WO2012140059A1 - Lcst polymers - Google Patents

Lcst polymers Download PDF

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Publication number
WO2012140059A1
WO2012140059A1 PCT/EP2012/056548 EP2012056548W WO2012140059A1 WO 2012140059 A1 WO2012140059 A1 WO 2012140059A1 EP 2012056548 W EP2012056548 W EP 2012056548W WO 2012140059 A1 WO2012140059 A1 WO 2012140059A1
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WO
WIPO (PCT)
Prior art keywords
formula
compound
molded article
compounds
cloud point
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Application number
PCT/EP2012/056548
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German (de)
French (fr)
Inventor
Thomas Weiss
Hans-Peter Seelmann-Eggebert
Andrea Misske
Wolfgang Spiegler
Original Assignee
Basf Se
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Basf Se filed Critical Basf Se
Priority to EP12712692.8A priority Critical patent/EP2697284A1/en
Priority to MX2013010424A priority patent/MX2013010424A/en
Priority to RU2013150131/04A priority patent/RU2013150131A/en
Priority to CN2012800179114A priority patent/CN103476830A/en
Priority to JP2014504292A priority patent/JP2014511927A/en
Priority to AU2012241931A priority patent/AU2012241931A1/en
Priority to SG2013073010A priority patent/SG194002A1/en
Priority to KR1020137029540A priority patent/KR20140038403A/en
Priority to BR112013023946A priority patent/BR112013023946A2/en
Publication of WO2012140059A1 publication Critical patent/WO2012140059A1/en

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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
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/22—Esters containing halogen
    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2633—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen the other compounds containing amide groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2639—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing elements other than oxygen, nitrogen or sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C08G65/3324—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof cyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation

Definitions

  • the invention relates to LCST polymers, their preparation and use.
  • LCST polymers based on polyalkylene oxides are known.
  • a LCST (Lower Critical Solution Temperature) polymer is understood as meaning a polymer which, although soluble at a lower temperature in a liquid medium, is above a certain temperature, namely the cloud point, or the LCST temperature, from the liquid medium fails. This process is reversible, so that the system becomes homogeneous again during cooling.
  • the temperature at which the solution becomes clear on cooling is called the cloud point (see German standard DIN EN 1890 of September 2006). This temperature is characteristic of a particular substance.
  • WO 01/60926 A1 discloses a process for coating particles with LCST polymers, in which the LCST polymer is dissolved in a solvent below the LCST, the resulting solution is mixed with the particles to be coated, and then the temperature of the obtained mixture is raised to a temperature above the LCST with precipitation of the LCST polymers on the particle surfaces.
  • LCST polymers based on polyalkylene oxides are known, which are terminally substituted with an optionally substituted acrylate. It is further known from WO 2004/046258 A2 to use these LCST polymers for coating particle-free and non-particulate substrate surfaces, the polymers being contacted with the particles or surfaces in a liquid medium below the LCST temperature , the temperature increases above the LCST temperature and polymerize the polymers via the double bonds at this or a higher temperature on the surface of the particles, or the surfaces.
  • the invention relates to formula I.
  • R 1 and R 2 are hydrogen or an alkyl radical, in particular with 1
  • A is a radical containing the radicals A1 and A2, in which mean
  • R 3 to R 6 are identical or different, H, C 1 - to C 5 -alkyl, in particular methyl, ethyl, propyl or aryl, in particular phenyl,
  • A1 is one of the following radicals
  • A2 is in particular one of the following radicals: PO - ⁇ CH 2 - CH
  • n and q are as defined above.
  • A preferably consists of the radicals A1 and A2 and in particular represents the group - A2-A1 -A2-.
  • the repeating units in residues A1 and A2 can be randomly distributed or in blocks. If the radical A 2 has both propylene glycol radicals and polytetrahydrofuran units, in a preferred embodiment the polytetrahydrofuran units are terminally attached.
  • the radicals A1 and A2 can be substituted, in particular with an alkyl radical having 1-4 C atoms or an aryl radical, in particular phenyl.
  • An example of a substituted repeating radical is the phenyl-substituted ethylene glycol radical (styrene oxide).
  • a particularly preferred embodiment is characterized in that A has the structure - (PO) x- (EO) y- (PO) z -, in which mean
  • x, z are the same or different, a number from 1 to 100, in particular 1 to 20
  • y is a number from 1 to 100, in particular 1 to 90
  • x, z, the same or different are from 5 to 10
  • y is a number from 60 to 80, in particular from 65 to 75.
  • the structure - (PO) x - (EO) y - (PO) z preferably has an EO content by weight of 5 to 85 wt .-% and a number average molecular weight (Mn) of 200 to 50,000 g / mol.
  • Mn number average molecular weight
  • x, z are a number, identical or different, of from 0.1 to 200, in particular from 5 to 20 y, a number, identical or different, of from 1 to 100, in particular from 60 to 80.
  • the compounds according to the invention are outstandingly suitable A method for producing coatings by applying the compounds to the surface of substrates and polymerization.
  • the invention therefore furthermore relates to a process for the preparation of coatings based on a compound of the formula I on the surface of a molded article of a fusible substrate S, in particular on fibers, in a melt spinning process or films after extrusion, wherein a) the substrate is provided in molten form becomes,
  • the molten substrate is formed via a suitable device V, preferably a nozzle or a gap, to a molded article, in particular to a fiber or a film, wherein
  • the molded article at the outlet from the device V has a temperature above the cloud point of the compound of formula I
  • the surface of the molded article above the cloud point with the compound of formula I is brought under deposition of the compound of formula I in contact, characterized in that after deposition on the surface, the polymerization of the double bonds of the compound of formula I is initiated to form a preferably crosslinked coating of the surface.
  • a preferred embodiment is characterized in that after leaving the device V, the molded article is passed into a preferably aqueous bath B which contains the compound of the formula I and, if appropriate, a polymerization initiator, the mold article entering the bath of the molded article has a temperature above the cloud point, the compound of formula I is deposited on the molded article and
  • the bath has a temperature below the cloud point and the polymerization is carried out at a temperature below the cloud point.
  • a further preferred embodiment is characterized in that the molded article is passed immediately after exiting the device V at a temperature above the cloud point in a spray and sprayed there with the compound of formula I, preferably in the form of an aqueous solution, wherein the temperature of the sprayed polymer is below the cloud point, depositing the compound of formula I on the surface of the substrate.
  • Particularly preferred substrates are polyamides, polyesters, polypropylene or polyurethanes.
  • the substrate is a glass, steel or wood.
  • the polymerization of the double bonds can be carried out in the bath B or subsequent to the treatment in the bath B.
  • a polymerization initiator is preferably added.
  • the polymerization of the acrylate groups of the compounds of the formula I according to the invention preferably takes place free-radically, in particular from aqueous or alcoholic solution.
  • the polymerization preferably takes place in the presence of radical formers, in particular inorganic or organic peroxides, azo compounds or metals or organometallic compounds.
  • radical formers in particular inorganic or organic peroxides, azo compounds or metals or organometallic compounds.
  • suitable polymerization regulators in particular mercaptans, organic halogen compounds, aldehydes or xanthates or nitroxyl radical formers may be added.
  • the polymerization is preferably carried out at temperatures of 50 to 100 ° C, in particular at 60 to 80 ° C.
  • the polymerization of the acrylate groups of the compounds of the formula I according to the invention can also be initiated by means of a photoinitiator.
  • Photoinitiators are generally present in amounts of 0.01 to 10 and especially 0.01 to 3 wt .-%, based on the compound of formula I. Suitable photoinitiators are those compounds which are capable of forming free radicals upon exposure to actinic light and which provide rapid photopolymerization. sation of the compound of formula I trigger.
  • photoinitiators come z. For example, acyloins and acyloin ethers, aromatic diketones and their derivatives and polynuclear quinones.
  • photoinitiators and thermal polymerization inhibitors such as hydroquinone, p-methoxyphenol, dinitrobenzene, p-quinone, methylene blue, beta-naphthol, N-nitrosamines such as N-nitrosodiphenylamine, phenothiazine, phosphorous acid esters such as triphenyl phosphite or the salts and in particular the alkali and aluminum salts of N-nitroso-cyclohexylhydroxylamine be used.
  • the inhibitors may be used in amounts of 0.001 to 3, preferably 0.01 to 1 wt .-%, based on the compound of formula I.
  • the acrylate end groups in the compounds of the formula I to be used according to the invention can be replaced in an amount of 0.1 to 99 mol%, in particular 20 to 50 mol%, by radicals of: a) maleic acid or maleic acid derivatives (in particular esters)
  • X is hydroxyl, halogen, preferably chlorine, an acid group, an alkyl group or an alkoxy group having 1 to 100 carbon atoms, in a molar ratio of at least 1: 1 to 1: 4, in particular 1: 2.
  • the reaction is preferably carried out in a solvent such as tertiary monools, preferably tert-butanol, tert-amyl alcohol, pyridine, poly-C 1 -C 4 -alkylene glycol-C 1 -C 4 -alkyl ethers, preferably polyethylene glycol-C 1 -C 4 -alkyl ethers, such as z. B.
  • a solvent such as tertiary monools, preferably tert-butanol, tert-amyl alcohol, pyridine, poly-C 1 -C 4 -alkylene glycol-C 1 -C 4 -alkyl ethers, preferably polyethylene glycol-C 1 -C 4 -alkyl ethers, such as z. B.
  • Preferred compounds of the formula I according to the invention can be prepared by 1. direct implementation of the preformed compounds HO - A ⁇ with (meth) acrylic acid, or (meth) acrylic acid derivatives
  • Aryl (meth) acrylates for example benzyl (meth) acrylate or phenyl (meth) acrylate, which may each be unsubstituted or have 1-4-substituted aryl radicals; other aromatic substituted (meth) acrylates such as naphthyl (meth) acrylate;
  • Amount of catalyst 0.1-10% by weight (preferably 0.5-5% by weight) with respect to starting materials
  • Reaction time 1 - 10 hours, preferably 1 - 6 hours
  • an entraining agent eg, cyclohexane or toluene
  • the esterification can be carried out without pressure, with overpressure or underpressure both continuously and discontinuously.
  • Catalyst quantity 0.01 to 10% by weight of catalyst, preferably from 0.1 to 5% by weight, more preferably from 0.2 to 2% by weight of catalyst, based on the total reaction mixture.
  • Catalysts organylmetal oxides, organylmetal halides such as diorganyltin oxides,
  • Diorganyltin halides alkali metal salts of inorganic acid, in particular of phosphoric acid, transition metal alcoholates such as titanium alkoxides, alkali metal amides such as lithium amide, alkali metal and alkaline earth metal alkoxides such as potassium tert-butylate, acids such as sulfuric acid, alkyl- or arylsulfonic acids, e.g.
  • the enzymatically catalyzed transesterification is preferably carried out under the following conditions: temperature: 10 ° -80 ° C., more preferably 20 ° -40 ° C.
  • Catalyst lipases with and without solvent in excess of (meth) acrylic acid esters of from 1:50 to 1: 500 mol / mol, more preferably from 1: 100 to 1: 400, relative to the substrate.
  • these have either a spraying device immediately following the exit of the fiber from the nozzle or a bath which preferably contains an aqueous solution of the polymer according to the invention.
  • This bath may additionally contain a polymerization initiator for carrying out the polymerization.
  • the plants known per se for the production of films for example based on an extruder, which promotes the melt of the substrate, or the substrate melts and extruded through a nozzle, in particular a slot die, to form a film.
  • effect substances are deposited on the shaped body together with the compounds of the formula I according to the invention.
  • effect substances are understood in particular compounds which improve the properties of the shaped body, in particular the films and fibers, such as UV stabilizers, pigments, nanoparticles, IR-absorbing compounds, etc.
  • the effect substances together with the compound of formula I, preferably in the bath B be included.
  • the molded articles according to the invention d. H. Films and fibers can be stretched in a manner known per se, in particular also after application and polymerization of the acrylate groups.
  • diethylene glycol 53.05 g, 0.5 mol
  • potassium t-butylate 10.2 g, 0.5 wt% of the final amount. It was made inert three times with nitrogen to 5 bar and dosed after reaching 120 ° C ethylene oxide mass controlled to (1364.0 g). The temperature was then increased to 130 ° C. and propylene oxide (638 g, 11 mol) was added over the course of 700 minutes. The mixture was allowed to react for 4 h and cooled to 80 ° C with stirring.
  • the crude product was mixed with magnesium silicate (3 wt .-%) and pressure-filtered after 1 h stirring on a rotary evaporator over a 900 Seitz filter medium.
  • PPG-PEG-PPG 250 g, 0.05 mol from example 1 .1, ethyl acrylate (1000 g, 10 mol), molecular sieve 5
  • a powder (Fluka) 55.5 g (10 -fold amount based on theoretical amount of resulting alcohol).
  • the stabilizers added were 4-methoxyphenol (MeHQ): 98.6 mg; (Aldrich) (99% [GC]) (400 ppm based on theoretical amount of product); Phenothiazine (PTZ): 3.0 mg (Fluka) (purum;> 98.0% [GC]) (10 ppm based on theoretical amount of product).
  • Novozym 435 (33.71 g) (7.0% by weight, based on starting material) was added at about 30.degree. The mixture was allowed to stir for 48 h at 40 ° C (bath 46 ° C) and 150 rpm by means of glass PTFE intensive stirrer with the introduction of air.
  • the mixture was then filtered off with suction through a 4 l glass filter chute G 2 filled with silica gel 60 (0.040-0.064 mm) at approx. 500-600 mbar, washed with 4 l acetone and at 60 ° C. with introduction of air to remove ethyl acrylate residues in Rotary evaporator dried.
  • Example 2 Fiber Coating The fiber coating is tested using the example of a melt spinning process for polypropylene. For this purpose, an aqueous solution of the following components (% by weight) is used:
  • adhesion promoter polyethyleneimine
  • microfibers 120 dtexf32
  • dtex is a unit of measure for the fineness of threads. Described is the weight in g at 10000 m fiber] obtained from a melt at a nozzle temperature of 295 ° C.
  • the fiber is brought into contact with the LCST polymer solution by spraying at a temperature of 80-100 ° C. (about 100 cm after the exit of the fiber material from the spinneret).
  • the resulting fiber-coated yarns are characterized by improved properties, in particular in terms of flexibility and Aufzieh App.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Toxicology (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Polyethers (AREA)

Abstract

The invention relates to LCST polymers and to the preparation and use thereof.

Description

LCST-Polymere Beschreibung Die Erfindung betrifft LCST Polymere, ihre Herstellung und Verwendung.  Description: The invention relates to LCST polymers, their preparation and use.
Sogenannte LCST-Polymere auf Basis von Polyalkylenoxiden sind bekannt. Unter einem LCST (Lower Critical Solution Temperature)-Polymer wird ein Polymer verstanden, welches zwar bei einer niedrigeren Temperatur in einem flüssigen Medium löslich ist, aber oberhalb einer be- stimmten Temperatur, nämlich des Trübungspunktes, bzw. der LCST-Temperatur, aus dem flüssigen Medium ausfällt. Dieser Vorgang ist umkehrbar, so dass das System beim Abkühlen wieder homogen wird. Die Temperatur, bei der die Lösung beim Abkühlen klar wird, wird als Trübungspunkt bezeichnet (siehe Deutsche Norm DIN EN 1890 vom September 2006). Diese Temperatur ist für einen bestimmten Stoff charakteristisch. So-called LCST polymers based on polyalkylene oxides are known. A LCST (Lower Critical Solution Temperature) polymer is understood as meaning a polymer which, although soluble at a lower temperature in a liquid medium, is above a certain temperature, namely the cloud point, or the LCST temperature, from the liquid medium fails. This process is reversible, so that the system becomes homogeneous again during cooling. The temperature at which the solution becomes clear on cooling is called the cloud point (see German standard DIN EN 1890 of September 2006). This temperature is characteristic of a particular substance.
Aus der WO 01/60926 A1 ist ein Verfahren zur Beschichtung von Partikeln mit LCST- Polymeren bekannt, bei dem das LCST-Polymer in einem Lösungsmittel unterhalb der LCST gelöst wird, die erhaltene Lösung mit den zu beschichtenden Partikeln gemischt wird und anschließend die Temperatur der erhaltenen Mischung erhöht wird auf eine Temperatur oberhalb der LCST unter Ausfällung der LCST-Polymere auf den Partikeloberflächen. WO 01/60926 A1 discloses a process for coating particles with LCST polymers, in which the LCST polymer is dissolved in a solvent below the LCST, the resulting solution is mixed with the particles to be coated, and then the temperature of the obtained mixture is raised to a temperature above the LCST with precipitation of the LCST polymers on the particle surfaces.
Aus der WO 2004/046258 A2 sind LCST-Polymere auf Basis von Polyalkylenoxiden bekannt, welche endständig mit einem gegebenenfalls substituierten Acrylat substituiert sind. Aus der WO 2004/046258 A2 ist weiterhin bekannt, diese LCST-Polymere zur Beschichtung von Parti- kein und nicht-partikulären Substratoberflächen zu verwenden, wobei man die Polymere in einem flüssigen Medium unterhalb der LCST-Temperatur mit den Partikeln, bzw. Oberflächen kontaktiert, die Temperatur bis über die LCST-Temperatur erhöht und die Polymere über die Doppelbindungen bei dieser oder einer höheren Temperatur auf der Oberfläche der Partikel, bzw. den Oberflächen polymerisiert. From WO 2004/046258 A2 LCST polymers based on polyalkylene oxides are known, which are terminally substituted with an optionally substituted acrylate. It is further known from WO 2004/046258 A2 to use these LCST polymers for coating particle-free and non-particulate substrate surfaces, the polymers being contacted with the particles or surfaces in a liquid medium below the LCST temperature , the temperature increases above the LCST temperature and polymerize the polymers via the double bonds at this or a higher temperature on the surface of the particles, or the surfaces.
Die Erfindung betrifft Formel I The invention relates to formula I.
Figure imgf000002_0001
Figure imgf000002_0001
Formel I  Formula I
worin bedeuten in which mean
Ri und R2 (unabhängig voneinander) Wasserstoff oder einen Alkylrest, insbesondere mit 1 R 1 and R 2 (independently of one another) are hydrogen or an alkyl radical, in particular with 1
4 C-Atomen, insbesondere Methyl  4 C-atoms, especially methyl
A einen Rest enthaltend die Reste A1 und A2,
Figure imgf000003_0001
Figure imgf000003_0002
worin bedeuten A is a radical containing the radicals A1 and A2,
Figure imgf000003_0001
Figure imgf000003_0002
in which mean
R3 bis R6 gleich oder verschieden, H, C1 - bis C5-Alkyl, insbesondere Methyl, Ethyl, Propyl oder Aryl, insbesondere Phenyl, R 3 to R 6 are identical or different, H, C 1 - to C 5 -alkyl, in particular methyl, ethyl, propyl or aryl, in particular phenyl,
I 1 oder 0 I 1 or 0
m 1 oder 0, wobei I + m mindestens 1 bedeuten,  m is 1 or 0, where I + m is at least 1,
n 1 bis 100  n 1 to 100
o 0 bis 5  o 0 to 5
P 0 bis 5, wobei o + p 3 bis 5 bedeuten,  P 0 to 5, where o + p is 3 to 5,
q 1 bis 100, dadurch gekennzeichnet, dass die Verbindung der Formel I gemäß Deutsche Norm DIN EN 1890 vom September 2006, Methode gemäß Verfahren E, einen Trübungspunkt von 40 bis 80 °C, insbesondere 60 bis 80 °C, aufweist und die Einheiten A2 endständig im Rest A enthalten sind.  q 1 to 100, characterized in that the compound of formula I according to German standard DIN EN 1890 of September 2006, method according to method E, a cloud point of 40 to 80 ° C, in particular 60 to 80 ° C, and the units A2 are contained terminally in the radical A.
Gemäß Deutsche Norm DIN EN 1890 vom September 2006, Methode gemäß Verfahren E werden 5 g der Probe in einen Erlenmeyerkolben eingebracht und 25 g der wässrigen Lösung von Diethylenglykolmono-n-butylether (BDG) mit einem Massenanteil von 25 % hinzugefügt. Es wird gerührt bis die Probe klar gelöst ist. Mit einer Heizeinrichtung ist dann unter langsamem Rühren die Flüssigkeit zu erhitzen, bis sie völlig trübe ist. Anschließend wird unter Rühren langsam abgekühlt. Die Temperatur, bei der die Trübung verschwindet, die Lösung also klar wird, ist der Trübungspunkt. According to German standard DIN EN 1890 of September 2006, method according to method E, 5 g of the sample are introduced into an Erlenmeyer flask and 25 g of the aqueous solution of diethylene glycol mono-n-butyl ether (BDG) in a mass fraction of 25% added. It is stirred until the sample is clearly dissolved. With a heating device, the liquid is then heated with slow stirring until it is completely cloudy. The mixture is then cooled slowly while stirring. The temperature at which the turbidity disappears and the solution becomes clear is the cloud point.
A1 ist insbesondere einer der folgenden Reste In particular, A1 is one of the following radicals
MO - ΟΗ,-Ο^
Figure imgf000003_0003
MO - ΟΗ, -Ο ^
Figure imgf000003_0003
A2 ist insbesondere einer der folgenden Reste: PO -■ CH2 - CH A2 is in particular one of the following radicals: PO - ■ CH 2 - CH
Figure imgf000004_0001
pTHF — ^CH2-CH2-CH2-CH2-0-h- worin n und q die oben angegebene Bedeutung haben.
Figure imgf000004_0001
pTHF - ^ CH 2 -CH 2 -CH 2 -CH 2 -O-h- wherein n and q are as defined above.
A besteht vorzugsweise aus den Resten A1 und A2 und bedeutet insbesondere die Gruppe - A2-A1 -A2-. A preferably consists of the radicals A1 and A2 and in particular represents the group - A2-A1 -A2-.
Die wiederkehrenden Einheiten in den Resten A1 und A2 können statistisch verteilt oder blockweise vorliegen. Falls der Rest A2 sowohl Propylenglycolreste als auch Polytetrahydrofuraneinheiten aufweist, sind in einer bevorzugten Ausführungsform die Polytetrahydrofuraneinheiten endständig ange- ordnet. The repeating units in residues A1 and A2 can be randomly distributed or in blocks. If the radical A 2 has both propylene glycol radicals and polytetrahydrofuran units, in a preferred embodiment the polytetrahydrofuran units are terminally attached.
Die Reste A1 und A2 können substituiert sein, insbesondere mit einem Alkylrest mit 1 - 4 C- Atomen oder einem Arylrest, insbesondere Phenyl. Ein Beispiel für einen substituierten wiederkehrenden Rest ist der mit Phenyl substituierte Ethylenglycolrest (Styroloxid). The radicals A1 and A2 can be substituted, in particular with an alkyl radical having 1-4 C atoms or an aryl radical, in particular phenyl. An example of a substituted repeating radical is the phenyl-substituted ethylene glycol radical (styrene oxide).
Eine besonders bevorzugte Ausführungsform ist dadurch gekennzeichnet, dass A die Struktur -(PO)x-(EO)y-(PO)z- aufweist, worin bedeuten A particularly preferred embodiment is characterized in that A has the structure - (PO) x- (EO) y- (PO) z -, in which mean
EO Ethylenglycolrest EO ethylene glycol residue
PO Propylenglycolrest  PO propylene glycol residue
x, z gleich oder verschieden, eine Zahl von 1 bis 100, insbesondere 1 bis 20 x, z are the same or different, a number from 1 to 100, in particular 1 to 20
y eine Zahl von 1 bis 100, insbesondere 1 bis 90 y is a number from 1 to 100, in particular 1 to 90
In einer weiteren bevorzugten Ausführungsform bedeuten x, z gleich oder verschieden, eine Zahl von 5 bis 10 In another preferred embodiment, x, z, the same or different, are from 5 to 10
y eine Zahl von 60 bis 80, insbesondere von 65 bis 75. y is a number from 60 to 80, in particular from 65 to 75.
Die Struktur -(PO)x-(EO)y-(PO)z weist vorzugsweise einen EO-Gewichtsanteil von 5 bis 85 Gew.-% und eine zahlenmittlere Molmasse (Mn) von 200 bis 50000 g/mol auf. Besonders bevorzugte Verbindungen entsprechen folgender Formel
Figure imgf000005_0001
The structure - (PO) x - (EO) y - (PO) z preferably has an EO content by weight of 5 to 85 wt .-% and a number average molecular weight (Mn) of 200 to 50,000 g / mol. Particularly preferred compounds correspond to the following formula
Figure imgf000005_0001
PCX EO„ PCX  PCX EO "PCX
worin bedeuten x, z eine Zahl, gleich oder verschieden, von 0,1 bis 200, insbesondere von 5 bis 20 y eine Zahl, gleich oder verschieden, von 1 bis 100, insbesondere von 60 bis 80. Die erfindungsgemäßen Verbindungen eignen sich in hervorragender Weise zur Herstellung von Beschichtungen durch Aufbringen der Verbindungen auf die Oberfläche von Substraten und Polymerisation. in which x, z are a number, identical or different, of from 0.1 to 200, in particular from 5 to 20 y, a number, identical or different, of from 1 to 100, in particular from 60 to 80. The compounds according to the invention are outstandingly suitable A method for producing coatings by applying the compounds to the surface of substrates and polymerization.
Die Erfindung betrifft deshalb weiterhin ein Verfahren zur Herstellung von Beschichtungen auf Basis einer Verbindung der Formel I auf der Oberfläche eines Formartikels aus einem schmelzbaren Substrat S, insbesondere auf Fasern, in einem Schmelzspinnverfahren oder Folien nach Extrusion, wobei a) das Substrat in geschmolzener Form bereitgestellt wird, The invention therefore furthermore relates to a process for the preparation of coatings based on a compound of the formula I on the surface of a molded article of a fusible substrate S, in particular on fibers, in a melt spinning process or films after extrusion, wherein a) the substrate is provided in molten form becomes,
b) das geschmolzene Substrat über eine geeignete Vorrichtung V, vorzugsweise eine Düse oder einen Spalt, zu einem Formartikel, insbesondere zu einer Faser oder einer Folie, geformt wird, wobei b) the molten substrate is formed via a suitable device V, preferably a nozzle or a gap, to a molded article, in particular to a fiber or a film, wherein
c) der Formartikel beim Austritt aus der Vorrichtung V eine Temperatur oberhalb des Trübungspunkts der Verbindung der Formel I aufweist und c) the molded article at the outlet from the device V has a temperature above the cloud point of the compound of formula I, and
d) die Oberfläche des Formartikels oberhalb des Trübungspunkts mit der Verbindung der Formel I unter Abscheidung der Verbindung der Formel I in Kontakt gebracht wird, dadurch gekennzeichnet, dass nach Abscheidung auf der Oberfläche die Polymerisation der Doppelbindungen der Verbindung der Formel I initiiert wird unter Ausbildung einer vorzugswei- se vernetzten Beschichtung der Oberfläche. d) the surface of the molded article above the cloud point with the compound of formula I is brought under deposition of the compound of formula I in contact, characterized in that after deposition on the surface, the polymerization of the double bonds of the compound of formula I is initiated to form a preferably crosslinked coating of the surface.
Eine bevorzugte Ausführungsform ist dadurch gekennzeichnet, dass der Formartikel nach dem Austritt aus der Vorrichtung V in ein vorzugsweise wäss- riges Bad B geführt wird, welches die Verbindung der Formel I und gegebenenfalls einen Polymerisationsinitiator enthält, wobei bei Eintritt des Formartikels in das Bad der Formartikel eine Temperatur oberhalb des Trübungspunktes aufweist, die Verbindung der Formel I sich auf dem Formartikel abscheidet und A preferred embodiment is characterized in that after leaving the device V, the molded article is passed into a preferably aqueous bath B which contains the compound of the formula I and, if appropriate, a polymerization initiator, the mold article entering the bath of the molded article has a temperature above the cloud point, the compound of formula I is deposited on the molded article and
das Bad eine Temperatur unterhalb des Trübungspunktes aufweist und die Polymerisation bei einer Temperatur unterhalb des Trübungspunktes durchgeführt wird. the bath has a temperature below the cloud point and the polymerization is carried out at a temperature below the cloud point.
In einer weiteren Ausführungsform betrifft die Erfindung ein Verfahren zur Herstellung von Be- Schichtungen auf der Oberfläche eines Formartikels aus einem schmelzbaren Substrat S, insbesondere auf Fasern, in einem Schmelzspinnverfahren oder Folien nach Extrusion gemäß den oben angegebenen Schritten a) bis d), dadurch gekennzeichnet, dass nach Abscheidung der erfindungsgemäßen Verbindungen der Formel I auf der Oberfläche die Polymerisation der Doppelbindungen der Verbindungen der Formel I mittels Photopolymerisation durchgeführt wird. Die Photopolymerisation kann dadurch ausgelöst werden, dass entweder elektromagnetischeIn a further embodiment, the invention relates to a process for the production of laminations on the surface of a molded article made of a fusible substrate S, in particular fibers, in a melt spinning process or films after extrusion according to steps a) to d), characterized in that after deposition of the compounds of the formula I according to the invention on the surface, the polymerization of the double bonds of the compounds of the formula I is carried out by means of photopolymerization. The photopolymerization can be triggered by either electromagnetic
Strahlung der Wellenlänge eingestrahlt wird, die direkt von den Verbindungen der Formel I absorbiert wird, oder dass die Polymerisation ausgelöst wird mittels Bestrahlung unter Verwendung eine Photoinitiators. Eine weitere bevorzugte Ausführungsform ist dadurch gekennzeichnet, dass der Formartikel unmittelbar nach dem Austritt aus der Vorrichtung V mit einer Temperatur oberhalb des Trübungspunktes in eine Sprüheinrichtung geführt wird und dort mit der Verbindung der Formel I, vorzugsweise in Form einer wässrigen Lösung, besprüht wird, wobei die Temperatur des gesprühten Polymers unterhalb des Trübungspunktes liegt, unter Abscheidung der Verbindung der Formel I auf der Oberfläche des Substrates. Radiation of the wavelength is absorbed directly from the compounds of formula I, or that the polymerization is initiated by irradiation using a photoinitiator. A further preferred embodiment is characterized in that the molded article is passed immediately after exiting the device V at a temperature above the cloud point in a spray and sprayed there with the compound of formula I, preferably in the form of an aqueous solution, wherein the temperature of the sprayed polymer is below the cloud point, depositing the compound of formula I on the surface of the substrate.
Besonders bevorzugte Substrate sind Polyamide, Polyester, Polypropylen oder Polyurethane. In einer weiteren bevorzugten Ausführungsform ist das Substrat ein Glas, Stahl oder Holz. Die Polymerisation der Doppelbindungen kann im Bad B oder anschließend an die Behandlung im Bad B durchgeführt werden. Zur Initiierung der Polymerisation wird vorzugsweise ein Polymerisationsinitiator zugesetzt. Particularly preferred substrates are polyamides, polyesters, polypropylene or polyurethanes. In a further preferred embodiment, the substrate is a glass, steel or wood. The polymerization of the double bonds can be carried out in the bath B or subsequent to the treatment in the bath B. To initiate the polymerization, a polymerization initiator is preferably added.
Die Polymerisation der Acrylatgruppen der erfindungsgemäßen Verbindungen der Formel I er- folgt vorzugsweise radikalisch, insbesondere aus wässriger oder alkoholischer Lösung. Vorzugsweise erfolgt die Polymerisation in Gegenwart von Radikalbildnern, insbesondere anorganischen oder organischen Peroxiden, Azoverbindungen oder Metallen bzw. metallorganische Verbindungen. Zur Steuerung der Molmasse der erhaltenen Polymere können geeignete Polymerisationsregler, insbesondere Merkaptane, organische Halogenverbindungen, Aldehyde oder Xanthogenate oder Nitroxylradikalbildner zugesetzt werden. Die Polymerisation wird vorzugsweise bei Temperaturen von 50 bis 100 °C, insbesondere bei 60 bis 80 °C durchgeführt. The polymerization of the acrylate groups of the compounds of the formula I according to the invention preferably takes place free-radically, in particular from aqueous or alcoholic solution. The polymerization preferably takes place in the presence of radical formers, in particular inorganic or organic peroxides, azo compounds or metals or organometallic compounds. For controlling the molecular weight of the polymers obtained, suitable polymerization regulators, in particular mercaptans, organic halogen compounds, aldehydes or xanthates or nitroxyl radical formers may be added. The polymerization is preferably carried out at temperatures of 50 to 100 ° C, in particular at 60 to 80 ° C.
Die Polymerisation der Acrylatgruppen der erfindungsgemäßen Verbindungen der Formel I kann auch mittels eines Photoinitiators ausgelöst werden. Photoinitiatoren sind im Allgemeinen in Mengen von 0,01 bis 10 und insbesondere 0,01 bis 3 Gew.-%, bezogen auf die Verbindung der Formel I, vorhanden. Als Photoinitiatoren sind dabei solche Verbindungen geeignet, die bei Einwirkung von aktinischem Licht Radikale zu bilden vermögen und eine rasche Photopolymeri- sation der Verbindung der Formel I auslösen. Als Photoinitiatoren kommen z. B. in Frage Acylo- ine und Acyloinether, aromatische Diketone und deren Derivate und mehrkernige Chinone. Sehr geeignet sind Benzoin und alpha-Hydroxymethyl-benzoinmethylether oder Benzoinme- thylether, Benzoinisopropylether, Benzilmonoketale wie Benzildimethylketal, Benzil-methyl- ethylketal, Benzil-methyl-benzylketal, Benzil-neopentylketal oder Diarylphosphinoxide, wie sie in der DE-OS 29 09 992 beschrieben sind, vorzugsweise 2,6-Dimethoxy- benzoyldiphenylphosphinoxid und insbesondere 2,4,6-Trimethylbenzoyl-diphenylphosphinoxid. Bevorzugt sind Photoinitiatoren in Art und Menge, dass sie für die Auslösung der Photopolymerisation bei bildmäßiger Belichtung mit aktinischem Licht, insbesondere UV-Licht, nur kurze Mindestbelichtungszeiten, bevorzugt nicht mehr als wenige Minuten, benötigen. The polymerization of the acrylate groups of the compounds of the formula I according to the invention can also be initiated by means of a photoinitiator. Photoinitiators are generally present in amounts of 0.01 to 10 and especially 0.01 to 3 wt .-%, based on the compound of formula I. Suitable photoinitiators are those compounds which are capable of forming free radicals upon exposure to actinic light and which provide rapid photopolymerization. sation of the compound of formula I trigger. As photoinitiators come z. For example, acyloins and acyloin ethers, aromatic diketones and their derivatives and polynuclear quinones. Benzoin and alpha-hydroxymethylbenzoin methyl ethers or benzoin methyl ethers, benzoin isopropyl ethers, benzil monoketals such as benzil dimethyl ketal, benzil methyl ethyl ketal, benzil methyl benzyl ketal, benzil neopentyl ketal or diaryl phosphine oxides, as described in DE-OS 29 09 992, are very suitable are, preferably 2,6-dimethoxy-benzoyldiphenylphosphine oxide and in particular 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. Preference is given to photoinitiators in nature and amount that they require only short minimum exposure times, preferably not more than a few minutes, for the initiation of the photopolymerization on imagewise exposure to actinic light, in particular UV light.
Zusätzlich können bei Verwendung von Photoinitiatoren auch Inhibitoren gegen die thermische Polymerisation, wie Hydrochinon, p-Methoxyphenol, Dinitrobenzol, p-Chinon, Methylenblau, beta-Naphthol, N-Nitrosamine wie N-Nitrosodiphenylamin, Phenothiazin, Phosphorigsäureester wie Triphenylphosphit oder die Salze und insbesondere die Alkali- und Aluminiumsalze des N- Nitroso-cyclohexylhydroxylamins verwendet werden. Die Inhibitoren können in Mengen von 0,001 bis 3, vorzugsweise 0,01 bis 1 Gew.-%, bezogen auf die Verbindung der Formel I verwendet werden. In einer weiteren Ausführungsform können die Acrylatendgruppen in den erfindungsgemäß zu verwendenden Verbindungen der Formel I in einer Menge von 0,1 bis 99 mol %, insbesondere 20 bis 50 mol %, ersetzt sein durch Reste von: a) Maleinsäure oder Maleinsäurederivaten (insbesondere Ester) In addition, when using photoinitiators and thermal polymerization inhibitors, such as hydroquinone, p-methoxyphenol, dinitrobenzene, p-quinone, methylene blue, beta-naphthol, N-nitrosamines such as N-nitrosodiphenylamine, phenothiazine, phosphorous acid esters such as triphenyl phosphite or the salts and in particular the alkali and aluminum salts of N-nitroso-cyclohexylhydroxylamine be used. The inhibitors may be used in amounts of 0.001 to 3, preferably 0.01 to 1 wt .-%, based on the compound of formula I. In a further embodiment, the acrylate end groups in the compounds of the formula I to be used according to the invention can be replaced in an amount of 0.1 to 99 mol%, in particular 20 to 50 mol%, by radicals of: a) maleic acid or maleic acid derivatives (in particular esters)
b) Fumarsäure und ihre Ester b) fumaric acid and its esters
c) Hydroxyalkylacrylate c) hydroxyalkyl acrylates
d) Vinylether d) vinyl ethers
e) Glycidyl (Meth)Acrylat e) Glycidyl (meth) acrylate
f) Allylglycidylether f) allyl glycidyl ether
g) Hydroxylbutylvinylether g) hydroxybutyl vinyl ether
Herstellung der Verbindungen der Formel I Preparation of the compounds of the formula I.
In einer bevorzugten Ausführungsform werden die erfindungsgemäßen Verbindungen der For- mel I o o In a preferred embodiment, the compounds of the formula I o o
H2C = C C O— f A— | C C = CH2 dadurch hergestellt, dass man eine Verbindung der allgemeinen Formel H 2 C = CCO- f A- | CC = CH 2 prepared by reacting a compound of general formula
H 0 - A OH worin A die oben angegebene Bedeutung hat, mit einer Verbindung der Formel
Figure imgf000008_0001
und ggf.
Figure imgf000008_0002
H 0 - A OH wherein A has the meaning given above, with a compound of formula
Figure imgf000008_0001
and possibly
Figure imgf000008_0002
worin wherein
Ri und R2 die oben angegebene Bedeutung haben und Ri and R2 have the abovementioned meaning and
X Hydroxyl, Halogen, vorzugsweise Chlor eine Säuregruppe, eine Alkylgruppe oder eine Alko- xygruppe mit 1 bis 100 C-Atome bedeutet, im Mol Verhältnis von mindestens 1 : 1 bis 1 : 4, insbesondere 1 : 2 umsetzt.  X is hydroxyl, halogen, preferably chlorine, an acid group, an alkyl group or an alkoxy group having 1 to 100 carbon atoms, in a molar ratio of at least 1: 1 to 1: 4, in particular 1: 2.
Vorzugsweise wird die Reaktion durchgeführt in einem Lösungsmittel, wie tertiäre Monoole, bevorzugt tert.-Butanol, tert.-Amylalkohol, Pyridin, Poly-C1 -C4-alkylenglykoldi-C1 -C4-alkylether, bevorzugt Polyethylenglycoldi-C1 -C4-alkylether, wie z. B. 1 ,2-Dimethoxyethan, Diethylenglycol- dimethylether, Polyethylenglycol-dimethylether 500, Methyl-tert.-butylether, Ethyltert.-butylether, C1 -C4-Alkylencarbonate, insbesondere Propylencarbonat, C3-C6-Alkylessigsäureester, insbesondere tert.-Butylessigsäureester, Tetrahydrofuran, Toluol, 1 ,3-Dioxolan, Aceton, iso- Butylmethylketon, Ethylmethylketon, 1 ,4-Dioxan, tert.-Butylmethylether, Cyclohexan, Methylcyc- lohexan, Toluol, Hexan, Dimethoxymethan, 1 ,1 -Dimethoxyethan, Acetonitril, sowie deren ein oder mehrphasige Mischungen. The reaction is preferably carried out in a solvent such as tertiary monools, preferably tert-butanol, tert-amyl alcohol, pyridine, poly-C 1 -C 4 -alkylene glycol-C 1 -C 4 -alkyl ethers, preferably polyethylene glycol-C 1 -C 4 -alkyl ethers, such as z. B. 1, 2-dimethoxyethane, diethylene glycol dimethyl ether, polyethylene glycol dimethyl ether 500, methyl tert-butyl ether, ethyl tert-butyl ether, C1-C4-alkylene, in particular propylene carbonate, C3-C6-alkyl acetic acid ester, especially tert-butyl acetate, Tetrahydrofuran, toluene, 1, 3-dioxolane, acetone, isobutyl methyl ketone, ethyl methyl ketone, 1, 4-dioxane, tert-butyl methyl ether, cyclohexane, methylcyclohexane, toluene, hexane, dimethoxymethane, 1, 1-dimethoxyethane, acetonitrile, and their one- or multi-phase mixtures.
Es kann vorteilhaft sein, freiwerdendes Wasser abzutrennen, insbesondere aber ohne Lösungsmittel, also in den Acrylsäurederivate selbst, die Reaktion durchzuführen, insbesondere bei einer Temperatur von 20 bis 200 °C in Gegenwart von geeigneten chemischen Katalysatoren oder biologischen Enzymen, vorzugsweise bei einem pH von 2 bis 1 1 . It may be advantageous to separate water liberated, but in particular without solvent, ie in the acrylic acid derivatives themselves, to carry out the reaction, in particular at a temperature of 20 to 200 ° C in the presence of suitable chemical catalysts or biological enzymes, preferably at a pH of 2 to 1 1.
Bevorzugte erfindungsgemäße Verbindungen der Formel I können hergestellt werden durch 1 . direkte Umsetzung der vorgebildeten Verbindungen H O - A Η mit (Meth)Acrylsäure, bzw. (Meth)Acrylsäurederivaten Preferred compounds of the formula I according to the invention can be prepared by 1. direct implementation of the preformed compounds HO - A Η with (meth) acrylic acid, or (meth) acrylic acid derivatives
2. durch Umesterungsverfahren von Acryl sä ureestern und Methacrylsäureestern 2. by transesterification of acrylic acid esters and methacrylates
a) chemisch  a) chemical
b) enzymatisch katalysiert.  b) enzymatically catalyzed.
Als Acryl- oder Methacrylsäureester zur Umesterung können beispielsweise eingesetzt werden: Alkyl(meth)acrylate von gradkettigen, verzweigten oder cycloaliphatischen Alkoholen mit 1 bis 40 C-Atomen, wie zum Beispiel Methyl(meth)acrylat, Ethyl(meth)acrylat, n-Butyl(meth)acrylat, i- Butyl(meth)acrylat, t-Butyl(meth)acrylat, Pentyl(meth)acrylat, 2-Examples of acrylic or methacrylic acid esters which can be used for transesterification include: alkyl (meth) acrylates of straight-chain, branched or cycloaliphatic alcohols having 1 to 40 carbon atoms, for example methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, 2-
Ethylhexyl(meth)acrylat, Stearyl(meth)acrylat, Lauryl(meth)acry-Iat, Cyclohexyl(meth)acrylat, lsobornyl(meth)acrylat; Aryl(meth)acrylate, wie zum Beispiel Benzyl(meth)acrylat oder Phe- nyl(meth)acrylat, die jeweils unsubstituiert oder 1 -4-fach substituierte Arylreste aufweisen kön- nen; andere aromatisch substituierte (Meth)acrylate, wie beispielsweise Naphthyl(meth)acrylat; Mono(meth)acrylate von Ethern, Polyethylenglycolen, Polypropylenglycolen oder deren Mischungen mit 5 - 80 C-Atomen, wie beispielsweise Tetrahydrofurfurylmethacrylat, Me- thoxy(m)ethoxy-ethylmethacrylat, 1 -Butoxypropylmethacrylat, Cyclohexyloxymethylmethacrylat, Benzyl-oxymethylmethacrylat, Furfurylmethacrylat, 2-Butoxyethylmethacrylat, 2- Ethoxy- ethylmethacrylat, Allyloxymethylmethacrylat, 1 -Ethoxybutylmethacrylat, 1 -Ethoxy- ethylmethacrylat, Ethoxymethylmethacrylat, Poly(ethylenglycol)-methylether(meth) acrylat und Poly(propylenglycol)methyl-ether(meth)acrylat. Ethylhexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate; Aryl (meth) acrylates, for example benzyl (meth) acrylate or phenyl (meth) acrylate, which may each be unsubstituted or have 1-4-substituted aryl radicals; other aromatic substituted (meth) acrylates such as naphthyl (meth) acrylate; Mono (meth) acrylates of ethers, polyethylene glycols, polypropylene glycols or mixtures thereof with 5-80 C atoms, such as, for example, tetrahydrofurfuryl methacrylate, methoxy (m) ethoxyethyl methacrylate, 1-butoxypropyl methacrylate, cyclohexyloxymethyl methacrylate, benzyl oxymethyl methacrylate, furfuryl methacrylate, 2- Butoxyethyl methacrylate, 2-ethoxyethyl methacrylate, allyloxymethyl methacrylate, 1-ethoxybutyl methacrylate, 1-ethoxyethyl methacrylate, ethoxymethyl methacrylate, poly (ethylene glycol) -methyl ether (meth) acrylate and poly (propylene glycol) methyl ether (meth) acrylate.
Bevorzugte Parameter bei der direkten Herstellung sind: Preferred parameters in the direct production are:
Temperatur: 80 - 160 °C, vorzugsweise 90 - 130 °C Temperature: 80-160 ° C, preferably 90-130 ° C
Alkohol/(Meth)acrylsäure: 1 : 0,7 - 1 ,2 (molar)  Alcohol / (meth) acrylic acid: 1: 0.7-1.2 (molar)
Katalysator: Schwefelsäure oder Sulfonsäuren, bevorzugt Methansulfonsäure Catalyst: sulfuric acid or sulfonic acids, preferably methanesulfonic acid
Katalysatormenge: 0,1 - 10 Gew.-% (vorzugsweise 0,5 - 5 Gew.-%) bzgl. EinsatzstoffeAmount of catalyst: 0.1-10% by weight (preferably 0.5-5% by weight) with respect to starting materials
Reaktionszeit: 1 - 10 Std., vorzugsweise 1 - 6 Std. Reaction time: 1 - 10 hours, preferably 1 - 6 hours
Gegebenenfalls wird ein Schleppmittel (z. B. Cyclohexan oder Toluol) zur Entfernung des Veresterungswassers eingesetzt. Die Veresterung kann drucklos, mit Überdruck oder Unterdruck sowohl kontinuierlich als auch diskontinuierlich durchgeführt werden. Optionally, an entraining agent (eg, cyclohexane or toluene) is used to remove the esterification water. The esterification can be carried out without pressure, with overpressure or underpressure both continuously and discontinuously.
Bevorzugte Parameter und Einsatzstoffe bei der Umesterung sind: Preferred parameters and starting materials in the transesterification are:
Temperatur: 30 - 180 °C bevorzugt 50 - 130 °C Temperature: 30-180 ° C, preferably 50-130 ° C
Katalysatormenge: 0,01 bis 10 Gew.-% Katalysator, bevorzugt von 0,1 bis 5 Gew.-%, be- sonders bevorzugt von 0,2 bis 2 Gew.-% Katalysator, bezogen auf die gesamte Reaktionsmischung durchgeführt. Katalysatoren: Organylmetaloxide, Organylmetallhalogenide wie Diorganylzinnoxide, Catalyst quantity: 0.01 to 10% by weight of catalyst, preferably from 0.1 to 5% by weight, more preferably from 0.2 to 2% by weight of catalyst, based on the total reaction mixture. Catalysts: organylmetal oxides, organylmetal halides such as diorganyltin oxides,
Diorganylzinnhalogenide, Alkalisalze der anorganischer Säure insbe- sondere der Phosphorsäure, Übergangsmetallalkoholate wie Titanalko- holate, Alkaliamide wie Lithiumamid, Alkali- und Erdalkalialkoholate wie Kalium-tert.butylat, Säuren wie Schwefelsäure, Alkyl- oder Arylsulfon- säuren z.B. p-Toluolsulfonsäure und Methansulfonsäure, anorganische saure oder basische (Misch)oxide wie Zeolite, Aluminiumsiliziummi- schoxid, Titaniumsiliziummischoxid bzw. Magnesiumoxid, oder Magne- siumsilicate mit und ohne Lösungsmittel in Überschüssen von (Meth)Acrylsäureestern von 1 : 50 bis 1 :500 mol/mol, besonders bevorzugt 1 :100 bis 1 :400 bezogen auf das Substrat.  Diorganyltin halides, alkali metal salts of inorganic acid, in particular of phosphoric acid, transition metal alcoholates such as titanium alkoxides, alkali metal amides such as lithium amide, alkali metal and alkaline earth metal alkoxides such as potassium tert-butylate, acids such as sulfuric acid, alkyl- or arylsulfonic acids, e.g. p-toluenesulfonic acid and methanesulfonic acid, inorganic acidic or basic (mixed) oxides such as zeolites, aluminum silicon mixed oxide, titanium-silicon mixed oxide or magnesium oxide, or magnesium silicates with and without solvent in excess of (meth) acrylic acid esters of from 1:50 to 1: 500 mol / mol, more preferably 1: 100 to 1: 400 based on the substrate.
Die chemische Umesterung kann drucklos, mit Uberdruck oder Unterdruck sowohl kontinuierlich als auch diskontinuierlich durchgeführt werden The chemical transesterification can be carried out without pressure, with overpressure or underpressure both continuously and discontinuously
Die enzymatisch katalysierte Umesterung erfolgt vorzugsweise unter folgenden Bedingungen: Temperatur: 10 - 80 °C, besonders bevorzugt bei 20 - 40°C The enzymatically catalyzed transesterification is preferably carried out under the following conditions: temperature: 10 ° -80 ° C., more preferably 20 ° -40 ° C.
pH: 5 - 8 pH: 5 - 8
Katalysator: Lipasen mit und ohne Lösungsmittel in Überschüssen von (Meth)Acrylsäureestern von 1 : 50 bis 1 : 500 mol/mol, besonders bevorzugt 1 : 100 bis 1 : 400 in Bezug auf das Substrat.  Catalyst: lipases with and without solvent in excess of (meth) acrylic acid esters of from 1:50 to 1: 500 mol / mol, more preferably from 1: 100 to 1: 400, relative to the substrate.
Die enzymatische Umesterung kann drucklos, mit Überdruck oder Unterdruck sowohl kontinuierlich als auch diskontinuierlich durchgeführt werden Bevorzugte Vorrichtungen V sind beispielsweise a) die zum Schmelzspinnverfahren für Fasern bekannten Vorrichtungen. The enzymatic transesterification can be carried out without pressure, with overpressure or underpressure both continuously and discontinuously. Preferred devices V are, for example, a) the devices known for the melt-spinning process for fibers.
Diese weisen für das erfindungsgemäße Verfahren je nach Ausführungsform entweder eine Sprühvorrichtung unmittelbar im Anschluss an den Austritt der Faser an die Düse auf oder ein Bad, welches vorzugsweise eine wässrige Lösung des erfindungsgemäßen Polymeren enthält. Dieses Bad kann zusätzlich einen Polymerisationsinitiator zur Durchführung der Polymerisation enthalten. Es ist aber auch möglich, den Polymerisationsinitiator in einem zusätzlichen weiteren Bad auf die Faser aufzubringen. Dies ist insbesondere vorteilhaft, um eine vorzeitige Polymerisation im Fällungsbad zu vermeiden. b) die zur Herstellung von Folien an sich bekannten Anlagen, beispielsweise auf Basis eines Extruders, der die Schmelze des Substrates fördert, bzw. das Substrat aufschmilzt und durch eine Düse, insbesondere eine Breitschlitzdüse, extrudiert unter Bildung eines Films. In einer weiteren bevorzugten Ausführungsform werden zusammen mit den erfindungsgemäßen Verbindungen der Formel I Effektstoffe auf dem Formkörper abgeschieden. Unter Effektstoffen werden insbesondere Verbindungen verstanden, welche die Eigenschaften des Formkörpers, insbesondere der Folien und Fasern verbessern, wie beispielsweise UV-Stabilisatoren, Pigmente, Nanopartikel, IR-absorbierende Verbindungen usw. Dazu können die Effektstoffe zusammen mit der Verbindung der Formel I vorzugsweise im Bad B enthalten sein. Depending on the embodiment, these have either a spraying device immediately following the exit of the fiber from the nozzle or a bath which preferably contains an aqueous solution of the polymer according to the invention. This bath may additionally contain a polymerization initiator for carrying out the polymerization. But it is also possible to apply the polymerization in an additional additional bath on the fiber. This is particularly advantageous in order to avoid premature polymerization in the precipitation bath. b) the plants known per se for the production of films, for example based on an extruder, which promotes the melt of the substrate, or the substrate melts and extruded through a nozzle, in particular a slot die, to form a film. In a further preferred embodiment, effect substances are deposited on the shaped body together with the compounds of the formula I according to the invention. Under effect substances are understood in particular compounds which improve the properties of the shaped body, in particular the films and fibers, such as UV stabilizers, pigments, nanoparticles, IR-absorbing compounds, etc. For this purpose, the effect substances together with the compound of formula I, preferably in the bath B be included.
Die erfindungsgemäßen Formartikel, d. h. Folien und Fasern können in an sich bekannter Weise gestreckt werden, insbesondere auch nach Auftrag und Polymerisation der Acrylatgruppen. The molded articles according to the invention, d. H. Films and fibers can be stretched in a manner known per se, in particular also after application and polymerization of the acrylate groups.
Beispiele Examples
Beispiel 1 .1 Synthese von Polyethylenglycol-Polyproyplenglycol Copolymeren Example 1 .1 Synthesis of Polyethylene Glycol Polypropylene Glycol Copolymers
HO^\o/^OH + m Ä ♦ 2n Λ H°+P°^f E°^P°^°H HO ^ \ o / ^ OH + m 2n Λ H ° + P ° ^ f E ° ^ P ° ^ ° H
In einen gereinigten 5 I- Stahlreaktor wurde Diethylenglycol (53,05 g, 0,5 mol) und Kalium-t- butylat (10,2 g; 0,5 Gew.-% der Endmenge) vorgelegt. Man inertisierte dreimal mit Stickstoff bis 5 bar und dosierte nach Erreichen von 120 °C Ethylenoxid massengesteuert zu (1364,0 g). An- schließend wurde die Temperatur auf 130 °C erhöht und innerhalb von 700 min Propylenoxid (638 g; 1 1 mol) zugegeben. Man ließ 4 h Nachreagieren und kühlte auf 80 °C unter Rühren. To a purified 5 l steel reactor was added diethylene glycol (53.05 g, 0.5 mol) and potassium t-butylate (10.2 g, 0.5 wt% of the final amount). It was made inert three times with nitrogen to 5 bar and dosed after reaching 120 ° C ethylene oxide mass controlled to (1364.0 g). The temperature was then increased to 130 ° C. and propylene oxide (638 g, 11 mol) was added over the course of 700 minutes. The mixture was allowed to react for 4 h and cooled to 80 ° C with stirring.
Das Rohprodukt wurde mit Magnesiumsilikat (3 Gew.-%) versetzt und nach 1 h Rühren am Rotationsverdampfer über ein 900er Seitz-Filtermedium druckfiltriert. The crude product was mixed with magnesium silicate (3 wt .-%) and pressure-filtered after 1 h stirring on a rotary evaporator over a 900 Seitz filter medium.
Das Produkt wurde mittels einer Bestimmung des Trübungspunkts gemäß des Verfahrens E gemäß EN 1890 charakterisiert: Dazu wurden 5 g Probe in 25 g wässrige Butyldiglykol-Lösung (c = 250 g/l) gelöst und erwärmt. The product was characterized by a cloud point determination according to Method E according to EN 1890: To this was dissolved 5 g sample in 25 g aqueous butyldiglycol solution (c = 250 g / l) and heated.
Ausbeute : 2101 ,33 g Yield: 2101, 33 g
Mn: 4700 Mn: 4700
Mw: 5000 Mw: 5000
Trübungspunkt: 71 °C Beispiel 1 .2: Synthese von (Polyethylenglycol-Polyproyplenglycol)diacrylat:
Figure imgf000012_0001
Cloud point: 71 ° C Example 1 .2: Synthesis of (polyethylene glycol-polyproylene glycol) diacrylate:
Figure imgf000012_0001
In einem 6 I-Vierhalskolben vereinte man PPG-PEG-PPG (250 g; 0,05 mol) aus Beispiel 1 .1 , Ethylacrylat (1000 g; 10 mol), Molsieb 5 Ä Pulver (Fluka) 55,5 g (10-fache Menge bezogen auf theoretische Menge an entstehendem Alkohol). Als Stabilisatoren wurden zugefügt 4-Methoxyphenol (MeHQ): 98,6 mg; (Aldrich) (99 % [GC]) (400 ppm bezogen auf theoretische Menge an Produkt); Phenothiazin (PTZ): 3,0 mg (Fluka) (purum; > 98,0 % [GC]) (10 ppm bezogen auf theoretische Menge an Produkt). PPG-PEG-PPG (250 g, 0.05 mol) from example 1 .1, ethyl acrylate (1000 g, 10 mol), molecular sieve 5 A powder (Fluka) 55.5 g (10 -fold amount based on theoretical amount of resulting alcohol). The stabilizers added were 4-methoxyphenol (MeHQ): 98.6 mg; (Aldrich) (99% [GC]) (400 ppm based on theoretical amount of product); Phenothiazine (PTZ): 3.0 mg (Fluka) (purum;> 98.0% [GC]) (10 ppm based on theoretical amount of product).
In der Aufheizphase wurden bei ca. 30 °C Novozym 435 (33,71 g) (7,0 wt% bezogen auf Ein- satzstoff) zugegeben. Den Ansatz ließ man 48 h bei 40 °C (Bad 46 °C) und 150 rpm mittels Glas-PTFE-Intensivrührer unter Lufteinleitung rühren. In the heating phase, Novozym 435 (33.71 g) (7.0% by weight, based on starting material) was added at about 30.degree. The mixture was allowed to stir for 48 h at 40 ° C (bath 46 ° C) and 150 rpm by means of glass PTFE intensive stirrer with the introduction of air.
Anschließend wurde der Ansatz über eine mit Kieselgel 60 (0,040-0,064 mm) gefüllte 4 I- Glasfilternutsche G 2 bei ca. 500-600 mbar abgesaugt, mit 4 I Aceton nachgewaschen und bei 60 °C unter Lufteinleitung zur Entfernung von Ethylacrylat- Resten im Rotationsverdampfer getrocknet. The mixture was then filtered off with suction through a 4 l glass filter chute G 2 filled with silica gel 60 (0.040-0.064 mm) at approx. 500-600 mbar, washed with 4 l acetone and at 60 ° C. with introduction of air to remove ethyl acrylate residues in Rotary evaporator dried.
Das Produkt wurde mittels einer Bestimmung des Trübungspunkts gemäß des Verfahrens E gemäß EN 1890 charakterisiert: Dazu wurden 5 g Probe in 25 g wässrige Butyldiglykol-Lösung (c = 250 g/l) gelöst und erwärmt. The product was characterized by a cloud point determination according to Method E according to EN 1890: To this was dissolved 5 g sample in 25 g aqueous butyldiglycol solution (c = 250 g / l) and heated.
Ausbeute: 260 g klares Öl, erstarrt bei Raumtemperatur Yield: 260 g of clear oil, solidified at room temperature
Mn: 4900  Mn: 4900
Mw: 5200 Mw: 5200
Trübungspunkt: 66 °C  Cloud point: 66 ° C
Beispiel 2: Fasercoating Die Faserbeschichtung wird am Beispiel eines Schmelzspinnverfahrens für Polypropylen geprüft. Dazu wird eine wässrige Lösung aus folgenden Komponenten (Gew.-%) verwendet: Example 2: Fiber Coating The fiber coating is tested using the example of a melt spinning process for polypropylene. For this purpose, an aqueous solution of the following components (% by weight) is used:
10 % LCST-Poylmer gemäß Beispiel 1 .3 10% LCST polymer according to Example 1 .3
0,5 % Ethylendiamintetraessigsäurenatriumsalz 0.5% ethylenediaminetetraacetic acid sodium salt
0,1 % Haftvermittler (Polyethylenimin) 0.1% adhesion promoter (polyethyleneimine)
0,5 % Radikalstarter 2,2'-Azobis[2-(2-imidazolin-2yl)propan]dihydrochlorid Rest: Wasser 0.5% radical initiator 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride Rest: water
In einer zweistufigen Extrusionsspinnanlage (POY, FDY) werden Mikrofasern (120 dtexf32) [dtex: ist eine Maßeinheit für die Feinheit von Fäden. Bezeichnet wird das Gewicht in g bei 10000 m Faser] aus einer Schmelze bei einer Düsenstemperatur von 295 °C erhalten. Im Verlauf des Abkühlungsprofils wird die Faser bei einer Temperatur von 80 - 100 °C (ca. 100 cm nach Austritt des Fasermaterials aus der Spinndüse) mit der LCST-Polymerlösung durch Besprühen in Kontakt gebracht. Die erhaltenen faserbeschichteten Garne zeichnen sich durch verbesserte Eigenschaften aus, insbesondere hinsichtlich Flexibilität und Aufziehverhalten. In a two-stage extrusion spinning line (POY, FDY) microfibers (120 dtexf32) [dtex: is a unit of measure for the fineness of threads. Described is the weight in g at 10000 m fiber] obtained from a melt at a nozzle temperature of 295 ° C. In the course of the cooling profile, the fiber is brought into contact with the LCST polymer solution by spraying at a temperature of 80-100 ° C. (about 100 cm after the exit of the fiber material from the spinneret). The resulting fiber-coated yarns are characterized by improved properties, in particular in terms of flexibility and Aufziehverhalten.

Claims

Patentansprüche claims
Verbindungen der allgemeinen Formel I Compounds of the general formula I
Figure imgf000014_0001
worin bedeuten
Figure imgf000014_0001
in which mean
Ri und R2 (unabhängig voneinander) Wasserstoff oder einen Alkylrest, insbesondere R 1 and R 2 (independently of one another) are hydrogen or an alkyl radical, in particular
Methyl  methyl
A einen Rest enthaltend die Reste A1 und A2,
Figure imgf000014_0002
Figure imgf000014_0003
A is a radical containing the radicals A1 and A2,
Figure imgf000014_0002
Figure imgf000014_0003
worin bedeuten in which mean
R3 bis R6 gleich oder verschieden, H, C1 - bis C5-Alkyl, insbesondere Methyl, Ethyl, Propyl oder Aryl, insbesondere Phenyl, R 3 to R 6 are identical or different, H, C 1 - to C 5 -alkyl, in particular methyl, ethyl, propyl or aryl, in particular phenyl,
I 1 oder 0 I 1 or 0
m 1 oder 0, wobei I + m mindestens 1 bedeuten,  m is 1 or 0, where I + m is at least 1,
n 1 bis 100  n 1 to 100
o 0 bis 5  o 0 to 5
p 0 bis 5, wobei o + p 3 bis 5 bedeuten,  p 0 to 5, where o + p is 3 to 5,
q 1 bis 100, dadurch gekennzeichnet, dass die Verbindung der Formel I gemäß Deutsche Norm DIN EN 1890 vom September 2006, Methode gemäß Verfahren E, einen Trübungspunkt von 40 bis 80 °C, insbesondere 60 bis 80 °C, aufweist und die Einheiten A2 endständig im Rest A enthalten sind. Verbindungen gemäß Anspruch 1 , dadurch gekennzeichnet, dass A aus den Resten A1 und A2 besteht. q 1 to 100, characterized in that the compound of formula I according to German standard DIN EN 1890 of September 2006, method according to method E, a cloud point of 40 to 80 ° C, in particular 60 to 80 ° C, and the units A2 are contained terminally in the radical A. Compounds according to claim 1, characterized in that A consists of the radicals A1 and A2.
Verbindungen gemäß wenigstens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass A1 einer der folgenden Reste ist
Figure imgf000015_0001
Compounds according to at least one of the preceding claims, characterized in that A1 is one of the following radicals
Figure imgf000015_0001
Verbindungen gemäß wenigstens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass A2 einer der folgenden Reste ist Compounds according to at least one of the preceding claims, characterized in that A2 is one of the following radicals
Figure imgf000015_0002
pTHF — ^CH2-CH2-CH2-CH2-04—
Figure imgf000015_0002
pTHF - ^ CH 2 -CH 2 -CH 2 -CH 2 -04-
Verbindungen gemäß wenigstens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass A eine der folgenden Strukturen aufweist Compounds according to at least one of the preceding claims, characterized in that A has one of the following structures
- (PO)x-(EO)y-(PO)z oder - (PO) x- (EO) y - (PO) z or
- -(pTHF-)x-(EO)y-(pTHF)z-, worin EO, PO und pTHF die in den Ansprüchen 2 und 3 angegebene Bedeutung haben und worin bedeuten - - (pTHF-) x - (EO) y - (pTHF) z -, wherein EO, PO and pTHF are as defined in claims 2 and 3 and wherein
x, z gleich oder verschieden, eine Zahl von 1 bis 100, insbesondere 1 bis 10 y eine Zahl von 1 bis 100, insbesondere von 10 bis 90. x, z are identical or different, a number from 1 to 100, in particular from 1 to 10, a number from 1 to 100, in particular from 10 to 90.
Verbindung gemäß Anspruch 5, dadurch gekennzeichnet, dass bedeuten gleich oder verschieden, eine Zahl von 5 bis 20 Compound according to Claim 5, characterized in that the same or different mean a number from 5 to 20
eine Zahl von 60 bis 80, insbesondere von 65 bis 75. Verwendung der Verbindungen gemäß wenigstens einem der vorhergehenden Ansprüche zur Herstellung von Beschichtungen durch Aufbringen der Verbindungen auf die Oberfläche eines Substrates und Polymerisation. a number from 60 to 80, especially from 65 to 75. Use of the compounds according to at least one of the preceding claims for the preparation of coatings by applying the compounds to the surface of a substrate and polymerization.
Verfahren zur Herstellung von Beschichtungen auf Basis einer Verbindung der Formel I gemäß wenigstens einem der vorhergehenden Ansprüche auf der Oberfläche eines Formartikels aus einem schmelzbaren Substrat S, insbesondere auf Fasern in einem Process for the preparation of coatings based on a compound of the formula I according to at least one of the preceding claims on the surface of a molded article made of a fusible substrate S, in particular fibers in one
Schmelzspinnverfahren oder Folien nach Extrusion, wobei a) das Substrat in geschmolzener Form bereitgestellt wird,  Melt spinning processes or films after extrusion, wherein a) the substrate is provided in molten form,
b) das geschmolzene Substrat über eine geeignete Vorrichtung V, vorzugsweise eine Düse oder einen Spalt, zu einem Formartikel, insbesondere zu einer Faser oder einer Folie, geformt wird, wobei  b) the molten substrate is formed via a suitable device V, preferably a nozzle or a gap, to a molded article, in particular to a fiber or a film, wherein
c) der Formartikel beim Austritt aus der Vorrichtung V eine Temperatur oberhalb des Trübungspunkts der Verbindung der Formel I aufweist und  c) the molded article at the outlet from the device V has a temperature above the cloud point of the compound of formula I, and
d) die Oberfläche des Formartikels oberhalb des Trübungspunkts mit der Verbindung der Formel I unter Abscheidung der Verbindung der Formel I in Kontakt gebracht wird, dadurch gekennzeichnet, dass nach Abscheidung auf der Oberfläche die Polymerisation der Doppelbindungen der Verbindung der Formel I initiiert wird unter Ausbildung einer vorzugsweise vernetzten Beschichtung der Oberfläche.  d) the surface of the molded article above the cloud point with the compound of formula I is brought under deposition of the compound of formula I in contact, characterized in that after deposition on the surface, the polymerization of the double bonds of the compound of formula I is initiated to form a preferably crosslinked coating of the surface.
Verfahren gemäß Anspruch 8, dadurch gekennzeichnet, dass der Formartikel nach dem Austritt aus der Vorrichtung V in ein vorzugsweise wäss- riges Bad B geführt wird, welches die Verbindung der Formel I und gegebenenfalls einen Polymerisationsinitiator enthält, wobei bei Eintritt des Formartikels in das Bad der Formartikel eine Temperatur oberhalb des Trübungspunktes aufweist, die Verbindung der Formel I sich auf dem Formartikel abscheidet A method according to claim 8, characterized in that the molded article is passed after exiting the device V in a preferably aqueous bath B containing the compound of formula I and optionally a polymerization initiator, wherein upon entry of the molded article in the bath of the Formed article has a temperature above the cloud point, the compound of formula I is deposited on the molded article
das Bad eine Temperatur unterhalb des Trübungspunktes aufweist und  the bath has a temperature below the cloud point and
die Polymerisation bei einer Temperatur unterhalb des Trübungspunktes durchgeführt wird oder dass  the polymerization is carried out at a temperature below the cloud point or
nach Abscheidung der erfindungsgemäßen Verbindungen der Formel I auf der Oberfläche die Polymerisation der Doppelbindungen der Verbindungen der Formel I mittels Photopolymerisation durchgeführt wird.  after deposition of the compounds of the formula I according to the invention on the surface, the polymerization of the double bonds of the compounds of the formula I is carried out by means of photopolymerization.
0. Verfahren gemäß Anspruch 8, dadurch gekennzeichnet, dass der Formartikel unmittelbar nach dem Austritt aus der Vorrichtung V mit einer Temperatur oberhalb des Trübungspunktes in eine Sprüheinrichtung geführt wird und dort mit der Verbindung der Formel I, vorzugsweise in Form einer wässrigen Lösung, besprüht wird, wobei die Temperatur des gesprühten Polymers unterhalb des Trübungspunktes liegt, unter Abscheidung der Verbindung auf der Oberfläche des Substrates. 0. The method according to claim 8, characterized in that the molded article is passed immediately after leaving the device V at a temperature above the cloud point in a spray and sprayed there with the compound of formula I, preferably in the form of an aqueous solution , the temperature of the sprayed polymer is below the cloud point, depositing the compound on the surface of the substrate.
1 1 . Verfahren nach wenigstens einem der vorhergehenden Ansprüche, dadurch gekenn- zeichnet, dass das Substrat ein Polyamid, Polyester, Polypropylen oder Polyurethan ist. 1 1. Method according to at least one of the preceding claims, characterized in that the substrate is a polyamide, polyester, polypropylene or polyurethane.
12. Verfahren nach wenigstens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Formartikel nach der Beschichtung gereckt und aufgewickelt wird. 13. Verfahren nach wenigstens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Substrat ein Glas, Stahl oder Holz ist. 12. The method according to at least one of the preceding claims, characterized in that the molded article is stretched and wound after the coating. 13. The method according to at least one of the preceding claims, characterized in that the substrate is a glass, steel or wood.
14. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass die Polymerisation der Doppelbindungen anschließend an die Behandlung im Bad B durchgeführt wird. 14. The method according to claim 7, characterized in that the polymerization of the double bonds is carried out subsequent to the treatment in the bath B.
15. Formartikel, erhältlich gemäß wenigstens einem der vorhergehenden Ansprüche. 15. A molded article obtainable according to at least one of the preceding claims.
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US9556395B2 (en) 2013-03-11 2017-01-31 Basf Se Use of polyalkoxylates in lubricant compositions
EP3397819A4 (en) * 2015-12-31 2019-05-29 CertainTeed Corporation Building assembly including a weather resistant barrier, a sheet for use as a weather resistant barrier, a liquid coating composition and methods of making the foregoing
US10508435B2 (en) 2015-12-31 2019-12-17 Certainteed Corporation Building assembly including a weather resistant barrier, a sheet for use as a weather resistant barrier, a liquid coating composition and methods of making the foregoing

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CN103476830A (en) 2013-12-25
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MX2013010424A (en) 2013-10-03
SG194002A1 (en) 2013-11-29
AU2012241931A1 (en) 2013-10-24
BR112013023946A2 (en) 2016-12-13
KR20140038403A (en) 2014-03-28
EP2697284A1 (en) 2014-02-19

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