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
  • C08G18/4804—Two or more polyethers of different physical or chemical nature
  • C08G18/482—Mixtures of polyethers containing at least one polyether containing 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
  • C08G18/28—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
• • 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
  • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment 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
  • C08G2101/00—Manufacture of cellular products
• • 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 present invention relates to a process for the production of polyurethane (PU) -
• Rigid foams by reacting polyisocyanates with compounds having at least two isocyanate-reactive hydrogen atoms in the presence of blowing agents.
• polyols having high functionalities and relatively short chains are used for the production of isocyanate-based rigid foams in order to achieve optimal crosslinking of the
• the preferably used polyether alcohols usually have a functionality of 4 to 8 and a hydroxyl number in the range between 300 to 600, in particular between 400 and 500 mg KOH / g. It is known that polyols with very high functionality and hydroxyl numbers in the range between 300 and 600 have a very high viscosity when based on propylene oxide. By contrast, such polyols based on ethylene oxide are less viscous by up to a quarter. Furthermore, it is known that such polyols are very polar and thus have poor solubility of hydrocarbons and poor compatibility with polyisocyanates. An essential requirement for the rigid foams is the shortening of the demolding time, without any limitations in the mechanical or the processing properties. Furthermore, the starting materials for the production of rigid foams should show good solubility for the blowing agent, especially when using hydrocarbons as blowing agent.
• polyols based on 1,2-butylene oxide have improved solubility for hydrocarbons compared with the corresponding propylene oxide-based polyols.
• the system should have optimum flow and curing times as well as a low viscosity of the polyol components, which allows processing in the production according to the prior art.
• a high solubility of the blowing agent in the system for setting low bulk densities in the component should be present and the system should have good demolding properties.
• this object has been achieved by the use of a poly (butylene oxide) polyol (i) having a hydroxyl number of 380 to 500 mg KOH / g and an amine-initiated polyether alcohol (ii) having a hydroxyl value of 360 to 450 mg KOH / g and optionally a polyether polyol (iii) (so-called "soft polyol”) having a hydroxyl number of 140 to 280 mg KOH / g.
• a poly (butylene oxide) polyol i) having a hydroxyl number of 380 to 500 mg KOH / g and an amine-initiated polyether alcohol (ii) having a hydroxyl value of 360 to 450 mg KOH / g and optionally a polyether polyol (iii) (so-called "soft polyol”) having a hydroxyl number of 140 to 280 mg KOH / g.
• the subject of the present invention is thus a process for the production of rigid polyurethane foams, by reacting a) at least one polyisocyanate with
• c) at least one propellant characterized in that for the compounds b) having at least two isocyanate-reactive hydrogen atoms, a mixture of b1) at least one polyether alcohol having a hydroxyl number of 380 to 500 mg KOH / g, prepared by addition of butylene oxide, optionally in Combination with at least one further alkylene oxide, to at least one OH or NH-functional starter compound having a functionality of 4 to 8 with the aid of a basic catalyst, preferably imidazole,
• the OH number is determined according to the invention according to DIN 53240.
• FIG. 1 Further objects of the invention are also a rigid polyurethane foam, which can be produced by the process according to the invention, and the use of a rigid polyurethane foam which can be produced by the process according to the invention as thermal insulation material, for example.
• a rigid polyurethane foam which can be produced by the process according to the invention as thermal insulation material, for example.
• thermal insulation material for example.
• refrigerators in hot water tanks, in district heating pipes or in construction, for example in sandwich panels.
• the poly (butylene oxide) polyol (b1) is prepared by conventional and well-known methods by ring-opening polymerization of butylene oxide (BO) using higher-functionality starter molecules.
• Suitable starter molecules are, for example, sugars (sucrose), sorbitol, mannose, pentaerythritol (F 4 - 8).
• NH or OH group-containing co-promoters may be employed (e.g., glycerol, TMP, MEG, DEG, MPG, DPG, EDA, TDA).
• alkylene oxides In addition to the butylene oxide isomers 1, 2-butylene oxide, 2,3-butylene oxide or isobutylene oxide, it is also possible to meter in further alkylene oxides in the so-called block procedure or else in the mixed procedure.
• Suitable comonomers here are the generally customary alkylene oxides propylene oxide (PO) and ethylene oxide (EO), 1, 2-pentenoxide, styrene oxide, epichlorohydrin, cyclohexene oxide and higher alkylene oxides such as Cs-Cao-a-alkylene oxides).
• alkylene oxide mixtures e.g., PO / EO and BO is also possible.
• the ring-opening polymerization is carried out - as is well known - with the aid of catalysts.
• catalysts are generally basic catalysts such as alkali or alkaline earth metal hydroxides or alkali metal or alkaline earth metal alcoholates (for example NaOH, KOH, CsOH or sodium methoxide, potassium methoxide).
• alkali or alkaline earth metal hydroxides for example NaOH, KOH, CsOH or sodium methoxide, potassium methoxide
• catalysts containing amino-containing functional groups e.g., DMEOA or imidazole
• carbenes as alkoxylation catalysts is possible.
• the catalyst which can be used for the preparation of the poly (butylene oxide) polyol (b1) is selected from the group comprising amino-functional catalysts.
• the catalyst useful for preparing the poly (butylene oxide) polyol (b1) is selected from the group consisting of trimethylamine, triethylamine, tripropylamine, tributylamine, N, N'-dimethylethanolamine, ⁇ , ⁇ '-dimethylcyclohexylamine, dimethylethylamine, di methylbutylamine, ⁇ , ⁇ '-dimethylaniline, 4-dimethylaminopyridine, ⁇ , ⁇ '-dimethylbenzylamine, pyridine, imidazole, N-methylimidazole, 2-methylimidazole, 4-methylimidazole, 5-methylimidazole, 2-ethyl-4-methylimidazole, 2 , 4-dimethylimi
• the catalyst which can be used for the preparation of (b1) is selected from the group of imidazoles, particularly preferably imidazole.
• the amine-started polyol (b2) is converted by alkylene oxide addition onto aromatic amines, such as, for example, vicinal toluenediamine, methylenedianiline (MDA) and / or polymeric methylenedianiline (pMDA).
• aromatic amines such as, for example, vicinal toluenediamine, methylenedianiline (MDA) and / or polymeric methylenedianiline (pMDA).
• MDA methylenedianiline
• pMDA polymeric methylenedianiline
• the amine-started polyol (b2) is prepared by alkylene oxide addition to aliphatic amines such as, for example, ethylenediamine.
• the optional polyether polyol (b3) having a hydroxyl number of 140 to 280 mg KOH / g is selected from the group comprising alkylene oxide addition products of sugar, glycerol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol , 1-4 butanediol, pentaerythritol, trimethylolpropane, water, sorbitol, aniline, TDA, MDA, EDA or combinations of said compounds, preferably glycerol, ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol.
• the ring-opening polymerization for the preparation of the polyol (bi), (bii) and (biii) is carried out under customary reaction conditions in the temperature range between 90 and 160 ° C, preferably between 100 and 130 ° C at pressures in the range between 0 and 20 bar, preferably between 0 and 10 bar.
• alkylene oxides for the preparation of the polyols (b1), (b2) and (b3) can be carried out in the semibatch process or also completely continuously or semicontinuously.
• a certain amount of product or precursor is also introduced into the reactor (Heel procedure).
• the polyols are usually worked up by customary methods by removing the unreacted alkylene oxides and volatile constituents, usually by distillation, steam or gas stripping and / or other methods of deodorization. If necessary, filtration can also be carried out.
• the poly (butylene oxide) polyol (b1) is characterized by OH numbers in the range from 380 to 500 mg KOH / g, preferably from 300 to 500 mg KOH / g.
• the amine-started polyether alcohol (b2) is characterized by OH numbers in the range from 360 to 450 mg KOH / g.
• the functionalities of the poly (butylene oxide) polyols (b1) is determined by the functionality of the starter mixture and is in the range between 3.5-8, preferably between 4-6 OH groups / molecule.
• the viscosities of the polyetherols (b1), (b2) and (b3) are in the range customary for this OH number range between 100 and 50,000 mPas, preferably between 200 and 30,000 mPas.
• the viscosity of the poly (butylene oxide) polyol (b1) is preferably between 5,000 and 30,000 mPas.
• the at least one polyisocyanate (a) is selected from the group comprising aromatic, aliphatic and / or cycloaliphatic diisocyanates, for example diphenylmethane diisocyanate (MDI), polymeric MDI (pMDl), Tolylene diisocyanate (TDI), tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methyl-pentamethylene-diisocyanate-1, 5, 2-ethyl-butylene-diisocyanate-1, 4, 1 - isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI
• the at least one blowing agent (c) is selected from the group consisting of physical blowing agents and chemical blowing agents.
• Physical blowing agents may also be used in combination with or in place of chemical blowing agents. 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. Useful physical blowing agents also include compounds which are gaseous at room temperature and are introduced or dissolved in the feed components under pressure, for example carbon dioxide, 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 ,
• the blowing agents (c) are hydrocarbons.
• the propellants are particularly preferably selected from the group comprising alkanes and / or cycloalkanes having at least 4 carbon atoms.
• pentanes preferably iso-pentane and cyclopentane, are used.
• cyclopentane is preferred.
• the hydrocarbons can be used in a mixture with water.
• blowing agents (c) which can be used according to the invention include propane, n-butane, isobutocyclobutane, n-, iso- and cyclopentane, cyclohexane, dimethyl ether, methyl ethyl ether, methyl butyl ether, methyl formate, acetone, and fluoroalkanes which are degraded in the troposphere and are therefore harmless to the ozone layer, such as trifluoromethane, difluoromethane, 1, 1, 1, 3,3-pentafluorobutane, 1,1,1,3,3-pentafluoropropane, 1,1,1,2-tetrafluoroethane , difluoroethane and 1, 1, 1, 2,3,3,3-heptafluoropropane, and perfluoroalkanes such as C3F8, C4F10, C5F12, C E F, and C7F16.
• the said physical blowing agents can be used alone
• hydrofluoroolefins such as 1, 3,3,3-tetrafluoropropene, or hydrochlorofluoroolefins, such as 1, chloro-3,3,3-trifluoropropene
• blowing agents are described, for example, in WO 2009/048826.
• the preparation according to the invention of the rigid polyurethane foams can be carried out in the presence of catalysts, flameproofing agents and customary auxiliaries and / or additives.
• the catalysts used are in particular compounds which greatly accelerate the reaction of the isocyanate groups with the groups reactive with isocyanate groups.
• Such catalysts are strongly basic amines, such as.
• secondary aliphatic amines imidazoles, amidines, and alkanolamines or organic metal compounds, in particular organic tin compounds.
• isocyanurate groups are to be incorporated in the rigid polyurethane foam, special catalysts are required for this purpose.
• the isocyanurate catalysts used are usually metal carboxylates, in particular potassium acetate and its solutions. The catalysts can, depending on requirements, be used alone or in any mixtures with one another.
• auxiliaries and / or additives are the substances known per se for this purpose, for example surface-active substances, foam stabilizers, cell regulators, fillers, pigments, dyes, flameproofing agents, hydrolysis protection agents, antistatic agents, fungistatic and bacteriostatic agents. Further details on starting compounds used can be found, for example, in the Kunststoffhandbuch, Volume 7 "Polyurethane", edited by Günter Oertel, Carl-Hanser-Verlag Kunststoff, 3rd edition, 1993.
• Polyol A Polyether alcohol from sucrose, glycerol and propylene oxide, functionality 5.1, hydroxyl number 450, viscosity 18500 mPa.s at 25 ° C
• Polyol B Polyether alcohol of vicinal TDA, ethylene oxide and propylene oxide, content of ethylene oxide: 15%, functionality 3.8, hydroxyl number 390, viscosity 13000 mPa.s at 25 ° C
• Polyol C Polyether alcohol from vicinal TDA, ethylene oxide and propylene oxide, content of ethylene oxide: 15%, functionality 3.9, hydroxyl number 160, viscosity 650 mPa.s at 25 ° C.
• Polyol D dipropylene glycol
• Viscosity 23,234 mPas (DIN 13421)
• Catalyst 1 dimethylcyclohexylamine (BASF SE)
• Catalyst 2 Pentamethyldiethylenetriamine (BASF SE)
• Catalyst 3 Lupragen® N600 (s-triazine) (BASF SE)
• Isocyanate Polymer-MDI (Lupranat® M20, BASF SE)
• a polyol component was prepared.
• a high pressure Puromatics® PU 30/80 IQ BASF Polyurethanes GmbH
• a discharge rate of 250 g / sec 250 g / sec.
• the polyol component was blended with the requisite amount of the indicated isocyanate so that an isocyanate index (unless otherwise noted) of 1.167 was achieved.
• the reaction mixture was injected into temperature-controlled molding tools measuring 2000 mm ⁇ 200 mm ⁇ 50 mm or 400 ⁇ 700 mm ⁇ 90 mm and allowed to foam there. The overcrowding was 15%.
• Polyol A (parts by weight) 54
• Polyol B (parts by weight) 22 22
• Polyol C (parts by weight) 15 15
• Polyol E (according to the invention) (parts by weight) 54
• Viscosity Polyol component [mPas @ 25 ° C] 6800 7400
• Example 1 represents a comparative example.
• the system in Example 2 (according to the invention) with a polyether alcohol based on sucrose, glycerol and butylene oxide has markedly improved demolding properties, which manifest themselves in a lower after-expansion. It could thus be shown that the method according to the invention leads to improved properties.

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

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• 2012
  • 2012-03-05 WO PCT/EP2012/053697 patent/WO2012119970A2/de not_active Ceased
  • 2012-03-05 KR KR1020137026663A patent/KR101903814B1/ko not_active Expired - Fee Related
  • 2012-03-05 ES ES12706615.7T patent/ES2543438T3/es active Active
  • 2012-03-05 RU RU2013144818/04A patent/RU2585290C2/ru not_active IP Right Cessation
  • 2012-03-05 CN CN201280012081.6A patent/CN103415544B/zh active Active
  • 2012-03-05 JP JP2013557058A patent/JP6155201B2/ja not_active Expired - Fee Related
  • 2012-03-05 HU HUE12706615A patent/HUE025167T2/en unknown
  • 2012-03-05 EP EP12706615.7A patent/EP2683755B1/de not_active Not-in-force
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