Silicone co-polymers and methods of use thereof to modify the surface of silicone elastomers by physical adsorption

Patent metadata

Field	Value
Publication number	US-2016130403-A1
Application number	US-201414895539-A
Country	US
Kind code	A1
Filing date	Jun 6, 2014
Priority date	Jun 6, 2013
Publication date	May 12, 2016
Grant date	—

Abstract

The present application relates to polymers of Formula (I) and (II) which, when combined with a silicone elastomer or a silicone pre-elastomer, modifies the surface properties of the elastomer, for example by making the elastomer surface more hydrophilic or reactive to other compounds resulting in the functionalization of the elastomer surface. Methods of using the polymers and silicone elastomers coated with the polymers are also included in the application.

First claim

1 . A compound of the formula (I) or (II):

wherein:
m and m′ are, independently, an integer from 2 to 20;
Silicone is a straight or branched chain silicone polymer;
Y is a linker moiety selected from a direct bond,
—(CH 2 ) p —, —(CH 2 ) p′ S—(CH 2 ) p —, —C(O)—, —(CH 2 ) p C(O)—, —C(O)O—, —C(O)NH—, —(CH 2 ) p O—, —(CH 2 ) p C(O)O—, —(CH 2 ) p OC(O)—, —(CH 2 ) p OC(O)O— and —(CH 2 ) p OC(O)NH—;
Y′ is a linker moiety selected from a direct bond,
—(CH 2 ) p′ —, —(CH 2 ) p′ S—(CH 2 ) p′ —, —C(O)—, —C(O)(CH 2 ) p —, —OC(O)—, —NHC(O)—, —O(CH 2 ) p′ —, —C(O)O(CH 2 ) p′ —, —OC(O)(CH 2 ) p′ —, —OC(O)O(CH 2 ) p′ - and —NHC(O)(CH 2 ) p′ —;
Z is a linker moiety selected from —(CH 2 ) n —, —(CH 2 ) n′ S—(CH 2 ) n —, —(CH 2 ) n triazoleC(O)—, —(CH 2 ) n C(O)—, —O(CH 2 ) n —, —(CH 2 ) n OC(O)—, and —OC(O)(CH 2 ) n —;
Z is a linker moiety selected from —(CH 2 ) n′ —, —(CH 2 ) n′ S—(CH 2 ) n —, —C(O)triazole(CH 2 ) n′ —, —C(O)(CH 2 ) n′ —, —(CH 2 ) n′ O—, —C(O)O(CH 2 ) n′ —, —(CH 2 ) n′ C(O)O—;
n and n′ are, independently, an integer from 1 to 6;
p and p′ are, independently, an integer from 1 to 6;
A and A′ are independently selected from C 1-20 alkyl, a trisiloxane, a tetrasiloxane, a pentasiloxane, a hexasiloxane, a heptasiloxane, a functional group that is displaceable by a nucleophile or an electrophile and

and R 1 , R 2 and R 3 are, independently, selected from C 1-20 alkyl, C 3-14 cycloalkyl and C 6 -14aryl.

2 . (canceled)

3 . The compound of claim 1 , wherein the straight chain silicone polymer comprises from about 10 to about 50 D monomeric repeat units.

4 . (canceled)

5 . The compound of claim 1 , wherein the branched chain silicone polymer comprises a mixture of at least two of M (Me 3 SiO), D (Me 2 SiO), T (MeSiO 3/2 ) and Q (SiO 4/2 ) monomeric repeat units.

6 . The compound of claim 5 , wherein the branched chain silicone polymer comprises a total number of M, D, T, Q units that is from about 10 to 50 monomeric repeat units.

7 . (canceled)

8 . The compound of claim 1 , wherein, in the compounds of Formula I, silicone-Z is selected from:

wherein , represents the point of attachment of the silicon-Z.

9 . The compound of claim 1 , wherein, in the compounds of Formula I, the branched silicone is:

wherein

represents the point of attachment the branched silicone.

10 . The compound of claim 1 , wherein:
Y is a direct bond or —(CH 2 ) p —; Y′ is a direct bond or —(CH 2 ) p′ —; p and p′ are, independently, an integer from 1 to 3; A and A° are, independently,

and
R 1 , R 2 and R 3 are independently selected from C 1-10 -alkyl, C 5-6 -cycloalkyl and phenyl.

11 .- 13 . (canceled)

14 . The compound of claim 1 , wherein Y-A and Y′-A′ are, independently, selected from:

wherein represents the point of attachment of Y-A and Y′-A′.

15 . The compound of claim 1 , having the formula

wherein
R 4 is C 1-20 alkyl or an activating group.

16 . The compound of claim 1 , having the formula

wherein:
R 4 and R 4′ are, independently, C 1-20 alkyl or an activating group.

17 .- 18 . (canceled)

19 . The compound of claim 1 , wherein m and m′ are independently 5, 6, 7, 8, 9, 10, 11 or 12.

20 . (canceled)

21 . The compound of claim 1 , having a structure selected from:

22 . A process for surface-modifying a silicone elastomer, the process comprising:
(a) mixing one or more of the compounds of Formula (I) and/or (II) of claim 1 , either neat or as a dispersion or solution, with a pre-cured silicone elastomer; and (b) allowing the mixture of pre-cured silicone elastomer and compounds of the Formula (I) and/or (II) to cure.

23 . The process of claim 22 , wherein the concentration of the one or more compounds of Formula (I) and/or (II) is from about 1 to about 20% (w/w).

24 . The process of claim 22 , wherein the solution of the one or more compounds of Formula (I) and/or (II) is prepared using at least one solvent selected from THF, dichloromethane and toluene or related aprotic organic solvents, or low molecular weight silicone oils, like (Me 2 SiO) 4 and (Me 2 SiO) 5 , or mixtures thereof.

25 .- 26 . (canceled)

27 . The process of claim 22 , wherein the surface modification allows for covalent attachment of nucleophiles comprising S, N and/or O to the silicone elastomer.

28 . The process of claim 27 , wherein the nucleophile is a biological molecule.

29 . A process for surface modifying a silicone elastomer, the process comprising:
(a) soaking a silicone elastomer in a solution or dispersion of one or more of the compounds of Formula (I) and/or (II) of claim 1 under conditions to produce a swollen elastomer; and (b) drying the swollen silicone elastomer to produce a surface-modified silicone elastomer.

30 . The process of claim 29 , wherein the concentration of the compound of Formula (I) and/or (II) added to the elastomer formulations is from about 1 to about 30% (w/w).

31 . A silicone elastomer that has been surface-modified by physical adsorption of one or more of the compounds of Formula (I) and/or (II) of claim 1 .

32 .- 33 . (canceled)

Assignees

• Chen Yang
• Univ Mcmaster
• McMaster Unviersity

Inventors

• Brook Michael A
• Chen Yang

Classifications

• C08J7/12 Primary

  Chemical modification · CPC title

• C08G77/38 Primary

  Polysiloxanes modified by chemical after-treatment · CPC title

• C08J2383/04

  Polysiloxanes · CPC title

• C08J2483/12

  containing polyether sequences · CPC title

• C08G77/46

  containing polyether sequences · CPC title