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WO2009077202A1 - Production et utilisation de copolymères greffés de polysaccharide - Google Patents

Production et utilisation de copolymères greffés de polysaccharide Download PDF

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Publication number
WO2009077202A1
WO2009077202A1 PCT/EP2008/010904 EP2008010904W WO2009077202A1 WO 2009077202 A1 WO2009077202 A1 WO 2009077202A1 EP 2008010904 W EP2008010904 W EP 2008010904W WO 2009077202 A1 WO2009077202 A1 WO 2009077202A1
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WIPO (PCT)
Prior art keywords
azobis
group
added
amino derivative
radical initiator
Prior art date
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Ceased
Application number
PCT/EP2008/010904
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German (de)
English (en)
Inventor
Joachim Storsberg
Jörg BOHRISCH
André LASCHEWSKY
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Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
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Publication of WO2009077202A1 publication Critical patent/WO2009077202A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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

Definitions

  • the present invention relates to a process for the preparation of polysaccharide graft copolymers, starting from amino derivatives of polysaccharides and polymerizing them with a free-radically polymerizable monomer with the addition of an oxidizing agent and a radical initiator.
  • the object of the present invention was to provide a process for the preparation of polysaccharide graft copolymers, with which high yields can be achieved. It was also an object of the present invention to provide by this method products which have better physical properties than previous derivatives.
  • the invention thus provides a process for the preparation of polysaccharide graft copolymers, starting from at least one amino derivative of a polysaccharide and / or a mixture containing at least one polysaccharide.
  • the amino derivative here has the general formula I:
  • a here is oxygen, NH, NC (O) -Me or a mixture of NC (O) -Me and NH;
  • R 1 independently selected from the group consisting of linear or branched Ci-Ci 2 - alkyl, Ci-Ci 2 alkenyl, Ci-Ci 2 alkynyl, C 7 -Ci 8 - aralkyl, C 6 -Ci 8 -aryl, heteroaryl, hydroxy, Ci-Ci 2 -alkoxy, amino substituents and / or two radicals R 1 of two vicinal carbon atoms together form a ring which may be aliphatic or aromatic, may contain heteroatoms and 1 to Has 8 ring members.
  • R 1 is hydrogen.
  • R 2 independently selected from the group consisting of hydrogen, linear or branched Ci-C12 alkyl, Ci-Ci2 alkenyl, Ci-Ci 2 - alkynyl, C 7 -C 8 -Aralkylsubstituenten and / or two R 2 radicals together form a ring which is aliphatic, may contain heteroatoms and has 1 to 8 ring members.
  • R 2 is particularly preferably a short-chain alkyl radical, such as, for example, methyl, ethyl, propyl, butyl, in particular an ethyl radical (Et).
  • R 3 may be the same or different for the illustrated monomeric units of the formula I.
  • R 3 if the polysaccharide is unsubstituted at the carbon atom 5 of the underlying glucopyranose unit, a -CH 2 OH grouping.
  • these free CH 2 OH groups are etherified, esterified, oxidized or ⁇ -1, 6-glycosidically bound.
  • the functionalities mentioned above may be appropriate here, with particular preference being given to carboxymethyl radicals (-CH 2 -O-CH 2 -COONa) and / or hydroxyethyl radicals (-CH 2 O (CH 2 ) 2 OH).
  • Two alternative preferred possibilities are conceivable here, namely that unsubstituted polysaccharide derivatives are used on the carbon atom 5, ie all of them
  • R 3 radicals of the grouping correspond to -CH 2 OH-, or that these -CH 2 OH groups are at least partially substituted. In this case, this is due to this partial substitution of the - CH 2 OH group by the above-mentioned possible
  • R 3 DS (R 3 )
  • R 3 DS (R 3 )
  • R 3 DS (R 3 )
  • R 3 DS (R 3 )
  • substitution of the -CH 2 OH groups of the glycopyranose units is carried out statistically with respect to the three monomeric units shown in formula I.
  • the index n mentioned in formula I is from 0 to 10 according to the invention.
  • the group B of the middle monomer unit of the formula I is independently selected from the group consisting of - [N (R 4 ) 3 ] + / X " , or groups of the formulas II, III or IV
  • a particularly preferred radical R 4 is methyl.
  • the underlying monomeric saccharide units of the amino derivative of the formula I also different than on the mapped manner, ⁇ -1,4- or ⁇ -1,4 glycosidically linked together and may also be included as monomers in the mixture.
  • this is understood to mean that any arrangement of the monomer units in the polymeric framework is possible, which may also be arranged, for example, in blocks, statistically or in any other way.
  • the possibility that both ⁇ -1,4- and ⁇ -1,4-glycosidic linkages are possible is indicated in the general formula I by the wavy bond at the anomeric carbon atom.
  • the units on which the amino derivative of the formula I is based can be present as monomers in the mixture. These monomers can be represented by the following formulas:
  • Monomeric saccharide unit 3 The variables A, B, R 1 , R 2 , R 3 and n given in the formulas have the same definitions as stated above.
  • the aminoderivative-containing mixture has been subjected to partial hydrolysis.
  • a hydrolytic degradation of the amino derivative of the formula I is possible to obtain the corresponding mixture.
  • the stated monomers can be present in both .alpha.- and .beta.-anomeric form.
  • the counterions X " and Y + have no particularly relevant influence, neither on the process nor on the graft copolymers produced, Thus, the counterions X ' and Y + can be selected by the person skilled in the art on the basis of his
  • Preferred counterions X “ are, for example: F “ , Cl “ , Br “ , I “ , triflate, tosylate, acetate, sulfate and / or monomethyl sulfate
  • Preferred counterions Y + are, for example: Li + , Na + , K + , Rb + , Cs +, Mg 2+, Ca 2+, Sr 2+, Ba 2+, Al 3+, Fe 2+,
  • the stoichiometry of the counterions is chosen according to their charge equivalents, so that the molecule of formula I or mixture containing the amino derivative of formula I, a total of charge-neutral molecule or mixture results.
  • the amino derivative of the formula I or mixture as defined above is mixed with at least one free-radically polymerizable monomer to be grafted on and introduced Oxidizing agent added in combination with a radical initiator.
  • the radical R mentioned in the equation here corresponds to the radical R 2 of the general formula I and is here preferably ethyl, - the radical M mentioned in the product formula represents the free-radically polymerized NVP chain.
  • the free-radical graft copolymerization of the NVP forms more or less long oligomeric or polymeric PVP strands whose radical intermediates can attack an ethyl group (radical R) and attach to it.
  • Chains may be present as graft chains, but there is also the possibility that the underlying polysaccharide chains will be cross-linked.
  • the radical R here represents the saccharide polymer backbone.
  • the method of the invention is not limited to this example. It is preferred if the at least one monomer contains a vinyl group.
  • the monomer is selected from the group consisting of vinylpyrrolidones, in particular N-vinylpyrrolidone; Alkylene glycol di (meth) acrylates, especially ethylene glycol dimethacrylate; Alkylene, - (meth) acrylates; ⁇ -hydroxyalkyl (meth) acrylates, especially 2-hydroxyethyl (meth) acrylate; acrylamide; styrenes; Vinyl lactams and / or mixtures thereof.
  • a preferred mixture of the abovementioned monomers is, for example, a mixture of a vinylpyrrolidone and an alkylene glycol di (meth) acrylate, in particular ethylene glycol di (meth) acrylate.
  • a further preferred mixture is, for example, 2-hydroxyethyl (meth) acrylate and ethylene glycol di (meth) acrylate.
  • the bracketed (meth) means that the methyl group is optional and the corresponding acrylate is also preferred.
  • Advantageous oxidizing agents are, for example, hypochlorites, permanganates, peroxodisulfates, e.g. Sodium persulfate, peroxides, hyperoxides, superoxides and / or hydrogen peroxide.
  • the substances mentioned can also be used as mixtures.
  • an azo initiator is used in particular.
  • a free radical initiator an azo initiator is used in particular.
  • azo initiator is used in particular.
  • Hydrophilic azo initiators such as 2, 2 ⁇ azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] disulphate dihydrate, 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate, 2,2'-azobis ⁇ 2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane ⁇ dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis (1) imino-1-pyrrolidino-2-ethylpropane) this hydrochloride, 2,2'-azobis ⁇ 2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide ⁇ , 2,2 ' Az
  • Lipophilic azo initiators such as 2, 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2-methylpropionitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2 ' -Azobis [N-
  • (2-propenyl) -2-methylpropionamide] 1- [(1-cyano-1-methylethyl) azo] formamide, 2,2'-azobis (N-butyl-2-methylpropionamide), 2,2'-azobis ( N-cyclohexyl-2-methylpropionamide);
  • Macroazoinitiators e.g. diazo compounds based on polysiloxane, polyethylene glycol and / or on their block copolymers formed with vinyl monometers, preferably having a weight-average molecular weight of between 500 and 20,000 g / mol,
  • the process is preferably carried out in water, furthermore in particular at least one base is added.
  • the base is preferably selected from the group consisting of sodium hydroxide solution, potassium hydroxide solution, and / or mixtures thereof.
  • a specific pH of the reaction mixture can be adjusted.
  • the pH is adjusted to between 6 and 14, preferably between 7 and 12, particularly preferably between 8 and 10, and the process is carried out at this pH.
  • the method is carried out in particular in a buffered system.
  • the buffer system is selected from the group consisting of aqueous solutions containing potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, phosphates, hydrogen phosphates and / or mixtures thereof.
  • the oxidizing agent and the radical initiator are added simultaneously or successively.
  • the time offset of the addition of the radical initiator is preferably 5 minutes to 20 hours after the addition of the oxidizing agent.
  • the preferred amount of the polymerizable monomer used with respect to the amino derivative of the general formula I is in a weight ratio of 0.1: 1 to 100: 1, preferably from 1: 1 to 20: 1, particularly preferably from 5: 1 to 15 :1.
  • the same weight ratios with respect to the amino derivative of the formula I also apply to the free-radical initiator, in particular in an amount between 0.01 and 100 wt .-%, preferably 1 to 20 wt .-%, particularly preferably between 2.5 and 7.5 wt .-% is added.
  • the process is preferably carried out at a temperature between 0 ° C. and 100 ° C., preferably between 20 and 80 ° C., particularly preferably between 40 and 60 ° C.
  • the temperature after addition of the oxidizing agent is set between 0 and 50 ° C., preferably between 5 and 30 ° C.
  • the temperature after addition of the radical initiator is increased to 30 to 80 0 C.
  • the weight-average molar mass M w of the aminoderivative of the formula I is not subject to any particular restriction. In particular may be included gomere the possibility olive, so that preferred molar masses between 20-50 '10 3 kg / mol, preferably between 50-20 ⁇ 10 3 kg / mol, more preferably between 100-1' 10 4 kg / mol are included.
  • the polymeric saccharide skeleton on which the formula I is based is deacetylated by starch, amylose, amylopectin, cellulose, chitosan, and / or partially deacetylated chitin (preferably from 40 to 100%).
  • Partially deacetylated chitins can be prepared by saponification reaction with an alkali or by chitin-deacetylase, starting from chitin.
  • amino derivatives of degraded polysaccharides such as maltodextrin
  • Maltodextrin is known to mean a water-soluble carbohydrate mixture which is prepared by (partial) hydrolysis of starch. The hydrolysis is carried out, for example, by acid or by enzymatic means; Maltodextrin is therefore a mixture of monomers, dimers, oligomers and polymers of glucose. Depending on the degree of hydrolysis, the percentage composition differs.
  • the product is purified, preferably by chromatographic methods, or dialysis, and the product thus obtained is isolated.
  • the present invention also provides a graft copolymer which can be prepared by the method described above.
  • a coating which contains the graft copolymer.
  • Such graft copolymers are used in the production of coatings.
  • CEDEAC chloroethyldiethylammonium chloride
  • DEAECMST diethylaminoethyl carboxymethyl starch.
  • DEAEHEC diethylaminoethyl-hydroxyethyl chitosan
  • DEAESPC Diethylaminoethyl sulfopropyl chitosan
  • HEMA hydroxyethyl methacrylate
  • K 2 CO 3 potassium carbonate (purum pa, 99%, Fluka,
  • NaPS sodium peroxodisulfate (98%, acros,
  • NVP N-vinylpyrrolidone (BASF)
  • PVP polyvinylpyrrolidone (e.g., Luviskol K30 and
  • VCAP N-vinylcaprolactam I. PREPARATION OF AMINO DERIVATIVES
  • the degree of substitution DS (per glucose unit) was determined by 1 H NMR spectroscopy.
  • the polymerization is dissolved after addition of 0.1005 g NaPS ( distilled in 1.1440 g. H 2 O) is then stirred for 5 h at RT. Thereafter, 0.1006 g of V50 are added and heated to 50 0 C for 24 hours. Yield:>90%; Solids content: 21.71% by weight (drying balance); Film formation with doctor blade (0.2 mm) on glass plate, drying in air.
  • the polymerization is initiated after addition of 0.0500 g of NaPS (dissolved in 0.5555 g of distilled H 2 O), followed by stirring at RT for 5 h. Thereafter, 0.0501 g of V50 (0.5193 grams least in. H 2 O) was added and at 50 0 C for 24 h heated. Yield: 26%; Solids content: 6.27% by weight; Film formation with doctor blade (0.2 mm) on glass plate.
  • the polymerization is initiated after addition of 0.0508 g of NaPS (dissolved in 1.011 g of distilled H 2 O), followed by stirring at RT for 5 h. Thereafter, 0.0503 g of V50 (0.5095 g in H 2 O) was added and at 50 0 C for 24 h heated. Yield: 85.3%; Solids content: 20.33% by weight; Film formation with doctor blade (0.2 mm) on glass plate.
  • the polymerization is initiated after addition of 0.0251 g of NaPS (dissolved in 0.5793 g of distilled H 2 O), followed by stirring at RT for 5 h. Thereafter, 0.0252 g of V50 (in 0.5162 g H 2 O dissolved) and heated to 5O 0 C for 24 hours. Yield: 83.73%; Solid content: 19.34% by weight; Film formation with doctor blade (0.2 mm) on glass plate.
  • starch-graft copolymers prepared by the 2-stage initiation process have distinct advantages over blends and / or blends.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Cosmetics (AREA)

Abstract

La présente invention concerne un procédé de production de copolymères greffés de polysaccharide à partir de dérivés aminés de polysaccharides, lequel procédé consiste à polymériser lesdits dérivés avec un monomère polymérisable par voie radicalaire, en ajoutant un oxydant et un amorceur radicalaire.
PCT/EP2008/010904 2007-12-19 2008-12-19 Production et utilisation de copolymères greffés de polysaccharide Ceased WO2009077202A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200710061087 DE102007061087A1 (de) 2007-12-19 2007-12-19 Herstellung und Verwendung von Polysaccharid-Pfropfcopolymerisaten
DE102007061087.6 2007-12-19

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WO2009077202A1 true WO2009077202A1 (fr) 2009-06-25

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112080181A (zh) * 2020-09-11 2020-12-15 曾万祥 一种无毒环保型水性涂料及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2075537A (en) * 1980-04-28 1981-11-18 Standard Brands Inc Derivatized and Thinned Starches
US20050287110A1 (en) * 2003-01-17 2005-12-29 Yasuhiko Onishi Cationic graft-compolymer for non-viral gene delivery vector

Family Cites Families (6)

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Publication number Priority date Publication date Assignee Title
GB765880A (en) 1953-06-10 1957-01-16 Nat Starch Products Inc Improvements in or relating to ungelatinized tertiary amino alkyl ethers of amylaceous materials
NL102330C (fr) 1953-06-10
US2917506A (en) 1956-11-21 1959-12-15 Nat Starch Chem Corp Cold water soluble amino alkyl ethers of starch
US2935436A (en) 1957-05-09 1960-05-03 Nat Starch Chem Corp Method of making paper containing a starch ether and product produced thereby
JPH0931107A (ja) * 1995-07-18 1997-02-04 Sanyo Chem Ind Ltd 吸水性樹脂の製造法
KR101107581B1 (ko) * 2003-12-03 2012-01-25 도아고세이가부시키가이샤 수용성 폴리머의 제조방법

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2075537A (en) * 1980-04-28 1981-11-18 Standard Brands Inc Derivatized and Thinned Starches
US20050287110A1 (en) * 2003-01-17 2005-12-29 Yasuhiko Onishi Cationic graft-compolymer for non-viral gene delivery vector

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
A.HEBEISH, Z.H. EL-HILW: "Preparation of DEAE Cotton-g-Poly(methacrylic acid) for Use as Ion Exchanger", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 67, no. 4, 1998, pages 739 - 745, XP002523963 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112080181A (zh) * 2020-09-11 2020-12-15 曾万祥 一种无毒环保型水性涂料及其制备方法

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