EP3555163A1 - Fluorhaltiges polyurethan-prepolymer sowie fluorhaltiges polyurethan, insbesondere zur beschichtung von gegenständen - Google Patents
Fluorhaltiges polyurethan-prepolymer sowie fluorhaltiges polyurethan, insbesondere zur beschichtung von gegenständenInfo
- Publication number
- EP3555163A1 EP3555163A1 EP17825175.7A EP17825175A EP3555163A1 EP 3555163 A1 EP3555163 A1 EP 3555163A1 EP 17825175 A EP17825175 A EP 17825175A EP 3555163 A1 EP3555163 A1 EP 3555163A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fluorine
- polyurethane prepolymer
- polyol
- containing polyurethane
- free
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
- C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
- B65H2404/00—Parts for transporting or guiding the handled material
- B65H2404/50—Surface of the elements in contact with the forwarded or guided material
- B65H2404/53—Surface of the elements in contact with the forwarded or guided material with particular mechanical, physical properties
Definitions
- Fluorine-containing polyurethane prepolymer and fluorine-containing polyurethane in particular for
- the present invention relates to a fluorine-containing polyurethane prepolymer, a process for producing a fluorine-containing polyurethane prepolymer, a fluorine-containing polyurethane, a process for producing a fluorine-containing polyurethane, a composition comprising a fluorine-containing polyurethane prepolymer or fluorine-containing polyurethane, and a fluorine-containing polyurethane Prepolymer or fluorine-containing polyurethane coated article, a process for coating an article, and the use of a fluorine-containing polyurethane prepolymer and a fluorine-containing polyurethane for coating a roll.
- Rubber materials suffer from the fundamental disadvantage that they have a comparatively limited wear resistance compared to other materials.
- the intended as roll covers rubber materials are therefore usually compounded with reinforcing fillers. In principle, this makes it possible to improve the wear resistance of the rubber covers and the service life of coated rolls.
- the surface properties of the roll covers can be influenced by the presence of fillers.
- both the correct amount (layer thickness) and the uniformity within the paper web width and in the machine direction are important.
- Surface properties, in particular surface polarity, of the rolls play an essential role in achieving an optimum result.
- the invention therefore has the object of providing polymer materials which are particularly suitable for the production of coatings or for use as coatings for rolls, preferably paper rolls, and which in particular known from the prior art, in connection with roll laminations or -bezeln described Avoid disadvantages as far as possible.
- the polymer materials should have surface properties which are at least comparable to conventional rubber coatings but have better mechanical properties, in particular higher wear resistance, than conventional rubber coatings.
- the invention relates to a fluorine-containing polyurethane prepolymer (fluorine-containing polyurethane prepolymer).
- the polyurethane prepolymer is characterized in particular by reacting a reaction mixture containing a precursor of the polyurethane prepolymer, a polyol and a polyisocyanate, wherein the precursor is a fluorine-containing precursor and / or the polyol is a fluorine-containing, preferably perfluorinated, polyol , manufactured or manufacturable.
- the preparation of the fluorine-containing polyurethane prepolymer is based on a polyaddition reaction between the above-mentioned reaction components to form so-called urethane groups (-NH-CO-O-).
- a block copolymeric polyurethane prepolymer is preferably obtained.
- fluorine-containing polyurethane prepolymer is to be understood as meaning an oligomeric or polymeric, preferably polymeric, precursor or intermediate of a polyurethane, in particular a high molecular weight polyurethane, which has fluorine atoms
- prepolymer is understood as meaning a prepolymer which has carbon-fluorine bonds or in which hydrogen atoms of carbon-hydrogen bonds are partially replaced, in particular only partially, by fluorine atoms or substituted.
- fluorine-containing polyurethane is to be understood as meaning a polyurethane, in particular a high molecular weight polyurethane, which has fluorine atoms. Has fluorine bonds or in which hydrogen atoms of carbon-hydrogen bonds partially replaced, in particular only partially, by fluorine atoms or substituted.
- a polyurethane in the context of the present invention is furthermore, as will be explained in more detail below, preferably prepared or preparable by mixing or reacting a fluorine-containing polyurethane prepolymer with a chain extender and / or crosslinking agent.
- the polyurethane may have, in addition to urethane groups (-NH-CO-O-), further structural elements, in particular urea groups (-NH-CO-NH-). In these cases, the polyurethane may also be referred to as a type of hybrid polymer.
- polyol is understood to mean a preferably organic compound having at least two hydroxyl groups (OH groups), ie two or more hydroxy groups. Accordingly, the term “polyol” in the context of the present invention is used for example Diols and triols are detected, with diols, ie Compounds having two hydroxy groups, are preferred, which will be discussed in more detail below.
- fluorine-free polyol defined in the context of the present invention, a polyol which is free of fluorine atoms, that has no fluorine atoms.
- fluorine-containing polyol for the purposes of the present invention defines a polyol which has fluorine atoms, in particular a polyol in which hydrogen atoms of Carbon-hydrogen bonds are at least partially, in particular only partially, replaced by fluorine atoms or substituted.
- perfluorinated polyol for the purposes of the present invention defines a polyol in which all hydrogen atoms of carbon-hydrogen bonds are replaced or substituted by fluorine atoms.
- polyisocyanate is understood to mean a preferably organic compound having at least two isocyanate groups (NCO groups), ie two or more isocyanate groups. Accordingly, the term “polyisocyanate” in the context of the present invention is used for example Diisocyanates and triisocyanates detected, with diisocyanates, ie Compounds with two isocyanate groups, are preferred, which will be discussed in more detail below.
- fluorine-free polyisocyanate defines a polyisocyanate which is free from fluorine atoms, ie has no fluorine atoms.
- the term "precursor" used in connection with a fluorine-containing polyurethane prepolymer according to the invention can mean a commercially available product which can be used as the starting material for the preparation of a fluorine-containing polyurethane prepolymer according to the invention or, alternatively, an intermediate which can be used
- the term "precursor” in the sense of the present invention preferably means a polyurethane prepolymer which has a lower number average molecular weight than the fluorine-containing (final) invention to be prepared Polyurethane prepolymer.
- fluorine-containing precursor in the sense of the present invention may mean a fluorine-containing, commercially available product which can be used as a starting material for the preparation of a fluorine-containing polyurethane prepolymer according to the invention, or alternatively a fluorine-containing intermediate which is used in the preparation of a fluorine-containing
- fluorine-containing precursor in the context of the present invention preferably means a fluorine-containing polyurethane prepolymer which has a lower number-average molecular weight than the (final) fluorine-containing polyurethane prepolymer of the invention to be prepared .
- fluorine-containing precursor should preferably be understood as meaning a prepolymer which has a lower number-average molar mass than the (final) fluorine-containing polyurethane prepolymer according to the invention and which additionally has carbon-fluorine bonds or in which Hydrogen atoms of carbon-hydr
- perfluorinated precursor defined in accordance with the present invention defines a perfluorinated, commercially available product, which can be used as starting material for the preparation of a fluorine-containing polyurethane prepolymer according to the invention, or alternatively a perfluorinated intermediate, which in the preparation of a fluorine-containing polyurethane according to the invention
- perfluorinated precursor preferably means a polyurethane prepolymer which has a lower number-average molar mass than the (final) fluorine-containing polyurethane prepolymer of the invention and in which additionally all the hydrogen atoms of Carbon-hydrogen bonds are replaced by fluorine atoms or substituted.
- number-average molecular weight is to be understood as meaning the molar mass in terms of number average molecular weight is preferably determined by means of gel permeation chromatography (GPC) the elution volume of polymers dissolved in THF whose number average molecular mass is to be determined is compared with the elution volume of a calibration polymer dissolved in THF.
- GPC gel permeation chromatography
- the invention is based on the surprising finding that fluorine-containing polyols, in particular perfluorinated diols, can be used to prepare fluorine-containing polyurethane prepolymers and fluorine-containing polyurethanes which, on account of their surface properties, in particular surface polarity, are preferably suitable as coating materials, in particular for rolls, preferably for paper rolls , Because of their fluorine content, polyurethane prepolymers according to the invention and polyurethanes are distinguished by hydrophobic and in particular oleophobic surface properties, which are particularly advantageous in the case of paper rolls, for example when transferring the coating mentioned above and / or finishing to produce a finished paper.
- polyurethane in particular a polyurethane according to the present invention, is characterized by excellent mechanical properties, such as a high abrasion resistance, from. These properties in particular ensure that, for example, rolls, in particular rolls of paper, which are coated with a polyurethane prepolymer according to the invention or a polyurethane according to the invention, have a longer service life than, for example, rolls coated with conventional rubber materials.
- the precursor may be a fluorine-containing precursor.
- the precursor is a fluorine-free precursor.
- the precursor is an NCO-functional polyurethane prepolymer, ie a polyurethane prepolymer having free NCO groups (isocyanate groups).
- the NCO-functional polyurethane prepolymer has an NCO functionality (number of free isocyanate groups per prepolymer molecule) of> 2, in particular 2 or 3, preferably of 2, on.
- the NCO groups are preferably terminal, ie terminal, NCO groups.
- the NCO-functional polyurethane prepolymer may in particular have an NCO content (measured according to DIN EN ISO 1 1909) of 2% by weight to 20% by weight, preferably 4% by weight to 15% by weight, based on the total weight of the polyurethane prepolymer (ie, the precursor of the fluorine-containing polyurethane prepolymer).
- the NCO-functional polyurethane prepolymer may be an unbranched, ie linear or branched polyurethane prepolymer.
- the NCO-functional polyurethane prepolymer may be a saturated or unsaturated polyurethane prepolymer.
- the NCO-functional polyurethane prepolymer may be a cyclic or acyclic polyurethane prepolymer. Furthermore, the NCO-functional polyurethane prepolymer may be an aliphatic, arylaliphatic or aromatic polyurethane prepolymer. Furthermore, the NCO-functional polyurethane prepolymer may be an oligomeric or polymeric polyurethane prepolymer.
- the NCO-functional polyurethane prepolymer has a number average molecular weight ⁇ 5500 g / mol, in particular from 500 g / mol to 3950 g / mol, preferably 940 g / mol to 2730 g / mol, particularly preferably 1690 g / mol to 2250 g / mol.
- number average molecular weight indicates which molecular weight has on average a random prepolymer molecule taken from a sample of the prepolymer NCO-functional polyurethane prepolymer to a fluorine-containing, in particular perfluorinated, polyurethane prepolymer or a fluorine-free Polyurethane prepolymer act.
- a fluorine-free, NCO-functional polyurethane prepolymer is particularly preferred.
- the precursor is a fluorine-free, NCO-functional polyurethane prepolymer.
- the precursor is an OH-functional polyurethane prepolymer, ie a polyurethane prepolymer having free OH groups (hydroxy groups).
- the OH-functional polyurethane prepolymer has an OH functionality (number of free hydroxyl groups per prepolymer molecule) of> 2, in particular 2 or 3, preferably of 2, on.
- the OH groups are preferably terminal, ie terminal, OH groups.
- the OH-functional polyurethane prepolymer may in particular have an OH content (measured according to DIN EN ISO 1 1909) of 2% by weight to 20% by weight, preferably 4% by weight to 15% by weight, based on the total weight of the polyurethane prepolymer (ie, the precursor of the fluorine-containing polyurethane prepolymer).
- the OH-functional polyurethane prepolymer may be an unbranched, ie linear or branched polyurethane prepolymer.
- the OH-functional polyurethane prepolymer may be a saturated or unsaturated polyurethane prepolymer.
- the OH-functional polyurethane prepolymer may be a cyclic or acyclic prepolymer. Furthermore, the OH-functional prepolymer may be an aliphatic, arylaliphatic or aromatic polyurethane prepolymer. Furthermore, the OH-functional polyurethane prepolymer may be an oligomeric or polymeric polyurethane prepolymer. Furthermore, the OH-functional polyurethane prepolymer may be a fluorine-containing, in particular perfluorinated, polyurethane prepolymer or a fluorine-free polyurethane prepolymer. Preference is given to an OH-functional, fluorine-free polyurethane prepolymer. In principle, the polyol may be a fluorine-free polyol.
- the polyol is a fluorine-containing, in particular perfluorinated, polyol.
- the precursor is a fluorine-free precursor, preferably fluorine-free, NCO-functional polyurethane prepolymer
- the polyol is a fluorine-containing, in particular perfluorinated, polyol.
- the fluorine-free, NCO-functional polyurethane prepolymer reference is made in full to the previous description.
- the polyol reference is made in particular to the following statements.
- the fluorine-free precursor in particular the fluorine-free, NCO-functional polyurethane prepolymer, is prepared or preparable by reacting a fluorine-free polyol with a fluorine-free polyisocyanate, preferably with an excess of fluorine-free polyisocyanate.
- the reaction mixture is prepared or preparable by means of a multistage, in particular two-stage, process in which, in a reaction step, in particular in a first reaction step, a fluorine-free polyol is reacted with a fluorine-free polyisocyanate to obtain the precursor, especially the fluorine-free, NCO-functional Polyurethane prepolymer reacted and added in a further, preferably immediately subsequent, reaction step, in particular in a second reaction step, a fluorine-containing, preferably perfluorinated, polyol to the resulting precursor, in particular to the obtained fluorine-free, NCO-functional polyurethane prepolymer ,
- the reaction mixture is prepared or preparable by means of a multistage, in particular two-stage, process in which, in one reaction step, in particular in a first reaction step, a fluorine-free polyol with an excess of fluorine-free polyisocyanate to obtain the precursor, especially the fluorine-free, NCO Functional polyurethane prepolymer reacted and in a further, preferably immediately subsequent, reaction step, in particular in a second reaction step, a fluorine-containing, preferably perfluorinated, polyol to the resulting precursor, in particular to the resulting fluorine-free, NCO-functional polyurethane prepolymer and is added to unreacted, preferably excess, polyisocyanate.
- the fluorine-containing, in particular perfluorinated, polyol is used in an amount of 0.1% by weight to 6% by weight, preferably 0.3% by weight to 4.5% by weight, in particular 0.5% by weight, to prepare the reaction mixture. to 2 wt .-%, to the Precursor, in particular the fluorine-free, NCO-functional polyurethane prepolymer, added, based on the weight of the precursor, in particular of the fluorine-free, NCO-functional polyurethane prepolymer.
- the fluorine-containing polyol is a saturated or unsaturated polyol.
- the fluorine-containing polyol is a cyclic or acyclic polyol.
- the fluorine-containing polyol is an aliphatic, arylaliphatic or aromatic polyol.
- the fluorine-containing polyol is a monomeric, oligomeric or polymeric polyol.
- the fluorine-containing polyol may be a polymeric polyol having a number average molecular weight of from 800 g / mol to 1000 g / mol.
- the fluorine-containing polyol is an unbranched (linear), saturated and aliphatic polyol.
- the fluorine-containing polyol is a fluorine-containing diol.
- the fluorine-containing polyol is a perfluorinated polyol, in particular perfluorinated diol.
- the fluorine-containing polyol is a fluorine-containing, preferably perfluorinated, polyether diol.
- the polyether diol has, in a further embodiment, a structure according to the following formula (I):
- n and m are each independently an integer from 1 to 5, in particular 2 to 4, mean.
- n and m in the formula (I) each independently of one another denote the number 3 or 4.
- n and m in the formula (I) can each denote the number 3 or 4.
- the polyether diol has a structure according to the following formula (II):
- n in the formula (I I) is 3 or 4 and m is 1.
- the fluorine-free polyol is an unbranched, i. linear or branched polyol.
- the fluorine-free polyol is a saturated or unsaturated polyol.
- the fluorine-free polyol is a cyclic or acyclic polyol.
- the fluorine-free polyol is an aliphatic, arylaliphatic or aromatic polyol.
- the fluorine-free polyol is a monomeric, oligomeric or polymeric polyol.
- the fluorine-free polyol may be a polymeric polyol having a number average molecular weight of from 500 g / mol to 2000 g / mol, preferably from 1000 g / mol to 2000 g / mol.
- the fluorine-free polyol is an unbranched (linear), saturated and aliphatic polyol.
- the fluorine-free polyol is a fluorine-free diol.
- the fluorine-free polyol is in a further embodiment, a polyester polyol such as polyester diol, a polyether polyol such as polyether diol, a polycarbonate polyol, a copolyol or a mixture of two or more of said polyols.
- fluorine-free polyol in particular fluorine-free diol, a polyester diol such as polycaprolactone diol, a polyether diol such as polytetraethylene glycol, a polycarbonate diol, a codiol such as codiol from ⁇ -caprolactone and tetrahydrofuran or a mixture of two or more of said diols.
- a polyester diol such as polycaprolactone diol
- a polyether diol such as polytetraethylene glycol
- a polycarbonate diol a codiol such as codiol from ⁇ -caprolactone and tetrahydrofuran or a mixture of two or more of said diols.
- a suitable polyester polyol can be prepared by reacting a dicarboxylic acid or a dicarboxylic acid anhydride with a polyhydric alcohol.
- the dicarboxylic acid may be an aliphatic dicarboxylic acid, especially having 2 carbon atoms to 12 carbon atoms.
- the dicarboxylic acid may be succinic, malonic, glutaric, adipic, suberic, azelaic, sebacic, decanedicarboxylic, maleic, fumaric, phthalic, isophthalic, terephthalic or a mixture of two or more of the carboxylic acids mentioned.
- the dicarboxylic acid anhydride may, for example, be phthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride or a mixture of two or more of the carboxylic anhydrides mentioned.
- the polyhydric alcohol may, for example, ethanediol, diethylene glycol, 1, 2-propanediol, 1, 3-propanediol, dipropylene glycol, 1, 3-methylpropanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol , Neopentyl glycol, 1, 10-decanediol, glycerol, trimethylolpropane or a mixture of two or more of said polyhydric alcohols.
- a suitable polyester polyol, especially polyester diol may also comprise a polyester polyol prepared by means of lactone.
- the polyester polyol can be a polyesterpolyol prepared from ⁇ -
- a suitable polyether polyol, in particular polyether diol can be prepared by methods known per se, for example by reacting an alkene oxide with a polyhydric alcohol starter in the presence of a catalyst.
- the catalyst may be an alkali metal hydroxide, alkali metal oxide, antimony pentachloride, borofluoride etherate or a mixture of two or more of said catalysts.
- the alkene oxide may be, for example, tetrahydrofuran, ethylene oxide, 1, 2-propylene oxide, 1, 2-butylene oxide, 2,3-butylene oxide, styrene oxide or a mixture of two or more of said alkene oxides.
- the polyhydric alcohol starter may be, for example, a polyvalent compound, such as in particular water, ethylene glycol, 1,2-propanediol, 1, 3 Propanediol, 1, 4-butanediol, diethylene glycol, trimethylolpropane or a mixture of two or more of said alcohol starter act.
- a polyvalent compound such as in particular water, ethylene glycol, 1,2-propanediol, 1, 3 Propanediol, 1, 4-butanediol, diethylene glycol, trimethylolpropane or a mixture of two or more of said alcohol starter act.
- a suitable polycarbonate diol can be prepared by reacting a diol with a dialkyl carbonate or diaryl carbonate or phosgene.
- the diol may be, for example 1,2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, diethylene glycol, trioxyethylene glycol or a mixture of two or more of the above Diols act.
- the polyisocyanate is an unbranched, i. linear or branched polyisocyanate.
- the polyisocyanate is a saturated or unsaturated polyisocyanate.
- the polyisocyanate is a cyclic or acyclic polyisocyanate.
- the polyisocyanate is an aliphatic, arylaliphatic or aromatic polyisocyanate.
- the polyisocyanate is a monomeric, oligomeric or polymeric polyisocyanate.
- the polyisocyanate is a non-polymeric polyisocyanate.
- the polyisocyanate is a monomeric polyisocyanate.
- the polyisocyanate is a fluorine-free polyisocyanate.
- the polyisocyanate is a diisocyanate, preferably fluorine-free diisocyanate.
- the diisocyanate is ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, toluene-2,4-diisocyanate, toluene 2,6-diisocyanate, the mixture of isomers of the latter two diisocyanates, m-tetramethylxylylene diisocyanate, paratetramethylxylylene diisocyanate, 1,5-naphthylene diisocyanate, 1,5-tetrahydronaphthylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4 ' Diphenyl
- reaction mixture further contains a catalyst.
- the catalyst may be an amine catalyst, an organometallic compound such as an organotin compound or a tin salt, or a mixture of these catalysts.
- a suitable amine catalyst may be, for example, triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylethylenediamine,
- Pentamethyldiethylenetriamine N, N-methylbenzylamine, ⁇ , ⁇ -dimethylbenzylamine or a mixture of two or more of said amine catalysts.
- a suitable organometallic compound or stannous salt may include, for example, stannous acetate, stannous octoate, stannous ethylhexanoate, stannous laurate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin carboxylate, dibutyltin laurate, dibutyltin dilaurate.
- the reaction mixture further contains an additive which is selected from the group consisting of filler, dye, pigment and mixtures of at least two of said additives.
- the filler may be, for example, calcium carbonate, titanium dioxide, iron oxide, alumina such as alumina trihydrate, wollastonite, boron nitride, silica, ultra-high molecular weight polyethylene (UHMWPE), glass fibers, polyester fibers, polymer fibers, or a mixture of two or more of said fillers.
- the dye may be, for example, a commercial liquid dye.
- the pigment may be, for example, graphite and / or carbon black.
- reaction mixture is solvent and / or diluent-free.
- reaction of the reaction mixture is carried out in the presence of an inert gas, such as nitrogen or argon.
- the reaction of the reaction mixture is carried out under vacuum or under reduced pressure.
- the reaction mixture can be reacted at a reduced pressure of from 1 mbar to 20 mbar, in particular from 1 mbar to 10 mbar.
- reaction of the reaction mixture is carried out over a period of 15 minutes to 60 minutes.
- reaction of the reaction mixture is carried out at a temperature of 60 ° C to 1 10 ° C.
- the fluorine-containing polyurethane prepolymer is a polyurethane prepolymer having free NCO groups (isocyanate groups), i. to an NCO-functional polyurethane prepolymer.
- the isocyanate groups are preferably terminal, i. terminal, NCO groups.
- the fluorine-containing polyurethane prepolymer has an NCO functionality (number of isocyanate groups per polyurethane prepolymer molecule)> 2, in particular 2 to 3, preferably 2.
- the fluorine-containing polyurethane prepolymer has a content of NCO groups (measured according to DIN EN ISO 1 1909) of 2 wt .-% to 20 wt .-%, preferably 4 wt .-% to 15 wt .-% , based on the total weight of the polyurethane prepolymer.
- the fluorine-containing polyurethane prepolymer is an unbranched, i. linear or branched polyurethane prepolymer.
- the fluorine-containing polyurethane prepolymer is a saturated or unsaturated polyurethane prepolymer.
- the fluorine-containing polyurethane prepolymer is a cyclic or acyclic polyurethane prepolymer. In another embodiment, the fluorine-containing polyurethane prepolymer is an aliphatic, arylaliphatic or aromatic polyurethane prepolymer.
- the fluorine-containing polyurethane prepolymer has a viscosity at 100 ° C. of from 300 mPas to 6000 mPas, preferably 1500 mPas to 4000 mPas (measured according to DIN N EN ISO 3219).
- the fluorine-containing polyurethane prepolymer has a content of free, that is unreacted, precursor, in particular fluorine-free precursor, of ⁇ 3% by weight, in particular ⁇ 2% by weight, preferably ⁇ 1% by weight , based on the total weight of the polyurethane prepolymer.
- the proportion of unreacted intermediate can, for example, by gas chromatography or
- High performance liquid chromatography (H PLC) can be determined.
- the fluorine-containing polyurethane prepolymer has a content of free, that is unreacted, polyol of ⁇ 3 wt .-%, in particular ⁇ 2 wt .-%, preferably ⁇ 1 wt .-%, based on the Total weight of the polyurethane prepolymer.
- the content of free polyol can be determined, for example, by gas chromatography or high performance liquid chromatography (HPLC).
- the fluorine-containing polyurethane prepolymer has a content of free, that is unreacted, polyisocyanate of ⁇ 3 wt .-%, in particular ⁇ 2 wt .-%, preferably ⁇ 1 wt .-%, based on the Total weight of the polyurethane prepolymer.
- the content of free polyisocyanate can be determined, for example, by means of gas chromatography or high performance liquid chromatography (HPLC).
- the fluorine-containing polyurethane prepolymer has a number-average molecular weight of 510 g / mol to 4150 g / mol, in particular 950 g / mol to 3000 g / mol, preferably 1100 g / mol to 2500 g / mol.
- number average molecular weight indicates which molecular weight averages to a polyurethane prepolymer molecule taken from a sample of the fluorine-containing polyurethane prepolymer.
- the fluorine-containing polyurethane prepolymer has a density of 1 kg / m 3 to 1 .5 kg / m 3 , in particular 1 kg / m 3 to 1 .3 kg / m 3 , preferably 1 .03 kg / m 3 up to 1 .28 kg / m 3 , on.
- the fluorine-containing polyurethane prepolymer has an abrasion resistance (according to ISO 4649) ⁇ 50 mg, in particular from 10 mg to 15 mg.
- the fluorine-containing polyurethane prepolymer is preferably used for coating rolls, in particular rollers for the automotive industry, building materials industry, printing industry, electrical industry, film industry, wood and / or furniture industry, food industry, sheet metal industry or paper industry.
- the fluorine-containing polyurethane prepolymer is particularly preferably used for producing a coating or coating composition for rolls, in particular for the automotive industry, building materials industry, printing industry, electrical industry, film industry, wood and / or furniture industry, food industry, sheet metal industry or paper industry.
- the invention further relates to a fluorine-containing polyurethane prepolymer which is prepared or preparable by reacting a reaction mixture comprising a fluorine-free polyol, a fluorine-containing polyol and a polyisocyanate, in particular fluorine-free polyisocyanate.
- a fluorine-containing polyurethane prepolymer which is prepared or preparable by reacting a reaction mixture comprising a fluorine-free polyol, a fluorine-containing polyol and a polyisocyanate, in particular fluorine-free polyisocyanate.
- the invention further relates to a process for the preparation of a fluorine-containing polyurethane prepolymer, the process comprising the step:
- the fluorine-containing polyurethane prepolymer, the precursor, the fluorine-free polyol, the fluorine-containing polyol and the polyisocyanate reference is made to avoid unnecessary repetition to the previous description.
- the invention further relates to a process for the preparation of a fluorine-containing polyurethane prepolymer, the process comprising the steps of: a) reacting a fluorine-free polyol with a polyisocyanate, preferably an excess of fluorine-free polyisocyanate, to give a precursor of the fluorine-containing polyurethane prepolymer, in particular Obtaining a fluorine-free, NCO-functional polyurethane prepolymer, b) adding a fluorine-containing, preferably perfluorinated, polyol to the resulting precursor, in particular fluorine-free, NCO-functional polyurethane prepolymer, and unreacted, preferably excess, polyisocyanate.
- the process is carried out in the presence of an inert gas, such as nitrogen or argon.
- an inert gas such as nitrogen or argon.
- the process is carried out under vacuum or under reduced pressure.
- the process can be carried out at a reduced pressure of 1 mbar to 20 mbar, preferably 1 mbar to 10 mbar.
- the process is carried out in the presence of a catalyst.
- the process is carried out in the presence of an additive which is selected from the group consisting of filler, dye, pigment and mixtures of at least two of said additives.
- the fluorine-containing polyurethane prepolymer in particular of the fluorine-free, NCO-functional polyurethane prepolymer, the fluorine-free polyol, the fluorine-containing polyol and the polyisocyanate, completely to avoid unnecessary repetition previous description with reference.
- the invention further relates to a fluorine-containing polyurethane prepolymer which is prepared or preparable by a process comprising the following steps: a) reacting a fluorine-free polyol with a polyisocyanate, preferably an excess of polyisocyanate, to obtain a precursor of the polyurethane prepolymer, in particular to obtain a fluorine-free, NCO-functional polyurethane prepolymer, and b) adding a fluorine-containing, preferably perfluorinated, polyol to the resulting precursor, in particular fluorine-free, NCO-functional polyurethane prepolymer, and unreacted, preferably excess, polyisocyanate.
- fluorine-containing polyurethane prepolymer in particular of the precursor (in particular of the fluorine-free, NCO-functional polyurethane prepolymer), of the fluorine-free polyol, of the fluorine-containing polyol and of the polyisocyanate, complete avoidance of unnecessary repetitions also occurs in this case the previous description reference.
- the invention further relates to a fluorine-containing polyurethane which is prepared or preparable by mixing a fluorine-containing polyurethane prepolymer according to the invention and a chain extender and / or crosslinking agent (hardener).
- a fluorine-containing polyurethane which is prepared or preparable by mixing a fluorine-containing polyurethane prepolymer according to the invention and a chain extender and / or crosslinking agent (hardener).
- the invention further relates to a fluorine-containing polyurethane which is prepared or preparable by reacting a reaction mixture comprising a fluorine-containing polyurethane prepolymer according to the invention and a chain extender and / or crosslinking agent.
- chain extender and / or crosslinking agent is to be understood as meaning a compound which is capable of extending molecular chains of the fluorine-containing polyurethane prepolymer and / or molecules of the present invention To crosslink fluorine-containing polyurethane prepolymer, in particular intramolecular and / or intermolecular. Due to the reaction taking place between the fluorine-containing polyurethane prepolymer and the chain extender and / or crosslinking agent, the mixture hardens.
- the chain-lengthening and / or crosslinking agent preferably has functional groups which are reactive toward NCO groups (isocyanate groups), in particular terminal NCO groups, of the fluorine-containing polyurethane prepolymer.
- the functional groups may in particular be hydroxy groups, amino groups such as primary amino groups, carboxy groups, epoxy groups or combinations of two or more of the said functional groups.
- the chain extender and / or crosslinker may be a fluorochemical chain extender and / or crosslinker.
- the chain extender and / or crosslinker is a fluorine-free chain extender and / or crosslinker.
- the chain extender and / or crosslinking agent may further be in particular a di- or trifunctional compound.
- the chain extender and / or crosslinking agent may be a diol, in particular having two carbon atoms to six carbon atoms in the alkylene radical, a triol, especially having two carbon atoms to six carbon atoms in the alkylene radical, a dialkanolamine, a trialkanolamine, a diamine such as an aliphatic diamine and / or aromatic diamine, or a mixture of two or more of said chain extenders and / or crosslinking agents.
- the chain extender and / or crosslinking agent may be ethanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerol, trimethylolpropane, pentaerythritol, diethanolamine, or a mixture of two or more of them Chain extenders and / or crosslinking agents act.
- the fluorine-containing polyurethane is prepared or preparable by mixing or reacting a polyurethane prepolymer according to the invention with an amino-containing chain extender and / or crosslinking agent
- the polyurethane has, in addition to urethane groups, also urea groups in the molecular chains.
- urethane groups also urea groups in the molecular chains.
- polyurethane can also be referred to as a hybrid polymer.
- the fluorine-containing polyurethane is a random polyurethane.
- the fluorine-containing polyurethane is a block-copolymer polyurethane.
- the fluorine-containing polyurethane preferably has at least one hard segment and at least one soft segment.
- hard segment and “soft segment” are to be understood as meaning individual blocks or sections of the fluorine-containing polyurethane which are microphase-separated.
- At least one hard segment in the sense of the present invention means a hard segment or a plurality of hard segments, that is, two or more hard segments.
- At least one soft segment in the context of the present invention means a soft segment or a plurality of soft segments, that is, two or more soft segments.
- the fluorine-containing polyurethane has terminal, i. terminal, hard segments on.
- the ends of the polyurethane molecules are formed as hard segments.
- only the ends of the polyurethane molecules are formed as hard segments.
- the structure of the at least one hard segment involves (essentially) the chain extender and / or crosslinking agent and the polyisocyanate, in particular an aromatic polyisocyanate.
- the at least one soft segment has a glass transition temperature of from -75.degree. C. to -11.degree. C., preferably -55.degree. C. to -30.degree.
- the fluorine-containing polyurethane is an unbranched, ie linear or branched polyurethane.
- the fluorine-containing polyurethane is a saturated or unsaturated polyurethane. In another embodiment, the fluorine-containing polyurethane is a cyclic or acyclic polyurethane.
- the fluorine-containing polyurethane is an aliphatic, arylaliphatic or aromatic polyurethane.
- the polyurethane has a water contact angle of 125 ° to 145 °, in particular 125 ° to 143 °, preferably 125 ° to 140 °.
- water contact angle is to be understood as meaning an edge angle or contact angle formed by a drop of water on the surface of the fluorine-containing polyurethane to this surface
- the size of the edge or contact angle between water and polyurethane depends on the interaction The smaller the interaction, the greater the edge or contact angle.
- certain properties of the polyurethane surface can be determined, such as, for example, the surface energy at low edge or contact angles, in particular at an edge or contact angle ⁇ 90 °, the surface is hydrophilic, at angles> 90 ° as hydrophobic and at angles> 140 ° as superhydrophobic.
- the fluorine-containing polyurethane has a sizing contact angle to a typical polyvinyl alcohol (PVA) -based adhesive of 1 10 ° to 135 °, preferably 120 ° to 130 °.
- PVA polyvinyl alcohol
- the term "size contact angle” defines a contact angle which a drop of an aqueous 20% strength by weight glue solution on the surface of the fluorine-containing polyurethane forms on this surface
- the expression "water edge angle” made explanations apply mutatis mutandis to the term "glue edge angle”.
- the fluorine-containing polyurethane has a density of 1 kg / m 3 to 1 .5 kg / m 3 , in particular 1 kg / m 3 to 1 .3 kg / m 3 , preferably 1 .03 kg / m 3 to 1 .28 kg / m 3 , on.
- the fluorine-containing polyurethane has a content of free, unreacted fluorine-containing polyol ⁇ 3 wt .-%, in particular ⁇ 2 wt .-%, preferably ⁇ 1 wt .-%, based on the total weight of the polyurethane.
- the content of free fluorine-containing polyol can be determined, for example, by gas chromatography or high performance liquid chromatography (HPLC).
- the fluorine-containing polyurethane has a content of free, that is unreacted, fluorine-free polyol ⁇ 3 wt .-%, in particular ⁇ 2 wt .-%, preferably ⁇ 1 wt .-%, based on the total weight of polyurethane.
- the content of the fluorine-free polyol can be determined, for example, by gas chromatography or high performance liquid chromatography (HPLC).
- the fluorine-containing polyurethane has a content of free, ie unreacted, precursor ⁇ 3 wt .-%, in particular ⁇ 2 wt .-%, preferably ⁇ 1 wt .-%, based on the total weight of the polyurethane ,
- the content of fluorine-free polyol for example, by gas chromatography or
- HPLC High performance liquid chromatography
- the fluorine-containing polyurethane has a content of free, that is unreacted, polyisocyanate ⁇ 3 wt .-%, in particular ⁇ 2 wt .-%, preferably ⁇ 1 wt .-%, based on the total weight of the polyurethane ,
- the content of free polyisocyanate can be determined, for example, by gas chromatography or high performance liquid chromatography (HPLC).
- the fluorine-containing polyurethane has an abrasion resistance (according to ISO 4649) ⁇ 50 mg, in particular from 10 mg to 15 mg.
- the fluorine-containing polyurethane is preferably used as a roll coating or cover.
- the polyurethane may be used as a roll coating or cover for the automotive, building materials, printing, electrical, film, wood and / or furniture, food, sheet or paper industries.
- the fluorine-containing polyurethane is particularly preferably used as a roll coating or cover for the paper industry.
- the invention further relates to a process for the preparation of a fluorine-containing polyurethane, in which a fluorine-containing polyurethane prepolymer according to the invention and a chain extender and / or crosslinking agent are mixed together.
- the process is carried out over a period of 15 minutes to 120 minutes, preferably 50 minutes to 70 minutes.
- the process is carried out at a temperature of 60.degree. C. to 130.degree. C., preferably 90.degree. C. to 100.degree.
- the chain extender and / or crosslinking agent is used in a proportion of from 3% by weight to 140% by weight, preferably from 70% by weight to 120% by weight, based on the total weight of one for the preparation of the polyurethane reaction mixture used.
- a reaction mixture preferably contains at least one fluorine-containing polyurethane prepolymer according to the invention and also a chain extender and / or crosslinking agent.
- the invention furthermore relates to a composition, in particular a coating composition, which comprises a fluorine-containing polyurethane prepolymer according to the invention and / or a fluorine-containing polyurethane according to the invention.
- the composition may comprise, in addition to the polyurethane prepolymer and / or polyurethane in particular an additive.
- the composition may be present as a compound, in particular a coating compound.
- the polyurethane prepolymer and / or the polyurethane can be prepared in the presence of an additive.
- the polyurethane prepolymer and / or the polyurethane may be provided after its preparation with an additive or additized, in particular compounded, be.
- suitable additives reference is made to the previous description.
- the composition is preferably used as a roll coating or cover.
- the composition may be used for roll coating or coating for the automotive, building materials, printing, electrical, film, wood and / or furniture, food, sheet or paper industries.
- the composition is particularly preferably used as roll coating or cover for the paper industry, preferably for paper rolls.
- composition in particular of the fluorine-containing polyurethane prepolymer and of the fluorine-containing polyurethane, reference is likewise made to the previous description in order to avoid unnecessary repetitions.
- fluorine-containing polyurethane prepolymer and the fluorine-containing polyurethane apply (mutatis mutandis) for the composition.
- the invention further relates to an article which is coated with a fluorine-containing polyurethane prepolymer according to the invention and / or a fluorine-containing polyurethane according to the invention.
- the article is preferably a roller, in particular a roller for the automotive industry, building materials industry, printing industry, electrical industry, film industry, wood and / or furniture industry, food industry, sheet metal industry or paper industry.
- the article is particularly preferably a roll for the paper industry, that is to say a so-called paper roll.
- the invention further relates to a method for coating an article.
- reaction mixture containing a fluorine-containing polyurethane prepolymer of the invention and a chain extender and / or crosslinking agent is applied to the surface of the article.
- the polyurethane prepolymer and the chain extender and / or crosslinking agent are spatially separated from each other supplied to a mixing chamber with application nozzle.
- Both the polyurethane prepolymer and the chain extender and / or crosslinking agent may each be stored in separate temperature chambers.
- the transfer of the polyurethane prepolymer and the chain extender and / or crosslinking agent into the mixing chamber can be effected in each case by means of a metering pump via corresponding valves and in particular via heatable pressure hoses.
- the polyurethane prepolymer and the chain extender and / or crosslinking agent are mixed in the above-mentioned mixing chamber and preferably applied by means of a heatable valve carrier via an application nozzle on the surface of the object to be coated.
- the reaction mixture can be applied to the surface of the roll, in particular the paper roll, by means of the so-called rotational casting or by means of so-called mold casting.
- the reaction mixture is applied to a rotating roll.
- an application nozzle preferably moves above and in the longitudinal direction of a rotating roller core.
- the roll is placed in a mold. Subsequently, the reaction mixture is fed into the mold. This causes the roll to be coated by a laminar flow of liquid due to the fed reaction mixture.
- the invention further relates to the use of a fluorine-containing polyurethane prepolymer according to the invention for producing a coating for articles, preferably rollers.
- rollers are preferably rollers for the automotive industry, building materials industry, electrical industry, film industry, wood and / or furniture industry, food industry, sheet metal industry or paper industry.
- Particularly preferred is the use of the polyurethane prepolymer to make a coating for rolls for the paper industry, i. for so-called paper rolls.
- the invention relates to the use of a fluorine-containing polyurethane according to the invention for coating objects, preferably rollers.
- rollers are preferably rollers for the automotive industry, building materials industry, electrical industry, film industry, wood and / or furniture industry, food industry, sheet metal industry or paper industry. Particularly preferred is the use of the polyurethane for coating rolls for the paper industry, ie of so-called paper rolls.
- reaction vessel tempered, evacuated, with adequate mixing devices
- the required amount for example, 5 kg of a z. B. preheated to 80 ° C prepolymer, degassed with stirring for about 30 min (at about 1 to 10 mbar final vacuum) and brought to the desired reaction temperature of for example 105 ° C.
- freshly polymerized prepolymer can also be used in the reaction vessel.
- the reactor is vented. This can be done with dried air, dried nitrogen or dried argon. Thereafter, the required amount of perfluorinated polyether, for example, 100 g with intensive mixing (for example, using a toothed disc) is added.
- the prepolymer assumes a distinctly white-milky color.
- Continuous temperature and torque monitoring provides information about a proper test procedure. After dispersion is evacuated again and degassed. After a reaction time of about 30 minutes is aerated and the modified prepolymer transferred to a prepared casting machine. In this case, a sample for determining the NCO-% value is taken to correctly calculate the mixing ratio with a corresponding hardener. After rinsing and calibrating the casting machine, a test roll can be cast in rotational molding, usually with the same parameters as for the corresponding unmodified casting system.
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Abstract
Description
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DE102016225500.2A DE102016225500A1 (de) | 2016-12-19 | 2016-12-19 | Fluorhaltiges Polyurethan-Prepolymer sowie fluorhaltiges Polyurethan, insbesondere zur Beschichtung von Gegenständen |
PCT/EP2017/082731 WO2018114551A1 (de) | 2016-12-19 | 2017-12-14 | Fluorhaltiges polyurethan-prepolymer sowie fluorhaltiges polyurethan, insbesondere zur beschichtung von gegenständen |
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EP3555163A1 true EP3555163A1 (de) | 2019-10-23 |
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EP (1) | EP3555163A1 (de) |
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US10995298B2 (en) | 2014-07-23 | 2021-05-04 | Becton, Dickinson And Company | Self-lubricating polymer composition |
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US4841007A (en) * | 1988-03-28 | 1989-06-20 | Becton Dickinson And Company | Fluorinated polyetherurethanes and medical devices therefrom |
IT1252660B (it) * | 1991-12-23 | 1995-06-20 | Ausimont Spa | Poliuretani e poliuretani-uree fluorurati e processi per la loro preparazione |
US6001923A (en) * | 1997-03-27 | 1999-12-14 | Pilkington Aerospace Inc. | Transparent fluorinated polyurethane coating compositions and methods of use thereof |
JP4199353B2 (ja) * | 1998-12-24 | 2008-12-17 | シンジーテック株式会社 | 基材上に多孔質被覆層を形成するための方法 |
DE102004046568A1 (de) * | 2004-09-24 | 2006-04-06 | Construction Research & Technology Gmbh | Fluormodifizierte Reaktivharzsysteme, Verfahren zu ihrer Herstellung und deren Verwendung |
US10240065B2 (en) * | 2015-12-18 | 2019-03-26 | Hrl Laboratories, Llc | Reversible, chemically or environmentally responsive polymers, and coatings containing such polymers |
EP3464493B1 (de) * | 2016-06-03 | 2022-02-23 | HRL Laboratories, LLC | Zusammensetzungen und verfahren zur herstellung von beständigen beschichtungen mit geringer vereisung |
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