Curable organosiloxane oligomer compositions

Patent metadata

Field	Value
Publication number	US-2016319081-A1
Application number	US-201415108827-A
Country	US
Kind code	A1
Filing date	Dec 22, 2014
Priority date	Dec 31, 2013
Publication date	Nov 3, 2016
Grant date	—

Abstract

A curable composition including (a) at least one organosiloxane compound, fluorinated organosiloxane compound, or combination thereof having reactive silane functionality including at least two hydroxysilyl moieties; (b) at least one organosiloxane oligomer, fluorinated organosiloxane oligomer, or combination thereof having reactive silane functionality including at least two hydrosilyl moieties; and (c) a catalyst composition including (1) at least one base selected from amidines, guanidines, phosphazenes, proazaphosphatranes, and combinations thereof, and (2) at least one Lewis acid. At least one of the components (a) and (b) has an average reactive silane functionality of at least three, and the composition is substantially free of organic solvent(s). An alkoxysilane compound may be optionally included in the curable composition. A process for coating the composition to prepare articles having the cross-linked composition on at least a portion of at least one major substrate surface is also disclosed.

First claim

1 . A composition comprising the following components:
(a) at least one organosiloxane compound, fluorinated organosiloxane compound, or a combination thereof, comprising reactive silane functionality comprising at least two hydroxysilyl moieties; (b) at least one organosiloxane oligomer, fluorinated organosiloxane oligomer, or a combination thereof, comprising reactive silane functionality comprising at least two hydrosilyl moieties; and (c) a catalyst composition comprising (1) at least one base selected from amidines, guanidines, phosphazenes, proazaphosphatranes, and combinations thereof, and (2) at least one Lewis acid; wherein at least one of said components (a) and (b) has an average reactive silane functionality of at least three, and further wherein the composition is substantially free of an organic solvent.

2 . The composition of claim 1 , wherein said components (a) and (b) each comprise an organosiloxane oligomer having a weight average molecular weight no greater than 5,000 Da, optionally wherein each organosiloxane oligomer is a dimethylsiloxand oligomer.

3 . (canceled)

4 . The composition of claim 1 , wherein said component (a) is hydroxyl-endblocked.

5 . The composition of claim 1 , wherein said component (a) is represented by:
(HO) p —Si(R′) 3-p -[G-Si(R′) 2 ] t —O—[(R′) 2 SiO] q —[Si(R′) 2 -G] t -Si(R′) 3-p —(OH) p
wherein each G is independently a divalent linking group; each R′ is independently selected from alkyl, fluoroalkyl, aryl, fluoroaryl, cycloalkyl, fluorocycloalkyl, heteroalkyl, heterofluoroalkyl, heteroaryl, heterofluoroaryl, heterocycloalkyl, heterofluorocycloalkyl; each p is independently an integer of 1, 2, or 3; q is an integer of 0 to 150; and each t is independently an integer of 0 or 1.

6 . (canceled)

7 . (canceled)

8 . The composition of claim 1 , wherein said component (a) comprises a mixture of (1) at least one polyorganosiloxane, fluorinated polyorganosiloxane, or combination thereof having a weight average molecular weight in the range of 10,000 to 1,000,000 and (2) at least one organosiloxane oligomer, fluorinated organosiloxane oligomer, or combination thereof having a weight average molecular weight in the range of about 150 to about 5,000 Da.

9 . (canceled)

10 . The composition of claim 1 , wherein said component (b) is represented by the following general formula:
R′ 2 R″SiO(R′ 2 SiO) r (HR′SiO) s SiR″R′ 2
wherein each R′ is independently selected from H, alkyl, alkenyl, fluoroalkyl, aryl, fluoroaryl, cycloalkyl, fluorocycloalkyl, heteroalkyl, heterofluoroalkyl, heteroaryl, heterofluoroaryl, heterocycloalkyl, heterofluorocycloalkyl; each R″ is independently H or R; r is an integer of 0 to 150, inclusive; and s is an integer of 2 to 150, inclusive.

11 - 13 . (canceled)

14 . The composition of claim 1 , wherein the base of component (c) is selected from:
(1) amidine compounds that are represented by the following general formula:

(2) guanidine compounds that are represented by the following general formula:

(3) phosphazene compounds that are represented by the following general formula:

(4) proazaphosphatrane compounds that are represented by the following general formula:

and combinations thereof;
wherein R1, R2, R3, R4, R5, R6, and R7 are each independently selected from hydrogen, monovalent organic groups, monovalent heteroorganic groups, and combinations thereof.

15 . The composition of claim 14 , wherein the base is selected to include at least two amidine compounds, guanidine compounds, phosphazene compounds, or combinations thereof, and further wherein any two or more of R1, R2, R3, R4, R5, R6, and R7 of said at least two amidine, guanidine, and phosphazene compounds are bonded together to form at least one ring structure.

16 - 19 . (canceled)

20 . The composition of claim 1 , wherein said Lewis acid is selected from metal salts, trialkylborates, triarylborates, and combinations thereof.

21 - 28 . (canceled)

29 . The composition of claim 1 , further comprising at least one carboxylic acid, at least one carboxylic acid anhydride, or a combination thereof.

30 . (canceled)

31 . The composition of claim 1 , wherein said composition is substantially free of a tin catalyst.

32 . (canceled)

33 . (canceled)

34 . A composition comprising:
(a) at least one organosiloxane oligomer, fluorinated organosiloxane oligomer, or combination thereof that is hydroxyl-endblocked; (b) at least one organosiloxane oligomer, fluorinated organosiloxane oligomer, or combination thereof comprising at least three hydrosilyl moieties; and (c) a catalyst composition comprising (1) at least one base selected from 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), 1,5-diazabicyclo[4.3.0]-5-nonene (DBN), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), 2-tert-butyl-1,1,3,3-tetramethylguanidine, and combinations thereof, and (2) at least one Lewis acid selected from metal salts, trialkylborates, triarylborates, and combinations thereof, wherein the composition is substantially free of an organic solvent.

35 . The composition of claim 34 , wherein said components (a) and (b) each comprise an organosiloxane oligomer having a weight average molecular weight no greater than 5,000 Da.

36 . The composition of 35 , wherein each organosiloxane oligomer is a dimethylsiloxane oligomer.

37 . The composition of claim 34 , wherein at least one of said component (a) or said component (b) is a fluorinated organosiloxane oligomer.

38 . The composition of claim 34 , wherein said Lewis acid is a zinc(II) salt that is used in a 1:1 molar ratio with said base.

39 . The composition of claim 1 , further comprising at least one alkoxysilane selected from:
(R″O) p —Si(R′) 3-p -[G-Si(W) 2 ] t —(R′) s —[(R′) 2 SiO] q —[Si(R′) 2 -G] t -Si(R′) 3-p —(OR″) p ; (R″O) p —Si(R′) 3-p —[(R′) 2 SiO] q —(W) s —[(R′) 2 SiO] q ]—Si(R′) 3-p —(OR″) p ; or R-[G-Si(R′) 2 ] t —(W) s —[(R′) 2 SiO] q —[Si(R′) 2 -G] t -[Si(R′) 3-p —(OR″) p ], wherein: G and W are each divalent linking groups independently selected from oxy, alkylene, arylene, hetroarylene, cycloalkylene, and hetrocycloalkylene; R is selected from alkyl, alkylene, fluoroalkyl, aryl, fluoroaryl, cycloalkyl, fluorocycloalkyl, etroalkyl, hetrofluoroalkyl, hetroaryl, hetrofluoroaryl, hetrocycloalkyl, and hetrofluorocycloalkyl; each R′ is independently selected from alkyl, alkylene, fluoroalkyl, aryl, fluoroaryl, cycloalkyl, fluorocycloalkyl, hetroalkyl, hetrofluoroalkyl, hetroaryl, hetrofluoroaryl, hetrocycloalkyl, hetrofluorocycloalkyl, oxyalkyl, oxyalkylene, oxyfluoroalkyl, oxyaryl, oxyfluoroaryl, oxycycloalkyl, oxyfluorocycloalkyl, oxyhetroalkyl, oxyhetrofluoroalkyl, oxyhetroaryl, oxyhetrofluoroaryl, oxyhetrocycloalkyl, and oxyhetrofluorocycloalkyl; each R″ is independently selected from alkyl; p is an integer selected from 1, 2 or 3; e

Assignees

• 3M Innovative Properties Co

Inventors

• Kumar Kanta
• Wolter James T

Classifications

• C08G77/08 Primary

  characterised by the catalysts used · CPC title

• C09J2483/005

  in the release coating · CPC title

• C09J2201/606

  Chemistry & Metallurgy · mapped topic

• C09J7/0228

  Chemistry & Metallurgy · mapped topic

• C09D183/10

  Block or graft copolymers containing polysiloxane sequences (obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C09D151/08, C09D153/00) · CPC title