Use of polyurethane elastomers based on MDI-polyadipate prepolymers and polyamine chain extenders, or use of kits of parts containing MDI-polyadipate prepolymers and polyamine chain extenders, preferably in the manufacture of die-cut pads, anvil covers, rollers and zero-crush wheels in pulp and paper applications.

Abstract

The present invention relates to the use of polyurethane elastomers based on MDI-polyadipate prepolymers and polyamine chain extenders in pulp and paper applications, particularly in the manufacture of die-cutting pads, anvil covers, zero-crush wheels, and rollers, and to the use of a kit of parts comprising MDI-polyadipate prepolymers and polyamine chain extenders, wherein the resulting products exhibit good dynamic performance, particularly with respect to elongation and tear resistance.

Description

Technical Field

[0001] In 2004, the European Commission issued a Directive (2004 / 37 / EC) to protect employees from the risks associated with exposure to carcinogenic or mutagenic substances in the workplace. This Directive was strengthened in 2017 (2017 / 2389) and functioned towards banning the use of these substances. 4,4'-Methylenebis(2-chloroaniline) (MOCA or MBOCA) is classified as a carcinogenic substance under this Directive.

[0002] MOCA is mainly used as a curing agent for polyurethane prepolymers in the manufacture of castable polyurethane products such as anvil covers, die cut pads and zero crash wheels. These products have hitherto been mainly manufactured from TDI-based prepolymers and MOCA as a curing agent (chain extender). Other diamines such as 3-(aminomethyl)-3,5,5-trimethylcyclohexane-1-amine (IPDA), 2,4-diethyl-6-methylbenzene-1,3-diamine (DETDA), 3,5-dimethylthio-2,4-toluenediamine and 3,5-dimethylthio-2,6-toluenediamine (DMTDA) have been used in combination with these prepolymers. However, the direct replacement of MOCA with these diamines does not result in the same performance in these applications and causes dynamic strain in the materials (see experimental section). Therefore, an alternative polyurethane system had to be developed to replace MOCA without losing the dynamic performance of the materials. According to the present invention, surprisingly, the use of polyurethane elastomers based on MDI-polyadipate prepolymers and polyamine chain extenders in the manufacture of die cut pads, anvil covers, rollers and zero crash wheels has been found to provide good dynamic performance of these products, particularly in terms of elongation and tear resistance.

[0003] U.S. Patent Application Publication 2009 / 076239 discloses, in Example 30, the use of a PU elastomer based on an MDI-polyadipate prepolymer and trimethylene glycol di-p-amino-benzoate diamine as a chain extender for manufacturing a wheel. Claim 15 refers to DMTDA (dimethylthiotoluenediamine) as a further suitable chain extender. The use of PU elastomers in pulp and paper applications is not disclosed in this document.

[0004] European Patent No. 1950234 discloses a PU elastomer based on an MDI-polyadipate prepolymer combined with isobutyl 3,5-diamino-4-chlorobenzoate as a chain extender (Examples 8 and 9). Section 0029 mentions the use of DMTDA as a further suitable chain extender. Furthermore, while the document discloses the use of a PU elastomer for manufacturing wheels (Claim 4), it does not disclose its use in pulp and paper applications.

[0005] U.S. Patent Application Publication No. 2014 / 194588 discloses a PU elastomer based on an MDI-polyadipate prepolymer combined with methylenedianiline as a chain extender (Example 3A). No other suitable chain extenders are mentioned in this document. The elastomer can be used to manufacture wheels, tires, and die-cut pads.

[0006] International Publication No. 2022 / 238285 discloses polyurethane elastomers that can be obtained from NCO-terminated prepolymers, preferably derived from TDI or MDI and polyether or polyester, in the latter case, polyadipate is preferred. Apart from the NCO-terminated prepolymer, the reaction mixture obligately contains a polyether carbonate polyol and may contain a polyamine and / or polyol chain extender. The use of MDI-polyadipate prepolymers in combination with a polyamine chain extender or a polyamine / polyol chain extender as the main component is not disclosed.

[0007] International application PCT / EP2022 / 084392 (priority date December 8, 2021) discloses polyurethane elastomers that can be obtained from NCO-terminated prepolymers, preferably derived from TDI or MDI and polyethers or polyesters. Apart from the NCO-terminated prepolymers, the reaction mixture obligately contains a polyol mixture, which can be obtained by mixing polyester polyols and carbodiimides, and, as further components, polyamines and / or polyol chain extenders. This international application does not disclose the use of NCO-terminated prepolymers based on polyadipate polyols having a residual monomer diisocyanate content of up to 8% by weight. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] U.S. Patent Application Publication No. 2009 / 076239 Specification [Patent Document 2] European Patent No. 1950234 [Patent Document 3] U.S. Patent Application Publication No. 2014 / 194588 [Patent Document 4] International Publication No. 2022 / 238285 [Patent Document 5] International Application No. PCT / EP2022 / 084392 [Overview of the project]

[0009] This invention relates to pulp and paper applications, (A) (A1) At least one diphenylmethane diisocyanate which may be modified with a urethane group and / or a carbodiimide group, (A2) At least one polyadipate polyol having a number-average molar mass Mn of 800-4000 g / mol and a functionality of 2-4, as determined by gel permeation chromatography as specified below. (A3) Depending on the case, at least one lactone-based polyester polyol, and (A4) Depending on the case, at least one catalyst and / or at least one additive The reaction (R P ) can be obtained from or can be obtained from at least one NCO-terminated prepolymer, (B) i) At least one polyamine selected from the group consisting of isophorone diamine, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, N-methylpropylene-1,3-diamine, N,N'-dimethylethylenediamine, 4,4'-methylenebis(2-chloroaniline), 2,4-toluenediamine, 2,6-toluenediamine, 6-methyl-2,4-bis(methylthio)phenylene-1,3-diamine, 2-methyl-4,6-bis(methylthio)phenylene-1,3-diamine, 3,5-diethyl-2,4-toluenediamine, 3,5-diethyl-2,6-toluenediamine, and primary mono-, di-, tri-, or tetraalkyl-substituted 4,4'-diaminodiphenylmethane, or ii) A mixture of at least one polyamine having at least 2 functionalities and at least one polyol having at least 2 functionalities. One of them is at least one type of chain extender, (C) Depending on the case, at least one catalyst, (D) Depending on the case, at least one additive, (E) Depending on the case, at least one type of filler, The reaction (R E ) obtained from (Embodiment I), or can be obtained from (Embodiment II), The use of polyurethane elastomer, However, the reaction (R E) No polyether carbonate polyol is present in the product, however, in Embodiment II, component (A) has a monomer diisocyanate content of 8% by weight or less, preferably 6% by weight or less, as determined by gas chromatography using an internal standard in accordance with DIN EN ISO 10283:2007-11.

[0010] The present invention also relates to pulp and paper applications, (A) (A1) At least one diphenylmethane diisocyanate which may be modified with a urethane group and / or a carbodiimide group, (A2) At least one polyadipate polyol having a number-average molar mass Mn of 800-4000 g / mol and a functionality of 2-4, as determined by gel permeation chromatography as specified below. (A3) Depending on the case, at least one lactone-based polyester polyol, and (A4) Depending on the case, at least one catalyst and / or at least one additive The reaction (R P ) can be obtained from or can be obtained from at least one NCO-terminated prepolymer, (B) i) At least one polyamine selected from the group consisting of isophorone diamine, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, N-methylpropylene-1,3-diamine, N,N'-dimethylethylenediamine, 4,4'-methylenebis(2-chloroaniline), 2,4-toluenediamine, 2,6-toluenediamine, 6-methyl-2,4-bis(methylthio)phenylene-1,3-diamine, 2-methyl-4,6-bis(methylthio)phenylene-1,3-diamine, 3,5-diethyl-2,4-toluenediamine, 3,5-diethyl-2,6-toluenediamine, and primary mono-, di-, tri- or tetraalkyl-substituted 4,4'-diaminodiphenylmethane, or (ii) A mixture of at least one polyamine having a functionality of at least 2 and at least one polyol having a functionality of at least 2 One of the following, at least one chain extender, and (C) optionally, at least one catalyst, and (D) optionally, at least one additive, and (E) optionally, at least one filler, Comprising (Embodiment III) or including these (Embodiment IV), the use of a kit of parts, Provided that there is no polyether carbonate polyol in the kit of parts, provided that in Embodiment IV, component (A) has a monomeric diisocyanate content of 8% by weight or less, preferably 6% by weight or less, determined by gas chromatography using an internal standard in accordance with DIN EN ISO 10283:2007-11, regarding the use.

[0011] In a preferred embodiment of Embodiment I and a preferred embodiment of Embodiment III, component (A) has a monomeric diisocyanate content of 8% by weight or less, preferably 6% by weight or less, determined by gas chromatography using an internal standard in accordance with DIN EN ISO 10283:2007-11.

[0012] According to the present invention, the term "elastomeric" or "elastomer" means a polyurethane / interleaved polyol polymer chain having a polyol polymer chain corresponding to a "soft segment" to which a urethane network is bonded to short segments called "hard segments" composed of urethane bonds.

[0013] The single components of the polyurethane elastomers and / or kits of parts used according to the present invention are described in detail below.

[0014] (One or more) NCO-terminated prepolymers (A): (A1) Diphenylmethane diisocyanate (A1) may be modified in one or more ways: At least one diphenylmethane diisocyanate, which may be modified with a urethane group and / or a carbodiimide group, is preferably diphenylmethane-4,4'-diisocyanate (4,4'-MDI), diphenylmethane-2,4'-diisocyanate (2,4'-MDI), diphenylmethane-2,2'-diisocyanate (2,2'-MDI), or diphenylmethane-2,4'-diisocyanate (2,4' A mixture of -MDI) / diphenylmethane-4,4'-diisocyanate (4,4'-MDI) is selected from the group consisting of urethane-modified liquid diphenylmethane-4,4'-diisocyanate and diphenylmethane-2,4'-diisocyanate and carbodiimide-modified diphenylmethane-2,2'-diisocyanate, diphenylmethane-2,4'-diisocyanate and diphenylmethane-4,4'-diisocyanate.

[0015] The diisocyanates mentioned can be used individually or in mixtures with each other.

[0016] Component (A1) is generally used in an amount of 2–30% by weight, based on the total weight of at least one NCO-terminated prepolymer (A).

[0017] (One or more) polyadipate polyols (A2): At least one polyadipate polyol has a number-average molar mass Mn of 800-4000 g / mol, preferably 1500-2500 g / mol (Mn is determined by gel permeation chromatography).

[0018] The number-average molecular weight (Mn) was determined by gel permeation chromatography (GPC) in tetrahydrofuran at 23°C. The procedure conformed to DIN 55672-1: "Gel permeation chromatography, Part 1 - Tetrahydrofuran as eluent" (SECurity GPC system from PSS Polymer Service, flow rate 1.0 ml / min; column: 2 × PSS SDV linear M, 8 × 300 mm, 5 μm; RID detector). A polystyrene sample of known molar mass was used for calibration. The number-average molecular weight was calculated using software support. The baseline point and evaluation limits were fixed according to DIN 55672 Part 1.

[0019] At least one polyadipate polyol has a functionality of 2 to 4, preferably 2.

[0020] Suitable polyadipate polyols can be produced, for example, from adipic acid and polyhydric alcohols. To produce polyester polyols, it may be advantageous to use, instead of adipic acid, the corresponding adipic acid derivatives, such as carboxylic acid diesters having 1 to 4 carbon atoms in the alcohol portion, adipic anhydride, adipoyl chloride, or monocarboxylic acid ester adipoyl chlorides having 1 to 4 carbon atoms in the alcohol portion, and mixtures thereof.

[0021] Examples of polyhydric alcohols include glycols having 2 to 10, preferably 2 to 6, carbon atoms, such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 1,3-propanediol, and dipropylene glycol. Polyhydric alcohols may be used alone or in mixtures with each other, as required by the desired properties.

[0022] Preferred polyadipate polyols used are ethanediol polyadipate, 1,4-butanediol polyadipate, ethanediol-1,4-butanediol-polyadipate, 1,6-hexanediol neopentyl glycol polyadipate, and 1,6-hexanediol-1,4-butanediol polyadipate.

[0023] Polyadipate polyols can be used individually or in mixtures with each other.

[0024] Component (A2) is generally used in an amount of 70–98% by weight, based on the total weight of at least one NCO-terminated prepolymer (A).

[0025] (One or more) lactone-based polyester polyols (A3): Lactone-based polyester polyols contain polymerization products of lactones, such as caprolactones that may be substituted. A preferred lactone-based polyester polyol is polycaprolactone.

[0026] Component (A3) is generally used in an amount of 0 to 15% by weight, based on the total weight of at least one NCO-terminated prepolymer (A).

[0027] (One or more) catalysts and / or at least one additive (A4): At least one diphenylmethane diisocyanate-terminated prepolymer (A) according to the present invention can optionally be obtained in the presence of at least one catalyst and / or at least one additive.

[0028] Suitable catalysts may be used in the method of the present invention. Conventional tertiary amines known from the prior art, such as triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol, diazabicyclo[2.2.2]octane (DABCO), diethylethanolamine, N-cocomorpholine, N,N-diethyl-3-diethylaminopropylamine dimethylbenzylamine, 1,8-diazabicycloundeca-7-ene (DBU), triazabicyclodecene (TBD), and N-methyltriazabicyclodecene (MTBD). Organometallic compounds, such as titanium compounds, iron compounds, bismuth compounds, zinc compounds, or tin compounds, such as tin diacetate, tin dioctanoate, tin dilaurate, or dialkyltin salts of aliphatic carboxylic acids, such as dibutyltin diacetate or dibutyltin dilaurate, are suitable catalysts for the production of PU elastomers. Preferred catalysts are amine compounds and / or organometallic compounds, particularly tin compounds.

[0029] Suitable additives may include lubricants, such as fatty acid esters, their metallic soaps, fatty acid amides, fatty acid ester amides, and silicone compounds; rheological agents such as defoamers and viscosity modifiers; gelling agents; antiblocking agents; inhibitors; and stabilizers against hydrolysis, UV or other light, heat, and discoloration.

[0030] In another preferred embodiment, additives used in small amounts may also be conventional monofunctional, difunctional, trifunctional, or polyfunctional compounds reactive to the isocyanate, in amounts of 0.001 mol% to a maximum of 2 mol%, preferably 0.002 mol% to 1 mol%, based on the total molar amount of component A, for example, as chain stoppers, aids, or release agents. Examples include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, isomers pentanol, hexanol, octanol and nonanol, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol and stearyl alcohol. Suitable triols include trimethylolethane, trimethylolpropane, or glycerol. Suitable highly functional alcohols include ditrimethylolpropane, pentaerythritol, dipentaerythritol, or sorbitol. Amines or thiols such as butylamine and stearylamine.

[0031] Component (A4) is generally used in an amount of 0 to 3% by weight, preferably 0 to 1% by weight, based on the total weight of at least one NCO-terminated prepolymer (A). Most preferably, catalyst (A4) is not used.

[0032] Synthesis of prepolymer (A): The NCO-terminated prepolymer (A) is obtained from the aforementioned components. The preparation of the prepolymer is generally known to those skilled in the art. The NCO-terminated prepolymer (A) can be obtained as follows: The component (A1) is generally provided in a suitable reactor under appropriate conditions known to those skilled in the art, for example, under vacuum, using a stirrer, preferably at a temperature of 40 to 100°C.

[0033] Next, components (A2) and optionally (A3) and optionally (A4) are prepared in the same reactor under vacuum. The mixture is stirred for 2 to 3 hours at a temperature preferably between 40 and 100°C. The product is then extracted and stored in a drum under nitrogen or vacuum.

[0034] Components (A1), (A2), and optionally (A3) are used in a molar ratio of isocyanate groups of component (A1) to isocyanate-reactive groups of component (A2) and optionally (A3) (the sum of both, if (A3) is present), preferably 1.5 to 4, more preferably 1.6 to 3.

[0035] The proportion of component (A), based on the total mass of the polyurethane elastomer, is preferably: The total amount of components (A) and (B) in the polyurethane elastomer is 100% by weight, and the weight is 80% to 98% by weight, particularly preferably 88% to 93% by weight.

[0036] Ingredient (B): Component (B) according to the present invention is i) At least one polyamine selected from the group consisting of isophorone diamine, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, N-methylpropylene-1,3-diamine, N,N'-dimethylethylenediamine, 4,4'-methylenebis(2-chloroaniline), 2,4-toluenediamine, 2,6-toluenediamine, 6-methyl-2,4-bis(methylthio)phenylene-1,3-diamine, 2-methyl-4,6-bis(methylthio)phenylene-1,3-diamine, 3,5-diethyl-2,4-toluenediamine, 3,5-diethyl-2,6-toluenediamine, and primary mono-, di-, tri-, or tetraalkyl-substituted 4,4'-diaminodiphenylmethane, or ii) A mixture of at least one polyamine having at least 2 functionalities and at least one polyol having at least 2 functionalities. It is one of them, at least one type of chain extender.

[0037] The functionality of the polyamine and polyol (B)ii) is preferably 2 or 3, more preferably 2. In one embodiment, the chain extender component (B)ii) may include a low molecular weight compound having a molar mass of 60 to 490 g / mol, preferably 62 to 400 g / mol, and particularly preferably 62 to 300 g / mol.

[0038] Suitable polyamines (B)ii) are (cyclo)aliphatic diamines, e.g., isophorone diamine, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, N-methylpropylene-1,3-diamine, N,N'-dimethylethylenediamine, and aromatic diamines, e.g., 4,4'-methylenebis(2-chloroaniline), 2,4-toluenediamine and 2,6-toluenediamine, 6-methyl-2,4-bis(methylthio)phenylene-1,3-diamine and 2-methyl-4,6-bis(methylthio)phenylene-1,3-diamine, 3,5-diethyl-2,4-toluenediamine and 3,5-diethyl-2,6-toluenediamine, and primary mono-, di-, tri-, or tetraalkyl-substituted 4,4'-diaminodiphenylmethane.

[0039] In preferred embodiments, 4,4'-methylenebis(2-chloroaniline) is excluded from the chain extender according to i) and ii).

[0040] At least one polyamine is preferably selected from the group consisting of isophorone diamine, 6-methyl-2,4-bis(methylthio)phenylene-1,3-diamine, and 2-methyl-4,6-bis(methylthio)phenylene-1,3-diamine.

[0041] Suitable polyols include diols, such as ethanediol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethylpropane-1,3-diol, 2-butyl-2-ethylpropane-1,3-diol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,3-propanediol, 1,5-hexanediol, 1,6-hexanediol, and 1,8-octanediol. Tanediol, 1,10-decanediol, 1,12-dodecanediol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, isosorbide, triisopropanolamine, glycerol monoester, glycerol monoether, trim 1,4-butanediol) terephthalic acid diesters, trimethylolpropane monoethers, pentaerythritol diesters, pentaerythritol diethers, and alkoxylated derivatives of any of these, diethylene glycols, triethylene glycols, tetraethylene glycols, for example high molecular weight poly(ethylene glycols), dipropylene glycols, tripropylene glycols, and high molecular weight poly(propylene glycols) having a number average molecular weight of 220 to 2000 g / mol, alkoxylated derivatives of compounds selected from the group consisting of diacids, diols, and hydroxy acids, polymer diols (preferably polymer diols are selected from the group consisting of polyethers, polyesters, hydroxy-terminated polyolefins, polyether-copolyesters, polycarbonate-copolyesters, polyoxymethylene polymers, and alkoxylated analogs thereof), diesters of terephthalic acid and glycols having 2 to 4 carbon atoms, for example bis(ethylene glycol) terephthalate or bis(1,4-butanediol) terephthalate, hydroxyalkylene ethers of hydroquinones, for example 1,These are 4-di(hydroxyethyl)hydroquinone, ethoxylated bisphenol, and reaction products of these with ε-caprolactone.

[0042] At least one polyol is preferably selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, trimethylolpropane, and 1,4-di(hydroxyethyl)hydroquinone, and more preferably selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and trimethylolpropane.

[0043] A relatively small amount of triol may be added.

[0044] In embodiment ii), at least one polyol (total amount of polyols in component (B)) is used in a maximum amount of preferably 80% by weight, more preferably 50% by weight, and most preferably 20% by weight, based on the total weight of component (B).

[0045] Embodiment i) is preferred over Embodiment ii).

[0046] Based on the total mass of the polyurethane elastomer, the proportion of component (B) is preferably 2 to 20% by weight, particularly preferably 7 to 12% by weight, provided that the sum of components (A) and (B) in the polyurethane elastomer is 100% by weight.

[0047] (One or more) catalysts (C): Suitable catalysts may be used in the method of the present invention. Conventional tertiary amines known from the prior art, such as triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol, diazabicyclo[2.2.2]octane (DABCO), diethylethanolamine, N-cocomorpholine, N,N-diethyl-3-diethylaminopropylamine dimethylbenzylamine, 1,8-diazabicycloundeca-7-ene (DBU), triazabicyclodecene (TBD), and N-methyltriazabicyclodecene (MTBD). Organometallic compounds, such as titanium compounds, iron compounds, bismuth compounds, zinc compounds, or tin compounds, such as tin diacetate, tin dioctanoate, tin dilaurate, or dialkyltin salts of aliphatic carboxylic acids, such as dibutyltin diacetate or dibutyltin dilaurate, are suitable catalysts for the production of PU elastomers. Preferred catalysts are amine compounds and / or organometallic compounds, particularly tin compounds.

[0048] The total amount of catalyst, based on the total mass of polyurethane elastomer, is generally about 0-5% by weight, preferably 0.0001-1% by weight, and particularly preferably 0.0002-0.5% by weight.

[0049] (One or more) additives D: Suitable additives may include lubricants, such as fatty acid esters, their metal soaps, fatty acid amides, fatty acid ester amides, and silicone compounds; rheological agents such as defoamers and viscosity modifiers; gelling agents; antiblocking agents; inhibitors; stabilizers against hydrolysis, UV or other light, heat, and discoloration; flame retardants; dyes; pigments; inorganic and / or organic fillers; and reinforcing agents. Reinforcing agents are particularly fibrous reinforcing materials, such as inorganic fibers, which may be manufactured according to prior art and treated with sizing agents.

[0050] In preferred embodiments, the additive (D), used in small amounts, may also be a conventional monofunctional, difunctional, trifunctional, or polyfunctional compound reactive to the isocyanate, in amounts of 0.001 mol% to a maximum of 2 mol%, preferably 0.002 mol% to 1 mol%, based on the total molar amount of component (A), for example, as a chain stopper, aid, or release agent. Examples include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, isomer pentanol, hexanol, octanol and nonanol, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol and stearyl alcohol. Suitable triol examples include trimethylolethane, trimethylolpropane, or glycerol. Suitable highly functional alcohols include ditrimethylolpropane, pentaerythritol, dipentaerythritol, or sorbitol. Also suitable are amines or thiols such as butylamine and stearylamine.

[0051] The total amount of additives, based on the total mass of the polyurethane elastomer, is generally about 0-5% by weight, preferably 0-3% by weight, and particularly preferably 0.2-1% by weight.

[0052] (one or more) fillers (E): Suitable fillers are preferred mineral fillers selected from the group consisting of CaCO3, SiO2, Al(OH)3, Al2O3, CaO, MgO, Na2O, K2O, B2O3, Fe2O3, P2O5, zirconia, cerium oxide, TiO2, silicates, particularly sodium aluminosilicate, calcium silicate, magnesium silicate, mixtures thereof, and hydrated modifiers of the above-mentioned fillers.

[0053] The at least one filler used in accordance with the present invention preferably has a particle size of 1 to 10 μm, particularly preferably 2 to 8 μm, for example, 5 μm.

[0054] The total amount of filler, based on the total mass of polyurethane elastomer, is generally 0 to 30% by weight, preferably 0 to 20% by weight, and particularly preferably 0 to 10% by weight.

[0055] Components (A) and (B) are used in a molar ratio of isocyanate groups of component (A) to isocyanate-reactive groups of component (B) of preferably 0.90 to 1.10, more preferably 0.95 to 1.05.

[0056] The polyurethane elastomer used in accordance with the present invention is obtained from the aforementioned components. The preparation of polyurethane elastomers is generally known to those skilled in the art. Polyurethane elastomers can be obtained as follows:

[0057] In a preferred embodiment, component (A) is provided in a suitable reactor, and components (B), optionally (C), optionally (D), and optionally (E) are added to component (A), and components (C), (D), and (E) may be added independently of each other, either before or after the addition of component (B), or mixed with component (B).

[0058] In a preferred embodiment of the above-described embodiment, component (A) is preheated to 60-100°C, preferably 60-85°C, before adding components (B), optionally (C), optionally (D), and optionally (E).

[0059] The provision, measurement, and weighing of single components (A) to (E) can be carried out by any method known to those skilled in the art, for example, manually, using a balance, by syringe, pump, automatic weighing in a reactor, low-pressure distributor, etc.

[0060] After all components (A), (B), and optionally (C), (D), and (E) are present in the reactor, preferably under an inert atmosphere, mixing is carried out for a period of, for example, 10 seconds to 3 minutes, preferably 30 to 90 seconds. In parallel with or after mixing, the mixture is degassed, preferably in a vacuum chamber, for, for example, 10 seconds to 2 minutes, until the mixture is free of bubbles, according to a method particularly known to those skilled in the art. The mixture is then poured, preferably into an open or closed mold, at a temperature of preferably 20 to 120°C, and then cured for 0.1 to 48 hours, preferably at a temperature of preferably 20 to 120°C. The molds themselves are also known to those skilled in the art.

[0061] The polyurethane elastomer is preferably demolded after a specific demolding time, for example, 1 minute to 2 hours, preferably 1 minute to 1 hour.

[0062] Next, a so-called maturation process may be carried out to complete the hardening and networking. This is done, for example, by leaving the cast polyurethane elastomer at an air humidity of 30-70% and a temperature of 10-40°C for 2-14 days.

[0063] The polyurethane cast elastomer according to the present invention has good mechanical properties.

[0064] The tensile strength of the polyurethane elastomer according to the present invention is at least 40 MPa, preferably at least 45 MPa, respectively, obtained in accordance with DIN 53504 (2009).

[0065] The tear strength of the polyurethane elastomer according to the present invention is at least 100 kN / m, preferably at least 120 kN / m, obtained in accordance with ISO 34-1 (2010).

[0066] The elongation of the polyurethane elastomer according to the present invention is at least 600%, preferably at least 700%, which is obtained in accordance with DIN 53504 (2009).

[0067] The wear amount of the polyurethane elastomer according to the present invention is obtained in accordance with ISO 4649 (2017), with a maximum of 50 mm. 3 Preferably a maximum of 35 mm 3 That is the case.

[0068] This application relates to the use of the above-mentioned polyurethane elastomer or the above-mentioned kit of parts in pulp and paper applications.

[0069] Pulp and paper applications in which the above-mentioned elastomers and kits of parts may be used are preferably die-cutting pads, anvil covers, rollers, and zero-crush wheels, preferably anvil covers.

[0070] Accordingly, this application also relates to the use of the above-mentioned polyurethane elastomer or the above-mentioned kit of parts in the manufacture of die-cut pads, anvil covers, zero-crash wheels and rollers, preferably in the manufacture of anvil covers.

[0071] This application also relates to die-cut pads, anvil covers, rollers, and zero-crash wheels manufactured using the above-mentioned polyurethane elastomer or the above-mentioned kit of parts.

[0072] This application also relates to die-cut pads, anvil covers, zero-crash wheels and rollers, preferably anvil covers, comprising or consisting of the above-mentioned polyurethane elastomer or the above-mentioned kit of parts.

[0073] Zero-crash wheels do not have a compact structure and are therefore unsuitable for transport. Examples of industrial uses of zero-crash wheels are as follows: Hold-down wheels for the corrugated cardboard and packaging industry Bottle spacing wheels that allow bottles and other containers to pass through. Labeling wheel for providing pressure to apply labels to objects Flex Grip Wheels for providing maximum surface area to an object being moved A weighing wheel that allows an object to pass through only at the appropriate time.

[0074] The present invention will be explained by the following examples. [Examples]

[0075] [Table 1]

[0076] Test method: Hydroxyl value: The hydroxyl value (mgKOH / g) was measured according to the standard ISO 4629-2 (2016).

[0077] Mn determination: The number-average molecular weight (Mn) was determined by gel permeation chromatography (GPC) in tetrahydrofuran at 23°C. The procedure conformed to DIN 55672-1: "Gel permeation chromatography, Part 1 - Tetrahydrofuran as eluent" (SECurity GPC system from PSS Polymer Service, flow rate 1.0 ml / min; column: 2 × PSS SDV linear M, 8 × 300 mm, 5 μm; RID detector). A polystyrene sample of known molar mass was used for calibration. The number-average molecular weight was calculated using software support. The baseline point and evaluation limits were fixed according to DIN 55672 Part 1.

[0078] Isocyanate value: The isocyanate value (%) was measured according to ISO 14896:2009.

[0079] Determination of isocyanate monomers: The isocyanate monomer value (%m) was measured according to DIN EN ISO 10283:2007-11 "Determination of monomer diisocyanates in isocyanate resins".

[0080] stretch: Elongation was measured at a tensile speed of 500 mm / min, in accordance with DIN 53504 (2009).

[0081] Tensile strength: Tensile strength was measured at a tensile speed of 500 mm / min in accordance with DIN 53504 (2009).

[0082] Tear resistance: Tear resistance was measured according to ISO 34-1(2010).

[0083] wear: Wear measurements were performed according to ISO 4649 (2017).

[0084] Preparation of prepolymers A-D Prepolymer A: The components were first preheated to 50°C. 141g of DESMODUR® T100 and 33g of DESMODUR® T80 were added to a reactor heated to 80°C under stirring and vacuum. 723g of DESMOPHEN® 20555-1A and 103g of DESMOPHEN® 1000 EING were added, and the mixture was homogenized at 80°C for 16 hours. The isocyanate value was then measured according to ISO 14896:2009, and 4.3% was found. The resulting material was then stored in a container under nitrogen and set aside.

[0085] Prepolymer B: The components were initially preheated to 50°C. 351g of DESMODUR® 0118T was added to a reactor heated to 80°C under stirring and vacuum. 432g of DESMOPHEN® 20555-1A and 216g of DESMOPHEN® 1000 EING were added, and the mixture was homogenized at 80°C for 2 hours. The isocyanate value was then measured according to ISO 14896:2009, and 8.0% was found. The resulting material was then stored in a container under nitrogen and set aside.

[0086] Prepolymer C: The components were first preheated to 50°C. 331g of DESMODUR® 0118T was added to a reactor heated to 80°C under stirring and vacuum. 669g of DESMOPHEN® 20555-1A was added, and the mixture was homogenized at 80°C for 2 hours. The isocyanate value was then measured according to ISO 14896:2009, and 8.2% was found. The resulting material was then stored in a container under nitrogen and set aside.

[0087] Prepolymer D: The components were first preheated to 50°C. 217g of DESMODUR® 0118T was added to a reactor heated to 80°C under stirring and vacuum. 778g of DESMOPHEN® 20555-1A was added, and the mixture was homogenized at 80°C for 2 hours. The isocyanate value was then measured according to ISO 14896:2009, and 4.0% was found. The resulting material was then stored in a container under nitrogen and set aside.

[0088] The isocyanate monomers of the prepolymer were measured according to ISO 10283:2007, and the values ​​are shown in the table below.

[0089] [Table 2]

[0090] In prior art, it is known that MDI prepolymers with a standard free monomer content (approximately over 10%) are extended with alcohol chain extenders to prevent them from becoming castable products due to their short pot life.

[0091] Preparation of polyurethane elastomers [Example 1]

[0092] (PU A1: Comparative example): 100g of prepolymer A, preheated to 80°C, was weighed into a flask. 13g of MOCA was added, and the mixture was stirred for 30 seconds to 1 minute. Then, a vacuum was applied to degas the reaction mixture until no bubbles remained. The mixture was poured into a sealed mold at 110°C for 30 minutes. The parts were then demolded and post-cured at 110°C for 16 hours.

[0093] The sheets were aged for 7 days at 23°C and 50% relative humidity.

[0094] [Example 2] (PU A2: Comparative example) 100g of prepolymer A, preheated to 80°C, was weighed into a flask. 10.4g of BAYTEC® XL1705 was added, and the mixture was stirred for 30 seconds to 1 minute. Then, a vacuum was applied to degas the reaction mixture until no bubbles remained. The mixture was poured into a sealed mold at 110°C for 30 minutes. The parts were then demolded and post-cured at 110°C for 16 hours.

[0095] The sheets were aged for 7 days at 23°C and 50% relative humidity.

[0096] [Example 3] (PU B: Comparative example) 0.05 g of CATALYST SD2.4 was weighed into a flask, and 8.4 g of BAYTEC XL(registered trademark) B was added. Then, 100 g of prepolymer B, preheated to 80°C, was weighed in, and the mixture was stirred for 30 seconds to 1 minute. Next, a vacuum was applied to degas the reaction mixture until no bubbles remained. The mixture was poured into a sealed mold at 110°C for 30 minutes. Then, the parts were demolded and post-cured at 100°C for 24 hours.

[0097] The sheets were aged for 7 days at 23°C and 50% relative humidity.

[0098] [Example 4] (PU C: Comparative example) 100g of prepolymer C, preheated to 80°C, was weighed into a flask. 8.6g of BAYTEC® XL B was added, and the mixture was stirred for 30 seconds to 1 minute. Then, a vacuum was applied to degas the reaction mixture until no bubbles remained. The mixture was poured into a sealed mold at 110°C for 30 minutes. The parts were then demolded and post-cured at 110°C for 16 hours.

[0099] The sheets were aged for 7 days at 23°C and 50% relative humidity. [Example 5] (PU D: According to the present invention) 100g of prepolymer D, preheated to 80°C, was weighed into a flask. 9.8g of BAYTEC® XL 1705 was added, and the mixture was stirred for 30 seconds to 1 minute. Then, a vacuum was applied to degas the reaction mixture until no bubbles remained. The mixture was poured into a sealed mold at 100°C for 30 minutes. The parts were then demolded and post-cured at 110°C for 24 hours.

[0100] The sheets were aged for 7 days at 23°C and 50% relative humidity.

[0101] Results: Elastomer properties [Table 3]

Claims

1. In pulp and paper applications, (A) (A1) At least one diphenylmethane diisocyanate which may be modified with a urethane group and / or a carbodiimide group, (A2) At least one polyadipate polyol having a number-average molar mass Mn of 800 to 4000 g / mol (Mn is determined by gel permeation chromatography as referred herein), and a functionality of 2 to 4. (A3) Depending on the case, at least one lactone-based polyester polyol, and (A4) Depending on the case, at least one catalyst and / or at least one additive The reaction (R Ｐ At least one NCO-terminated prepolymer that can be obtained from, (B) i) At least one polyamine selected from the group consisting of isophorone diamine, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, N-methylpropylene-1,3-diamine, N,N'-dimethylethylenediamine, 4,4'-methylenebis(2-chloroaniline), 2,4-toluenediamine, 2,6-toluenediamine, 6-methyl-2,4-bis(methylthio)phenylene-1,3-diamine, 2-methyl-4,6-bis(methylthio)phenylene-1,3-diamine, 3,5-diethyl-2,4-toluenediamine, 3,5-diethyl-2,6-toluenediamine, and primary mono-, di-, tri-, or tetraalkyl-substituted 4,4'-diaminodiphenylmethane, or ii) A mixture of at least one polyamine having at least two functionalities and at least one polyol having at least two functionalities. One of them is at least one type of chain extender, (C) Depending on the case, at least one catalyst, (D) Depending on the case, at least one additive, (E) Depending on the case, at least one type of filler, The reaction (R Ｅ ) obtained from (Embodiment I), or can be obtained from (Embodiment II), The use of polyurethane elastomer, However, the above reaction (R Ｅ ) No polyether carbonate polyol is present in the above, however, in Embodiment II, component (A) has a monomer diisocyanate content of 8% by weight or less, preferably 6% by weight or less, as determined by gas chromatography using an internal standard in accordance with DIN EN ISO 10283:2007-11.

2. In pulp and paper applications, (A) (A1) At least one diphenylmethane diisocyanate which may be modified with a urethane group and / or a carbodiimide group, (A2) At least one polyadipate polyol having a number-average molar mass Mn of 800 to 4000 g / mol (Mn is determined by gel permeation chromatography as referred herein), and a functionality of 2 to 4. (A3) Depending on the case, at least one lactone-based polyester polyol, and (A4) Depending on the case, at least one catalyst and / or at least one additive The reaction (R Ｐ At least one NCO-terminated prepolymer that can be obtained from, (B) i) At least one polyamine selected from the group consisting of isophorone diamine, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, N-methylpropylene-1,3-diamine, N,N'-dimethylethylenediamine, 4,4'-methylenebis(2-chloroaniline), 2,4-toluenediamine, 2,6-toluenediamine, 6-methyl-2,4-bis(methylthio)phenylene-1,3-diamine, 2-methyl-4,6-bis(methylthio)phenylene-1,3-diamine, 3,5-diethyl-2,4-toluenediamine, 3,5-diethyl-2,6-toluenediamine, and primary mono-, di-, tri-, or tetraalkyl-substituted 4,4'-diaminodiphenylmethane, or ii) A mixture of at least one polyamine having at least two functionalities and at least one polyol having at least two functionalities. One of them is at least one type of chain extender, (C) Depending on the case, at least one catalyst, (D) Depending on the case, at least one additive, (E) Depending on the case, at least one type of filler, The use of a kit of parts consisting of (Embodiment III) or including these (Embodiment IV), However, polyether carbonate polyols are not present in the kit of parts, except in Embodiment IV, component (A) has a monomer diisocyanate content of 8% by weight or less, preferably 6% by weight or less, as determined by gas chromatography using an internal standard in accordance with DIN EN ISO 10283:2007-11.

3. At least one diphenylmethane diisocyanate (A1), which may be modified with the aforementioned urethane group and / or carbodiimide group, is: diphenylmethane-4,4'-diisocyanate (4,4'-MDI), diphenylmethane-2,4'-diisocyanate (2,4'-MDI), diphenylmethane-2,2'-diisocyanate (2,2'-MDI), diphenylmethane-2,4'-diisocyanate (2,4'-MDI) / diphenylmethane-4,4'-diiso Use of the polyurethane elastomer according to claim 1, selected from the group consisting of cyanate (4,4'-MDI) mixtures, urethane-modified liquid diphenylmethane-4,4'-diisocyanate and diphenylmethane-2,4'-diisocyanate and carbodiimide-modified diphenylmethane-2,2'-diisocyanate, diphenylmethane-2,4'-diisocyanate and diphenylmethane-4,4'-diisocyanate, or use of the kit of parts according to claim 2.

4. The use of the polyurethane elastomer according to claim 1 or 3, or the use of the kit of parts according to claim 2 or 3, wherein the at least one polyadipate polyol (A2) is produced from adipic acid and / or at least one adipic acid derivative and at least one polyhydric alcohol, the at least one polyhydric alcohol being selected from the group consisting of ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 1,3-propanediol, and dipropylene glycol.

5. Use of the polyurethane elastomer according to any one of claims 1, 3, or 4, or use of the kit of parts according to any one of claims 2, 3, or 4, wherein components (A1), (A2), and optionally (A3) are used in a molar ratio of isocyanate groups of component (A1) to isocyanate-reactive groups of component (A2) and optionally (A3), preferably 1.5 to 4, more preferably 1.6 to 3.

6. At least one polyamine of the chain extender component Bii) is isophorone diamine, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, N-methylpropylene-1,3-diamine, N,N'-dimethylethylenediamine, and aromatic diamines, such as 4,4'-methylenebis(2-chloroaniline), 2,4-toluenediamine and 2,6-toluenediamine, 6-methyl-2,4-bis(methylthio)phenylene-1,3-diamine and Use of a polyurethane elastomer according to any one of claims 1 or 3 to 5, selected from the group consisting of 2-methyl-4,6-bis(methylthio)phenylene-1,3-diamine, 3,5-diethyl-2,4-toluenediamine, and 3,5-diethyl-2,6-toluenediamine, and primary mono-, di-, tri-, or tetraalkyl-substituted 4,4'-diaminodiphenylmethane, or use of a kit of parts according to any one of claims 2 to 5.

7. Use of the polyurethane elastomer according to any one of claims 1 or 3 to 6, or use of the kit of parts according to any one of claims 2 to 6, wherein at least one polyol of the chain extender component Bii) is used in a maximum amount of preferably 80% by weight, more preferably 50% by weight, and most preferably 20% by weight, based on the total weight of component (B).

8. The use of a polyurethane elastomer according to any one of claims 1 or 3 to 6, wherein component B) consists exclusively of a polyamine (Embodiment i), or the use of a kit of parts according to any one of claims 2 to 6.

9. The use of the polyurethane elastomer according to any one of claims 1 or 3 to 8, or the use of the kit of parts according to any one of claims 2 to 8, wherein the pulp and paper application is the manufacture of die-cutting pads, anvil covers, rollers, or zero-crush wheels.

10. A die-cut pad, anvil cover, zero-crash wheel, or roller comprising or consisting of a polyurethane elastomer as specified in any one of claims 1 or 2 to 8, or a kit of parts as specified in any one of claims 2 to 8.

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