NL1013658C2 - Hydrophobized polyols. - Google Patents

Description

The invention relates to hydrophobized polyols.

Numerous processes for the preparation of hydrophobized polyols have been described in the literature. For example, EP-A-0 384 167 describes a process starting from an ether-substituted polysaccharide, which is then reacted with a hydrophobic alkylaryl compound. By taking an ether-substituted polysaccharide instead of an unsubstituted polysaccharide, more of the hydrophobic alkylaryl compound is incorporated. Although this increases the efficiency of the hydrophobicization reaction, there is a great need to improve it even further.

15

EP-A-0 566 911 describes a process in which a polysaccharide in the presence of alkali is reacted with an alkyl halide, an alkylene oxide or chloroacetic acid and then with a compound having a hydrophobic alkyl or alkylaryl group with 8 to 24 carbon atoms and a reactive group such as a glycidyl ether, epoxide or isocyanate. As in the former patent publication, the drawback of a low substitution efficiency of the compounds with hydrophobic groups also applies here.

Finally, EP-A-0 189 935 describes a process for the preparation of water-soluble, hydrophobically derivatized polysaccharides, in particular hydroxyethyl cellulose (HEC). In addition, HEC is alkylated with a quaternary nitrogen-containing compound such as 3-chloro-2-hydroxypropyl trimethyl ammonium chloride and a hydrophobic alkyl halide such as dodecyl bromide. In an example (run No. 35), a Degree of Molar Substitution (= MS or the average number of moles bound of a given reactant per anhydroglucose unit) of 1 0 1 3 ml 2 0.016 was obtained. From this a hydrophobic substitution efficiency of 13% can be calculated.

A drawback of the method described therein is that the hydrophobically modified polysaccharide thus obtained always contains a quaternary ammonium group. Because of the high aquatic toxicity and tendency to adsorb on all surfaces, cationic polymers are less desirable, especially for environmental reasons.

The invention now provides hydrophobicized polyols which are free from quaternary ammonium groups and the preparation of which proceeds relatively quickly and without problems.

The invention consists in that the hydrophobized polyols are available by reacting at least part of the phosphate groups of a polyol phosphate with a molecular weight of at least 1000 with a nonionic mono-epoxide.

It is noted that reaction of a polyol phosphate such as polysaccharide phosphate with an epoxy compound is known per se from US-A-5,409,705. The epoxy compound used therein is an ionic mono-epoxide, i.e. an epoxidized quaternary ammonium compound. At most one epoxy compound is added per phosphate group.

WO 97/30090 also refers to the conversion of polysaccharide phosphate, in particular cellulose phosphate with an epoxy compound, although this only refers to the use of a bifunctional epoxide as cross-linking agent to reduce the solubility.

Surprisingly, it has been found that when using a nonionic mono-epoxy compound the reaction with polyol phosphates such as cellulose phosphate leads to a much higher substitution efficiency than when using an epoxide which contains a quaternary ammonium group. This is likely to be attributed to the fact that once one of the two acidic groups present in a polyol phosphate ester group has reacted with the epoxy group 5 of a nonionic mono-epoxide, the reactivity to an epoxy group of the remaining acidic group is much greater than that from both acid groups originally present. A consequence of this phenomenon is that the phosphate groups in the hydrophobized polyol consist almost entirely of monoester phosphate groups not yet reacted with epoxy groups on the one hand and triester phosphate groups fully converted with epoxy groups on the other hand. An important advantage of this is that two hydrophobic groups are always present per hydrophobed phosphate group. Therefore, in order to achieve the same effect, use can be made of hydrophobic groups with a much smaller molecular weight than 15 if only one hydrophobic group is present per phosphate group, as is the case with the known polysaccharide derivatives discussed above.

A further advantage is that the hydrophobized phosphate esters can be readily hydrolysed biologically, generally producing products which are harmless to nature. This is especially true for polyol phosphate esters based on polysaccharides, the degradation products of which are non-toxic to fish, crustaceans or algae. The special feature of these phosphate esters lies mainly in the fact that they have properties that are very similar to existing commercial products produced from non-renewable raw materials.

25

The polyols which are eligible in the context of the invention to be converted into a polyol phosphate with a nonionic mono-epoxide after conversion with phosphoric acid are preferably selected from the group of (a) polysaccharides, (b) fully or partially saponified polyvinyl acetate, and 1013658 4 (c) homo- or copolymers of polyhydroxyalkyl (meth) acrylate, of which in particular polyhydroxyethyl (meth) acrylate.

The polysaccharides preferably comprise compounds having at least 10 monosaccharide units and belong to the group of starch, amylose, amylopectin, maltose, cellulose, dextran and inulin.

Polyol phosphates can be obtained by a variety of methods known in the art. In a preferred embodiment 10, one usually proceeds in this way. First, a polyol is reacted with a polyphosphoric acid with a P2O5 content of greater than 72% (preferably between 82 and 84%). At a P2O5 content of more than about 85%, the number of diester phosphate groups and hence the degree of cross-linking increases substantially. Preferably, 15 amounts of polyphosphoric acid corresponding to 0.5 to about 1.0 mole equivalent of P2O5 for each polyole equivalent are used. By "polyole equivalent" is meant the equivalent number of hydroxyl groups present in the polyol. If desired, an excess of P2O5 can be used in the reaction.

An alternative method consists in that instead of P2O5 urea phosphate, i.e. urea mixed with orthophosphoric acid, is taken as phosphating agent. In the preparation of urea phosphate, a molar ratio of urea to orthophosphoric acid is preferably started from 1.0 to 2.0. In particular, in the phosphation of low molecular weight polyvinyl alcohol, urea phosphate is advantageously used.

Phosphated starch is supplied by AVEBA under the name "Nylgum".

When cellulose is taken for the polysaccharide, preference is given to a method in which cellulose is added in a kneader and / or mixer suitable for this purpose to a polyphosphoric acid with a P2O5 content of 72-85% by weight to obtain a solution composed of 94-100% by weight of the components cellulose, phosphoric acid and / or anhydrides thereof and water. Examples of suitable cellulose phosphate compositions are given in WO 96/06208 and WO 97/28298.

Within the scope of the invention, phosphoric acid is understood to mean all inorganic acids of phosphorus and / or mixtures thereof. Orthophosphoric acid 10 (H3PO4) is the acid of pentavalent phosphorus. The anhydrous equivalent thereof, i.e. the anhydride, is phosphorus pentoxide (P2O5). In addition to orthophosphoric acid and phosphorus pentoxide, depending on the amount of water in the system, a series of pentavalent acids with a water binding capacity between phosphorus pentoxide and orthophosphoric acid, such as 15 ((6Η4θι3, PPA), exist.

In addition to water, phosphoric acid and its anhydrides, and polyols and / or reaction products of phosphoric acid and polyols, other substances may also be present in the solution in the preparation of phosphated polyols. The solution can be obtained by mixing components which can be divided into four groups: polyols, in particular polysaccharides such as cellulose, water, inorganic acids of phosphorus including their anhydrides, and other components. These "other ingredients" can be materials that enhance the processability of the polyol solution, solvents other than phosphoric acid, wetting additives or auxiliary agents (additives), for example to prevent degradation of the polyols, or dyes and the like.

In the context of this disclosure, there are weight percentages of dissolved polyols, in particular dissolved polysaccharides, when the polysaccharides contain phosphorus bound thereto, these are related to the amounts converted back to phosphorus-free polyols. This applies mutatis mutandis to the weight percentages of dissolved phosphorus mentioned in the description.

It has been found that generally very good results are obtained when the hydrophobized polyols are obtained from phosphated polysaccharides or a polysaccharide phosphate with a substitution degree DSp between 0.001 and 3, with a substitution degree between 0.05 and 1.5 being preferred.

In the case of cellulose phosphate, optimal results are obtained at a molecular weight <250,000 and a degree of substitution between 0.1 and 1.0.

Hydrophobic polyols with favorable properties are compounds obtained by reacting polyol phosphates with a nonionic mono-epoxide of the formula: Ri- (OCH2CH (R2)) n-Q, in which

R 1 has the meaning of a C 1 -C 30 group, R 2 is hydrogen or methyl, n is ΟΙ 0 and Q represents a 1,2-epoxy group or a glycidyl ether group.

Products with very good properties have been obtained by reaction with an epoxide according to the aforementioned formula in which R1 has the meaning of straight or branched butyl such as n-butyl, isobutyl, tert-butyl or sec-butyl and n = 0.

Preference is given to products obtained by reaction with compounds according to the above formula in which R1 has the meaning of a C4-C22, preferably of a Cq-Czz group.

Suitable epoxides further include compounds of the formula indicated above wherein R 1 signifies a nonylphenyl, 2-ethylhexyl, dodecyl, tetradecyl, hexadecyl, octadecyl or hexacosyl group. R1 is often derived from naturally occurring fatty acids, derived from coconut oil, palm oil, talc, as well as hydrogenated talc. If desired, one or more alkylene oxide groups, such as ethylene oxide and propylene oxide, may be included in the 1013658 7 epoxides.

Typical examples of suitable epoxy compounds are: ethyl glycidyl ether, butyl glycidyl ether, butoxyethyl glycidyl ether, tert. 5 butyl glycidyl ether, iso-butyl glycidyl ether, propyl glycidyl ether, benzyl glycidyl ether.

Preferred are dodecyl glycidyl ether, tetradecyl glycidyl ether, hexadecyl glycidyl ether, octadecyl glycidyl ether, dodecyl bis (oxyethyl) glycidyl ether, tetradecyl bis (oxyethyl) glycidyl ether, 10 hexadecyl bis (oxyethyl) bis (oxyethyl) bis (oxyethyl) bis glycidyl ether, tetradecyl penta (oxyethyl) glycidyl ether, (2,3-epoxypropyl) benzene, styrene oxide, 1,2-epoxy-3-phenoxypropane, 2-methylphenylglycidyl ether, 3- (pentadecadienyl) phenyl glycidyl ether, 4-tert. butylphenyl glycidyl ether, 4-chlorophenyl glycidyl ether, 4-methoxyphenyl glycidyl ether or a mixture thereof.

In general preference is given to compounds for which in the above formula R2 represents hydrogen.

The aforementioned nonionic mono-epoxides may also carry 20 substituents, such as halogen or a blocked or unblocked reactive group, such as a blocked isocyanate group. Of particular interest are epoxides with an ethylenically unsaturated group as present in unsaturated fatty acids such as oleic acid or linoleic acid. In addition, both long chain and short chain fatty acids as present in allyl glycidol can be used. In particular in the presence of the latter compound, the hydrophobically modified polyol can advantageously be used as a cross-linking agent.

It goes without saying that in addition also other unsaturated or aromatic epoxides may be present.

1013658 8

Under certain circumstances, premature crosslinking may occur when allylglycidol is used.

It has been found that far fewer problems arise in this regard when the (meth) acrylate ester of glycidol is taken for the ethylenically unsaturated epoxide.

The reaction of polyol phosphate with a nonionic mono-epoxide usually proceeds as follows. First, the polyol phosphate to be derivatized is made into a suspension in an alcohol (ethanol, or preferably 2-propanol), the addition of water, provided that 2-propanol is the reaction medium, has a favorable effect on the derivatization result. Some derivatizations can also be performed in water.

The epoxide is then added with stirring, as such or as a solution in ethanol or an ethanol / water mixture. After the exothermic reaction has ended, the mixture is stirred at a temperature between 20 and 65 ° C for 1/2 to 3 hours. After cooling, the reaction mixture is precipitated, if necessary, in a non-solvent such as acetone and then filtered and dried in vacuo at a temperature between 65 and 75 ° C.

20

The hydrophobically modified polyol derivatives according to the invention can, depending on the nature of the starting polyol (polysaccharide, cellulose, polyvinyl alcohol or copolymer of polyhydroxyethyl (meth) acrylate), the molecular weight, the weight percentage of phosphorus, as well as the nature of the hydrophobic substituents applied to the most diverse areas are deployed. As an example may be mentioned: a) propylene oxide-modified cellulose phosphate for the manufacture of films, the preparation of ink and paper, in paste for textile printing and as a surfactant in emulsion polymerization, 1013658 9 b) glycidol-modified cellulose phosphate for the preparation of reversible gels in increasing the porosity around oil fracturing of boreholes, c) butylglycidol modified cellulose phosphate with a high degree of substitution: for use in coatings and ink, with an average degree of substitution: for use in coatings and inks and for coating of tablets, with a low degree of substitution: for use as a surfactant in detergents and cosmetics, 10 d) with a low degree of substitution with fatty alkyl glycidol modified cellulose phosphate or starch phosphate for use in detergents and cosmetics, e) glycidol methacrylate modified cellulose phosphate with low substitution degree as a cross-linking agent of polyacrylates, 15 f) with allylglycidol or 1,2-epoxy-but-3-a modified cellulose phosphate with a low degree of substitution as a cross-linking agent of polyacrylates for superabsorbents, g) with aryl group-containing epoxide modified cellulose phosphate as lubricant, 20 h) starch phosphate or inulin phosphate modified with butylglycidol and / or 2-ethylhexylglycidol for use as an emulsifying agent, i) with allylglycidol or 1,2-epoxy-but-a modified (co) polymers of hydroxyethyl (meth) acrylate phosphate with a low degree of crosslinking agent of polyacrylic for superabsorbents, 25 j) branched alkyl glycidyl ether modified starch, cellulose or inulin phosphate as a low or non-foaming emulsifying or dispersing agent, k) aryl-containing epoxide modified polyol phosphate as flocculant, 1013658 10 l) with a C4-Cu epoxide substituted cellulose or starch phosphate as an anti-deposition or anti-soiling agent (" soil release agent ") in detergents, m) butylglycidyl modified cellulose or starch phosphate in film form as packaging film, n) C10 - C22 epoxide substituted cellulose or starch phosphate with high molecular weight and low substitution degree as associative thickener, 0) with C10 - C22 epoxide substituted low molecular weight, low degree of substitution cellulose or starch phosphate as a "cleaning surfactant" in detergents, and p) starch phosphate or inulin phosphate modified with butyl and / or 2-ethylhexyl glycidyl ether for use as a co-surfactant.

The invention will now be illustrated by the following examples. It goes without saying that these are exemplary embodiments to which the invention is not limited.

For the preparation of polysaccharide derivatives, 3 hydroxyl groups are available per anhydroglycose unit. The examples use the terminology common in this art, where DS stands for "Degree of Substitution" and MS stands for "Degree of Molar Substitution", where DS represents the average number of substituted hydroxyl groups per anhydroglucose unit, and MS represents the average number of moles bound of a given reactant per 25 anhydroglucose unit.

Example I

Preparation of the reaction product of cellulose phosphate with propylene oxide.

4.6 g of 1 01 3658 11 cellulose phosphate (DSp = 0.42, corresponding to 20 meq acid) was placed in a 250 ml 3-neck flask equipped with a mechanical stirrer, a nitrogen inlet and a reflux condenser. in 23 g of water. 30 ml (425 mmol) of propylene oxide were suddenly added to this at room temperature. The reaction was highly exothermic, after which the flask was placed in an ice bath. Afterwards, it was stirred for another 45 minutes on a water bath at 40 ° C. Titration with 0.08N NaOH of the dried product showed that about 95% of the acid had been converted.

Example II

10 Esterification of cellulose phosphate with n-butyl glycidyl ether (BGE).

1g of a cellulose phosphate with a degree of substitution DSp = 0.39 was suspended in a mixture of 1.56g (11.98mmol) n-butylglycidyl ether and 10ml of ethanol and stirred at 60 ° C for 2 hours. After cooling to room temperature, 50 ml of ethanol were added and stirred. The precipitate formed was removed by filtration and then purified by washing with acetone, followed by filtration and drying in vacuo at 40 ° C.

0.91 g of product was obtained, which corresponds to 60% of the theory. Titration with 0.1 N NaOH showed that 95% of the acid had been converted. The product was and had moderate foam stabilizing properties in aqueous systems.

Example III

Esterification of cellulose phosphate with n-butyl glycidyl ether (BGE).

A cellulose phosphate with a degree of substitution DSp = 0.42 was used. 45 grams of this material were suspended for 10 minutes in 600 ml of a mixture of 94 parts by volume of 2-propanol and 6 parts by volume of water at approx. 65 ° C, after which suddenly 33 ml of n-butyl glycidyl ether of 95% purity (corresponding to approx. 219 mmol, versus 192 101 3658 12 meq acid from the cellulose phosphate) was added to the present suspension and the whole was further stirred for 4 hours at about 65 ° C.

After cooling, the suspension was poured into 1.5 liters of cold acetone with stirring and left overnight at 2 ° C, followed by decantation of supernatant, stirring again with 500 ml of fresh acetone, and finally the product was separated by filtration of the reaction medium.

After drying at 60 ° C for 16 hours in vacuo, 49 grams of the final product were obtained, corresponding to 70% of the theoretically expected amount.

Titration of a sample of dried material with 0.05 N NaOH showed that the degree of substitution of the available acid with n-butyl glycidyl ether was approximately 0.26, which corresponds to a degree of derivatization of (0.26 / 0.84) x 100% = 31%.

The resulting material was water soluble and exhibited excellent foam stabilizing properties.

The material was further found to be able to reduce the surface tension of water to about 34 mN / m, as determined by a solution containing 1.8 weight percent of the product. The surface tension of the water used without addition of the product was 70.5 mN / m.

Example IV

Preparation of the diglycidol diester of cellulose phosphate.

Glycidol was prepared in situ by reacting 3-chloro-1,2-propanediol with 25 NaOH. Cellulose phosphate with a degree of substitution DSp = 0.15 was added to this reaction mixture.

At the end of the reaction, titration showed that 79% of the available acid had been converted.

30 Example V

1013658 13

Esterification of cellulose phosphate with n-butyl glycidyl ether (BGE) and dodecyl glycidyl ether (DGE).

In an analogous manner as indicated in example II, 1 g of cellulose phosphate with a degree of substitution DSp = 1 was suspended in a mixture of 3.41 g of 5 n-butylglycidyl ether and 5 ml of ethanol (the reaction mixture contains 8.3 meq acidic protons versus 24.9 mmol glycidyl ether), followed by stirring at 65 ° C for 2 hours. After cooling to room temperature, 20 ml of ethanol was added and stirred. The precipitate formed was filtered and then purified by washing with acetone, then filtered again, followed by drying in vacuo at 50 ° C.

The products obtained had the following properties: a) after reaction with n-butylglycidyl ether alone: MSbge = 2.1.

b) after reaction with a mixture of CVC1 -glycidyl ethers: MSBge = 1.32 and MSdge = 0.87.

C) after reaction with C12 glycidyl ether only: MSdge = 0.13.

Example VI

Preparation of the diallyl glycidyl diester of cellulose phosphate.

In a 250 ml 3-necked flask equipped with a mechanical stirrer, a nitrogen inlet and a reflux condenser, 5 g of cellulose phosphate (DSP = 0.42, corresponding to 21.3 meq acid) was placed in 160 ml ethanol / water 75/25 v / v mixture, after which the whole was heated to 65 ° C. Then 5.62 g of allyl glycidyl ether (AGE), corresponding to 49.2 meq of epoxide, dissolved in 10 ml of ethanol, was added and the mixture was stirred at 65 ° C for 3 hours. After cooling in an ice bath, the reaction mixture was poured into 1200 ml of acetone with stirring and the suspension was filtered. The insoluble fraction was washed with fresh acetone. The gel fraction was separated and the precipitate purified by filtration and dried in vacuo. The yield of the title product was 2.9 g (corresponding to 39% of the theory). Via 1013658 14 titration with 0.08N NaOH, it was found that about 21% of the available protons had been converted, which corresponds to DSAge = 0.18 and a degree of derivatization of (0.18 / 0.84) x 100% = approx 21.4% .

Despite the relatively small number of derivatized groups, the product proved to be highly reactive and appeared to gel easily after addition of an ammonium persulfate-containing radical initiator and heating.

Example VII

Preparation of the diglycidyl methacrylate diester from cellulose phosphate.

In a 2 L rotary evaporator, 40 g of cellulose phosphate (DSp = 7.1, which corresponds to 183 meq of acid) was placed in 800 ml of ethanol and 50 ml of water, after which the whole was heated for 1 hour at 65 ° C in order to allow the fibers to swell.

Then 52 g of glycidyl methacrylate (corresponding to 366 meq epoxide) dissolved in 50 ml of ethanol was added and the reaction stirred for an additional 1.5 hours. After cooling on an ice bath and adding 500 ml of acetone, the reaction mixture was kept in a refrigerator for 48 hours. After decanting the supernatant and adding about 2 L of fresh acetone, a product was obtained which was easy to filter. After washing twice more with acetone, the filtered product was dried in vacuo at 40 ° C to obtain 36 g of the title product (55% of theory). The product was readily soluble in water and gelled on heating in the presence of ammonium persulfate.

1013658

Claims (7)

1. Hydrophobized polyols obtainable by reacting at least 5 part of the phosphate groups of polyol phosphates having a molecular weight of at least 1000 with a nonionic mono-epoxide. 2. Hydrophobicated polyols according to claim 1, characterized in that the polyol phosphates are selected from the group of phosphated (a) polysaccharides, (b) fully or partially saponified polyvinyl acetate, and (c) homo- or copolymers of polyhydroxyethyl (meth) acrylic. Hydrophobized polyols according to claim 2, characterized in that the polysaccharides comprise compounds having at least 10 monosaccharide units and belong to the group of starch, amylose, amylopectin, maltose, cellulose, dextran and inulin. Hydrophobized polyols according to claim 2, characterized in that the degree of substitution DSP of the polysaccharide phosphate is between 0.001 and 3. R1 has the meaning of straight or branched butyl and n = 0. Hydrophobized polyols according to claim 6, characterized in that R 1 has the meaning of a C8-C22 group. Hydrophobized polyols according to claim 6, characterized in that the nonionic mono-epoxide ters ethyl glycidyl ether, butyl glycidyl ether, butoxyethyl glycidyl ether. butyl glycidyl ether, iso-butyl glycidyl ether, propyl glycidyl ether, benzyl glycidyl ether, dodecyl glycidyl ether, tetradecyl glycidyl ether (octadecyl glycidyl ether, octadecyl glycidyl ether, octadecyl glycidyl ether, oxyethyl) glycidyl ether, dodecyl bis (oxyethyl) glycidyl ether oxyethyl) glycidyl ether, tetradecyl penta (oxyethyl) glycidyl ether, (2,3-epoxypropyl) benzene, styrene oxide, 1,2-epoxy-3-phenoxypropane, 2-methylphenylglycidyl ether, 3- (pentadecadienyl) phenylglycidyl ether or a mixture of which is. Hydrophobized polyols according to claim 1, characterized in that the nonionic mono-epoxide is allyl glycidyl ether. Hydrophobized polyols according to claim 6, characterized in that the nonionic mono-epoxide is the (meth) acrylate ester of glycidol. 1013658 REPORT ON NEWNESS RESEARCH OF INTERNATIONAL TYPE ION IDENTIFICATION OF NATIONAL APPLICATION Characteristic of applicant or authorized representative ACR 2743 PDNL Dutch application no. Filing date 24 November 1999 1013658 Claimed date Applicant (Name) Akzo Nobel NV Date of the application type Granted by the International Research Authority (ISA) to a request for an international type investigation. SN 34020EN I. CLASSIFICATION OF SUBJECT RP (when using different classifications. Specify all classification symbols) According to International Classification (IPC) lnt.CI.7: C08B37 / 00 C08B5 / 00 C08F8 / 00 II. FIELDS OF ENGINEERING EXAMINED Minimum documentation examined Classification system Classification symbols ln.CI.7: C08B »Please examine» other documentation to the minimum documentation to the extent that such documents are included in the areas studied (—re ---- Ui. | _J SEEN ΟΝΓΕΓΓΟΕΚ MCCÜ ' UK '' -'OOP. P.SP /./. L.UF! L.'t'FS ^ ptrePcinw on supplementinmnlsd) IV- II LACK OF UNIT OF INVENTION (comments on supplement sheet), - - 5. Hydrophobized polyols according to claim 2, characterized in that the degree of substitution DSp of the polysaccharide phosphate is between 0.05 and 1.5. Hydrophobized polyols according to claim 1, characterized in that the nonionic mono-epoxide comprises a compound of the formula: Rr (OCH2CH (R2)) n-Q, where 1013658 • V R 1 signifies a C 1 -C 30 group, R 2 is hydrogen or methyl, n is 0-10 and Q represents 1,2-epoxy group or a glycidyl ether group. Hydrophobized polyols according to claim 6, characterized in that 7 Perm. PCT / ISA / 20KJ) 07.1979