DE1618780B2 - Process for the production of phosphonates suitable for making polyurethane acids flame resistant. Elimination from: 1259338 - Google Patents

Process for the production of phosphonates suitable for making polyurethane acids flame resistant. Elimination from: 1259338

Info

Publication number
DE1618780B2
DE1618780B2 DE1618780A DE1618780A DE1618780B2 DE 1618780 B2 DE1618780 B2 DE 1618780B2 DE 1618780 A DE1618780 A DE 1618780A DE 1618780 A DE1618780 A DE 1618780A DE 1618780 B2 DE1618780 B2 DE 1618780B2
Authority
DE
Germany
Prior art keywords
dpg
glycol
foam
elimination
bisdipropylene
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.)
Granted
Application number
DE1618780A
Other languages
German (de)
Other versions
DE1618780A1 (en
DE1618780C3 (en
Inventor
Lester Whitestone N.Y. Friedman (V.St.A.)
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.)
Valtris Specialty Chemicals Ltd
Original Assignee
Pure Chemicals Ltd
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
Priority claimed from US129529A external-priority patent/US3081331A/en
Priority claimed from US135751A external-priority patent/US3142650A/en
Priority claimed from US145749A external-priority patent/US3142651A/en
Application filed by Pure Chemicals Ltd filed Critical Pure Chemicals Ltd
Publication of DE1618780A1 publication Critical patent/DE1618780A1/en
Publication of DE1618780B2 publication Critical patent/DE1618780B2/en
Application granted granted Critical
Publication of DE1618780C3 publication Critical patent/DE1618780C3/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/48—Lubricating compositions characterised by the base-material being a macromolecular compound containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/093—Polyol derivatives esterified at least twice by phosphoric acid groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/141—Esters of phosphorous acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/141—Esters of phosphorous acids
    • C07F9/1411—Esters of phosphorous acids with hydroxyalkyl compounds with further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4015—Esters of acyclic unsaturated acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657109—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms esters of oxyacids of phosphorus in which one or more exocyclic oxygen atoms have been replaced by (a) sulfur atom(s)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/657181—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • 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
    • C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
    • C08G18/388—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having phosphorus bound to carbon and/or to 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
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5075—Polyethers having heteroatoms other than oxygen having phosphorus
    • C08G18/5078—Polyethers having heteroatoms other than oxygen having phosphorus having phosphorus bound to carbon and/or to 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
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5075—Polyethers having heteroatoms other than oxygen having phosphorus
    • C08G18/5081—Polyethers having heteroatoms other than oxygen having phosphorus having phosphorus bound to oxygen only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5075—Polyethers having heteroatoms other than oxygen having phosphorus
    • C08G18/5081—Polyethers having heteroatoms other than oxygen having phosphorus having phosphorus bound to oxygen only
    • C08G18/5087—Phosphite 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
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5075—Polyethers having heteroatoms other than oxygen having phosphorus
    • C08G18/5093—Polyethers having heteroatoms other than oxygen having phosphorus having sulfur in addition to phosphorus
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/675—Low-molecular-weight compounds
    • C08G18/677—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups
    • C08G18/6785—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups containing phosphorus
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
    • C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/74—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/042—Metal salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/047—Thioderivatives not containing metallic elements
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2225/02—Macromolecular compounds from phosphorus-containg monomers, obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polyethers (AREA)

Description

Es ist eine Art von Mitteln zur Flammfestmachung von Polyurethanschäumen bekannt. Bei diesen handelt es sich um die sogenannten »nichtreaktiven« Typen, beispielsweise Trichloräthylphosphat. Da diese Typen keine Verbindung mit dem Schaum eingehen, diffundieren sie im Laufe der Zeit aus dem Schaum heraus, verdampfen leicht bei Wärmeeinwirkung und können außerdem herausgewaschen werden. Dadurch geht die Schwerentflammbarkeit leicht verloren. Daneben verleihen die »nichtreaktiven Typen« den Schäumen auf Grund ihrer plastifizierenden Wirkung schlechte mechanische Eigenschaften. Weiterhin neigen sie dazu, bei längerer Einwirkung von Feuchtigkeit HX zu erzeugen, wodurch Stabiütätsprobleme entstehen.One type of means for flame retarding polyurethane foams is known. With these acts these are the so-called "non-reactive" types, for example trichloroethyl phosphate. This one Types do not bond with the foam, they diffuse out of the foam over time out, evaporate easily when exposed to heat and can also be washed out. Through this the flame retardancy is easily lost. In addition, the "non-reactive types" give the Foams have poor mechanical properties due to their plasticizing effect. Continue to tend they tend to generate HX with prolonged exposure to moisture, which causes stability problems develop.

Es ist eine andere Art von Mitteln zur Flammfestmachung bekannt, bei denen es sich um die sogenannten »reaktiven Typen« handelt, die die oben beschriebenen Nachteile der »nichtreaktiven Typen« nicht aufweisen, da sie mit den Schäumen eine Verbindung eingehen.Another type of flame retardant is known which are the so-called "Reactive types" are concerned that do not have the disadvantages of the "non-reactive types" described above have, since they enter into a connection with the foams.

Durch die belgische Patentschrift 617 305 ist eine Verbindung, und zwar Tris-DPG-phosphit, bekannt, die in den Schaum chemisch eingebaut wird. Allerdings weist dieser Schaum relativ schlechte flammhemmende Eigenschaften auf, wie Vergleichsversuche zeigten, die weiter unten beschrieben sind.From the Belgian patent 617 305 a compound, namely Tris-DPG-phosphite, is known, which is chemically built into the foam. However, this foam has relatively poor flame retardancy Properties, as shown by comparative tests, which are described below.

Die Aufgabe der vorliegenden Erfindung besteht darin, Phosphonate des »reaktiven Typs« herzustellen, die die flammhemmenden Eigenschaften von Polyurethanschäumen verbessern.The object of the present invention is to produce phosphonates of the "reactive type", which improve the flame retardant properties of polyurethane foams.

Die Aufgabe wird dadurch gelöst, daß man in an sich bekannter Weise Bis-di-propylenglykolphosphit mit Äthylen- oder Propylenoxid oder mit Formaldehyd oder Azetaldehyd in Gegenwart eines Katalysators unter Erwärmung zur Reaktion bringt.The object is achieved in that bis-di-propylene glycol phosphite is used in a manner known per se with ethylene or propylene oxide or with formaldehyde or acetaldehyde in the presence of a catalyst reacts with heating.

Gemäß einer Weiterbildung der Erfindung wird als Katalysator ein Alkalikarbonat oder Triäthylamin eingesetzt.According to a further development of the invention, an alkali metal carbonate or triethylamine is used as the catalyst used.

Die sich bei der umsetzung abspielenden Reaktionen lassen sich durch die beiden folgenden allgemeinen Gleichungen veranschaulichenThe reactions that take place during implementation can be broken down into the following two general terms Illustrate equations

DPG ODPG O

I IlI Il

HO—P + CH3CH
DPGHO-P + CH 3 CH
DPG

DPGDPG

O=P-CHOH-CH3 O = P-CHOH-CH 3

DPGDPG

undand

DPGDPG

HO-P + CH,-HO-P + CH, -

j \j \

DPG
DPGDPG
DPG

-CH,-CH,

> O=P-CHOH-CH3 > O = P-CHOH-CH 3

DPGDPG

in denen DPG Dipropylenglykol bedeutet.in which DPG means dipropylene glycol.

Die Verbindungen, welche nach der vorliegenden Erfindung hergestellt werden und die freie Hydroxyl-The compounds which are prepared according to the present invention and the free hydroxyl

gruppen haben, sind besonders wertvoll als Reaktionspartner für Polyisozyanate, z. B. Toluoldiisozyanat, um geschäumte Polyurethane oder um Polyurethanelastomere herzustellen, die flammenfeist sind und gute Färbeigenschaften besitzen. Die Phosphonategroups are particularly valuable as reactants for polyisocyanates, e.g. B. toluene diisocyanate, to produce foamed polyurethanes or to produce polyurethane elastomers that are flame-retardant and have good coloring properties. The phosphonates

der vorliegenden Erfindung sind als antistatische Agenzien für Polyäthylen und Polypropylen und als Farbakzeptoren von besonderem Interesse, wenn sie Polyurethan-, Polyäthylen-, Epoxy- oder Polypropylenharzen beigemischt werden. Die Phosphonate,of the present invention are as antistatic agents for polyethylene and polypropylene and as Color acceptors of particular interest when they are polyurethane, polyethylene, epoxy, or polypropylene resins be mixed in. The phosphonates,

die freie Hydroxylgruppen enthalten, sind nicht nur für die Herstellung fiammenfester Polyurethane wertvoll, sondern können auch zum Flammenfestmachen von Polyestern verwendet werden, indem man sie mit den Polysäuren, z. B. Terephthalsäure, Phthal-which contain free hydroxyl groups are not only valuable for the production of flame-resistant polyurethanes, but can also be used to make polyesters flame retardant by making them with the polyacids, e.g. B. terephthalic acid, phthalic

säure und Adipinsäure umsetzt. Derartige Polyester lassen sich als Beschichtungsmittel für Holz oder Metall verwenden. Polyurethane können als Beschichtungsmittel für Textilien, z. B. Mäntel, Anzüge und Kleider, als auch für Isolationen in Gebäuden,acid and adipic acid. Such polyesters can be used as coating agents for wood or Use metal. Polyurethanes can be used as coating agents for textiles, e.g. B. coats, suits and clothes, as well as for insulation in buildings,

so Teppichunterlagen, Fäden, Becher und Schutzüberzüge für Stahl, Holz und Glas verwendet werden.so carpet underlays, threads, cups and protective covers for steel, wood and glass are used.

Die erfindungsgemäß hergestellten Phosphonate sind ebenfalls als Mittel zum Flammenfestmachen von Zellulose und Zelluloseestern geeignet; sie können an sich als Reaktionspartner für die Herstellung von Epoxyharzen verwendet werden können.The phosphonates made in accordance with the present invention are also useful as flame retardants suitable of cellulose and cellulose esters; they can act as reactants for the production of Epoxy resins can be used.

Die verbesserte Flammfestmachung durch die erfindungsgemäß hergestellten Verbindungen gegenüber den insbesondere durch die belgische Patentschrift 617 305 bekannten Verbindungen wurde durch die nachfolgend beschriebenen Vergleichsversuche nachgewiesen. Compared to the improved flame retardancy by the compounds produced according to the invention the compounds known in particular from the Belgian patent specification 617 305 was by the the comparative tests described below demonstrated.

Bei den Vergleichsversuchen wurden die zu untersuchenden Verbindungen in Schaumansätze einge-In the comparative experiments, those to be examined were Connections incorporated in foam

f>5 bracht. In einer Vorrichtung gemäß ASTM E-84 wurde dann die Flammausbreitungsgeschwindigkeit und die Länge der verbrannten Proben der Schäume gemessen. Für den Vergleichs versuch wurden zweif> 5 brings. In a device according to ASTM E-84 Then became the rate of flame propagation and the length of the burned samples of the foams measured. Two were used for the comparison test

1 5S81 5S8

der erfindungsgemäß hergestellten Phosphonate ausgesucht und mit der durch die belgische Patentschrift 617 305 bekannten Phosphorverbindung (Tris-DPG-phosphit) und einer Verbindung, die keinen Phosphor enthielt, verglichen.of the phosphonates produced according to the invention and selected with that of the Belgian patent 617 305 known phosphorus compound (Tris-DPG-phosphite) and a compound that does not contain phosphorus contained, compared.

Die Zusammensetzung der für die Brandvergleichsversuche herangezogenen Schäume ist der Tabelle 1 zu entnehmen.The composition of the foams used for the fire comparison tests is shown in Table 1 refer to.

Die Polyurethanschäume 1 und 2 sind unter Verwendung der erfindungsgemäß erhaltenen Verbindungen Bis-D PG-hydroxy-piopanphosphat und Bis-DPG-hydroxy-Äthan-Phosphonat hergestellt worden; im Schaum 3 ist das durch die belgische Aus.legeschrift 617 305 bekannte Phosphor-Polyol, nämlich Tris-DPG-phosphit verwendet, und Schaum 4 weist kein phosphorenthaltendes Polyol auf.The polyurethane foams 1 and 2 are made using the compounds obtained according to the invention Bis-D PG-hydroxy-propane phosphate and bis-DPG-hydroxy-ethane-phosphonate been made; in foam 3 this is due to the Belgian Aus.legeschrift 617 305 known phosphorus polyol, namely Tris-DPG-phosphite used, and foam 4 has no phosphorus-containing polyol.

TabelleTabel

BestandteileComponents

Oiradol-3-polyol Oiradol-3-polyol

Caradate-30-isocyanat Caradate 30 isocyanate

Pin ^phor-Polyol Pin ^ phor polyol

Silikon flüssig Liquid silicone

Dimeih} !amino- propylamirtDimeih}! Aminopropylamirt

Dibutylzinndilaurat Dibutyltin dilaurate

Trichlor-fluor-methan Trichlorofluoromethane

88,3 185,888.3 185.8

70,6 1,6 4,0 0,0870.6 1.6 4.0 0.08

60 Polyurethanschaum60 polyurethane foam

■> 3■> 3

87,5
185,287.5
185.2

74,6
1,6
4,0
0,0874.6
1.6
4.0
0.08

6060

85,6
181,285.6
181.2

78,9
1,6
4,0
0,0878.9
1.6
4.0
0.08

150
192,6150
192.6

1,51.5

3,75
0,08
603.75
0.08
60

Der Phosphorgehalt betrug bei den phosphorenthaltenden Polyurethanschäumen 1,6%. Die Ergebnisse der Versuche sind in der Tabelle 2 aufgeführt.The phosphorus content in the phosphorus-containing polyurethane foams was 1.6%. The results of the tests are shown in Table 2.

TabelleTabel

PhosphonatPhosphonate

NameSurname

1. Bis D PG-hydroxypropan-phosphonat.1. Bis D PG-hydroxypropane-phosphonate.

2. Bis-DPG-hydroxyäthan-phosphonat..2. Bis-DPG-hydroxyethane-phosphonate ..

3. Tris-DPG-phosphit (Standard) 3. Tris-DPG-phosphite (standard)

4. Kein Additiv (Standard) 4. No additive (standard)

ärechungs-accounting Phosphorgehalt, %Phosphorus content,% Theorietheory indexindex Experimentexperiment 8,48.4 1,45661.4566 8,78.7 8,68.6 1,46261.4626 8,58.5 7,27.2 1,4641.464 7,27.2

Verbrennungstest Pur
Polyui ethan-Schä urneCombustion test pure
Polyui ethane shank

Verbrannte
Länge
(cm)Burned
length
(cm)

21,6
20,3
22,921.6
20.3
22.9

Flammenausbreitungsgeschwindigkeit Flame Propagation Velocity

69,2
61,6
76,9
14069.2
61.6
76.9
140

Die Tabelle enthält als Vergleichsdaten die Ergebnisse aus Brechungsindexmessungen (in der Spalte 2), den Phosphatgehalt aus experimentellen und theoretischen (Spalte 3 und 4) Messungen, die verbrannten Längen (Spalte 5), und aus Messungen die Flammenausbreitungsgeschwindigkeit (Spalte 6). Der Fehler der Meßergebnisse des Verbrennungstests liegt unier 2%.The table contains the results from refractive index measurements (in column 2) as comparative data, the phosphate content from experimental and theoretical (column 3 and 4) measurements that burned Lengths (column 5), and from measurements the flame propagation speed (column 6). The mistake the measurement results of the combustion test are less than 2%.

Der Schaum 4, der keinen Phosphor enthält, weist eine sehr hohe Flammenausbreitungsgeschwindigkeit von 140 auf und verbrennt total. Der Schaum 3 mit der durch die belgische Patentschrift bekannten Phosphorverbindung weist immerhin noch eine Flammenausbreitungsgeschwindigkeit von 76,9 auf, und die Flamme erlischt, nachdem eine Länge der Probe von 22,9 cm verbrannt ist. Durch die Verwendung der erfindungsgemäß hergestellten Verbindungen in den Schäumen 1 und 2 verringert sich die Flammenausbreitungsgeschwindigkeit von 76,9 auf 69,2 bzw. 61,6 und die »verbrannte Länge« von 22,9 auf 21,6 bzw. 20,5 cm. Es wird also eine Verringerung der Flammenausbieitungsgeschwindigkeit für den Schaum 1 um 10% und für den Schaum 2 um 20% gegenüber Schaum 3 erreicht. Die Werte für die »verbrannte Länge« verbessern sich für Schaum 1 um 5,6% und für Schaum 2 um 11%.The foam 4, which does not contain phosphorus, has a very high flame propagation speed from 140 up and totally burns. The foam 3 with that known from the Belgian patent Phosphorus compound still has a flame spread rate of 76.9, and the flame is extinguished after a length of the sample of 22.9 cm has burned. By using of the compounds prepared according to the invention in foams 1 and 2, the flame propagation speed is reduced from 76.9 to 69.2 or 61.6 and the "burned length" from 22.9 to 21.6 and 20.5 cm. So there will be a decrease in Flame propagation rate for foam 1 by 10% and for foam 2 by 20% reached compared to foam 3. The values for the "burned length" improve for foam 1 by 5.6% and for foam 2 by 11%.

Wenn nichts anderes angegeben, beziehen sich alle erwähnten Prozentangaben auf Gewichtsprozent.Unless otherwise stated, all percentages mentioned relate to percentages by weight.

Dia Erfindung wird an Hand einiger Beispiele näher erläutert.The invention is explained in more detail using a few examples.

1.1 Mol Bisdipropylenglykolhydrogenphosphit wird mit 1 Mol Propylenoxid in Gegenwart von 5 g Kaliumkarbonat bei 75° C umgesetzt, um Bisdipropylenglykol-2-hydroxypropanphosphonat zu erhalten, mit der Formel1.1 moles of bisdipropylene glycol hydrogen phosphite is reacted with 1 mole of propylene oxide in the presence of 5 g of potassium carbonate at 75 ° C. to form bisdipropylene glycol 2-hydroxypropane phosphonate to get with the formula

DPG—P-DPG
CH2
CHOH
CH3 DPG-P-DPG
CH 2
CHOH
CH 3

55 (DPG),P(O)CH,CH(OH)CH3, Molgewicht = 372, OH-Zahl = 452, P-Gehalt = 8,4%.55 (DPG), P (O) CH, CH (OH) CH 3 , molecular weight = 372, OH number = 452, P content = 8.4%.

Ähnliche Reaktionen lassen sich mit Äthylenoxid oder Butylenoxid und unter Verwendung anderer Alkalikatalysatoren, wie z. B. gelöschtem Kalk, Tetrar >5 methylguanidin und Pentamethylguanidin, durchführen. Similar reactions can be carried out with ethylene oxide or butylene oxide and using others Alkali catalysts, such as. B. slaked lime, tetrar> 5 methylguanidine and pentamethylguanidine.

Wenn also Propylenoxid durch 1 Mol Äthylenoxid im Beispiel 1 ersetzt wird, ist das erhaltene ProduktSo if propylene oxide is replaced by 1 mole of ethylene oxide in Example 1, the product obtained is

Bisdipropylenglykol - 2 - hydroxyäthanphosphonat, P-Gehalt = 8,6%, Brechungsindex bei T = 20 CBisdipropylene glycol - 2 - hydroxyethane phosphonate, P content = 8.6%, refractive index at T = 20 C.

mit der Formel η 1,4620.with the formula η 1.4620.

2. Die im Beispiel 1 beschriebene Reaktion kann auch mit polymeren Dipropylenglykolhydrogenphos-5 phiten durchgeführt werden. So kann 1 Mol trimeren Dipropylenglykolhydrogenphosphits mit 3 Mol Propylenoxid in Gegenwart von 5 g Tetramethylguanidin umgesetzt werden, so daß das entsprechende Hydroxypropanphosphonat gemäß der folgenden Gleichung2. The reaction described in Example 1 can also be carried out with polymeric dipropylene glycol hydrogenphos-5 phiten are carried out. For example, 1 mole of trimeric dipropylene glycol hydrogen phosphite can be mixed with 3 moles of propylene oxide be reacted in the presence of 5 g of tetramethylguanidine, so that the corresponding hydroxypropane phosphonate according to the following equation

C14H31O8P, Molgewicht = 358, OH-Zahl = 469,6, ι ο entstehtC 14 H 31 O 8 P, molecular weight = 358, OH number = 469.6, ι ο is formed

DPG — P-DPGDPG - P-DPG

CH2
CH2OHCH 2
CH 2 OH

HHH
DPG—Ρ—DPG*—Ρ —DPG*—Ρ —DPG + PropylenoxidHHH
DPG — Ρ — DPG * —Ρ —DPG * —Ρ —DPG + propylene oxide

Il Il IiIl Il II

ο ο οο ο ο

ο ο οο ο ο

Il Il IlIl Il Il

DPG—Ρ —DPG*—Ρ—DPG—Ρ —DPG CH2 CH2 DPG — Ρ —DPG * —Ρ — DPG — Ρ —DPG CH 2 CH 2

CHOH CHOHCHOH CHOH

CH2 CH 2

CHOHCHOH

CH3 CH 3

CH,CH,

CH,CH,

C33H71018P3, Molgewicht = 848,8, OH-Zahl = 330,5, P-Gehalt = 10,9%, in der DPG Dipropylenglykol ist, von dem ein Hydroxylhydrogen entfernt worden ist, und DPG* ist Dipropylenglykol, von dem beide Hydroxylwasserstoffe entfernt worden sind. Das Ausgangs-Phosphii kann durch Erwärmen von Bisdipropylenglykolhydrogenphosphit im Vakuum und Abdestillieren der entsprechenden Menge von Dipropylenglykol, das sich dabei bildet, gewonnen werden.C 33 H 71 0 18 P 3 , molecular weight = 848.8, OH number = 330.5, P content = 10.9%, in which DPG is dipropylene glycol from which a hydroxyl hydrogen has been removed, and DPG is * Dipropylene glycol from which both hydroxyl hydrocarbons have been removed. The starting phosphate can be obtained by heating bisdipropylene glycol hydrogen phosphite in vacuo and distilling off the corresponding amount of dipropylene glycol that is formed in the process.

An Stelle von Propylenoxid kann Äthylenoxid und Butylenoxid verwendet werden. Wenn im Beispiel ?. also Propylenoxid durch 3 Mol Äthylenoxid ersetzt wird, hat das Produkt die FormelInstead of propylene oxide, ethylene oxide and butylene oxide can be used. If in the example ?. So propylene oxide is replaced by 3 moles of ethylene oxide, the product has the formula

4545

OOOOOO

Il Il IlIl Il Il

DPG— Ρ — DPG*— P — DPG*— P-DPG
CH2 CH2 CH2 DPG— Ρ - DPG * - P - DPG * - P-DPG
CH 2 CH 2 CH 2

CH2OH CH2OH CH2OHCH 2 OH CH 2 OH CH 2 OH

C30H65O18P3, Molgewicht = 806,8, OH-Zahl = 347,7, P-Gehalt = 11,5%.C 30 H 65 O 18 P 3 , molecular weight = 806.8, OH number = 347.7, P content = 11.5%.

Wenn ein Überschuß von Alkylenoxid, z. B. 6 Mol, in den Beispielen 1 und 2 verwendet wird, dann erfolgt eine Veresterung irgendeiner der freien Hydroxylgruppen. Dadurch wird der Prozentgehalt an Phosphor 6u im Molekül verringert, und die Verbindung ist für manche Zwecke weniger geeignet.If an excess of alkylene oxide, e.g. B. 6 moles, used in Examples 1 and 2, then takes place an esterification of any of the free hydroxyl groups. This will make the percentage of phosphorus 6u decreased in the molecule, and the compound is less suitable for some purposes.

3. 300 g (0,95 Mol) Bisdipropylenglykolhydrogenphosphit und 5 gTriäthylamin als Katalysator werden unter Kühlung mit 44 g (1 Mol) Azetaldehyd umgesetzt. Die Reaktion ist exotherm. Wenn die Reaktion beendet zu sein scheint, wird das Gemisch auf einem Dampfbad 1 Stunde erwärmt und dann im Vakuum bei 1000C zur Entfernung des Katalysators und überschüssigen Azetaldehyds erhitzt. Um die Entfernung dieser Stoffe zu erleichtern, wird mit Stickstoff gespült. Es wird Bisdipropylenglykol - a - hydroxyälhanphosphonat als Flüssigkeit mit dem Molgewicht 358 und der Hydroxylzahl 462 erhalten. Andere tertiäre Amine und basische Katalysatoren können ebenfalls verwendet werden.3. 300 g (0.95 mol) of bisdipropylene glycol hydrogen phosphite and 5 g of triethylamine as a catalyst are reacted with 44 g (1 mol) of acetaldehyde while cooling. The reaction is exothermic. When the reaction appears to be complete, the mixture is heated for 1 hour on a steam bath and then under vacuum at 100 0 C to remove the catalyst and excess acetaldehyde heated. To facilitate the removal of these substances, it is flushed with nitrogen. Bisdipropylene glycol - a - hydroxyalhanophosphonate is obtained as a liquid with a molecular weight of 358 and a hydroxyl number of 462. Other tertiary amines and basic catalysts can also be used.

Als Katalysator kann ein Anionaustauscherharz verwendet werden, beispielsweise ein quarternäres Aminomethylstyrol-divinylbenzol-Copolymer.An anion exchange resin, for example a quaternary one, can be used as the catalyst Aminomethylstyrene divinylbenzene copolymer.

4. 430 g Trisdipropylenglykolphosphit (1,0 Mol) und 0,2 ml konzentrierte Salzsäure werden mit 18 g Wasser behandelt, wodurch sich durch Hydrolyse Bisdipropylenglykolhydrogenphosphit bildet. Besonders starkes basisches Amberlite-IR-410-Ionenaustauscherharz wird dann zugesetzt, gefolgt von 50 g (einem Überschuß) Azetaldehyd. Wenn die Reaktion beendet zu sein scheint, wird das Gemisch 1 Stunde auf 1000C erhitzt.4. 430 g of trisdipropylene glycol phosphite (1.0 mol) and 0.2 ml of concentrated hydrochloric acid are treated with 18 g of water, whereby bisdipropylene glycol hydrogen phosphite is formed by hydrolysis. Extra strong Amberlite IR-410 basic ion exchange resin is then added, followed by 50 grams (an excess) of acetaldehyde. When the reaction appears to have ended, the mixture is heated to 100 ° C. for 1 hour.

Der Katalysator wird abfiltriert und das Filtrat im Hochvakuum unter Verwendung eines Stickstoffstroms zur Entfernung des Dipropylenglykols gereinigt. Das Produkt ist mit dem gemäß Beispiel 3 identisch.The catalyst is filtered off and the filtrate in a high vacuum using a stream of nitrogen Purified to remove the dipropylene glycol. The product is the same as in Example 3 identical.

5. Trisdipropylenglykoldihydrogendiphosphit, hergestellt durch saure Hydrolyse von Dipropylenglykoltetroldiphosphit in einer im Beispiel 4 für Bisdipropylenglykolhydrogenphosphit beschriebenen ähnlichen Art oder durch die Selbstkondensation von Bisdipropylenglykolhydrogenphosphit, in einer Menge von 225 g (0,5 Mol) wird zusammen mit 10 g Amberlite-IR-410 und 44 g (1 Mol) Azetaldehyd wie im Beispiel 4 behandelt. Die Reaktion verläuft exotherm und schnell. Das Gemisch wird auf 100" C erwärmt und 1 Stunde auf dieser Temperatur gehalten. Der Katalysator wird abfiltriert und das Filtrat im Vakuum zur Entfernung flüchtiger Stoffe behandelt. Das flüssige Produkt ist Trisdiprcpylenglykol - di-5. Trisdipropylene glycol dihydrogen diphosphite, produced by acid hydrolysis of dipropylene glycol tetrol diphosphite in a similar one described in Example 4 for bisdipropylene glycol hydrogen phosphite Kind or by the self-condensation of bisdipropylene glycol hydrogen phosphite, in an amount of 225 g (0.5 mol) together with 10 g of Amberlite-IR-410 and 44 g (1 mol) of acetaldehyde treated as in Example 4. The reaction is exothermic and fast. The mixture is heated to 100 ° C. and kept at this temperature for 1 hour The catalyst is filtered off and the filtrate is treated in vacuo to remove volatile substances. The liquid product is Trisdiprcpylene Glycol - di-

618 780618 780

(i(-hydroxyäthan)-diphosphosphonai mit der Formel O O(i (-hydroxyethane) -diphosphonai with the formula O O

Il IlIl Il

DPG — Ρ —DPG*— P— DPG CHCH3 CHCH3 OH OHDPG - Ρ - DPG * - P - DPG CHCH 3 CHCH 3 OH OH

C22H48O13P2, Molgewicht = 582,5, OH-Zahl = !!85,2, P-Gehalt = 10,6%.C 22 H 48 O 13 P 2 , molecular weight = 582.5, OH number = !! 85.2, P content = 10.6%.

6. In einer dem Beispiel 4 ähnlichen Art werden 30 g Formaldehyd, hergestellt durch Zersetzung von Trioxan, mit Bisdipropylenglykolhydrogenphosphit umgesetzl, wodurch sich Bisdipropylenglykolhydroxymethanphosphonat mit dem Molgewicht 344 und der Hydroxylzahl 480 bildet.6. In a manner similar to Example 4, 30 g of formaldehyde, produced by the decomposition of Trioxane, converted with bisdipropylene glycol hydrogen phosphite, resulting in bisdipropylene glycol hydroxymethane phosphonate with a molecular weight of 344 and a hydroxyl number of 480 forms.

In ähnlicher Weise kann Trisdipropylenglykoldihydroxymethandiphosphonat der FormelSimilarly, trisdipropylene glycol dihydroxymethane diphosphonate can be used the formula

O OO O

Il IlIl Il

DPG — Ρ —DPG*— P-DPGDPG - Ρ —DPG * - P-DPG

I II I

CH2OH CH2OHCH 2 OH CH 2 OH

C20H44O13P2, Molgewicht = 554,5, OH-Zahl = 404,7, P-Gehalt = 11,2% aus Formaldehyd und Trisdipropylcnglykoldihydrogendiphosphit hergestellt werden, was eine Flüssigkeit ist.C 20 H 44 O 13 P 2 , molecular weight = 554.5, OH number = 404.7, P content = 11.2% from formaldehyde and trisdipropylcnglycol dihydrogendiphosphite, which is a liquid.

7.1 Mol Biiidipropylenglykolhydrogenphosphit wird mit 1 Mol Propylcnoxid in Gegenwart von 2 g Triüthylamin bei 75" C umgesetzt. Nach Entfernung des Katalysators durch Erhitzen im Vakuum auf 100"C erhält man im wesentlichen reines Bisdipropylenglykolhydroxypropanphosphonat. 7.1 moles of Biiidipropyleneglykolhydrogenphosphit is reacted with 1 mol of propylene oxide in the presence of 2 g of triethylamine at 75 ° C. After removal of the Catalyst by heating in vacuo to 100 "C one obtains essentially pure bisdipropylene glycol hydroxypropane phosphonate.

8.1 Mol Bisdipropylcnglykolhydrogenphosphit wird8.1 mol of bisdipropylcnglycol hydrogen phosphite is

to mit 5 Mol (einem Überschuß) Propylenoxid in Gegenwart von 2 g Triäthylamin bei 75" C umgesetzt. Nach 4 Stunden wird der Katalysator und überschüssiges Propylenoxid entfernt. Der Rest beträgt 513 g und besitzt vier Propylenoxid-Gvuppen, die mit Bisdipropylenglykolphosphit kondensiert sind. Es scheint ein Propylenoxkl-Kondensationsprodukt mit Bisdipropylenglykolhydroxypropanphüsphonat zu sein.to with 5 moles (an excess) of propylene oxide in the presence of 2 g of triethylamine reacted at 75 ° C. After 4 hours, the catalyst and excess Removed propylene oxide. The remainder is 513 g and has four propylene oxide groups, the are condensed with bisdipropylene glycol phosphite. It appears to have a propylene oxkl condensation product Bisdipropyleneglykolhydroxypropanphüsphonat to be.

9.1 Mol Bisdipropylenglykolhydrogenphosphit wird mit 1 Mol Äthylenoxid in Gegenwart von 5 g Kaliumkarbonat bei 75" C zur Herstellung von Bisdipropylenglykolhydroxyäthanphosphonat zusammengebracht. Eine Reaktion dieses Produktes mit weiteren Mengen an Äthylenoxid, z. B. mit 4 Mol Äthylenoxid ergibt ein Polyoxyälhylen - Kondensationsprodukt (C22H47O12P, Molgewicht = 534, OH-Zahl = 315. P-Gehalt = 5,7%) des Bisdipropylenglykolhydroxy· äthanphosphonats (C14H31O8P, Molgewicht = 358 OH-Zahl = 469,6, P-Gehalt = 8,6%, Brechung*· index bei T = 200C 1,4620)... 9.1 mol Bisdipropylenglykolhydrogenphosphit is contacted with 1 mole of ethylene oxide in the presence of 5 g potassium carbonate at 75 "C for the preparation of Bisdipropylenglykolhydroxyäthanphosphonat A reaction of this product with further amounts of ethylene oxide, for example, with 4 moles of ethylene oxide results in a Polyoxyälhylen - condensation product (C 22 H 47 O 12 P, molecular weight = 534, OH number = 315. P content = 5.7%) of the bisdipropylene glycol hydroxyethane phosphonate (C 14 H 31 O 8 P, molecular weight = 358 OH number = 469.6, P. Content = 8.6%, refraction * index at T = 20 0 C 1.4620).

Claims (2)

Patentansprüche:Patent claims: 1. Verfahren zur Herstellung von zur Flammfestmachungvon Polyure .hanschäumen geeigneten Phosphonaten, dadurch gekennzeichnet, daß man in an sich bekannter Weise Bisdi-propylenglykolphosphit mit Äthylen- oder Propylenoxid oder mit Formaldehyd oder Azetaldehyd in Gegenwart eines Katalysators unter Erwärmung zur Reaktion bringt.1. Method of making for flame retardant Polyure .phosphonates suitable for foaming, characterized in that that one bisdi-propylene glycol phosphite in a manner known per se with ethylene or propylene oxide or with formaldehyde or acetaldehyde reacts in the presence of a catalyst with heating. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als Katalysator ein Alkalikarbonat oder Triäthylamin eingesetzt wird.2. The method according to claim 1, characterized in that an alkali carbonate is used as the catalyst or triethylamine is used.
DE1618780A 1961-08-07 1962-10-16 Process for the production of phosphonates suitable for making polyurethane foams flame resistant. Elimination from: 1259338 Expired DE1618780C3 (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
US129529A US3081331A (en) 1961-08-07 1961-08-07 Poly phosphorus ester condensates and their preparation
US135751A US3142650A (en) 1961-05-15 1961-09-05 Polyurethanes from tris-polypropylene glycol phosphites
US145749A US3142651A (en) 1961-08-07 1961-10-17 Polyurethanes from polyphosphorus phosphites and phosphonates
US186662A US3092651A (en) 1961-08-07 1962-04-11 2-hydroxyalkane phosphonate and polyphosphonate hydroxyalkyl esters
US201240A US3139450A (en) 1961-08-07 1962-06-11 Alkaneetherpolyol phosphonate esters
US37107964A 1964-05-28 1964-05-28
US68313467A 1967-11-15 1967-11-15

Publications (3)

Publication Number Publication Date
DE1618780A1 DE1618780A1 (en) 1971-01-14
DE1618780B2 true DE1618780B2 (en) 1974-01-24
DE1618780C3 DE1618780C3 (en) 1974-09-05

Family

ID=27568855

Family Applications (1)

Application Number Title Priority Date Filing Date
DE1618780A Expired DE1618780C3 (en) 1961-08-07 1962-10-16 Process for the production of phosphonates suitable for making polyurethane foams flame resistant. Elimination from: 1259338

Country Status (1)

Country Link
DE (1) DE1618780C3 (en)

Also Published As

Publication number Publication date
DE1618780A1 (en) 1971-01-14
DE1618780C3 (en) 1974-09-05

Similar Documents

Publication Publication Date Title
DE2104569C3 (en) Ethylenediphosphoric acid tetrakis (2-chloroethyl) ester, process for its preparation and its use
DE1923937C3 (en) Process for the preparation of phosphoric polyols containing ester groups
DE1171616B (en) Process for the production of flame-retardant, optionally foamed polyurethanes
DE1225856B (en) Process for the production of flame-retardant polyurethane foams
DE19540861A1 (en) Process for the preparation of mixtures of oligomeric phosphoric acid esters and their use as flame retardants for polyurethane foams
DE2023788B2 (en) PROCESS FOR MANUFACTURING FOAMED SELF-EXTINGUISHING POLYURETHANE, IF NECESSARY
DE2036587C3 (en)
DE2047195A1 (en) Preparations for making plastics flame retardant and processes for their manufacture
DE2828603A1 (en) NEW PHOSPHORUS COMPOUNDS AND THEIR USE IN FLAME RETARDANT COMPOSITIONS
DE2719738B2 (en) Phosphonic acid ester derivatives and polyurethane preparations containing them
EP0005497A1 (en) Spirocyclic boron compounds, process for their preparation and their use as flame-retardant additives
DE1618780C3 (en) Process for the production of phosphonates suitable for making polyurethane foams flame resistant. Elimination from: 1259338
DE1226780B (en) Process for the production of self-extinguishing, optionally foamed polyurethanes
DE2244543A1 (en) Tri-(2,3-dibromopropyl)-isocyanurate - prepd by brominating triallylisocya-nurate, useful as flame retardant for polyurethanes etc
DE2053631A1 (en) Urethane foams with little smoke development
DE2323702A1 (en) HALOGENATED POLYAETHER POLYOLS AND THE PROCESS FOR THEIR PRODUCTION
DE1745191C3 (en) Process for the production of phosphorus-containing polyols
AT357336B (en) FLAME RETARDING OF PLASTICS WITH BORED LINKS
DE1803747B2 (en) 2-TO (THIS OF PHOSPHONOMETHYL) - AMINO-1,3-DIHYDROXYPROPANES AND THE METHOD FOR THEIR PRODUCTION
DE2036595C3 (en) Phosphorus and halogen-containing polyols and processes for their production
DE1595189C3 (en) Stabilized basic mixture for a later reaction with a polyisocyanate precipitated from 1240283
DE2707498A1 (en) HALOGENALKYLPHOSPHATE WITH INCREASED HYDROLYTIC STABILITY
DE1544714C (en) Flame-proofing of molded polyurethane parts
DE1745134C3 (en) Process for the production of polyurethane foams
DE2036595B2 (en) POLYOLS CONTAINING PHOSPHORUS AND HALOGEN AND PROCESS FOR THEIR PRODUCTION

Legal Events

Date Code Title Description
C3 Grant after two publication steps (3rd publication)
E77 Valid patent as to the heymanns-index 1977
EHJ Ceased/non-payment of the annual fee