WO2003085021A1 - Systemes catalyseurs contenant des catalyseurs incorpores dans de la cire - Google Patents

Systemes catalyseurs contenant des catalyseurs incorpores dans de la cire Download PDF

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Publication number
WO2003085021A1
WO2003085021A1 PCT/EP2002/003986 EP0203986W WO03085021A1 WO 2003085021 A1 WO2003085021 A1 WO 2003085021A1 EP 0203986 W EP0203986 W EP 0203986W WO 03085021 A1 WO03085021 A1 WO 03085021A1
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Prior art keywords
catalyst
wax
catalyst system
weight
groups
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PCT/EP2002/003986
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German (de)
English (en)
Inventor
Martin Kreyenschmidt
Ekkehard Jahns
Original Assignee
Basf Aktiengesellschaft
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Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to DE10296717T priority Critical patent/DE10296717D2/de
Priority to AU2002302522A priority patent/AU2002302522A1/en
Priority to PCT/EP2002/003986 priority patent/WO2003085021A1/fr
Publication of WO2003085021A1 publication Critical patent/WO2003085021A1/fr

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    • 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
    • B01J33/00—Protection of catalysts, e.g. by coating
    • 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

Definitions

  • the invention relates to catalyst systems comprising at least one catalyst c) which catalyzes a reaction of polyisocyanates a) with compounds b) with at least two hydrogen atoms reactive toward isocyanate groups and is embedded in wax, a wax with polar groups being used.
  • the invention further relates to the use of the catalyst system for the production of polyisocyanate polyadducts, in particular elastic, cellular and compact polyurethanes, and to a process for their production.
  • the conversion of polyisocyanates to polyisocyanate polyaddition products, in particular to polyurethanes, is generally carried out in the presence of catalysts.
  • the reaction profile of a polyurethane system is largely controlled by the type and amount of the catalysts used.
  • the type and amount of the catalysts used on the one hand determines the start of the reaction after mixing the isocyanate and polyol components and on the other hand controls the demolding times of the molded part to be produced.
  • the demolding time describes the period of time after which a workpiece can be removed from the mold without being damaged during this process.
  • the demolding time is largely determined by the amount of catalysts used and should be as short as possible for economic reasons.
  • the amount of catalysts used in a PUR system cannot be increased arbitrarily, since the catalysis also significantly influences the start times of the systems. Above a certain catalyst concentration, which is specified by the system and the type of mechanical processing, the amount of catalyst can no longer be increased, since otherwise the system already reacts when the components are mixed. In these cases, processing is no longer possible.
  • Many polyurethane processors also demand that the system's start times should be as long as possible. The reason for this are increasingly complex and larger tools. It is to be avoided that in the case of large tools, material is still poured into the closed mold while the material filled in at the beginning is already reacting, since this leads to problems in the finished component. In addition, in the case of large components, the polyurethane is often inserted into the open mold; here too, the shot times are long and long Shot weights to ensure that the system does not react before all PUR has been entered into the mold and the tool is closed.
  • Acid-blocked tertiary amines are known in the prior art to achieve short demolding times, long open times and large flow paths.
  • the reaction of a tertiary amine catalyst with an acid produces an ammonium salt that is catalytically inactive.
  • the resulting heat of reaction in the reacting PUR system shifts the equilibria between salt and free amine or acid to the side of the free amines and activates the catalyst.
  • the significant disadvantage of these systems lies in the fact that combinations of amine catalysts are usually present in the PUR systems and that only one blocked catalyst leads to the formation of different acid-base equilibria between the catalysts.
  • the reaction profile of the entire system is influenced and a constant processing ability cannot be guaranteed.
  • the dissociation temperatures are often so high that the catalyst is only released to a limited extent.
  • this technology cannot block highly effective organometallic catalysts.
  • the acid partially released in the system leads to corrosion on the processing machine.
  • GB-B-1, 035.903 discloses a process for the production of polyurethane foams, wherein a catalyst encapsulated in a protective cover is used.
  • the protective sheath has a melting point of 30 to 40 ° C, serves to improve the storage stability of the system before implementation and is preferably removed by shear forces during mixing, dielectric heating or ultra-sound waves.
  • GB-B-1, 035, 903, gives no indication that the catalyst is only released by the heat of reaction which arises and that a faster reaction behavior over a long processing window is influenced by the particle size of the encapsulated catalysts.
  • GB-B-1, 053, 500 relates to a process for the production of polyurethanes by using isocyanates encapsulated in a protective layer.
  • the document discloses a large number of substances, including paraffin waxes.
  • GB-B-1, 053, 500 discloses that a small particle size of the encapsulated isocyanates is advantageous, in particular from 0.1 to 20 ⁇ m.
  • GB-B-1, 053, 500 does not teach that a larger particle size is advantageous in view of the polyurethane reaction.
  • GB-B-1, 053, 500 also does not disclose that catalysts are encapsulated in a protective layer.
  • the invention was based on the object of providing a catalyst system for the production of polyisocyanate polyaddition products, in particular polyurethanes, which has little effect on the start times of the systems but accelerates the curing behavior of the materials and thus the demolding times and similar parameters, such as the buckling times with integral foams, significantly reduced.
  • a way should be found to generate longer start times from PUR system, whereby the demolding times are not changed.
  • Another object of the invention was to provide a catalyst system which has the advantages mentioned above and comprises organometallic catalysts.
  • a c) catalyst suitable for the production of polyisocyanate polyaddition products is embedded in wax, the type of wax and the size of the resulting particles being selected such that the wax melts as a result of the heat of the polyurethane reaction used and releases the catalyst, ie the catalyst is not released, as in the prior art, by tearing open the encapsulation during mixing, by dielectric heating or by ultrasound.
  • the present invention therefore relates to a catalyst system comprising at least one catalyst c) which catalyzes a reaction of polyisocyanates a) with compounds b) with at least two hydrogen atoms which are reactive toward isocyanate groups and is embedded in wax, the wax having one or more polar atoms Contains groups and has a heat of fusion of 50 to 250 joules / gram.
  • the invention further relates to processes for the preparation of the catalyst system according to the invention.
  • the invention also relates to the use of the catalyst system according to the invention for the production of polyisocyanate polyaddition products, in particular polyurethanes.
  • the invention relates to a process for the preparation of polyisocyanate polyadducts by reacting
  • polyisocyanates with b) high molecular weight compound with at least two hydrogen atoms reactive towards isocyanate groups, in the presence of the c) catalyst system according to the invention and, if appropriate d) blowing agents, e) chain extenders and f) auxiliary substances or additives.
  • the present invention also relates to the polyisocyanate polyaddition products obtainable by this process.
  • wax is understood to mean compounds whose melting point is generally between 20 ° C. and 150 ° C., preferably between greater than 40 ° C. and less than 130 ° C.
  • the waxes of the present invention are generally kneadable or solid to brittle hard in the solid state, but not glassy.
  • the waxes of the present invention are relatively low viscous slightly above the melting point and preferably not stringy.
  • the waxes used contain one or more polar groups, so that the compatibility between wax and catalyst is increased.
  • Polar groups are groups that have a different electro-negativity compared to a pure hydrocarbon group. In general, oxygen atoms, nitrogen atoms, sulfur atoms and optionally halogen atoms can serve as the basis for polar groups. Pure alkane or paraffin waxes are not included in the present invention because they have no polar groups in the sense of the present invention.
  • the waxes are generally polymeric substances.
  • the polar groups can be present at the end and / or within the polymer. Examples of polar groups are acid, A in, imine, aid, ether, ester, acetate, keto, aldehyde or alcohol group.
  • the waxes used in the present invention have a heat of fusion of 50 to 250 joules / gram, preferably 100 to 200 joules / gram, in particular 120 to 190 joules / gram.
  • the heat of fusion is measured in accordance with ISO 11357-3 using the DSC (differential scanning caloremetry) method.
  • the polar group-containing wax is selected so that the heat of fusion of the wax is only slight, i.e. 20% by weight, of the catalyst component c). not more than 20%, preferably not more than 15%, particularly preferably not more than 10%, compared to the heat of fusion of the pure wax.
  • waxes includes natural waxes, chemically modified waxes and synthetic waxes, provided that they meet the above criterion of the polar groups.
  • Natural waxes include vegetable waxes such as montan wax, animal waxes such as beeswax, mineral waxes and petrochemical waxes such as petrolatu.
  • Chemically modified waxes include, for example, hard waxes such as montan ester waxes.
  • Synthetic waxes include, inter alia, polar alkane waxes, such as, for example, wax alcohols, in particular higher molecular weight water-insoluble fatty alcohols with preferably more than 12 carbon atoms, such as, for example
  • Lignoceryl, ceryl ,, myricyl Melissyl alcohol and polyalkylene oxides such as polyethylene oxide, poly-THF, polyvinyl ether waxes, polyolefin copoly waxes and oxidized polyolefin waxes.
  • waxes also includes higher molecular weight fatty acids, preferably with at least 9 carbon atoms, such as behenic acid, tetracosanoic acid and cerotic acid, which can optionally be esterified with alcohols, and high molecular weight polyesters with a molecular weight of> 1000 g / mol, preferably> 1500 g / mol which are obtainable by reacting di- or polycarboxylic acids having 2 to 20 carbon atoms with di- or polyalcohols having 2 to 30 carbon atoms, it being possible for the corresponding acids or alcohols to contain aliphatic and / or aromatic structural units. Mixtures of the waxes mentioned above can also be used.
  • polar polyolefin waxes are used.
  • the following are used as polyolefins: polyethylene, polypropylene, polybut-1-ene and copolymers of ethylene with 0 to 20 mol% of propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene or 1-undecene , Polyethylene wax with 0 to 10 mol% of propene, 1-butene, 1-pentene or 1-hexene is preferred.
  • the average molecular weight M w of these polyolefin waxes are from 500 to 20,000 g / mol, preferably from 2,000 to 15,000 g / mol and particularly preferably 3,000 to 10,000 g / mol.
  • Polar groups can generally be introduced into a wax by different process steps.
  • a preferred method is to partially break down the wax, for example by means of atmospheric oxygen or peroxide compounds, so that so-called oxidized polyolefin waxes are obtained.
  • hydrogen peroxide (H 2 O 2 ) or dialkyl peroxides can be used as peroxide compounds. Partial degradation methods introduce hydroxyl groups and carboxyl groups into the macromolecules as polar groups.
  • Oxidized polyolefin waxes are preferably used which have an acid number of at most 50, preferably from 10 to less than 50.
  • Another preferred method is to use polar comonomers such as acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester or vinyl acetate, which can optionally be saponified, and so-called copolymer-polyolefin waxes are obtained.
  • polar comonomers such as acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester or vinyl acetate, which can optionally be saponified, and so-called copolymer-polyolefin waxes are obtained.
  • Ethylene-vinyl acetate waxes with an M w of from 2000 to 15000 g / mol, in particular from 3000 to 10000 g / mol, and a content of 0.1 to 25% by weight of vinyl acetate, particularly preferably from 1 to 15, are preferably used % By weight of vinyl acetate, based on the total weight of the copolymer.
  • ethylene-acrylic acid waxes with a 1 of 2000 to 15000 g / mol, in particular from 3000 to 10000 g / mol, and a content of 0.1 to 20% by weight of vinyl acetate, particularly preferably from 1 to 15% by weight of acrylic acid, based on the total weight of the copolymer.
  • ethylene-acrylic acid-acrylate terpolymer waxes are used. These have an acrylic acid content of 0.1 to 20% by weight, preferably 1 to 5% by weight and an acrylate content of 0.1 to 40% by weight, preferably 1 to 20% by weight, with the proviso that the total content of acrylate and acrylic acid is below 50% by weight, preferably below 40% by weight, based on the total weight of the terpolymer.
  • polyether waxes are used. These generally have a molecular weight M w of 10,000 to 50,000 g / mol, preferably from 15,000 to 35,000 g / mol. Particularly suitable are polyvinyl ether waxes, for example poly-octadecyl vinyl ether or corresponding polyethers which have a 16, C17, C19, C20, C21 or C22 radical instead of an octadecyl radical.
  • monan waxes and montan ester waxes are used. These are based on long-chain fatty acids, generally made up of hydrocarbon chains with 20 to 40 carbon atoms, preferably with 30 to 36 carbon atoms.
  • polyisocyanate polyadducts includes addition products which generally contain urethane allophanate, urea, biuret, uretdione, A id, isocyanurate, carbodiimide and / or uretonimine groups. Urethane and urea groups are preferred.
  • the polyisocyanate polyaddition products according to the invention can be compact or cellular.
  • the polyisocyanate polyaddition products are flexible, rigid, semi-rigid or integral foams made of polyurethane or compact, preferably thermoplastic polyurethanes and / or cast elastomers.
  • the polyisocyanate polyaddition products can be produced as molded articles, for example as shoe soles.
  • the catalyst system according to the invention contains a catalyst c) which catalyzes a reaction of polyisocyanates a) with compounds having at least two hydrogen atoms b) which are reactive toward isocyanate groups, or mixtures thereof, comprising at least two different catalysts.
  • catalysts which catalyze a reaction of isocyanate with an OH-functional group to form a urethane bond so-called crosslinking catalysts
  • catalysts which in particular support the reaction of water with isocyanate to give carbaramic acid so-called blowing catalysts.
  • a mixture of crosslinking catalysts and blowing catalysts is also preferred.
  • organic amines such as triethylamine, triethylene diamine, tributylamine, dimethylbenzylamine, N, N, N ', N'-tetramethylethylene diamine, N, N, N', N'-tetramethylbutane diamine, N, N, N ', N' -tetramethyl-hexane-1, 6-diamine, dimethylcyclohexylamine, pentamethyldipropylenetriamine, pentamethyldiethylene triamine, 3-methyl-6-dimethylamino-3-azapentol, dimethylaminopropylamine, 1, 3-bisdimethylaminobutane, bis - (2-dimethylaminoethyl) ether, N, N, trimethyl-N-hydroxyethyl-bis (aminoethyl ether), triethylene glycol diamine, N- (2hydroxyethoxyethyl) -2-azanorbonane, N, N, N-N-
  • organic metal compounds can be used as catalysts for this purpose, preferably organic tin compounds, such as tin (II) salts of organic carboxylic acids, for example tin (II) acetate, tin (II) octoate, tin ( II) ethyl hexoate and tin (II) laurate and the dialkyltin (IV) salts of organic carboxylic acids, for example dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate.
  • tin (II) salts of organic carboxylic acids for example tin (II) acetate, tin (II) octoate, tin ( II) ethyl hexoate and tin (II) laurate
  • dialkyltin (IV) salts of organic carboxylic acids for example dibutyltin dia
  • Potassium salts of carboxylic acids such as, for example, may also be used Potassium acetate, and metal catalysts, ⁇ comprising bismuth iron or zirconium compounds, such as iron acetylacetonate, can be used.
  • the mixtures can preferably contain tertiary aliphatic and / or cycloaliphatic amines.
  • Mixtures which contain both catalysts based on amine and catalysts based on organic metal compounds can furthermore preferably be used as the catalyst.
  • the catalyst component c) to be encapsulated can also contain emulsifiers, acids, preferably carboxylic acids or alkylsulfonic acids, and / or alcohols, preferably alcohols which are solid at room temperature, particularly preferably phenol.
  • Emulsifiers increases the compatibility of the catalyst with the wax.
  • Emulsifiers are usually used in an amount of 0.2 to 100% by weight, preferably 0.5 to 90% by weight, based on the total weight of the non-embedded catalyst component c).
  • Preferred emulsifiers are long-chain mono- or multi-functional carboxylic acids, long-chain alkyl sulfonates, reaction products of alkyl maleic anhydride copolymers with mono- or ultimate functional polyethylene oxides or mono- or multi-functional polyisobutylenes, polybutylenes or their hydrogenated derivatives, and also diblock copolymers different polar chains, reaction products of mono- or multifunctional long-chain carboxylic acids with mono- or multi-functional polyethylene oxides.
  • carboxylic acids can also increase the compatibility of the catalyst with the wax and increase the effect of the catalyst blocking.
  • Long-chain saturated carboxylic acids are preferably used, ie CH 3 - (CH) n-COOH
  • Carboxylic acids are usually used in an amount of 0.2 to 100%, preferably 0.5 to 90% by weight, based on the total weight of the non-embedded catalyst component c).
  • the catalysts c) are generally dissolved or suspended in heated liquid wax. If necessary, a solution Intermediates are added, which gives a better solution of the catalyst in the wax.
  • the mixture of liquid wax and catalyst is now preferably cooled and dispersed in a polar liquid. If necessary, a dispersant can be added to the melt before this step, which leads to an advantageous dispersion.
  • the dispersion is carried out in such a way that the catalyst system according to the invention is in particulate form, comprising particles with an average particle diameter of from 10 to 500 ⁇ m, preferably more than 100 ⁇ m to less than 500 ⁇ m, more preferably from 110 to 480 ⁇ m, particularly preferably from 120 to 300 ⁇ m.
  • the mean particle diameter which is also referred to as the dso value of the integral mass distribution, is defined in the context of this invention as the particle diameter at which 50% by weight of the particles have a smaller diameter than the diameter which corresponds to the dso value. Likewise, 50% by weight of the particles then have a larger diameter than the dso value.
  • the particle diameter was determined by light microscopic measurement, with spherical particles being estimated for the equivalent sphere diameter.
  • Any liquid in which the wax is insoluble is generally suitable as the polar liquid.
  • Water or b) a compound having at least two hydrogen atoms reactive toward isocyanate groups is preferably used.
  • a polyol, in particular a polyetherol, is preferably used as the component, particularly preferably the polyol used in the production of polyisocyanate polyadducts. The use of this polyol is advantageous because it does not introduce any foreign matter into the system and, in the case of cellular products, a possible destabilization of the foam by foreign matters can be avoided.
  • compounds which, e.g. Can build hydrogen bonds to the catalysts c) and thereby improve solubility For example, polar polymers, such as e.g. Polyethylene oxide or polypropylene oxide or mixed polyether from ethylene oxide and propylene oxide.
  • the solubilizer is usually used in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the weight of wax and catalyst c).
  • Suitable dispersants are generally amphiphilic molecules which have a hydrophobic part compatible with the wax and a hydrophilic part with the polar liquid have an acceptable part.
  • stearic acid can be used.
  • the dispersant is usually used in an amount of 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the weight of wax and catalyst c).
  • the liquid mixture of catalyst c) and heated wax can be brought directly into a suitable, particulate form by spraying in an air stream, preferably a cold air stream, so that a, preferably granular, Powder is obtained.
  • an apparatus similar to a spray dryer is suitable, but is preferably operated with a cold air stream.
  • the catalyst system dispersed in the polar liquid can also be freeze-dried. The catalyst dispersion is first frozen and the dispersant is removed in vacuo. A dry powder is obtained. The average particle diameter of the resulting catalyst system can be adjusted by varying the temperature and thus the viscosity and the nozzle pressure.
  • Both methods are preferably carried out in such a way that they form powders comprising particles having an average particle diameter of 10 to 500 ⁇ m, preferably more than 100 ⁇ m to less than 500 ⁇ m, more preferably 110 to 480 ⁇ m, particularly preferably 120 to 300 ⁇ m.
  • the term "embed” is not within the scope of this invention. encapsulation in the strict sense, i.e. In the middle of the particulate catalyst system particle there is only catalyst which is surrounded by a layer which consists exclusively of wax, but rather is an embedding of the catalyst component c) by dissolving or dispersing in a, preferably well crystallizing, wax, i.e. a particle of the catalyst system according to the invention cannot be illustrated by a catalyst core / wax shell model, but consists of a wax matrix which contains the catalyst component c).
  • the matrix structure of the particles described above makes it possible that the catalyst is not already released by the shear forces occurring in the mixing head, in contrast to GB-1, 035, 903, where the protective cover is torn open during mixing.
  • the catalyst systems according to the invention can advantageously be used for the production of polyisocyanate polyaddition products, in particular polyurethanes.
  • the catalyst systems according to the invention make it possible to tailor the reaction profile, for example of a PUR system.
  • the catalysts c) embedded in the wax have almost no influence on the start times of the system. However, heat is released in the course of the reaction, the wax melts above a defined temperature and releases the catalyst. Depending on the melting point of the wax used, the catalyst can be released at a different time on the reaction coordinate. The increased catalyst concentration generally leads to significantly shorter demolding times.
  • a catalyst c) is used, part or all of the amount of catalyst c) being embedded in wax, i.e.
  • a conventional catalyst which is not embedded in wax can also be used.
  • the ratio of conventional catalyst to catalyst according to the invention is not restricted, in general it is from 0 to 3: 1, preferably from 0.1 to 1: 1.
  • the catalyst system according to the invention generally comprises 1 to 95% by weight, preferably 5 to 80% by weight, particularly preferably 10 to less than 50% by weight, in particular 10 to 45% by weight, of catalyst component c), the weight being given for component c) optionally also includes emulsifiers and other substances listed above, and 5 to 99% by weight, preferably 20 to 95% by weight, particularly preferably more than 50 to 90% by weight, in particular 55 to 90% by weight . ⁇ % Wax, based on the total weight of the catalyst system.
  • a proportion of less than 50% by weight of catalyst c) generally leads to more advantageous properties.
  • the polyisocyanates used include the aliphatic, cycloaliphatic and aromatic isocyanates known from the prior art. Examples are 4,4'-diphenylmethane diisocyanate, the mixtures of monomeric diphenylmethane diisocyanate and higher-core homologues of diphenylmethane diisocyanate (poly er-MDI), tetramethylene diisocyanate, tetramethylene diisocyanate trimers, hexamethylene diisocyanate, hexamethylene diisocyanate trimethane diisocyanate Trimer, 4 > 'methylene bis (cyclohexyl) diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, dodecyl diisocyanate, lysinalkyl ester diisocyanate, where alkyl is Ci to C ⁇ o, 2,2,4- or 2,4,4-tri -
  • polyisocyanates with NCO groups of different reactivity such as 2,4-tolylene diisocyanate (2,4-TDI), 2,4'-diphenylmethane diisocyanate (2,4 '-MDI), triisocyanatotoluene, isophorone diisocyanate (IPDI), 2-butyl -2-ethylpentamethylene diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 3 (4) -isocyanato-10 methyl-1-methylcyclohexyl-isocyanate, 1, 4-diisocyanato-4-methylpentane, 2,4'-methylenebis (cyclohexyl) diisocyanate and 4-methylcyclohexane-1,3-diisocyanate (H-TDI) can be used.
  • 2,4-tolylene diisocyanate (2,4-TDI)
  • 4, 4'-Diphenyl-15-methane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate (IPDI) and naphthylene diisocyanate (NDI) are preferably used as polyisocyanates.
  • 4, 4 '-MDI is particularly preferably used.
  • Compounds which have two or more reactive groups selected from OH groups, 25 SH groups, NH groups, NH 2 groups and CH-acidic groups, such as, for example, are suitable as compounds having at least two hydrogen atoms b) which are reactive toward isocyanate groups ß-Diketo groups, carry in the molecule.
  • Polyether polyamines and / or preferably polyols selected from the group of polyether polyols, polyester polyols, polythioether polyols, polyester amides, hydroxyl group-containing polyacetals and hydroxyl group-containing aliphatic
  • polyester polyols and / or polyether polyols are preferably used.
  • the hydroxyl number of the polyhydroxyl compounds is generally 10 to 1000 and preferably 20 to 300.
  • compounds b) having at least two H atoms reactive toward isocyanate groups are polyether polyols. They are by known methods, for example by anionic polymerization with alkali metal hydroxides or
  • alkali alcoholates as catalysts and with the addition of at least one starter molecule which contains 2 to 3 reactive hydrogen atoms bonded with one or more alkylene oxides 2 to 4 carbon atoms in the alkylene radical are produced.
  • Suitable alkylene oxides are, for example, tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide and preferably ethylene oxide and 1,2-propylene oxide.
  • the alkylene oxides can be used individually, alternately in succession or as mixtures. Mixtures of 1,2-propylene oxide and ethylene oxide are preferred, the ethylene oxide being used in amounts of 10 to 50% as an ethylene oxide end block (“EO-cap”), so that over 70% of the resulting polyols have primary OH end groups ,
  • Suitable starter molecules are water or dihydric and trihydric alcohols, such as ethylene glycol, 1,2-propanediol, 2,3 and 1,3, diethylene glycol, dipropylene glycol, 1,4-butanediol, glycerol, trimethylolpropane etc.
  • the polyether polyols, preferably Polyoxypropylene polyoxyethylene polyols have a functionality of 2 to 3 and molecular weights of 1000 to 8000, preferably 2000 to 7000.
  • polyetherols are polymer-modified polyether polyols, preferably graft polyether polyols, in particular those based on styrene and / or acrylonitrile, which are prepared by in situ polymerization of acrylonitrile, styrene or preferably mixtures of styrene and acrylonitrile.
  • Polyester polyols are also suitable. These can be prepared, for example, from organic dicarboxylic acids with 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids with 4 to 6 carbon atoms, polyhydric alcohols, preferably diols, with 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms.
  • suitable dicarboxylic acids are: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid.
  • the dicarboxylic acids can be used both individually and in a mixture with one another.
  • dicarboxylic acid derivatives such as, for example, dicarboxylic acid esters of alcohols having 1 to 4 carbon atoms or dicarboxylic acid anhydrides, can also be used.
  • Dicarboxylic acid mixtures of succinic, glutaric and adipic acid and aromatic diacids are preferably used.
  • dihydric and polyhydric alcohols examples are: ethanediol, diethylene glycol, 1,2- or 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,1 10-decanediol, glycerol and trimethylolpropane, and also dialcohols which contain aromatic or aliphatic ring systems, such as 1,4-bisdihydroxymethylbenzene or 1,4-bisdihydroxyethylbenzene.
  • Ethanediol is preferably used, Diethylene glycol, 1,4-butanediol, 1, 5-pentanediol and 1, 6-hexanediol. Also possible to use P 'olyesterpolyole from lactones, eg ⁇ -caprolactone or hydroxycarboxylic acids, eg ⁇ -hydroxy caproic acid. Mixing systems which contain both polyesterols and polyetherols can also be used.
  • blowing agents are necessary for the production of cellular polyisocyanate polyaddition products.
  • Water is preferably used as blowing agent d). Since components b) and optionally e) may have water due to their preparation and / or chemical composition, in some cases it is not necessary to add water separately to components b) and e) or the reaction mixture. If water has to be added to the polyurethane formulation to achieve the desired density, this is usually added in amounts of 0.05 to 4.0% by weight. preferably from 0.1 to 3.0% by weight and in particular from 0.3 to 2.5% by weight, based on the weight of components a) and b) and optionally e).
  • Low-boiling liquids which evaporate under the influence of the exothermic polyaddition reaction and advantageously have a boiling point under normal pressure in the range from -40 to 120 ° C., preferably from 10 to 90 °, can also be used as blowing agent d) instead of water or preferably in combination with water C, or gases are used.
  • blowing agent d) alkanes, cycloalkanes or mixtures having a boiling point of -40 to 50 ° C. under atmospheric pressure from alkanes and • cycloalkanes are preferably used.
  • the liquids of the above-mentioned type and gases suitable as blowing agents can e.g. selected from the group of alkanes such as Propane, n- and iso-butane, n- and iso-pentane and preferably the technical pentane mixtures, cycloalkanes and cycloalkenes such as e.g. Cyclobutane, cyclopentene, cyclohexene and preferably cyclopentane and / or cyclohexane and gases such as e.g. Nitrogen, carbon monoxide and noble gases such as Helium, neon and krypton.
  • alkanes such as Propane, n- and iso-butane, n- and iso-pentane and preferably the technical pentane mixtures
  • cycloalkanes and cycloalkenes such as e.g. Cyclobutane, cyclopentene, cyclohexene
  • blowing agents are salts which decompose thermally, such as, for example, ammonium bicarbonate and / or ammonium carbamate, or compounds which form such salts in situ, such as, for example, aqueous ammonia and / or amines and carbon dioxide, and ammonium salts of organic carboxylic acids, such as, for example Monoammonium salts of malonic acid, boric acid, formic acid or acetic acid.
  • HFC-245fa ® Honeywell
  • HFC365mfc ® Solvay
  • ⁇ 5 chain extender e) may also function both as a chain extender as a crosslinking agent, it low molecular weight include, polyhydric alcohols, preferably diols and / or triols having molecular weights of less than 400 Da, preferably from 60 to 300 Da, particularly preferably from 60 to
  • aliphatic, cycloaliphatic and / or araliphatic diols such as e.g. Alkanediols with 2 to 14, preferably 2 to 6 carbon atoms and / or dialkylene glycols with 4 to 8, preferably 4 to 6 carbon atoms, such as e.g. Ethylene glycol, propanediol-1, 3, decanediol-1, 10,
  • triplets e.g. 1,2,4-, 1,3, 5-trihydroxycyclohexane, trimethylolethane, glycerin and trimethylolpropane.
  • Diols and mixtures thereof are preferably used.
  • auxiliaries and additives can be added in the process according to the invention for the production of polyisocyanate polyadducts f).
  • auxiliaries and / or additives are surface-active substances, foam stabilizers, cell regulators, external and internal release agents, fillers and reinforcing materials, such as glass fibers, dyes, pigments, flame retardants, hydrolysis stabilizers, antioxidants, abrasion improvers, fungistatic and bacteriostatic substances.
  • the polyisocyanates a) are reacted with b) compounds having at least two hydrogen atoms which are reactive toward isocyanate and optionally e) chain extenders in amounts such that the equivalence ratio of NCO groups of the a) polyisocyanates to the sum of the reactive Hydrogen atoms of components b) and optionally e) 1: 0.5 to 1: 3.50 (corresponding to an isocyanate index of 50 to 350), preferably 1: 0.65 to 1: 1.30 and particularly preferably 1: 0.9 to 1: 1.15.
  • catalyst c) In general, 0.01 to 15% by weight, preferably 0.1 to 8% by weight, particularly preferably 0.5 to 4% by weight, of catalyst c) is used, based on the weight of components a) and b ) and possibly e).
  • the polyisocyanate polyaddition products are usually produced by the known one-shot or the likewise known prepolymer process.
  • a prepolymer is usually produced from a) and b) in a first step, preferably a prepolymer containing isocyanate groups, which is then reacted with further b) to give the desired products.
  • the starting components are usually mixed at a temperature of 0 ° C. to 100 ° C., preferably 15 ° C. to 70 ° C., and are reacted, for example, in a mold.
  • the mixing can take place, for example, mechanically by means of low-pressure technology or high-pressure technology, or by other mixing methods which are used in conventional PUR processing machines.
  • the polyisocyanate polyaddition products produced by the process according to the invention can be used as moldings.
  • Suitable PU systems are, for example, soft, soft integral, semi-rigid and rigid foams.
  • 640 g of polyoctadecyl vinyl ether with a melting point of about 15 ° C. and 160 g of diazabicycloundecane (DBU) were introduced.
  • the template was melted with stirring at 90 ° C. at 95 ° C. in an HWS vessel and conveyed to the nozzle in the paddle dryer by means of a prominent pump via a hose feed and at the same time sprayed with preheated nitrogen.
  • 20 cold nitrogen was blown into the paddle dryer to convey fine particles out of the dryer.
  • the paddle dryer was cooled in this example. Particles with a particle size of approximately 110 to 250 ⁇ m were obtained.
  • polyurethane foam 2 parts by weight of the catalyst system according to the invention from Example 1 were introduced into the following polyol component.
  • the polyol component contained:
  • the polyol component was then reacted with an isocyanate prepolymer at a weight ratio of 1: 1.4.
  • Example 2 Particulate catalyst system containing DBU in polyvinyl ether wax according to Example 1, the average particle size being 50 to 100 ⁇ m.
  • Example 3 Particulate catalyst system containing DBU in polyvinyl ether wax according to Example 1, the average particle size being 110 to 300 ⁇ m.
  • Comparative Example 5 DBU, not coated with wax.
  • the foam reaction resulting in the example or comparative examples 2 to 4 is characterized by a rising height measuring device.
  • Figure 1 shows the height of rise as a function of the reaction time.
  • the catalyst system according to the invention leads, as desired, to a longer time delay in the foam reaction; this effect is intensified with an average particle size of 110 to 250 ⁇ m.
  • the ultrasound rise height profile can be used to very well demonstrate when the foam system starts to react.
  • the wax catalyst is added to the conventional catalyst, it is desirable to be as close as possible to the rise profile of the zero system.
  • the graphic clearly shows that the wax catalyst mixture according to the invention, in particular the one with the larger particles, is significantly closer to the zero system than the catalyst not surrounded by wax.
  • the demolding times of the two systems according to the invention are identical, but the system with the larger particles has a longer processing window.
  • Example 6 uses a catalyst system according to the invention which was produced in accordance with Example 1 and contained 20% by weight of catalyst component c), based on the total weight of the catalyst system.
  • Example 7 uses a catalyst system according to the invention which was produced in accordance with Example 1 and contained 60% by weight of catalyst component c), based on the total weight of the catalyst system.
  • Comparative Example 8 contained no catalyst system according to the invention.
  • test results are illustrated by FIG. 2 and by the table below.
  • Examples 6 and 7 have significantly shorter buckling times compared to the zero system and start times that are still sufficiently long.
  • the wax with 20% catalyst (example 6) has long start times and is therefore even easier to handle from a processing point of view than the wax in example 7, although in example 7 there is a higher concentration of catalyst and the buckling times in example 7 are only slightly shorter than in Example 6.
  • the catalysts embedded in wax with lower concentrations (less than 50% by weight) of catalyst are therefore particularly advantageous.

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

Abstract

L'invention concerne un système catalyseur contenant au moins un catalyseur c) qui catalyse une réaction de polyisocyanate (a) avec des composés (b) comportant au moins deux atomes d'hydrogène réagissant vis-à-vis des groupes isocyanates. Ledit catalyseur est incorporé dans de la cire qui contient au moins un groupe polaire et présente une chaleur de fusion de 50 à 250 Joules/gramme.
PCT/EP2002/003986 2002-04-10 2002-04-10 Systemes catalyseurs contenant des catalyseurs incorpores dans de la cire WO2003085021A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE10296717T DE10296717D2 (de) 2002-04-10 2002-04-10 Katalysatorsysteme, enthaltend in Wachs eingebettete Katalysatoren
AU2002302522A AU2002302522A1 (en) 2002-04-10 2002-04-10 Catalyst systems containing catalysts that are embedded in wax
PCT/EP2002/003986 WO2003085021A1 (fr) 2002-04-10 2002-04-10 Systemes catalyseurs contenant des catalyseurs incorpores dans de la cire

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2002/003986 WO2003085021A1 (fr) 2002-04-10 2002-04-10 Systemes catalyseurs contenant des catalyseurs incorpores dans de la cire

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WO2003085021A1 true WO2003085021A1 (fr) 2003-10-16

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007090376A1 (fr) * 2006-02-09 2007-08-16 Fachhochschule Münster Polyuréthannes à faible taux d'émission
EP2809699A4 (fr) * 2012-02-02 2015-09-30 Arkema Inc Durée de stockage prolongée de mélanges de polyol contenant des oléfines halogénées par encapsulation de constituants actifs

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3160686A (en) * 1962-08-01 1964-12-08 Delavan Mfg Company Process for making capsules
GB1035903A (en) * 1961-11-10 1966-07-13 Courtaulds Ltd Polyurethane foams
EP0039137A1 (fr) * 1980-04-30 1981-11-04 Imperial Chemical Industries Plc Réactions d'isocyanate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1035903A (en) * 1961-11-10 1966-07-13 Courtaulds Ltd Polyurethane foams
US3160686A (en) * 1962-08-01 1964-12-08 Delavan Mfg Company Process for making capsules
EP0039137A1 (fr) * 1980-04-30 1981-11-04 Imperial Chemical Industries Plc Réactions d'isocyanate

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 113, no. 10, 3 September 1990, Columbus, Ohio, US; abstract no. 72909h, CARLTON ET AL: "Microencapsulated curing catalyst for manufacture of plastic-bonded explosives and energetic composition containing same" page 16; XP000182993 *
STATUTORY INVENTION REGISTRATION, US 778, 4 August 1986 (1986-08-04) *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007090376A1 (fr) * 2006-02-09 2007-08-16 Fachhochschule Münster Polyuréthannes à faible taux d'émission
EP2809699A4 (fr) * 2012-02-02 2015-09-30 Arkema Inc Durée de stockage prolongée de mélanges de polyol contenant des oléfines halogénées par encapsulation de constituants actifs
US9556335B2 (en) 2012-02-02 2017-01-31 Arkema Inc. Shelf life of polyol blends containing halogenated olefins by encapsulation of active components

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AU2002302522A1 (en) 2003-10-20

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