Tertiary Hydroxyl Functional Alkoxysilanes and Methods for Preparing Thereof

Abstract

Disclosed is a tertiary hydroxyl functional alkoxysilane of the general formula (I)

##STR00001##

wherein R.sup.1 is selected from the group consisting of hydrogen and a linear or branched, substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms; R.sup.2 and R.sup.3 are same or different and are, independent from one another, selected from a linear or branched, substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms; R.sup.4 is selected from a linear or branched, substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms; R.sup.5 is selected from a linear or branched, substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms; R.sup.6 and R.sup.7 are same or different and are, independent from one another, selected from a linear or branched, substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms; and n is 1, 2 or 3, a method for preparing thereof, and the use of the tertiary hydroxyl functional alkoxysilane of the general formula (I).

Claims

1-10 cancelled

11. A method for preparing the tertiary hydroxyl functional alkoxysilane according to claim 1, of the general formula (I) ##STR00009## wherein R.sup.1 is selected from the group consisting of hydrogen and a linear or branched, substituted or unsubstituted, hydrocarbon residue having 1 to 20 carbon atoms; R.sup.2 and R.sup.3 are same or different and are, independent from one another, selected from a linear or branched, substituted or unsubstituted, hydrocarbon residue having 1 to 20 carbon atoms; R.sup.4 is selected from a linear or branched, substituted or unsubstituted, hydrocarbon residue having 1 to 20 carbon atoms; R.sup.5 is selected from a linear or branched, substituted or unsubstituted, hydrocarbon residue having 1 to 20 carbon atoms; R.sup.6 and R.sup.7 are same or different and are, independent from one another, selected from a linear or branched, substituted or unsubstituted, hydrocarbon residue having 1 to 20 carbon atoms; and n is 1, 2 or 3; comprising: providing at least one di-substituted lactone compound; providing at least one aminosilane having at least one primary amino group or secondary amino group; providing a Lewis acid catalyst; and reacting the at least one di-substituted lactone compound and the at least one aminosilane having at least one primary amino group or secondary amino group in the presence of the Lewis acid.

12. The method according to claim 11, wherein the di-substituted lactone compound has the general formula (II) ##STR00010## wherein R.sup.5 is selected from a linear or branched, substituted or unsubstituted, hydrocarbon residue having 1 to 20 carbon atoms; and R.sup.6 and R.sup.7 are same or different and are, independent from one another, selected from a linear or branched, substituted or unsubstituted, hydrocarbon residue having 1 to 20 carbon atoms.

13. The method according to claim 11, wherein the aminosilane is an am inoalkylenealkoxysilane having the general formula (III) ##STR00011## wherein R.sup.1 is selected from the group consisting of hydrogen and a linear or branched, substituted or unsubstituted, hydrocarbon residue having 1 to 20 carbon atoms; R.sup.2 and R.sup.3 are same or different and are, independent from one another, selected from a linear or branched, substituted or unsubstituted, hydrocarbon residue having 1 to 20 carbon atoms; and R.sup.4 is selected from a linear or branched, substituted or unsubstituted, hydrocarbon residue having 1 to 20 carbon atoms.

14-15. cancelled

16. A material selected from an adhesion promoter, a urethane coupling agent, an end-capping agent, a surface treatment agent, a water scavenger, a fiber treatment agent, a paint additive, and/or a monomer for a polymer preparation comprising the tertiary hydroxyl functional alkoxysilane of the general formula (I) prepared using the method of claim 11 according to claim 1.

17. An end-capping agent for a moisture curable composition comprising the tertiary hydroxyl functional alkoxysilane of the general formula (I) prepared using the method of claim 11 according to claim 1.

18. The method according to claim 11, wherein R.sup.1 is selected from hydrogen or a C.sub.1-C.sub.8 alkyl residue.

19. The method according to claim 11, wherein R.sup.2 and R.sup.3 are selected from a linear or branched, substituted or unsubstituted Ci-Cs alkyl residue and n is 2 or 3.

20. The method according to claim 11, wherein R.sup.2 and R.sup.3 are selected from a linear or branched, substituted or unsubstituted methyl, ethyl, or n-propyl residue.

21. The method according to claim 11, wherein R.sup.2 is a C.sub.1-C.sub.20 alkyl, one or more carbon atom(s) are substituted with at least one heteroatom selected from O or N, and the carbon atom in alpha position to Si is substituted with O or N.

22. The method according to claim 11, wherein R.sup.4 is selected from a linear or branched, substituted or unsubstituted C.sub.1-C.sub.8 alkylene residue.

23. The method according to claim 11, wherein R.sup.4 is selected from a linear or branched, substituted or unsubstituted methylene, ethylene, 1,3-propylene, 2-methyl-1,3-propylene, 1,4-butylene, 3-methyl-1,4-butylene, or 3,3-dimethyl-1,4-butylene residue.

24. The method according to claim 11, wherein R.sup.5 is a linear or branched, substituted or unsubstituted, alkylene residue having 1 to 20 carbon atoms.

25. The method according to claim 11, wherein R.sup.5 is selected from methylene, ethylene or 1,3-propylene, 2-methyl-1,3-propylene, 1,4-butylene, 3-methyl-1,4-butylene, or 3,3-dimethyl-1,4-butylene residue.

26. The method according to claim 11, wherein R.sup.6 and R.sup.7 are independent from one another selected from a linear or branched, substituted or unsubstituted C.sub.1-C.sub.20 alkyl, alkenyl, or alkynyl, or C.sub.6-C.sub.18 aryl residue.

27. The method according to claim 11, wherein R.sup.6 and R.sup.7 are independent from one another selected from a linear or branched, substituted or unsubstituted C.sub.1-C.sub.8 alkyl or alkenyl residue.

28. The method according to claim 11, wherein the catalyst is present in an amount of from 0.01 to 5 mol. % based on the moles of amine functionality of the aminoalkoxysilane.

29. The method according to claim 11, carried out in the presence of a Lewis-acidic organoaluminium compound.

30. The method according to claim 11, which is carried out in the presence of triethylaluminium.

31. The method according to claim 11, further comprising the step of heating the at least one di-substituted lactone compound and the at least one aminosilane having at least one primary amino group or secondary amino group and the Lewis acid to a temperature in the range of from −50 to 200° C. during the reaction.

Description

EXAMPLES

Examples 1 to 3

Preparation of Tertiary Hydroxyl Functional Methoxysilanes

[0054] In a dry round bottom flask under argon atmosphere 5 g (27.9 mmol) of (3-aminopropyl)trimethoxysilane (AMMO) was stirred at 50° C. 0.28 ml of 1M triethylaluminium solution in hexane was slowly added (0.279 mmol, 1 mol %). Afterwards 27.9 mmol of the di-substituted lactone listed in Table 1 was added and vigorously stirred for 3 hours. The following compounds were obtained as colorless liquids in 96-98% purity.

Example 1

[0055] ##STR00005##

.sup.1H NMR (400 MHz, Chloroform-d) δ 6.44 (s, 1H), 3.54 (s, 4H), 3.18 (q, J=7.0, Hz, 1H), 2.28 (t, J=7.5, Hz, 1H), 1.82-1.65 (m, 1H), 1.63-1.52 (m, 1 H), 1.45-1.38 (m, 1 H), 1.25 (s, 3H), 1.11 (s, 2H), 0.85 (t, J=1.3 Hz, 1H), 0.66-0.57 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) δ=174.13, 71.51, 50.46, 42.54, 41.93, 36.69, 31.81, 29.89, 26.47, 23.99, 22.63, 22.57, 14.00, 6.46; .sup.29Si NMR (79 MHz, CDCl.sub.3) δ=−42.27.

Example 2

[0056] ##STR00006##

.sup.1H NMR (400 MHz, Chloroform-d) δ 6.51 (s, 0H), 5.22 (qd, J=6.1, 1.7 Hz, 1H), 3.45 (s, 4H), 3.11 (q, J=7.0, Hz, 1H), 2.21 (dd, J=6.2, 3.8 Hz, 1H), 2.04-1.85 (m, 2H), 1.77-1.56 (m, 1H), 1.55-1.44 (m, 1 H), 1.39 (dt, J=11.2, 4.2 Hz, 1H), 1.05 (d, J=1.9 Hz, 1 H), 0.84 (td, J=7.5, 2.1 Hz, 1H), 0.53 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) δ=174.12, 131.54, 128.91, 71.30, 50.39, 42.36, 41.92, 36.76, 30.93, 26.25, 22.60, 21.81, 20.37, 14.22, 6.43; .sup.29Si NMR (79 MHz, CDCl.sub.3) δ=−42.28.

Example 3

[0057] ##STR00007##

.sup.1H NMR (400 MHz, Chloroform-d) δ 6.83 (s, 0H), 3.57 (s, 6H), 3.31-3.19 (m, 1H), 3.04−2.59 (m, 1 H), 1.71-1.59 (m, 3H), 0.70-0.61 (m, 1 H); .sup.13C NMR (101 MHz, CDCl.sub.3) δ=171.16, 107.83, 81.59, 50.61, 41.97, 40.80, 23.35, 22.41, 6.56; .sup.29Si NMR (79 MHz, CDCl.sub.3) δ=−42.48.

Comparative Examples 1 and 2

Preparation of Secondary Hydroxyl Functional Methoxysilanes

[0058] In a dry round bottom flask under argon atmosphere 5 g (27.9 mmol) of (3-aminopropyl)trimethoxysilane (AMMO) was stirred at 50° C. 0.28 ml of 1M triethylaluminium solution in hexane was slowly added (0.279 mmol, 1 mol %). Afterwards 27.9 mmol of the mono-substituted lactone listed in Table 1 was added and vigorously stirred for 3 hours.

[0059] A yellowish and viscous following product from Comparative Example 1 was obtained.

##STR00008##

.sup.1H NMR (400 MHz, Chloroform-d) δ6.55 (s, 0H), 3.51 (s, 5H), 3.19-3.12 (m, 1H), 2.32-2.26 (m, 1 H), 1.84-1.71 (m, 1 H), 1.65-1.49 (m, 2H), 1.37 (m, 2H), 0.86 (t, J=7.0 Hz, 1 H), 0.63-0.55 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) δ=173.95, 70.74, 50.46, 41.92, 39.78, 33.10, 32.81, 22.62, 18.86, 14.03, 6.45; .sup.29Si NMR (79 MHz, CDCl.sub.3) δ=−42.22.

[0060] The NMR of the product from Comparative Example 2 showed a highly crosslinked structure, which cannot be used further.

Comparative Example 3

Preparation of Primary Hydroxyl Functional Methoxysilane

[0061] In a dry round bottom flask under argon atmosphere 5 g (27.9 mmol) of (3-aminopropyl)trimethoxysilane (AMMO) was stirred at 50° C. 0.28 ml of 1M triethylaluminium solution in hexane was slowly added (0.279 mmol, 1 mol %). Afterwards 27.9 mmol of δ-valerolactone was added and vigorously stirred for 3 hours. A yellow highly viscous product was obtained. The NMR of the product of Comparative Example 3 showed a highly crosslinked structure, which cannot be used further.

Testing the Stability of Prepared Silanes

[0062] After the preparation of the hydroxyl functional silanes as described above, a round bottom flask with the sample under the nitrogen atmosphere was placed in the heating oven at 50° C. for 8 days. A small amount of sample for the NMR analysis was withdrawn from the flask immediately before putting it the oven and after 2, 5 and 8 days. The degree of crosslinking and consequently the purity was assessed based the integration of the .sup.29Si NMR spectra. The peak at around −42 ppm corresponded to the non-hydrolyzed trimethoxysilane, the peak at around −41 ppm corresponded to self-dealcoholized product and the peaks below the value of −44 ppm correspond to the mono-, di- or three-hydrolized (oligomerized or crosslinked) silane. It was determined that only the silanes with purity higher than 90% after 8 days at 50° C. suffice the standards for further applications.

TABLE-US-00001 TABLE 1 Purity comparison of the hydroxyl functional silanes Purity (%) Right after Lactone reaction 2 days 5 days 8 days Example 1 4-methyl decalactone 98 98 98 97 Example 2 4-hydroxyl-4-methyl- 96 95 94 92 7-cis-decene gamma lactone Example 3 4-methyl-4- 97 94 93 91 (trichloromethyl)- 2-oxetanone Comp. gamma-heptalactone 92 88 85 82 Example 1 Comp. gamma-valerolactone Completely crosslinked Example 2 Comp. delta-valerolactone Completely crosslinked Example 3