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
  • C08G18/409—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
  • C08G18/70—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
  • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
  • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures

Definitions

• the invention relates to flame-retardant HR cold-molded foams with reduced flue gas intensity and toxicity, processes for their production and their use.
• Cold-curing flexible polyurethane foams are used, among other things. used as seats, backrests or headrests in automobiles, rail and water vehicles, airplanes and in the furniture sector.
• the flame retardancy of the foams plays a role in all of the above-mentioned areas.
• the requirements for flame retardancy are particularly high for rail vehicles, airplanes and furniture.
• To comply with the relevant standards e.g. To meet BS 5852, Part 2, Crib Ignition Source V, CSE RF4 / 83 or UIC 564/2 or DIN 54341, ASTM E 162, California TB 133, melamine is added to the foam as a flame retardant.
• the disadvantage here is that a solid with dust in the
• Polyol formulation must be stirred.
• the solid melamine sediments out of the polyol formulation, which makes processing difficult. Sedimentation of the melamine can be prevented by using special stabilized melamine dispersions in polyethers, as described in DE-OS 195 40 809 and EP-A 835 905.
• the melamine can be prevented by using special stabilized melamine dispersions in polyethers, as described in DE-OS 195 40 809 and EP-A 835 905.
• PHD or PIPA polymer polyols preserve HR cold molded foams with reduced flammability, smoke density and toxicity as well as improved mechanical properties.
• the subject of the invention is therefore an HR cold molded foam, obtainable by
• e) compounds having at least two isocyanate-reactive hydrogen atoms and a molecular weight of 32 to 399, and / or
• modified tolylene diisocyanate (TDI) is used as component a).
• the isomer ratio of 2,4-TDI to 2,6-TDI can be from 100: 0 to 65:35.
• the TDI is modified in a manner known to those skilled in the art, as described in G. Oertel (ed.): "Kunststoff-Handbuch", Volume VII, Carl
• biuretized tolylene diisocyanate types for example the high-performance TDI, can be used to produce the HR cold-molded foams according to the invention.
• the polyol component b) contains dispersions of polymers containing higher molecular weight hydroxyl compounds, which by reacting mono- and / or polyisocyanates with primary and / or secondary amino groups containing polyamines and / or hydrazines and / or hydrazides and or alkanolamines in a 1 to 8 primary and / or secondary hydroxyl group-containing polyethers with a number average molecular weight of 400 to 16,000 (“base polyol”). Base polyols with a number average molecular weight of 1,500 to 8,000 are preferably used. Hydroxyl compounds are preferably used which react with base polyols by reaction of base polyols Hydrazines have been produced (PHD polyols).
• Component b) preferably has an average OH functionality of 2.0 to 3.5. Preference is given to using polyether polyols which contain at least 60 mol% of primary OH groups. , preferably at least 70 mol% au f und.
• the component preferably contains, in addition to a base polyol with an ethylene oxide content of at most 40% by weight, at least one further polyether polyol with an average functionality of 2 to 6, a number average molecular weight of 1500 to 12000 in a proportion of 1 up to 50 wt .-%, based on the total amount of
• Component b) with an EO content of more than 40% by weight This execution form leads to better skin formation, increased open cell structure and allows greater scope for setting the NCO / OH index and thus better processability of the formulation.
• a foam is obtained which has an increased elasticity and whose hardness, which can be high due to the polymer dispersion, is reduced to such an extent that soft molded parts can also be produced.
• Chemical and / or physical blowing agents c) are used to produce the foams according to the invention.
• component c) water is preferably used as the chemical blowing agent which, by reaction with isocyanate groups, supplies carbon dioxide as the blowing gas. Water in an amount of 2-
• component b 8% by weight, particularly preferably 2 to 4% by weight, based on the amount of component b), is used.
• carbon dioxide can also be added as a gas or liquid online or in a batch process to the polyol or isocyanate component using the processes known per se.
• non-flammable physical blowing agents such as e.g.
• Dichloromethane dichloromonofluoromethane, difluoromethane, trifluoromethane, difluoroethane, 1,1,1,2-tetrafluoroethane, tetrafiuoroethane (R 134 or R 134a), 1,1,1,3,3,3-hexafluoropropane (R 356), 1 , 1,1,3,3-pentafluoropropane (R 245fa), chlorodifluoroethane, l, l-dichloro-2,2,2-trifluoroethane, 2,2-dichloro-2-fluoroethane, heptafluoropropane and sulfur hexafluoride can be used.
• blowing agent Since the blowing agent escapes almost completely from the foam during the manufacturing process, low-boiling hydrocarbons, e.g. Pentane, hexane and their isomers are used.
• Other suitable blowing agents are carboxylic acids such as formic acid, acetic acid, oxalic acid and chemical blowing agents, which release gases in the course of the foaming process, such as. B. Carbamates. Mixtures of these blowing agents can also be used. These blowing agents are preferably used in combination with water.
• Flame retardants d) which are liquid and / or soluble in one of components a) or b) or in both components are optionally used to produce the foams according to the invention.
• Commercially available phosphorus-containing flame retardants are preferably used, for example tricresyl phosphate, tris (2- chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (1,3-dichloropyl) phosphate, tetrakis (2-chloroethyl) ethylene diphosphate, dimethyl methane phosphonate, Diethylethanephosphonat, Diethanolaminomethylphosphonklathylester.
• Halogen- or or phosphorus-containing, flame-retardant polyols or mixtures of the aforementioned are also suitable
• the flame retardants are preferably used in an amount of at most 35% by weight, preferably at most 20% by weight, based on component b).
• compounds having at least two hydrogen atoms which are reactive toward isocyanates and a molecular weight of 32 to 399 e) are optionally used. This is taken to mean hydroxyl groups and / or amino groups and / or thiol groups and / or carboxyl group-containing compounds, preferably compounds containing hydroxyl groups and / or amino groups, which serve as chain extenders or crosslinking agents. These compounds generally have 2 to 8, preferably 2 to 4, hydrogen atoms which are reactive toward isocyanates. Examples of this are described in DE-OS 28 32 253, p.10-20. In a preferred embodiment, mixtures of at least two of these chain extenders and / or crosslinking agents are used. preferred
• Chain extenders and / or crosslinking agents are, for example, glycerol, triisopropanolamine, ethylene glycol, diethanolamine and triethanolamine.
• auxiliaries and additives f) can also be added in the production of the HR cold-molded foams according to the invention. These are, for example, catalysts which accelerate the reaction between the isocyanate component a) and the polyol component b).
• Suitable catalysts are organic tin compounds such as tin (II) salts of organic carboxylic acids, for example tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate and tin (II) laurate and the dialkyltin (IV) salts, for example Dibutyltin diacetate, dibutyltin dilaurate and dioctyltin diacetate.
• tin (II) salts of organic carboxylic acids for example tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate and tin (II) laurate and the dialkyltin (IV) salts, for example Dibutyltin diacetate, dibutyltin dilaurate and dioctyltin diacetate.
• Suitable catalysts are amines such as dimethyl aminopropylurea, dimethylaminopropylamine, bis (dimethylaminopropyl) amine, diazabicyclooctane, dimethylethanolamine, triethylamine, dimethylcyclohexylamine, dimethylbenzylamine, pentamethyldiethylenetriamine, N, N, N ', N'-tetramethylbutanediamine, bis (ether) methylamorphino (N) -dimethylmorphino-methyl, bis (ether) methylamorphamino alkyl) -s-hexahydrotriazines.
• the catalyst component preferably contains at least one aliphatic amine.
• Paraffins or fatty alcohols or dimethylpolysiloxanes as well as pigments or dyes, stabilizers against aging and weathering, plasticizers such as dioctyl phthalate and fungistatic and bacteriostatic substances can also be used. These are usually added to the polyol component in amounts of 0 to 10 parts by weight, preferably 0 to 5 parts by weight.
• plasticizers such as dioctyl phthalate and fungistatic and bacteriostatic substances.
• reaction components are usually according to the known
• the foaming is preferably carried out in closed molds.
• the reaction mixture is introduced into a mold.
• Metal e.g. As aluminum or plastic, e.g. B. epoxy, in question.
• the foamable reaction mixture foams in the mold and forms the shaped body.
• the foams according to the invention are preferably produced in such a way that the NCO / OH index, i.e. the stoichiometric ratio between reactive isocyanate groups and hydroxyl groups multiplied by 100, between 65 and
• the NCO / OH index is particularly preferably from 70 to 110.
• the density of the shaped bodies formed is preferably from 30 to 120 kg / m 3 .
• the ratio of the components is selected such that the filler content of the foam formulation, ie the proportion of the dispersed polymer component contained in component b) in the total amount of the foam formulation, is 3 to 30% by weight, preferably 4 to 16 % By weight.
• the invention also relates to the use of the foam materials according to the invention as cushioning material for z. B. seats, backrests and armrests and headrests in automobiles, rail vehicles, aircraft and watercraft and in furniture for private and public applications.
• Polyol A polyether triol, OHZ 28, EO content approx. 13.5% by weight, filled with
• Polyol B polyether triol, OHZ 28, EO content approx. 13.5% by weight, filled with 20% by weight styrene-acrylonitrile polymer
• Polyol C polyether polyol PIPA, preparation see below
• Polyol D polyether triol, OHZ 28, EO content approx. 13.5% by weight
• Polyol E polyether diol, OHZ 28, EO content approx. 13.5% by weight
• Polyol F polyether triol, OHZ 37, EO content approx. 85% by weight
• Polyol G polyether diol, OHZ 56, EO content approx. 50% by weight
• Isocyanate 1 modified TDI (biuret) with an NCO content of 42% by weight
• Isocyanate 2 modified TDI (biuret) with an NCO content of 37% by weight
• Isocyanate 3 modified TDI (AUophanat) with an NCO content of 40.7% by weight
• Isocyanate 4 modified TDI (prepolymerized with polyol D) NCO content of
• Isocyanate 5 TDI with 80% of the 2,4-isomer (Desmodur ® T80 from Bayer AG)
• Niax Catalyst AI bis (dimethylaminoethyl) ether, 70% in dipropylene glycol
• TCPP Tris (2-chloropropylphosphate) (Levagard PP from Bayer AG)
• the ratios given in the tables refer to parts by weight of the corresponding components.
• the polyol formulation was prepared by mixing the corresponding parts by weight of the individual components and mixed intensively with the corresponding parts by weight of the isocyanate (Examples 1 to 26) or processed using a high-pressure system.
• the reaction mixture was introduced into an aluminum mold preheated to 40 ° C., the mold was closed with an aluminum lid and the reaction mixture was allowed to foam. After 5 minutes, the foams were removed from the mold.
• the foams produced with a SAN-filled polyol or base polyol (example 1 or 2) using a modified TDI went into full fire in the fire test and had to be extinguished.
• the foams according to the invention (Examples 3 and 4) passed the test.
• the foams according to the invention pass the fire test even without further liquid flame retardants (Examples 25-27).
• Example 26 provides more favorable values of smoke density and toxicity than Comparative Example 34.
• Table 1 Fire test according to BS 5852. Part 2. Crib Iqnition Source V
• Table 2 Fire test according to BS 5852. Part 2, Crib Iqnition Source V
• Table 3 Fire test according to BS 5852. Part 2. Crib Iqnition Source V
• Table 4 Fire test according to BS 5852. Part 2. Crib Iqnition Source V
• Table 5 Paper pillow test according to DIN 54341 and UIC 564/2

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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)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Applications Claiming Priority (3)

Publications (1)

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• 1999
  • 1999-11-12 DE DE19954739A patent/DE19954739A1/de not_active Withdrawn
• 2000
  • 2000-10-31 BR BR0015524-1A patent/BR0015524A/pt not_active Application Discontinuation
  • 2000-10-31 CZ CZ20021585A patent/CZ20021585A3/cs unknown
  • 2000-10-31 WO PCT/EP2000/010766 patent/WO2001036509A1/de not_active Ceased
  • 2000-10-31 TR TR2002/01261T patent/TR200201261T2/xx unknown
  • 2000-10-31 CA CA002390074A patent/CA2390074A1/en not_active Abandoned
  • 2000-10-31 AU AU18551/01A patent/AU1855101A/en not_active Abandoned
  • 2000-10-31 PL PL00355447A patent/PL355447A1/xx not_active Application Discontinuation
  • 2000-10-31 EP EP00981229A patent/EP1237972A1/de not_active Withdrawn
  • 2000-10-31 HU HU0203424A patent/HUP0203424A3/hu unknown
  • 2000-10-31 US US10/129,766 patent/US6734217B1/en not_active Expired - Fee Related
• 2002
  • 2002-05-08 NO NO20022212A patent/NO20022212L/no not_active Application Discontinuation

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