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WO2002028936A1 - Procede de fabrication de mousses de polyurethanne rigides - Google Patents

Procede de fabrication de mousses de polyurethanne rigides Download PDF

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Publication number
WO2002028936A1
WO2002028936A1 PCT/EP2001/010143 EP0110143W WO0228936A1 WO 2002028936 A1 WO2002028936 A1 WO 2002028936A1 EP 0110143 W EP0110143 W EP 0110143W WO 0228936 A1 WO0228936 A1 WO 0228936A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyether polyol
polyol
foam
functionality
polyols
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.)
Ceased
Application number
PCT/EP2001/010143
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English (en)
Inventor
Juergen Kellner
Philippe Etienne Zarka
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.)
Huntsman International LLC
Original Assignee
Huntsman International LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huntsman International LLC filed Critical Huntsman International LLC
Priority to AU2002212197A priority Critical patent/AU2002212197A1/en
Publication of WO2002028936A1 publication Critical patent/WO2002028936A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5033—Polyethers having heteroatoms other than oxygen having nitrogen containing carbocyclic groups

Definitions

  • This invention relates to processes for the preparation of rigid polyurethane or urethane- modified polyisocyanurate foam, to foam prepared thereby, and to novel compositions useful in the process.
  • the present invention mainly focuses on providing a rigid polyurethane foam which is especially suitable for use as an insulating material for pipes.
  • Rigid polyurethane and urethane-modified polyisocyanurate foams are in general prepared by reacting the appropriate polyisocyanate and isocyanate-reactive compound (usually a polyol) in the presence of a blowing agent.
  • Rigid polyurethane foams are well known in the art and have numerous applications, particularly as an insulating material. Examples include insulation of refrigerators and freezers, insulation of pipes and tanks in industrial plants and use as an insulating material in the construction industry.
  • a number of different production methods can be used for the production of pre-insulated pipes.
  • discontinuous production techniques a pipe pre- assembly is made by positioning the steel inner pipe centrally in a slightly shorter casing pipe. To keep the steel pipe in the center of the casing pipe, distance holders are arranged around the steel pipe. At both ends the gap between the steel and the casing pipe is sealed off by end- caps that fit tightly around the steel and the HDPE casing pipe. The end-caps are equipped with holes for foam injection and air venting. In principle, pipes of any length up to approximately 16 meters can be used, but standard steel pipe lengths are 6, 12 and 16 m.
  • Continuous pipe production techniques consist of two stages. In a first stage, the foam is applied on the inner pipe.
  • the casing pipe is extruded or wound around the pre-shaped foam.
  • Continuous techniques allow a fast and consistent production of a large number of pipes of the same dimension. Although the initial investment into these techniques may be higher, cost savings are achieved due to reduction of foam filling density and a reduced thickness of the high-density polyethylene (HDPE) casing pipes.
  • the continuous spray technique is particularly useful for medium and large diameter pipes.
  • the reacting foam mixture is sprayed on the outside of the rotating medium pipe. Obviously the foam has to react very quickly, so that the foam adheres well to the pipe surface and does not spin off.
  • Various layers of foam may be applied to obtain the required insulation thickness. Very uniform foam is created over an extremely short flow path.
  • any insulation thickness can be produced by spray application.
  • Large and long pipes can be insulated using small foaming machines.
  • the HDPE casing pipe is extruded or wound around the insulation.
  • a polyurea coating can also be applied as casing using the spray techmque.
  • applied foam densities can be lower because of smaller difference between overall and core density.
  • the HDPE casing pipe can be thinner since it does not have to withstand the high foam pressure that occurs during conventional pipe filling and hence, material savings are possible.
  • the present invention aims to provide rigid polyurethane foams having excellent high temperature resistance and excellent mechanical properties, thus making them very suitable as insulating material for steel pipes used in the hot water transportation system of district heating networks and for oil and gas pipelines.
  • a specific isocyanate-reactive composition containing (a) from 20 to 60 wt% of an aromatic polyether polyol, (b) from 20 to 60 wt% of a polyether polyol of functionality 4 or more and (c) from 0 to 40 wt% of a polyether polyol of functionality less than 4, the total amounts of polyols (a), (b) and (c) equal to 100 wt%.
  • a polyether polyol is obtained by the alkoxylation, i.e. reaction with alkylene oxide, of a suitable polyhydric alcohol initiator.
  • alkylene oxides usually applied, and also useful for the present invention, are ethylene oxide, propylene oxide and butylene oxide, with propylene oxide being preferred for the purpose of this invention.
  • the aromatic polyether polyol for use in the present invention is a polyether polyol produced from an aromatic amine, a Mannich base having an aromatic ring or a polyfunctional phenol as the starting material.
  • these aromatic polyether polyols are used in an amount of between 25 and 50 % by weight based on the total of polyols (a), (b) and (c).
  • the polyether polyol produced by using the aromatic amine as a starting material is a polyol prepared by adding at least one alkylene oxide such as ethylene oxide and or propylene oxide (preferably solely propylene oxide) to at least one aromatic amine such as the various isomers of tolylenediamine (TDA) (preferably the ortho- and meta- isomers), diphenylmethanediamine (DADPM) and its higher homologues (polymethylene polyphenylene polyamine), aniline and toluidine.
  • TDA tolylenediamine
  • DADPM diphenylmethanediamine
  • aniline and toluidine aniline and toluidine.
  • the hydroxyl value of the aromatic amine initiated polyether polyol is usually between 200 and 600 mg KOH g.
  • Mannich polyols are a family of polyether polyols constructed from an initiator via Mannich condensation of formaldehyde, alkanolamine and a phenolic molecule.
  • the alkanolamines are usually diethanol and diisopropanol amine.
  • the phenolic species are usually phenol, nonyl-phenol and bisphenol A.
  • the hydroxyl value of the Mannich base initiated polyether polyols is usually between 170 and 600 mg KOH/g.
  • Suitable Mannich polyols are described, for example, in US 4137265 and US 4883826.
  • the polyether polyol of functionality 4 or more is made using an initiator of functionality at least 4 such as sorbitol, sucrose or ethylene diamine.
  • an initiator is sorbitol.
  • this high functionality polyether polyol is used in an amount of between 25 and
  • the polyether polyol of functionality less than 4 is made using an initiator of functionality less than 4 such as glycerol and trimethylolpropane.
  • a preferred initiator is glycerol.
  • this low functionality polyether polyol is used in an amount of between 2 and 30 % by weight based on the total of polyols (a), (b) and (c).
  • the hydroxyl value of polyol (a), (b) and (c) generally lies in the range of 200 to 800 mg KOH/g.
  • the total hydroxyl value of the isocyanate-reactive composition is preferably between 400 and 650 mg KOH/g.
  • At least one of each type of polyol (a), (b) and (c) is used in the process of the present invention.
  • the present invention also covers the use of two or more polyols of type (a), (b) or (c) as long as the total amount of polyols (a), (b) and (c) falls within the above ranges.
  • the isocyanate-reactive composition may contain other isocyanate-reactive compounds in an amount of up to 10 wt% based on the total isocyanate -reactive composition.
  • Suitable further isocyanate-reactive compounds to be used in the process of the present invention include any of those known in the art for the preparation of rigid polyurethane or urethane-modified polyisocyanurate foams.
  • rigid foams Of particular importance for the preparation of rigid foams are polyols and polyol mixtures having average hydroxyl numbers of from 300 to
  • Suitable polyols have been fully described in the prior art and include reaction products of alkylene oxides, for example ethylene oxide and/or propylene oxide, with initiators containing from 2 to 8 active hydrogen atoms per molecule.
  • Suitable initiators include: polyols, for example glycerol, trimethylolpropane, triethanolamine, pentaerythritol, sorbitol and sucrose; polyamines, for example ethylene diamine, tolylene diamine (TDA), diaminodiphenylmethane (DADPM) and polymethylene polyphenylene polyamines; and aminoalcohols, for example ethanolamine and diethanolamine; and mixtures of such initiators.
  • Other suitable polymeric polyols include polyesters obtained by the condensation of appropriate proportions of glycols and higher functionality polyols with dicarboxylic or polycarboxylic acids.
  • Still further suitable polymeric polyols include hydroxyl-terminated polythioethers, polyamides, polyesteramides, polycarbonates, polyacetals, polyolefins and polysiloxanes.
  • Suitable organic polyisocyanates for use in the process of the present invention include any of those known in the art for the preparation of rigid polyurethane or urethane-modified polyisocyanurate foams, and in particular the aromatic polyisocyanates such as diphenylmethane diisocyanate in the form of its 2,4'-, 2,2'- and 4,4'-isomers and mixtures thereof, the mixtures of diphenylmethane diisocyanates (MDI) and oligomers thereof known in the art as "crude” or polymeric MDI (polymethylene polyphenylene polyisocyanates) having an isocyanate functionality of greater than 2, toluene diisocyanate in the form of its 2,4- and 2,6-isomers and mixtures thereof, 1,5-naphthalene diisocyanate and 1,4-diisocyanatobenzene.
  • aromatic polyisocyanates such as diphenylmethane diisocyanate in the form of its 2,4
  • organic polyisocyanates which may be mentioned include the aliphatic diisocyanates such as isophorone diisocyanate, 1,6-diisocyanatohexane and 4,4'-diisocyanatodicyclohexylmethane.
  • a preferred polyisocyanate for use in the present invention is polymeric MDI including the higher functionality variants thereof (functionality of 2.9 or higher).
  • the quantities of the polyisocyanate compositions and the polyfunctional isocyanate-reactive compositions to be reacted will depend upon the nature of the rigid polyurethane or urethane- modified polyisocyanurate foam to be produced and will be readily determined by those skilled in the art.
  • the polyisocyanate/polyol volume ratio is higher than 100/100, more preferably higher than 120/100, most preferably around 150/100.
  • any of the physical blowing agents known for the production of rigid polyurethane foam can be used in the process of the present invention.
  • these include dialkyl ethers, cycloalkylene ethers and ketones, fluorinated ethers, chlorofluorocarbons, perfluorinated hydrocarbons, hydrochlorofluorocarbons, hydrofluorocarbons, and hydrocarbons, or mixtures thereof.
  • hydrochlorofluorocarbons examples include l-chloro-l,2-difluoroethane, 1- chloro-2,2-difluoroethane, l-cWoro-l,l ⁇ difluoroethane, 1,1-dichloro-l-fluoroethane and monochlorodifluoromethane.
  • hydrofluorocarbons examples include lower aliphatic or cyclic, linear or branched hydrocarbons such as alkanes, alkenes and cycloalkanes, preferably having from 2 to 8 carbon atoms, which are substituted with at least one, preferably at least three, fluorine atom(s).
  • HFC 134a 1,1,1,2-tetrafluoroethane
  • 1,1,2,2-tetrafluoroethane trifluoromethane
  • heptafluoropropane 1,1, 1-trifluoroethane, 1,1, 2-trifluoroethane, 1,1,1,2,2- pentafluoropropane, 1,1,1,3-tetrafluoropropane, 1,1,1,3,3-pentafluoropropane (HFC 245fa), 1,1,3,3,3-pentafluoropropane, 1,1,1,3,3-pentafluoro-n-butane (HFC 365mfc), 1,1,1,4,4,4- hexafluoro-n-butane, 1,1,1,2,3,3,3-heptafiuoropropane (HFC 227ea) and mixtures of any of the above.
  • Suitable hydrocarbon blowing agents include lower aliphatic or cyclic, linear or branched hydrocarbons such as alkanes, alkenes and cycloalkanes, preferably having from 4 to 8 carbon atoms. Specific examples include n-butane, iso-butane, 2,3-dimethylbutane, cyclobutane, n- pentane, iso-pentane, technical grade pentane mixtures, cyclopentane, methylcyclopentane, neopentane, n-hexane, iso-hexane, n-heptane, iso-heptane, cyclohexane, methylcyclohexane, 1-pentene, 2-methylbutene, 3-methylbutene, 1-hexene and any mixture of the above.
  • Preferred hydrocarbons are n-butane, iso-butane, cyclopentane, n-pentane and isopentane and any mixture thereof, in particular mixtures of n-pentane and isopentane (preferred weight ratio 3:8), mixtures of cyclopentane and isobutane (preferred weight ratio 8:3), mixtures of cyclopentane and n-butane and mixtures of cyclopentane and iso- or n-pentane (preferred weight ratio between 6:4 and 8:2).
  • water or other carbon dioxide-evolving compounds are used together with the physical blowing agents.
  • water is used as chemical co-blowing agent typical amounts are in the range from 0.2 to 5 %, preferably from 0.5 to 3 % by weight based on the isocyanate-reactive compound.
  • Water can also be used as the sole blowing agent without any additional physical blowing agent being present.
  • the total quantity of blowing agent to be used in a reaction system for producing cellular polymeric materials will be readily determined by those skilled in the art, but will typically be from 2 to 25 % by weight based on the total reaction system.
  • the foam-forming reaction mixture will commonly contain one or more other auxiliaries or additives conventional to formulations for the production of rigid polyurethane and urethane-modified polyisocyanurate foams.
  • Such optional additives include crosslinking agents, for examples low molecular weight polyols such as triethanolamine, urethane catalysts, for example tin compounds such as stannous octoate or dibutyltin dilaurate or tertiary amines such as dimethylcyclohexylamine or triethylene diamine, isocyanurate catalysts, surfactants, fire retardants, for example halogenated alkyl phosphates such as tris chloropropyl phosphate, and fillers such as carbon black.
  • low molecular weight polyols such as triethanolamine
  • urethane catalysts for example tin compounds such as stannous octoate or dibutyltin dilaurate or tertiary amines such as dimethylcyclohexylamine or triethylene diamine
  • isocyanurate catalysts for example surfactants, fire retardants, for example halogenated alkyl phosphates such as tris chloroprop
  • reaction systems employ a polyisocyanate-reactive composition which contains the major additives such as the blowing agent, the catalyst and the surfactant in addition to the polyisocyanate-reactive component or components.
  • the present invention also provides a polyisocyanate-reactive composition
  • a polyisocyanate-reactive composition comprising the present mixture of polyether polyols (a), (b) and (c), optionally together with the blowing agent and or catalyst and/or surfactant.
  • Polyol 1 A propoxylated glycerol initiated polyol of OH value 240-260 mg KOH/g
  • Polyol 2 A propoxylated sorbitol initiated polyol of OH value 495-525 mg KOH/g
  • Polyol 3 A propoxylated Mannich base polyol of OH value 510-550 mg KOH/g
  • Polyol 4 A propoxylated DADPM base polyol of OH value 485-515 mg KOH/g
  • Polyol 5 A propoxylated glycerol initiated polyol of OH value 635-665 mg KOH/g
  • a silicone surfactant A silicone surfactant
  • the foam systems were sprayed using a high pressure Gusmer H-2000-E machine with a GX- 7 spray gun.
  • the equipment allows using a variable mixing ratio of polyol to polyisocyanate.
  • Polyol and polyisocyanate compositions were pre-heated and the temperature was maintained via temperature controlled hoses.
  • the foam was sprayed on an in-house made rotating pipe equipment with outside diameters of 25 and 50 cm.
  • CCOT values exceeding the target of more than 120°C continuous resistance for a period of 30 years were achieved.
  • the foam softening temperatures (or short-term temperature resistance) were measured on a Perkin Elmer TMA7 Themial Analysis System in penetration mode using a heating rate of 10°C per minute.

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

Abstract

L'invention concerne un procédé de préparation de mousse rigide à base de polyuréthanne ou de polyisocyanurate modifié par un uréthane. Ce procédé consiste à faire réagir une composition de polyisocyanate organique avec une composition d'isocyanate réactif polyfonctionnelle en présence d'au moins un gonflant. La composition d'isocyanate réactif polyfonctionnelle comporte (a) de 20 à 60 % en poids d'un polyol de polyéther initié aromatique, (b) de 20 à 60 % en poids d'un polyol de polyéther de fonctionnalité supérieure ou égale à 4 et (c) de 0 à 40 % en poids d'un polyol de polyéther de fonctionnalité inférieure à 4, les quantités totales de polyols (a), (b) et (c) étant égales à 100 % en poids.
PCT/EP2001/010143 2000-10-05 2001-09-04 Procede de fabrication de mousses de polyurethanne rigides Ceased WO2002028936A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002212197A AU2002212197A1 (en) 2000-10-05 2001-09-04 Process for making rigid polyurethane foams

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP00121741.3 2000-10-05
EP00121741 2000-10-05

Publications (1)

Publication Number Publication Date
WO2002028936A1 true WO2002028936A1 (fr) 2002-04-11

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PCT/EP2001/010143 Ceased WO2002028936A1 (fr) 2000-10-05 2001-09-04 Procede de fabrication de mousses de polyurethanne rigides

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AU (1) AU2002212197A1 (fr)
WO (1) WO2002028936A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1428848A1 (fr) * 2002-12-09 2004-06-16 Basf Aktiengesellschaft Elements composites comprenant mousse de polyisocyanurate, en particulier tuyaux isolés
WO2006107342A1 (fr) * 2005-04-05 2006-10-12 Dow Global Technologies Inc. Mousses de renforcement en polyurethane-isocyanurate rigide

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4145488A (en) * 1977-05-12 1979-03-20 Owens-Corning Fiberglas Corporation Fire retardant polyurethane foams
WO1997014730A1 (fr) * 1995-10-19 1997-04-24 Imperial Chemical Industries Plc Mousses rigides de polyurethanne
DE19611367A1 (de) * 1996-03-22 1997-09-25 Bayer Ag Verfahren zur Herstellung Kohlenwasserstoff-getriebener Polyurethan-Hartschaumstoffe
DE19638257A1 (de) * 1996-09-19 1998-03-26 Basf Ag Verfahren zur Herstellung neuer Polyetherole sowie deren Verwendung
WO1998037116A1 (fr) * 1997-02-20 1998-08-27 Sumitomo Bayer Urethane Co., Ltd. Procede pour produire de la mousse polyurethane rigide

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4145488A (en) * 1977-05-12 1979-03-20 Owens-Corning Fiberglas Corporation Fire retardant polyurethane foams
WO1997014730A1 (fr) * 1995-10-19 1997-04-24 Imperial Chemical Industries Plc Mousses rigides de polyurethanne
DE19611367A1 (de) * 1996-03-22 1997-09-25 Bayer Ag Verfahren zur Herstellung Kohlenwasserstoff-getriebener Polyurethan-Hartschaumstoffe
DE19638257A1 (de) * 1996-09-19 1998-03-26 Basf Ag Verfahren zur Herstellung neuer Polyetherole sowie deren Verwendung
WO1998037116A1 (fr) * 1997-02-20 1998-08-27 Sumitomo Bayer Urethane Co., Ltd. Procede pour produire de la mousse polyurethane rigide

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1428848A1 (fr) * 2002-12-09 2004-06-16 Basf Aktiengesellschaft Elements composites comprenant mousse de polyisocyanurate, en particulier tuyaux isolés
WO2006107342A1 (fr) * 2005-04-05 2006-10-12 Dow Global Technologies Inc. Mousses de renforcement en polyurethane-isocyanurate rigide
US7579068B2 (en) 2005-04-05 2009-08-25 Dow Global Technologies, Inc. Rigid polyurethane-isocyanurate reinforcing foams

Also Published As

Publication number Publication date
AU2002212197A1 (en) 2002-04-15

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