Organopolysiloxane modified with polyether and higher apliphatic ether

A novel organopolysiloxane compound, which has high surface activity to form an emulsion of the water-in-oil type of various hardly emulsifiable materials, is proposed. The organopolysiloxane compound is a dimethylpolysiloxane having two types of modifying groups including polyether or polyoxyalkylene groups on one hand and higher alkyl groups bonded to the silicon atoms through an ether linkage on the other hand bonded to the silicon atoms. Different from conventional dually modified dimethylpolysiloxanes as an emulsifying agent having modifying groups of polyether groups and higher alkyl groups directly bonded to the silicon atoms, the dually modified dimethylpolysiloxane of the invention can be synthesized easily in a one-step process of the reaction in addition to the advantage of excellent emulsifying activity for various kinds of hardly emulsifiable liquids as compared with conventional emulsifying agents.

BACKGROUND OF THE INVENTION 
The present invention relates to a novel organopolysiloxane compound not 
known in the prior art nor described in any literatures or, more 
particularly, to a novel organopolysiloxane compound having excellent 
surface activity and useful as an emulsifying agent to prepare an aqueous 
emulsion of the water-in-oil type. 
Various types of organopolysiloxane compounds having surface activity are 
known in the prior art including those useful as an emulsifying agent in 
the preparation of a water-in-oil emulsion, of which Japanese Patent Kokai 
61-90732 discloses an organopolysiloxane compound modified jointly with 
polyether groups and long-chain alkyl groups having 8 to 18 carbon atoms. 
The above mentioned organopolysiloxane compound jointly modified with two 
types of modifying groups is useful as an emulsifying agent for silicones 
but not suitable for the emulsification of ester oils and glycerides due 
to the relatively low surface activity. In addition, such a jointly 
modified organopolysiloxane has a problem in the complicated synthetic 
preparation procedure thereof. Namely, such a jointly modified 
organopolysiloxane is prepared by a mixed hydrosilation reaction or 
so-called addition reaction of an allylated polyether for the modifying 
polyether groups and a long-chain .alpha.-olefin compound for the 
modifying long-chain alkyl groups to an organohydrogenpolysiloxane having 
silicon-bonded hydrogen atoms in the presence of a platinum catalyst 
according to a well known procedure. When the allylated polyether and the 
.alpha.-olefin compound are concurrently brought to the addition reaction 
with the organohydrogenpolysiloxane, the reaction cannot proceed evenly 
for these two different reactants eventually to cause phase separation of 
the reaction mixture because the velocities of the addition reaction of 
the two reactants greatly differ from each other, the allylated polyether 
being generally more reactive than the .alpha.-olefin. Therefore, the 
synthetic process must be conducted in two successive steps including a 
first step in which the .alpha.-olefin compound is brought to the addition 
reaction with a part of the silicon-bonded hydrogen atoms in the 
organohydrogenpolysiloxane and a second step in which the remaining 
silicon-bonded hydrogen atoms are reacted with the allylated polyether 
compound. 
Thus, it is eagerly desired to develope a novel organopolysiloxane useful 
as an emulsifying agent for the preparation of a water-in-oil emulsion of 
any hardly emulsifiable oily materials without the above described 
problems and disadvantages in the prior art in connection with the 
complicated preparation process. 
SUMMARY OF THE INVENTION 
The present invention accordingly has an object to provide a novel 
organopolysiloxane which can be prepared in a single-step process and 
useful as an emulsifying agent for the preparation of a water-in-oil 
emulsion of any hardly emulsifiable oily materials. 
Thus, the novel organopolysiloxane compound of the invention is an 
organopolysiloxane modified jointly with polyether groups and long-chain 
aliphatic ether groups as represented by the general formula 
EQU R.sup.4 --SiR.sup.1.sub.2 --O--SiR.sup.1.sub.2 --O).sub.p (SiR.sup.1 
R.sup.2 --O).sub.q (SiR.sup.1 R.sup.3 --O).sub.r --SiR.sup.1.sub.2 
--R.sup.4, (I) 
in which R.sup.1 is an alkyl group having 1 to 4 carbon atoms, R.sup.2 is a 
polyether group of the formula 
EQU --Q--O--C.sub.2 H.sub.4 --O).sub.a (C.sub.3 H.sub.6 --O).sub.b R.sup.5,(II) 
Q being a divalent hydrocarbon group having 2 to 4 carbon atoms, R.sup.5 
being a hydrogen atom, alkyl group having 1 to 4 carbon atoms or acetyl 
group, the subscript a being a positive integer and the subscript b being 
zero or a positive integer, R.sup.3 is a long-chain aliphatic ether group 
of the formula 
EQU --Q--O--R.sup.6, (III) 
Q having the same meaning as defined above and R.sup.6 being a monovalent 
hydrocarbon group having 8 to 30 carbon atoms, R.sup.4 is R.sup.1, R.sup.2 
or R.sup.3, the subscript p is zero or a positive integer and the 
subscripts q and r are each a positive integer.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
As is defined above, the most characteristic feature of the 
organopolysiloxane compound of the invention, which is a novel compound 
not knonw in the prior art nor described in any literatures, consists in 
the modification jointly with polyether groups of the formula (II) and 
long-chain aliphatic ether groups of the formula (III). This jointly 
modified organopolysiloxane can be prepared by a mixed hydrosilation 
reaction of an organohydrogenpolysiloxane with, for example, an allylated 
polyether compound on one hand and an allyl ether of a long-chain 
aliphatic alcohol on the other hand. Different from the above described 
mixed hydrosilation reaction in the preparation of the polyether and 
long-chain alkyl-modified organopolysiloxane by using an allylated 
polyether and a long-chain .alpha.-olefin as the reactants, 
advantageously, the velocities of the hydrosilation reactions of the two 
different reactants in this case are about the same so that the reaction 
can proceed uniformly without the trouble of eventual phase separation 
taking place in the reaction mixture even when the two different reactants 
are concurrently brought into the reaction with the 
organohydrogenpolysiloxane in one and the same reaction mixture. In 
addition, the jointly modified organopolysiloxane of the invention has 
excellent surface activity so that it is useful as an emulsifying agent 
not only for silicone compounds but also for other hardly emulsifiable 
materials, such as ester oils and glycerides, to give a water-in-oil 
emulsion. 
The jointly modified organopolysiloxane of the invention is represented by 
the general formula (I) given above, i.e.: 
EQU R.sup.4 --SiR.sup.1.sub.2 --O--SiR.sup.1.sub.2 --O).sub.p (SiR.sup.1 
R.sup.2 --O).sub.q (SiR.sup.1 R.sup.3 --O).sub.r --SiR.sup.1.sub.2 
--R.sup.4. (I) 
In the formula, R.sup.1 is an alkyl group having 1 to 4 carbon atoms such 
as methyl, ethyl, propyl and butyl groups or, preferably, a methyl group. 
The group denoted by R.sup.2, as the modifying group of the first class, 
is a polyether group represented by the formula 
EQU --Q--O--C.sub.2 H.sub.4 --O).sub.a (C.sub.3 H.sub.6 --O).sub.b R.sup.5,(II) 
in which Q is a divalent hydrocarbon group having 2 to 4 carbon atoms such 
as ethylene, propylene and butylene groups or, preferably, propylene group 
--CH.sub.2 CH.sub.2 CH.sub.2 --, R.sup.5 is a hydrogen atom, alkyl group 
having 1 to 4 carbon atoms such as methyl, ethyl, propyl and butyl groups 
or acetyl group, the subscript a is a positive integer and the subscript b 
is zero or a positive integer. The group denoted by R.sup.3, as the 
modifying group of the second class, is a long-chain aliphatic ether group 
of the formula 
EQU --Q--O--R.sup.6, (III) 
in which Q has the same meaning as defined above and R.sup.6 is a 
monovalent hydrocarbon group having 8 to 30 carbon atoms. The group 
denoted by R.sup.4 at the molecular chain end can be the same as R.sup.1, 
R.sup.2 or R.sup.3. The subscript p is zero or a positive integer and the 
subscripts q and r are each a positive integer so that the modified 
organopolysiloxane molecule has at least one of each of the two different 
types of the modifying groups. 
The above defined jointly modified organopolysiloxane can be prepared by a 
mixed hydrosilation reaction of an organohydrogenpolysiloxane represented 
by the general formula 
EQU R.sup.7 --SiR.sup.1.sub.2 --O--SiR.sup.1.sub.2 --O).sub.p (SiR.sup.1 
H--O).sub.q+r SiR.sup.1.sub.2 --R.sup.7, (IV) 
in which R.sup.1, p, q and r each have the same meaning as defined above 
and R.sup.7 is a hydrogen atom or R.sup.1, with a polyether etherified at 
one molecular chain end with a group ethylenically unsaturated at the 
.omega.-position, e.g., allyl group, as the first modifying agent and an 
ether of a long-chain alcohol with a group ethylenically unsaturated at 
the .omega.-position, e.g., allyl group, as the second modifying agent. 
The total amount of the above mentioned two classes of the modifying 
agents should be at least equimolar to the silicon-bonded hydrogen atoms 
in the organohydrogenpolysiloxane. As is well known, the hydrosilation 
reaction can be promoted by a catalytic amount of a platinum compound. 
The ethylenically .omega.-unsaturated group at one of the molecular chain 
ends of the polyether compound as the first modifying agent is preferably 
an allyl group or a methacryloxyalkyl group forming an ether while the 
group blocking the other molecular chain end of the polyether compound is 
a hydrogen atom, lower alkyl group, such as methyl, ethyl, propyl and 
butyl groups, or acetyl group. The polyoxyalkylene moiety, which can be a 
combination of a polyoxyethylene moiety and polyoxypropylene moiety, is 
preferably a polyoxyethylene moiety without polyoxypropylene units so that 
the subscript b in the formula (II) is equal to zero in view of the 
hydrophilicity of the modifying groups. 
The long-chain alcohol forming the ether as the second modifying agent has 
from 8 to 30 carbon atoms in a molecule but is preferably oleyl alcohol or 
isostearyl alcohol so that the group denoted by R.sup.6 in the formula 
(III) is oleyl or isostearyl group though not particularly limitative 
thereto including any known higher alcohols having 8 to 30 carbon atoms in 
a molecule. The ethylenically .omega.-unsaturated group forming the ether 
as the second modifying agent with the above mentioned long-chain alcohol 
is preferably an allyl or methacryloxyalkyl group. 
The platinum compound suitable as the catalyst for promoting the 
hydrosilation reaction is well known in the art. Although platinum in the 
elementary form, e.g., platinum black, is effective, the platinum catalyst 
should preferably be a platinum compound such as chloroplatinic acid, 
alcoholic solution of chloroplatinic acid or a complex of chloroplatinic 
acid with an olefin or vinyl siloxane. 
The respective amounts of the above described first and second modifying 
agents as the reactants on the organohydrogenpolysiloxane depend on the 
types of the respective reactants and desired surface activity of the 
product for forming a water-in-oil emulsion. As a rough measure to ensure 
good surface activity of the product, the amount of the long-chain 
aliphatic ether compound as the second modifying agent is in the range 
from 10 to 1000% by weight based on the organohydrogenpolysiloxane and the 
amount of the polyether compound as the first modifying agent is in the 
range from 10 to 30% by weight in the reaction mixture composed of the 
organohydrogenpolysiloxane and the first and the second modifying agents 
with the proviso that the total amount of them is at least equimolar to 
the silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane. When 
the total amount of the two modifying agents is in excess of the equimolar 
amount to the silicon-bonded hydrogen atoms in the 
organohydrogenpolysiloxane, unreacted modifying agents necessarily remain 
in the reaction mixture after completion of the reaction. The reaction 
mixture, however, can be used as such as the emulsifying agent in most 
cases without purification by removing the unreacted reactants. 
The hydrosilation reaction can easily proceed by heating the reaction 
mixture at a temperature in the range from 30.degree. to 200.degree. C. 
or, preferably, from 60.degree. to 110.degree. C. The reaction mixture can 
be undiluted or diluted according to need with a suitable organic solvent 
such as ethyl alcohol, isopropyl alcohol, toluene, tetrahydrofuran, 
dioxane, methyl acetate, methyl ethyl ketone, trichloroethane and the 
like. When an organic solvent is used as a diluent, the reaction mixture 
after completion of the reaction is subjected to a stripping treatment to 
remove the solvent under reduced pressure, 
A preferable way to conduct the hydrosilation reaction is that the 
organohydrogenpolysiloxane is admixed with the two types of the modifying 
agents in a total amount equimolar to the silicon-bonded hydrogen atoms 
therein together with a platinum catalyst and, when the reaction comes 
near to the end point as indicated by the analytical result for the 
silicon-bonded hydrogen atoms, a small amount of an additional portion of 
the long-chain aliphatic ether compound as the second modifying agent is 
added to the reaction mixture to complete the reaction and to obtain the 
desired product which has excellent surface activity for the 
emulsification of not only silicones but also ester oils, glycerides and 
other hardly emulsifiable liquids. 
In the following, the inventive organopolysiloxane modified jointly with 
the two classes of the modifying agents is described in more detail by way 
of examples. 
EXAMPLE 1 
A reaction mixture was prepared by mixing, in a flask of 2 liter capacity, 
183 g (0.1 mole) of a methyl hydrogen polysiloxane expressed by the 
average structural formula 
EQU Me.sub.3 Si--O--SiMe.sub.2 --O).sub.12 (SiMeH--O).sub.13 SiMe.sub.3, 
in which Me is a methyl group, 308 g (1 mole) of allyl oleyl ether, 136 g 
(0.3 mole) of an allylated polyoxyethylene expressed by the average 
formula 
EQU CH.sub.2 .dbd.CH--CH.sub.2 --O--(CH.sub.2 CH.sub.2 --O--).sub.9 H 
and 500 g of ethyl alcohol as the solvent with further admixture of 2 g of 
an ethyl alcohol solution of a vinyl siloxane complex of chloroplatinic 
acid in a concentration of 0.5% by weight as platinum and the reaction 
mixture was heated under reflux for 5 hours to effect the hydrosilation 
reaction. After completion of the reaction, the reaction mixture was freed 
from the solvent by evaporation under reduced pressure and the 
unevaporated residual liquid was filtered to give 570 g, corresponding to 
91% of the total amount of the reactants, of an oily product having a 
viscosity of 329 centistokes at 25.degree. C. and refractive index of 
1.4523 at 25.degree. C. 
The thus obtained product was subjected to the measurements of the .sup.1 
H-NMR spectrum and infrared absorption spectrum to give the results shown 
in FIGS. 1 and 2, respectively. The analytical result of the NMR spectrum 
led to a conclusion that this product compound was expressed by the 
formula 
EQU Me.sub.3 Si--O--SiMe.sub.2 --O).sub.12 (SiMeG.sup.1 --O).sub.3 (SiMeE.sup.1 
--O).sub.10 SiMe.sub.3, 
in which Me is a methyl group, G.sup.1 is a polyoxyethylene group of the 
formula --(CH.sub.2).sub.3 --O--(CH.sub.2 CH.sub.2 --O--).sub.9 H and 
E.sup.1 is a 3-oleyloxypropyl group of the formula --(CH.sub.2).sub.3 
--O--C.sub.18 H.sub.35. 
As is understood from comparison of the spectra of FIGS. 1 and 2 with those 
in FIGS. 3 and 4, which are a .sup.1 H-NMR spectrum and infrared 
absorption spectrum, respectively, of allyl oleyl ether, the NMR signals 
having chemical shifts of 4.8 to 5.0 ppm and 5.4 to 5.6 ppm in FIG. 3 
assignable to the allyl group are no longer found in the NMR spectrum of 
FIG. 1 indicating complete disappearance of the allyl groups in the 
reaction product as a consequence of the hydrosilation reaction of both of 
the modifying reactants. 
EXAMPLE 2 
A reaction mixture was prepared by mixing, in a flask of 2 liter capacity, 
183 g (0.1 mole) of the same methyl hydrogen polysiloxane as used in 
Example 1, 310 g (1 mole) of allyl isodtearyl ether, 136 g (0.3 mole) of 
the same allylated polyoxyethylene as used in Example 1 and 500 g of ethyl 
alcohol as the solvent with further admixture of 2 g of an ethyl alcohol 
solution of a vinyl siloxane complex of chloroplatinic acid in a 
concentration of 0.5% by weight as platinum and the reaction mixture was 
heated under reflux for 5 hours to effect the hydrosilation reaction. 
After completion of the reaction, the reaction mixture was freed from the 
solvent by evaporation under reduced pressure and the unevaporated 
residual liquid was filtered to give 610 g, corresponding to 95% of the 
total amount of the reactants, of an oily product having a viscosity of 
447 centistokes at 25.degree. C. and refractive index of 1.4462 at 
25.degree. C. 
The thus obtained product was subjected to the measurements of the .sup.1 
H-NMR spectrum and infrared absorption spectrum to give the results shown 
in FIGS. 5 and 6, respectively. The analytical result of the NMR spectrum 
led to a conclusion that this product compound was expressed by the 
formula 
EQU Me.sub.3 Si--O--SiMe.sub.2 --O).sub.12 (SiMeG.sup.1 --O).sub.3 (SiMeE.sup.2 
--O).sub.10 SiMe.sub.3, 
in which Me is a methyl group, G.sup.1 is a polyoxyethylene group of the 
formula --(CH.sub.2).sub.3 --O--(CH.sub.2 CH.sub.2 --O--).sub.9 H and 
E.sup.2 is a 3-isostearyloxypropyl group of the formula--(CH.sub.2).sub.3 
--O--C.sub.18 H.sub.37. 
As is understood from comparison of the NMR spectrum of FIG. 5 with that in 
FIG. 7, which is a .sup.1 H-NMR spectrum of allyl isostearyl ether, the 
NMR signals assignable to the allyl groups are no longer found in the NMR 
spectrum of FIG. 5 indicating complete disappearance of the allyl groups 
in the reaction product as a consequence of the hydrosilation reaction of 
both of the modifying reactants. 
EXAMPLE 3 
The reaction procedure was just the same as in Example 1 excepting 
replacement of 308 g (1 mole) of allyl oleyl ether with 254 g (1 mole) of 
allyl myristyl ether to give 527 g, corresponding to 92% of the total 
amount of the reactants, of an oily product having a viscosity of 209 
centistokes at 25.degree. C. and refractive index of 1.4445 at 25.degree. 
C. 
The result of the NMR measurement of this product led to a conclusion that 
this product could be expressed by the formula 
EQU Me.sub.3 Si--O--SiMe.sub.2 --O).sub.12 (SiMeG.sup.1 --O).sub.10 SiMe.sub.3, 
in which Me is a methyl group, G.sup.1 is a polyoxyethylene group of the 
formula --(CH.sub.2).sub.3 --O--(CH.sub.2 CH.sub.2 --O--).sub.9 H and 
E.sup.3 is a 3-myristyloxypropyl group of the formula --(CH.sub.2).sub.3 
--O--C.sub.14 H.sub.29. 
The NMR spectrum of this compound indicated complete disappearance of the 
allyl groups in the product. 
APPLICATION EXAMPLE 
The jointly modified organopolysiloxanes prepared in Examples 1 to 3 were 
each used as an emulsifying agent in the preparation of a water-in-oil 
emulsion. Thus, two water-in-oil emulsions, referred to as the Emulsions 
Ia and Ib hereinbelow, were prepared by taking 4.7 g of glycerin 
triisooctanoate (Trifat S-308, a product by Nikko Chemicals Co.) or 
isocetyl stearate (Nikkol ICS, a product of the same company, supra), 
respectively, 0.3 g of the jointly modified organopolysiloxane prepared in 
Example 1 as the emulsifying agent and 5.0 g of purified water in a test 
tube of 18 mm inner diameter and the test tube containing the mixture was 
heated for 10 minutes on a hot water bath at 68.degree. to 73.degree. C. 
followed by agitation for 60 seconds with a stirrer to give an emulsion. 
In just the same manner and in the same formulation as above, two more 
water-in-oil emulsions, referred to as the Emulsions IIa and IIb 
hereinbelow, were prepared from glycerin triisooctanoate or isocetyl 
stearate, respectively, excepting the use of the jointly modified 
organopolysiloxane prepared in Example 2 as the emulsifying agent. 
Further, two further more water-in-oil emulsions, referred to as the 
Emulsions IIIa and IIIb hereinbelow, were prepared in just the same manner 
and in the same formulation as above from glycerin triisooctanoate or 
isocetyl stearate, respectively, excepting the use of the jointly modified 
organopoly-siloxane prepared in Example 3 as the emulsifying agent. 
For comparison, two more emulsions, referred to as the Emulsions IVa and 
IVb hereinbelow, were prepared in just the same manner and in the same 
formulation as above from glycerin triisooctanoate or isocetyl stearate, 
respectively, excepting the use of a polyether-modified organopolysiloxane 
expressed by the formula 
EQU Me.sub.3 Si--O--SiMe.sub.2 --O).sub.40 (SiMeG.sup.1 --O).sub.2 SiMe.sub.3, 
in which each symbol has the same meaning as defined above, as the 
emulsifying agent in place of the jointly modified organopolysiloxane. 
For further comparison, two more emulsions, referred to as the Emulsions Va 
and Vb hereinbelow, were prepared in just the same manner and in the same 
formulation as above from glycerin triisooctanoate or isocetyl stearate, 
respectively, excepting the use of a polyether- and long-chain 
alkyl-modified organopolysiloxane expressed by the formula 
EQU Me.sub.3 Si--O--SiMe.sub.2 --O).sub.40 (SiMeG.sup.1 --O).sub.3 
(SiMeA--O).sub.10 SiMe.sub.3, 
in which Me and G.sup.1 each have the same meaning as defined above and A 
is a myristyl group --C.sub.14 H.sub.29, as the emulsifying agent in place 
of the jointly modified organopolysiloxane of the present invention. 
The thus prepared ten emulsions were kept standing at 20.degree. C. in the 
test tube up to 60 minutes after termination of agitation to examine the 
stability of the respective emulsions. The results were that the Emulsions 
Ia, Ib, IIa, IIb, IIIa and IIIb were quite stable showing absolutely no 
phase separation even after 60 minutes of standing. On the other hand, the 
Emulsion IVa was found that the emulsified state was kept at least 
visually unchanged after 1 minute from termination of agitation but phase 
separation had taken place after 60 minutes of standing. Further, phase 
separation took place in the Emulsion IVb already after 1 minute of 
standing. In the Emulsions Va and Vb, no phase separation was noted after 
1 minute of standing but the emulsion had been destroyed after 60 minutes 
of standing.