WO2000024813A1 - Procede de preparation d'une mousse de polyurethanne dure - Google Patents

Procede de preparation d'une mousse de polyurethanne dure Download PDF

Info

Publication number
WO2000024813A1
WO2000024813A1 PCT/EP1999/007691 EP9907691W WO0024813A1 WO 2000024813 A1 WO2000024813 A1 WO 2000024813A1 EP 9907691 W EP9907691 W EP 9907691W WO 0024813 A1 WO0024813 A1 WO 0024813A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyol
cyclopentane
polyurethane foam
rigid polyurethane
weight
Prior art date
Application number
PCT/EP1999/007691
Other languages
English (en)
Inventor
Takanori Chiba
Takuya Matsumoto
Keiichi Kitano
Original Assignee
Bayer Aktiengesellschaft
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 Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to BR9914803-0A priority Critical patent/BR9914803A/pt
Priority to AU63388/99A priority patent/AU6338899A/en
Priority to CA002347709A priority patent/CA2347709A1/fr
Priority to EP99950716A priority patent/EP1131376A1/fr
Publication of WO2000024813A1 publication Critical patent/WO2000024813A1/fr

Links

Classifications

    • 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
    • C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3442—Mixing, kneading or conveying the foamable material
    • 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
    • C08G18/1808—Catalysts containing secondary or tertiary amines or salts thereof having alkylene polyamine 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
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
    • C08G18/2036—Heterocyclic amines; Salts thereof containing one heterocyclic ring having at least three nitrogen atoms in the ring
    • 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
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6611—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • 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
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the present invention relates to a method of preparing a rigid polyurethane foam and an apparatus for preparing a rigid polyurethane foam.
  • the rigid polyurethane foam can be used as heat insulation materials for freezer, refrigerator, building and the like.
  • Rigid polyurethane foams are widely used as heat insulation materials for refrigerator-freezer, for example, refrigerators for household use, since they have a low product density, excellent heat insulating properties and a high mechanical strength.
  • chlorofluorocarbons hereinafter referred to as CFCs
  • CFC-11 trichlorofluoromethane
  • HCFC-141b (1,1-dichloro-l-fluoro- ethane), HCFC-22 (chlorodifluoromethane), HCFC-142b (l-chloro-l,l-difluoro- ethane) have been introduced and applied as blowing agents.
  • Hydrocarbon-based blowing agents which contain no chlorine atom and pose no risk of depleting the ozone layer, for example cyclopentane, have already been introduced and applied for some purposes.
  • cyclopentane is most suitable as an earth-friendly blowing agent, it involves some drawbacks.
  • gaseous cyclopentane itself has a high thermal conductivity and the heat insulating performance of the rigid polyurethane foams employing cyclopentane is therefore inferior to those employing conventional HCFC-141b. Accordingly, there is a need for improving the heat insulation characteristics of such rigid polyurethane foams.
  • the present invention provides a method of preparing a rigid polyurethane foam from
  • the blowing agent (3) is cyclopentane and water
  • the polyol (2) is a polyether polyol and/or polyester polyol having poor compatibility with cyclopentane, and
  • cyclopentane is mixed and dispersed in a polyol premix comprising the components (2) to (4).
  • the phrase "having poor compatibility with cyclopentane” means that the solubility of cyclopentane in the polyol is 20 g or below, for example 10 g or below, and particularly 5 g or below.
  • the term "solubility” means the number of grams of cyclopentane which are soluble in 100 g of the polyol at 25°C.
  • stirrer In order to mix and disperse cyclopentane in the polyol premix, it is preferred to use a stirrer of which circumferential speed is at least 5 m/s. In order to allow the dispersed liquid to exist stably in the tank of the foaming machine, it is preferred to stir the mixture at a circumferential speed of at least 0.5 m/s and circulate the mixture through a static mixer.
  • the present invention provides a composition for preparation of a rigid polyurethane foam, comprising
  • blowing agent comprising a mixture of cyclopentane and water
  • aromatic polyisocyanate (1) for example, polyisocyanates such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and polymethylene poly- phenyl polyisocyanate (polymeric MDI), or modified polyisocyanates thereof can be used alone or in combination with each other.
  • Modified polyisocyanates that is, products obtained by partial chemical reactions of organic di- and/or polyisocyanates may be used.
  • di- and/or polyisocyanates containing an ester, urea, biuret, allophanate, carbodiimide, isocyanurate and/or urethane group can be used.
  • the NCO content of the aromatic polyisocyanate (1) is preferably 30 to 50% by weight, for example, 30 to 33% by weight.
  • the polyol (2) is a polyether polyol and/or polyester polyol.
  • the polyether polyol may be obtained by addition polymerization of propylene oxide and/or ethylene oxide using a polyhydric alcohol such as ethylene glycol, propylene glycol, glycerine, trimethylolpropane, pentaerythritol, sorbitol, sucrose, or bisphenol A, an aliphatic amine such as triethanolamine or ethylenediamine, or an aromatic amine such as toluenediamine or methylenedianiline (MDA) as a starting material.
  • a polyhydric alcohol such as ethylene glycol, propylene glycol, glycerine, trimethylolpropane, pentaerythritol, sorbitol, sucrose, or bisphenol A
  • an aliphatic amine such as triethanolamine or ethylenediamine
  • an aromatic amine such as toluenediamine or methylenedianiline (MDA) as a starting material.
  • the polyether polyol may be obtained by a known method, for example, by anionic polymerization of an alkylene oxide using a starting material containing 2 to 8, preferably 3 to 8, reactive hydrogen atoms in its molecule, with using an alkali hydroxide such as potassium hydroxide or sodium hydroxide or an alkali alcoholate such as potassium methylate or sodium methylate as a catalyst.
  • an alkali hydroxide such as potassium hydroxide or sodium hydroxide or an alkali alcoholate such as potassium methylate or sodium methylate
  • the polyether polyol may also be obtained by cationic polymerization of an alkylene oxide using a Lewis acid such as antimony pentachloride or boron fluoride etherate as a catalyst.
  • Suitable alkylene oxides are tetrahydrofuran, ethylene oxide, 1,3 -propylene oxide, 1,2- or 2,3-butylene oxide, 1,2-propylene oxide, and styrene oxide. Ethylene oxide and 1,2-propylene oxide are particularly preferred. These alkylene oxides may be used alone or a mixture thereof.
  • reaction starting material examples include polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, and bisphenol A, or alkanolamines such as ethanolamine, diethanolamine, N-methyl- and N-ethyl-ethanolamine, N-methyl- and N-ethyl-diethanolamine, tri- ethanolamine, and ammonia.
  • polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, and bisphenol A
  • alkanolamines such as ethanolamine, diethanolamine, N-methyl- and N-ethyl-ethanolamine, N-methyl- and N-ethyl-diethanolamine, tri- ethanolamine, and ammonia.
  • aliphatic amines and aromatic amines may be used as the reaction starting material.
  • examples are ethylenediamine, diethylenetriamine, 1,3-propylene- diamine, 1,3- or 1 ,4-butylenediamine, 1,2-, 1,3-, 1,4-, 1,5-, and 1,6-hexamethylene- diamine, phenylenediamine, o-toluenediamine, m-toluenediamine, methylenedi- aniline (MDA), and polymethylenedianiline (P-MDA).
  • MDA methylenedi- aniline
  • P-MDA polymethylenedianiline
  • the polyether polyol preferably contains 3 to 8, especially preferably 3 to 6, functional groups, and those having a hydroxyl value of 300-800 mg KOH/g, more preferably of 300-500 mg KOH/g, are suitable.
  • polyester polyol a polyester polyol prepared from a polycarboxylic acid and a polyhydric alcohol, such as polyethylene terephthalate, can be used.
  • a suitable polyester polyol may be prepared from an organic carboxylic acid (particularly dicarboxylic acid) having 2-12 carbon atoms and a diol preferably having 2-12 carbon atoms, especially preferably 2-6 carbon atoms.
  • organic carboxylic acid examples include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, phthalic acid, isophthalic acid, and terephthalic acid.
  • a free carboxylic acid corresponding carboxylic acid derivatives, for example dicarboxylic acid monoester or diester of an alcohol having 1-4 carbon atoms or dicarboxylic anhydride, may also be used.
  • ethylene glycol diethylene glycol, 1,2- or 1,3-propanediol, dipropylene glycol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, or 1,10-decanediol may be used, and glycerine or trimethylolpropane may be used as a triol.
  • lactone- based polyester polyols may also be used.
  • the polyester polyol preferably contains 2 to 3, especially preferably 2, functional groups, and those having a hydroxyl value of 200-600 mg KOH/g, preferably of 350-
  • At least part of the polyol in particular at least 10% by weight of the polyol, for example at least 30% by weight, is a polyether polyol prepared by addition polymerization of ethylene oxide and propylene oxide to an initiator such as sorbitol.
  • a combination of cyclopentane and water is used as the blowing agent (3).
  • the amount of water used herein is 0.1 to 5 parts by weight, preferably 0.1 to 1 part by weight, per 100 parts by weight of the polyol.
  • the amount of cyclopentane is preferably 5 to 30 parts by weight, more preferably 10 to 25 parts by weight, per 100 parts by weight of the polyol.
  • the surfactant and other auxiliaries those conventionally known may be used.
  • Amine catalysts or metal catalysts may be used as the catalyst.
  • a tertiary amine such as triethylenediamine, tetramethylhexa- methylenediamine, pentamethyldiethylenetriamine, or methylmorpholine can be used.
  • an organic metal compound such as stannous octoate, dibutyltin dilaurate, or lead octylate can be used.
  • the amount of the catalyst is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 2.5 parts by weight, per 100 parts by weight of the polyol.
  • the surfactant usual organic silicone-based compounds may be used. For example, L6900, SZ-1684, SZ-1689 or the like manufactured by Nihon Unicar Company Limited, F395 or the like of Shin-Etsu Chemical Co., Ltd., or B8465, B8474 or the like available from Goldschmidt may be used.
  • the amount of the surfactant is 0 to 5 parts by weight, preferably 0.5 to 3 parts by weight, per 100 parts by weight of the polyol.
  • auxiliaries such as foaming stabilizers, foam controlling agents, fillers, dyes, pigments, flame retardant additives, anti-hydrolysis agents may be used in appropriate amounts.
  • the polyisocyanate and the polyol premix are injected into a mold to harden using a high pressure foaming machine.
  • the NCO index of the polyisocyanate and the polyol premix may be 90 to 150, for example, 110 to 130.
  • the high pressure foaming machine has a circulating line (for example, a high pressure circulating line) and a polyol tank.
  • the polyol premix is a mixture prepared by adding cyclopentane to a mixture of the polyol, the surfactant, the catalyst, water as a blowing agent and other auxiliaries, and mechanically mixing and dispersing them.
  • stirrer for mechanically stirring the polyol premix may be any of usual stirrers, those having a circumferential speed of at least 5 m/s is preferred.
  • cyclopentane may be mechanically mixed and dispersed by a stirrer having stirring wings of 7 cm in diameter at 1700 rpm (circumferential speed: 6 m/s), and fed into the polyol tank of a cyclopentane-compatible high pressure foaming machine having a static mixer in the high pressure circulating line.
  • a commercially available static mixer is sufficient for this purpose, and for example, a 1 inch x 8 blocks static mixer available from SULZER Corporation may be used.
  • the polyol dispersion liquid can stably exist by reasons that the circumferential speed of the stirrer of the polyol tank is at least 0.5 m/s and the circulating line of the high pressure foaming machine contains the static mixer.
  • rigid polyurethane foams may be prepared by a prepolymer process or a one-shot process using a batch method or a continuous method.
  • One particularly preferred method is a method of processing conducted according to a two-components process (Component A: isocyanate, Component B: polyol premix).
  • Components A and B are mixed at a temperature in the range of 15 to 35°C, and injected into a mold thermoregulated at 20 to 60°C (for example, 35 to 45°C), and foamed to give a rigid polyurethane foam.
  • the rigid polyurethane foam may be used as heat insulation materials for freezer, refrigerator, building and the like.
  • the measurement is conducted using a universal tester (TCM 1000 manufactured by Minebea Co., Ltd.) according to JIS-A-9514.
  • the core foam density refers to the density at the central part of the foam, and is calculated by measuring the weight down to 0.01 g and measuring the volume down to 0.1 cm 3 by a water displacement method.
  • Example 1 The measurement is conducted on a 200 mm x 200 mm x 25 mm sample cut from the core of the foam, using a thermal conductivity tester (Auto Lambda manufactured by EIKO Instruments Trading, Co.) according to ASTM-C-518.
  • a thermal conductivity tester Auto Lambda manufactured by EIKO Instruments Trading, Co.
  • a polyol mixture liquid was prepared by adding an amine catalyst (1.8 parts by weight of tetramethylhexamethylenediamine plus 1.0 part by weight of pentamethyl- diethylenetriamine plus 0.5 part by weight of trisdimethylaminopropyl-s-triazine), 2 parts by weight of a surfactant (L6900 manufactured by Nihon Unicar Company Limited), and 0.5 part by weight of water to 30 parts by weight of Polyol A, 25 parts by weight of Polyol B, 20 parts by weight of Polyol C, 20 parts by weight of Polyol D, and 10 parts by weight of Polyol E.
  • an amine catalyst 1.8 parts by weight of tetramethylhexamethylenediamine plus 1.0 part by weight of pentamethyl- diethylenetriamine plus 0.5 part by weight of trisdimethylaminopropyl-s-triazine
  • a surfactant Lihon Unicar Company Limited
  • cyclopentane blowing agent
  • a stirrer having 7-cm stirring wings at 2,000 revolutions/min (circumferential speed: 7 m s) to prepare the final polyol mixture.
  • the polyol mixture liquid was fed into a high pressure foaming machine equipped with a static mixer (a 1 inch x 8 blocks mixer manufactured by
  • the polyol mixture and polymeric MDI were mixed and foamed.
  • the urethane feedstocks were adjusted at the temperature of 20°C, and injected into a 600 mm x 400 mm x 50 mm aluminum mold adjusted at 45 °C, and the molded product was demolded from the mold after 7 minutes. Physical properties of the molded product are shown in Table 1.
  • a polyol mixture liquid was prepared according to Table 1.
  • a silicone-containing surfactant 2 parts by weight of F395 manufactured by Shin-Etsu Chemical Co., Ltd. was used. The other procedures were the same as those described in Example 1. Physical properties of the molded product are shown in Table 1. Comparative Examples 1 and 2
  • Example 1 a polyol mixture liquid was prepared according to Table 1. The mixture liquid was then mixed with cyclopentane, and fed into the high pressure foaming machine, and the molded product was obtained in the same manner as in Example 1. The difference between these Comparative Examples and Examples 1-3 is in that the polyol mixture liquid in these Comparative Examples was a liquid in which cyclopentane was completely dissolved. Physical properties of the molded product are shown in Table 1.
  • Polyol D A polyol obtained by addition of PO to trimethylolpropane as a starting material, having a hydroxyl value of 865 mg KOH/g
  • Polyol H Glycerin
  • Polyol M A polyol obtained by addition of PO to propylene glycol as a starting material, having a hydroxyl value of 500 mg KOH/g Table 1
  • a rigid polyurethane foam having a low thermal conductivity and excellent heat insulating properties can be prepared by using polyols having poor compatibility with cyclopentane.

Abstract

On décrit un procédé de préparation d'une mousse de polyuréthanne présentant d'excellentes propriétés d'isolation contre la chaleur. Le procédé de préparation d'une mousse de polyuréthanne dure comprend l'utilisation des ingrédients suivants: (1) un polyisocyanate organique comprenant un polyisocyanate aromatique, (2) un polyol comprenant un polyol de polyéther et/ou un polyol de polyester, (3) un agent gonflant, et (4) un tensioactif, un catalyseur et d'autres adjuvants, et se caractérise par le fait que: l'agent gonflant (3) est du cyclopentane et de l'eau, le polyol (2) est un polyol de polyéther et/ou un polyol de polyester présentant une faible compatibilité avec le cyclopentane, et que le cyclopentane est mélangé et dispersé dans un mélange préalable contenant les ingrédients (2), (3) et (4).
PCT/EP1999/007691 1998-10-26 1999-10-13 Procede de preparation d'une mousse de polyurethanne dure WO2000024813A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR9914803-0A BR9914803A (pt) 1998-10-26 1999-10-13 Processo de preparação de espuma de poliuretano rìgida
AU63388/99A AU6338899A (en) 1998-10-26 1999-10-13 Method of preparing rigid polyurethane foam
CA002347709A CA2347709A1 (fr) 1998-10-26 1999-10-13 Procede de preparation d'une mousse de polyurethanne dure
EP99950716A EP1131376A1 (fr) 1998-10-26 1999-10-13 Procede de preparation d'une mousse de polyurethanne dure

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP10-303794 1998-10-26
JP10303794A JP2000128951A (ja) 1998-10-26 1998-10-26 硬質ポリウレタンフォームの製造方法

Publications (1)

Publication Number Publication Date
WO2000024813A1 true WO2000024813A1 (fr) 2000-05-04

Family

ID=17925385

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/007691 WO2000024813A1 (fr) 1998-10-26 1999-10-13 Procede de preparation d'une mousse de polyurethanne dure

Country Status (7)

Country Link
EP (1) EP1131376A1 (fr)
JP (1) JP2000128951A (fr)
AU (1) AU6338899A (fr)
BR (1) BR9914803A (fr)
CA (1) CA2347709A1 (fr)
PL (1) PL347429A1 (fr)
WO (1) WO2000024813A1 (fr)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1219653A1 (fr) * 2000-12-29 2002-07-03 Huntsman International Llc Mousses rigides de polyuréthane ou mousses de polyisocyanurate modifiées par des groupes uréthane et leurs procédés de préparation
WO2002072680A1 (fr) * 2001-03-07 2002-09-19 Bfs Diversified Products, Llc Procede de melange d'agents d'expansion avec des reactifs polyurethanne pour la production de cartes en mousse de polyurethanne
WO2003064492A1 (fr) * 2002-01-29 2003-08-07 Huntsman International Llc Procede de fabrication de mousses de polyurethanne rigides
EP1371469A2 (fr) * 2002-06-12 2003-12-17 BRUGG Rohrsysteme GmbH Procédé pour la fabrication d'un tuyau isolé thermiquement
WO2006044365A1 (fr) * 2004-10-14 2006-04-27 Bayer Materialscience Llc Mousse de polyuréthane pistolée rigide haute température pour isolation de tuyau
US7387753B2 (en) 2003-08-25 2008-06-17 Bfs Diversified Products, Llc Method and apparatus to monitor the compressive strength of insulation boards
US7612120B2 (en) 2002-08-13 2009-11-03 Bfs Diversified Products, Llc Insulation boards and methods for their manufacture
US7838568B2 (en) 2002-08-02 2010-11-23 Bfs Diversified Products, Llc Insulation boards and methods for their manufacture
CN102356108A (zh) * 2009-03-24 2012-02-15 陶氏环球技术有限责任公司 硬质聚氨酯泡沫体的生产及其用途
WO2013030063A1 (fr) 2011-08-26 2013-03-07 Bayer Intellectual Property Gmbh Émulsions stables et utilisation de celles-ci pour la production de mousses à base d'isocyanate
WO2013030061A1 (fr) 2011-08-26 2013-03-07 Bayer Intellectual Property Gmbh Émulsions et utilisation de celles-ci pour la production de mousses à base d'isocyanates
WO2014019962A1 (fr) 2012-07-31 2014-02-06 Bayer Materialscience Ag Procédé pour la production de mousse de polyuréthane à l'aide d'un agent de soufflage émulsionné
EP2770002A1 (fr) 2013-02-25 2014-08-27 Bayer MaterialScience AG Moulage d'isolation et son procédé de fabrication
US9926421B2 (en) 2012-07-31 2018-03-27 Covestro Deutschland Ag Vacuum-supported method for the production of polyurethane foam
CN109900058A (zh) * 2017-12-11 2019-06-18 日立空调·家用电器株式会社 冰箱、预混多元醇组合物和硬质聚氨酯泡沫
CN110234674A (zh) * 2017-01-25 2019-09-13 巴斯夫欧洲公司 冷柔聚氨酯制剂
WO2020057840A1 (fr) * 2018-09-20 2020-03-26 Arcelik Anonim Sirketi Mousse de polyuréthane et son procédé de production et dispositif de refroidissement

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4146572B2 (ja) 1999-04-08 2008-09-10 住化バイエルウレタン株式会社 硬質ポリウレタンフォームの製造方法及び硬質ポリウレタンフォーム用組成物
JP4931454B2 (ja) * 2006-03-08 2012-05-16 アキレス株式会社 硬質ポリウレタンフォームの製造方法
ES2433722T3 (es) * 2007-07-20 2013-12-12 E. I. Du Pont De Nemours And Company Composiciones y uso de una composición formadora de espuma cis-1,1,1,4,4,4-hexafluoro-2-buteno en la preparación de espumas a base de poliisocianato
JP2009057482A (ja) * 2007-08-31 2009-03-19 Sumika Bayer Urethane Kk 硬質ポリウレタンフォームの製造方法
JP2009263647A (ja) * 2008-03-31 2009-11-12 Sanyo Chem Ind Ltd 硬質ポリウレタンフォームの製造方法
JP6996957B2 (ja) * 2017-12-11 2022-02-03 日立グローバルライフソリューションズ株式会社 プレミックスポリオール組成物
CN109130057B (zh) * 2018-09-25 2020-08-28 上海富铭密封材料有限公司 一种聚氨酯发泡机

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4275172A (en) * 1980-01-28 1981-06-23 Union Carbide Corporation Frothable polyurethane composition and a cellular foam produced therefrom suitable for use in joints between wallboards
DE19708570A1 (de) * 1997-03-03 1998-09-10 Basf Ag Verfahren zur Herstellung von Schaumstoffen enthaltend Polyisocyanat-Polyadditionsprodukte

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4275172A (en) * 1980-01-28 1981-06-23 Union Carbide Corporation Frothable polyurethane composition and a cellular foam produced therefrom suitable for use in joints between wallboards
DE19708570A1 (de) * 1997-03-03 1998-09-10 Basf Ag Verfahren zur Herstellung von Schaumstoffen enthaltend Polyisocyanat-Polyadditionsprodukte

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1219653A1 (fr) * 2000-12-29 2002-07-03 Huntsman International Llc Mousses rigides de polyuréthane ou mousses de polyisocyanurate modifiées par des groupes uréthane et leurs procédés de préparation
WO2002053615A1 (fr) * 2000-12-29 2002-07-11 Huntsman International Llc Mousses rigides de polyisocyanurate modifiees par urethane et procedes permettant de les preparer
WO2002072680A1 (fr) * 2001-03-07 2002-09-19 Bfs Diversified Products, Llc Procede de melange d'agents d'expansion avec des reactifs polyurethanne pour la production de cartes en mousse de polyurethanne
WO2003064492A1 (fr) * 2002-01-29 2003-08-07 Huntsman International Llc Procede de fabrication de mousses de polyurethanne rigides
EP1371469A2 (fr) * 2002-06-12 2003-12-17 BRUGG Rohrsysteme GmbH Procédé pour la fabrication d'un tuyau isolé thermiquement
EP1371469A3 (fr) * 2002-06-12 2004-06-16 BRUGG Rohr AG, Holding Procédé pour la fabrication d'un tuyau isolé thermiquement
CN1319719C (zh) * 2002-06-12 2007-06-06 布鲁格罗尔控股公司 用于加工一种隔热导管的方法
US7838568B2 (en) 2002-08-02 2010-11-23 Bfs Diversified Products, Llc Insulation boards and methods for their manufacture
US7612120B2 (en) 2002-08-13 2009-11-03 Bfs Diversified Products, Llc Insulation boards and methods for their manufacture
US8106106B2 (en) 2002-08-13 2012-01-31 Firestone Building Products Company, Llc Insulation boards and methods for their manufacture
US8153039B2 (en) 2003-08-25 2012-04-10 Firestone Building Products Co., LLC Method for producing and monitoring the compressive strength of foam insulation board
US7387753B2 (en) 2003-08-25 2008-06-17 Bfs Diversified Products, Llc Method and apparatus to monitor the compressive strength of insulation boards
US7987730B2 (en) 2003-08-25 2011-08-02 Timothy Tackett Method and apparatus to monitor the compressive strength of insulation boards
WO2006044365A1 (fr) * 2004-10-14 2006-04-27 Bayer Materialscience Llc Mousse de polyuréthane pistolée rigide haute température pour isolation de tuyau
CN102356108A (zh) * 2009-03-24 2012-02-15 陶氏环球技术有限责任公司 硬质聚氨酯泡沫体的生产及其用途
WO2013030063A1 (fr) 2011-08-26 2013-03-07 Bayer Intellectual Property Gmbh Émulsions stables et utilisation de celles-ci pour la production de mousses à base d'isocyanate
WO2013030061A1 (fr) 2011-08-26 2013-03-07 Bayer Intellectual Property Gmbh Émulsions et utilisation de celles-ci pour la production de mousses à base d'isocyanates
WO2014019962A1 (fr) 2012-07-31 2014-02-06 Bayer Materialscience Ag Procédé pour la production de mousse de polyuréthane à l'aide d'un agent de soufflage émulsionné
EP2879853B1 (fr) 2012-07-31 2018-06-20 Covestro Deutschland AG Procédé pour la production de mousse de polyuréthane à l'aide d'un agent de soufflage émulsionné
US9926421B2 (en) 2012-07-31 2018-03-27 Covestro Deutschland Ag Vacuum-supported method for the production of polyurethane foam
US9713886B2 (en) 2013-02-25 2017-07-25 Covestro Deutschland Ag Insulation moulding and method for its manufacture
EP2770003A1 (fr) 2013-02-25 2014-08-27 Bayer MaterialScience AG Moulage d'isolation et son procédé de fabrication
EP2770002A1 (fr) 2013-02-25 2014-08-27 Bayer MaterialScience AG Moulage d'isolation et son procédé de fabrication
CN110234674A (zh) * 2017-01-25 2019-09-13 巴斯夫欧洲公司 冷柔聚氨酯制剂
CN110234674B (zh) * 2017-01-25 2021-11-16 巴斯夫欧洲公司 冷柔聚氨酯制剂
CN109900058A (zh) * 2017-12-11 2019-06-18 日立空调·家用电器株式会社 冰箱、预混多元醇组合物和硬质聚氨酯泡沫
WO2020057840A1 (fr) * 2018-09-20 2020-03-26 Arcelik Anonim Sirketi Mousse de polyuréthane et son procédé de production et dispositif de refroidissement

Also Published As

Publication number Publication date
AU6338899A (en) 2000-05-15
PL347429A1 (en) 2002-04-08
CA2347709A1 (fr) 2000-05-04
EP1131376A1 (fr) 2001-09-12
BR9914803A (pt) 2001-07-03
JP2000128951A (ja) 2000-05-09

Similar Documents

Publication Publication Date Title
EP1131376A1 (fr) Procede de preparation d&#39;une mousse de polyurethanne dure
CA2206551C (fr) Melange de polyol a trois composantes pour mousses de polyurethane isolantes rigides
CA2289530A1 (fr) Compositions d&#39;isocyanate pour des mousses de polyurethane soufflees
US5786400A (en) Process for the production of a rigid polyurethane foam and a composition for the production of a rigid polyurethane foam
US6245826B1 (en) Isocyanate-based rigid foam
US5523334A (en) Insulating rigid polyurethane foams
US6346558B1 (en) Alkylene oxide modified silicone glycol compatibilizing agents for stable polyester polyol compositions
US5525641A (en) Method of making insulating rigid polyurethane foams
US6268402B1 (en) Process for making isocyanate-based rigid foam
CA2182741C (fr) Compositions de mousse de polyurethanne isolante rigide
US5264464A (en) On-site generation of polyurethane foam using an HCFC as a sole blowing agent
US5183583A (en) Catalysts for extending the shelf life of formulations for producing rigid polyurethane foams
US5328938A (en) On-site generation of polyurethane foam using an HCFC as a sole blowing agent
US5008299A (en) Rigid polyurethane foams with low thermal conductivities
US6713521B2 (en) Method of preparing rigid polyurethane foam and composition of rigid polyurethane foam
US5169877A (en) Rigid polyurethane foams with low thermal conductivities
CN112204066B (zh) 多元醇共混物和具有改进的低温r值的硬质泡沫
MXPA01004129A (en) Method of preparing rigid polyurethane foam
JP3808991B2 (ja) 硬質ポリウレタンフォームの製造方法及び硬質ポリウレタンフォーム用組成物
JP4178390B2 (ja) 硬質ポリウレタンフォーム成形用組成物、及び該組成物を用いた硬質ポリウレタンフォームの製造方法
JP2700521B2 (ja) 硬質ポリウレタンフォームの製造法
JPH07206966A (ja) 硬質ポリウレタンフォームの製造法
JPH10212334A (ja) 硬質ポリウレタンフォームの製造方法
WO2001012707A1 (fr) Procedes d&#39;amelioration des proprietes isolantes de mousses rigides de polyurethane a alveoles fermees
JPH0725968A (ja) 硬質ポリウレタンフォーム

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref country code: AU

Ref document number: 1999 63388

Kind code of ref document: A

Format of ref document f/p: F

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1999950716

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2347709

Country of ref document: CA

Ref country code: CA

Ref document number: 2347709

Kind code of ref document: A

Format of ref document f/p: F

WWE Wipo information: entry into national phase

Ref document number: PA/a/2001/004129

Country of ref document: MX

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWP Wipo information: published in national office

Ref document number: 1999950716

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 09807322

Country of ref document: US

WWW Wipo information: withdrawn in national office

Ref document number: 1999950716

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP