Mixtures, particularly low in volatile organic compounds (VOC), of olefinically functionalised siloxane oligomers based O alkoxy silanes

Patent metadata

Field	Value
Publication number	US-9296766-B2
Application number	US-201214360114-A
Country	US
Kind code	B2
Filing date	Nov 19, 2012
Priority date	Nov 22, 2011
Publication date	Mar 29, 2016
Grant date	Mar 29, 2016

Abstract

The invention relates to a composition containing olefinically functionalized siloxane oligomers which are derived from olefinically functionalized alkoxy silanes and optionally alkoxy silanes functionalized with saturated hydrocarbons and optionally a tetraalkoxysilane, at most comprising an olefinic group on the silicon atom having a reduced chloride content and the VOC content being lower with respect to the hydrolysable alkoxy-groups. The invention also relates to methods for the production thereof and to the use thereof.

First claim

The invention claimed is:

1. A composition comprising an olefinically functionalized siloxane oligomer having not more than one olefinic radical on a silicon atom,
wherein:
the olefinically functionalized siloxane oligomer comprises Si-O-crosslinked structural elements that form a catenary, cyclic, crosslinked or optionally three-dimensionally crosslinked structure corresponding to a formula I,
(R 1 O)[(R 1 O) z (R 2 ) x Si(A)O( 3-x-z)/2 ] a [Si(Y) 2 O] c [Si(B)(R 4 ) y (OR 3 ) w O( 3-y-w)/2 ] b R 3   (I),

the structural elements are derived from one or more alkoxysilanes,
A corresponds to 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,
B corresponds to a saturated hydrocarbon radical and is a linear, branched or cyclic alkyl radical having 1 to 16 C atoms,
Y corresponds to OR 3 or, in a crosslinked and optionally three-dimensionally crosslinked structure, independently of one another, to OR 3 or O 1/2 ,
R 1 independently at each occurrence corresponds to a linear, branched or cyclic alkyl radical having 1 to 4 C atoms or H,
R 2 corresponds independently at each occurrence to a linear, branched or cyclic alkyl radical having 1 to 15 C atoms,
R 3 independently at each occurrence corresponds to a linear, branched or cyclic alkyl radical having 1 to 4 C atoms or to H,
R 4 corresponds independently at each occurrence to a linear, branched or cyclic alkyl radical having 1 to 15 C atoms,
a, b, c, x and y independently correspond to integers with 1≦a, 0≦b, 0≦c, and (a+b+c)≧2,
z and x is 0 or 1,
y and w is 0 or 1,
a total chloride content in the composition is less than or equal to 250 mg/kg and
the structural elements [R 1 O) z(R 2 ) x Si(A)O( 3-x-z)/2 ] a , [Si(B)(R 4 ) y (OR 3 ) w O( 3-y-w)/2 ] b and [Si(Y) 2 O] c in the formula I are present together, in relation to all silicon atoms of the formula I, at greater than or equal to 10% as a T structure,
wherein the olefinically functionalized siloxane oligomer is present at greater than or equal to 30% (area %, GPC) in relation to the overall composition with a molecular weight (Mw) of 500 to 700 g/mol in the composition.

2. The composition of claim 1 , wherein the structural elements are derived from at least one selected from the group consisting of (i), (ii) and (iii),
(i) an olefinically functionalized alkoxysilane having a formula II,
A-Si(R 2 ) x (OR 1 ) z′   (II)

where A corresponds to 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 independently at each occurrence is a linear, branched or cyclic alkyl radical having 1 to 15 C atoms, x is 0 or 1, z′ is 2 or 3 and R 1 independently corresponds to a methyl, ethyl or propyl group,
(ii) an alkoxysilane of a formula III functionalized with a saturated hydrocarbon radical,
B—Si(R 4 ) y (OR 3 ) w′   (III)

where B corresponds to an unsubstituted hydrocarbon radical and is a linear, branched or cyclic alkyl radical having 1 to 16 C atoms, R 4 independently at each occurrence is a linear, branched or cyclic alkyl radical having 1 to 15 C atoms, y is 0 or 1, w′ is 2 or 3 and R 3 independently corresponds to a methyl, ethyl or propyl group, and
(iii) a tetraalkoxysilane of a formula IV
Si(OR 3 ) 4   (IV)

where R 3 independently at each occurrence is a methyl, ethyl or propyl group.

3. The composition of claim 1 , wherein one or more of conditions (i), (ii), (iii), (iv) and (v) is satisfied:
(i) the structural element [(R 1 O) z (R 2 ) x Si(A)O( 3-x-z)/2 ] a in the formula I is present, in relation to all silicon atoms of the formula I, at greater than or equal to 5%, as a T structure,
(ii) the structural elements [(R 1 O) z (R 2 ) x Si(A)O( 3-x-z)/2 ] a and [Si(B)(R 4 ) y (OR 3 ) w O( 3-y-w)/2 ] b and [Si(Y) 2 O] c in the formula I are present together, in relation to all silicon atoms of the formula I, at greater than or equal to 50% as a D structure,
(iii) the structural element [(R 1 O) z (R 2 ) x Si(A)O( 3-x-z)/2 ] a is present in the formula I, in relation to all silicon atoms of the formula I, at less than or equal to 35% as an M structure,
(iv) the structural element [Si(B)(R 4 ) y (OR 3 ) w O (3-y-w)/2 ] b in the formula I is present, in relation to all silicon atoms of the formula I, at less than or equal to 25% as an M structure, and
(v) the structural element [Si(Y) 2 O] c in the formula I is present at greater than or equal to 20% as a D structure, or more than 40% of the structural elements [Si(Y) 2 O] c in the formula I are present as D structure.

4. The composition of claim 2 , wherein:
in the olefinically functionalized alkoxysilane of the formula II, x is 0 and,
optionally, in the alkoxysilane of the formula III functionalized with a saturated hydrocarbon radical, y is 0.

5. The composition of claim 2 , wherein:
in formulae I and/or II, the olefinic radical A is a non-hydrolyzable olefinic radical selected from the group consisting of vinyl, allyl butenyl, 3-butenyl, pentenyl, hexenyl, ethylhexenyl, heptenyl, octenyl, cyclohexenyl-C1 to C8-alkylene, cyclohexenyl-2-ethylene, 3′-cyclohexenyl-2-ethylene, cyclohexadienyl-C1 to C8-alkylene, and cyclohexadienyl-2-ethylene, and independently thereof
in formulae I and/or 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, heptyl, octyl, n-octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, C 13 H 27 , C 14 H 29 , C 15 H 31 and hexadecyl, and
independently at each occurrence R 1 is a methyl, ethyl or propyl group and R 3 independently is a methyl, ethyl or propyl group.

6. The composition of claim 2 , wherein:
in formulae I and/or II, the olefinic radical A is a vinyl group, and independently thereof
in formulae I and/or 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, heptyl, octyl, n-octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, C 13 H 27 , C 14 H 29 , C 15 H 31 and hexadecyl, and
independently at each occurrence R 1 is a methyl, ethyl or propyl group and R 3 independently is a methyl, ethyl or propyl group.

7. The composition of claim 1 , wherein the olefinically functionalized siloxane oligomer comprises at least two siloxanes selected from the group consisting of trisiloxane, tetrasiloxane, pentasiloxane, cyclotetrasiloxane, cyclopentasiloxane and cyclohexasiloxane, wherein the oligomer is present in an amount of at least 60% of the composition.

8. The composition of claim 1 , wherein a mass loss of 50 wt %, determined by TGA, occurs at a temperature above 240° C.

9. The composition of claim 1 , wherein a loss of mass by the composition as determined by TGA, using a platinum crucible, a lid with hole, at 10 K/min, at a temperature up to and including 150° C. is less than 5 wt %.

10. The composition of claim 1 , wherein a loss of mass by the composition as determined by TGA, using a platinum crucible, a lid with hole, at 10 K/min, at a temperature up to and including 200° C. is less than 20 wt %.

11. The composition of claim 1 , wherein an alcohol content after complete hydrolysis of the hydrolyzable alkoxy groups is less than or equal to 20 wt %.

12. The composition of claim 2 , wh

Assignees

• Standke Burkhard
• Weissenbach Kerstin
• Monkiewicz Jaroslaw
• Roth Sven
• Nowitzki Bernd
• Friedel Manuel
• Evonik Degussa Gmbh

Inventors

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

Classifications

• C08G77/045 Primary

  containing less than 25 silicon atoms · CPC title

• C09D183/04

  Polysiloxanes · CPC title

• C07F7/1804 Primary

  Compounds having Si-O-C linkages (Si-O-acyl linkages C07F7/1896) · CPC title

• C08G77/20

  containing silicon bound to unsaturated aliphatic groups · CPC title

• C09J183/04

  Polysiloxanes · CPC title