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WO1998052988A1 - Compositions de polyol polymere comportant un sel d'acide insature greffe et utilisation de ces compositions pour preparer des mousses de polyurethanne - Google Patents

Compositions de polyol polymere comportant un sel d'acide insature greffe et utilisation de ces compositions pour preparer des mousses de polyurethanne Download PDF

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Publication number
WO1998052988A1
WO1998052988A1 PCT/US1998/009354 US9809354W WO9852988A1 WO 1998052988 A1 WO1998052988 A1 WO 1998052988A1 US 9809354 W US9809354 W US 9809354W WO 9852988 A1 WO9852988 A1 WO 9852988A1
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Prior art keywords
polyol
ethylenically unsaturated
unsaturated acid
foam
grafted
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PCT/US1998/009354
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English (en)
Inventor
Jose Godoy
Huy Phan Thanh
François M. CASATI
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Dow Chemical Co
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Dow Chemical Co
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Priority to AU72936/98A priority Critical patent/AU7293698A/en
Publication of WO1998052988A1 publication Critical patent/WO1998052988A1/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
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/633—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polymers of compounds having carbon-to-carbon double bonds
    • 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
    • C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular 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
    • C08G2110/0008—Foam properties flexible
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Definitions

  • This invention relates to copolymer polyol compositions and their use in the preparation of polyurethane foams having enhanced flame retardant properties. More specifically the present invention relates to the production of free-rise and molded flexible polyurethane foams.
  • Polyurethane foams are produced by simultaneous reaction of polyol, water and isocyanate. This reaction and cell structure of the resulting polyurethane foam are governed by proper catalysts and surfactants as described in "Polyurethane Handbook," edited by G. Oertel, Hanser publishers, Kunststoff and New York, 1985. Water reacts with isocyanate to release carbon dioxide, used as the blowing agent, and amines which react further with the isocyanate to form urea groups. The polyol and isocyanate reaction gives the polyurethane backbone leading to a stable foam. Conveniently crosslinkers are added to stabilize the rising foam or improve some foam physical properties. By using this process different types of polyurethane foams, from very soft to rigid, with different densities, as well as microcellular elastomeric products, can be obtained.
  • This poly-electrolyte can be a polyacrylate.
  • the purpose of these inventions is to get CFC-free soft polyurethane foams. No mention is made of fiammability characteristics of the resulting polyurethane foams. In fact, we have found that salt products soluble in water do not provide the desired fire resistance properties.
  • U.S. Patent No. 4,701 ,474 describes the use of reduced reactivity polyols as foam controllers in producing polyurethane foams.
  • foam controllers are acid grafted polyethers, such as acrylic acid grafted poly(alkylene oxides) and are used as additives at low concentrations in the foam formulation to control reactivity. They are used as such without neutralization with a basic component. No mention is made of fire resistance properties.
  • U.S. Patent No. 4,686,240 and its equivalent European Patent No. 0 220 697 describe a process for producing polyurethane foams using foam modifiers.
  • foam modifiers consist of an alkali metal or alkaline earth metal ion and an anion of Broensted acid having a pKa of greater than 1.
  • foam modifiers are used as additives and are introduced in the foam formulation at various levels depending on their chemical structures and the polyurethane formulations.
  • Example 7 of U.S. Patent No. 4,686,240 describes the preparation of a foam modifier based on a polyether fluid lubricant which is 10 weight percent of acrylic acid grafted onto a polyether mono alchol and subsequently neutralized with potassium hydroxide.
  • Example 26 of the same patent uses the foam modifier of Example 7 without giving any indications about fire resistance properties of the foam made with it. The only results of foam fiammability properties given in
  • U.S. Patent No. 4,686,240 are based on foam modifiers which are mineral salts or salts produced from polyols reacted with cyclic anhydride as described in U.S. Patent No. 4,701 ,474. It should be noted that this process for producing polyurethane foam modifiers is cumbersome. Moreover, it should be pointed out that foam modifiers so produced are not stable because of the presence of ester groups which hydrolyze when the foam modifiers are added to a water-amine polyol blend over a certain period of time, hence these foam modifiers are not stable in systems used for the production of automotive molded seating. In addition, the process for producing polyurethane foam described in these patents uses the foam modifiers as additives in the reaction of a polyol and isocyanate.
  • European Patent No. 0 220 697 also mentions the use of a "foam modifier- polymer/polyol" as useful polymer polyol in the preparation of a polyurethane foam.
  • This foam modifier-polymer/polyol is prepared by reacting the base polyol, an unsaturated monomer and any variety of other materials, including catalyst, polymer/polyol stabilizers, chain transfer agents and the foam modifiers (emphasis added) which are an alkali or alkaline earth metal salt of polycarboxy-substituted polyether grafted with acrylic or methacrylic acid.
  • This foam modifier-polymer/polyol is alleged to have the advantageous properties of both the foam modifier and the polymer/polyol.
  • the patent is completely silent and provides no examples demonstrating this advantage in the production of a polyurethane foam.
  • the process described and claimed in this patent requires the presence of a foam modifier in addition to the polyol and/or "foam modifier- polymer/polyol" in the foam reaction mixture.
  • the foam modifiers are alkali or alkaline earth metal salts grafted onto polycarboxy-substituted polyethers.
  • the copolymer polyols produced in the presence of these foam modifiers have unacceptable high viscosity to be used in commercial polyurethane foam production equipment.
  • the combustion resistance of the polyurethane foam produced using these foam modifiers has been increased, the foam suffers deterioration in one or more physical properties, such as wet compression set.
  • the present invention concerns a process for the preparation of a polymer polyol having grafted ethylenically unsaturated acid salt which process comprises the following steps:
  • step (b) in situ polymerization of an ethylenically unsaturated monomer or a mixture of ethylenically unsaturated monomers in the product obtained in step (a) in the presence of a free radical polymerization initiator;
  • step (c) neutralization of a product obtained in step (b) with an alkali metal or alkaline earth metal hydroxide or alkoxide.
  • the present invention concerns a process for the preparation of a polymer polyol having grafted ethylenically unsaturated acid salt which process comprises the following steps:
  • step (b) neutralization of the product obtained in step (a) with an alkali metal or alkaline earth metal hydroxide or alkoxide.
  • the present invention concerns a polymer polyol having grafted ethylenically unsaturated acid salt whenever prepared by either of the above described processes.
  • the present invention concerns a process for the preparation of a fire retardant, low fogging, flexible polyurethane foam by reacting an organic isocyanate with a polyol formulation comprising one or more polyols, a blowing agent, preferably water, a surfactant, a polyurethane catalyst and a polymer polyol having grafted an ethylenically unsaturated acid salt prepared by either of the above described processes.
  • the present invention concerns a fire retardant, low fogging, flexible polyurethane foam prepared by using a polyol formulation comprising the polymer polyol of the present invention having grafted an ethylenically unsaturated acid salt.
  • a polyol formulation comprising the polymer polyol of the present invention having grafted an ethylenically unsaturated acid salt.
  • Any known ethylenically unsaturated acid or mixtures thereof can be used in the process of the present invention to prepare the polymer polyol having grafted an ethylenically unsaturated acid salt.
  • Non-limiting examples of ethylenically unsaturated acids which can be employed in the present invention include acrylic acid, methyl acrylic acid, fumaric acid, maleic acid, crotonic acid, and itaconic acid.
  • Acrylic acid, methacrylic, acid and mixtures thereof are preferred ethylenically unsaturated acids.
  • the ethylenically unsaturated acid is used in an amount of from OJ percent to 20 percent, preferably from 0.5 percent to 10 percent, based on the total weight of the polyol.
  • Any known ethylenically unsaturated monomer or a mixture of ethylenically unsaturated monomers can be used in the process of the present invention to prepare the polymer polyol having grafted an ethylenically unsaturated acid salt.
  • Non-limiting examples of ethylenically unsaturated monomers which may be employed in the present invention include butadiene, isoprene, 1 ,4-pentadiene, styrene, ⁇ -methylstyrene, methylstyrene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene; substituted styrenes such as chlorostyrene, 2,5-dichlorostyrene, 2,5-dibromostyrene; the acrylic and substituted acrylic monomers such as acrylonitrile, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate,
  • ethylenically unsaturated monomers are preferred ethylenically unsaturated monomers.
  • the ethylenically unsaturated monomer is, however, preferably not an ethylenically unsaturated acid.
  • the amount of ethylenically unsaturated monomer or a mixture thereof employed in the process of the present invention is generally less than 60 percent, preferably from 10 to 60 percent, more preferably from 20 to 40 percent by weight, based on the total weight of the obtained polymer polyol.
  • the polymerization reactions in the processes of the present invention are conveniently carried out at a temperature of from 25°C to 180°C, preferably from 80°C to 135°C, in the presence of a free radical polymerization initiator.
  • the free radical polymerization initiator and temperature should be selected so that the free radical polymerization initiator has a reasonable rate of decomposition with respect to the resident time in the reactor for a continuous process or the feed time for a semi-batch process.
  • Any known free radical polymerization initiator can be employed in the present invention.
  • free radical initiators include t-alkyl peroxyester such as di-t-butyl perbenzoate, t-butyl peroxydiethylacetate, alkyl peroxide, azo compounds, with azobis-isobutyronitrile being preferred.
  • the amount of free radical polymerization initiator used is not critical. Typically, it can vary from 0J to 5.0, preferably from 0.2 to 1 weight percent, based on the total feed to the polymerization reactor.
  • Any known polyol or mixture of polyols can be employed in the process of the present invention to prepare the polymer polyol having grafted an ethylenically unsaturated acid salt.
  • polyol includes both base polyol and a polymer polyol.
  • polymer polyol means a stable dispersion of a solid polymer phase within a liquid carrier polyol or a mixture of polyols, wherein the solid polymer is formed by in situ polymerization of an ethylenically unsaturated monomer or mixtures of monomers in the liquid phase.
  • the polyol used in the present invention is often prepared by the catalytic condensation of an alkylene oxide or mixture of alkylene oxides either simultaneously or sequentially with an organic compound having at least two active hydrogen atoms.
  • Non-limiting examples of polyols useful in the present invention include polyhydroxyl-containing polyesters, polyoxyalkylene polyether polyols, alkylene oxide adducts of polyhydric polythioesters, polyacetals, aliphatic polyols and thiols, as well as mixtures thereof.
  • Any suitable hydroxyl-terminated polyester may be used such as prepared, for example, from polycarboxylic acids and polyhydric alcohols.
  • Any suitable polycarboxylic acid may be used such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimilic acid, or fumaric acid.
  • Any suitable polyhydric alcohol may be used such as ethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1 ,2-butanediol, 1 ,5-pentanediol, or 1 ,6-hexanediol.
  • Any suitable polyoxyalkylene polyether polyol may be used such as the polymerization product of an alkylene oxide or a mixture of alkylene oxide with a polyhydric alcohol.
  • Polyether polyols which are preferred include the ethylene oxide, propylene oxide, butylene oxide, and mixture of these oxides, addition products of trimethylolpropane, glycerol, pentaerythritol, sucrose, sorbitol, propylene glycol and mixtures thereof.
  • the polyether polyols generally have an average equivalent weight of from 800 to 5000, and preferably have an average equivalent weight from 1000 to 3000.
  • the polyether polyols useful in the present invention are characterized by having a nominal functionality of 2 to 6, preferably 2 to 4. Unsaturation is below 0.07 meq/g, preferably below 0.05 meq/g.
  • Suitable polyhydric polythioesters which may be condensed with alkylene oxides include the condensation product of thiodiglycol or the reaction product of a dicarboxylic acid with any other suitable thioether glycol.
  • Suitable polyacetals which may be condensed with alkylene oxides include the reaction product of formaldehyde or other suitable aldehyde with a dihydric alcohol or an alkylene oxide.
  • Suitable aliphatic thiols which may be condensed with alkylene oxides include alkanethiols containing one or two -SH groups such as 2-mercaptoethanol, 1 ,2-ethanedithiol, 1 ,2-propanedithiol, 1 ,3-propanedithiol, or 1 ,6-propanedithiol.
  • the polyol used to manufacture the polymer polyol of the present invention having grafted an ethylenically unsaturated acid salt can be the same as or different than the polyol used in the polyurethane foam formulation.
  • the polymer polyol of the present invention having grafted an ethylenically unsaturated acid salt can be used as the only polyol in the polyol formulation to prepare polyurethane foams of the present invention.
  • the carrier polyol is the polymer polyol obtained in the previous step.
  • steps (c) and (b), respectively of the present invention's processes for the preparation of the polymer polyol having grafted an ethylenically unsaturated acid salt the product obtained in steps (b) and (a), respectively is neutralized by the addition of an aqueous solution of an alkali or alkaline earth metal hydroxide, or an alcoholic solution of alkali or alkaline earth metal alkoxide.
  • suitable alkali or alkaline earth metal hydroxides include sodium hydroxide and potassium hydroxide.
  • the amount of alkali or alkaline earth metal hydroxide or alkoxide added depends on the amount of the ethylenically unsaturated acid used.
  • the polyol formulation employed in the process for the preparation of polyurethane foams of the present invention comprises one or more polyols, at least one of which shall be the polymer polyol having grafted an ethylenically unsaturated acid salt of the present invention, a blowing agent and a polyurethane catalyst.
  • the polyol formulation may comprise other components such as cross-linking agents, surfactants, chain extending agents, surfactants, dyes, fillers, and pigments.
  • any known polyol can be used in the polyol formulation.
  • the polyol can be the same as or different than the herein before described polyols used for the preparation of the polymer polyol of the present invention having grafted an ethylenically unsaturated acid salt.
  • the polymer polyol of the present invention having grafted an ethylenically unsaturated acid salt can be used as the only polyol in the polyol formulation.
  • Any known blowing agent can be used.
  • suitable blowing agents include water, low boiling non-halogenated or halogenated alkanes, liquid or gaseous carbon dioxide, air, nitrogen, or other inert gases. Water is the preferred blowing agent. Typically, water is used in an amount of from 2 to 8 parts, preferably from 3 to 5 parts per hundred parts of the polyol. Mixtures of blowing agents can also be used.
  • Suitable polyurethane catalysts include tertiary amines and organometallic compounds.
  • tertiary amine catalysts include triethylenediamine, N-methyl morpholine, N- ethyl morpholine, diethylethanolamine, 1-methyl-4-dimethyl-aminoethylpiperazine, bis(N,N- dimethylaminoethyl)ether, 3-methoxypropyldimethylamine, N,N,N'-trimethylisopropyl- propylenediamine, 3-diethylaminopropyldiethyiamine, and dimethylbenzylamine.
  • Tertiary amine catalysts are usually used in an amount of from 0.05 to 5.0, preferably from OJ to 2.0, parts per 100 parts of polyol formulation.
  • organometallic catalysts include organolead, organoiron, organomercury, and organobismuth.
  • Organotin compounds are preferred organometallic catalysts.
  • Any known isocyanate is suitable for the use in the process of the present invention for the preparation of polyurethane foams.
  • suitable isocyanates include m-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4-and 2,6-toluene diisocyanate (TDI), prepolymers of TDI, hexamethylene diisocyanate, tetramethylene diisocyanate, cyclohexane-1 ,4-diisocyanate, naphthalene-1 ,5-di isocyanate, 4,4'-diphenylmethane diisocyanate (MDI), and prepolymers of MDI.
  • TDI 2,4-toluene diisocyanate
  • 2,6-toluene diisocyanate mixtures of 2,4-and 2,6-toluene diisocyanate
  • isocyanates useful for the preparation of polyurethane foams are described in the "Polyurethane Handbook", edited by G. Oertel, Hanser publishers, Kunststoff and New York, 1985.
  • Preferred isocyanates are TDI 80/20, TDI 65/35, MDI, polymeric MDI's and mixtures thereof, and prepolymers or quasi prepolymers of MDI and TDI.
  • Isocyanate index is conveniently kept within the range between 70 and 120, preferably between 80 and 110.
  • Any known cross-linking agent can be used.
  • suitable cross- linking agents include alkanolamines such as monoethanolamine, diethanolamine, diisopropanolamine, triethanolamine, glycerol, sorbitol, or any polyfunctional short-chain amine.
  • Chain extending agents which may be employed in the preparation of polyurethane foams include those compounds having at least two functional groups bearing active hydrogen atoms such as water, hydrazine, primary and secondary diamines, amino alcohols, amino acids, hydroxy acids, glycols, or mixtures thereof.
  • Non-limiting examples of surfactants which can be used include silicone surfactants, most of which are block copolymers containing at least one polyoxyalkylene segment and one poly(dimethylsiloxane) segment, polyethylene glycol ethers of long chain alcohols, tertiary amine or alkanolamine salts of long-chain alkyl sulfate esters, alkyl sulfonic esters and aryl sulfonic acids. Silicone surfactants are preferred surfactants for use in the present invention. Any known pigment and filler or mixtures thereof may be used if required, but this is not a prerequisite of the present invention.
  • Non-limiting examples of fillers include calcium carbonate, guanidine carbonate, calcium sulfate, melamine, polyphosphates and polyphosphonates.
  • any general procedure conventionally used for the preparation of molded and free rise polyurethane foams can be used.
  • such procedures entail mixing together of the polyol formulation and the isocyanate component until the foaming reaction commences. After the foaming reaction is completed, the resulting product is then cured at a temperature in the range of from 20°C to 150°C for 5 minutes to 48 hours or longer if desired.
  • the polyol formulation and the isocyanate components are poured in a suitable mold, the mold lid is closed, and the foam allowed to rise and cure until the foam is demolded.
  • Free rise polyurethane foams can be produced with a batch or a continuous process.
  • the foam density and hardness are controlled by the pressure used during the foaming reaction.
  • fire retardant properties are evaluated using the following three tests: (1) the horizontal fiammability test described in the Federal Motor Vehicle Safety Standard, Standard No. 302 (49 CFR 571.302), fiammability of interior materials (1992), (MVSS-302 test), (2) the BS 5852 (1990), section 3 (gas flame source 1), and (3) the vertical fiammability test described in the Technical Bulletin No. 117 (1980), issued by the State of California Department of Consumer Affairs, Bureau of Home
  • the MVSS 302 fiammability test was used to evaluate fire retardant properties of the foam after the foam samples have been heat-aged for 100 hours at 100°C, or humid-aged for 100 hours at 40°C in a humid atmosphere (95 percent relative humidity).
  • the abbreviation DNI refers to the term "do not ignite” in the MVSS-302 fiammability test.
  • foam physical properties are determined according to the following test methods:
  • CPP A A copolymer-polyol having a hydroxyl number of 24 and containing about 33 percent SAN polymer, based on POLYOL A.
  • CPP B A copolymer-polyol having a hydroxyl number of 21 and containing about 40 percent SAN polymer based on POLYOL A.
  • DABCO 33LV A catalyst mixture of 33 weight percent 1 ,4-diazabicyclooctane (2,2,2) and 67 weight percent dipropylene glycol, sold by Air Products & Chemical Inc. under the trademark Dabco 33LV.
  • NAD Non aqueous dispersant stabilizer
  • NIAX A-1 A catalyst mixture of 70 weight percent bis(dimethylaminoethyl)ether and 30 weight percent dipropylene glycol, sold by Witco under the trademark NIAX A- 1.
  • NIAX A-107 Delayed action catalyst sold by Witco under the trademark NIAX A-107 sold by Witco under the trademark NIAX A-107.
  • Polyol A A high reactive polyalkylene oxide triol produced from propylene and ethylene oxides and glycerol having a hydroxyl number of about 35. The ethylene oxide (about 17 percent) is present primarily in blocks and is used to "cap" the triol.
  • Polyol B A highly reactive polyalkylene oxide polyol having a hydroxyl number of 32 sold by The Dow Chemical Company under the trademark Specflex NC 632 polyol.
  • SOKALAN CP 10S Polyacrylic Acid (50 percent) in water, sold by BASF Corporation under the trademark SOKALAN CP 10S.
  • SOKALAN PA 30 CL Polyacrylic Acid, Sodium Salt (45 percent) in water, sold by BASF Corporation under the trademark SOKALAN PA 30 CL.
  • TRIGONOX 27 tert butyl peroxydiethylacetate sold by Akzo Nobel under the trademark TRIGONOX 27.
  • VORANOL 4053 A polyalkylene oxide polyol produced from propylene and ethylene oxides, having a hydroxyl number of about 31 sold by The Dow Chemical Company under the trademark VORANOL 4053.
  • the hand mixed polyurethane foams were prepared according to the following procedure:
  • Polyol formulation components (a polyol, the polymer polyol of the present invention having grafted an ethylenically unsaturated acid salt, a blowing agent, a polyurethane catalyst, a surfactant and, if desired, other conventional polyurethane additives) were introduced into one liter and blended for 30 seconds at 3000 rpm.
  • Isocyanate was then added to the blended polyol formulation and mixing was continued for about 5 seconds.
  • the mixed reaction mixture was then poured quickly into a heated aluminum mold (30 cm by 30 cm by 10 cm) treated with a mold-release agent.
  • the resulting foam was removed from the mold after the foam was cured.
  • the cured foam was crushed and allowed to stand at ambient temperature at least 48 hours before the foam was tested for fire retardant and physical properties.
  • Mold Type Aluminum, Square 16 litters
  • a continuous polymerization system using a tank reactor fitted with baffles and an impeller was employed.
  • the polyol feed comprising Polyol A (98.8 percent by weight), acrylic acid (1.0 percent by weight), and Trigonox 27 (0.2 percent by weight) was pumped into the first reactor continuously after going through an in-line mixer to assure complete mixing of the feed components before entering the reactor.
  • the contents of the reactor were well mixed.
  • the internal temperature of the reactor controlled within 1°C, was kept at 125°C.
  • the product flowed out of the top of the first reactor and into a second reactor also kept at 125°C, controlled within 1°C.
  • the product then flowed out of the top of the second reactor continuously through a back pressure regulator that had been adjusted to give about 45 psig pressure on both reactors.
  • the crude polymer polyol product then flowed through a cooler into a collection vessel.
  • the obtained copolymer product was vacuum stripped to remove volatiles and had an acid number of 7.85 mg KOH/g.
  • a continuous polymerization system using a tank reactor fitted with baffles and an impeller was employed.
  • the copolymer polyol feed comprising the copolymer polyol product obtained in step (a) (75.5 percent by weight), styrene (3.8 percent by weight), acrylonitrile (9.2 percent by weight), NAD (1.5 percent by weight), and Vazo 67 (0.3 percent by weight) was pumped into the first reactor continuously after going through an in-line mixer to assure complete mixing of the feed components before entering the reactor.
  • the contents of the reactor were well mixed.
  • the internal temperature of the reactor controlled within 1°C, was kept at 125°C.
  • the product flowed out of the top of the first reactor and into a second reactor also kept at 125°°C, controlled within 1°C.
  • the product then flowed out of the top of the second reactor continuously through a back pressure regulator that had been adjusted to give about 45 psig pressure on both reactors.
  • the copolymer polyol product then flowed through a cooler into a collection vessel.
  • the obtained copolymer product was vacuum stripped to remove volatiles and had a Brookfield viscosity of 3400 cps at 25°C and an acid number of 5.95 mg KOH/g.
  • potassium hydroxide 75 g flake KOH, 85 percent by weight, in 100 g of water, basicity: 6.47 meq/g
  • a continuous polymerization system using a tank reactor fitted with baffles and an impeller was employed.
  • the polyol feed comprising the copolymer polyol (98.7 percent by weight) having a hydroxyl number of 28 mg KOH/g, a viscosity of 2200 cps at 25°C and a solids content of 21.0 percent by weight and obtained by polymerizing, in a continuous polymerization reactor, styrene (10.5 percent by weight) and acrylonitrile (10.5 percent by weight) in Polyol A (78.8 percent by weight) in the presence of Vazo 67 (0.3 percent by weight); acrylic acid (1.0 percent by weight); and Trigonox 27 (0.3 percent by weight) was pumped into the first reactor continuously after going through an in-line mixer to assure complete mixing of the feed components before entering the reactor.
  • the contents of the reactor were well mixed.
  • the internal temperature of the rector, controlled within 1 °C, was kept at 125°C.
  • the product flowed out of the top of the first reactor and into a second reactor also kept at 125°C, controlled within 1°C.
  • the product then flowed out of the top of the second reactor continuously through a back pressure regulator that had been adjusted to give about 45 psig pressure on both reactors.
  • the copolymer polyol product then flowed through a cooler into a collection vessel.
  • the copolymer polyol was vacuum stripped to remove volatiles.
  • the obtained copolymer polyol had a Brookfield viscosity of 2900 cps at 25°C and an acid number of 7.84 mg KOH/g.
  • copolymer polyol product obtained in Step (a) was mixed at room temperature for about 2 hours with 2.2 g of an aqueous solution of potassium hydroxide (75 g flake KOH, 85 percent by weight, in 100 g of water, basicity: 6.47 meq/g) per 100 g of the copolymer polyol.
  • potassium hydroxide 75 g flake KOH, 85 percent by weight, in 100 g of water, basicity: 6.47 meq/g
  • Example 3 (Preparation of Copolymer PolyoDStep (a): In a 2-liter reaction vessel fitted with a stirrer, thermometer, water-cooled condenser, nitrogen inlet, addition tube, and heated in a heating mantle, were charged CPP B (524 g) and Polyol A (267 g) with stirring under nitrogen and heated to 125°C. Then a mixture of Polyol A (197 g), acrylic acid (10 g) and Trigonox 27 (2 g) were added to the reaction vessel during a 30 minute period. When the addition was completed, the reaction mixture was allowed to react for an additional 30 minutes at 125°C. The reaction vessel and its contents were then allowed to cool under nitrogen. The resulting copolymer polyol had an acid number of 6.72 mg KOH/g, a Brookfield viscosity of 2200 cps at 25°C and 22 percent by weight solids.
  • potassium hydroxide 75 g flake KOH, 85 percent by weight in 100 g of water, basicity: 6.47 meq/g
  • Polyurethane foams were prepared using the general procedure B for making foams described herein before.
  • the polyurethane formulation component and the foam properties are given in Table I below.
  • Polyurethane foams were prepared using the general procedure A for making foams described herein before.
  • the polyurethane formulation components and the polyurethane foam properties are given in Table II below.
  • Polyurethane foams were prepared using the general procedure A for making foams described herein before.
  • the polyurethane formulation components and the polyurethane foam properties are given in Table III below.
  • Polyurethane foams were prepared using the general procedure A for making foams described herein before.
  • the polyurethane formulation components and the polyurethane foam properties are given in Table IV below.
  • Polyurethane foams were prepared using the general procedure B for making foams described herein before.
  • the polyurethane formulation components and the polyurethane foam properties are given in Table V below.
  • Polyurethane foams were prepared using the general procedure A for making foams described herein before.
  • the polyurethane formulation components and the polyurethane foam properties are given in Table VI below.

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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

Procédé pour préparer un polyol polymère comportant un sel greffé d'acide insaturé en éthylène. Ce procédé comprend les étapes suivantes: (a) polymérisation in situ d'un acide insaturé en éthylène pour former un polyol avec un nombre hydroxy allant de 15 à 80, en présence d'un amorceur de polymérisation radicalaire; (b) polymérisation in situ d'un monomère insaturé en éthylène ou d'un mélange de monomères insaturés en éthylène dans le produit obtenu dans l'étape (a), en présence d'un amorceur de polymérisation radicalaire; et (c) neutralisation du produit obtenu dans l'étape (b) avec un hydroxyde ou un alcoxyde de métal alcalin ou de métal alcalino-terreux. Les polyols polymères comportant un sel greffé d'acide insaturé en éthylène, obtenus par ce procédé, sont utilisés pour produire une mousse de polyuréthanne ignifuge, flexible, à faible nébulisation.
PCT/US1998/009354 1997-05-23 1998-05-07 Compositions de polyol polymere comportant un sel d'acide insature greffe et utilisation de ces compositions pour preparer des mousses de polyurethanne Ceased WO1998052988A1 (fr)

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AU72936/98A AU7293698A (en) 1997-05-23 1998-05-07 Polymer polyol compositions having grafted unsaturated acid salt and their use in the preparation of polyurethane foams

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GBGB9710772.6A GB9710772D0 (en) 1997-05-23 1997-05-23 Polymer polyol compositions having grafted unsaturated acid salt and their use in the preparation of polyurethane foams
GB9710772.6 1997-05-23

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6624209B2 (en) 1999-07-30 2003-09-23 Sanyo Chemical Industries, Ltd. Polymer polyol composition, process for producing the same, and process for producing polyurethane resin
US6756414B2 (en) 1999-07-30 2004-06-29 Sanyo Chemical Industries, Ltd. Polymer polyol composition, process for producing the same, and process for producing polyurethane resin
WO2006065345A1 (fr) * 2004-10-25 2006-06-22 Dow Global Technologies, Inc. Polyols polymeres et dispersions de polymeres formees a partir de matieres contenant de l'hydroxyle provenant d'huile vegetale
US7790804B2 (en) 2006-06-26 2010-09-07 Bayer Materialscience Ag Process for stripping polymer polyols
US8686057B2 (en) 2004-10-25 2014-04-01 Dow Global Technologies Llc Polyurethanes made from hydroxy-methyl containing fatty acids or alkyl esters of such fatty acids
US8901189B2 (en) 2006-10-30 2014-12-02 Johnsons Controls Technology Company Nop foam
WO2018063959A1 (fr) 2016-09-29 2018-04-05 Dow Global Technologies Llc Mousse de polyuréthane souple à inflammabilité réduite

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EP0017881A2 (fr) * 1979-04-18 1980-10-29 Bayer Ag Procédé de production de polyétherpolyols modifiés et leur utilisation dans des procédés de production de résines de polyuréthane
US4242249A (en) * 1979-04-03 1980-12-30 Union Carbide Corporation Polymer/polyols via non-aqueous dispersion stabilizers
EP0262653A2 (fr) * 1986-09-30 1988-04-06 ARCO Chemical Technology, L.P. Stabilisants pour polymères/polyols
EP0353071A2 (fr) * 1988-07-29 1990-01-31 ARCO Chemical Technology, L.P. Dispersants de polyol greffé par un polyacrylate

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US4242249A (en) * 1979-04-03 1980-12-30 Union Carbide Corporation Polymer/polyols via non-aqueous dispersion stabilizers
EP0017881A2 (fr) * 1979-04-18 1980-10-29 Bayer Ag Procédé de production de polyétherpolyols modifiés et leur utilisation dans des procédés de production de résines de polyuréthane
EP0262653A2 (fr) * 1986-09-30 1988-04-06 ARCO Chemical Technology, L.P. Stabilisants pour polymères/polyols
EP0353071A2 (fr) * 1988-07-29 1990-01-31 ARCO Chemical Technology, L.P. Dispersants de polyol greffé par un polyacrylate

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6624209B2 (en) 1999-07-30 2003-09-23 Sanyo Chemical Industries, Ltd. Polymer polyol composition, process for producing the same, and process for producing polyurethane resin
US6756414B2 (en) 1999-07-30 2004-06-29 Sanyo Chemical Industries, Ltd. Polymer polyol composition, process for producing the same, and process for producing polyurethane resin
WO2006065345A1 (fr) * 2004-10-25 2006-06-22 Dow Global Technologies, Inc. Polyols polymeres et dispersions de polymeres formees a partir de matieres contenant de l'hydroxyle provenant d'huile vegetale
AU2005317091B2 (en) * 2004-10-25 2010-07-29 Dow Global Technologies Inc. Polymer polyols and polymer dispersions made from vegetable oil-based hydroxyl-containing materials
RU2412954C2 (ru) * 2004-10-25 2011-02-27 Дау Глобал Текнолоджиз Инк. Полимерные полиолы и полимерные дисперсии, полученные из гидроксилсодержащих материалов на основе растительных масел
US8436063B2 (en) 2004-10-25 2013-05-07 Dow Global Technologies Llc Polymer polyols and polymer dispersions made from vegetable oil-based hydroxyl-containing materials
US8686057B2 (en) 2004-10-25 2014-04-01 Dow Global Technologies Llc Polyurethanes made from hydroxy-methyl containing fatty acids or alkyl esters of such fatty acids
US7790804B2 (en) 2006-06-26 2010-09-07 Bayer Materialscience Ag Process for stripping polymer polyols
US8901189B2 (en) 2006-10-30 2014-12-02 Johnsons Controls Technology Company Nop foam
WO2018063959A1 (fr) 2016-09-29 2018-04-05 Dow Global Technologies Llc Mousse de polyuréthane souple à inflammabilité réduite

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Publication number Publication date
AU7293698A (en) 1998-12-11
GB9710772D0 (en) 1997-07-23
ZA984361B (en) 1999-11-22

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