EP4077437A1 - Procédé de préparation de polyuréthanes ayant une enthalpie de réaction élevée - Google Patents

Procédé de préparation de polyuréthanes ayant une enthalpie de réaction élevée

Info

Publication number
EP4077437A1
EP4077437A1 EP20820189.7A EP20820189A EP4077437A1 EP 4077437 A1 EP4077437 A1 EP 4077437A1 EP 20820189 A EP20820189 A EP 20820189A EP 4077437 A1 EP4077437 A1 EP 4077437A1
Authority
EP
European Patent Office
Prior art keywords
component
mol
terminated prepolymer
diisocyanatobutane
hydroxy
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.)
Withdrawn
Application number
EP20820189.7A
Other languages
German (de)
English (en)
Inventor
Mathias Matner
Thomas König
Bernd GARSKA
Stephan Schubert
Dirk Achten
Rainer Bellinghausen
Claudia HOUBEN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Intellectual Property GmbH and Co KG
Original Assignee
Covestro Intellectual Property GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Covestro Intellectual Property GmbH and Co KG filed Critical Covestro Intellectual Property GmbH and Co KG
Publication of EP4077437A1 publication Critical patent/EP4077437A1/fr
Withdrawn legal-status Critical Current

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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0895—Manufacture of polymers by continuous processes
    • 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
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the invention relates to a multistage process for the continuous, solvent-free production of thermoplastic polyurethanes by reacting one or more diols with one or more diisocyanates, including aliphatic, cycloaliphatic and / or araliphatic diisocyanates, the isocyanate component and the diol Components are selected so that, if they are converted in a molar ratio of 1.0: 1.0, the total enthalpy of reaction over all process stages is from -900 kJ / kg to -500 kJ / kg, determined in accordance with DIN 51007: 1994-06.
  • Polyurethanes and in particular thermoplastic polyurethanes, have been used for a wide variety of purposes for years because of their excellent physical properties.
  • polyurethanes there are areas of application in which other plastics, such as, for example, polyamide plastics, are used because polyurethanes with suitable physical properties are not available or these are difficult to obtain.
  • Polyurethanes that are built up from short-chain aliphatic diols and aliphatic polyisocyanates have properties that are comparable or better than those of polyamide plastics. Up to now, however, they have not been able to be produced satisfactorily on an industrial scale, since decisive process engineering problems have not yet been solved. Due to the high density of reactive groups, the polyaddition of short-chain aliphatic diols with aliphatic polyisocyanates has a high heat release or enthalpy of reaction, which in the case of insufficient heat dissipation can lead to damage or even regression of monomers and destruction (incineration) of the polyurethane leads.
  • US 2284637 discloses a batch process for the production of linear polyurethanes from diisocyanates or dithioisocyanates and diols or thiols. For this purpose, the reactants are reacted in the presence of solvents and in solvent-free systems.
  • US3038884 discloses polyurethanes derived from 2,2,4,4-tetramethyl-1,3-cyclobutanediol, which have a higher melting point and improved thermal stability, in contrast to polyurethanes without cyclic groups in the polymer chain.
  • the reactants are converted in the presence of solvents and in solvent-free batch systems.
  • DE728981 and US2511544 disclose a batch process for converting diisocyanates with diols and / or diamines to form polyurethane or polyureas in a solvent-based or solvent-free process.
  • Product temperatures that are too high can in principle be prevented by a batch procedure in which at least one of the two monomers is slowly metered in according to the cooling capacity of the reactor. Cooling of highly viscous polymers in batch devices is, however, technically limited by the surface of the heat exchanger and the flow rate. Long residence times in combination with high temperatures increase the number of undesirable side reactions and have a disadvantageous effect on the product properties.
  • thermoplastics Following a batch process requires the molten polymer to be kept at a high temperature until the batch container is empty. For thermally sensitive products, this results in a product property profile that changes continuously over the granulation process / the granulation time.
  • Process sequences from batch processes can also be transferred only with difficulty, if at all, to continuous processes. From a procedural point of view, special attention is paid to the controlled dissipation of the released heat of reaction, which means that reactions with a high degree of exothermicity are difficult to handle.
  • the use of solvents is also disadvantageous, since residual solvents remaining in the product can be released into the environment and can cause undesirable properties such as, for example, odor, toxicity and / or a deterioration in the mechanical properties.
  • the complete removal of residual solvents from a polymer cannot succeed due to the principle involved; their removal up to a certain limit value is generally associated with increased technical effort and energy consumption.
  • No. 5,627,254 discloses a continuous process for the production of thermoplastic urethanes from diisocyanates, short-chain polyethylene glycols, butanediol and with more than 25% by weight of diols with a high molecular weight.
  • the polyaddition product of methylenediphenyl diisocyanate and butanediol is also described.
  • the components are reacted in a twin-screw extruder in the presence of a catalyst.
  • the tendency towards disruptive side reactions is very much lower than in corresponding conversions of aliphatic isocyanates. Transferring such processes to essentially aliphatic starting materials is therefore generally not possible.
  • the object of the present invention was therefore to provide a continuous, solvent-free process for polyurethane production which enables polyaddition reactions to be carried out for the first time on an industrial scale with a large negative enthalpy of reaction per kg of reaction mass.
  • thermoplastic polyurethanes by reacting the components
  • diisocyanates including aliphatic, cycloaliphatic and / or araliphatic diisocyanates
  • At least one diol of component A having a molecular weight of 62 g / mol to 250 g / mol, with at least one hydroxy-terminated prepolymer from the total amount or a first in at least one process stage of the multistage process
  • Subset of component A and a first subset of component B is formed, the sum of all subsets of component A or the sum of all subsets of component B over all process stages of the multi-stage process together the total amount of component A or component used B is characterized in that components A and B are selected so that when they are reacted in a molar ratio of 1.0: 1.0, the total enthalpy of reaction over all process stages is from -900 kJ / kg to -500 kJ / kg, determined according to DIN 51007: 1994-06.
  • the total enthalpy of reaction is determined in accordance with DIN 51007 June 1994 by heating 20 mg - 30 mg of a mixture of component A and component B in a gas-tight sealed glass ampoule at 3 K / min from -50 ° C to +450 ° C, the difference between the The temperature of the mixture and the temperature of an inert reference made of aluminum oxide are determined by means of thermocouples and component A and component B are present in the mixture in a molar ratio of 1.0: 1.0.
  • the advantage of the method according to the invention is that the temperature of the reaction mass can be controlled very well in the embodiment according to the invention and therefore there is no significant heat-related damage, such as speck formation or discoloration in the polyurethane product. Furthermore, the method according to the invention enables good scalability from the laboratory to an industrial scale.
  • Total reaction enthalpy in the context of the present invention is understood to mean the mass-specific change in enthalpy that occurs in the polymerization reaction (polyaddition) of component A with component B over all process stages and without dilution, with a molar ratio of component A to component B of 1.0: 1.0.
  • the enthalpy of reaction is given in kJ per kg of the total reaction mixture of component A and component B, with a molar ratio of component A to component B of 1.0: 1.0.
  • a reaction with a negative enthalpy of reaction is described as an exothermic reaction, which means that energy is released in the form of heat during the reaction.
  • a “solvent-free process” in the context of the present invention is understood to mean the reaction of components A and B without additional diluents, such as, for example, organic solvents or water, ie components A and B are preferably reacted with one another undiluted.
  • Components C and / or D can optionally be present in suitable diluents and added to components A and / or B as a solution.
  • the process in the context of the present invention is still to be regarded as solvent-free if the content of the solvent is up to 1% by weight, preferably up to 0.1% by weight, more preferably up to 0.01% by weight, based on is the total weight of the reaction mixture.
  • a solvent is understood to mean a substance in which at least one of components A and B and optionally C and / or D can be dissolved, dispersed, suspended or emulsified, but which cannot be mixed with one of components A and B and optionally C. and / or D or reacts with the polymer and the prepolymer (s).
  • a non-reactive prepolymer and / or Non-reactive polymers which do not react with one of the components A and B and optionally C and / or D or with the polymer and the prepolymer (s) of the reaction mixture are not regarded as “solvents”.
  • a “non-reactively terminated prepolymer” is understood to mean a prepolymer in which the reactive groups (NCO groups or OH groups) have been converted into chemical groups by reaction with suitable reaction partners (chain terminators) react neither with NCO groups nor with OH groups under the reaction conditions mentioned.
  • suitable chain terminators are, for example, monoalcohols such as methanol, monoamines such as diethylamine and monoisocyanates such as butyl isocyanate.
  • the molar fraction of chain terminators can be, for example, from 0.001 mol% to 2 mol% and preferably from 0.002 mol% to 1 mol%, based in each case on the total amount of the corresponding monomer component.
  • process stage means the technical implementation of at least one basic operation, such as mixing, reacting, transporting, heat transfer, etc. in combination with the metering of at least a portion of component A and / or B and / or a hydroxy-terminated one Prepolymer and / or an NCO-terminated prepolymer.
  • the process stage takes place in at least one given apparatus with a defined throughput.
  • An apparatus contains the reactors, machines, pipelines and measuring and control devices required for this.
  • a process stage can be carried out in one or more apparatuses.
  • Reactors which can be used for polymer reactions are known to the person skilled in the art and are described, for example, in Moran, S. and Henkel, K.-D. 2016, Reactor Types and Their Industrial Applications, Ullmann's Encyclopedia of Industrial Chemistry, 149.
  • Continuous process or “continuous process” within the meaning of the invention are those in which the feed of the starting materials into at least one apparatus and the discharge of the products from at least one identical or different apparatus simultaneously take place during continuous production, while with discontinuous processes, the feed of the educts, the chemical conversion and the discharge of the products usually take place one after the other.
  • the continuous procedure is usually of economic advantage, since system downtimes due to filling and emptying processes are avoided.
  • polymers and thus also prepolymers are not present as isolated species, but are always present as mixtures of molecules with different numbers of repeating units and thus different molecular weights and possibly also different end groups. Both the number of repeating units per molecule and, if appropriate, the end groups are generally distributed statistically.
  • the term “prepolymer” is understood to mean all reaction products or reaction product mixtures of components A, B and optionally C and D in which the molar ratio of the amounts of component B to component A used is between 0.1: 1.0 and 0.95: 1.0 or in which the molar ratio of the amounts of component A to component B used is between 0.1: 1.0 and 0.95: 1.0.
  • a “hydroxy-terminated prepolymer” is understood to mean a prepolymer mixture in which at least 90% by number of the molecule ends have a hydroxyl group and the remaining 10% by number of molecules end further hydroxyl groups, NCO groups and / or have non-reactive groups.
  • a “non-reactive group” is understood to mean a group which, under the reaction conditions according to the invention, reacts neither with NCO groups nor with OH groups in a unit of time which corresponds to the reaction time according to the invention.
  • a non-reactive group can, for example, be converted from a reactive NCO group or OH group into a non-reactive group by reacting with suitable reaction partners (chain terminators).
  • Suitable chain terminators are all monofunctional compounds which react either with an isocyanate group or with a hydroxyl group under the reaction conditions according to the invention, for example monoalcohols such as methanol, monoamines such as diethylamine and monoisocyanates such as butyl isocyanate.
  • the hydroxyl-terminated prepolymer can, for example, have a hydroxyl group at one end of the molecule and, for example, an alkyl group at the other end of the molecule.
  • a hydroxy-terminated prepolymer is spoken of in the context of the present invention, this also always includes a mixture of the at least one hydroxy-terminated prepolymer and a non-reactively terminated prepolymer.
  • the at least one hydroxy-terminated prepolymer can also be a mixture of at least one hydroxy-terminated prepolymer and at least one non-reactively terminated prepolymer.
  • part of the total enthalpy of reaction produced is removed in at least one process stage before the next process stage is reached.
  • a process stage from 25% to 98%, particularly preferably from 30% to 95% and even more preferably from 35% to 90% and very particularly preferably from 40% to 85% of the total enthalpy of reaction produced before the thermoplastic polyurethane is completed .
  • a large part of the enthalpy of reaction discharged is preferred in the preparation of the at least one hydroxy-terminated prepo Lymers and / or a mixture of at least one hydroxy-terminated prepolymer and at least one non-reactively terminated prepolymer removed by conduction.
  • the total enthalpy of reaction over all process stages is in the range from -900 kJ / kg to -550 kJ / kg, preferably in the range from -900 kJ / kg to -580 kJ / kg, more preferably in the range from -900 kJ / kg to -600 kJ / kg, more preferably in the range from -900 kJ / kg to -650 kJ / kg, according to DIN 51007: 1994-06, if components A and B are in a molar ratio of 1 : 1 to be implemented together.
  • the corresponding reaction enthalpies are determined by means of a screening differential thermal analysis (DTA) according to DIN 51007 (June 1994).
  • DTA differential thermal analysis
  • the corresponding monomers are mixed in a molar ratio of 1: 1 and the enthalpy of reaction is determined during a specific temperature profile.
  • the temperature profile used here starts at - 50 ° C and ends at +450 ° C.
  • the heating rate used is 3 K / min.
  • Aluminum oxide is used as an inert reference.
  • the overall molar ratio of component A to component B is from 1.0: 0.95 to 0.95: 1.0.
  • component A and component B are optionally reacted with one another continuously in the presence of components C and D.
  • the process steps for producing the thermoplastic polyurethanes can be carried out in a single apparatus or in a multiplicity of apparatuses. For example, a process stage can first be carried out in a first apparatus (e.g. loop reactor or coolable mixer) and then the reaction mixture can be transferred to another apparatus (e.g. extruder or other high-viscosity reactors) in which the reaction is continued.
  • a first apparatus e.g. loop reactor or coolable mixer
  • another apparatus e.g. extruder or other high-viscosity reactors
  • the mean residence time in the at least one process stage for producing the hydroxy-terminated prepolymer is between 5 seconds and 90 minutes, preferably between 10 seconds and 60 minutes, particularly preferably between 30 seconds and 30 minutes, each based on a process stage.
  • At least one hydroxy-terminated prepolymer from the total amount or a first partial amount of component A and a first partial amount of component B is formed in at least one process stage of the multistage process.
  • the at least one hydroxy-terminated prepolymer can also be a mixture of at least one hydroxy-terminated prepolymer and at least one non-reactively terminated prepolymer.
  • the at least one hydroxy-terminated prepolymer is used in at least one process stage from the total amount of component A and a first subset of component B formed.
  • the first partial amount of component B is preferably from 40% to 95%, preferably from 60% to 95%, more preferably from 75% to 93%, each based on the total molar amount of component B used in the process.
  • the total amount of component A with a first partial amount of component B can be reacted, for example, in a first apparatus in order to build up the at least one hydroxyl-terminated prepolymer.
  • further subsets of component B i.e. a second, third, etc. subset can then be added in order to build up further inventive, on average higher molecular weight, hydroxy-terminated prepolymers.
  • the other partial amounts of component B can be added in the first apparatus or the reaction mixture from the first apparatus can be transferred to a second apparatus and there reacted with a second partial amount of component B. All further partial amounts can then be added, for example, in the second apparatus or the reaction mixture is in each case transferred after the reaction with a partial amount of component B to a next apparatus and there reacted with a further partial amount of component B until the total amount of the component A with the total amount of component B has been implemented.
  • the spatially and / or temporally separated sequential addition of component B has the advantage that the released heat of reaction is generated step by step and can thus be better dissipated and / or used, for example to preheat components A and B before they are fed to the reactor.
  • amounts of non-reactively terminated prepolymers according to the invention one or more NCO-terminated prepolymers and / or chain terminators such as monoalcohols can also be added.
  • the at least one hydroxy-terminated prepolymer can also be a mixture of at least one hydroxy-terminated prepolymer and at least one non-reactively terminated prepolymer.
  • an “NCO-terminated prepolymer” is understood to mean a polymer or prepolymer in which at least 90% by number of the molecule ends have an NCO group and the remaining 10% by number of molecule ends have further NCO groups, hydroxy groups. Have groups and / or non-reactive groups.
  • an NCO-terminated prepolymer can also be a mixture of NCO-terminated prepolymers or a mixture of NCO-terminated prepolymers and non-reactively terminated prepolymers. It is preferably a mixture of NCO-terminated prepolymers.
  • the NCO-terminated prepolymers can be obtained by reacting a portion of component A with a portion of component B, component B being in excess.
  • the polyaddit on can take place in the presence of components C and D.
  • the temperatures for forming the at least one NCO-terminated prepolymer by the process according to the invention can be selected as a function of the compounds used. However, it is preferred here if the reaction is carried out at temperatures from 60 ° C to ⁇ 260 ° C, preferably from 80 ° C to 250 ° C, particularly preferably from 100 ° C to 245 ° C and very particularly preferably from ⁇ 100 ° C to ⁇ 240 ° C is carried out.
  • the NCO termination is statistically distributed and the average NCO functionality of the NCO-terminated prepolymer is between 1.8 and 2.2, preferably between 1.9 and 2.1 and very particularly preferably between 1.95 and 2.05.
  • the at least one NCO-terminated prepolymer can be a mixture of at least one NCO-terminated prepolymer and at least one non-reactively terminated prepolymer, the NCO functionality being randomly distributed and the average NCO functionality of the NCO-terminated prepolymer is between 1.8 and 2.2, preferably between 1.9 and 2.1 and very particularly preferably between 1.95 and 2.05.
  • the reaction is preferably in a temperature range from 30 K below to 150 K above the melting point, preferably from 15 K below to 100 K above, particularly preferably from 10 K below to 70 K above the melting point of the at least one NCO-terminated prepolymer carried out.
  • the at least one hydroxy-terminated prepolymer is formed in at least one process stage from a first subset of component A and a first subset of component B, the molar ratio of the subsets used of component B to component A from 0.65: 1.0 to 0.98: 1.0, preferably from 0.70: 1.0 to 0.97: 1.0, more preferably from 0.75: 1.0 to 0.96: 1.0 and very particularly preferably 0.75: 1.0 to 0.95: 1.0 and where the first partial amount A is at least 50%, preferably 70%, more preferably 90%, based on the total molar amount in the process component A used is used.
  • further partial amounts of component A and component B can then be added in order to build up further inventive, on average higher molecular weight, hydroxy-terminated prepolymers.
  • no NCO-terminated prepolymer is formed from the at least one hydroxy-terminated prepolymer by adding a further partial amount of component B.
  • it is statistical NCO-terminated prepolymers formed transiently but not stable are not counted.
  • the other partial amounts of components A, B, optionally at least one hydroxy-terminated prepolymer and / or at least one NCO-terminated prepolymer and optionally chain terminators such as monoalcohols can also be introduced into further apparatus, ie a second, third, etc.
  • the at least one hydroxy-terminated prepolymer can also be a mixture of at least one hydroxy-terminated prepolymer and at least one non-reactively terminated prepolymer.
  • components A and B and / or the prepolymers mentioned above are fed to the reaction mixture at a temperature which at least 30 K, preferably at least 50 K and particularly preferably 100 K below that of the reaction mixture.
  • the hydroxy-terminated prepolymer or the mixture comprising at least one hydroxy-terminated prepolymer can have a low or high viscosity in the melt under reaction conditions.
  • a low viscosity is 0.1 Pa * s, for example, and a high viscosity is 500 Pa * s, for example.
  • the Newtonian limiting viscosity at low shear rates is considered here.
  • a low viscosity of the hydroxy-terminated prepolymer or mixture compared to that of the thermoplastic polyurethane has the advantage that the heat exchangers used can work efficiently and heat exchangers with a small overall size or surface can be used.
  • the viscosity of the hydroxy-terminated prepolymer according to the invention of the first process stage or of the mixture of at least one hydroxy-terminated prepolymer and at least one non-reactively terminated prepolymer is preferably in the range from 0.1 Pa * s to 10 Pa * s, determined in of the melt under typical process conditions with regard to process temperature and shear.
  • the viscosity is preferably determined or calculated in the process, for example on the basis of the measurement of pressure losses in pipe sections or in static mixers.
  • the Hagen-Poiseuille equation can be used for laminar flow to calculate pressure losses ( ⁇ p in Pascal) in the form (Volume flow in cubic meters per second, D inside diameter of the pipe in meters, ⁇ 3.14159 ... number of circles, L length of the pipe in meters, h viscosity in Pascal times seconds) can be converted to the determining equation for the viscosity
  • the enthalpy of reaction removed is preferably removed with the aid of heat exchangers, which give off this enthalpy of reaction as heat to a heat transfer medium.
  • This heat transfer medium can be, for example, water in the liquid state, evaporating water or heat transfer oil, such as Marlotherm SH (from Sasol) or Diphyl (from Lanxess), in the liquid state.
  • the heat transfer medium When entering the heat exchanger, the heat transfer medium preferably has a temperature which is so high that blockages due to crystallization and / or solidification of the reaction mixture are avoided.
  • the heat transfer medium can also be used to initially preheat the product stream in the heat exchanger to a temperature at which the reaction begins.
  • the heat exchangers can be designed in various ways. For example, it can be a shell-and-tube heat transfer with empty tubes or a shell-and-tube heat transfer with built-in components to improve the heat transfer (e.g. static mixers such as the Kenics type, SMX from Sulzer or SMXL from Sulzer or CSE-X from Fluitec), or for example it can be plate heat exchangers or, for example, it can be temperature-controllable static mixers, which can be of the type SMR (from Sulzer) or CSE-XR (from Fluitec), for example.
  • static mixers such as the Kenics type, SMX from Sulzer or SMXL from Sulzer or CSE-X from Fluitec
  • plate heat exchangers or, for example, it can be temperature-controllable static mixers, which can be of the type SMR (from Sulzer) or CSE-XR (from Fluitec), for example.
  • the temperatures for forming the at least one hydroxy-terminated prepolymer by the process according to the invention can be selected as a function of the compounds used. However, it is preferred here if the reaction is carried out at temperatures from 40 ° C. to 260 ° C., preferably from 60 ° C. to 250 ° C., more preferably from 100 ° C. to 240 ° C., particularly preferably from 120 ° C to ⁇ 220 ° C. It is tolerated that the product experiences short-term ( ⁇ 60 seconds) deviations in the reaction temperature from the above-mentioned ranges during implementation.
  • the reaction is preferably carried out in a temperature range from 30 K below to 150 K above the melting point, preferably from 15 K below to 100 K above, particularly preferably from 10 K. carried out below to 70 K above the melting point of the at least one hydroxy-terminated prepolymer.
  • the hydroxy-terminated prepolymer has an average OH functionality, calculated from the functionalities of the starting materials, of 1.8 to 2.1, preferably 1.95 to 2.05, particularly preferably 1.97 to 2.0, very particularly preferably 1.975 to 2.0 in each case based on the amount of substance of the entire prepolymer mixture.
  • the at least one hydroxyl-terminated prepolymer is converted to the thermoplastic polyurethane.
  • the at least one hydroxy-terminated prepolymer in at least one further process stage following the formation of the at least one hydroxy-terminated prepolymer, is reacted with a further partial amount of component B to form thermoplastic polyurethane.
  • the further partial amount of component B is preferably from 5% to 60%, preferably from 5% to 40%, more preferably from 7% to 25%, each based on the total molar amount of component B used in the process, with the proviso that the sum of all partial amounts of component B over all process stages of the multistage process together is the total molar amount of component B used.
  • Either the at least one hydroxyl-terminated prepolymer can be reacted all at once with the remaining total amount of component B or it is initially only reacted with a partial amount of component B and then further partial amounts of component B are gradually added and used Brought reaction until the total amount of component B is consumed.
  • the step-by-step implementation has the advantage that the course of the reaction is better controlled, the thermoplastic polyurethane can be built up selectively and the heat of the reaction can be better dissipated.
  • the at least one hydroxy-terminated prepolymer with a second portion of component B and a second portion of component A is thermoplastic Polyurethane implemented, with the proviso that the sum of all subsets of component A and the sum of all subsets of component B over all process stages of the multi-stage process together is the total molar amount of component A or component B used.
  • Either the at least one hydroxyl-terminated prepolymer can be reacted at once with the remaining total amount of component B and component A or only a second partial amount of component B is initially reacted and then further partial amounts of component B are added step by step or initially only reacted with a second partial amount of component A and then gradually added further partial amounts of component A or further partial amounts of component A and further partial amounts of component B added together or alternately and reacted until the total amount of component B and component A is consumed.
  • the gradual implementation has the The advantage is that the course of the reaction is better controlled, the thermoplastic polyurethane is built up selectively and the heat of reaction can be dissipated better.
  • the at least one hydroxy-terminated prepolymer is formed in at least one process stage from a first subset of component A and a first subset of component B and in at least one further on the formation of the hydroxy-terminated one Prepolymers following process stage, the at least one hydroxy-terminated prepolymer is reacted with at least one NCO-terminated prepolymer to form thermoplastic polyurethane, the at least one NCO-terminated prepolymer in at least one further process stage from a second part of component A and a second Subset of component B is formed.
  • At least one hydroxy-terminated prepolymer can be prepared from a first subset of component A and a first subset of component B and at least one NCO-terminated prepolymer separately from a second subset of component A and a second subset of component B getting produced.
  • the first and second partial amounts of component A can correspond to the total amount of component A and the first and second partial amounts of component B can correspond to the total amount of component B. It is also possible for a further, unconverted subset of component A and / or B to be present in addition to the respective converted first and second partial amounts of component A and B.
  • the at least one hydroxy-terminated prepolymer can then be reacted with the at least one NCO-terminated prepolymer to form thermoplastic polyurethane. If the total amount of component A and / or B has not been consumed to produce the hydroxy-terminated prepolymer, NCO-terminated prepolymer and optionally non-reactively terminated prepolymer, then the remaining partial amount of component A and / or B is either included the reaction product, which results from the conversion of the prepolymers (hydroxy-terminated prepolymers, NCO-terminated prepolymers and non-reactive terminated prepolymers) with one another, converted in a separate process stage or converted together with the prepolymers in one process stage to form thermoplastic polyurethane .
  • the reaction of the reactants can take place step by step by adding any desired partial amounts or in one step by adding the total amount.
  • the order in which the partial quantities are added can be freely selected. However, it is preferred either to initially introduce the at least one hydroxy-terminated prepolymer and to add at least one NCO-terminated prepolymer for this purpose.
  • the total amount of the at least one NCO-terminated prepolymer produced can be reacted with the total amount of the at least one hydroxy-terminated prepolymer at once or a partial amount of the at least one NCO-terminated prepolymer is first reacted with the total amount of the at least one hydroxy-terminated prepolymer Prepolymers set and in subsequent process steps further partial amounts of the at least one NCO-terminated prepolymer are added and reacted.
  • a first partial amount of the at least one NCO-terminated prepolymer can be reacted with a first partial amount of the at least one hydroxy-terminated prepolymer and further partial amounts can be added and each reacted until the total amount of the at least a hydroxy-terminated prepolymer and the total amount of at least one NCO-terminated prepolymer produced has reacted.
  • the at least one hydroxy-terminated prepolymer and the at least one NCO-terminated prepolymer are preferably used in a molar ratio of 1.0: 0.95 to 0.95: 1.0, preferably in a molar ratio of 1.0: 0.98 to 0.98: 1.0 converted.
  • the OH- or NCO-functional prepolymers formed after the gradual addition are solids at 25.degree. C. with a melting point of preferably> 50.degree. C., preferably> 90.degree. C., particularly preferably> 120.degree very particularly preferably> 140 ° C.
  • the number-average molar mass (M n ) of the thermoplastic polyurethane formed can be adjusted by the molecular ratio of the components A and B used and / or by the conversion and / or by the use of chain terminators or by a combination of all possibilities.
  • the relationship between the molecular ratio of components A and B, the content of chain terminators, the conversion and the achievable number-average molar mass is known to the person skilled in the art as the Carothers equation.
  • thermoplastic polyurethane can be produced in the abovementioned embodiments in a large number of process stages.
  • Components C and D can only be added in individual process stages or in all process stages independently of one another.
  • components A and B and / or the prepolymers mentioned above are the reaction mixture at a temperature fed which is at least 30 K, preferably at least 50 K and particularly preferably 100 K below that of the reaction mixture.
  • the temperatures for forming the thermoplastic polyurethane by reacting the at least one hydroxy-terminated prepolymer with a second portion of component B im Processes according to the invention can be selected depending on the compounds used. However, it is preferred here if the reaction is carried out at temperatures from 60 ° C to ⁇ 260 ° C, preferably from 80 ° C to 250 ° C, particularly preferably from 100 ° C to 245 ° C and very particularly preferably from ⁇ 120 ° C to ⁇ 240 ° C is carried out. It is tolerated that the product experiences short-term ( ⁇ 60 seconds) deviations in the reaction temperature from the above-mentioned ranges during the conversion.
  • the reaction is preferably in a temperature range from 30 K below to 150 K above the melting point, preferably from 15 K below to 100 K above, particularly preferably from 10 K below to 70 K. carried out above the melting point of the thermoplastic polyurethane.
  • the at least one hydroxy-terminated prepolymer is produced in at least a first process stage and in at least a second process stage with a second partial amount of component B, component A and / or the at least one NCO-terminated prepolymer converted to thermoplastic polyurethane, the first process stage being able to have different reaction conditions with regard to temperature, pressure and / or shear rate compared to the at least second process stage and the process stages being connected to one another via at least one substance-transporting line .
  • the at least one NCO-terminated prepolymer is preferably produced in a third process stage which is separate from the at least one first and second process stage and has different reaction conditions in terms of temperature, pressure and shear rate compared to the at least one first and second process stage and with the at least one first or second process stage is connected via at least one substance-transporting line.
  • the at least one NCO-terminated prepolymer can also be produced independently in the at least one second process stage and, after the components have been converted to the at least one NCO-terminated prepolymer, in at least a third process stage with the at least one hydroxy-terminated one Prepolymer to be converted to thermoplastic polyurethane.
  • the wall temperature of the apparatus according to the invention is in a temperature range from 30 K below to 150 K above the melting point, preferably from 15 K below to 100 K above, particularly preferably from 10 K below to 70 K above the respective melting point of the hydroxy-terminated prepolymer or the optionally NCO-terminated prepolymer Lymers and / or the optionally non-reactive-terminated prepolymer or a mixture of at least two of these, held in the conversion stage.
  • a pumped-around reactor is used as the apparatus for producing the at least one hydroxy-terminated prepolymer or the at least one NCO-terminated prepolymer, in which components A and B in the desired proportions and, if appropriate, components C and D can be metered in in the desired proportions and in which the enthalpy of reaction is dissipated in a heat exchanger.
  • a mixer-heat exchanger is used to convert the components, in which the reaction and the dissipation of the heat take place at the same place.
  • the mean residence time in the process stage suitable for forming the thermoplastic polyurethane from the at least one hydroxyl-terminated prepolymer is from 5 seconds to 60 minutes, preferably from 30 seconds to 60 minutes, particularly preferably from 1 minute to 50 minutes and very particularly preferably from 10 minutes to 50 minutes.
  • thermoplastic polyurethane To react the at least one hydroxy-terminated prepolymer with a second portion of component B, component A and / or the at least one NCO-terminated prepolymer or any mixture thereof or a mixture of the respective components with at least one non- reactive prepolymer for thermoplastic polyurethane, it is necessary to adapt the process to the exponential increase in viscosity in this phase. Apparatuses in which the product is actively moved with mechanical energy are preferred for this. It is particularly preferred to use devices in which the material surfaces clean each other - apart from games.
  • Such apparatus are, for example, corotating multi-screw extruders such as twin or four-screw extruders or ring extruders, counter-rotating multi-screw extruders, co-kneaders or planetary roller extruders and rotor-stator systems.
  • Further suitable apparatus are single- or double-screw, large-volume kneaders.
  • the twin-screw, large-volume kneaders can be co-rotating or rotating in opposite directions.
  • kneaders examples include CRP (List Technology AG), Reacom (Buss-SMS-Canzler GmbH), Reasil (Buss-SMS-Canzler GmbH), KRC kneader (Kurimoto, Ltd).
  • CRP List Technology AG
  • Reacom Buss-SMS-Canzler GmbH
  • Reasil Buss-SMS-Canzler GmbH
  • KRC kneader Kurimoto, Ltd.
  • at least one such apparatus is combined with at least one static mixer, dynamic mixer or mixer heat exchanger, the static mixer, dynamic mixer or mixer heat exchanger being a mixture of component B, component A or at least one NCO-terminated prepolymer or any mixture thereof generated with the hydroxy-terminated prepolymer.
  • the temperature of the mixture is increased by suitable measures in a temperature range from 30 K below to 150 K above the melting point, preferably from 15 K below to 100 K above, particularly preferably from 10 K below to 70 K above the melting point of the component melting at the highest temperature or that of the highest temperature melting reaction product of the components held.
  • the residence time in the static mixer, dynamic mixer or mixer heat exchanger is so short that the increase in viscosity (due to the polyaddition reaction of the reactive components with one another) does not lead to clogging of the static mixer, dynamic mixer or mixer heat exchanger and / or a pressure build-up is limited to ⁇ 50 bar, preferably ⁇ 30 bar, particularly preferably ⁇ 20 bar and very particularly preferably ⁇ 10 bar, and the resulting mixture is fed to an apparatus which corresponds to the above list.
  • the ratio of the residence times in the static mixer, dynamic mixer or mixer heat exchanger to those in the subsequent apparatus is preferably from 1: 100 to 1: 2, particularly preferably from 1:50 to 1: 5 and very particularly preferably from 1:30 to 1: 10.
  • the components can also be present as a mixture with at least one non-reactive prepolymer.
  • the final process stage takes place in an extruder.
  • the final process stage takes place in a combination of a static mixer, dynamic mixer or mixer-heat exchanger with a heated conveyor belt.
  • the ratio of the residence time in the first apparatus to that in the second apparatus is preferably from 1: 100 to 1: 2, more preferably from 1:50 to 1: 3 and very particularly preferably from 1:30 to 1: 5.
  • thermoplastic polyurethane tends to crystallize and if it has a melting point
  • the temperature of the product on the belt reactor is controlled by suitable measures in a temperature range from 100 K below to 50 K above the melting point, preferably from 80 K below to 10 K above, particularly preferably from 50 K below to 10 K above the melting point, very particularly preferably from 30 K below to 10 K above the melting point.
  • the product is brought into a commercial form, typically granules.
  • the product is in the molten state, is comminuted in the molten state and solidified by cooling or first solidified by cooling and then comminuted. This can be done, for example, using the methods known to the person skilled in the art strand pelletizing, underwater strand pelletizing, water ring pelletizing and underwater pelletizing.
  • the cooling is preferably carried out with water; Cooling with air or other media is also possible.
  • the product After conversion in a belt reactor, the product can also be cooled, broken up and ground.
  • thermoplastic polyurethane obtained in this way can, according to the invention, be mixed in a solids mixing process and melted in a further extruder and granulated again. This is particularly preferred when the product is cooled and ground after the belt reactor, because this process also homogenizes the product shape.
  • a total throughput of polyurethane polymer of at least 0.5 kg / h is achieved.
  • the process comprises the following steps: i) continuous mixing of the total amount or a first partial amount of component A with a first partial amount of component B and optionally components C and / or D, ii) allowing the mixture from step i) to react continuously in at least one first process stage to form the at least one hydroxy-terminated prepolymer, the temperature of the reaction mixture in the at least one first process stage being kept below the decomposition temperature of the at least one hydroxy-terminated prepolymer iii) continuous transfer of the at least one hydroxy-terminated prepolymer formed in step ii) into a second process stage, the second process stage being connected to the first process stage by at least one mass transport line n is iv) optionally continuous mixing and reacting of the remaining partial amounts of components A and B in a third process stage to produce at least one NCO-terminated prepolymer, the temperature of the reaction mixture in the third process stage being below the decomposition
  • one or more diols are used as component A, at least one diol of component A having a molecular weight of 62 g / mol to 250 g / mol.
  • a mixture of diols can also be used in which only some of the diols have a molecular weight of 62 g / mol to 250 g / mol and the remaining part of the diols has a molecular weight of> 250 g / mol, the Total enthalpy of reaction must be in the claimed range over all process stages.
  • the diols and / or their precursor compounds can have been obtained from fossil or biological sources.
  • the person skilled in the art is aware that the total enthalpy of reaction in the reaction of a diisocyanate with various diols depends on the molecular weight of the diol.
  • the reaction of, for example, 1,6-diisocyanatohexane with a short-chain diol such as 1,4-butanediol has a significantly higher overall reaction depth than the reaction of, for example, 1,6-diisocyanatohexane with a long-chain diol such as a polytetramethylene glycol polyol with a number average molecular weight of 1000 g / mol.
  • long-chain diols are polyester, polyether, polycarbonate, poly (meth) acrylate and / or polyurethane polyols.
  • the reaction of one or more diisocyanates with a mixture of diols with a molecular weight of 62 g / mol to 250 g / mol and diols with a molecular weight of> 250 g / mol have a total enthalpy of reaction over all process stages that is not in the claimed range
  • the person skilled in the art knows that, for example by increasing the content of diols with a molecular weight of 62 g / mol to 250 g / mol and lowering the content of diols with a molecular weight of> 250 g / mol in the Mixture, the desired total enthalpy of reaction can be adjusted so that it is in the claimed range.
  • Diols of component A have a molecular weight of 62 g / mol to 250 g / mol and it is most preferred that the one or more diols of component A all have a molecular weight of 62 g / mol to 250 g / mol.
  • one or more difunctional alcohols in particular aliphatic, araliphatic or cycloaliphatic diols, with molecular weights of 62 g / mol to 250 g / mol are used.
  • these can be, for example, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2- Butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,3-cyclobutanediol, 1,3-cyclopentanediol,
  • Cyclohexanedimethanol 2-cyclohexene-1,4-diol, 2-methyl-1,4-cyclohexanediol, 2-ethyl-1,4-cyclohexanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, hydrogenated Bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane), 1,3-cycloheptanediol, 1,4-cycloheptanediol, 2-methyl-1,4-cycloheptanediol, 4-methyl-1,3-cycloheptanediol, 4, 4 '- (1-methylethylidene) biscyclohexanol, 1,3-cyclooctanediol, 1,4-cyclooctanediol, 1,5-cyclooctanediol, 5-methyl-1,4-cyclooctanediol,
  • component A can also be a mixture of at least two components A or a mixture of component (s) A and non-reactively terminated prepolymers. It is preferably a component A or a mixture of at least two components A.
  • one or more aliphatic, cycloaliphatic and / or araliphatic diols preferably one or more aliphatic or cycloaliphatic diols, particularly preferably one or more aliphatic diols with a molecular weight of 62 g / mol to 250 g / mol are used even more preferably selected from the group consisting of 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5 Pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,3-cyclobutanediol, 1,3-cyclopentanediol, 1,
  • Cyclohexanedimethanol and / or mixtures of at least two of these.
  • Pentanediol 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,3-cyclobutanediol, 1,3-cyclopentanediol, 1,2-, 1,3- and 1, 4-Cyclohexanediol, 1,4-Cyclohexanedimethanol and / or mixtures of at least two of these.
  • Aliphatic diols are preferably used as component A, selected from the group consisting of 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol , 1,5-pentanediol, 1,6-hexanediol, 1,7-
  • Pentanediol, 1,6-hexanediol, 1,7-heptanediol and / or mixtures of at least 2 thereof preferably 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1 , 6-hexanediol, and / or mixtures of at least 2 of these, more preferably 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol , 1,5-pentanediol, 1,6-hexanediol, and / or mixtures of at least 2 of these, more preferably 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-but
  • Aliphatic, araliphatic or cycloaliphatic diols with a molecular weight of 62 g / mol to 250 g / mol, more preferably 62 g / mol to 150 g / mol, even more preferably 62 g / mol to 120 g / mol are preferably used as component A .
  • Aliphatic or cycloaliphatic diols with a molecular weight of 62 g / mol to 250 g / mol, more preferably 62 g / mol to 150 g / mol, even more preferably 62 g / mol to 120 g / mol are preferably used as component A.
  • the diols and / or their precursor compounds can have been obtained from fossil or biological sources.
  • the diisocyanates used as component B according to the invention include aliphatic, cycloaliphatic and / or araliphatic diisocyanates.
  • the person skilled in the art is aware that the total enthalpy of reaction in the reaction of an aliphatic, cycloaliphatic and / or araliphatic diisocyanate with a diol is higher than the reaction of an aromatic diisocyanate with the same diol.
  • a mixture of one or more aliphatic, cycloaliphatic, aromatic and / or araliphatic diisocyanates can therefore also be used as component B, as long as the total enthalpy of reaction over all process stages is within the claimed range.
  • the reaction of a mixture of an aliphatic diisocyanate and an aromatic diisocyanate with one or more diols has a total enthalpy of reaction over all process stages that is not in the claimed range
  • the person skilled in the art knows that, for example, by increasing the content of aliphatic diisocyanate and By lowering the content of an aromatic diisocyanate in the mixture, the desired total enthalpy of reaction can be set so that it is within the claimed range.
  • aromatic diisocyanates are used in proportions of up to 2 mol% based on the amount of substance of component B.
  • diisocyanates and / or their precursor compounds can have been obtained from fossil or biological sources.
  • 1,6-Diisocyanatohexane (HDI) is preferably produced from 1,6-hexamethylenediamine, which is obtained from biological sources.
  • Suitable compounds are preferably those of the molecular weight range from 140 g / mol to 400 g / mol, it being irrelevant whether these were obtained by means of phosgenation or by phosgene-free processes.
  • component B when component B is mentioned in the context of the present invention, it can also be a mixture of at least two components B or a mixture of component (s) B and non-reactively terminated prepolymers. It is preferably a component B or a mixture of at least two components B.
  • Suitable aliphatic diisocyanates are 1,4-diisocyanatobutane (BDI), 1,5-diisocyanatopentane (PDI), 1,6-diisocyanatohexane (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2 , 2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,8-diisocyanatooctane and 1,10-diisocyanatodecane.
  • BDI 1,4-diisocyanatobutane
  • PDI 1,5-diisocyanatopentane
  • HDI 1,6-diisocyanatohexane
  • 2-methyl-1,5-diisocyanatopentane 1,5-diisocyanato-2
  • 2-dimethylpentane 2,2,4- or
  • Suitable cycloaliphatic diisocyanates are 1,3- and 1,4-diisocyanatocyclohexane, 1,4-diisocyanato-3,3,5-trimethylcyclohexane, 1,3-diisocyanato-2-methylcyclohexane, 1,3-diisocyanato-4-methylcyclohexane , 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate; IPDI), 1-isocyanato-1-methyl-4 (3) -isocyanatomethylcyclohexane, 2,4'- and 4,4'- Diisocyanatodicyclohexylmethane (H12MDI), 1,3- and 1,4-bis (isocyanatomethyl) cyclohexane, bis (isocyanatomethyl) norbornane (NBDI), 4,4'-diisocyanato-3
  • aromatic diisocyanates examples include 2,4- and 2,6-diisocyanatotoluene (TDI), 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI) and 1,5-diisocyanatonaphthalene.
  • TDI 2,4- and 2,6-diisocyanatotoluene
  • MDI 2,4'- and 4,4'-diisocyanatodiphenylmethane
  • 1,5-diisocyanatonaphthalene examples include 2,4- and 2,6-diisocyanatotoluene (TDI), 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI) and 1,5-diisocyanatonaphthalene.
  • araliphatic diisocyanates are 1,3- and 1,4-bis (isocyanatomethyl) benzene (xylylene diisocyanate; XDI), 1,3- and 1,4-bis (1-isocyanato-1-methylethyl) benzene (TMXDI ).
  • aliphatic and cycloaliphatic diisocyanates with a molecular weight of 140 g / mol to 400 g / mol, in particular aliphatic and cycloaliphatic diisocyanates selected from the group consisting of 1,4-diisocyanatobutane (BDI) and 1,5-diisocyanatopentane (PDI ), 1,6-diisocyanatohexane (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1 , 6-diisocyanatohexane, 1,8- diisocyanatooctane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,4-diisocyanato-3,3,5-trimethyl
  • diisocyanates are used, selected from the group consisting of 1,4- Diisocyanatobutane (BDI), 1,5-diisocyanatopentane (PDI), 1,6-diisocyanatohexane (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane, 1,8-diisocyanatooctane , 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3-diisocyanato-2-methylcyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate; IPDI) and / or mixtures of at least 2 thereof, more preferably 1,4-diisocyanatobutane (BDI), 1,5-diis
  • polyisocyanates are understood to mean organic compounds with more than two isocyanate groups, it being irrelevant whether these were obtained by means of phosgenation or by a phosgene-free process.
  • suitable polyisocyanates are triphenylmethane 4,4 ', 4 "-triisocyanate or 4-isocyanatomethyl-1,8-octane diisocyanate (TIN).
  • TIN 4-isocyanatomethyl-1,8-octane diisocyanate
  • derivatives of the aliphatic, cycloaliphatic and / or araliphatic diisocyanates mentioned below can also be used.
  • trimers examples are the commercially available trimers (biurets, allophanates or isocyanurates) of 1,4-diisocyanatobutane (BDI), 1,5-diisocyanatopentane (PDI), 1,6-diisocyanatohexane (HDI), 1-isocyanato-3,3,5 -trimethyl-5-isocyanatomethyl-cyclohexane or 2,4'- and 4,4'-diisocyanatodicyclohexyl methane
  • BDI 1,4-diisocyanatobutane
  • PDI 1,5-diisocyanatopentane
  • HDI 1,6-diisocyanatohexane
  • 1-isocyanato-3,3,5 -trimethyl-5-isocyanatomethyl-cyclohexane or 2,4'- and 4,4'-diisocyanatodicyclohexyl methane These polyisocyanates can
  • component B does not contain any aromatic diisocyanates, polyisocyanates and / or derivatives thereof.
  • thermoplastic polyurethanes components A, B and the various prepolymers (hydroxy-terminated prepolymers, NCO-terminated prepolymers, non-reactively terminated prepolymers) can be used in the process according to the invention, optionally in the presence of one or more catalysts, auxiliaries and / or additives are implemented.
  • Suitable catalysts according to the invention are the conventional tertiary amines known from the prior art, such as. B. triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethyl-piperazine, 2- (dimethylaminoethoxy) -ethanol, diazabicyclo- (2,2,2) -octane and the like, and in particular organic metal compounds such as titanic acid esters, Iron compounds, tin compounds, for example tin diacetate, tin dioctoate, tin dilaurate or the tin dialkyl salts of aliphatic carboxylic acids such as dibutyl tin diacetate, dibutyl tin dilaurate or the like.
  • Preferred catalysts are organic metal compounds, in particular titanic acid esters, iron and / or tin compounds.
  • the catalyst is used in amounts from 0.001% by weight to 2.0% by weight, preferably from 0.005% by weight to 1.0% by weight, particularly preferably from 0.01% by weight to 0.1% by weight .-% based on the diisocyanate component B used.
  • the catalyst can be used as such or dissolved in the diol component A.
  • One advantage here is that the thermoplastic polyurethanes then obtained do not contain any impurities from any catalyst solvents used.
  • the catalyst can be added in one or more portions or continuously, e.g. B. with the help of a suitable metering pump over the entire duration of the implementation.
  • catalyst solutions can also be used.
  • the degree of dilution of the catalyst solutions can be chosen freely within a very broad range. Solutions with a concentration of 0.001% or more are catalytically effective.
  • Suitable catalyst solvents are, for example, solvents which are inert towards isocyanate groups, such as, for example, hexane, toluene, xylene, chlorobenzene, ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl or ethyl ether acetate, propylene glycol acetate, ether ethyl acetate, diethylene glycol ethyl ether and ethyl acetate.
  • solvents which are inert towards isocyanate groups such as, for example, hexane, toluene, xylene, chlorobenzene, ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl or ethyl ether acetate, propylene glycol acetate
  • catalyst solvents which carry groups which are reactive toward isocyanates and which can be incorporated into the diisocyanate.
  • solvents are mono- or polyhydric simple alcohols, such as. B. methanol, ethanol, n-propanol, isopropanol, n-butanol, n-hexanol, 2-ethyl-1-hexanol, ethylene glycol, propylene glycol, the isomeric butanediols, 2-ethyl-1,3-hexanediol or glycerol; Ether alcohols, such as. B.
  • B ethylene glycol monoacetate, propylene glycol monolaurate, glycerine mono- and diacetate, glycerine monobutyrate or 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate; unsaturated alcohols such as. B. allyl alcohol, 1,1-dimethyl-allyl alcohol or O1-einalcohol; araliphatic alcohols such as. B. benzyl alcohol; N-monosubstituted amides, e.g. B. N-methylformamide, N-methylacetamide, cyanoacetamide or 2-pyrrolidinone or any mixtures of such solvents.
  • auxiliaries and / or additives can also be used. These can, for example, be additives common in the field of thermoplastic technology, such as dyes, fillers, processing aids, plasticizers, nucleating agents, stabilizers, flame retardants, mold release agents or reinforcing additives. More detailed information on the auxiliaries and additives mentioned can be found in the specialist literature, for example the monograph by J.H. Saunders and K.C. Frisch “High Polymers", Volume XVI, Polyurethane, Part 1 and 2, Interscience Publishers 1962 and 1964, the pocket book for plastic additives by R. Gumbleter and H. Müller (Hanser Verlag Kunststoff 1990) or DE -A 29 01 774 can be found. It can of course also be advantageous to use several additives of several types.
  • conventional isocyanate-reactive mono-, di-, tri- or polyfunctional compounds in proportions of 0.001 mol% to 2 mol%, preferably 0.002 mol% to 1 mol%, can also be obtained as additives in small amounts on the total amount of the component A, z. B. can be used as chain terminators, auxiliaries or demolding aids.
  • Examples include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomeric pentanols, hexanols, octanols and nonanols, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol , n-octadecanol, cyclohexanol and stearyl alcohol.
  • suitable triols are trimethylolethane, trimethylol propane or glycerol.
  • Suitable higher-functional alcohols are ditrimethylolpropane, pentaerythritol, dipentaerythritol or sorbitol.
  • Amines such as butylamine and stearylamine or thiols are also suitable.
  • At least one hydroxy-terminated prepolymer from the total amount or a first partial amount of component A and a first partial amount of component B is formed in at least one stage of the multistage process.
  • the at least one hydroxyl-terminated prepolymer is obtained in the process according to the invention as an intermediate which can in principle be isolated, by polyaddition of diol component A with diisocyanate component B, with diol component A being present in excess. The polyaddition can take place in the presence of components C and D.
  • the at least one NCO-terminated prepolymer and the at least one non-reactively terminated prepolymer can be obtained as intermediates which can in principle be isolated, by polyaddition of components A and B and optionally the at least one chain terminator. The polyaddition can take place in the presence of components C and D.
  • non-reactively terminated prepolymers can also be obtained or be present in a mixture with the hydroxy-terminated prepolymers.
  • the NCO-terminated prepolymers can also be present as a mixture with the non-reactively terminated prepolymers.
  • the non-reactive prepolymers are formed from components A, B, optionally C and D.
  • the non-reactive prepolymers are formed by manufacturing processes known to the person skilled in the art. The preparation of the non-reactive prepolymers can take place in the presence of component C.
  • the ratio of the non-reactive prepolymers to the hydroxy-terminated prepolymers and / or NCO-terminated prepolymers is preferably ⁇ 20: 80% by weight, preferably ⁇ 10:90% by weight in each case based on the total weight of all hydroxy-terminated prepolymers and / or NCO-terminated prepolymers.
  • the targeted admixing of non-reactively terminated prepolymers to the at least one hydroxy-terminated prepolymer has the advantage that the subsequent reaction of the at least one hydroxy-terminated prepolymer with a further portion of component B or with the at least one NCO -terminated prepolymer heat of reaction occurring can be better controlled. Furthermore, the addition of the non-reactively terminated prepolymers can influence the molecular weight distribution of the entire polyurethane according to the invention.
  • the at least one hydroxy-terminated prepolymer is formed by polyaddition of at least one combination of component A and component B selected from the group consisting of 1,4-diisocyanatobutane with 1,2-ethanediol, 1,4- Diisocyanatobutane with 1,2- and / or 1,3-propanediol, 1,4-diisocyanatobutane with 1,2-, 1,3- and / or 1,4-butanediol, 1,4-diisocyanatobutane with 1,5-pentanediol 1,4-diisocyanatobutane with 1,6-hexanediol, 1,4-diisocyanatobutane with 1,7-heptanediol, 1,4-diisocyanatobutane with 1,8-octanediol, 1,4-diisocyanatobutan
  • the at least one hydroxy-terminated prepolymer is formed by polyaddition of at least one combination of component A and component B selected from the group consisting of 1,4-diisocyanatobutane with 1,2-ethanediol, 1,4- Diisocyanatobutane with 1,2- and / or 1,3-propanediol, 1,4-diisocyanatobutane with 1,2-, 1,3- and / or 1,4-butanediol, 1,4-diisocyanatobutane with 1,5-pentanediol 1,4-diisocyanatobutane with 1,6-hexanediol, 1,4-diisocyanatobutane with 1,7-heptanediol, 1,4-diisocyanatobutane with 1,8-octanediol, 1,4-diisocyanatobutan
  • Diisocyanatopentane with 1,2- and / or 1,3-propanediol 1,5-diisocyanatopentane with 1,2-, 1,3- and / or 1,4-butanediol
  • 1,5-diisocyanatopentane with 1,5-pentanediol 1,5-diisocyanatopentane with 1,6-hexanediol
  • Diisocyanatohexane with 1,5-pentanediol more preferably selected from the group consisting of 1,4-diisocyanatobutane with 1,2-ethanediol, 1,4-diisocyanatobutane with 1,2- and / or 1,3-propanediol, 1, 4-diisocyanatobutane with 1,2-, 1,3- and / or 1,4-butanediol, 1,4-diisocyanatobutane with 1,5-pentanediol, 1,4-diisocyanatobutane with 1,6-hexanediol, 1,5- Diisocyanatopentane with 1,2-ethanediol, 1,5-diisocyanatopentane with 1,2- and / or 1,3-propanediol, 1,5-diisocyanatopentane with 1,2-, 1,3- and / or 1,4-butanedi
  • the at least one hydroxy-terminated prepolymer is formed by polyaddition of at least one combination of component A and component B selected from the group consisting of 1,4-diisocyanatobutane with 1,2-ethanediol, 1,4 -Diisocyanatobutane with 1,2- and / or 1,3-propanediol, 1,4- Diisocyanatobutane with 1,2-, 1,3- and / or 1,4-butanediol, 1,4-diisocyanatobutane with 1,5-pentanediol, 1,4-diisocyanatobutane with 1,6-hexanediol, 1,5-diisocyanatopentane with 1,2-ethanediol, 1,5-diisocyanatopentane with 1,2- and / or 1,3-propanediol, 1,5-diisocyanatop
  • the invention also relates to thermoplastic polyurethanes obtainable by the process according to the invention.
  • the thermoplastic polyurethane polymer has a proportion of component B from 30% by weight to 80% by weight, preferably from 40% by weight to 75% by weight, particularly preferably from 50% by weight to 70% by weight, very particularly preferably from 55% by weight to 70% by weight.
  • the thermoplastic polyurethane polymer has a proportion of urethane groups from 4.0 mol / kg to 10.0 mol / kg polymer, preferably from 6.0 mol / kg to 9.0 mol / kg polymer, particularly preferably from 6.5 mol / kg to 9.0 mol / kg polymer, very particularly preferably from 7.0 mol / kg to 9.0 mol / kg polymer.
  • the proportion of urethane groups is calculated from the molecular weight of the repeat unit.
  • the thermoplastic polyurethane polymer is obtained from the process according to the invention by reacting a diisocyanate component with 98% by weight to 100% by weight aliphatic diisocyanates and at least one aliphatic and / or cycloaliphatic diol with a molecular weight of 62 g / mol to 250 g / mol obtained.
  • the diisocyanate component preferably contains only aliphatic diisocyanates.
  • thermoplastic polyurethane polymer from the process according to the invention is obtained by reacting a diisocyanate component B containing 98% by weight to 100% by weight linear aliphatic diisocyanates and a diol component A containing 98% by weight to 100% by weight.
  • a polyurethane polymer prepared from a component B containing 98% by weight to 100% by weight of a diisocyanate based on the total amount of component B selected from the group consisting of 1,6-hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,4-butane diisocyanate and / or a mixture of at least 2 of these and a component A containing 98% by weight to 100% by weight of a diol based on the total amount of component A selected from the group consisting of 1.4 -Butanediol, 1,6-hexanediol, 1,5-pentanediol, 1,3-propanediol, 1,2-ethanediol and / or a mixture of at least 2 of these.
  • the thermoplastic polyurethane polymer from the process according to the invention is obtained by reacting a diisocyanate component B containing 98% by weight to 100% by weight linear aliphatic diisocyanates based on the total amount of component B and a diol component A. 98% by weight to 100% by weight linear aliphatic diols with a molecular weight of 62 g / mol to 250 g / mol based on the total amount of component A are obtained.
  • a polyurethane polymer which is composed of a component B containing 98% by weight to 100% by weight 1,6-hexamethylene diisocyanate based on the total amount of component B and a component A containing 98% by weight to 100% by weight .-% 1,4-butanediol based on the total amount of component A was obtained.
  • the product from the method according to the invention in the CIE-Lab color space has an L * value of> 70 and a b * value of ⁇ 3, preferably an L * value of> 75 and a b * value of ⁇ 2, particularly preferably an L * value of> 80 and a b * value of ⁇ 1.5.
  • the color values are determined with a Konica Minolta CM5 spectrophotometer, with the light type D 65, with a 10 ° observer in accordance with DIN EN ISO 11664-1 (July 2011).
  • thermoplastic polyurethanes by reacting the components
  • diisocyanates including aliphatic, cycloaliphatic and / or araliphatic diisocyanates
  • At least one diol of component A having a molecular weight of 62 g / mol to 250 g / mol, with at least one hydroxy-terminated prepolymer from the total amount or a first in at least one process stage of the multistage process
  • Subset of component A and a first subset of component B is formed, with the sum of all subsets of component A or the sum of all subsets amounts of component B over all process stages of the multi-stage process together is the total amount of component A or component B used, characterized in that components A and B are selected so that if they are used in a molar ratio of 1.0: 1.0 converts the total enthalpy of reaction over all process stages from -900 kJ / kg to -500 kJ / kg, determined according to DIN 51007: 1994-
  • Continuous solvent-free multi-stage process characterized in that in at least one process stage a part of the total enthalpy of reaction produced, preferably from 25% to 98%, particularly preferably from 30% to 95% and even more preferably from 35% to 90% and very particularly preferably from 40% to 85% of the total enthalpy of reaction is removed.
  • Continuous solvent-free multistage process characterized in that the average residence time in the at least one process stage for producing the hydroxy-terminated prepolymer is between 5 seconds and 90 minutes, preferably between 10 seconds and 60 minutes, is particularly preferably between 30 seconds and 30 minutes, based in each case on a process stage.
  • Continuous solvent-free multistage process according to one of the preceding embodiments characterized in that the at least one hydroxy-terminated prepolymer is formed in at least one process stage from the total amount of component A and a first subset of component B, preferably with the first subset of the component B from 40% to 95%, preferably from 60% to
  • 95% is based in each case on the total molar amount of component B used in the process.
  • Continuous solvent-free multistage process characterized in that the at least one hydroxy-terminated prepolymer is formed in at least one process stage from a first subset of component A and a first subset of component B, the molar ratio of the used Sub-amounts of component B to component A from 0.65: 1.0 to 0.98: 1.0, preferably from 0.70: 1.0 to 0.97: 1.0, more preferably from 0.75: 1, 0 to 0.96: 1.0 and very particularly preferably 0.75: 1.0 to 0.95: 1.0 and where the first subset A is at least 50%, preferably 70%, more preferably 90%, based on the total molar amount of component A used in the process is used.
  • the at least one hydroxy-terminated prepolymer has an average OH functionality of 1.8 to 2.1, preferably 1.95 to 2, calculated from the functionalities of the starting materials.
  • 05 particularly preferably 1.97 to 2.0, very particularly preferably 1.975 to 2.0, each based on the amount of substance of the entire prepolymer mixture.
  • Continuous solvent-free multistage process according to one of the preceding embodiments, characterized in that in at least one further process stage following the formation of the at least one hydroxy-terminated prepolymer, the at least one hydroxy-terminated prepolymer with a further portion of the component B is converted to thermoplastic polyurethane, preferably where the further partial amount of component B is from 5% to 60%, preferably from 5% to 40%, more preferably from 7% to 25%, based in each case on the total molar amount of im Component B used in the process, with the proviso that the sum of all partial amounts of component B over all process stages of the multi-stage process together is the total molar amount of component B used.
  • Continuous, solvent-free, multistage process according to one of the preceding embodiments, characterized in that in at least one further the formation of the at least one hydroxy-terminated prepolymer following process stage, the at least one hydroxy-terminated prepolymer reacted with a second portion of component B and a second portion of component A to form thermoplastic polyurethane, with the proviso that the The sum of all subsets of component A and the sum of all subsets of component B over all process stages of the multistage process together is the total molar amount of component A or component B used.
  • Continuous solvent-free multistage process characterized in that the at least one hydroxy-terminated prepolymer is formed in at least one process stage from a first subset of component A and a first subset of component B, and that in at least one further on the formation of the hydroxy-terminated prepolymer subsequent process stage, the at least one hydroxy-terminated prepolymer is reacted with at least one NCO-terminated prepolymer to form thermoplastic polyurethane, the at least one NCO-terminated prepolymer in at least one further process stage from one second subset of component A and a second subset of component B is formed.
  • Continuous solvent-free multistage process according to embodiment 12 characterized in that the at least one hydroxy-terminated prepolymer and the at least one NCO-terminated prepolymer in a molar ratio of 1.0:
  • Continuous solvent-free multistage process according to one of the preceding embodiments, characterized in that the at least one hydroxy-terminated prepolymer is produced in at least a first process stage and in at least a second process stage with a second portion of component B, component A and / or the at least one NCO-terminated prepolymer is converted to thermoplastic polyurethane, the first process stage being able to have different reaction conditions with regard to temperature, pressure and / or shear rate compared to the at least second process stage and the process stages with one another via at least one substance transporting line are connected, preferably wherein the at least one NCO-terminated prepolymer is produced in a third process stage which is separate from the at least one first and second process stage and different reaction conditions conditions with regard to temperature, pressure and shear rate in comparison to the at least one first and second process stage and with the at least one first or second process stage is connected via at least
  • Hydroxy-terminated prepolymer is from 5 seconds to 60 minutes, preferably from 30 seconds to 60 minutes, particularly preferably from 1 minute to 50 minutes and very particularly preferably from 10 minutes to 50 minutes.
  • Continuous solvent-free multistage process according to one of the preceding embodiments, characterized in that a total throughput of polyurethane polymer of at least 0.5 kg / h, preferably 2 kg / h, particularly preferably at least 100 kg / h and very particularly preferably of at least 1000 kg / h is achieved.
  • Continuous solvent-free multistage process comprising the following steps: i) continuous mixing of the total amount or a first partial amount of component A with a first partial amount of component B and optionally components C and / or D, ii) allowing the mixture from step i) to react continuously in at least one first process stage to form the at least one hydroxy-terminated prepolymer, the temperature of the reaction mixture in the at least one first process stage being below the decomposition temperature of the at least one hydroxy-terminated one Prepolymer is held, iii) continuous transfer of the at least one hydroxy-terminated prepolymer formed in step ii) to a second process stage, the second process stage being connected to the first process stage by at least one mass transport line, iv) optionally continuous mixing and reacting of the remaining portions of components A and B in a third process stage in order to produce at least one NCO-terminated prepolymer, the temperature of the reaction mixture in the third process stage being below the decomposition
  • the one or more diols of component A all have a molecular weight of 62 g / mol to 250 g / mol, preferably a molecular weight of 62 g / mol to 150 g / mol, particularly preferably have a molecular weight of 62 g / mol to 120 g / mol.
  • aliphatic, cycloaliphatic and / or araliphatic diols preferably one or more aliphatic or cycloaliphatic diols, particularly preferably one or more aliphatic Diols with a molecular weight of 62 g / mol to 250 g / mol are used, even more preferably selected from the group consisting of 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1, 3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,3-cyclobut
  • aliphatic or cycloaliphatic diols are used as component A, selected from the group consisting of 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7- Heptanediol, 1,8-octanediol, 1,9-nonanediol,
  • Cyclohexanedimethanol and / or mixtures of at least two of these, preferably aliphatic diols are used as component A, selected from the group consisting of 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol , 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol and / or mixtures of at least 2 of these, preferably 1, 2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanedi
  • 1,4-butanediol and / or mixtures of at least two of these.
  • aliphatic or cycloaliphatic diisocyanates are used as component B, preferably selected from the group consisting of 1,4-diisocyanatobutane (BDI) , 1,5-diisocyanatopentane (PDI), 1,6-diisocyanatohexane (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- and 2 , 4,4-trimethyl-1,6-diisocyanatohexane, 1,8-diisocyanatooctane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,4-diisocyanato-3,3,5-trimethylcyclohexane, 1,3
  • BDI 1,4-diisocyanatobutane
  • PDI 1,5-di
  • component B is aromatic Diisocyanates in proportions of up to 2 mol% based on the total amount of the component B contains.
  • PDI 1,5-diisocyanatopentane
  • HDI 1,6-diisocyanatohexane
  • 2-methyl-1,5-diisocyanatopentane 1,5-diisocyanato-2,2-dimethylpentane
  • 1,8-diisocyanatooctane 1,10-diisocyanatodecane
  • 1,3- and 1,4-diisocyanatocyclohexane 1,3-diisocyanato-2-methylcyclohexane
  • IPDI isophorone diisocyanate
  • IPDI isophorone diisocyanate
  • BDI 1,4-diisocyanatobutane
  • PDI 1,5-diisocyanatopentane
  • HDI 1,6-diisocyanatohexane
  • 2-methyl-1,5-diisocyanatopentane 1,5-diisocyanato-2,2-di
  • HDI 1,6-Diisocyanatohexane
  • 1,2- and / or 1,3-propanediol 1,5-diisocyanatopentane with 1,2-, 1,3- and / or 1,4-butanediol, 1,5-diisocyanatopentane with 1,5-pentanediol, 1,5 -Diisocyanatopentane with 1,6-hexanediol, 1,6-diisocyanatohexane with 1,2-ethanediol, 1,6-diisocyanatohexane with 1,2- and / or 1,3-propanediol, 1,6-diisocyanatohexane with 1,2- , 1,3- and / or 1,4-butanediol and 1,6-diisocyanatohexane with 1,5-pentanediol, even more preferably selected from the group consisting of 1,4-diisocyanatobutane with 1,2-ethanediol
  • 1,3- and / or 1,4-butanediol and most preferably from 1,4-diisocyanatobutane with 1,2-ethanediol, 1,4-diisocyanatobutane with 1,2- and / or 1,3-propanediol, 1,4-diisocyanatobutane with 1,2-, 1,3- and / or 1,4-butanediol, 1,4-diisocyanatobutane with 1,5-pentanediol, 1,4-diisocyanatobutane with 1,6-hexanediol, 1,5-diisocyanatopentane with 1 , 2- Ethanediol, 1,5-diisocyanatopentane with 1,2- and / or 1,3-propanediol, 1,5-diisocyanatopentane with 1,2-, 1,3- and / or 1,4-butanediol, 1,6
  • thermoplastic polyurethane polymer has a proportion of urethane groups of 4.0 mol / kg to 10.0 mol / kg polymer, preferably 6.0 mol / kg to 9.0 mol / kg polymer, particularly preferably from 6.5 mol / kg to 9.0 mol / kg polymer, very particularly preferably from 7.0 mol / kg to 9.0 mol / kg polymer. shows.
  • thermoplastic polyurethane polymer is produced by reacting a diisocyanate component B containing 98% by weight to 100% by weight of linear aliphatic diisocyanates based on the total amount of component B. and a diol component A containing 98% by weight to 100% by weight linear aliphatic
  • Diols with a molecular weight of 62 g / mol to 250 g / mol based on the total amount of component A is obtained.
  • thermoplastic polyurethane polymer is selected from component B containing 98% by weight to 100% by weight of a diisocyanate based on the total amount of component B by reacting the group consisting of 1,6-hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,4-butane diisocyanate and / or a mixture of at least 2 of these and a component A containing 98% by weight to 100% by weight of a diol based on the total amount of component A selected from the group consisting of 1,4-butanediol, 1,6-hexanediol, 1,5-pentanediol, 1,3-propanediol, 1,2-ethanediol and / or a mixture of at least 2 from this, is obtained
  • thermoplastic polyurethane obtainable from the continuous solvent-free multistage process according to one of the preceding embodiments.
  • the thermoplastic polyurethanes produced by the process according to the invention can be processed into molded articles, in particular extrusion articles, injection-molded articles, films, thermoplastic foams, or powders.
  • Figure 1 Preferred embodiment of a structure for carrying out a two-stage continuous production of a thermoplastic polyurethane according to the invention, by reaction sequence in a temperature-controlled polymerization reactor and extruder.
  • Figure 2 Preferred embodiment of a structure for carrying out a two-stage continuous production of a thermoplastic polyurethane according to the invention, by reaction sequence in a loop reactor and extruder.
  • HDI 1,6-hexamethylene diisocyanate
  • PDI 1,5-pentamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • H12MDI 4,4'-diisocyanatodicyclohexylmethane
  • XDI xylylene diisocyanate
  • 1,4-Butanediol (BDO) was obtained from Ashland.
  • 1,3-propanediol (PDO), 1,6-hexanediol (HDO) and 1,4-cyclohexanedimethanol were obtained from Sigma-Aldrich. The purity of the raw materials was ⁇ 99% in each case. Color values
  • the color values in the CIE-Lab color space were determined with a Konica Minolta CM5 spectrophotometer, with the light type D 65, with a 10 ° observer in accordance with DIN EN ISO 11664-1 (July 2011).
  • the melting point was determined by means of DSC (differential scanning calorimetry) with a Mettler DSC 12E (Mettler Toledo GmbH, Giessen, DE) in accordance with DIN EN 61006 (November 2004). Calibration was carried out using the temperature of the melting onset of indium and lead. 10 mg of substance were weighed into normal capsules. The measurement was carried out by means of three heatings from -50 ° C to +200 ° C at a heating rate of 20 K / min with subsequent cooling at a cooling rate of 20 K / min. The cooling was carried out with liquid nitrogen. Nitrogen was used as the purge gas. The values given are based on the evaluation of the 2nd heating curve.
  • the enthalpy data were determined by means of a screening DTA and carried out in an ISO 17025 accredited laboratory.
  • the samples were weighed into glass ampoules, sealed gas-tight and heated in the measuring device at 3 K / min from -50 ° C to +450 ° C.
  • the difference between the sample temperature and the temperature of an inert reference (aluminum oxide) was determined by means of thermocouples.
  • the initial weight was 20 mg - 30 mg.
  • Ahe measurements were carried out according to DIN 51007 (June 1994). The measuring error of the device is ⁇ 2%.
  • Table 1 Reaction enthalpies determined experimentally by means of DTA. The molar ratio of diisocyanate component to diol component in the determinations is 1.0: 1.0.
  • a twin-screw extruder ZSK 53 from Werner & Pfleiderer
  • 64.4 kg / h of 1,6-hexamethylene diisocyanate heated to 105 ° C.
  • a mixture of 22.8 kg / h of a poly-THF diol ( 1000 g / mol, BASF) with 32.9 kg / h 1,4-butanediol heated to 110 ° C., metered.
  • the speed of the extruder was 270 rpm.
  • the residence time in the extruder was approx. 42 seconds.
  • the melt was filtered through a single-layer metal sieve with a mesh size of 200 micrometers, drawn off as a strand, cooled in a water bath and granulated.
  • the temperature in the extruder rose to values above 240 ° C in 7 of 12 housings despite maximum cooling.
  • the product obtained had a yellowish discoloration as a result of the intense heating and had dark brown to black specks and was therefore not commercially usable.
  • Comparative Example 2 1,4-Butanediol (1.35 kg) were placed under nitrogen (1 bar) in a 51 pressure vessel with anchor stirrer, bottom drain and internal thermometer, which had been rendered inert with nitrogen, and the mixture was stirred until one Internal temperature of 90 ° C was reached. The total amount of 1,6-hexamethylene diisocyanate was then continuously metered into the pressure vessel (2.5 kg) over a period of 2 hours, while the reactor temperature was continuously increased to 190 ° C. at the same time. Owing to the heat of reaction released by the polyaddition, the temperature of the reaction mixture was up to 15 ° C. above the given reactor temperature over the entire reaction time.
  • the melting point of the polymer is 174.9 ° C. (DSC 2nd heating after cooling at 20 K / min).
  • EP 0 135 111 A2 discloses the production of thermoplastic polyurethanes by reacting a polyester polyol, MDI, NDI and 1,4-butanediol, 1,6-hexanediol and trimethylolpropane.
  • 1,5-NDI each have two isocyanate groups, is the concentration of the isocyanate end groups
  • EP 0 900812A1 discloses the production of thermoplastic polyurethanes by reacting a polyester or polyether polyol, MDI and 1,4-butanediol and in some cases also 1,6- Hexanediol.
  • n HDO n HDO ⁇ M m
  • HDO 9.45 g
  • Figure 1 shows schematically the structure for carrying out the two-stage continuous production of a thermoplastic polyurethane.
  • the residence time in the reactor was 5 minutes
  • the prepolymer emerging continuously from reactor 100 was transferred through a pipeline heated to 200 ° C. into the second housing of a 2-screw extruder (Mini-extruder Process 11 / Thermo Fisher). The extruder was heated to 200 ° C. over its entire length and the speed of rotation of the pans was 100 rpm.
  • the mean residence time over all process stages was approx. 6 minutes.
  • the temperature of the heating medium at the entrance of the reactor 100 170 ° C.
  • the product temperature at the outlet of the reactor 100 was 172 ° C. With this, 71% of the total enthalpy of reaction in reactor 100 was removed.
  • the melting point of the polymer produced is 182.9 ° C. (DSC 2nd heating after cooling at 20 K / min).
  • the L * value is 82.7, the b * value is 0.2.
  • the mean residence time over all process stages was approx. 6 minutes.
  • the melting point of the polymer produced is 168.6 ° C. (DSC 2nd heating after cooling at 20 K / min).
  • the temperature at the entry into reactor 100 was 100 ° C.
  • the heating medium temperature of the reactor 100 was 155 ° C.
  • the temperature at the outlet was 160 ° C. In this way, 70% of the total enthalpy of reaction in reactor 100 was removed.
  • the mean residence time over all process stages was approx. 6 minutes.
  • the melting point of the polymer produced is 152.7 ° C. (DSC 2nd heating after cooling at 20 K / min).
  • Hexamethylene diisocyanate with the pump 100 176.1 g / h 1,3-propanediol with the pump 200, and 73.9 g / h 1,6-hexamethylene diisocyanate with the pump 300 and reacted.
  • the temperature at the entry into reactor 100 was 162 ° C.
  • the heating medium temperature of the reactor 100 was 165 ° C, the temperature at the outlet 168 ° C. 76% of the enthalpy of reaction in the reactor 100 was thereby removed.
  • Example 5 according to the invention:
  • the mean residence time over all process stages was approx. 7 minutes.
  • the melting point of the polymer produced is 153.3 ° C. (DSC 2nd heating after cooling at 20 K / min).
  • the mean residence time over all process stages was approx. 7 minutes.
  • the melting point of the polymer produced is 160.9 ° C. (DSC 2nd heating after cooling at 20 K / min).
  • the L * value is 81.5, the b * value is 0.7.
  • Example 8 according to the invention:
  • the mean residence time over all process stages was approx. 6 minutes.
  • the melting point of the polymer produced is 166.1 ° C. (DSC 2nd heating after cooling at 20 K / min).
  • Hexamethylene diisocyanate and m-xylylene diisocyanate (8: 2 amount of substance) are dosed with the pump 300 and reacted.
  • the temperature at the entry into reactor 100 was 40 ° C.
  • the heating medium temperature of the reactor 100 was 176.degree. C., the temperature at the outlet 180.degree.
  • 61% of the enthalpy of reaction in the reactor 100 was removed.
  • the mean residence time over all process stages was approx. 7 minutes.
  • the melting point of the polymer produced is 163.6 ° C. (DSC 2nd heating after cooling at 20 K / min).
  • Hexamethylene diisocyanate and isophorone diisocyanate (8: 2 amount of substance) are metered in with the pump 300 and reacted.
  • the temperature at the entry into reactor 100 was 40 ° C.
  • the heating medium temperature of the reactor 100 was 174.degree. C., the temperature at the outlet 180.degree. Thus 61% of the enthalpy of reaction in the reactor 100 was removed.
  • a 1,6-hexamethylene diisocyanate stream A was conveyed to a static mixer 7 from a 250 liter receiver for 1,6-hexamethylene diisocyanate 1 with the aid of a toothed ring pump 2 (from HNP, MZR 7255).
  • the throughput of the 1,6-hexamethylene diisocyanate stream A was measured by means of a mass flow meter 3 (from Bronkhorst, Mini Cori-Flow MIX, max. Flow rate 12 kg / h) and adjusted to a value of 2.911 kg / h. From a 250 liter template for
  • 1,4-butanediol 4 was conveyed to the static mixer 7 with the aid of a gerotor pump 5 (from HNP, MZR 7205).
  • the throughput of the 1,4-butanediol stream was measured by means of a mass flow meter 6 (from Bronkhorst, Mini Cori-Flow MIX, max. Flow 8 kg / h) and adjusted to a value of 2,000 kg / h.
  • the temperature of the 1,6-hexamethylene diisocyanate was ambient temperature, approx. 25 ° C.
  • the temperature of the 1,4-butanediol was 40 ° C.
  • the temperature of stream D was 182 ° C.
  • the mixed and partially already reacted stream H was fed into a temperature-controllable static mixer 9.
  • the main part of the reaction takes place there and the heat of reaction generated was dissipated.
  • the temperature-controllable static mixer 9 was constructed similarly to a Sulzer SMR reactor with internal, crossed tubes. It had an internal volume of 1.9 liters and a heat exchange area of 0.44 square meters. It was heated / cooled with thermal oil. The heating medium temperature at the inlet was 180 ° C.
  • the product stream emerged from the temperature-controllable static mixer 9 as largely fully reacted stream E at a temperature of 183.degree.
  • the stream E was split into two substreams F and G at a branch 11.
  • the pressure of partial flow F was increased at a gear pump 10. After the pump, the partial flow F became the above-mentioned partial flow D.
  • the gear pump 10 (Witte Chem 25.6-3) had a volume per revolution of 25.6 cubic centimeters and a speed of 50 per minute.
  • the entire circuit consisted of double-walled pipelines and apparatus that were heated with thermal oil.
  • the heating medium temperature was 182 ° C.
  • the flow G was led past a three-way valve 13. There it could be moved to a waste container 14, an open 200-liter metal barrel with suction, when it was started up and shut down or in the event of a malfunction. In regular operation, the stream G was passed to an extruder 18.
  • a 1,6-hexamethylene diisocyanate stream J was withdrawn from 1,6-hexamethylene diisocyanate initial charge 1 with the aid of a micro annular gear pump 15 (MZR 6355 from HNP).
  • the throughput of the 1,6-hexamethylene diisocyanate stream J was measured by means of a mass flow meter 16 (Bronkhorst, Mini Cori-Flow, MIX, maximum flow 2 kg / h) and adjusted to 0.784 kilograms per hour.
  • the temperature of 1,6-hexamethylene diisocyanate stream J was also room temperature, about 25 ° C. This stream was also directed to the extruder 18.
  • the extruder 18 was a ZSK 26 MC from Coperion, which was operated at temperatures of 200 ° C. and a speed of 66 revolutions per minute.
  • stream G was freed from any inert gases and possible volatile reaction products entrained with streams A and B via a vent 17, which was operated at about 1 mbar negative pressure compared to ambient pressure.
  • the 1,6-hexamethylene diisocyanate stream J was added and the reaction to form the polymer was carried out.
  • the resulting polymer stream was freed from volatile constituents via a vent 19.
  • the pressure in this degassing was 200 mbar below ambient pressure.
  • the polymer stream K was pressed out through two nozzles, cooled in a water bath filled with deionized water and cut into granules by a granulator 21.
  • the mean residence time over all process stages was 51 minutes.
  • the melting point of the polymer is 185.2 ° C. (DSC 2nd heating after cooling at 20 K / min).
  • the temperatures of the raw materials and the temperatures of the other material flows as well as the system parts and heating means corresponded to those as described in Example 11.
  • the heating temperatures were 165 ° C.
  • the mean residence time over all process stages was 53 minutes.
  • the melting point of the polymer produced is 159.0 ° C. (DSC 2nd heating after cooling at 20 K / min). 62% of the total reaction enhalpy was dissipated in the temperature-controlled static mixer 9.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un procédé à plusieurs étapes pour la préparation continue de polyuréthanes thermoplastiques par réaction d'un ou de plusieurs diols aliphatiques, cycloaliphatiques et/ou araliphatiques avec un ou plusieurs diisocyanates aliphatiques, cycloaliphatiques et/ou araliphatiques, l'enthalpie de réaction totale étant ≤ 500 kJ/kg sur l'ensemble des étapes de traitement à un rapport molaire de diol à diisocyanate de 1,0 : 1,0.
EP20820189.7A 2019-12-17 2020-12-10 Procédé de préparation de polyuréthanes ayant une enthalpie de réaction élevée Withdrawn EP4077437A1 (fr)

Applications Claiming Priority (2)

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EP19216835.9A EP3838942A1 (fr) 2019-12-17 2019-12-17 Procédé de fabrication de polyuréthanes à enthalpie de réaction élevée
PCT/EP2020/085473 WO2021122279A1 (fr) 2019-12-17 2020-12-10 Procédé de préparation de polyuréthanes ayant une enthalpie de réaction élevée

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EP20820189.7A Withdrawn EP4077437A1 (fr) 2019-12-17 2020-12-10 Procédé de préparation de polyuréthanes ayant une enthalpie de réaction élevée

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US (1) US20220396655A1 (fr)
EP (2) EP3838942A1 (fr)
JP (1) JP2023505964A (fr)
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WO (1) WO2021122279A1 (fr)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2511544A (en) 1937-11-12 1950-06-13 Rinke Heinrich Diol-dilsocyanate high molecular polymerization products
DE728981C (de) 1937-11-13 1942-12-07 Ig Farbenindustrie Ag Verfahren zur Herstellung von Polyurethanen bzw. Polyharnstoffen
US2284637A (en) 1938-09-29 1942-06-02 Du Pont Polymeric carbamates and their preparation
US3038884A (en) 1960-01-25 1962-06-12 Eastman Kodak Co Linear polyurethanes from 2, 2, 4, 4-tetraalkyl-1, 3-cyclobutanediols
DE2901774A1 (de) 1979-01-18 1980-07-24 Elastogran Gmbh Rieselfaehiges, mikrobenbestaendiges farbstoff- und/oder hilfsmittelkonzentrat auf basis eines polyurethan-elastomeren und verfahren zu seiner herstellung
DE3329775A1 (de) * 1983-08-18 1985-02-28 Bayer Ag, 5090 Leverkusen Thermoplastische polyurethane hoher waermestandfestigkeit auf basis von naphthylendiisocyanat, verfahren zu ihrer herstellung und ihre verwendung
US5627254A (en) 1996-05-03 1997-05-06 The Dow Chemical Company Rigid thermoplastic plyurethane comprising units of butane diol and a polyethylene glycol
DE19738498A1 (de) * 1997-09-03 1999-03-04 Bayer Ag Verfahren zur kontinuierlichen Herstellung von thermoplastisch verarbeitbaren Polyurethanen in einem Zweiwellenextruder mit spezieller Temperaturführung

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EP3838942A1 (fr) 2021-06-23
WO2021122279A1 (fr) 2021-06-24
JP2023505964A (ja) 2023-02-14
US20220396655A1 (en) 2022-12-15
CN114761454A (zh) 2022-07-15

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