WO2001051538A1 - Formulation de polyols - Google Patents

Formulation de polyols Download PDF

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Publication number
WO2001051538A1
WO2001051538A1 PCT/EP2000/012164 EP0012164W WO0151538A1 WO 2001051538 A1 WO2001051538 A1 WO 2001051538A1 EP 0012164 W EP0012164 W EP 0012164W WO 0151538 A1 WO0151538 A1 WO 0151538A1
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WO
WIPO (PCT)
Prior art keywords
polyol
component
range
average
combination
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Application number
PCT/EP2000/012164
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English (en)
Inventor
Claudio Galina
Francoise Marie-Paule Michele Van Tiggelen
Koen Christophe Jeroom Vanlandschoot
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Shell Internationale Research Maatschappij B.V.
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Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij B.V. filed Critical Shell Internationale Research Maatschappij B.V.
Priority to AU2001230056A priority Critical patent/AU2001230056A1/en
Publication of WO2001051538A1 publication Critical patent/WO2001051538A1/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
    • C08G18/28—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

Definitions

  • the present invention relates to a polyol combination, to a formulation comprising such polyol combination, to a process for preparing a polyurethane foam using said polyol combination and to shaped articles comprising such a polyurethane foam.
  • Rigid polyurethane foams are widely used in the building insulation market as well as in appliances where heat insulation is important, for instance in refrigerators. Often the foams are used in a laminate structure: a core of rigid polyurethane foam is covered on two sides with e.g. a metal facing. Rigid foams are also frequently used as the core material in vacuum insulation panels. Such panels usually comprise a core material enclosed in a vacuum container of metal and/or plastic films.
  • the rigid polyurethane When used as insulating material the rigid polyurethane must meet certain fire- retardancy requirements. To that effect fire retardants are normally added to the foaming formulations. Such fire retardants often contain phosphorus compounds and/or halogen-containing compounds. In rigid polyurethane laminates the fire retardant conventionally used is dimethyl methyl phosphonate (DMMP). This fire retardant is generally considered to be one of the most efficient liquid non-reactive fire retardants available in the marketplace. However, despite its excellent fire retardancy properties, DMMP more and more becomes the subject of criticism. One important reason for this criticism is the fact that DMMP is prone to be emitted when the waste produced in manufacturing the rigid foam laminates is recycled, e.g. into press boards.
  • DMMP dimethyl methyl phosphonate
  • phosphorus compounds originating from DMMP may be emitted, which is undesired from a health and environmental perspective.
  • the rigid polyurethane foam produced from such formulation should not release any toxic compounds when being subjected to a recycling treatment. Furthermore, this rigid polyurethane foam should have excellent mechanical properties in order to give the laminates the necessary mechanical strength and, when used in laminates, should also have a good adhesion to the plastic or metal facings.
  • the present invention relates to a polyol combination comprising
  • Component (a) of the polyol combination is a rigid polyether polyol component which constitutes the largest part of the polyol combination.
  • polyether polyol refers to polyols comprising poly(alkylene oxide) chains, which polyols are normally obtained by reacting an initiator compound containing two or more active hydrogen atoms, e.g. in the form of hydroxyl or amine groups, with at least one alkylene oxide and optionally other compounds.
  • the term “molecular weight” as used throughout this specification refers to number average molecular weight.
  • aromaticity as used throughout this specification is defined as the weight percentage of aromatic carbon atoms (i.e.
  • the polyol component (a) is preferably present in an amount of from 70 to 90 parts by weight. It may consist of a blend of two or more polyols, which blend then has to meet the requirements of functionality, hydroxyl value and aromaticity as defined above.
  • the average nominal functionality of polyol component (a) suitably is from 2.5 to 8, more suitably from 2.5 to 6.
  • the average hydroxyl value suitably ranges from 300 to 650 mg KOH/g, more suitably from 350 to 600 mg KOH/g.
  • the average aromaticity of polyol component (a) suitably ranges from 10 to 30 wt%.
  • the average molecular weight of polyol component (a) suitably ranges from 200 to 1500, more suitably from 400 to 1200, whilst most suitably the average molecular weight will not exceed 1000.
  • the polyol component (a) may consist of a blend of at least two polyols, suitably two or three polyols.
  • the polyol component (a) comprises (al) an aromatic polyol having an average nominal functionality of at least 2, an aromaticity in the range of from 10 to 40 wt% and a hydroxyl value in the range of from 200 to 700 mg KOH/g; and (a2) an aliphatic polyol having an average nominal functionality of at least 3, a hydroxyl value in the range of from 200 to 700 mg KOH/g and a molecular weight in the range of from 300 to 1500.
  • component (al) and (a2) are such that the overall component (a) meets the requirements of average functionality, average aromaticity and average hydroxyl value specified above for component (a).
  • component (al) constitutes from 30 to 80 wt%, more suitably 40 to 75 wt%, of the total of component (a).
  • Component (a2) is then used in an amount adding up to 100 wt%.
  • Polyol component (al) suitably has an average nominal functionality of from 2 to 6, preferably between 2 and 4, an aromaticity in the range of from 15 to 35 wt% and a hydroxyl value in the range of from 300 to 650 mg KOH/g, preferably 400 to 600 mg KOH/g.
  • the molecular weight of polyol component (al) suitably ranges from 200 to 1500, but preferably is at the low end of this range, i.e. from 200 to 500.
  • Polyol component (a2) suitably has an average nominal functionality of from 3 to 8, preferably 3.5 to 7, a hydroxyl value in the range of from 350 to 675 mg KOH/g, preferably 450 to 650 mg KOH g and a molecular weight in the range of from 300 to 1000, preferably 350 to 700.
  • Both polyol components (al) and (a2) are polyether polyols and typically are alkylene oxide adducts of initiators, such as sucrose, sorbitol, pentaerythritol, glycerol, diethanolamine, diethylene glycol, bisphenol A and blends of two or more of these.
  • initiators such as sucrose, sorbitol, pentaerythritol, glycerol, diethanolamine, diethylene glycol, bisphenol A and blends of two or more of these.
  • the alkylene oxides most frequently used are propylene oxide and ethylene oxide.
  • polyether polyols based on propylene oxide as the sole alkylene oxide are preferred.
  • the polyols are typically prepared by reacting the initiator or mixture of initiators with one or more alkylene oxides in the presence of a suitable alkoxylation catalyst.
  • Suitable alkoxylation catalysts are well known and include alkali metal hydroxides as well as amine catalysts.
  • Suitable amine catalysts include alkanolamines like diethanolamine and triethanolamine, tertiary amines like N,N-dimethylcyclohexylamine, and combinations of two or more of these catalysts. Examples of suitable amine catalysts are, for instance, given in EP-A- 0 045 544.
  • Suitable polyethylene glycols to be used as component (b) are those polyethylene glycols having a molecular weight in the range of from 200 to 1000, preferably from 250 to 800, more preferably from 300 to 600. It will be understood that polyethylene glycols contain two hydroxyl groups, which are available to react with alkylene oxide.
  • the polyethylene glycol component (b) may consist of one or more, preferably one or two, polyethylene glycols. If more than one polyethylene glycol is used, they should all meet the above requirement as to molecular weight.
  • Suitable polyethylene glycols are commercially available from several suppliers or can be prepared by methods known in the art. In a further aspect the present invention relates to a polyol formulation comprising:
  • Fire retardants other than dimethyl methyl phosphonate that may be employed as component (ii) are those fire retardants commonly used in manufacturing rigid polyurethane foams. Such fire retardants include both reactive and non-reactive fire retardants.
  • the term "reactive" as used in this connection refers to reactive towards isocyanate groups.
  • non-reactive fire retardants include tris chloro isopropyl phosphate (TCPP). diethyl ethyl phosphonate (DEEP) and triethyl phosphate.
  • Reactive fire retardants typically are halogenated polyols.
  • the fire retardant is typically used in an amount of from 20 to 150 parts by weight (pbw) per 100 pbw of polyol component (a) of the polyol combination, preferably 30 to 100 pbw per 100 pbw of polyol component (a) and more preferably from 40 to 75 pbw per 100 pbw of polyol component (a).
  • Suitable blowing agents which can be used as component (iii), are those conventionally applied in rigid polyurethane production and include water, partly halogenated alkanes, aliphatic alkanes and alicyclic alkanes. Fully halogenated hydrocarbons may also be used, but are less preferred due to their ozone depleting effect.
  • blowing agents examples include water, 1 -chloro- 1,1-difluoroethane, cyclopentane, cyclohexane, n-pentane, isopentane and mixtures of two or more of these.
  • water 1 -chloro- 1,1-difluoroethane
  • cyclopentane cyclohexane
  • n-pentane isopentane and mixtures of two or more of these.
  • a combination of water on the one hand and n-pentane or cyclopentane on the other hand has been found particularly useful.
  • the amount of blowing agent used may range from 0.1 to 10 pbw, preferably 1 to 5 pbw, per 100 pbw of polyol component (a) of the polyol combination for water and 0.1 to 40 pbw, preferably 5 to 25 pbw, per 100 pbw of polyol component (a) in case of partly halogenated hydrocarbons, aliphatic alkanes and alicyclic alkanes.
  • low boiling blowing agents which give a frothing effect can also be used. Examples of such blowing agents include liquid carbon dioxide, HFC-134a (1,1,1,2- tetrafluoroethane) and HFC- 152a (1,1-difluoroethane).
  • the polyurethane catalyst that may be employed as component (iv), can be any urethane catalyst known to be suitable in urethane production.
  • Suitable catalysts are those described in e.g. EP-A-0,358,282 and US-A-5,011,908 and include tertiary amines, salts of carboxylic acids and organometallic catalysts.
  • suitable tertiary amines are triethylene diamine, N,N-dimethyl cyclohexyl amine, N-methyl morpholine, diethyl ethanol amine, diethanol amine, dimethyl benzyl amine and dimethyl cyclohexyl amine.
  • Suitable organometallic catalysts include stannous octoate, stannous oleate, stannous acetate, stannous laureate, lead octoate, nickel naphthenate and dibutyltin dichloride. Further examples of organometallic catalysts are described in US-A-2.846,408. Of course, mixtures of two or more of the aforementioned catalysts may also be used.
  • Suitable polyisocyanurate catalysts or trimerisation catalysts are also well known in the art and include sodium acetate, potassium octoate or potassium acetate, e.g.
  • polyurethane catalyst dissolved in diethylene glycol, and strong basic materials, such as quaternary ammonium salts and tris(dimethylaminopropyl) triazine.
  • the amounts of polyurethane catalyst will usually be in the range of from 0.01 to 8.0 parts by weight (pbw), more suitably 0.1 to 5.0 pbw, per 100 pbw of polyol component (a) of the polyol combination.
  • the auxiliaries, which form component (v) are the usual components and may include foam stabilisers, colouring agents and fillers.
  • the foam stabiliser (or surfactant) used may be any polyurethane foam stabiliser useful in the production of rigid polyurethane foams.
  • Organosilicone or organopolysiloxane surfactants are most conventionally applied as foam stabilisers in polyurethane production.
  • a large variety of such surfactants is commercially available.
  • foam stabiliser is used in an amount of up to 3 pbw, per 100 pbw of polyol component (a).
  • the present invention relates to a process for preparing a fire- retardant rigid polyurethane foam, which process comprises reacting a polyol combination as described herein before with a polyisocyanate component in the presence of at least a catalyst, a foam stabilising agent and a blowing agent.
  • the polyisocyanate component may be any polyisocyanate or combination of polyisocyanates known to be suitable for preparing rigid polyurethane foams.
  • aromatic polyisocyanates are used and any di-, tri-, tetra- and higher functional aromatic polyisocyanate may be used.
  • a list with suitable polyisocyanates is given.
  • Preferred polyisocyanates are 2,4- and 2,6- toluene diisocyanate as well as mixtures thereof; 4,4'-diphenylmethane diisocyanate (MDI); polymethylene polyphenylene polyisocyanate and polymeric MDI, a mixture of polyisocyanates with MDI as the main component.
  • MDI 4,4'-diphenylmethane diisocyanate
  • MDI polymethylene polyphenylene polyisocyanate
  • polymeric MDI a mixture of polyisocyanates with MDI as the main component.
  • the quantity of polyisocyanate component to be used should suitably be such that the isocyanate index has a value between 50 and 160, more suitably between 80 and 150 and most suitably between 100 and 145. However, isocyanate indices outside these ranges may also be used. As is well known in the art, the isocyanate index is defined as the 100 times the equivalence ratio of isocyanate groups to active hydrogen atoms present in the polyol combination and water.
  • the catalyst, foam stabilising agent and blowing agent(s) and the amounts in which they are used in the process of the present invention are the same as those described above in relation to the formulation. However, for the purpose of the present invention it has been found particularly useful to use water and/or at least one alkane, more preferably water and n-pentane, as blowing agent(s).
  • the present invention also extends to shaped articles comprising a fire-retardant rigid polyurethane foam obtained by the process described above.
  • shaped article suitably is a laminate consisting of two metal facings with the fire-retardant rigid polyurethane foam therein between.
  • Polyol A an aromatic, propylene oxide based polyol having an OH value of 510 mg KOH/g, a molecular weight of about 265, a functionality of 2.4 and an aromaticity of 31 wt%.
  • Polyol B an aromatic, propylene oxide-based rigid polyol having an OH value of 520 mg KOH g, a molecular weight of 325, a functionality of 3.0 and an aromaticity of 16 wt%.
  • Polyol C an aliphatic, propylene oxide-based rigid polyol having an OH value of 575 mg KOH/g, a molecular weight of 390 and a functionality of 4.0.
  • PS3152 STEPANPOL PS3152: a polyester polyol ex Stepan based on phthalic anhydride and diethylene glycol having an OH value of
  • PEG400 Polyethylene glycol having a molecular weight of 400.
  • CARADATE 30 polymeric MDI ex Shell (CARADATE is a trade mark).
  • PHT-4-diol a brominated aromatic polyol based on tetrabromo phthalate diol ex Great lakes.
  • IXOL PF50 a halogenated aliphatic polyol based on a brominated diol and epichlorohydrin ex Solvay (IXOL is a trademark).
  • TCPP tris chloro isopropyl phosphate.
  • DEEP diethyl ethyl phosphonate.
  • DMMP dimethyl methyl phosphonate.
  • B8455 TEGOSTAB B8455, a silicone surfactant ex Goldschmidt
  • TAGOSTAB is a trade mark
  • TEGOSTAB B8404 TEGOSTAB B8404, a silicone surfactant ex Goldschmidt.
  • JEFFCAT TR catalyst blend ex Huntsman (JEFFCAT is a trademark).
  • DMCHA N,N-dimethylcyclohexylamine.
  • Polyol formulations having a composition as indicated in Table 1 were prepared by mixing the ingredients in the relative amounts indicated while stirring, using an explosion proof stirrer at a speed of 3000 rpm. Subsequently, the polyisocyanate was added to the formulations over a period of five seconds and the resulting foaming mixtures were stirred for another five seconds before they were poured into open polyethylene bags, where the foaming occurred.
  • DIN4102 B2 small scale fire test a flame height of 15.0 cm or less means that the foam has passed the test. For this test samples having a thickness of 2 cm were used.
  • Free rise density was determined on a cube of 10x10x10 cm ⁇ , cut from the centre of the bag foam, according to ISO 845. Compressive strength in the rise direction of the foam was determined on samples of 5x5x2.5 cm J according to the standard test BS4370/l .
  • Example 1 was repeated except that different formulations were used: a standard DMMP-containing formulation (Comparative Example 1) and two formulations not containing a polyethylene glycol, but instead a higher amount of fire retardant (Comparative Examples 2 and 3).
  • a standard DMMP-containing formulation Comparative Example 1
  • two formulations not containing a polyethylene glycol but instead a higher amount of fire retardant (Comparative Examples 2 and 3).
  • the formulations and the foam properties are indicated in Table 1 ,
  • the DMMP-free foams based on a polyol combination in accordance with the present invention exhibit a fire retardancy which is comparable to a conventional DMMP-containing foam and to DMMP-free foams based on polyol combinations free of polyethylene glycol. Moreover, the foams of the present invention contain less phosphorus and have excellent mechanical properties.

Abstract

La présente invention concerne une combinaison de polyols comprenant (a) de 60 à 95 parties en poids d'un constituant polyol ayant une fonctionnalité nominale moyenne d'au moins 2,1, une aromaticité moyenne située dans la fourchette comprise entre 5 et 35 % en poids et une valeur hydroxyle moyenne située dans la fourchette comprise entre 200 et 700 mg KOH/g; et (b) de 5 à 40 parties en poids pour un total de 100 parties en poids d'au moins un polyéthylène glycol dont le poids moléculaire se situe dans la fourchette comprise entre 200 et 1000. Le constituant polyol (a) peut être formé d'un mélange d'au moins deux polyols, plus particulièrement un polyol aromatique et un polyol aliphatique. La combinaison de polyols est particulièrement adaptée pour être utilisée dans une formulation qui comprend en outre au moins un agent retardateur de flamme qui n'est pas du diméthyl méthyl phosphonate, au moins un agent gonflant, au moins un catalyseur et des adjuvants classiques. On peut préparer des mousses de polyuréthane dures difficilement combustibles en faisant réagir une combinaison de polyols avec un constituant polyisocyanate en présence d'au moins un catalyseur, d'un agent de stabilisation de mousse et d'un agent gonflant.
PCT/EP2000/012164 2000-01-13 2000-12-04 Formulation de polyols WO2001051538A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001230056A AU2001230056A1 (en) 2000-01-13 2000-12-04 Polyol formulation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP00200114 2000-01-13
EP00200114.7 2000-01-13

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WO2001051538A1 true WO2001051538A1 (fr) 2001-07-19

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005052018A2 (fr) * 2003-11-21 2005-06-09 Albemarle Corporation Produits ignifuges, additifs ignifuges, et polyurethanes ignifuges
EP3176195A1 (fr) * 2015-12-01 2017-06-07 SELENA LABS Sp.z o.o. Montage de la mousse et son application comme adhésif, mastic, pour réaliser des revetements ou pour remplir des structures vides a l'intérieur

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4427797A (en) * 1981-06-09 1984-01-24 Thermocell Development Ltd. Non-burning, non-smoking thermoset foam composition
EP0459622A1 (fr) * 1990-04-25 1991-12-04 ARCO Chemical Technology, L.P. Mousses de polyuréthane uniquement gonflées avec de l'eau
DE4439994A1 (de) * 1993-11-10 1995-06-08 Alcare Co Ltd Wasseraushärtbarer Stützverband
EP0778302A1 (fr) * 1995-12-07 1997-06-11 Shell Internationale Researchmaatschappij B.V. Polyether polyol pour la préparation de mousses de polyuréthane rigide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4427797A (en) * 1981-06-09 1984-01-24 Thermocell Development Ltd. Non-burning, non-smoking thermoset foam composition
EP0459622A1 (fr) * 1990-04-25 1991-12-04 ARCO Chemical Technology, L.P. Mousses de polyuréthane uniquement gonflées avec de l'eau
DE4439994A1 (de) * 1993-11-10 1995-06-08 Alcare Co Ltd Wasseraushärtbarer Stützverband
EP0778302A1 (fr) * 1995-12-07 1997-06-11 Shell Internationale Researchmaatschappij B.V. Polyether polyol pour la préparation de mousses de polyuréthane rigide

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005052018A2 (fr) * 2003-11-21 2005-06-09 Albemarle Corporation Produits ignifuges, additifs ignifuges, et polyurethanes ignifuges
WO2005052018A3 (fr) * 2003-11-21 2005-08-18 Albemarle Corp Produits ignifuges, additifs ignifuges, et polyurethanes ignifuges
US7153901B2 (en) 2003-11-21 2006-12-26 Albemarle Corporation Flame retardant, additive compositions, and flame retardant polyurethanes
EP3176195A1 (fr) * 2015-12-01 2017-06-07 SELENA LABS Sp.z o.o. Montage de la mousse et son application comme adhésif, mastic, pour réaliser des revetements ou pour remplir des structures vides a l'intérieur
CN106810662A (zh) * 2015-12-01 2017-06-09 赛磊那实验室有限公司 安装泡沫及其作为粘结剂、制造涂层或填充内部缝隙结构的用途

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