Process and composition for preparing a dental polymer product

Abstract: The invention concerns a process for preparing a polymer composition, that is free-radical/photochemical and thermal curing epoxide-methacrylate and/or isocyanate-methacrylate adhesives in broadest terms, dental/medical adhesives, and dental restoratives. Furthermore the dual curing epoxide-methacrylate and/or isocyanate-methacrylate adhesives can be used in the optical industry, in optoelectronics and microelectronics, for example for the adhesion of complicated optical components in the combination glass/ glass, glass/metal. Advantageous is the small shrinkage during polymerization and the good mechanical properties in combination with the possibility of step-wise or one-step polymerization.

Description: The invention relates to a dental composition or kit of parts for preparing a polymer, to a process for preparing said polymers and polymer products obtained thereby, notably artificial teeth. Background of the invention Dental filling materials mainly consist of liquid polymerizable organic monomers and/or polymers, reactive diluents, polymerization initiators, stabilizers, and fillers. These composite materials have their good mechanical properties such as high flexural strengths, high compressive strengths and their hardness. Furthermore they are polishable and it is possible to adjust their dye. The most frequently used monomers are esters of methacrylates and higher multifunctional alcohols or isocyanates such as the bismethacrylate of bisphenol-A diglycidyl ether, urethane bismethacrylates. US-A 3.629.187 discloses such materials. One of the main disadvantages using composites as dental filling materials is the relatively high shrinkage of organic monomers during polymerization. The shrinkage causes the well known effect of contraction gaps and subsequent cracks. Common dental composites show a shrinkage of 2.5 up to 4.0 vol-%. It is well known that the shrinkage directly depends on the molecular weight of polymerizable organic monomers. On the other hand, increasing molecular weights of the monomers are combined with an increasing viscosity of the resin. Therefore reactive diluents, such as triethyleneglycoldimethacrylates, are necessary to obtain a lower viscosity and the possibility to incorporate the desired amount of fillers. However, reactive diluents show a relatively high shrinkage by themselves, for example 12.89-% for pure triethylenglyccldimethacrylate. Moreover, conventional used composites show a relatively low self-adhesion to teeth, metals and ceramics. In numerous experiments using epoxide polymers and methacrylates for the preparation of IPNs (J.Polym.Sci. Part A. Polym.Chem 30 (1992) 1941, J.Appl.Chrom. 24 (1991) 692, Polym. 31 (1990) 2066, ) multiphase systems were obtained which have insufficient mechanical, thermal and optical properties or which result in microphase separated polymers (Acta Polymerics 38 (1987) 547 and DO 226731) with insufficient adhesion to teeth and ceramics. Description of the invention Therefore it is the object of the invention to provide a process and composition for preparing a polymer composition for dental purposes exhibiting a low shrinkage and a high self-adhesion to ceramics and metals. This object is achieved by a process according to claim 1. Preferably the macromonomers have a general formula I or II: wherein A and D are unsaturated moieties, B is a moiety derived from a diepoxide or a diisocyanate and C is a HX-residue selected from the group consisting of -OH, - COOH, -NH 2 , -NH-, -SH. The macromonomers I and II preferably are α,ω-terminated poly (epoxide-carboxylic acid) macromonomers of formulas M-1, M-8 and M-9, α,ω-terminated poly(epoxide-amine) macromonomers of formulas M-2 to M-5, M-10 and M-11 or α,ω-terminated poly(epoxide-phenol) macromonomers of formulas M-6, M-7 and M-12 are described in the following literature (J. Klee, H.-H. Hörhold, H. Schütz, Acta Polym. 42 (1991) 17-20; J. Klee et. al. Polym. Bull. 27 (1992) 511-517) and in the patent literature (DD 277 689, DO 279 667, DE-P 42 17 761.8). They are characterized by the structures M-1 to M-12 : wherein R is a residue derived from a diepoxide, notably a residue of the following formula whereby X is C(CH 3 ) 2 , -CH 2 -, -O-, -S-, -CO-, -SO 2 - R 1 denotes hydrogen or a substituted or unsubstituted C 1 to C 12 alkyl group or an oxyalkyl group, C 2 to C 12 alkenyl group, C 5 to C 12 cycloalkyl, C 6 to C 12 aryl or C 7 to C 12 aralkyl R 2 is a difunctional substituted or unsubstituted C 1 to C 12 alkyl group, C 2 to C 12 alkenyl group, C 5 to C 12 cycloalkyl, C 6 to C 12 aryl or C 7 to C 12 aralkyl, R 3 denotes hydrogen or a substituted or unsubstituted C 1 to C 12 alkyl group, C 2 to C 12 alkenyl group, C 5 to C 12 cycloalkyl, C 6 to C 12 aryl or C 7 to C 12 aralkyl, R 4 is a substituted or unsubstituted C 6 to C 12 aryl, such as whereby X is C(CH 3 ) 2 , -CH 2 -, -O-, -S-, -CO-, -SO 2 - and n is an integer of n =1, 2, 3, 4, 5, 6, 7, 8 Macromonomers M-1, M-2, M-3, M-6 are synthesised in two steps. At first by reaction of excessive bisphenol-A diglycidyl ether DGEBA, bisphenol-F diglycidyl ether DGEBF, butanediol diglycidyl ether BDODGE, tetrahydro terephthalic acid diglycidyl ether or diglycidyl aniline and methacrylic acid MAA (x>2y) an oligomer mixture is obtained. This mixture contains the bismethacrylate of DGEBA (Bis-GMA, n=0) along with mono-GMA and unreacted DGEBA as well as governed by the epoxide-comonomer ratio. The formation of macromonomers follows in a second reaction of DGEBA and mono-GMA, respectively with primary monoamines to M-2, disecondary diamines to M-3 (J. Klee et al. Polym.Bull. 27 (1992) 511-517, DD 279667), carboxylic acids to M-1 (DE 4217761.8), or biphenols to M-6 (J. E. Klee et al., Acta Polym. 44 (1993) 163). During the epoxide ring cleavage by carboxylic acids an amount of approximately 20 % of the epoxide groups is opened to the corresponding primary alcohols. Consequently, macromonomers M-1, M-2, M-3 and M-6 contains both types of molecules having primary and/or secondary alcohol units. Macromonomers M-4 and M-5 are prepared by one- or two-step reactions of the diepoxides, primary monoamines or disecondary diamines and 2,3-epoxypropyl-methacrylate using amine in excess and a mol ratio a<b, and 2c+a=b. The macromonomers M-4 and M-5 also obtainable by terminating reaction of α,ω-amino terminated prepolymers with 2,3-epoxypropyl-methacrylate (DD 277689, J.Klee, H.-H. Hörhold, H.Schütz, Acta Polym. 42 (1991) 17-20). Instead of amines also were used bisphenols or dicarboxylic acids to produce macromonomers M-7 and M-8, respectively. Macromonomers M-9 to M-12 are prepared by one- or two-step reactions of the diepoxides, primary monoamines, disecondary diamines, dicarboxylic acids, or phenols and amino alkyl methacrylates. The polymer composition comprises α,ω-terminated poly(urethane) macromonomers, α,ω-terminated poly(urea) macromonomers or α,ω-terminated poly(thiourethane) macromonomers of the following formulas M-13 to M-24 which are polymerizable in a mixture with di-or polyepoxides and/or di- or polyisocyanates and polyamines and/or primary monoamines and/or disecondary diamines or dicarb-oxylic acids, dicarboxylic acid anhydrides, diphenols, or dithiols: wherein R is a residue derived from a diisocyanate, notably a residue of the following formula R 1 denotes hydrogen or a substituted or unsubstituted C 1 to C 12 alkyl group, C 2 to C 12 alkenyl group, C 5 to C 12 cycloalkyl, C 6 to C 12 aryl or C 7 to C 12 aralkyl R 2 is a difunctional substituted or unsubstituted C 1 to C 12 alkyl group, C 2 to C 12 alkenyl group, C 5 to C 12 cycloalkyl, C 6 to C 12 aryl or C 7 to C 12 aralkyl R 3 denotes hydrogen or a substituted or unsubstituted C 1 to C 12 alkyl group, C 2 to C 12 alkenyl group, C 5 to C 12 cycloalkyl, C 6 to C 12 aryl or C 7 to C 12 aralkyl, R 4 is a substituted or unsubstituted C 6 to C 12 aryl, such as whereby X is C(CH 3 ) 2 , -CH 2 -, -O-, -S-, -CO-, -SO 2 - and n is an integers of n =1, 2, 3, 4, 5, 6, 7, 8,... It is possible to use the polymer composition as an one-part composition or as two part-composition. A two-part composition which is mixed immediately before use contains for example the following substances in the parts A and B : part A: macromonomer, reactive diluent, di- or polyepoxide or di-or polyisocyanate and polymerization initiator part B: macromonomer, reactive diiuent, coinitiator and amine or dicarboxylic acid, dicarboxylic acid anhydride, diphenol, or dithiol, respectively. The composition contains 1 to 99 mol-% of a macromonomer relative to said monomers, preferably 10 to 90 mol-% of a macromonomer relative to said monomers, most preferably 30 to 70 mol-% of a macromonomer relative to said monomers. The prepared adhesives, adhesive cements and composites are polymerizable in two different polymerization reactions, namely in a free-radical/photochemical and a thermal polymerization reaction which may run subsequently or simultaneously. In both cases interpenetrating networks or semi-IPNs were prepared depending on the comonomer used for the addition reaction namely if polyamines, primary monoamines, disecondary diamines or dicarboxylic acids, dicarboxylic acid anhydrides, diphenols or dithiols were used for epoxide-addition polymerization. The methacrylate networks and the epoxide networks and linear polymers, respectively are compatible. The polymer compositions exhibit of the invention advantageous mechanical properties and a small shrinkage during polymerization. The polymer compositions of the invention may contain reactive diluents such as diethyleneglycoldimethacrylate, triethyleneglycoldimethacrylate, polypropyleneglycoldimethacrylate, methacrylate substituted spiroortho esters, glycerintrimethacrylate, furfurylmethacrylate, urethandimethacrylate, Bis-GMA in a content of 5 to 50 wt-%. The invented polymer compositions may contain stabilisers such as hydroquinon or 2,6-di-tert.-butyl-p-cresol. The polymer compositions of the invention may comprise redox-initiator systems such as azobisisobutyronitril, dibenzoylperoxid/amine, Cu-acetylacetonate/Li-sulfinate, trialkylboranes or photo initiators such as benzoinmethylether, benzilketal, camphor quinon or acylphosphinoxides in contents of 0,1 to 3 wt-%. When using the polymer compositions of the invention as composite, fillers can be mixed into the epoxide/macromonomer or isocyanate/macromonomer matrix. As fillers were used inorganic glasses such as barium-alumosilicat glasses, silica gels, xero gels or inorganic compounds such as La 2 O 3 , ZrO 2 , BiPO 4 , CaWO 4 , BaWO 4 , SrF 2 , Bi 2 O 3 or organic fillers such as broken organic polymers. The polymer compositions of the invention reveals interesting mechanical properties such as a high flexural and compressive strength, a low expansion, good adhesion to metal, glass and ceramics, a low shrinkage and a high radio-opacity between RO= 2 and 10 mm/mm Al depending on the nature of the filler used. When applying the invented dual curing material of the invention as adhesive, the viscosity and the adhesion properties of the material are adjustable through evaluation of the macromonomer and the chain length of these. In many cases reactive diluents are necessary for the use of the materials of the invention. Reference example 1 Preparation of macromonomer M-2 (n=1, R= -OC 6 H 4 -C(CH 3 ) 2 -C 6 H 4 O-, R 1 = CH 3 -, R 3 = C 6 H 4 COOC 4 H 9 ) 20,000 g (58,75 mmol) bisphenol-A diglycidyl ether, 5,058 g (58,75 mmol) methacrylic acid, 0,253 g triethylbenzylammoniumchlorid, 0,194 g 2,6-di-tert.-butyl-p-cresol (BHT), 7,747 g triethyleneglycoldimethacrylate and 5,677 g (29,38 mmol) p-amino-benzoic butyl ester were mixed and reacted for 16 hours at 80 °C. In the IR-spectrum of the macromonomer no absorption of epoxide groups at 915 cm -1 was found. Reference example 2 Preparation of macromonomer M-3 (n=1, R= -OC 6 H 4 -C(CH 3 ) 2 -C 6 H 4 O-, R 1 =CH 3 -, R 2 = -(CH 2 ) 4 O(CH 2 ) 4 -, R 3 = C 6 H 5 CH 2 -) 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 ethoxylated Bis-GMA were homogeneously mixed under slow 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 was kept for additional 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 was observed. A new absorption of ester groups was found at 1720 cm -1 . Reference example 3 Preparation of macromonomer M-5 (n=1; R= -OC 6 H 4 -C(CH 3 ) 2 -C 6 H 4 O-, R 1 = CH 3 -, R 2 = -(CH 2 ) 4 O(CH 2 ) 4 -, R 3 = C 6 H 5 CH 2 -) 20,000 g (58,75 mmol) bisphenol-A diglycidyl ether and 40,012 g (117,50 mmol) N,N'-dibenzyl-5-oxanonanediamine-1,9 were homogeneously mixed under slow heating. The mixture was kept for two hours at 90 °C. After this time 16,704 g (117,50 mmol) 2,3-epoxypropyl methacrylate were added to the mixture while stirring and were kept 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 were observed. Reference example 4 Preparation of macromonomer M-21 (n=1, R 1 = CH 3 -, R 2 = -CH 2 CH 2 -, R 4 = -(CH 2 ) 2 O(CH 2 ) 2 O(CH 2 ) 2 -,) 15,000 g (67,790 mmol) isophorondiisocyanate, 6,179 g ( 33,895mmol) 1,8-dimercapto-3,6-dioxaoctane, 8,822 g (67,790 mmol) hydroxyethylmethacrylate and 0,060 g BHT were homogeneously mixed and reacted for 8h hours at 45 °C. The obtained macromonomer does not show an absorption of the isocyanate group at 2200 cm -1 in the IR spectrum. Example 1-5 3,0 g (15,4 mmol) 3(4),8(9)-Bis(aminomethyl)tricyclo-5.2.1.0. 2,6 -decan TCD and 10,5 g (30,8 mmol) 2,2-Bis[4-(2,3-epoxypropoxy)phenyl]propane DGEBA were mixed to give the epoxide-amine addition polymer AP. Different amounts (see table 1) of macromonomer M-5 (n=0, R= -OC 6 H 4 -C(CH 3 ) 2 -C 6 H 4 O-, R 1 = CH 3 -, R 2 = -(CH 2 ) 4 O(CH 2 ) 4 -, R 3 = C 6 H 5 CH 2 ) N, N'-Dibenzyl-N,N'-bis-(2-hydroxy-3-methacryloyloxypropyl)-5-oxanonandiamin-1,9. and 0.5% photo initiator IRGACURE 651 (Ciba Geigy) were added and the parts thoroughly mixed. To remove gas bubbles the mixture was exposed to vacuum of an oil pump and then filled into moulds to prepare test samples for dynamic mechanic analysis (DMA). Methacrylate groups were polymerized upon exposure to UV light of a stroboscope UV lamp for 6 minutes. Then the samples were already stiff enough to be released from the mould. The polymeri-zation of epoxide with amine was then completed by storing over night at 85°C. The glass transition temperatures of the resulting materials were determined by differential scanning calorimetry (DSC) and the maximum of tan δ in DMA. Results are shown in table 1. Only one glass transition appears. Under scanning electron microscope phase separation is not being found (resolution 500 nm). Composition and glass temperatures of IPN and homopolymers of M-5 and AP Example originally weight-in quantity of ratio of M-5/AP Tg (DSC) Tg (DMA) DGEBA TCD M-5 g mmol g mmol g mmol wt-% °C °C M-5 - - - - 10,0 16,0 100/0 10 18 1 2,00 5,88 0,57 2,94 25,70 41,13 90/10 9 20 2 5,00 14,69 1,43 7,71 19,29 30,87 75/25 37 36 3 10,50 30,84 3,00 15,42 13,50 21,61 50/50 60 69 4 10,50 30,84 3,00 15,42 4,50 7,20 25/75 98 103 5 10,50 30,84 3,00 15,42 1,94 3,11 10/90 140 125 AP 10,50 30,84 3,00 15,42 - - 0/100 154 156 Example 6 (one-paste system) 3,000 g of macromonomer M-2 of reference example 1 and 1,142 g (3,35 mmol) bisphenol-A diglycidyl ether, 1,142 g (3,35 mmol) N,N'-Dibenzyl-5-oxanonandiamine-1,9 and 0,02 g camphor quinon were homogeneously mixed and polymerized as described in example 1-5. The shrinkage of the photochemical polymerization is 0,68 vol-% and of the thermal addition polymerization 2,44 vol-%. Example 7 (one-paste system) 3,000 g of macromonomer M-2 of reference example 1 were homogeneously mixed with 1,142g (3,35 mmol) bisphenol-A diglycidyl ether, 0,806g (3,35 mmol) N,N'-di-benzylethylenediamine and 0,02g camphor quinon and polymerized as described in example 1-5. The shrinkage of the photochemical polymerization is 0,56 vol-% and of the thermal addition polymerization 3,43 vol-%. Example 8 (one-paste system) 3,000 g of macromonomer M-2 of reference example 1 were homogeneously mixed with 1,142 g (3,35 mmol) bisphenol-A diglycidyl ether, 0,176 g (1,34 mmol) N,N-dipropylentriamine and 0,02g camphor quinon and polymerized as described in example 1-5. A shrinkage of dV= 3,5%, dV= 1,8% was measured which is caused by the photochemical step and dV= 1,7% which is caused by the thermal epoxide-amine addition polymerization. Example 9 (two-paste system) Part A) 2,000 g of macromonomer M-2 of reference example 1 were homogeneously mixed with 4,246 g (3,35 mmol) Araldit-F, 0,054 g dibenzoylperoxide 19,500 g of a mixture of CaWO 4 /ZrO 2 (4:1) and 0,100 g aerosil. Part B) 2,000 g of macromonomer M-2 of reference example 1 were homogeneously mixed with 1,086 g ( 5,59 mmol) 3(4),8(9)-bis(amino methyl)-tricyclo-5.2.1.0. 2,6 -decan, 0,054 g N,N-bis(β-hydroxyethyl)-p-aminobenzoic acid ethylester, 9,441 g of a mixture of CaWO 4 / ZrO 2 (4:1) and 0,100 g aerosil. Parts A and B were mixed immediately before use in a weight ratio of 2:1 and polymerized for 10 minutes at 37 °C. The shrinkage was measured as follows: dV= 0,99 vol.-% and the radio-opacity RO= 8,3 mm/mm Al. Example 10 (two-paste system) Part A) 10,000 g of macromonomer M-3 of reference example 2 were homogeneously mixed with 7,010 g (20,60 mmol) Araldit MY-790, 0,010 g dibenzoylperoxide and 23,000 g Barium-Alumosilicate-glass and 0,100 g aerosil. Part B) 2,000 g of macromonomer M-3 of reference example 2 were homogeneously mixed with 2,001 g (10,30 mmol) 3(4),8(9)-bis(amino methyl)-tricyclo-5.2.1.0. 2,6 -decan, 0,015 g N,N-bis(β-hydroxyethyl)-p-aminobenzoic acid ethyl ester, 22,000 g Barium-Alumosilicate-glass and 0,100 g aerosil. Parts A and B were mixed immediately before use in a weight ratio of 1:0,706 and polymerized at 37 °C for 10 minutes. The shrinkage was measured of dV= 1,55 vol.-%. Example 11 (two-paste system) Part A) 10,000 g of macromonomer M-5 of reference example 3 were homogeneously mixed with 7,010 g (20,60 mmol) Araldit MY-790 and 0,010 g dibenzoylperoxide. Part B) 10,000 g of macromonomer M-5 of reference example 3 were homogeneously mixed with 2,001 g (10,30 mmol) 3(4),8(9)-bis(amino methyl)-tricyclo-5.2.1.0. 2,6 -decan and 0,015 g N,N-bis(β-hydroxy-ethyl)-p-aminobenzoic acid ethyl ester. Parts A and B were mixed immediately before use in a weight ratio of 1:0,707. The first polymerization step occurs during radiation at λ > 365 nm for 360 seconds and the second step as thermal epoxide-amine polymerization at 85 °C for 16 hours. The following values were measured: Tg = 69 °C, ΔV = 1,75 vol.-%. Example 12 (one-paste system) 8,650 g (7,25 mmol) of macromonomer M-5 of reference example 3 (R= -OC 5 H 4 -C(CH 3 ) 2 -C 6 H 4 O-, R 1 = CH 3 -, R 2 = -(CH 2 ) 4 O(CH 2 ) 4 -, R 3 = C 6 H 5 CH 2 -), 3,707 g triethyleneglycoldimethacrylate, 1,35g (3,62 mmol) 3(4),8(9)-Bis(aminomethyl)tricyclo-5.2.1.0. 2,6 -decan, 2,467 g (7,25 mmol) bisphenol-A diglycidyl ether, 0,124 g camphor quinon and 0,124 g N,N-bis(β-hydroxy-ethyl)-p-toluidine were mixed homogeneously immediately befor use. A smal layer of this mixture was put on a ceramic tooth and polymerized with visible light for 40 seconds. Thereafter a composite TP.H (De Trey Dentsply) was applied to this layer and polymerized for 40 seconds. Then material was reacted for 24 hours at 37°C. After this time the adhesion of the material is 7,4 ± 1,3 MPa. Comparison example (Acta Polym. 38 (1987) 547) 7,000 g (13,66 mmol) Bis-GMA, 3,000 g triethyleneglycoldimethacrylate, 5,0960 g (14,97 mmol) bisphenol-A diglycidyl ether, 4,917g (14,97 mmol) N,N'-Dibenzyl-3,6-dioxaoctanediamine-1,8 (Acta Polym. 38 (1987) 547 and DD 226731), 0,050 g camphor quinon and 0,0050 g N,N-bis(β-hydroxy-ethyl)-p-toluidine were mixed homogeneously immediately before use. A smal layer of this mixture was put on a ceramic tooth and polymerized with visible light for 40 seconds. Thereafter a composite TP.H (De Trey Dentsply) was applied to this layer and polymerized for 40 seconds. Then the material was reacted in water for 24 hours at 37°C. After this time the adhesion of the material is 4,1 ± 1,2 MPa. Example 13 5,000 g (7,532 mmol) of M-21, 1,373 g (7,532 mmol) 1,8-dimercapto-3,6-dioxaoctane, 2,564 g (7,532 mmol) bisphenol-A diglycidyl ether, 0,089 g camphor quinon and 0,089 g N,N-bis(β-hydroxy-ethyl)-p-toluidine were mixed homogeneously immediately befor use. A smal layer of this mixture was put on a ceramic tooth and polymerized with visible light for 40 seconds. Thereafter a composite TP.H (De Trey Dentsply) was applied to this layer and polymerized for 40 seconds. Then the material was reacted in water for 24 hours at 37°C. After this time the adhesion of the material is 6,9 ± 0,7 MPa.

Claims: A process for preparing a polymer composition, comprising the steps of: A preparing a liquid mixture comprising (i) at least one monomer having at least two double bonds, (ii) at least one polyaddition component having at least two moieties capable of addition reaction selected from the group consisting of epoxide and isocyanate moieties, and (iii) an H-active component having at least two HX-residues selected from the group consisting of -OH, -COOH, -NH 2 , -HN-, and -SH, B polymerizing said monomer (i) and C subjecting said polyaddition component (ii) and said H-active component (iii) to a polyaddition reaction; whereby steps B and C are carried out either simultaneously or one after the other, characterized in that for preparing a single-phase polymer composition having an interpenetrating network with a single glass transition temperature, wherein said macromonomers and addition polymers are comprised in a weight ratio between 1:99% and 99:1%, whereby said macromonomer has a molecular weight of at least 600 and and whereby said macromonomer is within the scope of one of the following formulas I and II A-B-(-C-B) x -A D-C-(-B-C-) x -D wherein A and D are unsaturated moieties, B is a moiety derived from a diepoxide or a diisocyanate and C is at least a moiety having two H-active residues selected from the group consisting of -OH, -COOH, -NH 2 , -NH-, -SH. The process of claim 1 wherein each said macromonomer is a α,ω-terminated poly (epoxide-carboxylic acid) macromonomer within the scope of formulas M-1, M-8 and M-9, a α,ω-terminated poly epoxide-amine) macromonomer within the scope of one of the formulas M-2, M-3, M-4, M-5, M-10 and M-11 or a α,ω-terminated poly(epoxide-phenol) macromonomer within the scope of one of formulas M-6, M-7 and M-12 wherein R is a residue derived from a diepoxide, notably a residue of the following formula whereby X is C(CH 3 ) 2 , -CH 2 -, -O-, -S-, -CO-, -SO 2 - R 1 denotes hydrogen or a substituted or unsubstituted C 1 to C 12 alkyl group or an oxyalkyl group, C 2 to C 12 alkenyl group, C 5 to C 12 cycloalkyl, C 6 to C 12 aryl or C 7 to C 12 aralkyl R 2 is a difunctional substituted or unsubstituted C 1 to C 12 alkyl group, C 2 to C 12 alkenyl group, C 5 to C 12 cycloalkyl, C 6 to C 12 aryl or C 7 to C 12 aralkyl R 3 denotes hydrogen or a substituted or unsubstituted C 1 to C 12 alkyl group, C 2 to C 12 alkenyl group, C 5 to C 12 cycloalkyl, C 6 to C 12 aryl or C 7 to C 12 aralkyl R 4 is a substituted or unsubstituted C 6 to C 12 aryl, such as whereby X is C(CH 3 ) 2 , -CH 2 -, -O-, -S-, -CO-, -SO 2 - and n is an integer from 1 to 8. The process of claim 1 wherein said macromonomers having at least one repetitive unit selected of the group or urethanes, ureas or thioureas of the following formulas M-13 to M-24: wherein R is a residue derived from a diisocyanate, notably a residue of the following formula R 1 denotes hydrogen or a substituted or unsubstituted C 1 to C 12 alkyl group, C 2 to C 12 alkenyl group, C 5 to C 12 cycloalkyl group, C 6 to C 12 aryl group or C 7 to C 12 aralkyl group R 2 is a difunctional substituted or unsubstituted C 1 to C 12 alkyl group, C 2 to C 12 alkenyl group, C 5 to C 12 cycloalkyl group, C 6 to C 12 aryl group or C 7 to C 12 aralkyl group R 3 denotes hydrogen or a substituted or unsubstituted C 1 to C 12 alkyl group, C 2 to C 12 alkenyl group, C 5 to C 12 cycloalkyl group, C 6 to C 12 aryl group or C 7 to C 12 aralkyl group, R 4 is a substituted or unsubstituted C 6 to C 12 aryl, such as whereby X is C(CH 3 ) 2 , -CH 2 -, -O-, -S-, -CO-, -SO 2 - and n is an integer of n =1, 2, 3, 4, 5, 6, 7, 8. The process of claim 1 wherein said macromonomer and addition polymers are in a weight ratio between 10:90 % and 90:10%, preferably 30:70% and 70:30%. The process of claim 1 wherein said liquid mixture further comprises reactive diluent selected from the group consisting of triethyleneglycol bismethacrylate, diethyleneglycol bismethacrylate, dioxolan bismethacrylate, vinyl-, vinylene- or vinylidenacrylate- or methacrylate substituted spiroorthoesters, spiroorthocarbonates or bicycloortho esters, and ethoxylated (2,2-Bis-[p-(2-hydroxy-3-methacryloyloxypropoxy)-phenyl]-propane) (Bis-GMA) in a content of 5 to 50 percent by weight. The process of claim 1 wherein said liquid mixture further comprises di- or polyepoxide selected from a group consisting of bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether, novolakepoxides, N,N,N',N'-tetraglycidyl diaminodiphenylmethane and Δ 3 -tetrahydrophthalic acid diglycidyl ester. The process of claim 1 wherein said liquid mixture further comprises primary monoamine benzylamine, 1-adamantaneamine, α-phenethylamine and ethanol amine and selected from the group consisting of disecondary diamines N,N'-dibenzyl-ethylenediamine, N,N'-dimethyl-ethylenediamine, and N, N'-dibenzyl-3,6-dioxaoctandiamine-1, 8; N,N'-dibenzyl-5-oxanonandiamine-1,9; N,N'-dibenzyl-(2, 2, 4)(2, 4, 4)-trimethylhexamethylenediamine and polyamines selected from the group consisting of N,N-dipropylenetriamine, tripropylenetetramine, isophorondiamine, (2, 2, 4) (2, 4, 4)-trimethylhexamethylenediamine-1,6; 3 (4), 8 (9)-bis(aminomethyl) tricyclo-5.2.1.0 2,6 -decan and O,O'-bis-amino(polypropyleneglycol). The process of claim 1 wherein said diisocyanate is toluenediisocyanate, hexamethylenediisocyanate, 2, 2, 4- (2, 4 ,4)-trimethylhexamethylenediisocyanate, isophorondiisocyanate or 4,4'-diphenylmethanediisocyanate. The process of claim 1 wherein the dicarboxylic acid is a substituted or unsubstituted aliphatic, araliphatic, cycloaliphatic (bi- and tricyclic) and/or aromatic dicarboxylic acid such as succinic acid, adipic acid, hexahydrophthalic acid, phthalic acid, terephthalic acid. The process of claim 1 wherein the dicarboxylic acid anhydride is a substituted or unsubstituted aliphatic, araliphatic, cycloaliphatic (bi-and tricyclic) and/or aromatic dicarboxylic acid anhydride such as succinic acid anhydride, methylsuccinic acid anhydride, hexahydrophtalic acid anhydride, dichlormaleic acid anhydride, tetrahydro- phthalic acid anhydride, phthalic acid and 3,4,5,6-tetrachloro-7,7-difluoro-3,6-endomethylene tetrahydro phthalic acid anhydride. The process of claim 1 wherein said phenol is a substituted or unsubstituted phenol such as phenol, resorcinol, hydroquinone, 2,2-bis(4-hydroxyphenyl)-propane, 4,4'-dihydroxy sulphone. The process of claim 1 wherein said dithiole is a substituted or unsubstituted aliphatic, araliphatic, cycloaliphatic(bi-and tricyclic) and/or aromatic dithiole such as thiocole, 1,8-dimercapto-3,6-dioxaoctane, 1,7-di-mercapto-3,5-dioxaheptane, 1,9-di-mercapto-5-oxa-nonane, 1,14-dimercapto-5,10-dioxatetradecane, mercapto acid-1,4-butandiol ester, 4,4'-oxydithiophenol. The process of claim 1 whereby additional compounds which undergo polyaddition with di- and polyepoxides are added, notably cyanuric acid, melamine- and urea-formaldehyde-resins, amides, di- and polyisocyanates or inorganic acids such as phosphoric acid or phosphonic acid. The process of claim 1 wherein said liquid mixture further comprises a photo initiator selected from the group consisting of benzoinmethylether, benzilketal, camphorquinon, acylphosphinoxides in a ratio of 0,1 to 3 percent by weight. The process of claim 1 wherein said liquid mixture further comprises thermal initiators selected from the group consisting of azobisisobutyronitrile and dibenzoylperoxide in a portion of 0,1 to 3 percent by weight or redox initiator systems. The process of claim 1 characterized by polymerizing photochemically for 10 to 300 seconds having a rapid fixation followed by the thermal polymerization in a temperature range of 20 to 200°C during 0.5 to 40 hours. The process of claim 1 characterized by polymerizing in two thermal initiated steps whereas the first polymerization occurs at 35° to 130°C for 10 to 600 seconds and the second polymerization occurs at 20° to 200 °C for 0.5 to 40 hours. The process of claim 1 wherein said liquid mixture further comprises filler particles selected from the group consisting of barium-alumosilicate glass, xerogel, La 2 O 3 , ZrO 2 , BiPO 4 , CaWO 4 , BaWO 4 , SrF 2 , Bi 2 O 3 and organic polymer. The process of claim 1, wherein the liquid mixture contains dye pigments. The process of claim 1 wherein said liquid mixture is obtainable from a two-part system comprising two pastes, which require mixing prior to their application wherein a first paste comprises at least one said macromonomer, a reactive diluent, a di- or polyepoxide or di- or polyisocyanate, and a polymerization initiator and a second paste comprises at least one said macromonomer, a reactive diluent, a coinitiator, an amine or a dicarboxylic acid, a dicarboxylic acid anhydride, a diphenol, or a dithiol, respectively. Polymer composition obtainable by the process according to claim 1. An artificial dental tooth composed of said polymer of claim 21.

Inventors: KLEE JOACHIM E, LEUBE WALTER, KLEE, JOACHIM E., LEUBE, WALTER
Applicants: DENTSPLY GMBH
Application year: 1995
Main classification: C08F290
IPC codes: C08G59, A61K6, C08G18, C08F290