EP2245082A1 - Polyéthérols hautement fonctionnels et leur production et utilisation - Google Patents

Polyéthérols hautement fonctionnels et leur production et utilisation

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Publication number
EP2245082A1
EP2245082A1 EP09711329A EP09711329A EP2245082A1 EP 2245082 A1 EP2245082 A1 EP 2245082A1 EP 09711329 A EP09711329 A EP 09711329A EP 09711329 A EP09711329 A EP 09711329A EP 2245082 A1 EP2245082 A1 EP 2245082A1
Authority
EP
European Patent Office
Prior art keywords
groups
reaction
alcohols
functional
acid
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP09711329A
Other languages
German (de)
English (en)
Inventor
Rolf Mülhaupt
Anne Fiedler
Fabian Schüler
Bernd Bruchmann
Markus SCHÜTTE
Daniel SCHÖNFELDER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Priority claimed from EP08151527A external-priority patent/EP2090606A1/fr
Priority claimed from EP08163767A external-priority patent/EP2161295A1/fr
Application filed by BASF SE filed Critical BASF SE
Priority to EP09711329A priority Critical patent/EP2245082A1/fr
Publication of EP2245082A1 publication Critical patent/EP2245082A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/46—Post-polymerisation treatment, e.g. recovery, purification, drying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S424/00—Drug, bio-affecting and body treating compositions
    • Y10S424/16—Dendrimers and dendritic polymers

Definitions

  • the present invention relates to a process for the preparation of highly functional polyetherols by reacting at least one tri- or higher-functional alcohol and optionally further di- and / or monofunctional alcohols and / or modifying reagents with the aid of acidic catalysts, the tri- or higher-functional alcohol is not glycerin.
  • the present invention relates to highly functional polyetherols obtainable by such a process and the use of these highly functional polyetherols as adhesion promoters, thixotropic agents, rheology modifiers of polymers, phase transfer reagents, micro- or nanocontainers for biologically active substances, for example for medicinal agents, biocides , Herbicides or fungicides, as pigment dispersants, additives in printing inks, as building blocks for the preparation of polyaddition or polycondensation polymers or for the treatment of seeds according to the not yet published application PCT / EP2008 / 060673.
  • Polyetherols are usually prepared from the reaction of water, alcohols or amines by ring-opening polymerization with alkylene oxides, for example with ethylene oxide, propylene oxide or butylene oxide or mixtures thereof.
  • alkylene oxides for example with ethylene oxide, propylene oxide or butylene oxide or mixtures thereof.
  • polyetherols based on water, glycols, glycerol, trimethylolpropane, pentaerythritol or sugars as starter molecule, which react with ethylene oxide, propylene oxide or ethylene oxide / propylene oxide mixtures to form linear diols or star-shaped polyols.
  • Such processes are described, for example, in Becker / Braun, Kunststoff-Handbuch Bd. 7, Polyurethane, Carl-Hanser-Verlag, Kunststoff 1993, pages 58-67.
  • DE 103 07 172 also discloses the polycondensation of glycerol in the presence of acidic catalysts, for example HCl, H 2 SO 4, sulfonic acid or H 3 PO 4 in the presence of Essence of water at temperatures of 200 to 280 0 C within 5 to 15 hours.
  • acidic catalysts for example HCl, H 2 SO 4, sulfonic acid or H 3 PO 4
  • the reaction product thus obtained is tarry and is not suitable for use in technically relevant formulations.
  • EP 141253, DE 4446877 and US 5,728,796 disclose the reaction of tri- and higher-functional alcohols under acidic reaction conditions in the presence of acetone or epoxy compounds.
  • the products obtained are low molecular weight, modified alcohols.
  • WO 2004/074346 discloses the alkaline polycondensation of glycerol and the subsequent reaction of the resulting condensation product under acidic conditions with a fatty alcohol. In this case, a polyglycerol modified with fatty alcohol is obtained. Further condensation of the polyglycerol to higher molecular weight reaction products does not take place under the reaction conditions mentioned.
  • Hyperbranched polyglycerol ethers are described in DE 199 47 631 and DE 102 11 664.
  • the preparation is carried out by ring-opening reaction of glycidol, optionally in the presence of a polyfunctional starter molecule.
  • the handling of glycidol requires a high security effort, therefore, this synthesis strategy is costly and suitable for transfer to an industrial scale only limited.
  • Hyperbranched polyetherols can also be prepared, as disclosed, for example, in WO 00/56802, by polymerizing 1-ethyl-1-hydroxymethyl-oxetane ring-opening with special catalysts.
  • the polymer backbone here consists exclusively of trimethylolpropane units.
  • 3,3-bis (hydroxymethyl) oxetane can, according to Nishikubo et al., Polymer Journal 2004, 36 (5) 413, ring-opening to a highly branched polyether polyol, consisting exclusively of pentaerythritol units. Chen et. al, J. Poyy. Be. Part A: Polym. Chem.
  • the ring-opening polymerization of oxetanes according to the aforementioned syntheses is very selective and substantially free of side reactions, therefore, the polymers are characterized by a high purity.
  • a disadvantage of these methods is that the preparation of the oxetanes as a starting material for the polymerization is complicated and the polymer synthesis requires special reaction conditions and catalysts, which makes the production of hyperbranched polyetherols on an industrial scale less attractive from a commercial point of view.
  • WO 03/062306 discloses that these highly branched polyetherols are used as core molecules for the reaction with alkylene oxides in order to positively influence the property profile via the attachment of linear alkylene oxide chains.
  • the object could be achieved by a process in which at least one tri- or higher-functional alcohol and optionally further di- and / or monofunctional alcohols and / or modifying reagents is reacted with the aid of acidic catalysts, no glycerol is used as a trifunctional alcohol.
  • a highly functional polyetherol is to be understood as meaning a product which, in addition to the ether groups which form the polymer backbone, has at least three, preferably at least six, particularly preferably at least ten, OH groups.
  • the polymer backbone may be linear or branched.
  • the number of terminal or pendant functional groups is not limited to the top, but products having a very large number of functional groups may have undesirable properties such as high viscosity or poor solubility.
  • the high-functionality polyetherols of the present invention generally have not more than 500 terminal or pendant functional groups, preferably not more than 100 terminal or pendant functional OH groups.
  • the high-functionality polyetherol according to the invention is preferably the condensation product of on average at least 3, particularly preferably at least 4, more preferably at least 5 and in particular at least 6, di-, tri- or higher functionality alcohols. It is further preferred that this is the condensation product of on average at least 3, more preferably at least 4, especially at least at least 5 and in particular at least 6 tri- or higher-functional alcohols.
  • the high-functionality polyethers are hyperbranched polyetherols.
  • hyperbranched polyether polyols are understood as meaning uncrosslinked polymer molecules having hydroxyl and ether groups which are structurally as well as molecularly nonuniform. They can be analogous to a central molecule on the one hand
  • Dendrimers but constructed with uneven chain length of the branches. On the other hand, they can also have linear regions with functional side groups.
  • PJ Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chem. Eur. J. 2000, 6, no. 14, 2499.
  • hypobranched in the context of the present invention is meant that the degree of branching (DB), that is the average number of dendritic linkages plus the average number of end groups per molecule, divided by the sum of the average number of dendritic , linear and terminal linkages, multiplied by 100, 10 to 99.9%, preferably 20 to 99%, particularly preferably 20 to 95%
  • DB degree of branching
  • dendrimer in the context of the present invention it is meant that the degree of branching is 99.9-100 % is. For the definition of the degree of branching see H. Frey et al., Acta Polym. 1997, 48, 30.
  • triols such as trimethylolmethane, trimethylolethane, trimethylolpropane (TMP), 1, 2,4-butanetriol, tris-hydroxymethyl isocyanurate, tris-hydroxyethyl isocyanurate (THEIC)
  • TMP trimethylolpropane
  • TEEIC tris-hydroxyethyl isocyanurate
  • tetrols can be used, such as bis-trimethylolpropane (Di-TMP) or pentaerythritol.
  • higher functional polyols such as bis-pentaerythritol (di-penta) or inositols can be used.
  • alkoxylation products of the aforementioned alcohols and of glycerol can also be used, preferably with 1-40 alkylene oxide units per molecule.
  • Aliphatic alcohols and in particular those containing primary hydroxyl groups are particularly preferably used as tri- and higher-functional alcohols, such as trimethylolmethane, trimethylolethane, trimethylolpropane, di-TMP, pentaerythritol, di-penta and their alkoxylates having 1 to 30 ethylene oxide units per molecule and glycerol. Ethoxylates with 1-30 ethylene oxide units per molecule.
  • trimethylolpropane pentaerythritol and their ethoxylates having on average 1 to 20 ethylene oxide units per molecule and glycerol ethoxylates having 1-20 ethylene oxide units per molecule.
  • the alcohols mentioned can be used in a mixture.
  • Less suitable as tri- and higher-functional alcohols are compounds which carry OH groups on two directly adjacent C atoms. These compounds tend to undergo elimination reactions under conditions of the present invention which may be preferred over the etherification reaction.
  • the unsaturated compounds which form are formed under the etherification conditions according to the invention by-products which lead to the reaction product being unusable for use in technically relevant formulations. In particular, such side reactions occur in glycerol.
  • the tri- and higher-functional alcohols can also be used in mixture with difunctional alcohols.
  • suitable compounds having two OH groups include ethylene glycol, diethylene glycol, triethylene glycol, 1,2- and 1,3-propanediol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 1, 2, 1, 3 and 1, 4-butanediol, 1, 2-, 1, 3- and 1,5-pentanediol, hexanediol, dodecanediol, cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, bis (4-hydroxycyclohexyl) methane, bis (4-hydroxycyclohexyl) ethane, 2,2-bis (4-hydroxycyclohexyl) propane, difunctional polyether polyols based on ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, or polytetrahydrofuran.
  • the diols serve to fine tune the properties of the polyether polyol. If difunctional alcohols are used, the ratio of difunctional alcohols to the tri- and higher-functional alcohols is determined by the person skilled in the art, depending on the desired properties of the polyether. As a rule, the amount of difunctional or difunctional alcohols is 0 to 99 mol%, preferably 0-80, more preferably 0-75 mol% and very particularly preferably 0-50 mol% with respect to the total amount of all alcohols. It is also possible to obtain block copolyethers, for example diol-terminated polyethers, by alternating addition of tri- and higher-functional alcohols and diols during the course of the reaction.
  • difunctional alcohols may also be precondensed to give OH-terminated oligomers and then the tri- or higher-functional alcohol may be added.
  • the tri- or higher-functional alcohol may be added.
  • monools can also be added to control the OH functionality during or after the reaction of the trifunctional and higher-functional alcohols.
  • Such monools can be, for example, linear or branched-chain aliphatic or aromatic monools. Preferably, these have more than 3, more preferably more than 6 carbon atoms.
  • monofunctional polyethers Preferably, a maximum of 50 mol% monool, based on the total amount of tri- and higher-functional alcohol is added.
  • acidic catalysts or catalyst mixtures are added. Suitable catalysts are, for example, acids having a pKa value of less than 2.2, particularly preferred are strong acids.
  • acids with a pKa value of less than 2.2 are, for example, phosphoric acid (H3PO4), phosphorous acid (H3PO3), pyrophosphoric acid (H4P2O7), polyphosphoric acid, hydrogen sulfate (HSO 4 " ), sulfuric acid (H2SO4), perchloric acid, Hydrochloric acid, hydrobromic acid, chlorosulfonic acid, methanesulfonic acid, trichloromethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid or p-toluenesulfonic acid.
  • acidic catalysts according to the invention are acidic ion exchangers or ion exchange resins.
  • Ion exchange is the collective term for solids or liquids which are capable of accepting positively or negatively charged ions from an electrolyte solution with the release of equivalent amounts of other ions. Preference is given to using solid grains and particles whose matrix was obtained by condensation (phenol-formaldehyde) or by polymerization (copolymers of styrene and divinylbenzene and also methacrylates and divinylbenzene).
  • the acidic ion exchangers used according to the invention carry, for example, sulfonic acid groups, carboxylic acid or phosphonic acid groups. It is also possible to use ion exchangers which have a hydrophilic cellulose skeleton or consist of crosslinked dextran or agarose and carry acidic functional groups, for example carboxylmethyl or sulfoethyl groups. It is also possible to use inorganic ion exchangers, such as zeolites, montmorillonites, palygorskites, bentonites and other aluminum silicates, zirconium phosphate, titanium tungstate and nickel hexacyanoferrate (II).
  • Acid ion exchangers are, for example, in solid or dissolved form available under the product name Amberlite TM, Ambersept TM or Amberjet TM from Rohm and Haas.
  • catalysts of the invention are phosphoric acid, polyphosphoric acid, chlorosulfonic acid, methanesulfonic acid, trichloromethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid or acidic ion exchangers.
  • methanesulfonic acid trifluoromethanesulfonic acid, p-toluenesulfonic acid or acidic ion exchangers.
  • the addition of the acid as a catalyst is generally carried out in an amount of 50 ppm to 10 wt .-%, preferably from 100 ppm to 5 wt .-%, more preferably 1000 ppm to 3 wt .-% based on the amount of the alcohol or alcohol mixture used.
  • an acidic ion exchanger is used as the catalyst, it is customary to use an amount of from 1000 ppm to 30% by weight, preferably from 1 to 25% by weight, particularly preferably from 1 to 20% by weight, based on the amount of used alcohol or alcohol mixture.
  • the catalysts can also be used in a mixture.
  • the average molecular weight of the polymer and its structure can be adjusted via the composition of the starting components and over the residence time.
  • the reaction is usually carried out at a temperature of 0 to 300 0 C, preferably 0 to 250 0 C, more preferably at 60 to 250 0 C and most preferably at 80 to 250 0 C in bulk or in solution.
  • all solvents can be used which are inert to the respective starting materials. If solvent is used, preference is given to using organic solvents, for example decane, dodecane, benzene, toluene, chlorobenzene, xylene, dimethylformamide, dimethylacetamide or solvent naphtha.
  • the condensation reaction is carried out in bulk, that is without addition of solvent.
  • the liberated in the reaction water can be removed to accelerate the reaction from the reaction equilibrium, for example by distillation, optionally at reduced pressure.
  • the preparation of the high-functionality polyetherpolyols according to the invention is usually carried out in a pressure range from 0.1 mbar to 20 bar, preferably at 1 mbar to 5 bar, in reactors which are operated batchwise, semicontinuously or continuously.
  • the reaction is carried out in a so-called "one-pot procedure" in which the monomer is completely charged and the reaction is carried out in a back-mixed reactor.
  • Conceivable are also reaction guides in a multistage reactor system, for example a stirred tank cascade or a tube reactor.
  • the reaction can be carried out in a kneader, extruder, intensive mixer or paddle dryer. If appropriate, the reaction can also be carried out with the aid of ultrasound or microwave radiation.
  • the temperature can be lowered to a range in which the reaction comes to a standstill and the condensation product is storage-stable.
  • a basic component such as a Lewis base or an organic or inorganic base.
  • the polyetherols according to the invention may contain, in addition to the OH groups already obtained by the reaction, further functional groups.
  • further functional groups include mercapto groups, primary, secondary or tertiary amino groups, ester groups, carboxylic acid groups or derivatives thereof, sulfonic acid groups or their derivatives, phosphonic acid groups or their derivatives, silane groups, siloxane groups, aryl radicals or short- or long-chain alkyl radicals.
  • modifying reagents are used. These are compounds which have such a further functional group and an alcohol-reactive group.
  • Such alcohol-reactive groups may be, for example, isocyanate groups, acid groups, acid derivatives, epoxide groups or alcohol groups.
  • the modifying reagents may be added to the high-functionality polyether before or during the reaction of the trifunctional or higher-functional alcohols.
  • a polyether polymer having randomly distributed functionalities different from the hydroxyl groups is obtained.
  • Such functionalization can be achieved, for example, by adding compounds which contain mercapto groups, primary, secondary or tertiary amino groups, ester groups, carboxylic acid groups or derivatives thereof, sulfonic acid groups or their derivatives, phosphonic acid groups or derivatives thereof, silane groups, siloxane groups, aryl groups or short or long chain Carry alkyl radicals.
  • Mercaptoethanol can be used for the modification with mercapto groups, for example.
  • Tertiary amino groups can be produced, for example, by incorporation of amino-containing alcohols, such as triethanolamine, tripropanolamine, triisopropanolamine, N-methyldiethanolamine, N-methyldipropanolamine or N, N-dimethylethanolamine.
  • dicarboxylic acids, tricarboxylic acids, dicarboxylic acid esters such as, for example, adipic acid, dimethyl terephthalate or tricarboxylic esters, it is possible to produce ester groups.
  • ester groups can be converted by Settlement of OH groups with lactones, especially with caprolactone, can be obtained.
  • long-chain alkyl radicals By reaction with long-chain alkanols or alkanediols, long-chain alkyl radicals can be introduced.
  • the reaction with alkyl or aryl isocyanates, - diisocyanates or - oligoisocyanates generates corresponding urethane groups containing polyether.
  • Subsequent functionalization can be obtained by reacting the resulting highly functional, highly branched or hyperbranched polyether polyol in an additional process step with a suitable functionalizing reagent which can react with the OH groups of the polyether.
  • the high-functionality polyethers according to the invention can be modified, for example, by adding modifying reagents containing acid, acid halide or isocyanate groups.
  • polyethers containing acid groups can be obtained by reacting the OH groups with compounds containing anhydride groups.
  • Ester groups can be subsequently introduced, for example, by reaction with caprolactone. The length of the ester chains can be controlled by the amount of caprolactone used.
  • high-functionality polyetherols according to the invention can also be converted by reaction with alkylene oxides, for example ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, as modifying reagents into highly functional polyether polyols containing linear polyether chains with adjustable polarity.
  • alkylene oxides for example ethylene oxide, propylene oxide, butylene oxide or mixtures thereof
  • Amphiphilic molecules obtained by modification can be used as phase transfer reagents or as micro or nanocontainers, for example for biologically active or medicinal active substances.
  • hydrophobic polyethers can be modified with hydrophilic groups so that they are soluble in an aqueous medium. These can then be loaded with hydrophobic substances, for example medical active substances, which can thus be transported via the bloodstream to their site of action.
  • hydrophilically modify hydrophilic polyethers it is also possible to hydrophilically modify hydrophilic polyethers and then load them with hydrophilic molecules.
  • reaction conditions such as pressure and temperature
  • concentration of the alcohols and optionally the modifying reagents depends on the reactivity of the alcohols and the Modcertainsreagentien. In principle, a lower temperature, a higher reactivity of the modifying reagents and a higher concentration of the modifying reagents tend to lead to lower molecular weight modified alcohols, with a higher temperature, a lower concentration of modifying reagents and a lower reactivity of the modifying reagents rather leading to condensation products which have several di- , tri- and higher-functional alcohols per molecule.
  • suitable processes are preferably selected so that the polyether polyols obtained have condensation products of on average at least 3, more preferably at least 4, more preferably at least 5, and especially at least 6, higher, dihydric alcohols. More preferably, the reaction conditions are chosen so that the resulting high-functionality polyether polyols are condensation products of on average at least 3, more preferably at least 4, more preferably at least 5 and especially at least 6 tri- or higher functional alcohols.
  • the number of di-, tri- or higher-functional alcohols in the condensation product can be determined, for example, from the number-average molecular weight M n determined by GPC.
  • the products according to the invention can be further processed after preparation without further purification.
  • the reaction product is purified by stripping, that is to say by removing low molecular weight, volatile compounds.
  • stripping that is to say by removing low molecular weight, volatile compounds.
  • the low molecular weight volatiles for example, solvents, starting monomers, volatile fission products, volatile oligomeric or cyclic compounds or water by distillation, optionally with the introduction of a gas, preferably nitrogen, carbon dioxide or air, optionally at reduced pressure removed.
  • a gas preferably nitrogen, carbon dioxide or air
  • reaction may result in condensation products having different structures that have branches and cyclic moieties but no crosslinks.
  • the number of reactive groups results from the nature of the monomers used and the degree of polycondensation, which according to the invention should be chosen so that the gel point is not reached.
  • the polyether polyols based on trimethylolpropane according to the invention have lower molecular weights, lower degradation temperatures and lower glass transition temperatures than products obtained by ring-opening polymerization.
  • products according to the invention which are composed of TMP units, can have molecular parts in which the OH groups of a terminal TMP unit are present as formaldehyde acetal.
  • the content of acetal groups can be adjusted by means of the reaction conditions for the polyether polyols according to the invention.
  • the highly functional highly branched polyethers formed by the process according to the invention dissolve well in various solvents, for example in water, alcohols, such as methanol, ethanol, butanol, alcohol / water mixtures, acetone, 2-butanone, ethyl acetate, butyl acetate, methoxypropyl acetate, methoxyethyl acetate, Tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene carbonate or propylene carbonate.
  • alcohols such as methanol, ethanol, butanol, alcohol / water mixtures, acetone, 2-butanone, ethyl acetate, butyl acetate, methoxypropyl acetate, methoxyethyl acetate, Tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene carbonate or propylene carbonate.
  • a great advantage of the method according to the invention lies in its economy. Both the reaction to the polycondensation product and the reaction of the condensation products to form polyethers with other functional groups or elements can be carried out in a reaction apparatus, which is technically and economically advantageous.
  • the highly functional hyperbranched or hyperbranched polyetherols of the invention may i.a. as adhesion promoters, thixotropic agents, rheology modifiers of polymers, phase transfer reagents, micro- or nanocontainers for biologically active substances, for example for medicinal agents, biocides, herbicides or fungicides, as pigment dispersants, additives in printing inks or as building blocks for the preparation of polyaddition or polycondensation polymers
  • adhesion promoters i.a. as adhesion promoters, thixotropic agents, rheology modifiers of polymers, phase transfer reagents, micro- or nanocontainers for biologically active substances, for example for medicinal agents, biocides, herbicides or fungicides, as pigment dispersants, additives in printing inks or as building blocks for the preparation of polyaddition or polycondensation polymers
  • thixotropic agents rheology modifiers of polymers
  • polyethers according to the invention for the treatment of seed according to the not yet published application PCT / EP2008 / 060673 can be used technically advantageous.
  • the polyethers according to the invention are suitable for the production of low-viscosity printing inks, such as flexographic or gravure printing inks for packaging printing. They can be used for various purposes in printing inks, but in particular as a binder, possibly also in admixture with other binders.
  • the polyethers according to the invention are formulated for this purpose with suitable solvents, colorants, optionally further binders and additives typical of printing inks.
  • suitable solvents, colorants, optionally further binders and additives typical of printing inks for further details on the formulation and preparation of printing inks with hyperbranched polymers, reference is expressly made to WO 02/36695 and WO 02/26697, in particular to the statements in WO 02/36695, page 10, line 19 to page 15, line 14 and WO 02 / 36697, page 7, line 14 to page 10, line 18 and the examples cited in said documents.
  • Printing inks containing the polyethers according to the invention have a particularly good, hitherto unknown, adhesion to the substrates, in particular to metal and / or polymer films.
  • the printing inks are therefore also particularly suitable for the production of laminates of two or more polymer and / or metal foils, in which a film is printed with one or more layers of a printing ink and a second film is laminated onto the printed layer.
  • Such composites are used for example for the production of packaging.
  • Example 1 Preparation of a polyether polyol according to the invention based on trimethylolpropane
  • the polycondensation was carried out in a 2 l glass flask equipped with stirrer and distillation bridge.
  • the mixture of 990 g of trimethylolpropane and 10 g of p-toluenesulfonic acid (1 wt .-%) were heated by means of an oil bath at 200 0 C and stirred under normal pressure under these conditions for 6 h, with water and volatile by-products were distilled off. Thereafter, the reaction mixture was allowed to cool and treated with 2 l of methanol.
  • the solution was admixed with 4.5 g of zinc oxide, stirred overnight, filtered off via Celite insoluble constituents and the reaction mixture then evaporated to dryness on a rotary evaporator at 40 0 C and a reduced pressure of up to 22 mbar.
  • the crude product was then dissolved in 1, 5 I isohexane, insoluble constituents were filtered through Celite and the reaction mixture then evaporated again on a rotary evaporator at 40 0 C and a reduced pressure of up to 22 mbar to dryness.
  • the product had the following characteristics: Tg (10 ° C / min): -32 ° C
  • the polycondensation was carried out in a 2 l glass flask equipped with stirrer, a Vigreux column with descending condenser and vacuum connection.
  • the mixture of 990 g of trimethylolpropane and 10 g of p-toluenesulfonic acid (1 wt .-%) was evacuated and heated to 170 0 C by means of an oil bath at a pressure of 20 mbar. After reaching the reaction temperature, the mixture was stirred for 18 hours at this temperature and volatile components distilled off. Thereafter, the reaction mixture was allowed to cool under vacuum and treated with 2 l of methanol.
  • the product had the following characteristics: Tg (10 ° C / min): -9 ° C
  • the polycondensation was carried out in a 1 l glass flask equipped with stirrer, a Vigreux column with descending condenser and vacuum connection.
  • the mixture of 450 g of trimethylolpropane and 50 g of ion exchanger Amberlite IR 120 from Rohm & Haas (10 wt .-%, solid material, dried from aqueous solution) was evacuated and at a pressure of 12 mbar by means of oil bath to 200 0 C. heated. After reaching the reaction temperature, the mixture was stirred for 24 h at this temperature and volatile components distilled off. Thereafter, the reaction mixture was allowed to cool under vacuum, and 1 liter of methanol was added.
  • the product had the following characteristics: T g (10 ° C / min): - 13 ° C Mw / Mn (GPC; DMF): 1 100/900 [g / mol] OH: 617 mgKOH / g Branching degree: 31%
  • the polymerization was carried out in a 250 ml glass flask equipped with a stirrer, reflux condenser and a vacuum-distillation distillation bridge.
  • the mixture of 25 g of trimethylolpropane (0.19 mol), 28 g of triethylene glycol (0.19 mol) and 1.1 g of Amberlite TM IR 120 ion exchanger (2% by weight, solid material, dried from aqueous solution) was evacuated and at a pressure of 12 mbar slowly heated by means of oil bath to 160 0 C. After reaching the reaction temperature, the reaction mixture was stirred for 24 h and volatiles were removed by distillation. Thereafter, the reaction mixture was allowed to cool under vacuum.
  • the crude product was taken up in methanol, the ion exchanger filtered off and the reaction solution was then evaporated to dryness on a rotary evaporator at 40 0 C and a reduced pressure of up to 22 mbar.
  • the crude product was then used to remove volatile by-products and unreacted starting materials twice by thin-film evaporator at an oil temperature of 195 0 C purified under a pressure of 1-5 * 10 "2 mbar and. This gave 22.5 g (43 wt .-%) of polyetherol.
  • the reaction product had the following characteristics: T g (10 ° C / min): - 60 ° C Mw / Mn (GPC; DMF): 1 110/760 [g / mol]
  • the polymerization was carried out in a 1 l glass flask equipped with stirrer and a Vigreux column with distillation bridge and vacuum connection.
  • the mixture of 350 g of trimethylolpropane (2.61 mol), 100 g of pentaerythritol (0.74 mol) and 50 g of Amberlite TM IR 120 ion exchanger (10% by weight, solid material, dried from aqueous solution) was evacuated and concentrated at room temperature Pressure of 12 mbar heated by means of oil bath to 200 0 C. After reaching the reaction temperature, the mixture was stirred for 24 hours. Thereafter, the reaction mixture was allowed to cool under vacuum.
  • the crude product was taken up in methanol, the ion exchanger and unreacted pentaerythritol filtered off and the reaction solution was evaporated to dryness on a rotary evaporator at 40 0 C and a reduced pressure of up to 22 mbar.
  • the crude product was then removed to remove volatile by-products and unreacted Feedstock 10 "2 mbar cleaned twice with a thin-film evaporator at an oil temperature of 195 ° C and a pressure of 1-5 *. This gave 236 g (58 wt .-%) polyetherol.
  • the product had the following characteristics: T g (10 ° C / min): - 9 ° C Mw / Mn (GPC; DMF) 670/560 [g / mol]
  • the polymerization was carried out in a 1 l glass flask equipped with a stirrer, reflux condenser and a vacuum-distillation distillation bridge.
  • the mixture of 225.9 g of pentaerythritol (1.66 mol), 249.1 g of triethylene glycol (1.66 mol) and 4.8 g of p-toluenesulfonic acid monohydrate (1 wt .-%) was evacuated and at a pressure of 12 mbar slowly heated to 200 0 C by means of oil bath. After reaching the reaction temperature, the reaction mixture was stirred for 15 hours. Thereafter, the reaction mixture was allowed to cool under vacuum.
  • the crude product was taken up in 1 l of methanol and unreacted pentaerythritol filtered off. Added, stirred for 2 h and overnight at - incubated 20 0 C; for neutralizing the reaction solution, 10 g of basic alumina (04571, MP MP Ecochrom ALUMINA B ACTIVITY SUPER I). After thawing insoluble constituents were filtered through Celite and the reaction mixture was then evaporated to dryness on a rotary evaporator at 40 0 C and a reduced pressure of up to 22 mbar.
  • the product had the following characteristics: T g (10 ° C / min): - 36 ° C Mw / Mn (GPC; DMF) 4820/1540 [g / mol] OH number: 539 mg KOH / g
  • Example 7 Preparation of a polyetherpolyol based on pentaerythritol according to the invention
  • the polymerization was carried out in a 250 ml glass flask equipped with a stirrer, a Vigreux column with descending condenser and a vacuum condenser reflux condenser.
  • 49.75 g of pentaerythritol (0.37 mol) and 0.25 g of p-toluenesulfonic acid monohydrate (1 wt%) was evacuated and heated at a pressure of 12 mbar by means of an oil bath at 210 0 C. After reaching the reaction temperature, the reaction mixture was 30 min touched. Thereafter, the reaction mixture was allowed to cool under vacuum.
  • the crude product was taken up in water, refluxed for 1 h and filtered while hot. The residue was dried at 80 ° C. in a vacuum oven. This gave 17.91 g (36% by weight) of polyether polyol.
  • the product was acetylated with acetic anhydride.
  • the product had the following characteristics: T g (10 ° C / min): 32 ° C Mw / Mn (GPC; CHCl 3 ): 3310/1600 [g / mol] Degree of branching: 56.5%
  • Example 8 Preparation of a polyether polyol based on trimethylolpropane according to the invention, randomly etherified with 3 mol of ethylene oxide
  • the polycondensation was carried out in a 250 ml glass flask equipped with stirrer, a Vigreux column with descending condenser and vacuum connection.
  • the mixture of 45 g of trimethylolpropane, statistically etherified with 3 mol of ethylene oxide, and 5 g of Amberlite TM IR 120 from Rohm & Haas (10% by weight, solid material, dried from aqueous solution) was evacuated and dried under a pressure of 12 mbar by means of oil bath to 200 0 C heated. After reaching the reaction temperature, the mixture was stirred for 24 h at this temperature and volatile components distilled off. Thereafter, the reaction mixture was allowed to cool under vacuum, and 200 ml of methanol was added.
  • the product had the following characteristics: Tg (10 ° C / min): -62 ° C
  • the product had the following characteristics: Mw / Mn (GPC; CHCl 3 ): 1000/740 [g / mol]
  • the product had the following characteristics: T g (10 ° C / min): - 54 ° C Mw / Mn (GPC; CHCl 3 ): 4820/1540 [g / mol]
  • Example 1 1 Preparation of a derivative of a polyether polyol based on trimethylolpropane and methyl stearate
  • the product had the following characteristics: T m (10 ° C / min): 33 ° C Mw / Mn (GPC; CHCl 3 ): 1520/1240 [g / mol] Degree of derivatization: 44%
  • Example 13 Preparation of a derivative of a polyether polyol based on pentaerythritol and triethylene glycol and methyl stearate
  • the product had the following characteristics: T m (10 ° C./min): 44 ° C. M w / M n (GPC; CHCl 3 ): 4740/2420 [g / mol] Degree of derivatization: 45%
  • Example 14 Preparation of a derivative of a polyether polyol based on pentaerythritol and triethylene glycol and methyl stearate
  • the product had the following characteristics: T m (10 ° C./min): -48 ° C. Degree of derivatization: 50%
  • Example 16 (comparative example): Preparation of a polyether polyol based on glycerol
  • the polycondensation was carried out in a 500 ml glass flask equipped with stirrer and distillation bridge.
  • the mixture of 100 g of glycerol and 1 g of p-toluenesulfonic acid (1 wt .-%) were heated by means of oil bath to 200 0 C and stirred under atmospheric pressure under these conditions for 1.5 h, with water and volatile by-products (ca. 30 g) distilled off. Thereafter, the reaction mixture was allowed to cool. A black, tarry, pungent-smelling product was obtained which was unsuitable for use in technically relevant formulations.
  • Example 17 (Comparative Example): Polyether polyol based on 1-ethyl-1-hydroxymethyl-oxetane according to Yan et al., Macromolecules 2003, 36, 9667
  • the reaction mixture is stirred for a total of 48 h at RT.
  • the reaction is stopped by adding 10 ml of ethanol, then allowed to stir for a further 1 - 2 h.
  • the solution is then concentrated to dryness at 70 ° C. and a reduced pressure of up to 350 mbar on a rotary evaporator, the residue is admixed with 15-20 ml of ethanol and stirred at 60 ° C. until a homogeneous solution has formed.
  • the polymer is precipitated in 200 ml of water.
  • the product is dried for several days at 80 0 C in a vacuum. There are obtained 45 g (90%) of a colorless solid.
  • the product had the following characteristics: Mw / Mn (GPC; CHCl 3 ): 7900/4970 [g / mol]
  • Example 19 Comparison of the properties of the polyethers according to the invention with a polyether of the prior art
  • polyether polyols based on trimethylolpropane according to the invention have lower molecular weights, lower degradation temperatures and lower glass transition temperatures than the literature system.
  • the products according to the invention have TMP units which are present as formaldehyde acetal.
  • the content of acetal groups can be adjusted by means of the reaction conditions for the polyether polyols according to the invention.
  • the literature system however, has no acetal functionalities.
  • Table 1 Solubility behavior of 100 mg of the polyether polyols according to the invention based on trimethylolpropane and the literature system in 3 ml of solvent at room temperature.
  • polyether polyols based on trimethylolpropane according to the invention have a significantly better solubility than the literature system, which is insoluble in many common solvents such as methanol and acetone. This can be attributed on the one hand to the presence of the formaldehyde acetals as well as to the lower molecular weights of the polyether polyols according to the invention (see Table 1). The solubility of the polyether polyols according to the invention in nonpolar solvents increases with the number of incorporated TMP units present as formaldehyde acetal.
  • Example 20 Loading capacity of a derivative of a polyether polyol according to the invention, modified with methyl stearate
  • the derivatized polyether polyols from Examples 11, 12 and 13 were dissolved in different concentrations in chloroform and layered with a constant amount of an aqueous solution of Congorot, an anionic dye insoluble in chloroform. After shaking and subsequent phase separation, the chloroform phase was examined by fluorescence spectroscopy. A fluorescence intensity increasing in the chloroform phase with increasing concentration of the polyether polyol was observed for all polyether polyols.
  • Degree of branching was determined from quantitative 13 C NMR spectra of products acylated with acetic anhydride, using inverse gated decoupling, 4000 scans, a pulse delay of 3.1 seconds, and a very small amount of Cr (acac) 3 as the relaxation reagent. The quaternary carbon atoms were integrated in each case.
  • the degree of branching was calculated according to literature known formulas for AB2 and AB3 systems (Frey, H. et al., Acta Polym. 1997, 48, 30). In systems containing TEG units, the degree of branching could not be determined because of unknown length of the internal ethylene glycol units.
  • Molecular weights and molecular weight distributions were determined by GPC against polystyrene standards. GPC measurements were performed at 30 0 C in chloroform or DMF with PSS SDVB column (5 micron particle 10 3 -, 10 4 -, 10 5 -, 10 6 -ae) is performed. The polymer concentration was about 2 mg / ml.
  • the DSC measurement was carried out using a heat flow calorimeter DSC-7 from Perkin-Elmer. For this purpose, 5 - 7 mg of the sample were weighed into an aluminum crucible and measured in a temperature range of - 100 to + 100 0 C at a heating and cooling rate of 10 K-min- 1 . T 9 and T m were determined from the second heating curve.
  • the hydroxyl number was determined according to the following procedure:
  • the fluorescence measurements were performed on a TIDAS absorption and photoluminescence diode array spectrometer with a SPECTRALYS monochromator. For this purpose, an excitation wavelength of 360 nm was selected and the respective maximum fluorescence intensity was determined.

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Abstract

La présente invention concerne un procédé de production de polyéthérols hautement fonctionnels, dans lequel on convertit au moins un alcool tri-fonctionnel ou d'une fonctionnalité supérieure et éventuellement, d'autres alcools di- et/ou monofonctionnels et/ou des réactifs de modification à l'aide de catalyseurs acides, l'alcool tri-fonctionnel ou d'une fonctionnalité supérieure n'étant pas la glycérine. La présente invention concerne en outre des polyéthérols hautement fonctionnels, pouvant être obtenus selon ce procédé et l'utilisation de ces polyéthérols hautement fonctionnels en tant qu'agents adhésifs, agents thixotropes, modificateurs de la rhéologie de polymères, réactifs de transfert de phase, micro- ou nano-conteneurs d'une substance biologiquement active, par exemple, un principe actif médical, des biocides, herbicides ou fongicides, comme agents de dispersion de pigment, additif d'encres d'imprimerie, éléments de production de polymères par poly-addition ou polycondensation ou pour le traitement de graines.
EP09711329A 2008-02-15 2009-02-12 Polyéthérols hautement fonctionnels et leur production et utilisation Withdrawn EP2245082A1 (fr)

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