Note: Descriptions are shown in the official language in which they were submitted.
0050/45899 CA 02219071 1997-11-14
,. ~
Mixtures of polymers and surfactants, the preparation thereof and
the use thereof
5 The invention relates to mixtures of polymers of vinylim;AA7oles,
vinylpyrrolidone, open-chain vinylAm;A~s, N-vinyloxazolidone or
N-vinyltriazole, with or without other copolymerizable
monoethylenically unsaturated monomers and with or without
monomers having at least 2 non-conjugated ethylenic double bonds
10 and surfactants, to a process for preparing the mixtures and to
the use of the mixtures as additive to detergents.
Polymers of l-vinylimidazole are prepared, for example, by
free-radical polymerization of l-vinylimidazole in aqueous
15 solution or in alcohols, cf. DE-A-28 14 287. In order to prepare
high molecular weight or crossl;nkeA polymers of l-vinyl;~;AA7ole
it is possible to carry out precipitation polymerization in
benzene, cf. EP-A-0 162 388. In addition, European Polymer
Journal, 24 (1988) 1019 discloses the precipitation
20 polymerization of l-vinyl; m; AA7ole in carbon tetrachloride,
benzene or toluene. However, the polyvinyl; ;AA7oles prepared in
carbon tetrachloride have only low molecular weights, whereas the
polymers prepared in benzene or toluene result as crossl;nkeA
gels.
WO-A-92/07011 discloses the preparation of polyvinylpyrrolidones
which are slightly crossl;nk~A and highly swellable by
polymerizing N-vinylpyrrolidone in, for example, aliphatic
hydrocarbons. The polymers obtA;nAhle in this way are isolated by
30 filtration, washing and drying or by direct drying of the
reaction mixture. The known processes have the disadvantage that
the organic solvents used are toxicologically objectionable or
very flAmm~hle The resulting polymers have to be isolated from
these solvents and, in some cases, undergo elaborate
35 purification.
It is an object of the present invention to provide polymers in a
formulation which can be used directly and without isolating the
polymers. It is also an object of the invention to develop a
40 process for preparing polymers contA;n;ng ; ;A~7ole and/or lactam
groups which dispenses with the use of toxicologically
objectionable solvents.
we have found that this object is achieved by mixtures of
45 polymers and surfactants when they contain from 1 to 50~ by
weight of a polymer of
0050/45899 CA 02219071 1997-11-14
.. . .
a) lO-100% by weight of at least one vinyl;m;~A7.ole of the
formula
Rl .
H2C = CH N ~ N (I),
R2 ~ R3
where Rl, R2 and R3 are identical or different and are H,
C l-C4-alkyl,
monomers of the formula
O
~2C = CH - I - C - R5 (II),
R4
where R4 and R5 are identical or different and are H,
C1-C4-alkyl or together form a ring of 3 to 5 methylene
groups,
N-vinyloxazolidone, N-vinyltriazole, 4-vinylpyridine N-oxide
or mixtures of said monomers,
b) 0-90% by weight of other copolymerizable monoethylenically
unsaturated monomers and
c) 0-30% by weight of at least one monomer having at least two
non-conjugated ethylenic double bonds,
in suspended form in at least one surfactant.
The invention also relates to a process for preparing the
mixtures by free-radical polymerization of
a) lO-100% by weight of at least one vinyl; ;~ole of the
formula
0050/45899 CA 02219071 1997-11-14
.. . .
H2C = CH - N ~ N (I),
~
R2 R3
where R1, R2 and R3 are identical or different and are H,
Cl-C4-alkyl,
monomers of the formula
H2C = CH - N - C - R5 (II),
R4
where R4 and R5 are identical or different and are H,
C1-C4-alkyl or together form a ring of 3 to 5 methylene
groups,
N-vinyloxazolidone, N-vinyltriazole, 4-vinylpyridine N-oxide
or mixtures of said monomers,
25 b) 0-90% by weight of other copolymerizable monoethylenically
unsaturated monomers and
c) 0-30% by weight of at leàst one monomer having at least two
non-conjugated ethylenic double bonds,
in at least one surfactant at not below 50~C, or comprises
free-radical polymerization of the monomers (a) with or without
(b) and/or with or without (c) in the aqueous phase of a
water-in-oil suspension and, after completion of the
35 polymerization, replacing the oil phsae of the water-in-oil
suspension by at least one surfactant.
Examples of monomers of form~llA I are 1-vinylimidazole,
2-methyl-1-vinyl; ;~A7ole, 2-ethyl-l-vinyl;m;t.~A7.ole,
40 2-propyl-1-vinyl; ;t.~A~ole, 2-butyl-l-vinyl;m;~zole~
2,4-dimethyl-1-vinylimidazole, 2,5-dimethyl-1-vinylimidazole,
2-ethyl-4-methyl-1-vinyl;~;~A~ole, 2-ethyl-5-methyl-1-
vinylimidazole, 2,4,5-trimethyl-1-viny~ A7ole,
4,5-diethyl-2-methyl-1-vinylimidazole, 4-methyl-1-vinyl;m;,.~A~ole,
45 5-methyl-1-vinylimidazole, 4-ethyl-1-viny~ A7ole,
4,5-dimethyl-1-viny~ A7ole or 2,4,5-triethyl-1-vinyli ;~A7ole.
Mixtures of said monomers in any desired ratio can be used.
0050/45899 CA 02219071 1997-11-14
,
Monomers of formula II are open-chain and cyclic N-vinylAmi~.c,
eg. N-vinylformamide, N-vinylacetamide,
N-methyl-N-vinylacetamide, N-vinylpyrrolidone, N-vinylpiperidone
or N-vinylcaprolactam. Of the compounds of the formula II,
5 preferably N-vinylpyrrolidone is used to prepare the mixtures
according to the invention.
Particularly preferred monomers of group a) are l-vinyl;m;~A~ole,
l-vinyl-2-methyl;m;~Azole or l-vinylpyrrolidone, and mixtures of
10 said monomers in any desired ratio. The polymers contain at least
10% by weight of monom~rs a) as copolymerized units. Monomers a)
are used in amounts of from 10 to 100, preferably 50 to 100, in
particular 85 to 99.5% of the total weight of the monomers used
in the polymerization.
Suitable monomers of group b) are other monoethylenically
unsaturated monomers which are copolymerizable with monomers of
group a). Examples of such monomers are (meth)acrylates such as
methyl, ethyl, hydroxyethyl, propyl, hydroxypropyl, butyl,
20 ethylhexyl, decyl, lauryl, isobornyl, cetyl, palmityl,
phenoxyethyl or stearyl acrylate or the corresponding
methacrylates, (meth)acrylamides such as acrylamide,
N-methylolacrylamide, NrN-dimethyl Am; nQpropylacrylamide,
N,N-diethylaminopropylacrylamide, N-tert-butylacrylAm;~
25 N-tert-octylacrylamide, N-undecylacrylAmi~e or the corresponding
methacrylamides, vinyl esters having 2 to 30, in particular 2 to
14, carbon atoms in the molecule, such as vinyl acetate, vinyl
propionate, vinyl laurate, vinyl neooctanoate, vinyl
neononanoate, vinyl neodecanoate, styrene, vinyltoluene,
30 a-methylstyrene, unsaturated carboxylic acids such as acrylic
acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid,
itaconic acid or the corresponding anhydrides,
2-acryl A ; ~o-2-methylpropanesulfonic acid, acrylic esters which
have a basic nitrogen atom, such as diethylAm;noethyl acrylate,
35 dimethylaminoethyl acrylate, dimethylAm;nopropyl acrylate or the
corresponding methacrylates, 2-vinylpyridine or 4-vinylpyridine.
Alkyl (meth)acrylates, vinyl acetate, styrene, acrylic acid,
methacrylic acid, maleic acid and monomers which have a basic
nitrogen atom are particularly preferred.
If monomers b) are used, they are present in amounts of up to 90,
preferably up to 50, % of the total weight of all the monomers.
Suitable monomers of group c) are compounds having at least 2
45 non-conjugated ethylenic double bonds in the molecule. Compounds
of this type are crosslinkers. Examples of suitable crossl;nkr~rs
are acrylates, methacrylates, allyl ethers or vinyl ethers of at
OO~O/45899 CA 02219071 1997-11-14
least dihydric alcohols. The OH groups in the underlying alcohols
can be wholly or partly etherified or esterified; however, the
crosslinkers contain at least two ethylenically unsaturated
groups. Examples of the underlying alcohols are dihydric alcohols
5 such as 1,2-et h~ ne-l;ol, 1,2-propanediol, 1,3-propanediol,
1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol,
2-butene-1,4-diol, 1,2-pentanediol, 1,5-pentanediol,
1,2-hexanediol, 1,6-h~ne~;ol, 1,10-dec~neA;ol,
1,2-dodec~ne~;ol, 1,12-dodecanediol, neopentyl glycol,
lO 3-methyl-1,5-pent~ne~;ol, 2,5-dimethyl-1,3-hexanediol,
2,2,4-trimethyl-1,3-pentanediol, 1,2-cycloh~ne~;ol,
1,4-cyclohexanediol, 1,4-bis(hydroxymethyl)cyclohexAne, neopentyl
glycol mono(hydroxypivalate), 2,2-bis(4-hydroxyphenyl)propane,
2,2-bist4-(2-hydroxypropyl)phenyl]propane, diethylene glycol,
15 triethylene glycol, tetraethylene glycol, dipropylene glycol,
tripropylene glycol, tetrapropylene glycol,
3-thia-1,5-pentanediol, and polyethylene glycols, polypropylene
glycols and polytetrahydrofurans having molecular weights of, in
each case, from 200 to 10,000. Apart from homopolymers of
20 ethylene oxide or propylene oxide, it is also possible to use
block copolymers of ethylene oxide or propylene oxide or
copolymers which contain ethylene oxide and propylene oxide
groups incorporated. Examples of underlying alcohols having more
than two OH groups are trimethylolpropane, glycerol,
25 pentaerythritol, 1,2,5-pentanetriol, 1,2,6-he~netriol,
triethoxycyanuric acid, sorbitan, sugars such as sucrose,
glucose, mannose. It is, of course, also possible for the
polyhydric alcohols to be used as the corresponding ethoxylates
or propoxylates after reaction with ethylene oxide or propylene
30 oxide. The polyhydric alcohols can also be initially converted
into the corresponding glycidyl ethers by reaction with
epichlorohydrin.
Further suitable crossl;nkers are the vinyl esters or the esters
35 of monohydric unsaturated alcohols with ethylenically unsaturated
C3-C6-carboxylic acids, for example acrylic acid, methacrylic
acid, itaconic acid, maleic acid or fumaric acid. Examples of
such alcohols are allyl alcohol, 1-buten-3-ol, 5-hexen-1-ol,
1-octen-3-ol, 9-decen-1-ol, dicyclopentenyl alcohol,
40 10-undecen-1-ol, cinnamyl alcohol, citronellol, crotyl alcohol or
cis-9-octadecen-1-ol. However, it is also possible for the
monohydric unsaturated alcohols to be esterified with polybasic
carboxylic acids, for example malonic acid, tartaric acid,
trimellitic acid, phthalic acid, terephthalic acid, citric acid
45 or succinic acid.
0050/45899 CA 02219071 1997-11-14
Further suitable crossl; nk~r5 are esters of unsaturated
carboxylic acids with the polyhydric alcohols described above,
for example of oleic acid, crotonic acid, c;nnAm;c acid or
10-undecenoic acid.
Also suitable are straight-chain or branched, linear or cyclic,
aliphatic or aromatic hydrocarbons which have at least two double
bonds which, in the case of aliphatic hydrocarbons, must not be
conjugated, eg. divinylbenzene, divinyltoluene, 1,7-octadiene,
10 l,9-decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane or
polybutadienes having molecular weights of 200-20,000. Also
suitable as crosslinkers are the acrylamides and methacrylAm;r~r~s
of at least difunctional amines. Examples of such Am;neS are
diaminomethane, 1,2-dir ;noethane, 1~3-~; ~m; nopropane,
15 1,4-~;Am;nohutane, 1,6-~;Am;nohe~Ane, 1,12-dodecaner1;Am;nQ,
piperazine, diethylenetr;Am;ne or isophoronediamine. Also
suitable are the amides from allylamine and unsaturated
carboxylic acids such as acrylic acid, methacrylic acid, itaconic
acid, maleic acid, or at least dibasic carboxylic acids as
20 described above.
Also suitable are N-vinyl compounds of urea derivatives, at least
difunctional amides, cyanurates or urethanes, for example of
urea, ethyleneurea, propyleneurea or tartaramide.
Further suitable crosslinkers are divinyl~;o~Ane,
tetraallylsilane or tetravinylsilane. It is, of course, also
possible to use mixtures of the abov~ ~ntioned compounds. The
crosslinkers which are preferably used are those which are
30 soluble in the reaction mixture. Particularly preferred
crosslinkers are methylenebisacrylamide, di- and triallyl~m;ne,
divinylimidazole, divinylethyleneurea, products of the reaction
of polyhydric alcohols with acrylic acid or methacrylic acid,
methacrylates and acrylates of polyalkylene oxides or of
35 polyhydric alcohols which have been reacted with ethylene oxide
and/or propylene oxide and/or epichlorohydrin, and allyl
methacrylate and divinylbenzene. Methylenebisacrylamide,
N,N'-divinylethyleneurea, acrylates and methacrylates of at least
dihydric C2-C4-alcohols, allyl methacrylate and divinylbenzene are
40 very particularly preferred. If crossl;nk~s are used in the
polymerization, they can be employed in amounts of up to 30,
preferably from 0.2 to 20, and very particularly preferably from
0.5 to 10, % of the total weight of monomers used in the
polymerization.
0050/45899 CA 02219071 1997-11-14
: 7
The mixtures according to the invention comprise polymers and
surfactants. Suitable surfactants are described, for example, in
M. and I. Ash, Handbook of Industrial Surfactants, Gower
Publishing Co., Hants, 1993. Surfactants can be low molecular
5 weight or polymeric compounds. Nonionic surfactants are
particularly preferred.
Low molecular weight nonionic surfactants generally contain a
straight-chain or branched, saturated or unsaturated, cyclic or
10 acyclic, aromatic or aliphatic alkyl radical having 8 to 40,
preferably 10 to 30, very particularly preferably 12 to 22,
carbon atoms in the molecule. The alkyl r~; CA 1 can also be
wholly or partly fluorinated. The alkyl radical is linked to a
hydrophilic moiety which contains at least one oxygen or nitrogen
15 atom. Examples of preferred compounds are ethers and esters of
sugars or sugar derivatives, such as sucrose esters, mannose
esters, xylose esters or sorbitan esters, esters and ethers of
glycerol, diglycerol, polyglycerol or glycerol/sugar condensates,
ceramides and glycosyl-ceramides, fatty acid alkanolamides such
20 as fatty acid ethanolamides, fatty acid isopropanolamides, fatty
acid diethanolamides, fatty acid polydiethanolamides,
N-alkylpyrrolidone derivatives, alkyl pyrrolidone-5-carboxylates,
citric and tartaric esters, Cl-Cl8-alkyl (poly)glycosides,
hydroxyalkyl polyglycosides, fatty acid esters of polyhydroxy
25 compounds such as trimethylolpropane, erythritol,
pentaerythritol, neopentyl diglycol, triethanolamine or
condensates derived therefrom, alkoxylates, especially the
adducts of ethylene oxide and/or propylene oxide with the
abo~t -ntioned compounds and with oxo alcohols, C8-C30-alcohols,
30 alkylphenols, fatty acid ~m;~es, fatty amines, fatty acids and
derivatives such as hydroxy carboxylic acids, it being possible
for the polyalkylene oxide ch~; n~ to be modified at one end or
both ends. In the case of modification at both ends, the
modifying portions can be identical or different and, for
35 example, also represent in part a C1-C4-ether functionality.
Further surface-active compounds a) are sorbitan esters, sucrose
esters or glycerol esters of C8-C30-carboxylic acids or
alkoxylation products of these esters. The abo~ ~ntioned esters
40 are preferably derived from Cl2-C22-carboxylic acids. Alkoxylation
products are preferably the adducts of ethylene oxide with the
esters. The adducts may contain up to 80 mol of ethylene oxide
per mol of the relevant esters. Also suitable as surface-active
compounds are adducts of ethylene oxide and propylene oxide
45 and/or of butylene oxides with the esters. Alkyldimethylamine
oxides are likewise suitable.
0050/4~899 CA 022l907l l997-ll-l4
r 8
Polymeric surfactants which contain ethylene oxide and/or
propylene oxide units as hydrophilic part of the molecule are not
crosslinked and have molecular weights of from 500 to 100,000,
preferably 700 to 20,000. The polymeric surfactants may, besides
5 at least one hydrophilic block, contain at least one hydrophobic
block or are composed of a hydrophilic chain with hydrophobic
branches arranged like a comb. The hydroph;l;c part of the
polymeric surfactants is formed from homopolymers of ethylene
oxide or propylene oxide or from block copolymers of ethylene
lO oxide and propylene oxide and from block and comb polymers with
blocks of polyethylene oxide, polypropylene oxide or poly
co(ethylene oxide, propylene oxide), while the hydrophobic part
of the polymeric surfactants consists of blocks of polysLylene
polyalkyl (meth)acrylates, silicone oils, polyhydLoxy fatty
15 acids, polyamidoamines, polyisobutylene or polytetrahydrofurans.
It is also possible for general polymers which have at least one
amino group, one hydroxyl group which can be deprotonated with
bases, or one anionic group, and have a molecular weight of from
100 to 5000, such as ethylene oxide, propylene oxide or mixtures
20 thereof, to be converted into suitable polymeric surfactants.
Particularly preferred surfactants among those mentioned above
are adducts of ethylene oxide and/or propylene oxide with
Cl0-C30-alcohols, alkylphenols, fatty ~m; neC or fatty acids,
25 sucrose esters, sorbitan esters, (poly)glycerol esters or their
corresponding ethoxylates, and alkyl (poly)glycosides. Adducts of
ethylene oxide and/or propylene oxide with C12-C22-alcohols or
alkylphenols, sorbitan esters, glycerol esters or their
corresponding ethoxylates with 12 to 22 carbon atoms in the alkyl
30 chain, and alkyl (poly)glycosides with 8 to 22 carbon atoms in
the alkyl chain, are very particularly preferred. The surfactants
have, for example, a softening point below 100 C, preferably below
60~C and particularly preferably below 40~C.
35 Polymers of monomers a) with or without b) and/or with or without
c) are known. They can be prepared by various processes.
Particularly suitable processes are inverse suspension or
emulslon polymerization, where an aqueous solution of the
monomers is emulsified in an inert organic liquid and
40 polymerized, and precipitation polymerization. It is possible and
expedient in water-in-oil polymerization to use protective
colloids or emulsifiers. After the polymerization is complete,
the water can be removed, for example by azeotropic distillation,
and the inert organic solvent can be replaced by a nonionic
45 surfactant by, for example, l~ ~ving the inert organic solvent by
0050/45899 CA 02219071 1997-11-14
t
distillation and preferably adding an amount of surfactants which
corresponds to the amount L~ ~ved by distillation.
The solvents used in precipitation polymerization are those which
5 dissolve the monomers, at least in part, but not the polymers
resulting therefrom, so that they precipitate in fine-particle
form. Examples of solvents suitable for water-in-oil emulsion
polymerization are saturated, straight-chain or branched or
cyclic hydrocarbons such as pentane, h~ne~ cyclohexane,
10 heptane, octane or isooctane, ~l;ph~tic ethers such as dimethyl
ether, diethyl ether, diamyl ether, tert-butyl methyl ether or
dibutyl ether, ketones such as acetone, methyl ethyl ketone,
diethyl ketone or methyl amyl ketone, Cl-C18-carboxylic esters,
for example ethyl formate, methyl acetate, ethyl acetate,
15 isopropyl acetate, isobutyl acetate, stearyl acetate, ethylhexyl
ethylhexanoate, isopropyl myristate or isopropyl palmitate,
silicone oils such as octamethylcyclotetrasilane, liquid or
supercritical carbon dioxide, aromatic hydrocarbons such as
toluene or xylene. These inert organic solvents are substantially
20 replaced by a surfactant after the polymerization.
The mixtures are preferably obt~;n~hle by free-radical
polymerization of
25 a) 10-100% by weight of at least one vinyl; ;~ole of the
formula
.
Rl
H2C = CH--N~W (I),
R2 R3
where Rl, R2 and R3 are identical or different and are H,
Cl--C4-alkyl,
monomers of the formula
O
H2C = CH I - C - R5 (II),
OO~O/45899 CA 02219071 1997-11-14
where R4 and R5 are identical or different and are H,
Cl-C4-alkyl or together form a ring of 3 to 5 methylene
groups,
N-vinyloxazolidone, N-vinyltriazole, 4-vinylpyridine N-oxide
or mixtures of said monomers,
b) 0-90% by weight of other copolymerizable monoethylenically
unsaturated monomers and
10 c) 0-30% by weight of at least one monomer having at least two
non-conjugated ethylenic double bonds,
in at least one surfactant.
15 The mixtures according to the invention can, of course, also be
prepared by polymerizing the monomers in a mixture of a solvent
and a surfactant in any desired ratio, with the solvent being
removed as completely as possible from the reaction mixture
following the polymerization. The amount of the organic phase
20 during the polymerization is preferably chosen so that the
resulting reaction mixture can be stirred during the
polymerization. The solids content of the mixtures is, for
example, in the range from 1 to 60, preferably 15 to 40, % by
weight.
It is also possible to add small amounts, for example up to 10%
by weight, preferably up to 4% by weight, based on the monomers
used, of water, methanol, ethanol, isopropanol or protective
colloids to the reaction mixture in order to improve the
30 solubility of individual components of the reaction mixture or in
order to influence the properties of the resulting copolymers.
For example, the morphology of the polymers can be infuenced in
the presence of protective colloids in such a way that the
resulting mixtures have a particularly high polymer content.
35 Examples of suitable protective colloids are
polyvinylpyrrolidones with K values of from 10 to 100, partially
hydrolyzed polyvinyl acetates, cellulose ethers, copolymers of
maleic acid or maleic anhydride with alkenes, preferably
isobutylene or diisobutylene, or copolymers of N-pyrrolidone and
40 vinyl acetate. If water is present in the precipitation
polymerization, it is used only in the amounts needed to make the
mixture of all the components appear homogeneous before the start
of the polymerization.
45 The molecular weight of the resulting polymers can, where
appropriate, be reduced by adding regulators to the polymerizing
mixture. Examples of regulators which can be used are halogen
0050/45899 CA 02219071 1997-11-14
t
- 11
compounds such as tetrachloromethane, chloroform,
bromotrichloromethane, allyl compounds such as allyl alcohol or
2,5-diphenyl-1-hexene, aldehydes, formic acid or formic esters.
However, the polymerization regulators preferably used are
5 compounds which contain sulfur in bound form, for example
bisulfites, sulfites, disulfites and dithionites or compounds
which contain sulfur l;nke~ to a carbon atom, such as organic
sulfides, disulfides, polysulfides, sulfoxides, sulfones and
mercapto compounds. Particularly preferably used are mercapto
10 alcohols, mercapto carboxylic acids and mercaptoalkanes having 2
to 30 carbon atoms in the molecule, for example
2-mercaptoethanol, 3-mercaptopropanol,
3-mercapto-1,2-propanediol, 4-mercaptobutanol, cysteine,
mercaptoacetic acid, 3-mercaptopropionic acid, mercaptosuccinic
15 acid, N-butyl mercaptan, N-hexyl mercaptan, N-dodecyl mercaptan
or tert-dodecyl mercaptan. If polymerization regulators are used,
they are employed in amounts of from 0.1 to 10, preferably 0.1 to
5, % of the weight of monomers in the reaction mixture.
20 The abo~.entioned monomers are normally polymerized with use of
free-radical initiators, as a rule under an inert gas atmosphere.
Free-radical initiators which can be used are hydrogen peroxide
or inorganic persulfates, as well as organic compounds of the
peroxide, peroxy ester, percarbonate or azo type, such as
25 dibenzoyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide,
dilauroyl peroxide, t-butyl perpivalate, t-amyl perpivalate,
t-butyl perneo~c~noate, 2,2~-azobis(2-amidinopropane)
dihydrochloride, 4,4'-azobis(4-cyanovaleric acid),
2,2~-azobis~2-(2-;mi~olin-2-yl)propane] dihydrochloride,
30 2,2'-azobis(2,4-dimethylvaleronitrile),
2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile)
and dimethyl 2,2'-azobis(isobutyrate). It is, of course, also
possible to use mixtures of initiators or the known redox
initiators. The initiators which are preferably used are those
3S which, when the polymerization is carried out in surfactants, are
soluble in the surfactants to the extent of more than 5% by
weight at 25 C. The initiators are used in conventional
quantities, eg. from 0.02 to 5% of the weight of monomers to be
polymerizedO
The precipitation polymerization is norr~lly carried out under an
inert gas atmosphere. The polymerization can be carried out, for
example, by introducing all the components which are present
during the polymerization into a polymerization vessel, starting
45 the reaction, and cooling the reaction mixture where appropriate
to control the polymerization temr~ature. However, it is also
possible to introduce only one or some of the components, to
0050/45899 CA 02219071 1997-11-14
, r
- 12
start the polymerization, and to meter the rr~-;n~r of the
components in singly or together at different intervals depending
on the progress of the polymerization, continuously or batchwise.
However, it is also possible to introduce first only the diluent
S and to add the monomers and the polymerization initiator in
separate feeds thereto, batchwise or continuously.
The monomers are generally polymerized at from 40 to 200,
preferably 50 to 120, C. The temperature can be varied during the
10 reaction in a program-controlled ~nn~r. The polymerization is
preferably carried out under atmospheric pressure, but can also
be carried out under reduced or elevated pressure. If the
polymerization is carried out above the boiling point of the
solvent, pressure-tight apparatus with pressures of up to 16 bar
15 is used.
In the preparation of crosslinked copolymers, it is well known
that there is often formation of deposits, which are difficult to
remove, on the walls of the reaction vessels and on the stirrers.
Z0 In the preparation according to the invention of the mixtures by
copolymerization of the monomers in, preferably, nonionic
surfactants as precipitant there is virtually none of the
otherwise unwanted deposit formation.
25 Polymers which (formally) contain 4-vinylpyridine N-oxide as
copolymerized unit are preferably prepared by polymerization or
copolymerization of 4-vinylpyridine followed by N-oxidation of
the pyridine ring with, for example, peracetic acid prepared in
situ.
Polymers which have basic, N-cont~ining groups can be converted
after the reaction into a quaternized form with a suitable
reagent. Examples suitable for the quaternization are alkyl
halides having 1 to 18 carbon atoms in the molecule, eg. methyl
35 chloride, ethyl chloride, propyl chloride, hexyl chloride,
dodecyl chloride or lauryl chloride, and benzyl halides such as
benzyl chloride. The corresponding iodine or bromine compounds
are, of course, also suitable. Further suitable quaternizing
agents are dialkyl sulfates, in particular dimethyl sulfate and
40 diethyl sulfate. In some cases, it is sufficient to convert the
polymers into the salt form by treatment with an acid. The
quaternization can take place completely or partially.
The reaction mixture can be subjected after the polymerization to
45 a physical or ch~ical treatment. Examples thereof are the known
processes for reducing residual monomers, such as addition of
polymerization initiators or mixtures of a plurality of
0050J45899 CA 02219071 1997-11-14
~ F
13
polymerization initiators at suitable temperatures or heating of
the polymerization solution to temperatures above the
polymerization temperature, treatment of the polymer solution
with steam or stripping with nitrogen or treatment of the
5 reaction mixture with oxidizing or reducing reagents.
If the polymers are soluble in water, they have K values of from
lO to 300 (determined by the method of H. Fikentscher in aqueous
solution at 25 C with a polymer concentration of 1%~. The average
10 diameter of the polymers is, for example, from 0.1 to 1000,
preferably 0.5 to 80, ~m.
The suspensions according to the invention of the copolymers in
the surfactants are used, for example, as additive for
15 ph~r~Aceutical or cosmetic compositions, as additive in paper
manufacture, for stabilizing enzymes or for adsorbing metal ions,
dyes or acids. The particularly preferred use is as additive to
detergents. The effect of the polymers in the washing of colored
and white textiles is to inhibit transfer of dye to the uncolored
20 textiles.
In particular, crosslinked copolymers of N-viny~ zole and
N-vinylpyrrolidone are particularly suitable for use in heavy
duty detergents because they are distinctly more effective than
25 soluble polymers when the dye co~centrations in the wash li~uor
are low. However, as a rule, in the full wash it is mainly white
and slightly colored l~lln~ry, and lA~ln~ry with very washfast
colors, which is washed. T~nn~ry which releases dye to a large
extent is, as a rule, present in the lAlln~ry only by mistake and
30 thus as a very small proportion, eg. when a colored sock is
included in the wash. The crosslinked polymers, which bind small
amounts of dye distinctly more strongly than do water-soluble
color transfer inhibitors, therefore have a great advantage in
use over the water-soluble products.
The detergents can be in powder form or in a liquid formulation.
The composition of the detergents and cleaners may vary widely.
Detergent and cleaner fo l~tions nor~lly contain from 2 to 50%
by weight of surfactants, with or without bn;l~rs . These data
40 apply both to li~uid and to powder detergents. Detergent and
cleaner formulations, c~ -nly used in Europe, the USA and Japan
are tabulated, for example, in Chemical and Engn. News, 67 (1989)
35. Further details of the composition of detergents and cleaners
can be found in Ull~-nn~ Enzyklopadie der technischen Chemie,
45 Verlag Chemie, Weinheim 1983, 4th edition, pages 63-160. The
detergents may also contain a bleach, eg. sodium perborate or
sodium percarbonate, whose content when used can be up to 30% of
0050/45899 CA 02219071 1997-11-14
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14
the weight of the detergent formulation. The detergents or
cleaners may contain further conventional additives, eg.
complexing agents, opacifying agents, optical brighteners,
enzymes, perfume oils, other color transfer inhibitors,
5 antiredeposition agents, soil release polymers and/or bleach
activators. They contain the mixtures according to the invention
in amounts of from 0.1 to 10, preferably 0.2 to 3, % by weight.
Examples
Example 1
440 g of a Cl3/Cl5 oxo alcohol which had been reacted with 7 units
of ethylene oxide per molecule were heated with 50 g of
15 N-vinyl;~;~ole, 50 g of N-vinylpyrrolidone, 5 g of
divinylethyleneurea and 1 g of tert-butyl perpivalate while
stirring in a flask which had a capacity of 2000 ml and was
equipped with a stirrer, reflux condenser, thermometer and
apparatus for working under protective gas, to 80~C. The mixture
20 was stirred at this t~mr~rature for 5 hours. The result was a
fine-particle, white polymer suspension with an average particle
size of 14.3 ~m. The suspension was easy to pour out of the
polymerization vessel without leaving solid deposits behind.
25 Example 2
900 g of cyclohexane, 50 g of N-vinylimidazole, 50 g of
N-- vinylpyrrolidone, 5 g of divinylethyleneurea and 1 g of
tert-butyl perpivalate were heated in a flask which had a
30 capacity of 1000 ml and was equipped with a stirrer, reflux
condenser, thermometer and an apparatus for working under
protective gas while stirring to 80~C. The mixture was stirred at
this temperature for 5 hours. Subsequently 595 g of a Cl3/Cl5 oxo
alcohol which had been reacted with 7 units of ethylene oxide per
35 molecule were added dropwise over the course of 1 hour and, at
the same time, the cyclohexane was lel..oved by distillation under
a gentle stream of nitrogen. The result was a fine-particle
polymer suspension with an average particle size of 18.1 ~m.
40 Example 3
400 ml of a polyoxyethylene sorbitan stearate, 100 g of
N-- vinylpyrrolidone, 8 g of divinylethyleneurea and 1 g of
tert-amyl perneodecanoate were stirred in a flask which had a
45 capacity of 1000 ml and was equipped with a stirrer, reflux
condenser, th~ -ter and an apparatus for working under
OO~O/45899 CA 02219071 1997-11-14
protective gas at 72 C for 6 hours. The result was a fine-particle
polymer suspension with an average particle size of 12.4 ~m.
Example 4
400 g of sorbitan monolaurate, 100 g of vinylimidazole and 2 g of
allyl methacrylate were heated to 80 C in a flask which had a
capacity of 1000 ml and was equipped with a stirrer, reflux
condenser, thel -Ler and an apparatus for working under
lO protective gas. At this temperature, 1 g of
2,2'-azobis(2-methylisobutyronitrile) in 50 ml of sorbitan
monolaurate was fed in over the course of 4 hours. The reaction
mixture was left at 80 C for a further 2 hours. The result was a
fine-particle polymer suspension with an average particle size of
15 17.2 ~m.
Example 5
800 g of cyclohex~ne~ 5 g of sorbitan monolaurate and 5 g of an
20 ABA block copolymer of polyhydroxystearic acid and polyethylene
oxide with a molecular weight of about 7500, marketed by ICI
under the name Hyp~ -r B 246, were heated to 65~C in a flask
which had a capacity of 2000 ml and was equipped with a stirrer,
reflux condenser, ther -Ler and an apparatus for working under
25 protective gas. As soon as this temperature was reached, 100 g of
N-vinylpyrrolidone, 100 g of vinyl; ;A~ole, 10 g of
divinylethyleneurea and 0.5 g of 2,2'-azobis(Am;Ainopropane)
dihydrochloride in 140 g of water were added dropwise over the
course of 30 minutes. The mixture was then stirred at this
30 temperature for a further 6 hours. The t~ ~rature was
subsequently raised to the boiling point of the mixture, and the
water was ,~,..oved by azeotropic distillation. Subsequently 800 g
of a C8/C10-alkyl polyglycoside were added dropwise over the
course of one hour and, at the same time, the cycloh~ne was
35 le,.loved by distillation under a gentle stream of nitrogen. The
result was a fine-particle polymer suspension with an average
particle size of 7.3 ~m.
Use Examples
Test method
White cotton test fabric was washed under the conditions
specified in Table 1 with the addition of the detergent indicated
45 in Table 2 in the presence of dye. The dye was released during
the washing from cotton test dyeings.
0050/45899 CA 02219071 1997-11-14
16
Table 1 contains the washing conditions for the examples. Table 2
indicates the composition of the detergents used. The coloring of
the test fabric was measured by photometry. The strengths of each
of the colorings were det~rm;ne~ by the method described by
5 A. Kud, Seifen, Ole, Fette, Wachse, 119 (1993) 590-594 from the
reflectance measurements on the individual test fabrics. The
color-transfer inhibiting effect of the test substance was
determined as a % from the color strengths for the test with the
particular test substance, the color strength for the test
10 without test substance and the color strength of the test fabric
before washing by the method described in the above reference
(color transfer inhibition is treated in the same way as
antiredeposition for this purpose). The effectiveness results for
the various dyes are listed in Table 3.
Table 1:
Washing conditions
Machine T~lln~er-o-meter
20 Cycles
Duration 30 min
Temperature 60 C
Water hardness 3 mmol/l
Dye introduction Colored fabric
25 Test fabric 2.5 g of cotton cheesecloth
(bleached)
Amount of liquor 250 ml
Detergent concentration 4.5 g/l
30 Table 2:
Detergent composition
Ingredients Amount t~]
35 Linear Na C10/Cl3-alkylbenzenesulfonate
(50% strength) 8.6
Na fatty alcohol sulfate 2.7
Adduct of 10 mol of ethylene oxide
at 1 mol of Cl3/Cl5 oxo alcohol 6.3
40 Zeolite A 55
Na citrate 5.5 H20 9.0
Copolymer of 70% by weight acrylic acid and
30% by weight maleic acid, molecular
weight 70,000 4.0
45 Na carbonate 6.0
Na sulfate 5.8
0050/45899 CA 02219071 1997-11-14
. . I ~
17
Carboxymethylcellulose 0.5
Test substance 1.0
The washing results with the polymers according to the invention
5 are shown in Table 3.
0050~45899CA 02219071 1997-11-14
18
Table 3
Direct Direct Direct
blue black orange
71 22 39
Mixture of Example 1 95.6 71.4 45.8
Mixture of Example 2 96.0 82.7 48.2
Comparative Example 1
10 (polyvinylpyrrolidone . 94.7 60.2 23.9
with K value of 30)
Comparative Example 2
(1:1 vinylimidazole/
vinylpyrrolidone 94.1 60.4 28.7
copolymer with K value
15 ~f 18)
The washing results in Table 3 show that the polymers according
to the invention are very effective as color transfer inhibitors
and are in many cases distinctly superior to the color transfer
20 inhibitors polyvinylpyrrolidone or
polyvinylpyrrolidone-co-vinyl;mi~ole (Comparative Example 2)
which are used in many detergents. The results also show that the
color-transfer inhibiting effect operates with many direct dyes
and is not confined to a few representatives.
