CA2221609A1 - Graft copolymers based on mono-, oligo- and polysaccharides, process for preparing the same and their use - Google Patents
Graft copolymers based on mono-, oligo- and polysaccharides, process for preparing the same and their use Download PDFInfo
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- CA2221609A1 CA2221609A1 CA002221609A CA2221609A CA2221609A1 CA 2221609 A1 CA2221609 A1 CA 2221609A1 CA 002221609 A CA002221609 A CA 002221609A CA 2221609 A CA2221609 A CA 2221609A CA 2221609 A1 CA2221609 A1 CA 2221609A1
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3788—Graft polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- Oil, Petroleum & Natural Gas (AREA)
- Graft Or Block Polymers (AREA)
- Detergent Compositions (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
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Abstract
Water-soluble graft copolymers of monosaccharides, oligosaccharides, polysaccharides and their derivatives are obtained by radically initiated copolymerisation of (A) monomer mixtures of (a) more than 40-100 % by weight of at least one .alpha.-.beta.-unsaturated aldehyde having general formula (I), in which R1 stands for hydrogen or linear or branched C1-C4 alkyl, and R2 stands for hydrogen or methyl, (b) 0-60 % by weight of monoethylenically unsaturated monomers different from (a) but copolymerisable with (a), and (c) 0-5 % by weight of at least two ethylenically unsaturated monomers having no conjugated double bonds in their molecule, in the presence of (B) monosaccharides, oligosaccharides, polysaccharides, polysaccharides decomposed by oxidation, hydrolysis or enzymes, chemically modified mono-, oligo- or polysaccharides or mixtures of said compounds; and (C) one or several oxidants. The weight ratio between (A) and (B) extends from (95: 20) to (5:
80) and the weight ratio between (C) and (A) + (B) extends from (5: 100) to (50: 50). Used as builders or co-builders, these graft copolymers have good scale-inhibiting properties and are extremely biodegradable.
80) and the weight ratio between (C) and (A) + (B) extends from (5: 100) to (50: 50). Used as builders or co-builders, these graft copolymers have good scale-inhibiting properties and are extremely biodegradable.
Description
,. ~
Graft copolymers based on mono-, oligo- and polysaccharides, process for preparing the same and their use S This invention relates to graft copolymers based on natural raw materials, the graft copolymers being obtainable by the copolymerisation of ethylenically unsaturated monomers in the presence of saccharides or derivatives thereof. This invention also relates to a process for producing copolymers of this type and to the use of the graft copolymers as a water treatment agent, an incrustation inhibitor and as a detergent additive, namely as a so-called cobuilder.
The use of copolymers, which are obtained by grafting acrylic acid and methacrylic acid on to starch or other hydroxy compounds, in detergents for inhibiting re-soiling is known from US 3,558,499.
According to JP-A-55/155 097, an oxidised starch grafted with sodium acrylate, an oxidised starch grafted with hydroxypropyl methacrylate, or a maize starch-polyvinyl alcohol graft copolymer are used in an amount of 0.05 to 5 ~ by weight in detergent formulations to prevent the re-soiling of laundry during washing.
Copolymers of acrylic acid with other unsaturated compounds, which can be produced by polymerisation in the presence of monosaccharides which are capable of enolate formation, are known from EP 0 239 895 B1. The aforementioned patent also describes their use as cobuilders in detergents and cleaning materials.
DE 40 03 172 A1 or EP 0 441 197 discloses graft copolymers of monosaccharides, oligosaccharides and polysaccharides which are obtainable by radical-initiated graft copolymerisation from _W0 96/37530 PCT/EP96/01922 A) monomer mixtures comprising a) 90 to 10 ~ by weight of monoethylenically unsaturated C4 to C8 dicarboxylic acids, or anhydrides or alkali and/or ammonium salts thereof, b) 10 to 90 ~ by weight of monoethylenically unsaturated C3 to C10 carboxylic acids, or alkali and/or ammonium salts thereof, c) 0 to 40 ~ by weight of other monoethylenically unsaturated monomers which are copolymerisable with monomers (a) and (b), and~5 d) 0 to 5 ~ by weight of monomers containing at least two ethylenically unsaturated unconjugated double bonds in their molecule, in the presence of B) monosaccharides, oligosaccharides, polysaccharides;
oxidatively, hydrolytically or enzymatically decomposed polysaccharides; oxidised, hydrolytically decomposed or oxidised, enzymatic.ally decomposed polysaccharides; chemically modified mono-, oligo-and polysaccharides or mixtures of the said compounds in a weight ratio (A) : (B) of (95 to 20) : (5 to 80).
DE 40 38 908 A1 relates to the use of graft copolymers according to DE 40 03 172 A1 as cobuilders.
Graft copolymers are known from DE 42 21 381 C1 which are obtainable by the radical copolymerisation of an ethylenically unsaturated monocarboxylic acid or a salt thereof and monomers containing monoethylenically unsaturated sulphonic acid groups, and optionally of -~
. CA 0222l609 lgg7-ll-l9 _WO 96/37530 PCT/EP96/01922 other water-soluble monomers. The use of graft copolymers of this type as cobuilders is also described.
.
DE 23 57 036 relates to polycarboxylates having a defined biodegradability. These known polycarboxylates are used as builders in the formulation of solid or liquid cleaning materials. They are produced by the oxidative polymerisation of acrolein, on its own or in the presence OL aclylic acid, in the presence of thioethylene glycol.
DE 23 30 260 discloses a process for producing polycarboxylates by the oxidative polymerisation of acrolein on its own or together with acrylic acid, polymerisation being carried out with the addition of n-dodecylmercaptan.
EP 0 609 777 relates to detergent compositions having an improved dirt-carrying capacity, with the use of a suitable polycarboxylate. The co-builders disclosed are obtained by the copolymerisation of acrolein and acrylic acid, for example, under suitable conditions.
In Polym. J. 11 (1979) 85, G. Maher describes graft copolymers which are produced by the polymerisation of vinyl monomers on to starch xanthate. Acrolein, acrylamide, acrylic acid, acrylonitrile, methyl acrylate or styrene were investigated as the vinyl monomers. In the course of this procedure, the respective monomer was reacted with an aqueous system comprising completely soluble starch xanthate and hydrogen peroxide (at an alkaline pH), and a gel-like,-crosslinked product was formed in each case, comprising graft copolymers in a self-generated acidic medium. For example, a gel-like product was formed with acrolein, and vigorous gas evolution occurred during the polymerisation reaction, with the formation of bubbles which could not escape rapidly enough on account of the rapid formation of gel.
This effect led to the proposal that this reaction and -~
~ CA 0222l609 lgg7-ll-l9 the products thereof be employed in the production of foam rubber (US-4,005,040).
Polycarboxylates are known from DE 44 17 734.8 which are produced by the polymerisation of acrolein and vinyl acetate in aqueous solution in the presence of hydrogen peroxide and optionally of other batch materials. The polymers exhibit a biodegradability of , 30 ~.
Derwent Abstract 86-085028/13 of JP-61 031 498 discloses graft polymers of acrylic acid or maleic acid on glucose, fructose or other defined sugars. As mixtures of cobuilders, these are claimed to provide enhanced washing power and improved biodegradability.
It has in fact been shown that the incrustation of textiles during washing can be reduced by the polycarboxylate products which are commonly available on the market. However, further optimisation of cobuilders is desirable in order to increase the efficacy of detergents and thus further to improve the usage properties of textiles at the same time. The underlying object of the invention described below is accordingly to provide polymers, which as far as possible are based on reproductively grown raw materials and inexpensive batch materials, which exhibit an incrustation-inhibiting effect which is better than or at least as good as that of the products used hitherto, and which at the same time exhibit outstanding biodegradability.
The said object, and other objects not mentioned in detail, are achieved by means of the water-soluble graft copolymers of monosaccharides, oligosaccharides, polysaccharides and derivatives thereof according to the invention, which are obtainable by the radical-initiated copolymerisation of A) monomer mixtures comprising -~
~ CA 0222l609 lgg7-ll-l9 a) more than 40 - 100 ~ by weight of at least one ~ unsaturated aldehyde of general formula I
.~,0 R1 _ GH = C - C (I), H
where Rl represents hydrogen or a linear or branched Cl-C4 alkyl, and R2 represents hydrogen or methyl, b) ~ ~ 60 ~ by weight of a) different monoethylenically unsaturated monomers which are copolymerisable with a), and c) 0 - 5 ~ by weight of monomers containing at least two ethylenically unsaturated, unconjugated double bonds in their molecule, in the presence of B) monosaccharides, oligosaccharides, polysaccharides;
oxidatively, hydrolytically or enzymatically decomposed polysaccharides; chemically modified mono-, oligo- or polysaccharides; or mixtures of the said compounds, and C) one or more oxidising agents, wherein the weight ratio of A) to B) extends from (95 : 20) to (5 : 80) and the weight ratio of C) to - A) + B) extends from (5 : 100) to (50 : 50).
Because the graft copolymers of the present invention are based on natural, reproductively grown raw materials, namely the said saccharides and their derivatives B), they give little cause for concern ecologically and they are relatively inexpensive. The ~,~-unsaturated aldehydes of formula I, which as component (a) constitute -~
CA 0222l609 l997-ll-l9 WO 96/37530 . PCT/EP96/01922 the major part of the monomer mixtures A) which are grafted on to component B), are also relatively inexpensive raw materials, particularly acrolein.
However, the graft copolymers which are obtainable in this manner exhibit a good incrustation-inhibiting effect and at the same are outstandingly biodegradable.
The ~,~-unsaturated aldehydes of formula I which can successfully be used according to the invention comprise those in which R1 is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl and/or tert.-butyl, whilst R2 represents hydrogen or methyl.
One or more compounds of formula I may be used in admixture with each other as component (a).
Acrolein and/or methacrolein are particularly suitable as monomers of group (a). The use of acrolein is particularly advantageous on economic grounds.
Monoethylenically unsaturated C3 to C10 monocarboxylic acids and alkali and/or ammonium salts thereof are suitable as monomers of group (b). Examples of these monomers include acrylic acid, methacrylic acid, ethylacrylic acid, allylacetic acid and vinylacetic acid.
From this group of monomers, acrylic acid, methacrylic acid, mixtures thereof and their sodium, potassium or ammonium salts or mixtures thereof are preferably used.
These monomers are either polymerised on their own as component (b), or are polymerised in admixture with monoethylenically unsaturated dicarboxylic acids or anhydrides thereof as component (b), together with (a) and optionally (c) in the presence of natural products (B) under oxidising conditions. In this respect, the expression "under oxidising conditions" is to be understood as the use of an oxidising agent C) in a weight ratio of C) to A) + B) of (5 : 100) to (50 : 50), wherein C) has sufficient oxidising power to effect the -~
t . CA 02221609 1997-11-19 oxidation of carbonyl groups and the oxidation and decomposition of the polysaccharide used and thus to initiate the polymerisation of mixture a) to c) star~ing from the polysaccharide.
Suitable unsaturated dicarboxylic acids contain 4 to 8 C
atoms, e.g. maleic acid, fumaric acid, itaconic acid, methylenemalonic acid, citraconic acid, maleic anhydride, itaconic anhydride and methylenemalonic anhydride. The monoethylenically unsaturated C4 to C8 dicarboxylic acids may be used in the graft polymerisation in the form of the free acids or in the form in which they are neutralised with alkali metal bases, ~mmo~; a or amines.
Of the dicarboxylic acids or anhydrides thereof which are suitable, maleic acid, maleic anhydride, itaconic acid or itaconic anhydride and the sodium, potassium or ammonium salts of maleic acid or itaconic acid are preferably used. These salts can be obtained, for example, from maleic anhydride or itaconic anhydride by neutralising the said anhydrides in aqueous solution with sodium hydroxide solution or potassium hydroxide solution, or with ammonia or amines.
Examples of monomers of group (b) which can also be used in the graft polymerisation include C1 to C6 alkyl esters and hydroxyalkyl esters of the said compounds, e.g.
methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, maleic acid monomethyl ester, maleic acid diethyl ester, hydroxyethyl acrylate, hydroxypropyl acrylates, hydroxybutyl acrylates, hydroxyethyl methacrylate and hydroxypropyl methacrylate. The amides and N-substituted alkyl amides of the said compounds are also suitable as monomers of group (b), e.g. acrylamide, methacrylamide, N-alkylacrylamides containing 1 to 18 C
atoms in the alkyl group, such as N-methylacrylamide, N-dimethylacrylamide, N-tert.-butylacrylamide, N-octadecylacrylamide, maleic acid monoethylhexylamide, maleic acid monododecylamide, dimethylaminopropyl -methacrylamide and acrylamidoglycolic acid.
Alkylaminoalkyl (meth)acrylates are also suitable as monomer (b), e.g. dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate and dimethylaminopropyl methacrylate.
Monomers which contain sulphonic acid groups are also suitable as monomers of group (b), such as vinylsulphonic acid, allylsulphonic acid, methallylsulphonic acid, styrenesulphonic acid, acrylic acid-3-sulphopropylester, methacrylic acid-3-sulphopropyl ester and acrylamidomethyl-propanesulphonic acid for example, as well as monomers containing phosphonic acid groups, such as vinylphosphonic acid, allylphosphonic acid and acrylamidomethylpropane-phosphonic acid for example. This group of monomers also includes N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinyl-N-methylformamide, 1-vinylimidazole, 1-vinyl-2-methylimidazole, vinyl acetate and vinyl propionate.
Also suitable as monomers of group (b) are the esters of alkoxylated C1 to C18 alcohols which are reacted with 2 to 50 moles of ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with the monoethylenically unsaturated carboxylic acids of group (a), e.g. the esters of acrylic acid, methacrylic acid or maleic acid with a C13/C1s oxoalcohol which has been reacted with different amounts of ethylene oxide, e.g. 3 moles, 5 moles, 7 moles, 10 moles or 30 moles of ethylene oxide.
Both the mono- and diesters of the dicarboxylic acids are suitable as the esters.
The basic monomers are preferably used in the form of their salts with mineral acids, e.g. hydrochloric acid, sulphuric acid or nitric acid, or in quaternarised form -~
(examples of suitable quaternarisation agents include dimethyl sulphate, diethyl sulphate, methyl chloride, ethyl chlQride or benzyl chloride).
Amides of monoethylenically unsaturated C3 to C8 carboxylic acids with amide groups of the said structure are also suitable as monomers of group (b).
-The prefer.ed monomers of group (b) are acrylic acid, methacrylic acid, maleic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, vinyl acetate, N-vinyl pyrrolidone, acrylamidomethyl-propanesulphonic acid and N-vinyl-imidazole.
A further modification of the graft copolymers can be obtained by conducting the graft polymerisation in the presence of monomers of group (c). In this case, the monomer mixtures contain up to 5 ~ by weight of a monomer having at least two ethylenically unsaturated unconjugated double bonds in its molecule. These compounds are usually employed as crosslinking agents in copolymerisation reactions. They may be added to the monomers of group (a) or to the monomer mixtures of (a) and (b) used for copolymerisation. When they are used, the amount of monomers (c) which is used is preferably 0.05 to 2 ~ by weight. The use in conjunction of monomers of group (c) during the copolymerisation effects an increase in the molecular weight of the copolymer.
Examples of suitable compounds of this type include methylene-bis-acrylamide, esters of acrylic acid and methacrylic acid with polyhydric alcohols, e.g. glycol diacrylate, glycerine triacrylate, glycol dimethacrylate, glycerine trimethacrylate, and polyols which are esterified at least twice with acrylic acid or methacrylic acid, such as pentaerythritol and glucose.
In addition, divinylbenzene, divinyldioxane, pentaerythritol triallyl ether and pentaallyl sucrose are suitable crosslinking agents. Water-soluble monomers, --, CA 0222l609 lgg7-ll-l9 such as glycol diacrylate or diacrylates of polyethylene glycols having a molecular weight up to 3000, are preferably used from this group of compounds.
s Polymerisation of monomers (a) and optionally of (b) and (c) in addition is effected in the presence of natural products based on polysaccharides, oligosaccharides, monosaccharides and derivatives thereof. These natural products may, for example, be saccharides of vegetable or ~n;m~l origin or products of the metabolism of microorganisms, or decomposition and modification products thereof which are already dispersible or soluble in water or alkali, or which, during the polymerisation of monomers (a) and optionally (b) and (c), become directly, completely or partially dispersible or soluble in the form in which they are neutralised with alkali, ammonia or amines.
Examples of these substances include starch, pectin, algin, chitin, chitosan, heparin, carrageenan, agar, gum arabic, gum tragacanth, karaya gum, ghatti gum, carob seed grain, guar gum, Tara gum, inulin, xanthan, dextran, saccharose, nigeran and pentosans such as xylan and araban, the major constituents of which consist of D-glucuronic acid, D-galacturonic acid, D-galacturonic acid methyl ester, D-mannuronic acid, L-guluronic acid, D- and L-galactose, 3,6-anhydro-D-galactose, L-arabinose, L-rhamnose, D-glucoronic acid, D-xylose, L-fucose, D-mannose, D-fructose and D-glucose, 2-amino-2-desoxy-D-glucose and 2-amino-2-desoxy-D-galactose and the N-acetyl - derivatives thereof.
Considered from an economic standpoint, the following are preferably used as polysaccharides of component (B) during the graft copolymerisation: starch, thermally and/or mechanically treated starch, starches decomposed oxidatively, hydrolytically or by enzymatic oxidation, oxidised starches decomposed by enzymatic hydrolysis or -~
. CA 0222l609 lgg7-ll-l9 by enzymatic oxidation, and also chemically modified starches and chemically modified monosaccharides and oligosaccharides.
In principle, all starches are suitable. Starches from maize, wheat, rice or tapioca, and starches from potatoes in particular, are preferred, however. Starches are practically insoluble in water and can be converted into a water-soluble form in the known manner by thermal and/or mechanical treatment or by enzyme- or acid-catalysed decomposition. Oxidatively decomposed starches are also suitable as component (B). The following compounds should be cited as examples of starch decomposition products which are obtainable by the oxidative, hydrolytic or enzymatic decomposition of starch: dextrins such as white and yellow dextrins, maltodextrins, glucose syrups, maltose syrups, hydrolysates with a high content of D-glucose, products of the conversion of starches into sugars, and maltose and D-glucose and their isomerisation product fructose.
Mono- and oligosaccharides are also of course suitable as component (B), such as galactose, mannose, ribose, saccharose, raffinose, lactose and trehalose, as well as decomposition products of cellulose, for example cellubiose and oligomers thereof.
Oxidised starches are also suitable as component (B), such as dialdehyde starch and oxidised starch decomposition products, for example gluconic acid and glucuronic acid. Compounds such as these are obtained, - for example, by the oxidation of starch with periodate, chromic acid, hydrogen peroxide, nitrogen dioxide, nitrogen tetroxide, nitric acid or hypochlorite.
Chemically modified polysaccharides, particularly chemically modified starches, are also suitable as component (B), e.g. starches and starch decomposition products which are reacted with acids to form esters and -~
CA 0222l609 l997-ll-l9 WO 96/37530 12 PCT~EP96/01922 which are reacted with alcohols or alkyl halides, such as chloroacetic acid, for example, to form ethers. It is possible to esterify these substances both with inorganic and with organic acids or anhydrides or chlorides thereof. Phosphated and acetylated starches, carboxymethyl starch and starch decomposition products are of particular commercial interest. The commonest method of etherifying starch is the treatment of starch and of starch decomposition products with organic-halogen compounds, epoxides or sulphates in aqueous alkaline solution. Bxamples of starch ethers include the alkyl ethers, hydroxyalkyl ethers, carboxyalkyl ethers and allyl ethers of starch. In relation to component (B), the expression "chemically modified starches" should also be understood as comprising cationically modified starches, e.g. starches reacted with 2,3-epoxypropyl-trimethylammonium chloride, such as those described in US-PS 3,649,616 for example.
Examples of chemically modified polysaccharides also include carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethyl-hydroxyethylcellulose, sulphoethylcellulose, carboxymethyl-sulphoethylcellulose, hydroxypropyl-sulphoethylcellulose, hydroxyethyl-sulphoethylcellulose, methyl-sulphoethylcellulose and ethyl-sulphoethylcellulose.
Chemically modified decomposed starches are also suitable as component (B), for example the hydrogenatio~ products of starch hydrolysates, such as sorbitol and mannitol, maltitol and hydrogenated glucose syrups, or oxidised, hydrolytically decomposed starches or oxidised, enzymatically decomposed starches.
All the oxidising agents familiar to one skilled in the art are suitable as component (C). These comprise, amongst others, hydrogen peroxide, hypochlorite, nitrogen CA 0222l609 lgg7-ll-l9 dioxide, nitrogen tetroxide, nitric acid, chromic acid and/or periodate. Hydrogen peroxide is preferably used as the oxidising agent. Mixtures of a plurality of oxidising agents may also be used.
The graft copolymers according to the invention are preferably composed of 20 to 95 ~ by weight of monomer mixture (A) and 5 to 80 ~ by weight of component (B). In this connection, products containing 25 to 70 ~ by weight of monomer mixture (A) and 30 to 75 ~ by weight of component (B) are particularly preferred.
If the content of monomer mixture is less than 20 ~ by weight, the washing properties are unsatisfactory. On the other hand, if the content of monomer mixture is greater than 95 ~ by weight the biodegradability is unsatisfactory.
The present invention also relates to a process for producing graft copolymers of monosaccharides, polysaccharides and derivatives thereof by the radical-initiated copolymerisation of A) 95 to 20 ~ by weight of ethylenically unsaturated monomers in the presence of B) 5 to 80 ~ by weight of at least one monosaccharide, oligosaccharide, polysaccharide, decomposed or chemically modified mono-, oligo- and polysaccharide or mixtures thereof, and C) one or more oxidising agents in an inert diluent at temperatures up to 180~C, wherein mixtures comprising a) 40 - 100 ~ by weight of at least one ~,~-unsaturated aldehyde of general formula I
R1 _ CH=C-C (I), H
, CA 0222l609 lgg7-ll-l9 Wo 96/37530_ PCT/EP96/01922 where R1 represents hydrogen or a linear or branched C1-C4 alkyl, and R2 represents hydrogen or methyl, .
b) ~ ~ 60 ~ by weight of a) different monoethylenically unsaturated monomers which are copolymerisable with a), and c) 0 - 5 ~ by weight of monomers containing at least two ethylenically unsaturated, unconjugated double bonds in their molecule, are used as the ethylenically unsaturated monomers A), and the one or more oxidising agents C) are used in a weight ratio of C) to A) + B) of (5 : 100) to (50 : 50).
If the oxidising agent is present in a weight ratio of C) to A) + B) which is less than (5 : 100), insufficient carboxyl groups are produced in the molecule to achieve satisfactory washing properties. However, if the weight ratio of C) to A) + B) is greater than (50 : 50), the molecular weight of the graft polymer is too low due to oxidative decomposition and no advantageous washing properties are obtained.
Polymers are obtained by the polymerisation of ~,~-unsaturated aldehydes under oxidising conditions which can still contain, as structural elements, free aldehyde groups or the acetal thereof, acid groups, acid groups esterified with 3-hydroxypropionic acid, alcohol groups, and also ether groups. A precise determination of the structure of the polymers is difficult, however.
The production of the polymers according t-o the invention also results in the oxidation of the mono- or polysaccharides used, wherein carboxyl groups, which presumably also contribute to the observed washing effect, are incorporated therein, and radicals on to which ~,~-unsaturated aldehydes and other monomers can polymerise are produced on the saccharide molecules. In addition, bonding of component (B) to the polymers formed --WO 96/37530 _ 15 PCT/EP96/01922 from (A) can occur via the aldehyde groups of component (A) with the formation of a semi-acetal or acetal.
As mentioned above, the preceding statements are merely an attempted explanation; the technical teaching given in the claims is independent of the correctness thereof, however.
Suitable initiators for the polymerisation comprise hydrogen peroxide, persulphuric acid and the sodium, potassium and ammonium salts thereof, and percarbonic acid, perboric and perphosphoric acid, peroxycarboxylic acids and salts thereof. Hydrogen peroxide is preferably used as the initiator.
Since hydrogen peroxide is also a preferred oxidising agent, in one advantageous embodiment of the invention hydrogen peroxide is most preferably used both as an initiator and as an oxidising agent.
Production of the polymer according to the invention is preferably conducted in aqueous solution, wherein components (A) and (B) and the oxidising agent may be placed in the reaction vessel or added during the reaction. Preferably, component (B) is placed in the reaction vessel and (A) is added. Oxidising agent (C) may be placed in the vessel or added during the reaction, according to choice. The mono- or polysaccharide B) may also firstly be pre-oxidised and partially decomposed with oxidising agent C) before commencing the addition of monomer mixture A). The temperature range which is suitable for the reaction is between 50 and 100~C;
temperatures between 65 and 85~C are preferred. The components are typically added at a metered rate over a period of 1 to 6 hours. Heating is then continued for a further 1 to 6 hours at temperatures between 70 and 100~C
in order to ensure that the reaction proceeds to completion. --, CA 0222l609 l997-ll-l9 WO 96/37530 . PCT/EP96/01922 The product obtained may be used without further treatment or may be concentrated before use, or may be dried by methods known to one skilled in the art, such as spray-drying for example. In particular, it may also be mixed with other detergent and cleaning material components before work-up.
The graft copolymers according to the invention are polycarboxylates which have the advantage~that in addition to a good bonding capacity for lime they exhibit outstanding biodegradability and effect an outstanding inhibition of incrustation.
The polycarboxylates according to the invention may be used both as cobuilders and as builders in detergents.
When employed as cobuilders, they can be used in addition to known builders such as zeolite A for example, or layer silicates such as SKS-6, or amorphous disilicates.
They can be used in combination with water-soluble or water-insoluble, inorganic and/or organic builder materials. Examples of suitable inorganic builder substances include zeolites, phosphates and sodium silicates.
The zeolite used is preferably finely divided zeolite NaA. Zeolite NaX and Zeolite NaP and mixtures of these three zeolites are also suitable, however. In particular, zeolites of this type have an average 30 particle size less than 10 ~m and preferably contain 18 to 22 ~ by weight of water (determined as the loss on ignition at 1000~C for one hour). The zeolites may also be used as a stabilised suspension, however. In this connection, small amounts of added nonionic surfactants 35 effect stabilisation of the suspension.
Amorphous or crystalline alkali silicates may be present as a replacement or partial replacement for phosphates --, CA 0222l609 lgg7-ll-l9 and zeolites. The preferred alkali silicates are sodium silicates, particularly amorphous sodium silicates, with an Na2O : SiO2 molar ratio of 1.5 to 3. Amorphous alkali silicates of this type are obtainable under the name Portil~ (Henkel), for example. Co-granulates of soda and amorphous sodium disilicates, which are known by the trade name Nabion 15~ (Rhone-Poulenc), for example, may also be used. Crystalline layer sodium silicates of general formula NaMSix02x+l.yH2o~ where-M denotes sodium or hydrogen, x is a number from 1.9 to 4, y is a number from 0 to 20, and a preferred value of x = 2, are preferably used as crystalline silicates which may be present on their own or in admixture with amorphous silicates.
Crystalline layer silicates of this type are described in European Patent EP 0 164 514. Both ~- and ~-sodium disilicates are particularly preferred.
Examples of organic builders which can be used include polycarboxylic acids, which are preferably used in the form of their sodium salts, such as polyacrylic acid, polymethacrylic acid and copolymers thereof with maleic acid, as well as tartaric acid, citric acid, succinic acid, adipic acid, glutaric acid, saccharic acids, aminocarboxylic acids, nitrilotriacetic acid and mixtures of these, for example.
In a combination of the compound according to the invention with the aforementioned inorganic and/or organic builders, it is immaterial whether the compound is introduced into the detergent preparation in the form of spray-dried compounds or compounds premixed in another manner with the said builders or is introduced directly.
The present invention also relates to methods of washing and cleaning textile fabrics in which the graft polymers according to the invention are used as a builder.
, CA 02221609 1997-11-19 The present invention further relates to detergents and cleaning materials which contain the graft polymers according to the invention.
The invention is described in detail below with reference to examples.
. CA 0222l609 lgg7-ll-l9 I. Methods:
A) Molecular weight determination Molecular weight determination was effected via gel permeation chromatography (GPC) on LiChrospher Diol columns (Merck) using phosphate buffer (pH = 7) as the eluent solution. Calibration can best be effected with closely distributed polyacrylic acid. In this connection, the fact that the chemical composition of the copolymers according to the invention was not constant resulted in an error in the absolute value of the molecular weight. This source of error, which is generally known, could not easily be eliminated, so that all the molecular weight data given here are to be understood as being relative to the calibration with polyacrylic acid.
B) Determination of the lime bo~; n~ capacity The lime bonding capacity (LBC) is a numerical measure which indicates how many grams of calcium carbonate (CaCO~) are held in solution or are dispersed to a certain degree per gram of complex-former. It was determined by turbidimetric titration.
200 mg of the polymer (calculated as solid) were dissolved in 100 ml deionised water. The pH of this solution should be > 6 and had to be correspondingly corrected with sodium hydroxide solution if necessary.
Thereafter, 10 ml of 2 % soda solution were added and the pH was adjusted to 10 with sodium hydroxide solution or acetic acid. This solution was titrated with calcium acetate (44.1 g/l) and the turbidity caused by precipitated calcium carbonate was measured and recorded using a fibre optic measuring cell (wavelength = 650 nm).
The transmission of the measuring cell was adjusted to 100 ~ before the titration. The LBC was determined at 50 % transmission.
. CA 02221609 1997-11-19 WO 96/37530 _ PCT/EP96/01922 C) Determination of the Zahn-Wellens biodegradability The Zahn and Pellens decomposition test is a means of assessing the biodegradability of a substance or liquid effluent. It operates at a fixed ratio of COD to biomass.
About 2 litres of biomass suspension were stirred and aerated via glass frits in a tall 3 litre glass beaker.
385 mg NH4Cl and 89 mg NaH2PO4.H2O were weighed in, mixed with the calculated amount of polymer and made up to about 2 litres with cold tap-water. The activated sludge from a commlln~l sewage works was allowed to settle for 30 - 60 minutes so that it thickened by about half. The supernatant water was removed by decantation and the sludge was kept stirred and aerated. A portion of sludge was removed for each test and centrifuged at 2000 rpm for 5 minutes. 24 g of the centrifuged sludge from a 2 litre batch gave a solids content of 1 g/l (~ 20 ~). Before adding the sludge to the polymer solution, the pH was adjusted to 6.5 - 7.0 and a sample was analysed for COD
content. A sample could be taken again after the activated sludge had become finely distributed. The height of the liquid in the beaker was then marked. A
test liquid was used for comparison which contained nutrient salts and activated sludge only, and no polymer.
This batch was used to determine the COD due to the activated sludge. Each day, the bio-sludge deposited on the rim of the beaker was transferred back into the solution with a rubber wiper, the pH was adjusted again and the water lost by evaporation was replaced by demineralised water. Two samples, a filtered sample and an unfiltered sample, were analysed for their COD content in order to determine the substance adsorbed on the bio-sludge. The unfiltered sample was taken directly from the well-mixed reaction vessel and measured. For the filtered sample an aliquot portion, 40 ml for example, was taken, allowed to settle, and filtered using a --, CA 0222l609 lgg7-ll-l9 Millipore 2.5 ~ filter (Millipore Millex GS, for example). The clear solution was likewise analysed for its COD_content.
Calculation In order to determine the COD content of the substance which was adsorbed on the biomass, the COD value of the filtered sample and the blank value with biomass were subtracted from the COD in the sample solution with biomass.
P1 unfiltered sample solution with biomass P2 filtered sample solution Bls unfiltered blank value ad adsorbed substance P1 - P2 - Bls = ad.
The dissolved substance was obtained by subtracting the filtered blank value from the filtered sample P2.
Bl filtered blank value S dissolved substance P2 - Bl = S.
The adsorbed and dissolved substance together gave the initial content of substance to be decomposed or the current content .
The degree of decomposition ~ was calculated from A- (ad+S) .100 where A is the initial value, and ~ is the degree of decomposition.
Graft copolymers based on mono-, oligo- and polysaccharides, process for preparing the same and their use S This invention relates to graft copolymers based on natural raw materials, the graft copolymers being obtainable by the copolymerisation of ethylenically unsaturated monomers in the presence of saccharides or derivatives thereof. This invention also relates to a process for producing copolymers of this type and to the use of the graft copolymers as a water treatment agent, an incrustation inhibitor and as a detergent additive, namely as a so-called cobuilder.
The use of copolymers, which are obtained by grafting acrylic acid and methacrylic acid on to starch or other hydroxy compounds, in detergents for inhibiting re-soiling is known from US 3,558,499.
According to JP-A-55/155 097, an oxidised starch grafted with sodium acrylate, an oxidised starch grafted with hydroxypropyl methacrylate, or a maize starch-polyvinyl alcohol graft copolymer are used in an amount of 0.05 to 5 ~ by weight in detergent formulations to prevent the re-soiling of laundry during washing.
Copolymers of acrylic acid with other unsaturated compounds, which can be produced by polymerisation in the presence of monosaccharides which are capable of enolate formation, are known from EP 0 239 895 B1. The aforementioned patent also describes their use as cobuilders in detergents and cleaning materials.
DE 40 03 172 A1 or EP 0 441 197 discloses graft copolymers of monosaccharides, oligosaccharides and polysaccharides which are obtainable by radical-initiated graft copolymerisation from _W0 96/37530 PCT/EP96/01922 A) monomer mixtures comprising a) 90 to 10 ~ by weight of monoethylenically unsaturated C4 to C8 dicarboxylic acids, or anhydrides or alkali and/or ammonium salts thereof, b) 10 to 90 ~ by weight of monoethylenically unsaturated C3 to C10 carboxylic acids, or alkali and/or ammonium salts thereof, c) 0 to 40 ~ by weight of other monoethylenically unsaturated monomers which are copolymerisable with monomers (a) and (b), and~5 d) 0 to 5 ~ by weight of monomers containing at least two ethylenically unsaturated unconjugated double bonds in their molecule, in the presence of B) monosaccharides, oligosaccharides, polysaccharides;
oxidatively, hydrolytically or enzymatically decomposed polysaccharides; oxidised, hydrolytically decomposed or oxidised, enzymatic.ally decomposed polysaccharides; chemically modified mono-, oligo-and polysaccharides or mixtures of the said compounds in a weight ratio (A) : (B) of (95 to 20) : (5 to 80).
DE 40 38 908 A1 relates to the use of graft copolymers according to DE 40 03 172 A1 as cobuilders.
Graft copolymers are known from DE 42 21 381 C1 which are obtainable by the radical copolymerisation of an ethylenically unsaturated monocarboxylic acid or a salt thereof and monomers containing monoethylenically unsaturated sulphonic acid groups, and optionally of -~
. CA 0222l609 lgg7-ll-l9 _WO 96/37530 PCT/EP96/01922 other water-soluble monomers. The use of graft copolymers of this type as cobuilders is also described.
.
DE 23 57 036 relates to polycarboxylates having a defined biodegradability. These known polycarboxylates are used as builders in the formulation of solid or liquid cleaning materials. They are produced by the oxidative polymerisation of acrolein, on its own or in the presence OL aclylic acid, in the presence of thioethylene glycol.
DE 23 30 260 discloses a process for producing polycarboxylates by the oxidative polymerisation of acrolein on its own or together with acrylic acid, polymerisation being carried out with the addition of n-dodecylmercaptan.
EP 0 609 777 relates to detergent compositions having an improved dirt-carrying capacity, with the use of a suitable polycarboxylate. The co-builders disclosed are obtained by the copolymerisation of acrolein and acrylic acid, for example, under suitable conditions.
In Polym. J. 11 (1979) 85, G. Maher describes graft copolymers which are produced by the polymerisation of vinyl monomers on to starch xanthate. Acrolein, acrylamide, acrylic acid, acrylonitrile, methyl acrylate or styrene were investigated as the vinyl monomers. In the course of this procedure, the respective monomer was reacted with an aqueous system comprising completely soluble starch xanthate and hydrogen peroxide (at an alkaline pH), and a gel-like,-crosslinked product was formed in each case, comprising graft copolymers in a self-generated acidic medium. For example, a gel-like product was formed with acrolein, and vigorous gas evolution occurred during the polymerisation reaction, with the formation of bubbles which could not escape rapidly enough on account of the rapid formation of gel.
This effect led to the proposal that this reaction and -~
~ CA 0222l609 lgg7-ll-l9 the products thereof be employed in the production of foam rubber (US-4,005,040).
Polycarboxylates are known from DE 44 17 734.8 which are produced by the polymerisation of acrolein and vinyl acetate in aqueous solution in the presence of hydrogen peroxide and optionally of other batch materials. The polymers exhibit a biodegradability of , 30 ~.
Derwent Abstract 86-085028/13 of JP-61 031 498 discloses graft polymers of acrylic acid or maleic acid on glucose, fructose or other defined sugars. As mixtures of cobuilders, these are claimed to provide enhanced washing power and improved biodegradability.
It has in fact been shown that the incrustation of textiles during washing can be reduced by the polycarboxylate products which are commonly available on the market. However, further optimisation of cobuilders is desirable in order to increase the efficacy of detergents and thus further to improve the usage properties of textiles at the same time. The underlying object of the invention described below is accordingly to provide polymers, which as far as possible are based on reproductively grown raw materials and inexpensive batch materials, which exhibit an incrustation-inhibiting effect which is better than or at least as good as that of the products used hitherto, and which at the same time exhibit outstanding biodegradability.
The said object, and other objects not mentioned in detail, are achieved by means of the water-soluble graft copolymers of monosaccharides, oligosaccharides, polysaccharides and derivatives thereof according to the invention, which are obtainable by the radical-initiated copolymerisation of A) monomer mixtures comprising -~
~ CA 0222l609 lgg7-ll-l9 a) more than 40 - 100 ~ by weight of at least one ~ unsaturated aldehyde of general formula I
.~,0 R1 _ GH = C - C (I), H
where Rl represents hydrogen or a linear or branched Cl-C4 alkyl, and R2 represents hydrogen or methyl, b) ~ ~ 60 ~ by weight of a) different monoethylenically unsaturated monomers which are copolymerisable with a), and c) 0 - 5 ~ by weight of monomers containing at least two ethylenically unsaturated, unconjugated double bonds in their molecule, in the presence of B) monosaccharides, oligosaccharides, polysaccharides;
oxidatively, hydrolytically or enzymatically decomposed polysaccharides; chemically modified mono-, oligo- or polysaccharides; or mixtures of the said compounds, and C) one or more oxidising agents, wherein the weight ratio of A) to B) extends from (95 : 20) to (5 : 80) and the weight ratio of C) to - A) + B) extends from (5 : 100) to (50 : 50).
Because the graft copolymers of the present invention are based on natural, reproductively grown raw materials, namely the said saccharides and their derivatives B), they give little cause for concern ecologically and they are relatively inexpensive. The ~,~-unsaturated aldehydes of formula I, which as component (a) constitute -~
CA 0222l609 l997-ll-l9 WO 96/37530 . PCT/EP96/01922 the major part of the monomer mixtures A) which are grafted on to component B), are also relatively inexpensive raw materials, particularly acrolein.
However, the graft copolymers which are obtainable in this manner exhibit a good incrustation-inhibiting effect and at the same are outstandingly biodegradable.
The ~,~-unsaturated aldehydes of formula I which can successfully be used according to the invention comprise those in which R1 is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl and/or tert.-butyl, whilst R2 represents hydrogen or methyl.
One or more compounds of formula I may be used in admixture with each other as component (a).
Acrolein and/or methacrolein are particularly suitable as monomers of group (a). The use of acrolein is particularly advantageous on economic grounds.
Monoethylenically unsaturated C3 to C10 monocarboxylic acids and alkali and/or ammonium salts thereof are suitable as monomers of group (b). Examples of these monomers include acrylic acid, methacrylic acid, ethylacrylic acid, allylacetic acid and vinylacetic acid.
From this group of monomers, acrylic acid, methacrylic acid, mixtures thereof and their sodium, potassium or ammonium salts or mixtures thereof are preferably used.
These monomers are either polymerised on their own as component (b), or are polymerised in admixture with monoethylenically unsaturated dicarboxylic acids or anhydrides thereof as component (b), together with (a) and optionally (c) in the presence of natural products (B) under oxidising conditions. In this respect, the expression "under oxidising conditions" is to be understood as the use of an oxidising agent C) in a weight ratio of C) to A) + B) of (5 : 100) to (50 : 50), wherein C) has sufficient oxidising power to effect the -~
t . CA 02221609 1997-11-19 oxidation of carbonyl groups and the oxidation and decomposition of the polysaccharide used and thus to initiate the polymerisation of mixture a) to c) star~ing from the polysaccharide.
Suitable unsaturated dicarboxylic acids contain 4 to 8 C
atoms, e.g. maleic acid, fumaric acid, itaconic acid, methylenemalonic acid, citraconic acid, maleic anhydride, itaconic anhydride and methylenemalonic anhydride. The monoethylenically unsaturated C4 to C8 dicarboxylic acids may be used in the graft polymerisation in the form of the free acids or in the form in which they are neutralised with alkali metal bases, ~mmo~; a or amines.
Of the dicarboxylic acids or anhydrides thereof which are suitable, maleic acid, maleic anhydride, itaconic acid or itaconic anhydride and the sodium, potassium or ammonium salts of maleic acid or itaconic acid are preferably used. These salts can be obtained, for example, from maleic anhydride or itaconic anhydride by neutralising the said anhydrides in aqueous solution with sodium hydroxide solution or potassium hydroxide solution, or with ammonia or amines.
Examples of monomers of group (b) which can also be used in the graft polymerisation include C1 to C6 alkyl esters and hydroxyalkyl esters of the said compounds, e.g.
methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, maleic acid monomethyl ester, maleic acid diethyl ester, hydroxyethyl acrylate, hydroxypropyl acrylates, hydroxybutyl acrylates, hydroxyethyl methacrylate and hydroxypropyl methacrylate. The amides and N-substituted alkyl amides of the said compounds are also suitable as monomers of group (b), e.g. acrylamide, methacrylamide, N-alkylacrylamides containing 1 to 18 C
atoms in the alkyl group, such as N-methylacrylamide, N-dimethylacrylamide, N-tert.-butylacrylamide, N-octadecylacrylamide, maleic acid monoethylhexylamide, maleic acid monododecylamide, dimethylaminopropyl -methacrylamide and acrylamidoglycolic acid.
Alkylaminoalkyl (meth)acrylates are also suitable as monomer (b), e.g. dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate and dimethylaminopropyl methacrylate.
Monomers which contain sulphonic acid groups are also suitable as monomers of group (b), such as vinylsulphonic acid, allylsulphonic acid, methallylsulphonic acid, styrenesulphonic acid, acrylic acid-3-sulphopropylester, methacrylic acid-3-sulphopropyl ester and acrylamidomethyl-propanesulphonic acid for example, as well as monomers containing phosphonic acid groups, such as vinylphosphonic acid, allylphosphonic acid and acrylamidomethylpropane-phosphonic acid for example. This group of monomers also includes N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinyl-N-methylformamide, 1-vinylimidazole, 1-vinyl-2-methylimidazole, vinyl acetate and vinyl propionate.
Also suitable as monomers of group (b) are the esters of alkoxylated C1 to C18 alcohols which are reacted with 2 to 50 moles of ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with the monoethylenically unsaturated carboxylic acids of group (a), e.g. the esters of acrylic acid, methacrylic acid or maleic acid with a C13/C1s oxoalcohol which has been reacted with different amounts of ethylene oxide, e.g. 3 moles, 5 moles, 7 moles, 10 moles or 30 moles of ethylene oxide.
Both the mono- and diesters of the dicarboxylic acids are suitable as the esters.
The basic monomers are preferably used in the form of their salts with mineral acids, e.g. hydrochloric acid, sulphuric acid or nitric acid, or in quaternarised form -~
(examples of suitable quaternarisation agents include dimethyl sulphate, diethyl sulphate, methyl chloride, ethyl chlQride or benzyl chloride).
Amides of monoethylenically unsaturated C3 to C8 carboxylic acids with amide groups of the said structure are also suitable as monomers of group (b).
-The prefer.ed monomers of group (b) are acrylic acid, methacrylic acid, maleic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, vinyl acetate, N-vinyl pyrrolidone, acrylamidomethyl-propanesulphonic acid and N-vinyl-imidazole.
A further modification of the graft copolymers can be obtained by conducting the graft polymerisation in the presence of monomers of group (c). In this case, the monomer mixtures contain up to 5 ~ by weight of a monomer having at least two ethylenically unsaturated unconjugated double bonds in its molecule. These compounds are usually employed as crosslinking agents in copolymerisation reactions. They may be added to the monomers of group (a) or to the monomer mixtures of (a) and (b) used for copolymerisation. When they are used, the amount of monomers (c) which is used is preferably 0.05 to 2 ~ by weight. The use in conjunction of monomers of group (c) during the copolymerisation effects an increase in the molecular weight of the copolymer.
Examples of suitable compounds of this type include methylene-bis-acrylamide, esters of acrylic acid and methacrylic acid with polyhydric alcohols, e.g. glycol diacrylate, glycerine triacrylate, glycol dimethacrylate, glycerine trimethacrylate, and polyols which are esterified at least twice with acrylic acid or methacrylic acid, such as pentaerythritol and glucose.
In addition, divinylbenzene, divinyldioxane, pentaerythritol triallyl ether and pentaallyl sucrose are suitable crosslinking agents. Water-soluble monomers, --, CA 0222l609 lgg7-ll-l9 such as glycol diacrylate or diacrylates of polyethylene glycols having a molecular weight up to 3000, are preferably used from this group of compounds.
s Polymerisation of monomers (a) and optionally of (b) and (c) in addition is effected in the presence of natural products based on polysaccharides, oligosaccharides, monosaccharides and derivatives thereof. These natural products may, for example, be saccharides of vegetable or ~n;m~l origin or products of the metabolism of microorganisms, or decomposition and modification products thereof which are already dispersible or soluble in water or alkali, or which, during the polymerisation of monomers (a) and optionally (b) and (c), become directly, completely or partially dispersible or soluble in the form in which they are neutralised with alkali, ammonia or amines.
Examples of these substances include starch, pectin, algin, chitin, chitosan, heparin, carrageenan, agar, gum arabic, gum tragacanth, karaya gum, ghatti gum, carob seed grain, guar gum, Tara gum, inulin, xanthan, dextran, saccharose, nigeran and pentosans such as xylan and araban, the major constituents of which consist of D-glucuronic acid, D-galacturonic acid, D-galacturonic acid methyl ester, D-mannuronic acid, L-guluronic acid, D- and L-galactose, 3,6-anhydro-D-galactose, L-arabinose, L-rhamnose, D-glucoronic acid, D-xylose, L-fucose, D-mannose, D-fructose and D-glucose, 2-amino-2-desoxy-D-glucose and 2-amino-2-desoxy-D-galactose and the N-acetyl - derivatives thereof.
Considered from an economic standpoint, the following are preferably used as polysaccharides of component (B) during the graft copolymerisation: starch, thermally and/or mechanically treated starch, starches decomposed oxidatively, hydrolytically or by enzymatic oxidation, oxidised starches decomposed by enzymatic hydrolysis or -~
. CA 0222l609 lgg7-ll-l9 by enzymatic oxidation, and also chemically modified starches and chemically modified monosaccharides and oligosaccharides.
In principle, all starches are suitable. Starches from maize, wheat, rice or tapioca, and starches from potatoes in particular, are preferred, however. Starches are practically insoluble in water and can be converted into a water-soluble form in the known manner by thermal and/or mechanical treatment or by enzyme- or acid-catalysed decomposition. Oxidatively decomposed starches are also suitable as component (B). The following compounds should be cited as examples of starch decomposition products which are obtainable by the oxidative, hydrolytic or enzymatic decomposition of starch: dextrins such as white and yellow dextrins, maltodextrins, glucose syrups, maltose syrups, hydrolysates with a high content of D-glucose, products of the conversion of starches into sugars, and maltose and D-glucose and their isomerisation product fructose.
Mono- and oligosaccharides are also of course suitable as component (B), such as galactose, mannose, ribose, saccharose, raffinose, lactose and trehalose, as well as decomposition products of cellulose, for example cellubiose and oligomers thereof.
Oxidised starches are also suitable as component (B), such as dialdehyde starch and oxidised starch decomposition products, for example gluconic acid and glucuronic acid. Compounds such as these are obtained, - for example, by the oxidation of starch with periodate, chromic acid, hydrogen peroxide, nitrogen dioxide, nitrogen tetroxide, nitric acid or hypochlorite.
Chemically modified polysaccharides, particularly chemically modified starches, are also suitable as component (B), e.g. starches and starch decomposition products which are reacted with acids to form esters and -~
CA 0222l609 l997-ll-l9 WO 96/37530 12 PCT~EP96/01922 which are reacted with alcohols or alkyl halides, such as chloroacetic acid, for example, to form ethers. It is possible to esterify these substances both with inorganic and with organic acids or anhydrides or chlorides thereof. Phosphated and acetylated starches, carboxymethyl starch and starch decomposition products are of particular commercial interest. The commonest method of etherifying starch is the treatment of starch and of starch decomposition products with organic-halogen compounds, epoxides or sulphates in aqueous alkaline solution. Bxamples of starch ethers include the alkyl ethers, hydroxyalkyl ethers, carboxyalkyl ethers and allyl ethers of starch. In relation to component (B), the expression "chemically modified starches" should also be understood as comprising cationically modified starches, e.g. starches reacted with 2,3-epoxypropyl-trimethylammonium chloride, such as those described in US-PS 3,649,616 for example.
Examples of chemically modified polysaccharides also include carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethyl-hydroxyethylcellulose, sulphoethylcellulose, carboxymethyl-sulphoethylcellulose, hydroxypropyl-sulphoethylcellulose, hydroxyethyl-sulphoethylcellulose, methyl-sulphoethylcellulose and ethyl-sulphoethylcellulose.
Chemically modified decomposed starches are also suitable as component (B), for example the hydrogenatio~ products of starch hydrolysates, such as sorbitol and mannitol, maltitol and hydrogenated glucose syrups, or oxidised, hydrolytically decomposed starches or oxidised, enzymatically decomposed starches.
All the oxidising agents familiar to one skilled in the art are suitable as component (C). These comprise, amongst others, hydrogen peroxide, hypochlorite, nitrogen CA 0222l609 lgg7-ll-l9 dioxide, nitrogen tetroxide, nitric acid, chromic acid and/or periodate. Hydrogen peroxide is preferably used as the oxidising agent. Mixtures of a plurality of oxidising agents may also be used.
The graft copolymers according to the invention are preferably composed of 20 to 95 ~ by weight of monomer mixture (A) and 5 to 80 ~ by weight of component (B). In this connection, products containing 25 to 70 ~ by weight of monomer mixture (A) and 30 to 75 ~ by weight of component (B) are particularly preferred.
If the content of monomer mixture is less than 20 ~ by weight, the washing properties are unsatisfactory. On the other hand, if the content of monomer mixture is greater than 95 ~ by weight the biodegradability is unsatisfactory.
The present invention also relates to a process for producing graft copolymers of monosaccharides, polysaccharides and derivatives thereof by the radical-initiated copolymerisation of A) 95 to 20 ~ by weight of ethylenically unsaturated monomers in the presence of B) 5 to 80 ~ by weight of at least one monosaccharide, oligosaccharide, polysaccharide, decomposed or chemically modified mono-, oligo- and polysaccharide or mixtures thereof, and C) one or more oxidising agents in an inert diluent at temperatures up to 180~C, wherein mixtures comprising a) 40 - 100 ~ by weight of at least one ~,~-unsaturated aldehyde of general formula I
R1 _ CH=C-C (I), H
, CA 0222l609 lgg7-ll-l9 Wo 96/37530_ PCT/EP96/01922 where R1 represents hydrogen or a linear or branched C1-C4 alkyl, and R2 represents hydrogen or methyl, .
b) ~ ~ 60 ~ by weight of a) different monoethylenically unsaturated monomers which are copolymerisable with a), and c) 0 - 5 ~ by weight of monomers containing at least two ethylenically unsaturated, unconjugated double bonds in their molecule, are used as the ethylenically unsaturated monomers A), and the one or more oxidising agents C) are used in a weight ratio of C) to A) + B) of (5 : 100) to (50 : 50).
If the oxidising agent is present in a weight ratio of C) to A) + B) which is less than (5 : 100), insufficient carboxyl groups are produced in the molecule to achieve satisfactory washing properties. However, if the weight ratio of C) to A) + B) is greater than (50 : 50), the molecular weight of the graft polymer is too low due to oxidative decomposition and no advantageous washing properties are obtained.
Polymers are obtained by the polymerisation of ~,~-unsaturated aldehydes under oxidising conditions which can still contain, as structural elements, free aldehyde groups or the acetal thereof, acid groups, acid groups esterified with 3-hydroxypropionic acid, alcohol groups, and also ether groups. A precise determination of the structure of the polymers is difficult, however.
The production of the polymers according t-o the invention also results in the oxidation of the mono- or polysaccharides used, wherein carboxyl groups, which presumably also contribute to the observed washing effect, are incorporated therein, and radicals on to which ~,~-unsaturated aldehydes and other monomers can polymerise are produced on the saccharide molecules. In addition, bonding of component (B) to the polymers formed --WO 96/37530 _ 15 PCT/EP96/01922 from (A) can occur via the aldehyde groups of component (A) with the formation of a semi-acetal or acetal.
As mentioned above, the preceding statements are merely an attempted explanation; the technical teaching given in the claims is independent of the correctness thereof, however.
Suitable initiators for the polymerisation comprise hydrogen peroxide, persulphuric acid and the sodium, potassium and ammonium salts thereof, and percarbonic acid, perboric and perphosphoric acid, peroxycarboxylic acids and salts thereof. Hydrogen peroxide is preferably used as the initiator.
Since hydrogen peroxide is also a preferred oxidising agent, in one advantageous embodiment of the invention hydrogen peroxide is most preferably used both as an initiator and as an oxidising agent.
Production of the polymer according to the invention is preferably conducted in aqueous solution, wherein components (A) and (B) and the oxidising agent may be placed in the reaction vessel or added during the reaction. Preferably, component (B) is placed in the reaction vessel and (A) is added. Oxidising agent (C) may be placed in the vessel or added during the reaction, according to choice. The mono- or polysaccharide B) may also firstly be pre-oxidised and partially decomposed with oxidising agent C) before commencing the addition of monomer mixture A). The temperature range which is suitable for the reaction is between 50 and 100~C;
temperatures between 65 and 85~C are preferred. The components are typically added at a metered rate over a period of 1 to 6 hours. Heating is then continued for a further 1 to 6 hours at temperatures between 70 and 100~C
in order to ensure that the reaction proceeds to completion. --, CA 0222l609 l997-ll-l9 WO 96/37530 . PCT/EP96/01922 The product obtained may be used without further treatment or may be concentrated before use, or may be dried by methods known to one skilled in the art, such as spray-drying for example. In particular, it may also be mixed with other detergent and cleaning material components before work-up.
The graft copolymers according to the invention are polycarboxylates which have the advantage~that in addition to a good bonding capacity for lime they exhibit outstanding biodegradability and effect an outstanding inhibition of incrustation.
The polycarboxylates according to the invention may be used both as cobuilders and as builders in detergents.
When employed as cobuilders, they can be used in addition to known builders such as zeolite A for example, or layer silicates such as SKS-6, or amorphous disilicates.
They can be used in combination with water-soluble or water-insoluble, inorganic and/or organic builder materials. Examples of suitable inorganic builder substances include zeolites, phosphates and sodium silicates.
The zeolite used is preferably finely divided zeolite NaA. Zeolite NaX and Zeolite NaP and mixtures of these three zeolites are also suitable, however. In particular, zeolites of this type have an average 30 particle size less than 10 ~m and preferably contain 18 to 22 ~ by weight of water (determined as the loss on ignition at 1000~C for one hour). The zeolites may also be used as a stabilised suspension, however. In this connection, small amounts of added nonionic surfactants 35 effect stabilisation of the suspension.
Amorphous or crystalline alkali silicates may be present as a replacement or partial replacement for phosphates --, CA 0222l609 lgg7-ll-l9 and zeolites. The preferred alkali silicates are sodium silicates, particularly amorphous sodium silicates, with an Na2O : SiO2 molar ratio of 1.5 to 3. Amorphous alkali silicates of this type are obtainable under the name Portil~ (Henkel), for example. Co-granulates of soda and amorphous sodium disilicates, which are known by the trade name Nabion 15~ (Rhone-Poulenc), for example, may also be used. Crystalline layer sodium silicates of general formula NaMSix02x+l.yH2o~ where-M denotes sodium or hydrogen, x is a number from 1.9 to 4, y is a number from 0 to 20, and a preferred value of x = 2, are preferably used as crystalline silicates which may be present on their own or in admixture with amorphous silicates.
Crystalline layer silicates of this type are described in European Patent EP 0 164 514. Both ~- and ~-sodium disilicates are particularly preferred.
Examples of organic builders which can be used include polycarboxylic acids, which are preferably used in the form of their sodium salts, such as polyacrylic acid, polymethacrylic acid and copolymers thereof with maleic acid, as well as tartaric acid, citric acid, succinic acid, adipic acid, glutaric acid, saccharic acids, aminocarboxylic acids, nitrilotriacetic acid and mixtures of these, for example.
In a combination of the compound according to the invention with the aforementioned inorganic and/or organic builders, it is immaterial whether the compound is introduced into the detergent preparation in the form of spray-dried compounds or compounds premixed in another manner with the said builders or is introduced directly.
The present invention also relates to methods of washing and cleaning textile fabrics in which the graft polymers according to the invention are used as a builder.
, CA 02221609 1997-11-19 The present invention further relates to detergents and cleaning materials which contain the graft polymers according to the invention.
The invention is described in detail below with reference to examples.
. CA 0222l609 lgg7-ll-l9 I. Methods:
A) Molecular weight determination Molecular weight determination was effected via gel permeation chromatography (GPC) on LiChrospher Diol columns (Merck) using phosphate buffer (pH = 7) as the eluent solution. Calibration can best be effected with closely distributed polyacrylic acid. In this connection, the fact that the chemical composition of the copolymers according to the invention was not constant resulted in an error in the absolute value of the molecular weight. This source of error, which is generally known, could not easily be eliminated, so that all the molecular weight data given here are to be understood as being relative to the calibration with polyacrylic acid.
B) Determination of the lime bo~; n~ capacity The lime bonding capacity (LBC) is a numerical measure which indicates how many grams of calcium carbonate (CaCO~) are held in solution or are dispersed to a certain degree per gram of complex-former. It was determined by turbidimetric titration.
200 mg of the polymer (calculated as solid) were dissolved in 100 ml deionised water. The pH of this solution should be > 6 and had to be correspondingly corrected with sodium hydroxide solution if necessary.
Thereafter, 10 ml of 2 % soda solution were added and the pH was adjusted to 10 with sodium hydroxide solution or acetic acid. This solution was titrated with calcium acetate (44.1 g/l) and the turbidity caused by precipitated calcium carbonate was measured and recorded using a fibre optic measuring cell (wavelength = 650 nm).
The transmission of the measuring cell was adjusted to 100 ~ before the titration. The LBC was determined at 50 % transmission.
. CA 02221609 1997-11-19 WO 96/37530 _ PCT/EP96/01922 C) Determination of the Zahn-Wellens biodegradability The Zahn and Pellens decomposition test is a means of assessing the biodegradability of a substance or liquid effluent. It operates at a fixed ratio of COD to biomass.
About 2 litres of biomass suspension were stirred and aerated via glass frits in a tall 3 litre glass beaker.
385 mg NH4Cl and 89 mg NaH2PO4.H2O were weighed in, mixed with the calculated amount of polymer and made up to about 2 litres with cold tap-water. The activated sludge from a commlln~l sewage works was allowed to settle for 30 - 60 minutes so that it thickened by about half. The supernatant water was removed by decantation and the sludge was kept stirred and aerated. A portion of sludge was removed for each test and centrifuged at 2000 rpm for 5 minutes. 24 g of the centrifuged sludge from a 2 litre batch gave a solids content of 1 g/l (~ 20 ~). Before adding the sludge to the polymer solution, the pH was adjusted to 6.5 - 7.0 and a sample was analysed for COD
content. A sample could be taken again after the activated sludge had become finely distributed. The height of the liquid in the beaker was then marked. A
test liquid was used for comparison which contained nutrient salts and activated sludge only, and no polymer.
This batch was used to determine the COD due to the activated sludge. Each day, the bio-sludge deposited on the rim of the beaker was transferred back into the solution with a rubber wiper, the pH was adjusted again and the water lost by evaporation was replaced by demineralised water. Two samples, a filtered sample and an unfiltered sample, were analysed for their COD content in order to determine the substance adsorbed on the bio-sludge. The unfiltered sample was taken directly from the well-mixed reaction vessel and measured. For the filtered sample an aliquot portion, 40 ml for example, was taken, allowed to settle, and filtered using a --, CA 0222l609 lgg7-ll-l9 Millipore 2.5 ~ filter (Millipore Millex GS, for example). The clear solution was likewise analysed for its COD_content.
Calculation In order to determine the COD content of the substance which was adsorbed on the biomass, the COD value of the filtered sample and the blank value with biomass were subtracted from the COD in the sample solution with biomass.
P1 unfiltered sample solution with biomass P2 filtered sample solution Bls unfiltered blank value ad adsorbed substance P1 - P2 - Bls = ad.
The dissolved substance was obtained by subtracting the filtered blank value from the filtered sample P2.
Bl filtered blank value S dissolved substance P2 - Bl = S.
The adsorbed and dissolved substance together gave the initial content of substance to be decomposed or the current content .
The degree of decomposition ~ was calculated from A- (ad+S) .100 where A is the initial value, and ~ is the degree of decomposition.
II. Examples Example 1 1260 g deionised water, 105 g of 50 ~ hydrogen peroxide and 240 g Aeromyl 115 (starch soluble in cold water, supplied by Sudstarke) were placed in a reactor fitted with a condenser, a stirrer, and with a device for controlled heating and metered a-ddition, and were heated to 70~C. A mixture of 189 g acrolein and 21.6 g acrylic acid was added at a metered rate, with stirring, over a period of 3.5 hours. In parallel with this, a further 105 g of 50 ~ hydrogen peroxide were added at a metered rate. The reaction batch was then heated to 90~C over a period of 1 hour and was maintained at this temperature for a further 4 hours. A pH of 1.5 was measured after cooling to room temperature. The reaction batch was adjusted to pH 10 with 50 ~ NaOH and was concentrated to a solids content of 40 ~.
LBC(23~C) = 820 mg CaCO3/g, LBC(60~C) = 150 mg CaCO3/g, molecular weight (GPC) = 27,900 g/mole Example 2 630 g deionised water, 51 g of 50 ~ hydrogen peroxide and 79.4 g Aeromyl 115 (starch soluble in cold water, supplied by Sudstarke) were placed in a reactor fitted with a condenser, a stirrer, and with a device for controlled heating and metered addition, and were heated to 70~C. A mixture of 91.7 g acrolein and 13.1 g acrylic acid was added at a metered rate, with stirring, over a period of 3 hours. In parallel with this, a further 51 g of 50 ~ hydrogen peroxide were added at a metered rate.
The reaction batch was then heated to 95~C and was maintained at this temperature for 4 hours.
WO 96/37530 . PCT/EP96/01922 LBC(23~C) = 1200 mg CaC03/g, LBC(60~C) = 180 mg CaCO3/g, molecular weight (GPC) = 8050 g/mole, degree of decomposition ~ after 28 days = 63 %.
Example 3 630 g deionised water, 44.9 g of 50 % hydrogen peroxide and 79.4 g Aeromyl 115 (starch soluble in cold water, supplied by Sudstarke) were placed in a reactor fitted with a condenser, a stirrer, and with a device for controlled heating and metered addition, and were heated to 70~C. A mixture of 80. 2 g acrolein and 25.2 g acrylic acid was added at a metered rate, with stirring, over a period of 3 hours. In parallel with this, a further 44.9 g of 50 % hydrogen peroxide were added at a metered rate.
The reaction batch was then heated to 95~C and was maintained at this temperature for 4 hours.
LBC(23~C) = 1280 mg CaC03/g, LBC(60~C) = 200 mg CaCO3/g, molecular weight (GPC) = 10,450 g/mole, degree of decomposition ~ after 28 days = 52 %.
Example 4 630 g deionised water, 30.3 g of 50 % hydrogen peroxide and 79.4 g Aeromyl 115 (starch soluble in cold water, supplied by Sudstarke) were placed in a reactor fitted with a condenser, a stirrer, and with a device for controlled heating and metered addition, and were heated to 70~C. A mixture of 54.1 g acrolein, 28.0 g vinyl acetate and 23.2 g acrylic acid was added at a metered rate, with stirring, over a period of 3 hours. In parallel with this, a further 30.3 g of 50 % hydrogen peroxide were added at a metered rate. The reaction batch was then heated to 95~C and was maintained at this temperature for 4 hours. -CA 0222l609 lgg7-ll-l9 LBC(23~C) = 1350 mg CaCO3/g, LBC(60~C) = 140 mg CaCO3/g, molecular weight (GPC) = 7835 g/mole, degree of decomposition ~ after 28 days = 62 ~.
Exampl-e 5 1200 g deionised water, 150 g of 50 ~ hydrogen peroxide -and 234 g potato flour were placed in a reactor fitted with a condenser, a stirrer, and with a device for controlled heating and metered addition, and were heated to 70~C. The reaction batch was maintained at this temperature for 2 hours. A mixture of 180 g acrolein and 20.0 g acrylic acid was then added at a metered rate, with stirring, over a period of 3.5 hours. In parallel with this, a further 50 g of 50 ~ hydrogen peroxide were added at a metered rate. The reaction batch was then heated to 95~C and was maintained at this temperature for 4 hours.
(GPC) = 17300 g/mole Example 6 865 g deionised water, 150 g of 50 ~ hydrogen peroxide and 200 g white dextrin were placed in a reactor fitted with a condenser, a stirrer, and with a device for controlled heating and metered addition, and were heated to 70~C. A mixture of 180 g acrolein and 20 g acrylic acid was then added at a metered rate, with stirring, over a period of 3.5 hours In parallel with this, a further 50 g of 50 ~ hydrogen peroxide were added at a metered rate. The reaction batch was then heated to 95~C
and was maintained at this temperature for 4 hours.
LBC(23~C) = 1360 mg CaCO3/g, LBC(60~C) = 825 mg CaCO3/g Example 7 268.5 g deionised water, 238.8 g of S0 ~ hydrogen peroxide and 108.0 g white dextrin were placed in a reactor fitted with a condenser, a stirrer, and with a device for controlled heating and metered addition, and were heated to 70~C. A mixture of 262.8 g acrolein and 29.2 g acrylic acid was then added at a metered rate, ~ with stirring, over a period of 3.5 hours. In paral-lel with this, a further 79.6 g of 50 ~ hydrogen peroxide were added at a metered rate. The reaction batch was then heated to 90~C over 1 hour and was maintained at this temperature for 4 hours.
After cooling, the pH was adjusted to pH = 8.6 by adding 50 ~ sodium hydroxide solution. A clear, yellowish solution with a solids content of 43 ~ was obtained.
LBC(23~C) = 1600 mg CaCO3/g, LBC(60~C) = 300 mg CaCO3/g, pour point = -19~C, degree of decomposition ~ after 28 days = 45 ~.
Example 8 320.5 g deionised water, 196.6 g of 50 ~ hydrogen peroxide and 177.4 g white dextrin were placed in a reactor fitted with a condenser, a stirrer, and with a device for controlled heating and metered addition, and were heated to 70~C. A mixture of 216 g acrolein and 24 g acrylic acid was then added at a metered rate, with stirring, over a period of 3.5 hours. In parallel with this, a further 65.5 g of 50 ~ hydrogen peroxide were added at a metered rate. The reaction batch was then heated to 90~C and was maintained at this temperature for 3 hours.
After cooling, the pH was adjusted to pH = 8.6 by adding 50 ~ sodium hydroxide solution. A clear, yellow solution with a solids content of 45 ~ was obtained.
, CA 0222l609 lgg7-ll-l9 LBC(23~C) = 1220 mg CaCO3/g, LBC(60~C) = 160 mg CaCO3/g, pour point = -16~C, degree of decomposition ~ after 28 days = 45 ~.
Comparative example 1 420 parts by weight deionised water and 307 parts of 50 %
hydrogen peroxide were placed in a reactor fitted with a condenser, a stirrer, and with a device for controlled heating and metered addition, and were heated to 70~C.
1012 parts acrolein and 338 parts vinyl acrylate, together with 922 parts hydrogen peroxide (50 ~) were steadily metered in, with stirring, over a period of 4 hours. After the addition was complete, a further 120 g of hydrogen peroxide (50 ~) were added and the temperature was increased to 90~C over 1 hour. The batch was maintained at this temperature until the excess hydrogen peroxide had decomposed. After cooling to room temperature, the polymer solution had a pH of 1.4. The pH was adjusted to pH 10 with 50 ~ NaOH solution.
LBC(23~C) = 1060 mg CaCO3/g, LBC(60~C) = 80 mg CaCO3/g, molecular weight (GPC) = 2790 g/mole, degree of decomposition ~ after 28 days = 37 ~.
Comparative example 2 (EP-A-0 441 197) 253.4 g water, 89.7 g white dextrin (89.2 ~ solids content), 63.8 g maleic anhydride, 3.5 g of a 0.1 ~
aqueous solution of iron(II) ammonium sulphate and 94 g of 50 ~ aqueous sodium hydroxide solution were heated to boiling in a heatable reactor fitted with a stirrer, reflux condenser, thermometer, admission devices, and nitrogen inlet and outlet devices. After the reaction mixture had started to boil, a solution of 178.2 g acrylic acid in 141.9 g water was steadily added over 5 hours, with boiling, and a solution of 16.6 g of 50 ~ --, CA 0222l609 l997-ll-l9 WO 96/37530 _ 27 PCT/EP96/01922 hydrogen peroxide in 44.4 g water was steadily added over 6 hours, with boiling. After the metered addition of hydrogen peroxide was complete, the reaction mixture was heated to boiling for a further 1 hour and was thereafter neutralised to a pH of 7.3 by adding 50 ~ aqueous sodium hydroxide solution and cooled. A clear, viscous, dark brown solution was obtained, with a solids content of 42.8 ~.
LBC(23~C) = 1010 mg CaC03/g, LBC(60~C) = 950 mg CaCO~/g, pour point = -6~C, degree of decomposition ~ after 28 days = 16 ~.
Comparative example 3 (EP-A-0 441 197) 248.6 g water, 134.5 g white dextrin (89.2 ~ solids content), 55.9 g maleic anhydride, 3.5 g of a 0.1 ~
aqueous solution of iron(II) ammonium sulphate and 82.2 g of 50 ~ aqueous sodium hydroxide solution were placed in the reactor described in comparative example 2 and heated to boiling. Immediately after the commencement of boiling, a solution of 155.9 g acrylic acid in 141.9 g water was steadily added over 5 hours, and, separately from this, a solution of 14.5 g of 50 ~ hydrogen peroxide in 44.9 g water was steadily added over 6 hours, the reaction mixture being heated to its boiling point with stirring. After the addition of hydrogen peroxide was complete, the reaction mixture was heated to boiling for a further 1 hour and was thereafter neutralised to a pH
of 7 by adding 132. 5 g of 50 ~ aqueous sodium hydroxide solution. A turbid, highly viscous, light brown solution was obtained, with a solids content of 43.7 ~.
LBC(23~C) = 920 mg CaC03/g, LBC(60~C) = 660 mg CaCO~/g, pour point = -5~C, degree of decomposition ~ after 28 days = 26 ~.
, CA 0222l609 lss7-ll-lg Comparative example 4 (EP-A-0 441 197) 254.7 g water, 160 g maltodextrin with a DE value of about 3, 47.9 g maleic anhydride, 3.5 g of a 0.1 %
aqueous solution of iron(II) ammonium sulphate and 70.5 g of 50 % aqueous sodium hydroxide solution were placed in the reactor described in comparative example 2 and heated to boiling. Immediately after the commencement of boiling, a solution of 133. 6 g acrylic acid in 141.9 g water was steadily added at a metered rate over 5 hours, and a solution of 12.45 g of 50 % hydrogen peroxide in 44.4 g water was steadily added over 6 hours, whilst keeping the reaction mixture boiling. After the addition of hydrogen peroxide was complete, the reaction mixture was heated to boiling for a further 1 hour. A turbid, brown gel was obtained.
LBC(23~C) = 770 mg CaC03/g, LBC(60~C) = 650 mg CaC03/g, degree of decomposition ~ after 28 days = 29 %.
Comparative example 5 (JP-A-61 03 1498) 253.4 g water, 89.7 g white dextrin (89.2 % solids content) and 3.5 g of a 0.1 % aqueous solution of iron(II) ammonium sulphate and 82.2 g of 50 % aqueous sodium hydroxide solution were heated to boiling in the reactor described in comparative example 2. After reaction mixture had started to boil, a solution of 178.2 g acrylic acid in 141.9 g water was steadily added over 5 hours, and a solution of 16.6 g of 50 % hydrogen peroxide in 44.4 g water was steadily added over 6 hours, with boiling. After the addition of hydrogen peroxide was complete, the reaction mixture was heated to boiling for a further 1 hour, and was thereafter neutralised to a pH
of 7.2 by adding 50 ~ aqueous sodium hydroxide solution and cooled. A turbid, viscous, brown solution was obtained, with a solids content of 38.4 %. -. CA 0222l609 lgg7-ll-l9 Wo 96/37530 PCT/EP96/01922 LBC(23~C) = 1230 mg CaCO3/g, LBC(60~C) = 500 mg CaCO3/g, pour point = -8~C, degree of decomposition ~ after 28 days = 25 ~.
Consistency and colour:
The products from the comparative examples were intensely coloured and were mostly turbid. They were viscous liquids, and a gel was even formed in one case.
The products which are claimed exhibited properties which were surprisingly more favourable. They were clear liquids with only a slight yellow coloration.
Pour point:
The pour points of the products were measured following ISO 3016-19741. The flow point denotes the temperature at which the substance clearly still exhibits perceptible flow after it has been cooled under specified conditions.
The flow behaviour of the solutions on cooling is surprisingly better for the compounds claimed than for the comparative products. Due to this effect, they can still be handled satisfactorily even under unfavourable external conditions (cold), i.e. they can be pumped and conveyed even at low temperatures. The pour points of the examples and comparative examples are compared in Table la.
1 In departure from the Standard, a test tube with a round bottom was used instead of a test tube with a flat bottom. The effect of this alteration on the measured results was judged to be negligible, particularly since all the tests were performed in the same vessel and are thus comparable with each other in each case. The error in measurement within a series of measurements is quoted as + 3~C.
, CA 0222l609 lgg7-ll-lg Table la: Flow points Product Pour point [~C]
Example 7 -19 Example 8 -16 Comparative example 2 -6 Comparative example 3 -5 Comparative example 4 A gel even at RT
Comparative example 5 -8 RT = room temperature Zahn-Wellens biodegradability:
The claimed products were decomposed considerably better than those of the comparative tests. The degree of decomposition of the examples and comparative examples is compared in Table 2a.
Table 2a: Degree of decomposition ~ in the Zahn-Wellens test after 28 days Product Degree of decomposition after 28 days [%]
Example 2 63 Example 3 52 Example 4 62 Example 7 45 Example 8 45 Comparative example 1 37 Comparative example 2 16 Comparative example 3 26 Comparative example 4 29 Comparative example 5 25 . , CA 0222l609 lgg7-ll-l9 Washing tests In order to characterise the graft polymers according to the invention as regards their incrustation-inhibiting effect, they were incorporated in detergent compositions.
Test fabrics comprising huckaback towelling, white cotton textile and cotton textile with green stripes were washed with each of these detergent formulations. 25 wash ~ cycles were performed. The fabric was dry-ironed after each wash. After each 10 and 25 washes the test fabric was ashed (double determination). 2 g fabric in each case were calcined in a pre-incinerator at 500~C for 1 hour, and were then ashed in a muffle furnace at 800~C
for 1 hour. The crucibles were re-weighed and the ash contents were determined as a percentage. The more effective a polymer is, the lower is the ash content.
The LSD values (least significant deviations) were calculated according to DIN 44 983, Part 50. A ranking was obtained by assigning marks to the individual measured values determined for different fabrics.
Detergent A
10.00 ~ Marlon ARL
1.00 ~ Dehydrol TA5 6.00 ~ Dehydrol LT7 1.00 ~ Edenor HT35 0.15 ~ Blankophor MBBH-766 0.02 ~ Tinopal CBS-X
0.23 ~ Trilon B
12.00 ~ soda 2.70 % Portil N
1.10 ~ Relatin DM 4050 2.50 ~ sodium perborate tetrahydrate 11.70 ~ sodium perborate monohydrate 30.30 ~ Wessalith CS
0.60 ~ anti-foaming agent 6.00 ~ EDTA
~ , CA 02221609 1997-11-19 WO 96/37530 _ 32 PCT/EP96/01922 5.40 ~ graft copolymer according to Example 1 (solids content) 0.50 ~ lipolase 0.70 ~ Esperase 4.0 T
0.36 ~ sodium sulphate Detergent B
10.00 ~ Marlon ARL
1.00 ~ Dehydrol TA5 6.00 ~ Dehydrol LT7 1.00 ~ Edenor HT35 0.15 ~ Blankophor MBBH-766 0.02 ~ Tinopal CBS-X
0.23 ~ Trilon B
12.00 ~ soda 2.70 ~ Portil N
1.10 ~ Relatin DM 4050 2.50 ~ sodium perborate tetrahydrate 11.70 ~ sodium perborate monohydrate 30.30 ~ Wessalith CS
0.60 ~ anti-foaming agent 6.00 ~ EDTA
5.40 ~ copolymer according to comparative example 1 (solids content) 0.50 ~ lipolase 0.70 ~ Esperase 4.0 T
0.36 ~ sodium sulphate Detergent C
10.00 ~ Marlon ARL
1.00 ~ Dehydrol TA5 6.00 ~ Dehydrol LT7 1.00 ~ Edenor HT35 0.15 ~ Blankophor MBBH-766 0.02 ~ Tinopal CBS-X
0.23 ~ Trilon B
12.00 ~ soda 2.70 ~ Portil N .-, . , CA 0222l609 lgg7-ll-lg Wo 96/37530 _ 33 PCT/EP96/01922 1.10 ~ Relatin DM 4050 2.50 ~ sodium perborate tetrahydrate 11.70 ~ sodium perborate monohydrate 30.30 ~ Wessalith CS
0.60 ~ anti-foaming a~ent 6.00 ~ EDTA
5.40 % Sokalan CP5 (solids content; widely-used commercial product) 0.50 ~ lipolase 0.70 ~ Esperase 4.0 T
0.36 ~ sodium sulphate Washing conditions Secondary wash capacity: 1 cycle corresponding to 25 washes Temperature / hardness: 60~ Celsius / 20~ dH
Washing machine type: Miele W 763 Program: boiling/coloured wash without pre-wash Amount of detergent: 80.0 g (6.15 g/l) Ballast material: 18 pieces of white cotton (about 2.7 kg) 3 pieces of terry cloth 3 pieces of towelling (on to which the soiling materials were sewn) White fabric: 1 piece of terry cloth in each case (about 0.8 kg) 1 piece of towelling in each case 2 pieces of white cotton in each case (cotton / white) 2 pieces of green striped cotton in each case (cotton /
GS) , ., , CA 0222l609 lgg7-ll-l9 34 -.
Soiling material: blood (EMPA 111) standard (EMPA 101) cutaneous fat (WFK 10 G) tea (WFK 10 G) Hardening: in each odd washing operation blood (EMPA 111) standard (EMPA 101) cutaneous fat (WFK 1-0 G) tea (WFK 10 G) Waschereiforschung Krefeld (WFK) [Krefeld Laundry Research] (WFK) and the Eidgenossische Material Prufanstalt (EMPA) Schweiz [Swiss Material Testing Institute] sell test soiling materials for washing tests.
These test soiling materials are designated, for example, as EMPA 111 for blood soiling material.
Table 1 Incrustation-inhibiting effect of the polymer according to the invention from Example 1 Number of washes Fabric Detergent A
ash content [~]
terry cloth 0.62 towelling 0.47 cotton / GS 0.58 cotton / white 0.68 mean value 0.59 terry cloth 1.40 towelling 1.13 cotton / GS 1.15 cotton / white 1.31 mean value 1.25 LSD values: F: 0.06 ~; HT: 0.08 ~; cotton/GS 0.04 ~;
cotton / white: 0.18 ~
~. , CA 0222l609 lgg7-ll-l9 Table 2 Incrustation-inhibiting effect of the comparative examples 5 Number of FabricDetergent B Detergent C
washes ash content [~] ash content [~]
terry cloth 0.67 1.06 towelling 0.74 0.67 cotton / GS 0.79 ~ 1.14 cotton / 0.97 0.72 white mean value 0.79 0.90 terry cloth 1.61 1.58 towelling 1.47 1.60 cotton / GS 1.74 1.88 cotton / 1.68 1.45 white mean value 1.63 1.63 LSD values: F: 0.06 ~; HT: 0.08 ~; cotton/GS 0.04 ~;
cotton / white: 0.18 ~
The following ranking for the effectiveness of the various polymers was obtained from the test results given in Tables 1 and 2:
After 10 washes:
graft copolymer according to the invention more effective than that of comparative example 1, which was more effective than the commercial product Sokalan CP 5.
and after 25 washes:
graft copolymer according to the invention more effective than that of comparative example 1, the effectiveness of which was similar to that of the commercial product Sokalan CP 5.
~ , CA 02221609 1997-ll-lg Other advantages and embodiments of the invention follow from the following claims.
LBC(23~C) = 820 mg CaCO3/g, LBC(60~C) = 150 mg CaCO3/g, molecular weight (GPC) = 27,900 g/mole Example 2 630 g deionised water, 51 g of 50 ~ hydrogen peroxide and 79.4 g Aeromyl 115 (starch soluble in cold water, supplied by Sudstarke) were placed in a reactor fitted with a condenser, a stirrer, and with a device for controlled heating and metered addition, and were heated to 70~C. A mixture of 91.7 g acrolein and 13.1 g acrylic acid was added at a metered rate, with stirring, over a period of 3 hours. In parallel with this, a further 51 g of 50 ~ hydrogen peroxide were added at a metered rate.
The reaction batch was then heated to 95~C and was maintained at this temperature for 4 hours.
WO 96/37530 . PCT/EP96/01922 LBC(23~C) = 1200 mg CaC03/g, LBC(60~C) = 180 mg CaCO3/g, molecular weight (GPC) = 8050 g/mole, degree of decomposition ~ after 28 days = 63 %.
Example 3 630 g deionised water, 44.9 g of 50 % hydrogen peroxide and 79.4 g Aeromyl 115 (starch soluble in cold water, supplied by Sudstarke) were placed in a reactor fitted with a condenser, a stirrer, and with a device for controlled heating and metered addition, and were heated to 70~C. A mixture of 80. 2 g acrolein and 25.2 g acrylic acid was added at a metered rate, with stirring, over a period of 3 hours. In parallel with this, a further 44.9 g of 50 % hydrogen peroxide were added at a metered rate.
The reaction batch was then heated to 95~C and was maintained at this temperature for 4 hours.
LBC(23~C) = 1280 mg CaC03/g, LBC(60~C) = 200 mg CaCO3/g, molecular weight (GPC) = 10,450 g/mole, degree of decomposition ~ after 28 days = 52 %.
Example 4 630 g deionised water, 30.3 g of 50 % hydrogen peroxide and 79.4 g Aeromyl 115 (starch soluble in cold water, supplied by Sudstarke) were placed in a reactor fitted with a condenser, a stirrer, and with a device for controlled heating and metered addition, and were heated to 70~C. A mixture of 54.1 g acrolein, 28.0 g vinyl acetate and 23.2 g acrylic acid was added at a metered rate, with stirring, over a period of 3 hours. In parallel with this, a further 30.3 g of 50 % hydrogen peroxide were added at a metered rate. The reaction batch was then heated to 95~C and was maintained at this temperature for 4 hours. -CA 0222l609 lgg7-ll-l9 LBC(23~C) = 1350 mg CaCO3/g, LBC(60~C) = 140 mg CaCO3/g, molecular weight (GPC) = 7835 g/mole, degree of decomposition ~ after 28 days = 62 ~.
Exampl-e 5 1200 g deionised water, 150 g of 50 ~ hydrogen peroxide -and 234 g potato flour were placed in a reactor fitted with a condenser, a stirrer, and with a device for controlled heating and metered addition, and were heated to 70~C. The reaction batch was maintained at this temperature for 2 hours. A mixture of 180 g acrolein and 20.0 g acrylic acid was then added at a metered rate, with stirring, over a period of 3.5 hours. In parallel with this, a further 50 g of 50 ~ hydrogen peroxide were added at a metered rate. The reaction batch was then heated to 95~C and was maintained at this temperature for 4 hours.
(GPC) = 17300 g/mole Example 6 865 g deionised water, 150 g of 50 ~ hydrogen peroxide and 200 g white dextrin were placed in a reactor fitted with a condenser, a stirrer, and with a device for controlled heating and metered addition, and were heated to 70~C. A mixture of 180 g acrolein and 20 g acrylic acid was then added at a metered rate, with stirring, over a period of 3.5 hours In parallel with this, a further 50 g of 50 ~ hydrogen peroxide were added at a metered rate. The reaction batch was then heated to 95~C
and was maintained at this temperature for 4 hours.
LBC(23~C) = 1360 mg CaCO3/g, LBC(60~C) = 825 mg CaCO3/g Example 7 268.5 g deionised water, 238.8 g of S0 ~ hydrogen peroxide and 108.0 g white dextrin were placed in a reactor fitted with a condenser, a stirrer, and with a device for controlled heating and metered addition, and were heated to 70~C. A mixture of 262.8 g acrolein and 29.2 g acrylic acid was then added at a metered rate, ~ with stirring, over a period of 3.5 hours. In paral-lel with this, a further 79.6 g of 50 ~ hydrogen peroxide were added at a metered rate. The reaction batch was then heated to 90~C over 1 hour and was maintained at this temperature for 4 hours.
After cooling, the pH was adjusted to pH = 8.6 by adding 50 ~ sodium hydroxide solution. A clear, yellowish solution with a solids content of 43 ~ was obtained.
LBC(23~C) = 1600 mg CaCO3/g, LBC(60~C) = 300 mg CaCO3/g, pour point = -19~C, degree of decomposition ~ after 28 days = 45 ~.
Example 8 320.5 g deionised water, 196.6 g of 50 ~ hydrogen peroxide and 177.4 g white dextrin were placed in a reactor fitted with a condenser, a stirrer, and with a device for controlled heating and metered addition, and were heated to 70~C. A mixture of 216 g acrolein and 24 g acrylic acid was then added at a metered rate, with stirring, over a period of 3.5 hours. In parallel with this, a further 65.5 g of 50 ~ hydrogen peroxide were added at a metered rate. The reaction batch was then heated to 90~C and was maintained at this temperature for 3 hours.
After cooling, the pH was adjusted to pH = 8.6 by adding 50 ~ sodium hydroxide solution. A clear, yellow solution with a solids content of 45 ~ was obtained.
, CA 0222l609 lgg7-ll-l9 LBC(23~C) = 1220 mg CaCO3/g, LBC(60~C) = 160 mg CaCO3/g, pour point = -16~C, degree of decomposition ~ after 28 days = 45 ~.
Comparative example 1 420 parts by weight deionised water and 307 parts of 50 %
hydrogen peroxide were placed in a reactor fitted with a condenser, a stirrer, and with a device for controlled heating and metered addition, and were heated to 70~C.
1012 parts acrolein and 338 parts vinyl acrylate, together with 922 parts hydrogen peroxide (50 ~) were steadily metered in, with stirring, over a period of 4 hours. After the addition was complete, a further 120 g of hydrogen peroxide (50 ~) were added and the temperature was increased to 90~C over 1 hour. The batch was maintained at this temperature until the excess hydrogen peroxide had decomposed. After cooling to room temperature, the polymer solution had a pH of 1.4. The pH was adjusted to pH 10 with 50 ~ NaOH solution.
LBC(23~C) = 1060 mg CaCO3/g, LBC(60~C) = 80 mg CaCO3/g, molecular weight (GPC) = 2790 g/mole, degree of decomposition ~ after 28 days = 37 ~.
Comparative example 2 (EP-A-0 441 197) 253.4 g water, 89.7 g white dextrin (89.2 ~ solids content), 63.8 g maleic anhydride, 3.5 g of a 0.1 ~
aqueous solution of iron(II) ammonium sulphate and 94 g of 50 ~ aqueous sodium hydroxide solution were heated to boiling in a heatable reactor fitted with a stirrer, reflux condenser, thermometer, admission devices, and nitrogen inlet and outlet devices. After the reaction mixture had started to boil, a solution of 178.2 g acrylic acid in 141.9 g water was steadily added over 5 hours, with boiling, and a solution of 16.6 g of 50 ~ --, CA 0222l609 l997-ll-l9 WO 96/37530 _ 27 PCT/EP96/01922 hydrogen peroxide in 44.4 g water was steadily added over 6 hours, with boiling. After the metered addition of hydrogen peroxide was complete, the reaction mixture was heated to boiling for a further 1 hour and was thereafter neutralised to a pH of 7.3 by adding 50 ~ aqueous sodium hydroxide solution and cooled. A clear, viscous, dark brown solution was obtained, with a solids content of 42.8 ~.
LBC(23~C) = 1010 mg CaC03/g, LBC(60~C) = 950 mg CaCO~/g, pour point = -6~C, degree of decomposition ~ after 28 days = 16 ~.
Comparative example 3 (EP-A-0 441 197) 248.6 g water, 134.5 g white dextrin (89.2 ~ solids content), 55.9 g maleic anhydride, 3.5 g of a 0.1 ~
aqueous solution of iron(II) ammonium sulphate and 82.2 g of 50 ~ aqueous sodium hydroxide solution were placed in the reactor described in comparative example 2 and heated to boiling. Immediately after the commencement of boiling, a solution of 155.9 g acrylic acid in 141.9 g water was steadily added over 5 hours, and, separately from this, a solution of 14.5 g of 50 ~ hydrogen peroxide in 44.9 g water was steadily added over 6 hours, the reaction mixture being heated to its boiling point with stirring. After the addition of hydrogen peroxide was complete, the reaction mixture was heated to boiling for a further 1 hour and was thereafter neutralised to a pH
of 7 by adding 132. 5 g of 50 ~ aqueous sodium hydroxide solution. A turbid, highly viscous, light brown solution was obtained, with a solids content of 43.7 ~.
LBC(23~C) = 920 mg CaC03/g, LBC(60~C) = 660 mg CaCO~/g, pour point = -5~C, degree of decomposition ~ after 28 days = 26 ~.
, CA 0222l609 lss7-ll-lg Comparative example 4 (EP-A-0 441 197) 254.7 g water, 160 g maltodextrin with a DE value of about 3, 47.9 g maleic anhydride, 3.5 g of a 0.1 %
aqueous solution of iron(II) ammonium sulphate and 70.5 g of 50 % aqueous sodium hydroxide solution were placed in the reactor described in comparative example 2 and heated to boiling. Immediately after the commencement of boiling, a solution of 133. 6 g acrylic acid in 141.9 g water was steadily added at a metered rate over 5 hours, and a solution of 12.45 g of 50 % hydrogen peroxide in 44.4 g water was steadily added over 6 hours, whilst keeping the reaction mixture boiling. After the addition of hydrogen peroxide was complete, the reaction mixture was heated to boiling for a further 1 hour. A turbid, brown gel was obtained.
LBC(23~C) = 770 mg CaC03/g, LBC(60~C) = 650 mg CaC03/g, degree of decomposition ~ after 28 days = 29 %.
Comparative example 5 (JP-A-61 03 1498) 253.4 g water, 89.7 g white dextrin (89.2 % solids content) and 3.5 g of a 0.1 % aqueous solution of iron(II) ammonium sulphate and 82.2 g of 50 % aqueous sodium hydroxide solution were heated to boiling in the reactor described in comparative example 2. After reaction mixture had started to boil, a solution of 178.2 g acrylic acid in 141.9 g water was steadily added over 5 hours, and a solution of 16.6 g of 50 % hydrogen peroxide in 44.4 g water was steadily added over 6 hours, with boiling. After the addition of hydrogen peroxide was complete, the reaction mixture was heated to boiling for a further 1 hour, and was thereafter neutralised to a pH
of 7.2 by adding 50 ~ aqueous sodium hydroxide solution and cooled. A turbid, viscous, brown solution was obtained, with a solids content of 38.4 %. -. CA 0222l609 lgg7-ll-l9 Wo 96/37530 PCT/EP96/01922 LBC(23~C) = 1230 mg CaCO3/g, LBC(60~C) = 500 mg CaCO3/g, pour point = -8~C, degree of decomposition ~ after 28 days = 25 ~.
Consistency and colour:
The products from the comparative examples were intensely coloured and were mostly turbid. They were viscous liquids, and a gel was even formed in one case.
The products which are claimed exhibited properties which were surprisingly more favourable. They were clear liquids with only a slight yellow coloration.
Pour point:
The pour points of the products were measured following ISO 3016-19741. The flow point denotes the temperature at which the substance clearly still exhibits perceptible flow after it has been cooled under specified conditions.
The flow behaviour of the solutions on cooling is surprisingly better for the compounds claimed than for the comparative products. Due to this effect, they can still be handled satisfactorily even under unfavourable external conditions (cold), i.e. they can be pumped and conveyed even at low temperatures. The pour points of the examples and comparative examples are compared in Table la.
1 In departure from the Standard, a test tube with a round bottom was used instead of a test tube with a flat bottom. The effect of this alteration on the measured results was judged to be negligible, particularly since all the tests were performed in the same vessel and are thus comparable with each other in each case. The error in measurement within a series of measurements is quoted as + 3~C.
, CA 0222l609 lgg7-ll-lg Table la: Flow points Product Pour point [~C]
Example 7 -19 Example 8 -16 Comparative example 2 -6 Comparative example 3 -5 Comparative example 4 A gel even at RT
Comparative example 5 -8 RT = room temperature Zahn-Wellens biodegradability:
The claimed products were decomposed considerably better than those of the comparative tests. The degree of decomposition of the examples and comparative examples is compared in Table 2a.
Table 2a: Degree of decomposition ~ in the Zahn-Wellens test after 28 days Product Degree of decomposition after 28 days [%]
Example 2 63 Example 3 52 Example 4 62 Example 7 45 Example 8 45 Comparative example 1 37 Comparative example 2 16 Comparative example 3 26 Comparative example 4 29 Comparative example 5 25 . , CA 0222l609 lgg7-ll-l9 Washing tests In order to characterise the graft polymers according to the invention as regards their incrustation-inhibiting effect, they were incorporated in detergent compositions.
Test fabrics comprising huckaback towelling, white cotton textile and cotton textile with green stripes were washed with each of these detergent formulations. 25 wash ~ cycles were performed. The fabric was dry-ironed after each wash. After each 10 and 25 washes the test fabric was ashed (double determination). 2 g fabric in each case were calcined in a pre-incinerator at 500~C for 1 hour, and were then ashed in a muffle furnace at 800~C
for 1 hour. The crucibles were re-weighed and the ash contents were determined as a percentage. The more effective a polymer is, the lower is the ash content.
The LSD values (least significant deviations) were calculated according to DIN 44 983, Part 50. A ranking was obtained by assigning marks to the individual measured values determined for different fabrics.
Detergent A
10.00 ~ Marlon ARL
1.00 ~ Dehydrol TA5 6.00 ~ Dehydrol LT7 1.00 ~ Edenor HT35 0.15 ~ Blankophor MBBH-766 0.02 ~ Tinopal CBS-X
0.23 ~ Trilon B
12.00 ~ soda 2.70 % Portil N
1.10 ~ Relatin DM 4050 2.50 ~ sodium perborate tetrahydrate 11.70 ~ sodium perborate monohydrate 30.30 ~ Wessalith CS
0.60 ~ anti-foaming agent 6.00 ~ EDTA
~ , CA 02221609 1997-11-19 WO 96/37530 _ 32 PCT/EP96/01922 5.40 ~ graft copolymer according to Example 1 (solids content) 0.50 ~ lipolase 0.70 ~ Esperase 4.0 T
0.36 ~ sodium sulphate Detergent B
10.00 ~ Marlon ARL
1.00 ~ Dehydrol TA5 6.00 ~ Dehydrol LT7 1.00 ~ Edenor HT35 0.15 ~ Blankophor MBBH-766 0.02 ~ Tinopal CBS-X
0.23 ~ Trilon B
12.00 ~ soda 2.70 ~ Portil N
1.10 ~ Relatin DM 4050 2.50 ~ sodium perborate tetrahydrate 11.70 ~ sodium perborate monohydrate 30.30 ~ Wessalith CS
0.60 ~ anti-foaming agent 6.00 ~ EDTA
5.40 ~ copolymer according to comparative example 1 (solids content) 0.50 ~ lipolase 0.70 ~ Esperase 4.0 T
0.36 ~ sodium sulphate Detergent C
10.00 ~ Marlon ARL
1.00 ~ Dehydrol TA5 6.00 ~ Dehydrol LT7 1.00 ~ Edenor HT35 0.15 ~ Blankophor MBBH-766 0.02 ~ Tinopal CBS-X
0.23 ~ Trilon B
12.00 ~ soda 2.70 ~ Portil N .-, . , CA 0222l609 lgg7-ll-lg Wo 96/37530 _ 33 PCT/EP96/01922 1.10 ~ Relatin DM 4050 2.50 ~ sodium perborate tetrahydrate 11.70 ~ sodium perborate monohydrate 30.30 ~ Wessalith CS
0.60 ~ anti-foaming a~ent 6.00 ~ EDTA
5.40 % Sokalan CP5 (solids content; widely-used commercial product) 0.50 ~ lipolase 0.70 ~ Esperase 4.0 T
0.36 ~ sodium sulphate Washing conditions Secondary wash capacity: 1 cycle corresponding to 25 washes Temperature / hardness: 60~ Celsius / 20~ dH
Washing machine type: Miele W 763 Program: boiling/coloured wash without pre-wash Amount of detergent: 80.0 g (6.15 g/l) Ballast material: 18 pieces of white cotton (about 2.7 kg) 3 pieces of terry cloth 3 pieces of towelling (on to which the soiling materials were sewn) White fabric: 1 piece of terry cloth in each case (about 0.8 kg) 1 piece of towelling in each case 2 pieces of white cotton in each case (cotton / white) 2 pieces of green striped cotton in each case (cotton /
GS) , ., , CA 0222l609 lgg7-ll-l9 34 -.
Soiling material: blood (EMPA 111) standard (EMPA 101) cutaneous fat (WFK 10 G) tea (WFK 10 G) Hardening: in each odd washing operation blood (EMPA 111) standard (EMPA 101) cutaneous fat (WFK 1-0 G) tea (WFK 10 G) Waschereiforschung Krefeld (WFK) [Krefeld Laundry Research] (WFK) and the Eidgenossische Material Prufanstalt (EMPA) Schweiz [Swiss Material Testing Institute] sell test soiling materials for washing tests.
These test soiling materials are designated, for example, as EMPA 111 for blood soiling material.
Table 1 Incrustation-inhibiting effect of the polymer according to the invention from Example 1 Number of washes Fabric Detergent A
ash content [~]
terry cloth 0.62 towelling 0.47 cotton / GS 0.58 cotton / white 0.68 mean value 0.59 terry cloth 1.40 towelling 1.13 cotton / GS 1.15 cotton / white 1.31 mean value 1.25 LSD values: F: 0.06 ~; HT: 0.08 ~; cotton/GS 0.04 ~;
cotton / white: 0.18 ~
~. , CA 0222l609 lgg7-ll-l9 Table 2 Incrustation-inhibiting effect of the comparative examples 5 Number of FabricDetergent B Detergent C
washes ash content [~] ash content [~]
terry cloth 0.67 1.06 towelling 0.74 0.67 cotton / GS 0.79 ~ 1.14 cotton / 0.97 0.72 white mean value 0.79 0.90 terry cloth 1.61 1.58 towelling 1.47 1.60 cotton / GS 1.74 1.88 cotton / 1.68 1.45 white mean value 1.63 1.63 LSD values: F: 0.06 ~; HT: 0.08 ~; cotton/GS 0.04 ~;
cotton / white: 0.18 ~
The following ranking for the effectiveness of the various polymers was obtained from the test results given in Tables 1 and 2:
After 10 washes:
graft copolymer according to the invention more effective than that of comparative example 1, which was more effective than the commercial product Sokalan CP 5.
and after 25 washes:
graft copolymer according to the invention more effective than that of comparative example 1, the effectiveness of which was similar to that of the commercial product Sokalan CP 5.
~ , CA 02221609 1997-ll-lg Other advantages and embodiments of the invention follow from the following claims.
Claims (10)
1. Water-soluble graft copolymers of monosaccharides, oligosaccharides, polysaccharides and derivatives thereof, with the exception of starch xanthates, which are obtainable by the radical-initiated copolymerisation of A) monomer mixtures comprising a) more than 40 - 100 % by weight of at least one .alpha.,.beta.-unsaturated aldehyde of general formula I
(I), where R1 represents hydrogen or a linear or branched C1-C4 alkyl, and R2 represents hydrogen or methyl, b) 0 - 60 % by weight of a) different monoethylenically unsaturated monomers which are copolymerisable with a), and c) 0 - 5 % by weight of monomers containing at least two ethylenically unsaturated, unconjugated double bonds in their molecule, in the presence of B) monosaccharides, oligosaccharides, polysaccharides;
oxidatively, hydrolytically or enzymatically decomposed polysaccharides; chemically modified mono-, oligo- or polysaccharides; or mixtures of the said compounds, and C) one or more oxidising agents, wherein the weight ratio of A) to B) extends from (95 : 20) to (5 : 80) and oxidising agent C) is used at a weight ratio of C) to A) + B) from (5 : 100) to (50 : 50).
(I), where R1 represents hydrogen or a linear or branched C1-C4 alkyl, and R2 represents hydrogen or methyl, b) 0 - 60 % by weight of a) different monoethylenically unsaturated monomers which are copolymerisable with a), and c) 0 - 5 % by weight of monomers containing at least two ethylenically unsaturated, unconjugated double bonds in their molecule, in the presence of B) monosaccharides, oligosaccharides, polysaccharides;
oxidatively, hydrolytically or enzymatically decomposed polysaccharides; chemically modified mono-, oligo- or polysaccharides; or mixtures of the said compounds, and C) one or more oxidising agents, wherein the weight ratio of A) to B) extends from (95 : 20) to (5 : 80) and oxidising agent C) is used at a weight ratio of C) to A) + B) from (5 : 100) to (50 : 50).
2. Graft copolymers according to claim 1, characterised in that R1 and R2 are hydrogen in general formula I.
3. Graft copolymers according to claim 1 or 2, characterised in that component b) comprises acrylic acid, maleic acid, maleic anhydride, vinyl acetate and/or one or more monoethylenically unsaturated sulphonic acids.
4. Graft copolymers according to one or more of the preceding claims, characterised in that component C) is hydrogen peroxide.
5. A process for producing graft copolymers of monosaccharides, oligosaccharides, polysaccharides and derivatives thereof, with the exception of starch xanthates, by the radical-initiated copolymerisation of A) 95 to 20 % by weight of ethylenically unsaturated monomers in the presence of B) 5 to 80 % by weight of at least one monosaccharide, oligosaccharide, polysaccharide, decomposed or chemically modified mono-, oligo- and polysaccharide or mixtures thereof and C) one or more oxidising agents in an inert diluent at temperatures up to 180°C, wherein mixtures comprising a) more than 40 - 100 % by weight of at least one .alpha.,.beta.-unsaturated aldehyde of general formula I
(I), where R1 represents hydrogen or a linear or branched C1-C4 alkyl, and R2 represents hydrogen or methyl, b) 0 - 60 % by weight of a) different monoethylenically unsaturated monomers which are copolymerisable with a), and c) 0 - 5 % by weight of monomers containing at least two ethylenically unsaturated, unconjugated double bonds in their molecule, are used as ethylenically unsaturated monomers A), and the one or more oxidising agent C) is used at a weight ratio of C) to A) + B) of (5 : 100) to (50 : 50).
(I), where R1 represents hydrogen or a linear or branched C1-C4 alkyl, and R2 represents hydrogen or methyl, b) 0 - 60 % by weight of a) different monoethylenically unsaturated monomers which are copolymerisable with a), and c) 0 - 5 % by weight of monomers containing at least two ethylenically unsaturated, unconjugated double bonds in their molecule, are used as ethylenically unsaturated monomers A), and the one or more oxidising agent C) is used at a weight ratio of C) to A) + B) of (5 : 100) to (50 : 50).
6. A process according to claim 5, characterised in that hydrogen peroxide is used as oxidising agent C).
7. A process according to either one of claims 5 or 6, characterised in that hydrogen peroxide is used for initiating the radical copolymerisation.
8. Use of the graft copolymers according to one or more of claims 1 to 4 as cobuilders or builders in detergents.
9. A method of washing and cleaning textile fabrics, characterised in that a graft copolymer according to one or more of claims 1 to 4 is used.
10. A detergent and cleaning material containing a graft copolymer according to one or more of claims 1 to 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19518620A DE19518620C2 (en) | 1995-05-24 | 1995-05-24 | Graft copolymers based on mono-, oligo- and polysaccharides, process for their preparation and their use |
| DE19518620.6 | 1995-05-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2221609A1 true CA2221609A1 (en) | 1996-11-28 |
Family
ID=7762473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002221609A Abandoned CA2221609A1 (en) | 1995-05-24 | 1996-05-08 | Graft copolymers based on mono-, oligo- and polysaccharides, process for preparing the same and their use |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0828771B1 (en) |
| JP (1) | JPH11505864A (en) |
| KR (1) | KR19990021874A (en) |
| AT (1) | ATE177766T1 (en) |
| BR (1) | BR9609077A (en) |
| CA (1) | CA2221609A1 (en) |
| DE (2) | DE19518620C2 (en) |
| DK (1) | DK0828771T3 (en) |
| ES (1) | ES2131948T3 (en) |
| GR (1) | GR3029803T3 (en) |
| HU (1) | HUP9801246A3 (en) |
| IL (1) | IL118409A0 (en) |
| WO (1) | WO1996037530A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103797038A (en) * | 2011-06-02 | 2014-05-14 | 朗盛德国有限责任公司 | Polysaccharide and/or polypeptide based graft polymers as synthetic tannins |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6090884A (en) * | 1998-05-07 | 2000-07-18 | S. C. Johnson Commercial Markets, Inc. | Starch degradation/graft polymerization composition, process, and uses thereof |
| GB0117768D0 (en) * | 2001-07-20 | 2001-09-12 | Unilever Plc | Use of polymers in fabrics cleaning |
| US8674021B2 (en) | 2006-07-21 | 2014-03-18 | Akzo Nobel N.V. | Sulfonated graft copolymers |
| WO2011025624A1 (en) | 2009-07-31 | 2011-03-03 | Akzo Nobel N.V. | Graft copolymers |
| US8841246B2 (en) | 2011-08-05 | 2014-09-23 | Ecolab Usa Inc. | Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage |
| US8636918B2 (en) | 2011-08-05 | 2014-01-28 | Ecolab Usa Inc. | Cleaning composition containing a polysaccharide hybrid polymer composition and methods of controlling hard water scale |
| US8853144B2 (en) | 2011-08-05 | 2014-10-07 | Ecolab Usa Inc. | Cleaning composition containing a polysaccharide graft polymer composition and methods of improving drainage |
| US8679366B2 (en) | 2011-08-05 | 2014-03-25 | Ecolab Usa Inc. | Cleaning composition containing a polysaccharide graft polymer composition and methods of controlling hard water scale |
| EP2773320B1 (en) | 2011-11-04 | 2016-02-03 | Akzo Nobel Chemicals International B.V. | Hybrid dendrite copolymers, compositions thereof and methods for producing the same |
| MX2014005089A (en) | 2011-11-04 | 2014-08-08 | Akzo Nobel Chemicals Int Bv | Graft dendrite copolymers, and methods for producing the same. |
| US8945314B2 (en) | 2012-07-30 | 2015-02-03 | Ecolab Usa Inc. | Biodegradable stability binding agent for a solid detergent |
| US9365805B2 (en) | 2014-05-15 | 2016-06-14 | Ecolab Usa Inc. | Bio-based pot and pan pre-soak |
| DE102016225151A1 (en) | 2016-12-15 | 2018-06-21 | Clariant International Ltd | Hybrid polymers and use as additives in deep wells |
| DE102016225147A1 (en) | 2016-12-15 | 2018-06-21 | Clariant International Ltd | Hybrid polymers and use as additives in deep wells |
| CN117164128B (en) * | 2023-11-03 | 2024-01-02 | 烟台康恩环保科技有限公司 | Organic scale and corrosion inhibitor for high-dissolved-oxygen water quality and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2330260A1 (en) * | 1973-06-14 | 1975-01-16 | Degussa | PROCESS FOR THE PRODUCTION OF POLYCARBOXYLATES WITH IMPROVED BIODEGRADABILITY |
| US4005040A (en) * | 1975-11-10 | 1977-01-25 | The United States Of America As Represented By The Secretary Of Agriculture | Foamed and solid rubber-starch graft copolymer compositions and method of preparation |
| JPS6131498A (en) * | 1984-07-20 | 1986-02-13 | 三洋化成工業株式会社 | Builder and detergent composition |
| IT1230862B (en) * | 1989-06-06 | 1991-11-08 | Ausidet Spa | WATER SOLUBLE COPOLYMERS OF MALEIC ANHYDRIDE. |
| DE4003172A1 (en) * | 1990-02-03 | 1991-08-08 | Basf Ag | PFROPOPOPOLYMERISATES OF MONOSACCHARIDES, OLIGOSACCHARIDES, POLYSACCHARIDES AND MODIFIED POLYSACCHARIDES, PROCESS FOR THEIR PREPARATION AND THEIR USE |
| DE4139826A1 (en) * | 1991-12-03 | 1993-06-09 | Basf Ag, 6700 Ludwigshafen, De | WASHING AND CLEANING AGENT |
| DE4201452A1 (en) * | 1992-01-21 | 1993-07-22 | Basf Ag | POLYMERS TANNERS |
| DE4303320C2 (en) * | 1993-02-05 | 1995-12-21 | Degussa | Detergent composition having improved soil carrying power, process for its preparation and use of a suitable polycarboxylate therefor |
-
1995
- 1995-05-24 DE DE19518620A patent/DE19518620C2/en not_active Expired - Fee Related
-
1996
- 1996-05-08 DE DE59601461T patent/DE59601461D1/en not_active Expired - Fee Related
- 1996-05-08 AT AT96919711T patent/ATE177766T1/en not_active IP Right Cessation
- 1996-05-08 ES ES96919711T patent/ES2131948T3/en not_active Expired - Lifetime
- 1996-05-08 KR KR1019970708349A patent/KR19990021874A/en not_active Application Discontinuation
- 1996-05-08 DK DK96919711T patent/DK0828771T3/en active
- 1996-05-08 WO PCT/EP1996/001922 patent/WO1996037530A1/en not_active Application Discontinuation
- 1996-05-08 JP JP8535301A patent/JPH11505864A/en active Pending
- 1996-05-08 BR BR9609077A patent/BR9609077A/en not_active Application Discontinuation
- 1996-05-08 HU HU9801246A patent/HUP9801246A3/en unknown
- 1996-05-08 EP EP96919711A patent/EP0828771B1/en not_active Expired - Lifetime
- 1996-05-08 CA CA002221609A patent/CA2221609A1/en not_active Abandoned
- 1996-05-23 IL IL11840996A patent/IL118409A0/en unknown
-
1999
- 1999-03-26 GR GR990400892T patent/GR3029803T3/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103797038A (en) * | 2011-06-02 | 2014-05-14 | 朗盛德国有限责任公司 | Polysaccharide and/or polypeptide based graft polymers as synthetic tannins |
| CN109265610A (en) * | 2011-06-02 | 2019-01-25 | 朗盛德国有限责任公司 | The graft polymers based on polysaccharide and/or polypeptide as syntannins |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1996037530A1 (en) | 1996-11-28 |
| JPH11505864A (en) | 1999-05-25 |
| EP0828771B1 (en) | 1999-03-17 |
| DE19518620A1 (en) | 1996-11-28 |
| HUP9801246A2 (en) | 1998-08-28 |
| ES2131948T3 (en) | 1999-08-01 |
| DE59601461D1 (en) | 1999-04-22 |
| IL118409A0 (en) | 1996-09-12 |
| EP0828771A1 (en) | 1998-03-18 |
| DE19518620C2 (en) | 1998-04-09 |
| DK0828771T3 (en) | 1999-10-11 |
| ATE177766T1 (en) | 1999-04-15 |
| KR19990021874A (en) | 1999-03-25 |
| GR3029803T3 (en) | 1999-06-30 |
| BR9609077A (en) | 1999-02-02 |
| HUP9801246A3 (en) | 1999-03-29 |
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