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
  • C08G18/4816—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
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
  • C08G18/1825—Catalysts containing secondary or tertiary amines or salts thereof having hydroxy or primary amino 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
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
  • C08G18/1833—Catalysts containing secondary or tertiary amines or salts thereof having ether, acetal, or orthoester 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
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
  • C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
  • C08G18/3834—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing hydrazide or semi-carbazide 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
  • C08G18/409—Dispersions of polymers of C08G in organic compounds having active hydrogen
• • 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
  • C08G18/4833—Polyethers containing oxyethylene units
  • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
  • C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end 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
  • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
  • C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 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
  • C08G18/28—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
  • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
  • C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
  • C08K5/24—Derivatives of hydrazine
  • C08K5/26—Semicarbazides
• • 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
  • C08G2110/0008—Foam properties flexible
• • 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
  • C08G2110/0041—Foam properties having specified density
  • C08G2110/0058—≥50 and <150kg/m3
• • 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
  • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
• • 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
  • C08G2290/00—Compositions for creating anti-fogging
• • 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
  • C08G2350/00—Acoustic or vibration damping material

Definitions

• the object of the present invention was therefore to develop a process for the production of polyurethane foams which leads to polyurethane foams with reduced formaldehyde emission and wherein the activity of the raw material mixture is not significantly affected and the mechanical properties of the resulting foam (in particular compression set and wet aging behavior) are not negative to be influenced.
• the resulting foams should also have a low migration and emission behavior with respect to the activators and additives used.
• the present invention is a process for the preparation of polyurethane foams with reduced formaldehyde emission by reacting
• A2 optionally with isocyanate-reactive hydrogen-containing compounds having a molecular weight of 62-399,
• A5 compounds having at least one semicarbazide group having at least one semicarbazide group
• the amount used of component A5 according to the invention is 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight.
• the present invention particularly relates to a process for the preparation of polyurethane foams having reduced formaldehyde emission by reacting
• Component A is a compound having Component A:
• A2 0 to 10 parts by weight, preferably 0, 1 to 2 parts by weight (based on the sum of the parts by weight of components AI to A4) of isocyanate-reactive hydrogen-containing compounds having a molecular weight of 62-399,
• A3 0.5 to 25 parts by weight, preferably 2 to 5 parts by weight (based on the sum of the parts by weight of components A I to A4) of water and or physical blowing agents,
• auxiliaries and additives such as
• A5 0.1-10 parts by weight, preferably 0.2-7.5 parts by weight (based on the sum of the parts by weight of components A I to A4) of compounds having at least one semicarbazide group,
• Component B is a compound having Component B:
• the preparation is carried out at a ratio of 50 to 250, preferably 70 to 130, more preferably 75 to 1 15, and wherein all parts by weight of the components AI to A4 in the present application are normalized such that the sum of the parts by weight of the components A 1 + A2 + A3 + A4 in the composition 100 results.
• compounds having at least one semicarbazide group component A5 surprisingly act as formaldehyde scavengers.
• Another object of the invention is therefore the use of the compounds having at least one Semicarbazidense (component A5) in polyurethane compositions or in processes for the production of polyurethane foams to reduce the formaldehyde emission.
• isocyanate-based foams are known per se and e.g. in DE-A 1 694 142, DE-A 1 694 215 and DE-A 1 720 768 and in the Kunststoff-Handbuch Volume VII, Polyurethane, edited by Vieweg and Höchtlein, Carl Hanser Verlag Kunststoff 1966, as well as in the new edition of this book, edited by G. Oertel, Carl Hanser Verlag Kunststoff, Vienna 1993.
• foams having urethane and / or uretdione and / or urea and / or carbodiimide groups.
• the use according to the invention is preferably carried out in the production of polyurethane and polyisocyanurate foams.
• Starting components according to component AI are compounds having at least two isocyanate-reactive hydrogen atoms of a molecular weight, generally from 400 to 15,000. This is understood as meaning, in addition to amino groups, thio groups or carboxyl-containing compounds, preferably compounds containing 2 to 8 hydroxyl groups especially those of molecular weight 1000 to 6000, preferably 2000 to 6000, for example at least 2, usually 2 to 8, but preferably 2 to 6, hydroxyl-containing polyethers and polyesters and polycarbonates and polyester amides, as they are known per se for the preparation of homogeneous and cellular polyurethanes and as described for example in EP-A 0 007 502, pages 8-1 5 ,
• the polyethers containing at least two hydroxyl groups are preferred according to the invention.
• component A2 compounds having at least two isocyanate-reactive hydrogen atoms and a molecular weight of from 32 to 399 are used as component A2.
• component A2 compounds having at least two isocyanate-reactive hydrogen atoms and a molecular weight of from 32 to 399 are used as component A2.
• These are to be understood as meaning hydroxyl-containing and / or amino-containing and / or thiol-containing and / or carboxyl-containing compounds, preferably hydroxyl-containing and / or amino-containing compounds which serve as chain extenders or crosslinkers.
• These compounds generally have from 2 to 8, preferably from 2 to 4, isocyanate-reactive hydrogen atoms.
• ethanolamine, diethanolamine, triethanolamine, sorbitol and / or glycerol can be used as component A2. Further examples of compounds according to component A2 are described in EP-A 0 007 502, pages 16-17.
• component A3 water and / or physical blowing agents are used.
• physical blowing agents for example, carbon dioxide and / or volatile organic substances are used as blowing agents.
• auxiliary agents and additives are optionally used, such as
• surfactants such as emulsifiers and foam stabilizers insbesodere those with low emissivity such as products of Tegostab ® LF series,
• reaction retarders e.g., acidic species such as hydrochloric acid or organic acid halides
• cell regulators such as paraffins or fatty alcohols or
• Dimethylpolysiloxanes Dimethylpolysiloxanes
• pigments dyes
• flame retardants such as tricresyl phosphate
• stabilizers against aging and weathering plasticizers
• fungistatic and bacteriostatic substances fillers (such as barium sulfate, diatomaceous earth, soot or whiting) and release agents.
• auxiliaries and additives are described, for example, in EP-A 0 000 389, pages 18-21. Further examples of auxiliaries and additives which may optionally be used according to the invention and details of the use and mode of action of these auxiliaries and additives are published in the Kunststoff-Handbuch, Volume VII, by G. Oertel, Carl-Hanser-Verlag, Kunststoff, 3rd edition, 1993, for example described on pages 104-127.
• the catalysts used are preferably aliphatic tertiary amines (for example trimethylamine, tetramethylbutanediamine), cycloaliphatic tertiary amines (for example 1,4-diaza (2,2,2) bicyclooctane), aliphatic aminoethers (for example dimethylaminoethyl ether and ⁇ , ⁇ , ⁇ -trimethyl-N- hydroxyethyl bisaminoethyl ethers), cycloaliphatic amino ethers (for example N-ethylmorpholine), aliphatic amidines, cycloaliphatic amidines, urea, derivatives of urea (such as aminoalkyl ureas, see, for example, EP-A 0 176 013, in particular (3-dimethylaminopropylamine) urea) and Tin catalysts (such as dibutyltin oxide, dibutyltin dilaurate, tin octo
• ß ß
• ß ß
• amines and amino ethers which each contain a functional group which reacts chemically with the isocyanate.
• the functional group is a hydroxyl group, a primary or secondary amino group.
• catalysts are: (3-dimethylaminopropylamine) urea, 2- (2-dimethylaminoethoxy) ethanol, N, N-bis (3-dimethyl-aminopropyl) -N-isopropanolamine, ⁇ , ⁇ , ⁇ -trimethyl N-hydroxyethyl bisaminoethyl ether and 3-dimethylaminopropylamine.
• the compounds according to component A5 are compounds having at least one semicarbazide group, ie having the structural element shown in the following formula (I),
• R is an alkyl, an alkylaryl or an aryl radical, which may in turn have or may be substituted by a semicarbazide group and / or other functional groups.
• other functional groups are, for example, a hydrazone group, an ester group, a urea group, a urethane group, an anhydride group.
• a substituted alkyl, an alkylaryl or an aryl radical is understood to mean that the radical R can also contain heteroatoms such as, for example, halogen atoms, phosphorus atoms, sulfur atoms and can also be branched with alkyl or aryl groups.
• An alkyl radical is preferably C
• An aryl radical is preferably phenyl, which may also be substituted by alkyl.
• An alkaryl group contains alkyl and aryl groups. Examples of compounds having at least one semicarbazide group (component A5) are, by way of example and by way of preference, the compounds according to formulas (II) to (VIII).
• m is an integer from 1 to 16, preferably from 6 to 12, particularly preferably 6 or 12.
• compounds having at least one semicarbazide group are also compounds having an oligomeric or polymeric structure ("polyhydrazodicarbonamides"), as illustrated by way of example in formula (X),
• formula (X) i is an integer from 2 to 100,000, preferably from 1,000 to 50,000, more preferably from 5,000 to 25,000.
• the compounds according to component A5 can be prepared, for example, by reacting the underlying isocyanates with hydrazine according to the processes known to those skilled in the art, as exemplified in the experimental part of the present invention or in Mihail lonescu: "Chemistry and Technology of Polyols for Polyurethanes", Rapra Technology, Shawbury, Shrewsbury, Shropshire, 2005, pp. 215-219.
• component B aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates are used, as they are e.g. by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, for example those of the formula (V)
• n 2 - 4, preferably 2 -3,
• Q is an aliphatic hydrocarbon radical having 2 to 18, preferably 6 to 10 C atoms, a cycloaliphatic hydrocarbon radical having 4 to 15, preferably 6 to 13 C atoms or an araliphatic hydrocarbon radical having 8 to 15, preferably 8 to 13, C atoms.
• polyisocyanates as described in EP-A 0 007 502, pages 7-8.
• Particularly preferred are generally the technically readily available polyisocyanates, e.g. the 2,4- and 2,6-toluene diisocyanate, as well as any mixtures of these isomers ("TDI”); polyphenyl polymethylene polyisocyanates, as prepared by aniline-formaldehyde condensation and subsequent phosgenation (“crude MDI”) and carbodiimide groups, urethane groups, allophanate groups , Isocyanurate groups, urea groups or biuret polyisocanates ("modified polyisocyanates”), especially those modified polyisocyanates derived from 2,4- and / or 2,6-toluene diisocyanate or from 4,4'- and / or 2,4 '
• component B at least one compound selected from the group consisting of 2,4- and 2,6-toluene diisocyan
• reaction components are reacted according to the conventional one-shot process, the prepolymer process or the semi-prepolymer process, often using machinery, e.g. those described in EP-A 355 000. Details of processing means which are also contemplated by this invention are described in the Kunststoff-Handbuch, Volume VII, edited by Vieweg and Hochtlen, Carl-Hanser-Verlag, Kunststoff 1993, e.g. on pages 139 to 265.
• the polyurethane foams can be produced as molded or also as block foams. Molded foams can be produced hot or cold-curing.
• the invention therefore relates to a process for the preparation of the polyurethane foams, the polyurethane foams produced by this process and their use for the production of moldings and the moldings themselves.
• polyurethane foams obtainable according to the invention find, for example, the following application: furniture upholstery, Texti lein layers, mattresses, automobile seats, headrests, armrests, sponges and components, as well as seats and armature panels.
• Polyether polyol of OH number 28 prepared by addition of propylene oxide and ethylene oxide in the ratio 86.2 to 13.8% using glycerol as a starter with at least 80% primary OH groups.
• Polyether polyol of OH number 37 prepared by addition of ethylene oxide and propylene oxide in the ratio of 72.5% and 27.5% using glycerol as a starter with at least 80% primary OH groups.
• Component A2-1 Diethanolamine
• Component A3-1 Water
• Component A4-1 is a compound having Component A4-1:
• Activator Dabco ® NE 300 (Air Products); contains a urea derivative.
• Component A5-1 is a compound having Component A5-1:
• Toluylene bis-semicarbazide mixture of 2,4-isomer (IV) and 2,6-isomer (V) in the ratio 80:20.
• Polyhydrazodicarbonamide used as a dispersion in a polyether polyol, the dispersion containing 20 wt .-% Polyhydrazodicarbonamid.
• the dispersion of polyhydric dicarbonamide was prepared by reacting in a polyether polyol by reacting toluene diisocyanate (mixture of 2,4-isomer and 2,6-isomer in the ratio 80:20) with hydrazine.
• MDI Isocyanate mixture
• Polyphenylpolymethylenpolyisocyanat (“multi-core MDI"). Production of molded parts
• the starting components are introduced into a heated to 60 ° C form of the volume 12.5 L and after 4 min. removed from the mold.
• the input quantity of the raw materials was selected so that a calculated molding density of 55 kg / m3 results.
• Table 1 gives the actual density of the formed part, which was determined by weighing the compression hardness specimen.
• the index (isocyanate index) gives the percentage ratio of the actual amount of isocyanate used to the stoichiometric, i. calculated isocyanate groups (NCO) amount:
• the compression set DVR 50% and DVR 75% were determined according to DIN EN ISO 1856-2001 -03 at 50% and 75% deformation.
• the formaldehyde content was carried out on the basis of that of BMW method AA-C291, in contrast to this method (a) square glass bottles were used instead of round polyethylene bottles, (b) the test specimen used a thickness of 1 cm (instead of 4 mm ), (c) a calibration standard from Cerilliant was used and (d) the moisture content of the sample was not determined.

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

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