WO2011092028A1 - Nanoparticules et nanoencres - Google Patents

Nanoparticules et nanoencres Download PDF

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Publication number
WO2011092028A1
WO2011092028A1 PCT/EP2011/000398 EP2011000398W WO2011092028A1 WO 2011092028 A1 WO2011092028 A1 WO 2011092028A1 EP 2011000398 W EP2011000398 W EP 2011000398W WO 2011092028 A1 WO2011092028 A1 WO 2011092028A1
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Prior art keywords
radical
divalent
replaced
atom
groups
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PCT/EP2011/000398
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German (de)
English (en)
Inventor
Heinz Langhals
Simon Kinzel
Tim Pust
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Ludwig-Maximilians-Universität München
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Priority claimed from DE102010006182A external-priority patent/DE102010006182A1/de
Priority claimed from DE102010011564A external-priority patent/DE102010011564A1/de
Application filed by Ludwig-Maximilians-Universität München filed Critical Ludwig-Maximilians-Universität München
Publication of WO2011092028A1 publication Critical patent/WO2011092028A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
    • C09B5/62—Cyclic imides or amidines of peri-dicarboxylic acids of the anthracene, benzanthrene, or perylene series
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/109—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing other specific dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/22—Luminous paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom

Definitions

  • the present invention relates to polymers which contain organic chromophores and are suitable for the formation of nanoparticles.
  • Nanoparticles are gaining increasing interest in science and technology and are used in numerous technical products. In this case, water-dispersible nanoparticles are of particular importance.
  • the introduction of chromophores as light-absorbing structures turns these nanoparticles into functional optical materials. When fluorescent structures are used, the absorbed light energy is not converted into heat, but is available for further processes.
  • Organic materials are of particular interest as chromophores because they are characterized by a strong light absorption capacity, a broad and effective variation possibility and a special environmental compatibility.
  • ink is widely used in printing techniques, such as today's popular inkjet printers, and as writing ink.
  • chromophores homogeneously dissolved in water have two disadvantages, in particular for such applications.
  • the dyeing can be washed out of the material relatively easily, so that such printed products are not water-resistant and in general are also non-documentary.
  • the relatively small amount of dye applied adversely affects the light fastness of such products.
  • a much higher concentration of chromophores brings the use of pigments.
  • Nanoparticles occupy an intermediate position between homogeneous, molecularly disperse solutions and colloids with macroscopic particles, e.g. Pigments. Nanoparticles are much larger than molecular structures and therefore offer many of the advantages that are appreciated for pigment particles. On the other hand, they have many properties of homogeneously dissolved material. However, the use of nanoparticles often faces health and environmental concerns, especially with long-lived inorganic nanoparticles. This can be problematic in their use in outspoken mass-produced articles.
  • organic polymers which have hydroxyl groups as polar groups and thus are hydrophilic have proved to be ideal starting materials for nanoparticles.
  • Flexible organic polymers can form random coils that are present in the aqueous phase as nanoparticles.
  • polyvinyl alcohol hereinafter also referred to as PVA
  • PVA polyvinyl alcohol
  • M n 15000 of the PVA
  • nanoparticles with a particle size of 70 nm form in water.
  • perylene dyes are particularly attractive because they are characterized by their high light fastness, high fluorescence quantum yields and chemical resistance.
  • perylene-3,4 9,10-tetracarboxylic bisimides of the following structure (structure 1) in which the radicals R independently represent an alkyl radical, are high photostability, high absorption coefficient and strong fluorescence because of their remarkable properties interesting fluorescent dyes for
  • perylene dyes have been considered to be particularly suitable chromophores for fluorescent nanoparticles within the scope of the invention.
  • perylene dyes are usually sparingly soluble and are used as pigments.
  • Perylene dyes of the above structure 1 which are soluble in lipophilic media are, for example, those in which the two radicals R are secondary alkyl radicals, e.g. a hexylheptyl radical (compound 1a).
  • R secondary alkyl radicals
  • compound 1a a hexylheptyl radical
  • polyvinyl alcohol dissolves as pronounced polar polymer preferably in polar media, while the perylene have pronounced lipophilic properties.
  • polymers with polyvinyl alcohol and perylene dyes as chromophores can be prepared simply and in good yields using the techniques of the present invention.
  • the present invention accordingly provides a modified polyvinyl alcohol covalently linked to chromophoric moieties and which can form the nanoparticles described above.
  • the invention relates to a modified polyvinyl alcohol in the form of a compound which comprises repeating units of the formula I below and repeating units of the formula II below:
  • Y in formula II represents a chromophoric structural unit which absorbs light in the wavelength range from 350 to 3500 nm.
  • the invention provides nanoparticles formed from the modified polyvinyl alcohol according to the invention, as well as their colloidal solutions or nanoparticles in a liquid.
  • the invention also relates to inks in which the modified polyvinyl alcohol is used as a colorant.
  • Fig. 1 shows schematically the synthesis of the modified polyvinyl alcohol 3 from 1b and polyvinyl alcohol 2 (PVA, molecular weight of 15,000) under acid catalysis as polymer-analogous reaction.
  • the polymer chain in polymer 3 also contains unreacted OH groups of the polyvinyl alcohol.
  • 3a 50 mg 1b to 5 g
  • 3b 5 mg 1b to 5 g 2.
  • Fig. 2 shows the size distribution of the modified polyvinyl alcohol-based nanoparticles, as according to the reaction.
  • Fig. 1 emerge, in water.
  • Dashed line Polyvinyl alcohol (2) with a molecular weight of 15,000 (PVA 15,000).
  • Thick, solid line nanoparticles from the reaction of 5g PVA 15000 and 50 mg 1 b.
  • Thin, solid line nanoparticles from the reaction of 5g PVA 15000 and 5 mg 1 b.
  • Figure 3 shows UV / Vis absorption (left) and fluorescence spectra (right) of nanoparticles formed by the modified polyvinyl alcohol 3a in water (thick lines) compared to perylene dye 1a in chloroform (thin dashed lines) and compound 4 in chloroform ( thin, solid lines).
  • Fig. 4 shows UV / Vis absorption (left) and fluorescence spectra (right) of nanoparticles in water: 3a at various concentrations c.
  • FIG. 5 Synthesis of the Modified Polyvinyl Alcohol 1 1 According to the Invention
  • FIG. 6 Synthesis of the Modified Polyvinyl Alcohol 10 According to the Invention
  • Fig. 7 Size distribution of the nanoparticles in water, determined by the DLS method (dynamic light scattering), modified polyvinyl alcohol 10: thick, solid line; modified polyvinyl alcohol 11: thin, dashed line.
  • Figure 9 Solid UV / Vis absorption (left) and fluorescence spectra (right) of the modified polyvinyl alcohol 10 as drawn on paper (thick lines) compared to the modified polyvinyl alcohol 11 on paper (thin, dashed lines).
  • the invention relates to a modified polyvinyl alcohol in the form of a compound which comprises repeating units of the above formula I and repeating units of the above formula II.
  • the square brackets indicate in this and the following formulas according to general practice in the field of polymer chemistry repeating units that are present within a polymer.
  • the bonds that are broken by the bracket are those with which the repeating units are bound to adjacent units.
  • Y in formula II is a chromophoric moiety which absorbs light in the wavelength range of 350 to 3500 nm, preferably in the wavelength range of 400 to 1000 nm and most preferably in the range of 400 to 750 nm , Preferably, an absorption maximum is present within the specified wavelength range.
  • the absorption spectrum of the modified polyvinyl alcohol according to the invention and the covalently bound chromophore residues is determined with a commercial UV / Vis spectrometer.
  • Suitable chromophoric structural units Y form e.g. covalently bonded moieties formed from a nitro dye, nitrosyl dye, diphenylmethane dye, triphenylmethane dye, acridine dye, indigoid dye, quinoidal vat dye, indigosol, sulfur dye, stilbene dye, xanthene dye, azine dye, methine dye, quinoneimine, anthraquinone dye, thiazole dye, azo dye, phthalocyanine, porphyrins, squarylium dye or a dye comprising a perylene skeleton.
  • a structural unit Y comprising a perylene skeleton is preferred.
  • the sum of the number of units of the formula I and of the formula II in the compound according to the invention is generally in the range from 5 to 10,000, preferably in the range from 100 to 5000, in particular in the range from 100 to 2000.
  • the ratio of the total number of units of the formula I to those of the formula II, ie mol (I) / mol (II) is typically in the range of 1 to 200, in particular from 10 to 100.
  • the modified polyvinyl alcohol of this embodiment of the invention may comprise, in addition to the units of formulas I and II, other polymerized units.
  • the units of formulas I and II provide at least 80 mol%, more preferably at least 90 mol% and especially at least 95 mol%, based on the total number of polymerized units of the modified polyvinyl alcohol.
  • Units that may still be present in addition to the units of the formulas I and II are not particularly limited, provided that they can form a copolymer with the units of the formulas I and II. These may be, for example, units in which the OH group shown in formula I is esterified.
  • ester-forming acids are formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic, caprylic, capric, lauric, palmitic and stearic acids, their unsaturated variants such as oleic, linoleic and linolenic acid, lactic acid, the natural amino acids, benzoic acid, 1-naphthoic acid and 2-naphthoic acid, nicotinic acid and isonicotinic acid, with units containing acetic acid, due to the production of the polyvinyl alcohol, most frequently occurring in the modified polyvinyl alcohol of the present invention.
  • the modified polyvinyl alcohol of the present invention very particularly preferably consists of units of the formulas I and II or consists essentially of units of the formulas I and II.
  • the term "consists essentially of” is understood to mean that apart from the units of the formulas I and II, only a small amount of units may be present in which the OH group of formula I is esterified by an acetyl group Such groups may be present in a commercially available polyvinyl alcohol, preferably as starting material for the modified polyvinyl alcohol of the present invention
  • a "small amount” here typically means a maximum of 5 mol%, based on the total number of polymerized units.
  • a preferred embodiment of the invention is a modified polyvinyl alcohol of the formula III
  • Y is as defined above.
  • the indices m and n independently represent integers in the range of 1 to 1000, preferably 10 to 350.
  • the sum m + n is preferably in the range from 5 to 2000, particularly preferably from 100 to 1000.
  • the ratio m / n is preferably in the range from 1 to 200, in particular from 10 to 100. It should be understood that in the above notation of formula III is a common schematic in the field of polymer chemistry, which also describes alternating consequences of the repeating units contained.
  • a modified polyvinyl alcohol is provided in the form of a compound which comprises repeating units of the following formula I and repeating units of the following formula IIa, IIb and / or IIc:
  • radicals R 1a , R 1b , R 1c , R 2b and R 2c , the radicals R 3a , R 4a , R 53 , R 6a , R 3b , R 4b , R 5b , R 3c , R 4c and R 50 which Radicals R 7b and R 2c are identical or different in the formulas IIa, IIb and Ilc and independently of one another in each occurrence represent hydrogen or a linear alkyl radical having at least one and at most 37 C atoms or one of the halogen atoms F, Cl, Br or I.
  • 2,3-, 2,6- or 2,7-naphthalene radical in which one or two CH groups can be replaced by nitrogen atoms, and a divalent anthracene radical (for example 1, 2, 1, 3,
  • CH 2 groups in which a hydrogen atom is replaced as described above, may also be linked together to form a ring, ie instead of carrying substituents, the free valencies of the methine groups or the quaternary C atoms may be linked in pairs, so that Rings are formed, such as cyclohexane rings.
  • the radical R 12c may furthermore have the formula Vc:
  • a CH 2 unit which can be replaced by definition can also be a terminal unit in an alkyl group / an alkyl chain, ie a corresponding unit within a -CH 3 group.
  • a divalent ring or a divalent ring system which can replace a CH 2 unit for example, divalent phenyl radicals or 1, 2, 1, 3 or 1, 4-phenyl
  • one of the two valences can also be saturated with an H atom.
  • This also includes the situation where, starting from a methyl group, by replacing a formal CH 2 unit contained therein, a phenyl group, pyridine group, thiophene group, etc.
  • the radicals R 1a , R 1b , R c , R 2b and R 2c , the radicals R 3a , R 4a , R 5a , R 6a , R 3b , R 4b , R 5 , R 3c , R 4c and R 5c and R 7 are hydrogen or a linear alkyl group having at least one and at most 37 C atoms.
  • Phenyl radical divalent naphthalene radical (eg 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-naphthalene radical), and a divalent anthracene radical (eg 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10, 2,3, 2,6, 2,7, 2,9, 2,10 or 9,10-anthracene).
  • divalent naphthalene radical eg 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10, 2,3, 2,6, 2,7, 2,9, 2,10 or 9,10-anthracene
  • the radicals R 3a , R 43 , R 53 , R 6a , R 3b , R 4b , R 5b , R 3c , R 40 and R 50 and the radical R 7b are hydrogen or an alkyl radical which may be branched, and containing from 1 to 20 carbon atoms, most preferably hydrogen.
  • the radical R 12c is a radical of the formula Vc, where the radicals R 3c , R 14c , R 5c , R 16c and R 7c are as defined above:
  • the radicals R 13c , R 14c , R 15c , R 16c and R 17c are hydrogen or a linear alkyl radical having at least one and at most 37 C atoms.
  • divalent naphthalene radical eg 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1 , 8-, 2,3-, 2,6- or 2,7-naphthalene radical
  • divalent anthracene radical eg 1, 2,
  • 1,4-phenyl radical a divalent thiophene radical (for example 2,3-, 2,4-, 2,5- or 3,4-thiophene radical), a divalent naphthalene radical (for example 1, 2, 1, 3, 1, 4 -, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-naphthalene radical), and a divalent anthracene radical (eg 1, 2, 1, 3, 1, 4,
  • radicals R 1 c , R 14c , R 15c , R 16c and R 17c are hydrogen or an alkyl radical which may be branched and which contains 1 to 20 carbon atoms, most preferably hydrogen.
  • CH 2 groups in which a hydrogen atom has been replaced as described above may also be linked together to form a ring, ie instead of carrying substituents, the free valences of the methine groups or of the quaternary C atoms may be linked in pairs, so that rings arise, such as cyclohexane rings.
  • a divalent phenyl radical eg 1,2-, 1,3- or 1,4-phenyl
  • the unit X a most preferably represents one to 12 CH 2 units in which one or more may be replaced independently of one another by a divalent phenyl radical (eg 1,2-, 1,3- or 1,4-phenyl radical).
  • a divalent phenyl radical eg 1,2-, 1,3- or 1,4-phenyl radical.
  • the linker unit X b is preferably a divalent radical of the formula IVb, wherein the radicals R 8b , R 9b , R 10b and R 11b are the same or different and independently at each occurrence represent hydrogen or a linear Aikylrest having at least one and at most 37 C-atoms or one of the halogen atoms F, Cl, Br or I.
  • CH 2 groups in which a hydrogen atom is replaced as described above, may also be linked together to form a ring, ie instead of carrying substituents, the free valencies of the methine groups or the quaternary C atoms may be linked in pairs, so that Rings are formed, such as cyclohexane rings.
  • the radicals R 8b , R 9b , R 0b and R 11b are hydrogen or a linear alkyl radical having at least one and at most 37 C atoms.
  • a divalent phenyl radical eg 1, 2, 1, 3 or 1, 4-phenyl radical
  • divalent naphthalene radical eg 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2 , 7-naphthalene radical
  • a divalent anthracene radical eg 1, 2, 1, 3, 1, 4, 1, 5, 1,
  • the linker unit Xc preferably represents a divalent radical of the formula IVc
  • radicals R 8c , R 9 °, R 10c and R 11c are identical or different and independently of one another in each occurrence represent hydrogen or a linear alkyl radical having at least one and at most 37 C atoms or one of the halogen atoms F, Cl , Br or I.
  • CH 2 groups in which a hydrogen atom is replaced as described above, may also be linked together to form a ring, ie instead of carrying substituents, the free valencies of the methine groups or the quaternary C atoms may be linked in pairs, so that Rings are formed, such as cyclohexane rings.
  • the radicals R 8c , R 9c , R 0c and R 11c are hydrogen or a linear alkyl radical having at least one and at most 37 C atoms.
  • Phenyl radical divalent naphthalene radical (eg 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-naphthalene radical), and a divalent anthracene radical (eg 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10, 2,3, 2,6, 2,7, 2,9, 2,10 or 9,10-anthracene).
  • divalent naphthalene radical eg 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10, 2,3, 2,6, 2,7, 2,9, 2,10 or 9,10-anthracene
  • radicals R 8c , R 9c , R 10c and R 11c are hydrogen or an alkyl radical which may be branched and which contains 1 to 20 carbon atoms, most preferably hydrogen.
  • the units I may occur together with a single type of units IIa, IIb or Ilc, or several types of units IIa, IIb and Ilc may be combined in the modified polyvinyl alcohol with the units I. Preference is given to compounds which have units I together with units IIb and those which have units I together with units Ilc.
  • the sum of the number of units of the formula I and of the formulas IIa, IIb and IIc in the compounds according to the invention is generally in the range from 5 to 10,000, preferably in the range from 100 to 5000, in particular in the range from 100 to 2000.
  • the ratio the total number of units of formula I to those of formula IIa, IIb and Ilc, ie mol (I) / (mol (IIa) + mol (IIb) + mol (Ilc)) is preferably in the range of 1 to 200, especially 10 to 100.
  • the modified polyvinyl alcohol of this embodiment of the invention may comprise, in addition to the units of the formulas I and IIa, IIb or IIc, other polymerized units. However, it is preferred that the units of the formulas I and IIa, IIb or IIc provide at least 80 mol%, more preferably at least 90 mol% and in particular at least 95 mol%, based on the total number of polymerized units of the modified polyvinyl alcohol. Units which may still be present in addition to the units of the formulas I and II are not particularly limited, provided that they can form a copolymer with the units of the formulas I and IIa, IIb or IIc. These may be, for example, units in which the OH group shown in formula I is esterified.
  • ester-forming acids are formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic, caprylic, capric, lauric, palmitic and stearic acids, their unsaturated variants such as oleic, linoleic and linolenic acid, lactic acid, the natural amino acids, benzoic acid, 1-naphthoic acid and 2- Naphthoic acid, nicotinic acid and isonicotinic acid, wherein acetyl group-containing units, due to the production of the polyvinyl alcohol, most frequently occur in the modified polyvinyl alcohol of the present invention.
  • the modified polyvinyl alcohol of the present invention consists of units of the formulas I and IIa, of units of the formulas I and IIb or of units of the formulas I and IIc or consists essentially of these units.
  • the term "consists essentially of” is understood to mean that apart from the units mentioned, only a small amount of units may be present in which the OH group of the formula I is esterified by an acetyl group In this case, a "small amount” typically means a maximum of 5 mol%, based on the total number of polymerized units.
  • the indices m and n independently represent integers in the range from 1 to 1000, preferably 10 to 350.
  • the sum m + n is preferably in the range from 5 to 2000, more preferably in the range from 100 to 1000.
  • the ratio m / n is preferably in the range from 1 to 200, in particular from 10 to 100.
  • modified polyvinyl alcohol in any of the foregoing embodiments of the present invention may be a linear polymer or, in the presence of suitable higher functional units, may have one or more branches in the polymer chain.
  • linear polymers are preferred.
  • the modified polyvinyl alcohol according to the invention is capable of forming nanoparticles in polar solvents and solvent mixtures. Colloidal solutions or nanoparticles of such nanoparticles form spontaneously after introduction of the modified polyvinyl alcohol in the solvent.
  • Particularly suitable solvents for the formation of the nanoparticles are water or aqueous solvents. Water is particularly preferred.
  • aqueous solvents here are referred solvent mixtures containing a volume fraction (Vol./Vol.) Of water of at least 50%, preferably at least 70%, in particular at least 90%, based on the total volume of the solvent.
  • nanoparticles are particles whose diameter is in the range from 1 to 1000 nm.
  • nanoparticles typically have size distributions determined by means of dynamic laser scattering (DLS) on a nanodivision of the nanoparticles in water, with a maximum in the range from 10 to 1000 nm, preferably from 10 to 500 nm
  • DLS dynamic laser scattering
  • bimodal or multimodal size distributions may occur, in which case it is preferable that all maxima of the size distribution are within the above ranges.
  • the nanoparticles can be colloidally dissolved in liquids, preferably water or aqueous solutions, but also in polymeric solids.
  • liquids and solids-soluble nanoparticles due to their size, occupy an intermediate position between solid dispersions on one side and molecularly disperse solutions on the other side.
  • colloidal solutions or equivalently as nanodivisions are referred to herein as colloidal solutions or equivalently as nanodivisions.
  • the preparative accessibility of the modified polyvinyl alcohols of this invention may be considered a particular advantage over other colorants, such as the cyclophan of structure 4.
  • Another advantage is, for example, in the case of compounds according to the invention having chromophoric structural units of perylene dyes in the readily achievable water solubility or water dispersibility of the substance.
  • the aqueous phase is easily accessible to the usually highly lipophilic perylene dyes. Since the link between polymer and chromophore is covalent, there is also no risk of segregation or separation.
  • the aqueous phase offers many advantages for the modified polyvinyl alcohols according to the invention, because it is not only characterized by its low cost and easy accessibility, but is also incombustible and has a very large heat capacity.
  • the chromophene-modified polyvinyl alcohols of the present invention can be used, for example, as colorants for dyeing purposes, also for decorative and artistic purposes. Specific examples are glue colors and related colors such as watercolor paints, water colors, ink jet printer colors, paper colors, printing inks, inks and inks, and other colors for painting and writing.
  • paints can be used as colorants in paints, as colorants in paints, preferably synthetic resin paints such as acrylic or vinyl resins, polyester paints, novolaks, nitrocellulose paints (nitro lacquers) or natural products such as zapon lacquer, shellac or Qi lacquer (Japanese lacquer or Chinese varnish or East Asian varnish), for bulk dyeing of polymers such as polyvinyl chloride, polyvinylidene chloride, polyacrylic acid, polyacrylamide, polyvinylbutyral, polyvinylpyridine, cellulose acetate, nitrocellulose, polycarbonates, polyamides, polyurethanes, polyimides, polybenzimidazoles, melamine resins, silicones such as polydimethylsiloxane, polyesters , Polyethers, polystyrene, polydivinylbenzene, polyvinyltoluene, polyvinylbenzyl chloride, polymethyl methacrylate, polyethylene, polypropylene, poly
  • the modified polyvinyl alcohols of the present invention may also be used for coloring natural products such as paper, wood, straw or natural fiber materials such as wool, hair, animal hair, bristles, cotton, jute, sisal, hemp, flax or their transformation products such as the viscose fiber , Nitrate silk or copper rayon (rayon), as mordant dyes, eg for coloring natural products, examples are paper, wood, straw, or natural fiber materials such as wool, hair, animal hair, bristles, cotton, jute, sisal, hemp, flax or their transformation products such as
  • the viscose fiber, nitrate silk or copper rayon (rayon) preferred salts for pickling are aluminum, chromium and iron salts.
  • modified polyvinyl alcohols of the present invention are marking, safety and display purposes, especially taking into account their fluorescence, such as colorants or fluorescent colorants for signal colors, preferably for highlighting logos and drawings or other graphic products, for characterizing Signs and other objects and in display elements for a variety of display, reference and marking purposes, where a particular visual color impression is to be achieved, for passive display elements, traffic signs, such as traffic lights for security marking purposes, the large chemical and photochemical Resistance and possibly also the fluorescence of the substances of importance, this is preferred for checks, check cards, banknotes, coupons, documents, identity documents and the like, in which a special, unmistakable color impression is to be achieved.
  • fluorescence such as colorants or fluorescent colorants for signal colors, preferably for highlighting logos and drawings or other graphic products, for characterizing Signs and other objects and in display elements for a variety of display, reference and marking purposes, where a particular visual color impression is to be achieved, for passive display elements, traffic signs, such as traffic lights for security marking purposes, the large
  • the modified polyvinyl alcohols of the present invention are furthermore suitable for marking articles in order to enable machine recognition of these objects via fluorescence; preferred is the automatic recognition of objects for sorting, eg also for the recycling of plastics, as fluorescent dyes for machine-readable markings; preferred are alphanumeric imprints or barcodes, as colorants or fluorescence colorants in display, illumination or image converter systems, in which the excitation by electrons, ions or UV radiation takes place, for example in fluorescent displays, Braun tubes or in fluorescent tubes, for tracer purposes, eg in biochemistry, medicine, technology and natural sciences, as dyes or fluorescent dyes in chemiluminescent systems, eg in chemiluminescent light rods, in luminescence immunoassays or other luminescence detection methods and as a material for leak testing our systems.
  • the modified polyvinyl alcohols of the present invention can be used as functional materials, such as in data storage, preferably in optical storage, such as the CD or DVD disks, in OLEDS (organic light-emitting diodes), in photovoltaic systems, as colorants in electrophotography eg for dry copying systems (Xerox process) and laser printers ("non-impact printing"), for the frequency conversion of light, eg to make longer-wave visible light from short-wave light, as starting material for superconducting organic materials, as fluorescent colorant in scintillators, as dyes or fluorescence colorants in optical Lichtsammeisystemen, such as the fluorescent solar collector or fluorescence-activated displays, in liquid crystals for deflecting light, as a colorant or fluorescent colorant in cold light sources for light-induced polymerization for the preparation of plastics, as dyes or fluorescent color Materials for testing materials, eg in the production and testing of semiconductor circuits and semiconductor components, as colorants or fluorescent colorants in photoconductors, as
  • an article of the present invention is also an ink comprising one or more modified polyvinyl alcohols as defined above.
  • the term ink herein includes compositions in which the modified polyvinyl alcohol is present alone or as a mixture of different compounds in a liquid solvent. It preferably comprises compositions in which the modified polyvinyl alcohol forms nanoparticles in the solvent. Such compositions are also referred to herein as "nanoinks.” These nanoparticles are generally in the form of a nano-distribution in the solvent.
  • the chromophene-modified polyvinyl alcohols which have a perylene unit have advantageous properties, and in particular the modified polyvinyl alcohols having units of the formula IIa, IIb or IIc or the modified polyvinyl alcohols of the formulas IIIa, IIIb or None. Because of their light absorption properties, the modified polyvinyl alcohols having units of the formula IIb or IIc or the modified polyvinyl alcohols of the formulas IIIb or IIIc are particularly suitable as colorants for inks, since they produce dark shades.
  • Suitable solvents for these inks are, in particular, substances or mixtures of substances which, at standard application temperatures, e.g. over a range of 5 ° C to 40 ° C, preferably from 5 ° C to 80 ° C, in liquid form.
  • Particularly advantageous solvents are water or aqueous solvents, in particular water.
  • the modified polyvinyl alcohols of the present invention typically spontaneously form nanoparticles.
  • aqueous solvents here are referred solvent mixtures containing a volume fraction (Vol./Vol.) Of water of at least 50%, preferably at least 70%, in particular at least 90%, based on the total volume of the solvent.
  • the ink of the invention is suitable for both printing and writing purposes. It can be advantageously used in devices in which the ink is passed through narrow fluid channels.
  • the modified polyvinyl alcohols of the invention tend Unlike pigment particles, including in the form of nanoparticles, they do not clog these fluid channels.
  • a preferred application is machine printing, especially ink jet printers.
  • the inks according to the invention can also be used in spring writing instruments and drawing instruments (ink fountain pen, glass pen or corresponding fountain pen), ballpoint pen writing and drawing instruments (ballpoint pens), or felt-writing and drawing instruments (felt-tip pens).
  • the ink can be used in high pressure, intaglio and in planographic printing;
  • the planographic printing is of particular interest because the modified polyvinyl alcohols generally have hydrophilic properties and are therefore suitable for special interactions with surfaces, as required in planographic printing. Further interesting fields of application result from the fluorescence properties of the inks or the resulting colorations.
  • NIR near infrared range
  • machine-readable documents can advantageously be produced.
  • a modified polyvinyl alcohol in which both the light absorption and the fluorescence wavelength are in the visible range can be used, for example, for visual security markings.
  • the concentration of the modified polyvinyl alcohols in the ink of the present invention is not particularly limited. Typical amounts are in the range of 0.01 g / l to 10 g / l, preferably 0.03 to 5 g / l.
  • a single type of modified polyvinyl alcohol may be used which may be modified with one or more different chromophores. It is also possible to use mixtures of different types of modified polyvinyl alcohols.
  • the ink according to the invention preferably contains exclusively as the colorant the modified polyvinyl alcohols, and very particularly preferably only the modified polyvinyl alcohols having units of the formula IIb or IIc or the modified polyvinyl alcohols of the formulas IIIb or IIIc.
  • no pigments i. in the solvent used insoluble colorant with particle sizes in the range above 1 ⁇ included.
  • conventional inks may also be added to the ink, e.g. Viscosity modifier (thickener), preservative or flow or wetting property improver.
  • the colored nanoparticles according to the invention can be applied to surfaces such as paper or alumina.
  • surfaces such as paper or alumina.
  • 10 is applied from aqueous phase on paper, then results in a strong blue color.
  • the resulting color on the substrate can surprisingly be removed neither with water nor with ethanol nor with DMF or DMF / water, nor is it possible to bleach the dye by concentrated sodium hypochlorite solution (25%).
  • concentrated sodium hypochlorite solution 25%
  • the solid fluorescence excitation spectrum is bathochromically shifted in relation to that of the nanoparticles in solution, while the fluorescence spectrum is almost congruent with the spectrum of the particles in water; See Figure 9. It can be seen that much of the fluorescence extends into the NIR region. This makes it easy to read out with machines.
  • the dye 11 also draws on paper, and it does not succeed after drying here to remove a stain with water, ethanol or DMF or bleach with concentrated hypochlorite solution. The staining with 11 has a clear red nuance with respect to 10, and there is a visually striking red fluorescence.
  • chromophoric compounds also referred to as
  • Aldehydes are used in aldehyde form and react with polyvinyl alcohol .
  • Corresponding aldehydes have the general formula VI, wherein Y is as defined above:
  • Perylene dyes which are used in a preferred embodiment of the invention have as aldehydes the formula via, all variables, including their preferred embodiments, being as defined above (see formula IIa):
  • Perylene dyes which are used in further preferred embodiments of the invention can react as aldehydes of the formula VIb or VIc, wherein here too all variables, including their preferred embodiments, are as defined above (see formulas IIb and IIc, respectively).
  • perylene-aldehydes of formula VIb e.g. from a compound having a perylene-3,4: 9,10-tetracarboxylic bisimide skeleton of the above-mentioned structure 1 as a chromophore.
  • the compound 1a can be converted into the imidazole derivative 8 with sodium amide and benzonitrile. Its NH group can be alkylated with a nucleophile, such as benzyl bromide, which is substituted with an aldehyde protected as an ethylene acetal.
  • aldehyde 9 As a synthetic building block for the reaction with polyvinyl alcohol to 11.
  • a benzonitrile 5 is used, which is provided with a protected as ethylene acetal aldehyde function. This results in the reaction with sodium amide and 1a and subsequent deprotection in an analogous manner, the aldehyde 6, which can also react with polyvinyl alcohol.
  • the aldehyde-form chromophores can react with polyvinyl alcohol (schematically as compound 2 in FIG. 1).
  • polyvinyl alcohol a commercially available polyvinyl alcohol can be used.
  • the number average molecular weight of the PVA may, for example, be between 200 and 500,000, preferably between 10,000 and 200,000. It is preferred to use a fully hydrolyzed PVA whose acetyl groups have been removed as far as possible.
  • the reaction between the aldehydes and the polyvinyl alcohol preferably takes place in a suitable solvent, such as DMSO, as reaction medium and under acid catalysis, for example by addition of 4-toluenesulfonic acid as catalyst.
  • the reaction with the corresponding acetal of the polyvinyl alcohol (compare Formulas II including IIa-c and III including IIa-c above, by way of example compounds 3, 10 and 11 in Fig. 1, Fig. 5 and Fig. 6) is surprisingly smooth.
  • the material obtained in this way shows good water solubility and usually forms strongly fluorescent solutions, even if the starting aldehyde is insoluble in water.
  • Two types of nanoparticles with frequency maxima at two different diameters may form in this reaction, for example in the case of the reaction shown at 70 and 350 nm in FIG. 1, see FIG. 2.
  • a strong staining of the aqueous phase by the polymer clearly shows the linkage of the polyvinyl alcohol with the chromophore;
  • the colored components of the polymer can not be washed out by lipophilic media such as chloroform - this demonstrates the covalent linkage of the hydrophilic polymer chain with the chromophoric compound.
  • the chromophore-polymer combination results in particles in water with a diameter that is typically in the scale range of nanoparticles, but greater than that of pure polyvinyl alcohol in water; See Figure 2. Further evidence for the nanometer dimension of the particles is the fact that they can not be filtered off with a D5 glass frit.
  • FIG. 2 shows two maxima, of which the maximum at approx. 70 nm is presumably due to unreacted polyvinyl alcohol particles, since this size distribution is also found in pure polyvinyl alcohol in water, while the second, newly added maximum at 350 nm the polyacetal 3 (Figure 1) is assigned. This is also shown by the fact that the second maximum increases at the expense of the first, if the proportion of perylenaldehyde used for the acetalization is increased, as can also be seen from FIG. 2.
  • FIG. 7 shows the size distribution for nanoparticles obtained according to the reactions in FIGS. 5 and 6 and containing the polymeric compounds 10 and 11. One finds for 10 a maximum at 25 nm and a second at about 100 nm; this corresponds to the behavior of 3.
  • the substance is therefore particularly suitable as a dark fluorescent ink, in which the fluorescence should be seen under normal lighting.
  • the UV / Vis absorption and fluorescence spectra are shown in FIG.
  • the spectra differ significantly from the spectra of the chromophores in homogeneous organic solution.
  • the fluorescence spectra are long-wavelength shifted, while the absorption spectra are hypsochromic shifted. This is an indication that an aggregation of chromophores occurs, with their skewed arrangement is likely.
  • the UVA / is absorption spectrum of the nanoparticles of compound 3 of Figure 1 in water does not correspond to the spectrum of perylene dyes, e.g. 1a in lipophilic media, but rather the perylene cylophane 4; see FIG. 3.
  • the structure of the spectra hardly changes, as can be seen, for example, from the spectra of FIG. 4.
  • the similarity of the spectra of the nanoparticles to the spectrum of a solution of compound 4 indicates that the chromophores are preferably in direct proximity to each other. Also, a reaction of the polyvinyl alcohol even with only very small proportionate amounts of the dye to completely analogous spectra.
  • the fluorescence quantum yield of 3a at 37% is comparable to the fluorescence quantum yield of 4 at 40%.
  • the strong bathochromic shift of the fluorescence spectrum compared to monochromophoric perylene dyes and the resulting increase in the Stokes shift are extremely interesting for practical applications of the nanoparticles, since this reduces the reabsorption of the fluorescence light. This is important for laser applications as well as for analytical applications or for applications in fluorescence solar collectors.
  • spectroscopic data were obtained to characterize the following exemplary compounds as with the following devices: IR spectra: FT 1000; UV / Vis spectra: Varian Cary 5000; Fluorescence spectra: Varian Eclipse; NMR spectroscopy: Varian Vnmrs 600 (600 MHz); Mass spectrometry: Finnigan MAT 95.
  • UV / Vis (3a, water): * ( ⁇ /) 470 (2.38), 495 (3.19), 539 nm (1.86).
  • UV / Vis (3b, water): / * (£ e /) 469 (1.19), 494 (1.50), 537 nm (1.07).
  • Fluorescence (3a, water): 549 (88),
  • O-bisimide (1a, 200 mg, 0.265 mmol) and sodium amide (0.200 g, 5.13 mmol) were heated in 4- [1,3] dioxolan-2-yl-benzonitrile (5.5 g) at 165 ° C for 5 h (Blue color), allowed to cool, evaporated to dryness and taken up with a 1: 1 mixture of 2N aqueous HCl and chloroform (300 mL).
  • IR (ATR): v 3291.4 br, 2952.7 m, 2920.2 s, 2853.1 s, 1699.9 s, 1681.1 vs, 1649.8 s, 1637.0 s, 161 1.5 m, 1592.2 vs, 1575.7 m, 1537.8 w, 1495.4 w, 1465.8 w, 1436.5 w, 1414.0 w, 1388.0 w, 1340.6 vs, 1305.4 m, 1259.1 m, 1213.4 m, 1 172.8 w, 1 122.8 w, 1060.1 w, 1015.9 w, 967.4 w, 871.2 vw, 845.7 w, 813.9 m, 753.8 m, 729.6 wcm -1 .
  • IR (ATR): v 2953.6 m, 2923.6 s, 2854.9 m, 1687.8 vs, 1641.9 vs, 1591.3 s, 1530.0 w, 1485.8 w, 1465.3 w, 1424.3 w, 1406.1 vw, 1377.7 vw, 1358.1 vw, 1331.8 vs, 1253.0 m, 1209.3 w, 1 181.7 w, 1 107.2 w, 1027.8 vw, 931.4 vw, 872.1 w, 843.5 w, 809.2 m, 772.3 w, 749.5 m, 724.0 vw, 702.1 vw cm -1 .

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Abstract

La présente invention concerne un alcool polyvinylique modifié qui est lié par covalence à des motifs constitutifs chromophores et qui est susceptible de former des nanoparticules, en particulier un alcool polyvinylique modifié sous la forme d'un composé présentant des motifs de répétition de formule (I) suivante et des motifs de répétition de formule (II) suivante, Y dans la formule (Il) représentant un motif constitutif chromophore.
PCT/EP2011/000398 2010-01-29 2011-01-28 Nanoparticules et nanoencres WO2011092028A1 (fr)

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DE102010006182A DE102010006182A1 (de) 2010-01-29 2010-01-29 Fluoreszierende Nanopartikel durch eine polymeranaloge Reaktion von Polyvinylalkohol
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DE102010011564.9 2010-03-16
DE102010011564A DE102010011564A1 (de) 2010-03-16 2010-03-16 Organische Nanotinte - Fluoreszenztinte

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CN114105953A (zh) * 2021-11-05 2022-03-01 常州大学 一种可用于检测水中甲醇含量的荧光分子及其制备方法与应用

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014083011A2 (fr) * 2012-11-27 2014-06-05 Ludwig-Maximilians-Universität München Colorants à base de péri-arylène à substitution amino
WO2014083011A3 (fr) * 2012-11-27 2014-07-24 Ludwig-Maximilians-Universität München Colorants à base de péri-arylène à substitution amino
CN114105953A (zh) * 2021-11-05 2022-03-01 常州大学 一种可用于检测水中甲醇含量的荧光分子及其制备方法与应用
CN114105953B (zh) * 2021-11-05 2022-08-26 常州大学 一种可用于检测水中甲醇含量的荧光分子及其制备方法与应用

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