Composition Comprising Silylated Polymer

Abstract

The present invention relates to a liquid composition comprising at least one silylated polymer and at least one tin-free polyhedral oligomeric titanium silsesquioxane in liquid form.

Claims

1. A liquid composition comprising at least one silylated polymer and at least one tin-free polyhedral oligomeric titanium silsesquioxane in liquid form, which is a compound of formula (I): ##STR00002## wherein, Z is —OH or —O—C.sub.1-10alkyl, preferably —O—C.sub.1-4 alkyl, more preferably —O-methyl or —O— ethyl; wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6 and R.sub.7 are independently selected from substituted or unsubstituted C.sub.8-20 alkyl, substituted or unsubstituted C.sub.8-20 cycloalkyl, substituted or unsubstituted C.sub.8-20 alkenyl, or substituted or unsubstituted C.sub.8-20 aryl; Or wherein R.sub.1 to R.sub.7 are each substituted or unsubstituted C.sub.8 alkyl or C.sub.9 alkyl or C.sub.10 alkyl or C.sub.11 alkyl or C.sub.12 alkyl or C.sub.13 alkyl or C.sub.14 alkyl or C.sub.15 alkyl or C.sub.16 alkyl or C.sub.17 alkyl or C.sub.18 alkyl or C.sub.19 alkyl or C.sub.20 alkyl or combinations thereof; Or wherein at least one first radical of R.sub.1 to R.sub.7 is chosen from substituted or unsubstituted C.sub.8-20 alkyl, substituted or unsubstituted C.sub.8-20 cycloalkyl, substituted or unsubstituted C.sub.8-20 alkenyl, or substituted or unsubstituted C.sub.8-20 aryl, and wherein at least one second radical of R.sub.1 to R.sub.7, different from said at least one first radical, is selected from substituted or unsubstituted C.sub.1-7 alkyl, substituted or unsubstituted C.sub.1-7 cycloalkyl, substituted or unsubstituted C.sub.1-7 alkenyl, or substituted or unsubstituted C.sub.1-7 aryl, and wherein the remaining radicals of R.sub.1 to R.sub.7 are independently selected from substituted or unsubstituted C.sub.1-7 alkyl, substituted or unsubstituted C.sub.1-7 cycloalkyl, substituted or unsubstituted C.sub.1-7 alkenyl, or substituted or unsubstituted C.sub.1-7 aryl, substituted or unsubstituted C.sub.8-20 alkyl, substituted or unsubstituted C.sub.8-20 cycloalkyl, substituted or unsubstituted C.sub.8-20 alkenyl, or substituted or unsubstituted C.sub.8-29 Aryl.

2. The composition according to claim 1, wherein at least 2 radicals from R.sub.1 to R.sub.7 are selected from substituted or unsubstituted C.sub.8-20 alkyl, substituted or unsubstituted C.sub.8-20 cycloalkyl, substituted or unsubstituted C.sub.8-20 alkenyl, or substituted or unsubstituted C.sub.8-20 aryl, and wherein the remaining ones are independently selected from substituted or unsubstituted C.sub.1-7 alkyl, substituted or unsubstituted C.sub.1-7 cycloalkyl, substituted or unsubstituted C.sub.1-7 alkenyl, or substituted or unsubstituted C.sub.1-7 aryl.

3. The composition according to claim 1, wherein at least 2 radicals from R.sub.1 to R.sub.7 are each substituted or unsubstituted C.sub.8 alkyl or C.sub.9 alkyl or C.sub.10 alkyl or Cu alkyl or C.sub.12 alkyl or C.sub.13 alkyl or C.sub.14 alkyl or C.sub.15 alkyl or C.sub.16 alkyl or C.sub.17 alkyl or C.sub.18 alkyl or C.sub.19 alkyl or C.sub.20 alkyl, and wherein the remaining ones are independently selected from substituted or unsubstituted C.sub.1-7 alkyl, substituted or unsubstituted C.sub.1-7 cycloalkyl, substituted or unsubstituted C.sub.1-7 alkenyl, or substituted or unsubstituted C.sub.1-7 aryl.

4. The composition according to claim 1, wherein at least 20% in mole of R.sub.1 to R.sub.7 are individually selected from the list consisting of substituted or unsubstituted C.sub.8-20 alkyl, preferably C.sub.8-18 alkyl C.sub.8-20 cycloalkyl, substituted or unsubstituted C.sub.8-20 alkenyl, or substituted or unsubstituted C.sub.8-20 aryl, when Z is OH or O—C.sub.1-4 alkyl.

5. The composition according to claim 1, wherein said silylated polymer comprises a silane moiety with at least one radical, when Z is respectively, O-methyl or O-ethyl.

6. The composition according to claim 1, wherein said at least one tin-free polyhedral oligomeric titanium silsesquioxane is in liquid form, in the absence of solvent.

7. The composition according to claim 1, wherein silylated polymer is selected from the group consisting of silylated polyether, silylated silicone and silylated polyurethanes.

8. The composition according to claim 7, wherein said silylated polymer comprises alkoxysilyl or silanol moieties.

9. The composition according to claim 7, wherein said silylated polymer is obtained by reaction of at least one isocyanate with at least one isocyanate reactive compound and with at least one alkoxysilane compound.

10. The composition according to claim 1, wherein the amount of said tin-free polyhedral oligomeric titanium silsesquioxane is ranging from 0.001 wt % to 5 wt % based on total weight of the composition.

11. The composition according to claim 1, wherein said composition contains less than 0.001 wt % of tin.

12. A moisture curable silylated polymer composition obtainable by applying the following steps: providing at least one silylated polymer as defined according to any one claim 1; and mixing said at least one silylated polymer with at least one tin-free polyhedral oligomeric titanium silsesquioxane in liquid form as defined according to claim 1.

13. A process for manufacturing a moisture curable silylated polymer composition, which process comprises the following steps: adding said at least one silylated polymer composition to at least one tin-free polyhedral oligomeric titanium silsesquioxane in liquid form as defined according to claim 1; and curing said silylated polymer composition.

14. (canceled)

Description

EXAMPLE 1

[0126] A solution comprising 99.52 wt % of silylated polymer 1 and 0.48 wt % of POSS compound corresponding to formula I, wherein Z is O-methyl and R.sub.1 to R.sub.7 are each i-octyl is provided. The solution is flushed with nitrogen and mixed at 2500 rpm for 5 min. The final content of POSS compound in the silylated polymer is 0.48 wt % and Ti loading is 0.018 wt %. Castings of 500 μm are made and cure characteristics are studied with BK dryer recorder.

[0127] Start open time: 44 min and end of scratch time: 58 min.

EXAMPLE 2

[0128] A solution comprising 99.5 wt % of silylated polymer 1 and 0.5 wt % of POSS compound corresponding to formula I, wherein Z is O-methyl and R.sub.1 to R.sub.7 are randomly selected between i-octyl and i-butyl. The solution is flushed with nitrogen and mixed at 2500 rpm for 5 min. The final content of POSS compound in the silylated polymer is 0.5 wt % (75% in mole of i-octyl and 35% in mole of i-butyl) and Ti loading 0.021 wt %. Castings of 500 μm are made and cure characteristics are studied with BK dryer recorder.

[0129] Start open time: 60 min and end of scratch time: 80 min.

Comparative Example 1

[0130] A solution comprising 99.54 wt % of silylated polymer 1 and 0.46 wt % of DBTDL compound is provided. The solution is flushed with nitrogen and mixed at 2500 rpm for 5 min. The final content of DBTDL compound in the silylated polymer is 0.46 wt % and Sn loading is 0.086 wt %. Castings of 500 μm are made and cure characteristics are studied with BK dryer recorder.

[0131] Start open time: 60 min and end of scratch time: 71 min.

EXAMPLE 3

[0132] A solution comprising 99.5 wt % of silylated polymer 2 and 0.5 wt % of POSS compound corresponding to formula I, wherein Z is O-methyl and R.sub.1 to R.sub.7 are each i-octyl is provided. The solution is flushed with nitrogen and mixed at 2500 rpm for 5 min. The final content of POSS compound in the silylated polymer is 0.5 wt % and Ti loading is 0.018 wt %. Castings of 500 μm are made and cure characteristics are studied with BK dryer recorder.

[0133] Start open time: 4.5 hours.

EXAMPLE 4

[0134] A solution comprising 99.5 wt % of silylated polymer 2 and 0.5 wt % of POSS compound, which is obtained by mixing 75% in mole of a first POSS compound corresponding to formula I, wherein Z is O-methyl and R.sub.1 to R.sub.7 are each i-octyl with 25% in mole of a second POSS compound corresponding to formula I, wherein Z is O-methyl and R.sub.1 to R.sub.7 are each i-butyl. The solution is flushed with nitrogen and mixed at 2500 rpm for 5 min. The final content of POSS compound in the silylated polymer is 0.5 wt % and Ti loading is 0.019 wt %. Castings of 500 μm are made and cure characteristics are studied with BK dryer recorder.

[0135] Start open time: 7.75 hours.

Comparative Example 2

[0136] A solution comprising 99.5 wt % of silylated polymer 2 and 0.5 wt % of DBTDL compound is provided. The solution is flushed with nitrogen and mixed at 2500 rpm for 5 min. The final content of DBTDL compound in the silylated polymer is 0.5 wt % and Sn loading is 0.086 wt %. Castings of 500 μm are made and cure characteristics are studied with BK dryer recorder.

[0137] Start open time: >24 hours.

[0138] Although the invention describes the use of tin-free polyhedral oligomeric titanium silsesquioxane for catalysis of silylated polymers, said tin-free polyhedral oligomeric titanium silsesquioxane can be used to catalyze every compounds carrying at least one Si(OR.sup.50).sub.pR.sup.51.sub.3-p groups, including low molecular weight materials, which could be silanes; for example, wherein R.sub.50 can be selected from H; optionally substituted C.sub.1-24alkyl; optionally substituted C.sub.3-24cycloalkyl; optionally substituted C.sub.6-24aryl; optionally substituted heteroaryl; and wherein R.sub.51 can be selected from H; optionally substituted C.sub.1-24alkyl; optionally substituted C.sub.3 24cycloalkyl; optionally substituted C.sub.6-24aryl; optionally substituted heteroaryl; wherein, p can be 0 or 1. Non-limiting examples of suitable substituents for the alkyl, cycloalkyl, aryl or heteroaryl groups can be selected from, for example, halogen atoms and COOH groups.

[0139] As used herein, the singular forms “a”, “an”, and “the” include both singular and plural referents unless the context clearly dictates otherwise.

[0140] The terms “comprising”, “comprises” and “comprised of” as used herein are synonymous with “including”, “includes” or “containing”, “contains”, and are inclusive or open-ended and do not exclude additional, non-recited members, elements or method steps. It will be appreciated that the terms “comprising”, “comprises” and “comprised of” as used herein comprise the terms “consisting of”, “consists” and “consists of”.

[0141] The recitation of numerical ranges by endpoints includes all numbers and fractions subsumed within the respective ranges, as well as the recited endpoints.

[0142] All references cited in the present specification are hereby incorporated by reference in their entirety. In particular, the teachings of all references herein specifically referred to are incorporated by reference.

[0143] Unless otherwise defined, all terms used in disclosing the invention, including technical and scientific terms, have the meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. By means of further guidance, term definitions are included to better appreciate the teaching of the present invention.

[0144] Whenever the term “substituted” is used in the present invention, it is meant to indicate that one or more hydrogens on the atom indicated in the expression using “substituted” is replaced with a selection from the indicated group, provided that the indicated atom's normal valency is not exceeded.

[0145] Where groups may be optionally substituted, such groups may be substituted once or more, and preferably once, twice or thrice. Substituents may be selected from but are not limited to, for example, the group comprising alcohol, carboxylic acid, ester, amino, amido, ketone, ether and halide functional groups; such as for example halogen, hydroxyl, oxo, amido, carboxy, amino, haloC.sub.1-6 alkoxy, and haloC.sub.1-6 alkyl.

[0146] As used herein the terms such as “substituted or unsubstituted C.sub.1-20 alkyl”, “substituted or unsubstituted C.sub.8-20 cycloalkyl”, “substituted or unsubstituted C.sub.8-20 alkenyl”, or “substituted or unsubstituted C.sub.8-20 aryl” are respectively synonymous to C.sub.1-20 alkyl“, C.sub.8-20 cycloalkyl”, C.sub.8-20 alkenyl“, C.sub.8-20 aryl, each being optionally substituted with . . . ”.

[0147] As used herein the terms such as “alkyl, alkenyl, aryl, or cycloalkyl, each being optionally substituted with . . . ” or “alkyl, alkenyl, aryl, or cycloalkyl, optionally substituted with . . . ” encompasses “alkyl optionally substituted with . . . ”, “alkenyl optionally substituted with . . . ”, “aryl optionally substituted with . . . ” and “cycloalkyl optionally substituted with . . . ”.

[0148] For instance, the term “C.sub.8-20 alkyl”, as a group or part of a group, refers to a hydrocarbyl radical of formula C.sub.nH.sub.2n+1, wherein n is a number ranging from 8 to 20. Preferably, the alkyl group comprises from 8 to 20 carbon atoms, for example 8 to 15 carbon atoms, for example 8 to 10 carbon atoms, for example 8 to 9 carbon atoms. Alkyl groups may be linear or branched and may be substituted as indicated herein. When a subscript is used herein following a carbon atom, the subscript refers to the number of carbon atoms that the named group may contain. Thus, for example, C.sub.8-20 alkyl means an alkyl of 8 to 20 carbon atoms. Thus, for example, C8-10 alkyl means an alkyl of 8 to 10 carbon atoms.

[0149] The term “C.sub.8-20 cycloalkyl” as a group or part of a group, refers to a cyclic alkyl group, i.e. a monovalent, saturated, or unsaturated hydrocarbyl group having 1 or 2 cyclic structure. Cycloalkyl includes all saturated hydrocarbon groups containing 1 to 2 rings, including monocyclic or bicyclic groups. Cycloalkyl groups may comprise 8 or more carbon atoms in the ring and generally, according to this invention comprise from 8 to 20, preferably 8 to 15 carbon atoms.

[0150] The term “C.sub.8-20 alkenyl” as a group or part of a group, refers to an unsaturated hydrocarbyl group, which may be linear, or branched, comprising one or more carbon-carbon double bonds. Preferred alkenyl groups thus comprise between 8 and 20 carbon atoms, for example between 8 and 15 carbon atoms, for example between 8 and 10 carbon atoms.

[0151] The term “aryl”, as a group or part of a group, refers to a polyunsaturated, aromatic hydrocarbyl group having a single ring (i.e. phenyl) or multiple aromatic rings fused together (e.g. naphthyl) or linked covalently, typically containing 8 to 20 carbon atoms; preferably 8 to 15 carbon atoms, wherein at least one ring is aromatic. The aromatic ring may optionally include one to two additional rings fused thereto. Aryl is also intended to include the partially hydrogenated derivatives of the carbocyclic systems enumerated herein.