WO1996037524A1 - Polymer and surfactant mixtures, process for their preparation and their use - Google Patents

Polymer and surfactant mixtures, process for their preparation and their use Download PDF

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Publication number
WO1996037524A1
WO1996037524A1 PCT/EP1996/002178 EP9602178W WO9637524A1 WO 1996037524 A1 WO1996037524 A1 WO 1996037524A1 EP 9602178 W EP9602178 W EP 9602178W WO 9637524 A1 WO9637524 A1 WO 9637524A1
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monomers
wt
mixtures
formula
alkyl
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PCT/EP1996/002178
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German (de)
French (fr)
Inventor
Christian Schade
Dieter Boeckh
Axel Sanner
Hans-Ulrich JÄGER
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Basf Aktiengesellschaft
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0021Dye-stain or dye-transfer inhibiting compositions
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F26/00Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F26/02Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F26/00Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F26/06Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00Post-polymerisation treatments
    • C08F6/24Treatment of polymer suspensions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles, amines
    • C11D3/3776Heterocyclic compounds, e.g. lactam

Abstract

The invention concerns polymer and surfactant mixtures containing in suspended form in at least one surfactant between 1 and 50 wt.% of a polymer comprising: a) between 10 and 100 wt.% of at least one vinylimidazole or a derivative thereof, an open-chain or cyclic N-vinylamide, N-vinyloxazolidone, N-vinyltriazole or mixtures of said monomers; b) between 0 and 90 wt.% of other copolymerizable monoethylenically unsaturated monomers; and c) between 0 and 30 wt.% of at least one monomer with at least two ethylenically unsaturated, non-conjugated double bonds. The invention further concerns a process for preparing these mixtures by polymerization of said monomers in a surfactant, and the use of the mixtures as additives for washing agents.

Description

Mixtures of polymers and surfactants, processes for their preparation and their use

description

The invention relates to blends of polymers of vinyl imidazoles, vinyl pyrrolidone, open-chain vinylamides, N-vinyl oxazolidone and N-vinyltriazole and optionally other copolymerizable merisierbaren monoethylenically unsaturated monomers and if appropriate monomers having at least 2 ethylenically unsaturated, nonconjugated double bonds, and surfactants, a process for the preparation of the mixtures and the use of the mixtures as additive to detergents.

Polymers of 1-vinylimidazole example, be prepared by free-radical polymerization of 1-vinylimidazole in aqueous solution or in an alcohol, see. DE-A-28 14 287. In order to produce high molecular weight or crosslinked polymers of 1-vinylimidazole, one may use the precipitation in benzene, see FIG. EP-A-0 162 388. In addition, the precipitation polymerization of 1-vinylimidazole in carbon tetrachloride, benzene or toluene is known from European Polymer Journal, Volume 24, 1019 (1988) are known. However, the polyvinyl produced in carbon tetrachloride imidazole have only low molecular weights, while incurred the polymers prepared in benzene or toluene as crosslinked gels.

From WO-A-92/07011 the production of lightly crosslinked, highly swellable polyvinyl pyrrolidones by polymerizing N-vinyl pyrrolidone is in, for example, aliphatic Kohlenwasser¬ materials known. The polymers obtainable in this way are isolated by filtration, washing and drying, or by direct drying of the reaction mixture. The known processes have the disadvantage that the organic agents used are lots toxikolo¬ cally questionable or flammable. The resulting polymer must be isolated from these lots grants and partly cleaned thoroughly.

The object of the present invention is based is to make polymers in a formulation for AV supply which can be used directly and without isolation of the polymers. In addition, it is an object of the invention to develop a process for the preparation of imidazole and / or lactam containing polymers, the medium without the use of toxicologically unacceptable Löse¬. The object of the invention is achieved with mixtures of Poly mers and surfactants, when 1 to 50 wt .-% of a polymer of

a) 10 to 100 wt .-% of at least one vinylimidazole of the formula

R i

H 2 C == CH-KΓ ^ N (I!

Y ^ ^ R3

in which R 1, R 2 and R 3 are the same or different and stand for H, Ci to C 4 -alkyl, monomers of the formula

O ||

H 2 C = CH NCR 5 (II),

R4

in which R 4 and R 5 are identical or different and represent H, Ci to C 4 alkyl or a ring of 3 to 5 methylene groups together form,

N-vinyloxazolidone, N-vinyltriazole, 4-vinylpyridine-N-oxide or mixtures of said monomers,

b) 0 to 90 wt .-% of other copolymerizable monoethylenically unsaturated monomers and

c) 0 to 30 wt .-% of at least one monomer compounds having at least two ethylenically unsaturated, nonconjugated Doppel¬

in suspended form in at least one surfactant.

The invention is also a process for the production position of the mixtures, in which

a) 10 to 100 wt .-% of at least one vinylimidazole of the formula R l

H 2 C = CH N ' "^ N (I)' ^^ R 3

in which R 1, R 2 and R 3 are the same or different and stand for H, Ci to C 4 -alkyl, monomers of the formula

H 2 C = CH NCR 5: II:

R 4

in which R 4 and R 5 are identical or different and represent H, Cι ~ to C 4 alkyl or a ring of 3 to 5 methylene groups together form,

N-vinyloxazolidone, N-vinyltriazole, 4-vinylpyridine-N-oxide or mixtures of said monomers,

b) 0 to 90 wt .-% of other copolymerizable monoethylenically unsaturated monomers and

c) 0 to 30 wt .-% fertilize at least one monomer having at least two ethylenically unsaturated, nonconjugated Doppelbin-

free radical polymerization in at least one surfactant, at temperatures of at least 50 ° C or at the polymerizing the monomers (a) and optionally (b) and / or optionally (c) in the aqueous phase of a water-in-oil suspension radical and after completion of the polymerization, the oil phase of the water-in-oil suspension replaced by at least one surfactant.

Monomers of formula I are, for example, 1-vinylimidazole, 2-methyl-l-vinylimidazole, 2-ethyl-l-vinylimidazole, 2-propyl-l-vinylimidazole, 2-butyl-l-vinylimidazole, 2,4-dimethyl-l- vinylimidazole, 2,5-dimethyl-l-vinylimidazole, 2-Ethy1-4-methyl-l-vinylimidazole, 2-ethyl-5-methyl-l-vinylimidazole, 2,4, 5-trimethyl-l-vinylimidazole, 4,5-diethyl-2-methyl-1-vinylimidazole, 4-methyl-l-vinylimidazole, 5-methyl-l-vinylimidazole, 4-ethyl-l-vinylimidazole, 4, 5-dimethyl-l-vinylimidazole or 2, 4,5-triethyl-l-vinylimidazole. One can use mixtures of said monomers in any Verhält¬ nits. Monomers of the formula II are open-chain and cyclic N-vinylamides such as N-vinylformamide, N-vinylacetamide, N-methyl-N-vmylacetamid, N-vinylpyrrolidone, N-vinylpiperidone or N-vinylcaprolactam. N-vinyl pyrrolidone is preferably used for the preparation of Inventions gemaßen mixtures of the compounds of formula II.

Particularly preferred monomers of group a) are 1-vinylimidazole, l-vinyl-2-methylimidazole or 1-vinylpyrrolidone, and mixtures of said monomers in any proportion. The Poly merisate contained 10 wt .-% of at least monomer a) in one polymerized form. The monomers a) are used in amounts of 10 to 100, preferably 50 to 100, in particular 85 to 99.5 wt .-%, based on the total amount of verwen¬ in the polymerization Deten monomers.

Suitable monomers of group b) other join the Mσnomeren the group a) monoethylenically unsaturated monomers copolymerizable considered. Such monomers are, for example,

(Meth) Acrylester such as methyl, ethyl, hydroxyethyl, propyl, hydroxypropyl, butyl, ethylhexyl, decyl, lauryl, i-bornyl, cetyl, palmityl, stearyl acrylate or phenoxyethyl or the corresponding methacrylates , (meth) crylamide, such as acrylamide, N-methylol acrylamide, N, N-dimethylaminopropyl acrylamide, N, N-di- ethylaminopropylacrylamid, N-ter.-butylacrylamide, N-tert-octyl acrylamide, N-undecylacrylamide or the corresponding methacrylamides, Vinylester having from 2 to 30, in particular 2 to 14 Kohlen¬ atoms in the molecule such as vinyl acetate, vinyl propionate, vinyl laurate, Neooctansaurevinylester, Neononansaurevinylester, Neodecansaurevinylester, styrene, vinyltoluene, α-methylstyrene, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid , maleic acid, fumaric acid, itaconic acid or their anhydrides entspre¬ sponding, 2-acrylamido-2-methylpropansulfonsaure, acrylic ester, the grout on a basic N atom, such as ethyl acrylate diethylamino, dimethylaminoethyl acrylate, Dimeth yla inopropyl- acrylate or the corresponding methacrylates, 2-vinylpyridine or 4-vinylpyridine. Alkyl (meth) are particularly preferred acryl¬ ester, vinyl acetate, styrene, acrylic acid, methacrylic acid, maleic acid and monomers grouting a basic N-atom.

If the monomers b) are used, they are present in amounts up to 90, preferably up to 50 wt .-%, based on the total amount of all monomers present. Suitable monomers of group c) compounds having at least 2 ethylenically unsaturated, nonconjugated double bonds in the molecule considered. Compounds of this type are crosslinkers. Suitable crosslinkers are, for example, Acrylester, methacrylic esters, allyl ethers or vinyl ethers of at least dihydric alcohols. The OH groups of the parent alcohols can here be completely or partially etherified or esterified; however, the crosslinkers comprise at least two ethylenically unsaturated groups. Examples of the parent alcohols are dihydric alcohols such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol , but-2-en-l, 4-diol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1, 6-hexanediol, 1,10-decanediol, 1,2-dodecanediol, 1 , 12-dodecanediol, neopentyl glycol, 3-methylpentane-l, 5-diol, 2, 5-dimethyl-l, 3-hexane diol, 2,2,4-trimethyl-l, 3-pentanediol, 1,2-cyclohexanediol .

1,4-cyclohexanediol, 1,4-bis (hydroxymethyl) cyclohexane, hydroxy pivalic acid-neopentylglykolmonoester, 2,2-bis (4-hydroxy-phenyDpropan, 2,2-bis [4- (2-hydroxypropyl) phenyl] propane , diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 3-thio-pentane-1,5-diol, and also polyethylene glycols, polypropylene glycols and polytetrahydrofurans with molecular weights of in each case 200 to 10 000. Apart from the homopolymers of ethylene oxide or propylene oxide can also will contain incorporated block copolymers of ethylene oxide or propylene oxide or copolymers which comprise ethylene oxide and propylene oxide groups, are used. Bei¬ games of parent alcohols with more than two OH groups are trimethylolpropane, glycerol, pentaerythritol, 1,2,5-pentane - triol, 1,2, 6-hexanetriol, hoxycyanursaure Trie, sorbitan, sugars such as sucrose, glucose, mannose course, the polyhydric alcohols following reaction with ethyleneoxy. d or propylene oxide are used as the corresponding ethoxylates or propoxylates. The polyhydric alcohols can be converted at first by reaction with epichlorohydrin in the corresponding glycidyl ethers.

Further suitable crosslinkers are the Vinylester or the esters of monohydric unsaturated alcohols with ethylenically unsaturated C 3 - to C ß -Carbonsauren, for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid. Examples of such alcohols are allyl alcohol, l-butene-3-ol, 5-hexen-l-ol, l-octen-3-ol, 9-decen-l-ol, dicyclopentenyl, 10-unde- cen-l-ol alcohol, cinnamyl alcohol, citronellol, crotyl alcohol or cis-9-octadecene-l-ol. However, one can esterify the monohydric, unsaturated alcohols with polybasic carboxylic acids, for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.

Further suitable crosslinkers are esters of unsaturated carboxylic acids with the polyhydric alcohols described above, for example the oleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid.

Also suitable are straight-chain or branched, linear or cyclic, aliphatic or aromatic hydrocarbons, which jointing at least two double bonds which must not be conjugated in aliphati¬ rule hydrocarbons, for example divinylbenzene, divinyltoluene, 1,7-0ctadien, 1, 9-decadiene , 4-vinyl-l-cyclohexene, trivinylcyclohexane or polybutadienes having molecular weights from 200 to 20 000. suitable crosslinkers are also suitable, the Acrylsaureamide, Methacrylsaureamide and N-allyl amine of at least difunctional amines. Such amines are, for example, diaminomethane, 1,2-diaminoethane, 1,3-Diammopropan, 1,4-diaminobutane, 1,6-diaminohexane, 1,12-dodecanediamine, piperazine, diethylenetriamine or isophoronediamine. Also suitable are the amides of allylamine and unsaturated carboxylic acid are as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or at least dibasic carboxylic acids as have been described above beschrie¬ ben. Also suitable are N-vinyl compounds of urea derivatives, at least difunctional amides, cyanurates or urethanes, spielsweise of urea, ethylene urea, propylene urea or Weinsaurediamid.

Further suitable crosslinkers are tetraallylsilane or tetravinylsilane. Of course, mixtures of the aforementioned compounds can be used. Preferably, such crosslinking agents are used which are soluble in the reaction mixture. Particularly preferred crosslinkers are methylenebisacrylamide, urea di- and triallylamine, divinylimidazole, divinylethyleneurea, reaction products of polyhydric alcohols with acidic or Acryl¬ methacrylic acid, methacrylic esters and Acrylsaure- esters of polyalkylene oxides or polyhydric alcohols with ethylene oxide and / or propylene oxide and / or epichlorohydrin are reacted, allyl methacrylate and divinylbenzene. Very particular preference is methylenebisacrylamide, N, N'-divinyl ethylene urea, Acrylsaure- and methacrylic esters of minde¬ least divalent C 2 - to C 4 alcohols, allyl methacrylate and divinylbenzene. If crosslinking agents are used in the polymerization, they can be up to 30 in amounts, preferably from 0.2 to 20 and very particularly preferably from 0.5 to 10 wt .-%, based on the total monomers used in the polymerization is used, ,

The inventive mixtures consist of polymers and surfactants. Suitable surfactants are, for example, in M. and I. Ash, Handbook of Industrial Surfactants, Gower Publishing Co., Hants, described 1,993th Surfactants may be low molecular weight or polymeric compounds. nonionic surfactants are particularly preferred.

Low molecular weight, non-ionic surfactants include a straight chain in general or branched, saturated or ten ungesättig¬, cyclic or acyclic, aromatic or aliphatic alkyl radical having 8 to 40, preferably 10 to 30, most preferably 12 to 22 carbon atoms in the molecule. The alkyl group may also be completely or partially present fluorinated. The alkyl group is bound to a hydrophilic part of the molecule which contains at least one oxygen or nitrogen atom. Preferred compounds are derivatives, for example, ethers and esters of sugars or sugar, as Saccharoseester, Mannoseester, Xyloseester or sorbitan esters, esters and ethers of glycerol, diglycerol, polyglycerol or glycerol sugar condensates, ceramides and glycosyl ceramides, Fettsaurealkanolaird.de like fatty acid ethanol amides, fatty saureisopropanolamide, Fettsaurediethanolamide, diethanolamides Fettsaurepoly-, N-Alkylpyrrolidonderivate, pyrrolidone-5-carboxylic acid alkyl esters, citric and Weinsaureester, Ci to Ciβ- alkyl (poly) glycosides, Hydroxyalkylpolyglycoside, Fettsaureester of polyhydroxy compounds such as trimethylolpropane , erythritol, pentaerythritol, Neopentyldiglykol, triethanolamine or condensates derived therefrom, alkoxylates, in particular the addition products of ethylene oxide and / or propylene oxide to the above compounds, as well auf¬ guided on oxo alcohols, Cs to C 3 o-alcohols, alkylphenols, fatty acid amides, fatty amines, fatty acids and derivatives such as hydroxycarboxylic acid wherein the polyalkylene oxide chain may be modified one or both sides. At bilateral Modifi¬ cation, the modifying moieties can be the example and constitute a part of a Ci to C 4 -Etherfunktion same or verschie¬.

Other surface-active compounds a) are sorbitan esters, Saccharoseester or Glycerinester of Cs to C ~ 3 o carboxylic acids or alkoxylation products of these esters. The above-th genann¬ esters are preferably derived from Cι 2 - to C 22 from -Carbonsauren. Under alkoxylation preferably the addition cross are to be understood of ethylene oxide to the esters modulation products. up to 80 mol of ethylene oxide can be added per mole of suitable esters. In addition, addition products of ethylene oxide and propylene oxide and / or butylene oxides to the ester as surface-active compounds. Also suitable are alkyl dimethyl.

Polymeric surfactants, the ethylene oxide and / or propylene oxide Einhei- th as hydrophilic part of the molecule contain, are uncrosslinked and have molecular weights of 500 to 100,000, preferably 700 to 20000. The polymeric surfactants may besides at least one hydro¬ philic block at least one hydrophobic comprise block or they are composed of a hydrophilic chain having a comb-like arrangement hydrophobic branches. The hydrophilic portion of the polymeric surfactants is oxide of homopolymers of ethylene oxide or ethylene oxide or Propylen¬ of Blockcopolymerisäten of ethylene oxide and Propylen¬ oxide and block and Kammpolymerisaten with blocks of poly, polypropylene oxide or formed Polyco (ethylene oxide, Propylen¬ oxide), while the hydrophobic part of the polymeric surfactants of blocks of polystyrene, polyalkyl (meth) acrylates, oils Silikon¬ consists Polyhydroxifettsäuren, polyamidoamines, polyisobutylene or polytetrahydrofurans. It can also mere general poly-, which are reacted via at least one amino group, with bases include deprotonation tonierbare hydroxyl group or an anionic group and a molecular weight of 100 to 5000 have, such as ethylene oxide, propylene oxide or mixtures thereof on suitable polymeric Ten¬ Šiden ,

Of the above surfactants are adducts of ethylene oxide and / or propylene oxide to CIO to C3o-alcohols, phenols alkyl, fatty amines or fatty acids, Saccharoseester, Sorbitan¬ ester, (poly) Glycerinester or their corresponding ethoxylates and alkyl (poly) glycosides particularly preferably , Very particularly preferred are addition products of ethylene oxide and / or propylene oxide with Cι 2 - to C 22 ~ alcohols or alkylphenols, Sorbitan¬ ester, Glycerinester or their corresponding ethoxylates containing 12 to 22 carbon atoms in the alkyl chain, and alkyl (poly) glycosides with 8 to 22 carbon atoms in the alkyl chain. The surfactants, for example, have a softening point below 100 ° C, preferably below 60 ° C and most preferably below 40 ° C.

The polymers of the monomers a) and optionally b) and / or optionally c) are known. They can be prepared by verschiede¬ NEN method. Particularly suitable methods are the inverse suspension or emulsion polymerization, wherein an aqueous solution of monomers is emulsified in an inert liquid organi¬ rule and polymerized as well as the lungspolymerisation Fäl-. In the water-in-oil polymerization can conveniently use protective colloids or E ulgatoren. After completion of the polymerization, the water may be removed, for example by azeotropic distillation and the inert organic solvent-are replaced by a nonionic surfactant, by distilling off, for example, the inert organic solvent-preferably one of the amount distilled off added corresponding 5 amount of surfactants ..

In the precipitation polymerization such agents are lots sets einge¬ which dissolve the monomers at least partially, but not so that they precipitate the polymer resulting in a finely divided form 0. For the water-in-oil emulsion suitable wireless means, for example, saturated, straight-chain are, branched or cyclic hydrocarbons such as pentane, hexane, cyclohexane, heptane, octane or isooctane, aliphatic ethers such as dimethyl ether, diethyl ether, diamyl ether, tert-butyl

15 methyl ether or dibutyl ether, ketones such as acetone, Methylet yl ketone, diethyl ketone or methyl amyl ketone, Ci- to Cis-Carbonsaure- ester, for example ethyl formate, methyl acetate, ethyl acetate, iso-propyl, iso-butyl acetate, stearyl acetate, ethylhexanoic acid-ethylhexyl, iso propyl myristate or iso-Pro

20 pylpalmitat, silicone oils such as octamethyl cyclotetrasilane, LIQUID or supercritical carbon dioxide, aromatic hydrocarbons such as toluene or xylene. These inert organic solvent-exchanged be largely aus¬ after polymerization to a surfactant.

25

The mixtures are preferably obtainable by radical polymerization of a) 10 to 100 wt .-% of at least one vinylimidazole of the formula

-30

rl

H 2 C = CH- • N '• N (I)

35 R 2 'R 3 *

in which R 1, R 2 and R 3 are identical or different and represent H, Ci to C 4 alkyl,

Monomers of the formula

40

45

Figure imgf000011_0001
in which R 4 and R 5 are identical or different and represent H, Ci to C 4 alkyl or a ring of 3 to 5 methylene groups together form •,

N-vinyloxazolidone, N-vinyltriazole, 4-vinylpyridine-N-oxide or mixtures of said monomers,

b) 0 to 90 wt .-% of other copolymerizable monoethylenically unsaturated monomers and

c) 0 to 30 wt .-% of at least one monomer compounds having at least two ethylenically unsaturated, nonconjugated Doppel¬

in at least one surfactant.

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 the desired ratio, where the solvents are completely removed subsequent to the polymerization of the reaction mixture. The amount of the organic phase is preferably chosen in the polymerization that the resulting reaction mixture can be stirred during the polymerization. The solids content of the mixtures is, for example in the range of 1 to 60, preferably 15 to 40 wt .-%.

Can be the reaction mixture, small amounts, for example up to 10 wt .-%, preferably up to 4 enforce wt .-%, based on the monomers used, water, methanol, ethanol, isopropanol or protective colloids to increase the solubility of individual Kompo¬ to improve components of the reaction mixture or the Eigen¬ the copolymers formed unions to influence. Spielsweise, the morphology of the polymers in the presence of protective colloids are so influenced that mixtures Anfal len, which have a particularly high polymer content.

Suitable protective colloids are, for example, polyvinylpyrrolidones with K-values ​​of 10 to 100, partially saponified polyvinyl acetates, cellulose ethers, copolymers of maleic acid or maleic anhydride with alkenes, preferably isobutylene or diisobutylene or copolymers of N-pyrrolidone and vinyl acetate. If water is also used in the precipitation, it uses it only in amounts such that the mixture of all components still appears homogeneous before the polymerization.

The molecular weight of the resulting polymer may optionally by adding regulators to the polymerizing mixture lowers the wer¬. For example, compounds as regulators halogen compounds such as carbon tetrachloride, chloroform, bromotrichloromethane, allyl such as allyl alcohol or 2, 5-diphenyl-l-hexene, use aldehydes, formic acid or Ameisensaureester. Preferably, however, compounds are used as polymerization regulators which contain sulfur in bound form, beispiels¬ as bisulfites, sulfites, disulfites and dithionites or compounds bound sulfur to a carbon atom ent hold such as organic sulfides, disulfides, polysulfides, sulfoxides, sulfones and mercapto compounds , Mercapto alcohols, and Mercaptocarbonsauren Mercaptoalkane are particularly preferably employed with 2 to 30 carbon atoms in the molecule, for example, 2-mercaptoethanol, 1,3-mercapto-propanol, 3-mercapto propan-l, 2-diol, 1,4-mercaptobutanol, cysteine, thioglycolic acid, 3- mercaptopropionic acid, Mercaptobernsteinsaue, n-butyl mercaptan, n-hexyl mercaptan, n-dodecyl mercaptan or tert-dodecyl mercaptan. If polymerization regulators are employed, they are used in amounts of 0.1 to 10, preferably 0.1 to 5 wt .-%, based on the monomers in the reaction mixture.

The monomers mentioned above are customarily polymerized under Verwen¬ dung free-radical initiators, usually in an inert gas atmosphere. As radical initiators, hydrogen peroxide or inorganic persulfates may be used as organic compounds of the peroxide, peroxyester, carbonate Perfluorinated or azo type, such as dibenzoyl peroxide, di-t-butylper- oxide, t-butyl hydroperoxide, dilauroyl peroxide, t-butyl perpivalate, t-amyl perpivalate, t-butyl perneodecanoate, 2,2'-azobis (2-amidino- propane) dihydrochloride, 4,4'-azobis (4-cyanovaleriansaure), 2,2'-azobis [2- (2-imιdazolin-2 -yl) propane] dihydrochloride, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile,

2,2'-azobis (2-methylbutyronitrile) and dimethyl 2,2'-azobis (iso-butyrate). It is of course also use initiator mixtures or the known redox initiators. Is preferable to use those initiators which - when the polymerization is carried out in surfactants - to more than 5 wt .-% at 25 ° C are soluble in the surfactants. The initiators are used in the usual amounts, for example in amounts of 0.02 to 5 wt .-%, based on the monomers to be polymerized.

The precipitation polymerization is usually carried out under a Inert¬ gas atmosphere. The polymerization can beispiels¬ example in the manner carried out in that, introducing all components that are present during polymerization in an Polymeri¬ sationsgefäß, starts the reaction and the reaction rate, if appropriate, cooled mixed, to control the polymerization temperature. However, one can also proceed such that a part of the components to initially charge only ein¬ zelne or, starting the polymerization and the rest of the components individually or together, at different intervals depending on the progress of the Polymerisa¬ tion continuously or intermittently added. However, one may also proceed by first introducing only the diluent and the monomers and the polymerization batch in separate tapering in the template or introduced continuously.

The polymerization of the monomers is generally performed at tempera- tures from 40 to 200, preferably 50 to 120 ° C. The temperature can be controlled while Tempe¬ unterschied¬ Lich the reaction according to a program. The polymerization is preferably carried out under atmospheric pressure, but may also take place under verminder¬ system or elevated pressure. Insofar as the polymerization temperature is above the boiling point of the lots agent used, the polymerization in the pressure-tight apparatus is carried out at pressures up to 16 bar.

In the production of crosslinked copolymers produced most - often borrowed heavily removable pads on the walls of the reaction onsgefaße and the stirrers. In the inventive mixtures of Her¬ position by copolymerizing the monomers preferably in Not-ionic surfactants as the precipitating agent, the otherwise interfering deposit formation is practically not observed.

The preparation of polymers, the (formal) in copolymerized form 4-vinylpyridine-N-oxide is carried out, preferably by polymerization or copolymerization of 4-vinylpyridine followed by N-oxidation of the pyridine ring with, for example prepared in situ peracetic acid.

The polymers which grout on a basic N-containing groups can be converted to the reaction by a suitable reagent in a quaternized form in the terminal. For quaternization, for example, alkyl halides such as methyl chloride, ethyl chloride, propyl chloride, hexyl chloride, dodecyl chloride and lauryl chloride or benzyl halides such as benzyl chloride with 1 to 18 Kohlen¬ atoms in the molecule. Of course, the corresponding iodine or bromine compounds are suitable. Suitable quaternizing agents are dialkyl sulfates further, in particular dimethyl and diethyl sulfate. In some cases, it is also sufficient to convert the polymers by treatment with an acid in the salt form. Quaternization can be complete or partial. 12

The reaction mixture may be subsequent to the polymerization process to a physical or chemical aftertreatment unter¬ worfen. Such methods, the known method of reducing residual monomers, such as, for example, an aftertreatment by addition of polymerization initiators or mixtures of several polymerization initiators at suitable temperatures or heating the polymerization solution to temperatures above the polymerization, a post-treatment of the polymer solution by steam or nitrogen stripping or Be - act of the reaction mixture with oxidizing or reducing reagents.

If the polymers are soluble in water, they have K-values ​​of 10 to 300 (determined according to H. Fikentscher in aqueous solution at 25 ° C and a polymer concentration of 1). The average diameter of the polymer is for example 0.1 to 1000, preferably 0.5 to 80 μ.

The suspensions according to the invention of the copolymers in the Tensi- to be used for example as an additive for pharmaceutical or cosmetic preparations, as an additive in papermaking, for the stabilization of enzymes or for the adsorption of metal ions, dyes or acids. Particularly preferred to use as detergent additives is. The polymers cause the washing of colored and white fabrics inhibition of dye transfer to the non-colored Textilien.Insbe¬ sondere the cross-linked copolymers of N-vinylimidazole and N-pyrrolidone Vi¬ are for use in heavy-duty detergents beson¬ DERS suitable because they at low dye concentrations in the wash liquor are significantly more effective than mere soluble Poly. In the full laundry but mainly wei¬ usually SSES and small colored laundry and very fast to washing colored laundry is washed. Washload that makes dye is highly, usually contain only by mistake, and thus in a very small proportion in the material to be washed, for example, when a colored

Sock in the wash. The crosslinked copolymers that bind small amounts of dye transfer inhibitors significantly stronger than water-soluble dyes, therefore, have a great advantage in the application with regard to wasserlösli¬ chen products.

The detergents can be in powder form or else in liquid. supply medium, the composition of detergents and cleaners may vary widely. Washing and cleaning supply ¬ formulations normally contain from 2 to 50 weight surfactants and optionally builder. These data apply both to liquid and powder detergents. Detergent and cleaner formulations customary in Europe, in the United States and Japan may be found for example in Chemical and Engn. News 67, 35 (1989) tabulated. Wei¬ direct information on the composition of detergents and cleaning preparations can Ullmann's Encyclopedia of Industrial Chemistry, Verlag Chemie, Weinheim 1983, 4th edition, pages 63 to 160, are removed. The detergent may optionally contain a bleach such as sodium perborate or Natriumper- carbonate, which may be contained in the case of its use in amounts of up to 30 wt .-% in the detergent formulation. The washing or cleaning agent can optionally further customary

Additives include, for example, complexing agents, opacifiers, optical brighteners, enzymes, perfume oils, other Farbübertragμngsinhibitoren, graying inhibitors, soil release polymers and / or Bleich¬ activators. They contain mixtures of the invention in amounts of 0.1 to 10, preferably 0.2 to 3 wt .-%.

Examples

example 1

In a 2000 ml flask thermometer and an apparatus for working equipped with a stirrer, reflux flußkühler, under protective gas, 440 g of a C 13 / C 15 oxo alcohol which is reacted with 7 units of ethylene oxide per molecule, were was 50 g N-vinylimidazole, 50 g N-vinylpyrrolidone 5 g divinylethyleneurea and 1 g of tert-butyl perpivalate under Rüh¬ ren to 80 ° C heated. The reaction was stirred at this temperature for 5 hours. A finely divided, white Polymer¬ suspension with an average particle size of 14.3 μrn. The suspension was allowed to pour out well from the polymerization vessel, leaving no solid surfaces.

example 2

In a 1000 ml flask, the flußkühler, thermometer equipped with a stirrer, reflux and an apparatus for working equipped under a protective gas were charged 900 g of cyclohexane, 50 g of N-vinylimidazole, 50 g N-vinylpyrrolidone 5 g Divinylethylenharn- material and 1 g of tert-butyl perpivalate heated up with stirring to 80 ° C. The reaction was stirred at this temperature for 5 hours. Subsequently, 595 g of a C 3 / Cιs oxo alcohol that had been reacted with 7 units of ethylene oxide per molecule, were added dropwise over 1 hour while distilling off the cyclohexane via a distillation in a weak stream of nitrogen. A finely divided polymer suspension was obtained with a μ mitt¬ sized particle size of 18.1. example 3

In a 1000 ml flask thermometer and an apparatus for working equipped with a stirrer, reflux flußkühler, under protective gas, 400 ml of a polyoxyethylene were ethylensorbitanstearats, ethylene urea, 100 g N-vinyl pyrrolidone, 8 g of divinyl and 1 g to stirred tert-Amylperneodecanoat for 6 Stun at 72 ° C. A finely divided Polymersuspen¬ sion was obtained having a mean particle size of 12.4 microns.

example 4

In a 1000 ml flask thermometer and an apparatus for working equipped with a stirrer, reflux flußkühler, under a protective gas, 400 g rat Sorbitanmonolau- heated 100 g vinyl imidazole and 2 g of allyl methacrylate at 80 ° C. At this temperature, an inlet of 1 g of 2,2'-Azo¬ bis (2-methylisobutyronitrile) was added in 50 ml sorbitan monolaurate for 4 hours. The reaction mixture was left for a further 2 hours at 80 ° C. A finely divided polymer suspension was obtained with an average particle size of 17.2 microns.

example 5

In a 2000 ml flask, the flußkühler, thermometer equipped with a stirrer, reflux and an apparatus for working equipped under a protective gas, 800 g of cyclohexane, 5 g of sorbitan monolaurate, and 5 g of an ABA block copolymer hydroxystearic of poly- and polyethylene oxide with a molecular weight of about 7500, sold by the company ICI under the

Name Hypermer B 246, heated to 65 ° C. Once this temperature was reached, a feed of 100 g N-vinylpyrrolidone, 100 g of vinylimidazole, 10 g divinylethyleneurea water was added dropwise over 30 minutes urea and 0.5 g of 2,2'-azobis (amidinopropane) dihydrochloride in 140 g. Subsequently, the mixture further 6 hours at this temperature was stirred. The temperature was then raised to the boiling point of the mixture and the water azeotropically via a water from the mixing Reaktionsge¬ distilled off. Subsequently, 800 g of a Cs / Cio-alkyl polyglycoside were added dropwise over one hour, while distilling off the material flow cyclohexane over a distillation bridge in the weak Stick¬. A finely divided Polymer¬ was obtained suspension with an average particle size of 7.3 microns. Application Examples

Test method

White building wool test fabric was washed under the genann¬ in Table 1 th wash conditions and with the addition of the detergent according to Table 2 in the presence of dye. The dye was dissolved abge¬ during washing of cotton test dyeings.

Table 1 contains the washing conditions for the examples. The composition of the detergent used is given in Table 2 below. The measurement of the staining of the test was carried out by photometry. the respective color strengths of the dyeings were determined by the in A. Kud, soaps, oils, fats, waxes, Volume 119, 590-594 (1993) described methods from the measured at the individual test reflectance values. From the Farb¬ strengthen for the test with the respective test substance, the color intensity for the test without test substance, and the color strength of the test before washing, after the point in the above-mentioned literature references described method determines the dye transfer inhibiting effect of the test substance in% (Farbübertragungsinhibie- tion is analogously treated to graying inhibition). The performances are shown in Table 3 for the different dyes.

Table 1: washing conditions

Device Launder-O-meter

cycles 1

Duration 30 min

Temperature 60 ° C

Water hardness 3 mmol / 1 dye Entry Color tissue

Test fabric 2.5 g cotton cloth (bleached)

Amount of liquor 250 ml

Detergent concentration 4.5 g / 1 Table 2:

detergent composition

Ingredients Amount [%]

Linear Cιo / Ci3-Alkylbenzolsulf onth Na salt

(50%) 8, 6

Fatty alcohol sulfate sodium salt 2, 7

Addition product of 10 mol of ethylene oxide to 1 mol Cι 3 / Ci 5 oxo alcohol 6, 3

Zeolite A 5f

Na-citrate 5 5 H 2 0 9 0

Copolymer of 70 wt .-% acrylic acid and

30 wt .-% of maleic acid, molecular weight of 70 000 4 0 Na-carbonate 6, 0

Na-sulphate 5, 8

Carboxymethylcellulose 0 5

Test substance 1 0

The wash results with the novel polymer are given in Table 3 below.

table 3

Figure imgf000019_0001

The washing results in Table 3 show that the polymers of invention according to the invention have very good activity as dye transfer inhibitors, the color transfer inhibitors often employed in detergent polyvinylpyrrolidone or polyvinylpyrrolidone-covinylimidazol (Comparative Example 2) in many cases significantly exceeded. The results also show that the color transfer inhibiting effect on many Direktfarb¬ occurring materials and is not limited to individual representatives.

Claims

claims
1. mixtures of polymers and surfactants, characterized gekennzeich- net that it contains 1 to 50 wt .-% of a polymer of
a) 10 to 100 wt .-% of at least one vinylimidazole of the formula
R l
H 2 C = CH N "^ N t 1 2) '* R 3
in which R 1, R 2 and R 3 are the same or different and stand for H, Ci to C 4 -alkyl, monomers of the formula
Figure imgf000020_0001
in which R 4 and R 5 are identical or different and represent H, Ci to C 4 alkyl or form a ring of 3 to 5 methylene groups,
N-vinyloxazolidone, N-vinyltriazole, 4-vinylpyridine-N-oxide or mixtures of said monomers,
b) 0 to 90 wt .-% of other copolymerizable mono-ethylenically unsaturated monomers and
c) 0 to 30 wt .-% of at least one monomer compounds having at least two ethylenically unsaturated, nonconjugated Doppel¬
in suspended form.
2. Mixtures according to claim 1, characterized in that they are obtainable by free radical polymerization of a) 10 to 100 wt .-% of at least one vinylimidazole of the formula
Ri
H 2 C = CH "^ N (I),
Y ^ R 3
in which R 1, R 2 and R 3 are the same or different and stand for H, Ci to C 4 -alkyl, monomers of the formula
H 2 C = CH NCR 5 (III
R 4
in which R 4 and R 5 are identical or different and represent H, Ci to C 4 alkyl or form a ring of 3 to 5 methylene groups, N-vinyloxazolidone, N-vinyltriazole, 4-vinylpyridine-N-oxide, or mixtures of said monomers,
b) 0 to 90 wt .-% of other copolymerizable monoethylenically unsaturated monomers and
c) 0 to 30 wt .-% of at least one monomer compounds having at least two ethylenically unsaturated, nonconjugated Doppel¬
in at least one surfactant.
3. Mixtures according to claim 1, characterized in that the polymers
(A) N-vinylimidazoles of the formula (I), N-vinyl pyrrolidone or mixtures of these monomers, and (c) compounds of at least one monomer having at least two ethylenically unsaturated, nonconjugated Doppel¬
in copolymerized form. 23
4. A mixture according to claim 2, characterized in that they are obtainable by polymerizing
(A) N-vinylimidazoles of the formula I, N-vinylpyrrolidone or mixtures of these monomers and
(C) compounds of at least one monomer having at least two ethylenically unsaturated, nonconjugated Doppel¬
in at least one nonionic surfactant.
5. Mixtures according to claim 2, characterized in that they are obtainable by polymerizing
(A) N-vinylimidazoles of the formula I, N-vinyl pyrrolidone or mixtures of these monomers, and (c) at least one monomer compounds having at least two ethylenically unsaturated, nonconjugated Doppel¬
in at least one alkoxylated with ethylene oxide and / or propylene oxide alcohol.
6. A process for the preparation of the mixtures according to claim 1, characterized in that
(A) 10 to 100 wt .-% of at least one vinylimidazole of the formula
R 1
H 2 C = CH ^^ N (I)
'R 3
in which R, R2 and R3 are the same or different and represent H, Ci to C alkyl,
Monomers of the formula
0
H 2 C = CH N c R 5 (II) '
R 4 in which R 4 and R 5 are identical or different and represent H, Ci to C 4 alkyl or form a ring of 3 to 5 methylene groups,
N-vinyloxazolidone, N-vinyltriazole, 4-vinylpyridine-N-oxide or mixtures of said monomers,
(B) 0 to 90 wt .-% of other copolymerizable monoethylenically unsaturated monomers and
(C) 0 to 30 wt .-% of at least one non-conjugated monomer having at least two ethylenically unsaturated double bonds
free radical polymerization in at least one surfactant, at temperatures of at least 50 ° C or in that the monomers (a) and optionally (b) and / or optionally (c) is polymerized in the aqueous phase of a water-in-oil suspension radical and after completion the polymerization, the oil phase of the water-in-oil suspension replaced by at least one surfactant.
7. Use of the mixtures according to claim 1 as additive to detergents.
PCT/EP1996/002178 1995-05-26 1996-05-21 Polymer and surfactant mixtures, process for their preparation and their use WO1996037524A1 (en)

Priority Applications (2)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2814287A1 (en) * 1978-04-03 1979-10-11 Henkel Kgaa Detergent compsn. contg. N-vinyl! imidazole polymer - as discoloration-inhibiting additive
DE4421179A1 (en) * 1994-06-17 1995-12-21 Basf Ag Dye transfer inhibitors for detergents and cleaning products

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2814287A1 (en) * 1978-04-03 1979-10-11 Henkel Kgaa Detergent compsn. contg. N-vinyl! imidazole polymer - as discoloration-inhibiting additive
DE4421179A1 (en) * 1994-06-17 1995-12-21 Basf Ag Dye transfer inhibitors for detergents and cleaning products

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