EP2190895A1 - Production continue de polyuréthanes/polyurées - Google Patents

Production continue de polyuréthanes/polyurées

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Publication number
EP2190895A1
EP2190895A1 EP08803476A EP08803476A EP2190895A1 EP 2190895 A1 EP2190895 A1 EP 2190895A1 EP 08803476 A EP08803476 A EP 08803476A EP 08803476 A EP08803476 A EP 08803476A EP 2190895 A1 EP2190895 A1 EP 2190895A1
Authority
EP
European Patent Office
Prior art keywords
hot surface
reaction composition
rotating body
polyurethanes
thin film
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Withdrawn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
EP08803476A
Other languages
German (de)
English (en)
Inventor
Laurent Marc
Helmut Mack
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.)
Construction Research and Technology GmbH
Original Assignee
Construction Research and Technology GmbH
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
Priority claimed from DE102007051274A external-priority patent/DE102007051274A1/de
Application filed by Construction Research and Technology GmbH filed Critical Construction Research and Technology GmbH
Publication of EP2190895A1 publication Critical patent/EP2190895A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1887—Stationary reactors having moving elements inside forming a thin film
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1862—Stationary reactors having moving elements inside placed in series
    • 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
    • C08G18/088—Removal of water or carbon dioxide from the reaction mixture or reaction components
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4866—Polyethers having a low unsaturation value
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00159—Controlling the temperature controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling

Definitions

  • the present invention relates to a process for the preparation of polyurethanes / polyureas and polyurethanes / polyureas, which can be prepared by this process.
  • Polyurethanes / polyureas are to date produced on an industrial scale usually in discontinuous processes in which the well-known disadvantages of discontinuous driving, such as long loading and unloading times, poor heat and mass transfer, fluctuating quality of products, etc., come to fruition.
  • these disadvantages should at least be present to a lesser degree.
  • process intensification for the large-scale production of polyurethanes / polyureas, which may be related to the temperature sensitivity of the polyurethanes / polyureas.
  • DE-C-19 924 089 proposes a "one shot dosing process" for the preparation of homogeneous polyurethanes with improved softening behavior, according to which first the entire reaction mixture comprising polyisocyanate, polyol and chain extender in a static mixer at high shear rates between 500 and 50,000 S " 1 is homogeneously mixed under defined temperatures within a short mixing time of a maximum of 1 s and the reaction mixture thus prepared, optionally via a second static mixer, is metered into an extruder.
  • a major disadvantage of both methods is the lack of self-cleaning of the mixing device (stirred tubular reactor).
  • product deposits that constrict and finally close the free flow cross-section of the tubular reactor and limit the stability and continuity of the production process.
  • Object of the present invention is to provide a processually flexible and economical process for the production of polyurethanes / polyureas, which ensures good product quality.
  • the solution to this problem is a process for the preparation of polyurethanes / polyureas, which is carried out in continuous operation in a reactor which comprises
  • the components of a starting reaction composition are applied individually and / or as a mixture by means of the dosing system in a thin film on an inner region of the hot surface of the rotating body A, so that the thin film over the hot surface of the rotating body A to an outer Area of the hot surface of the rotating body A flows,
  • a polyol / polyamine component comprising polyols and / or polyamines
  • the temperature of the hot surface of 70 to 400 0 C, and the means of the translucent Quen- direction was abrupt cooling of the reaction composition is at least 30 0 C.
  • the reactor in which the process according to the invention is carried out enables a process control in which the combination of particularly short residence times and high reaction temperatures is realized.
  • the process of the invention ensures that the components of the Trustre soskomposition are suddenly heated sharply and reacted accordingly fast, which is spared by the subsequent quenching the product obtained from thermally induced undesirable side reactions.
  • the abrupt cooling of the reaction composition by means of the quenching device takes place within a maximum of five seconds, preferably within only one second.
  • the method according to the invention offers the possibility of a flexible and simple process optimization. It is readily possible to apply various components at different locations on the hot surface as components of the starting composition.
  • the scale-up which is often problematic in process engineering, is particularly simple due to the simplicity and usually relatively small size of the reactor used, and it should be mentioned that the investment costs as well as the maintenance costs (purification, etc.) of said reactor are quite low
  • the quality of the product obtained ie the polyurethanes / polyurea-containing reaction composition, can be varied easily by changing the process parameters (residence time, temperature, metering of the components of the starting reaction composition).
  • the molar ratio of the isocyanate groups of the polyisocyanate component used to the sum of the amide no phenomenon and hydroxyl groups of the polyol / polyamine component used from 0.1 to 10, preferably 0.7 to 1, third
  • the starting reaction composition not only corresponding ratios of polyisocyanates and polyol / polyamines are frequently used in the process according to the invention, but plasticizers, lubricants, molecular chain regulators, flame retardants, inorganic / organic fillers, dyes, pigments and stabilizers are also frequently used (Regarding hydrolysis, light and thermally induced degradation), chain extenders, solvents and catalysts are used as further components.
  • polyisocyanates as is customary in polyurethane chemistry, 4 to 30 C-containing species containing aliphatic, cycloaliphatic, araliphatic and / or aromatically bound isocyanate groups can be used.
  • the diisocyanates are preferably suitable.
  • Particularly noteworthy are diisocyanates X (NCO) 2, wherein X is an aliphatic hydrocarbon radical having 4 to 12 carbon atoms, a cycloaliphatic or aromatic hydrocarbon radical having 6 to 15 carbon atoms or an araliphatic hydrocarbon radical having 6 to 15 carbon atoms.
  • Suitable aromatic polyisocyanates are the isomers of toluene diisocyanate (TDI), either in the isomerically pure form or as an isomer mixture.
  • suitable species are naphthalene-1, 5-diisocyanate, diphenylmethane-4,4'-diisocyanate (4,4-MDI) or diphenylmethane-2,4'-diisocyanate (2,4-MDI) or polymeric MDI ( either in isomerically pure forms or as isomeric mixtures).
  • Suitable cycloaliphatic polyisocyanates are hydrogenation products of the aforementioned aromatic diisocyanates, e.g. 4,4'-dicyclohexylmethane diisocyanate (H12MDI), iso-cyanoatomethyl-3-isocyanato-1,5-trimethylcyclohexane (isophorone diisocyanate, IPDI), cyclohexane-1,4-diisocyanate, hydrogenated xylylene diisocyanate
  • aromatic diisocyanates e.g. 4,4'-dicyclohexylmethane diisocyanate (H12MDI), iso-cyanoatomethyl-3-isocyanato-1,5-trimethylcyclohexane (isophorone diisocyanate, IPDI), cyclohexane-1,4-diisocyanate, hydrogenated xylylene diisocyanate
  • H ⁇ XDI 1-methyl-2,4-diisocyanato-cyclohexane, m- or p-tetramethylxylene diisocyanate (m-TMXDI, p-TMXDI) and dimer fatty acid diisocyanate.
  • Suitable aliphatic polyisocyanates are tetramethoxybutane-1,4-diisocyanate, butane-1,4-diisocyanate, hexane-1,6-diisocyanate (HDI), 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6 -Diisocyanato-2,4,4-trimethylhexane and 1, 12-dodecane diisocyanate (C12DI).
  • HDI hexane-1,6-diisocyanate
  • C12DI 1, 12-dodecane diisocyanate
  • oligomeric urethanes / ureas are available.
  • polyol component is not critical to the present invention.
  • polyol / polyamine component both low molecular weight polyols and higher molecular weight polyols / polyamines can be used.
  • Suitable polyols are preferably the liquid at room temperature, glassy solid / amorphous or crystalline polyhydroxy compounds having two or three hydroxyl groups per molecule and a number average molecular weight of 400 to 200,000, preferably from 1000 to 18,000.
  • difunctional polypropylene glycols to call It is also possible to use hydroxyl-containing random copolymers and / or block copolymers of ethylene oxide and propylene oxide.
  • Suitable polyetherpolyols are the polyethers known per se in polyurethane chemistry, such as the polyols prepared from starter molecules of styrene oxide, propylene oxide, butylene oxide or epichlorohydrin.
  • poly (oxytetramethylene) glycol (polyTHF), 1,2-polybutylene glycol or mixtures thereof are also suitable in particular.
  • Preferred molecular weight ranges (number average) for suitable Polyetherospezies are 400 to 200,000, especially 1000 to 18000.
  • polyol component type of copolymer having terminal hydroxyl groups can be prepared for example by means of "Controlled” High Speed Anionic Polymerization according to Macromolecules 2004 , 37, 4038-4043):
  • R is the same or different and is preferably represented by OMe, OiPr, Cl or Br.
  • liquid, glassy amorphous or crystalline polyesters which are obtained by condensation of di- or tricarboxylic acids, such as adipic acid, sebacic acid, glutaric acid, azelaic acid, suberic acid, undecanedioic acid, dodecanedioic acid, 3,3-dimethylglutaric acid, terephthalic acid, isophthalic acid, Hexahydrophthalic acid and / or dimer fatty acid, with low molecular weight.
  • di- or tricarboxylic acids such as adipic acid, sebacic acid, glutaric acid, azelaic acid, suberic acid, undecanedioic acid, dodecanedioic acid, 3,3-dimethylglutaric acid, terephthalic acid, isophthalic acid, Hexahydrophthalic acid and / or dimer fatty acid, with low molecular weight.
  • molecular diols or triols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,1-dodecanediol, dimer fatty alcohol , Glycerol and / or trimethylolpropane, can be produced.
  • diols or triols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,1-dodecanediol, dimer fatty alcohol , Glycerol and / or trimethylolpropane
  • polystyrene resin Another suitable group of polyols are the caprolactone-based polyesters, which are also referred to as "polycaprolactones".
  • Other usable polyols are polycarbonate polyols and dimer diols and castor oil and its derivatives.
  • hydroxyl-containing polycarbonates which are obtained by reaction of carbonic acid derivatives, eg. As diphenyl carbonate, dimethyl carbonate or phosgene, are available with diols.
  • ethylene glycol 1, 2- and 1, 3-propanediol, 1, 3- and 1, 4-butanediol, 1, 6-hexanediol, 1, 8-octanediol, neopentyl glycol, 1, 4-bishydroxymethylcyclohexane, 2-methyl -1, 3-propanediol, 2,2,4-trimethylpentanediol-1, 3, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenol A, tetrabromobisphenol A, glycerol, trimethylolpropane, hexanetriol-1, 2,6, butanetriol-1 , 2,4, trimethylolpropane, pentaerythritol, quinitol, mannitol, sorbitol, methyl glycoside and 1, 3,4,6-dianhydrohexite.
  • hydroxy-functional polybutadienes which u.a. marketed under the trade name "Poly-bd®” can be used as polyols as well as their hydrogenated analogs, as well as hydroxy-functional polysulfides sold under the trade name "Thiokol® NPS-282" and hydroxy-functional ones Polysiloxanes in question.
  • Particularly suitable polyamines which can be used according to the invention are hydrazine, hydrazine hydrate and substituted hydrazines, such as N-methylhydrazine, N, N'-dimethylhydrazine, acid dihydrazides, adipic acid, methyl adipic acid, sebacic acid, hydracrylic acid, terephthalic acid, semicarbazidoalkylene hydrazides, such as 13-semicarbazidopropionic acid hydrazide , Semicarbazidoalkylen-carbazinester such.
  • Polyamines e.g. those sold under the tradename Jeffamine® (polyether polyamines) are also suitable.
  • the polyol / polyamine component used according to the invention contains norma Either exclusively polyols or mixtures of polyols and polyamines.
  • polyol / polyamine component are also suitable as the polyol / polyamine component.
  • chain extenders which react with excess isocyanate groups, normally have a molecular weight below 400 and are frequently in the form of polyols, aminopolyols or aliphatic, cycloaliphatic or araliphatic polyamines.
  • Suitable chain extenders are, for example:
  • Alkanediols such as ethanediol, 1,2- and 1,3-propanediol, 1,4- and 2,3-butanediol, 1,5-pentanediol, 1,3-dimethylpropanediol, 1,6-hexanediol, neopentyl glycol, cyclopentane lohexanedimethanol, 2-methyl-1,3-propanediol,
  • Ether diols such as diethylene diglycol, triethylene glycol or hydroquinone dihydroxyethyl ether
  • Polyamines such as ethylenediamine, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, isomer mixture of 2,2,4- and 2,4,4-trimethyl-hexamethylenediamine, 2- Methyl-pentamethylenediamine, diethylenetriamine,
  • the polyol / polyamine component may contain species with double bonds, which may be e.g. from long-chain, aliphatic carboxylic acids or fatty alcohols can result.
  • a functionalization with olefinic double bonds is z.
  • Solvents may also be used as components of the starting reaction composition (these solvents may escape boiling during the reaction or remain in the mixture). Suitable solvents are, for example, ethyl acetate, butyl acetate, 1-methoxypropyl-2-acetate, 3-methoxy-n-butyl acetate, 2-butanone, 4-methyl-2-pentanone, cyclohexanone, toluene, xylene, chlorobenzene or white spirit.
  • Solvent mixtures containing especially higher-substituted aromatics such as commercially available as solvent naphtha, Solvesso ® (Exxon Chemicals, Houston, USA), Cypar ® (Shell Chemicals, Eschborn, DE), Cyclo Sol ® (Shell Chemicals, Eschborn, DE), ToIu Sol ® (Shell Chemicals, Eschborn, DE), Shellsol ® (Shell Chemicals, Eschborn, DE) are likewise suitable.
  • Useful solvents are also carbonic acid esters, such as dimethyl carbonate, diethyl carbonate, 1, 2-ethylene carbonate and 1, 2-propylene carbonate; Lactones, such as 1,3-propiolactone, i-butyrolactone, caprolactone, methylcaprolactone, propylene glycol diacetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl acetate, N-methylpyrrolidone and N-methylcaprolactam.
  • carbonic acid esters such as dimethyl carbonate, diethyl carbonate, 1, 2-ethylene carbonate and 1, 2-propylene carbonate
  • Lactones such as 1,3-propiolactone, i-butyrolactone, caprolactone, methylcaprolactone, propylene glycol diacetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl acetate, N-methylpyrrolidone
  • no catalyst suitable for the preparation of polyurethanes is used in the process according to the invention.
  • This process variant is used in particular at high temperatures and using reactive starting components.
  • the absence of the catalyst in the polymeric process product is considered to be a significant qualitative advantage.
  • a catalyst suitable for the preparation of polyurethanes is used as component of the starting reaction composition.
  • Suitable catalysts are the conventional catalysts of polyurethane chemistry known per se which contain atoms such as e.g. Sn, Mn, Fe, Co, Cd, Ni, Cu, Zn, Zr, Ti, Hf, Al, Th, Ce, Bi, N, P.
  • the molar ratio catalyst / isocyanate depends on the type of isocyanate and the type of catalyst and is usually between 0 and 0.1, preferably 0 to 0.03.
  • the process parameters are adjusted so that at least 93%, preferably at least 98%, of the maximum amount of isocyanate groups of the polyisocyanate component which can be reacted with the amount of polyols and polyamines used after the abrupt cooling of the reaction composition by means of the quencher with hydroxyl and / or amine groups of the polyol / Polyamine component have reacted.
  • the process parameters to be mentioned in particular include the temperature, the residence time, the layer thickness of the applied film, the dosage, the type and concentration of the components used in the starting reaction composition.
  • the body A rotating around an axis of rotation and having a hot surface is preferably located as a horizontal or slightly horizontal one. at an angle of up to approx. 30 °).
  • the body A having the hot surface may also be vase-shaped, ring-shaped or conical.
  • the body A having the hot surface has a diameter of 0.10 m to 3.0 m, preferably 0.20 m to 2.0 m, and more preferably 0.20 m to 1.0 m.
  • the hot surface may be smooth or, alternatively, may have corrugated or spiral formations which influence the residence time of the reaction mixture.
  • the body A having the hot surface is incorporated in a container which is resistant to the conditions of the method according to the invention.
  • the temperature of the hot surface is preferably between 100 and 300 ° C., more preferably between 120 and 250 ° C.
  • the temperature of the hot surface is an important parameter which is selected by the person skilled in the art with other relevant influencing variables, such as residence time, type and amount of components of the Initial reaction mixture should be tuned.
  • the hot surface extends to further rotating bodies, so that the reaction composition passes before cooling by means of the quenching device from the hot surface of the rotating body A on the hot surface of at least one further rotating body having the hot surface.
  • the other rotating bodies are suitably designed according to the body A.
  • body A virtually feeds the other bodies with the reaction mixture, i.
  • the thin film flows from the body A to at least one other body, leaving it at least one other body, and then being cooled abruptly by means of the quencher.
  • the quenching device is generally preferably in the form of one or more cooling walls, which allows the abrupt cooling of the reaction mixture.
  • the cooling walls which are often cylindrical or conical, have either a smooth or a rough surface, whose temperature is typically between -50 0 C and 200 0 C.
  • the means of the quench was abrupt cooling of the reaction composition is preferably at least 50 0 C, preferably at least 100 0 C.
  • the dosing system employed allows the components of the starting reaction composition to be added at any desired hot surface positions.
  • a subset or the whole Components of the starting reaction composition may be premixed and then applied to the hot surface by the dosing system.
  • the rotating body A is present as a hub having the hot surface on top, in which the components of the Ninre soskomposition be applied individually and / or as a mixture with the aid of the dosing system in the middle region as a thin film and the Quensch adopted a cooling wall surrounding the turntable is present, upon which the reaction composition impinges upon leaving the hot surface.
  • the rotational speed of the hot surface body A and the rate of dosing of the components of the starting reaction mixture are variable.
  • the rate of revolution in revolutions per minute is from 1 to 20,000, preferably 100 to 5,000, and most preferably 500 to 2,000.
  • the volume of the reaction mixture, which is per unit area of the hot surface on the rotating body A, is typically 0.1 to 10 mL / dm 2 , preferably 1, 0 to 5.0 mL / dm 2 .
  • the mean residence time (frequency spectrum of the residence time spectrum) of the reaction mixture depends inter alia on the size of the hot surface, the type and amount of the components of the starting reaction mixture, the temperature of the hot surface and the rotational speed of the rotating body A and is normally 0 , 01 to 100 s, preferably 0.1 to 10 s, particularly preferably 1 to 10 s and is therefore to be regarded as extremely short. This ensures that the level of undesirable side reactions is greatly reduced, thus producing high quality products.
  • the process parameters set are a layer thickness of the thin film applied by the metering system of 0.1 ⁇ m to 1.0 mm, preferably 20 to 80 ⁇ m, and a mean residence time of the components of the starting reaction composition on the hot surface from 0.01 to 20 seconds, preferably from 0.1 to 10 seconds.
  • the process according to the invention is preferably carried out under atmospheric pressure and in an atmosphere of dry protective gas, but the process is carried out alternatively for degassing the residual isocyanate under vacuum or to increase the temperature under pressure can be operated.
  • the present invention also relates to polyurethanes / polyureas, which can be prepared according to the method described above.
  • the quenching device is a metallic wall in which coolant flows.
  • Example 1 Polyol with aliphatic isocyanate
  • Lupranol® 1000 polypropylene glycol synthesized with KOH technology, diol, molecular weight about 2000 g / mol, OH number 55, viscosity 325 mPa.s
  • Elastogran 104 g of Vestanat® IPDI (Isophorone diisocyanate, CAS 4098-71-9) from Degussa GmbH, 1.50 g of additives Tl (p-Toluenesulfonyl isocyanate (PTSI), CAS 4083-64-1) from Borchers and 0.2 g of DBTDL (dibutyltin dilaurate, CAS (Chemical Abstracts Service) 77-58-7).
  • PTSI p-Toluenesulfonyl isocyanate
  • the mixture is stirred for 30 minutes at room temperature with KPG stirrer.
  • the body A present as a 20 cm diameter smooth disc, is heated at 180 ° C. with oil and rotated at 400 rpm. With a gear pump, the premix is added at 5.00 ml / s under nitrogen.
  • the polyurethane / polyurea product is cooled by cooled (-10 0 C) walls. It leaves the system at 50 ° C. with a residual NCO of 4.49% by weight.
  • the conversion is about 100% with a viscosity (measured according to DIN EN ISO 2555 EN, as in the examples below) of 6250 mPa.s.
  • Pluracol 1044 S polypropylene glycol synthesized with KOH technology, diol, molecular weight about 4000 g / mol, OH number 30, viscosity 790 mPa.s
  • BASF SE 375 g Pluracol 220 S (polypropylene glycol Synthesized with KOH technology, triol, molecular weight about 6000 g / mol, OH number 26, viscosity 1300 mPa.s) of BASF SE and 0.28 g bismuth octoate (CAS 67874-71-9) submitted and mixed with KPG stirrer.
  • the polyurethane / polyurea product is cooled by cooled (-10 0 C) walls. It leaves the system at 50 ° C. with a residual NCO of 2.1% by weight. The conversion is about 100% with a viscosity of 13800 mPa.s.
  • Example 3 Polyol, chain extender with aliphatic isocyanate
  • the premix is added at 5.00 ml / s under nitrogen.
  • the polyurethane / polyurea product is cooled by cooled (-10 0 C) walls. It leaves the system at 50 ° C. with a residual NCO of 0.9% by weight.
  • the conversion is about 100% with a viscosity of 30,000 mPa.s.
  • Example 4 Polyol, chain extender with aliphatic isocyanate on a smaller disk
  • the premix is added at 1.25 ml / s under nitrogen.
  • the polyurethane / polyurea product is cooled by cooled (-10 0 C) walls. It leaves the system at 50 ° C. with a residual NCO of 0.9% by weight.
  • the conversion is 100% with a viscosity of 30,000 mPa.s.
  • Example 5 Polyol / diamine with aromatic isocyanate without catalyst
  • the body A a 20 cm diameter smooth disc is heated at 180 0 C with oil and rotated at 1000 rpm.
  • the polyols / diamine masterbatch at 4.68 g / s and the isocyanate masterbatch at 0.32 g / s are metered in a static mixer under nitrogen.
  • This static mixer provides a continuous premix of 5.00 g / s on the body A.
  • the polyurethane / polyurea product is cooled by cooled (-10 0 C) walls. It leaves the system at 50 ° C. with an NCO residual of 2.31% by weight.
  • the conversion is about 100% with a viscosity of 35400 mPa.s.
  • the reactions on the disk were done in less than 2 seconds thanks to the high temperatures.
  • the quenching device allows the collection of products without side reactions.
  • the products leave the machine after a few seconds.
  • the process is fully continuous and can be stopped abruptly.
  • the "scale-up" is successful and simple with the comparison between examples 4 and 3. No purification process between the batches is necessary since the first 50 ml of impure product have been removed Furthermore, there are no encrustations, variations in viscosity, and in continuous operation Remaining NCO noticeable.

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

Abstract

L'invention concerne un procédé continu pour la production de polyuréthanes/polyurées. Selon ce procédé, les constituants d'une composition réactionnelle de départ sont appliqués individuellement et/ou en tant que mélange en couche mince sur une zone interne d'une surface chaude d'un corps A en rotation de sorte que la couche mince s'écoule sur la surface chaude du corps A en rotation vers une zone externe de la surface chaude du corps A en rotation. La couche mince quitte la surface chaude sous forme de composition réactionnelle qui contient du polyuréthane/de la polyurée et qui est refroidie brusquement à sa sortie de la surface chaude. Selon l'invention, la composition réactionnelle de départ contient un constituant polyisocyanate et un constituant polyol/polyamine, la température de la surface chaude est comprise entre 70 et 400 °C et le refroidissement brusque de la composition réactionnelle est d'au moins 30 °C.
EP08803476A 2007-09-12 2008-09-01 Production continue de polyuréthanes/polyurées Withdrawn EP2190895A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102007043509 2007-09-12
DE102007051274A DE102007051274A1 (de) 2007-10-26 2007-10-26 Kontinuierliche Herstellung von Polyurethanen/Polyharnstoffen
PCT/EP2008/061495 WO2009033975A1 (fr) 2007-09-12 2008-09-01 Production continue de polyuréthanes/polyurées

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EP2190895A1 true EP2190895A1 (fr) 2010-06-02

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AR (1) AR068441A1 (fr)
AU (1) AU2008297316B2 (fr)
BR (1) BRPI0816718A2 (fr)
CA (1) CA2698175A1 (fr)
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EP2300149B1 (fr) * 2008-07-08 2012-12-12 Construction Research & Technology GmbH Procédé servant à éliminer l'isocyanate non décomposé de son produit de décomposition
EP2313445B1 (fr) * 2008-08-08 2011-11-02 Construction Research & Technology GmbH Production de polyurées et/ou de polyuréthanes silylés
CN102239198B (zh) * 2008-12-05 2015-01-21 巴斯夫欧洲公司 作为粘合剂和密封剂用增塑剂的环己烷多羧酸衍生物
BR112012013895A2 (pt) * 2009-12-08 2016-05-03 Basf Se componente isocianato altamente reativo, processo para a produção de materiais contendo lignocelulose, material contendo lignocelulose, e, usos de um material contendo lignocelulose, e de um componente de isocianato altamente reativo
EP3486230A1 (fr) 2011-03-09 2019-05-22 Mitsui Chemicals, Inc. Pentaméthylène diisocyanate, procédé de production de pentaméthylène diisocyanate, composition de polyisocyanate, résine de polyuréthane résine de polyurée
DE18742632T1 (de) * 2017-06-26 2019-11-07 Advansix Resins & Chemicals Llc Verfahren und zusammensetzungen für polyurethandispersionen mit verwendung von aus caprolactam gewonnenen lösungsmitteln
JP7197602B2 (ja) * 2018-03-27 2022-12-27 アドバンシックス・レジンズ・アンド・ケミカルズ・リミテッド・ライアビリティ・カンパニー チクソトロピー性レオロジー改質剤組成物
CN114426695B (zh) * 2021-12-24 2023-06-02 宁波长阳科技股份有限公司 一种提升热塑性聚氨酯弹性体薄膜力学性能的方法

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DE19924090C1 (de) * 1999-05-26 2001-01-25 Bayer Ag Verfahren zur kontinuierlichen Herstellung von thermoplastisch verarbeitbaren Polyurethanen mit verbessertem Erweichungsverhalten
GB2378953B8 (en) * 2001-07-20 2005-07-18 Protensive Ltd Improvements relating to polymerisation reactions
DE10221047A1 (de) * 2002-05-10 2003-11-27 Degussa Verfahren zur lösemittelfreien,kontinuierlichen Herstellung von Polyharnstoffen
DE102005004967A1 (de) * 2005-02-03 2006-08-10 Basf Ag Verfahren zur kontinuierlichen Herstellung thermoplastisch verarbeitbarer Polyurethan-Elastomere
US7666950B2 (en) * 2006-06-01 2010-02-23 Lanxess Deutschland Gmbh Process for preparing hydrogenated nitrile rubbers

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AU2008297316B2 (en) 2013-02-07
CN101802038A (zh) 2010-08-11
KR20100075905A (ko) 2010-07-05
US20100204430A1 (en) 2010-08-12
WO2009033975A1 (fr) 2009-03-19
BRPI0816718A2 (pt) 2015-02-24
MX2010002849A (es) 2010-04-09
CL2008002684A1 (es) 2009-03-20
AU2008297316A1 (en) 2009-03-19
JP2010539266A (ja) 2010-12-16
PE20090870A1 (es) 2009-07-08
CA2698175A1 (fr) 2009-03-19
AR068441A1 (es) 2009-11-18

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