EP2089467A2 - Procédé pour produire des polymères remplis d'oxydes métalliques nanométriques - Google Patents

Procédé pour produire des polymères remplis d'oxydes métalliques nanométriques

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Publication number
EP2089467A2
EP2089467A2 EP07822205A EP07822205A EP2089467A2 EP 2089467 A2 EP2089467 A2 EP 2089467A2 EP 07822205 A EP07822205 A EP 07822205A EP 07822205 A EP07822205 A EP 07822205A EP 2089467 A2 EP2089467 A2 EP 2089467A2
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EP
European Patent Office
Prior art keywords
acid
polymerizable compound
compounds
compound
metal oxides
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.)
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Application number
EP07822205A
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German (de)
English (en)
Inventor
Andrey Karpov
Hartmut Hibst
Claudia Mettlach
Lionel Gehringer
Motonori Yamamoto
Berend Eling
Hans-Helmut Goertz
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BASF SE
Original Assignee
BASF SE
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Application filed by BASF SE filed Critical BASF SE
Priority to EP07822205A priority Critical patent/EP2089467A2/fr
Publication of EP2089467A2 publication Critical patent/EP2089467A2/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the invention relates to a process for the preparation of polymers filled with nanoscale metal oxides and polymers produced there after.
  • Nanoscale additives impart a number of excellent properties to polymers in a known manner because of their high specific surface area. These are particularly highly effective wherever, for example, it is necessary to move out of the environment through their surface in interaction with electromagnetic radiation. In addition, they can be uniformly distributed in other substances down to the submicroscopic range, resulting in a highly homogeneous property profile. Due to their particular fineness they are not only invisible as such, the substances containing them often do not even show any turbidity and appear transparent. Due to quantum effects, nanoparticles often have new and different properties than less finely divided materials of the same chemical composition.
  • WO 2005/075548 describes, for example, a process for the preparation of polyester resins with nanoscale additives for powder coatings, the nanoscale additives being introduced in the form of a suspension in an external liquid phase, for example liquid diols, into the reaction batch of the resin synthesis.
  • EP-B 0 236 945 describes a process for producing a polyester film using a glycol suspension of an amorphous inorganic oxide obtained by hydrolysis of a corresponding organometallic compound at a temperature in the range from 0 to 100 ° C., preferably between 0 and 50 ° C. is obtained. In this case, however, relatively expensive starting materials are used and amorphous particles are obtained which can only interact in an insufficient manner with electromagnetic radiation from the environment.
  • WO 01/72881 describes another polyester-based composition containing a polyester-based matrix and nanoscale mineral particles which are introduced into the polyester synthesis approach as a glycol sol.
  • EP-A 1 199 389 describes a glycoluct for polyester containing dispersed superfine ceramic particles having an average particle size of between 0.05 and 0.5 ⁇ m and a narrow particle size distribution, the superfine ceramic particles being dispersed by a complex treatment of a glycol containing a conventional particle - Ceramic powder having a particle size between 1 and 30 microns and having a broad particle size distribution, by pulverizing in an ultrasonic homogenizer or a jet mill can be obtained.
  • polyol route for the preparation of submicron monodisperse metal oxide particles by heating the corresponding metal salts in polyols in the presence of hydrous sources, for example, water of crystallization or free water, which are hydrolyzed or decomposed to the corresponding metal oxides is known and disclosed, for example, in J. Chem. of SoI-GeI Science and Technology 26, 2003, pages 261-265.
  • the solution consists of a process for the preparation of nanoscale metal oxide-filled polymers, characterized by the following process steps:
  • a) preparation of a nanosuspension of one or more crystalline metal oxides, hydroxides or oxide hydroxides by heating a suspension of one or more compounds containing the corresponding metals in a first polymerizable compound to a temperature greater than the boiling point of water under process pressure and smaller than the boiling temperature of the first polymerizable compound and lower than the temperature at which the polymerization of the first polymerizable compound starts,
  • a nanosuspension containing one or more crystalline metal oxides, oxide hydrides or hydroxides is prepared in a first process step a) by heating a suspension of one or more compounds of the corresponding metals in the presence of water in a first polymerizable compound.
  • a first polymerizable compound is also understood as meaning a mixture of polymerizable compounds.
  • the starting point is therefore one or more metal-containing compounds, preferably one or more salts of metals, which in process step a) are converted into the corresponding oxide hydroxide, hydroxide or oxide, preferably into the corresponding oxide.
  • These may in particular be salts of monocarboxylic acids, such as formic acid, acetic acid, propionic acid, isobutyric acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid and stearic acid, unsaturated fatty acids, such as acrylic acid, methacrylic acid, crotonic acid, oleic acid and linolenic acid, saturated polybasic Carboxylic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid and ⁇ , ⁇ -dimethylglutaric acid, unsaturated polybasic carboxylic acids such as maleic acid and fumaric acid, saturated alicyclic acids such as cyclohexanecarboxylic acid, aromatic carboxylic acids such as the aromatic monocarboxylic acids, especially phenylacetic acid and toluic acid, and unsaturated polybasic acids Carboxylic acids, such as phthalic acid, isophthal
  • Preferred salts or salts are one or more salts of monocarboxylic acids, in particular of formic acid, acetic acid, propionic acid, stearic acid, acrylic acid and / or of oleic acid and / or one or more salts of dicarboxylic acids, in particular of oxalic acid, adipic acid, isophthalic acid and or terephthalic acid used.
  • the metal component in the salts zinc, titanium, cerium, zirconium, iron, cobalt, copper, aluminum or manganese or mixtures thereof can be advantageously used.
  • the first polymerizable compound which may also be a mixture, in particular one or more substances selected from the following list can be used: styrene, caprolactam or an acrylate.
  • the process according to the invention is preferably carried out in such a way that firstly the nanosuspension of one or more crystalline metal oxides, oxide hydroxides or hydroxides is prepared in the first polymerisable compound in process step a) and these in process step b) is polymerized under the conditions of temperature and pressure customary for the first polymerizable compound.
  • the addition of a further polymerizable compound is not required.
  • a further amount of the same compound prepared in process step a) is added.
  • the first polymerisable compound used in process step a) is a diol or a diol derivative, in particular a diol ether or a diol ester.
  • Particularly suitable diol compounds are branched or linear alkanediols having 2 to 18 carbon atoms, preferably 4 to 14 carbon atoms, cycloalkanols having 5 to 20 carbon atoms or aromatic diols.
  • alkanediols examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1, 8-octanediol,
  • Tridecanediol 2,4-dimethyl-2-ethyl-1,3-hexanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-2-butyl-1,3-propanediol, 2 Ethyl 2-isobutyl-1,3-propanediol or 2,2,4-
  • Trimethyl-1,6-hexanediol Particularly suitable are ethylene glycol, 1, 3-propanediol, 1, 4-butanediol and 2,2-dimethyl-1, 3-propanediol, 1, 6-hexanediol or 1, 12-dodecanediol.
  • cycloalkanediols examples include 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol (1,2-dimethylolcyclohexane), 1,3 Cyclohexanedimethanol (1,3-dimethylolcyclohexane), 1, 4-cyclohexanedimethanol (1,4-dimethylolcyclohexane) or 2,2,4,4-tetramethyl-1,3-cyclobutanediol.
  • aromatic diols examples include 1, 4-dihydroxybenzene, 1, 3-dihydroxybenzene, 1, 2-dihydroxybenzene, bisphenol A (2,2-bis (4-hydroxyphenyl) -propane), 1, 3-dihydroxynaphthalene, 1, 5-dihydroxynaphthalene or 1, 7-dihydroxynaphthalene.
  • polyether diols for example diethylene glycol, triethylene glycol, polyethylene glycol (with> 4 ethylene oxide units), propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol (with> 4 propylene oxide units) and polytetrahydrofuran (polyTHF), in particular diethylene glycol, triethylene glycol and Polyethylene glycol (with> 4 ethylene oxide units) can be used.
  • polyTHF polyethylene glycol or polypropylene glycol find compounds whose number average molecular weight (M n ) is usually in the range of 50 to 100,000, preferably from 200 to 10,000, more preferably from 600 to 5000 g / mol.
  • mixtures of the aforementioned diol compounds can be used.
  • the polymerization in process step b) is carried out with the addition of a second polymerizable compound which in particular comprises a dicarboxylic acid compound, a dicarboxylic acid ester compound, a diamino compound, a hydroxycarboxylic acid compound, an aminoalcohol compound, an aminocarboxylic acid compound or a may be further compound having at least three hydroxy primary or secondary amino and / or carboxy groups per molecule, aliphatic or aromatic diisocyanates or mixtures of the aforementioned compounds.
  • a second polymerizable compound which in particular comprises a dicarboxylic acid compound, a dicarboxylic acid ester compound, a diamino compound, a hydroxycarboxylic acid compound, an aminoalcohol compound, an aminocarboxylic acid compound or a may be further compound having at least three hydroxy primary or secondary amino and / or carboxy groups per molecule, aliphatic or aromatic diisocyanates or mixtures of the aforementioned compounds.
  • dicarboxylic acid compounds it is possible in principle to use all C 2 -C 4 0-aliphatic, C 3 -C 2 0-cycloaliphatic, aromatic or heteroaromatic compounds which have two carboxylic acid groups (carboxy groups; -COOH) or derivatives thereof.
  • carboxylic acid groups carboxylic acid groups; -COOH
  • derivatives are used in particular Ci-Ci o alkyl, preferably methyl, ethyl, n-propyl or isopropyl, mono- or diesters of the aforementioned dicarboxylic acids, the corresponding dicarboxylic acid halides, especially the dicarboxylic acid dichlorides and the corresponding dicarboxylic anhydrides.
  • Examples of such compounds are ethanedioic acid (oxalic acid), propanedioic acid (malonic acid), butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nonanedioic acid (azelaic acid), decanedioic acid (Sebacic acid), undecanedioic acid, dodecanedioic acid, tridecanedioic acid (Brassylic acid), C 32 -dimer fatty acid (commercial product from Cognis Corp., USA), benzene-1, 2-dicarboxylic acid (phthalic acid), benzene-1,3-dicarboxylic acid (isophthalic acid) or benzene-1, 4 dicarboxylic acid (ter
  • Suitable diamine compounds are all organic diamine compounds which have two primary or secondary amino groups, preference being given to primary amino groups.
  • the organic backbone having the two amino groups may have a C 2 -C 2 o-aliphatic, C 3 -C 2 o-cycloaliphatic, aromatic or heteroaromatic structure.
  • Examples of compounds having two primary amino groups are 1, 2-diaminoethane, 1, 3-diaminopropane, 1, 2-diaminopropane, 2-methyl-1,3-diaminopropane, 2,2-dimethyl-1,3-diaminopropane (neo- pentyldiamine), 1, 4-diaminobutane, 1, 2-diaminobutane, 1, 3-diaminobutane, 1-methyl-1, 4-diaminobutane, 2-methyl-1,4-diaminobutane, 2,2-dimethyl-1,4 diaminobutane, 2,3-dimethyl-1,4-diaminobutane, 1,5-diaminopentane, 1,2-diaminopentane, 1,3-diamino-pentane, 1,4-diaminopentane, 2-methyl-1,5-diaminopentane , 3-methyl-1,5-
  • 1,6-diaminohexane 1,1,2-diaminododecane, 2,2-dimethyl-1,3-diaminopropane, 1,4-diaminocyclohexane, isophoronediamine, 3,3'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexyl methane, m-xylylenediamine or p-xylylenediamine used as optional diamine compounds.
  • Hydroxycarboxylic acid compounds which can be used are the free hydroxycarboxylic acids, their C 1 -C 5 -alkyl esters and / or their lactones.
  • Examples include glycolic acid, D-, L-, D, L-lactic acid, 6-hydroxyhexanoic acid (6-hydroxycaproic acid), 3-hydroxybutyric acid, 3-hydroxyvaleric acid, 3-hydroxycaproic acid, p-hydroxybenzoic acid, their cyclic derivatives such as glycolide ( 1, 4-dioxane-2,5-dione), D-, L-, D, L-dilactide (3,6-dimethyl-1,4-dioxane-2,5-dione), ⁇ -caprolactone, ⁇ - Butyrolactone, ⁇ -butyrolactone, dodecanolide (oxacyclotridecan-2-one), undecanolide (oxacyclododecan-2-one) or pentadecanolide (oxa
  • C 5 -C cycloaliphatic or aromatic organic compounds aliphatic, C 5 -C be used, which have only one hydroxyl group and one secondary or primary, but preferably have a primary amino group - as amino alcohol compounds in principle all, but preferably C 2 -C second Examples which may be mentioned are 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol, 2-aminocyclopentanol, 3-aminocyclopentanol, 2-aminocyclohexanol, 3-aminocyclohexanol, 4-aminocyclohexanol and 4-aminomethylcyclohexanemethanol (1-methylol -4-aminomethyl).
  • Suitable aminocarboxylic acid compounds are all organic compounds which have an amino and a carboxy group in free or derivatized form, but in particular the C 2 -C 30 -aminocarboxylic acids, the C 1 -C 5 -alkyl esters of the abovementioned aminocarboxylic acids, the corresponding Cs-cis Lactam compounds, the C ⁇ Cso-Aminocarbon Textreamide or the C ⁇ Cso Aminocarbon Aciditrile.
  • Examples of the free C 2 -C 3 o-aminocarboxylic acids are the naturally occurring aminocarboxylic acids, such as VaNn, leucine, isoleucine, threonine, methionine, phenylalanine, tryptophan, lysine, alanine, arginine, aspartic acid, cysteine, glutamic acid, glycine, Histidine, proline, serine, tryosine, asparagine or glutamine, and also 3-aminopropionic acid, 4-aminobutyric acid, 5-aminovaleric acid, 6-aminocaproic acid, 7-aminoanthic acid, 8-aminocaprylic acid, 9-aminopelargonic acid, 10-amino capric acid, 1-aminoundecanoic acid, 12-aminolauric acid, 13-aminotridecanoic acid, 14-aminotetradecanoic acid or 15-aminopentadecanoic acid
  • Exemplary of the -C 5 - alkyl esters of the aforementioned aminocarboxylic acids the 3-aminopropionamide, 4- aminobutyric acid, 5-Aminovalerian Textre-, 6-aminocaproic acid, 7-Aminoönanth- are acid-, 8-Aminocaprylklare-, 9-Aminopelargonklare-, 10-aminocapric -, 1 1- AminoundecanTalkre-, 12-Aminolaurinklare-, 13-Aminotridecan Textre-, 14-Aminotetradecankladadecanklad.
  • Examples of the C 3 -C 5 -lactam compounds are ⁇ -propiolactam, ⁇ -butyrolactam, ⁇ -valerolactam, ⁇ -caprolactam, 7-enantholactam, 8-caprylolactam, 9-pelargolactam, 10-caprinlactam, 1 l-undecanoic acid lactam , ⁇ -laurolactam, 13-tridecanoic acid lactam, 14-tetradecanoic acid lactam or 15-pentadecanoic acid lactam.
  • aminocarboxamides are 3-aminopropionic acid, 4-aminobutyric acid, 5-aminovaleric acid, 6-aminocaproic acid, 7-amino-nicantric acid, 8-aminocaprylic acid, 9-aminopelargonic acid, 10-aminocapric acid, 11 Aminoundecanoic acid, 12-aminolauric acid, 13-aminotridecanoic acid, 14-aminotetradecanoic acid or 15-aminopentadecanoic acid amide and as examples of the aminocarboxylic acid nitriles are 3-aminopropionic, 4-aminobutyric, 5-aminovaleric, 6-aminocaproic acid , 7-aminoanthant, 8-aminocapryl, 9-aminopelargon, 10-aminocaprine, 1 1-aminoundecane, 12-aminolaurin, 13-aminotridecane, 14-aminotetradecane or 15-amino
  • Further components which can be used in the process according to the invention are organic compounds which have at least 3 hydroxyl, primary or secondary amino and / or carboxy groups per molecule.
  • examples which may be mentioned are tartaric acid, citric acid, malic acid, trimethylolpropane, trimethylolethane, pentaerythritol, polyether triols, glycerol, sugars (for example glucoses, mannose, fructose, galactose, glucosamine, sucrose, lactose, trehalose, maltose, cellobiose, gentianose, kestose, maltotriose, Raffinose, trimesic acid (1, 3,5-benzenetricarboxylic acid and its esters or anhydrides), trimellitic acid (1, 2,4-benzenetricarboxylic acid and its esters or anhydrides), pyromellitic acid (1, 2,4,5-benzotetracarboxylic acid and their esters
  • 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate are particularly preferred.
  • the latter diisocyanates are used as a mixture.
  • trinuclear isocyanate is also tri (4-isocyanophenyl) methane into consideration.
  • the polynuclear aromatic diisocyanates are obtained, for example, in the preparation of mono- or binuclear diisocyanates.
  • aliphatic diisocyanates in the present invention especially linear or branched alkylenediisocyanates or Cycloalkylendiisocyanate having 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms, e.g. 1, 6-hexamethylene diisocyanate, isophorone diisocyanate or methylene bis (4-isocyanatocyclohexane) understood.
  • Particularly preferred aliphatic diisocyanates are 1,6-hexamethylene diisocyanate and isophorone diisocyanate.
  • Preferred isocyanurates include the aliphatic isocyanurates derived from alkylene diisocyanates or cycloalkylene diisocyanates having 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms, e.g. Isophorone diisocyanate or methylene bis (4-isocyanatocyclohexane), derived.
  • the alkylene diisocyanates can be both linear and branched. Particular preference is given to isocyanurates based on n-hexamethylene diisocyanate, for example cyclic trimers, pentamers or higher oligomers of n-hexamethylene diisocyanate.
  • diol 1, 4-butanediol, 1, 2-ethanediol, 1, 2-propanediol or 1, 3-propanediol or a mixture of said diols, more preferably 1, 4-butanediol.
  • dicarboxylic acids are adipic acid and terephthalic acid.
  • dicarboxylic acid esters are particularly preferably dimethyl or Diethyladipat or dimethyl or Diethlyterephthalat. Very particular preference is given to combinations of the abovementioned dicarboxylic acids or dicarboxylic esters, in each case with 1,4-butanediol.
  • a nanosuspension of one or more metal oxide-oxide hydroxides or hydroxides in crystalline form is obtained;
  • the above-described suspension of one or more compounds of the corresponding metals in a first polymerizable compound must be heated to a temperature above the boiling point of water under the process pressure in process step a) and below the temperature of the boiling point of the first polymerizable compound and below the temperature at which the polymerization of the first polymerizable compound begins.
  • the process pressure in process step a) atmospheric pressure, but it is also possible, at a pressure in the range of 10 "3 mbar to 100 kbar, preferably at a pressure in a range of 10 " 3 bar to 10 2 bar, more preferably at a pressure in the range of 1 to 100 bar, to work.
  • the reaction in process step a) takes place in the presence of water, which may be free water or else water of crystallization, in an amount corresponding to 1 to 10 oxygen atoms per metal atom of the salts or salts of the metals corresponding to the metal oxides, preferably 2 to 4 oxygen atoms per metal atom and more preferably 2 oxygen atoms per metal atom.
  • water which may be free water or else water of crystallization
  • the ratio of the one or more salts used in process step a) to the first polymerizable compound is preferably adjusted such that the nanosuspension obtained has a concentration of ⁇ 50% by weight, preferably ⁇ 20% by weight and in particular ⁇ 10% by weight. % Metal oxides based on the total weight of the nanosuspension.
  • the nanosuspension obtained in process step a) has, in particular, an average particle size in the range from 1 to 500 nm, more preferably from 5 to 150 nm.
  • the temperature profile in process step a) can be arbitrary, however, fast heating rates and shorter heating times lead to smaller particles.
  • Preferred heating rates are between 200 ° C / second and 800 ° C / hour, more preferably between 200 ° C / minute and 200 ° C / hour.
  • Preferred heating times are between 1 minute and 24 hours, more preferably between 1 minute and 1 hour.
  • the polymers filled with nanoscale metal oxides are crystalline.
  • the polymers filled with nanoscale metal oxides are amorphous.
  • the polymers filled with nanoscale metal oxides obtained by the process according to the invention can preferably be used as precursors for the preparation of polyurethanes filled with crystalline nanoscale metal oxides.
  • Example 1 shows the transmission electron microscopic (TEM) uptake of ZnO particles-filled polybutylene terephthalate, prepared according to Example 1 described below,
  • FIG. 3 a TEM image of the ZnO-filled polybutylene terephthalate prepared according to the comparative example
  • FIG. 4 shows a TEM image of the ZnO suspension in 1,4-butanediol prepared according to Example 2 described below, process step a),
  • FIG. 5 a TEM image of the ZnO-filled polybutylene adipate prepared according to Example 2 described below, process step b),
  • FIG. 6 a TEM image of the ZnO-filled polybutylene adipate prepared according to Example 3 described below, process step b)
  • FIG. 7 shows a TE M absorption of the ZnO-filled polybutylene adipate prepared according to Example 3 described below, process step b), with a higher resolution compared to the representation in FIG. 6, FIG.
  • FIG. 8 shows a TE M absorption of the ZnO-filled polyesterol prepared according to Example 4 described below, process step b),
  • FIG. 9 shows a TE M absorption of the ZnO-filled polyesterol prepared according to Example 4 described below, process step b), with a higher resolution compared to the illustration in FIG. 8, and FIG. 9
  • FIG. 10 a TEM image of the ZnO-filled polypropylene terephthalate prepared according to Example 5 described below, process step b).
  • Nanoparticulate ZnO powder A mixture of 100 g Zn acetate dihydrate and 1,000 g of 1, 4-butanediol was heated with stirring (350 rpm) at 100 0 C heated in air within 15 minutes. After reaching 100 ° C, 20 ml of H 2 O were added, the mixture was heated to 150 ° C, heated for 1 hour at this temperature and then cooled to room temperature. The resulting suspension was centrifuged in a centrifuge type Sorvall RC6 Fa. ThermoElektron at 13000 rpm. The settled ZnO powder was separated from 1, 4-butanediol, redispersed twice in ethanol and then dried at 50 0 C for 5 hours in a drying oven.
  • Process step b) polycondensation of the ZnO powder prepared in process step a) with 1,4-butanediol and dimethyl terephthalate
  • part of the suspension was re-dispersed in ethanol and characterized by means of transmission electron microscopy (TEM). After the TEM investigations, the ZnO particles obtained had a mean diameter of about 80 nm (FIG. 4).
  • a portion of the suspension was re-dispersed in ethanol and characterized by transmission electron microscopy (TEM).
  • TEM transmission electron microscopy
  • the resulting powder had an average particle size of 20 to 40 nm.
  • Another part of the suspension was redispersed in ethanol and dried at 50 ° C. in a drying oven. From the half-width of the X-ray reflections, the crystal size was calculated to be between 20 nm [for the (1 10) reflection] and 34 nm [for the (002) reflection].
  • a mixture of 400 g Zn acetate dihydrate, 2000 g 1, 4-butanediol and 2000 g of ethylene glycol was heated at 100 0 C within 15 minutes in air. After reaching the temperature of 100 0 C 40 ml of H 2 O were added, the mixture was heated to 150 0 C and heated for 1 hour at this temperature.
  • a mixture of 200 g of Zn acetate dihydrate and 2000 g of 1,2-propanediol was heated to 100 ° C within 15 minutes in air. After reaching a temperature of 100 0 C, 20 ml of H 2 O were added, the mixture was heated to 150 0 C, refluxed at this temperature for 30 minutes and heated for a further 30 minutes without reflux.
  • a cross-flow ultrafiltration laboratory system type SF Alpha, PES cassette, cut off 100 kD from Sartorius the liquid portion of the suspension obtained was exchanged for pure 1,2-propanediol. Subsequently, the suspension obtained was concentrated to 3.6% by weight of ZnO.
  • a portion of the suspension was re-dispersed in ethanol and characterized by transmission electron microscopy (TEM).
  • TEM transmission electron microscopy
  • the obtained powder had an average particle size of 20 to 30 nm.
  • Another part of the suspension was redispersed in ethanol and dried at 50 ° C in a drying oven. From the half-width of the X-ray reflections, a crystal size was calculated that was between 20 nm [for the (1 10) reflection] and 30 nm [for the (002) reflection].

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  • Oxygen, Ozone, And Oxides In General (AREA)

Abstract

L'invention concerne un procédé pour la production de polymères remplis d'oxydes métalliques nanométriques. Le procédé selon l'invention est caractérisé par les étapes suivantes : a) production d'une nanosuspension d'un ou de plusieurs oxydes, hydroxydes ou oxyhydroxydes métalliques cristallins par chauffage d'une suspension d'un ou de plusieurs composés contenant les métaux correspondants dans un premier composé polymérisable à une température supérieure au point d'ébullition de l'eau à la pression de traitement, inférieure à la température d'ébullition du premier composé polymérisable et inférieure à la température à laquelle commence la polymérisation du premier composé polymérisable, et ce en présence d'eau dans une quantité correspondant à 1 à 10 atomes d'oxygène par atome métallique du ou des composés contenant les métaux correspondants et b) polymérisation du premier composé polymérisable dans des conditions de température et de pression habituelles pour le premier composé polymérisable.
EP07822205A 2006-11-07 2007-11-05 Procédé pour produire des polymères remplis d'oxydes métalliques nanométriques Withdrawn EP2089467A2 (fr)

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EP07822205A EP2089467A2 (fr) 2006-11-07 2007-11-05 Procédé pour produire des polymères remplis d'oxydes métalliques nanométriques

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EP06123559 2006-11-07
EP07822205A EP2089467A2 (fr) 2006-11-07 2007-11-05 Procédé pour produire des polymères remplis d'oxydes métalliques nanométriques
PCT/EP2007/061876 WO2008055869A2 (fr) 2006-11-07 2007-11-05 Procédé pour produire des polymères remplis d'oxydes métalliques nanométriques

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EP2089467A2 true EP2089467A2 (fr) 2009-08-19

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US (1) US20100036052A1 (fr)
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CN104140666B (zh) * 2014-07-30 2016-05-18 东莞市吉鑫高分子科技有限公司 用于球膜的高耐磨透明热塑性聚氨酯弹性体及其制备方法
CN104177817B (zh) * 2014-07-30 2016-08-24 东莞市雄林新材料科技股份有限公司 一种高耐磨透明tpu球膜及其制备方法
US10266925B2 (en) * 2015-07-14 2019-04-23 Iowa State University Research Foundation, Inc. Stable undercooled metallic particles for engineering at ambient conditions
CN111978522B (zh) * 2020-09-08 2022-12-20 常州美胜生物材料有限公司 一种亲水抗静电抗菌共聚酯母粒的制备方法

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WO2008055869A2 (fr) 2008-05-15
US20100036052A1 (en) 2010-02-11

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