Low chloride compositions of olefinically functionalised siloxane oligomers based on alkoxysilanes

Patent metadata

Field	Value
Publication number	US-9828392-B2
Application number	US-201214360120-A
Country	US
Kind code	B2
Filing date	Nov 19, 2012
Priority date	Nov 22, 2011
Publication date	Nov 28, 2017
Grant date	Nov 28, 2017

Abstract

The invention relates to a composition comprising olefinically functionalized siloxane oligomers derived from olefinically functionalized alkoxysilanes and optionally alkoxysilanes functionalized with saturated hydrocarbons, and also, optionally, a tetraalkoxysilane, which have not more than one olefinic radical on the silicon atom, and whose chloride content is reduced, and also to processes for preparing them and to the use thereof.

First claim

The invention claimed is:

1. A process for preparing a composition comprising olefinically functionalized siloxane oligomers, the process comprising reacting:
(i) an olefinically functionalized alkoxysilane of formula II,
A-Si(R 2 ) x (OR 1 ) 3-x   (II)

wherein A in formula II represents an olefinic radical and is a linear, branched or cyclic alkenyl- or cycloalkenyl-alkylene-functional group having in each case 2 to 16 C atoms;
R 2 represents a linear, branched or cyclic alkyl radical having 1 to 15 C atoms and x is 0 or 1; and
each R 1 , independently, represents a linear, branched or cyclic alkyl radical having 1 to 4 C atoms,
(ii) in the presence of at least one of a hydrolysis and a condensation catalyst that comprises hydrogen chloride;
(iii) and in the presence of water and alcohol as solvent, to produce the olefinically functionalized siloxane oligomers; and
(iv) removing the hydrolysis alcohol and the solvent present; and
(v) at least once during said (iv) removing or subsequently, further adding alcohol and carrying out removal;
(vi) wherein the total chloride content of the composition is less than or equal to 100 mg/kg; and
(vii) the weight-average molecular weight (Mw) is 410 g/mol to 580 g/mol,
wherein
a) in (iii) the reaction takes place in the presence of water and an alcohol in an amount of 0.001 to 5.0 volume units of alcohol per volume unit of alkoxysilane, and/or
b) in (v), at least once during step (iv) or subsequently, additional alcohol is added and removal is carried out 1 to 6 times.

2. The process of claim 1 , further comprising reacting the olefinically functionalized alkoxysilane of formula II the presence of at least one of a hydrolysis and a condensation catalyst with
(i.1) at least one alkoxysilane of formula III,
B—Si(R 4 ) y (OR 3 ) 3-y   (III),

wherein B represents a saturated hydrocarbon radical and is a linear, branched or cyclic alkyl radical having 1 to 16 C atoms;
each R 3 , independently, represents a linear, branched or cyclic alkyl radical having 1 to 4 C atoms;
R 4 represents a linear, branched or cyclic alkyl radical having 1 to 15 C atoms; and
y is 0 or 1.

3. The process of claim 1 , further comprising reacting the olefinically functionalized alkoxysilane of general formula II in the presence of at least one of a hydrolysis and a condensation catalyst with
(i.2) at least one tetraalkoxysilane of formula IV,
Si(OR 3 ) 4   (IV),

wherein:
each R 3 , independently, represents a linear, branched or cyclic alkyl radical having 1 to 4 C atoms.

4. The process of claim 1 , wherein
the alcohol is methanol, ethanol or any combination thereof.

5. The process of claim 1 , wherein
the composition is obtained following (v) as a liquid-phase product.

6. The process of claim 2 , wherein:
in the olefinically functionalized alkoxysilane of general formula II:
A-Si(R 2 ) x (OR 1 ) 3-x   (II)

A is selected from the group consisting of vinyl, allyl, butenyl, pentenyl, hexenyl, ethylhexenyl, heptenyl, octenyl, cyclohexenyl-C1 to C8-alkylene, and a 3′-cyclohexenyl-2-ethylene group;
x is 0 or 1; and
R 1 are each independently a methyl, ethyl or propyl group; and
in the alkoxysilane of formula III:
B—Si(R 4 ) y (OR 3 ) 3-y   (III)

the unsubstituted hydrocarbon radical B is selected from the group consisting of methyl, ethyl, propyl, butyl, isobutyl, n-butyl, tert-butyl, pentyl, n-pentyl, isopentyl, neopentyl, hexyl, isohexyl, neohexyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 2-methylpentyl, 3-methylpentyl, octyl, n-octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, C 13 H 27 , C 14 H 29 , C 15 H 31 and a hexadecyl group; and
R 3 is a methyl, ethyl or propyl group; and
y is 0 or 1.

7. The process of claim 2 , wherein
in the olefinically functionalized alkoxysilane of the general formula II
x is 0 and/or in the alkoxysilane of the formula III functionalized with a saturated hydrocarbon radical y is 0.

8. The process of claim 2 , wherein
water is added of greater than or equal to 0.60 to 1.48 mol of water per mole of silicon atoms in the alkoxysilanes of at least one of formula II and formula III.

9. The process of claim 2 , further comprising
at least partial hydrolysis and condensation of the alkoxysilane of at least one of formula II and formula Ill in the presence of an acidic catalyst; and, optionally
removing the alcohol.

10. The process of claim 9 , wherein
the acidic catalyst is hydrogen chloride.

11. The process of claim 1 , wherein
in (iii) the reaction takes place in the presence of water and an alcohol in an amount of 0.0.5 to 2.5 volume units of alcohol per volume unit of alkoxysilane.

12. The process of claim 2 , wherein the olefinically functionalized alkoxysilane of formula II is selected from the group consisting of vinyltriethoxysilane, allyltriethoxysilane, butenyltriethoxysilane, pentenyltriethoxysilane, hexenyltriethoxysilane, ethylhexenyltriethoxysilane, heptenyltriethoxysilane, octenyltriethoxysilane, cyclohexenyl-C1 to C8-alkylenetriethoxysilane, cyclohexenyl-2-ethylenetriethoxysilane, 3′-cyclohexenyl-2-ethylenetriethoxysilane, cyclohexadienyl-C1 to C8-alkylenetriethoxysilane, cyclohexadienyl-2-ethylenetriethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, butenyltrimethoxysilane, pentenyltrimethoxysilane, hexenyltrimethoxysilane, ethylhexenyltrimethoxysilane, heptenyltrimethoxysilane, octenyltrimethoxysilane, cyclohexenyl-C1 to C8-alkylenetrimethoxy silane, cyclohexenyl-2-ethylenetrimethoxysilane, 3′-cyclohexenyl-2-ethylenetrimethoxysilane, cyclohexadienyl-C1 to C8-alkylenetrimethoxysilane and cyclohexadienyl-2-ethylenetrimethoxysilane; and
in each case independently
the alkoxysilane of formula III is selected from the group consisting of methyltriethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, isopropyltriethoxysilane, butyltriethoxysilane, n-butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, n-hexyltriethoxysilane, isohexyltriethoxysilane, heptyltriethoxysilane, octyltriethoxysilane, n-octyltriethoxysilane, isooctyltriethoxysilane, undecyltriethoxysilane, decyltriethoxysilane, nonadecyltriethoxysilane, dodecyltriethoxysilane, C 13 H 27 -triethoxysilane, C 14 H 29 -triethoxysilane or C 15 H 31 -triethoxysilane, hexadecyltriethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, n-hexyltrimethoxysilane, isohexyltrimethoxysilane, heptyltrimethoxysilane, octyltrimethoxysilane, n-octyltrimethoxysilane, isooctyltrimethoxysilane, undecyltrimethoxysilane, decyltrimethoxysilane, nonadecyltrimethoxysilane, dodecyltrimethoxysilane, C 13 H 27 -trimethoxysilane, C 14 H 29 -trimethoxysilane or C 15 H 31 -trimethoxysilane and hexadecyltrimethoxysilane.

13. The process of claim 1 , wherein
the hydrolysis alcohol and the solvent are removed by distillation.

14. The process of claim 3 , further comprising
at least partial hydrolysis and condensation of the alkoxysilane of at least one of formula II and formula IV in the presence of an acidic catalyst; and, optionally
removing the alcohol.

15. The process of claim 12 , wherein
in (iii) the reaction takes place in the presence of water and an alcohol in an amount of 0.1 to 2.0 volume units of alcohol per volume unit of alkoxysilane.

16. The process of claim 1 , further comprising reacting the olefinically functionalized alkoxysilane of formula II the presence of at least one of a hydrolysis and a condensation catalyst with at least

Assignees

• Evonik Degussa Gmbh

Inventors

• Standke Burkhard
• Weissenbach Kerstin
• Monkiewicz Jaroslaw
• Roth Sven
• Nowitzki Bernd

Classifications

• C07F7/0838

  Compounds with one or more Si-O-Si sequences (compounds with a ring containing only alternating Si and O atoms, i.e. cyclosilanes C07F7/21) · CPC title

• C08G77/20

  containing silicon bound to unsaturated aliphatic groups · CPC title

• C07F7/0874 Primary

  Reactions involving a bond of the Si-O-Si linkage · CPC title

• C09J183/04

  Polysiloxanes · CPC title

• C08L83/04

  Polysiloxanes · CPC title