EP2091992A1 - Polyphénylène polyméthylène polyisocyanate et son utilisation pour la fabrication de mousses en polyuréthanne - Google Patents

Polyphénylène polyméthylène polyisocyanate et son utilisation pour la fabrication de mousses en polyuréthanne

Info

Publication number
EP2091992A1
EP2091992A1 EP07822476A EP07822476A EP2091992A1 EP 2091992 A1 EP2091992 A1 EP 2091992A1 EP 07822476 A EP07822476 A EP 07822476A EP 07822476 A EP07822476 A EP 07822476A EP 2091992 A1 EP2091992 A1 EP 2091992A1
Authority
EP
European Patent Office
Prior art keywords
weight
polyisocyanate
component
isocyanate
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07822476A
Other languages
German (de)
English (en)
Inventor
Hans-Jürgen Reese
Imbridt Murrar
Ralf Fritz
Andres Cabrera
Birgit Magg
Bärbel GUSCHEL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP07822476A priority Critical patent/EP2091992A1/fr
Publication of EP2091992A1 publication Critical patent/EP2091992A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • C07C263/18—Separation; Purification; Stabilisation; Use of additives
    • C07C263/20—Separation; Purification
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy 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
    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
    • C08G18/4252—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids derived from polyols containing polyether groups and polycarboxylic acids
    • 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
    • C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy groups
    • 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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
    • 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 specially composed Polyphenylenpoly- methylene polyisocyanate (MDI), a process for its preparation and its use for the production of polyurethanes, in particular polyurethane foams.
  • MDI Polyphenylenpoly- methylene polyisocyanate
  • Polyurethane foams have long been known and described many times. They can be used for many technical applications. They are usually prepared by reacting polyisocyanates with compounds having at least two isocyanate-reactive hydrogen atoms.
  • polyurethane foams Two commonly used classes of polyurethane foams are rigid polyurethane foams and one-component foams, also referred to as aerosol foams.
  • rigid polyurethane foams are mainly for heat insulation, for example in refrigerators, transport or buildings and for the production of components, in particular sandwich elements.
  • polyisocyanates In the preparation of said polyurethanes are used as polyisocyanates usually aromatic polyisocyanates, in particular MDI and its higher homologues used.
  • One-component foams made from aerosol containers are frequently used in the field of construction for the installation of windows and doors in buildings as well as filling material for building-related cavities or wall openings for pipe installations.
  • Such an aerosol container includes a prepolymer as well as propellants and additives. By discharging its contents by means of blowing agent, its foaming by Froth für and by its curing with atmospheric moisture, the desired foam.
  • One-component foams based on NCO-containing prepolymers are the most well-known foams of this type. There are different products which, depending on the composition, lead to hard to soft elastic foams.
  • Dimensional stability means that the foam does not change its volume after curing, in particular does not shrink.
  • shrinkage can cause voids in the foam as well as detachment from the cover layers.
  • the shrinkage can lead to inadequate stability of the installed doors and windows.
  • foams are required on the market, which have a light color.
  • the hitherto offered foams which were prepared using the polyphenylene polymethylene polyisocyanates commonly used, are mostly colored brown. This can be particularly annoying for applications where the foam is visible.
  • the object of the invention was therefore to provide polyurethane foams which have good processing properties and performance properties, in particular good dimensional stability. Furthermore, the demands of the market for bright foams should be met. According to the process, foams for various fields of application, in particular one-component assembly foams and rigid polyurethane foams, should be producible.
  • the object could surprisingly be achieved by the use of a mixture of diphenylmethane diisocyanates and Polyphenylenpolymethylenpolyisocy- anaten with a special composition as an isocyanate component in the production of the foams.
  • the invention accordingly provides a polyphenylene polymethylene polyisocyanate
  • (B4) the 5-core product of the polyphenylene polymethylene polyisocyanate, wherein the components (B2), (B3) and (B4) at a content of (B1) of up to 55% by weight, based on the weight of (B), in the weight ratio (B2): (B3): ( B4) of 8 ⁇ 4: 3.5 ⁇ 1, 8: 1, 2 ⁇ 0.9 and component (B) at least 85 wt .-%, based on the weight of component (B), the constituents (B1 ), (B2), (B3) and (B4).
  • the invention further provides a process for preparing polyurethane foams by reacting (A) compounds having at least two isocyanate-reactive hydrogen atoms, hereinafter also referred to as polyol component, with (B) polyisocyanates, characterized in that as polyisocyanate ( B) the polyphenylenepolymethylene polyisocyanate according to the invention is used.
  • the invention furthermore relates to a process for preparing the polyphenylene polymethylene polyisocyanate according to the invention, comprising the steps
  • the polyphenylenepolymethylene polyisocyanate according to the invention has, in addition to components (B1) to (B4), further constituents.
  • the polyphenylenepolymethylene polyisocyanate (B) according to the invention also contains polyphenylenepolymethylene polyisocyanates with 6 or more cores.
  • the term "nucleus” is understood here to mean an aromatic ring, and the compounds containing more than two aromatic nuclei may also be referred to as higher homologs in the following.
  • the polyphenylenepolymethylene polyisocyanate (B) according to the invention may further comprise other compounds containing isocyanate groups, such as reaction products of isocyanates with one another, in particular uretonimines, and / or polyphenylenepolymethylene polyisocyanates having 6 or more cores.
  • the proportion of such further constituents of component (B) is preferably at most 15% by weight, based on the weight of component (B).
  • the polyphenylenepolymethylene polyisocyanate (B) preferably contains not more than 1% by weight, more preferably not more than 6% by weight and in particular not more than 3% by weight, based on the weight of (B), of uretonimines. These belong to the 15% by weight, based on the weight of (B), of the other compounds.
  • the determination of the contents of Polyphenylenpolymethylenpolyisocyanaten with different core contents is usually carried out by gas chromatography.
  • the content of uretonimines in polyphenylenepolymethylene polyisocyanate is determined by FT-IR analysis on the basis of a calibration with 3-core uretonimine (test method PFO / A 00 / 22-03).
  • the polyphenylenepolymethylene polyisocyanate according to the invention preferably has a content of free NCO end groups of from 31.0 to 33.3% by weight.
  • the polyphenylenepolymethylene polyisocyanate (B) according to the invention which has been obtained by means of extraction, preferably has an iodine color number of less than 5 iodine, an L * value of greater than 96 and a b * value of less than 15, determined in accordance with DIN 6162 and DIN 6164 ,
  • the polyphenylene polymethylene polyisocyanates according to the invention can be prepared by the usual methods. These are well known and include the preparation of diphenylmethanediamine (MDA) and its higher homologues by acid-catalyzed reaction of aniline and formaldehyde, neutralization and workup of the amine mixture thus obtained, its reaction with phosgene to polyphenylenpolymethylenpolyisocyanat and purification, work-up and optionally partial separation of the 2-core MDI.
  • MDA diphenylmethanediamine
  • the polyphenylenepolymethylene polyisocyanate (B) according to the invention prepared in this way preferably has an iodine color number of less than 10 iodine, an L * value of greater than 89 and a b * value of less than 30, determined in accordance with DIN 6162 and DIN 6164.
  • polyphenylenepolymethylene polyisocyanates according to the invention are prepared in a preferred process by first reacting polyphenylenepolymethylenepolyamine with phosgene in a process step a) in a conventional manner and liberating it in a subsequent process step b) from by-products, for example uretonimines.
  • by-products for example uretonimines.
  • alternative procedures are possible if they lead to the same products.
  • the process step a) is well known and comprises, as described above, the acid-catalyzed reaction of aniline with formaldehyde, neutralization and workup of the resulting polyamine, its reaction with phosgene to the corresponding polyisocyanate, its work-up and purification.
  • the polyphenylenepolymethylene polyisocyanate according to the invention in step b) is freed from secondary compounds, such as uretonimine. These are formed during the production and work-up, in particular by thermal loading of the polyisocyanates.
  • These secondary compounds from the production process are contained in the starting polyisocyanate to a maximum of 25 wt .-%.
  • the removal is preferably carried out by liquid-liquid extraction with polar or non-polar solvents.
  • preferred solvents are hydrocarbons, such as cyclohexane.
  • step b) the polyphenylene lenpolymethylenpolyisocyanat used with cyclohexane in the ratio of isocyanate: solvent of 1: 1 to 1: 15, preferably 1: 1, 5 to 1: 12 and more preferably 1: 2.5 to 1: 10 at a temperature of 20 to 90 0 C and preferably 30 to 80 0 C for 1 to 180 minutes, and preferably for 5 to 150 min in contact.
  • the product mixture is allowed to stand until complete phase formation at 20 to 40 0 C and preferably at room temperature.
  • the lower phase is the so-called "raffinate" containing the uretonimine to be separated as well as higher nuclear MDI homologs.
  • the upper phase is the so-called "extract" which contains the desired low-urethane polyphenylene polymethylene polyisocyanate and solvent. Both phases are separated and the solvent is almost completely removed, for example by means of vacuum distillation.
  • the residual content of cyclohexane is preferably less than 20 ppm.
  • the polyphenylenepolymethylene polyisocyanate (B) according to the invention which has been obtained by means of extraction, preferably has an iodine color number of less than 5 iodine, an L * value of greater than 96 and a b * value of less than 15, determined in accordance with DIN 6162 and DIN 6164.
  • polyphenylene polymethylene polyisocyanate batches which do not have the composition according to the invention can be subject.
  • the content of secondary compounds of more than 15% by weight can be reduced to the content according to the invention. It is also possible in this way to shift the core distribution in the direction of low-nuclear products.
  • the extraction of the polyphenylenepolymethylene polyisocyanate can also be carried out following the partial separation of 2-core MDI, since in this case there is frequently an increase in the content of secondary compounds.
  • the polyphenylenepolymethylene polyisocyanate (B) according to the invention which was obtained by the process characteristics described above in polyphenylenepolymethylene polyisocyanate preparation, preferably has a content of 2-core product (B1) of from 20 to 50% by weight, based on the weight of (B), wherein components (B2), (B3) and (B4) are in the weight ratio (B2): (B3): (B4) of 8 ⁇ 4: 3.5 ⁇ 1, 8: 1, 2 ⁇ 0.9 and component (B) contains at least 85% by weight, based on the weight of component (B), of components (B1), (B2), (B3) and (B4).
  • a content of 2-core product (B1) of from 20 to 50% by weight, based on the weight of (B), wherein components (B2), (B3) and (B4) are in the weight ratio (B2): (B3): (B4) of 8 ⁇ 4: 3.5 ⁇ 1, 8: 1, 2 ⁇ 0.9
  • component (B) contains at least
  • the polyphenylenepolymethylene polyisocyanate (B) When the polyphenylenepolymethylene polyisocyanate (B) according to the invention has been obtained by extraction, it preferably has a content of 2-core product (B1) of from 20 to 55% by weight, based on the weight of (B), where the constituents ( B2), (B3) and (B4) in the weight ratio (B2) :( B3) :( B4) of 8 ⁇ 4: 3.5 ⁇ 1, 8: 1, 2 ⁇ 0.9, and the component (B) at least 85% by weight, based on the weight of component (B), of components (B1), (B2), (B3) and (B4).
  • a content of 2-core product (B1) of from 20 to 55% by weight, based on the weight of (B), where the constituents ( B2), (B3) and (B4) in the weight ratio (B2) :( B3) :( B4) of 8 ⁇ 4: 3.5 ⁇ 1, 8: 1, 2 ⁇ 0.9
  • the polyphenylene polymethylene polyisocyanate (B) of the present invention is obtained by partial removal of the 2-core MDI and subsequent extraction, it preferably has a content of 2-core product (B1) of 2 to 20% by weight, based on the weight of ( B), wherein the components (B2), (B3) and (B4) in the weight ratio (B2) :( B3) :( B4) of 8 ⁇ 4: 3.5 ⁇ 1, 8: 1, 2 ⁇ 0.9 and component (B) contains at least 85% by weight, based on the weight of component (B), of components (B1), (B2), (B3) and (B4).
  • the polyphenylenepolymethylene polyisocyanate according to the invention can be used for the production of polyurethane foams.
  • Preferred applications here are 1-component polyurethane foams and rigid polyurethane foams.
  • the polyphenylenepolymethylene polyisocyanate (B) according to the invention is reacted with compounds having at least two isocyanate-reactive hydrogen atoms (A).
  • the reaction of the isocyanate component (B) with the compounds having at least two isocyanate-reactive hydrogen atoms (A) takes place in the presence of a blowing agent in a pressure vessel, preferably in an aerosol can.
  • a blowing agent in a pressure vessel, preferably in an aerosol can.
  • the polyol component (A) and the isocyanate component (B) are charged in the abovementioned ratio together with a blowing agent into a pressure vessel so that the prepolymer according to the invention with a lower content of free isocyanate groups is formed in the pressure vessel.
  • Typical blowing agents for preparing the 1-component mounting foams are, for example, R134a (tetrafluoroethane), R152a (1,1-difluoroethane), dimethyl ether, propane, n-butane, isobutane, preferably mixtures of propane, n-butane and isobutane ,
  • the NCO content of the prepolymers in the aerosol can is preferably in the range of about 5 to 28 wt .-%, preferably 8 to 24 wt .-%, particularly preferably 9 to 18 wt .-%.
  • Prepolymers with a lower NCO content lead to softer aerosol foams, those having a higher NCO content corresponding to harder foams.
  • the pressure vessel is expanded.
  • the exiting prepolymer is foamed by the Froth effect of the propellant and hardens by the humidity.
  • Trialkylphosphates and trichloroalkylphosphates are mostly used as additive flame retardants.
  • the alkyl radicals preferably have 1 to 4, more preferably 1 to 3 carbon atoms.
  • Particularly preferred compounds are trimethyl phosphate, triethyl phosphate, tripropyl phosphate, trichloromethyl phosphate, trichloroethyl phosphate and trichloropropyl phosphate. These can be used individually or in any mixtures with each other.
  • the amount of additive flame retardant depends on the requirements of the foam.
  • the canned NCO prepolymer must be present in the
  • an isocyanate component in the present process the polyphenylenepolymethylene polyisocyanate (B) according to the invention being used, with the compounds having at least two isocyanate-reactive hydrogen atoms (A) in the presence of catalysts and blowing agents Implementation brought.
  • blowing agent water can be used which reacts with isocyanate groups with the cleavage of carbon dioxide.
  • physical blowing agents can also be used. 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. fen. The boiling point of these compounds is preferably 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, low-boiling alkanes and fluoroalkanes.
  • the compounds are for the most part selected from the group comprising alkanes and / or cycloalkanes having at least 4 carbon atoms, dialkyl ethers, esters, ketones, acetals,
  • 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 are harmless, such as trifluoromethane, difluoromethane, 1, 1, 1, 3,3-pentafluorobutane, 1,1,1,3,3-pentafluoropropane, 1,1,1,2-tetrafluoroethane, difluoroethane and heptafluoropropane. Particular preference is given to using cyclopentane and / or n-pentane.
  • the said physical blowing agents can be used alone or in any combination with each other.
  • the polyol component (A) and the polyisocyanates (B) are reacted in amounts such that the isocyanate index is in a range between 100 and 220, preferably between 125 and 195.
  • the rigid polyurethane foams can be prepared batchwise or continuously by means of known mixing devices.
  • the rigid polyurethane foams according to the invention are usually prepared by the two-component process.
  • the compounds are mixed with at least two isocyanate-reactive hydrogen atoms (A), with the flame retardants, the blowing agents, the catalysts and other auxiliaries and / or additives to the so-called polyol and these with the polyisocyanates or mixtures of the polyisocyanates and, if appropriate, flame retardants and blowing agents, also referred to as the isocyanate component, for the reaction.
  • A isocyanate-reactive hydrogen atoms
  • the starting components are usually mixed at a temperature of 15 to 35 0 C, preferably from 20 to 30 0 C.
  • the reaction mixture can be poured into closed support tools with high or low pressure metering machines. According to this technology z. B. manufactured discontinuous sandwich panels.
  • the foams produced by the process according to the invention have a very light, sometimes even white color.
  • the foams are dimensionally stable and can be applied very well.
  • Suitable compounds having at least two isocyanate-reactive hydrogen atoms (A) which can be used for the process according to the invention are in particular polyether alcohols and / or polyester alcohols in the production of the rigid foams and in the preparation of the prepolymers for the 1-component structural foams OH numbers in the range of 100 to 1200 mgKOH / g are used.
  • the polyester alcohols used 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, suberic acid, azelaic acid, sebacic acid, Decanedicarboxylic acid, maleic acid, fumaric acid and preferably phthalic acid, isophthalic acid, terephthalic acid and the isomeric naphthalenedicarboxylic acids.
  • the polyether alcohols used usually have a functionality between 2 and 8, in particular 3 to 8.
  • polyether polyols 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 trimethylolpropane, glycerol, pentaerythritol, sugar compounds such as glucose, sorbitol, mannitol and sucrose, polyhydric phenols, resoles such as oligomeric condensation products of phenol and formaldehyde and Mannich condensates from phenols, formaldehyde and dialkanolamines and melamine used.
  • starting molecules having at least two primary amino groups in the molecule are preferably aromatic di- and / or polyamines, for example phenylenediamines, 2,3-, 2,4-, 3,4- and 2,6-toluenediamine and 4,4'-, 2 , 4'- and 2,2'-diamino-diphenyl methane and aliphatic di- and polyamines, such as ethylenediamine used.
  • aromatic di- and / or polyamines for example phenylenediamines, 2,3-, 2,4-, 3,4- and 2,6-toluenediamine and 4,4'-, 2 , 4'- and 2,2'-diamino-diphenyl methane and aliphatic di- and polyamines, such as ethylenediamine used.
  • the polyether polyols have a functionality of preferably 3 to 8 and hydroxyl numbers of preferably 100 mgKOH / g to 1200 mgKOH / g and especially 240 mgKOH / g to 570 mgKOH / g.
  • polyols in particular polyether alcohols having a hydroxyl number of less than 100 mg KOH / g and a functionality of from 2 to 3.
  • the properties of the foams can be adjusted, for example in the case of 1-component assembly foams, in the direction of greater flexibility.
  • the compounds having at least two isocyanate-reactive hydrogen atoms (A) also include the optionally used chain extenders and crosslinkers.
  • chain extenders and crosslinkers are preferably used alkanolamines and in particular diols and / or triols having molecular weights less than 400, preferably 60 to 300.
  • Chain extenders, crosslinking agents or mixtures thereof are expediently used in an amount of from 1 to 20% by weight, preferably from 2 to 5% by weight, based on the polyol component (A).
  • chain extenders and crosslinkers monoolers can in the field of 1-component polyurethane foams for the production of the required polyol component (A) as further OH-functional compounds as a targeted agent for molecular weight control, to form a permeable foam skin and finally Storage stability improvement can be used.
  • These monools having molecular weights of up to 1400 g / mol (OH number about 40 mgKOH / g) are usually used, if necessary, in proportions of up to 10% by weight, based on the polyol component (A).
  • the polyol component (A) is a mixture of
  • (A1) a polyester polyol having a molecular weight of at most 600 g / mol and
  • (A2) a polyether polyol or polyether polyol mixture having an average molecular weight of 1000 to 5000 g / mol.
  • polyester polyol (A1) a polyester polyol based on phthalic anhydride / diethylene glycol / polyethylene glycol is preferably used.
  • the polyols (A1) and (A2) are preferably used in a weight ratio of polyester polyol (A1) to polyether polyol or polyether polyol mixture (A2) in the range from 1: 6 to 3: 1.
  • 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. As secondary aliphatic amines, imidazoles, amidines, and alkanolamines.
  • isocyanurate groups are to be incorporated into the rigid foam, special catalysts are required.
  • the isocyanurate catalysts used are usually metal carboxylates, in particular potassium acetate and its solutions.
  • the reaction of components (A) and (B) is usually carried out at an index of 160 to 450
  • Embodiment 1 - (One Component Foam)
  • Polyphenylene polymethylene polyisocyanate (trade name: Lupranat ® M20), having a monomeric MDI content of 37%, an NCO content of 31, 2 wt .-%, a viscosity of 213 mPa-s at 25 0 C, a color number of 20 Iodine an L * value of 85.6, a b * value of 70.1 and a uretonimine content of 8.4 wt% was extracted in a one-step extraction process as described below with cyclohexane.
  • Polyphenylenepolymethylene was cyanate with cyclohexane in the ratio of iso-: solvent of 1: 3 at 50 0 C for 60 min contacted. Thereafter, the product mixture was allowed to stand at room temperature until complete phase formation.
  • the upper phase was the so-called "extract" containing the desired polyphenylene polymethylene polyisocyanate and solvent.
  • the solvent was removed from the
  • Viscosity 50 mPas (25 ° C)
  • NCO content 32.6% by weight
  • the product prepared as described above was used in this form as an isocyanate component for the subsequent 1-component assembly foam production.
  • the discharge was carried out in foam strands, whereby a wetting of the foam surface with water took place between the foam strands discharged in layer form.
  • the cured foam was tested for its properties (see Table 1.4).
  • Exemplary embodiment 2 (two-component rigid polyurethane foam)
  • Lupranol 3424 polyether polyol based on sucrose, pentaerythritol, diethylene glycol and propylene oxide having an OH number of 403 mgKOH / g
  • 230 g of Lupranol 3423 polyether polyol based on sucrose, glycerol and propylene oxide having an OH number of 490 mgKOH / g
  • 20 g glycerine 300 g Lupranol 1 100 (polyether polyol based on propylene glycol and propylene oxide with an OH number of 104 mgKOH / g), 54 g Lupranol VP9319 (polyether polyol based on trimethylolpropane and propylene oxide with an OH number of 160 mg KOH / g), 10 g of stabilizer Tegostab B8443, 5 g of stabilizer Niax SiIi cone SR 393 and 4.5 g of water, a polyol
  • This mixture was mixed both 34 g of a catalyst mixture (23.3% N, N-dimethylcyclohexylamine, 18.7% 1-methylimidazole, 28% tetramethylhexanediamine and 30% Lupranol 1200 [polyether polyol based on propylene glycol and propylene oxide having an OH number of 248 mg KOH / g]) as well as 50 g of an aqueous glycerol / glycol mixture (containing 9% gyzerin and 31% dipropylene glycol) were added and the polyol component made therefrom.
  • a catalyst mixture 23.3% N, N-dimethylcyclohexylamine, 18.7% 1-methylimidazole, 28% tetramethylhexanediamine
  • Lupranol 1200 polyether polyol based on propylene glycol and propylene oxide having an OH number of 248 mg KOH / g]
  • the isocyanate component according to Embodiment 1.2 was used.
  • the foam had (free-foamed) the following properties:
  • composition analog execution example 2.1 rigid foam sandwich panels are relatively analogous to the composition according to execution example 1.2 and the other using previously commercially available polyphenylene polymethylene polyisocyanate (trade name: Lupranat ® M20) on the one hand by using an isocyanate component prepared and measure their shrinkage after curing.
  • polyphenylene polymethylene polyisocyanate trade name: Lupranat ® M20

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

Abstract

L'invention concerne des polyphénylène polyméthylène polyisocyanates (B), contenant (B1) le produit principal 2 du polyphénylène polyméthylène polyisocyanate, (B2) le produit principal 3 du polyphénylène polyméthylène polyisocyanate, (B3) le produit principal 4 du polyphénylène polyméthylène polyisocyanate, (B4) le produit principal 5 du polyphénylène polyméthylène polyisocyanate, les constituants (B2), (B3) et (B4) étant présents, pour une teneur de (B1) inférieure ou égale à 55 % en poids, par rapport au poids de (B), en un rapport pondéral (B2):(B3):(B4) de 8 ± 4:3,5 ± 1,8:1,2 ± 0,9 et le composant (B) contenant au moins 85 % en poids, par rapport au poids du composant (B), des constituants (B1), (B2), (B3) et (B4).
EP07822476A 2006-11-17 2007-11-12 Polyphénylène polyméthylène polyisocyanate et son utilisation pour la fabrication de mousses en polyuréthanne Withdrawn EP2091992A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07822476A EP2091992A1 (fr) 2006-11-17 2007-11-12 Polyphénylène polyméthylène polyisocyanate et son utilisation pour la fabrication de mousses en polyuréthanne

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EP06124306 2006-11-17
PCT/EP2007/062188 WO2008058920A1 (fr) 2006-11-17 2007-11-12 Polyphénylène polyméthylène polyisocyanate et son utilisation pour la fabrication de mousses en polyuréthanne
EP07822476A EP2091992A1 (fr) 2006-11-17 2007-11-12 Polyphénylène polyméthylène polyisocyanate et son utilisation pour la fabrication de mousses en polyuréthanne

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EP2091992A1 true EP2091992A1 (fr) 2009-08-26

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US9657133B2 (en) * 2007-01-12 2017-05-23 Basf Se Rigid polyurethane foams
GB201106774D0 (en) * 2011-04-21 2011-06-01 Occutec Ltd Polymers for contact lenses
ES2570353T3 (es) * 2012-01-18 2016-05-18 Basf Se Método para la producción de espumas duras de poliuretano
US10472454B2 (en) 2012-01-18 2019-11-12 Basf Se Preparing rigid polyurethane foams
KR102074533B1 (ko) * 2012-04-30 2020-02-06 코베스트로 도이칠란드 아게 발포 성형체의 제조 방법
EP3077435B1 (fr) * 2013-12-04 2018-01-31 Covestro Deutschland AG Système réactionnel pour une mousse de polyuréthane à un component à faible taux de monomère
PL235304B1 (pl) * 2014-01-14 2020-06-29 Selena Labs Spolka Z Ograniczona Odpowiedzialnoscia Jednoskładnikowa mieszanina prepolimeru izocyjanianu oraz sposób wytwarzania pianki poliuretanowej w pojemniku dozującym w jednoetapowym procesie
JP6480775B2 (ja) * 2015-03-26 2019-03-13 積水化学工業株式会社 ウレタン樹脂組成物、建材の耐火補強方法、および建材の耐火補強構造
KR20170139022A (ko) * 2015-04-21 2017-12-18 코베스트로 도이칠란트 아게 단열성 조건 하에 제조된 폴리이소시아누레이트 중합체를 기재로 하는 고형물

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PL1518874T3 (pl) * 2003-09-24 2007-05-31 Basf Se Mieszanina zawierająca polimeryczny MDI, o małej zawartości monomeru
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US9657133B2 (en) * 2007-01-12 2017-05-23 Basf Se Rigid polyurethane foams
US20090082481A1 (en) * 2007-09-21 2009-03-26 O'connor James Preparation of liquid isocyanurate-modified polymethylene bis(phenylisocyanate) compositions of controlled viscosities
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JP2010510339A (ja) 2010-04-02
WO2008058920A1 (fr) 2008-05-22
US20100076101A1 (en) 2010-03-25
KR20090091739A (ko) 2009-08-28
CN101563387A (zh) 2009-10-21

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