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
  • C08G18/48—Polyethers
  • C08G18/50—Polyethers having heteroatoms other than oxygen
  • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/50—Polyethers having heteroatoms other than oxygen
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
  • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
  • C08G65/2669—Non-metals or compounds thereof
  • C08G65/2672—Nitrogen or compounds thereof
• • 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
  • C08G2110/0025—Foam properties rigid

Definitions

• the invention relates to a process for the production of rigid polyurethane foams by reacting polyisocyanates with compounds having at least two isocyanate-reactive hydrogen atoms in the presence of blowing agents.
• Polyurethane rigid foams have long been known and are mainly used for thermal and cold insulation, z. B. in refrigerators, in hot water tanks, in district heating pipes or in construction, for example in sandwich panels used.
• a summary of the production and application of rigid polyurethane foams can be found, for example, in the Kunststoff-Handbuch, Volume 7, Polyurethane 1st Edition 1966, edited by Dr. med. R. Vieweg and dr. A. Höchtlen, and 2nd edition, 1983, edited by dr. Günter Oertel, and 3rd edition 1993, edited by Dr. med. Günter Oertel, Carl Hanser Verlag, Kunststoff, Vienna.
• Fluorochloroalkanes preferably trichlorofluoromethane
• CFCs Fluorochloroalkanes
• EP-A-421 269 describes the use of cyclopentane and / or cyclohexane, optionally mixed with other hydrocarbons, as blowing agent.
• propellants differ in various respects from the halogenated propellants. So they are less compatible with the other components of the polyurethane systems. This leads to a rapid separation of the components containing blowing agent.
• the alkane-driven foams tend to have a higher density than those driven by CFCs.
• the polyurethane rigid foam located in the cavity has a lower density, which in addition to the saving of material also leads to a reduction in the weight of the end products, such as refrigerated cabinets.
• Flowability of the foam is understood to mean the flow behavior of the reacting mixture of polyisocyanate and the compound having at least two hydrogen atoms reactive with isocyanate groups. Flowability is usually determined by determining the path length that the reacting mixture travels. This can be done by the reaction mixture in a flexible hose made of plastic film, hereinafter referred to as a hose test, or in a normalized elongated shape, for example, a so-called Boschlanze introduced, and the length of the resulting shaped body is determined.
• the flowability of the reaction mixtures is usually determined by determining the flow factor.
• the flow factor represents the ratio of minimum filling density to free-foamed density and is determined with the help of the Boschlanze.
• the minimum filling density is obtained by varying the shot weight and corresponds to the minimum necessary density, which is required to fill a Boschlanze completely for a given free density.
• polyols which were prepared by addition of alkylene oxides to compounds having at least two active hydrogen atoms in the presence of at least one compound having at least one amino group as catalyst.
• the invention relates to a process for the preparation of rigid polyurethane foams by reacting a) polyisocyanates with b) compounds having at least two isocyanate-reactive hydrogen atoms in the presence of c) blowing agents, characterized in that the compounds have at least two isocyanates.
• the polyether alcohol b1) can be used as the only compound of component b).
• the polyether alcohol b1) is preferably used in an amount of 10-90% by weight, based on the weight of component b).
• the polyether alcohol b1) For the preparation of the polyether alcohol b1), it is preferred to use mixtures containing at least two hydrogen atoms reactive with alkylene oxides which contain at least one compound bl ai) which is solid at room temperature.
• the compound bl ai) preferably has a functionality of at least 3, particularly preferably of at least 4, in particular of 3-8 and particularly preferably of 4-8.
• Such compounds bl ai) are known and are frequently used for the preparation of polyether alcohols, in particular those for use in rigid polyurethane foams.
• the compounds bl ai) are selected from the group comprising trimethylolpropane, pentaerythritol, glucose, sorbitol, mannitol and Sucrose, polyhydric phenols, resoles, such as oligomeric condensation products of phenol and formaldehyde, oligomeric condensation products of aniline and formaldehyde (MDA), toluenediamine (TDA) and Mannich condensates of phenols, formaldehyde and dialkanolamines and melamine and mixtures of at least two of the listed alcohols ,
• the compound bl ai) is selected from the group comprising sucrose, sorbitol and pentaerythritol, more preferably sucrose or sorbitol.
• b1 is a) sucrose.
• the aromatic amines used as compounds bl ai) are in particular selected from the group comprising toluenediamine (TDA) or diphenylmethanediamine (MDA) or polymeric MDA (p-MDA).
• TDA toluenediamine
• MDA diphenylmethanediamine
• p-MDA polymeric MDA
• 2,3- and 3,4-isomers, also referred to as vicinal TDA are used in TDA.
• the starter substance of component b1) contains, in addition to the compound bl ai), a compound bl aii) which is liquid at room temperature and contains hydrogen atoms reactive with alkylene oxides.
• the compound bl aii) may be alcohols or amines. These have, in particular, 1 to 4, preferably 2 to 4, hydrogen atoms reactive with alkylene oxides.
• the component bl aii) is in particular selected from the group comprising glycerol, monofunctional alcohols having 1-20 carbon atoms, ethylene glycol and its higher homologues and propylene glycol and its higher homologs, hydroxyalkylamines, such as monoethanolamine, diethanolamine, triethanolamine, and their reaction products with propylene oxide.
• glycerol is used.
• the liquid at room temperature (bl aii) may, as I said, also be compounds having a reactive with alkylene oxides hydrogen atom and 1-20 carbon atoms. Preference is given here to monofunctional alcohols, such as methanol, ethanol, propanol, octanol, dodecanol.
• the starting substance of component b1) comprises a mixture of at least one amine blAi) which is solid at room temperature and an alcohol which is liquid at room temperature.
• the amines bl ai) which are solid at room temperature may, as stated above, preferably be MDA and polymeric MDA.
• liquid alcohols bl aii) are then preferably ethylene glycol and its higher homologues and propylene glycol and its higher homologues.
• concentrations of the amine homologs in p-MDA are dependent on the process operations. In general, the distribution (in weight percent) is as follows:
• Binuclear MDA 50-80% by weight
• Trinuclear MDA 10-25% by weight
• a preferred p-MDA mixture has the composition:
• Trinuclear MDA 25% by weight
• Another preferred p-MDA mixture has the composition: binuclear MDA: 80% by weight
• Trinuclear MDA 10% by weight
• the starting substance of component b1) contains a mixture of at least one (bl ai)) which is solid at room temperature and an alcohol which is liquid at room temperature (bl aii)).
• the alcohols (bl ai) which are solid at room temperature are preferably the sugar alcohols glucose, sorbitol, mannitol and sucrose, in particular sucrose, characterized in detail above.
• the liquid at room temperature alcohols (bl aii) are preferably monofunctional alcohols having 1-20 carbon atoms, ethylene glycol and its higher homologues, propylene glycol and its higher homologs, hydroxyalkylamines, such as monoethanolamine, diethanolamine, triethanolamine, as well as their propylene oxide based analogues and glycerin, especially glycerin.
• the starting substance of component b1) may also contain water. If water is also used, the amount is in particular at most 25 wt .-%, based on the weight of the starting substance of component b1).
• the alkylene oxide b1 b) used is preferably propylene oxide, ethylene oxide, butylene oxide, isobutylene oxide, styrene oxide or mixtures of at least two of the abovementioned alkylene oxides.
• alkylene oxide b1 b) propylene oxide, ethylene oxide or mixtures of propylene oxide and ethylene oxide used.
• Particular preference is given to using alkylene oxide b1b) as propylene oxide.
• catalyst b1 c) is one of the components used as component (a)). These may be primary, secondary or tertiary amines and also aliphatic or aromatic, in particular tertiary amines. In another embodiment, it may be aromatic heterocyclic compounds having at least one, preferably a nitrogen atom in the ring.
• the amines b1 c) are preferably selected from the group comprising trialkylamines, in particular trimethylamine, triethylamine, tripropylamine, tributylamine, dimethylalkylamines, in particular dimethylethanolamine; Dimethylethoxyethanolamine, dimethylcyclohexylamine, dimethylethylamine, dimethylbutylamine, aromatic amines, in particular dimethylaniline, dimethylaminopyridine, dimethylbenzylamine, pyridine, imidazoles, in particular imidazole, N-methylimidazole, 2-methylimidazole, 4-methylimidazole, 5-methylimidazole, 2-ethyl-4-methylimidazole 2,4-dimethylimidazole, 1-hydroxypropylimidazole, 2,4,5-trimethylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, N-phenylimidazole, 2-phenylimidazo
• the catalyst b1 c) is dimethylethanolamine.
• the catalyst b1 c) is an imidazole.
• the amine b1 c) is preferably present in an amount of 0.01-5.0 wt .-%, preferably 0.05-3.0 wt .-% and particularly preferably 0.1 -1, 0 wt .-% based on the overall approach, used. Undernovaansatz the amount of all starting materials used for the preparation of the polyether alcohol b1) is understood.
• the constituents of the starting substance mixture b1 a) and b1c) are usually added to the reactor and mixed. There is initially an inerting of the mixture. Thereafter, the alkylene oxide is metered.
• the addition of the alkylene oxides is preferably carried out at a temperature between 90 and 150 ° C and a pressure between 0.1 to 8 bar.
• To the dosage of Alkylene oxides usually include a post-reaction phase for complete conversion of the alkylene oxides.
• a post-reaction phase in which the alkylene oxide reacts. Thereafter, if necessary, a post-reaction phase can follow. It usually follows a distillation for the separation of volatile components, preferably under vacuum.
• the amine catalysts b1 c) can remain in the polyether alcohol. This simplifies their preparation, since the removal of the catalysts necessary when using oxides and hydroxides of alkali metals is no longer necessary. This leads to an improvement in the space-time yield.
• the salt removal by filtration forms a filter cake.
• the polyol loss in the filter cake is usually a few percent. The improved space-time yield and avoidance of filter loss lead to a reduction in manufacturing costs.
• alkali metal hydroxide and amine catalysts are particularly suitable for producing polyols with a low hydroxyl number.
• the products obtained can be worked up analogously to the alkali metal hydroxide-catalyzed polyols.
• only the neutralization step with acid can be carried out for workup.
• carboxylic acids e.g. Michklare, acetic acid or 2-ethylhexanoic acid used.
• the amine catalysts b1 c) can themselves be alkoxylated in the course of the reaction. The alkoxylated amines therefore have a higher molecular weight and a lower volatility in the later product.
• polyether alcohols prepared using amines as catalysts have a structure different from the construction of such polyether alcohols made using other catalysts. This different molecular structure has advantages in the production of polyurethanes.
• the polyols of the invention have distinct advantages in polyurethane applications, especially in the production process of polyurethane foams.
• the polyether alcohols b1) are used for the preparation of polyurethanes.
• Suitable organic polyisocyanates are preferably aromatic polyfunctional isocyanates.
• TDI 2,4- and 2,6-toluene diisocyanate
• MDI 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate
• MDI 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate
• CAde MDI polyphenyl polymethylene polyisocyanates
• the polyether alcohols b1) according to the invention are usually used in admixture with other compounds having at least two isocyanate-reactive hydrogen atoms.
• Suitable compounds having at least two isocyanate-reactive hydrogen atoms which can be used together with the polyether alcohols b1) are, in particular, polyether alcohols and / or polyester alcohols having OH numbers in the range from 100 to 1200 mgKOH / g.
• the polyester alcohols used together with the polyether alcohols b1) are usually obtained by condensation of polyfunctional alcohols, preferably diols, having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, with polyfunctional carboxylic acids having 2 to 12 carbon atoms, for example succinic acid, glutaric acid, adipic acid, Nuclear acid, azelaic acid, sebacic acid, decane dicarboxylic acid, maleic acid, fumaric acid and preferably phthalic acid, isophthalic acid, terephthalic acid and the isomeric naphthalenedicarboxylic acids.
• polyfunctional alcohols preferably diols, having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms
• polyfunctional carboxylic acids having 2 to 12 carbon atoms
• the polyether alcohols used together with the polyether alcohols b1) usually have a functionality between 2 and 8, in particular 3 to 8.
• polyether alcohols which are prepared by known processes, for example by anionic polymerization of alkylene oxides in the presence of catalysts, preferably alkali metal hydroxides, are used.
• alkylene oxides are usually ethylene oxide and / or propylene oxide, preferably pure 1, 2-propylene oxide used.
• compounds having at least 3, preferably 4 to 8 hydroxyl groups or having at least two primary amino groups in the molecule are used as starting molecules.
• starting molecules having at least 3, preferably 4 to 8 hydroxyl groups in the molecule are preferably trimethylopropane, glycerol, pentaerythritol, sugar compounds such as glucose, sorbitol, mannitol and sucrose, polyhydric phenols, resoles, such as oligomeric condensation products of phenol and formaldehyde, condensation products of aniline and Formaldehyde, toluene diamine and Mannich condensates of phenols, formaldehyde and dialkanolamines and melamine used.
• the polyether alcohols have a functionality of preferably 3 to 8 and hydroxyl numbers of preferably 100 mgKOH / g to 1200 mgKOH / g and especially 120 mgKOH / g to 570 mgKOH / g.
• difunctional polyols for example polyethylene glycols and / or polypropylene glycols, having a molecular weight in the range from 500 to 1500 in the polyol component, the viscosity of the polyol component can be adjusted.
• the compounds having at least two isocyanate-reactive hydrogen atoms also include the optionally used chain extenders and crosslinkers.
• the rigid polyurethane foams can be prepared without or with the concomitant use of chain extenders and / or crosslinking agents.
• difunctional chain extenders, trifunctional and higher functional crosslinking agents or optionally also mixtures thereof may prove to be advantageous.
• chain extenders and / or crosslinking agents are preferably used alkanolamines and in particular diols and / or triols having molecular weights less than 400, preferably 60 to 300.
• Chain extenders, crosslinkers or mixtures thereof are suitably used in an amount of 1 to 20 wt .-%, preferably 2 to 5 wt .-%, based on the polyol component.
• blowing agents As propellant preferably water can be used which reacts with isocyanate groups with elimination of carbon dioxide. Another commonly used chemical blowing agent is formic acid, which reacts with isocyanate to release carbon monoxide and carbon dioxide. In combination with or in place of the chemical blowing agents, so-called physical blowing agents can also be incorporated. be set. These are compounds which are inert to the starting components and which are usually liquid at room temperature and evaporate under the conditions of the urethane reaction. Preferably, the boiling point of these compounds is below 50 ° C.
• the physical blowing agents also include compounds which are gaseous at room temperature and are introduced under pressure into or dissolved in the starting components, for example carbon dioxide, alkanes, in particular low-boiling alkanes and fluoroalkanes, preferably, alkanes, in particular low-boiling alkanes and fluoroalkanes.
• the physical blowing agents are usually selected from the group comprising alkanes and / or cycloalkanes having at least 4 carbon atoms, dialkyl ethers, esters, ketones, acetals, fluoroalkanes having 1 to 8 carbon atoms, and tetraalkylsilanes having 1 to 3 carbon atoms in the alkyl chain, in particular tetramethylsilane.
• Examples which may be mentioned are propane, n-butane, iso- and cyclobutane, n-, iso- and cyclopentane, cyclohexane, dimethyl ether, methyl ethyl ether, methyl butyl ether, methyl formate, acetone, and fluoroalkanes, which can be degraded in the troposphere and therefore for the ozone layer is harmless, such as trifluoromethane, difluoromethane, 1,1,1,3,3-pentafluorobutane, 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-pentafluoropropane, 1-chloro-3,3,3-trifluoropropene, 1, 1, 1, 1, 2-tetrafluoroethane, difluoroethane and
• 1, 1, 1, 1, 2,3,3,3-heptafluoropropane, and perfluoroalkanes such as, C3F8, C4F10, C5F12, C6F14, and C7F17.
• Particular preference is given to hydrocarbons, preferably pentanes, in particular cyclopentane.
• the said physical blowing agents can be used alone or in any combination with each other.
• a mixture of physical and chemical blowing agents may be used.
• Particularly preferred are mixtures of physical blowing agents and water, especially hydrocarbons and water.
• hydrocarbons the pentanes, and especially cyclopentane, are particularly preferred.
• the preparation of the polyurethanes may, if necessary, be carried out in the presence of catalysts, flame retardants and customary auxiliaries and / or additives auxiliaries and / or additives.
• the PU rigid foams are preferably used as a heat-insulating intermediate layer in composite elements and for foaming cavities in refrigeration cabinets, in particular for refrigerators and freezers, and daymantel of hot water storage.
• the products are also suitable for the isolation of heated materials, as engine cover and as pipe shells.
• suitable heat and cold-insulating rigid PU foams can be known by reacting organic polyisocyanates with one or more compounds having at least two isocyanate-reactive groups, preferably polyester and / or polyether polyols and usually with the concomitant use of chain extenders and / or crosslinking agents in the presence of propellant - Mittein, catalysts and, where appropriate, auxiliaries and / or additives are produced.
• PU rigid foams can be obtained with a low thermal conductivity and good mechanical properties.
• a 250 l pressure reactor with stirrer, jacket heating and cooling, metering devices for solid and liquid substances and alkylene oxides and equipment for nitrogen inertization and a vacuum system was heated to 80 ° C and repeatedly inertized. 18.38 kg of glycerol and 1.26 kg DMEOA were charged and the stirrer in Operation taken. Subsequently, sucrose (191, 6 kg) was added to the reactor and the temperature raised to 95 ° C. The mixture was reacted at 95 ° C with 54.0 kg of propylene oxide. After a postreaction time of 30 minutes, an additional 0.64 kg of DMEOA was added. Then the temperature was increased to 1 12 ° C and added 1 16 kg of propylene oxide. The post-reaction of 3 hours proceeded at 1 12 ° C. The product was stripped for 2 h at 105 ° C (vacuum, nitrogen). There were obtained 352 kg of product with the following parameters
• a 600 l pressure reactor with stirrer, jacket heating and cooling, metering devices for solid and liquid substances and alkylene oxides and equipment for nitrogen inertization and a vacuum system was heated to 80 ° C and repeatedly inertized. 58.2 kg of glycerin and 6.0 kg of dimethylethanolamine were charged to the reactor and the stirrer was put into operation. Subsequently, sucrose (191.6 kg) was added to the reactor and the temperature was raised to 95.degree. The mixture was reacted at 105 ° C with 195.0 kg of propylene oxide. Then the temperature was raised to 1212 ° C and the product was reacted with another 352.7 kg of propylene oxide. The post-reaction of 3 hours proceeded at 1 12 ° C. The remaining propylene oxide was stripped off in a stream of nitrogen. 770 kg of product were obtained with the following parameters.
• a 600 l pressure reactor with stirrer, jacket heating and cooling, metering devices for solid and liquid substances and alkylene oxides as well as devices for nitrogen inversion and a vacuum system was heated to 75 ° C and repeatedly inertized. 47.00 kg of glycerol and 3.09 kg of dimethylethanolamine were charged and the stirrer was put into operation. Subsequently, sucrose (154.75 kg) was added to the reactor and 157.50 kg PO at 75 ° C to 95 ° C added.
• a 50 l pressure reactor with stirrer, jacket heating and cooling, metering devices for solid and liquid substances and alkylene oxides, as well as equipment for nitrogen inertization and a vacuum system was heated to 90 ° C and inertized several times. 2.87 kg of glycerol, 0.188 kg of 48% KOH solution and 0.065 kg of water were charged and the stirrer was put into operation. Subsequently, sucrose (9.48 kg) was added. The temperature was raised to 105 ° C and 7.53 kg were added. After a reaction time of 1 h, the temperature was increased to 1 12 ° C and the remaining PO (19.85 kg) was added. The resulting polyetherol was hydrolyzed with water, neutralized with phosphoric acid, filtered and vacuum stripped. There were obtained 39.1 kg of the product. Hydroxyl number 450 mg KOH / g
• a 50 l pressure reactor with stirrer, jacket heating and cooling, metering devices for solid and liquid substances and alkylene oxides, as well as equipment for nitrogen inertization and a vacuum system was heated to 90 ° C and inertized several times. 4.00 kg of glycerol, 0.245 kg of 48% KOH solution and 0.049 kg of water were introduced and the stirrer was put into operation. Subsequently, sucrose (13.16 kg) was added and 1, 7 kg of PO were added at 105 ° C added. After a post-reaction of 3 h, the temperature was increased to 1212C and the residual PO (22.3 kg) was added. The resulting polyetherol was hydrolyzed with water, neutralized with phosphoric acid, filtered and vacuum stripped. 41.5 kg of the product were obtained.
• Viscosity measurements The viscosity of the polyols and of the polyol mixtures was, unless stated otherwise, at 25 ° C. using a Rheotec RC 20 rotational viscometer using the spindle CC 25 DIN (spindle diameter: 12.5 mm, measuring cylinder inner diameter: 13.56 mm) at a shear rate of 50 1 / s. hydroxyl
• the thermal conductivity was determined according to DIN 52616. To prepare the test specimens, the polyurethane reaction mixture was poured into a shape of the dimensions 200 ⁇ 20 ⁇ 5 cm (10% overfilling) and after a few hours a test specimen of dimension 20 ⁇ 20 ⁇ 2 cm from the Middle cut.
• Foam production for mechanical testing The following basic formulation was used to carry out the foaming experiments: 100 parts by weight Polyol (or polyol mixture)
• Polymer MDI (Lupranat M20® from BASF SE)
• the foams are produced at an isocyanate index of 100.
• the amounts of dimethylcyclohexylamine and cyclopentane were so dimensioned that in a beaker test with a total weight of 50 g and with a stirring time of 10 s and a setting time of 55 s, a free-foamed bulk density of 35 g / l was achieved.
• the components were thoroughly mixed by means of a laboratory stirrer and made to foam in a cube-shaped steel mold (500 g reaction mixture, volume of the mold: 1 1, 4 L).
• the fully reacted foam samples were removed from the mold after 20 min and stored under standard conditions for a further 3 days.
• the determination of the density was carried out according to ISO 845, the determination of the compressive strength according to ISO 604.
• Table 1 gives an overview of the polyols used. Table 1: Overview of the polyols used and pentane solubilities
• Table 2 presents a comparison of the properties of a sucrose-polyol based system.
• Tables 3 and 4 give an overview of the systems obtained with polyol blends.
• Polyol 1 [wt.T.I.] 65
• Thread pulling time [s] 52 56 Bulk density [kg / m 3 ] 35.2 35.6
• the amine-catalyzed polyols show better utilization of the cyclopentane used as blowing agent. With a smaller amount of cyclopentane, a foam with the same density can thus be produced. Due to the autocatalytic properties of the amine-catalyzed polyols, the amount of catalyst used can be reduced. Improved pentane solubility and lower viscosity were evident not only with the exclusive use of amine-catalyzed polyols (Table 2) but also with blends containing such polyols (Tables 3 and 4). The mechanical properties are the same.
• Polyol 1 [parts by weight] 63.45 -
• Polyol 3 [parts by weight] - 63.45
• Polyol 8 [parts by weight] 25.00 25.00
• Polyol 6 [parts by weight] 5.00 5.00
• Silicone stabilizer [parts by weight] 2.00 2.00
• the viscosity of the DMEOA-catalyzed polyol is lower by 3000 mPas. This is significant and also manifests itself in a likewise lower viscosity of the polyol component and in the flow factor and an improved surface quality (reduced voids rate). All other properties which are important for rigid foams of this application are comparable.

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• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polyurethanes Or Polyureas (AREA)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

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