EP2531538A1 - Produits de polyaddition de polyisocyanate, procédé pour leur production et leur utilisation - Google Patents

Produits de polyaddition de polyisocyanate, procédé pour leur production et leur utilisation

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Publication number
EP2531538A1
EP2531538A1 EP11701278A EP11701278A EP2531538A1 EP 2531538 A1 EP2531538 A1 EP 2531538A1 EP 11701278 A EP11701278 A EP 11701278A EP 11701278 A EP11701278 A EP 11701278A EP 2531538 A1 EP2531538 A1 EP 2531538A1
Authority
EP
European Patent Office
Prior art keywords
catalysts
switching
nco
polyisocyanate polyaddition
polyaddition products
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.)
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Application number
EP11701278A
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German (de)
English (en)
Inventor
Jens Krause
Stephan Reiter
Hartmut Nefzger
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.)
Bayer Intellectual Property GmbH
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Bayer Intellectual Property GmbH
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Filing date
Publication date
Application filed by Bayer Intellectual Property GmbH filed Critical Bayer Intellectual Property GmbH
Publication of EP2531538A1 publication Critical patent/EP2531538A1/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Withdrawn legal-status Critical Current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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
    • C08G18/2063—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having two nitrogen atoms in the condensed ring system
    • 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
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/242—Catalysts containing metal compounds of tin organometallic compounds containing tin-carbon bonds
    • 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
    • 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
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • 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
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups

Definitions

  • the invention relates to polyisocyanate polyaddition products, a process for their preparation and their use.
  • Polyurethanes have been known for a long time and are used in many fields. Frequently, the actual polyurethane reaction must be carried out using catalysts, since otherwise the reaction takes place too slowly and, if appropriate, leads to polyurethane products having poor mechanical properties. In most cases, the reaction between the hydroxyl component (NCO-reactive group, OH group) and the NCO component must be catalyzed. In the conventional catalysts, a distinction is made between metal-containing and non-metal-containing catalysts.
  • Typical common catalysts are, for example, amine catalysts, such as 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1,4-diazabicyclo [2.2.2] octane (DABCO) or triethanolamine.
  • Metal-containing catalysts are usually Lewis acid compounds, such as dibutyltin dilaurate, lead octoate, tin octoate, titanium and zirconium complexes, but also C admium, bismuth (for example bismuth neodecanoate) and iron compounds.
  • One requirement of the catalyst is that it catalyzes as defined as possible only one of the many polyurethane reactions, such as only the reaction between OH and NCO groups.
  • switchable catalysts These switchable catalysts are in turn subdivided into thermal, photochemical, chemical (eg via dissociation) or optically switchable. In general, this also refers to latent catalysts and in the thermal case of thermolatenten catalysts. These catalysts rest until the reaction mixture reaches a certain temperature. Above this temperature, they are then active, preferably abruptly active. These latent catalysts enable long pot lives and fast demolding times.
  • the latent catalysts known to date and preferably used are mercury compounds. The most prominent representatives here is the Phenylquecksilberneodecanoat (Thorcat ® 535 and COCURE ® 44).
  • This catalyst discloses a latent reaction profile, wherein the catalyst is initially almost inactive and only after slow heating of the mixture, usually due to the exothermic nature of the uncatalyzed reaction of NCO- with OH groups, at a certain temperature (usually around 70 ° C) abruptly becomes active.
  • a certain temperature usually around 70 ° C
  • very long open times can be achieved with very short curing times. This is particularly advantageous when a lot of material must be discharged (eg a large mold must be filled) and after the completion of the reaction, the reaction should be completed quickly and thus economically.
  • a particular advantage of the latent catalysts is that, in the finished polyurethane material, they cause the cleavage of urethane groups, for example due to their decreasing catalytic activity. accelerate only slightly at room temperature compared to conventional catalysts. They thus contribute to favorable long-term use properties of the polyurethanes.
  • WO 2008/018601 describes the use of catalysts based on mixtures of amines, cyclic nitrogen compounds, carboxylates and / or quaternary ammonium salts. However, such blends have the disadvantages known to the skilled person.
  • carboxylates and quaternary ammonium salts also catalyze the polyisocyanurate reaction, which must definitely be ruled out in certain applications, for example high-performance elastomers.
  • Certain combinations of catalysts cause the gel reaction to be largely separate from the curing reaction, since many of these catalysts are only selective.
  • bismuth (III) neodecanoate is combined with zinc neodecanoate and neodecanoic acid. Often additionally added is l, 8-diazabicyclo [5.4.0] undec-7-ene.
  • WO 2005/058996 describes the combination of titanium and zirconium catalysts with bismuth catalysts.
  • a decisive disadvantage of the catalyst combinations described, however, is that they are not as broad and universally applicable as the mercury catalysts and are prone to formulation fluctuations.
  • the titanium catalysts described in WO 2008/1 55569 also have some disadvantages compared with the mercury catalysts. For acceptable results, the addition of an amine-based co-catalyst is necessary. This is a trimerization
  • Catalyst which has negative effects on the physical properties of polyurethanes in certain applications (eg cast elastomers).
  • By varying the mixing ratio of the catalyst components either a very good latency or very good material properties can be achieved, but not both at the same time.
  • the described Catalyst combinations must therefore be matched with regard to their mixing ratio to the respective requirements, ie you can not cover all applications with a combination of catalysts, which is a major disadvantage.
  • thermolatent catalysts based on N-heterocyclic carbenes, which, however, have some significant disadvantages.
  • the preparation of the compounds is very complicated and therefore expensive, which makes the use of the catalysts economically unattractive in most applications.
  • the compounds also catalyze the polyisocyanurate reaction, which in certain applications, e.g. High performance elastomers, must be excluded.
  • thermolatent tin catalysts which, however, have a significant disadvantage.
  • polyurethane reaction mixtures which fall below a certain content of reactive NCO groups, the exothermicity of the uncatalyzed reaction of NCO- with OH groups is not sufficient for the full activation of the thermolatenten catalysts. This is especially true for thin-walled moldings, in the curing of which only relatively low temperatures are achieved due to the large surface area to volume ratio.
  • the system and catalyst should also be free of toxic heavy metals such as cadmium, mercury and lead.
  • the mechanical properties of Shafts of the polyisocyanate polyaddition products are at least at the level of those obtained with mercury catalysts.
  • this object has been achieved by the combination of two blocked at different temperatures, blocked amine and / or amidine catalysts [for example, blocked l, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), l, 4-diazabicyclo [2.2.2] octane (DABCO), l, 5-diazabicyclo [4.3.0] non-5-ene (DBN)] in combination with a metal catalyst.
  • blocked amine and / or amidine catalysts for example, blocked l, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), l, 4-diazabicyclo [2.2.2] octane (DABCO), l, 5-diazabicyclo [4.3.0] non-5-ene (DBN)
  • the switching temperature of a catalyst is considered by the catalyst manufacturers as one of the important product properties (TEDA & TOYOCAT TECHNICAL DATA No. EE-003 (Issue Date 09-02-2004)).
  • Tosoh Corporation determines this switching temperature by differential thermal analysis (DSC) by heating a reaction mixture containing the catalyst at a heating rate of 5 ° C / min in the temperature range of 30 ° C to 250 ° C.
  • the temperature at which the maximum exotherm occurs is usually given as the switching temperature (deblocking temperature).
  • the initial temperature is the temperature at which the exothermic reaction sets in (beginning of the exothermic reaction).
  • the invention relates to polyisocyanate polyaddition products having good mechanical properties, obtainable from a) polyisocyanates and b) NCO-reactive compounds from the group of bl) long-chain polyols having an OH number of 27 to 112 mg KOH / g and a functionality of 1 , 9 to 2.3 and b2) short-chain hydroxyl compounds having an OH number of 300 to 1810 mg KOH / g and a functionality of 1.9 to 2.3 in the presence of c) latent catalysts d) optionally further of c) Catalysts and / or activators with the addition of e) optionally fillers and / or fiber materials f) optionally auxiliaries and / or additives, g) optionally blowing agents characterized in that as latent catalysts (c) mixtures of at least one metal catalyst selected from the group consisting of tin, titanium, zirconium, hafnium, bismuth, zinc, aluminum and iron catalysts and at least two
  • Switching temperature switching amine and / or amidine (T A ) is between 30 ° and 60 ° C and the so-called switching temperature of the other switching at higher switching temperature amine and / or amidine (T max ) between 80 ° C and 150 ° C and the difference between T A and T max is at least 20 ° C and at most 100 ° C, preferably at least 30 ° C and at most 80 ° C, more preferably at least 40 ° C and at most 70 ° C.
  • the low temperature switching amine or amidine may also be a mixture of several amines and / or amidines, each having an initial temperature (T A ) between 30 ° C and 60 ° C.
  • the higher temperature switching amine or amidine may also be a mixture of several amines and / or amidines, each having a switching temperature (T max ) between 80 ° C and 150 ° C.
  • the switching temperature is indicated in TEDA & TOYOCAT TECHNICAL DATA No. EE-003 (Issue Date 09-02-2004).
  • the switching temperature is the temperature at which the maximum exotherm occurs, also referred to as deblocking temperature.
  • the initial temperature is defined as the temperature at which the exothermic reaction begins.
  • the exothermicity is determined by means of differential thermal analysis (DSC) by heating a reaction mixture containing the catalyst at a heating rate of 5 ° C / min in the temperature range from 30 ° C to 250 ° C.
  • DSC differential thermal analysis
  • the metal catalyst used is preferably tin catalysts, more preferably organotin mercaptides, very particularly preferably organotin dimercaptides.
  • the NCO-reactive compounds bl) (long-chain polyols) are preferably polyester polyols, particularly preferably polyester polyols having OH numbers of 27 to 12 mg KOH / g, very particularly preferably 40 to 80 mg KOH / g more preferably from 50 to 70 mg KOH / g.
  • the functionalities are preferably in the range from 1.9 to 2.3, particularly preferably in the range from 1.95 to 2.2, very particularly preferably in the range from 2.0 to 2.15, particularly preferably in the range from 2.02 to 2.09.
  • the short-chain, NCO-reactive hydroxyl compounds b2) are preferably short-chain diols, such as 1, 2-ethanediol, 1, 2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, HQEE (hydroquinone di ( ⁇ -hydroxy) ethyl) ether), HER (resorcinol di ( ⁇ -hydroxyethyl) ether) and / or triols (eg glycerol, trimethylolpropane) and / or tetraols (eg pentaerythritol).
  • diols such as 1, 2-ethanediol, 1, 2-propanediol, 1,3-propanediol, 1,3-butan
  • Particularly preferred short-chain hydroxyl compounds b2) are the short-chain diols, such as 1, 2-ethanediol, 1, 2-propanediol, 1,3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1,6-hexanediol, used; very particular preference is 1, 4-butanediol.
  • the polyisocyanates (a) are preferably NCO prepolymers of diphenylmethane diisocyanate (MDI) and / or carbodiimidized / uretoniminized diphenylmethane diisocyanate and / or allophanatized MDI.
  • MDI diphenylmethane diisocyanate
  • the content of the carbodiimidized / - uretoniminis faced diphenylmethane diisocyanate and / or allophanatized MDI in the prepolymer in the range of 0.02 to 6.5 wt .-%, particularly preferably in the range of 0.4 to 5 wt .-%, most preferably in the range of 0.7 to 2.5% by weight.
  • the 4,4'-isomer of MDI is preferably contained in proportions of 80 to 100 wt .-%, particularly preferably from 95 to 100 wt .-%.
  • the NCO contents are preferably in the range of 12 to 22 wt .-%, more preferably in the range of 14 to 20 wt .-%, most preferably in the range of 15 to 17 wt .-%.
  • the ratio of NCO-reactive to NCO groups is preferably in the range of 0.9 to 1.25, more preferably in the range of 0.92 to 1.00, most preferably in the range of 0.94 to 0.98.
  • Zeolites which are preferably introduced via the NCO-reactive compounds (b) are preferably used as auxiliary agents and additives (f).
  • the hardness of the polyisocyanate polyaddition products is preferably in the range from 50 to 96 Shore A, particularly preferably in the range from 60 to 96 Shore A, very particularly preferably in the range from 60 to 85 Shore A.
  • Another object of the invention is a process for the preparation of the polyisocyanate polyaddition products according to the invention, wherein
  • Polyisocyanates (a) with NCO-reactive compounds (b) in the presence of latent catalysts (c) and optionally additional of (c) different catalysts and / or activators (d) with the addition of optionally blowing agents (g), optionally
  • Fillers and / or fiber materials (e) and optionally auxiliaries and / or additives (f) are reacted, characterized in that as latent catalysts (c) mixtures of at least one metal catalyst selected from the group consisting of tin, titanium, zirconium , Hafnium, bismuth, zinc, aluminum and iron catalysts and at least two blocked, switching at different temperatures amines and / or amidines are used, wherein the so-called initial temperature of a switching at low switching temperature amine and / or amidine (T A ) is between 30 ° and 60 ° C and the so-called switching temperature of the other higher switching temperature switching amine and / or amidine (T max ) is between 80 ° C and 150 ° C and the so-called initial temperature of a switching at low switching temperature amine and / or amidine (T A ) is between 30 ° and 60 ° C and the so-called switching temperature of the other higher switching temperature switching amine and / or amidine (T max ) is between 80
  • T A and T max Difference between T A and T max is at least 20 ° C and at most 100 ° C, preferably at least 30 ° C and at most 80 ° C, more preferably at least 40 ° C and at most 70 ° C.
  • the metal catalyst used is preferably tin catalysts, more preferably organotin mercaptides, very particularly preferably organotin dimercaptides.
  • the blocked amine / amidine TOYOCAT ® DB 30 shows an exotherm from 32 ° C (the beginning of the exothermic reaction) and 57 ° C (maximum exotherm). Accordingly, one finds 41 values of 36 and 69 ° C for TOYOCAT ® DB, DB 60 of 61 and 127 ° C and for DB 70 of 125 and 143 ° C. For non-blocked catalysts such as Dabco 33 LV, these values are 35 and 48 ° C and for DBTL 33 and 54 ° C. For the comparative catalyst Thorcat ® 535, 37 and 94 ° C were determined.
  • the NCO-reactive compounds bl) are preferably polyester polyols, more preferably polyester polyols having OH numbers of 27 to 12 mg KOH / g, very particularly preferably 40 to 80 mg KOH / g, even more preferably 50 to 70 mg KOH / g.
  • the functionalities are preferably in the range from 1.9 to 2.3, particularly preferably in the range from 1.95 to 2.2, very particularly preferably in the range from 2.0 to 2.15, even more preferably in the range from 2, 02 to 2.09.
  • the short-chain, NCO-reactive hydroxyl compounds b2) are preferably short-chain diols such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2 , 3-butanediol, 1,5-pentanediol, 1, 6-hexanediol, HQEE (hydroquinone di (.beta.-hydroxyethyl) ether), HER (resorcinol di (.beta.-hydroxyethyl) ether) and / or triols (eg Glycerol, trimethylol propane) and / or tetraols (eg pentaerythritol).
  • diols such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,3-
  • short-chain hydroxyl compounds b2) are the short-chain diols such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol , very particular preference is 1, 4-butanediol.
  • the polyisocyanates (a) are preferably NCO prepolymers of diphenylmethane diisocyanate (MDI) and carbodiimidized / uretoniminized diphenylmethane diisocyanate and / or allophanatized MDI.
  • MDI diphenylmethane diisocyanate
  • the content of the carbodiimidized / uretoniminêtm diphenylmethane diisocyanate and / or allophanatized MDI in the prepolymer in the range of 0.02 to 6.5 wt .-%, most preferably in the range of 0.4 to 5 wt .-%, even more preferably in the range of 0.7 to 2.5% by weight.
  • the 4,4'-isomer of MDI is preferably contained in proportions of 80 to 100 wt .-%, particularly preferably from 95 to 100 wt .-%. Preference is given to prepolymers based on polyester polyols, more preferably based on polyadipate polyols, very particularly preferably based on poly (butylene-co-ethylene adipate) polyols.
  • the NCO contents are preferably in the range of 12 to 22 wt .-%, more preferably in the range of 14 to 20 wt .-%, most preferably in the range of 15 to 17 wt .-%.
  • the ratio of NCO-reactive to NCO groups is preferably in the range of 0.9 to 1.25, more preferably in the range of 0.92 to 1.00, most preferably in the range of 0.94 to 0.98.
  • the hardness of the polyisocyanate polyaddition products is preferably in the range from 50 to 96 Shore A, particularly preferably in the range from 60 to 96 Shore A, very particularly preferably in the range from 60 to 85 Shore A.
  • the blocked amines and / or amidines are separated via the NCO-reactive compounds b) and the metal catalyst separately, e.g. added via the mixing head.
  • the blocked amines and / or amidines and the metal catalyst are added via the NCO-reactive compounds b).
  • the blocked amines and / or amidines and part of the metal catalyst are added via the NCO-reactive compounds b) and the remainder of the metal catalyst via the mixing head. Also conceivable is a metered addition via the isocyanate component.
  • Another object of the invention are latent catalysts consisting of a mixture of at least one metal catalyst selected from the group consisting of tin, titanium, zirconium, hafnium, bismuth, zinc, aluminum and iron catalysts and at least two blocked, at different Temperatur switching amines and / or amidines, wherein the so-called initial temperature of one switching at low switching temperature amine and / or amidine (T A ) is between 30 ° and 60 ° C and the so-called switching temperature of the other switching at higher switching temperature amine and / or amidine (T max ) is between 80 ° C and 150 ° C and the difference between T A and T max at least 20 ° C and at most 100 ° C, preferably at least 30 ° C and at most 80 ° C, more preferably at least 40 ° C and at most 70 ° C.
  • T A so-called initial temperature of one switching at low switching temperature amine and / or amidine
  • T max switching temperature of the other switching at higher switching temperature amine and / or am
  • Another object of the invention is the use of latent catalysts of the invention for the preparation of polyisocyanate polyaddition products, preferably polyurethane cast elastomers, more preferably solid polyurethane cast elastomers.
  • the solid polyurethane cast elastomers are preferably used for the manufacture of screens, pigs, rollers, wheels, rollers, scrapers, plates, cyclones, conveyor belts, doctor blades, couplings, gaskets, buoys and pumps. They preferably have hardnesses in the range of 50 to 96 Shore A, more preferably in the range of 60 to 96 Shore A, most preferably in the range of 60 to 85 Shore A.
  • Another object of the invention is the use of the polyisocyanate polyaddition products according to the invention for the production of screens, pigs, rollers, wheels, rollers, scrapers, plates, cyclones, conveyor belts, doctor blades, couplings, seals, buoys and pumps.
  • polyisocyanates (a) which are suitable for the preparation of polyisocyanate polyaddition compounds, in particular polyurethanes, are the organic aliphatic, cycloaliphatic, aromatic or heterocyclic polyisocyanates known to the person skilled in the art having at least two isocyanate groups per molecule and mixtures thereof.
  • suitable aliphatic or cycloaliphatic polyisocyanates are di- or triisocyanates, e.g.
  • cyclic systems e.g. 4,4'-methylenebis (cyclohexylisocyanate), 3,5,5-trimethyl-1-isocyanato-3-isocyanatomethylcyclohexane (isophorone diisocyanate, I
  • aromatic polyisocyanates e.g. 1,5-naphthalene diisocyanate, diisocyanatodiphenylmethane (2,2'-, 2,4'- and 4,4'-MDI or mixtures thereof), Diisocyanatomethylbenz- (2,4- and 2,6-Toluylendiiso- cyanat, TDI) and technical Mixtures of the two isomers and l, 3-bis (isocyanatomethyl) - benzene (XDI) can be used.
  • aromatic polyisocyanates e.g. 1,5-naphthalene diisocyanate, diisocyanatodiphenylmethane (2,2'-, 2,4'- and 4,4'-MDI or mixtures thereof), Diisocyanatomethylbenz- (2,4- and 2,6-Toluylendiiso- cyanat, TDI) and technical Mixtures of the two isomers and l, 3-bis (isocyanatomethyl)
  • TODI (3,3'-dimethyl-4,4'-biphenyl diisocyanate)
  • PPDI 1,4-paraphenylene diisocyanate
  • CHDI cyclohexyl diisocyanate
  • polyisocyanate component (a) may be in a suitable solvent. Suitable solvents are those which have sufficient solubility of the polyisocyanate component and are free of isocyanate-reactive groups.
  • solvents examples include acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, methyl isoamyl ketone, diisobutyl ketone, ethyl acetate, n-butyl acetate, ethylene glycol diacetate, butyrolactone, diethyl carbonate, propylene carbonate, ethylene carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, N Methylpyrrolidone, N-ethylpyrrolidone, methylal, ethylal, butylal, 1,3-dioxolane, glycerolformal, benzene, toluene, n-hexane, cyclohexane, solvent naphtha, 2-methoxypropylacetate (MPA).
  • MPA 2-methoxypropylacetate
  • the isocyanate component may also contain conventional adjuvants and admixtures, e.g. Rheology improvers (for example, ethylene carbonate, propylene carbonate, dibasic esters, citric acid esters), stabilizers (for example, Bronsted and Lewis acids such as hydrochloric acid, phosphoric acid, benzoyl chloride, organomercinic acids such as dibutyl phosphate, adipic acid, malic acid, succinic acid, racemic acid or citric acid) UV protectants (for example 2,6-di-butyl-4-methylphenol), hydrolysis protectants (for example sterically hindered carbodiimides), emulsifiers optionally incorporable into the later-to-be-formed polyurethane dyes (which therefore have Zerewitinoff-active hydrogen atoms) and / or color pigments included.
  • Rheology improvers for example, ethylene carbonate, propylene carbonate, dibasic esters, citric acid esters
  • NCO-reactive compounds (b) it is possible to use all compounds known to the person skilled in the art which have an average OH functionality of at least 1.5.
  • These may, for example, low molecular weight polyols b2) such as diols (eg, 1, 2-ethanediol, 1,3- and 1, 2-propanediol, 1, 4-butanediol), triols (eg, glycerol, trimethylolpropane) and tetraols (eg, Penta - erythritol), but also higher molecular weight polyhydroxy bl) such as polyether polyols, polyester polyols, polycarbonate polyols, polysiloxane and polybutadiene.
  • polyether polyols eg, 1, 2-ethanediol, 1,3- and 1, 2-propanediol, 1, 4-butanediol
  • triols eg, glycerol
  • Polyether polyols can be obtained in a manner known per se by alkoxylation of suitable starter molecules under base catalysis or by using double metal cyanide compounds (DMC compounds).
  • Suitable starter molecules for the preparation of polyether polyols are, for example, simple, low molecular weight polyols, water, organic polyamines having at least two NH bonds or any mixtures of such starter molecules.
  • Preferred starter molecules for the preparation of polyether polyols by alkoxylation, in particular by the DMC process are in particular simple polyols such as ethylene glycol, propylene glycol-1, 3 and butanediol-1, 4, hexanediol-1, 6, neopentyl glycol, 2-ethylhexanediol-l , 3, glycerol, trimethylolpropane, pentaerythritol and low molecular weight, hydroxyl-containing esters of such polyols with dicarboxylic acids of the type exemplified below or low molecular weight ethoxylation or propoxylation of such simple polyols or any mixtures of such modified or unmodified alcohols.
  • simple polyols such as ethylene glycol, propylene glycol-1, 3 and butanediol-1, 4, hexanediol-1, 6, neopentyl glycol, 2-eth
  • Alkylene oxides which are suitable for the alkoxylation are, in particular, ethylene oxide and / or propylene oxide, which can be used in any desired sequence or else in a mixture in the alkoxylation.
  • Polyester polyols can be prepared in a known manner by polycondensation of low molecular weight polycarboxylic acid derivatives such as succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, tetrahydrophthalic anhydride, hexahydro-phthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimer fatty acid Trimer fatty acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, citric acid or trimellitic acid, with low molecular weight polyol
  • polyester polyols such as, for example, lactic acid, cinnamic acid or ⁇ -hydroxycaproic acid can also be polycondensed to form polyester polyols.
  • polyester polyols of oleochemical origin can be prepared, for example, by complete ring opening of epoxidized triglycerides of an at least partially olefinically unsaturated fatty acid-containing fat mixture with one or more alcohols having 1 to 12 carbon atoms and subsequent partial transesterification of the triglyceride derivatives to alkyl ester polyols having 1 to 12 carbon atoms be prepared in the alkyl radical.
  • suitable polyacrylate polyols are known per se to the person skilled in the art. They are obtained by free-radical polymerization of hydroxyl-containing, olefinically unsaturated monomers or by free-radical copolymerization of hydroxyl-containing, olefinically unsaturated monomers with optionally other olefinically unsaturated monomers, such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, Cyclohexyl methacrylate, isobornyl methacrylate, styrene, acrylic acid, acrylonitrile and / or methacrylonitrile.
  • olefinically unsaturated monomers such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isoborny
  • Suitable hydroxyl-containing olefinically unsaturated monomers are, in particular, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, the hydroxypropyl acrylate isomer mixture obtainable by addition of propylene oxide onto acrylic acid, and the hydroxypropyl methacrylate isomer mixture obtainable by addition of propylene oxide over methacrylic acid ,
  • Suitable free-radical initiators are those from
  • azo compounds such as azoisobutyronitrile (AIBN)
  • AIBN azoisobutyronitrile
  • peroxides such as di-tert-butyl peroxide
  • Component (bl) may be in a suitable solvent.
  • suitable solvents are those which have sufficient solubility of the component. Examples of such solvents are acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, methyl isoamyl ketone,
  • MPA 2-methoxypropyl acetate
  • the solvents may also carry isocyanate-reactive groups.
  • examples of such reactive solvents are those which have an average functionality towards isocyanate-reactive groups of at least 1.8.
  • These may also be, for example, the low molecular weight polyols b2) such as, for example, the diols (for example 1,2-ethanediol, 1,3- or 1,2-propanediol, 1,4-butanediol) and / or triols (for example glycerol, Trimethylolpropane).
  • Typical latent blocked usable amine and amidine catalysts include catalysts of the Manufacturer Air Products (such as Polycat ® SA-1/10 Dabco KTM 60) and Tosoh Corporation (such as TOYOCAT ® DB 2, DB 30, DB 31, DB 40, DB 41, DB 42, DB 60, DB 70).
  • Examples of typical metal catalysts are salts and organo compounds of the elements zirconium, titanium, tin, copper, lead, bismuth, zinc.
  • the process for preparing the polyisocyanate polyaddition products can be carried out in the presence of customary rheology improvers, stabilizers, UV protectants, catalysts, hydrolysis stabilizers, emulsifiers, fillers, optionally incorporable dyes (which therefore have Zerewitoff-active hydrogen atoms) and / or color pigments. Preference is also given to adding zeolites.
  • auxiliaries and additives are fillers such as, for example, chalk, carbon black flame retardants, color pastes, microbe protection agents, flow improvers, thixotropic agents, surface modifiers, silicone oils, degassing aids and retarders in the preparation of the polyisocyanate polyaddition products, most preferably zeolites.
  • fillers such as, for example, chalk, carbon black flame retardants, color pastes, microbe protection agents, flow improvers, thixotropic agents, surface modifiers, silicone oils, degassing aids and retarders in the preparation of the polyisocyanate polyaddition products, most preferably zeolites.
  • the latent catalysts can be used for the preparation of polyisocyanate polyaddition products, especially polyurethane elastomers such as coatings, adhesives and sealants, cast elastomers, resins and binders. Preference is given to the inventive latent Catalysts used for the production of polyurethane cast elastomers, particularly preferably for the production of solid polyurethane cast elastomers.
  • MDQ 23165 MDI prepolymer of Fa Baule SAS, constructed from poly (ethylene-co-butylene) adipate hydroxyl number 56 mg KOH / g, Desmodur ® 44M and Desmodur CD-S with a proportion of carbodiimidized / MDI uretonimininstrumentem of about 2% by weight and an NCO content of 16.4 wt .-%.
  • Desmodur ® 44M polyisocyanate from Bayer MaterialScience AG with an NCO content of about 33.5 wt .-%..
  • Desmodur ® CD-S polyisocyanate (carbodiimidated / uretonimin analystes diphenylmethane diisocyanate based on the 4,4-isomer) from Bayer Material Science AG and having an NCO content of about 29.5 wt .-% and a. Proportion of carbodiimidized / uretonimi- nized MDI of approx. 23.5% by weight.
  • Baytec® ® D20 Polyadipatpolyol from Bayer Material Science with hydroxyl.
  • Dabco KTM 60 switchable amine of the company Air Products, which according to the manufacturer at 60 ° C switched / latent.
  • TIB KAT 214 (Dioctylzinndimercaptid) from TIB Chemicals AG, Mannheim.
  • Polyol 1 a mixture of 98.002 parts Baytec ® D20, 1.96 parts UOP L-paste 0.01 parts
  • Example 2 Preparation of a casting elastomer having a hardness of 85 Shore A 100 parts by weight of MDQ 23165 (preheated to 45 ° C.) with 80 parts by weight of polyol 1 (preheated to 60 ° C.), 13.6 parts by weight of 1 4-butanediol (preheated to 45 ° C) and, 0.0005 wt .-% (based on total formulation) TIB KAT 214 mixed and poured into a preheated to 80 ° C mold. It was removed from the mold after about 30 minutes and post-baked in the heating cabinet at 80 ° C. for 16 hours. The properties were determined after 1 week storage at room temperature. The hardness was determined to be 85 Shore-A. This hardness is typical for hard screen coverings and pig discs. Further mechanical properties see table 1.
  • the demolding time was in all examples at about 30 min.
  • the cast elements were inhomogeneous and schlierenhaltig regardless of the amount of catalyst.
  • the hardness was lower by 3-5 Shore A units. The hardness varied with the layer thickness.
  • the cast elements were inhomogeneous and schlierenhaltig regardless of the amount of catalyst.
  • the hardness was lower by 3-5 Shore A units. The hardness varied with the layer thickness.
  • Ad. 13 The dissolution time was significantly longer than in the other examples 1 to 6 (about 30 min.), And there were inhomogeneous zones.
  • Ad. 14 The hardness was lower by 3-5 Shore A units than the samples of Examples 3 and 6 prepared with the same butanediol content.
  • Ad. 15 The dissolution time (> 60 min.) Was significantly longer than in Examples 1 to 6 (approximately 30 min.), And inhomogeneous zones appeared.
  • Ad 16 The hardness was lower by 3-5 Shore A units than the samples of Examples 3 and 6 prepared with the same butanediol content.
  • Table 2 shows that with the catalyst combinations used in these comparative examples in no case can polyurethanes with the good properties can be prepared, as can be prepared with the novel catalysts [Examples 1 to 3 (Table 1)].
  • the results of Examples 1-3 also show that the pouring times compared to the Comparative Examples 4 to 6 (Thorcat ® 535 catalysis) are the same or extended with otherwise the same recipe, which is a great advantage.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne des produits de polyaddition de polyisocyanate, un procédé pour leur production et leur utilisation.
EP11701278A 2010-02-02 2011-01-28 Produits de polyaddition de polyisocyanate, procédé pour leur production et leur utilisation Withdrawn EP2531538A1 (fr)

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EP3392284A1 (fr) 2017-04-18 2018-10-24 Covestro Deutschland AG Produit pultrudé, sa fabrication et son utilisation
WO2020200885A1 (fr) 2019-03-29 2020-10-08 Covestro Intellectual Property Gmbh & Co. Kg Boîtier de batterie et son utilisation dans des véhicules électriques
WO2022013182A1 (fr) 2020-07-15 2022-01-20 Covestro Deutschland Ag Système réactif à base de polyuréthane pour la pultrusion

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