Compounds having two or more exovinylene cyclocarbonate units

Abstract

What are described are compounds having two or more exovinylene cyclocarbonate units, wherein the exovinylene cyclocarbonate units are bonded to one another via at least one organic, siloxane-free connecting group which is not bonded directly to the exovinylene double bonds, excluding connecting groups formed by polymerization of (meth)acrylic monomers. The connecting group preferably has at least one acetal group. Also described are a process for preparing the compounds, two-component binders comprising the compounds, and uses of the compounds.

Claims

1. A compound having two or more exovinylene cyclocarbonate units, where the exovinylene cyclocarbonate units are joined to one another via at least one organic, siloxane-free connecting group, wherein the connecting group is not bonded directly to the exovinylene double bonds and connecting groups formed by polymerization of (meth)acrylic monomers are excluded, and wherein, if the compound has exactly two exovinylene cyclocarbonate units, the connecting group has at least one acetal group.

2. The compound according to claim 1, wherein the exovinylene cyclocarbonate units are 5-vinylidene-1,3-dioxolan-2-one units of the formula (I): ##STR00022## wherein: the at least one organic, siloxane-free connecting group is between the 4 positions of the 5-vinylidene-1,3-dioxolan-2-one units; and R.sub.1 to R.sub.3 are each independently hydrogen or an organic radical.

3. The compound according to claim 1, wherein the connecting group has at least one acetal group.

4. The compound according to claim 1, which has the formula (II): ##STR00023## wherein: R.sub.1 to R.sub.3 are independently hydrogen or an organic radical; n is a number not less than 2; and A is a siloxane-free organic connecting group, excluding a connecting group formed by polymerization of (meth)acrylic monomers; or which has the formula (III): ##STR00024## wherein: R.sub.1 to R.sub.b are independently hydrogen or an organic radical; and A is a siloxane-free organic connecting group, excluding a connecting group formed by polymerization of (meth)acrylic monomers; or which has the formula (IV): ##STR00025## wherein: R.sub.1 to R.sub.6 are independently hydrogen or an organic radical, R.sub.7 is hydrogen, an OH group or an organic radical, A is a siloxane-free organic connecting group, excluding a connecting group formed by polymerization of (meth)acrylic monomers, and n is a number not less than 1; or which has the formula (V): ##STR00026## wherein: R.sub.1 to R.sub.3 are independently hydrogen or an organic radical, R.sub.7 and R.sub.8 are independently hydrogen, an OH group or an organic radical and R.sub.7 and/or R.sub.8 optionally comprise an exovinylene cyclocarbonate group, A is a siloxane-free organic connecting group, excluding a connecting group formed by polymerization of (meth)acrylic monomers, and n is a number not less than 1, if at least one of the R.sub.7 and R.sub.8 radicals comprises at least one exovinylene cyclocarbonate group, and n is a number not less than 2, if R.sub.7 and R.sub.8 radicals do not comprise an exovinylene cyclocarbonate group.

5. The compound according to claim 4, wherein A has at least one acetal group.

6. The compound according to claim 4, wherein: in the formula (II), -A is defined as B-Q; in the formula (III), -A- is defined as B-Q-B; the compound is a compound of the formula (IVa): ##STR00027## the compound is a compound of the formula (Va): ##STR00028## wherein: R.sub.1 to R.sub.6 are independently hydrogen or an organic radical, R.sub.7 and R.sub.8 are independently hydrogen, an OH group or an organic radical, B in each case is a divalent hydrocarbyl group, Q in each case is an organic radical; and n in the formula (IVa) is a number not less than 1; and in the formula (Va) is a number not less than 1, if at least one of the R.sub.7 and R.sub.8 radicals comprises at least one exovinylene cyclocarbonate group, and n is a number not less than 2, if the R.sub.7 and R.sub.8 radicals do not comprise an exovinylene cyclocarbonate group.

7. The compound according to claim 4, wherein: R.sub.1, R.sub.2, R.sub.5 and R.sub.6 are independently a C1- to C10-alkyl group; and R.sub.3 and R.sub.4 are independently a C1 to C10 alkyl group or a hydrogen atom.

8. The compound according to claim 4, which is a compound of the formula (Vb): ##STR00029## or of the formula (Vc): ##STR00030## or of the formula (IVb): ##STR00031## or of the formula (VI): ##STR00032## wherein: B is an alkylene group; Q is a group derived from a polyol, a polyol being an alcohol having at least two hydroxyl groups; n in the formulae (Vb) and (Vc) is a number not less than 2, n in the formula (IVb) is a number not less than 1, and n in the formula (VI) is a number not less than 0.

9. The compound according to claim 4, which is a compound of the formula (VIa): ##STR00033## or of the formula (IVc): ##STR00034## or of the formula (Vd): ##STR00035## or of the formula (Ve): ##STR00036## wherein: O-Q-O in the formulae VIa, IVc, Vd and Ve is in each case the radical of a divalent alcohol, n in the formula (IVc) is 1, 2 or 3, and n in the formulae (Vd) and (Ve) is a number not less than 2.

10. The compound according to claim 4, wherein: R.sub.1, R.sub.2, R.sub.5 and R.sub.6 are each a hydrogen atom; R.sub.3 and R.sub.4 are independently methyl or a hydrogen atom; and R.sub.7, R.sub.8 and A are independently radicals of polyhydric alcohols having 2 to 12 carbon atoms that are optionally interrupted by a O, S or NR.sub.2 group, wherein R is H or C1- to C12-alkyl.

11. The compound according to claim 1, which is prepared by transacetalization of an exovinylene cyclocarbonate of the formula (VII): ##STR00037## wherein: R.sub.1 to R.sub.3 and R.sub.9 are independently hydrogen or an organic radical, R.sub.10 and R.sub.11 are independently an organic radical, and A is an organic connecting group.

12. The compound according to claim 11, wherein: R.sub.1 and R.sub.2 are each a hydrogen atom; R.sub.3 and R.sub.9 are independently methyl or a hydrogen atom, R.sub.10 and R.sub.11 are independently alkyl groups having 1 to 4 carbon atoms, and A is an alkylene group having 1 to 4 carbon atoms.

13. A process for preparing the compound according to claim 1, comprising reacting a compound having an exovinylene cyclocarbonate unit and at least one acetal group with at least one compound selected from the group consisting of a diol and a polyol.

14. The process according to claim 13, wherein the reacting occurs under catalysis by at least one Lewis acid or by at least one protic acid.

15. A reaction product obtained by the process of claim 13.

16. A binder for a varnish, paint, ink, building material, elastomer, foam, fiber or particle, the binder comprising a two-component composition comprising: a first component comprising at least one compound of claim 1; and a second component comprising at least one polyfunctional hardener having at least two functional groups selected from the group consisting of a primary amino group, secondary amino group, hydroxyl group, phosphine group, phosphonate group and mercaptan group.

17. The binder according to claim 16, wherein the two-component composition comprises at least one catalyst for catalyzing the reacting the exovinylene cyclocarbonate groups with the functional groups of the hardener.

18. A composition, comprising the compound according to claim 1, wherein the composition is at least one selected from the group consisting of a coating composition, varnish, paint, ink, building material, elastomer and foam.

Description

EXAMPLES

Example 1: Synthesis of an Exovinylene Cyclocarbonate Dimethyl Acetal

(1) The preparation is effected in two stages.

(2) ##STR00021##

(3) 1.) Ethynylation of 4,4-dimethoxybutan-2-one: TMS-acetylene (982 g, 10 mol) is initially charged under argon in THF (17 L, dried over molecular sieve) and cooled down to 68 C. While stirring, within 1 h, n-butyllithium (2.5 M in hexane, 4 L) is added dropwise at 68 C. and stirred for a further 1 h. Within 30 min, the ketone (1.319 kg, 10 mol) is then added dropwise at 68 C. to 54 C. and the mixture is subsequently stirred for a further 15 min. Thereafter, the mixture is warmed to 9 C. and water (2.9 L) is added in one portion. The temperature rises to about 17 C. The reaction mixture is concentrated thoroughly at 45 C./8 Torr. By GC analysis, it is ensured that no TMS-protected product is present any longer. The residue is suspended in diethyl ether (750 mL) and filtered, and the filtration residue is washed once again with diethyl ether. The filtrate is concentrated under reduced pressure. About 1.2 kg of raw material remain as a brown liquid. By vacuum distillation (5 mbar), about 1.1 kg (7 mol, 70%) of ethynylated product are obtained therefrom at 64-68 C. as a colorless oil.

(4) Purity: >96% (GC area %)

(5) 2.) Ring Closure with CO.sub.2: The acetylene alcohol obtained in stage 1 (1233 g; 7.79 mol) is initially charged in acetonitrile (1.2 L) and, in a stirred autoclave, PMDETA (pentamethyldiethylenetriamine; 138.9 g; 0.8 mol) and AgOAc (12.9 g; 0.078 mol) are added. CO.sub.2 is injected to 50 bar and the mixture is stirred for 2.5 h. The temperature rises up to 75 C. After cooling to room temperature, the reaction mixture is decompressed to standard pressure, filtered and concentrated at 100 C./5 mbar. About 1.5 kg of raw material remain as a brown liquid. By vacuum distillation at 5 mbar, about 1.39 kg of the carbonate are obtained therefrom at 114-115 C. as an orange oil which crystallizes through overnight (possibly after addition of a few seed crystals). The mass of crystals is stirred with cyclohexane (1.34 L) and filtered with suction, and the residue is washed once again with cyclohexane (0.45 L). After drying under reduced pressure, 1.29 kg (6.38 mol, 64%) of almost colorless solids are obtained. Purity: >99% (GC area %)

Example 2: Transacetalization with Hexane-1,6-Diol

(6) In a 3-neck flask with stirrer, thermometer and vacuum connection, 30 g of the compound from example 1, 22.8 g of hexane-1,6-diol, 0.5 g of p-toluenesulfonic acid were suspended in 30 g of acetonitrile and heated to 45 C. Reduced pressure was applied and the solvent was distilled off, distilling at 45 C. for a total of 8 h and at room temperature for 40 h. This was followed by washing 3 times with 150 ml of demineralized water and decanting-off, and drying under reduced pressure.

(7) Yield: 40 g of yellow viscous liquid

(8) Zero-shear viscosity at 23 C.: 2 Pa s

Example 3: Transacetalization with Butane-1,4-Diol

(9) In a 3-neck flask with stirrer, thermometer and vacuum connection, 100 g of the compound from example 1, 57.9 g of butane-1,4-diol were dissolved in 50 g of acetonitrile. 1.5 g of p-toluenesulfonic acid were dissolved in 10 g of acetonitrile and added to the mixture. The solvent was distilled off and vacuum was applied at room temperature for 40 h and distillation was continued at 45 C. for 8 h. This was followed by washing 3 times with 50 ml of demineralized water and decanting-off, and drying under reduced pressure.

(10) Yield: 100 g of brown viscous liquid

Example 4: Transacetalization with Triethylene Glycol

(11) In a 3-neck flask with stirrer, thermometer and vacuum connection, 100 g of the compound from example 1, 96.5 g of triethylene glycol (dried over molecular sieve), 1.36 g of p-toluenesulfonic acid were suspended in 50 g of acetonitrile and heated to 45 C. Reduced pressure was applied and the solvent was distilled off, and distillation was continued at 45 C. for 8 h and at room temperature for 40 h. This was followed by washing 3 times with 150 ml of demineralized water and decanting-off, and drying under reduced pressure.

(12) Yield: 153 g of brown viscous liquid

Example 5: Transacetalization with Hexane-1,6-Diol (Buffered, Dried Workup)

(13) In a 3-neck flask with stirrer, thermometer and vacuum connection, 100 g of the compound from example 1, 75.98 g of hexane-1,6-diol, 1.7 g of p-toluenesulfonic acid were suspended in 100 g of acetonitrile and heated to 45 C. Reduced pressure was applied and the solvent was distilled off, distilling at 45 C. for a total of 8 h and at room temperature for 12 h. Then the product was taken up in 200 g of methyl tert-butyl ether, washed 3 times with 50 ml of pH7 buffer solution, dried with MgSO4 and filtered, and the solvent was removed by rotary evaporation.

(14) Yield: 131 g of yellow viscous liquid

Example 6: Transacetalization with Hexane-1,6-Diol (with Heterogeneous Catalyst)

(15) In a 3-neck flask with stirrer, thermometer and vacuum connection, 20 g of the compound from example 1, 15.2 g of hexane-1,6-diol, 2.5 g of Amberlyst 15 dry, acidic (Sigma-Aldrich) were suspended in 20 ml of acetonitrile and heated to 45 C. Reduced pressure was applied and the solvent was distilled off, distilling at 45 C. for a total of 8 h and at room temperature for 40 h. Then the product was taken up in 100 g of methyl tert-butyl ether (MTBE), the heterogeneous catalyst was filtered off and the solvent was removed by rotary evaporation.

(16) Yield: 19 g of brown viscous liquid

Example 7: Transacetalization with Poly-THF

(17) In a 3-neck flask with stirrer, thermometer and vacuum connection, 20 g of the compound from example 1, 32 g of poly-THF 250, 0.34 g of p-toluenesulfonic acid were dissolved in 20 g of acetonitrile and heated to 45 C. Reduced pressure was applied and the solvent was distilled off, distilling at 45 C. for a total of 8 h and at room temperature for 40 h. Then the product was taken up in 100 g of methyl tert-butyl ether, washed 3 times with 50 ml of pH7 buffer solution, dried with MgSO4 and filtered, and the solvent was removed by rotary evaporation.

(18) Yield: 37 g of yellow viscous liquid

Example 8: Transacetalization with 3-Methylpentanediol

(19) In a 3-neck flask with stirrer, thermometer and vacuum connection, 50 g of the compound from example 1, 38 g of 3-methylpentane-1,5-diol, 0.85 g of p-toluenesulfonic acid were suspended in 50 g of acetonitrile and heated to 45 C. Reduced pressure was applied and the solvent was distilled off, distilling at 45 C. for a total of 8 h and at room temperature for 12 h. Then the product was taken up in 100 g of methyl tert-butyl ether, washed 3 times with 50 ml of pH7 buffer solution, dried with MgSO4 and filtered, and the solvent was removed by rotary evaporation.

(20) Yield: 50.5 g of yellow viscous liquid

(21) Zero-shear viscosity at 23 C.: 40 Pa s

Example 9: Transacetalization with Cyclohexane-1,6-Dimethanol

(22) In a 3-neck flask with stirrer, thermometer and vacuum connection, 20 g of the compound from example 1, 18.5 g of cyclohexane-1,6-dimethanol, 0.34 g of p-toluenesulfonic acid were suspended in 20 g of acetonitrile and heated to 45 C. Reduced pressure was applied and the solvent was distilled off, distilling at 45 C. for a total of 8 h and at room temperature for 12 h. Then the product was taken up in 100 g of methyl tert-butyl ether, washed 3 times with 50 ml of pH7 buffer solution, dried with MgSO4 and filtered, and the solvent was removed by rotary evaporation.

(23) Yield: 27 g of yellow, highly viscous liquid

(24) Zero-shear viscosity at 23 C.: 425 Pa s

Example 10: Transacetalization with Butanediol in Methanol

(25) In a 3-neck flask with stirrer, thermometer and vacuum connection, 30 g of the compound from example 1, 17.4 g of butane-1,4-diol were dissolved in 30 g of methanol. 0.51 g of methanesulfonic acid was dissolved in 10 g of methanol and added to the mixture. The solvent was distilled off and vacuum was applied at room temperature for 40 h and distillation was continued at 45 C. for 8 h. This was followed by washing 3 times with 150 ml of cold demineralized water and 3 times with 150 ml of warm demineralized water, which was decanted off, and drying under reduced pressure.

(26) Yield: 14 g of brown viscous liquid

Example 11: Transacetalization with Octane-1,8-Diol

(27) In a 3-neck flask with stirrer, thermometer and vacuum connection, 300 g of the compound from example 1, 282 g of octane-1,8-diol, 2.5 g of p-toluenesulfonic acid were suspended in 410 g of acetonitrile and then heated to external temperature 55 C. Reduced pressure was applied and the solvent was distilled off, in the course of which the internal temperature was not to fall below 50 C. (total of 8 h). Then vacuum was applied at room temperature for 15 h and degassing was effected once again at external temperature 50 C. for 8 h. Then the product was taken up in 400 g of methyl tert-butyl ether, washed 3 times with 150 ml of pH7 buffer solution, dried with MgSO4 and filtered, and the solvent was removed by rotary evaporation.

(28) Yield: 457 g of red-brown viscous liquid

(29) Zero-shear viscosity at 23 C.: 14 Pa s

Example 12: Transacetalization with Diglycerol

(30) In a 3-neck flask with stirrer, thermometer and vacuum connection, 300 g of the compound from example 1, 123.3 g of diglycerol (CAS. No 59113-36-9 Inovyn) were dissolved in 100 g of methanol. 2.5 g of p-toluenesulfonic acid were dissolved in 10 g of methanol and added to the mixture. The solvent was distilled off and the mixture was distilled at room temperature for 8 h. This was followed by extractive stirring with 150 ml of pH 8 buffer solution, and the product was taken up in 300 ml of ethyl acetate, extracted by shaking twice with 150 ml of pH 7 buffer solution, dried with MgSO4, and the solvent was distilled off.

(31) Yield: 298 g of very dark, very viscous liquid

(32) Zero-shear viscosity at 23 C.: 4298 Pa s

Example 13 (Comparison): Transacetalization with a Hydroxyalkyl Acrylate Copolymer (Acrylate Polymer as Connecting Group)

(33) In a 3-neck flask with stirrer, thermometer and vacuum connection, 7 g of the compound from example 1 were dissolved together with 22.8 g of a hydroxyalkyl acrylate copolymer having an OH number of 85 mg KOH/g (Joncryl 960, BASF) in 10 g of acetonitrile. 0.07 g of methanesulfonic acid was dissolved in 5 g of acetonitrile and added to the mixture. The solvent was distilled off and vacuum was applied at room temperature for 48 h until no OH band was visible any longer in the IR spectrum. The product is very highly viscous and hardly stirrable any more. This was followed by washing 3 times with 50 ml of demineralized water and decanting-off, and drying under reduced pressure.

(34) Yield: 20 g of yellow, very viscous gel, no longer stirrable

(35) Two-Component Coating Compositions

(36) 10 g of the product described in example 3 were blended with 2.0 g of the diamine 4,9-dioxadodecane-1,12-diamine (DODA) as hardener, and the resulting reactive two-component coating composition, immediately after mixing, was applied in a layer thickness of 3 m to a printed 36 m-thick polyester film. Then, in a calender, a second 36 m-thick polyester film was laminated onto the coating layer under a pressure of 6.5 bar at a calendering speed of 5 m/min. The resulting laminate was cut into strips of width 15 mm and the peel strength of these strips was ascertained at room temperature (23 C.) after 4 h [N/15 mm]. This was done using a tensile testing machine, and the peel strength test was conducted at a peel angle of 90 (T-peel test). The results are shown in table 1.

(37) Analogously, 10 g of the product described in example 5 were blended with 3.15 g of DODA as hardener, and processed and examined.

(38) TABLE-US-00001 TABLE 1 Results of the peel test measurements Peel strength after 4 h [N/15 mm] 10 g of example 3 3.2 blended with 2 g of DODA 10 g of example 5 1.6 blended with 3.15 g of DODA

(39) A peel strength of greater than 1 N after 4 h is sufficient for applications of the coating composition, for example for production of flexible packings, and builds up within a sufficiently short time to be industrially utilizable.