U.S. patent application number 12/065788 was filed with the patent office on 2008-08-28 for hydrophilic organofunctional silicone copolymers.
This patent application is currently assigned to WACKER CHEMIE AG. Invention is credited to Kurt Stark.
Application Number | 20080207825 12/065788 |
Document ID | / |
Family ID | 37651074 |
Filed Date | 2008-08-28 |
United States Patent
Application |
20080207825 |
Kind Code |
A1 |
Stark; Kurt |
August 28, 2008 |
Hydrophilic Organofunctional Silicone Copolymers
Abstract
Hydrophilic silicone copolymers are the addition polymerization
product of an unsaturated silicone macromer, and unsaturated
polyoxyalkylene polyether, and optionally further unsaturated
addition polymerizable monomers.
Inventors: |
Stark; Kurt; (Neuhaus,
DE) |
Correspondence
Address: |
BROOKS KUSHMAN P.C.
1000 TOWN CENTER, TWENTY-SECOND FLOOR
SOUTHFIELD
MI
48075
US
|
Assignee: |
WACKER CHEMIE AG
Munich
DE
|
Family ID: |
37651074 |
Appl. No.: |
12/065788 |
Filed: |
August 30, 2006 |
PCT Filed: |
August 30, 2006 |
PCT NO: |
PCT/EP06/65802 |
371 Date: |
March 5, 2008 |
Current U.S.
Class: |
524/547 ;
526/279 |
Current CPC
Class: |
C08F 220/14 20130101;
C08F 220/08 20130101; C08F 283/12 20130101; C08F 230/08 20130101;
C08G 77/38 20130101; C08G 77/46 20130101; C08F 2/04 20130101 |
Class at
Publication: |
524/547 ;
526/279 |
International
Class: |
C08F 230/08 20060101
C08F230/08 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 8, 2005 |
DE |
10 2005 042 752.9 |
Claims
1.-17. (canceled)
18. A hydrophilic organofunctional silicone copolymer prepared by a
process comprising free radical polymerizing, neat or in solution,
a) one or more silicone macromers having at least one unsaturated
group, b) one or more polyethers having at least one unsaturated
group, and optionally, c) one or more ethylenically unsaturated
monomers different from a) and b).
19. A hydrophilic organofunctional silicone copolymer of claim 18,
wherein the silicone macromers comprise linear, branched, cyclic,
and/or three-dimensionally crosslinked polysiloxanes having at
least 5 repeating siloxane units and having at least one functional
group capable of free radical polymerization.
20. A hydrophilic organofunctional silicone copolymer of claim 18,
wherein the silicone macromers comprise silicones having the
general formula
R.sup.1.sub.aR.sub.3-aSiO(SiR.sub.2O).sub.nSiR.sub.3-aR.sup.1.sub-
.a in which R is identical or different and are monovalent,
optionally substituted alkyl or alkoxy radicals having 1 to 18 C
atoms, R.sup.1 is a polymerizable group, a is 0 or 1, at least one
a being 1, and n is from 5 to 10,000.
21. A hydrophilic organofunctional silicone copolymer of claim 18,
wherein the silicone macromers used are one or more selected from
the group consisting of
.alpha.,.omega.-divinylpolydimethylsiloxanes,
.alpha.,.omega.-di(3-acryloyloxypropyl)polydimethylsiloxanes,
.alpha.,.omega.-di(3-methacryloyloxypropyl)polydimethylsiloxanes,
.alpha.,.omega.-di(acryloyloxymethyl)polydimethylsiloxanes,
.alpha.,.omega.-di(methacryloyloxymethyl)polydimethylsiloxanes,
.alpha.-monovinylpolydimethylsiloxanes,
.alpha.-mono(3-acryloyloxypropyl)polydimethylsiloxanes,
.alpha.-mono(acryloyloxymethyl)polydimethylsiloxanes, and
.alpha.-mono(3-methacryloyloxypropyl)polydimethylsiloxanes.
22. A hydrophilic organofunctional silicone copolymer of claim 18,
wherein polyoxyalkylene polymers which have at least 3 repeating
units and bear one or more alkenyl groups suitable for addition
polymerization are used as polyethers having at least one
unsaturated group.
23. A hydrophilic organofunctional silicone copolymer of claim 22,
wherein one or more polyethers selected from the group consisting
of polyoxyethylene glycol divinyl ether, polyoxyethylene glycol
diallyl ether, polyoxypropylene glycol divinyl ether,
polyoxypropylene glycol diallyl ether, polyoxyethylene glycol
di(meth)acrylate, polyoxypropylene glycol di(meth)acrylate,
polyoxyethylene glycol monovinyl ether, polyoxyethylene glycol
monoallyl ether, polyoxyethylene glycol monoacrylate,
polyoxyethylene glycol monomethacrylate, polyoxypropylene glycol
monoacrylate, polyoxypropylene glycol monomethacrylate,
polyoxyethylenepolyoxypropylene glycol monovinyl ether,
polyoxyethylenepolyoxypropylene glycol monoallyl ether,
polyoxyethylenepolyoxypropylene glycol monoacrylate, and
polyoxyethylenepolyoxypropylene glycol monomethacrylate are used as
polyethers having at least one unsaturated group.
24. A hydrophilic organofunctional silicone copolymer of claim 18,
wherein the ethylenically unsaturated monomers comprise one or more
monomers selected from the group consisting of vinyl esters of
straight chain or branched alkylcarboxylic acids having 1 to 15 C
atoms, (meth)acrylates of alcohols having 1 to 15 C atoms,
(meth)acrylamides, vinylaromatics, olefins, dienes, vinyl halides,
vinyl ketones, vinyl ethers, polymerizable silanes, unsaturated
mono- and dicarboxylic acids and salts thereof, ethylenically
unsaturated carboxamides and carbonitriles, mono- and diesters of
fumaric and maleic acid, ethylenically unsaturated sulfonic acids
and salts thereof, ethylenically unsaturated phosphorus-containing
monomers, and cationic monomers.
25. A hydrophilic organofunctional silicone copolymer of claim 18,
wherein a) from 5 to 60% by weight of silicone macromer, b) from 30
to 90% by weight of polyether having at least one unsaturated
group, and c) optionally from 5 to 50% by weight of ethylenically
unsaturated monomer are copolymerized, the data in % by weight
being based on the total weight of the monomers a), b) and c) and
totaling 100% by weight.
26. A process for the preparation of hydrophilic organofunctional
silicone copolymers of claim 18, comprising free radical
polymerizing, net or in solution, a) one or more silicone macromers
having at least one unsaturated group, b) one or more polyethers
having at least one unsaturated group, and c) optionally one or
more ethylenically unsaturated monomers.
27. In a composition wherein a dispersant or emulsifier is
employed, the improvement comprising selecting as at least one
dispersant or emulsifier, a hydrophilic organofunctional silicone
copolymer of claim 18.
28. A cosmetic composition comprising at least one hydrophilic
organofunctional silicone copolymer of claim 18.
29. A release agent or coating comprising at least one hydrophilic
organofunctional silicone copolymer of claim 18.
30. A building material composition optionally containing cement, a
structure protecting composition, an antifoam formulation, a
hydrophilizing agent, a water repellent agent, a textile softant,
an anti-wrinkling agent, or a paper treatment agent, comprising at
least one copolymer of claim 18.
Description
[0001] The invention relates to hydrophilic organofunctional
silicone copolymers, a process for the preparation thereof and the
use thereof.
[0002] Hydrophilic organofunctional silicone copolymers are
silicone polyethers, i.e. polysiloxanes modified with polyalkylene
oxides. Such products are used in cosmetics as dimethicone
copolyols, as a protective colloid and emulsifier, as an antifoam
or in the finishing of textiles (hydrophilic softening).
[0003] The prior art to date regarding the preparation of such
compounds is to subject H-siloxanes to hydrosilylation with
unsaturated polyethers (polyalkylene oxides). The presence of a
platinum catalyst is required for this purpose, which, however,
introduces heavy metals into the end product. A further
disadvantage of this reaction is the insufficient linkage of the
unsaturated polyether to the silicone chain, so that free polyether
is still present in the product even after the reaction. The
linkage is to some extent satisfactorily possible only when the
unsaturated polyether has allyl groups, but this results in
undesired rearrangement reactions and in the formation of
byproducts. It is therefore generally necessary to employ an excess
of allylpolyether. Vinyl or (meth)acryloyl groups lead to even
poorer linkage. In the case of acryloyl or methacryloyl functions,
1,4-addition and the formation of an unstable Si--O--C bond, i.e. a
very labile and virtually unstable linkage, very frequently result.
This insufficient linkage can lead to inhomogeneities of the
product (e.g. phase separation) and to negative properties during
the use thereof.
[0004] DE 10020670 A1 describes organosiloxanyl derivatives which
have been modified with polyalkylene glycol and are obtained by
means of hydrosilylation of H-siloxanes with a vinyl-functional
polyalkylene oxide. EP 1097701 A1 and EP 1284282 A1 disclose
polyoxyalkylene-polysiloxane copolymers which are obtained by means
of hydrosilylation of H-siloxanes with unsaturated polyethers in
the presence of a metal catalyst and are used as an emulsifier or
antifoam. WO 99/10412 A1 relates to polysiloxane-polyalkylene oxide
block copolymers which are obtainable by means of hydrosilylation.
WO 02/15853 A1 describes the use of vinyl ester copolymers in
cosmetic hair formulations, the polymerization of the vinyl ester
being effected in the presence of polyether-containing compounds
which may contain silicone moieties. JP 2000-044639 relates to the
preparation of aqueous synthetic resin emulsions for coating
materials and adhesives, ethylenically unsaturated monomers being
polymerized in an aqueous medium in the presence of a macromonomer
which is obtained by reaction of a silicone having a terminal
unsaturated group and a polyalkylene glycol(meth)acrylate.
[0005] It was the object to provide hydrophilic organofunctional
silicone copolymers in a simple manner, which are distinguished by
stable and complete bonding of the hydrophilic moiety to the
silicone moiety.
[0006] The invention relates to hydrophilic organofunctional
silicone copolymers obtainable by means of free radical
polymerization, in the absence of a solvent or in solution, of one
or more silicone macromers having in each case at least one
unsaturated group and one or more polyethers having in each case at
least one unsaturated group and optionally one or more
ethylenically unsaturated monomers.
[0007] The invention furthermore relates to a process for the
preparation of hydrophilic organofunctional silicone copolymers by
means of free radical polymerization in the absence of a solvent or
in solution, of one or more silicone macromers having in each case
at least one unsaturated group and one or more polyethers having in
each case at least one unsaturated group and optionally one or more
ethylenically unsaturated monomers.
[0008] Silicone macromers suitable for the preparation of the
hydrophilic organofunctional silicone copolymers are linear,
branched, cyclic and three-dimensionally crosslinked polysiloxanes
having at least 5 repeating siloxane units and having at least one
functional group capable of free radical polymerization.
Preferably, the chain length is from 5 to 10 000 repeating siloxane
units. Ethylenically unsaturated groups, such as alkenyl groups,
are preferred as polymerizable, functional groups.
[0009] Preferred silicone macromers are silicones having the
general formula
R.sup.1.sub.aR.sub.3-aSiO(SiR.sub.2O).sub.nSiR.sub.3-aR.sup.1.sub-
.a, in which R is identical or different and is a monovalent,
optionally substituted alkyl radical or alkoxy radical having in
each case 1 to 18 C atoms, R.sup.1 is a polymerizable group, a is 0
or 1, at least one a being 1, and n is from 5 to 10 000.
[0010] In the general formula
R.sup.1.sub.aR.sub.3-aSiO(SiR.sub.2O).sub.nSiR.sub.3-aR.sup.1.sub.a
examples of radicals R are the methyl, ethyl, n-propyl, isopropyl,
1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl,
neopentyl and tert-pentyl radical, hexyl radicals, such as the
n-hexyl radical, heptyl radicals, such as the n-heptyl radical,
octyl radicals, such as the n-octyl radical, and isooctyl radicals,
such as the 2,2,4-trimethylpentyl radical, nonyl radicals, such as
the n-nonyl radical, decyl radicals, such as the n-decyl radical,
dodecyl radicals, such as the n-dodecyl radical, and octadecyl
radicals, such as the n-octadecyl radical, cycloalkyl radicals,
such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl
radicals. The radical R is preferably a monovalent hydrocarbon
radical having 1 to 6 carbon atoms, such as the methyl, ethyl,
n-propyl, isopropyl, n-butyl, sec-butyl, amyl and hexyl radical,
the methyl radical being particularly preferred.
[0011] Preferred alkoxy radicals R are those having 1 to 6 carbon
atoms, such as the methoxy, ethoxy, propoxy and n-butoxy radical,
which can optionally also be substituted by oxyalkylene radicals,
such as oxyethylene or oxymethylene radicals. The methoxy and
ethoxy radicals are particularly preferred. Said alkyl radicals and
alkoxy radicals R can optionally also be substituted, for example
by halogen, mercapto groups, epoxy functional groups, carboxyl
groups, keto groups, enamine groups, amino groups, aminoethylamino
groups, isocyanato groups, aryloxy groups, alkoxysilyl groups and
hydroxyl groups.
[0012] Suitable polymerizable groups R.sup.1 are alkenyl radicals
having 2 to 8 C atoms. Examples of such polymerizable groups are
the vinyl, allyl, butenyl, styryl and acryloyloxyalkyl and
methacryloyloxy alkyl group, the alkyl radicals containing 1 to 4 C
atoms. The vinyl group, 3-methacryloyloxypropyl,
3-acryloyloxypropyl, methacryloyloxymethyl and acryloyloxymethyl
group are preferred.
[0013] .alpha.,.omega.-Divinylpolydimethylsiloxanes,
.alpha.,.omega.-di(3-acryloyloxypropyl)polydimethylsiloxanes,
.alpha.,.omega.-di(3-methacryloyloxypropyl)polydimethylsiloxanes,
.alpha.,.omega.-di(acryloyloxymethyl)polydimethylsiloxanes,
.alpha.,.omega.-di(methacryloyloxymethyl)polydimethylsiloxanes are
preferred. In the case of the silicones only monosubstituted by
unsaturated groups, .alpha.-monovinylpolydimethylsiloxanes,
.alpha.-mono(3-acryloyloxypropyl)polydimethylsiloxanes,
.alpha.-mono(acryloyloxymethyl)polydimethylsiloxanes and
.alpha.-mono(3-methacryloyloxypropyl)polydimethylsiloxanes are
preferred. In the case of the monofunctional polydimethylsiloxanes,
an alkyl or alkoxy radical, for example a methyl or butyl or
methoxy radical is present at the other chain end.
[0014] The polymerizable silicone macromers as described in EP-A
614924 are also suitable.
[0015] .alpha.,.omega.-Divinylpolydimethylsiloxanes,
.alpha.-mono(3-methacryloyloxypropyl)polydimethylsiloxanes,
.alpha.,.omega.-di(3-acryloyloxypropyl)polydimethylsiloxanes, and
.alpha.,.omega.-di(3-methacryloyloxypropyl)polydimethylsiloxanes
are most preferred as silicone macromers.
[0016] Polyalkylene oxides which have at least 3 repeating units
and one or more alkenyl groups suitable for polymerization are
suitable as unsaturated polyethers. The unsaturated group may be a
vinyl, allyl, styryl, methacryloyl or acryloyl group and is
preferably at the chain end. The hydrophilic alkylene oxide units
in the polyether are those having 1 to 8 C atoms and may be
identical or different and may be distributed randomly or
blockwise. Preferred alkylene oxide units are ethylene oxide,
propylene oxide and butylene oxide, and ethylene oxide, propylene
oxide and mixtures thereof are particularly preferred. Chain
lengths of from 3 to 1000 repeating units are preferred.
.alpha.,.omega.-Divinylpolyethers,
.alpha.,.omega.-diallylpolyethers and
.alpha.,.omega.-di(meth)acryloylpolyethers are suitable. In the
case of the polyethers only monosubstituted by unsaturated groups,
.alpha.-monovinylpolyethers, .alpha.-monoallylpolyethers,
.alpha.-mono(meth)acryloylpolyethers are preferred. In the case of
the monofunctional polyethers, an alkyl radical having 1 to 6 C
atoms or a hydroxyl group is at the other chain end.
[0017] Polyethylene glycol divinyl ether, polyethylene glycol
diallyl ether, polypropylene glycol divinyl ether, polypropylene
glycol diallyl ether, polyethylene glycol di(meth)acrylate,
polypropylene glycol di(meth)acrylate, polyethylene glycol
monovinyl ether, polyethylene glycol monoallyl ether, polyethylene
glycol monoacrylate, polyethylene glycol monomethacrylate,
polypropylene glycol monoacrylate, polypropylene glycol
monoacrylate, polypropylene glycol monomethacrylate, polyethylene
glycol polypropylene glycol monovinyl ether, polyethylene glycol
polypropylene glycol monoallyl ether, polyethylene glycol
polypropylene glycol monoacrylate or polyethylene glycol
polypropylene glycol monomethacrylate is most preferred as
unsaturated polyethers.
[0018] One or more monomers from the group consisting of vinyl
esters of straight-chain or branched alkylcarboxylic acids having 1
to 15 C atoms, (meth)acrylates of alcohols having 1 to 15 C atoms,
(meth)acrylamides, vinylaromatics, olefins, dienes, vinyl halides,
vinyl ketones, vinyl ethers, polymerizable silanes, unsaturated
mono- and dicarboxylic acids or salts thereof, ethylenically
unsaturated carboxamides and carbonitriles, mono- and diesters of
fumaric and maleic acid, ethylenically unsaturated sulfonic acids
or salts thereof, ethylenically unsaturated phosphorus-containing
monomers and cationic monomers are suitable as ethylenically
unsaturated monomers.
[0019] Suitable vinyl esters are vinyl esters of straight-chain or
branched carboxylic acids having 1 to 15 C atoms. Preferred vinyl
esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl
2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl
pivalate and vinyl esters of .alpha.-branched monocarboxylic acids
having 5 to 13 C atoms, for example VeoVa9.sup.R or VeoVa10.sup.R
(trade names of Resolution Performance Products). Vinyl acetate is
particularly preferred.
[0020] Suitable monomers from the group consisting of the esters of
acrylic acid or methacrylic acid are esters of straight-chain or
branched alcohols having 1 to 15 C atoms. Preferred methacrylates
or acrylates are methyl acrylate, methyl methacrylate, ethyl
acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate,
n-, iso- and tert-butyl acrylate, n-, iso- and tert-butyl
methacrylate, 2-ethylhexyl acrylate and norbornyl acrylate. Methyl
acrylate, methyl methacrylate, n-, iso- and tert-butyl acrylate,
2-ethylhexyl acrylate and norbornyl acrylate are particularly
preferred.
[0021] Suitable dienes are 1,3-butadiene and isoprene. Examples of
copolymerizable olefins are ethene and propene. Styrene and
vinyltoluene can be copolymerized as vinylaromatics. From the group
consisting of the vinyl halides, vinyl chloride, vinylidine
chloride or vinyl fluoride are usually used, preferably vinyl
chloride.
[0022] Suitable ethylenically unsaturated mono- and dicarboxylic
acids or salts thereof are, for example, crotonic acid, itaconic
acid, acrylic acid, methacrylic acid, fumaric acid and maleic acid.
Suitable ethylenically unsaturated carboxamides and carbonitriles
are acrylamide and acrylonitrile. Diethyl and diisopropyl esters
and maleic anhydride can be used as mono- and diesters of fumaric
acid and maleic acid. Ethylenically unsaturated sulfonic acids and
salts thereof are preferably vinylsulfonic acid and
2-acrylamido-2-methylpropanesulfonic acid. Vinyl phosphonate can be
used as an ethylenically unsaturated phosphorus-containing monomer.
For example, diallyldimethylammonium chloride (DADMAC),
3-trimethylammoniumpropyl(meth)acrylamide chloride (MAPTAC) and
2-trimethylammoniumethyl(meth)acrylate chloride are used as
cationic monomers.
[0023] Suitable polymerizable silanes are .gamma.-acryloyl- and
.gamma.-methacryloyloxypropyltri(alkoxy)silanes,
.alpha.-(meth)acryloyloxymethyltri(alkoxy)silanes,
.gamma.-(meth)acryloyloxypropylmethyldi(alkoxy)silanes,
vinylalkyldi(alkoxy)silanes and vinyltri(alkoxy)silanes, it being
possible to use, for example, methoxy, ethoxy, methoxyethylene,
ethoxyethylene, methoxypropylene glycol ether and ethoxypropylene
glycol ether radicals as alkoxy groups. Examples of these are
vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane,
vinyltriisopropoxysilane, vinyltris(1-methoxy)isopropoxysilane,
vinyltributoxysilane, vinyltriacetoxysilane,
3-methacryloyloxypropyltrimethoxysilane,
3-methacryloyloxypropylmethyldimethoxysilane,
methacryloyloxymethyltrimethoxysilane,
3-methacryloyloxypropyltris(2-methoxyethoxy)silane,
vinyltrichorosilane, vinylmethyldichlorosilane,
vinyltris(2-methoxyethoxy)silane, trisacetoxyvinylsilane and
3-(triethoxysilyl)propyl(succinic anhydride)silane.
[0024] Further suitable monomers are functionalized (meth)acrylates
and functionalized allyl or vinyl ethers, in particular
epoxy-functional ones, such as glycidyl acrylate, glycidyl
methacrylate, allyl glycidyl ether or vinyl glycidyl ether, or
hydroxyalkyl-functional ones, such as hydroxyethyl(meth)acrylate,
or substituted or unsubstituted aminoalkyl(meth)acrylates, or
cyclic monomers, such as N-vinylpyrrolidone; or N-vinylformamide or
N-vinylacetamide.
[0025] Further examples of suitable monomers are pre-crosslinking
comonomers, such as polyethylenically unsaturated comonomers, for
example divinyl adipate, divinylbenzene, diallyl maleate, allyl
methacrylate, butanediol diacrylate or triallyl cyanurate, or
post-crosslinking comonomers, for example acrylamidoglycolic acid
(AGA), methyl methylacrylamidoglycolate (MAGME), N-methylol
acrylamide (NMA), N-methylol-methacrylamide, N-methylolallyl
carbamate, alkyl ethers, such as the isobutoxy ether or ester of
N-methylolacrylamide, of N-methylolmethacrylamide or of
N-methylolallyl carbamate.
[0026] Use of abovementioned organic monomers leads to a
multiplicity of positive properties. Thus--owing to their high
mobility--they act as effective additional bridging aids in the
coupling between the silicone macromer and the unsaturated
polyether. Moreover, the hydrophilic and hydrophobic properties of
the organofunctional silicone copolymer can additionally be
controlled by the choice of certain monomers. It is also possible
to introduce (both anionic and cationic) charges into the
hydrophilic organofunctional silicone copolymer through the organic
monomers. Furthermore, by the introduction and use of monomers, the
adhesion to the substrates is substantially increased, particularly
if the monomers have functional groups. If monomers which carry
different functional groups which can react with one another and
form a bond are used, the hydrophilic organofunctional silicone
copolymer can also be crosslinked. This has the advantages that the
strength can be increased and, on use in the textile sector, it is
also possible to obtain, for example, high permanence to washing.
The use of organic monomers in addition to the silicone macromers
and the unsaturated hydrophilic polyethers is therefore very
advisable.
[0027] In general, from 1 to 99% by weight, preferably from 5 to
60% by weight, particularly preferably from 10 to 45% by weight, of
silicone macromer are copolymerized. In general from 1 to 99% by
weight, preferably from 30 to 90% by weight, particularly
preferably from 50 to 80% by weight, of unsaturated polyether are
copolymerized. In general, from 0 to 98% by weight, preferably from
5 to 50% by weight, particularly preferably from 10 to 30% by
weight, of ethylenically unsaturated monomer are copolymerized. The
data in % by weight are based in each case on the total weight of
the monomers (silicone macromer, unsaturated polyether,
ethylenically unsaturated monomer) and in each case sum to 100% by
weight.
[0028] The hydrophilic organofunctional silicone copolymers are
prepared by means of polymerization in the absence of a solvent or
in a solvent, in the presence of free radical initiators. The
polymerization temperature is in general from 20.degree. C. to
150.degree. C., preferably from 40.degree. C. to 90.degree. C. In
general, polymerization is effected at atmospheric pressure. In the
copolymerization of monomers which are gaseous at room temperature,
such as ethylene, the procedure is carried out under pressure, in
general from 1 to 100 bar. In general, the polymerization is
carried out up to a solids content of from 10 to 100%, preferably
up to a solids content of from 20 to 60%.
[0029] Suitable free radical initiators are oil-soluble initiators,
such as tert-butyl peroxy-2-ethylhexanoate, tert-butyl
peroxypivalate, tert-butyl peroxyneodecanoate, dibenzoyl peroxide,
tert-amyl peroxypivalate, di(2-ethylhexyl)peroxydicarbonate,
1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane and
di(4-tert-butylcyclohexyl)peroxydicarbonate. Azo initiators, such
as azobisisobutyronitrile, are also suitable. The initiators are
generally used in an amount of from 0.005 to 5.0% by weight,
preferably from 0.1 to 3.0% by weight, based on total monomer.
[0030] The adjustment of the molecular weight and of the degree of
polymerization is known to the person skilled in the art. This can
be effected, for example, by addition of regulators, by the solvent
content, by variation of the initiator concentration and by
variation of the temperature. Regulators or chain-transfer agents
are, for example, acetaldehyde, butyraldehyde or compounds
containing mercapto groups, such as dodecyl mercaptan.
[0031] Suitable organic solvents are, for example, tetrahydrofuran
(THF), chloroform, petroleum ether, heptane, cyclohexane, ethyl
acetate, methyl acetate, isopropanol, ethanol, methanol,
tert-butanol, acetone, toluene, benzene, methyl ethyl ketone,
diethyl ether or p-dioxane. Another suitable solvent is water, but
only as a mixture with suitable organic solvents. Abovementioned
solvents can be used alone or as mixtures with various ratios for
the polymerization. Preferred solvents are ethyl acetate, methyl
acetate, acetone, methyl ethyl ketone, ethanol and isopropanol.
Solvent mixtures with isopropanol are particularly preferred; a
mixture of ethyl acetate and isopropanol is most preferred.
[0032] The polymerization can be carried out by initially
introducing all or individual constituents of the reaction mixture
or by partly initially introducing and subsequently metering the or
individual constituents of the reaction mixture, or by the metering
method without initial introduction. In a preferred procedure, from
3 to 40% by weight, based on the total weight of the monomers, of a
mixture of the monomers a) (=silicone macromer), b) (=unsaturated
polyether) and optionally c) (=organic monomer) are initially
introduced in the desired ratios and the remainder of the monomers
a), b) and optionally c) is metered in as a mixture. It is
furthermore preferable initially to introduce a portion of the
initiator, preferably from 3 to 50% by weight, and to meter in the
remainder. Particularly preferably, the monomers a), b) and
optionally c) are added so that their ratio always remains constant
at any time during the polymerization.
[0033] After the end of the polymerization, postpolymerization can
be effected for removal of residual monomers, using known methods.
Volatile residual monomers and further volatile constituents can
also be removed by means of distillation, preferably under reduced
pressure.
[0034] The working-up of the hydrophilic organofunctional silicone
copolymers is effected according to composition and hence according
to their properties.
[0035] The hydrophilic organofunctional silicone copolymers can be
isolated as 100% system, i.e. the total solvent is removed. It is
also possible to use the hydrophilic organofunctional silicone
copolymers in solution. In this case, either the solvent (mixture)
already used for the polymerization can be used or an exchange of
solvent takes place. The latter variant is preferred, for example,
in the case of water-soluble or water-dispersible hydrophilic
organofunctional silicone copolymers. Here, the organic solvent is
distilled off and gradually replaced by water until the total
solvent has been exchanged for water.
[0036] Owing to the wide range of possibilities for the composition
of the hydrophilic organofunctional silicone copolymers according
to the invention and their unique combination of hydrophilic
polyether blocks in addition to hydrophobic silicone chains, these
products are very suitable for very many applications:
[0037] The hydrophilic organofunctional silicone copolymers are
used as dispersants and emulsifiers; preferably as stabilizers or
protective colloid. Thus, for example, silicone oil emulsions can
be stabilized therewith, or the stability of polyurethane foams is
dramatically increased therewith. In the case of emulsion
polymerization, too, the hydrophilic organofunctional silicone
copolymers can be added as a stabilizer or protective colloid.
[0038] The hydrophilic organofunctional silicone copolymers are
also suitable as a constituent or additive for cosmetics, such as
hairsprays, creams, lotions, gels, hair conditioner or hair setting
composition.
[0039] The hydrophilic organofunctional silicone copolymers are
furthermore suitable as release agents and coating materials, for
example for the production of abhesive (non-tacky) coverings in the
release coating sector. They are also suitable for the coating of
textile, paper, wood, plastics or sheets and metals, for example as
a protective coating or as an anti-fouling coating.
[0040] Further fields of use are in the building sector as an
additive in cement-containing and non-cement-containing systems and
for the protection of structures, in particular for the production
of weather-resistant coatings or sealing compounds.
[0041] The hydrophilic organofunctional silicone copolymers are
very advantageously also used in the polish sector. The hydrophilic
organofunctional silicone copolymers are also used as additives in
antifoam formulations since--depending on composition--they may
have an antifoam effect. In this context, the use of the
hydrophilic organofunctional silicone copolymers as antifoams in
paints and finishes may also be mentioned. The hydrophilic
organofunctional silicone copolymers are--depending on composition
and depending on the system where they are used--also very suitable
as modifiers, hydrophilizing agents or water repellants.
[0042] The hydrophilic organofunctional silicone copolymers are,
however, particularly suitable as hydrophilizing softeners for
textiles. Synthetically produced fibers (such as polyester,
polyamide or polyolefin fibers) are often so hydrophobic that no
water or no perspiration can be absorbed. This very unpleasant
property for the wearer of such textiles can be completely
eliminated by treatment of the textile fibers or of the textiles
with the hydrophilic organofunctional silicone copolymers according
to the invention. The textiles are rendered hydrophilic thereby,
perspiration can be absorbed and furthermore the textiles acquire a
pleasant soft handle. The hydrophilic organofunctional silicone
copolymers are also suitable as an anti-wrinkling agent in the
textile sector, i.e. the wrinkling of the textiles is avoided
thereby. The hydrophilic organofunctional silicone copolymers are
recommended for the treatment of paper, for example in the tissue
sector, where they ensure a soft effect on a paper tissue.
[0043] The following examples serve for further explanation of the
invention without limiting it in any way:
EXAMPLE 1
[0044] 1100.00 g of ethyl acetate, 176.51 g of isopropanol, 22.89 g
of polyethylene glycol polypropylene glycol monomethacrylate having
20 EO units and 20 PO units, 17.17 g of methyl acrylate and 17.17 g
of .alpha.,.omega.-di(3-methacryloyloxypropyl)polydimethylsiloxane
having a chain length (number of SiOMe.sub.2 repeating units) of
135 and 3.05 g of PPV (tert-butyl perpivalate, 75% strength
solution in aliphatics) were initially introduced into a 3 l glass
pot having an anchor stirrer, reflux condenser and metering
apparatuses. The initially introduced mixture was then heated to
70.degree. C. at a stirrer speed of 200 rpm. After the internal
temperature of 70.degree. C. had been reached, the metering of
initiator (85.83 g of ethyl acetate and 12.21 g of PPV (75%
strength solution in aliphatics) was started at a rate of 21.37
ml/h. Ten minutes after the start of the metering of initiator,
monomer metering 1 (77.24 g of methyl acrylate and 154.49 g of
.alpha.,.omega.-di(3-methacryoyloxypropyl)polydimethylsiloxane
having a chain length (number of SiOMe.sub.2 repeating units) of
135) was started at a rate of 60.54 ml/h, and monomer metering 2
(205.98 g of polyethylene glycol polypropylene glycol
monomethacrylate) having 20 EO units and 20 PO units and 77.24 g of
methyl acrylate) was started at a rate of 72.26 ml/h. The metering
of initiator extended over a period of 310 min and the two monomer
meterings ran for 240 minutes (in succession). After the end of the
meterings postpolymerization was effected for a further 60 min at
70.degree. C. The polymer solution obtained was then completely
evaporated down, i.e. the solvent was completely removed. A
hydrophilic organofunctional silicone copolymer remained behind in
the form of an almost transparent oil.
[0045] Analyses of the hydrophilic organofunctional silicone
copolymer (pure form): solids content: 99.9%, viscosity (Hoppler,
10% strength solution in ethyl acetate)=2.4 mPas, DSC measurement:
no melting point/crystallization point, glass transition
temperature Tg=-60.4.degree. C.; weight average molecular weight
from GPC: M.sub.W=133 800 g/mol.
[0046] 1H-NMR spectroscopy: No free double bonds were detectable.
The composition of the hydrophilic organofunctional silicone
copolymer determined with the aid of NMR corresponded within the
accuracy of measurement to the composition of the starting
materials (about 40% by weight proportion of polyether, about 30%
by weight proportion of silicone, about 30% by weight proportion of
polymethyl acrylate).
[0047] Properties of an aqueous solution of the hydrophilic
organofunctional silicone copolymer: solids content: 34.22%;
colloidal turbid solution; Brookfield viscosity 20 (spindle 2): 83
mPas; mean particle size (Nanosizer): 165 nm; Coulter: Dn (number
average particle diameter) 0.091 .mu.m; Dv (volume-average particle
diameter) 0.145 .mu.m; surface area 47.8 m.sup.2; static surface
tension .sigma. of a 1% strength aqueous solution: 27.5 mN/m.
EXAMPLE 2
[0048] 431.47 g of ethyl acetate, 208.00 g of isopropanol, 20.04 g
of .alpha.,.omega.-di(3-methacryloyloxypropyl)polydimethylsiloxane
having an average chain length of 168, 21.05 g of polyethylene
glycol monomethacrylate having 10 EO, 21.05 g of polypropylene
glycol monomethacrylate having 9 PO, 14.03 g of hydroxyethyl
acrylate (HEA), 4.01 g of glycidyl methacrylate (GMA) and 5.92 g of
PPV (75% strength solution in aliphatics) were initially introduced
into a stirred 3 l glass pot having an anchor stirrer, reflux
condenser and metering apparatuses. The initially introduced
mixture was then heated to 70.degree. C. at a stirrer speed of 200
rpm. After the internal temperature of 70.degree. C. had been
reached, metering of the initiator (53.87 g of methyl acetate and
22.97 g of PPV (75% strength solution in aliphatics)) was started
at a rate of 17.35 ml/h. Ten minutes after the start of the
metering of the initiator, the monomer metering (160.52 g of
.alpha.,.omega.-di(3-methacryoyloxypropyl)poly-dimethylsiloxane
having an average chain length of 168, 168.55 g of polyethylene
glycol monomethacrylate having 10 EO, 168.55 g of polypropylene
glycol monomethacrylate having 9 PO, 112.37 g of hydroxyethyl
acrylate (HEA) and 32.10 g of glycidyl methacrylate (GMA)) was
started at a rate of 160.52 g/h. The metering of initiator extended
over a period of 310 minutes, and the monomer metering ran for 240
minutes. After the end of the meterings, postpolymerization was
effected for a further 60 minutes at 70.degree. C. The polymer
solution obtained was then completely evaporated down, i.e. the
solvent was completely removed. A hydrophilic organofunctional
silicone copolymer remained behind in the form of an almost
transparent oil.
[0049] Analyses of the hydrophilic organofunctional silicone
copolymer (pure form): Solids content: 99.8%, viscosity (Hoppler,
10% strength solution in ethyl acetate)=2.6 mPas, DSC measurement:
no melting point/crystallization point, glass transition
temperature Tg=-40.6.degree. C.; weight average molecular weight
from GPC: M.sub.W=120 000 g/mol.
[0050] 1H-NMR spectroscopy: No free double bonds were detectable.
The composition of the hydrophilic organofunctional silicone
copolymer determined with the aid of NMR corresponded within the
accuracy of measurement to the composition of the starting
materials.
[0051] Properties of an aqueous solution of the hydrophilic
organofunctional silicone copolymers: solids content: 30.5%;
colloidal slightly turbid solution (almost transparent); Brookfield
viscosity 20 (spindle 2): 96 mPas; mean particle size (Nanosizer):
121 nm; Coulter: Dn 0.041 .mu.m; Dv 0.105 .mu.m; surface area 69.8
m.sup.2;
[0052] Static surface tension .sigma. of a 1% strength aqueous
solution: 31.8 mN/m.
[0053] Remark: The hydrophilic organofunctional silicone copolymer
could be very readily dissolved/dispersed in water.
EXAMPLE 3
[0054] 730.36 g of ethyl acetate, 117.68 g of isopropanol, 152.58 g
of polyglycol ether having 20 EO and 20 PO and functionalized with
a terminal allyl group, 19.07 g of vinyl acetate, 114.43 g of
.alpha.,.omega.-divinyl-functionalized polydimethylsiloxane having
about 133 SiOMe.sub.2 repeating units and 2.03 g of PPV (75%
strength solution in aliphatics) were initially introduced into a 2
l stirred glass pot having an anchor stirrer, reflux condenser and
metering apparatuses. The initially introduced mixture was then
heated to 70.degree. C. at a stirrer speed of 200 rpm. After the
internal temperature of 70.degree. C. had been reached, the
metering of initiator (57.22 g of ethyl acetate and 8.14 g of PPV
(75% strength solution in aliphatics)) was started at a rate of
14.25 ml/h. Ten minutes after the start of the metering of the
initiator, the monomer metering (95.36 g of vinyl acetate) was
started at a rate of 25.64 ml/h. The metering of initiator extended
over a period of 310 minutes, and the monomer metering ran for 240
minutes. After the end of the meterings, postpolymerization was
effected for a further 60 minutes at 70.degree. C. The polymer
solution obtained was then completely evaporated down, i.e. the
solvent was completely removed. A hydrophilic organofunctional
silicone copolymer remained behind in the form of a turbid,
slightly transparent oil.
[0055] Analyses of the hydrophilic organofunctional silicone
copolymer (pure form): Solids content: 99.8%, DSC measurement: no
melting point/crystallization point, glass transition temperature
Tg=-55.9.degree. C.; weight average molecular weight from GPC:
M.sub.W=18 700 g/mol.
[0056] 1H-NMR spectroscopy: No free double bonds were detectable.
The composition of the hydrophilic organofunctional silicone
copolymer determined with the aid of NMR corresponded within the
accuracy of measurement to the composition of the starting
materials. Properties of an aqueous solution of the hydrophilic
organofunctional silicone copolymer: solids content: 28.1%;
colloidal turbid solution; Brookfield viscosity 20 (spindle 2): 20
mPas; mean particle size (Nanosizer): 126 nm; Coulter: Dn 0.074
.mu.m; Dv 0.100 .mu.m; surface area 67.5 m.sup.2;
[0057] Static surface tension .sigma. of a 1% strength aqueous
solution: 28.8 mN/m.
EXAMPLE 4
[0058] 733.36 g of ethyl acetate, 118.16 g of isopropanol, 153.21 g
of polyglycol ether having 20 EO and 20 PO and functionalized with
a terminal allyl group, 25.55 g of vinyl acetate, 76.6 g of
.alpha.,.omega.-divinyl-functionalized polydimethylsiloxane having
about 100 SiOMe.sub.2 repeating units and 2.04 g of PPV (75%
strength solution in aliphatics) were initially introduced into a 2
l stirred glass pot having an anchor stirrer, reflux condenser and
metering apparatuses. The initially introduced mixture was then
heated to 70.degree. C. at a stirrer speed of 200 rpm. After the
internal temperature of 70.degree. C. had been reached, the
metering of initiator (57.45 g of ethyl acetate and 8.17 g of PPV
(75% strength solution in aliphatics)) was started at a rate of
14.31 ml/h. Ten minutes after the start of the metering of the
initiator, the monomer metering (127.66 g of vinyl acetate) was
started at a rate of 34.32 ml/h. The metering of initiator extended
over a period of 310 minutes, and the monomer metering ran for 240
minutes. After the end of the meterings, postpolymerization was
effected for a further 60 minutes at 70.degree. C. The polymer
solution obtained was then completely evaporated down, i.e. the
solvent was completely removed. A hydrophilic organofunctional
silicone copolymer remained behind in the form of a turbid oil.
[0059] Analyses of the hydrophilic organofunctional silicone
copolymer (pure form): Solids content: 99.9%, DSC measurement: no
melting point/crystallization point, glass transition temperature
Tg=-49.6.degree. C.; weight average molecular weight from GPC:
M.sub.W=14 400 g/mol.
[0060] 1H-NMR spectroscopy: No free double bonds were detectable.
The composition of the hydrophilic organofunctional silicone
copolymer determined with the aid of NMR corresponded within the
accuracy of measurement to the composition of the starting
materials. Properties of an aqueous solution of the hydrophilic
organofunctional silicone copolymer: solids content: 28.8%;
colloidal turbid solution; Brookfield viscosity 20 (spindle 2): 24
mPas; mean particle size (Nanosizer): 165 nm; Coulter: Dn 0.088
.mu.m; Dv 0.138 .mu.m; surface area 50.3 m.sup.2;
[0061] Static surface tension .sigma. of a 1% strength aqueous
solution: 29.7 mN/m.
EXAMPLE 5
[0062] 721.49 g of ethyl acetate, 116.25 g of isopropanol, 301.45 g
of polyglycol ether having 20 EO and 20 PO and functionalized with
a terminal allyl group, 75.36 g of
.alpha.,.omega.-divinyl-functionalized polydimethylsiloxane having
about 133 SiOMe.sub.2 repeating units and 2.01 g of PPV (75%
strength solution in aliphatics) were initially introduced into a 2
l stirred glass pot having an anchor stirrer, reflux condenser and
metering apparatuses. The initially introduced mixture was then
heated to 70.degree. C. at a stirrer speed of 200 rpm. After the
internal temperature of 70.degree. C. had been reached, the
metering of initiator (56.52 g of ethyl acetate and 8.04 g of PPV
(75% strength solution in aliphatics)) was started at a rate of
14.07 ml/h. The metering of initiator extended over a period of 310
minutes. After the end of the meterings, postpolymerization was
effected for a further 60 minutes at 70.degree. C. The polymer
solution obtained was then completely evaporated down, i.e. the
solvent was completely removed. A hydrophilic organofunctional
silicone copolymer remained behind in the form of a turbid oil
(slight transparency).
[0063] Analyses of the hydrophilic organofunctional silicone
copolymer (pure form): Solids content: 99.7%, DSC measurement: no
melting point/crystallization point, glass transition temperature
Tg=-71.5.degree. C.; weight average molecular weight from GPC:
M.sub.W=10 000 g/mol.
[0064] 1H-NMR spectroscopy: The double bonds of the unsaturated
silicone macromer were completely incorporated by polymerization.
The composition of the hydrophilic organofunctional silicone
copolymer determined with the aid of NMR corresponded within the
accuracy of measurement to the composition of the starting
materials. Properties of an aqueous solution of the hydrophilic
organofunctional silicone copolymer: solids content: 28.6%; milky
turbid solution; Brookfield viscosity 20 (spindle 2): 17 mPas; mean
particle size (Nanosizer): 247 nm; Coulter: Dn 0.118 .mu.m; Dv
1.178 .mu.m; surface area 17.9 m.sup.2;
[0065] Static surface tension .sigma. of a 1% strength aqueous
solution: 34.6 mN/m.
[0066] Remark: Stable solution or dispersion; generally good
solubility/dispersiblity in water.
EXAMPLE 6
[0067] 667.39 g of ethyl acetate, 116.67 g of isopropanol, 245.82 g
of polyglycol ether having 20 EO and 20 PO and functionalized with
a terminal allyl group, 0.95 g of acrylic acid, 113.46 g of
.alpha.,.omega.-divinyl-functionalized polydimethylsiloxane having
about 133 SiOMe.sub.2 repeating units and 2.02 g of PPV (75%
strength solution in aliphatics) were initially introduced into a 2
l stirred glass pot having an anchor stirrer, reflux condenser and
metering apparatuses. The initially introduced mixture was then
heated to 70.degree. C. at a stirrer speed of 200 rpm. After the
internal temperature of 70.degree. C. had been reached, the
metering of initiator (56.73 g of ethyl acetate and 8.07 g of PPV
(75% strength solution in aliphatics)) was started at a rate of
14.13 ml/h. Ten minutes after the start of the metering of the
initiator, the monomer metering (17.96 g of acrylic acid and 56.73
g of ethyl acetate) was started at a rate of 20.01 ml/h. The
metering of initiator extended over a period of 310 minutes, and
the monomer metering ran for 240 minutes. After the end of the
meterings, postpolymerization was effected for a further 60 minutes
at 70.degree. C. The polymer solution obtained was then completely
evaporated down, i.e. the solvent was completely removed. A
hydrophilic organofunctional silicone copolymer remained behind in
the form of a turbid oil.
[0068] Analyses of the hydrophilic organofunctional silicone
copolymer (pure form): Solids content: 99.8%, DSC measurement: no
melting point/crystallization point, glass transition temperature
Tg=-68.2.degree. C.; weight average molecular weight from GPC:
M.sub.W=17 500 g/mol.
[0069] 1H-NMR spectroscopy: No free double bonds were detectable.
The composition of the hydrophilic organofunctional silicone
copolymer determined with the aid of NMR corresponded within the
accuracy of measurement to the composition of the starting
materials. Properties of an aqueous solution of the hydrophilic
organofunctional silicone copolymer: solids content: 25.2%;
colloidal slightly turbid solution; Brookfield viscosity 20
(spindle 2): 15 mPas; mean particle size (Nanosizer): 135 nm;
Coulter: Dn 0.090 .mu.m; Dv 0.117 .mu.m; surface area 67.9
m.sup.2;
[0070] Static surface tension .sigma. of a 1% strength aqueous
solution: 38.6 mN/m.
[0071] Remark: Stable solution or dispersion; generally very good
solubility/dispersibility in water.
EXAMPLE 7
[0072] The procedure was as in example 6, except that, instead of
acrylic acid, the same amount of diallyldimethylammonium chloride
(DADMAC) was used in the form of a 64% strength solution in
water.
[0073] A hydrophilic organofunctional silicone copolymer remained
behind in the form of a turbid oil.
[0074] Analysis of the hydrophilic organofunctional silicone
copolymer (pure form): Solids content: 99.7%, DSC measurement: no
melting point/crystallization point, glass transition temperature
Tg=-71.5.degree. C.; weight average molecular weight from GPC:
M.sub.W=21 600 g/mol.
[0075] Properties of an aqueous solution of the hydrophilic
organofunctional silicone copolymer: Solids content: 30.0%;
colloidal turbid solution; Brookfield viscosity 20 (spindle 2): 16
mPas; mean particle size (Nanosizer): 301 nm; Coulter: Dn 0.267
.mu.m; Dv 0.443 .mu.m; surface area 67.9 m.sup.2;
[0076] Static surface tension .sigma. of a 1% strength aqueous
solution: 16.7 mN/m.
[0077] Remark: Stable solution or dispersion; generally very good
solubility/dispersibility in water.
EXAMPLE 8
[0078] 842.92 g of ethyl acetate, 131.52 g of isopropanol, 198.7 g
of polyglycol ether having 20 EO and 20 PO and functionalized with
a terminal allyl group, 24.84 g of
.alpha.,.omega.-divinyl-functionalized polydimethylsiloxane having
about 177 SiOMe.sub.2 repeating units and 1.32 g of PPV (75%
strength solution in aliphatics) were initially introduced into a 2
l stirred glass pot having an anchor stirrer, reflux condenser and
metering apparatuses. The initially introduced mixture was then
heated to 70.degree. C. at a stirrer speed of 200 rpm. After the
internal temperature of 70.degree. C. had been reached, the
metering of initiator (37.26 g of ethyl acetate and 5.30 g of PPV
(75% strength solution in aliphatics)) was started at a rate of
9.28 ml/h. T minutes after the start of the metering of the
initiator, the monomer metering (24.84 g of
.alpha.,.omega.-divinyl-functionalized polydimethylsiloxane having
about 177 SiOMe.sub.2 repeating units) was started at a rate of
8.28 ml/h. The metering of initiator extended over a period of 310
minutes, and the monomer metering ran for 180 minutes. After the
end of the meterings, postpolymerization was effected for a further
60 minutes at 70.degree. C. The polymer solution obtained was then
completely evaporated down, i.e. the solvent was completely
removed. A hydrophilic organofunctional silicone copolymer remained
behind in the form of an almost transparent oil.
[0079] Analyses of the hydrophilic organofunctional silicone
copolymer (pure form): Solids content: 99.9%, DSC measurement: no
melting point/crystallization point, glass transition temperature
Tg=-71.4.degree. C.; weight average molecular weight from GPC:
M.sub.W=11 200 g/mol.
[0080] 1H-NMR spectroscopy: No free double bonds were detectable.
The composition of the hydrophilic organofunctional silicone
copolymer determined with the aid of NMR corresponded within the
accuracy of measurement to the composition of the starting
materials. Properties of an aqueous solution of the hydrophilic
organofunctional silicone copolymer: solids content: 28.4%; almost
transparent solution (minimum colloidal turbidity); Brookfield
viscosity 20 (spindle 2): 19 mPas; mean particle size (Nanosizer):
168 nm; Coulter: Dn 0.082 .mu.m; Dv 0.13 .mu.m; surface area 54.3
m.sup.2;
[0081] Static surface tension .sigma. of a 1% strength aqueous
solution: 34.5 mN/m.
[0082] Remark: Stable solution or dispersion; generally very good
solubility/dispersibility in water.
EXAMPLE 9
[0083] 32.99 g of butyraldehyde, 577.37 g of polyglycol ether
having 20 EO and 20 PO and functionalized with a terminal allyl
group, 49.49 g of .alpha.,.omega.-divinyl-functionalized
polydimethylsiloxane having about 133 SiOMe.sub.2 repeating units,
4.12 g of vinyl acetate and 2.20 g of PPV (75% strength solution in
aliphatics) were initially introduced into a stirred 2 l glass pot
having an anchor stirrer, reflux condenser and metering
apparatuses. The initially introduced mixture was then heated to
70.degree. C. at a stirrer speed of 200 rpm. After the internal
temperature of 70.degree. C. had been reached, the metering of the
initiator (19.8 g of PPV (75% strength solution in aliphatics)) was
started at a rate of 4.89 ml/h. Ten minutes after the start of the
metering of the initiator, monomer metering 1 (197.96 g of
.alpha.,.omega.-divinyl-functionalized polydimethylsiloxane having
about 133 SiOMe.sub.2 repeating units) was started at a rate of
68.03 ml/h and monomer metering 2 (49.49 g of butyraldehyde and
37.12 g of vinyl acetate) was started at a rate of 34.37 ml/h. The
metering of the initiator extended over a period of 300 minutes,
and the two monomer meterings ran for 180 minutes. After the end of
the metering of the initiator, postpolymerization was effected for
a further 60 minutes at 70.degree. C. Finally, distillation was
effected in vacuo in order to expel the volatile fractions--such as
the stabilizer of the initiator. The hydrophilic organofunctional
silicone copolymer remained behind in the form of a turbid oil.
[0084] Analyses of the hydrophilic organofunctional silicone
copolymer (pure form): Solids content: 99.8%, DSC measurement: no
melting point/crystallization point, glass transition temperature
Tg=-67.8.degree. C.; weight average molecular weight from GPC:
M.sub.W=15 900 g/mol.
[0085] 1H-NMR spectroscopy: No free double bonds were detectable.
The composition of the hydrophilic organofunctional silicone
copolymer determined with the aid of NMR corresponded within the
accuracy of measurement to the composition of the starting
materials. The solubility in water was not investigated.
EXAMPLE 10
[0086] 344.39 g of ethyl acetate, 69.14 g of isopropanol, 51.36 g
of polyglycol ether having 20 EO and 20 PO and functionalized with
a terminal allyl group, 15.80 g of
.alpha.,.omega.-divinyl-functionalized polydimethylsiloxane having
about 177 SiOMe.sub.2 repeating units, 11.85 g of vinyl acetate and
4.21 g of PPV (75% strength solution in aliphatics) were initially
introduced into a stirred 2 l glass pot having an anchor stirrer,
reflux condenser and metering apparatuses. The initially introduced
mixture was then heated to 70.degree. C. at a stirrer speed of 200
rpm. After the internal temperature of 70.degree. C. had been
reached, the metering of the initiator (118.53 g of ethyl acetate
and 16.86 g of PPV (75% strength solution in aliphatics)) was
started at a rate of 29.51 ml/h. Ten minutes after the start of the
metering of the initiator, monomer metering 1 (142.23 g of
.alpha.,.omega.-divinyl-functionalized polydimethylsiloxane having
about 177 SiOMe.sub.2 repeating units and 106.68 g of vinyl
acetate) was started at a rate of 64.24 ml/h and monomer metering 2
(462.26 g of polyglycol ether having 20 EO and 20 PO and
functionalized with a terminal allyl group) was started at a rate
of 115.56 ml/h. The metering of the initiator extended over a
period of 310 minutes, and the two monomer meterings ran for 240
minutes. After the end of the metering of the initiator,
postpolymerization was effected for a further 60 minutes at
70.degree. C. The polymer solution obtained was then completely
evaporated down, i.e. the solvent was completely removed. A
hydrophilic organofunctional silicon copolymer remained behind in
the form of a slightly turbid oil.
[0087] Analyses of the hydrophilic organofunctional silicone
copolymer (pure form): Solids content: 99.8%, DSC measurement: no
melting point/crystallization point, glass transition temperature
Tg=-67.0.degree. C.; weight average molecular weight from GPC:
M.sub.W=21 400 g/mol.
[0088] 1H-NMR spectroscopy: No free double bonds were detectable.
The composition of the hydrophilic organofunctional silicone
copolymer determined with the aid of NMR corresponded within the
accuracy of measurement to the composition of the starting
materials.
* * * * *