Classifications

• • 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
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
  • A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
  • A61L24/06—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
  • A61P1/00—Drugs for disorders of the alimentary tract or the digestive system
  • A61P1/02—Stomatological preparations, e.g. drugs for caries, aphtae, periodontitis
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/08—Homopolymers or copolymers of acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/02—Applications for biomedical use

Definitions

• the present invention relates to thermally cleavable compounds and their use as crosslinking monomer components in particular ⁇ special in polymerization resins and polymers such as adhesives, composites, stereolithography materials, moldings, thermosets and chemically reversible mounting and fastening elements and in particular in dental materials such as adhesives, cements and Batungskompositen.
• Releasable adhesive bonds are becoming increasingly important in various fields of technology. Examples include the removal of components in the context of automated manufacturing processes, the repair of complex components with glued Partkomponen ⁇ th or the simplification of material separation in the recycling of such components at the end of the product life.
• the debonding of adhesive bonds can be achieved selectively (on demand) by significantly reducing the strength of the adhesive composite layer, for example, by heating.
• DE 198 32 629 A1 describes an adhesive system for forming reversible adhesive compounds based on polyurethanes, polyureas or epoxy resins, in which an additional component can be activated by introduction of energy in such a way that degradation of the adhesive components takes place. For example, by the input of heat or radiation energy from blocked precursors, organic bases or acids can be released, which cause degradation of the adhesive resin.
• WO 2010/128042 A1 describes technical adhesive compositions for releasable adhesive bonds for aircraft or vehicle construction, which consist of a conventional adhesive matrix and a particulate expansion substance such as azodicarbonamide. This takes place the dissolution of the components by heating the adhesive connection mindes ⁇ least to the expansion temperature of the expansion substance.
• compositions based on dimethacrylates having acid-labile tertiary carbonate groups and photoacids such as e.g. Triarylsulfonium salts.
• These compositions can be photochemically cured (photobonding) with suitable initiators such as the bisacylphosphine oxide Irgacure 819 with light in the visible range and soften again by irradiation with UV light at elevated temperature (photothermal debonding).
• WO 2013/034777 A2 describes dental materials which contain polymerizable compounds with a thermolabile or photolabile group, such as a thermolabile Diels-Alder group.
• a thermolabile or photolabile group such as a thermolabile Diels-Alder group.
• thermolabile Diels-Alder group such as a thermolabile Diels-Alder group.
• these materials must be exposed to relatively high temperatures, typically greater than 100 ° C, to effect a sufficiently rapid softening.
• the invention is based on the object observed ⁇ compositions which are polymerizable at room temperature, stable in storage and to form network polymers and polymerized Condition reversible thermally softened even at relatively low temperatures of insbeson ⁇ less than 100 ° C and thus especially for the production of materials with self ⁇ healing or debonding on demand properties such as chemically reversible mounting and fastening elements and Dentalwerk ⁇ materials such as adhesives, cements and filling composites are suitable.
• each independently a linear, branched or cyclic aliphatic or aromatic C 1 -C 30 radical represented by -O-, -S-, -CO-O-, -O-CO-, -CO-NR 3 -, -NR 3 -CO-, -O-CO-NR 3 -, -NR 3 -CO-O- or -NR 3 -CO-NR 3 may be interrupted, or an oligomeric group having a molecular weight of 200 to 2000 g / mol .
• Each U is independently CH 2 , S, NH, O,
• Each Y is independently H, R 4 , aryl, heteroaryl, -CN, -OR 4 , -N (R 4 ) 2 or -P (O) (OR 4 ) 2 ,
• one of the groups R is a bond and the other groups R are independently H or a linear or branched Ci-Cg-alkyl radical,
• R 1 , R 2 and R 3 are each independently H or a linear or branched Ci-Cg-alkyl radical
• Each R 4 is independently a linear or branched C 1 -C 6 -alkyl radical
• m can assume the values 2 to 6,
• n can independently assume the values 1, 2 or 3
• p can assume the values 0 to 10.
• a radical may be interrupted by a group such as -0- is understood to mean that the group is inserted into the carbon chain of the rest, that is bounded on both sides by carbon atoms ⁇ .
• the number of these groups is therefore at least 1 smaller than the number of carbon atoms, and the groups can not be terminal. According to the invention, radicals which are not interrupted by the groups mentioned are preferred.
• A represents an m-valent linear or branched aliphatic or aromatic C 2 -C 20 radical, in particular C 4 -C 8 radical, be ⁇ vorzugt C 8 -C 6 radical and particularly preferably C 0 -C 4 radical, by -0-, -C0-0-, -0-C0-, -CO-NR 3 - or -NR 3 -C0-0- interrupted -, -NR 3 -C0-, -0-CO-NR 3 may be, or is an oligomeric group having a molecular weight of 400 to 1000 g / mol,
• Q each independently absent or an (n + 1) -value strength linear or branched aliphatic or aromatic C 2 -C 5 radical, in particular C 3 -C 2 radical, preferably C 5 -C 0 radical is represented by -O-, -CO-O-, -O-CO-, -CO-NR 3 -, -NR 3 -CO-, -O-CO-NR 3 - or -NR 3 -CO-O- may be interrupted and special ⁇ DERS preferably represents -CH 2 -phenylene-CO-0-CH 2 -CH 2 -,
• Sp are each independently a linear or branched ali ⁇ phatic or aromatic C 2 -C 20 radical, in particular C 4 -C 8 - radical, preferably C 8 -C 6 radical and particularly preferably Ci 0 -C 4 - radical, the by -0-, -CO-O-, -O-CO-, -CO-NR 3 -, -NR 3 -CO-, -O-CO-NR 3 - or -NR 3 -CO-O- be interrupted may be, or an oligo ⁇ mer group having a molecular weight of 400 to 1000 g / mol,
• R 1, R 2 and R 3 are each independently H or a Ci-C 7 alkyl radical, in particular H or a Ci-C 5 alkyl radical and before ⁇ Trains t H or a Ci-C 3 alkyl radical stand,
• R 4 are each independently a C 1 -C 7 -alkyl radical, in particular a C 1 -C 5 -alkyl radical, preferably a C 1 -C 3 -alkyl radical and particularly preferably methyl, ethyl or isopropyl, m are the values Can assume 2, 3 or 4 and is preferably 2, n can each independently assume the values 1 or 2 and is preferably 1 and
• p can assume the values 0, 1, 2 or 3, in particular 0 or 1 and is preferably 0.
• T independently is selected from
• Each R is independently H or a Ci-C 7 alkyl residue, in the special ⁇ H or a Ci-C 5 alkyl radical, preferably H or a Ci-C 3 alkyl radical, and particularly preferably represents H.
• V stands for S
• W is omitted or is CH 2 or 0 and
• Each Y independently represents heteroaryl or -P (O) (OR 4 ) 2 and in particular represents pyridyl or -P (O) (OEt) 2 . Particularly preferred are in each case those groups in which all variables each have one of the preferred meanings defined above.
• thermolabile polymerizable compound of formula I can be very radically polymerize into network polymers that are stable at room temperature but even at moderately elevated temperatures of preferably less than 100 ° C show a significant reversible thermal cleavage.
• These compositions are therefore particularly suitable for the production of materials with self-healing or debonding-on-demand properties, especially for the preparation of polymerization resins and polymers such as adhesives, composites, stereolithography materials, mold ⁇ parts, duromers and mounting and fastening elements and Production of dental materials such as adhesives, cements and filling composites.
• compositions according to the invention are suitable for the preparation of polymers which have a half-life temperature of less than 120 ° C., in particular less than 110 ° C., preferably less than 100 ° C. and particularly preferably less than 90 ° C.
• half-life temperature denotes that temperature at which half of the thermolabile groups T contained in a sample are present in split form.
• the Bestim ⁇ mung the half-life temperature can be effected at a heating rate of 10 K / min, in particular on the basis of spectral ⁇ spectroscopic tracking of the retro Diels-Alder reaction by means of a spectrometer with temperaturregulierbarem sample holder.
• thermolabile polymerizable compounds of the formula I can be prepared simply. So can the synthesis hetero-Diels-Alder adduct groups according to the invention (HDA adduct groups) according to the following general formula:
• HDA adducts In the reaction of, for example, functionalized with OH groups diene building blocks (eg, furan derivative) and dienophiles (eg dithioester), one comes directly to HDA adducts by reaction with appropriate difunctional compounds, for example in the case of the OH-functionalized HDA adducts with diisocyanates or Dicarbonsaurederivaten, can be oligomerized, wherein one uses for OH-terminated oligomers, an excess of HDA adduct:
• diene building blocks eg, furan derivative
• dienophiles eg dithioester
• Suitable starting materials for the synthesis of the polymerization ⁇ capable di- or multifunctional Diels-Alder or hetero Diels-Alder adducts of the general formula I are suitable diene derivatives mainly substituted butadiene-1, 3- cyclopentadiene Derive (Cp) or furan derivatives.
• a special class are the photoenol derivatives, since here the diene species is first formed in situ. Photoenols can be prepared via a multistage synthesis from oxidation (DM Bauer, A. Rogge, L. Stolzer, C. Barner-Kowollik, L. Fruk, Chem. Commun.
• 1,3-butadiene derivatives are commercially available, such as 2,4-hexadiene-1-ol or sorbic acid. Further derivatives can be prepared by addition reactions (WM Grammer, G. Theryo, MA Hillmyer, Polym. Chem. 2012, 3, 1510-1516) as in 2-methylenebut-3-en-1-ol or by substitution reactions (Y. Jing, VV Sheares, Macromolecules 2000, 33, 6255-6261) syntheti ⁇ Sieren as in 3-methylene-4-pentenenitrile.
• Suitable Cp derivatives can be prepared, for example, by substitution reactions from the corresponding bromo-substituted derivatives with NaCp (S.Bian, AM Scott, Y. Cao, Y. Liang, S. Osuna, KN Houk, AB Braunschweig, J. Am. Chem. Soc. 2013, 135, 9240-9243) or NiCp 2 (M. Langer, J. Brandt, A. Lederer, AS Goldmann, Schach suer, C. Barner-Kowollik, Polym. Chem. 2014, 5, 5330- 5338).
• Cp derivatives such as (1-methyl-2,4-cyclopentadien-1-yl) methanol.
• Particularly suitable dienophiles for the synthesis of polymerisation ⁇ tion capable di- or multi-functional hetero-Diels-Alder adducts of the formula I are thioesters derivatives, such as 4- ((((Diethoxyphosphoryl) carbonothioyl) thio) methyl) benzoic acid or 4- (((pyridine-2-carbonothioyl) thio) methyl) benzoic acid, which can be prepared via substitution reactions or salt metathesis (A. Alberti, M. Benaglia , M. Laus, K. Sparnacci, J. Org. Chem. 2002, 67, 7911-7914).
• thioesters derivatives such as 4- ((((Diethoxyphosphoryl) carbonothioyl) thio) methyl) benzoic acid or 4- (((pyridine-2-carbonothioyl) thio) methyl) benzoic acid, which can be prepared via substitution reactions or salt metathesis (A. Alberti
• Thioaldehydes which in photochemi ⁇ rule cleavage of Phenacylsulfiden arise, may also be used as dienophiles (M. Glassner, KK Oeh- lenschlaeger, A. shaft, M. Bruns, C. Barner-Kowollik, Chem. Commun., 2013, 49, 633-635). They can be prepared by the reaction of phenacyl bromides with thiols (GA-N Gohar, SN Khattab, 0, 0 Farahat, HH Khalil, J. Phys., Org. Chem., 2012, 25, 343-350).
• dienophiles with an electron withdrawing group ⁇ in conjugation with the double bond such as substituted maleimides (AS Quick, H. Rothfuss, A. shaft, B. Richter, J. Fischer, M. Wegener, C. Barner-Kowollik, Adv. Funct Mater. 2014, 24, 3571-3580) suitable for (hetero) -Diels- Alder reactions.
• substituted maleimides AS Quick, H. Rothfuss, A. shaft, B. Richter, J. Fischer, M. Wegener, C. Barner-Kowollik, Adv. Funct Mater. 2014, 24, 3571-3580
• Hetero-Diels-Alder reactions typically proceed using a catalyst such as ZnCl 2 (see M. Langer, J. Brandt, A. Lederer, AS Goldmann, FH Schacher, C. Barner-Kowollik, Polym. Chem , 5, 5330-5338) or TFA (AJ Inglis, L. Nebhani, O. Altintas, FG Schmidt, C. Barner-Kowollik, Macromolecules 2010, 43, 5515-5520) or else free of catalyst (M. Glassner, G. Delaittre, M. Kaupp, JP Blinco, C. Barner-Kowollik, J. Am. Chem. Soc., 2012, 134, 7274-7277).
• a reaction medium both organic solvent and water can be used.
• Examples of the novel thermolabile polymerizable compounds of the formula I are: - 12 -
• compositions according to the invention preferably comprise one or more additional free-radically polymerizable monomers (co-monomers), in particular monofunctional or polyfunctional (meth) acrylic acid derivatives.
• monofunctional (meth) acrylic acid derivatives are meant compounds having a polyfunctional (meth) acrylic acid derivative compounds having two or more, preferably from 2 to 4 (meth) acrylic acid groups.
• Polyfunctional monomers have a crosslinking effect.
• Preferred mono- or polyfunctional (meth) acrylic acid derivatives according to the invention are methyl, ethyl, hydroxyethyl, butyl, benzyl, tetrahydrofurfuryl or isobornyl (meth) acrylate, bisphenol-A-di (meth) acrylate, bis-GMA (an addition product of methacrylic acid and bisphenol A diglycidyl ether), UDMA (an addition product of 2-hydroxyethyl methacrylate (HEMA) and 2, 2, 4-trimethylhexamethylene diisocyanate), di-, tri- or tetraethylene glycol di (meth) acrylate, Trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,10-decanediol di (meth
• Particularly preferred mono- or polyfunctional (meth) acrylic acid derivatives are N-mono- or disubstituted acrylamides such as N-ethylacrylamide, N, -dimethacrylamide, N- (2-hydroxyethyl) acrylamide or N-methyl-N- (2-hydroxyethyl ) acrylamide, N-mono-substituted Methacrylamides such as N-ethylmethacrylamide or N- (2-hydroxyethyl) methacrylamide and also N-vinylpyrrolidone and allyl ether.
• These mono ⁇ mers are characterized by a high degree of hydrolytic stability and are suitable because of their relatively low viscosity especially as diluting.
• Preferred polyfunctional (meth) acrylic acid derivatives with high stability to hydrolysis are crosslinking pyrrolidones such as 1,6-bis (3-vinyl-2-pyrrolidonyl) hexane, bisacrylamides such as methylene or ethylenebisacrylamide and bis (meth) acrylamides such as N, N'-diethyl - 1, 3-bis (acrylamido) propane, 1, 3-bis (methacrylamido) propane, 1, 4-bis (acrylamido) -butane or 1, 4-bis (acryloyl) piperazine obtained by reaction from the corresponding diamines with (meth) acrylic acid chloride can be synthesized.
• crosslinking pyrrolidones such as 1,6-bis (3-vinyl-2-pyrrolidonyl) hexane
• bisacrylamides such as methylene or ethylenebisacrylamide
• bis (meth) acrylamides such as N, N'-diethyl - 1, 3-bis (acrylamid
• compositions according to the invention may also contain other thermolabile crosslinking monomers as co-monomers.
• Thermo ⁇ labile cross-linking monomers comprise at least a thermolabile group between two polymerizable groups. Examples are polyfunctional (meth) acrylates or (meth) acrylamides having at least one thermolabile group between two (meth) acrylic groups. Suitable thermolabile groups are in particular thermolabile alkoxyamine, oxime ester, oximurethane or azo groups, peroxides and disulfones.
• Examples are the reaction products of N-hydroxy (meth) acrylamide with di- or triisocyanates, such as hexamethylene-1,6-diisocyanate (HDI), 2,2,2-trimethylhexamethylene-1,6-diisocyanate or the HDI trimer as well as products obtained by stoichiometric reaction of di- or triisocyanates with 1-Hydroxymethylacryl Acid Troreestern such as 1-hydroxymethylacrylic acid ethyl ester or with ß-ketoester (meth) acrylates such as 2-acetoacetoxy-ethyl methacrylate.
• Particularly suitable are gas-releasing thermolabile Vernet zermonomere.
• Examples are the esterification products of azobis (4-cyanovaleric acid) with hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate or with N- (hydroxyalkyl) (meth) acrylic amides such as N- (5-hydroxypentyl) methacrylamide or N-methyl-N- (2-hydroxyethyl) acrylamide.
• compositions according to the invention may preferably also contain radical-chain transfer-active additives which influence the structure of the polymers, in particular molecular weight, molecular weight distribution, network density and the adjustment of Properties such as glass transition temperature, width of the glass transition, impact and fracture toughness allow.
• compositions according to the invention may preferably also contain free-radically polymerizable, acid group-containing monomers (adhesive monomers).
• acid groups are carboxylic acid groups, phosphonic acid groups, phosphoric acid groups and Sulfonic acid groups.
• Preferred monomers with polymerizable carboxylic acids are maleic ⁇ acid, acrylic acid, methacrylic acid, 2- (hydroxymethyl) acrylic acid, 4- (meth) acryloyloxyethyltrimellitklareanhydrid, decylmalonkla 10-methacryloyloxy, N- (2-hydroxy-3-methacryloyloxypropyl) -N-phenyl- glycine and 4-vinylbenzoic acid.
• Preferred monomers with polymerizable phosphonic acid groups are vinylphosphonic acid, 4-vinylphenylphosphonic acid, 4-vinylbenzylphosphonic acid, 2-methacryloyloxyethylphosphonic acid, 2-methacrylamidoethylphosphonic acid, 4-methacrylamido-4-methylpentylphosphonic acid, 2- [4- (dihydroxyphosphoryl) -2 -oxa-butyl] -acrylic acid, 2- [4- (dihydroxyphosphoryl) -2-oxa-butyl] -acrylic acid ethyl and -2,4,6-trimethylphenyl ester.
• Preferred monomers having polymerizable phosphoric acid groups are 2-methacryloyloxypropyl mono- or dihydrogenphosphate, 2-methacryloyloxyethylmono- or dihydrogenphosphate, 2-methacrylyloxyethylphenylhydrogenphosphate, dipentaerythritol pentamethacryloyloxyphosphate, 10-methacryloyloxydecyldihydrogenphosphate, phosphoric mono (1-acryloylpiperidine-4 -yl) ester, 6- (methacrylamido) hexyl dihydrogen phosphate and 1,3-bis (N-acryloyl-N-propylamino) -propan-2-yl dihydrogen phosphate.
• Preferred monomers having polymerizable sulfonic acid groups are vinylsulfonic acid, 4-vinylphenylsulfonic acid and 3- (methacrylamido) propylsulfonic acid.
• mixtures of the aforementioned monomers are used.
• Preferred monomer mixtures contain, based on the total weight of the monomer mixture:
• 0 to 70 wt .-% preferably 1 to 60 wt .-%, particularly before Trains t ⁇ 5 to 50 and most preferably 10 to 30 wt .-% comonomer, and more particularly monofunctional and / or polyfunctional (meth) acrylates .
• Adhesive monomer 0-40 0-30 0-30 0-20 0-20 0-30
• compositions of this invention before ⁇ preferably also contain an initiator for the radical polymerization.
• an initiator for the radical polymerization is preferential ⁇ , benzophenone, benzoin and their derivatives or CC-diketones or their derivatives such as 9, 10-phenanthrenequinone, 1-phenyl-propan-1,2-dione, Diacetyl or 4, 4 'dichlorobenzil used.
• amines such as 4- (dimethylamino) benzoate, N, N-dimethylamino-ethyl methacrylate, N, -dimethyl -sym. -xylidine or triethanolamine used as a reducing agent.
• Norrish type I photoinitiators in particular acyl or bisacylphosphine oxides, monoacyltrialkyl or diacyldialkylgermanium compounds such as benzoyltrimethylgermanium, dibenzoyldiethylgermanium or bis (4-methoxybenzoyl) diethylgermanium. It is also possible to use mixtures of the various photoinitiators, for example dibenzoyldiethylgermanium in combination with camphorquinone and ethyl 4-dimethylaminobenzoate.
• redox initiator Kombinat are preferably ions, such as combinations of benzoyl peroxide with N, dimethyl-sym. -Xylidin or N, N-dimethyl-p-toluidine used.
• redox systems consisting of peroxides and such Reducing agents such as ascorbic acid, barbiturates or sulfinic acids are particularly suitable.
• compositions according to the invention may additionally contain a thermally gas-releasing additive.
• gas-releasing additives are e.g. Azo compounds such as azodicarbonamide, 2,2'-azobisisobutyronitrile or 2, 2 'azobis (4-cyano-pentanoic acid), N-nitroso compounds, hydrazides such as benzenesulfonylhydrazide, peroxides such as dicumole peroxide or acetonedicarboxylic acid. Examples of such compounds are described, for example, in St. Quinn, Plastics, Additives & Compounding 2001, 3, 16-21.
• the decomposition temperature can be adjusted in a manner known per se by the substituent pattern (cf D. Braun, R. Jakobi, Monatshefte Chemie 1982, 113, 1403-1414).
• compositions according to the invention may contain an additive which can convert irradiated electromagnetic radiation into heat.
• radiation-heat converters are organic, inorganic or organometallic substances or hybrid ⁇ components which are capable, UV, NIR or IR-radiation, visible light, microwave, or radio wave radiation, convert it to heat to thermally labile groups columns.
• ⁇ absorbent for UV, NIR or IR radiation dyes and pigments examples of dyes absorbing in the IR range are azo, methine, anthraquinone or porphyrin dyes.
• NIR radiation absorbing pigments are antimony and indium tin oxide, phthalocyanine, carbon black, Ni and Pt-dithiolene complexes.
• UV-absorbing compounds are benzotriazoles, triazines, benzophenones, cyanoacrylates, salicylic acid derivatives and hindered amine light stabilizers (HALS).
• additives that absorb in the frequency range of microwaves (1 to 300 GHz) or radio waves (10 kHz to 1 GHz) are ferromagnetic ceramic materials, so-called ferrites, which consist of the iron oxides hematite (Fe 2 O 3 ) or magnetite ( Fe 3 0 4 ) and others Oxides, for example, the metals Zn, Mn, or Ni built and are commercially available as a powder.
• ferrites consist of the iron oxides hematite (Fe 2 O 3 ) or magnetite ( Fe 3 0 4 ) and others Oxides, for example, the metals Zn, Mn, or Ni built and are commercially available as a powder.
• compositions according to the invention preferably also contain organic or inorganic filler particles in order to improve the mechanical properties or to adjust the viscosity.
• Preferred inorganic particulate fillers are amorphous spherical materials based on oxides such as ZrO 2 and TiO 2 or mixed oxides of SiO 2 , ZrO 2 and / or TiO 2 with an average average particle size of 0.005 to 2 ⁇ m, preferably 0.1 to 1 ⁇ m.
• nanoparticulate or microfine fillers such as fumed silica or precipitated silica having a mean average particle size of 5 to 200 nm, preferably 10 to 100 nm
• mini fillers such as quartz, glass ceramic or glass powder having an average particle size of 0.01 to 10 .mu.m, preferably 0.1 to 1 pm
• radiopaque fillers such as ytterbium trifluoride or nanoparticulate tantalum (V) oxide or barium sulfate having a mean average particle size of 10 to 1000 nm, preferably 100 to 300 nm.
• novel compositions can contain further additives, in particular solvents such as water or ethanol or corresponding solvent mixtures, as well as for example stabilizers, flavoring agents, coloring agents, microbicidal agents, fluoride ion-releasing additives, optical brighteners, or soft ⁇ wheeler.
• solvents such as water or ethanol or corresponding solvent mixtures
• stabilizers flavoring agents, coloring agents, microbicidal agents, fluoride ion-releasing additives, optical brighteners, or soft ⁇ wheeler.
• compositions based on a thermolabile polymerizable compound of the formula I which contain the following constituents: a) 0.1 to 50% by weight, in particular 1 to 40% by weight, preferably 2 to 30% by weight % and particularly preferably 5 to 30% by weight of compound of the formula I, b) 0.01 to 10 wt .-%, preferably 0.1 to 3.0 wt .-%, and particular ⁇ DERS preferably 0.2 to 2 wt .-% of initiator,
• Filled polymerization resins and composites on the basis of the inventive compounds of formula I preferably contain the following ingredients: a) 0.1 to 50 wt .-%, particularly 1 to 40 wt .-% and before ⁇ Trains t 1 by weight to 20th % Compound of the formula I,
• Dental materials based on the compounds of the formula I according to the invention preferably contain the following constituents: a) 0.1 to 50% by weight, in particular 1 to 40% by weight, preferably 2 to 30% by weight and more preferably 5 to 30% by weight of compound of the formula I,
• Adhesives preferably contain from 0 to 20% by weight and cements and composites preferably from 20 to 80% by weight of filler.
• Adhesives preferably contain preferably 0 to 60% by weight and more preferably 1 to 50% by weight of solvent.
• Compositions containing water as a solvent are preferred. Particularly preferred are compositions containing 0 to 20 wt .-% and in particular 1 to 10 wt .-% water.
• the debonding properties of compositions based on the novel compounds of the formula I can be influenced in a targeted manner by the composition of the materials.
• the setting of an appropriate for a particular purpose together ⁇ setting is part of the general knowledge and skill of the art.
• the concentration of thermolabile components ie the compounds of the formula I and, if appropriate, further thermolabile crosslinkers or gas-releasing additives in the adhesive or cement
• the ability for targeted debonding by heating increases.
• the debonding properties can also be varied by selecting the comonomers. In this case, the choice of monomers can specifically influence the glass transition region and thus the softening range of the polymers.
• the proportion of crosslinking monomers or by addition of monofunctional monomers the crosslinking ⁇ density and thus vary the strength and modulus of elasticity.
• the invention also provides the use of a polymerizable composition according to the invention as dental material or for producing a dental material, in particular an adhesive, cement or filling composite, and the use of a thermolabile polymerisable compound of the formula I. for the preparation of dental materials, preferably adhesives, cements or filling composites, and particularly preferably even ⁇ corrosive adhesives, cements or filling composites.
• a polymerizable composition according to the invention for producing a dental material, in particular an adhesive, cement or filling composite
• a thermolabile polymerisable compound of the formula I for the preparation of dental materials, preferably adhesives, cements or filling composites, and particularly preferably even ⁇ corrosive adhesives, cements or filling composites.
• the novel compounds of formula I can also be used for the production of materials with self-healing properties. In this case, the polymer network structure can be changed and voltages reduced or microcracks removed by targeted tempering of such materials. Furthermore, the compounds of the formula I can be
• Stereolithographically prepared wax models containing a polymer network based on the compounds of the formula I according to the invention can be easily removed again by degrading the polymer network at elevated temperature and then allowing the wax to expand.
• compounds of formula I can be used for producing che ⁇ mixing reversible assembling and fastening, for the reversible anchoring materials or tools in particular, anchors, screws, fittings and other fasteners in masonry, concrete, lightweight or other devices.
• the invention is therefore also the use of an inventive polymerizable composition as poly ⁇ merisationsharz, in particular as an adhesive, composite or stereo lithography materials, or for the preparation of a polymer, in particular a molding, thermoset, assembly or Fixed To ⁇ restriction member, as well as the use of a thermolabile poly ⁇ merisierbaren compound of formula I for the preparation of a polymerization resin or polymer and more particularly for manufacturing Position of an adhesive, composite, stereolithography material, molded part, duromer or mounting or fastening element.
• an inventive polymerizable composition as poly ⁇ merisationsharz, in particular as an adhesive, composite or stereo lithography materials, or for the preparation of a polymer, in particular a molding, thermoset, assembly or Fixed To ⁇ restriction member, as well as the use of a thermolabile poly ⁇ merisierbaren compound of formula I for the preparation of a polymerization resin or polymer and more particularly for manufacturing Position of an adhesive, composite, stereolithography material, molded part
• the Sus ⁇ pension was filtered.
• the filtration residue was washed with AN (100 ml).
• the filtrate was treated with methyl tert. butyl ether (MtBE, 200 ml) and saturated aqueous NaCl solution (100 ml) were added and the phases were separated.
• the organic phase was washed with saturated aqueous NaCl solution (2 ⁇ 100 ml).
• the combined water phases were reextracted with MtBE (100 ml).
• the combined organic phases were dried over anhydrous Na 2 S0 4 , filtered and concentrated on a rotary evaporator.
• the residue was combined with the above-obtained filtration residue, combined with AN (200 ml) and stirred at RT.
• Step 5 Bis-l, 10- ⁇ 10- (3- ⁇ 4- [2- (methacryloyloxy) -ethoxycarbonyl] -benzylsulfanyl ⁇ -3-pyridin-2-yl-2-thia-bicyclo [2.2.1] hept-5-en-1-ylmethyl) -decane
• the DiHDA linker prepared in Example 2 was admixed with 0.2% by weight of Ivocerin (bis (4-methoxybenzoyl) -diethylgermanium) as a photoinitiator, filled into a UV-Vis cuvette with a layer thickness of 1 mm and irradiated (30 min) with 3 Osram Dulux Blue lamps (3x 18 W,> 200 mW / cm 2 ) polymerized.
• Ivocerin bis (4-methoxybenzoyl) -diethylgermanium
• FIG. 1 shows quantitatively, on the basis of the VIS-spectroscopically detected regression of the colored dithioester unit by the retro-HDA reaction, the breaking up of the polymeric network as a function of the temperature.
• the absorption increases in the visible region of the spectrum (Abs. Max : 530 nm) until it reaches a maximum at 130 ° C., which indicates the complete course of the retro-HDA reaction.
• the absorption increases in the visible region of the spectrum (Abs. Max : 530 nm) until it reaches a maximum at 130 ° C., which indicates the complete course of the retro-HDA reaction.
• At 25 ° C no absorption in the visible region of the spectrum can be detected, indicating that the equilibrium of the HDA reaction at this temperature is completely on the side of the closed HDA form.
• the fact that only the closed form is present at room temperature could also be confirmed by 1 H NMR spectroscopy of the DiHDA linker.
• test specimens with the dimensions L: 25 mm, W: 5 mm, D: 1 mm were irradiated (30 min) with 3 Osram Dulux Blue lamps (3x 18 W,> 200 mW / cm 2 ).
• test samples were from the urethane di- methacrylate UDMA, with the addition of 0.2 wt .-% Ivocerin as a photo initiator and subsequent irradiation ⁇ prepared.
• the measurement of the storage modulus G 'of the prepared samples was carried out by means of ARES-G2 rheometer (TA Instruments), which is a strain-controlled rotational rheometer.
• the rheometer has a Kraftaus ⁇ DC to DC converter, the torques of between 50 m and 200 nN mN * m with an accuracy of 1 m nN allows * *.
• the applied oscillation ⁇ frequency may be between 10 -7 rad / s and 628 rad / s can be varied.
• a forced air oven with nitrogen feed was used for the temperature control.
• the temperature-dependent measurements were carried out with an axial force of 0.3 N, an excitation frequency of 1 Hz and a deformation of 0.1% in a temperature range of 25 to 130 ° C (heating rate: 1.5 K / min) and the G 'results for the Polymer networks of the DiHDA linker and UDMA are shown in FIG.
• G ' represents the flow resistance of a substance and is thus a measure of the strength of a material.
• the DiHDA-linker polymer network and the UDMA network show very different behavior with increasing temperature.
• the memory module G 'of the UDMA Net zwerkes shows in the range of 25 to 130 ° C, only a slight drop, as it is expected for non-thermoresponsive networks (1.1 * 10 3 MPa at 25 ° C to 3.8 * 10 2 MPa at 120 ° C).
• G 'for the DiHDA linker network decreases drastically in the same temperature range from 8.5 * 10 2 MPa at 25 ° C to 5.5 MPa at 120 ° C, which corresponds to a significant splitting of the network.
• I polymer networks are accessible on the basis of the polymerizable multi-functional ⁇ Hetero-Diels-Alder adducts of the general formula, which can be interpreting ⁇ Lich at temperatures degrade thermally reversible below 100 ° C.
• the DiHDA linker (20 mol%) prepared in Example 2 was mixed with isopropyl methacrylate (iPMA). After addition of 0.2% by weight of Ivocerin as photoinitiator, specimens with the dimensions L: 25 mm, W: 5 mm, D: 1 mm were irradiated (30 min) with 3 Osram Dulux Blue lamps (3 ⁇ 18 W, 200 mW / cm 2 ). As a reference sample ⁇ analog test specimens were composed of a mixture of commercial information ⁇ len decanediol dimethacrylate crosslinking agent (D 3 MA) and IPMA (80 mol%) with addition of 0.2 wt .-% Ivocerin as photoinitiator and after ⁇ following irradiation produced.
• D 3 MA commercial information
• IPMA 80 mol%
• Fig. 3 shows comparison of the storage modulus G ⁇ ' a network of IPMA and the dimethacrylate D 3 MA with a network of IPMA and the DiHDA linker.
• the memory ⁇ modulus G 'of the D 3 MA-IPMA Net zwerkes shows the range of 25 to 130 ° C a clear drop due to the high proportion of the flexible monomethacrylate IPMA.
• G 'for the DiHDA-linker iPMA-Net zwerk which contains only 20 mol% of thermally reversibly degradable DiHDA linker, decreases significantly more significantly in the same temperature range.
• Crowns and abutments were each sandge ⁇ radiates (110 pm A1 2 0 3, 1 bar), cleaned in deionized water by Ultra ⁇ sound for about 2 minutes, dried, and then with Monobond Plus (Ivoclar Vivadent AG, processing according to use: Apply , let it act for 60 s, blow dry with oil-free air) for cementing.
• DiHDA difunctional crosslinker DiHDA of Example 2 (A cement) for cementing a self bicomponent ⁇ cement (w 1 w / mixing ratio of 1).
• ⁇ the first component held 25.06 (BuMA), 0.01 wt .-% 2, 6-di-tert-butyl-p-cresol (BHT), 60.35 wt wt .-% n-butyl methacrylate.
• the second component contained 33.33 weight percent BuMA, 63.67 weight percent DiHDA linker and 3 weight percent 3, 5-di-tert-butyl-N, -diethylaniline (DABA).
• BuMA BuMA
• DiHDA linker 3 weight percent 3, 5-di-tert-butyl-N, -diethylaniline
• DABA 3,5-di-tert-butyl-N, -diethylaniline
• a self Two ⁇ components cement (mixing ratio 1: 1 w / w) was prepared analogously touched difunctional crosslinker, bisphenol-A-glycidyl methacrylate (BisGMA) (cement B) containing 20 mol% (based on the monomer mixture) of the non-thermally cleavable.
• the first component contained 47.90% by weight BuMA, 47.10% by weight BisGMA and 5% by weight BP-50-FT.
• the second component contained 54.30 wt% BuMA, 42.70 wt% BisGMA and 3 wt% DABA. Two drops each of the mixed cement were placed in a prepared test crown and the test abutment also prepared. After loading with a weight of approx.
• test pieces cemented with cement A or cement B were randomly divided into two groups of 5 test pieces of equal size and water heated to 23 ° C. (first group) or 80 ° C. (second group) for 1 min dipped. Subsequently, the test specimens were each clamped in a universal tensile testing machine (Zwick-Roell Z010), the crowns were withdrawn from the abutment at a constant crosshead speed of 1.0 mm / min, and the maximum force occurring in each case was recorded as the withdrawal force. The mean value of the deduction force thus determined is shown in the following table.

Landscapes

• Health & Medical Sciences (AREA)
• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Animal Behavior & Ethology (AREA)
• General Health & Medical Sciences (AREA)
• Public Health (AREA)
• Veterinary Medicine (AREA)
• Oral & Maxillofacial Surgery (AREA)
• Epidemiology (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Plastic & Reconstructive Surgery (AREA)
• Surgery (AREA)
• Engineering & Computer Science (AREA)
• Bioinformatics & Cheminformatics (AREA)
• General Chemical & Material Sciences (AREA)
• Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
• Pharmacology & Pharmacy (AREA)
• Dental Preparations (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Materials For Medical Uses (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=54541930

Family Applications (1)

Country Status (6)

Families Citing this family (5)

Citations (6)

Family Cites Families (1)

• 2015
  • 2015-10-13 ES ES15189615T patent/ES2759899T3/es active Active
  • 2015-10-13 EP EP15189615.6A patent/EP3156031B9/de active Active
• 2016
  • 2016-10-11 JP JP2018518717A patent/JP6726276B2/ja active Active
  • 2016-10-11 CN CN201680059264.1A patent/CN108348402B/zh active Active
  • 2016-10-11 US US15/743,731 patent/US10667993B2/en active Active
  • 2016-10-11 WO PCT/EP2016/074305 patent/WO2017064042A1/de not_active Ceased

Patent Citations (8)

Non-Patent Citations (18)

Also Published As

Similar Documents

Legal Events