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WO2024132976A1 - Polyester polyol à base de polybutylène téréphtalate - Google Patents

Polyester polyol à base de polybutylène téréphtalate Download PDF

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Publication number
WO2024132976A1
WO2024132976A1 PCT/EP2023/086177 EP2023086177W WO2024132976A1 WO 2024132976 A1 WO2024132976 A1 WO 2024132976A1 EP 2023086177 W EP2023086177 W EP 2023086177W WO 2024132976 A1 WO2024132976 A1 WO 2024132976A1
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WO
WIPO (PCT)
Prior art keywords
polybutylene terephthalate
polyester polyol
acid
fatty acid
optionally
Prior art date
Application number
PCT/EP2023/086177
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English (en)
Inventor
Denny Proksch
Erika Sibylle Juliane VON BOMHARD
Rene Leuthold
Olaf Jacobmeier
Kristian LOHDE
Martin Ruebenacker
Original Assignee
Basf Se
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Filing date
Publication date
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Publication of WO2024132976A1 publication Critical patent/WO2024132976A1/fr

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    • 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
    • C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
    • C08G18/092—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to isocyanurate 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
    • C08G18/4252—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids derived from polyols containing polyether groups and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4288—Polycondensates having carboxylic or carbonic ester groups in the main chain modified by higher fatty oils or their acids or by resin acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—Dicarboxylic acids and dihydroxy 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
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • 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
    • C08G2110/005—< 50kg/m3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/184—Binary blends of expanding agents of chemical foaming agent and physical blowing agent, e.g. azodicarbonamide and fluorocarbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/10—Rigid foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons

Definitions

  • the present invention relates to a polyester polyol, a process for the production of a polyester polyol, its use in the production of polyurethanes, a process for the production of polyurethanes with the polyester polyols, as well as the polyurethane produced according to the production process.
  • Polyester polyols are used in the preparation of polyurethanes, in particular of polyurethane foams (Pll foams). They are part of the polyol component, which is reacted with an isocyanate component to form the polyurethane.
  • Pll foams polyurethane foams
  • Examples of formed polyurethanes are flexible, semirigid, and rigid Pll foams, integral foams, and compact polyurethanes.
  • polyester polyols based on aromatic dicarboxylic acids, and the use thereof for the production of rigid polyurethane foams.
  • the polyester polyols comprise the esterification product of a dicarboxylic acid composition, one or more fatty acids and/or fatty acid derivatives, one or more aliphatic or cycloaliphatic diols and a polyether polyol which is prepared by alkoxylation of a polyol with a functionality of greater than or at least 2.
  • polyester polyols are as colorless as possible.
  • Polyester polyols tend to have a yellowish color, which is problematic because it affects the appearance of the polyurethane foam.
  • polyester polyols should be stable against hydrolysis. This is important both during storage of the polyester polyol and the polyol component comprising the polyester polyol as well as for the stability of the polyurethane foam comprising the polyester polyol. Additionally, the viscosity of the polyester polyols should not be too high. A good pentane solubility is important.
  • Polyurethane foams containing polyester polyols are used in diverse applications such as cooling systems, heat storage systems, insulation panels for construction, mobile transport systems, water boilers, burners, chimneys, instrument panels, roofs of industry halls, engines, or caravans, furniture (e.g. matrasses and upholstery), interiors in the transportation sector like automotive interior (e.g. car roof lining, interior lining of car doors), interiors of aircrafts and trains; packaging and construction (e.g. sound absorption).
  • cooling systems heat storage systems, insulation panels for construction, mobile transport systems, water boilers, burners, chimneys, instrument panels, roofs of industry halls, engines, or caravans, furniture (e.g. matrasses and upholstery), interiors in the transportation sector like automotive interior (e.g. car roof lining, interior lining of car doors), interiors of aircrafts and trains; packaging and construction (e.g. sound absorption).
  • good mechanical properties of the foam are essential.
  • the foam should have good flame retardant properties.
  • polyester polyols that are light in color and that yield polyurethane foams with good mechanical properties while maintaining the foam structure and foaming properties.
  • the polyester polyols should have a good hydrolysis stability.
  • polybutylene terephthalate PBT
  • PBT polybutylene terephthalate
  • the use of PBT as one of the starting materials of polyester polyols also improves the stability of the polyester polyols against hydrolysis.
  • polybutylene terephthalate as one of the educts of the polyester polyols according to the present invention has additionally the advantage that PBT from various sources can be utilized without prior treatment.
  • One aspect of the invention is therefore a polyester polyol comprising an esterification product of at least a) a polybutylene terephthalate; b) a fatty acid and/or fatty acid derivative; c) a polyhydric component with a functionality between greater than 2 and 8; d) a C2 to Cis diol or an alkoxylate thereof; and e) optionally a dicarboxylic acid and/or dicarboxylic acid derivative, wherein the esterification product makes up at least 80 % of the polyester polyol.
  • Further aspects of the invention are a process for the production of such a polyester polyol, the use of the polyester polyol for the production of polyurethanes, and a process for the production of polyurethanes by reacting a polyol composition comprising such polyester polyols and an organic polyisocyanate component as well as polyurethanes produced by the reaction of an organic polyisocyanate component and a polyol composition containing such polyester polyols.
  • the polyester polyols according to the invention are light in color: the typical yellow tone of the polyester polyols is reduced in comparison to polyester polyols produced without PBT. Additionally, the polyester polyols yield polyurethane foams which have good mechanical properties, especially good tensile strength, while the other foam properties remain unaffected.
  • PBT in the polyester polyols can originate from various sources; in addition to virgin raw material, PBT from waste streams of PBT production and/or compounding plants as well as recycled PBT can be used directly without prior transesterification or purification or other treatments. This decreases the need of virgin raw materials and of energy due to avoiding of additional process steps. Therefore, the CO2 footprint of the polyester polyol production is reduced. Additionally, the amount of waste is decreased due to the utilization of PBT from waste streams of the production or processing plants which would otherwise be discarded.
  • the polyester polyol according to the invention comprises an esterification product of at least a) a polybutylene terephthalate; b) a fatty acid and/or fatty acid derivative; c) a polyhydric component with a functionality between greater than 2 and 8; d) a C2 to Cis diol or an alkoxylate thereof; and e) optionally a dicarboxylic acid and/or dicarboxylic acid derivative, wherein the esterification product makes up at least 80 wt.-% of the polyester polyol, based on the total weight of the polyester polyol.
  • the esterification product makes up at least 90 wt.-%, more preferred at least 95 wt.- % of the polyester polyol, based on the total weight of the polyester polyol.
  • the polyester polyol is an esterification product of at least a) a polybutylene terephthalate; b) a fatty acid and/or fatty acid derivative; c) a polyhydric component with a functionality between greater than 2 and 8; d) a C2 to Cis diol or an alkoxylate thereof; and e) optionally a dicarboxylic acid and/or dicarboxylic acid derivative.
  • polyester polyol as used herein means an organic compound that contains at least two OH groups reactive towards isocyanates and at least two, preferably more than two, ester bonds.
  • Polyester polyols are usually OH terminated polyesters.
  • the polyester polyols Preferably the polyester polyols have acid numbers of less than 3 mg KOH/g, more preferably less than 2 mg KOH/g of sample. The lower limit is usually 0.3 mg KOH/g of sample.
  • Polyester polyols are a well-known class of compounds which can, for example, be used in the synthesis of polyurethanes (Pll).
  • the polyester polyols comprise an esterification product of at least a polybutylene terephthalate, a fatty acid and/or fatty acid derivative, a polyhydric component with a functionality between greater than 2 and 8, a C2 to C18 diol or an alkoxylate thereof, and optionally a dicarboxylic acid and/or dicarboxylic acid derivative.
  • the OH number also called hydroxyl number can be determined by means of well-established methods.
  • the OH number can be determined according to DIN 53240 (1971-12).
  • the functionality of a polyol, especially of the polyols to be used according to the invention, within the context of the present invention means the number of alkylene oxide reactive hydrogen atoms per mole of starter compound or per mole of mixture of the starter compounds prior to the time of alkylene oxide metering.
  • the time of the alkylene oxide metering is in this case the start of the addition of the alkylene oxide component to the starter compound(s).
  • the calculation takes into account all alkylene oxide-reactive hydrogen atoms of the starter compound(s) that are present in the starter mixture.
  • a polyether polyol has a functionality of 5.12 when 626.48 mol of glycerol (functionality 3), 559.74 mol of sucrose (functionality 8) and 67.31 mol of dimethylethanolamine (functionality 1) are used.
  • the functionality F determined by the formula presented above is also called equivalent functionality or average functionality and is known to those skilled in the art as a readily accessible method for determining the functionality of polyols, see M. lonescu “Chemistry and Technology of Polyols for Polyurethanes”, 2005, Rapra Technology Limited, pages 34 to 39.
  • the functionality of the polyols can differ from the functionality after commencement of the addition of at least one alkylene oxide, that is, during the reaction of the at least one alkylene oxide with a starter compound, or of the reaction product, since during the reaction there is formation of by-products such as glycols and unsaturated monofunctional constituents.
  • the side-reactions are known in the literature.
  • the functionality of the polyols can thus also be referred to as the functionality of the starter compound or starter compound mixture used for the preparation of the respective polyol.
  • the amount of the polybutylene terephthalate a) is preferably at least 0.5 wt-%, more preferred at least 1 wt.-%, even more preferred at least 3 wt.-%, particularly preferably at least 4 wt.-%, based on the total weight of the reaction components.
  • the amount of polybutylene terephthalate a) is preferably at most 45 wt-%, more preferred at most 32 wt-%, even more preferred at most 15 wt.-%, particularly preferably at most 10 wt.-%, based on the total weight of the components a) to e).
  • the amount of the polybutylene terephthalate a) is preferably 0.5 to 45 wt.-%, more preferred 1 to 32 wt.-%, even more preferred 3 to 15 wt.-%, even more preferred 4 to 10 wt.-%, based on the total weight of the components a) to e).
  • the polybutylene terephthalate preferably has a number average molecular weight of 8000 to 100 000 g/mol, more preferred 9000 to 85 000 g/mol, even more preferred 15 000 to 60 000 g/mol, particularly preferably 25 000 to 55 0000 g/mol, determined by gel permeation chromatography (GPC) using hexafluoro-2-isopranole as solvent.
  • GPC gel permeation chromatography
  • the amount of the fatty acid and/or fatty acid derivative b) is preferably at least 10 wt.-%, more preferred at least 11 wt-%, even more preferred 12 wt.-%, based on the total weight of the components a) to e).
  • the amount of the fatty acid and/or fatty acid derivative b) is preferably at most 30 wt-%, more preferred at most 29 wt-%, even more preferred at most 28 wt.-%, based on the total weight of the components a) to e).
  • the amount of the fatty acid and/or fatty acid derivative b) is preferably 10-30 wt.-%, more preferred 11-29 wt.-%, even more preferred 12-28 wt.-%, based on the total weight of the components a) to e).
  • the fatty acid and/or fatty acid derivative is a monomeric fatty acid and has one carboxyl group.
  • Monomeric fatty acids and/or fatty acid derivatives are individual fatty acid molecules that are not chemically linked to form dimers or any other higher-order structures. They are incorporated terminally into the polyester polyol and have direct influence on the OH number of the polyester polyol.
  • esters as used herein means the esters, half esters and anhydrides of these acids.
  • Preferred esters are esters of Ci to C4 alcohols, e.g. esters of methanol, ethanol and glycerol.
  • the fatty acid and/or fatty acid derivative may be selected from castor oil, polyhydroxy fatty acids, ricinoleic acid, hydroxyl-modified oils, grapeseed oil, black cumin oil, pumpkin kernel oil, borage seed oil, soybean oil, wheat germ oil, rapeseed oil, sunflower oil, peanut oil, apricot kernel oil, pistachio oil, almond oil, olive oil, macadamia nut oil, avocado oil, sea buckthorn oil, sesame oil, hemp oil, hazelnut oil, primula oil, wild rose oil, safflower oil, and walnut oil.
  • the fatty acid and/or fatty acid derivative may be selected from myristoleic acid, palmitoleic acid, oleic acid, vaccenic acid, petroselic acid, gadoleic acid, erucic acid, nervonic acid, linoleic acid, alpha- and gamma-linolenic acid, stearidonic acid, arachidonic acid, timnodonic acid, clupanodonic acid and cervonic acid, their derivatives, and hydroxyl-modified fatty acids and fatty acid esters based on these acids. It is also possible to use mixtures of different fatty acids or fatty acid derivatives, e.g. so called “biodiesel” which comprises mainly methyl esters of saturated and unsaturated C16 to C18 fatty acids. Preferred fatty acids and fatty acid derivatives are oleic acid, linolic acid, and palmitic acid.
  • the amount of the polyhydric component c) is preferably at least 20 wt.-%, more preferred at least 30 wt.-%, even more preferred at least 35 wt.-%, based on the total weight of the components a) to e).
  • the amount of the polyhydric component c) is preferably at most 60 wt.-%, more preferred at most 55 wt.-%, even more preferred at most 50 wt.-%, based on the total weight of the components a) to e).
  • the amount of the polyhydric component c) is preferably 20-60 wt.-%, more preferred 30-55 wt.- %, even more preferred 35-50 wt.-%, based on the total weight of the components a) to e).
  • the polyhydric component is selected from aliphatic and cycloaliphatic polyols and polyether polyols.
  • polyether polyol refers to an organic compound that contains at least ether (-O-) and OH groups as functional groups. They are often the alkoxylation products of monomeric polyhydric compounds like aliphatic alcohol such as glycerol, trimethylolpropane, pentaerythritol, etc.; phenols; amines; carboxylic acid; or natural based compounds like sucrose, sorbitol and mannitol; which were reacted with C2 to C4 alkylene oxides ethylene oxide, propylene oxide and/or butylene oxide and/or tetra hydrofuran, preferably with ethylene oxide and/or propylene oxide.
  • the polyhydric component c) is preferably selected from glycerol, trimethylolpropane, pentaerythritol, sucrose, sorbitol, ethylenediamine, diethylenetriamine, 3-(dimethylamino)propylamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,3-diaminotoluene, 3,4-dia- minotoluene, mixtures thereof and reaction products of the aforementioned products or their mixtures with an alkylene oxide. More preferably, the polyhydric component is selected from glycerol, trimethylolpropane, mixtures thereof and reaction products of the aforementioned products or their mixtures with ethylene oxide and/or propylene oxide.
  • the polyhydric component is a reaction product of glycerol with ethylene oxide and/or propylene oxide, preferably ethylene oxide.
  • the polyhydric component is a reaction product of trimethylolpropane with ethylene oxide and/or propylene oxide, preferably ethylene oxide.
  • the polyhydric component preferably has a functionality of at least greater than 2, more preferred at least 2.2, even more preferred at least 2.5.
  • the polyhydric component preferably has a functionality of at most 8, more preferred at most 6, even more preferred at most 4.
  • the polyhydric component has a functionality between greater than 2 and 8.
  • the polyhydric component has a functionality between 2.2 and 6; more preferably, the polyhydric component has a functionality between 2.5 and 4.
  • the polyhydric component preferably has an OH number of at least 100 mg KOH/g, more preferred at least 150 mg KOH/g, particularly preferred at least 240 mg KOH/g.
  • the polyhydric component preferably has an OH number of at most 1250 mg KOH/g, more preferred at most 950 mg KOH/g, particularly preferred at most 800 mg KOH/g.
  • the polyhydric component preferably has an OH number in the range of 100-1250 mg KOH/g, more preferred 150-950 mg KOH/g, particularly preferred 240-800 mg KOH/g.
  • the polyhydric component preferably has a functionality between 2 and 8 and an OH number in the range of 100-1250 mg KOH/g. More preferably, the polyhydric component has a functionality between 2.2 and 6 and an OH number in the range of 150-950 mg KOH/g. More preferably, the polyhydric component has a functionality between 2.5 and 4 and an OH number between 240-800 mg KOH/g.
  • the polyhydric component is a reaction product of glycerol or trimethylolpropane with ethylene oxide and/or propylene oxide and has an OH number in the range of 240-800 mg KOH/g. More preferably, the polyhydric component is a reaction product of trimethylolpropane with ethylene oxide and/or propylene oxide and has an OH number in the range of 240-800 mg KOH/g. More preferably, the polyhydric component is a reaction product of glycerol with ethylene oxide and/or propylene oxide and has an OH number in the range of 240-800 mg KOH/g.
  • the amount of the C2 to C18 diol or an alkoxylate thereof d) is at least 10 wt-%, more preferably at least 15 wt.-%, even more preferably at least 20 wt.-%, based on the total weight of the components a) to e).
  • the amount of the C2 to C18 diol or an alkoxylate thereof d) is preferably at most 35 wt-%, more preferably at most 30 wt.-%, even more preferably at most 25 wt.-%, based on the total weight of the components a) to e).
  • the amount of the C2 to C18 diol or an alkoxylate thereof d) is preferably 10 to 35 wt.-%, more preferably 15 to 30 wt.-%, even more preferably 20 to 25 wt.-%, based on the total weight of the components a) to e).
  • the C2 to Cis diol or an alkoxylate thereof d) is preferably selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, 1 ,3-propanediol, 1 ,2-butanediol, 1 ,3- butanediol, 1 ,4-butanediol, 1 ,4-pentanediol, 1 ,5-pentanediol, 2,4-pentanediol, 1 ,6-hexanediol, 2- methyl-1 ,3-propanediol, 3-methyl-1 ,5-pentanediol, and alkoxylates thereof.
  • the C2 to C18 diol or an alkoxylate thereof d) is preferably diethylene glycol.
  • the dicarboxylic acid e) is preferably present in the esterification reaction, the product of which is comprised by the polyester polyol.
  • the amount of the dicarboxylic acid e) is preferably at least 10 wt-%, more preferably at least 15 wt.-%, even more preferably at least 20 wt.-%, based on the total weight of the components a) to e).
  • the amount of the dicarboxylic acid e) is preferably at most 35 wt-%, based on the total weight of the components a) to e).
  • the amount of the dicarboxylic acid e) is preferably 0 to 35 wt.-%, more preferably 10 to 35 wt.- %, even more preferably 15 to 35 wt.-%, particularly preferably 20 to 35 wt.-%, based on the total weight of the components a) to e).
  • the dicarboxylic acid e) preferably comprises an aromatic dicarboxylic acid, an aromatic dicarboxylic acid monoester, an aromatic dicarboxylic acid diester, an aromatic dicarboxylic acid anhydride, or mixtures thereof.
  • the dicarboxylic acid e) is preferably selected from the group consisting of terephthalic acid, dimethyl terephthalate (DMT), polyethylene terephthalate (PET), phthalic acid, phthalic acid anhydride (PSA), and isophthalic acid. More preferably, the dicarboxylic acid e) is selected from the group consisting of terephthalic acid, phthalic acid, phthalic anhydride, and isophthalic acid. Particularly preferably, the dicarboxylic acid e) is terephthalic acid.
  • the polyester polyol preferably comprises an esterification product of at least a) a polybutylene terephthalate; b) a fatty acid and/or fatty acid derivative selected from oleic acid, linolic acid and palmitic acid; c) a polyhydric component with a functionality between greater than 2 and 8 selected from glycerol, trimethylolpropane, mixtures thereof and reaction products of the aforementioned compounds or their mixtures with an alkylene oxide; d) a C2 to Cis diol or an alkoxylate thereof selected from diethylene glycol, monoethylene glycol, 1 ,4-butanediol and 1 ,5-pentanediol; and e) optionally a dicarboxylic acid and/or dicarboxylic acid derivative selected from terephthalic acid, phthalic acid, phthalic anhydride and isophthalic acid, wherein the esterification product makes up at least 80 % of the polyester polyol
  • the polyester polyol is an esterification product of at least a) a polybutylene terephthalate; b) a fatty acid and/or fatty acid derivative selected from oleic acid, linolic acid and palmitic acid; c) a polyhydric component with a functionality between greater than 2 and 8 selected from glycerol, trimethylolpropane, mixtures thereof and reaction products of the aforementioned compounds or their mixtures with an alkylene oxide; d) a C2 to Cis diol or an alkoxylate thereof selected from diethylene glycol, monoethylene glycol, 1,4-butanediol and 1,5-pentanediol; and e) optionally a dicarboxylic acid and/or dicarboxylic acid derivative selected from terephthalic acid, phthalic acid, phthalic anhydride and isophthalic acid.
  • polyester polyols comprising monomeric units derived from a-1) 0 to 18 wt.-%, preferably 0.1 to 18 wt.-%, more preferred 0.5 to 13 wt.-%, even more preferred 1 to 6 wt.-%, particularly preferably 1.5 to 4 wt.-% butane diol; a-2) at least 0.2 wt.-%, preferably 0.5 to 34 wt.-%, more preferred 1 to 24 wt.-%, even more preferred 2 to 11 wt.-%, even more preferred 2.8 to 7.5 wt.-% terephthalic acid; b) 10 to 30 wt.-%, preferably 11 to 29 wt.-%, more preferred 12 to 28 wt.-% fatty acid and/or fatty acid derivative; c) 20 to 60 wt.-%, preferably 30 to 55 wt.-%, more preferred 35 to 50 wt.-% polyhydric component with
  • the components b), c), d), and e) are the ones described above and described above as preferred. These polyester polyols can be obtained by a reaction process described below, in which polybutylene terephthalate and the components b), c) and d) as well as optionally e) are reacted, optionally in the presence of a catalyst.
  • the components a-1) and a-2) originate from polybutylene terephthalate described above and below.
  • the polyester polyol preferably comprises monomeric units derived from at least 0.1 wt.-% butane diol, more preferred at least 0.5 wt.-%, even more preferred at least 1 wt.-%, particularly preferred at least 1 wt.-%, based on the sum of components a-1) to e).
  • the polyester polyol preferably comprises monomeric units derived from at most 18 wt.-% butane diol, more preferred 13 wt.-%, even more preferred 6 wt.-%, particularly preferred 4 wt.-%, based on the sum of components a-1) to e).
  • the polyester polyol preferably comprises monomeric units derived from 0 to 18 wt.-% butane diol, more preferably 0.1 to 18 wt.-%, even more preferred 0.5 to 13 wt.-%, even more preferred 1 to 6 wt.-%, particularly preferred 1.5 to 4 wt.-%, based on the sum of components a-1) to e).
  • the polyester polyol preferably comprises monomeric units derived from at least 0.2 wt.-% terephthalic acid, more preferred at least 0.5 wt.-%, even more preferred at least 1 wt.-%, even more preferred at least 2 wt.-%, particularly preferred at least 2.8 wt.-%, based on the sum of components a-1) to e).
  • the polyester polyol preferably comprises monomeric units derived from at most 34 wt.-% terephthalic acid, more preferably 24 wt.-%, even more preferably 11 wt.-%, even more preferred 7.5 wt.-% based on the sum of components a-1) to e).
  • the polyester polyol preferably comprises monomeric units derived from at least 0.2 wt.-% terephthalic acid, more preferred 0.5 to 34 wt.-% terephthalic acid, more preferred 1to 24 wt.-%, even more preferred 2 to 11 wt.-%, even more preferred 2.8 to 7.5 wt.-% based on the sum of components a-1) to e).
  • a further aspect of the present invention is a process for the production of the polyester polyol described above by reacting at least a) polybutylene terephthalate; b) a fatty acid and/or fatty acid derivative; c) a polyhydric component with a functionality between greater than 2 and 8; d) a C2 to Cis diol or an alkoxylate thereof; and e) optionally a dicarboxylic acid and/or dicarboxylic acid derivative; optionally in the presence of f) one or more catalysts.
  • the components a) to e) are the ones described above and described above as preferred.
  • the polybutylene terephthalate a) can be applied as such or as a mixture with further materials. Examples of such further materials are monomers of polybutylene terephthalate e.g. from a polybutylene terephthalate production process and additives from a compounding process.
  • the polybutylene terephthalate a) is preferably obtained from a polybutylene terephthalate production process, a polybutylene terephthalate processing process, and/or recycled material.
  • Polybutylene terephthalate production process means the production of polybutylene terephthalate raw material.
  • the polybutylene terephthalate or polybutylene terephthalate composition a) obtained from a polybutylene terephthalate production or processing process can be the final product of the polybutylene terephthalate production or processing process or be obtained from a side stream of said processes. The side stream of a production or processing process is defined further below.
  • the product of the polybutylene terephthalate production process can also be called virgin polybutylene terephthalate raw material.
  • virgin raw material means unused raw material that has not been subjected to any processing other than its production.
  • the product of the polybutylene terephthalate production process can be further processed in a polybutylene terephthalate processing process.
  • processing process can for example be a compounding process of polybutylene terephthalate.
  • the polybutylene terephthalate raw material is mixed and/or blended with one or several additives in a molten state to achieve the desired characteristics.
  • the product of a compounding process is a polybutylene terephthalate composition.
  • Typical additives in such a polybutylene terephthalate compounding process include but are not limited to glass fiber, minerals, glass beads, antioxidants, flame retardants, dyes, and pigments.
  • the polybutylene terephthalate or polybutylene terephthalate composition a) can be obtained from a side stream of a polybutylene terephthalate production or processing process.
  • a side stream according to the invention means material that does not meet the requirements of the product of the production or processing process.
  • a side stream preferably consists of discarded material. It can also be called a waste stream.
  • the side stream of a polybutylene terephthalate production process often originates from the start-up or shut-down phase of the production plant, malfunction of the plant, or when the final product or the material at any earlier stage of the process does not meet the specifications for any reason.
  • the polybutylene terephthalate product may at first not meet the specifications and must be discarded in the side stream.
  • the product is not fully polymerized and does not have the desired molar weight.
  • some produced material is discarded during the shut-down phase.
  • the produced material is discarded in the waste stream due to a plant malfunction, a mistake of the plant operator, a shift in process parameters, or due to any other reason.
  • granules or pellets that are not within the predefined size range can be discarded.
  • the discarded granules or pellets may be over- and/or undersized.
  • Examples of specifications a product of a polybutylene terephthalate production process must meet are molecular weight, preferably number average molecular weight, the size of granules or pellets, color, melt volume rate, melt flow rate, moisture, and dirt.
  • the side stream in a compounding process often comprises material that does not meet the specifications of the final product. Such material can be discarded at any stage of the compounding process for the same reasons described above regarding the polybutylene terephthalate production process. Additionally, it may be that the mixing ratio of polybutylene terephthalate and the additives is not within the specifications. Further examples of reasons for the discarding of material during a compounding process are insufficient drying and too low molecular weight and/or viscosity of the material due to thermal stress.
  • Examples of specifications a product of a polybutylene terephthalate processing process must meet are granule I pellet size, molecular weight, viscosity, color, melt volume rate, melt flow rate, moisture, dirt, density, and melting point.
  • the side stream according to the invention may be a continuous stream of material over a certain period of time, such as the material that is produced during a start-up phase of the production plant, or material that is discarded in batches.
  • the material of the side stream may be collected in containers or reservoirs until a desired amount of side stream material has been obtained.
  • the process for the production of the polyester polyol comprises the steps of i. providing polybutylene terephthalate or polybutylene terephthalate composition a), wherein the polybutylene terephthalate or the polybutylene terephthalate composition a) is obtained from i-a) a polybutylene terephthalate production process; i-b) a polybutylene terephthalate processing process; and/or i-c) recycled material; and ii.
  • the polybutylene terephthalate a) with at least b) a fatty acid and/or fatty acid derivative, c) a polyhydric component with a functionality between greater than 2 and 8, d) a C2 to Cis diol or an alkoxylate thereof, and e) optionally a dicarboxylic acid, a dicarboxylic acid derivative and/or a dicarboxylic acid composition; optionally in the presence of f) one or more catalysts.
  • the polybutylene terephthalate is preferably obtained from the side stream of the polybutylene terephthalate production process i-a) or the side stream of the polybutylene terephthalate processing process i-b). Particularly preferred, the polybutylene terephthalate or polybutylene terephthalate composition is obtained from the side stream of the polybutylene terephthalate production process i-a).
  • the polybutylene terephthalate a) may be added into the reaction as pellets, granules, flakes, powder, regrind, or pieces of material.
  • the polybutylene terephthalate a) preferably comprises at least 45 wt-%, polybutylene terephthalate, more preferred at least 70 wt.-%, even more preferred at least 85 wt.-%, based on the total weight of the polybutylene terephthalate a).
  • the polybutylene terephthalate a) preferably comprises 45 to 100 wt.-% polybutylene terephthalate, more preferred 70 to 100 wt.-%, even more preferred 85 to 100 wt.-%, based on the total weight of the polybutylene terephthalate a).
  • the polybutylene terephthalate or the polybutylene terephthalate composition a) can be reacted with the other reaction components with or without purifying it before the reaction or after prior purification. Filtering is a typical purification step.
  • the polybutylene terephthalate or the polybutylene terephthalate composition A) is reacted with the other reaction components without purifying it before the reaction.
  • the polybutylene terephthalate comprised in the polybutylene terephthalate a) preferably has a number average molecular weight of at least 8000 g/mol, more preferred at least 9000 g/mol, even more preferred at least 15 000 g/mol, particularly preferred at least 25 000 g/mol.
  • the polybutylene terephthalate comprised in the polybutylene terephthalate a) preferably has a number average molecular weight of at most 100 000 g/mol, more preferred at most 85 000 g/mol, even more preferred at most 60 000 g/mol, particularly preferred at most 55 000 g/mol.
  • the polybutylene terephthalate comprised in the polybutylene terephthalate a) has a number average molecular weight of 8000 to 100 000 g/mol, more preferred 9000 to 85 000 g/mol, even more preferred 15 000 to 60 000 g/mol, particularly preferred 25 000 to 55 000 g/mol, determined by gel permeation chromatography (GPC) using hexafluoro-2-propanol as solvent.
  • GPC gel permeation chromatography
  • the reaction components can be reacted through polycondensation catalyst-free or preferably in the presence of esterification catalysts, expediently in an atmosphere of inert gas, such as nitrogen, carbon monoxide, helium, argon, and others, in the melt at temperatures of 100 to 300 °C, preferably 130 to 280 °C, more preferred 150-280 °C, even more preferred 160-260 °C, particularly preferred 180 to 260 °C, optionally under reduced pressure, to the desired acid number, which is advantageously less than 3, preferably less than 2.
  • inert gas such as nitrogen, carbon monoxide, helium, argon, and others
  • the esterification mixture is polycondensed at the above temperatures up to an acid number of 0.2 to 1.5, preferably 0.3 to 1.0, under normal pressure and then under a pressure of less than 500 mbar, preferably 20 to 400 mbar until the desired acid number has been obtained.
  • Suitable esterification catalysts include, for example, iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tin catalysts in the form of metals, metal oxides or metal salts.
  • the polycondensation can also be carried out in the liquid phase in the presence of diluents and/or entraining agents, such as benzene, toluene, xylene or chlorobenzene, for azeotropic distillation of the condensation water.
  • diluents and/or entraining agents such as benzene, toluene, xylene or chlorobenzene
  • the production of the polyester polyols can be a batch, a semi-batch or a continuous process.
  • the production of the polyester polyols is a batch process. All reaction components are preferably dosed into the reactor in one step.
  • the polybutylene terephthalate can be dosed into the reactor in a molten or solid state.
  • the polybutylene terephthalate is dosed into the reactor in a solid state.
  • the polyester polyols according to the invention preferably have an average functionality in the range of 1.8 to 4, more preferred in the range of 2 to 3.5, even more preferred in the range of 2 to 3, particularly preferred 2.2 to 3.
  • the polyester polyols preferably have a number average molecular weight of 300 to 3000 g/mol, more preferred 400 to 1000 g/mol, even more preferred 450 to 800 g/mol, determined by gel permeation chromatography, using tetrahydrofurane as solvent.
  • the polyester polyols preferably have hydroxyl numbers of 100 to 500 mg KOH/g, preferably 200 to 400 mg KOH/g.
  • polyester polyol as described above, the polyester polyol produced according to the process as described above, or the polyol composition described above for the production of polyurethanes, preferably for polyurethane foams. More preferred these polyester polyols are used for the production of rigid polyurethane foams, in particular for rigid polyurethane foams used in insulation.
  • Another aspect of the invention is a process for the production of polyurethanes by reacting
  • a yet further aspect of the invention are polyurethanes produced according to the process described below.
  • the polyurethanes are preferably foams, in particular rigid polyurethane foams.
  • a polyurethane is obtained from the reaction of a polyisocyanate component and a polyol component in a reaction mixture. It has proven to be particularly advantageous to employ a two- component system and to combine the mixture of polyols, catalysts, chain extenders, crosslinking agents, blowing agents, auxiliaries and additives as a polyol component, also called Component B, and to use the organic polyisocyanates as the isocyanate component or Component A.
  • An advantage of this method is that the isocyanate and the polyol components can be stored separately and can be transported in a space saving manner.
  • the components B) to E) are combined to form a polyol component.
  • polyol for the polyurethane production or a mixture of different polyols, e.g. a mixture of two or more polyester polyols or a mixture of one or more polyester polyols and/or one or more compounds having at least two H-atoms reactive towards isocyantes, e.g. having 2 to 8 H-atoms reactive towards isocyanates and molecular weights of 400 to 15000 g/mol.
  • examples of such compounds are polyether polyols, polyesterpolyols, and polyetherester polyols.
  • a polyol component typically comprises a polyol or a polyol composition as well as other compounds such as blowing agents, catalysts, and/or auxiliary agents.
  • polyurethane comprises all known polyisocyanate polyaddition products. These comprise addition products made from isocyanate and alcohol, and also modified polyurethanes which can comprise isocyanurate structures, allophanate, structures, urea structures, carbodiimide structures, uretonimine structures, biuret structures, and other isocyanate addition products. These polyurethanes of the invention in particular comprise compact polyisocyanate polyaddition products, for example thermosets, and foams based on polyisocyanate polyaddition products, for example flexible foams, semirigid foams, rigid foams and integral foams, and also polyurethane coatings and binders.
  • the polyurethanes of the invention are preferably polyurethane foams or compact polyurethanes which comprise no polymers other than the polyurethanes described herein.
  • the polyurethanes according to the invention comprise functional units selected from urethane and isocyanurate.
  • polyurethane foams mean foams in accordance with DIN 7726.
  • the compressive stress at 10% compression or, respectively, compressive strength in accordance with DIN 53 421 1 DIN EN ISO 604 of flexible polyurethane foams of the invention here is 15 kPa or less, preferably from 1 to 14 kPa and in particular from 4 to 14 kPa.
  • the compressive stress at 10% compression of semirigid polyurethane foams of the invention in accordance with DIN 53 421 1 DIN EN ISO 604 is from more than 15 to less than 80 kPa.
  • the open-cell factor of semirigid polyurethane foams and flexible polyurethane foams of the invention in accordance with DIN ISO 4590 is preferably more than 85%, particularly preferably more than 90%. Further details concerning flexible polyurethane foams and semirigid polyurethane foams of the invention are found in "Kunststoffhandbuch [Plastics handbook], volume 7, Polyurethane [polyurethanes]", Carl Hanser Verlag, 3rd edition 1993, chapter s.
  • the compressive stress at 10% compression of rigid polyurethane foams of the invention is greater than or equal to 80 kPa, preferably greater than or equal to 120 kPa, particularly preferably greater than or equal to 150 kPa.
  • the closed-cell factor of the rigid polyurethane foam in accordance with DIN ISO 4590 is moreover more than 80%, preferably more than 90%. Further details concerning rigid polyurethane foams of the invention are found in "Kunststoffhandbuch [Plastics handbook], volume 7, Polyurethane [polyurethanes]", Carl Hanser Verlag, 3rd edition 1993, chapter s.
  • the expression elastomeric polyurethane foams mean polyurethane foams in accordance with DIN 7726 which exhibit no residual deformation above 2% of their initial thickness 10 minutes after brief deformation by 50% of their thickness in accordance with DIN 53 577.
  • the material here can be a rigid polyurethane foam, a semirigid polyurethane foam or a flexible polyurethane foam.
  • Integral polyurethane foams are polyurethane foams in accordance with DIN 7726 with a peripheral zone that, as a result of the shaping process, has higher density than the core.
  • the overall envelope density averaged across the core and the peripheral zone here is preferably above 100 g/L.
  • integral polyurethane foams for the purposes of the invention can be rigid polyurethane foams, semirigid polyurethane foams or flexible polyurethane foams. Further details concerning integral polyurethane foams of the invention are found in "Kunststoffhandbuch [Plastics handbook], volume 7, Polyurethane [Polyurethanes]", Carl Hanser Verlag, 3rd edition 1993, chapter 7.
  • the organic polyisocyanate A) is preferably an aliphatic, cycloaliphatic, or aromatic polyisocyanate.
  • alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene radical such as 1 ,12-dodecane diisocyanate, 2-ethyltetramethylene-1 ,4, 2- methylpentamethylene-1 ,5-diisocyanate, tetramethylene-1 , 4-di isocyanate and preferably hexamethylene-1,6-diisocyanate; cycloaliphatic diisocyanates such as cyclohexane 1 ,3-and 1,4- diisocyanate and any desired mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocy- anatomethylcyclohexane (I PDI), 2,4- and 2,6- hexahydrotoluylene diisocyanate and the corresponding isomer mixtures, 4,4'-, 2,2'- and 2,4'-dicyclohexylmethane diisocyanate and the
  • Preferred diisocyanates and polyisocyanates are tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and, in particular, mixtures of diphenylmethane diisocyanate and polyphenylenepolymethylene polyisocyanates (polymeric MDI or PMDI).
  • TDI tolylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • PMDI polyphenylenepolymethylene polyisocyanates
  • modified polyfunctional isocyanates i.e., products obtained by chemical reaction of organic diisocyanates and/or polyisocyanates, are also frequently used.
  • the polyol composition B) comprises the polyester polyol as described above or the polyester polyol produced according to the process as described above. Preferably, it also comprises additional polyols.
  • the additional polyols may for example be further polyester polyols; polyether polyols; polyetherester polyols; graft polyether polyols or polyester polyols; hydroxyl-containing polyesteramides, polyacetals, polycarbonates and/or polyetherpolyamines; and/or further compounds having at least two isocyanate-reactive groups.
  • Suitable further polyester polyols can be prepared, for example, from organic dicarboxylic acids having 2 to 12 carbon atoms, preferably aromatic or a mixture of aromatic and aliphatic dicarboxylic acids, and polyhydric alcohols, preferably diols, having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms.
  • suitable dicarboxylic acids are succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid.
  • the dicarboxylic acids can be used either individually or as a mixture with one another.
  • dicarboxylic acid derivatives such as, for example, dicarboxylic esters of alcohols having 1 to 4 carbon atoms or dicarboxylic anhydrides.
  • the aromatic dicarboxylic acids used are preferably phthalic acid, phthalic anhydride, and/or isophthalic acid in a mixture or alone.
  • the aliphatic dicarboxylic acids used are preferably mixtures of succinic, glutaric and adipic acid in proportions of, for example, from 20 to 35:35 to 50:20 to 32 parts by weight, and in particular adipic acid.
  • dihydric and polyhydric alcohols examples are ethanediol, diethylene glycol, 1,2-and 1,3-propanediol, dipropylene glycol, 1 ,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1 ,10-decanediol, glycerol, trimethylolpropane, and pentaerythritol.
  • biobased starting materials and/or derivatives thereof are also suitable, such as castor oil, polyhydroxy fatty acids, ricinoleic acid, hy- droxyl-modified oils, grape seed oil, black caraway oil, pumpkin seed oil, borage seed oil, soybean oil, wheat seed oil, rapeseed oil, sunflower seed oil, peanut oil, apriac seed oil, pistachio oil, almond oil, olive oil, avocado oil, sand mandrel oil, sesame oil, hemp oil, hazelnut oil, primrose oil, wild rose oil, safflower oil, walnut oil, hydroxyl-modified fatty acids and fatty acid esters based on myristoleic acid, palmitoleic acid, oleic acid, vaccenic acid, petroselic acid, gadoleic acid, erucic acid, nervonic acid, linoleic acid, a-and y-lin
  • the polyol composition B) comprises polyether polyols. They are typically prepared by known processes from at least one starter molecule with 2 to 8, preferably 2 to 6, reactive hydrogen atoms and one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical.
  • the polyether polyols can be prepared by anionic polymerization using alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide, or alkali metal alcoholates, such as sodium methylate, sodium ethylate or potassium ethylate or potassium isopropylate as catalysts.
  • alkali metal hydroxides such as sodium hydroxide or potassium hydroxide
  • alkali metal alcoholates such as sodium methylate, sodium ethylate or potassium ethylate or potassium isopropylate as catalysts.
  • Another possibility is the cationic polymerization of the alkylene oxides catalyzed by Lewis acids, such as antimony pentachloride or boron fluoride etherate, or bleach
  • Suitable alkylene oxides are, for example, 1 ,3-propylene oxide, 1 ,2- or 2,3-butylene oxide, styrene oxide and preferably ethylene oxide and 1 ,2-propylene oxide.
  • the alkylene oxides can be used individually, alternately in succession or as mixtures. Instead of or in addition to an alkylene oxide, tetrahydrofuran may also be used.
  • Preferred alkylene oxides are propylene oxide and ethylene oxide, ethylene oxide being particularly preferred.
  • starter molecules are water; organic dicarboxylic acids, such as succinic acid, adipic acid, phthalic acid and terephthalic acid; aliphatic and aromatic, unsubstituted or kimono-, N, N-and N, N '-dialkyl-substituted diamines having 1 to 4 carbon atoms in the alkyl radical, such as optionally mono-and dialkyl-substituted ethylenediamine, diethylenetriamine, triethylenetetramine, 1 ,3-propylenediamine, 1 ,3- and 1 ,4-butylenediamine, 1 ,2-, 1 ,3-, 1 ,4-, 1 ,5-and 1 ,6-hexamethylenediamine, phenylenediamines, 2,3-, 2,4- and 2,6-toluylenediamine and 4,4 '-, 2,4'-and 2,2 '-diaminodiphenylmethan
  • suitable starter molecules are alkanolamines, for example ethanolamine, N-methyl- and N-ethylethanolamine, dialkanolamines, for example diethanolamine, N-methyl- and N-ethyldi- ethanolamine, and trialkanolamines, for example triethanolamine, and ammonia.
  • Further suitable starter molecules are dihydric or polyhydric alcohols, such as ethanediol, 1,2-and 1,3- propanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose. Preference is given to using dihydric or polyhydric alcohols.
  • the polyether polyols preferably polyoxypropylene polyols and/or polyoxyethylene polyols, have a functionality of preferably from 2 to 8, more preferably 2 to 6 and in particular from 2 to 5 and number average molecular weights of from 150 to 3000 g/mol, preferably from 200 to 2000 g/mol and in particular from 250 to 1000 g/mol.
  • polyether polyols are polymer-modified polyether polyols, preferably graft polyether polyols, in particular those based on styrene and/or acrylonitrile, which are obtained by in situ polymerisation of acrylonitrile, styrene or preferably mixtures of styrene and acrylonitrile, for example in a weight ratio of 90:10 to 10:90, preferably 70:30 to 30:70, are prepared in an expedient manner analogously to the instructions of German patent specifications 1 1 1 1 394, 12 22 669 (U.S. PAT. NOs.
  • polyether polyol dispersions which are prepared as disperse phase, the following are usually present in an amount of from 1 to 50% by weight, preferably from 2 to 25% by weight: for example polyureas, polyhydrazides, polyurethanes containing bonded tert-amino groups and/or melamine and are described, for example, in EP-B 01 1 752 (U.S. Pat. no.
  • the polyether polyols may be used individually or in the form of mixtures. They may also be mixed with the graft polyether polyols, polyester polyols, the hydroxylcontaining polyesteramides, polyacetals, polycarbonates, and/or polyetherpolyamines.
  • Suitable hydroxyl-containing polyacetals are, for example, the compounds which can be prepared from glycols, such as diethylene glycol, triethylene glycol, 4,4 '-dihydroxyethoxydiphenyldimethylmethane, hexanediol and formaldehyde.
  • Suitable polyacetals can also be prepared by polymerization of cyclic acetals.
  • Suitable hydroxyl-containing polycarbonates are those of the type known per se which can be prepared, for example, by reacting diols, such as propane-1, 3-diol, butane-1,4-diol and/or hex- ane-1,6-diol, diethylene glycol, triethylene glycol or tetraethylene glycol, with diaryl carbonates, for example diphenyl carbonate, alkylene carbonate or phosgene.
  • the polyesteramides include, for example, the predominantly linear condensates obtained from polybasic, saturated and/or unsaturated carboxylic acids or anhydrides thereof and polyhydric saturated and/or unsaturated amino alcohols or mixtures of polyhydric alcohols and amino alcohols and/or polyamines.
  • Suitable polyetherpolyamines can be prepared from the abovementioned polyetherpolyols by known processes. Examples which may be mentioned are the cyanoalkylation of polyoxyalkylene polyols and subsequent hydrogenation of the nitrile formed (U.S. PAT. no. 3,267,050) or the partial or complete amination of polyoxyalkylene polyols with amines or ammonia in the presence of hydrogen and catalysts (DE 12 15 373).
  • Suitable further compounds having at least two isocyanate-reactive groups are, in particular, those which contain two or more reactive groups selected from OH groups, SH groups, NH groups, NH2-groups and CH-acidic groups, such as, for example, p-diketo groups.
  • the polyurethanes are prepared by addition of at least one blowing agent (C).
  • the at least one blowing agent is added to the reaction mixture prior to the reaction.
  • Blowing agents (C) which are used for producing the polyurethane foams include chemical blowing agents and/or physical blowing agents. Examples of chemical blowing agents are water and carboxylic acids such as formic acid. Examples of physical blowing agents are non-halogenated, partially halogenated and halogenated hydrocarbons.
  • Blowing agents (C) which are used for producing the rigid polyurethane foams preferably include chemical and physical blowing agents.
  • chemical blowing agents are water, formic acid and mixtures thereof. These react with isocyanate groups to form carbon dioxide and, in the case of formic acid, to form carbon dioxide and carbon monoxide.
  • physical blowing agents are low-boiling hydrocarbons. Suitable liquids are those which are inert toward the organic, modified or unmodified polyisocyanates and have boiling points below 100 °C, preferably below 50 °C, at atmospheric pressure, so that they evaporate under the influence of the exothermic polyaddition reaction.
  • liquids which can preferably be used are alkanes, such as heptane, hexane, n- and isopentane, preferably industrial mixtures of n- and isopentanes, n- and isobutane and propane, cycloalkanes, such as cyclopentane and/or cyclohexane, ethers, such as furan, dimethyl ether and diethyl ether, ketones, such as acetone and methyl ethyl ketone, carboxylic acid alkyl esters, such as methyl formate, dimethyl oxalate and ethyl acetate, and halogenated hydrocarbons, such as methylene chloride, dichloromonofluoromethane, difluoromethane, trifluoromethane, difluoroethane, tetrafluoroethane, chlorodifluoroethane, 1 , 1 -dichloro-2,
  • the amount of blowing agent or blowing agent mixture used is from 1 to 45 wt.-%, preferably from 1 to 30 wt.-%, more preferred 1.5 to 30 wt.-%, even more preferred 2 to 30 wt.-%, particularly preferably from 3 to 25 wt.-%, in each case based on the weight of the polyol component.
  • water is used as blowing agent, it is preferably added to the polyol composition B) in an amount of from 0.2 to 5% by weight, based on the weight of the polyol component.
  • the addition of water can be carried out in combination with the use of the other blowing agents described.
  • the blowing agents are either wholly or partly present in the polyol component or are metered into the polyol component via a static mixture directly before foaming.
  • Water or formic acid are usually completely or partly dissolved in the polyol component and the physical blowing agent (for example pentane) and, if desired, the remainder of the chemical blowing agent are metered "online", i.e. , during the foam preparation process.
  • Pentane possibly parts of the chemical blowing agent, and/or some or all of the catalysts are metered into the polyol component in situ, but the polyol component usually already contains at least portions thereof (with the exception of the pentane).
  • the auxiliaries and additives, as well as the flame retardants, are already present in the polyol blend, if present.
  • Catalysts D) used for the production of the rigid polyurethane foams are, in particular, compounds which greatly accelerate the reaction of the compounds of component B) containing reactive hydrogen atoms, in particular hydroxyl groups, with the organic polyisocyanates A).
  • basic polyurethane catalysts for example tertiary amines, such as triethylamine, tributylamine, dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine, N,N,N',N'-tetramethyldiaminodiethyl ether, Bis(dimethylaminopropyl)urea, N-methylmorpholine and N-ethylmorpholine, respectively, N-cyclohexylmorpholine, N,N,N',N'-tetramethylethylenedia- mine, N,N,N',N'-tetramethylbutanediamine, N,N,N',N'-tetramethylhexanediamine-1 ,6, N-dime- thylaminoethylpiperidine, 1,2-dimethylimidazole, 1-azabicyclo(2,2,0)octane,1,4-diazabic
  • metal salts such as iron(ll)chloride, zinc chloride, lead octoate and preferably tin salts, such as tin dioctoate, tin diethylhexoate and dibutyltin dilaurate, and in particular mixtures of tertiary amines and organic tin salts, are also suitable.
  • amidines such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine
  • tetraalkylammonium hydroxides such as tetramethylammonium hydroxide
  • alkali metal hydroxides such as sodium hydroxide
  • alkali metal alcoholates such as sodium methylate and potassium isopropylate
  • alkali metal salts of long-chain fatty acids having from 10 to 20 carbon atoms and, if desired, lateral OH groups.
  • Preference is given to using from 0.001 to 5% by weight, in particular from 0.05 to 2% by weight, of catalyst or catalyst combination, based on the total weight of the polyol component.
  • the catalytic activity of polyols started with amines is utilized.
  • suitable catalysts for the tri- merization reaction of the excess NCO groups with one another are catalysts which form isocy- anurate groups, for example ammonium ion or alkali metal salts, alone or in combination with tertiary amines. Isocyanurate formation leads to flame-resistant PIR foams which are preferably used in industrial rigid foam, for example in the building industry as insulating panels or sandwich elements.
  • the rigid polyurethane foams according to the invention can be prepared using chain extenders and/or crosslinking agents (E).
  • chain extenders and/or crosslinking agents E
  • the addition of chain extenders, crosslinking agents or, where appropriate, also mixtures thereof may prove advantageous for modifying the mechanical properties, for example the hardness.
  • the chain extenders and/or crosslinking agents used are diols and/or triols having molecular weights of less than 400, preferably from 60 to 300.
  • suitable diols are aliphatic, cycloaliphatic and/or araliphatic diols having 2 to 14, preferably 4 to 10, carbon atoms, such as ethylene glycol, propane-1 -diol, 3-diol, decane-1 -diol, 10-diol, o-, m-, diethylene glycol, dipropylene glycol and preferably butane-1,4-diol, hexane-1,6-diol and bis (2- hydroxyethyl) hydroquinone, triols, such as 1,2,4-and 1 ,3,5-trihydroxycyclohexane, glycerol and trimethylolpropane, and low molecular weight polyalkylene oxides containing hydroxyl groups and based on ethylene oxide and/or 1,2-propylene oxide and the abovementioned diols and/or triols as initiator molecules.
  • ethylene glycol propane-1 -dio
  • chain extenders include particularly difunctional compounds having molecular weights of 18 to less than 450, preferably 60 to 300.
  • aliphatic diols having 2 to 6 carbon atoms such as ethylene glycol, 1,4-butanediol, and 1,6- hexanediol and aromatic-aliphatic diols such as di-(P-hydroxyethyl)-hydroquinone.
  • the molar ratio of polyester polyol to chain extender is a function of the desired physical properties of the polyurethane flexible foam and may be varied within wide limits.
  • auxiliary agents and/or additives F may optionally be added to the reaction mixture for the production of the rigid polyurethane foams.
  • auxiliary agents and/or additives F may optionally be added to the reaction mixture for the production of the rigid polyurethane foams. Examples which may be mentioned are surface-active substances, foam stabilizers, cell regulators, fillers, dyes, pigments, flame retardants, hydrolysis stabilizers, as well as fungistatic and bacteriostatic substances.
  • Suitable surface-active substances are, for example, compounds which serve to assist the homogenization of the starting materials and, if appropriate, are also suitable for regulating the cell structure of the plastics.
  • emulsifiers such as the sodium salts of castor oil sulfates or of fatty acids, and salts of fatty acids with amines, for example diethylamine oleate, diethanolamine stearate, diethanolamine ricinolate, salts of sulfonic acids, for example alkali metal or ammonium salts of dodecylbenzene-or dinaphthylmethanedisulfonic acid and ricinoleic acid; foam stabilizers, such as siloxane-oxyalkylene copolymers and other organopolysiloxanes, oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffin oils, castor oil or ricinoleic acid esters, sul
  • the oligomeric acrylates described above having polyoxyalkylene and fluoroalkane radicals as side groups are suitable for improving the emulsifying action, the cell structure and/or stabilizing the foam.
  • the surfactants are normally used in quantities of 0.01 to 10 wt.-%, based on the total weight of the polyol component.
  • Fillers, in particular reinforcing fillers are to be understood as meaning the customary organic and inorganic fillers, reinforcing agents, weighting agents, agents for improving the abrasion behavior in paints, coating compositions, etc., which are known per se.
  • inorganic fillers such as silicate minerals, for example phyllosilicates, such as antigorite, serpentine, horn blends, amphiboles, chryisotil and talc, metal oxides, such as kaolin, aluminum oxides, titanium oxides and iron oxides, metal salts, such as chalk, barite and inorganic pigments, such as cadmium sulfide and zinc sulfide, and glass, inter alia.
  • silicate minerals for example phyllosilicates, such as antigorite, serpentine, horn blends, amphiboles, chryisotil and talc
  • metal oxides such as kaolin, aluminum oxides, titanium oxides and iron oxides
  • metal salts such as chalk, barite and inorganic pigments, such as cadmium sulfide and zinc sulfide, and glass, inter alia.
  • Kaolin (china clay), aluminum silicate and coprecipitates of barium sulfate and aluminum silicate and natural and synthetic fibrous minerals such as wollastonite, metal fibers and, in particular, glass fibers of various lengths, which may optionally be sized, are preferably used.
  • suitable organic fillers are: carbon, melamine, rosin, cyclopentadienyl resins and graft polymers, and also cellulose fibers, polyamide fibers, polyacrylonitrile fibers, polyurethane fibers, polyester fibers based on aromatic and/or aliphatic dicarboxylic esters and, in particular, carbon fibers.
  • the inorganic and organic fillers can be used individually or as mixtures and are added to the reaction mixture advantageously in amounts of from 0.5 to 50 wt.-%, preferably from 1 to 40 wt.-%, based on the weight of components A) and B), but the content of mats, nonwovens and woven fabrics of natural and synthetic fibers may reach values of up to 80 wt.-%.
  • Flame retardants which can generally be used are the flame retardants known from the prior art.
  • suitable flame retardants are brominated substances which cannot be incorporated, brominated esters, brominated ethers (Ixol), or brominated alcohols such as dibromoneopentyl alcohol, tri bromoneopentyl alcohol and PHT-4-diol, and also chlorinated phosphates such as tris(2-chloroethyl)phosphate, tris (2-chloropropyl) phosphate, tris (1 ,3-dichloropropyl) phosphate, tricresyl phosphate, tris (2,3-dibromopropyl) phosphate, tetrakis (2-chloroethyl) ethylene diphosphate, dimethyl methanephosphonate, diethyl diethanolaminomethylphosphonate and commercial halogen-containing flame retardant polyols.
  • liquid flame retardants which can be used are phosphates or phosphonates such as diethyl ethanephosphonate (DEEP), triethyl phosphate (TEP), dimethyl propyl phosphonate (DM PP), diphenyl cresyl phosphate (DPK) and others.
  • DEEP diethyl ethanephosphonate
  • TEP triethyl phosphate
  • DM PP dimethyl propyl phosphonate
  • DPK diphenyl cresyl phosphate
  • inorganic or organic flameproofing agents such as red phosphorus, red phosphorus-containing finishes, aluminum oxide hydrate, antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate, expandable graphite or cyanuric acid derivatives, e.g. melamine, or mixtures of at least two flame retardants, such as ammonium polyphosphates and melamine, and optionally corn starch or ammonium polyphosphate, melamine and expandable graphite, and/or optionally aromatic polyesters, are used to render the rigid polyurethane foams flame-resistant.
  • inorganic or organic flameproofing agents such as red phosphorus, red phosphorus-containing finishes, aluminum oxide hydrate, antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate, expandable graphite or cyanuric acid derivatives, e.g. melamine, or mixtures of at least two flame retardants, such as ammonium polyphosphates and
  • the organic polyisocyanates A), the polyol composition B) and optionally blowing agents C), catalysts D), and/or chain extenders and/or crosslinking agents (E) are reacted in amounts such that the equivalent ratio of NCO groups of the polyisocyanates A) to the sum of the reactive hydrogen atoms of components B), optionally C) to E) is from 1 to 6:1 , preferably from 1.1 to 5:1 and in particular from 1.2 to 3.5:1.
  • the rigid polyurethane foams are advantageously produced by a one-shot process, for example with the aid of the high-pressure or low-pressure technique, in open or closed molds, for example metallic molds.
  • the continuous application of the reaction mixture to suitable belt trains for producing panels is also customary.
  • the starting components are mixed at a temperature of from 15 to 90 °C, preferably from 20 to 60 °C and in particular from 20 to 35 °C, and introduced into the open mold or, if appropriate, under elevated pressure into the closed mold or, at a continuous workstation, applied to a belt which receives the reaction mass.
  • the mixing can be carried out mechanically by means of a stirrer or a stirring screw.
  • the mixing is preferably carried out as a high-pressure mixing process in a mixing chamber through counter flow injection.
  • the temperature of the molding tool is advantageously from 20 to 110 °C, preferably from 30 to 70 °C and in particular from 40 to 65 °C.
  • the rigid polyurethane foams produced by the process according to the invention preferably have an overall density of from 15 to 300 g/l, particularly preferred from 20 to 100 g/l and in particular from 25 to 60 g/l.
  • the polyurethane containing polyester polyols and produced in accordance with this invention are used in many areas, for example, in cooling systems like fridges and refrigerators, heat storage systems, sandwich element and insulation boards for construction, spray foam for construction, insulation of window frames, doors, blinds and roller shutters, insulated pipes, mobile transport systems, water boilers, instrument panels, engines, caravans, trailers, or insulated truck bodies.
  • the viscosity of the polyester polyols was determined at 25°C to DIN EN ISO 3219 (October 1994) with a Rheotec RC 20 rotary viscometer using the CO 25 DIN spindle (spindle diameter: 12.5 mm; internal measuring cylinder diameter: 13.56 mm) at a shear rate of 50 1/s.
  • the results for the polyester polyols prepared are given above.
  • Color index was determined to DIN EN ISO 6271 (May 2016) using a spectrophotometer capable of measuring transmitted color and reporting the result in the Pt-Co (Hazen or APHA number) color scale.
  • polyester polyols according to the invention have a lower color index than the comparative polyester polyols.
  • Polyester polyol A polyester polyol according to comparative example 1. Average functionality 2.54, OH-number 249 mg KOH/g
  • Polyester polyol B polyester polyol according to inventive example 1. Average functionality 2.54, OH-number 234.4 mg KOH/g
  • Polyether polyol C polyether polyol based on diethylene glycol and ethylene oxide. Average functionality 2, OH-number 180 mg KOH/g
  • Catalyst 1 Catalyst mixture comprising of oxydi propanol, N,N,N',N'-Tetramethyl-2,2'-ox- ybis(ethylamine) and water
  • Catalyst 2 Catalyst mixture comprising of ethanediol, potassium formiate and water
  • Blowing agent 2 formic acid, 85 %
  • Polyisocyanate 4,4’-diphenylmethane diisocyanate (MDI) (Lupranat M50 ®, BASF)
  • the compounds were reacted with water as blowing agent according to the compositions given in Table 3 to produce polyurethane foams.
  • the amounts are given in parts by weight.
  • mixtures of the indicated polyols, flame retardant, blowing agent, and stabilizer were prepared. These mixtures were mixed with the isocyanates according to the index displayed in Table 3 and put into an open form. The total amount of polyols, isocyanates and additives were about 2.6 kg.
  • the foams were stored for 10 minutes at 80°C in a heating cabinet and then for 24 hours at room temperature. Then samples with a thickness of 50 mm were cut from the Pll foams for the measurements of the mechanical properties. The results of the measurements are shown in Table 4.
  • Table 3 Compositions used for the preparation of freely foamed Pll foams
  • the mechanical properties of the foam prepared with the polyester polyols according to the invention are better than those of the comparative foam, while the densities of both foams are comparable.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

La présente invention concerne un polyester polyol comprenant un produit d'estérification d'au moins a) un polybutylène téréphtalate ; b) un acide gras et/ou un dérivé d'acide gras ; c) un composant polyhydrique ayant une fonctionnalité comprise entre plus de 2 et 8 ; d) un diol en C2 à C18 ou un alcoxylate de celui-ci ; et e) éventuellement un acide dicarboxylique et/ou un dérivé d'acide dicarboxylique, le produit d'estérification représentant au moins 80% en poids du polyester polyol et le polyester polyol ayant un indice d'hydroxyle dans la plage de 100 à 500 mg KOH/g.
PCT/EP2023/086177 2022-12-21 2023-12-15 Polyester polyol à base de polybutylène téréphtalate WO2024132976A1 (fr)

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