WO2001038398A1 - Polyols modifies de maniere hydrophobe - Google Patents

Polyols modifies de maniere hydrophobe Download PDF

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Publication number
WO2001038398A1
WO2001038398A1 PCT/EP2000/011782 EP0011782W WO0138398A1 WO 2001038398 A1 WO2001038398 A1 WO 2001038398A1 EP 0011782 W EP0011782 W EP 0011782W WO 0138398 A1 WO0138398 A1 WO 0138398A1
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WO
WIPO (PCT)
Prior art keywords
glycidyl ether
polyol
phosphate
hydrophobically modified
group
Prior art date
Application number
PCT/EP2000/011782
Other languages
English (en)
Inventor
Jan Gerardus Batelaan
Original Assignee
Akzo Nobel N.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Akzo Nobel N.V. filed Critical Akzo Nobel N.V.
Priority to AU21628/01A priority Critical patent/AU2162801A/en
Publication of WO2001038398A1 publication Critical patent/WO2001038398A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0051—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Fructofuranans, e.g. beta-2,6-D-fructofuranan, i.e. levan; Derivatives thereof
    • C08B37/0054—Inulin, i.e. beta-2,1-D-fructofuranan; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B5/00—Preparation of cellulose esters of inorganic acids, e.g. phosphates
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups

Definitions

  • the invention pertains to hydrophobically modified polyols, and to inulin phosphate.
  • EP-A-0 384 167 discloses a process in which use is made of a polysaccharide with ether substitution which is then converted with a hydrophobic alkylaryl compound. Using a polysaccharide with ether substitution instead of an unsubstituted polysaccharide results in more of the hydrophobic alkylaryl compound being built in. While this makes for a more efficient hydrophobizing reaction, there is great need for yet further enhancement thereof.
  • EP-A-0 566 911 discloses a process in which a polysaccharide is reacted with an alkyl halide, an alkylene oxide or chloroacetic acid in the presence of alkali and then reacted with a compound containing a hydrophobic alkyl group or alkylaryl group having 8 to 24 carbon atoms and a reactive group such as a glycidyl ether, epoxide or isocyanate.
  • a hydrophobic alkyl group or alkylaryl group having 8 to 24 carbon atoms and a reactive group such as a glycidyl ether, epoxide or isocyanate.
  • EP-A-0 189 935 discloses a process for the preparation of water- soluble, hydrophobe-derivatized polysaccharides, more particularly hydroxy- ethyl cellulose (HEC).
  • HEC hydroxy- ethyl cellulose
  • 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.
  • hydrophobically modified polysaccharide will always contain a quaternary ammonium group. Because of their high aquatoxicity and their tendency to adsorb on all surfaces, cationic polymers are less desirable particularly for environmental reasons.
  • the invention now provides hydrophobically modified polyols which are free of quaternary ammonium groups and which can be prepared comparatively quickly and without any problems.
  • the invention consists in that the hydrophobically modified polyols are obtainable by reacting at least a portion of the phosphate groups of a polyol phosphate having a molecular weight of at least 1 ,000 with a non-ionic mono- epoxide.
  • the reaction of a polyol phosphate such as polysaccharide phosphate with an epoxy compound is known as such from US- A-5,409,705.
  • the epoxy compound employed in that document is an ionic mono-epoxide, viz. an epoxidized quaternary ammonium compound. Per phosphate group not more than one epoxy compound is added.
  • the invention also pertains to a hydrophobically modified phosphorylated polyol having a molecular weight of at least 1 ,000, characterized in that at least a portion of the phosphate groups of the polyol contains a non-ionic hydroxy group-containing moiety, the hydroxy group being in the ⁇ position of the moiety with regard to the phosphate group.
  • hydrophobically modified phosphorylated polyol having a weight average molecular weight of at least 1 ,000 comprising monoester phosphate groups and hydrophobically modified triester phosphate groups.
  • the ratio of monoester phosphate groups and hydrophobically modified triester phosphate groups is 1000:1 to 1 :10, more preferably 100:1 to 1 :1.
  • hydrophobically modified phosphate esters are easy to hydrolyze by the biological route, which as a rule produces products harmless to nature. This holds particularly in the case of polysaccharide-based polyol phosphate esters, the decomposition products of which are non-toxic to fish, crustaceans or algae. What is especially remarkable about these phosphate esters is that they have properties which closely match those of existing commercial products made of non-recyclable raw materials.
  • the term "hydrophobic group” as used in this invention means a group that is bonded to a phosphate group and that increases the hydrophobicity of the polyol.
  • the hydrophobic modified polyols are more hydrophobic than the unmodified polyols.
  • the hydrophobic groups contains 1-30 C atoms, more preferably 4 to 22 C atoms.
  • polyols which, according to the invention, after reaction with phosphoric acid are eligible for reaction with a non-ionic mono-epoxide to form polyol- phosphates are preferably selected from the group of polysaccharides, wholly or partially saponified polyvinyl acetate, and homo- or copolymers of polyhydroxyalkyl(meth)acrylate, more in particular polyhydroxyethyl(meth)acrylate.
  • the polysaccharides preferably comprise compounds having at least 10 monosaccharide units and belong to the group of starch, amylose, amylopectine, maltose, cellulose, dextran, and inulin.
  • Polyolphosphates can be obtained with the aid of many processes known from the state of the art.
  • the procedure usually is as follows. First, a polyol is reacted with a polyphosphoric acid having a P 2 O 5 content of greater than 72% (preferably from 82 to 84%). When the P 2 O 5 content exceeds about 85%, the number of diester phosphate groups, and thus the degree of cross-linking, will increase substantially.
  • P 2 O 5 content exceeds about 85%, the number of diester phosphate groups, and thus the degree of cross-linking, will increase substantially.
  • use is made of amounts of polyphosphoric acid which correspond to 0.5 to about 1.0 mole equivalent P 2 Os for every polyol equivalent.
  • polyol equivalent is meant the equivalent number of hydroxyl groups present in the polyol. If so desired, an excess of P 2 O 5 may be employed in the reaction.
  • urea phosphate i.e. urea mixed with orthophosphoric acid is employed as phosphatizing agent.
  • urea phosphate i.e. urea mixed with orthophosphoric acid is employed as phosphatizing agent.
  • a molar ratio of urea to orthophosphoric acid in the range of 1.0 to 2.0. More particularly, when phosphorylating low-molecular weight polyvinyl alcohol advantageous use is made of urea phosphate.
  • Phosphorylated starch is supplied by AVEBA under the trade designation "NylgumTM”.
  • the polysaccharide used is cellulose
  • suitable cellulose phosphate compositions are listed in WO 96/06208 and WO 97/28298.
  • Inulin phosphates having a molecular weight of at least 1000 that are suitable for making the hydrophobically modified polyols of the invention are not known as such. They can be made in a manner analogously to that of the synthesis of other phosphorylated polysaccharides, such as the phosphorylation of cellulose, starch, dextran, and the like.
  • phospho ⁇ c acid means all inorganic acids of phosphorus and/or their mixtures.
  • Orthophosphoric acid H 3 PO
  • P 2 O 5 phosphorus pentoxide
  • orthophosphoric acid and phosphorus pentoxide there is, depending on the amount of water in the system, a series of acids of pentavalent phosphorus with a water-binding capacity in between those of phosphorus pentoxide and orthophosphoric acid, e.g. (H 6 P 4 O 13 , PPA).
  • the solution can be obtained by mixing constituents classifiable into four groups: polyols, more particularly polysaccharides such as cellulose, water, inorganic acids of phosphorus including their anhydrides, and other constituents.
  • polyols more particularly polysaccharides such as cellulose, water, inorganic acids of phosphorus including their anhydrides, and other constituents.
  • other constituents may be substances which benefit the processability of the polyol solution, solvents other than phosphoric acid, moisturizing additives or adjuvants (additives), e.g., to counter polyol degradation as fully as possible, or dyes and the like.
  • weight percentages of dissolved polyols relate to quantities calculated back on the phosphorus-free polyols.
  • these weight percentages relate to quantities calculated back on the phosphorus-free polyols.
  • weight percentages of dissolved phosphorus listed in the description It was found that, in general, very favorable results are achieved when the hydrophobically modified polyols are obtained from phosphorylated polysaccharides or a polysaccharide phosphate having a degree of substitution DSp in the range of 0.001 to 3, preference being given to a degree of substitution of 0.05 to 1.5.
  • cellulose phosphate optimum results are obtained with a molecular weight ⁇ 250,000 and a degree of substitution of 0.1 to 1.0.
  • Hydrophobically modified polyols with favorable properties are compounds obtained by reacting polyol phosphates with a non-ionic mono-epoxide of the formula: R 1 -(OCH 2 CH(R 2 )) n -Q, wherein Ri has the meaning of a C C3o group, R 2 is hydrogen or methyl, n is 0-10, and Q stands for a 1 ,2-epoxy group or a glycidyl ether group.
  • Preferred are products which are obtained by reaction with compounds of the aforementioned formula wherein Ri has the meaning of a C -C 22 group, more particularly a C 8 -C 22 group.
  • Suitable epoxides also comprise compounds of the aforementioned formula wherein Ri has the meaning of a nonylphenyl, 2-ethylhexyl, dodecyl, tetradecyl, hexadecyl, octadecyl or hexacosyl group. Ri usually is derived from fatty acids such as are found in nature, originating from coconut oil, palm oil, talc, and hydrogenated talc. If so desired, one or more alkylene oxide groups may be incorporated into the epoxides, e.g., ethylene oxide and propylene oxide.
  • Suitable epoxy compounds which after reaction with the phosphate are transferred to hydrophobic groups attached to said phosphate, are: ethyl glycidyl ether, butyl glycidyl ether, butoxyethyl glycidyl ether, tert-butyl glycidyl ether, isobutyl glycidyl ether, propyl glycidyl ether, benzyl glycidyl ether.
  • Preferred in this case are the dodecyl glycidyl ether, tetradecyl glycidyl ether, hexadecyl glycidyl ether, octadecyl glycidyl ether, dodecyl bis-(oxyethyl)-glycidyl ether, tetradecyl bis-(oxyethyl)-glycidyl ether, hexadecyl bis-(oxyethyl)-glycidyl ether, octadecyl-bis-(oxyethyl)-glycidyl ether, tetradecyl-penta(oxyethyl)-glycidyl ether, (2,3-epoxypropyl)benzene, styrene oxide, 1 ,2-epoxy-3-phenoxypropane, 2-methylphenyl glycidyl ether, 3-
  • non-ionic mono-epoxides may carry substituents such as halogen or a blocked or unblocked reactive group, for instance a blocked isocyanate group.
  • substituents such as halogen or a blocked or unblocked reactive group, for instance a blocked isocyanate group.
  • Particularly important are epoxides with an ethylenically unsaturated group such as are present in unsaturated fatty acids like oleic acid or linoleic acid.
  • both long-chain fatty acids and short-chain compounds such as are present in allyl glycidol are employed.
  • the hydrophobically modified polyol can be put to advantageous use as a cross- linking agent in particular when said last compound is present.
  • other epoxides which may be unsaturated or not or aromatic or not may be present.
  • allyl glycidol may give rise to premature cross-linking.
  • (meth)acrylate ester of glycidol is used as the ethylenically unsaturated epoxide.
  • the reaction of polyol phosphate with a non-ionic mono-epoxide generally proceeds as follows. First, a suspension is made of the polyol phosphate to be derivatized in an alcohol (ethanol, or preferably 2-propanol), the addition of water, when 2-propanol is the reaction medium, having a favorable effect on the derivatization result. Some derivatizations can also be carried out in water.
  • an alcohol ethanol, or preferably 2-propanol
  • Some derivatizations can also be carried out in water.
  • the epoxide is added, either as such or as a solution in ethanol or an ethanol/water mixture.
  • the mixture is stirred for a further 1/2 to 3 hours at a temperature in the range of 20 to 65°C.
  • the reaction mixture if necessary is precipitated in a non-solvent such as acetone and then filtered and dried in vacuo at a temperature in the range of 65 to 75°C.
  • the hydrophobically modified polyol derivatives according to the invention can be put to the widest possible range of uses.
  • propylene oxide-modified cellulose phosphate for the manufacture of films, the preparation of ink and paper, in paste for printing textiles, and as surface active agent in emulsion polymerization
  • glycidol-modified cellulose phosphate for the preparation of reversible gels to enhance oil drill holes porosity (fracturing)
  • fatty alkyl glycidol-modified cellulose phosphate or starch phosphate having a low degree of substitution: for use in detergents and cosmetics
  • glycidol methacrylate-modified cellulose phosphate having a low degree of substitution as polyacrylates cross-linking agent, allyl glycidol-
  • MS representing the average number of moles of a particular reaction component bound per anhydroglucose unit.
  • the material proved capable of reducing the surface tension of water to about 34 mN/m, as was determined on a solution containing 1.8 wt.% of the product.
  • the surface tension of water used without addition of the product was 70.5 mN/m.
  • a 65 wt.% suspension of NaH 2 PO in water was made, and 90 g of inulin (Frutafit type EXLTM, ex. Sensus) was slurried into 250 ml of this suspension.
  • the slurry was heated to 65°C, whereupon the NaH 2 PO 4 was dissolved completely.
  • the system was kept at that temperature for 30 minutes, after which the solids were separated by filtration under vacuum.
  • the cake was spread into a thin layer and dried overnight under a nitrogen vent at reduced pressure, in a stove at 90°C.
  • Phosphate salt impregnated inulin powder was obtained having a weight of 167 g.
  • Phosphatation of the inulin was performed by submersing a round-bottomed flask in silicon oil and heating it to a set temperature of 190°C, after which the phosphate salt impregnated inulin powder was added under stirring and applying a vacuum atmosphere. After 10 minutes of residence time the phosphatation reaction was completed. The roasted product was dissolved in water, to obtain a 40 wt.% solution and the non-reacted phosphates were removed by dialysis.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Molecular Biology (AREA)
  • General Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

L'invention concerne des polyols modifiés de manière hydrophobe pouvant être obtenus de préférence par réaction avec un mono-époxyde non ionique, d'au moins une partie des groupes phosphate de phosphates de polyols ayant une masse moléculaire moyenne d'au moins 1000. Les phosphates de polyols sont de préférence des composés sélectionnés dans le groupe (a) des polysaccharides phosphorylés, (b) des polyvinyle acétates entièrement ou partiellement saponifiés, et (c) des homopolymères ou copolymères de polyhydroxyéthyl(méth)acrylate. Le mono-époxyde non ionique contient de manière avantageuse un composé de formule R1-(OCH2CH(R2))n-Q, dans laquelle R1 représente un groupe C1-C30, R2 représente de l'hydrogène ou du méthyle, n est compris entre 0 et 10, et Q représente un groupe 1,2-époxy ou un groupe glycidyle éther.
PCT/EP2000/011782 1999-11-24 2000-11-20 Polyols modifies de maniere hydrophobe WO2001038398A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU21628/01A AU2162801A (en) 1999-11-24 2000-11-20 Hydrophobically modified polyols

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1013658 1999-11-24
NL1013658A NL1013658C2 (nl) 1999-11-24 1999-11-24 Gehydrofobeerde polyolen.

Publications (1)

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WO2001038398A1 true WO2001038398A1 (fr) 2001-05-31

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5409705A (en) * 1991-05-20 1995-04-25 Kao Corporation Phosphobetaine and detergent and cosmetic containing the same
WO1996001849A1 (fr) * 1994-07-07 1996-01-25 Tiense Suikerraffinaderij Naamloze Vennootschap Compositions polydispersees fractionnees
WO1997030090A1 (fr) * 1996-02-14 1997-08-21 Akzo Nobel N.V. Procede de preparation d'un materiau ayant une forte capacite d'absorption de l'eau et des solutions salines

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3229619B2 (ja) * 1990-07-20 2001-11-19 花王株式会社 新規多糖誘導体及びその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5409705A (en) * 1991-05-20 1995-04-25 Kao Corporation Phosphobetaine and detergent and cosmetic containing the same
WO1996001849A1 (fr) * 1994-07-07 1996-01-25 Tiense Suikerraffinaderij Naamloze Vennootschap Compositions polydispersees fractionnees
WO1997030090A1 (fr) * 1996-02-14 1997-08-21 Akzo Nobel N.V. Procede de preparation d'un materiau ayant une forte capacite d'absorption de l'eau et des solutions salines

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AU2162801A (en) 2001-06-04
NL1013658C2 (nl) 2001-05-28

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