Compositions With Controlled Network Structure

Abstract

Radically polymerizable dental material, which contains at least one compound of Formula I:

##STR00001##

The material preferably additionally contains a radically polymerizable monomer, an initiator for the radical polymerization and filler. It is characterized by a low polymerization contraction stress.

Claims

1. Radically polymerizable dental material, which contains at least one compound of Formula I: ##STR00021## with: A=H; CN; a phenyl residue which can carry one or more substituents; or an aliphatic linear or branched C.sub.1-C.sub.20 alkylene residue which can be interrupted by one or more 1,4-phenylene groups, urethane groups, 0 or S and which can carry in the terminal position a polymerizable vinyl, (meth)acryloyloxy or (meth)acrylamide group; R.sup.1=H, an aliphatic linear or branched C.sub.1-C.sub.9 alkyl radical, tolyl or phenyl; L=SR.sup.2, CO-phenyl, SO.sub.2R.sup.3, PO(R.sup.4R.sup.5), PO(OR.sup.6)(R.sup.7), PO(OR.sup.8)(OR.sup.9) or halogen, wherein R.sup.2-9 in each case independently of each other are a phenyl residue which can carry one or more substituents; or are an aliphatic linear or branched C.sub.1-C.sub.20 alkylene residue which can be interrupted by O or S and which can carry in the terminal position a polymerizable vinyl, (meth)acryloyloxy, (meth)acrylamide group, C(CH.sub.2)COOR.sup.11 or C(CH.sub.2)CONR.sup.12R.sup.13, wherein R.sup.11-13 in each case independently of each other are a linear or branched C.sub.1-6 radical; X=COO, CON(R.sup.10) or is absent, wherein the bond to A takes place via O or N and R.sup.10=H; or is an aliphatic linear or branched C.sub.1-C.sub.20 alkylene residue which can be interrupted by one or more O or S and which can carry in the terminal position a polymerizable vinyl, (meth)acryloyloxy, (meth)acrylamide group, C(CH.sub.2)COOR.sup.11 or C(CH.sub.2)CONR.sup.12R.sup.13, wherein R.sup.11-13 in each case independently of each other are a linear or branched C.sub.1-6 radical; n=an integer from 1 to 6.

2. Dental material according to claim 1, which additionally contains at least one radically polymerizable monomer and at least one initiator for the radical polymerization.

3. Dental material according to claim 1, wherein the variables of Formula I have the following meanings: A H, CN, a phenyl residue, an aliphatic linear or branched C.sub.1-C.sub.15 alkyl residue which can be interrupted by one or more 1,4-phenylene groups, urethane groups or O and which can carry in the terminal position a polymerizable (meth)acryloyloxy group; R.sup.1 H, phenyl, tolyl, an aliphatic linear C.sub.1-C.sub.3 alkyl residue; L SR.sup.2 or SO.sub.2R.sup.3, wherein R.sup.2-3 in each case independently of each other are an aliphatic linear or branched C.sub.1-C.sub.20 alkylene residue which can be interrupted by O and which can carry in the terminal position a polymerizable (meth)acryloyloxy group or C(CH.sub.2)COOR.sup.11, wherein R.sup.11 is a linear or branched C.sub.1-3 radical; or a phenyl radical which can carry one or more substituents; X COO or CON(R.sup.10), wherein R.sup.10 is methyl, or is absent; n 1 or 2.

4. Dental material according to claim 3, wherein the variables of Formula I have the following meanings: A a saturated, linear aliphatic hydrocarbon residue with 1 to 12 carbon atoms which can be interrupted by one or more 1,4-phenylene groups, urethane groups or O and which can carry a methacryloyloxy group, X COO or CON(R.sup.10), wherein R.sup.10 is methyl, or is absent; R.sup.1 H, L SO.sub.2R.sup.3, wherein R.sup.3 is CH.sub.3 or tolyl, n 1 or 2.

5. Dental material according to claim 4, wherein the variables of Formula I have the following meanings: A a saturated, linear aliphatic hydrocarbon radical with 6 to 12 carbon atoms which can be interrupted by 1 to 3 O atoms, X COO; R.sup.1 H, L SO.sub.2R.sup.3, wherein R.sup.3 is CH.sub.3 or tolyl, n 1 or 2.

6. Dental material according to claim 1, which contains at least one multifunctional (meth)acrylate or a mixtures of mono- and multifunctional (meth)acrylates.

7. Dental material according to claim 1, which contains at least one filler.

8. Dental material according to claim 1, which additionally contains at least one photoinitiator for the radical polymerization.

9. Dental material according to claim 1, which contains 0.5 to 60 wt.-% of at least one compound of general formula I, 0.01 to 5.0 wt.-% initiator(s) for the radical polymerization, and optionally 5 to 80 wt.-% multifunctional (meth)acrylate(s), in each case relative to the total mass of the dental material.

10. Dental material according to claim 9, which has the following composition: (a) 5 to 80 wt.-% multifunctional (meth)acrylate(s), (b) 0.01 to 5.0 wt.-% initiator(s), (c) 0.5 to 60 wt.-% of at least one compound of general formula I, (d) 0 to 50 wt.-% monofunctional (meth)acrylate(s), (e) 0 to 90 wt.-% filler(s), and (f) 0 to 5 wt.-% additive(s), in each case relative to the total mass of the dental material.

11. Dental material according to claim 1, which does not contain volatile mercaptans.

12. Dental material according to claim 1 for intraoral use to restore damaged teeth.

13. Dental material according to claim 12 for use as cement, filling composite or veneering material.

14. Method of using the dental material according to claim 1 comprising extraorally manufacturing or repairing dental restorations.

15. Method of using the dental material according to claim 14 wherein the dental restorations comprise inlays, onlays, crowns or bridges.

16. Method of using the compound of Formula (I), comprising defining the variables in claim 1 to reduce the polymerization shrinkage stress of dental materials.

17. Dental material according to claim 9, which contains 1.0 to 50 wt.-% of at least one compound of general formula I, 0.1 to 5.0 wt.-% initiator(s) for the radical polymerization, and optionally 10 to 70 wt.-% multifunctional (meth)acrylate(s), in each case relative to the total mass of the dental material.

18. Dental material according to claim 9, which contains 1.0 to 40 wt.-% of at least one compound of general formula I, 0.1 to 3.0 wt.-% initiator(s) for the radical polymerization, and optionally 10 to 60 wt.-% multifunctional (meth)acrylate(s), in each case relative to the total mass of the dental material.

19. Dental material according to claim 10, which comprises: (a) 10 to 70 wt.-% multifunctional (meth)acrylate(s), (b) 0.1 to 5.0 wt.-% initiator(s), (c) 1.0 to 50 wt.-% of at least one compound of general formula I, (d) 0 to 40 wt.-% monofunctional (meth)acrylate(s), (e) 5 to 90 wt.-% filler(s), and (f) 0 to 3 wt.-% additive(s), in each case relative to the total mass of the dental material.

20. Dental material according to claim 10, which comprises: (a) 10 to 60 wt.-% multifunctional (meth)acrylate(s), (b) 0.1 to 3.0 wt.-% initiator(s), (c) 1.0 to 40 wt.-% of at least one compound of general formula I, (d) 0 to 30 wt.-% monofunctional (meth)acrylate(s), (e) 0 to 80 wt.-% filler(s), and (f) 0.2 to 3 wt.-% additive(s), in each case relative to the total mass of the dental material.

21. Dental material according to one of claim 1, which does not contain any mercaptans at all.

22. Dental material according to claim 1, which does not contain other sulphur compounds.

23. Dental material according to claim 1, wherein the substituents in A comprise one or more of CH.sub.3, C.sub.2H.sub.5, OH, OCH.sub.3, OCOCH.sub.3, a polymerizable vinyl, (meth)acryloyloxy or (meth)acrylamide group.

24. Dental material according to claim 1, wherein the substituents in R.sup.2-9 comprise one or more of CH.sub.3, C.sub.2H.sub.5, OH, OCH.sub.3, OCOCH.sub.3, a polymerizable vinyl, (meth)acryloyloxy, (meth)acrylamide group, C(CH.sub.2)COOR.sup.11 or C(CH.sub.2)CONR.sup.12R.sup.13.

25. Dental material according to claim 3, wherein the substituents in R.sup.2-3 comprise one or more CH.sub.3, C.sub.2H.sub.5, OCH.sub.3 and/or OCOCH.sub.3.

Description

EXAMPLES

Example 1

Synthesis of 2-(toluene-4-sulfonylmethyl)-acrylic acid lauryl ester (1)

[0076] ##STR00007##

[0077] First of all, in a yellow-light laboratory, 3.81 g (15 mmol) iodine was dissolved in 70 ml ethanol and slowly added dropwise to a 0.1 M solution of sodium p-toluene sulfinate (15 mmol) in water. The yellow solid that forms (4-methylbenzene-1-sulfonyl iodide, MBSI) was filtered and subsequently washed with water. The solid was then dissolved in CH.sub.2Cl.sub.2 (50 ml) and dried with anhydrous Na.sub.2SO.sub.4. The desiccant was filtered and the solution with the freshly prepared MBSI was stirred together with 2.54 g (10 mmol) lauryl methacrylate (LMA). The reaction was monitored using thin-layer chromatography (PE/EE 20/1). After all of the LMA had been used up, the reaction solution was washed with 5 wt.-% sodium dithionite solution (225 ml) and with water (125 ml). The aqueous phase was re-extracted with CH.sub.2Cl.sub.2 (125 ml) and the combined organic phases were dried over anhydrous Na.sub.2SO.sub.4. 50 ml ethyl acetate was then added to the solution and the CH.sub.2Cl.sub.2 was evaporated on a rotary evaporator. 5.06 g (50 mmol) triethylamine was then added to the reaction solution under an Ar atmosphere and then boiled under reflux overnight. Once the reaction was complete, the solution was washed with 1N HCl (250 ml) and dist. water (150 ml). The aqueous phases were re-extracted and the combined organic phases were dried over anhydrous Na.sub.2SO.sub.4. The solvent was drawn off on a rotary evaporator and the crude product was purified using column chromatography with a mixture of PE/EE 5/1 (R.sub.f=0.39). The yield was approx. 28.8 g (73% theoretical).

[0078] .sup.1H-NMR (200 MHz, CDCl.sub.3, ): 7.71 (d, J=8.2 Hz, 2H; ArH), 7.30 (d, J=8.2 Hz, 2H; ArH), 6.47 (s, 1H; CH.sub.2), 5.89 (s, 1H; CH.sub.2), 4.12 (s, 2H; SO.sub.2CH.sub.2), 3.94 (t, 2H; OCH.sub.2CH.sub.2), 2.42 (s, 3H; ArCH.sub.3), 1.52 (m, 2H; OCH.sub.2CH.sub.2), 1.25 (s, 18H; OCH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.3); 0.86 (m, 3H; CH.sub.2CH.sub.3);

[0079] .sup.13C-NMR (50 MHz, CDCl.sub.3, ): 164.9 (CO), 144.8 (C.sub.4), 135.5 (C.sub.4), 133.1 (C.sub.2), 129.6 (C.sub.3), 129.2 (C.sub.4), 128.8 (C.sub.3), 65.6 (C.sub.2), 57.5 (C.sub.2), 31.9 (C.sub.2), 29.6 (C.sub.2, C.sub.2, C.sub.2), 29.5 (C.sub.2), 29.3 (C.sub.2), 29.2 (C.sub.2), 28.4 (C.sub.2), 25.8 (C.sub.2), 22.7 (C.sub.2), 21.6 (C.sub.1), 14.1 (C.sub.1).

Example 2

Synthesis of tetraethylene glycol bis[2-(toluene-4-sulfonylmethyl) acrylate] (2)

[0080] ##STR00008##

[0081] Tetraethylene glycol dimethacrylate (TTEGDMA: 5.29 g, 16 mmol) and 4-toluenesulfonyl iodide (9.03 g, 32 mmol) were stirred together in CH.sub.2Cl.sub.2 (approx. 50 ml) at room temperature in yellow light. The reaction was monitored using .sup.1H-NMR spectroscopy. After all of the TTEGDMA had been used up (decrease in the double-bond signals), the reaction solution was washed with 5 wt.-% sodium dithionite solution (225 ml) and with water (125 ml). The aqueous phase was re-extracted with CH.sub.2Cl.sub.2 (125 ml) and the combined organic phases were dried over Na.sub.2SO.sub.4. 50 ml ethyl acetate was then added to the solution and the CH.sub.2Cl.sub.2 was evaporated on a rotary evaporator. A further 50 ml ethyl acetate was then added to the reaction solution and triethylamine (8.1 g, 80 mmol) was added dropwise under an Ar atmosphere (solid precipitated out). The reaction solution was then boiled under reflux overnight. Once the reaction was complete, the solution was washed with 1N HCl (250 ml) and dist. water (150 ml). The aqueous phases were re-extracted and the combined organic phases were dried over Na.sub.2SO.sub.4. The solvent was drawn off on a rotary evaporator and the crude product was purified using column chromatography with a mixture of PE/EE 1/4. (R.sub.f0.32). Yield 70%.

[0082] .sup.1H-NMR (200 MHz, CDCl.sub.3, ): 7.73 (d, J=8.2 Hz, 4H; ArH), 7.32 (d, J=8.2 Hz, 4H; ArH), 6.52 (s, 2H; CH.sub.2), 5.89 (s, 2H; CH.sub.2), 4.14 (m, 8H; OOCCH.sub.2, SO.sub.2CH.sub.2), 3.62 (m, 12H; CH.sub.2OCH.sub.2CH.sub.2), 2.43 (s, 6H; ArCH.sub.3).

[0083] .sup.13C-NMR (50 MHz, CDCl.sub.3, ): 164.9 (CO), 144.9 (C.sub.4), 135.4 (C.sub.4), 133.6 (C.sub.2), 129.7 (C.sub.3), 128.9 (C.sub.4), 128.8 (C.sub.4), 70.7 (C.sub.2), 68.8 (C.sub.2), 64.5 (C.sub.2), 57.5 (C.sub.2), 21.6 (C.sub.1).

Example 3

Synthesis of triethylene glycol bis[2-(toluene-4-sulfonylmethyl) acrylate] (3)

[0084] ##STR00009##

[0085] In a brown glass flask, sodium p-toluenesulfinate (39.20 g, 0.22 mol) was reacted with iodine (55.83 g, 0.22 mol) and worked up according to Example 1 to prepare MBSI 1. The yellow solid was dissolved in dichloromethane (300 ml). Triethylene glycol dimethacrylate (28.63 g, 0.10 mol) was added and the reaction mixture was stirred at RT. After 24 h triethylamine (22.26 g, 0.22 mol) was added dropwise. The red-brown solution was stirred for 2 h at ambient temperature and then concentrated on a rotary evaporator. The dark brown oil was taken up in n-hexane/ethyl acetate 1:1 (100 ml) and filtered over a frit filled with silica gel (silica gel 60, n-hexane/ethyl acetate 1:1). The filtrate was concentrated on a rotary evaporator. The residue was dissolved in ethyl acetate (400 ml) and triethylamine (22.26 g, 0.22 mol) was added. The brownish solution was heated under reflux for 6 h. After cooling, the reaction solution was washed with hydrochloric acid (1N; 2200 ml) and water (200 ml), dried over Na.sub.2SO.sub.4, filtered and concentrated on a rotary evaporator. The brownish oil was purified using column chromatography (silica gel 60, n-hexane/ethyl acetate 1:2; R.sub.f=0.35). 48.44 g (81% yield) of a yellow oil was obtained.

[0086] .sup.1H-NMR (200 MHz, CDCl.sub.3, ): 7.73 (d, J=8.2 Hz, 4H; ArH), 7.32 (d, J=8.2 Hz, 4H; ArH), 6.52 (s, 2H; CH.sub.2), 5.89 (s, 2H; CH.sub.2), 4.14 (m, 8H; OOCCH.sub.2, SO.sub.2CH.sub.2), 3.62 (m, 12H; CH.sub.2OCH.sub.2CH.sub.2), 2.43 (s, 6H; ArCH.sub.3);

[0087] .sup.13C-NMR (50 MHz, CDCl.sub.3, ): 164.9 (CO), 144.9 (C.sub.4), 135.4 (C.sub.4), 133.6 (C.sub.2), 129.7 (C.sub.3), 128.9 (C.sub.4), 128.8 (C.sub.4), 70.7 (C.sub.2), 68.8 (C.sub.2), 64.5 (C.sub.2), 57.5 (C.sub.2), 21.6 (C.sub.1);

Example 4

[0088] Preparation of Composites with Transfer Reagent 1 from Example 1

[0089] A 1/1 mixture (mol/mol) of the monomers UDMA and D.sub.3MA was prepared (resin mixture 2M). Part of this mixture was mixed with monomer 1 from Example 1. The second mixture had the following composition: UDMA (39 wt.-%), D.sub.3MA (26 wt.-%) and 1 (35 wt.-%). The photoinitiator Ivocerin (1 wt.-%) was added to both mixtures. Composite pastes based on these mixtures were prepared by adding 30 wt.-% of the pyrogenic silicic acid O50. The composite paste with monomer 1 had the total composition: UDMA (27 wt.-%), D.sub.3MA (18 wt.-%), 1 (24.3 wt.-%), initiator (0.7 wt.-%) and O50 (30 wt.-%). The formulations were poured into silicone moulds and polymerized in a Lumamat 100 (Ivoclar AG) using program 2 (P2: 10 min irradiation with an intensity of approx. 20 mW/cm.sup.2). The rods were turned and cured again using P2. The test rods were ground and then measured on an Anton Paar Rheometer MCR301 with a CTD oven (Convection Temperature Control) and an installed solid-clamping device (SRF12 for rectangular cross-sections up to 12 mm). The heating rate set was 2 C./min. All samples were heated from 100 C. to 200 C. and oscillated at a constant frequency of 1 Hz and 0.1% deflection. The storage modulus graphs represented in FIG. 1 show that the addition of transfer reagent 1 both in the case of the cured resin sample and in the case of the composite similarly leads to a reduction in the glass transition temperature and to a deeper and significantly narrower glass transition range.

TABLE-US-00001 Formulation T.sub.G [ C.] 2M.sup.a)* 148 2M + Ox50* 162 2M + monomer 1 50 2M + monomer 1 + Ox50 50 .sup.a)2M: UDMA/D.sub.3MA (1/1) *Comparison example

Example 5

[0090] Preparation of Composites with Transfer Reagent 2 from Example 2

[0091] Test pieces were prepared and investigated analogously to Example 4. The following formulations were used: 1/1 mixture (mol/mol) of UDMA and D.sub.3MA (mixture 2M) and a mixture of UDMA (43 wt.-%), D.sub.3MA (28 wt.-%) with monomer 2 (29 wt.-%). Corresponding composite pastes were obtained by adding 60 wt.-% O50. The composite paste with monomer 2 had the following total composition: UDMA (17 wt.-%), D.sub.3MA (11 wt.-%), 2 (12 wt.-%) and O50 (60 wt.-%). FIG. 2 again shows the storage modulus as a function of the temperature for the unfilled and filled resins. The storage modulus graphs shown in FIG. 2 show that the addition of transfer reagent 2 (Example 2) both in the case of the unfilled resin and in the case of the composite leads to a significantly narrower glass transition range with a reduced glass transition temperature (T.sub.G)

TABLE-US-00002 Formulation T.sub.g [ C.] 2M.sup.a)* 148 2M + Ox50* 157 2M + monomer 2 73 2M + monomer 2 + Ox50 78 .sup.a)2M: UDMA/D.sub.3MA (1/1) *Comparison example

Example 6

[0092] Preparation of Filling Composites with Transfer Reagent 3 from Example 3

[0093] The composites were prepared in a Linden kneader. For this, two monomer mixtures were prepared first of all: Monomer mixture A (all values in mass-%): Bis-GMA (28.9%), UDMA (26.0%), SR-348c (14.1%), chain transfer reagent 3 (30.0%), photoinitiator (CQ, 0.2%), EDMAB (0.4%), MBDEGe (0.05%), Lucerin TPO (2,4,6-trimethylbenzoyl diphenylphosphine oxide; 0.25%), stabilizer (hydroquinone monomethyl ether (MEHQ), 0.1%). Monomer mixture B: Bis-GMA (41.3%), UDMA (37.4%), SR-348c (20.3%), CQ (0.2%), EDMAB (0.4%), MBDEGe (0.05%), Lucerin TPO (0.25%), MEHQ (0.1%). To prepare composites, 22.5 mass-% of monomer mixture A (composite A) or monomer mixture B (composite B) was incorporated in each case with 77.5 mass-% of a filler mixture (17% Tetric EvoCeram isofiller (Ivoclar Vivadent AG), 45.5% silanized BaAl-borosilicate glass filler (average particle size of 0.7 m, Schott), 10% Spherosil (silanized SiO.sub.2ZrO.sub.2 mixed oxide, average particle size of 1.2 m, Tokoyama Soda), 5% YbF.sub.3 (ytterbium trifluoride, average particle size of 0.2 m, Auer-Remy; the percentages relate in each case to the total mass of the composite). From the materials, bending test rods with a length of 20 mm and a cross-section of 22 mm were prepared which were irradiated twice for 3 minutes with a dental light source (Spectramat, Ivoclar Vivadent AG) and thus cured. The bending strength and the bending E modulus were determined according to ISO standard 4049 (DentistryPolymer-based filling, restorative and luting materials). To determine the polymerization shrinkage force (PF), the samples were fixed on one side to a silanized object holder and bonded to a Zwick universal testing machine using a steel post (d=10 mm) treated with the Monobond adhesion promoter (Ivoclar Vivadent AG). After setting the layer thickness (0.8 mm) and removing the excess, the measurement was started.

[0094] The illumination (Bluephase 20i, high power, 10 s) was carried out through the object holder and started 120 s after the start of the measurement. The change in force while keeping the crosshead position constant was recorded over a total of 10 minutes. The PCS was obtained by dividing the measured force by the surface area of the test pieces. The resulting measured values are collated in Table 1. The results demonstrate that composite sample A with a compound of Formula I exhibits a significantly reduced polymerization shrinkage force and at the same time does not have worse mechanical properties compared with reference composite B.

TABLE-US-00003 TABLE 1 Properties of the composites Composite Property Composite A B* Bending strength (MPa) after 24 h 105.3 5.9 115.0 12.9 Bending strength (MPa) after 24 h 140.9 10.3 129.1 8.0 WS.sup.1) Bending E modulus (GPa) 9.57 0.73 10.23 0.38 after 24 h Bending E modulus (GPa) 9.91 0.56 10.00 0.20 after 24 h WS PCS (MPa) after 80 s 0.18 0.26 PCS (MPa) after 480 s 0.23 0.30 .sup.1)WS = water storage of the test pieces *Comparison example

Example 7

Measurement of the Impact Strength (Dynstat Impact Test)

[0095] The impact strength properties were determined using the DYNSTAT apparatus in accordance with DIN 53435, wherein the impact strength (impact energy) of unnotched test pieces was determined in the impact bending apparatus. Sample rods (10.450.15 cm) were prepared from the formulations named in Table 2 and Dynstat impact tests were carried out using a 2-kg/cm hammer (0.2 J). The values obtained are listed in Table 2 given below.

TABLE-US-00004 TABLE 2 Impact strength Formulation Impact energy [kJ/m.sup.2].sup.a) 2M.sup.b)* 4.0 2M + monomer 2 (25 wt.-%) 6.8 2M + monomer 2 (29 wt.-%) 18.0 .sup.a)Standardized for width and thickness .sup.b)2M: UDMA/D.sub.3MA (1/1) *Comparison example

[0096] It can be clearly seen that an increase in impact strength was achieved. The impact strength was increased by more than 50% in the case of a proportion of 25 wt.-% of compound 2 (transfer reagent).

Example 8

Synthesis of 2-propenoic acid 2-[(diethoxyphosphinyl)-methyl]-ethyl ester (4)

[0097] ##STR00010##

[0098] For the synthesis of 4, ethyl 2-bromomethylacrylate (1.5 g, 0.008 mol) was heated under reflux with distilled triethyl phosphite (1.3 g, 0.008 mol) for 7 h under an Ar atmosphere in a 10-ml round-bottomed flask and then reacted for 12 h at RT. The product was transferred into a pear-shaped flask and EtBr (bp=38 C. at 1.013 bar) was removed at 5 mbar. Purification using MPLC with petroleum ether (PE)/ethyl acetate (EE) 3:2 was then carried out (Rf0.13). The yield of 4 purified using column chromatography was 1.6 g (82% theoretical).

[0099] .sup.1H-NMR (200 MHz, CDCl.sub.3, ): 0.92-1.34 (9.1H, m, 3 CH.sub.2CH.sub.3), 2.77 (1H, d, J=0.78 Hz, C(COOEt)CH.sub.2PO(OEt).sub.2), 2.87 (1H, d, J=0.78 Hz, C(COOEt)CH.sub.2PO(OEt).sub.2), 3.87-4.18 (6.1H, m, 3 OCH.sub.2CH.sub.3), 5.73 (1H, dd, J=5.46 Hz, J=0.78 Hz, H.sub.2CC(COOEt)), 6.22 (1H, dd, J=5.66 Hz, J=0.58 Hz, H.sub.2CC(COOEt)).

Example 9

Synthesis of 2-propenoic acid 2-[(dodecylthio)methyl]-ethyl ester (5)

[0100] ##STR00011##

[0101] For the synthesis of 5, triethylamine (1.1 g, 0.011 mol) and freshly distilled dodecylthiol (1.6 g, 0.008 mol) were placed in a 50-ml round-necked flask with 10 ml THF and ethyl 2-bromomethylacrylate (1.5 g, 0.008 mol) were flushed into the reaction flask with 9 ml THF. On addition of the acrylate a fine, white precipitate precipitated out immediately. The end of the reaction, after stirring at room temperature (RT) for 21 h, was confirmed using thin-layer chromatography (TLC). The working up was carried out by dissolving unreacted salt in 15 ml deionized water. The aqueous phase was extracted 3 with 15 ml petroleum ether, the combined organic phases were dried over Na.sub.2SO.sub.4 and PE was drawn off on a rotary evaporator. Purification using medium-pressure liquid chromatography (MPLC) with PE/EE 10:1 was then carried out (R.sub.f0.46 (PE/EE 12:1)). The yield of 5 purified using column chromatography was 1.2 g (50% theoretical).

[0102] .sup.1H-NMR (200 MHz, CDCl.sub.3, ): 0.85 (3.5H, t, J=6.46 Hz, C.sub.10H.sub.20CH.sub.3), 1.10-1.65 (27.1H, m, CH.sub.2C.sub.10H.sub.20CH.sub.3 and OCH.sub.2CH.sub.3), 2.42 (2.1H, t, J=7.24 Hz, SCH.sub.2C.sub.11H.sub.23), 3.35 (2H, s, C(COOC.sub.2H.sub.5)CH.sub.2S), 4.21 (2.2H, q, J=7.11 Hz, OCH.sub.2CH.sub.3), 5.61 (1H, d, J=1.17 Hz, H.sub.2CC(COOC.sub.2H.sub.5)), 6.17 (1H, d, J=1.98 Hz, H.sub.2CC(COOC.sub.2H.sub.5)).

Example 10

Synthesis of 2-{[2-(ethoxycarbonyl)-2-propenyl]-sulfanyl]-methyl}-acrylic acid ethyl ester (6)

[0103] ##STR00012##

[0104] For the synthesis of 6, ethyl 2-bromomethylacrylate (10.0 g, 0.052 mol) was placed in a 50-ml round-bottomed flask and sodium sulfide (5.9 g, 0.021 mol), freshly recrystallized from deionized H.sub.2O, in 2 ml deionized H.sub.2O was added in one go and rinsed using 8 ml H.sub.2O. Stirring was carried out for 24 h at RT and, after controlling the reaction using TLC, dilution was carried out with 15 ml deionized H.sub.2O to dissolve any salt formed. Extraction was carried out 3 with 15 ml petroleum ether, the combined organic phases were extracted with saturated saline solution and then dried over Na.sub.2SO.sub.4. After drawing off the solvent on a rotary evaporator, purification was carried out using MPLC in PE/EE 6:1 (R.sub.f0.49) and yielded 4.0 g 6 (30% theoretical yield).

[0105] .sup.1H-NMR (200 MHz, CDCl.sub.3, ): 1.18 (6.1H, t, J=7.13 Hz, 2 CH.sub.2CH.sub.3), 3.20 (3.8H, d, J=0.58 Hz, 2 C(COOC.sub.2H.sub.5)CH.sub.2S), 4.10 (4.1H, q, J=7.11 Hz, OCH.sub.2CH.sub.3), 5.55 (2H, d, J=0.98 Hz, 2 H.sub.2CC(COOC.sub.2H.sub.5)), 6.09 (2H, d, J=0.98 Hz, 2 H.sub.2CC(COOC.sub.2H.sub.5)).

Example 11

Synthesis of 2-{[2-(ethoxycarbonyl)-2-propenyl]-sulfonyl]-methyl}-acrylic acid ethyl ester (7)

[0106] ##STR00013##

[0107] For the synthesis of 7, compound 6 (3.0 g, 0.012 mol) in 100 ml DMF was placed in a 500-ml round-necked flask, potassium peroxosulfate (13.9 g, 0.045 mol) was added and rinsed with 200 ml DMF. Stirring was carried out for 4 h at RT under an Ar atmosphere and, after controlling the reaction using TLC, deionized H.sub.2O (900 ml) was added. Extraction was carried out 3 with 130 ml diethyl ether, 1 with 150 ml saturated saline solution, followed by drying over Na.sub.2SO.sub.4. After drawing off the solvent on a rotary evaporator, purification was carried out using MPLC in PE/EE 10:1 (R.sub.f0.67 (PE/EE 1:1)) and yielded 1.2 g 7 (37% theoretical yield).

[0108] .sup.1H-NMR (200 MHz, CDCl.sub.3, ): 1.24 (6.4H, t, J=7.14 Hz, 2 CH.sub.2CH.sub.3), 4.03 (4.1H, s, 2 C(COOC.sub.2H.sub.5)CH.sub.2S), 4.18 (4.1H, q, J=7.17 Hz, OCH.sub.2CH.sub.3), 6.08 (2H, s, 2 H.sub.2CC(COOC.sub.2H.sub.5)), 6.53 (2H, s, 2 H.sub.2CC(COOC.sub.2H.sub.5)).

Example 12

Synthesis of 2-(tosylmethyl)acrylonitrile (8)

[0109] ##STR00014##

[0110] Tosyl iodide (4.88 g, 17 mmol) and methacrylonitrile (1.16 g, 17 mmol) were dissolved in 100 ml carbon tetrachloride and stirred at room temperature for 4 h. The solvent and any iodine formed were then evaporated under vacuum. After the renewed addition of 100 ml carbon tetrachloride, the solution had 4 equivalents of triethylamine added to it and was heated under reflux for 12 h. The resulting brown solution was washed with 5% sodium dithionite solution (220 ml), 1N HCl (120 ml) and saturated NaCl solution (120 ml) to remove any remaining iodine and triethylamine. The collected organic phases were dried over 15 g Na.sub.2SO.sub.4 and the solvent drawn off on a rotary evaporator. The crude product was purified using column chromatography with pure dichloromethane as mobile solvent. The yield was 789 mg (21% theoretical) 2-(tosylmethyl)acrylonitrile 8 as fine white needles.

[0111] .sup.1H-NMR (200 MHz, CDCl.sub.3) =7.73 (d, 8.45 Hz, 2H; ArH), 7.33 (d, J=8.45 Hz, 2H; ArH), 6.15 (s, 1H; CH.sub.2), 5.94 (s, 1H; CH.sub.2), 3.84 (s, 2H; SO.sub.2CH.sub.2), 2.41 (s, 3H; ArCH.sub.3) ppm.

Example 13

Synthesis of 1-methyl-4-((2-phenylallyl)sulfonyl)benzene (9)

[0112] ##STR00015##

[0113] Methylstyrene (2.95 g, 25 mmol), tosyl chloride (4.77 g, mmol), Cu(I)Cl (2.48 g, 25 mmol) and triethylamine (2.53 g, mmol) were placed in 70 ml dry acetonitrile and heated under reflux for 3 h under an argon atmosphere. After drawing off the solvent on a rotary evaporator, the crude product was taken up in 30 ml dichloromethane and washed with 1N HCl (220 ml), saturated NaHCO.sub.3 solution (ix 20 ml) and saturated NaCl solution (120 ml). After purification using column chromatography with dichloromethane as mobile solvent, 1-methyl-4-((2-phenylallyl)sulfonyl)benzene 9 was obtained in a yield of 3.60 g (53% theoretical).

[0114] .sup.1H-NMR (200 MHz, CDCl.sub.3) =7.59 (d, J=7.64 Hz, 2H; ArH), 7.5-6.9 (m, 7H; ArH), 5.51 (s, 1H; CH.sub.2), 5.14 (s, 1H; CH.sub.2), 4.18 (s, 2H; SO.sub.2CH.sub.2), 2.32 (s, 3H; ArCH.sub.3) ppm.

Example 14

Synthesis of 2-(tosylmethyl)acrylic acid (10)

[0115] ##STR00016##

[0116] Bromomethacrylic acid (8.25 g, 50 mmol) was dissolved in 250 ml hot MeOH and NaOH (2 g, 50 mmol) was added to it. Then sodium p-toluenesulfinate (8.91 g, 50 mmol) was added in portions and heated for 2 h under reflux. After drawing off the solvent on a rotary evaporator, the solid residue was taken up in 500 ml water and 2-(tosylmethyl)acrylic acid 10 was precipitated using 1 N HCl. Yield 7.44 g (62% theoretical).

[0117] .sup.1H-NMR (200 MHz, CDCl.sub.3) =8.81 (bs, 1H), 7.67 (d, J=8.6 Hz, 2H; ArH), 7.27 (d, J=8.6 Hz, 2H; ArH), 6.55 (s, 1H; CH.sub.2), 5.94 (s, 1H; CH.sub.2), 4.04 (s, 2H; SO.sub.2CH.sub.2), 2.36 (s, 3H; ArCH.sub.3) ppm.

Example 15

Synthesis of N-methyl-N-propyl-2-(tosylmethyl)acrylamide (11)

[0118] ##STR00017##

[0119] 2-(Tosylmethyl)acrylic acid 10 (3.00 g, 12.5 mmol) was heated under reflux in 30 ml thionyl chloride for 2 h. After drawing off the excess SOCl.sub.2, the acid chloride was taken up in 100 ml dichloromethane and 6 equivalents of propyl methyl amine were slowly added to it at 0 C. After stirring at RT for 12 h, the solvent was drawn off on a rotary evaporator and, after being taken up in 20 ml dichloromethane, the crude product was washed with 1 N HCl (220 ml) and saturated NaCl solution (120 ml). After purification using column chromatography (PE:EE (1:1)+0.5% acetic acid), 701 mg (19% theoretical)N-methyl-N-propyl-2-(tosylmethyl)acrylamide 11 was obtained.

[0120] .sup.1H-NMR (200 MHz, CDCl.sub.3) =7.78 (d, J=8.1 Hz, 2H; ArH), 7.34 (d, J=8.1 Hz, 2H; ArH), 5.51 (bs, 1H; CH.sub.2), 5.41 (s, 1H; CH.sub.2), 4.09 (s, 2H; SO.sub.2CH.sub.2), 3.5-2.7 (m, 5H; NCH.sub.3, NCH.sub.2CH.sub.2CH.sub.3), 2.38 (s, 3H; ArCH.sub.3), 1.7-1.3 (m, 2H; NCH.sub.2CH.sub.2CH.sub.3), 0.85 (t, J=7.5 Hz, 3H; NCH.sub.2CH.sub.2CH.sub.3) ppm.

Example 16

Synthesis of 14-methyl-13-oxo-3,6,9,12-tetraoxapentadec-14-en-1-yl 2-(tosylmethyl)acrylate (12)

[0121] ##STR00018##

[0122] Tetraethylene glycol dimethacrylate (TTEGDMA, 14.6 g, 44.7 mmol) and 4-toluenesulfonyl iodide (12.6 g, 44.7 mmol) were stirred together in CH.sub.2Cl.sub.2 (approx. 100 ml) at room temperature under yellow light. The synthesis took place analogously to the synthesis of Example 2. Triethylamine (22.6 g, 223.4 mmol) was added dropwise (solid precipitated out). The crude product was purified using column chromatography with a mixture of PE/EE 1/3. (R.sub.f0.38). Yield 24%.

[0123] .sup.1H-NMR (200 MHz, CDCl.sub.3, ): 7.70 (d, J=8.2 Hz, 2H; ArH), 7.31 (d, J=8.2 Hz, 2H; ArH), 6.49 (s, 1H; CH.sub.2), 6.10 (m, 1H; CH.sub.2), 5.86 (s, 1H; CH.sub.2), 5.50 (m, 1H; CH.sub.2), 4.27 (m, 2H; OOCCH.sub.2), 4.12 (m, 4H; OOCCH.sub.2, SO.sub.2CH.sub.2), 3.71 (m, 2H; OOCCH.sub.2CH.sub.2), 3.63 (m, 10H; CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2), 2.41 (s, 6H; ArCH.sub.3) 1.92 (m, 3H; COCCH.sub.3).

[0124] .sup.13C-NMR (50 MHz, CDCl.sub.3, ): 164.9 (CO), 145.0 (C.sub.4), 136.2 (C.sub.4) 135.5 (C.sub.4), 133.7 (C.sub.2), 129.8 (C.sub.3), 129.0 (C.sub.4), 128.9 (C.sub.3), 125.9 (C.sub.2), 70.7 (C.sub.2), 69.2 (C.sub.2), 68.9 (C.sub.2), 64.6 (C.sub.2), 64.0 (C.sub.2), 57.7 (C.sub.2), 21.8 (C.sub.1), 18.4 (C.sub.1).

Example 17

Synthesis of 2-(methylsulfonylmethyl)-acrylic acid ethyl ester (13)

[0125] ##STR00019##

[0126] Ethyl 2-(bromomethyl)acrylate (1.1 g, 5.8 mmol), sodium methanesulfinate (0.7 g, 6.7 mmol) and 0.1 g polyethylene oxide 400 were placed in 10 ml absolute THF under an argon atmosphere. Heating then took place under reflux for 20 hours, wherein the progress of the reaction was monitored using NMR and TLC. Once the reaction was complete, the reaction solution was diluted with 10 ml deionized water and 10 ml diethyl ether. The aqueous phase was extracted three times with 25 ml diethyl ether in each case. The combined organic phases were then washed with saturated saline solution, dried over sodium sulfate and evaporated on a rotary evaporator. The crude product obtained was purified using column chromatography with a mixture of PE/EE 1/1. (R.sub.f0.45). Yield 33%.

[0127] .sup.1H-NMR (200 MHz, CDCl.sub.3, ): 6.64 (s, 1H; CH.sub.2), 6.15 (s, 1H; CH.sub.2), 4.28 (q, J=7.1 Hz, 2H; COOCH.sub.2CH.sub.3), 4.06 (s, 2H; SO.sub.2CH.sub.2C), 2.90 (s, 3H; SO.sub.2CH.sub.3), 1.33 (t, J=7.1 Hz, 3H; COOCH.sub.2CH.sub.3).

[0128] .sup.13C-NMR (50 MHz, CDCl.sub.3, ): 165.3 (CO), 133.9 (C.sub.2), 129.1 (C.sub.4), 61.9 (C.sub.2), 56.4 (C.sub.2), 40.5 (C.sub.1), 14.1 (C.sub.1).

Example 18

Synthesis of 2-methylene-3-[(4-methylphenyl) sulfonyl]butyric acid methyl ester (14)

[0129] ##STR00020##

[0130] (Z)-Methyl-2-(bromomethyl)but-2-enoate (2.7 g, 14.0 mmol) and 0.5 g polyethylene oxide 400 were placed in 15 ml absolute THF and cooled to 20 C. Sodium p-toluenesulfinate (0.8 g, 4.7 mmol) was then added slowly. Stirring was carried out at 20 C. for 10 hours. Purification was carried out using column chromatography with a mixture of PE/EE 2/1. (R.sub.f0.50). Yield 36%.

[0131] .sup.1H-NMR (200 MHz, CDCl.sub.3, ): 7.69 (d, J=8.2 Hz, 2H; ArH), 7.30 (d, J=8.2 Hz, 2H; ArH), 6.53 (s, 1H; CH.sub.2), 5.98 (s, 1H; CH.sub.2), 4.58 (q, J=7.2 Hz, 1H; SO.sub.2CH), 3.60 (s, 3H; COOCH.sub.3), 2.42 (s, 3H; ArCH.sub.3), 1.54 (d, J=7.2 Hz, 3H; SO.sub.2CHCH.sub.3).

Example 19

[0132] Preparation and Characterization of Polymers with Dimethacrylates and Transfer Reagents

[0133] A 1/1 mixture (mol/mol) of UDMA and D.sub.3MA (2M) as well as mixtures of UDMA, D.sub.3MA and in each case one transfer reagent (compounds nos. 1, 2, 5-14) were prepared according to Table 3. The formulations additionally contained 1 wt.-% Ge initiator (Ivocerin). To check the photoreactivity, the formulations prepared were measured using a photorheometer (MCR 302 WESP model, Anton Paar). A plate-plate measuring system of the PP25 type was used and the measuring gap was set to 0.1 mm. Before and during curing with a UV lamp (Omnicure 2000 model; 400-500 nm; 1 W/cm.sup.2 and 3 W/cm.sup.2 respectively), the storage modulus and loss modulus of the sample were measured in the oscillation mode (1% deflection, 1 Hz).

[0134] The double-bond conversion (DBC) achieved at the gel point (intersection of the storage modulus and the loss modulus) serves as a measure of the polymerization shrinkage occurring. The double-bond conversion at the gel point does not lead to the build-up of stresses as the polymerization shrinkage occurring is compensated for by flow processes. The higher the double-bond conversion is at the gel point, the lower are consequently the double-bond conversion and the polymerization shrinkage in the gel condition, which thus also leads to a lower polymerization shrinkage force. To determine the glass transition, the formulations were poured into silicone moulds and polymerized in a light furnace (Lumamat 100 model, Ivoclar AG) using program 2 (P2: 10 min irradiation with an intensity of approx. 20 mW/cm.sup.2). The rods were turned and cured again using P2. The test rods were ground and then measured on a rheometer (MCR 302 model) with a CTD oven (Convection Temperature Control) and an installed solid-clamping device (SRF12 for rectangular cross-sections up to 12 mm). The heating rate set was 2 C./min. All samples were heated from 100 C. to 200 C. and oscillated at a constant frequency of 1 Hz and 0.1% deflection.

[0135] The glass transition temperatures shown in Table 3 (maxima of the loss modulus graphs) show that the addition of the transfer reagents leads to a deeper and significantly narrower glass transition range, which makes debonding-on-demand substantially easier in the compositions according to the invention. Moreover, it can be seen that the double-bond conversion at the gel point is increased by the transfer reagents. A lower shrinkage stress is therefore to be expected because stresses can be dissipated by flow processes up to the gel point.

TABLE-US-00005 TABLE 3 Formulation T.sub.G [ C.] HW [ C.] DBC [%] 2M.sup.a)* 150 152 18 2M.sup.c)* 148 145 18 2M + 35 wt.-% 1 50 28 .sup.b) 2M + 29 wt.-% 2 75 32 23 2M + 29 wt.-% 5 48 51 30 2M + 14 wt.-% 6 134 51 24 2M + 16 wt.-% 7 68 51 29 2M + 6 wt.-% 8.sup.c) 129 93 51 2M + 7 wt.-% 9.sup.c) 126 82 28 2M + 6 wt.-% 10.sup.c) 114 55 25 2M + 34 wt.-% 11.sup.c) 74 57 36 2M + 45 wt.-% 12 64 23 .sup.b) 2M + 20 wt.-% 13 66 26 .sup.b) 2M + 26 wt.-% 14 65 74 .sup.b) *Comparison example T.sub.G Glass transition temperature HW Half width DBC Double-bond conversion at the gel point .sup.a)2M: UDMA/D.sub.3MA (1/1) .sup.b) Not measured .sup.c)Curing with 3 W/cm.sup.2