ALKENYL ETHER POLYOLS

Abstract

The invention relates to a method for producing radiation-curable alkenyl ether polyols, to radiation-curable alkenyl ether polyols produced using the method according to the invention, and to the use thereof for the synthesis of radiation-interlinkable oligomers or polymers by means of polyaddition reactions or polycondensation reactions, in particular for the synthesis of radiation-curable polyesters, polyethers, polyurethanes and polyureas, particularly preferably UV-curable polyurethanes. The invention also relates to radiation-curable polyurethane polymers that are obtained by reacting at least one alkenyl ether polyol according to the invention with a polyisocyanate.

Claims

1. A method for manufacturing an alkenyl ether polyol containing at least one alkenyl ether group and at least two hydroxyl groups (—OH), comprising: A) conversion of an alkenyl ether containing at least one alkenyl ether group and at least one functional group selected from —OH, —COOH, —SH, —NH.sub.2 and derivatives thereof, with (i) an epoxide or (ii) a cyclic carbonate or derivative thereof; or B) conversion of an alkenyl ether containing at least one alkenyl ether group and at least one functional group selected from (i) epoxide groups and (ii) cyclic carbonate groups or derivatives thereof, with an alcohol, thiol, a carboxylic acid, or an amine or derivative thereof.

2. The method as set forth in claim 1, wherein the alkenyl ether polyol is manufactured through conversion of an alkenyl ether containing at least one alkenyl ether group and at least one functional group selected from —OH, —COOH, —SH, —NH.sub.2 and derivatives thereof with (i) an epoxide or (ii) a cyclic carbonate or derivative thereof, wherein: the alkenyl ether polyol is an alkenyl ether polyol of formula (I) ##STR00036## where R.sub.1 is selected from a divalent organic residue; a divalent linear or branched, substituted or unsubstituted, alkyl with 1 to 20 carbon atoms; or a linear or branched, substituted or unsubstituted, heteroalkyl with 1 to 20 carbon atoms and at least one oxygen or nitrogen atom, R.sub.2 is selected from an organic residue; an organic residue with at least one —OH group and/or 1 to 1000 carbon atoms; an optionally divalent or polyvalent, linear or branched, substituted or unsubstituted, alkyl with 1 to 20 carbon atoms; or a linear or branched, substituted or unsubstituted, heteroalkyl with 1 to 20 carbon atoms and at least one oxygen or nitrogen atom, X is O, S, C(═O)O, OC(═O)O, C(═O)OC(═O)O, N R.sub.x, NR.sub.xC(═O)O, NR.sub.xC(═O)NR.sub.x, or OC(═O)NR.sub.x, each R and R′ is selected independently from H, C.sub.1-20 alkyl, and C.sub.2-20 alkenyl; or one of R and R′ is H and the other is C.sub.1-4 alkyl; or both R and R′ are H, each A, B, and C is independently selected from among CR″R′″, R″ and R′″ are selected independently from H, a functional group, an organic residue, C.sub.1-20 alkyl; or R″ and R′″ together or with the carbon atom to which they are bonded are an organic residue; or two of R″ and R′″ that are bonded to neighboring carbon atoms form a bond together in order to form a double bond between the neighboring carbon atoms, is a single or double bond, and if it is a double bond, the carbon atom that is bonded to R.sub.2 bears only one substituent R″ or R′″, m is an integer from 1 to 10, preferably 1, n, p, and o are each 0 or an integer from 1 to 10, and R.sub.x is H, an organic residue, nr ##STR00037## and if X is not NR.sub.x where ##STR00038## R.sub.2 has at least one substituent that is selected from among —OH and ##STR00039##

3. The method as set forth in claim 2 wherein n+p+o=1 or 2.

4. The method as set forth in claim 2, wherein the alkenyl ether, which contains at least one alkenyl ether group and at least one functional group selected from ##STR00040## among —OH, —COOH, —SH, NH.sub.2 and derivatives thereof, is an alkenyl ether of formula (II) where R.sub.1 is selected from a divalent organic residue; a divalent, linear or branched, substituted or unsubstituted, alkyl with 1 to 20 carbon atoms; or a linear or branched, substituted or unsubstituted, heteroalkyl with 1 to 20 carbon atoms and at least one oxygen or nitrogen atom, X.sub.1 is a functional group selected from among OH, —COOH, —SH, —NHR.sub.y and derivatives thereof, R.sub.y is H or an organic residue, each R and R′ is selected independently from among H, C.sub.1-20 alkyl, and C.sub.2-20 alkenyl; or one of R and R′ is H and the other is C.sub.1-4 alkyl; or both R and R′ are H, and m is an integer from 1 to 10.

5. The method as set forth in claim 4, wherein in the alkenyl ether of formula (II), m is 1, X.sub.1 is —OH or —NH.sub.2, R.sub.1 is selected from a divalent, linear or branched C.sub.1-10 alkyl residue, ethyl, propyl, butyl, pentyl, or hexyl, and one of R and R′ is H and the other is H or —CH.sub.3.

6. The method as set forth in claim 1, wherein the epoxide is an epoxide of formula (III) ##STR00041## where R.sub.2 is selected from an organic residue; an organic residue with at least one —OH group; an optionally divalent or polyvalent, linear or branched, substituted or unsubstituted, alkyl with 1 to 20 carbon atoms; or a linear or branched, substituted or unsubstituted, heteroalkyl with 1 to 20 carbon atoms and at least one oxygen or nitrogen atom, and q is an integer from 1 to 10.

7. The method as set forth in claim 6, wherein: q is 1 or 2, and if q is 2, R.sub.2 is —CH.sub.2—O—C.sub.1-10-alkylenyl-—O—CH.sub.2—; and if q is 1, R.sub.2 is —CH.sub.2—O—C.sub.1-10-alkyl.

8. The method as set forth in claim 1, wherein the cyclic carbonate is an ethylene carbonate of formula (IV) ##STR00042## where R.sub.2 is selected from an organic residue; an organic residue with at least one —OH group; an optionally divalent or polyvalent, linear or branched, substituted or unsubstituted, alkyl with 1 to 20 carbon atoms; a linear or branched, substituted or unsubstituted, heteroalkyl with 1 to 20 carbon atoms and at least one oxygen or nitrogen atom; or a C1-10 hydroxyalkyl, a single or double bond, d is 0 or 1, and r is an integer from 1 to 10.

9. The method as set forth in claim 4, wherein: (i) X.sub.1 is —NH.sub.2 or a derivative thereof, and q or r is 1; or (ii) X.sub.1 is —OH or a derivative thereof, and q or r is 2.

10. The method as set forth in claim 1, wherein the alkenyl ether is manufactured through conversion of an alkenyl ether containing at least one alkenyl ether group and at least one functional group selected from among (i) epoxide groups and (ii) cyclic carbonate groups or derivatives thereof with an alcohol, thiol, a carboxylic acid, or an amine or derivative thereof, wherein the alkenyl ether polyol is an alkenyl ether polyol of formula (V) ##STR00043## where R.sub.1 is selected from a divalent organic residue; a divalent linear or branched, substituted or unsubstituted, alkyl with 1 to 20 carbon atoms; or a linear or branched, substituted or unsubstituted, heteroalkyl with 1 to 20 carbon atoms and at least one oxygen or nitrogen atom, R.sub.3 is selected from an organic residue; an organic residue with 1 to 1000 carbon atoms; an optionally divalent or polyvalent, linear or branched, substituted or unsubstituted, alkyl with 1 to 20 carbon atoms; a linear or branched, substituted or unsubstituted, heteroalkyl with 1 to 20 carbon atoms and at least one oxygen or nitrogen atom; a (poly)alkylene glycol of the formula —O—[CHR.sub.aCH.sub.2O].sub.b—R.sub.b, where b is 1 to 100, R.sub.a is H or a C.sub.1-4 alkyl residue, R.sub.b is H; or ##STR00044## X is O, S, OC(═O), OC(═O)O, OC(═O)OC(═O), NR.sub.z, NR.sub.zC(═O)O, NR.sub.zC(═O)NR.sub.z, or OC(═O)NR.sub.z, each R and R′ is selected independently from H, C.sub.1-20 alkyl, C.sub.2-20 alkenyl; or one of R and R′ is H and the other is C.sub.1-4 alkyl; or both R and R′ are H, each A and B is independently selected from among CR″R′″, R″ and R′″ are selected independently from H, a functional group, an organic residue, H and C.sub.1-20 alkyl; or R″ and R′″ together or with the carbon atom to which they are bonded are an organic residue; or two of R″ and R′″ that are bonded to neighboring carbon atoms form a bond together in order to form a double bond between the neighboring carbon atoms, m is an integer from 1 to 10, s and t are each 0 or an integer from 1 to 10, where s+t=1 or 2, and R.sub.z is H, an organic residue ##STR00045## and if X is not NR.sub.z where ##STR00046## than R.sub.3 has at least one substituent that is selected from among —OH and ##STR00047##

11. The method as set forth in claim 10, wherein the alkenyl ether, which contains at least one alkenyl ether group and at least one functional group selected from among (i) epoxide groups and (ii) cyclic carbonate groups or derivatives thereof, is an alkenyl ether of formula (VI) or (VII) ##STR00048## where Ri is selected from a divalent organic residue; a divalent linear or branched, substituted or unsubstituted alkyl with 1 to 20 carbon atoms; or a linear or branched, substituted or unsubstituted, heteroalkyl with 1 to 20 carbon atoms and at least one oxygen or nitrogen atom, each R and R′ is selected independently from among H, C.sub.1-20 alkyl, and C.sub.2-20 alkenyl; or one of R and R′ is H and the other is C.sub.1-4 alkyl; or both R and R′ are H, d is 0 or 1, and m is an integer from 1 to 10.

12. The method as set forth in claim 11, wherein in the alkenyl ethers of formula (VI) or (VII), R.sub.1 is —C.sub.1-10-alkylenyl-O—CH.sub.2—.

13. The method as set forth in claim 11, wherein the alkenyl ether is converted with an alcohol, with the alcohol being a diol or polyol or a corresponding alcoholate.

14. The method as set forth in claim 11, wherein the alkenyl ether is converted with a polyalkylene glycol of the formula HO—[CHR.sub.aCH.sub.2O].sub.b—H, where R.sub.a is H or a C.sub.1-4 alkyl residue and b is 1 to 100.

15. An alkenyl ether polyol of formula (I) or (V) ##STR00049## where R.sub.1 is selected from a divalent organic residue; an at least divalent linear or branched, substituted or unsubstituted, alkyl with 1 to 20 carbon atoms; or a linear or branched, substituted or unsubstituted, heteroalkyl with 1 to 20 carbon atoms and at least one oxygen or nitrogen atom, R.sub.2 is selected from an organic residue; an organic residue with at least one —OH group and/or 1 to 1000 carbon atoms; an optionally divalent or polyvalent, linear or branched, substituted or unsubstituted, alkyl with 1 to 20 carbon atoms; or a linear or branched, substituted or unsubstituted, heteroalkyl with 1 to 20 carbon atoms and at least one oxygen or nitrogen atom, R.sub.3 is selected from an organic residue; an organic residue with 1 to 1000 carbon atoms; an optionally divalent or polyvalent, linear or branched, substituted or unsubstituted, alkyl with 1 to 20 carbon atoms; a linear or branched, substituted or unsubstituted, heteroalkyl with 1 to 20 carbon atoms and at least one oxygen or nitrogen atom; a (poly)alkylene glycol of the formula —O—[CHR.sub.aCH.sub.2O].sub.b—R.sub.b, where b is 1 to 100, R.sub.a is H or a C.sub.1-4 alkyl residue, and R.sub.b is OH or ##STR00050## in formula (I), X is O, S, C(═O)O, OC(═O)O, C(═O)OC(═O)O, NR.sub.x, NR.sub.xC(═O)O, NR.sub.xC(═O)NR.sub.x, or OC(═O)NR.sub.x, in formula (V), X is O, S, OC(═O), OC(═O)O, OC(═O)OC(═O), NR.sub.z, NR.sub.zC(═O)O, NR.sub.zC(═O)NR.sub.z, or OC(═O)NR.sub.z, each R and R′ is selected independently from among H, C.sub.1-20 alkyl, and C.sub.2-20 alkenyl; or one of R and R′ is H and the other is C.sub.1-4 alkyl; or both R and R′ are H, each A, B, and C is independently selected from among CR″R′″, R″ and R′″ are selected independently from among H, a functional group, an organic residue, and C.sub.1-20 alkyl; or R″ and R′″ together or with the carbon atom to which they are bonded are an organic residue; or two of R″ and R′″ that are bonded to neighboring carbon atoms form a bond together in order to form a double bond between the neighboring carbon atoms, is a single or double bond, and if it is a double bond, the C that is bonded to R.sub.2 bears only one substituent R″ or R′″, m is an integer from 1 to 10, n, p and o are each 0 or an integer from 1 to 10, where n+p+o=1 or 2, s and t are each 0 or an integer from 1 to 10, where s+t=1 or 2, R.sub.x is H, an organic residue, or ##STR00051## and if X is not NR.sub.x where ##STR00052## R.sub.2 has at least one substituent that is selected from among —OH and ##STR00053## R.sub.z is H, an organic residue, or ##STR00054## and if X is not NR.sub.z where ##STR00055## than R.sub.3 has at least one substituent that is selected from among —OH and ##STR00056##

16. A radiation-crosslinkable oligomers or polymers that is the reaction product of a mixture comprising at least one alkenyl ether polyol as set forth in claim 15.

17. UV- and EB-curable polyesters, polyethers, polyurethanes, and polyureas that are the reaction product of a mixture comprising at least one alkenyl ether polyol as set forth in claim 15.

18. A UV-curable polyurethane polymer that is the reaction product of a mixture comprising at least one alkenyl ether polyol as set forth in claim 15 and a polyisocyanate.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0157] FIG. 1 schematically illustrates one scheme for synthesizing vinyl ether-functionalized polyurethanes (VEPUs).

[0158] FIG. 2A schematically illustrates a setup to simultaneously measure the viscoelastic characteristics and the absorption of near-infrared (NIR) spectra after UV initiation of a composition.

[0159] FIG. 2B shows a sc-VEPU film applied to a glass surface and cured to produce a colorless and highly transparent film.

[0160] FIG. 2C shows rheometric plots for the synthesized polyurethanes i-PU, t-VEPU, sc-VEPU, and hsc-VEPU.

[0161] FIG. 3 shows the curing of side chain-functionalized polyurethane (sc-VEPU) over the development of the storage moduli and relative vinyl ether contents by means of in-situ NIR measurement at different temperatures (25° C., 40° C., and 60° C.).

[0162] FIG. 4 shows the NIR spectra of the sc-VEPU (example 7) with UV-initiated curing at 60° C.

[0163] FIG. 5 shows the IR spectrum for i-PU synthesis (inactive alkyl-terminated polyurethane).

[0164] FIG. 6 shows the IR spectrum of the t-VEPU synthesis (vinyl ether-terminated polyurethane).

[0165] FIG. 7 shows the IR spectrum of the sc-VEPU synthesis (side chain vinyl ether-functionalized polyurethane).

[0166] FIG. 8 shows the IR spectrum of the hsc-VEPU synthesis (hydrated side chain vinyl ether-functionalized polyurethane).