Lubricating polyorganosiloxane oil, aqueous emulsion containing same, preparation and use thereof for stripping metals
The invention concerns a lubricating organo-functional silicone oil, whether or not in emulsion. The invention aims at improving oils and lubricating silicone emulsions, in terms of emulsion stability, transfer and flow of the oil in emulsion on metal surfaces, of stripping lubricating power, non-clogging of molds and paintability of molded metal articles when used for stripping. In order to achieve said aim, the inventive POS oil is functionalized with the lubricating organophilic radical W (C12-C20 alkyl) and with a radical bearing one or several adhering functions such as diacid, thiol, phosphonate, sulphonate hydroxy, hydroxyamine, amine, ether, amide and their combinations. The invention also concerns emulsions whether or not containing additives, based on said WY functionalized POS oils, the preparation of said oils and said emulsions and their uses when stripping metal articles molded in metal moulds.
1. A polyorganosiloxane comprising siloxyl units:
D: R 2 SiO 2/2
optionally M: R 3 SiO 1/2 , and
with R corresponding to hydrogen or to substituted or unsubstituted hydrocarbon-based radicals which are identical or different;
wherein:
at least some of the radicals R correspond to the definitions below:
R=W representing a radical comprising at least 8 and preferably from 8 to 50 carbon atoms and bearing at least one lubricating organophilic function, and
R=Y representing a radical bearing at least one attachment function capable of forming hydrogen bonds and/or ionic interactions with a metal support;
and said polyorganosiloxane correspond to the general formula (I) below:
M α [D w ] a [D y ] b [D R ] c M ω (I)
wherein:
the radicals M α , M ω are units M, which are be identical or different, in each of which R corresponds independently to a linear or branched C 1 -C 12 (cyclo)alkyl group, to an aryl, to an aralkyl or to an alkylaryl, or, alternatively, to a radical W or Y;
the radicals D w are units D, which are identical or different, in each of which at least one radical R corresponds to W; W being:
linear or branched C8-C30 alkyls R o ,
C8-C30 alkenyls,
aryls, alkylaryls, aralkyls,
hydrocarbon-based monovalent radicals of general formula (II):
—R 1 —COOR 2 ,
wherein
R 1 is a divalent hydrocarbon-based radical containing at least 1 to 29 carbon atoms; and
R 2 is hydrogen or a monovalent hydrocarbon-based radical containing at least from 1 to 30 atoms;
the monovalent hydrocarbon-based radicals of general formula (III):
—R 3 —COOR 4 ,
wherein:
R 3 is a divalent hydrocarbon radical containing at least 1 to 29 carbon atoms; and
R 4 is a monovalent hydrocarbon radical containing at least 1 to 30 atoms;
the monovalent hydrocarbon-based radicals of general formula (IV):
wherein:
R 5 is a divalent hydrocarbon-based radical containing between 1 and 30 carbon atoms, and
R 6 is a monovalent hydrocarbon-based radical containing from 1 to 30 carbon atoms;
the radicals D y are units D, which are identical or different, in each of which at least one radical R corresponds to Y which is a monovalent radical of general formula (V):
-Sp-Uac
wherein Sp is a spacer unit which is a divalent hydrocarbon-based radical of general formula (VI) below:
wherein:
A represents, independently:
wherein T 1 , T 2 independently representing a C1-C6 alkyl or alkoxy,
R 8 corresponds to hydrogen or to a hydroxyl;
d=0 to 30
e=0 to 1
f=0 to 30
d+e+f≦40
and wherein Uac is an attachment unit comprising at least one attachment functions, Uac being a monovalent hydrocarbon radical, chosen from:
esterified or nonesterified diacids,
thiols,
phosphonates,
sulfonates,
mono- or polyhydroxy,
mono- or polyhydroxy(poly)amine,
mono- or polyamine,
(poly)ether,
(poly)amides,
a monovalent radicals of general formula (VII) below:
wherein:
D is N or CH;
E and E′ are identical or different and correspond to:
g and i are identical or different and correspond to an integer between 1 and 10;
h and j are identical or different and correspond to 0 or 1, with the condition that if g=h=0,
then i and j≠0, and vice versa:
a monovalent radicals of general (VIII)
wherein:
G independently represents an alkyl or halogen substituent;
J independently represents SH, OH, NH 2 , N[CH 2 ) 2 —OH] 2 , SO 3 − , or M + ;
x=0 to 4
y=1 to 5 (preferably y=1 with J in the para position)
x+y=5
a monovalent radicals of general formula (IX)
—SO 3 − , M +
with M + being a monovalent cation selected from the group comprising: Na + ; K + , Li + , NH 4 + ; and
a monovalent radicals of general formula (X)
—O—PO 3 H 2
the radicals D R are units D, which are be identical or different, each of which contain two radicals R having the same definition as that given above in the section relating to M α and M ω ;
10≦a+b≦200;
a/b≧0.5
0≦c≦10, and
said polyorganosiloxane having residual units D OH which are identical or different, in each of which one of the radicals R is OH and the other radical R is a C1-C3 alkyl, with the further proviso that:
the polyorganosiloxanes (I) comprise at least one siloxyl unit D′ substituted with a radical of formula:
—(OSiR′ 2 ) x —H
with R′ independently being a monovalent hydrocarbon group free of ethylenic unsaturation and x between 1 and 20; and
the polyorganosiloxanes (I), wherein at least one of the radicals W or Y comprises at least one perfluoroalkyl unit, are being excluded.
2. A process for preparing the polyorganosiloxanes as defined in claim 1 , said process comprising the steps of reacting at least one polyalkylhydrogenosiloxane oil with at least one olefinic precursor OP Y of at least one radical Y or of a portion of at least one radical Y, and with at least one olefinic precursor OP W of at least one radical W and/or of a portion of a radical W, in the presence of an effective amount of metallic hydrosilylation catalyst, and wherein precursors OP Y are bearing at least one reactive function Fr per molecule, said function Fr being
3. The process as claimed in claim 2 , wherein the functions Fr of the grafts derived from the hydrosilylation of the groups OP Y are reacted with all or a portion of a precursor of at least one attachment unit Uac.
4. An aqueous silicone emulsion, comprising at least one polyorganosiloxane as defined in claim 1 , at least one surfactant and, optionally, antifoams, elongational viscosity promoters, waxes, extreme-pressure additives, antirusts, or antioxidants, wherein the surfactant is an alkyldiphenyl ether disulfonate salt.
5. A process for molding a metal article using a metallic mold comprising the step of lubricating the metal surface of the mold, before or during the molding, with the POS oil as claimed in claim 1 .
6. A process for molding a metal article using a metallic mold comprising the step of lubricating the metal surface of the mold, before or during the molding, with the emulsion as claimed in claim 4 .
7. The polyorganosiloxane as claimed in claim 1 , wherein the attachment unit Uac of the radical Y is:
8. A polyorganosiloxane comprising siloxyl units:
D: R 2 SiO 2/2
optionally M: R 3 SiO 1/2 , and
with R corresponding to hydrogen or to substituted or unsubstituted hydrocarbon-based radicals which are identical or different;
wherein:
at least some of the radicals R correspond to the definitions below:
R=W representing a radical comprising at least 8 and preferably from 8 to 50 carbon atoms and bearing at least one lubricating organophilic function, and
R=Y representing a radical bearing at least one attachment function capable of forming hydrogen bonds and/or ionic interactions with a metal support;
and said polyorganosilane correspond to the general formula (I) below:
M α [D w ] a [D y ] b [D R ] c M ω (I)
wherein:
the radicals M α , M ω are units M, which are be identical or different, in each of which R corresponds independently to a linear or branched C1-C12 (cyclo)alkyl group, to an aryl, to an aralkyl or to an alkylaryl, or, alternatively, to a radical W or Y;
the radicals D w are units D, which are identical or different, in each of which at least one radical R corresponds to W; W being:
linear or branched C8-C30 alkyls R o ,
C8-C30 alkenyls,
aryls, alkylaryls, aralkyls,
hydrocarbon-based monovalent radicals of general formula (II):
—R 1 —COOR 2 ,
wherein
R 1 is a divalent hydrocarbon-based radical containing at least 1 to 29 carbon atoms; and
R 2 is hydrogen or a monovalent hydrocarbon-based radical containing at least from 1 to 30 atoms;
the monovalent hydrocarbon-based radicals of general formula (III):
—R 3 —COOR 4 ,
wherein:
R 3 is a divalent hydrocarbon radical containing at least 1 to 29 carbon atoms; and
R 4 is a monovalent hydrocarbon radical containing at least 1 to 30 atoms;
the monovalent hydrocarbon-based radicals of general formula (IV):
wherein:
R 5 is a divalent hydrocarbon-based radical containing between 1 and 30 carbon atoms, and
R 6 is a monovalent hydrocarbon-based radical containing from 1 to 30 carbon atoms;
the radicals D y are units D, which are identical or different, in each of which at least one radical R corresponds to Y which is a monovalent radical of general formula (V):
-Sp-Uac
wherein Sp is a spacer unit which is a divalent hydrocarbon-based radical of general formula (VI) below:
wherein:
A represents, independently:
wherein T 1 , T 2 independently representing a C1-C6 alkyl or alkoxy,
R 8 corresponds to hydrogen or to a hydroxyl;
d=0 to 30
e=0 to 1
f=0 to 30
d+e+f≦40
wherein the attachment unit Uac of the radical Y is:
9. A process for preparing the polyorganosiloxanes as defined in claim 8 , said process comprising the steps of reacting at least one polyalkylhydrogenosiloxane oil with at least one olefinic precursor OP Y of at least one radical Y or of a portion of at least one radical Y, and with at least one olefinic precursor OP W of at least one radical W and/or of a portion of a radical W, in the presence of an effective amount of metallic hydrosilylation catalyst.
10. A process for preparing the polyorganosiloxanes as defined in claim 8 , said process comprising the steps of reacting at least one polyalkylhydrogenosiloxane oil with at least one olefinic precursor OP Y of at least one radical Y or of a portion of at least one radical Y, and with at least one olefinic precursor OP W of at least one radical W and/or of a portion of a radical W, in the presence of an effective amount of metallic hydrosilylation catalyst, and wherein precursors OP Y are bearing at least one reactive function Fr per molecule, said function Fr being
11. The process as claimed in claim 10 , wherein the functions Fr of the grafts derived from the hydrosilylation of the groups OP Y are reacted with all or a portion of a precursor of at least one attachment unit Uac.
12. An aqueous silicone emulsion, comprising at least one polyorganosiloxane as defined in claim 8 , at least one surfactant and, optionally, antifoams, elongational viscosity promoters, waxes, extreme-pressure additives, antirusts, or antioxidants, wherein the surfactant is an alkyldiphenyl ether disulfonate salt.
13. A process for molding a metal article using a metallic mold comprising the step of lubricating the metal surface of the mold, before or during the molding, with the POS oil as claimed in claim 8 .
14. A process for molding a metal article using a metallic mold comprising the step of lubricating the metal surface of the mold, before or during the molding, with the emulsion as claimed in claim 12 .