMF and THF.
- organic solvents such as chloroform, DMF and THF.
- epoxide groups at 915 and 3050 cm ⁇ 1 is observed.
- Absorption of ester groups is found at 1720 cm ⁇ 1 .
- the obtained methacrylate terminated macromonomer is soluble in organic solvents such as chloroform, DMF and THF. No absorption of epoxide groups at 915 and 3050 cm ⁇ 1 is observed in the IR-spectrum. Absorption of ester groups is found at 1720 cm ⁇ 1 .
- the hydroxyl groups of macromonomer M-1A made by following the procedure of reference example 1 are esterified by adding 16.023 g (160.13 mmol) succinic anhydride to 56.900 g of a macromonomer-triethylenglycol dimethacrylate mixture containing 40.000 g (40.03 mmol) macromonomer M-1A and 16.9 g of triethylenglycol dimenthacrylate) while stirring for two hours at 90° C.
- the esterified macromonomer containing dicarboxylic half ester units shows no absorption of hydroxyl groups at 3400 cm ⁇ 1 .
- the hydroxyl groups of macromonomer M-1B made by following the procedure of reference example 2 are esterified by adding 197.93 g (1.98 mol) succinic anhydride and 0.56 g triethylamine to 362.71 g macromonomer M-1B while stirring for four hours at 90° C.
- the esterified macromonomer containing dicarboxylic half ester units shows no absorption of hydroxyl groups at 3400 cm ⁇ 1 .
- the hydroxyl groups of macromonomer M-1F made by following the procedure of reference example 3 are esterified by adding 31.58 g (0.32 mol) succinic anhydride, 0.11 g triethylamine and 13.58 g triethyleneglycol dimethacrylate to 107.57 g of a macromonomer-triethylenglycol dimethacrylate mixture (containing 74.40 g, 0.08 mol macromonomer M-1F) while stirring for two hours at 90° C.
- a macromonomer-triethylenglycol dimethacrylate mixture containing 74.40 g, 0.08 mol macromonomer M-1F
- the hydroxyl groups of macromonomer M-3 wherein each E is hydroxyl made by following the procedure of reference example 4 are esterified by adding to 40.000 g of a macromonomer-triethyleneglycol dimethacrylate mixture (containing 27.844 g, 23.32 mmol macromonomer M-3 wherein each E is a hydroxy moiety), 9.338 g (93.32 mmol) succinic anhydride and 12.156 g triethylenglycol dimethacrylate while stirring for two hours at 90° C.
- the IR-spectrum does not show any absorption of hydroxyl groups at 3400 cm ⁇ 1 of the newly modified macromonomer containing dicarboxylic half ester units.
- the hydroxyl groups of macromonomer M-5 wherein each E is hydroxyl made by following the procedure of reference example 5 are esterified by adding 23.516 g (235.00 mmol) succinic anhydride to a macromonomer M-5 wherein each E is hydroxyl for four hours at 90° C.
- the esterified macromonomer containing dicarboxylic half ester units show no absorption of hydroxyl groups at 3400 cm ⁇ 1 .
- the macromonomer is characterised by the following analytical data:
- hydroxyl groups of macromonomer M-5 wherein each E is hydroxyl made by following the procedure of reference example 5 are esterified by adding 8.239 g (42.88 mmol) trimellitic anhydride, 0.2 g N,N-bis( ⁇ -hydroxyethyl)-p-toluidin, 140 ml dioxane and 9.247 g triethylenglycol dimethacrylate to 40.008 g of a macromonomer-triethylenglycol dimethacrylate-mixture (containing 28.000 g, 21.44 mmol macromonomer M-5 wherein each E is hydroxyl) and kept for eight hours at 90° C.
- the macromonomer was washed with petrol ether and dried at 40° C. within six hours.
- the newly modified macromonomer containing two dicarboxylic half ester units and two hydroxylic groups per average molecule show absorption of hydroxyl groups at 3400 cm ⁇ 1 and of the ester unit at 1720 cm ⁇ 1 .
- the hydroxyl groups of macromonomer M-5 wherein each E is hydroxyl made by following the procedure of reference example 6 are esterified by adding 29.384 g (293.67 mmol) succinic anhydride to a macromonomer and kept for four hours at 90° C.
- hydroxyl groups of macromonomer M-6 wherein each E is hydroxyl made by following the procedure of reference example 7 are esterified by adding 12.966 g (0.130 mol) succinic anhydride and 0.2 g N,N-bis( ⁇ -hydroxyethyl)-p-toluidin to 50.000 g of a macromonomer-triethylenglycol dimethacrylate mixture (containing 35.000 g, 0.032 mol macromonomer M-6 wherein each E is hydroxyl) while stirring and were kept for eight hours at 50° C.
- esterified macromonomer containing dicarboxylic half ester units shows no absorption of hydroxyl groups at 3400 cm ⁇ 1 .
- the hydroxyl groups of macromonomer M-7 wherein each E is hydroxyl made by following the procedure of reference example 8 are esterified by adding 12.966 g (0.130 mol) succinic anhydride and 0.2 g N,N-bis( ⁇ -hydroxyethyl)-p-toluidin to 50.000 g of a macromonomer-triethylenglycol dimethacrylate mixture (containing 35.000 g, 0.032 mol macromonomer M-7 wherein each E is hydroxyl) while stirring and kept for two hours at 80° C.
- the IR-spectrum does not show any absorption of hydroxyl groups at 3400 cm ⁇ 1 of the esterified macromonomer containing dicarboxylic half ester units.
- hydroxyl groups of macromonomer M-6 wherein each E is hydroxyl made by following the procedure of reference example 7 are esterified by adding 29.760 g (0.297 mol) succinic anhydride and 0.2 g N,N-bis( ⁇ -hydroxyethyl)-p-toluidin to a macromonomer M-6 wherein each E is hydroxyl while stirring and were kept for eight hours at 50° C.
- the newly modified macromonomer containing dicarboxylic half ester units shows no absorption of hydroxyl groups at 3400 cm ⁇ 1 .
- the hydroxyl groups of macromonomer M-1A made by following the procedure of reference example 1 are esterified by adding 40.000 g (40.03 mmol) of a macromonomer M-1A dissolved in 100 ml THF 16.204 g triethylamine in 50 ml THF. After adding 24.553 g POCl 3 (153.33 mmol) drops by drops while stirring at 0° to 5° C. the solution is stirred for further two hours at room temperature. Than the triethylamine hydrochloride is filtered off and the mixture is hydrolysed with 20 ml water. The organic solution is extracted three times with Na 2 CO 3 solution and is separated from water. From the solution, dried over MgSO 4 , the solvent is evaporated and the macromonomer is dried.
- hydroxyl groups of macromonomer with M-3 wherein each E is hydroxyl made by following the procedure of reference example 4 are esterified by adding 60.000 g (50.26 mmol) of a macromonomer M-3 wherein each E is hydroxyl dissolved in 150 ml THF to 20.346 g triethylamine in 50 ml THF. After adding 30.829 g (201.06 mmol) POCl 3 drops by drops while stirring at 0° to 5° C. the solution is stirred for further two hours at room temperature. Than the triethylamine hydrochloride is filtered off and the mixture is hydrolysed with 20 ml water.
- the organic solution is extracted three times with Na 2 CO 3 solution and is separated from water. From the solution, dried over MgSO 4 , the solvent is evaporated and the macromonomer is dried.
- the hydroxyl groups of macromonomer M-6 wherein each E is hydroxyl made by following the procedure of reference example 7 are esterified by adding 40.000 g (37.83 mmol) of a macromonomer M-6 wherein each E is hydroxyl dissolved in 100 ml THF to 15.312 g triethylamine in 50 ml THF. After adding 23.200 g (151.31 mmol) POC 3 drops by drops while stirring at 0° to 5° C. the solution is stirred for further two hours at room temperature. Than the triethylamine hydrochloride is filtered off and the mixture is hydrolysed with 20 ml water. The organic solution is extracted three times with Na 2 CO 3 solution and is separated from water.
- the teeth are transferred for 24 hours to a chamber at 37 ⁇ 2° C. and 100% relative humidity.
- the adhesion is 0.45 ⁇ ,20 Mpa, when measured with a Zwick-apparatus model number 1455, manufactured by Zwick GmbH & Co.
- paste A and paste B were mixed in the wt.-ratio 1:1 homogeneously.
- the gel time at 23° C. is about 96 minutes, and the gel time at 32° C. is 19 min.
- the radioopacity of the obtained material is about about 6.7 mm/mm Al.
- adhesion to dentine 7.68 ⁇ 1.5 MPa compressive strength: 261 ⁇ 14 MPa
- Elastic modules 2917 ⁇ 76 MPa shrinkage: 2.30% (percent reduction in volume) expansion: 1.17% (after storage for (expansion in length) 14 weeks in water at 37° C.)
- fluoride release 5.33 ⁇ g/cm 2 (after storage for 9 weeks in water at 37° C.).
- adhesion to dentine 7.7 ⁇ 0.8 MPa compressive strength: 295 ⁇ 9 MPa (ISO 9917, EN 29917) flexural strength: 77.1 ⁇ 7.1 MPa (ISO 4049, EN 24049) Elastic modulus: 4482 ⁇ 147 MPa (ISO 4049, EN 24049) Opacity: 90.6% (ISO 9912, EN 29912) shrinkage ⁇ V: 5.8 ⁇ 0.5% expansion ⁇ L: 1.52% (after storage for 28 weeks in water at 37° C.) fluoride release: 64.01 ⁇ g/cm 2 (after storage for 27 weeks in water at 37° C.).
Abstract
wherein Z is an organic moiety, R1 is hydrogen or a substituted or unsubstituted alkyl having from 1 to 12 carbon atoms, oxyalkyl having from 1 to 12 carbon atoms, alkenyl having from 2 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, aryl having from 6 to 12 carbon atoms or aralkyl having from 7 to 12 carbon atoms, each E independently is a hydroxyl group, an organic ester moiety or an inorganic ester containing moiety and at least one E is an ester containing moiety, n and m each independently is an integer from 2 to 12. The esterified macromonomer is obtainable by esterification of at least a portion of the —OH groups of a macromonomer having at least one terminal double bond with at least one derivative of an inorganic or organic acid which introduces pendant groups exhibiting at least one acid moiety selected from the group of consisting of —COOH, —PO3H2, —SO3H, —BO2H or salts thereof. The number of the acid moieties is chosen such that a polymer obtained by polymerizing those monomers has an adhesive strength to dentine of at least 2 MPa.
Description
- This is a continuation-in-part of U.S. patent application Ser. No. 231,535 filed Apr. 22, 1994 (Case 1723) which is a continuation-in-part of U.S. patent application Ser. No. 217,998 filed Mar. 25, 1994 (Case 1718), which is a continuation-in-part of U.S. patent application Ser. No. 067,774 filed May 26, 1993 (Case 1710).
- The invention relates to polymerizable macromonomers and dental and medical compositions containing polymerizable macromonomers. The invention provides macromonomers for dental compositions and a process for preparing them. Dental/medical compositions which include macromonomers of the invention have a high adhesion to hard dental tissue and low volumetric shrinkage.
-
- wherein Z is an organic moiety, R1 is hydrogen or a substituted or unsubstituted alkyl having from 1 to 12 carbon atoms, oxyalkyl having from 1 to 12 carbon atoms, alkenyl having from 2 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, aryl having from 6 to 12 carbon atoms or aralkyl having from 7 to 12 carbon atoms. Each E independently is a hydroxyl group, an organic ester moiety or an inorganic ester moiety and at least one E is a ester containing moiety. n and m each independently is an integer from 2 to 12.
- It is the object of the invention to provide an esterified macromonomer obtainable by esterification of at least a portion of the —OH groups of a macromonomer having at least one terminal double bond with at least one derivative of an inorganic or organic acid which introduces pendant groups exhibiting at least one acid moiety selected from the group of consisting of —COOH, —PO3H2, —SO3H, —BO2H and salts thereof. The number of the acid moieties is chosen such that a polymer obtained by polymerizing said monomers has an adhesive strength to dentine of at least 2 MPa.
- Prior Art dental/medical compositions such as cements are either water-based ionic cements or resin based materials. The water-based cements have the advantage of a modest adhesion to hard tooth tissues and of a high fluoride ion release from inorganic filler material. They have the disadvantage of high water solubility, low abrasion resistance and an excessive opacity. The resin-based materials have the advantage of excellent mechanical properties, a suitable opacity and low water solubility. They have the disadvantage of a lack of adhesion, a very poor release of fluoride ions from an inorganic filler and a high volumetric shrinkage.
- Engelbrecht et al in U.S. Pat. No. 4,806,381 discloses Polymerizable Compounds Containing Acid and Acid Derivatives, Mixtures Containing the Same, and Use Thereof. Blackwell et al in U.S. Pat. No. 4,816,495 discloses Biologically Compatible Adhesive Visible Light Curable Compositions.
- These disadvantages of prior art dental compounds and compositions are overcome by the novel and nonobvious compounds and compositions of the invention.
-
- wherein Z is an organic moiety. R1 is hydrogen or a substituted or unsubstituted alkyl having from 1 to 12 carbon atoms, oxyalkyl having from 1 to 12 carbon atoms, alkenyl having from 2 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, aryl having from 6 to 12 carbon atoms or aralkyl having from 7 to 12 carbon atoms. Each E independently is a hydroxyl group, an organic ester moiety, or an inorganic ester moiety. At least one E is an ester moiety. n and m each independently is an integer from 2 to 12. The esterified macromonomer is obtainable by esterification of at least a portion of the —OH groups of a macromonomer having at least one terminal double bond with at least one derivative of an inorganic or organic acid which introduces pendant groups exhibiting at least one acid moiety selected from the group of consisting of —COOH, —PO3H2, —SO3H, —BO2H or salts thereof. The number of the acid moieties is chosen such that a polymer obtained by polymerizing those monomers has an adhesive strength to dentine of at least 2 MPa.
- The invention provides macromonomers esterfied, with organic acids or inorganic acids or derivatives thereof. The esterified macromonomers are useful in composition with or without water, such as water free self-adhesive dental/medical composite. The dental/medical composite comprises a modified macromonomer, and/or di-or poly(methacrylates) containing phosphoric acid ester groups or salts thereof, polymerizable monomers, acid-reactive and/or reactive and/or non-reactive fillers, diluents, polymerization initiators and stabilizers. Composition in accordance with the invention include polymerization initiators, such as thermal initiators, redox initiators and/or photoinitiators. The new adhesive dental composite develops adhesion to dentine of about 4 MPa. Fillers of high X-ray absorbence provide radio-opacity values greater than that of the same thickness of aluminium.
- Preperation of Epoxide-macromonomers
- Macromonomers in accordance with the invention are produced by chemical modification of macromonomers containing hydroxyl groups. Macromonomer containing hydroxyl groups useful for making esterified macromonomer in accordance with the invention are described for example in Polym. Bull. 27 (1992) 511-517, Acta Polym. 42 (1991) 17-20 and DE 4217761.8 incorporated herein by reference. Preferred polymerizable compounds for use in compositions in accordance with the invention are within the scope of general formulas M1-M12 as follows:
- wherein
- each E independently is a hydroxyl group, an organic ester moiety or an inorganic ester moiety,
- at least one E is an ester moiety,
- R is a diether or a diester containing moiety or tertiary amine,
- R1 is hydrogen or a substituted or unsubstituted alkyl having from 1 to 12 carbon atoms, oxyalkyl having from 1 to 12 carbon atoms, alkenyl having from 2 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, aryl having from 6 to 12 carbon atoms or aralkyl having from 7 to 12 carbon atoms,
- R2 is a difunctional substituted or unsubstituted alkyl group having from 1 to 12 carbon atoms, alkenyl group having from 2 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, aryl having from 6 to 12 carbon atoms or aralkyl having from 7 to 12 carbon atoms,
- R3 is hydrogen or a substituted or unsubstituted alkyl group having from 1 to 12 carbon atoms, alkenyl group having from 2 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, aryl having from 6 to 12 carbon atoms or aralkyl having from 7 to 12 carbon atoms,
- R4 is a substituted or unsubstituted aryl having from 6 to 12 carbon atoms,
- and n is an integer of at least 1.
-
- (according to R of the foreclosures)
- wherein
- X is C(CH3)2, —CH2—, —O—, —S—, —CO—, or —SO2—.
-
- wherein X is C(CH3)2, —CH2—, —O—, —S—, —CO—, —SO2—.
- Preferably E is a hydroxyl group, an ester moiety, a boric acid moiety, a sulfuric acid moiety or a phosphoric acid moiety.
- Macromonomers within the scope of general formula M-1 are synthesized in two steps. At first an oligomer mixture is obtained by reaction of an α,β-unsaturated acids with excessive amounts of a diepoxide, such as bisphenol-A diglycidyl ether (DGEBA), bisphenol-F diglycidyl ether (DGEBF), butanediol diglycidyl ether (BDODGE), tetrahydro terephtalic acid diglycidyl ether or diglycidyl aniline. This mixture contains the bis-ester of the diepoxicle along with the mono-ester and unreacted diepoxide as governed by the ratio of the diepoxide and the unsaturated acid. The formation of macromonomers follows in a second reaction of the previous reacted oligomers with dicarboxylic acids to M-1 (DE 4217761.8).
- Instead of dicarboxylic acids in the second step also primary monoamines were used which react to macromonomers M-2, disecondary diamines which react to macromonomers M-3, (J. Klee et. al. Polym. Bull. 27 (1992) 511-517, DD 279667) and bisphenols which react to macromonomers M-6.
-
- Consequently, macromonomers M-1, M-2, M-3 and M-6 wherein each E is hydrogen contain both types of molecules having primary and/or secondary alcohol units.
- The resulting macromonomers are viscous liquids or solids which are soluble in THF, CHCl3 and DMF. Their glass transition temperatures are relatively low (between 0 and 50° C.) depending on the nature of the comonomer and the molecular mass of the macromonomers.
-
- respectively using r=z/x. That means each macromonomer M is a definite mixture of a series of homologous oligomers (n=1,2,3,4,5, . . . ) and contains a certain amount of the molecule (n=0).
-
- A second route to obtain macromonomers M-5 wherein each E is hydrogen is a two-step reaction. In the first step the diepoxide is reacted with the disecondary diamine to an α,ω-terminated prepolymer. In the second step the obtained prepolymer is reacted with 2,3-epoxypropyl-(meth) acrylate (DD 277689, J. Klee, H.-H. Hörhold, H. Schütz, Acta Polym. 42 (1991)17-20).
- Instead of disecondary diamines in the second step also were used primary monoamines react to macromonomers M-4, bisphenols react to macromonomers M-7 or dicarboxylic acids react to macromonomers M-8.
-
- M-9 (wherein E is hydrogen)
- Instead of dicarboxylic acids, primary monoamines were used to prepare macromonomers M-10, disecondary diamines were used to prepare macromonomers M-11, bis-phenols were used to prepare macromonomers M-12.
- Specific macromonomers M-1 to M-12 representing molecules of n=0, n=1 or n=2 may be isolated from the mixture by fractionated precipitation or by chromatography and subjected to esterification as described.
- Esterification of Macromonomers
- The reaction of epoxide macromonomers M-1 to M-12 with organic acids or inorganic acids or derivatives thereof leads to macromonomers having ester moieties.
- As derivatives of organic acids preferably were used succinic acid anhydride, maleic acid anhydride, dichloromaleic acid anhydride, dimethyl maleic acid anhydride, malonic acid anhydride, aconit acid anhydride, adipic acid anhydride, 3,3-tetramethylen glutaric acid anhydride, cyclohexen-1,2 acid anhydride, nadinic acid anhydride, phthalic acid anhydride, trimellitic acid anhydride, 2-sulfo-benzoic acid anhydride, 2-sulfo succinic acid anhydride, phthalic acid anhydride p-(O-phosphat), phthaloylchloride, succinic acid dimethyl ester.
- As derivatives of inorganic acids preferably were used phosphorous penta chloride, phosphorous trichloride, phosphorous oxychloride, sulfuryl chloride, thionyl chloride, phosphor thionyl chloride, boric acid anhydride, boron trichloride.
- It is possible to synthesize the esterified macromonomers without using any catalysts in the cases of M-2 to M-5, M-10, M11 (n>0). These macromonomers contain the catalytic active amine in the backbone of the molecule. The use of catalysts such as tertiary amines or quarterly ammonium salts is possible and in the case of esterification of M-1, M-6, M-7, M-8, M-9 and M-12 necessary.
- The esterification of the macromonomer hydroxyl groups is carried out in pure substance or in diluted solutions. Preferably, solvents such as tetrahydro furane, dioxane, or polymerizable monomers such as triethylenglycol bismethacrylate, diethylenglycol bismethacrylate, dioxolan bismethacrylate, vinyl-, vinylen- or vinyliden-, acrylate- or methacrylate substituted spiroorthoesters and 2,2-Bis[p-(acryloxyethoxy)phenyl]propane are present during esterification of the macromonomers. The temperature is in the preferred range of 60° C. to 120° C.
- Dental/medical Application
- A dental/medical composite, a dental/medical sealant, a dental/medical adhesive and a dental/medical primer have been developed comprising a modified α,ω-(meth) acryloyl terminated macromonomer notably a di- or poly(meth)acrylate monomer having phosphorous ester groups or salts thereof, polymerizable monomers, fillers, polymerization initiators and stabilizers.
- As di- or poly(meth)acrylate monomer having phosphorous ester groups and salts thereof are employed pentaerythrit triacrylate monophosphate, dipentaerythrit penta-acrylate monophosphate, glycerol di(meth)acrylate monophosphate, triethylenglycol (meth)acrylate monophosphate.
- As organic polymerizable monomers were used mono- and polyfunctional (meth)acrylates, such as polyalylenoxide di- and poly(meth)acrylates, urethane di- and poly(meth)acrylates, vinyl-, vinylen- or vinyliden-, acrylate- or methacrylate substituted spiroorthoesters, spiroorthocarbonates or bicyloorthoesters. Preferably were used diethylenglycol dimethacrylate, triethylenglycol dimethacrylate, 3,(4),8,(9)-dimethacryloyloxymethyltricyclodecane, dioxolan bismethacrylate, glycerol trimethacrylate, furfuryl methacrylate in a content of 5 to 80 wt-%.
- As polymerization initiators are used thermal initiators, redox initiators and/or photo initiators in a content of 0.001 to 3 wt-%.
- Thermal initiators are initiators such as peroxides, peresters, perketals, peroxy carbonates, hydroxyperoxides, persulfates and azo compounds preferably dibenzoyl peroxide, cumol hydroperoxide, diisopropyl peroxycarbonate, dipotassium persulfate, azobisisobutylonitril.
- Preferred redox initiator systems for use in compositions in accordance with the invention are peroxide/amine systems, such as peracid/amine, perester/amine, perketal/amine, peroxycarbonate/amine and hydroxyperoxide/amine systems; peroxide/metal ion salts, such as ascorbic acid/peroxide/metal ion compounds, (thio)barbituric acid/peroxide/metal ion compounds, metal ion compounds/sulfinates, metal ion compounds/(thio)barbituric acid; transition metal carbonyl compounds and halogenids of organic compounds; boralkyl compounds, peroxysulfates and thiols. Most preferred redox-initiators are benzoylperoxide/N,N-bis-(β-hydroxyethyl)-p-toluidine, benzoylperoxide/N,N-bis-(β-hydroxyethyl)-p-benzoic acid ethylester, benzoylperoxide/tributylamine, cumol hydroperoxide/N,N-bis-(β-hydroxyethyl)-p-toluidine, diisopropyl peroxycarbonate/dimethylbenzylamine.
- Preferred photoinitiators for use in polymerizable compositions in accordance with the invention which include macromonomers with the scope of general formulas M-1 through M-12 are camphorquinone, benzophenone and 2,2-dimethylbenzylketal.
- Preferred fillers for use in compositions in accordance with the invention include inorganic compounds, such as La2O3, ZrO2, BiPO4, CaWO4, BaWO4, SrF2, Bi2O3, glasses and/or organic fillers, such as polymer granulate. Dental/medical composite compositions of the invention preferably include filler in an amount from about 50 to about 85 percent by weight. Dental/medical adhesive compositions of the invention preferably include filler in an amount from about 50 to about 65 percent by weight. Dental/medical sealant compositions of the invention preferably include filler in an amount from about 10 to about 50 percent by weight.
- Dental/medical composite compositions, adhesives and sealant of the invention include one-component and two-component paste/paste and powder/liquid-material which is to be mixed immediately before use.
- Shrinkage of composite compositions of the invention is preferably less than 4.5 and more preferably less than 1.5 percent by volume. Adhesive dental composite compositions of the invention containing radio-opaque fillers preferably provide a radio-opacity of at least 1.5 mm/mm Al, more preferably at least 3 to 7 mm/mm Al, and most preferably at least 7 mm/mmAl.
- The self-adhesive dental/medical composites compositions in accordance with a preferred embodiment of the invention have a fluoride release of at least 1 μg/cm2, more preferably at least 1-3 μg/cm2, and most preferably at least 3-10 μg/cm2.
- Self-adhesive dental/medical composites compositions in accordance with a preferred embodiment of the invention have an opacity of at least 40%, more preferably at least 20-40%, and most preferably at least 5-20%.
- The setting time of the adhesive dental/medical adhesive compositions in accordance with a preferred embodiment of the invention at 37° C. is between 1 minute and 60 minutes, more preferably between 5 and 30 minutes and most preferably between 2 and 5 minutes. The setting time of adhesive compositions in accordance with a preferred embodiment of the invention at 23° C. is preferably between 10 minutes and 300 minutes more, preferably between 5 and 100 minutes and most preferably between 5 and 20 minutes.
- Dental/medical composition in accordance with the invention is characterised by having an adhesion to dentine of at least 2 MPa; a fluoride release of at least 1 μg F− per week and per cm2 of the exposed surface of the composition; an opacity of at least C0.7=40%; and a compressive strength of at least 200 Mpa.
- In the following examples bond strength to dentin is measured using extracted human teeth. The teeth used for the shear bond strength test are treated in 1% sodium hypochlorite for one hour and then stored in distilled water in a refrigerator at about 4° C. until needed. The teeth are washed with water, mechanically sanded with 320 grit carborundum paper until a flat dentin surface is exposed.
- The teeth are then individually blown dry with compressed dry air to ensure the dentin surface is free from noticeable moisture. A small plastic straw with 5 mm inner diameter and 2 to 3 mm in length is filled with the polymerizable composition being tested and seated on the dentin so as to form a post without pressure. The upper open end of the straw is covered with a thin film and cured. The specimens are then stored in distilled water at 37° C. for 24 hours. The teeth are then vertically mounted in a 7 cm ring using gypsum to provide a base for testing with the post at right angles thereto. The mounted specimens are then loaded in shear in an Zwick device model number 1455 manufactured by Zwick GmbH for measurement of adhesion of the post to dentin at 1 mm/minute crosshead speed. The load is applied parallel to the prepared tooth surface and at right angles to the post until fracture occurred. The shear bond strength is then calculated.
- In the examples Fluoride Release is measured by making three 1×20 mm (diameter) discs of each material. Each disc is placed in 25 ml water stored for a week at 37° C. Using an ion selective electrode, the fluoride concentration in mg F−/cm2 is determined for each disc. The average value of the three discs is recorded.
- In the Examples compressive strength is measured according to ISO 9917, EN 29917; flexural strength is measured according to ISO 4049, EN 24049; elastic modulus is measured according to ISO 4049, EN 24049; opacity is measured according to ISO 9912, EN 29912; IR spectra are measured using a Fourier transformation Infra Red spectrometer at 23° C.
- The macromonomer of formula M-1 wherein n is 1, R is —OC6H4—C(CH3)2—C6H4O—, R1 is —CH3, R2 is —(CH2)4— is referred to hereinafter as macromonomer M-1A and is prepared by reacting 150.000 g (0.441 mol) bisphenol-A diglycidyl ether, 32.200 g (0.220 mol) adipic acid and 2.000 g triethylbenzylammoniumchloride for four hours at 80° C. while stirring. To the obtained glycidyl terminated prepolymer are added 37.900 g (0.441 mol) methacrylic acid and 0.444 g 2.6-di-tert.-butyl-p-cresol and are reacted for another four hours at 80° C. The methacrylate terminated macromonomer is soluble in organic solvents such as chloroform, DMF and THF. In the IR-spectrum no absorption of epoxide groups at ν=915 and 3050 cm−1 is observed. Absorption of ester groups is seen at ν=1720 cm−1. In the 1H NMR spectrum are found signals of the olefinic double bond at δ(CH2=)=6,137/6,119/6,115 ppm and at δ(CH2=)=5,587/5,582/5,555/5,548 ppm.
- Preparation of the Macromonomer of Formula M-1B wherein E is Hydroxyl, n is 1, R is —O(CH2)4O—, R1 is —CH3, R2 is —(CH2)4—.
- 200.00 g (0.99 mol) butanediol diglycidyl ether, 72.26 g (0.49 mol) adipic acid, 85.13 g (0.99 mol) methacrylic acid, 4.72 g triethylbenzylammoniumchloride and 0.60 g 2,6-di-tert.-butyl-p-cresol are stirred together and heated for four hours at 90° C. The obtained methacrylate terminated macromonomer is soluble in organic solvents such as chloroform, DMF and THF. In the IR-spectrum no absorption of epoxide groups at 915 and 3050 cm−1 is observed. Absorption of ester groups is seen at 1720 cm−1. The viscosity measured with a Bohlin rheometer is ηdyn=3.3 Pas (25° C.).
- Preparation of the Macromonomer of Formula M-1F wherein E is Hydroxyl, n is 1, R is —OC6H4—CH2—C6H4O—, R1 is —CH3, R2 is —(CH2)4—.
- 100.00 g (0,32 mol) bisphenol-F diglycidyl ether, 23.39 g (0.16 mol) adipic acid, 27.56 g (0.32 mol) methacrylic acid, 65.47 g triethylenglycol dimethacrylate, 1.53 g triethylbenzylammoniumchloride and 0.30 g 2,6-di-tert.-butyl-p-cresol are stirred together and heated for four hours at 90° C. The obtained methacrylate terminated macromonomer is soluble in organic solvents such as chloroform, DMF and THF. In the IR-spectrum no absorption of epoxide groups at 915 and 3050 cm−1 is observed. Absorption of ester groups is seen at 1720 cm−1. The viscosity measured with a Bohlin rheometer is ηdyn=3.6 Pas (25° C.).
- Preparation of the Macromonomer of Formula M-3 wherein E is Hydroxyl n is 1, R is —OC6H4—C(CH3)2—C6H4O—, R1 is —CH3, R2 is —CH3, R2 is —(CH2)4O(CH2)4—, R3 is C6H5CH2—.
- 150.000 g (0.441 mol) bisphenol-A diglycidyl ether, 37.935 g (0.441 mol) methacrylic acid, 2.000 g triethylbenzylammonium chloride, 1.115 g 2,6-di-tert.-butyl-p-cresol (BHT) and 111.695 g triethylenglycol dimethacrylate were homogeneously mixed while heating. The mixture was kept for two hours at 90° C. After this time 75.020 g (0.221 mol) N,N′-dibenzyl-5-oxanonanediamine-1,9 were added to the mixture while stirring and kept for additional two hours at 90° C. The obtained methacrylate terminated macromonomer is soluble in organic solvents such as chloroform, DMF and THF. No absorption of epoxide groups at 915 and 3050 cm−1 is observed in the IR-spectrum. Absorption of ester groups were found at 1720 cm−1.
- Preparation of the Macromonomer of Formula M-5 wherein E is Hydroxyl, n is 1, R is —OC6H4—C(CH3)2—C6H4O—, R1 is —CH3, R2 is —(CH2)4O(CH2)4—, R3 is C6H5CH2—. 20.000 g (58.75 mmol) bisphenol-A diglycidyl ether and 40.012 g (117.50 mmol) N,N′-dibenzyl-5-oxanonanediamine-1,9 are homogeneously mixed while heating. The mixture is kept for two hours at 90° C. After this time 16.704 g (117.50 mmol) 2,3-epoxypropyl methacrylate is added to the mixture while stirring and the mixture is for another two hours at 90° C. The obtained methacrylate terminated macromonomer is soluble in organic solvents such as chloroform, DMF and THF. In the IR-spectrum no absorption of epoxide groups at 915 and 3050 cm−1 is observed.
- Preparation of the Macromonomer of Formula M-5 wherein E is Hydroxyl, n is 0, R1 is —CH3, R2 is —(CH2)4O(CH2)4—, R3 is C6H5CH2—.
- 50.000 g (146.83 mmol) N,N′-dibenzyl-5-oxanonianediamine-1.9, 41.750 g (293.67 mmol) 2,3-epoxypropyl methacrylate and 0.213 g BHT are homogeneously mixed while heating. The mixture is kept for two hours at 90° C. The obtained methacrylate terminated macromonomer is soluble in organic solvents such as chloroform, DMF and THF. In the IR-spectrum no absorption of epoxide groups at 915 and 3050 cm−1 are observed.
- Preparation of the Macromonomer of Formula M-6 wherein E is Hydroxyl, n is 1, R is —OC6H4—C(CH3)2—C6H4O—, R1 is —CH3, R4 is —C6H4—C(CH3)2—C6H4—.
- 150.000 g (0.441 mol) bisphenol-A diglycidyl ether, 50.299 g (0.220 mol) 2,2-bis-(4-hydroxy-phenyl)propane, 37.901 g (0.441 mol) methacrylic acid, 102.086 g triethylenglycol dimethacrylate, 2.000 g triethylbenzylammoniumchloride and 0.959 g 2,6-di-tert.-butyl-p-cresol are heated for four hours at 80° C.
- The obtained methacrylate terminated macromonomer is soluble in organic solvents such as chloroform, DMF and THF. In the IR-spectrum no absorption of epoxide groups at 915 and 3050 cm−1 is observed. Absorption of ester groups is found at 1720 cm−1.
- Preparation of the Macromonomer of Formula M-7 wherein E is Hydroxyl, n is 1, R is —OC6H4—C(CH3)2—C6H4O—, R1 is —CH3, R4 is —C6H4—C(CH3)2—C6H4—.
- 100.000 g (0.294 mol) bisphenol-A diglycidyl ether, 134.235 g (0.588 mol) 2,2-bis-(4-hydroxy-phenyl)propane, 83.520 g (0.588 mmol) 2,3-epoxypropylmethacrylate, 2.000 g triethylbenzylammonium chloride, 0.794 g 2,6-di-tert.-butyl-p-cresol (BHT) and 79.439 g triethylenglycol dimethacrylate are homogeneously mixed while heating. The mixture is kept for two hours at 80° C. The obtained methacrylate terminated macromonomer is soluble in organic solvents such as chloroform, DMF and THF. No absorption of epoxide groups at 915 and 3050 cm−1 is observed in the IR-spectrum. Absorption of ester groups is found at 1720 cm−1.
- The hydroxyl groups of macromonomer M-1A made by following the procedure of reference example 1 are esterified by adding 16.023 g (160.13 mmol) succinic anhydride to 56.900 g of a macromonomer-triethylenglycol dimethacrylate mixture containing 40.000 g (40.03 mmol) macromonomer M-1A and 16.9 g of triethylenglycol dimenthacrylate) while stirring for two hours at 90° C. In the IR-spectrum the esterified macromonomer containing dicarboxylic half ester units shows no absorption of hydroxyl groups at 3400 cm−1.
- The hydroxyl groups of macromonomer M-1B made by following the procedure of reference example 2 are esterified by adding 197.93 g (1.98 mol) succinic anhydride and 0.56 g triethylamine to 362.71 g macromonomer M-1B while stirring for four hours at 90° C. In the IR-spectrum the esterified macromonomer containing dicarboxylic half ester units shows no absorption of hydroxyl groups at 3400 cm−1. The viscosity measured with a Bohlin rheometer is θdyn=245 Pas (25° C.).
- The hydroxyl groups of macromonomer M-1F made by following the procedure of reference example 3 are esterified by adding 31.58 g (0.32 mol) succinic anhydride, 0.11 g triethylamine and 13.58 g triethyleneglycol dimethacrylate to 107.57 g of a macromonomer-triethylenglycol dimethacrylate mixture (containing 74.40 g, 0.08 mol macromonomer M-1F) while stirring for two hours at 90° C. In the IR-spectrum the esterified macromonomer containing dicarboxylic half ester units shows no absorption of hydroxyl groups at 3400 cm−1. θdyn=55.2 Pas (25° C.).
- The hydroxyl groups of macromonomer M-3 wherein each E is hydroxyl made by following the procedure of reference example 4 are esterified by adding to 40.000 g of a macromonomer-triethyleneglycol dimethacrylate mixture (containing 27.844 g, 23.32 mmol macromonomer M-3 wherein each E is a hydroxy moiety), 9.338 g (93.32 mmol) succinic anhydride and 12.156 g triethylenglycol dimethacrylate while stirring for two hours at 90° C. The IR-spectrum does not show any absorption of hydroxyl groups at 3400 cm−1 of the newly modified macromonomer containing dicarboxylic half ester units.
- The hydroxyl groups of macromonomer M-5 wherein each E is hydroxyl made by following the procedure of reference example 5 are esterified by adding 23.516 g (235.00 mmol) succinic anhydride to a macromonomer M-5 wherein each E is hydroxyl for four hours at 90° C. In the IR-spectrum the esterified macromonomer containing dicarboxylic half ester units show no absorption of hydroxyl groups at 3400 cm−1. The macromonomer is characterised by the following analytical data:
- Melting point: Fp.=46.6° C.
- Elemental analysis: (C93H120N4O24) 1678,01
calc. C 66.57 H 7.24 N 3.34 found C 66.60 H 6.80 N 2.73 - The hydroxyl groups of macromonomer M-5 wherein each E is hydroxyl made by following the procedure of reference example 5 are esterified by adding 8.239 g (42.88 mmol) trimellitic anhydride, 0.2 g N,N-bis(β-hydroxyethyl)-p-toluidin, 140 ml dioxane and 9.247 g triethylenglycol dimethacrylate to 40.008 g of a macromonomer-triethylenglycol dimethacrylate-mixture (containing 28.000 g, 21.44 mmol macromonomer M-5 wherein each E is hydroxyl) and kept for eight hours at 90° C. After evaporation of the dioxane, the macromonomer was washed with petrol ether and dried at 40° C. within six hours. In the IR-spectrum the newly modified macromonomer containing two dicarboxylic half ester units and two hydroxylic groups per average molecule show absorption of hydroxyl groups at 3400 cm−1 and of the ester unit at 1720 cm−1.
- The hydroxyl groups of macromonomer M-5 wherein each E is hydroxyl made by following the procedure of reference example 6 are esterified by adding 29.384 g (293.67 mmol) succinic anhydride to a macromonomer and kept for four hours at 90° C. In the IR-spectrum the esterified macromonomer M-5 wherein each E is hydrogen (n=0) containing dicarboxylic half ester units shows no absorption of hydroxyl groups at 3400 cm−1.
- The hydroxyl groups of macromonomer M-6 wherein each E is hydroxyl made by following the procedure of reference example 7 are esterified by adding 12.966 g (0.130 mol) succinic anhydride and 0.2 g N,N-bis(β-hydroxyethyl)-p-toluidin to 50.000 g of a macromonomer-triethylenglycol dimethacrylate mixture (containing 35.000 g, 0.032 mol macromonomer M-6 wherein each E is hydroxyl) while stirring and were kept for eight hours at 50° C.
- In the IR-spectrum the esterified macromonomer containing dicarboxylic half ester units shows no absorption of hydroxyl groups at 3400 cm−1.
- The hydroxyl groups of macromonomer M-7 wherein each E is hydroxyl made by following the procedure of reference example 8 are esterified by adding 12.966 g (0.130 mol) succinic anhydride and 0.2 g N,N-bis(β-hydroxyethyl)-p-toluidin to 50.000 g of a macromonomer-triethylenglycol dimethacrylate mixture (containing 35.000 g, 0.032 mol macromonomer M-7 wherein each E is hydroxyl) while stirring and kept for two hours at 80° C. The IR-spectrum does not show any absorption of hydroxyl groups at 3400 cm−1 of the esterified macromonomer containing dicarboxylic half ester units.
- The hydroxyl groups of macromonomer M-6 wherein each E is hydroxyl made by following the procedure of reference example 7 are esterified by adding 29.760 g (0.297 mol) succinic anhydride and 0.2 g N,N-bis(β-hydroxyethyl)-p-toluidin to a macromonomer M-6 wherein each E is hydroxyl while stirring and were kept for eight hours at 50° C. In the IR-spectrum the newly modified macromonomer containing dicarboxylic half ester units shows no absorption of hydroxyl groups at 3400 cm−1.
- The hydroxyl groups of macromonomer M-1A made by following the procedure of reference example 1 are esterified by adding 40.000 g (40.03 mmol) of a macromonomer M-1A dissolved in 100 ml THF 16.204 g triethylamine in 50 ml THF. After adding 24.553 g POCl3 (153.33 mmol) drops by drops while stirring at 0° to 5° C. the solution is stirred for further two hours at room temperature. Than the triethylamine hydrochloride is filtered off and the mixture is hydrolysed with 20 ml water. The organic solution is extracted three times with Na2CO3 solution and is separated from water. From the solution, dried over MgSO4, the solvent is evaporated and the macromonomer is dried.
- In the IR-spectrum the esterified macromonomer containing phosphoric ester units shows no absorption of hydroxyl groups at ν=3400 cm−1. New absorptions were found at ν=1007 cm−1, ν=2362 cm−1 and as shoulder at ν=3302 cm−1. In the 1H NMR spectrum signals of the olefinic double bonds at δ(CH2=)=6.06/6.12 ppm and at δ(CH2=)=5.58/5.59 ppm were found. The signals of the methine protons (CH—OP) appears at δ(CH)=5.22 and 5.88 ppm. Those of unreacted macromonomer (CH—OH) appears at δ(CH)=4.34/4.35 ppm.
- The HPLC analysis of the modified macromonomer shows the same distribution of oligomers as those of unreacted M-1. Consequently, only the oligomer analogous reaction takes place which does not change the distribution, and no side reaction or crosslinking was observed.
- The hydroxyl groups of macromonomer with M-3 wherein each E is hydroxyl made by following the procedure of reference example 4 are esterified by adding 60.000 g (50.26 mmol) of a macromonomer M-3 wherein each E is hydroxyl dissolved in 150 ml THF to 20.346 g triethylamine in 50 ml THF. After adding 30.829 g (201.06 mmol) POCl3 drops by drops while stirring at 0° to 5° C. the solution is stirred for further two hours at room temperature. Than the triethylamine hydrochloride is filtered off and the mixture is hydrolysed with 20 ml water. The organic solution is extracted three times with Na2CO3 solution and is separated from water. From the solution, dried over MgSO4, the solvent is evaporated and the macromonomer is dried. In the IR-spectrum the esterified macromonomer containing phosphoric ester units shows no absorption of hydroxyl groups at ν=3400 cm−1. New absorptions are found at ν=1007 cm−1, ν=2362 cm−1 and as shoulder at ν=3302 cm−1 and an broad absorption at ν=2600 to 2800 cm−1 of the ammonium salt.
- The hydroxyl groups of macromonomer M-6 wherein each E is hydroxyl made by following the procedure of reference example 7 are esterified by adding 40.000 g (37.83 mmol) of a macromonomer M-6 wherein each E is hydroxyl dissolved in 100 ml THF to 15.312 g triethylamine in 50 ml THF. After adding 23.200 g (151.31 mmol) POC3 drops by drops while stirring at 0° to 5° C. the solution is stirred for further two hours at room temperature. Than the triethylamine hydrochloride is filtered off and the mixture is hydrolysed with 20 ml water. The organic solution is extracted three times with Na2CO3 solution and is separated from water. From the solution, dried over MgSO4, the solvent is evaporated and the macromonomer is dried. In the IR-spectrum the esterified macromonomer containing phosphoric ester units shows no absorption of hydroxyl groups at ν=3400 cm−1. New absorptions are found at ν=1007 cm−1, ν=2362 cm−1 and as shoulder at ν=3302 cm−1.
- 1) 75% of hydroxyl groups of the macromonomer M-1A made by following procedure of reference example 1 are esterified with succinic acid anhydride by adding 148.387 g (0.116 mol) of a macromonomer M-1A to 34.890 g (0.349 mol) succinic anhydride and 0.183 g triethylamine and reacted for two hours at 80° C. while stirring. The macromonomer is dissolved in 250 ml THF and stirred for a further hour. The esterified macromonomer M-1A containing (n+2)-carboxylic half ester groups show in the IR-spectrum an absorption of νCO=1720 cm−1.
- 2) Esterification of the residual unreacted hydroxy groups of the macromonomer with POCl3.
-
- 100.00 g (161.29 mmol) of a monophosphate ester of pentaerythrit pentmethacrylate and 27.29 g (161.29 mmol) dimethylaminoethyl methacylate are dissolved in 84.86 g triethyleneglycol dimethacrylate and reacted for two hours at 50° C. In the IR spectrum at 2600 to 2850 cm−1 an absorption of the ammonium salt is found. At 3400 cm−1 no absorption of OH-groups is observed. The pH of the salt is 3.9.
- (Dental Adhesive)
- 1.242 g of the esterified macromonomer M-5 wherein each E is succinic acid half ester made by following the procedure of example 5, 0.411 g triethyleneglycol dimethacrylate, 0.008 g N,N-bis(β-hydroxyethyl)-p-toluidine and 0.006 g camphorquinone were homogeneously mixed. This mixture was applied in a ring (2 mm high, 5 mm i.d.) on the surface of teeth and exposed with visible light (irradiation lamp Prismetics Lite De Trey Dentsply) for 40 seconds. Immediately after fixation, the teeth are transferred for 24 hours to a chamber at 37±2° C. and 100% relative humidity. The adhesion measured with a Zwick-apparatus is 3.74±1.29 MPa.
-
- 2.420 g of 2,2-Bis-[p-(2-hydroxy-3-methacryloyloxypropoxy)-phenyl]-propan (Bis-GMA) which is modified with succinic anhydride at the hydroxyl groups, 0.821 g triethylenglycol dimethacrylate, 0,016 g N,N-bis(β-hydroxyethyl)-p-toluidine and 0.012 g camphorquinone were homogeneously mixed. This mixture is applied in a ring (2 mm high, 5 mm i.d.) on the surface of teeth and exposed with visible light (irradiation lamp Prismetics Lite De Trey Dentsply) for 40 seconds. Immediately after fixation, the teeth are transferred for 24 hours to a chamber at 37±2° C. and 100% relative humidity. The adhesion is 0.45±,20 Mpa, when measured with a Zwick-apparatus model number 1455, manufactured by Zwick GmbH & Co.
- (Dental Adhesive)
- 1.276 g of the esterified macromonomer M-5 wherein each E is succinic acid half ester made by following the procedure of example 5, 2.126 g triethylenglycol dimethacry-late, 6.5 g Strontium-alumo-silicate glass, 0.036 g camphorquinone and 0.045 g N,N-bis(β-hydroxyethyl)-p-toluidine are homogeneously mixed and polymerized photochemical. The product has the following properties: adhesin to dentine of 3.7±1.1 MPa, compressive strength 177±3.5 MPa, Elastic Modulus of 2383±71 MPa.
- (Dental Adhesive)
- 1.755 g of macromonomer M-5 wherein each E is succinic acid half ester of example 5, 0.752 g methylmethacrylate, 4.652 g Strontium-alumo-silicate glass, 0.010 g camphorquinone and 0.012 g N,N-bis(β-hydroxyethyl)-p-toluidine are homogeneously mixed and polymerized photochemically. The product obtained has the following properties: adhesion to dentine: 3.9±1.2 MPa, compressive strength 134±9.7 MPa, Elastic Modulus 2528±158 MPa.
- (Dental Adhesive)
- Paste A:
- 3.0404 g of macromonomer M-5 wherein each E is succinic acid half ester of example 5, 2.2512 g triethylenglycol dimethacrylate, 6.0 g CaWO4/ZrO2 (80/20) and 0.3135 g Strontium-alumo-silicate glass containing 10% lithium-sulfinate are homogeneously mixed.
- Paste B):
- 3.0404 g of macromonomer M-5 wherein each E is succinic acid half ester of example 5, 2.2512 g triethylenglycol dimethacrylate, 6.0 g CaWO4/ZrO2 (80/20), 0.0057 g octophen and 0.0668 g Strontium-alumo-silicate glass containing 1% Cu-(I)-thiourea complex are homogeneously mixed.
- Immediately before use paste A and paste B were mixed in the wt.-ratio 1:1 homogeneously. The gel time at 23° C. is estimated to be 32 min. and the gel time at 23° C. is 7 minutes. The radio-opacity (RO) of the obtained material is 6.5 mm/mm Al.
- (Dental Adhesive)
- Paste A:
- 8.001 g of macromonomer M-1A of example 1, 5.334 g triethylenglycol dimethacrylate, 14.467 g CaWO4/ZrO2 (80/20), 0.014 g 2.6-di-tert.-butyl-p-cresol and 0.533 g Strontium-alumo-silicate glass containing 10% lithium-sulfinate are homogeneously mixed.
- Paste B:
- 8.001 g of macromonomer M-1A of example 1, 5.334 g triethylenglycol dimethacrylate, 14.467 g CaWO4/ZrO2 (80/20), 0.014 g 2.6-di-tert.-butyl-p-cresol, 0.065 g octophen and 0.0533 g Strontium-alumo-silicate glass containing 1% Cu-(I)-thiourea complex are homogeneously mixed.
- Immediately before use paste A and paste B were mixed in the wt.-ratio 1:1 homogeneously. The gel time at 23° C. is about 96 minutes, and the gel time at 32° C. is 19 min. The radioopacity of the obtained material is about about 6.7 mm/mm Al.
- (Dental Adhesive)
- Powder:
- 15.000 g silylated Strontium-alumo-silicate glass and 2.000 g silylated Strontium-alumo-silicate glass containing 10% dibenzoylperoxide were mixed homogeneously.
- Liquid:
- 14.000 g of a macromonomer M-5 wherein each E is succinic acid half ester of example 5, 6.000 g tetrahydrofurfuryl-methacrylate, 0.405 g N,N-bis(β-hydroxyethyl)-p-toluidine, 0.0130 g 2,6-di-tert.-butyl-p-cresol are mixed homogeneously.
- Immediately before use powder and liquid were mixed in the wt.-ratio 1.73:1.00 homogeneously. The working time is 3.50 minutes and the setting time is 3.25 minutes. The adhesion to dentine is measured to be 2.2±0.7 MPa. The composite shows the following mechanical properties: compressive strength: 152±15 MPa, and elastic modulus of 1788±81 MPa.
- (Dental Adhesive)
- Paste A:
- 3.000 g of an ammonium salt of dipenta erthrytrol pentamethacrylate monophosphate and 2-(dimetyl)aminoethyl methacrylate (AP-1), 2.000 g macromonomer M-1A of example 1, 5.000 g triethylenglycol dimethacrylate, 15.000 g Strontium-alumo-silicate glass, 0.005 g 2,6-di-tert.-butyl-p-cresol and 0.200 g cumenhydroperoxide are mixed homogeneously.
- Paste B:
- 3.000 g of AP-1, 2.000 g macromonomer M-1A of example 1, 5.000 g triethylenglycol dimethacrylate, 15.000 g Strontium-alumo-silicate glass, 0.005 g 2,6-di-tert.-butyl-p-cresol, 0.4081 g of a 0.1% solution of cupric acetylacetonate in 2-hydroxy propylmethacrylate and 0.041 g ascorbic acid palmitate are mixed homogeneously.
- The following values are measured: gel time (gt) at 23° C. is 3:55 minutes, gel time is 37° C. is 2.10 minutes, adhesion to dentine 5.12 MPa, shrinkage (reduction in volume) is 4.33%.
- Application Example 8
- (Dental adhesive)
- Paste A:
- 3.000 g of AP-1, 2.000 g of macromonomer M-1,A of example 1, 5.000 g triethylenglycol dimethacrylate, 15.000 g Strontium-alumo-silicate glass, 0.005 g 2,6-di-tert.-butyl-p-cresol and 0.200 g tert.-butyl peroxy benzoate are mixed homogeneously.
- Paste B:
- 3.000 g of AP-1, 2.000 g macromonomer M-1A of example 1, 5.000 g triethylenglycol dimethacrylate, 15.000 g Strontium-alumo-silicate glass, 0.005 g 2,6-di-tert.-butyl-p-cresol, 0.6186 g of a 0.1% solution of cupric acetyacetonate in 2-hydroxy-propylmethacrylate and 0.051 g ascorbic acid palmitate are mixed homogeneously.
- The following values were measured: gel time (gt) at 23° C. is 6.10 minutes, (gt) at 37° C. is 3.20 minutes, adhesion to dentine 4.02 MPa, shrinkage (or reduction in volume) is 4.33%.
- (Dental Adhesive)
- Powder:
- 41.842 g silylated Strontium-alumo-silicate glass and 0.423 g dibenzoyl peroxide are mixed homogeneously.
- Liquid:
- 18.000 g of AP-1, 12.000 g triethylenglycoldimethacrylate, 0.180 g N,N-dimethyl-3,5-dimethyl aniline and 0.009 g 2,6-di-tert.-butyl-p-cresol were mixed homogeneously. Immediately before use powder and liquid were mixed in the weight ratio 1.40:1.00 homogeneously. The working time is 1:30 minutes and the setting time is 2:30 minutes.
- The following properties are measured:
adhesion to dentine: 7.68 ± 1.5 MPa compressive strength: 261 ± 14 MPa Elastic modules: 2917 ± 76 MPa shrinkage: 2.30% (percent reduction in volume) expansion: 1.17% (after storage for (expansion in length) 14 weeks in water at 37° C.) fluoride release: 5.33 μg/cm2 (after storage for 9 weeks in water at 37° C.). - (Dental Adhesive)
- Powder:
- 47.0 g silylated Strontium-alumo-silicate glass, 07544 g dibenzoyl peroxide and 2.52 g SrF2 are mixed homogeneously.
- Liquid:
- 28.570 g of an ammonium salt of dipentaerthrytrolpentamethacrylate monophosphate and 2-(dimetyl)aminoethyl methacrylate (ALP-1) containing 8.570 9 triethylenglycol dimethacrylate, 7.140 g macromonomer M-1A of example 1 containing 2.140 g triethylenglycol dimethacrylate, 13.990 g triethylenglycol dimethacrylate 0.250 g N,N-bis(β-hydroxyethyl)-p-toluidine and 0.05 g 2,6-di-tert.-butyl-p-cresol are mixed homogeneously.
- Immediately before use powder and liquid are mixed in the weight ratio 1.40:1.00 homogeneously. The working time is 5:50 minutes and the setting time is 4:15 minutes.
- The following properties are measured:
adhesion to dentine: 7.7 ± 0.8 MPa compressive strength: 295 ± 9 MPa (ISO 9917, EN 29917) flexural strength: 77.1 ± 7.1 MPa (ISO 4049, EN 24049) Elastic modulus: 4482 ± 147 MPa (ISO 4049, EN 24049) Opacity: 90.6% (ISO 9912, EN 29912) shrinkage ΔV: 5.8 ± 0.5% expansion ΔL: 1.52% (after storage for 28 weeks in water at 37° C.) fluoride release: 64.01 μg/cm2 (after storage for 27 weeks in water at 37° C.). - (Dental Adhesive)
- Powder:
- 46.2480 g silylated Strontium-alumo-silicate glass, 0.6937 g dibenzoyl peroxide and 2.3124 g SrF2 are mixed homogeneously.
- Liquid:
- 20.0000 g of AP-1 containing 14.0000 g triethylenglycol dimethacrylate, 5.0000 g macromonomer M-1A of example 1 containing 1.5000 g triethylenglycol dimethacrylate, 1.323 g demineralised water, 4.0000 g UDMA, 4.7000 g triethylenglycol dimethacrylate, 0.1485 g N,N-bis(β-hydroxyethyl)-p-toluidine and 0.0098 g 2,6-di-tert.-butyl-p-cresol are mixed homogeneously. The viscosity measured with a Bohlin rheometer is θdyn=1.086±0.005 Pas (23° C.).
- Immediately before use powder and liquid are mixed in the weight ratio 1.40:1.00 homogeneously. The working time is 4:00 minutes and the setting time is 4:00 minutes. The following properties were measured:
adhesion to dentine: 5.86 ± 1.53 MPa compressive strength: 301 ± 11 MPa flexural strength: 74.8 ± 4.8 MPa Elastic modulus: 5320 ± 271 MPa expansion ΔL: 1.10% (after storage for 5 weeks in water at 37° C.) fluoride release: 114.05 μg/cm2 (after storage for 28 weeks in water at 37° C.). - Application Example 12
- (Dental Sealant)
- 20.00 g macromonomer M-1A of example 1, 19.63 g triethylenglycol dimethacrylate, 0.18 g N,N-bis(β-hydroxyethyl)-p-toluidine, 0.12 g camphorquinone, 0.07 g 2,6-di-tert.-butyl-p-cresol and 60.00 g Strontium-alumo-silicate glass are mixed homogeneously. Results are given in table 1.
- (Dental Sealant)
- 20.00 g macromonomer M-1A of example 14, 19.63 g triethylenglycol dimethacrylate, 0.18 g N,N-bis(β-hydroxyethyl)-p-toluidine, 0.12 g camphoro quinone, 0.07 g 2,6-di-tert.-butyl-p-cresol and 60.00 g Strontium-alumo-silicate glass are mixed homogeneously. Results are given in table 1.
-
TABLE 1 Bis-GMA Macromonomer Macromonomer according M-1A according M-1A according comparative example 12 example 13 example 2 Adhesion to dentin 2.35 2.42 1.04 MPa Standard deviation ±0.79 ±1.06 ±0.34 MPa Molecular weight of 1399.4 1379.3 712.3 modified Macromo- nomer Molecular weight 349.9 344.8 356.2 per ester unit - (Dental Sealant)
- 10.00 g of AP-1 containing 3.00 g triethylenglycol dimethacrylate, 2.50 g macromonomer M-1A of example 1 containing 0.75 g triethylenglycol dimethacrylate, 1.25 g triethylenglycol dimethacrylate, 0.0875 g N,N-bis(β-hydroxyethyl)-p-toluidine, 0.0875 g camphor quinone, 11.49 g Strontium-alumo-silicate glass, 0.30 g Aerosil and 0.0088 g 2,6-di-tert.-butyl-p-cresol are mixed homogeneously. The viscosity measured with a Bohlin rheometer is θdyn=1.086±0.005 Pas (23° C.).
- (Dental/medical Composite)
- 2.000 g macromonomer M-6 of example 8 containing 0.400 g triethylenglycol dimethacrylate, 5.273 g Strontium-alumo-silicate glass, 0.010 g champhorquinon and 0.012 g N,N-bis(β-hydroxyethyl)-p-toluidin are homogeneously mixed and polymerized photochemical. The composite shows the following mechanical properties:
flexural strength: 76.6 ± 4.5 MPa flexural modules: 5074.0 ± 321 MPa compressive strength: 215.0 ± 6.0 MPa Elastic modules: 3180.0 ± 88 Mpa - It should be understood that while the present invention has been described in considerable detail with respect to certain specific embodiments thereof, it should not be considered limited to such embodiments but may be used in other ways without departure from the spirit of the invention and the scope of the appended claims.
Claims (23)
1. An esterified macromonomer within the scope of the general formula:
wherein
Z is an organic moiety,
R1 is hydrogen or a substituted or unsubstituted alkyl having from 1 to 12 carbon atoms, oxyalkyl having from 1 to 12 carbon atoms, alkenyl having from 2 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, aryl having from 6 to 12 carbon atoms or aralkyl having from 7 to 12 carbon atoms,
each E independently is a hydroxyl group, an organic or inorganic ester moiety and at least one E is an organic or inorganic ester moiety,
n and m each independently is an integer from 2 to 12.
2. The esterified macromonomer of claim 1 wherein said esterified macromonomer is within the scope at least one of formulas M-1 to M-12:
wherein
each E independently is a hydroxyl group, an organic or inorganic ester moiety and at least one E is an organic ester moiety or inorganic ester moiety,
R is a diether containing moiety, or diester containing moiety or tertiary amine containing moiety,
R1 is hydrogen or a substituted or unsubstituted alkyl having from 1 to 12 carbon atoms, oxyalkyl having from 1 to 12 carbon atoms, alkenyl having from 2 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, aryl having from 6 to 12 carbon atoms or aralkyl having from 7 to 12 carbon atoms,
R2 is a difunctional substituted or unsubstituted alkyl group having from 1 to 12 carbon atoms, alkenyl group having from 2 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, aryl having from 6 to 12 carbon atoms or aralkyl having from 7 to 12 carbon atoms,
R3 is hydrogen or a substituted or unsubstituted alkyl group having from 1 to 12 carbon atoms, alkenyl group having from 2 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, aryl having from 6 to 12 carbon atoms or aralkyl having from 7 to 12 carbon atoms,
R4 is a substituted or unsubstituted aryl having from 6 to 12 carbon atoms,
and n is an integers of at least 1.
6. The esterified macromonomer of claim 2 wherein at least one E comprises a carboxyl group.
7. The esterified macromonomer of claim 1 wherein E is derived from succinic acid anhydride, maleic acid anhydride, dichloro maleic acid anhydride, dimethyl maleic acid anhydride, malonic acid anhydride, aconit acid anhydride, adipic acid anhydride, 3,3-tetramethylen glutaric acid anhydride, cyclohexen-1,2 acid anhydride, nadinic acid anhydride, phthalic acid anhydride, trimellitic acid anhydride, 2-sulfobenzoic acid anhydride, 2-sulfo succinic acid anhydride, phthalic acid anhydride p-(O-phosphate), phthaloylchloride, succinic acid dimethyl ester, phosphorous penta chloride, phosphorous trichloride, phosphorous oxychloride, sulfuryl chloride, thionyl chloride, phosphor thionyl chloride, boric acid anhydride and boron trichloride.
8. The epoxide macromonomer of claim 1 wherein at least one E is a salt selected from the group consisting of ammonium, sulfonium, sodium, potassium, strontium, calcium and magnesium salts.
9. The esterified macromonomer of claim 2 wherein said macromonomer is esterified with a derivative of an inorganic or organic acid whereby at least a portion of —OH groups is converted into groups selected from the group consisting of —COOH, —PO3H2, —SO3H, —BO2H and salt thereof.
10. The macromonomer of claim 9 wherein said esterification is carried out in a solvent selected from the group consisting of THF, triethylenglycol bismethacrylate, diethylenglycol bismethacrylate, dioxolan bismethacrylate, vinyl-, vinylen- or vinyliden-, acrylate- or methacrylate substituted spiro-orthoester, spiroorthocarbonate or bicyloorthoester and 2,2-Bis[p-(acryloxyethoxy)phenyl]propane.
11. The macromonomer of claim 9 wherein said esterification is carried out in the presence of a tertiary amine.
12. The macromonomer of claim 2 further comprising a filler, a polymerizable monomer having at least one phosphorous ester group, a polymerization initiator and a stabilizer.
13. The composition according to claim 12 further comprising a polymerizable monomer selected from the group consisting of mono- and polyfunctional (meth)-acrylate, a urethane di- and poly(meth) acrylate, a vinyl-, vinylen- or vinyliden-, acrylate- or methacrylate substituted spiro-orthoester, a spiroorthocarbonate or a bicyloorthoester, and said monomer comprises from about 5 to about 80 percent by weight.
14. The composition according to claim 12 wherein said polymerization initiator is a thermal initiator, a redox-initiator or a photoinitiator.
15. The composition according to claim 12 wherein said filler comprises an inorganic filler and/or an organic filler.
16. The composition according to claim 15 wherein said filler is a fluoride releasing inorganic filler.
17. The composition formed by polymerizating the composition of claim 12 to form a polymeric product having an adhesion to dentine of at least 2 MPa, a fluoride release of at least 1 μg F− per week and per cm2 of the exposed surface of the composition, an opacity of at least C0.7=40% and a compressive strength of at least 200 MPa.
18. The composition of claim 2 comprising
from about 5 to about 20 percent by weight of said esterified macromonomer,
from about 10 to about 25 percent by weight of a di- or poly(meth)acrylate monomer having at least one phosphorous acid ester group,
from about 20 to about 35 percent by weight of a polymerizable monomer,
from about 50 to about 65 percent by weight of a filler and polymerization initiator and stabilizers.
19. The composition of claim 2 comprising
from about 3 to about 15 percent by weight of said esterified macromonomer,
from about 5 to about 25 percent by weight of di- or poly(meth)acrylate monomer having at least one phosphorous acid ester group,
from about 7 to about 40 percent by weight of a polymerizable monomer,
from about 50 to about 85 percent by weight of a filler and polymerization initiator and stabilizers.
20. The composition of claim 2 comprising
from about 5 to about 25 percent by weight of said esterified macromonomer,
from about 10 to about 30 percent by weight of di- or poly(meth)acrylate monomer having at least one phosphorous acid ester group,
from about 20 to about 40 percent by weight of a polymerizable monomer,
from about 10 to about 50 percent by weight of a filler and polymerization initiator and stabilizers.
21. The composition of claim 2 comprising
from about 5 to about 25 percent by weight of said esterified macromonomer,
from about 5 to about 30 percent by weight of di- or poly(meth)acrylate monomer having at least one phosphorous acid ester group,
from about 10 to about 40 percent by weight of a polymerizable monomer,
from about 30 to about 90 percent by weight of a diluent and polymerization initiator and stabilizers.
22. The composition of claim 2 comprising from about 1 to about 25 percent by weight of said esterified macromonomer, di- or poly(meth) acrylate monomer having at least one phosphous acid ester group and a polymerizable monomer and polymerization initiator from about 75 to about 99 percent by weight of an organic solvent and polymerization co-initiator.
23. An esterified macromonomer obtainable by esterification of at least a portion of the —OH groups of a macromonomer having at least one terminal double bond with at least one derivative of an inorganic or organic acid which introduces pendant groups exhibiting at least one acid moiety selected from the group of consisting of —COOH, —PO3H2, —SO3H, —BO2H and salts thereof, whereby the number of said acid moieties is chosen such that a polymer obtained by polymerizing said monomers has an adhesive strength to dentine of at least 2 MPa.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/054,360 US20020143108A1 (en) | 1993-05-26 | 2002-01-22 | Polymerizable compounds and compositions |
US10/938,459 US20050043490A1 (en) | 1993-05-26 | 2004-09-10 | Polymerizable compounds and compositions |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US6777493A | 1993-05-26 | 1993-05-26 | |
US08/217,998 US5624976A (en) | 1994-03-25 | 1994-03-25 | Dental filling composition and method |
US23153594A | 1994-04-22 | 1994-04-22 | |
US35921794A | 1994-12-19 | 1994-12-19 | |
US08/582,235 US6369164B1 (en) | 1993-05-26 | 1996-01-03 | Polymerizable compounds and compositions |
US10/054,360 US20020143108A1 (en) | 1993-05-26 | 2002-01-22 | Polymerizable compounds and compositions |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US23153594A Continuation-In-Part | 1993-05-26 | 1994-04-22 | |
US08/582,235 Continuation US6369164B1 (en) | 1993-05-26 | 1996-01-03 | Polymerizable compounds and compositions |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/938,459 Continuation US20050043490A1 (en) | 1993-05-26 | 2004-09-10 | Polymerizable compounds and compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
US20020143108A1 true US20020143108A1 (en) | 2002-10-03 |
Family
ID=27490659
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/582,235 Expired - Lifetime US6369164B1 (en) | 1993-05-26 | 1996-01-03 | Polymerizable compounds and compositions |
US10/054,360 Abandoned US20020143108A1 (en) | 1993-05-26 | 2002-01-22 | Polymerizable compounds and compositions |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/582,235 Expired - Lifetime US6369164B1 (en) | 1993-05-26 | 1996-01-03 | Polymerizable compounds and compositions |
Country Status (1)
Country | Link |
---|---|
US (2) | US6369164B1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1547571A1 (en) * | 2003-12-23 | 2005-06-29 | DENTSPLY DETREY GmbH | Dental root canal filling material |
DE102007029640A1 (en) | 2007-06-26 | 2009-01-02 | S&C Polymer Silicon- und Composite-Spezialitäten GmbH | Root canal filling material |
WO2020111022A1 (en) * | 2018-11-28 | 2020-06-04 | 昭和電工株式会社 | Ethylenic unsaturated resin composition and photosensitive resin composition |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050043490A1 (en) * | 1993-05-26 | 2005-02-24 | Klee Joachim E. | Polymerizable compounds and compositions |
US6369164B1 (en) * | 1993-05-26 | 2002-04-09 | Dentsply G.M.B.H. | Polymerizable compounds and compositions |
US20030045604A1 (en) * | 2001-08-13 | 2003-03-06 | Klee Joachim E. | Dental root canal filling cones |
US6723095B2 (en) * | 2001-12-28 | 2004-04-20 | Hemodynamics, Inc. | Method of spinal fixation using adhesive media |
EP1891127B1 (en) * | 2005-06-13 | 2010-03-24 | Alcon Inc. | Ophthalmic and otorhinolaryngological device materials |
US20080287566A1 (en) * | 2005-09-28 | 2008-11-20 | Essential Dental Systems, Inc. | Epoxy based oil free root canal sealer |
JP2008019183A (en) * | 2006-07-11 | 2008-01-31 | Gc Corp | Dental cement |
ATE525056T1 (en) * | 2007-07-05 | 2011-10-15 | G C Dental Ind Corp | DENTAL CEMENT |
WO2015095296A1 (en) | 2013-12-20 | 2015-06-25 | 3M Innovative Properties Company | Quantum dot article with improved edge ingress |
US10322069B2 (en) * | 2014-04-07 | 2019-06-18 | The Board Of Regents Of The University Of Texas System | Restorative resin compositions and methods of use |
CN108431172B (en) | 2015-12-31 | 2021-04-13 | 3M创新有限公司 | Article comprising particles with quantum dots |
WO2017116820A1 (en) | 2015-12-31 | 2017-07-06 | 3M Innovative Properties Company | Curable quantum dot compositions and articles |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4806381A (en) * | 1985-10-09 | 1989-02-21 | Ernst Muhlbauer Kg | Polymerizable compounds containing acid and acid derivatives, mixtures containing the same, and use thereof |
US6369164B1 (en) * | 1993-05-26 | 2002-04-09 | Dentsply G.M.B.H. | Polymerizable compounds and compositions |
Family Cites Families (226)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE277689C (en) | 1900-01-01 | |||
CA878006A (en) | 1971-08-10 | Ii Henry L. Lee | Dental filling material | |
CA563464A (en) | 1958-09-16 | General Electric Company | Oxygenated polymerizable acrylic acid type esters and methods of preparing and polymerizing the same | |
US173850A (en) | 1876-02-22 | Improvement in syringes | ||
US150262A (en) | 1874-04-28 | Improvement in caps for glass syringes | ||
US543829A (en) | 1895-07-30 | Isaac q | ||
CA817442A (en) | 1969-07-08 | M. Samour Carlos | Polymerizable monomers, copolymers thereof and adhesive made therefrom | |
US212975A (en) | 1879-03-04 | Improvement in syringes | ||
DE229140C (en) | 1908-02-25 | 1910-12-02 | ||
SU52106A1 (en) | 1937-02-17 | 1937-11-30 | Ю.Ю. Лурье | Compression Tester |
CH227363A (en) | 1942-03-06 | 1943-06-15 | Oppliger Ernst | Process for the production of stencil prints. |
DE1003448B (en) | 1953-03-28 | 1957-02-28 | Degussa | Process for the preparation of polymerization products |
US3066112A (en) | 1959-01-30 | 1962-11-27 | Rafael L Bowen | Dental filling material comprising vinyl silane treated fused silica and a binder consisting of the reaction product of bis phenol and glycidyl acrylate |
US3150801A (en) | 1960-09-06 | 1964-09-29 | Clark H Hamilton | Syringe |
US3200142A (en) | 1963-02-01 | 1965-08-10 | Rafael L Bowen | Surface-active comonomer and method of preparation |
US3327017A (en) | 1963-10-03 | 1967-06-20 | Japan Gas Chemical Co | Molding composition comprising a thermosetting aromatic hydrocarbon-aldehyde-phenol resin and a thermoplastic linear polymer |
NL128018C (en) | 1963-12-11 | |||
US3327016A (en) | 1964-07-09 | 1967-06-20 | Epoxylite Corp | Epoxide compositions cured with 1, 4-bis (aminomethyl) cyclohexane |
US3256226A (en) | 1965-03-01 | 1966-06-14 | Robertson Co H H | Hydroxy polyether polyesters having terminal ethylenically unsaturated groups |
US3595969A (en) | 1966-03-09 | 1971-07-27 | Princeton Chemical Res Inc | Anaerobic adhesive composition |
US3503128A (en) | 1966-03-21 | 1970-03-31 | Dentsply Int Inc | Dental filling composition of a coefficient of thermal expansion approximating that of natural tooth enamel |
US3564074A (en) | 1966-11-28 | 1971-02-16 | Dow Chemical Co | Thermosetting vinyl resins reacted with dicarboxylic acid anhydrides |
US3466259A (en) | 1966-12-15 | 1969-09-09 | Dow Chemical Co | Thickened thermosetting vinyl ester resins |
SU549150A1 (en) | 1967-09-14 | 1977-03-05 | Composition for filling teeth | |
CH557674A (en) | 1968-05-15 | 1975-01-15 | Espe Pharm Praep | MATERIAL FOR THE PRODUCTION OF FILLINGS AND DENTAL REPLACEMENT PARTS. |
CA878004A (en) | 1968-06-14 | 1971-08-10 | Ii Henry L. Lee | Dental filling package |
US3539533A (en) | 1968-06-14 | 1970-11-10 | Johnson & Johnson | Dental filling material |
US3754054A (en) | 1968-12-23 | 1973-08-21 | Mitsubishi Rayon Co | Radiation curable coating compositions and process for the preparation thereof |
US3586527A (en) | 1969-08-04 | 1971-06-22 | Ford Motor Co | Tetravinyl-unsaturated resin paint composition and painting process |
US3634542A (en) | 1969-08-04 | 1972-01-11 | Shell Oil Co | Unsaturated polyesters esterified with polycarboxylic acid anhydride and containing polyepoxide |
US3845056A (en) | 1970-01-29 | 1974-10-29 | Union Carbide Corp | Piperazinalkyl diacrylates |
CH529559A (en) | 1970-03-10 | 1972-10-31 | Pennwalt Corp | Composition for the preparation of a dental cement |
US3673558A (en) | 1970-05-04 | 1972-06-27 | Ciba Ltd | Polyaddition products and process for their manufacture |
US3709866A (en) | 1970-06-01 | 1973-01-09 | Dentsply Int Inc | Photopolymerizable dental products |
FR2126833A5 (en) | 1971-02-10 | 1972-10-06 | Showa Highpolymer | |
GB1381123A (en) | 1971-03-11 | 1975-01-22 | Shell Int Research | Process for curing epoxy resins |
CH545778A (en) | 1971-03-26 | 1974-02-15 | ||
US3769336A (en) | 1971-05-24 | 1973-10-30 | Lee Pharmaceuticals | Polyethylene glycol diacrylate |
US3815239A (en) | 1972-01-13 | 1974-06-11 | H Lee | Method of filling and sealing developmental pit and fissures |
US3835090A (en) | 1972-02-03 | 1974-09-10 | Johnson & Johnson | Dental restorative cement compositions |
US3853962A (en) | 1972-02-03 | 1974-12-10 | Johnson & Johnson | Novel methacrylate monomer |
US3845009A (en) | 1972-02-03 | 1974-10-29 | Johnson & Johnson | Cement compositions employing novel methacrylate monomer |
US3889385A (en) | 1972-02-11 | 1975-06-17 | Emery W Dougherty | Liquid dental opaquer and method |
US3742949A (en) | 1972-02-14 | 1973-07-03 | C Hill | Syringe assembly |
US3980483A (en) | 1972-04-24 | 1976-09-14 | Nippon Oil Seal Industry Co., Ltd. | Photocurable composition |
GB1461597A (en) | 1973-05-15 | 1977-01-13 | Ucb Sa | Unsaturated compounds and compositions containing them |
AT339523B (en) | 1973-09-21 | 1977-10-25 | Jenaer Glaswerk Schott & Gen | CERAMIC GLASS FOR FULL DENTALS |
GB1464250A (en) | 1973-12-27 | 1977-02-09 | Ciba Geigy Ag | Acrylate derivatives and their use as anaerobically-curing adhesives |
DE2406557C3 (en) | 1974-02-12 | 1981-02-19 | Kulzer & Co Gmbh, 6380 Bad Homburg | Hydroxyl group-containing diesters of acrylic acids and dental filling material containing them |
SU545353A1 (en) | 1975-03-04 | 1977-02-05 | Composition for filling teeth | |
US4097569A (en) | 1975-06-23 | 1978-06-27 | Youngstown Sheet And Tube Company | Modified vinyl ester resin and pipe made therefrom |
DE2534012C3 (en) | 1975-07-30 | 1981-05-14 | Bayer Ag, 5090 Leverkusen | Process for the production of binders |
US4097994A (en) * | 1975-11-24 | 1978-07-04 | Monsanto Company | Dental restorative composition containing oligomeric BIS-GMA resin and Michler's ketone |
US4051195A (en) | 1975-12-15 | 1977-09-27 | Celanese Polymer Specialties Company | Polyepoxide-polyacrylate ester compositions |
US4100045A (en) | 1975-12-29 | 1978-07-11 | The Dow Chemical Company | Radiation curable epoxy coating composition of dimer acid modified vinyl ester resin |
CA1107751A (en) | 1976-01-07 | 1981-08-25 | Gerhardt P. Werber | Anaerobic monomers and adhesives |
DE2612843B2 (en) | 1976-03-26 | 1979-10-31 | Dynamit Nobel Ag, 5210 Troisdorf | Bis-acrylic esters and bis-methacrylic esters, processes for the preparation of these compounds and their use |
JPS5330193A (en) | 1976-08-31 | 1978-03-22 | Kuraray Co | Human body hard tissue adhesive compostion |
US4187382A (en) | 1976-12-28 | 1980-02-05 | Union Carbide Corporation | Process for producing low color residue acrylate ester monomers |
US4187383A (en) | 1976-12-28 | 1980-02-05 | Union Carbide Corporation | Process for producing low color residue acrylate esters |
US4150012A (en) | 1977-01-21 | 1979-04-17 | Minnesota Mining And Manufacturing Company | Discernible dental sealant |
US4098735A (en) | 1977-02-14 | 1978-07-04 | Mobil Oil Corporation | Water reducible epoxy ester using monocarboxylic acid to control molecular weight |
US4135868A (en) | 1977-04-05 | 1979-01-23 | Herbert Schainholz | Supports for instrument sterilization |
US4284742A (en) | 1977-04-28 | 1981-08-18 | The B. F. Goodrich Company | Puncture-sealing tire |
DE2728764A1 (en) | 1977-06-25 | 1979-01-18 | Bayer Ag | FORMULATED DENTAL FILLING MATERIALS |
US4104257A (en) | 1977-07-27 | 1978-08-01 | The Dow Chemical Company | Process for preparing high molecular weight polyether resins from bisphenols and epoxy resins |
US4141865A (en) | 1977-10-06 | 1979-02-27 | The Dow Chemical Company | Catalysts for reaction of carboxylic acids with polyepoxides |
US4182833A (en) | 1977-12-07 | 1980-01-08 | Celanese Polymer Specialties Company | Cationic epoxide-amine reaction products |
CH631341A5 (en) | 1978-09-27 | 1982-08-13 | Behring Horst | CONTAINER FOR DENTAL INSTRUMENTS FOR ROOT TREATMENT. |
CH637150A5 (en) | 1978-10-30 | 1983-07-15 | Ciba Geigy Ag | EPOXY RESIN MOLDING. |
US4220582A (en) | 1979-01-03 | 1980-09-02 | Lee Pharmaceuticals | Dental restorative compositions of improved X-ray opacity |
US4362889A (en) | 1979-02-09 | 1982-12-07 | The American Dental Association Health Foundation | Use of a polyfunctional surface-active comonomer and other agents to improve adhesion between a resin or composite material and a substrate |
US4197390A (en) | 1979-02-22 | 1980-04-08 | Shell Oil Company | Thickenable thermosetting vinyl ester resins |
US4368889A (en) | 1979-03-05 | 1983-01-18 | Reker Jr Louis M | Game apparatus for simulating school experience |
DD141677A1 (en) | 1979-03-15 | 1980-05-14 | Hoerhold Hans Heinrich | METHOD FOR PRODUCING HIGH-MOLECULAR THERMOPLASTIC EPOXY-AMINE POLYADDUCTS |
US4229559A (en) | 1979-05-01 | 1980-10-21 | Union Carbide Corporation | Novel bis(half ester) and compositions containing the same |
US4253830A (en) | 1979-06-08 | 1981-03-03 | North Pacific Dental, Inc. | Autoclavable dental bur block |
US4256910A (en) | 1979-09-06 | 1981-03-17 | The B. F. Goodrich Company | Liquid reactive polymers |
US4296004A (en) | 1979-09-10 | 1981-10-20 | Henkel Corporation | Polycyclic polyamines |
US4229376A (en) | 1979-09-10 | 1980-10-21 | Henkel Corporation | Polycyclic polyamines |
US4255468A (en) | 1979-10-12 | 1981-03-10 | H. B. Fuller Company | Method of marking paved surfaces and curable two-part epoxy systems therefor |
US4293074A (en) | 1979-12-04 | 1981-10-06 | Dunsky Joel L | Root canal equipment packaging |
US4595734A (en) | 1980-02-04 | 1986-06-17 | Interplastic Corporation | Molding compositions |
FR2478650A1 (en) | 1980-03-24 | 1981-09-25 | Commissariat Energie Atomique | CEMENT FOR USE IN FIXING BONE PROSTHESES |
CA1219990A (en) | 1980-06-09 | 1987-03-31 | Ronald S. Bauer | Saturated epoxy resin compositions exhibiting improved gloss retention |
ATE11909T1 (en) | 1980-07-23 | 1985-03-15 | Blendax Werke Schneider Co | ADDUCT OF DIISOCYANATES AND METHACRYLOYLALKYLETHERN, ALKOXYBENZOLEN RESPECTIVELY. ALKOXYCYCLOALKANES AND THEIR USE. |
US4366108A (en) | 1980-07-25 | 1982-12-28 | Ciba-Geigy Corporation | Liquid matrix system based on a mixture of epoxide resin and an amine curing agent for producing fibre-reinforced plastics components |
US4308085A (en) | 1980-07-28 | 1981-12-29 | Jenoptik Jena Gmbh | Process for the preparation of high molecular thermoplastic epoxide-amine-polyadducts |
US4406625A (en) | 1980-09-15 | 1983-09-27 | Scientific Pharmaceuticals, Inc. | Adducts of 1,4-bis[(3-Methacroyl-2-hydroxypropoxy)methyl]cyclohexane and derivatives thereof with isocyanates |
US4319049A (en) | 1980-10-06 | 1982-03-09 | Henkel Corporation | Bis hydroxymethyl tricyclo (5,2,1,02,6) decane |
EP0053442B2 (en) | 1980-12-03 | 1993-05-19 | Imperial Chemical Industries Plc | Dental compositions |
US4384853B1 (en) | 1981-04-09 | 1993-11-09 | Dentsply Research & Development Corp. | Ejector holder for capsule-like cartridge |
US4391590A (en) | 1981-04-09 | 1983-07-05 | Dentsply Research & Development Corp. | Cartridge for viscous material |
US4774063A (en) | 1981-04-20 | 1988-09-27 | Mdt Biologic Company | Container for use with sterilizers |
US4936775A (en) | 1981-05-04 | 1990-06-26 | Dentsply Research & Development, Corp. | Dental adhesive system |
DE3173960D1 (en) | 1981-05-15 | 1986-04-10 | Dow Chemical Rheinwerk Gmbh | Stabilized thermosettable ethylenically unsaturated epoxy ester resin compositions |
US4435497A (en) | 1981-06-19 | 1984-03-06 | Ciba-Geigy Corporation | Carboxyl-containing compositions and their polymerization |
US4569662A (en) | 1981-10-26 | 1986-02-11 | Dragan William B | Bulk cartridge for packaging and dispensing a dental material |
US4431421A (en) | 1981-10-28 | 1984-02-14 | Kanebo, Ltd. | Dental restorative composition |
DE3273225D1 (en) | 1981-11-13 | 1986-10-16 | Lingner & Fischer Gmbh | Curing compositions |
US4412056A (en) | 1981-12-22 | 1983-10-25 | Shell Oil Company | Polyglycidyl ethers, their preparation and use in curable compositions |
US4514342A (en) | 1982-02-16 | 1985-04-30 | Dentsply Limited | Polyethylenically unsaturated monophosphates |
SU1050706A1 (en) | 1982-04-07 | 1983-10-30 | 1-Й Ленинградский Ордена Трудового Красного Знамени Медицинский Институт Им.И.П.Павлова | Filling composition |
GB2123003B (en) | 1982-06-07 | 1985-09-18 | Ciba Geigy Ag | Hydroxyl terminated polyfunctional epoxy curing agents |
JPS5921646A (en) | 1982-06-25 | 1984-02-03 | Nippon Kayaku Co Ltd | Ethylenically unsaturated compound and preparation thereof |
US4405766A (en) | 1982-07-30 | 1983-09-20 | The Dow Chemical Company | Phosphonium bicarbonate catalysts for promoting reaction of epoxides with carboxylic acids or anhydrides |
US4446246A (en) | 1982-09-09 | 1984-05-01 | Three Bond Co., Ltd. | Catalyst systems for two-pack acrylic adhesive formulations |
AU568601B2 (en) | 1982-09-13 | 1988-01-07 | Dow Chemical Company, The | Process for making epoxy resins |
US4579904A (en) | 1982-09-24 | 1986-04-01 | Blendax Werke R. Schneider Gmbh & Co. | Diacrylic and dimethacrylic esters and their use |
GB8331151D0 (en) | 1982-12-06 | 1983-12-29 | Ici Plc | Aromatic oligomers and resins |
US4578504A (en) | 1983-06-03 | 1986-03-25 | Minnesota Mining And Manufacturing Company | Acrylate and methacrylate monomers and polymers |
US4541992A (en) | 1983-08-10 | 1985-09-17 | Hu-Friedy Manufacturing Co. | Apparatus for organizing, sterilizing, and maintaining medical/dental instruments |
GB8322710D0 (en) | 1983-08-24 | 1983-09-28 | Shell Int Research | Preparing aqueous binder composition |
US4548689A (en) | 1983-09-28 | 1985-10-22 | Mitsui Petrochemical Industries, Ltd. | Photocurable resin composition |
US4515634A (en) | 1983-10-17 | 1985-05-07 | Johnson & Johnson Dental Products Company | Castable glass-ceramic composition useful as dental restorative |
US4557848A (en) | 1983-12-08 | 1985-12-10 | Texaco Inc. | Crankcase lubricant |
US4714571A (en) | 1984-02-13 | 1987-12-22 | The Liposome Company, Inc. | Process for purification of phospholipids |
US5137990A (en) | 1984-02-28 | 1992-08-11 | Shell Oil Company | Heat-curable polyepoxide-(meth)acrylate ester compositions |
AU580775B2 (en) | 1984-05-14 | 1989-02-02 | Imperial Chemical Industries Plc | Aromatic oligomers |
CA1276648C (en) | 1984-07-19 | 1990-11-20 | Rafael L. Bowen | Method for obtaining strong adhesive bonding of composites to dentin, enamel and other substrates |
US4535148A (en) | 1984-08-01 | 1985-08-13 | Henkel Corporation | Polyglycidyl ethers of tricyclodecane and cured epoxy resins therefrom |
US4547531A (en) | 1984-08-02 | 1985-10-15 | Pentron Corporation | Two component (paste-paste) self-curing dental restorative material |
EP0182744B1 (en) | 1984-11-14 | 1992-08-12 | Ciba-Geigy Ag | Radiation curable filled epoxy resin compositions and their use |
US4657941A (en) * | 1984-11-29 | 1987-04-14 | Dentsply Research & Development Corp. | Biologically compatible adhesive containing a phosphorus adhesion promoter and a sulfinic accelerator |
WO1986003404A1 (en) | 1984-12-12 | 1986-06-19 | Sankinkogyo Kabushiki Kaisha | X-ray image forming material for dental use |
DE3447355A1 (en) | 1984-12-24 | 1986-07-03 | Basf Ag, 6700 Ludwigshafen | CROSSLINKABLE RESIN, LIGHT SENSITIVE RECORDING MATERIAL BASED ON THIS CROSSLINKABLE RESIN AND METHOD FOR PRODUCING A FLAT PRINTING PLATE BY MEANS OF THIS LIGHT SENSITIVE RECORDING MATERIAL |
US4713482A (en) | 1985-03-26 | 1987-12-15 | Ciba-Geigy Corporation | Maleic or phthalic acid half esters of alkoxylated fatty amines |
US4874799A (en) | 1985-05-17 | 1989-10-17 | M&T Chemicals Inc. | Aqueous akaline developable, UV curable urethane acrylate compounds and compositions useful for forming liquid 100 percent solids, solvent-free solder mask coatings |
JPS61268610A (en) | 1985-05-24 | 1986-11-28 | G C Dental Ind Corp | Dental adherent resin composition |
EP0204659B1 (en) | 1985-06-06 | 1991-11-21 | Ciba-Geigy Ag | Polyepoxydes and their use |
DE3671449D1 (en) | 1985-06-06 | 1990-06-28 | Ciba Geigy Ag | 2,6-DISUBSTITUTED 4-EPOXYPROPYLPHENYLGLYCIDYL ETHER AND THEIR USE. |
DE3522005A1 (en) | 1985-06-20 | 1987-01-02 | Bayer Ag | (METH) ACRYLIC ACID ESTERS AND THEIR USE |
US4854475A (en) | 1985-07-22 | 1989-08-08 | Hu-Friedy Manufacturing Co., Inc. | Instrument cassette |
IT1190382B (en) | 1985-07-26 | 1988-02-16 | Montedison Spa | ACRYLIC DIHESTERS FOR BISPHENOL ALCHYL ETHER, RELATED POLYMERS AND COMPOSITES FOR DENTAL USE |
US4795475A (en) | 1985-08-09 | 1989-01-03 | Walker Michael M | Prosthesis utilizing salt-forming oxyacids for bone fixation |
DE3536076A1 (en) | 1985-10-09 | 1987-04-09 | Muehlbauer Ernst Kg | POLYMERIZABLE CEMENT MIXTURES |
US4643303A (en) | 1985-10-15 | 1987-02-17 | Micromedics, Inc. | Modular sterilizing system |
JPS62161742A (en) | 1986-01-08 | 1987-07-17 | Nippon Paint Co Ltd | Terminal carboxyl group-containing reactive acrylic monomer and production thereof |
US4789620A (en) * | 1986-03-03 | 1988-12-06 | Mitsubishi Rayon Co. Ltd. | Liquid photosensitive resin composition containing carboxylated epoxy acrylates or methacrylates |
US4816528A (en) | 1986-06-23 | 1989-03-28 | E. I. Dupont De Nemours And Company | Chip resistant coating compositions containing epoxy-polyester graft copolymers |
DE3621039A1 (en) | 1986-06-24 | 1988-01-07 | Bayer Ag | METHOD FOR PRODUCING OLIGOESTERS HAVING HYDROXYL GROUPS AND THE USE THEREOF |
US4781921A (en) | 1986-10-06 | 1988-11-01 | The University Of Akron | Hydrogels of quadrol methacrylate polymers |
KR950003688B1 (en) | 1986-10-30 | 1995-04-17 | 미쓰이세끼유 가가꾸 고오교오 가부시끼가이샤 | Curable coposition |
SU1510131A1 (en) | 1986-11-21 | 1991-02-15 | 1-Й Московский Медицинский Институт Им.И.М.Сеченова | Composition filling root canals of teeth |
US4767326A (en) | 1986-11-25 | 1988-08-30 | Dentsply Research & Development Corp. | Cartridge container and ejector piston therefor |
US5106301A (en) | 1986-12-26 | 1992-04-21 | G-C Dental Industrial Corp. | Method for inspecting the root canal with a radiopaque impression material |
JPS63165302A (en) | 1986-12-26 | 1988-07-08 | G C Dental Ind Corp | Contrasting impression material for root canal inspection |
JPS63268780A (en) | 1987-04-28 | 1988-11-07 | G C Dental Ind Corp | Dentin bonding compound |
DE3730921A1 (en) | 1987-09-15 | 1989-03-23 | Degussa | HITZEHAERTBARE DENTAL MASSES |
US4964911A (en) | 1987-10-13 | 1990-10-23 | Den-Mat Corporation | Adhesive bonding of acrylic resins, especially in dentistry |
US4863993A (en) | 1987-12-09 | 1989-09-05 | Opi Products, Inc. | Surface priming composition for proteinaceous substrates; method of making and using same |
US5129825A (en) | 1987-12-21 | 1992-07-14 | Discko John Jr | Dental syringe and capsule for use therewith |
JPH01294609A (en) | 1988-02-09 | 1989-11-28 | Toyo Kagaku Kenkyusho:Kk | Dental sealer for root canal filling |
US4959199A (en) | 1988-02-19 | 1990-09-25 | Brewer Charles A | Autoclavable modular cassette and tray for holding dental instruments |
US4918136A (en) | 1988-03-28 | 1990-04-17 | Tokuyama Soda Kabushiki Kaisha | Adhesive composition |
US5160737A (en) | 1988-05-03 | 1992-11-03 | Perio Products Ltd. | Liquid polymer composition, and method of use |
EP0356868A3 (en) | 1988-09-01 | 1991-03-20 | Dentsply International, Inc. | A method of treating a tooth with adhesive dental cavity basing composition |
US4950697A (en) | 1988-09-15 | 1990-08-21 | Block Drug Co., Inc. | Thermoplastic and injectable endodontic filling compositions |
US5052927A (en) | 1988-10-24 | 1991-10-01 | Discko John Jr | Syringe and disposable capsule with cannula for use therewith |
JPH0667816B2 (en) | 1988-11-11 | 1994-08-31 | 株式会社クラレ | Dental restorative |
CA2005912A1 (en) | 1988-12-19 | 1990-06-19 | Peter Jochum | Dental compounds which contain bifunctional acrylic-acid esters or methacrylic-acid esters |
DE3843843A1 (en) | 1988-12-24 | 1990-07-05 | Henkel Kgaa | METHOD FOR IMPROVED PRODUCTION OF (METH) ACRYLIC ACIDES OF PRESCRIBED ALCOHOLS (IV) |
DE3843938A1 (en) | 1988-12-24 | 1990-06-28 | Henkel Kgaa | METHOD FOR IMPROVED PRODUCTION OF (METH) ACRYLIC ACIDES OF PRESCRIBED ALCOHOLS (II) |
DE3843930A1 (en) | 1988-12-24 | 1990-06-28 | Henkel Kgaa | METHOD FOR IMPROVED PRODUCTION OF (METH) ACRYLIC ACIDES OF PRECIOUS ALCOHOLS (III) |
DE3843854A1 (en) | 1988-12-24 | 1990-06-28 | Henkel Kgaa | METHOD FOR IMPROVED PRODUCTION OF (METH) ACRYLIC ACIDES OF PRESCRIBED ALCOHOLS (I) |
US4910329A (en) | 1989-01-11 | 1990-03-20 | Rohm And Haas Company | Process for preparing hydroxyalkyl esters |
DE69028488T4 (en) | 1989-01-27 | 1997-04-30 | Neil Rex Hall | REINFORCED COMPOSITE RESIN |
US4963093A (en) | 1989-02-06 | 1990-10-16 | Dragan William B | Dental syringe tip and syringe holder therefor |
US5083921A (en) | 1989-02-06 | 1992-01-28 | Dragan William B | Dental syringe tip |
DE3903407A1 (en) | 1989-02-06 | 1990-08-09 | Blendax Werke Schneider Co | DENTAL FUELING MATERIAL |
USD315956S (en) | 1989-02-06 | 1991-04-02 | Dragan William B | Dental syringe tip |
US5028638A (en) | 1989-02-09 | 1991-07-02 | Bayer Aktiengesellschaft | Hybrid plastic filling material |
US5006066A (en) | 1989-02-17 | 1991-04-09 | Rouse Melvin R | Autoclavable dental burr holder |
US4975055A (en) | 1989-03-02 | 1990-12-04 | A-Dec, Inc. | Flexible conduit structure for dental appliances |
US5084491A (en) | 1989-03-16 | 1992-01-28 | The Ohio University | Reinforcing glass ionomer dental filling material with stainless steel, or metals thereof |
US4969816A (en) | 1989-03-20 | 1990-11-13 | Melvin Drumm | Dental material carrier and applicator |
CA2012824A1 (en) | 1989-03-22 | 1990-09-22 | Marian D. Sullivan | Swag centerpiece with taper candle/chimney glass insert |
US4948848A (en) | 1989-04-07 | 1990-08-14 | Gaf Chemicals Corporation | Solution feed, slurry polymerization process for the production of copolymers of maleic anhydride and an alkyl vinyl ether having predetermined specific viscosities |
DE3911929A1 (en) | 1989-04-12 | 1990-10-18 | Hoechst Ag | AMPHIPHILES MONOMERS AND POLYMERS AND FILM OF AT LEAST ONE MONOMOLECULAR LAYER THEREOF |
JPH02279615A (en) | 1989-04-20 | 1990-11-15 | Mitsubishi Rayon Co Ltd | Adhesive composition for dental use |
NZ233540A (en) | 1989-05-03 | 1992-01-29 | Cowper Norman T | Pumping lump coal in a coal slurry having the same density as the lump coal |
FR2647794B1 (en) | 1989-06-02 | 1991-09-27 | Norsolor Sa | METHOD AND SYSTEM FOR PRIMING ANIONIC POLYMERIZATION OF (METH) ACRYLATES |
JP2926607B2 (en) | 1989-06-05 | 1999-07-28 | エルク アトケム ソシエテ アノニム | Ion polymerization method of acrylic monomer and polymerization initiation system |
US4889900A (en) | 1989-06-12 | 1989-12-26 | Shell Oil Company | Preparation of alkyl methacrylate monomers for anionic polymerization |
US5210157A (en) | 1989-08-15 | 1993-05-11 | Akzo N.V. | Interpenetrating network of ring-containing allyl polymers and epoxy resin, and a laminate prepared therefrom |
JP2780722B2 (en) | 1989-10-02 | 1998-07-30 | 三井化学株式会社 | Acrylic copolymer, its production method and its use |
FR2653036B1 (en) | 1989-10-17 | 1992-01-10 | Inst Francais Du Petrole | CATALYTIC COMPOSITION COMPRISING TITANIUM AND PHOSPHORUS, ITS PREPARATION AND ITS USE FOR THE CONDENSATION OF AN EPOXIDE ON A CARBOXYLIC ACID ANHYDRIDE. |
DE3937265A1 (en) | 1989-11-09 | 1991-05-16 | Metallgesellschaft Ag | SORTING METHOD AND DEVICE |
AU644618B2 (en) | 1989-12-28 | 1993-12-16 | G-C Shika Kogyo Kabushiki Kaisha | Odontotherapeutical materials |
DE69007956T2 (en) | 1990-01-03 | 1994-10-20 | Minnesota Mining & Mfg | Dental active ingredient containing anti-shrinkage additive. |
US5100320A (en) | 1990-01-16 | 1992-03-31 | Minnesota Mining And Manufacturing Company | Dental packaging material and cartridge |
CA2035650C (en) | 1990-02-14 | 1997-02-25 | Hajime Yasuda | Process of preparing polymer or copolymer of unsaturated carboxylic acid ester |
CA2041828A1 (en) | 1990-03-05 | 1992-11-04 | Richard L. Lindstrom | Viscoelastic solution |
DE4008696A1 (en) | 1990-03-17 | 1991-09-19 | Basf Ag | METHOD FOR THE PRODUCTION OF HOMO- AND COPOLYMERISES OF MONOETHYLENICALLY DISPRODUCED DICARBONE ACIDS AND THEIR USE |
CA2026417C (en) | 1990-03-28 | 1996-07-02 | Atsufumi Manabe | Dental adhesives |
FR2663926B1 (en) | 1990-06-27 | 1994-04-15 | Norsolor | NOVEL ACRYLATE CYCLES WITH ALCOHOL, ALDEHYDE AND / OR ETHER FUNCTION, MANUFACTURING METHOD THEREOF AND APPLICATION THEREOF TO OBTAIN NEW POLYMERS AND COPOLYMERS. |
FR2664272B3 (en) | 1990-07-06 | 1992-11-27 | Norsolor | PROCESS FOR THE SELECTIVE EPOXIDATION OF UNSATURATED (METH) ACRYLATES, NEW FUNCTIONAL (METH) ACRYLATES OBTAINED AND THEIR APPLICATION TO THE SYNTHESIS OF NEW POLYMERS. |
US5235008A (en) * | 1990-08-03 | 1993-08-10 | The Dow Chemical Company | Polymer modified adducts of epoxy resins and active hydrogen containing compounds containing mesogenic moieties |
HUT58266A (en) | 1990-08-31 | 1992-02-28 | Hoechst Celanese Corp | Acrylic esters of 1,1,1-tris/hydroxy-phenyl/-ethane, process for producing them, utilizing them as monofunctional polymerizable monomere and homo-and copolymeres from them |
JPH0819173B2 (en) | 1990-09-14 | 1996-02-28 | テルモ株式会社 | Polymerization initiator composition for controlling polymerization at interface and curable composition containing the same |
CA2026467A1 (en) | 1990-09-28 | 1992-03-29 | Ralph G. Moyer | Intertube thermal conductance rate limiting device |
US5173273A (en) | 1990-10-11 | 1992-12-22 | Brewer Charles A | Cassette for dental instruments |
US5171763A (en) | 1990-12-14 | 1992-12-15 | Tokuyama Soda Kabushiki Kaisha | Curable composition |
US5267859A (en) | 1991-01-07 | 1993-12-07 | Centrix, Inc. | Bulk dental cartridge |
US5165890A (en) | 1991-01-07 | 1992-11-24 | Centrix, Inc. | Dosing dental cartridge |
US5122057A (en) | 1991-01-07 | 1992-06-16 | Centrix, Inc. | Dosing dental cartridge |
GB2255781B (en) | 1991-02-15 | 1995-01-18 | Reactive Ind Inc | Adhesive system |
DE4105550A1 (en) | 1991-02-22 | 1992-08-27 | Bayer Ag | ADHESIVE COMPONENT FOR TREATING THE DENTAL SUBSTANCE |
DE4109048A1 (en) | 1991-03-15 | 1992-09-17 | Tech Hochschule C Schorlemmer | Modified epoxy-(meth)acrylate(s) for prods. with low water absorption - obtd. by esterification of epoxide oligomers, e.g. bisphenol=A di:glycidyl ether, with (meth)acrylic acid and satd. mono:carboxylic acid |
JP3034650B2 (en) | 1991-06-19 | 2000-04-17 | 株式会社ジーシー | Tooth adhesive |
US5294413A (en) | 1991-07-17 | 1994-03-15 | Hu-Friedy Mfg. Co., Inc. | Sterilization and storage cassette |
US5215726A (en) | 1991-07-17 | 1993-06-01 | Hu-Friedy Mfg. Co., Inc. | Two-tiered sterilization and storage cassette |
US5108287A (en) | 1991-09-05 | 1992-04-28 | Nancy Yee | Autoclavable drill bit container |
DE4129613A1 (en) | 1991-09-06 | 1993-03-11 | Wacker Chemie Gmbh | STORAGE-RESISTANT, PERMANENTLY WET-WETTABLE VULCANISATE-RESULTING POLYSILOXANE |
US5236362A (en) | 1991-10-11 | 1993-08-17 | Essential Dental Systems, Inc. | Root canal filling material and adhesive composition |
US5172810A (en) | 1991-11-06 | 1992-12-22 | Brewer Charles A | Receptacle for holding dental burrs |
CA2086770A1 (en) | 1992-01-10 | 1993-07-11 | Jyi-Faa Hwang | Epoxy interpenetrating polymer networks having internetwork bonds |
USD353673S (en) | 1992-02-27 | 1994-12-20 | Centrix, Inc. | Combined dental syringe tip and a sealing cap |
US5204398A (en) | 1992-03-17 | 1993-04-20 | Essential Dental Systems, Inc. | Composite dental cement composition containing a lanthanide series compound |
US5384103A (en) | 1992-03-17 | 1995-01-24 | Micromedics, Inc. | Instrument tray |
DE4217761A1 (en) | 1992-05-29 | 1993-12-02 | Univ Schiller Jena | â, þ-methacrylate-terminated epoxy-carboxylic acid macromonomers |
US5346677A (en) | 1992-09-04 | 1994-09-13 | Risk William B | Instrument cassette |
US5217372A (en) | 1992-09-17 | 1993-06-08 | Truocchio Michael A | Dentistry practice |
US5324273A (en) | 1992-09-30 | 1994-06-28 | Centrix, Inc. | Disposable barrel dental impression material syringe |
US5322440A (en) | 1992-10-20 | 1994-06-21 | Kerr Manufacturing Company | Dental syringe tip |
US5279800A (en) | 1992-11-25 | 1994-01-18 | C/T Med-Systems Ltd., Inc. | Dental cassette kit |
-
1996
- 1996-01-03 US US08/582,235 patent/US6369164B1/en not_active Expired - Lifetime
-
2002
- 2002-01-22 US US10/054,360 patent/US20020143108A1/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4806381A (en) * | 1985-10-09 | 1989-02-21 | Ernst Muhlbauer Kg | Polymerizable compounds containing acid and acid derivatives, mixtures containing the same, and use thereof |
US6369164B1 (en) * | 1993-05-26 | 2002-04-09 | Dentsply G.M.B.H. | Polymerizable compounds and compositions |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1547571A1 (en) * | 2003-12-23 | 2005-06-29 | DENTSPLY DETREY GmbH | Dental root canal filling material |
WO2005063171A1 (en) * | 2003-12-23 | 2005-07-14 | Dentsply Detrey Gmbh | Dental root canal filling material |
US20080234404A1 (en) * | 2003-12-23 | 2008-09-25 | Dentsply Detrey Gmbh | Dental Root Canal Filling Material |
US8044113B2 (en) | 2003-12-23 | 2011-10-25 | Dentsply International, Inc | Dental root canal filling material |
DE102007029640A1 (en) | 2007-06-26 | 2009-01-02 | S&C Polymer Silicon- und Composite-Spezialitäten GmbH | Root canal filling material |
US20110053117A1 (en) * | 2007-06-26 | 2011-03-03 | Engelbrecht Juergen | Root Canal Filling Material |
WO2020111022A1 (en) * | 2018-11-28 | 2020-06-04 | 昭和電工株式会社 | Ethylenic unsaturated resin composition and photosensitive resin composition |
CN113166342A (en) * | 2018-11-28 | 2021-07-23 | 昭和电工株式会社 | Ethylenically unsaturated resin composition and photosensitive resin composition |
Also Published As
Publication number | Publication date |
---|---|
US6369164B1 (en) | 2002-04-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6369164B1 (en) | Polymerizable compounds and compositions | |
US5876210A (en) | Dental polymer product | |
EP0861230B1 (en) | Liquid crystalline (meth)acrylate compounds, composition and method | |
US5026902A (en) | Dental compsition of perfluoroalkyl group-containing (meth-)acrylate esters | |
EP0323521B1 (en) | Curable composition | |
US5171763A (en) | Curable composition | |
EP0799016B1 (en) | Polymerizable compounds and compositions | |
US7241856B2 (en) | Dental resins, dental composite materials, and method of manufacture thereof | |
JPH0237349B2 (en) | ||
EP1879544B1 (en) | Materials and dental composites made therefrom | |
US20040229972A1 (en) | Low shrinking polymerizable dental material | |
US5260476A (en) | Diacrylate compounds | |
US20050043490A1 (en) | Polymerizable compounds and compositions | |
US8163815B2 (en) | Dental resin composition, method of manufacture, and method of use thereof | |
JP2001509179A (en) | Polymerizable dental material with low shrinkage | |
US4243763A (en) | Tertiary aromatic amine accelerators in acrylic resin | |
EP1176937B1 (en) | Self-adhesive polymerizable monomer and dental/medical compositions therefrom | |
US7560500B2 (en) | Materials leading to improved dental composites and dental composites made therefrom | |
EP0571983B1 (en) | Alpha, omega-acrylate terminated macromonomer compounds | |
Klee et al. | Branched macromonomers and their application in dental composites. Monomers for low‐shrinking composites, 3 | |
US20050124722A1 (en) | Branched highly-functional monomers exhibiting low polymerization shrinkage | |
US4439554A (en) | Dioxo-piperidine substituted tertiary aromatic amine accelerators in acrylic resin | |
US7495038B2 (en) | Materials leading to improved dental composites and dental composites made therefrom | |
JP2578212B2 (en) | Maleic acid monoester compounds and adhesives containing them | |
US4390714A (en) | Tertiary aromatic amine accelerators in acrylic resin |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |