EP2430005A1 - Polymerisierbare benzoxazin-verbindungen mit grenzflächenaktiven bzw. oberflächenaktiven eigenschaften - Google Patents

Polymerisierbare benzoxazin-verbindungen mit grenzflächenaktiven bzw. oberflächenaktiven eigenschaften

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Publication number
EP2430005A1
EP2430005A1 EP10720383A EP10720383A EP2430005A1 EP 2430005 A1 EP2430005 A1 EP 2430005A1 EP 10720383 A EP10720383 A EP 10720383A EP 10720383 A EP10720383 A EP 10720383A EP 2430005 A1 EP2430005 A1 EP 2430005A1
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EP
European Patent Office
Prior art keywords
benzoxazine
carbon atoms
formula
polymerizable
compounds
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
EP10720383A
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German (de)
English (en)
French (fr)
Inventor
Andreas Taden
Stefan Kreiling
Rainer SCHÖNFELD
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP2430005A1 publication Critical patent/EP2430005A1/de
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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
    • 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
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
    • C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
    • C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D265/16—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with only hydrogen or carbon atoms directly attached in positions 2 and 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/54—Aqueous solutions or dispersions

Definitions

  • the present invention relates to polymerizable benzoxazine compounds having surface-active or surface-active properties which comprise at least one polyalkylene oxide structural element, and to a process for the preparation of said compounds.
  • the invention further relates to benzoxazine (co) polymers comprising at least one of said benzoxazine compounds in polymerized form.
  • Benzoxazine (co) polymers generally have a high glass transition temperature and are characterized by their good electrical properties and their positive fire protection behavior. Due to the lack of solubility in aqueous media, both the known benzoxazine (co) polymers and conventional polymerizable benzoxazine compounds can generally not be applied in the form of aqueous solutions, emulsions or dispersions.
  • German patent application DE102005046546 A1 teaches curable mixtures based on benzoxazines whose environmental compatibility has been increased by the fact that the substances mentioned can be diluted with water. Nevertheless, there is still a need to improve or increase the environmental compatibility and the potential use of polymerizable benzoxazine compounds and the corresponding benzoxazine (co) polymers by improving their solubility in aqueous media.
  • the aim of the present invention was therefore to provide polymerizable benzoxazine compounds and the corresponding benzoxazine (co) polymers which have a high solubility and / or good dispersibility in aqueous solutions and which can therefore be applied without the use of questionable organic solvents.
  • a first aspect of the present invention is a polymerizable benzoxazine compound of the general formula (I)
  • q is formula (I) wherein q is an integer of 1 to 4, n is a number of 2 to 20,000, R in each repeating unit is independently selected from hydrogen or linear or branched, optionally substituted alkyl groups comprising 1 to 8 carbon atoms
  • R 1 is a covalent bond or is a divalent linking group containing 1 to 100 Includes carbon atoms
  • R 2 is selected from hydrogen, halogen, alkyl and alkenyl, or R 2 is a divalent radical which renders the benzoxazine structure a corresponding naphthoxazine structure;
  • a further subject of the present invention is a process for preparing the polymerizable benzoxazine compound according to the invention, comprising the step of reacting at least one phenolic compound of the general formula (IV),
  • benzoxazine (co) polymer comprising in polymerized form at least one polymerizable benzoxazine compound according to the invention.
  • the polymerizable benzoxazine compounds and the benzoxazine (co) polymers of the present invention generally have a good solubility in aqueous media, which is why the substances mentioned can be used in water-based formulations that are substantially free of organic solvents.
  • polymerizable benzoxazine compounds of the present invention have surfactant properties, and therefore, these compounds can be used as surfactants in a variety of applications.
  • benzoxazine (co) polymers of the present invention also exhibit good interaction with a variety of different surfaces, whereby the polymers mentioned can be used to coat or modify surfaces.
  • compositions or detergents and cleaning agents as well as textile treatment compositions which comprise at least one polymerizable benzoxazine compound and / or at least one benzoxazine (co) polymer and the use of said benzoxazine compounds as surfactant, in particular as nonionic surfactant ,
  • the present invention is the use of the benzoxazine (co) polymers according to the invention as sizing agents for fibers, coating compositions, for example as antibacterial coating compositions, as corrosion inhibitors and / or for the improvement of Removal of dirt or reducing the resusability on textile or hard surfaces.
  • a final object of the present invention is a process for the treatment and / or coating of surfaces, wherein at least one surface is treated with at least one polymerizable benzoxazine compound according to the invention and / or with at least one benzoxazine (co) polymer according to the invention.
  • the divalent organic compound group R 1 in formula (I) preferably comprises 2 to 50, more preferably 2 to 25 and especially 2 to 20 carbon atoms. Further, the divalent organic compound group R 1 may be selected from each of linear or branched, optionally substituted alkylene groups comprising 1 to 15 carbon atoms, wherein the alkylene groups are optionally interrupted by at least one heteroatom selected from oxygen, sulfur or nitrogen.
  • the term "interrupted" means that in a divalent alkylene group at least one non-terminal carbon atom of the group mentioned is replaced by a heteroatom, the heteroatom preferably being selected from * - S- * (sulfur), * - O- * (oxygen), and * - NR a - * (nitrogen), wherein R a is in particular hydrogen or a linear or branched, optionally substituted alkyl groups having 1 to 15 carbon atoms.
  • the divalent organic linking group R 1 is selected from alkylene groups comprising 2 to 8 C atoms.
  • R 1 is selected from linear alkylene groups comprising 2 to 6, especially 2 or 3 carbon atoms, such as ethylene, propylene, butylene, pentylene and hexylene groups.
  • R 1 in formula (I) is a covalent bond.
  • the divalent organic linking group R 1 may comprise at least one arylene group and / or at least one biphenylene group, each preferably containing from 6 to 12 carbon atoms.
  • the arylene groups and biphenylene groups may be substituted or unsubstituted, suitable substituents being selected, for example, from alkyl, alkenyl, halogen, amine, thiol, carboxyl and hydroxyl groups.
  • at least one carbon atom of the aromatic ring system of said groups can be replaced by a heteroatom, wherein the heteroatom is preferably selected from oxygen, nitrogen and sulfur.
  • R in each repeating unit is independently selected from hydrogen or methyl.
  • the polymerizable benzoxazine compounds of the general formula (I) are selected from compounds of the general formula (II)
  • n or x + y therefore has as the lower limit a value of at least 3, 4, 6, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 50, 60, 80, 100, 150 or 200.
  • a useful upper limit for n and / or x + y in the benzoxazine compounds of the general formula (I) or (II) according to the invention is preferably at a value of at most 10,000, 2000, 1800, 1600, 1400, 1200, 1000, 800, 600 or 400.
  • Y in formula (I) and / or formula (II) is an alkyl group comprising 1 to 8 C atoms, in particular 1 to 6 C atoms, wherein Y is preferably a methyl group.
  • the polymerizable benzoxazine compounds of the general formula (I) and (II) according to the invention have a good solubility.
  • the present invention means the maximum amount of a substance that can hold the solvent (water) at a particular temperature and pH, e.g. the proportion of the solute in a solution saturated at the temperature in question. If a solution contains more solute than it is likely to contain at thermodynamic equilibrium at a given temperature (for example, solvent evaporation), it is called supersaturated. By seeding with germs, for example, it is possible to cause the excess to precipitate out as the body of the now only saturated solution.
  • Supersaturated solutions are not to be used in determining the solubility of the polymerizable benzoxazine compounds of the invention.
  • the person skilled in the art knows methods of avoiding the production of supersaturated solutions. Also, those skilled in suitable methods for determining the solubility of any substance are familiar.
  • the novel polymerizable benzoxazine compounds at 20 0 C and a pH of 7 have a solubility of at least 10 g / 1000 g of water, preferably of at least 50 g / 1000 g of water and more preferably of 100 g / 1000 g of water.
  • a further subject of the present invention is a process for the preparation of the polymerizable benzoxazine compounds according to the invention, which essentially comprises the following process step: reaction of at least one phenolic compound of the general formula (IV),
  • R in each repeating unit is independently selected from hydrogen or linear or branched, optionally substituted alkyl groups comprising 1 to 8 carbon atoms
  • R 1 is a covalent bond or is a divalent linking group comprising 1 to 100 carbon atoms
  • Y is selected straight chain aliphatic radicals of 1 to 15 carbon atoms, branched aliphatic radicals of 1 to 15 carbon atoms, cycloaliphatic radicals, cycloaliphatic radicals containing one or more heteroatoms, aryl radicals, aryl radicals containing one or more heteroatoms
  • * - (C O) R 3 , wherein R 3 is selected from straight-chain aliphatic radicals of 1 to 15 carbon atoms, branched aliphatic radicals of 1 to 15 carbon atoms and XR 4 , wherein X is selected from S, O, and NH and R 4 is selected from unbranched aliphatic radicals of 1 to 12 carbon atoms and branched alipha
  • Suitable phenolic compounds can be selected, for example, from mono- or biphenolic compounds such as phenol, bisphenol A, bisphenol F, bisphenol S or thiodiphenol.
  • formaldehyde and / or a formaldehyde-releasing compounds paraformalehyde, trioxane or polyoxymethylene or any desired mixtures thereof can be used in addition to formaldehyde itself.
  • the divalent organic compound group R 1 preferably comprises 2 to 50, particularly preferably 2 to 25 and in particular 2 to 20 carbon atoms. Further, the divalent organic compound group R 1 may be selected from each of linear or branched, optionally substituted alkylene groups comprising 1 to 15 carbon atoms, wherein the alkylene groups are optionally interrupted by at least one heteroatom selected from oxygen, sulfur or nitrogen.
  • the term "interrupted" means that in a divalent alkylene group at least one nonterminal carbon atom of the group mentioned is replaced by a heteroatom, the heteroatom preferably being selected from * S * * (sulfur), * ⁇ O ⁇ * (oxygen), and * ⁇ NR a ⁇ * (nitrogen), wherein R a is in particular hydrogen or a linear or branched, optionally substituted alkyl groups having 1 to 15 carbon atoms.
  • the divalent organic linking group R 1 is selected from alkylene groups comprising 2 to 8 C atoms.
  • R 1 is selected from linear alkylene groups comprising 2 to 6, especially 2 or 3 carbon atoms, such as ethylene, propylene, butylene, pentylene and hexylene groups.
  • R 1 in formula (V) is a covalent bond.
  • the divalent organic linking group R 1 may comprise at least one arylene group and / or at least one biphenylene group, each preferably containing from 6 to 12 carbon atoms.
  • the arylene groups and biphenylene groups may be substituted or unsubstituted, suitable substituents being selected, for example, from alkyl, alkenyl, halogen, amine, thiol, carboxyl and hydroxyl groups.
  • at least one carbon atom of the aromatic ring system of said groups can be replaced by a heteroatom, wherein the heteroatom is preferably selected from oxygen, nitrogen and sulfur.
  • R in each repeating unit is independently selected from hydrogen or methyl.
  • the primary amines of the general formula (V) are selected from compounds of the general formula (VI)
  • n and / or x + y in the primary amines of the general formula (V) or (VI) has a lower limit of at least 3, 4, 6, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 50, 60, 80, 100, 150 or 200.
  • a useful upper limit for n and / or x + y in the primary amines of the general formula (V) or (VI) is preferably at a value of at most 10,000, 2000, 1800, 1600, 1400, 1200, 1000, 800, 600 or 400th
  • Y in formula (V) and / or formula (VI) is an alkyl group which comprises 1 to 8 C atoms, in particular 1 to 6 C atoms, wherein Y is preferably a methyl group.
  • Particularly preferred primary amines of the general formula (V) and / or (VI) are commercially available and are available from Huntsman Corp. Texas under the brand names Jeffamine® M-600, Jeffamine® M-1000, Jeffamine® M-2005, Jeffamine® M-2070, Jeffamine® M-2095 and Jeffamine® M-3000.
  • a further subject of the present invention is a benzoxazine (co) polymer comprising in polymerized form at least one polymerizable benzoxazine compound according to the invention.
  • a benzoxazine (co) polymer is understood as meaning both a benzoxazine homopolymer and a benzoxazine copolymer.
  • Benzoxazine homopolymers in polymerized form contain only a polymerizable benzoxazine compound according to the invention, while benzoxazine copolymers in addition to at least one polymerizable benzoxazine compound according to the invention further polymerizable benzoxazine compounds according to the invention and / or other polymerizable benzoxazine compounds.
  • the polymerization of the at least one polymerizable benzoxazine compound according to the invention for the benzoxazine (co) polymer can be carried out at elevated temperatures according to a self-initiating mechanism (thermal polymerization) or by addition of cationic initiators.
  • Suitable cationic initiators are, for example, Lewis acids or other cationic initiators, for example metal halides, organometallic reagents, such as metalloporphyrins, methyl tosylates, methyltriflates or trifluorosulphonic acids.
  • basic reagents may be used to effect the polymerization of the at least one polymerizable benzoxazine compound of the present invention initiate. Suitable basic reagents may for example be selected from imidazole or imidazole derivatives.
  • the thermal polymerization of the at least one polymerizable benzoxazine compound according to the invention takes place at temperatures of 150 to 300 ° C., in particular at temperatures of 160 to 220 ° C.
  • the polymerization temperature may also be lower .
  • the polymerization process is based essentially on the thermally-induced ring opening of the oxazine ring of a benzoxazine system.
  • the benzoxazine (co) polymer in polymerized form comprises, in addition to at least one polymerizable benzoxazine compound according to the invention, at least one further benzoxazine compound which is selected from compounds of the general formula (III)
  • the radical A in formula (IM) represents a hydroxyl group or a nitrogen-containing heterocycle.
  • nitrogen-containing heterocycle is understood in particular to mean those ring systems which contain 3 to 8 ring atoms, preferably 5 to 6 ring atoms, where the ring system comprises at least one nitrogen atom and at least two carbon atoms.
  • Said nitrogen-containing heterocycle can have a saturated, unsaturated or aromatic structure and, in addition to the abovementioned atoms, also comprise further heteroatoms, for example sulfur and / or oxygen atoms.
  • the nitrogen-containing heterocycle is linked to the nitrogen atom of the oxazine ring of the benzoxazine structure via the divalent compound group R 6 according to formula (III).
  • the divalent linking group R 6 may be substituted by any nitrogen or carbon ring atom of the nitrogenous Heterocycle be linked by R formally replaced by a covalently bonded to a nitrogen or carbon ring hydrogen atom.
  • nitrogen-containing heterocycles are selected, for example, from 5-membered nitrogen-containing heterocycles, such as imidazoles, imidazolidones, tetrazoles, oxazoles, pyrroles, pyrrolidines and pyrazoles or 6-membered nitrogen-containing heterocycles, such as piperidines, piperidones, piperazines, pyridines, diazines and morpholines.
  • 5-membered nitrogen-containing heterocycles such as imidazoles, imidazolidones, tetrazoles, oxazoles, pyrroles, pyrrolidines and pyrazoles
  • 6-membered nitrogen-containing heterocycles such as piperidines, piperidones, piperazines, pyridines, diazines and morpholines.
  • Preferred benzoxazine compounds of the general formula (III) are selected in particular from compounds of the general formula (VII) and / or from compounds of the general formula (VIII),
  • c is formula (VIII) wherein R 7 and R 8 are each independently selected from hydrogen, halogen, linear or branched, optionally substituted alkyl groups, alkenyl groups and aryl groups, wherein c, B, R 5 and R 6 are each as defined above.
  • R 7 and R 8 in formula (VII) are independently selected from hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl and iso-butyl, wherein R 7 and R 8 in particular stand for hydrogen or methyl.
  • benzoxazine compounds of the general formula (VII) are selected from the following benzoxazine compounds: wherein c, B, R 5 , 'R 6 , R 7 and R 8 are as defined above.
  • the illustrated benzoxazine compounds bearing an imidazole ring as a nitrogen-containing heterocycle can be obtained, for example, by the reaction of a phenolic compound with an aldehyde such as formaldehyde and an aminoalkylimidazole compound.
  • Suitable phenolic compounds may be, for example, mono- or biphenolic
  • trioxane in addition to formaldehyde and paraformaldehyde, trioxane or polyoxymethylene or any mixtures thereof may be used.
  • preferred aminoalkylimidazole compounds have a primary amino group and can be selected, for example, from compounds of general formula (A-I),
  • R7 formula (AI) wherein R:> 6, D R7 and R are as defined above.
  • 1-aminoalkylimidazole compounds of the general formula (A-II), or 2-aminoalkylimidazole compounds of the general formula (A-III) are particularly advantageous.
  • 1-Aminoalkylimidazole compound of the general formula (A-II) suitable for the purposes of the present invention are known from the prior art and are commercially available. Examples are about 1- (3-aminopropyl) imidazole, available under the trade name Lupragen® API from BASF SE, 3-imidazol-1-yl-2-methyl-propylamine (ChemPacific), 2-methyl-1H-imidazole 1-propanamine (3B Scientific Corporation), 3-imidazol-1-yl-2-hydroxypropylamine (Ambinter, Paris Collection), 1- (4-aminobutyl) imidazole (Ambinter, Paris Collection), 2-ethyl-1H-imidazole 1-propanamine (ChemBridge Corp.).
  • 2-Aminoalkylimidazole compounds of the general formula (A-III) are also known from the prior art.
  • the preparation can be carried out by means of common organic synthesis methods.
  • a workable synthesis is described for example in Tetrahedron 2005, Vol. 61, at pages 11 148 to 11 155.
  • the illustrated benzoxazine compounds bearing a free hydroxyl group can be obtained by any conventional synthesis method, such as by a method described in Japanese Patent Application JP 2002-302486 at page 11 in lines 66 to 100.
  • the said method is based on the reaction of a phenolic compound with an aldehyde, such as formaldehyde and an aminoalcohol.
  • the reaction time can vary from a few minutes to several hours and depends strongly on the reactivity of the individual reactants.
  • Suitable phenolic compounds can be selected, for example, from mono- or biphenolic compounds such as phenol, bisphenol A, bisphenol F, bisphenol S or thiodiphenol.
  • trioxane in addition to formaldehyde and paraformaldehyde, trioxane or polyoxymethylene or any mixtures thereof may be used.
  • Suitable amino alcohols such as 2-aminoethanol, 3-amino-1-propanol, amino-2-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 4-amino-2-butanol, 5-amino 1-pentanol, 6-amino-1-hexanol, 7-amino-1-heptanol, 3-amino-1,2-propanediol, 2- (2-aminoethoxy) ethanol and 2-amino-1,3-propanediol are commercially available and can be obtained, for example, from Sigma-Aldrich or Tokyo Chemical Industry.
  • the polymerizable benzoxazine compounds of the general formula (III) can be used in addition to the polymerizable benzoxazine compounds of the general formula (I) for the preparation of the benzoxazine (co) polymer of the present invention, wherein important Material properties can be influenced by the respective mixing ratio of the individual polymerizable benzoxazine compounds to each other.
  • the benzoxazine comprises (co) polymer in polymerized form
  • the weight ratio of the at least one polymerizable benzoxazine compound of the general formula (I) according to the invention to the at least one polymerizable benzoxazine compound of the general formula (VII) is preferably between 10: 1 and 1:10; more preferably between 5: 1 and 1: 5 and in particular between 2: 1 and 1: 2, wherein for certain applications, a weight ratio of 1: 1 is appropriate.
  • the benzoxazine comprises (co) polymer in polymerized form
  • the weight ratio of the at least one polymerizable benzoxazine compound of the general formula (I) according to the invention to the at least one polymerizable benzoxazine compound of the general formula (VIII) is preferably between 10: 1 and 1:10; more preferably between 5: 1 and 1: 5 and in particular between 2: 1 and 1: 2, wherein for certain applications, a weight ratio of 1: 1 is appropriate.
  • the benzoxazine comprises (co) polymer in polymerized form
  • the proportion of the individual benzoxazine compounds on the benzoxazine (co) polymer can vary within a wide range. Based on the total amount of the benzoxazine (co) polymer, the proportion of the benzoxazine compound (in polymerized form) of the general formula (I) is preferably 5 to 90% by weight, more preferably 10 to 80% by weight and most preferably From 25 to 50% by weight; the proportion of the benzoxazine compound (in polymerized form) of the general formula (VII) is preferably 5 to 90 wt .-%, particularly preferably 10 to 80 wt .-% and most preferably 25 to 50 wt .-% and the proportion
  • the benzoxazine compound (in polymerized form) of the general formula (VIII) is preferably 5 to 90 wt .-%, particularly preferably 10 to 80 wt .-% and most preferably 25 to
  • benzoxazine (co) polymer may comprise, in addition to the already described benzoxazine compounds, further polymerizable benzoxazine compounds in polymerized form, which differ from the abovementioned polymerizable benzoxazine compounds.
  • Suitable benzoxazine compounds are preferably described by formula (B-XVIII),
  • R 1 is selected from the group consisting of hydrogen, alkyl, alkenyl and aryl
  • R 4 is selected from the group consisting of hydrogen, halogen, alkyl and alkenyl, or R 4 is a divalent radical which forms a corresponding naphthoxazine from the benzoxazine structure Structure makes.
  • Preferred benzoxazine compounds are furthermore compounds of the general formula (B-IXX),
  • Y ' is selected from the group consisting of biphenyl, diphenylmethane, diphenylisopropane, diphenylsulfide, diphenylsulfoxide, diphenylsulfone, diphenyl ketone and R 4 is from the group consisting of hydrogen, halogen, alkyl and alkenyl, or R 4 is a divalent radical that makes the benzoxazine structure of a corresponding naphthoxazine structure.
  • benzoxazine compounds are furthermore compounds of the general formula (B-XX) to (B-XXII),
  • R 1 and R 4 are as defined above and R 3 and R 2 ' are defined as R 1 .
  • benzoxazine compounds shown are commercially available and are described i.a. by Huntsman Advanced Materials; Georgia-Pacific Resins, Inc. and Shikoku Chemicals Corporation, Chiba, Japan.
  • the benzoxazine compounds may also be obtained by reacting a phenolic compound such as bisphenol A, bisphenol F, bisphenol S or thiophenol with an aldehyde such as formaldehyde in the presence of a primary amine.
  • a phenolic compound such as bisphenol A, bisphenol F, bisphenol S or thiophenol
  • an aldehyde such as formaldehyde
  • Suitable H 11 first methods are disclosed for example in US Patent 5543516, in particular in Examples 1 to 19 in columns 10 to 14, wherein the reaction time of the corresponding reaction, depending on the concentration, reactivity and reaction temperature may last from a few minutes to a few hours , Further manufacturing possibilities can be found in US patents 4607091, 5021484, 5200452 and 544391 1.
  • the weight-average molecular weight "M w " of the benzoxazine (co) polymers is preferably between 500 and 100,000 g / mol, particularly preferably between 1,000 and 100,000 g / mol and very particularly preferably between 3,000 and 50,000 g / mol.
  • the weight-average molecular weight can be determined by gel permeation chromatography (GPC) using polystyrene as standard.
  • the benzoxazine (co) polymer according to the invention has a linear or branched structure. Linear structures are preferred for their high water solubility and good interaction with a variety of surfaces.
  • the water solubility of the benzoxazine (co) polymer of the present invention can be further increased in a targeted manner by converting the said polymers into their protonated forms by treatment with suitable acids.
  • degree of protonation which is approximately by the concentration and the Strength of the acid used can be varied, protonated benzoxazine (co) polymers can be obtained, whose solubility is optimized for a particular purpose.
  • a further subject of the present invention is an aqueous composition which comprises at least one polymerizable benzoxazine compound according to the invention and / or at least one benzoxazine (co) polymer of the present invention.
  • benzoxazine compounds or benzoxazine (co) polymers in aqueous compositions is advantageous since the substances described each have surface-active or surface-active properties and are therefore used, for example, as emulsifiers, dispersants or as surfactants, in particular as nonionic surfactant (nonionic surfactant) can be.
  • Another object of the present invention is therefore also a detergent and cleaner which contains at least one polymerizable benzoxazine compound according to the invention and / or at least one benzoxazine (co) polymer of the present invention, and the use of said compounds as surfactants, in particular as nonionic surfactants ,
  • the content of the at least one benzoxazine compound of the present invention and / or the at least one benzoxazine (co) polymer of the present invention in the aqueous composition or in the textile or surface treatment agent should be such that the surface treated with said agent is sufficiently covered ,
  • the textile or surface treatment agents of the present invention are, in particular, liquid or gel-like agents.
  • the textile or surface treatment agent of the present invention preferably comprises not only the benzoxazine (co) polymer according to the invention or the mixture of various benzoxazine (co) polymers, but also surfactants, these being selected in particular from anionic, cationic, ampholytic and nonionic surfactants and also from any desired mixtures thereof.
  • Anionic surfactants usually comprise a water-solubilizing, anionic group such.
  • glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule.
  • Sulfosuccinic acid mono-alkyl polyoxyethyl esters having 8 to 24 C atoms in the alkyl group and 1 to
  • Alpha-sulfofatty acid methyl esters of fatty acids having 8 to 30 carbon atoms are alpha-sulfofatty acids having 8 to 30 carbon atoms.
  • Alkyl sulfates and alkyl polyglycol ether sulfates of the formula R 1 -O (CH 2 -CH 2 O) x -OSO 3 H, in which R 14 is a preferably linear alkyl group having 8 to 30 C atoms and x 0 or 1 to 12,
  • esters of tartaric acid and citric acid with alcohols the addition products of about 2-15
  • R 14 is preferably an aliphatic hydrocarbon radical having 8 to 30 carbon atoms
  • R 15 is hydrogen, a radical (CH 2 CH 2 O) n R 16 or X
  • h is from 1 to 10
  • X is hydrogen, an alkali metal radical or alkaline earth metal or NR 17 R 18 R 19 R 20 , where R 17 to R 19 independently of one another represent hydrogen or a C 1 to C 4 hydrocarbon radical, is a sulfated fatty acid alkylene glycol ester of the formula (E1-II)
  • R 20 CO- for a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 C atoms, Alk for CH 2 CH 2 , CHCH 3 CH 2 and / or CH 2 CHCH 3 , h for numbers from 0.5 to 5 and M is a cation, monoglyceride sulfates and monoglyceride ether sulfates of the formula (E1-III) CH 2 O (CH 2 CH 2 O) x - COR 21
  • R 21 CO represents a linear or branched acyl radical having 6 to 22 carbon atoms
  • x, y and i in total represents 0 or numbers of 1 to 30, preferably 2 to 10
  • X represents an alkali or alkaline earth metal.
  • monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride and their ethylene oxide adducts with sulfur trioxide or chlorosulfonic acid in the form of their sodium salts.
  • monoglyceride sulfates of the formula (E1-III) are used in which R 21 CO is a linear acyl radical having 8 to 18 carbon atoms, amide ether carboxylic acids,
  • Condensation products of C 8 - C 30 - fatty alcohols with protein hydrolysates and / or amino acids and their derivatives which are known to the skilled person as protein fatty acid condensates, such as Lamepon ® - types Gluadin ® - types Hostapon ® KCG or Amisoft ® - types.
  • Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, sulfosuccinic acid mono- and dialkyl esters having 8 to 18 carbon atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethyl ester having 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups, Monoglycerdisulfate, alkyl and Alkenyletherphosphate and Eiweissfettkladensate.
  • Cationic surfactants of the quaternary ammonium compounds, esterquats and amidoamines type are preferred according to the invention.
  • Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g.
  • the long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.
  • Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element.
  • Preferred esterquats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines.
  • Such products are sold, for example, under the trademarks Stepantex®, Dehyquart® and Armocare®.
  • alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines.
  • a particularly suitable compound according to the invention from this group of substances is stearamidopropyl-dimethylamine, which is commercially available under the name Tegoamid® S 18.
  • the agents may contain other surfactants or emulsifiers, with both anionic and ampholytic and nonionic surfactants and all types of known emulsifiers being suitable in principle.
  • the group of ampholytic or amphoteric surfactants includes zwitterionic surfactants and ampholytes. The surfactants may already have emulsifying effect.
  • Zwitterionic surfactants are those surface-active compounds which carry in the molecule at least one quaternary ammonium group and at least one -COO () or -SO 3 ⁇ group.
  • Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N-acylaminopropyl N, N-dimethylammonium glycinates, for example cocoacylaminopropyl dimethylammonium glycinate, and 2-alkyl 3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethyl hydroxyethylcarboxymethylglycinate.
  • a preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidoprop
  • Ampholytes are to be understood as meaning those surface-active compounds which, in addition to a C 8 -C 24 -alkyl or -acyl group in the molecule, contain at least one free amino group and at least one -CC 1 C 1 H or -SO 3 H group and form internal Salts are capable.
  • ampholytes are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 24 C Atoms in the alkyl group.
  • Particularly preferred ampholytes are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C 12 -C 18 acylsarcosine.
  • Nonionic surfactants contain, for example, a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group as the hydrophilic group. Such compounds are, for example,
  • Polyol fatty acid esters such as the commercial product Hydagen ® HSP (Cognis) or Sovermol
  • R 22 CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms
  • R 23 is hydrogen or methyl
  • R 24 is linear or branched alkyl radicals having 1 to 4 carbon atoms
  • w is a number from 1 to 20 stands
  • R 25 is an alkyl or alkenyl radical having 4 to 22 carbon atoms
  • G is a sugar radical having 5 or 6 carbon atoms
  • p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry.
  • the alkyl and alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
  • alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred.
  • the alkyl or alkenyl radical R 25 may differ from Derive primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis.
  • the alkyl or alkenyl radical R 25 can furthermore also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms.
  • Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, and technical mixtures thereof which can be obtained as described above.
  • Alkyl oligoglucosides based on hydrogenated Ci 2 / i 4 coconut alcohol with a DP of 1 to 3.
  • R 26 is CO for an aliphatic acyl radical having 6 to 22 carbon atoms
  • R 27 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms
  • [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 12 carbon atoms and 3 to 10 hydroxyl groups stands.
  • the fatty acid N-alkyl polyhydroxyalkylamides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the fatty acid N-alkylpolyhydroxyalkylamides are derived from reducing sugars having 5 or 6 carbon atoms, especially glucose.
  • the fatty acid N-alkylpolyhydroxyalkylamides used are preferably glucamides of the formula (E4-IV) in which R 29 is hydrogen or an alkyl group and R 28 CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitic acid, Stearic acid, isostearic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, arachidic acid, gadoleic acid, behenic acid or erucic acid or technical mixtures of these acids.
  • R 29 is hydrogen or an alkyl group
  • R 28 CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitic acid, Stearic acid, isostearic acid, oleic acid, elaidic acid, petroselic acid
  • fatty acid N-alkylglucamides of the formula (E4-IV) which are obtained by reductive Amination of glucose with methylamine and subsequent acylation with lauric acid or C12 / 14 coconut fatty acid or a corresponding derivative can be obtained.
  • the polyhydroxyalkylamides can also be derived from maltose and palatinose.
  • the preferred nonionic surfactants are the alkylene oxide addition products of saturated linear fatty alcohols and fatty acids having in each case 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid. Agents having excellent properties are also obtained if they contain fatty acid esters of ethoxylated glycerin as nonionic surfactants.
  • the alkyl group contains 6 to 22 carbon atoms and may be both linear and branched. Preference is given to primary linear and methyl-branched in the 2-position aliphatic radicals.
  • Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl.
  • the sugar surfactants may be present as nonionic surfactants.
  • the compounds used as surfactant with alkyl groups may each be uniform substances. However, it is generally preferred to use native vegetable or animal raw materials in the production of these substances, so that substance mixtures having different alkyl chain lengths depending on the respective raw material are obtained.
  • the surfactants which are adducts of ethylene oxide and / or propylene oxide with fatty alcohols or derivatives of these addition products both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used.
  • normal homolog distribution are meant mixtures of homologs obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Narrowed homolog distributions, on the other hand, are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with narrow homolog distribution may be preferred.
  • the amount of surfactant in the textile or surface treatment agent of the present invention depends largely on the intended use and is preferably in a range of 0.1 to 50% by weight, more preferably in a range of 0.5 to 25% by weight, and especially preferably in a range of 1 to 10 wt .-%, each based on the total amount of n means.
  • the textile or surface treatment agent of the present invention may contain at least one perfume which preferably gives the composition a pleasant and / or fresh scent impression.
  • the at least one fragrance is not subject to any restrictions. So for example, as at least one perfume, individual perfume compounds, synthetic or natural compounds of the ester type, ethers, aldehydes, ketones, alcohols, hydrocarbons, acids, carbonic esters, aromatic hydrocarbons, aliphatic hydrocarbons, saturated and / or unsaturated hydrocarbons and mixtures thereof can be used.
  • fragrance aldehydes and fragrance ketones can be used, which are typically used to bring about a pleasant fragrance sensation.
  • Suitable fragrance aldehydes and fragrance ketones are well known to those skilled in the art.
  • the proportion of the at least one perfume in the textile or surface treatment agent according to the invention is preferably between 0.01 and 5 wt .-%, particularly preferably between 0.1 and 3 wt .-% and most preferably between 0.5 and 2 wt. -% based on the total amount of the agent.
  • the total amount of the at least one perfume is the amount of all the perfumes in the mixture together relative to the total amount of the agent.
  • the textile or surface treatment agent is a textile treatment agent which can be used, for example, for textile pretreatment as well as textile aftertreatment and textile washing.
  • the textile treatment agent can be used both in the private sector and in the textile industry, wherein the benzoxazine (co) polymers according to the invention can be used both for permanent and for temporary textile treatment.
  • the said textile treatment agent is a detergent, fabric softener, softening detergent or washing assistant, said means in addition to the ingredients already mentioned other ingredients such as builders, bleach, bleach activators, enzymes, electrolyte ⁇ , non-aqueous solvents, pH Surfactants, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, wrinkle inhibitors, dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, phobizers and Impregnating, swelling and slip-resistant, neutral fillers and UV absorbers may contain.
  • other ingredients such as builders, bleach, bleach activators, enzymes, electrolyte ⁇ , non-aqueous solvents, pH Surfactants, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils, anti redeposition agents,
  • the present invention is a process for the treatment and / or coating of surfaces, wherein at least one surface is treated with at least one benzoxazine (co) polymer of the present invention.
  • the benzoxazine (co) polymer of the present invention is applied to the respective surface in the form of aqueous solutions, dispersions or emulsions.
  • aqueous solutions, dispersions or emulsions which preferably have, based on the total amount of the agent, a water content of at least 5 wt .-%, preferably of at least 50 wt .-% and particularly preferably of at least 90 wt .-%.
  • alcohol-based solutions, dispersions and emulsions which, based on the total amount of the agent, have an alcohol content of at least 5% by weight, preferably of at least 50% by weight and more preferably of at least 90% by weight.
  • Preferred alcohols are in particular selected from ethanol, isopropanol or any of their mixtures.
  • the solutions, dispersions or emulsions mentioned can also contain any mixtures of water and water-miscible alcohols, such as water / ethanol and water / propanol mixtures.
  • Preferred surfaces are selected from carbon fibers, hard surfaces and textile
  • Carbon fibers are u.a. used for the production of fiber reinforced composites.
  • Fiber-reinforced composites usually consist of at least two components as mixed materials.
  • the fiber-reinforced composites comprise a carbon fiber component, which may consist, for example, of unidirectional as well as woven or short fibers.
  • the carbon fiber component used imparts high strength to the material in combination with the resin component used, which is why fiber reinforced composites are used as composite materials in high structural material properties applications such as aircraft or automotive.
  • carbon fibers have low ductility and are brittle, they tend to be fuzzy as a result of mechanical friction and often have poor wettability with respect to the matrix resins used.
  • carbon fibers used as reinforcing materials of fiber reinforced composite materials are usually pretreated with a sizing agent.
  • Carbon fibers which are treated with the benzoxazine (co) polymer according to the invention are distinguished by improved handling in the production process of fiber-reinforced composite materials.
  • the treated carbon fibers show improved wettability with the respective matrix resin.
  • the wettability of the carbon fibers with respect to benzoxazine-based resin systems is improved.
  • a further subject of the present invention is therefore the use of the benzoxazine (co) polymers according to the invention as sizing agent, in particular as sizing agent for carbon fibers.
  • the benzoxazine (co) polymers according to the invention can likewise be used as sizing agents for textile fibers or textile fabrics.
  • Hard surfaces which are treated with the benzoxazine (co) polymer according to the invention can, in the context of the present invention, particularly preferably be selected from porcelain, glass, ceramic, plastic and / or metal.
  • Another object of the present invention is therefore the use of benzoxazine (co) polymers of the invention as corrosion inhibitors.
  • Textile surfaces or hard surfaces which are treated with the benzoxazine (co) polymer according to the invention can be selected in the context of the present invention from textile fabrics or from the abovementioned hard surfaces.
  • textile surfaces are textile fabrics of wool, silk, jute, hemp, cotton, linen, sisal, ramie; Rayon, cellulose esters, polyvinyl derivatives, polyolefins, polyamides, viscose or polyesters or mixtures thereof, while hard.
  • textile surfaces made of cotton or cotton blend fabrics are particularly preferred.
  • the treated textile or hard surfaces are characterized by a reduced Wiederzusmutz sadness and improved soil release.
  • Another object of the present invention is therefore the use of benzoxazine (co) polymers according to the invention for improving the removal of soil from and / or to reduce the Wiederzusmutz sadness on textile or hard surfaces.
  • the surfaces mentioned above, after treatment with the benzoxazine (co) polymer according to the invention show less contamination with harmful microorganisms than untreated surfaces.
  • a further subject of the present invention is therefore the use of the benzoxazine (co) polymers according to the invention for coating surfaces, in particular for antibacterial coating of surfaces.
  • Paraformaldehyde was introduced into ethyl acetate and the p-cresol, likewise dissolved in ethyl acetate, was added dropwise within 10 minutes. The mixture was then added within 30 minutes of Jeffamine M-2070, wherein the temperature is maintained below 10 0 C. After stirring for 10 minutes, the reaction mixture was refluxed for 6 hours. After cooling, the reaction mixture was filtered and the solvent and water formed were removed in vacuo. This gave 318.90 g of the corresponding polymerizable benzoxazine compound.
  • Paraformaldehyde was initially charged in ethyl acetate and the p-cresol, also dissolved in ethyl acetate, was added dropwise over 10 minutes. The mixture was then added within 30 minutes Lupragen API, while the temperature was kept below 10 0 C. After stirring for 10 minutes, the reaction mixture was refluxed for 6 hours. After cooling, the reaction mixture was filtered and the solvent and water formed were removed in vacuo. 322.74 g of the corresponding polymerizable benzoxazine compound were obtained.
  • Paraformaldehyde was initially charged in ethyl acetate and the p-cresol, also dissolved in ethyl acetate, was added dropwise over 10 minutes. Ethanolamine was then added over 30 minutes keeping the temperature below 10 ° C. After stirring for 10 minutes, the reaction mixture was refluxed for 6 hours. After cooling, the reaction mixture was filtered and the solvent and water formed were removed in vacuo. 328.6 g of the corresponding polymerizable benzoxazine compound were obtained.
  • the benzoxazine (co) polymers of the present invention could be taken up under these conditions in an amount of at least 10 g / 1000 g of water without turbidity in water.
  • the non-inventive benzoxazine (co) polymers 3 and 4 show under the conditions mentioned a poorer solubility in water than the inventive benzoxazine (co) polymers 1, 2, 8, 12 and 16.

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EP10720383A 2009-05-12 2010-05-06 Polymerisierbare benzoxazin-verbindungen mit grenzflächenaktiven bzw. oberflächenaktiven eigenschaften Withdrawn EP2430005A1 (de)

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US9205633B2 (en) * 2013-03-15 2015-12-08 Henkel IP & Holding GmbH Prepreg curing process for preparing composites having superior surface finish and high fiber consolidation
US9427943B2 (en) * 2013-03-15 2016-08-30 Henkel IP & Holding GmbH Prepreg curing process for preparing composites having superior surface finish and high fiber consolidation
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