Organopolysiloxanes and methods for preparing same
The present invention concerns an organopolysiloxane (A) able to be obtained by the reaction, at a temperature of between 10° C. and 75° C., between—at least one compound (C) chosen from the organic compounds comprising at least one alkene or alkyne functional group, at least one of the substituents of which is an acid functional group and the organic compounds comprising at least one acid functional group and at least one alkene or alkyne functional group, at least one of the substituents of which is an electron-withdrawing group; and—at least one organopolysiloxane (B) chosen from the organopolysiloxanes comprising siloxyl units (I.1) and (I.2) of the following formulae: (I) The present invention also concerns compositions comprising said organopolysiloxanes (A) and the uses thereof. ( I ) Y a Z b 1 SiO 4 - ( a + b ) 2 ; ( I .1 ) Z c 2 SiO 4 - c 2 ( I .2 )
1. An organopolysiloxane (A), comprising a filler, which may be obtained by reaction, at a temperature comprised between 10 and 75° C., between:
at least one compound (C) selected from the group consisting of the organic compounds comprising at least one alkene or alkyne function for which at least one of the substituents is an acid function and the organic compounds comprising at least one acid function and at least one alkene or alkyne function for which at least one of the substituents is an electroattractor group; and
at least one organopolysiloxane (B) selected from the group consisting of the organopolysiloxanes comprising siloxyl units (I.1) and (I.2) of the following formulae:
Y
a
Z
b
1
SiO
4
-
(
a
+
b
)
2
;
and
(
I
.1
)
Z
c
2
SiO
4
-
c
2
(
I
.2
)
wherein:
a=1 or 2, b=0, 1 or 2 and a+b=1, 2 or 3
c=1, 2, 3 or 4
the symbols Y, either identical or different, represent a functional group of formula (I.3):
-E-(NH-G) h -(NH 2 ) i (I.3)
wherein:
h=0 or 1;
i=0 or 1;
h+i=1 or 2;
E represents an aliphatic, cycloaliphatic or aromatic divalent hydrocarbon comprising from 1 to 30 carbon atoms;
when it is present, G represents an aliphatic hydrocarbon radical comprising from 1 to 10 carbon atoms, monovalent when i=0 or divalent when i=1;
the symbols Z 1 and Z 2 , either identical or different, represent a monovalent hydrocarbon radical having from 1 to 30 carbon atoms and optionally comprising one or several unsaturations and/or one or several fluorine atoms, a hydroxyl group, or a radical-OR 1 with R 1 which represents a linear, cyclic or branched C 1 -C 10 hydrocarbon radical;
said polyorganosiloxane (B) comprising, per molecule, at least one siloxyl unit (I.1) bearing at least one functional group of formula (I.3),
the reaction being made in the presence of a filler.
2. The organopolysiloxane (A) according to claim 1 wherein the temperature is comprised between 10 and 70° C.
3. The organopolysiloxane (A) according to claim 1 , wherein the compound (C) is selected from among the organic compounds comprising at least a double carbon-carbon bond for which at least one of the substituents is a carboxylic acid function.
4. The organopolysiloxane (A) according to claim 1 , wherein the compound (C) is selected from among the compounds of formula (II)
wherein:
R 2 , R 3 and R 4 , either identical or different, represent a hydrogen atom, a COOH group or a C 1 -C 6 ;
R 5 represents a hydrogen atom, an alkyl group or an aryl group, wherein the alkyl and the aryl comprise at least one COOH group.
5. The organopolysiloxane (A) according to claim 1 , wherein the compound (C) is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, 2-carboxyethylacrylate, 3-carboxypropylacrylate, maleic acid, fumaric acid, 2-(acryloyloxy)acetic acid, 2-(acryloyloxy)propanoic acid, 3-(acrylolyloxy)propanoic acid, 2-(acryloyloxy)-2-phenylacetic acid, 4-(acryloyloxy)butanoic acid, 2-(acryloyloxy)-2-methylpropanoic acid, 5-(acryloyloxy)pentanoic acid, (E)-but-2-enoic acid, (Z)-prop-1-ene-1,2,3-tricarboxylic acid, cinnamic acid, sorbic acid, 2-hexenoic acid, 2-pentenoic acid, 2,4-pentadienoic acid, ethenesulfonic acid, vinylphosphonic acid, (1-phenylvinyl)phosphonic acid, 3-(vinylsulfonyl)propanoic acid, 2-(vinylsulfonyl)acetic acid, 2-(vinylsulfonyl)succinic acid, acetylene dicarboxylic acid and propiolic acid.
6. The organopolysiloxane (A) according to claim 1 , wherein the organopolysiloxane (B) is selected from the group consisting of the organopolysiloxanes comprising siloxyl units (I.1) and (I.2) of the following formulae:
Y
a
Z
b
1
SiO
4
-
(
a
+
b
)
2
;
and
(
I
.1
)
Z
c
2
SiO
4
-
c
2
(
I
.2
)
wherein:
Y and Z 1 and Z 2 are definitions given in claim 1 ;
a=1 or 2, b=0, 1 or 2 and a+b=2 or 3
c=1 or 2.
7. The organopolysiloxane (A) according to claim 1 , characterized in that the organopolysiloxane (B) has a degree of polymerization comprised between 2 and 5,000.
8. The organopolysiloxane (A) according to claim 1 , wherein the organopolysiloxane (B) has a dynamic viscosity measured at 25° C. with a rheometer with imposed stress comprised between 1 and 100,000 mPa·s.
9. The organopolysiloxane (A) according to claim 1 , characterized in that its viscosity, measured at 25° C. with a rheometer with imposed stress, is at least 10 times greater than that of the organopolysiloxane (B).
10. A method for preparing an organopolysiloxane (A) comprising putting into contact at a temperature comprised between 10 and 75° C.:
at least one compound (C) selected from the group consisting of the organic compounds comprising at least one alkene or alkyne function for which at least one of the substituents is an acid function and the organic compounds comprising at least one acid function and at least one alkene or alkyne function for which at least one of the substituents is an electronattractor group; and at least an acid function, and
at least one organopolysiloxane (B) selected from the group consisting of the organopolysiloxanes comprising siloxyl units (I.1) and (I.2) of the following formulae:
Y
a
Z
b
1
SiO
4
-
(
a
+
b
)
2
;
and
(
I
.1
)
Z
c
2
SiO
4
-
c
2
(
I
.2
)
wherein:
a=1 or 2, b=0, 1 or 2 and a+b=1, 2 or 3
c=1, 2, 3 or 4
the symbols Y, either identical or different, represent a functional group of formula (I.3):
-E-(NH-G) h -(NH 2 ) i (I.3)
wherein:
h=0 or 1;
i=0 or 1;
h+i=1 or 2;
E represents an aliphatic, cycloaliphatic or aromatic divalent hydrocarbon radical comprising from 1 to 30 carbon atoms;
when it is present, G represents an aliphatic hydrocarbon radical comprising from 1 to 10 carbon atoms, monovalent when i=0 or divalent when i=1;
the symbols Z 1 and Z 2 , either identical or different, represent a monovalent hydrocarbon radical having from 1 to 30 carbon atoms and optionally comprising one or several unsaturations and/or one or several fluorine atoms, a hydroxyl group, or a radical-OR 1 with IV which represents a linear, cyclic or branched C 1 -C 10 hydrocarbon radical;
said polyorganosiloxane (B) comprising, per molecule at least one siloxyl unit (I.1) bearing at least one functional group of formula (I.3),
the method being carried out in the presence of a filler.
11. The method according to claim 10 , applied at a temperature comprised between 10 and 70° C.
12. The method according to claim 10 , applied in bulk or in the presence of a solvent.
13. The method according to claim 10 , wherein the obtained organopolysiloxane (A) has a dynamic viscosity, measured at 25° C. with a rheometer with imposed stress, at least 10 times greater than that of the organopolysiloxane (B).
14. The method according to claim 10 , wherein the ratio r representing the ratio between the number of moles of alkene or alkyne function of the compound (C) for which at least one of the substituents is an electroattractor group or an acid function, and the number of moles of N—H bonds borne by the organopolysiloxane (B)
r
=
n
(
C=C
ou
C≡C
)
n
(
N—H
)
is comprised between 0.01 and 10.
15. The method according to claim 10 , wherein the ratio J representing the ratio between the number of mole of acid functions of the compound (C) and the number of mole of the amine function of the organopolysiloxane (B)
l
=
number
of
moles
of
the
compound
(
C
)
×
number
of
acid
functions
of
the
compound
(
C
)
number
of
moles
of
the
compound
(
B
)
×
number
of
a
mine
functions
of
the
compound
(
B
)
is comprised between 0.01 and 20.
16. A composition K1 comprising at least one organopolysiloxane (A) according to claim 1 , and at least one filler and optionally at least one other organopolysiloxane and/or one or several usual functional additives, and/or an organopolysiloxane comprising at least one carboxylic function and/or at least one organopolysiloxane (B) as defined in claim 1 .
17. The use of A method of using at least one organopolysiloxane (A) according to claim 1 , comprising using said at least one organopolysiloxane in wound care; for the encapsulation of electronic components; as coatings; as additives; for temporary printing, or for thin layer coating.
18. A method of using at least one organopolysiloxane (A) according to claim 1 , comprising using said at least one organopolysiloxane in paints, coatings, adhesives, sealants, personal care, health care, textile treatment, electronics, automotive field, rubbers, or anti-foam compositions.
19. A composition X for the preparation of an organopolysiloxane (A) according to claim 1 , comprising:
at least one compound (C) selected from the group consisting of the organic compounds comprising at least one alkene or alkyne function for which at least one of the substituents is an acid function and the organic compounds comprising at least one acid function and at least one alkene or alkyne function for which at least one of the substituents is an electroattractor group; and
at least one organopolysiloxane (B) selected from the group consisting of the organopolysiloxanes comprising siloxyl units (I.1) and (I.2) of the following formulae:
Y
a
Z
b
1
SiO
4
-
(
a
+
b
)
2
;
and
(
I
.1
)
Z
c
2
SiO
4
-
c
2
(
I
.2
)
wherein:
a=1 or 2, b=0, 1 or 2 and a+b=1, 2 or 3
c=1, 2, 3 or 4
the symbols Y, either identical or different, represent a functional group of formula (I.3):
-E-(NH-G) h -(NH 2 ) i (I.3)
wherein:
h=0 or 1;
i=0 or 1;
h+i=1 or 2;
E represents an aliphatic, cycloaliphatic or aromatic divalent hydrocarbon radical comprising from 1 to 30 carbon atoms;
when it is present, G represents an aliphatic hydrocarbon radical comprising from 1 to 10 carbon atoms, monovalent when i=0 or divalent when i=1;
the symbols Z 1 and Z 2 , either identical or different, represent a monovalent hydrocarbon radical having from 1 to 30 carbon atoms and optionally comprising one or several unsaturations and/or one or several fluorine atoms, a hydroxyl group, or a radical-OR 1 with IV which represents a linear, cyclic or branched C 1 -C 10 hydrocarbon radical;
said polyorganosiloxane (B) comprising, per molecule, at least one siloxyl unit (I.1) bearing at least one functional group of formula (I.3).
20. The organopolysiloxane (A) according to claim 1 , wherein the filler is a mineral filler.
21. The organopolysiloxane (A) according to claim 10 , wherein the filler is a mineral filler.