US20020176826A1 - Storage stable polymerizable compositions - Google Patents

Storage stable polymerizable compositions Download PDF

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Publication number
US20020176826A1
US20020176826A1 US09/419,497 US41949799A US2002176826A1 US 20020176826 A1 US20020176826 A1 US 20020176826A1 US 41949799 A US41949799 A US 41949799A US 2002176826 A1 US2002176826 A1 US 2002176826A1
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Prior art keywords
substituted
carbon atoms
unsubstituted
arylalkyl
peroxide
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US09/419,497
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English (en)
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Dr. Joachim E. Klee
Uwe Walz
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Individual
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Priority to US09/419,497 priority Critical patent/US20020176826A1/en
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Priority to US10/634,506 priority patent/US6998111B2/en
Abandoned legal-status Critical Current

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    • 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

Definitions

  • the invention relates to storage stable polymerizable dental compositions.
  • a polymerizable composition of the invention includes a peroxide which decomposes by fifty percent during 10 hours at temperatures higher than 75° C., a protected reducing agent which forms an active reducing form under acidic or basic conditions, a metal salt or an organ-metallic compound and an amine.
  • Compositions of the invention comprising the protected reducing agent are stable under the conditions of increased temperature and humidity.
  • Thermal polymerization initiators are required for a number of dental materials that polymerize under conditions in which a light polymerization is inefficient or only insecurity. Frequently, thermal setting dental cements are used for the adherence of ceramic or metallic restorations. Also the application of more opaque materials makes a self-curing thermal polymerization initiator necessary.
  • a thermal polymerization initiator in cases when a polymerization in the depth is required or a larger quantity of material is used, such as for a temporary crown and bridge material.
  • a large number of thermal setting materials comprise peroxide/amine initiators; most of them comprise BPO or modified BPO and amines.
  • dental materials must fulfill some special conditions for patient comfort, convenience and safety. Polymerization of dental materials must occur at relatively low temperatures (about 37° C.) in bulk with high rates of polymerization and high degree of polymerization (resulting in at most a minute percentage of residual monomer). They should have a long shelf-life for a period of at least 18 month, which means that they should be thermostable at ambient temperature and do not decompose under moisture conditions. Furthermore, the oxygen inhibited layer should be minimized.
  • the commonly used dibenzoyl peroxide/amine initiator systems have the advantage of a rapid polymerization of monomers and a relatively thin oxygen inhibited layer. Furthermore, such initiators resist moisture. Disadvantages of commonly used dibenzoyl peroxide/amine initiator systems are the thermal-self decomposition of dibenzoyl peroxide (BPO) and the discoloration of the aromatic amines used. Due to the thermal decomposition of BPO the useful life-time (storage period after which the composition remains useful) of a prior art dental/medical composition is very short.
  • BPO dibenzoyl peroxide
  • sulfinate were used benzolsulfinate and as amine N,N-di-(hydroxyethyl)-p-toluidine.
  • Polymerization initiators comprising of sulfinate/metal ions are suitable for production of artificial teeth, inlays and onlays. Furthermore the are usable in dental composites comprising MMA/PMMA. Disadvantageous is the bulk polymerization of methacrylates with this initiator due to the formation of an unpolymerized layer between the tooth and the polymer, which avoid the adhesion to teeth tissues.
  • Bredereck had used as polymerization initiators inorganic salts of sulfinic acid, hydrohalogenides and some times peroxide (DE 1 003 448).
  • One of the main desires of the prior art has been to find an efficient thermal polymerization initiator that has a long term thermal stability and a long term moisture stability. provides an efficient thermal polymerization initiator that has a long term thermal stability and a long term moisture stability.
  • Substituted as used herein refers to a fully or partially a halogen substituted moiety.
  • Unsubstituted as used herein refers to a moiety in which hydrogen is not substituted for by other atoms.
  • Alkyl as used herein refers to a paraffinic hydrocarbon group.
  • Alkylene refers to a hydrocarbon moiety having at least one double bond between two adjacent carbon atoms.
  • Cyclo alkenyl as used herein refers to a cyclic alkenyl moiety.
  • Cyclo alkyl as used herein refers to a cyclic alkyl moiety.
  • Arylalkenyl as used herein refers to a moiety having an aryl group and an olefinic group.
  • Arylalkyl as used herein refers to a moiety having an aryl group and an olefinic group.
  • Alkyl aryl refers to a moiety having an alkyl group and an aryl group. For a moiety having the structural formula
  • Alkenyl aryl refers to a moiety having an alkenyl group and an aryl group.
  • Alkyl aryl alkyl refers to a moiety having two alkyl groups and an aryl group.
  • Acylalkyl refers to a moiety having an acyl group and an alkyl group.
  • Acyl aryl alky refers to a moiety having an acyl group, an aryl group and an alkyl group.
  • the invention provides a thermal polymerization initiating composition, that withstands the temperatures of from 0° C. to 40° C. and humidity of from 0 percent to 100 percent, comprising from 0.2 to 5 percent by weight of a peroxide which decomposes by at most fifty percent by weight of the peroxide within 10 hours at a temperature of at least 75° C., from 0.2 to 3 percent by weight of a metal containing material, from 0.1 to 3 percent by weight of an inactive protected reducing agent that forms the active reducing agent, from 0 to 1 percent by weight of an amine.
  • FIG. 1 is a graph of differences in setting time (d ST) verses time for compositions made in accordance with the invention.
  • the invention provides a polymerizable composition, that withstands the temperatures of from 0° C. to 40° C. and humidity of from 0 percent to 100 percent.
  • the composition includes from 0.2 to 5 percent by weight of a peroxide which decomposes by at most fifty percent by weight within 10 hours at a temperature of at least 75° C., from 0.2 to 3 percent by weight of a metal containing material, from 0.1 to 3 percent by weight of an inactive protected reducing agent that forms the active reducing agent, and from 0 to 1 percent by weight of an amine.
  • protected reducing agent compounds useful in accordance with the inventio are characterized by the following structure
  • R 1 is hydrogen, substituted or unsubstituted alkyl having from 1 to 18 carbon atoms, a substituted or unsubstituted alkenyl having from 2 to 18 carbon atoms, substituted or unsubstituted acylalkyl having from 2 to 18 carbon atoms, substituted or unsubstituted cycloalkyl having from 5 to 18 carbon atoms, substituted or unsubstituted acylcycloalkyl having from 5 to 18 carbon atoms, substituted or unsubstituted acylcycloalkyl having from 5 to 18 carbon atoms, substituted or unsubstituted arylalkyl having from 5 to 18 carbon atoms or substituted or unsubstituted heteroarylalkyl having from 5 to 18 carbon atoms, substituted or unsubstituted acylarylalkyl having from 5 to 18 carbon atoms or substituted or unsubstituted acylheteroarylalkyl having from
  • R 1 is Si(R 5 ) 3, wherein R 5 is substituted or unsubstituted alkyl having from 1 to 18 carbon atoms, substituted or unsubstituted cycloalkyl having from 5 to 18 carbon atoms, substituted or unsubstituted arylalkyl having from 6 to 18 carbon atoms, substituted or unsubstituted alkenyl arylalkyl having from 7 to 30 carbon atoms,
  • R 2 is a substituted or unsubstituted alkyl having from 1 to 18 carbon atoms, substituted or unsubstituted acylalkyl having from 2 to 18 carbon atoms, substituted or unsubstituted cycloalkyl having from 5 to 18 carbon atoms, substituted or unsubstituted acylcycloalkyl having from 5 to 18 carbon atoms, substituted or unsubstituted arylalkyl having from 5 to 18 carbon atoms or substituted or unsubstituted heteroarylalkyl having from 5 to 18 carbon atoms, substituted or unsubstituted acylarylalkyl having from 5 to 18 carbon atoms or substituted or unsubstituted acylheteroarylalkyl having from 5 to 18 carbon atoms, substituted or unsubstituted alkyl arylalkyl having from 7 to 30 carbon atoms, substituted or unsubstituted acylalkyl having
  • R 2 is Si(R 5 ) 3 , wherein R 5 is substituted or unsubstituted alkyl having from 1 to 18 carbon atoms, substituted or unsubstituted cycloalkyl having from 5 to 18 carbon atoms, substituted or unsubstituted arylalkyl having from 6 to 18 carbon atoms, substituted or unsubstituted alkyl arylalkyl having from 7 to 30 carbon atoms,
  • X and Z are substituted or unsubstituted alkyl having from 1 to 18 carbon atoms, substituted or unsubstituted acylalkyl having from 1 to 18 carbon atoms, substituted or unsubstituted cycloalkyl having from 5 to 18 carbon atoms, substituted or unsubstituted acylcycloalkyl having from 5 to 18 carbon atoms, substituted or unsubstituted arylalkyl having from 5 to 18 carbon atoms or substituted or unsubstituted heteroarylalkyl having from 6 to 18 carbon atoms, substituted or unsubstituted acylaryl alkyl having from 5 to 18 carbon atoms or substituted or unsubstituted acylheteroarylalkyl having from 6 to 18 carbon atoms, substituted or unsubstituted alkyl arylalkyl having from 7 to 30 carbon atoms, substituted or unsubstituted acylalkyl having
  • Preferred substituted moieties are fully or partially halogen substituted protected reducing agent compounds include derivatives of ascorbic acid, 2,3-dihydroxy propenal, squaric acid, 1,2-dihydroxy cyclopenten-3,4,5-trion, dihydroxy fumaric acid
  • R 1 is a hydrogen atom, substituted or unsubstituted alkyl having from 1 to 18 carbon atoms, a substituted or unsubstituted alkenyl having from 2 to 18 carbon atoms, substituted or unsubstituted acylalkyl having from 2 to 18 carbon atoms, substituted or unsubstituted acylalkyl having from 2 to 18 carbon atoms, substituted or unsubstituted cycloalkyl having from 5 to 18 carbon atoms, substituted or unsubstituted acylcycloalkyl having from 5 to 18 carbon atoms, substituted or unsubstituted acylcycloalkyl having from 5 to 18 carbon atoms, substituted or unsubstituted arylalkyl having from 5 to 18 carbon atoms or substituted or unsubstituted heteroarylalkyl having from 5 to 18 carbon atoms, substituted or unsubstituted acylaryl alkyl having from 5
  • R 2 , R 3 and R 4 each independently are substituted or unsubstituted alkyl having from 1 to 18 carbon atoms, substituted or unsubstituted alkenyl having from 2 to 18 carbon atoms, substituted or unsubstituted acylalkyl having from 2 to 18 carbon atoms, substituted or unsubstituted acylalkyl having from 2 to 18 carbon atoms, substituted or unsubstituted cycloalkyl having from 5 to 18 carbon atoms, substituted or unsubstituted acylcycloalkyl having from 5 to 18 carbon atoms, substituted or unsubstituted acylcycloalkyl having from 5 to 18 carbon atoms, substituted or unsubstituted arylalkyl having from 5 to 18 carbon atoms or substituted or unsubstituted heteroarylalkyl having from 5 to 18 carbon atoms, substituted or unsubstituted acylarylalkyl having from
  • the modified ascorbic acid is modified by acetalisation, silylation, esterification, etherification in this manner, that these protecting groups are removable under acid conditions.
  • ascorbic acid is modified using 3,4-Dihydro-2H-pyran, p-nitro-benzoic acid, benzaldehyd, t-butyl alcohol, hexamethyldisilazane (HMDS).
  • Useful peroxides in this system are those of the type of diacyl peroxides, peresters, perketales, peroxy dicarbonates, dialkyl peroxides, ketone peroxides or alkyl hydroxy peroxides.
  • tert.-Butylperoxybenzoate 104 tert.-Butylamyl peroxide 104° C. Di-(tert.-butyl) peroxide 125° C. tert.-Butylhydro peroxide 170° C.
  • Amines useful in compositions in accordance with the invention include alkyl aryl amines, dialkyl aryl amines, trialkyl amines or derivatives therefrom.
  • Preferred amines useful in compositions in accordance with the invention are N,N-bis(hydroxyethyl)-p-toluidine, N,N-diethyl-p-benzoic acid ethyl ester, tributylamine.
  • Metal containing material useful in compositions in accordance with the invention include salts of a metal or an organo-metalic compounds. Organo-metalic compounds may be derived from the side-group elements of the periodic table of elements. Preferred salts of a metal and organo-metalic compounds useful in compositions in accordance with the invention include Cu, Ag, Ce, Fe, Cr, Co, Ni, V, Mn. Most preferred metal containing material are copper thiourea complex, copper acetyl acetonate, copper saccarinate, copper naphenoate, nickel acetyl acetonate, nickel salicylate, vanadium saccarinate, iron chloride, chromium salicylate, chromium acetate.
  • Preferred dental/medical compositions in accordance with the invention comprise at least a monomer having at least one polymerizable group, a polymerizable monomer as diluent, a filler and a stabilizer.
  • the monomer preferably has at least one polymerizable group is a mono- or polyfunctional (meth) acrylate or a macromonomer.
  • monomers are 2,2-Bis-[p-(2-hydroxy-3-methacryloyloxypropoxy)-phenyl]-propane, 7,7,9-trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexadecan-1,16-diol methacrylate, dipentaerthrytrolpentamethacrylate monophosphate, ⁇ , ⁇ -methacryloyl terminated epoxide-amine macromonomers, ⁇ , ⁇ -methacryloyl terminated epoxide-carboxylic acid macromonomers, ⁇ , ⁇ -methacryloyl terminated epoxide-phenol macromonomers.
  • Usable polymerizable diluents are mono(meth) acrylates and polyfunctional (meth) acrylates, such as polyalkylenoxide di-(meth) acrylates or poly(meth) acrylates, urethane di(meth) acrylates or poly (meth) acrylates, vinyl-, vinylen- or vinyliden-, acrylate- or methacrylate substituted spiroorthoesters, spiroorthocarbonates or bicycloorthoesters.
  • mono(meth) acrylates and polyfunctional (meth) acrylates such as polyalkylenoxide di-(meth) acrylates or poly(meth) acrylates, urethane di(meth) acrylates or poly (meth) acrylates, vinyl-, vinylen- or vinyliden-, acrylate- or methacrylate substituted spiroorthoesters, spiroorthocarbonates or bicycloorthoest
  • diethyleneglycol dimethacrylate triethyleneglycol dimethacrylate, 3,(4),8,(9)-dimethacryloyloxymethyltricyclodecane, dioxolan bismeth-acrylate, glycerol trimethacrylate, furfuryl methacrylate in an amount of 5 to 80 weight percent.
  • the filler may be inorganic fillers such as La 2 O 3 , ZrO 2 , BiPO 4 , CaWO 4 , BaWO 4 , SrF 2 , Bi 2 O 3 , glasses or an organic fillers, such as polymer granulate or a combination of organic/or inorganic fillers.
  • inorganic fillers such as La 2 O 3 , ZrO 2 , BiPO 4 , CaWO 4 , BaWO 4 , SrF 2 , Bi 2 O 3 , glasses or an organic fillers, such as polymer granulate or a combination of organic/or inorganic fillers.
  • a preferred cement composition in accordance with the invention has from 10 to 30 weight percent of an acidic monomer having at least one polymerizable group, 15 to 35 weight percent of a polymerizable monomer as diluent and a stabilizer, 50 to 65 weight percent of a filler and 0.34 to 12 weight percent of the polymerization initiator.
  • a preferred composite composition in accordance with the invention has from 5 to 25 weight percent of an acidic monomer having at least one polymerizable group, 5 to 20 weight percent of a polymerizable monomer as diluent and a stabilizer, 50 to 85 weight percent of a filler and 0.34 to 12 weight percent of the polymerization initiator.
  • a preferred sealer composition in accordance with the invention has from 15 to 55 weight percent of an acidic monomer having at least one polymerizable group, 20 to 40 weight percent of a polymerizable monomer as diluent and a stabilizer, 10 to 50 weight percent of a filler and 0.34 to 12 weight percent of the polymerization initiator.
  • the initiator system is distributed between a liquid component and a powder component wherein the liquid component includes acidic monomer having at least one polymerizable group, polymerizable monomer as diluent, peroxide and stabilizer; and the powder component includes filler, modified ascorbic acid, metal salt and an organic metal compound and amine. Also, it is preferred that the initiator system be distriubted between a liquid component and a powder component, wherein the liquid component includes acidic monomer having at least one polymerizable group, polymerizable monomer as diluent, peroxide, amine and stabilizer; and the powder component includes filler, modified ascorbic acid and metal salt or an organic metal compound.
  • reaction mixture was filtered and the ammonium chloride was rinsed with 2 ⁇ 20 ml of dry tetrahydrofuran. Removal of solvent in vacuo from the combined filtrate yielded 23.48 g (87.1%) of 3,5-Bis (trimethylsiloxy)-6-O-palmitoyl-L-ascorbic acid.
  • Table 3 shows Setting times (ST) of a composite comprising initiator stored at 30° C. and 70% of relative humidity. Difference dST of initial setting time immediately measured after preparation and setting times after storage at 30° C. and 70% relative humidity TABLE 3 time ST dST days min min 0 3.23 0.00 1 3.30 0.07 2 3.50 0.27 5 3.63 0.40 6 3.58 0.35 7 3.50 0.27 8 3.47 0.24 9 3.50 0.27 12 3.42 0.19 28 3.67 0.44 33 3.75 0.52 42 4.05 0.82
  • FIG. 1 is a graph of differences in setting time (d ST) verses time for compositions made in Example 1 indicated along line 10 and compositions made in Comparative Example 1 indicated along line 20.
  • silylated Strontium-alumo-silicate glass 23.000 g of silylated Strontium-alumo-silicate glass, 0.875 g of silylated Strontium-alumo-silicate glass comprising 2 weight percent copper thio urea complex, 1.000 g of silylated Strontium-alumo-silicate glass containing 5 weight percent silylated ascorbic acid and 0.125 g aerosil A 200 were mixed homogeneously.
  • silylated Strontium-alumo-silicate glass 25.1820 g of silylated Strontium-alumo-silicate glass, 1.0773 g of silylated Strontium-alumo-silicate glass comprising 2 weight percent copper thio urea complex and 0.5387 g of silylated Strontium-alumo-silicate glass containing 10 weight percent silylated ascorbic acid were homogeneously mixed.
  • powder and liquid are mixed in the weight ratio of 3.20:1.00 homogeneously.
  • the working time is 3.75 minutes and the setting time is 3:00 minutes.
  • the mixture is applied to a tooth in a patient's mouth and polymerizes to form polymeric composite filling material.
  • the composite has a compressive strength of 256.6 ⁇ 11.9 MPa, a flexural strength of 87.0 ⁇ 3.4 and E-modules of 7780 ⁇ 785 MPa.

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  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Dental Preparations (AREA)
  • Polymerization Catalysts (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US09/419,497 1998-04-23 1999-10-18 Storage stable polymerizable compositions Abandoned US20020176826A1 (en)

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US10/634,506 US6998111B2 (en) 1998-04-23 2003-08-05 Storage stable polymerizable compositions

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US09/419,497 US20020176826A1 (en) 1998-04-23 1999-10-18 Storage stable polymerizable compositions

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EP (1) EP0951894B1 (fr)
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US10470981B2 (en) 2015-08-28 2019-11-12 Gc Corporation Dental cement
US11325993B2 (en) 2017-12-26 2022-05-10 Tokuyama Dental Corporation Chemical polymerization initiator, adhesive composition, adhesive composition kit, dental material, dental material kit, and method of storing adhesive composition

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10470981B2 (en) 2015-08-28 2019-11-12 Gc Corporation Dental cement
US11325993B2 (en) 2017-12-26 2022-05-10 Tokuyama Dental Corporation Chemical polymerization initiator, adhesive composition, adhesive composition kit, dental material, dental material kit, and method of storing adhesive composition

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EP0951894B1 (fr) 2010-07-14
EP0951894A3 (fr) 2000-08-02
JPH11343304A (ja) 1999-12-14
DE69942571D1 (de) 2010-08-26
US6998111B2 (en) 2006-02-14
EP0951894A2 (fr) 1999-10-27
US20040029995A1 (en) 2004-02-12

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