EP2212363A1 - Procédé pour préparer des élastomères alvéolaires de coulée de polyuréthane (pur) à partir de prépolymères stables au stockage de diisocyanate de 1,5-naphtalène (ndi) - Google Patents

Procédé pour préparer des élastomères alvéolaires de coulée de polyuréthane (pur) à partir de prépolymères stables au stockage de diisocyanate de 1,5-naphtalène (ndi)

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Publication number
EP2212363A1
EP2212363A1 EP08850436A EP08850436A EP2212363A1 EP 2212363 A1 EP2212363 A1 EP 2212363A1 EP 08850436 A EP08850436 A EP 08850436A EP 08850436 A EP08850436 A EP 08850436A EP 2212363 A1 EP2212363 A1 EP 2212363A1
Authority
EP
European Patent Office
Prior art keywords
ndi
reaction
polyols
stable
optionally
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Withdrawn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
EP08850436A
Other languages
German (de)
English (en)
Inventor
Jens Krause
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 Deutschland AG
Original Assignee
Bayer MaterialScience AG
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 Bayer MaterialScience AG filed Critical Bayer MaterialScience AG
Publication of EP2212363A1 publication Critical patent/EP2212363A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/70—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
    • C08G18/7678—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing condensed aromatic rings
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0066—≥ 150kg/m3
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
    • 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
    • C08G2350/00—Acoustic or vibration damping material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
    • Y10T428/24496—Foamed or cellular component
    • Y10T428/24504—Component comprises a polymer [e.g., rubber, etc.]
    • Y10T428/24512—Polyurethane

Definitions

  • the present invention relates to a process for the preparation of cellular polyurethane (PUR) cast elastomers / moldings based on 1,5-naphthalene diisocyanate (NDI) prepolymers.
  • PUR polyurethane
  • NDI 1,5-naphthalene diisocyanate
  • microcellular polyisocyanate polyaddition products usually polyurethanes (PU) and / or polyisocyanurates, obtainable by reacting isocyanates with isocyanate-reactive compounds and processes for their preparation are well known.
  • PU polyurethanes
  • polyisocyanurates obtainable by reacting isocyanates with isocyanate-reactive compounds and processes for their preparation are well known.
  • a particular embodiment of these products are cellular, in particular microcellular polyurethane elastomers, which differ from conventional polyurethane foams by their significantly higher density of 300 to 600 kg / m 3 , their particular physical properties and the possible applications thereof (Günter Oertel, 3rd revised edition, Becker / Braun Kunststoff Handbuch 7, Hanser Verlag, pages 378 to 381 (Chapter 7.3.3.2) and page 428.
  • Such polyurethane elastomers are used, for example, as vibration and shock-absorbing elements, in particular in the automotive industry In automobiles, for example, within the overall strut construction, consisting of shock absorber, coil spring and the elastomeric spring, are pushed onto the piston rod of the shock absorber.
  • One of the most important requirements is to achieve excellent dynamic-mechanical and static h-mechanical properties, for example, excellent tensile strength, elongation, tear propagation and compression set residues, so that the polyurethane elastomers can meet the high mechanical requirements that are placed on the damping elements over the longest possible period.
  • the cellular polyisocyanate polyaddition products are prepared in a mold.
  • 1,5-NDI based cellular polyurethane elastomers have been produced for years (DE-A 29 40 856).
  • a disadvantage of the known processes is that 1,5-NDI-based prepolymers are stable on storage only for a limited period of time. Thus, no stockpiling is possible, and the prepolymer must be made on site and converted directly to the elastomer.
  • NDI-based PUR exclusively as non-storage-stable prepolymers
  • the scale-form NDI requires a comparatively complicated continuous solids metering to ensure that a continuously produced NCO prepolymer having a constant NCO value and a constant composition is obtained.
  • occupational hygiene aspects which result from the comparatively high tendency to sublimation of NDI, require increased technical effort.
  • a way out of this problem opens up a way to prepare a NDI Prepolymer, which had to be homogeneous in terms of its structure.
  • the group of NDI prepolymers only those which have sufficient storage stability are useful.
  • Classical NDI prepolymers as used on a large scale for the preparation of NDI cast elastomers, are characterized in that the unreacted monomer NDI due to its Schwerlohnhchkeit and the high melting point in storage conditions, eg at temperatures below 50 0 C, fails.
  • simply heating to temperatures above the melting point of NDI is not effective for the following reasons.
  • the high temperature load associated with the reflow process leads to side reactions and ultimately to a decrease in the NCO index, coupled with an increase in viscosity, so that simple processing is at least made difficult, if not impossible.
  • NCO index the ratio of NCO groups to Zerewitinoff active hydrogen atoms
  • the prepolymer is non-storable and must be prepared for use with a prepolymer route , the next stage in the process, viz. the cham extension, should take place as soon as possible but within a maximum of 30 minutes. " . [ “6.2.1 Unstable prepolymer solutions (Vulkollan) (Vulkollan ®; trade name ßir G manelastomersysteme based naphthalene (NDI) from Bayer MaterialScience AG).
  • Vulkollan is produced by a prepolymer process, however, the prepolymer is not storable and must be processed within a short period of time.
  • the resulting prepolymer is relatively unstable, since further undesired side reactions can take place.
  • the next step, chain extension should be as fast as possible, but within a maximum of 30 minutes.
  • cellular PUR cast elastomers based on NDI can be prepared by reacting special, storage-stable NDI-based NCO prepolymers with crosslinkers.
  • the present invention is a process for the preparation of cellular Polyurethanang manelastomeren, wherein
  • NDI 1,5-naphthalene diisocyanate
  • Storage-stable NCO prepolymers based on 1,5-naphthalene isocyanate (NDI) are those having an NCO content of 2.5 to 6 wt .-% and with a measured at 100 0 C viscosity of ⁇ 5000 mPas, by reacting
  • polyester polyols mentioned under B) are prepared according to the prior art usually by polycondensation of one or more polycarboxylic acids, optionally Polycarbonklarede ⁇ vat with molar excess short-chain polyol, optionally polyol mixtures, wherein catalysts can be used.
  • Typical short-chain polyols are alkylene diols having 2 to 12 carbon atoms.
  • Poly- ⁇ -caprolactone polyols are obtained by ⁇ -caprolactone polymerization by employing predominantly bifunctional starter molecules, including water.
  • Polycarbonate polyols are hydroxyl end-containing compounds containing on average at least 3 carbonate groups.
  • Polyether polyols are polypropylene or polypropylene propylene co-ethylene oxides polymerized predominantly with bifunctional initiators, which are obtained, for example, by catalysis of alkahydroxides or double metal complexes.
  • ⁇ -Hydro- ⁇ -hydroxy-poly (oxytetramethylene) polyols are obtained by the subsequent polymerization of tetrahydrofuran with the aid of strongly acidic catalysts.
  • the polyols are conveniently stabilized with acids
  • the preparation of the NDI prepolymers is carried out by the polyol is heated to a temperature of 80 to 15O 0 C and stirred with NDI
  • the exact starting temperature for the prepolymer formation depends on the size of the approach and the type of vessel and is in preliminary experiments determined so that due to the exothermicity of the reaction, a temperature maximum is reached, which is sufficient to melt the NDI used in the reaction mixture or to obtain a clear homogeneous melt
  • the required temperature maximum is approximately in the range of 120 to 135th ° C, more preferably 125-130 0 C.
  • the already cooled Mate ⁇ al is present in a stirred tank, wherein the temperature is selected depending on the proportions of new to old Matenal so that the temperature of the mixture after the end of Ablrawsch ⁇ ttes is at most 100 0 C
  • the discharge itself has to be designed here be that for all proportions of old and new product all Randbedm- conditions related to. the cooling rate can be adhered to the thus obtained, is heated to temperatures exceeding 100 0 C quenched mixture of old and new product fraction thereafter if necessary by cooling of the vessel to temperatures further cooled below 70 0 C.
  • m storage container is parallel to an extent operating, which ensures both that sufficient product remains in the drain tank at a temperature that allows to ensure the quenching of the next part of the batch to the above temperature, as well as to minimize the overall temperature load.
  • a further variant of the process is therefore to carry out the process for preparing the storage-stable NCO prepolymers continuously on reaction extruders.
  • the reaction mixture of polyol and NDI is heated in one of the first zones of the extruder to temperatures of at least 180 ° C to at most 240 0 C and in the subsequent zones of the extruder under application of a negative pressure for extensive degassing and by cooling rapidly to temperatures of preferably cooled below 100 0 C, more preferably below 80 0 C.
  • the melt obtained is filled into vessels filled with inert gas and stored.
  • an anti-aging agent in the polyol mixture is expediently an anti-aging agent in the polyol mixture.
  • the polyols used to prepare the NCO prepolymers are preferably stored at elevated temperature prior to their use in a storage vessel.
  • the storage of the polyester in the temperature range of 100 to 14O 0 C and the storage of the polyether polyols at temperatures of 80 to 120 0 C in this case has been found.
  • the storage-stable NDI prepolymers furthermore have the advantage that the unreacted NDI still present after the reaction is not removed and in amounts of more than 0.3% by weight and less than 5% by weight, based on the prepolymer , is present.
  • the storage-stable NDI prepolymer is therefore prepared separately. It can be used in a period of up to 6 months after its manufacture.
  • the storage-stable prepolymers show no significant change in the NCO content and no sedimentation of free, unreacted 1,5-NDI over this period.
  • the preparation of the casting elastomers (moldings) is advantageously carried out at an NCO / OH ratio of 0.85 to 1.20, wherein the heated starting components are mixed and in an amount corresponding to the desired mold density in a heated, preferably dichssendes
  • the lists must be mold surface temperature of the mold inner wall is from 75 to 90 0 C.
  • the moldings are cured after 10 to 60 minutes and demold.
  • the amount of the introduced into the mold mixture is usually measured so that the resulting molded articles have the density already shown.
  • the starting components are customary hchgue at a temperature from 30 to 110 0 C in the mold incorporated the degrees of compression between 1.1 and 8 and preferably between 2 and 6.
  • the zelhgen elastomers are expediently with a low-stick-Techmk or in particular the Reakhons- Sp ⁇ tztechnik (RIM) produced in open, preferably closed molds.
  • Additives such as castor oil or carbodnmides (eg Stabaxole Rheinchemie as hydrolysis, 2,2 ', 6,6'-Tetraisopropyldiphenylcarbod ⁇ mid is a known representative) can be added to both the polyol and the prepolymer.
  • Water, emulsifiers, catalysts and / or auxiliaries and / or additives usually form the polyol component with the polyol.
  • the molds For better demolding, it is common to provide the molds with external release agents, for example, compounds wax or Sihkonbasis or consultedss ⁇ ge Suds
  • external release agents for example, compounds wax or Sihkonbasis or consultedss ⁇ ge Suds
  • the corresponding integral moldings are usually tempered for 1 to 48 hours at temperatures of 70 to 120 0 C.
  • Another object of the invention are cellular polyurethane casting elastomers / -formkorper available from
  • isocyanates which can be used in addition to the 1,5-NDI prepolymer are generally known (cyclo) aliphatic and / or aromatic polyisocyanates. Particularly suitable are aromatic dinocyanates, preferably 2,2'-, 2,4'- and / or 4,4'-diphenylmethane isocyanate (MDI), 2,4- and / or 2,6-tolylene diisocyanate (TDI), 3, 3'-dimethyl-diphenyl-dnsocyanate (TODI), 1, 2-diphenylethane diisocyanate, Phenylend ⁇ socyanat (PPDI) and / or (cyclo) aliphatic isocyanates such as, for example, 1, 6-hexamethylene-dansocyanate (HDI), l-isocyanato-3 , 3,5-t ⁇ -methyl-5-isocyanato-methylcyclohexane and / or polyisocyanates, such as, for example, polyphenylpolym
  • the isocyanates may be in the form of the pure compound, in mixtures and / or in modified form, for example in the form of uretdiones, isocyanurates, Allophanates or biurets, preferably in the form of urethane and isocyanate group-containing reaction products, of 1,5-NDI prepolymer different Icocyanatprepolymere be used are preferably optionally modified 2,2'-, 2,4'- and / or 4,4 ' Diphenylmethane isocyanate (MDI), 2,4- and / or 2,6-toluene diisocyanate (TDI) and / or mixtures d ieser isocyanates used.
  • MDI Diphenylmethane isocyanate
  • TDI 2,6-toluene diisocyanate
  • d ieser isocyanates used.
  • Low molecular chain extenders and / or crosslinking agents having a molecular weight of less than 500, preferably 60 to 499 are used as component bl), for example from the group of di- and / or tetrahydrofolic alcohols, di- to tetrafunctional polyoxyalkylene polyols and alkyl-substituted aromatic diamines or of mixtures of at least two of the chain extenders and / or crosslinking agents used as (bl), for example alkanediols having 2 to 12, preferably 2, 4, or 6 carbon atoms can be used, for example ethane, 1,3-propane , 1,5-pentane, 1,6-hexane, 1,7-heptane, 1,8-octane, 1,9-nonane, 1,10-decanediol and preferably 1,4-butanediol, dialkylene glycols with 4 to 8 carbon atoms, such as diethylene glycol and dipropy
  • alkanediols having usually not more than 12 carbon atoms such as, for example, 1,2-propanediol, 2-methyl-, 2,2-dimethyl-1,3-propanediol, 2-butyl-2
  • branched-chain and / or unsaturated alkanediols having usually not more than 12 carbon atoms are also suitable -ethylpropanediol-1,3-butene-2-diol-1,4-and-but-2-diol-1,4-diester of terephthalic acid with glycols having 2 to 4 carbon atoms, such as, for example, terephthalic acid-bis-ethylene glycol or butanediol-1,4, hydroxyalkylene ethers of hydroquinone or Resorcms, such as l, 4-di- (b-hydroxyethyl) hydroquinone or l, 3-di (b-hydroxyethyl) -resorcm
  • higher-functional crosslinking nipples are trifunctional and higher-functional alcohols, such as, for example, glycene, trimethylolpropane, pentaerythritol and trihydroxycyclohexanes, and also trialkanolamines, such as, for example, ethanolamine.
  • chain extenders it is possible to use: alkyl-substituted aromatic polyamines having molecular weights preferably from 122 to 400, in particular circular aromatic diamines having at least one alkyl substituent in the ortho position relative to the amino groups, which reduce the reactivity of the amino group by steric hindrance, at room temperature are liquid.
  • alkyl-substituted aromatic polyamines in admixture with the abovementioned low molecular weight polyhydric alcohols, preferably dihydric and / or trihydric alcohols or dialkylene glycols.
  • polyhydric alcohols preferably dihydric and / or trihydric alcohols or dialkylene glycols.
  • aromatic diamines preference is not given to using aromatic diamines.
  • the preparation of the products according to the invention thus takes place in the absence of aromatic diamines.
  • polyester polyols can be prepared, for example, from dicarboxylic acids having 2 to 12 carbon atoms and dihydric alcohols
  • dicarboxylic acids having 2 to 12 carbon atoms and dihydric alcohols
  • dihydric alcohols examples include glycols having 2 to 16 carbon atoms, preferably 2 to 6 carbon atoms, such as.
  • ethylene glycol diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, decane-1,10,10, 10 2-methylpropane-l, 3-diol, 2,2-Dimethylpropandiol-l , 3, 1,3-propanediol and dipropylene glycol.
  • the dihydric alcohols may be used alone or optionally in mixtures with each other.
  • Preferred polyester polyols are ethanediol polyadipates, 1,4-butanediol polyadipates, ethanediol butanediol polyadipates, 1,6-hexanediol neopentyl glycol polyadipates, 1,6-hexanediol di, 4-butanediol polyadipates, 2-methyl-1,3-propanediol-1,4-butanediol polyadipates and / or polycaprolactones.
  • Suitable polyoxyalkylene glycols containing polycarbonate groups are polycondensates of these with alkyl or aryl carbonates or phosgene. Exemplary embodiments are given in DE-A 19535 48 771, page 6, lines 26 to 59
  • emulsifier (b3) for example, sulfonated fatty acids and other well-known emulsifiers are used, such as polyglycol esters of fatty acids, Alkylarylpolyglykolether, alkoxylates of fatty acids, preferably polyethylene glycol esters, polypropylene glycol esters, polyethylenepolypropylenglykolester, ethoxylates and / or propoxylates of linoleic acid, linolenic acid, oleic acid , Arachidonic acid, more preferably oleic acid ethoxylates
  • polysiloxanes can be used.
  • Salts of fatty acids with amines for example, oleic diethylamine, diethanolamine stearate, diethylamine hydrochloride, salts of sulfonic acids, e.g. Alkali or ammonium salts of dodecylbenzene or dinaphthylmethanedisulfonic acid are also preferred
  • the sulfonated fatty acids can preferably be used as aqueous solutions, for example as a 50% solution.
  • Typical known products are additives SV and SM from Rheinchemie, as well as non-aqueous emulsifier additive WM from Rheinchemie
  • the process for the preparation of cellular PUR cast elastomers is carried out in the presence of water.
  • the water acts both as a crosslinker to form urea groups and as a result of reaction with isocyanate groups to form carbon dioxide as a blowing agent.
  • the amounts of water that can be conveniently used are 0, From 01 to 5% by weight, preferably from 0.3 to 3.0% by weight, based on the weight of component (b)
  • the water can be used completely or partially in the form of aqueous solutions of the sulfonated fatty acids.
  • the catalysts (b4) can be added individually as well as in admixture with each other.
  • these are organometallic compounds, such as Zmn (II) salts of organic car- Bonklaren, z.
  • organometallic compounds such as Zmn (II) salts of organic car- Bonklaren, z.
  • tin (II) dioctoate tin ( ⁇ ) -dilaurate, dibutyltin diacetate and dibutyltin dilaurate and tertiary amines
  • tetramethyl-ethylenediamine N-methylmorpholine, diethylbenzylamine, triethylamine, dimethylcyclohexylamine, diazabicyclooctane, N, N'-dimethyl piperazine, N-methyl.
  • amidines such as, for example, 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tris (dialkylaminoalkyl) -s-hexahydrotriazines, in particular tris (N, N-dimethyl - Amino-propyl) -s-hexahydrotriazine, tetraalkylammonium hydroxides, such as tetramethyl ammonium hydroxide, alkali metal hydroxides, such as sodium hydroxide, and alkali metal, such as sodium and potassium isopropylate, and alkali metal salts of long-chain fatty acids having 10 to 20 carbon atoms and optionally pendant OH groups , Depending on the reactivity to be set, the catalysts (
  • Auxiliaries and additives (b5) can be used in the production of cast elastomers according to the invention.
  • These include, for example, well-known surface-active substances, hydrolysis protectants, fillers, antioxidants, cell regulators, flame retardants and dyes.
  • Suitable surface-active substances are compounds which serve to assist the homogenization of the starting materials and, if appropriate, are also suitable for regulating the cell structure.
  • foam stabilizers come into consideration, such as e.g. oxethylated alkylphenols, ethoxylated fatty alcohols, paraffin oils, castor oil or ricinoleic acid esters, Turkish red oil and peanut oil and cell regulators, such as paraffins and fatty alcohols.
  • the surface-active substances are usually used in amounts of from 0.01 to 5 parts by weight, based on 100 parts by weight of components Qa).
  • the cellular PU cast elastomers of the invention also referred to as moldings, as damping elements in vehicle construction, for example in the automotive industry, for.
  • Example as additional springs, bump stop, wishbone bearing, Schuachsenfahrschemellager, stabilizer bearings, longitudinal strut bearings, strut support bearings, shock absorber bearings, bearings for wishbones and as on-the-rim emergency, which causes, for example in a puncture, that the vehicle on the cellular elastomer drives and remains controllable.
  • They can also be used as a coating for rollers, wheels and rollers.
  • neo-pentylglycol started poly- ⁇ -caprolactone having a hydroxyl number of 79 mgKOH / g
  • Desmodur® 15 (naphtha-diisocyanate) from Bayer Mate ⁇ alScience AG
  • Example 1 Preparation of an NDI-based, storage-stable NCO prepolymer based on Capa l
  • Example 2 Preparation of a Cellular Casting Elastomer from NDI-Based. storage-stable NCO prepolymer
  • Mixture B consists of 10 parts by weight Vulkollan® 2001 KS, 1.65 parts by weight of additive SV (50% aqueous solution of a fatty acid sulfonate, available from Rheinchemie) and 0.02 part by weight of cyclohexyldimethylamm
  • the compression set (DVR) is extremely low, so that the moldings of the invention can also be used at high temperatures.
  • the dynamic test was performed.
  • the molded body was loaded and unloaded 400,000 times (load change) by 65%.
  • the frequency was in this case 2 Hz.
  • the spring characteristic curve 2 (see Figure 2, 2nd static test, implementation analog spring characteristic 1 with the same clamping height and three cycles) was added.
  • the spring characteristic is a smoothed curve of several measuring points. The upper curve is the static load curve and the lower curve is the unloading curve.
  • the set amount is a measure of the permanent deformation of the cellular PU elastomer. The smaller this value, the higher the dynamic performance of the material.

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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)
  • Polyurethanes Or Polyureas (AREA)
  • Springs (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé pour préparer des corps moulés/élastomères alvéolaires de coulée en polyuréthane (PUR) à base de prépolymères de diisocyanate de 1,5-naphtalène (NDI).
EP08850436A 2007-11-17 2008-11-12 Procédé pour préparer des élastomères alvéolaires de coulée de polyuréthane (pur) à partir de prépolymères stables au stockage de diisocyanate de 1,5-naphtalène (ndi) Withdrawn EP2212363A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007054983A DE102007054983A1 (de) 2007-11-17 2007-11-17 Verfahren zur Herstellung von zelligen Polyurethan(PUR)-Gießelastomeren aus lagerstabilen 1,5-Naphthalindiisocyanat(NDI)-Prepolymeren
PCT/EP2008/009521 WO2009062672A1 (fr) 2007-11-17 2008-11-12 Procédé pour préparer des élastomères alvéolaires de coulée de polyuréthane (pur) à partir de prépolymères stables au stockage de diisocyanate de 1,5-naphtalène (ndi)

Publications (1)

Publication Number Publication Date
EP2212363A1 true EP2212363A1 (fr) 2010-08-04

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EP08850436A Withdrawn EP2212363A1 (fr) 2007-11-17 2008-11-12 Procédé pour préparer des élastomères alvéolaires de coulée de polyuréthane (pur) à partir de prépolymères stables au stockage de diisocyanate de 1,5-naphtalène (ndi)

Country Status (11)

Country Link
US (1) US20090127921A1 (fr)
EP (1) EP2212363A1 (fr)
JP (1) JP2011506624A (fr)
KR (1) KR20100102587A (fr)
CN (1) CN101861346A (fr)
BR (1) BRPI0820542A2 (fr)
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CN103608374B (zh) * 2011-06-29 2015-11-25 拜耳知识产权有限责任公司 高价值聚氨酯弹性体及其制备
CN102391468B (zh) * 2011-09-30 2013-04-10 南京金三力橡塑有限公司 基于1,5-萘二异氰酸酯的存储稳定的预聚物的制备方法
KR101364550B1 (ko) * 2011-12-27 2014-02-20 에스케이씨 주식회사 초미세 발포 폴리우레탄 탄성체 제조용 유화제
KR101351432B1 (ko) * 2011-12-27 2014-01-15 에스케이씨 주식회사 초미세 발포 폴리우레탄 탄성체의 제조방법
EP3071424B1 (fr) * 2013-11-22 2021-05-26 Compagnie Générale des Etablissements Michelin Support en polyuréthane pour bandage non-pneumatique
EP2977394A1 (fr) * 2014-07-25 2016-01-27 Basf Se Polyuréthane micro-cellulaire à base de polycaprolactone
JP6836706B2 (ja) * 2015-05-28 2021-03-03 Dic株式会社 発泡ウレタン組成物、及び、ストラットマウント
CN105837788A (zh) * 2016-04-07 2016-08-10 苏州绿朗新材料科技有限公司 一种稳定的nco预聚物及其制备方法和用途
CN105820310A (zh) * 2016-04-07 2016-08-03 苏州绿朗新材料科技有限公司 一种nco预聚物及其制备方法和用途
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CN114008101A (zh) 2019-07-11 2022-02-01 朗盛公司 用于生产ndi预聚物的方法
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CN101861346A (zh) 2010-10-13
KR20100102587A (ko) 2010-09-24
JP2011506624A (ja) 2011-03-03
WO2009062672A1 (fr) 2009-05-22
BRPI0820542A2 (pt) 2015-06-16
DE102007054983A1 (de) 2009-05-20
MX2010004339A (es) 2010-04-30
US20090127921A1 (en) 2009-05-21
TW200940580A (en) 2009-10-01
CA2705979A1 (fr) 2009-05-22

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