VINYL-ETHERS AND METHODS OF THEIR PRODUCTION

Abstract

The present invention relates to methods for producing at least one vinyl ether compound of formula (1) and to a vinyl ether compound of formula (1) preferably obtainable by the methods according to the invention. Furthermore, the present invention relates to a polymer obtainable by polymerizing the vinyl ether compound of formula (1) according to the invention, to an adhesive comprising the at least one polymer according to the invention and to the use of at least one vinyl ether compound of formula (I) according to the invention or at least one polymer according to the invention for the production of UV adhesives, cationic curings or 1-component or 2-component systems.

Claims

1. A method for producing at least one vinyl ether compound of formula (I) ##STR00021## wherein n is an integer of 0 to 5; R.sub.1, R.sub.3 and R.sub.4 are independently selected from —OH, —O—CH═CH.sub.2, —H or a substituted or unsubstituted C.sub.1-C.sub.10 alkyl or C.sub.2-C.sub.10 alkenyl group; and R.sub.2 and R.sub.5 are independently selected from —H or a substituted or unsubstituted C.sub.1-C.sub.10 alkyl or C.sub.2-C.sub.10 alkenyl group; with the proviso that at least two of R.sub.1, R.sub.3 and R.sub.4 are —OH or —O—CH═CH.sub.2, and wherein at least one of R.sub.1, R.sub.3 and R.sub.4 is —O—CH═CH.sub.2; wherein the method comprises or consists of the following steps: reacting a compound of formula (II) ##STR00022## wherein R.sub.6 is —C(═O)R.sub.12, or an unsubstituted C.sub.1-C.sub.10 alkyl or C.sub.2-C.sub.10 alkenyl group; and R.sub.12 is an unsubstituted C.sub.1-C.sub.10 alkyl group, with a compound of formula (III) ##STR00023## wherein n is an integer of 0 to 5; R.sub.7, R.sub.9 and R.sub.11 are independently selected from —OH, —H or a substituted or unsubstituted C.sub.1-C.sub.10 alkyl or C.sub.2-C.sub.10 alkenyl group; and R.sub.8 and R.sub.10 are independently selected from —H or a substituted or unsubstituted C.sub.1-C.sub.10 alkyl or C.sub.2-C.sub.10 alkenyl group; with the proviso that at least two of R.sub.7, R.sub.9 and R.sub.11 are —OH; in the presence of a catalyst and optionally a bidentate ligand and/or a base.

2. The method of claim 1, wherein in formula (I) n is 1; and/or R.sub.1 is —OH or —O—CH═CH.sub.2; and/or R.sub.2 is —CH.sub.3; and/or R.sub.3 is —H; and/or R.sub.4 is —OH or —O—CH═CH.sub.2; and/or R.sub.5 is —H; wherein at least one of R.sub.1 and R.sub.4 is —O—CH═CH.sub.2; and/or wherein R.sub.6 in the compound of formula (II) is an unsubstituted C.sub.2 alkyl group; and/or wherein in formula (III) n is 1; and/or R.sub.7 is —OH; and/or R.sub.8 is —CH.sub.3; and/or R.sub.9 is —H; and/or R.sub.10 is —H; and/or R.sub.11 is —OH.

3. The method of claim 1, wherein the reaction temperature is between 20 to 90° C.

4. The method of claim 1, wherein (i) the catalyst is selected from Pd catalysts; and/or (ii) the bidentate ligand is selected from phenanthrolines and bipyridines, preferable 2,2′-bipyridine; and/or (iii) the base is a tertiary amine.

5. The method of claim 1, wherein the method is carried out (i) in the presence of at least one solvent; or (ii) in the absence of any additional solvent; and/or (ii) under oxygen or air.

6. The method of claim 1, wherein the compound of formula (II) is added in molar excess over the compound of formula (III).

7. The method of claim 1, wherein the vinyl ether compound of formula (I) is a mixture of divinyl ether and mono vinyl ether compounds based on the total weight of the mixture.

8. A method for producing at least one vinyl ether compound of formula (I) ##STR00024## wherein n is an integer of 0 to 5; R.sub.1, R.sub.3 and R.sub.4 are independently selected from —OH, —O—CH═CH.sub.2, —H or a substituted or unsubstituted C.sub.1-C.sub.10 alkyl or C.sub.2-C.sub.10 alkenyl group; and R.sub.2 and R.sub.5 are independently selected from —H or a substituted or unsubstituted C.sub.1-C.sub.10 alkyl or C.sub.2-C.sub.10 alkenyl group; with the proviso that at least two of R.sub.1, R.sub.3 and R.sub.4 are —OH or —O—CH═CH.sub.2, and wherein at least one of R.sub.1, R.sub.3 and R.sub.4 is —O—CH═CH.sub.2; wherein the method comprises or consists of the following steps: reacting a compound of formula (III) ##STR00025## wherein n is an integer of 0 to 5, preferably 1, 2 or 3; R.sub.7, R.sub.9 and R.sub.11 are independently selected from —OH, —H or a substituted or unsubstituted C.sub.1-C.sub.10 alkyl or C.sub.2-C.sub.10 alkenyl group; and R.sub.8 and R.sub.10 are independently selected from —H or a substituted or unsubstituted C.sub.1-C.sub.10 alkyl or C.sub.2-C.sub.10 alkenyl group; with the proviso that at least two of R.sub.7, R.sub.9 and R.sub.11 are —OH; with (i) acetylene in the presence of a catalyst and under pressure, wherein preferably the catalyst is selected from the group of transition metal acetylides, metal carbonyles, metal carbonyl hydrides, (alkaline (earth)) metal alkoxides or (alkaline (earth)) metal hydroxides or oxides; and/or wherein preferably the vinylization can be carried out in liquid phase or gas phase; or (ii) calcium carbide, water and a base, wherein the reaction is preferably carried out in a solvent.

9. The method of claim 8, wherein in formula (I) n is 1; and/or R.sub.1 is —OH or —O—CH═CH.sub.2; and/or R.sub.2 is —CH.sub.3; and/or R.sub.3 is —H; and/or R.sub.4 is —OH or —O—CH═CH.sub.2; and/or R.sub.5 is —H; wherein at least one of R.sub.1 and R.sub.4 is —O—CH═CH.sub.2; and/or wherein in formula (III) n is 1; and/or R.sub.7 is —OH; and/or Ra is —CH.sub.3; and/or R.sub.9 is —H; and/or R.sub.10 is —H; and/or R.sub.11 is —OH.

10. The method of claim 1, wherein the compound of formula (III) is bio-based.

11. A vinyl ether compound of formula (I) ##STR00026## n is an integer of 0 to 5; R.sub.1, R.sub.3 and R.sub.4 are independently selected from —OH, —O—CH═CH.sub.2, —H or a substituted or unsubstituted C.sub.1-C.sub.10 alkyl or C.sub.2-C.sub.10 alkenyl group; and R.sub.2 and R.sub.5 are independently selected from —H or a substituted or unsubstituted C.sub.1-C.sub.10 alkyl or C.sub.2-C.sub.10 alkenyl group; with the proviso that at least two of R.sub.1, R.sub.3 and R.sub.4 are —OH or —O—CH═CH.sub.2, and wherein at least one of R.sub.1, R.sub.3 and R.sub.4 is —O—CH═CH.sub.2; obtained by a method according to claim 1.

12. The compound of claim 11, wherein the vinyl ether compound is of formula (IV) ##STR00027## wherein n is 0, 1, 2, 3, 4 or 5; R.sub.1 and R.sub.4 are —OH or —O—CH═CH.sub.2, with the proviso that at least one of R.sub.1 and R.sub.4 is —O—CH═CH.sub.2; or the vinyl ether compound is any one of the compounds of formulae (V) to (VII) ##STR00028## or a mixture thereof; wherein n is 0, 1, 2, 3, 4 or 5.

13. A polymer obtainable by polymerizing a compound of claim 11 optionally together with at least one comonomer.

14. An adhesive comprising at least one polymer according to claim 13.

Description

EXAMPLES

Example 1

[0088] ##STR00017##

Vinylation at Room Temperature

[0089] A round bottom flask (1000 mL) was charged with (0.5 mol %; 638.4 mg) Pd(OOCCF.sub.3) and (0.5 mol %; 300 mg) 2,2′-bipyridine. Subsequently, ethyl vinyl ether (15 eq.; 415 mL) and (1.6 mL; 3 mol %) NEt.sub.3 were added. The mixture was allowed to stir for 10 min. Thereafter (40 g; 0.384 mol) 1,4-pentanediol was added. The flask was sealed and stirred at room temperature during the course of the reaction (48 h). The catalyst was filtered off by using a pleated filter whereupon the excess of ethyl vinyl ether was distilled off from the resulting filtrate on a rotary evaporator (40° C., 700 mbar.fwdarw.300 mbar). The crude mixture was then distilled under vacuum in order to obtain the first fraction at 45° C. and 0.5 mbar (exclusively P-2-divin) and the second fraction at 60° C. and 0.1 mbar (mixture of P-1-prim. and P-1-sek.)

Conversion 1,4-Pentanediol: 96%

[0090] Yield P-2-divin: 57%
Yield P-1-prim.+P-1-sek.: 35%+1.4%

Vinylation at 80° C.

[0091] A round bottom flask (1000 mL) equipped with a condenser was charged with (0.5 mol %; 638.4 mg) Pd(OOCCF.sub.3) and (0.5 mol %; 300 mg) 2,2′-bipyridine. Subsequently, ethyl vinyl ether (15 eq.; 415 mL) and (1.6 mL; 3 mol %) NEt.sub.3 were added. The mixture was allowed to stir for 10 min at room temperature. Thereafter (40 g; 0.384 mol) 1,4-pentanediol was added. The mixture was stirred at 80° C. during the course of the reaction (16 h). The catalyst was filtered off by using a pleated filter whereupon the excess of ethyl vinyl ether was distilled off from the resulting filtrate on a rotary evaporator (40° C., 700 mbar.fwdarw.300 mbar). The crude mixture was then distilled under vacuum in order to obtain the first fraction at 45° C. and 0.5 mbar (exclusively P-2-divin) and the second fraction at 60° C. and 0.1 mbar (mixture of P-1-prim. and P-1-sek.)

Conversion 1,4-Pentanediol: 98%

[0092] Yield P-2-divin: 72%
Yield P-1-prim.+P-1-sek.: 15%+3%

Isolation of Pure Mono Vinyl Ether P-1-Prim.

[0093] By using column chromatography on silica gel with diethyl ether/n-pentane (1:4) as eluent, the single compound P-1-prim. was isolated from the mixture (P-1-prim./P-1-sek.) and collected as a yellowish liquid. After applying vacuum distillation as previously described the pure mono vinyl ether P-1-prim. was then obtained as a colorless and odorless liquid. P-1-sek. underwent self-cyclization during the separation process of column chromatography.

##STR00018##

NMR-Data (in D-Chloroform)

[0094] .sup.1H-NMR (300 MHz, CDCl.sub.3): 6.44 (dd, 1H, .sup.3J=6.74 Hz, .sup.3J=14.33 Hz); 6.29 (dd, 1H, .sup.3J=6.60 Hz, .sup.3J=14.12 Hz); 4.24 (dd, 1H, .sup.3J=14.12 Hz, .sup.2J=1.53 Hz); 4.14 (dd, 1H, .sup.3J=14.33 Hz, .sup.2J=1.95 Hz); 3.96 (dt, 2H, .sup.3J=6.64 Hz); 3.93-3.86 (m, 1H); 3.70-3.63 (m, 2H); 1.80-1.57 (m, 4H); 1.20 (d, 3H, .sup.3J=6.20 Hz).

[0095] .sup.13C-NMR (75 MHz, CDCl.sub.3): 151.9; 150.9; 88.1; 86.4; 75.4; 67.8; 32.9; 25.1; 19.9 (see FIG. 1).

GC-MS

[0096] (m/z): 127; 112; 99; 84; 69; 57; 43; 41; 31.

IR-Data (ATR-Method)

[0097] ATR-IR (cm.sup.−1): v(C—H, sp.sup.2) 3117; v(C—H, sp.sup.3) 2973; v(C—H, sp.sup.3) 2932; v(C—H, sp.sup.3) 2874; (C═C) 1633; (C═C) 1612; (═C—O—C) 1193.

##STR00019##

NMR-Data (in D-Toluene)

[0098] .sup.1H-NMR (300 MHz, d-toluene): 6.37 (dd, 1H, .sup.3J=6.84 Hz, .sup.3J=14.42 Hz); 4.13 (dd, 1H, .sup.3J=14.42 Hz, .sup.2J=1.71 Hz); 3.92 (dd, 1H, .sup.3J=6.84 Hz, .sup.2J=1.71 Hz); 3.53 (sextett, 1H, .sup.3J=6.21 Hz); 3.43 (td, 2H, .sup.4J=1.44 Hz, .sup.3J=6.32 Hz); 2.18 (br, 1H); 1.68-1.45 (m, 2H); 1.35-1.26 (m, 2H); 1.00 (d, 3H, .sup.3J=6.20 Hz).

[0099] .sup.13C-NMR (75 MHz, d-toluene): 152.3; 86.2; 68.0; 67.4; 36.0; 25.8; 23.7.

GC-MS

[0100] (m/z): 130, 115, 102, 87, 69, 58, 45, 43, 31.

IR-Data (ATR-Method)

[0101] ATR-IR (cm.sup.−1): v(0-H) 3362; v(C—H, sp.sup.2) 3118; v(C—H, sp.sup.3) 2964; v(C—H, sp.sup.3) 2928; v(C—H, sp.sup.3) 2873; (C═C) 1636; (C═C) 1613; (═C—O—C) 1197.

##STR00020##

NMR-Data (in D-Toluene)

[0102] .sup.1H-NMR (300 MHz, d-toluene): 6.37 (dd, 1H, .sup.3J=6.84 Hz, .sup.3J=14.34 Hz); 6.15 (dd, 0.04H, .sup.3J=6.60 Hz, .sup.3J=14.14 Hz); 4.29 (dd, 0.04H, .sup.3J=14.14 Hz, .sup.2J=1.33 Hz); 4.13 (dd, 1H, .sup.3J=14.34 Hz, .sup.2J=1.78 Hz); 3.94 (dd, 0.04H, .sup.3J=6.60 Hz, .sup.2J=1.33 Hz); 3.92 (dd, 1H, .sup.3J=6.83 Hz, .sup.2J=1.78 Hz); 3.60-3.48 (m, 1H, 0.04H); 3.43 (td, 2H, 0.08H .sup.4J=1.40 Hz, .sup.3J=6.34 Hz); 2.20 (d, 1H, .sup.3J=4.64 Hz); 2.17 (br, 0.04H); 1.67-1.45 (m, 2H, 0.08H); 1.35-1.23 (m, 2H, 0.08H); 1.02 (d, 0.12H, .sup.3J=6.19 Hz); 1.00 (d, 3H, .sup.3J=6.20 Hz).

[0103] .sup.13C-NMR (75 MHz, d-toluene): 152.3; 151.3; 88.0; 86.2; 75.6; 68.0; 67.4; 62.3; 36.0; 33.1; 29.0; 25.8; 23.7; 19.9.