Composition of olefinically functionalised siloxane oligomers based on alkoxy silanes

Patent metadata

Field	Value
Publication number	US-9273186-B2
Application number	US-201214360127-A
Country	US
Kind code	B2
Filing date	Nov 19, 2012
Priority date	Nov 22, 2011
Publication date	Mar 1, 2016
Grant date	Mar 1, 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 tetra alkoxysilane, at most comprising an olefinic group on the silicon atom and which has a reduced chloride content and a weight average molecular mass (Mw) of more than 315 g/mol.

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 thereof, wherein
the olefinically functionalized siloxane oligomer has a Si—O-crosslinked structural element which forms catenary, cyclic, crosslinked or optionally three-dimensionally crosslinked structures, with a structure of formula I,
(R 1 O)[(R 1 O) 1-x (R 2 ) x Si(A)O] a [Si(Y) 2 O] c [Si(B)(R 4 ) y (OR 3 ) 1-y O] b R 3   (I),

the structural elements are derived from alkoxysilanes,
wherein A is an olefinic radical selected from a linear, branched or cyclic alkenyl- or cycloalkenyl-alkylene-functional group having in each case 2 to 16 C atoms, and
B is a saturated hydrocarbon radical selected from a linear, branched or cyclic alkyl radical having 1 to 16 C atoms,
Y is OR 3 or, in crosslinked and optionally three-dimensionally crosslinked structures, independently at each occurrence, OR 3 or O 1/2 , where
R 1 independently at each occurrence is a linear, branched or cyclic alkyl radical having 1 to 4 C atoms or H,
R 2 independently at each occurrence is a linear, branched or cyclic alkyl radical having 1 to 15 C atoms,
R 3 independently at each occurrence is a linear, branched or cyclic alkyl radical having 1 to 4 C atoms or H, and
R 4 independently at each occurrence is a linear, branched or cyclic alkyl radical having 1 to 15 C atoms,
a, b, c, x and y are each independently an integer, wherein 1≦a, 0≦b, 0≦c, x independently at each occurrence is 0 or 1, y independently at each occurrence is 0 or 1, and (a+b+c)≧2,
the structural elements [(R 1 O) 1-x (R 2 ) x Si(A)O] a , [Si(B)(R 4 ) y (OR 3 ) 1-y O] b and [Si(Y) 2 O] c , in relation to all silicon atoms of formula I, are present at less than or equal to 80% and greater than or equal to 30% as M structure,
a weight-average molecular weight (Mw) is greater than or equal to 315 g/mol, and
an amount of residues of the acid catalyst during preparation is less than or equal to 250 mg/kg of composition,
wherein
a weight-average molecular weight (Mw) is greater than 315 g/mol
a number-average molecular weight (Mn) is greater than 300 g/mol, and a polydispersity (D), as a ratio of Mw/Mn, is from 1.05 to 1.25.

2. The composition according to claim 1 ,
wherein
the siloxane oligomer has derived structural elements from at least one alkoxysilane selected from:
(i) olefinically functionalized alkoxysilanes of formula II,
A-Si(R2) x (OR1)3 −x   (II)

wherein A is an olefinic radical selected from a linear, branched or cyclic alkenyl- or cycloalkenyl-alkylene-functional group having in each case 2 to 16 C atoms, where R 2 independently at each occurrence is a linear, branched or cyclic alkyl radical having 1 to 15 C atoms and x is 0 or 1, and R 1 independently at each occurrence is a methyl, ethyl or propyl group, and optionally
(ii) alkoxysilane of formula III, functionalized with a saturated hydrocarbon radical,
B—Si(R 4 ) y (OR 3 ) 3-y   (III)

wherein B is an unsubstituted hydrocarbon radical selected from a linear, branched or cyclic alkyl radical having 1 to 16 C atoms,
where R 4 independently at each occurrence is a linear, branched or cyclic alkyl radical having 1 to 15 C atoms and y is 0 or 1, and R 3 independently at each occurrence is a methyl, ethyl or propyl group, and optionally
(iii) a tetraalkoxysilane of formula IV which is Si(OR 3 ) 4 , wherein R 3 independently at each occurrence is as defined above.

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

4. The composition according to claim 3 ,
wherein
the amount of residues of the acid catalyst in the preparation, in terms of chlorine, chloride or total chloride, is less than or equal to 250 mg/kg of the composition.

5. The composition according to claim 1 ,
wherein,
selected in each case independently of one another
(i) the structural element [(R 1 O) 1-x (R 2 ) x Si(A)O] a in formula I is present, in relation to all silicon atoms of formula I, at 0.0% to 8.0% as T structure,
(ii) the structural elements [(R 1 O) 1-x (R 2 ) x Si(A)O] a and [Si(B)(R 4 ) y (OR 3 ) 1-y O] b and [Si(Y) 2 O] c in formula I are present together, in relation to all silicon atoms of formula I, at less than or equal to 75% to 40% as D structure,
(iii) the structural element [(R 1 O) 1-x (R 2 ) x Si(A)O] a in formula I is present, in relation to all silicon atoms of formula I, at 25% to 55% as M structure,
(iv) the structural element [Si(B)(R 4 ) y (OR 3 ) 1-y O] b in formula I, is present, in relation to all silicon atoms of formula I, at less than or equal to 40% as M structure,
(v) the structural element [Si(Y) 2 O] c in formula I is present at greater than 20% as D structure, and
(vi) the structural element [Si(Y) 2 O] e in formula I is present at 0.0% to 1% as T structure.

6. The composition according to claim 1 ,
wherein
a weight-average molecular weight (Mw) is from greater than or equal to 350 g/mol to 800 g/mol.

7. The composition according to claim 6 ,
wherein
the weight-average molecular weight (Mw) is from greater than or equal to 350 g/mol to 750 g/mol.

8. The composition according to claim 2 ,
wherein
in formulae I, II, or both, the olefinic radical A, independently at each occurrence, is selected from a 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 or cyclohexadienyl-2-ethylene group, and independently thereof
in formulae I, III, or both, the unsubstituted hydrocarbon radical B, independently at each occurrence, is selected from a methyl, ethyl, propyl, isobutyl, octyl or hexadecyl group, 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.

9. The composition according to claim 2 ,
wherein
in formulae I, II, or both, the olefinic radical A is a vinyl group, and independently thereof
in formulae I, III, or both, the unsubstituted hydrocarbon radical B is selected from a methyl, ethyl, propyl, butyl, isobutyl, n-butyl, tert-butyl, pentyl, n-pentyl, isopentyl, neopentyl, hexyl, isohexyl, neohexyl, heptyl, 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 hexadecyl group, 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.

10. The composition according to claim 1 ,
wherein the olefinically functionalized siloxane oligomer is present at greater than or equal to 90% (area %) in relation to the overall composition, with a molecular weight of less than or equal to 1000 g/mol in the composition.

11. The composition according to claim 1 ,
wherein
c in formula I is 0.

12. The composition according to claim 1 ,
wherein
a weight-average molecular weight (Mw) is greater than or equal to 420 g/mol, a number-average molecular weight (Mn) is greater than or equal to 400 g/mol, and a polydispersity (D), as a ratio of Mw/Mn, is from 1.05 to 1.25.

13. The composition according to claim 1 ,
wherein
a weight-average molecular weight (Mw) is greater than 450 g/mol to 590 g/mol, a number-average molecular weight (Mn) is greater than 410 g/mol to 510 g/mol, and a polydispersity (D

Assignees

• Evonik Degussa Gmbh

Inventors

• Standke Burkhard
• Mihailescu Ioana-Elena
• Monkiewicz Jaroslaw
• Roth Sven
• Ioannidis Aristidis
• Weissenbach Kerstin

Classifications

• C08G77/70

  Siloxanes defined by use of the MDTQ nomenclature · CPC title

• C08L83/04

  Polysiloxanes · CPC title

• C08G77/20 Primary

  containing silicon bound to unsaturated aliphatic groups · CPC title

• C09D183/04

  Polysiloxanes · CPC title

• C09J183/04

  Polysiloxanes · CPC title