WO1998033832A1 - Utilisation de melanges de polyols dans les mousses rigides et semi-rigides de polyurethane - Google Patents

Utilisation de melanges de polyols dans les mousses rigides et semi-rigides de polyurethane Download PDF

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Publication number
WO1998033832A1
WO1998033832A1 PCT/EP1998/000545 EP9800545W WO9833832A1 WO 1998033832 A1 WO1998033832 A1 WO 1998033832A1 EP 9800545 W EP9800545 W EP 9800545W WO 9833832 A1 WO9833832 A1 WO 9833832A1
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Prior art keywords
polyol
mixture
polyolefin
polydiene
weight
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PCT/EP1998/000545
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English (en)
Inventor
Veerle Maria Rafaela Dirckx
Eric-Jack Gerard
Hans Ferdinand Vermeire
Jurgen Klaus Leopold Schneider
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Shell Internationale Research Maatschappij B.V.
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Priority to PCT/EP1998/000545 priority Critical patent/WO1998033832A1/fr
Priority to DE69805162T priority patent/DE69805162T2/de
Priority to EP98905386A priority patent/EP0961796B1/fr
Priority to CA002278680A priority patent/CA2278680A1/fr
Priority to BR9806728-1A priority patent/BR9806728A/pt
Priority to JP53254898A priority patent/JP2001509834A/ja
Publication of WO1998033832A1 publication Critical patent/WO1998033832A1/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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6204—Polymers of olefins
    • C08G18/6208—Hydrogenated polymers of conjugated dienes
    • 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
    • C08G18/4063—Mixtures of compounds of group C08G18/62 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
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • C08G18/698—Mixtures with compounds of group C08G18/40
    • 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
    • C08G2110/0016—Foam properties semi-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
    • C08G2110/0025—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
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Definitions

  • This invention relates to rigid and semi-rigid polyurethane foams containing a mixture of polyols, especially polyurethane foams having a strong adhesion to polyolefins and block copolymers comprising more than 50% by weight of at least one polyolefin block.
  • Polyurethane foams are typically produced from a polyol and a polyisocyanate.
  • Rigid and semi-rigid polyurethane foams are well known in the art and are used in a wide variety of applications, in turn requiring an extensive range of foam properties.
  • a significant number of different polyol grades are required to be able to manufacture the different foams. Yet, it remains difficult to meet all the desired properties and compromises may have to be made.
  • a variety of polyols have been proposed for use in the manufacture of polyurethane foams, including polyether polyols such as those marketed under the tradename CARADOL, TERATHANE and POLYTHF and polyester polyols such as those marketed under the tradename TONE and FORMREZ.
  • polyol mixtures for use in the preparation of rigid and semi-rigid polyurethane foams include those marketed under the tradenames CARADOL PP520-03, LP585-01, LP530-03, GB450-01, GB475-01, and GB250.
  • United States Patent No. 4,752,626 describes the preparation of a high resilience urethane foam.
  • the foaming system is composed of a thixotropic polyisocyanate component and a thixotropic polyol component.
  • the polyol component comprises a polyol blend of a polyolefinic polyol and a polyoxyalkylene polyol n a weight ratio between 95/5 to 50/50.
  • polyurethane foams strongly to polyolefms without the use of a separate adhesive layer.
  • polyurethane foams are known not to adhere strongly to thermoplastic polyolefms without the use of a separate adhesive layer.
  • foams having one or more advantageous properties as compared to prior art foams of this type.
  • foams have been found which are capable of adhering very strongly to polyolefms and block copolymers comprising more than 50% by weight of at least one polyolefin block, by using a specific polyol mixture.
  • the present invention relates to a mixture of polyols for use in the preparation of polyurethane foam comprising:
  • the polyolefin polyol is present in an amount of from 2 to 20% by weight, more preferably 2 to 5%.
  • the polyolefin polyol can be linear or radial, preferably linear.
  • the polyolefin polyol typically has a functionality in the range from 0.8 to 8, preferably, from 0.8 to 3.
  • the functionality of the polyester polyol and/or polyether polyol is typically in the range from 0.8 to 8, but preferably in the range from more than 2 to 8, more preferably m the range from more than 2 to 5.
  • the weight average functionality of the polyol mixture is more than 2, preferably in the range from 2.5 to 8, more preferably in the range from 2.5 to 5.
  • the functionality is defined as the number of functional groups, this case hydroxy groups, per molecule.
  • the functionality can be determined by NMR or chemical titration techniques .
  • the weight average functionality of the mixture is determined by the following formula (I). [Fp 0 *% t po + F es *%wt es + F et *%wt et ]/100 (I)
  • the polymer backbone of the polyolefin polyol is typically the polymerised product of an olefin monomer or an olefin monomer and a vinylaromatic monomer.
  • the olefin monomer typically contains from 2 to 12 carbon atoms.
  • the olefin monomer is a diene containing from 4 to 10 carbon atoms, more preferably from 4 to 6 carbon atoms, even more preferably butadiene or isoprene, most preferably butadiene .
  • the vinylaromatic monomer is preferably a vinylmonoaromatic monomer, such as styrene or alkyl- substituted styrene, wherein the alkyl-substituent ( s ) contain from 1 to 4 carbon atoms. More preferably, the vinylaromatic monomer is styrene or mono-alkyl- substituted styrene.
  • the polyolefin polyol may contain up to 50% by weight of polymerised vinylaromatic monomer, preferably from 0 to 20% by weight, more preferably from 0 to 5% by weight.
  • the polyolefin polyol contains less than 20% olefinic unsaturation in the polymer backbone. More preferably, the olefinic unsaturation is less than 5%.
  • Olefinic unsaturation as used -herein is intended to exclude unsaturation present in any aromatic groups in the polymer. Ways to determine olefinic unsaturation are known to those skilled in the art.
  • the polyolefin polyol is preferably a polydiene polyol, more preferably a polydiene diol or a polydiene mono-ol or mixtures thereof. Most preferably, the polyolefin polyol is a polydiene diol. Typically, the polydiene diol has a functionality in the range from 1.5 to 2.5 hydroxyl groups per molecule, preferably in the range from 1.8 to 2.0, more preferably in the range from 1.9 to 2.0. The functionality of the polydiene mono-ol is typically in the range between 0.8 and 1.5, preferably from 0.85 to 1.15, more preferably from 0.9 to 1.0.
  • the polymer backbone of the polydiene diol and mono- ol, that is the polydiene, is typically the hydrogenated polymerised product of conjugated diene monomers containing from 4 to 10 carbon atoms; preferably, from 4 to 6 carbon atoms; more preferably butadiene or isoprene, in particular butadiene.
  • hydrogenated polybutadiene diol is used having a 1,2- addition between 30% and 70% to minimise viscosity and subsequent crystallisation.
  • the polydiene diol and/or mono-ol preferably used in this invention may be prepared anionically such as described in United States Patents Nos. 5,376,745, 5,391,663, 5,393,843, 5,405,911, and 5, 416, 168.
  • Polymerisation of the polydiene diol commences with a monolithium or dilithium initiator which builds a living polymer backbone at each lithium site.
  • the anionic polymerisation is carried out in solution in an organic solvent, typically a hydrocarbon like hexane, cyclohexane or benzene, although polar solvents such as tetrahydrofuran can also be used.
  • the molar ratio of initiator to monomer determines the molecular weight of the polymer.
  • the anionic polymerisation of butadiene in a hydrocarbon solvent like cyclohexane is typically controlled with structure modifiers such as diethylether or glyme (1, 2-d ⁇ ethoxy- ethane) to obtain the desired amount of 1 , 2-add ⁇ t ⁇ on .
  • structure modifiers such as diethylether or glyme (1, 2-d ⁇ ethoxy- ethane) to obtain the desired amount of 1 , 2-add ⁇ t ⁇ on .
  • the optimum balance between low viscosity and high solubility in a hydrogenated polybutadiene polymer occurs at a 60/40 ratio of 1, 4-butad ⁇ ene / 1 , 2-butad ⁇ ene .
  • This butadiene microstructure may, e.g., be achieved during polymerisation at 50°C in cyclohexane containing about 6% by volume of diethylether or about 1000 ppm of glyme.
  • each mole of living polymer is preferably capped with two moles of ethylene oxide and terminated with two moles of methanol to yield the desired polydiene diol.
  • the polydiene diol can also be made using a mono- lithium initiator which contains a hydroxyl group which has been blocked as the silyl ether (as in United States patent specification Nos. 5,376,745 and 5,416,168).
  • a suitable initiator is hydroxypropyllithium in which the hydroxyl group is blocked as the t ⁇ methylsilyl ether.
  • This mono-lithium initiator can be used to polymerise butadiene in hydrocarbon or polar solvent. Each mole of living polymer is then capped with one mole of ethylene oxide and terminated with one mole of methanol to yield the mono-hydroxy polydiene polymer.
  • the silyl ether is then removed by acid catalysed cleavage in the presence of water yielding the desired polydiene diol.
  • the polydiene mono-ol may be prepared in a way analogous to the preparation process of the polydiene diol. In the preparation of polydiene mono-ol a mono- lithium initiator is typically used, not containing any hydroxy groups as discussed above.
  • the conjugated diene monomer is polymerised with the initiator to yield a living polymer. Preferably, each mole of living polymer is then capped with one mole of ethylene oxide and terminated with one mole of methanol.
  • the polydiene diol and/or mono-ol is preferably hydrogenated such that at least 90%, more preferably at least 95%, of the olefinic carbon to carbon double bonds in the polydiene is saturated. Hydrogenation of these polymers may be carried out by a variety of well established processes including hydrogenation in the presence of such catalysts as Raney Nickel, noble metals such as platinum and palladium, soluble transition metal catalysts and titanium catalysts as in United States patent specification No. 5,039,755.
  • a particularly preferred catalyst is a mixture of nickel 2- ethylhexanoate and triethylaluminum.
  • the polybutadiene polymer preferably has no less than about 30% 1, 2-butadiene addition because, after hydrogenation, the polymer will be a waxy solid at room temperature if it contains less than about 30% 1,2- butadiene addition.
  • the 1, 2-butadiene content is preferably between 40 and 60%.
  • the isoprene polymers preferably have no less than 80% 1,4-isoprene addition in order to reduce Tg and viscosity.
  • the diene microstructures are typically determined by I ⁇ nuclear magnetic resonance (NMR) in chloroform.
  • the polydiene mono-ols preferably have hydroxyl equivalent weights in the range of from 500 to 15,000, more preferably in the range of from 1,000 to 12,500.
  • the polydiene diols preferably have hydroxyl equivalent weights in the range of from 250 to 10,000, more preferably in the range of from 500 to 7,500, most preferably between 1,500 and 3,000.
  • suitable number average molecular weights will be between 500 and 20,000, more preferably between 1,000 and 15,000, most preferably between 3,000 and 6,000.
  • suitable number average molecular weights will be between 500 and 15,000, more preferably between 1,000 and 12,500, most preferably between 1,500 and 6,000.
  • the number average molecular weights referred to here are number average molecular weights measured by gel permeation chromatography (GPC) calibrated with polybutadiene standards having known number average molecular weights.
  • the solvent for the GPC analyses is tetrahydrofuran .
  • Polyether polyols and polyester polyols are well known to those skilled in the art, and available commercially. Of the group of polyester polyols and polyether polyols, preferably a polyether polyol is used .
  • the polyether polyols are typically the reaction product of an alkylene oxide and an initiator.
  • alkylene oxide preferably propylene oxide or mixtures of propylene oxide and ethylene oxide are used.
  • Initiators are also well known to those skilled in the art.
  • suitable initiators for making polyether polyol used in the preparation of rigid and semi-rigid foams include glycerol, sucrose, sorbitol, amines, glycols, or phenolic compounds as well as mixtures thereof.
  • the structure of the polyether polyol chains is very important as it determines the properties of the final polyurethane foam.
  • the polyether polyol ' s molecular weight and functionality are the most important factors . It belongs to the skill of the skilled person in this field to select the appropriate polyether polyol for a desired range of properties.
  • the polyether polyols preferably have a number average molecular weight in the range of from 200 to 2000, preferably from 250 to 1500, more preferably from 250 to 1000.
  • the polyether polyols are often characterised by their hydroxyl value.
  • the hydroxyl value preferably ranges from 200 to 1500 mg KOH/g, more preferably from 250 to 1000 mg KOH/g, as determined by
  • the hydroxyl value preferably ranges from 100 to 400 mg KOH/g. If mixtures of polyether polyols are used, it will be appreciated that the hydroxyl values of the individual polyether polyols may suitably lie outside the above ranges, but, preferably, the average hydroxyl value of the polyether polyol mixture is kept within the ranges given above.
  • the present invention relates to a process for preparing polyurethane foams comprising the steps of: combining 1 to 20 parts of at least one polyolefin polyol and 80 to 99 parts of at least one polyester polyol and/or polyether polyol, the total of polyolefin polyol and polyester polyol and/or polyether polyol being 100, with a blowing agent, a catalyst and optionally a surfactant to form a blend; adding a polyisocyanate having a functionality of more than two isocyanate groups per molecule, in such an amount that the NCO : OH molar ratio is at least 0.9:1; and foaming the combined blend and polyisocyanate to form a polyurethane foam.
  • the NCO:OH molar ratio is between 0.9:1 and 1.3:1. If water is used as a blowing agent, more preferably the NCO:OH molar ratio is more than 1:1.
  • water is used as a blowing agent, more preferably the NCO:OH molar ratio is more than 1:1.
  • any polyisocyanate, and mixtures of polyisocyanates can be used for the preparation of rigid and semi-rigid polyurethane foams.
  • the polyisocyanate and/or the mixture of polyols must have a functionality above 2 to enable cross-linking to form a three-dimensional network.
  • both the mixture of polyols and the polyisocyanate (s ) have an average functionality above 2.
  • the functionality of the polyisocyanate is preferably between 2 and 8, more preferably between 2 and 5.
  • the polyisocyanate is an aromatic polyisocyanate, most preferably polymeric diphenylmethane dusocyanate (MDI) .
  • MDI polymeric diphenylmethane dusocyanate
  • Polymeric MDI sometimes referred to as crude MDI, is commercially available.
  • a polymeric MDI grade is marketed by Shell under the tradename CARADATE 30.
  • Surfactants are often added to improve the miscibility of the components, which m turn promotes the hydroxyl/isocyanate reaction. Further, the surface tension of the mixture is reduced, which influences the cell nucleation and stabilises the expanding foam, leading to a fine cell structure.
  • the surfactant is a silicone oil.
  • TEGOSTAB-B8404 An example of a suitable commercially available silicone oil is TEGOSTAB-B8404 (TEGOSTAB is a trademark) .
  • the surfactant, if present, is normally added in an amount of from 0.5 to 5 parts by weight (pbw) per 100 pbw of the total polyol mixture, preferably from 0.5 to 2 pbw.
  • any catalyst known to catalyse one or more of the foaming reactions in the system may be used.
  • suitable catalysts are described in European patent specification No. 0 358 282 and include amines such as tertiary amines, salts of carboxylic acids, and organometallic catalysts.
  • tertiary amines examples include triethylene diamine, N-methylmorpholine, N-ethylmorpholine, diethyl- ethanol-amine, N-cocomorpholine, l-methyl-4-dimethyl- amino-ethylpiperazine, 3-methoxypropyldimethylamine, N, N, N ' -tri-methylisopropyl propylenediamine, 3- diethylamino propyl-diethylamine, dimethylbenzylamine and dimethylcyclohexylamine .
  • An example of a carboxylic acid salt useful as a catalyst is sodium acetate.
  • Suitable organometallic catalysts include stannous octoate, stannous oleate, stannous acetate, stannous laureate, lead octoate, lead naphthenate, nickel naphthenate, cobalt naphthenate and dibutyltin dichloride. Further examples of organometallic compounds useful as catalyst in the production of polyurethanes are described in U.S. Patent Specification No. 2,846,408. Of course, mixtures of two or more of the above catalysts may also be applied.
  • the amount in which the catalyst, or the mixture of catalysts, is used normally lies in the range of from 0.01 to 5.0 pbw, preferably in the range of from 0.2 to 2.0 pbw, per 100 parts of polyol mixture.
  • blowing agents include halogenated hydrocarbons, aliphatic alkanes, and alicyclic alkanes, as well as water which is often referred to as a chemical blowing agent. Due to the ozone depleting effect of the fully chlorinated, fluormated alkanes (CFC's), the use of this type of blowing agent is not preferred, although it is possible to use them within the scope of the present invention.
  • CFC's fully chlorinated, fluormated alkanes
  • HCFC's The halogenated alkanes, wherein at least one hydrogen atom has not been substituted by a halogen atom
  • HCFC's have a lower ozone depleting potential and therefore are the preferred halogenated hydrocarbons to be used m physically blown foams.
  • a very suitable HCFC type blowing agent is 1-chloro-l , 1- difluoroethane . Even more preferred as blowing agents are hydrofluorohydrocarbons which are thought to have a zero ozone depletion potential.
  • water as a (chemical) blowing agent is also well known. Water reacts with isocyanate groups according to the well known NCO/H2O reaction, thereby releasing carbon dioxide which causes the blowing to occur .
  • the aliphatic and alicyclic alkanes were developed as alternative blowing agents for the CFC's.
  • alkanes are n-pentane, isopentane, and n-hexane (aliphatic) , and cyclopentane and cyclohexane (alicyclic) .
  • blowing agents may be used singly or in mixtures of two or more.
  • water and cyclopentane have been found to be particularly suitable as blowing agent for the purpose of the present invention.
  • the amounts wherein the blowing agents are to be used are those conventionally applied, i.e.
  • the blowing agent is water.
  • Water is preferably added in an amount of from 0.5 to 3.5 parts by weight (pbw) per 100 parts of polyol mixture.
  • pbw parts by weight
  • distilled or de-mineralised water is used, as impurities may affect the foam reaction.
  • a variety of amines, organometallic catalysts, and silicone surfactants for making polyurethane foams are commercially available from Air Products under the tradename DABCO .
  • flame retardants may be added. It belongs to the skill of the average skilled person in this field to select appropriate additional compounds to be added to the composition to be foamed.
  • the polyurethane foams are preferably prepared by blending all of the components except the polyisocyanate.
  • the polyol mixture is preferably preheated to reduce viscosity- prior to blending. After blending, the polyisocyanate is quickly added and briefly stirred before pouring the mixture into a mould to hold the expanding foam.
  • the mould typically contains a polyolefinic substrate to which the foam must adhere.
  • the polyurethane foam may be subjected to a curing treatment by heating the foam to an elevated temperature, usually between 100 and 160 °C for a certain period of time, typically in the range from 10 minutes to 96 hours, preferably from 30 minutes to 48 hours. Usually, however, the heat generated by the exothermic polyurethane forming reaction is sufficient to ensure complete curing, and the process is carried out adiabatically .
  • the present invention relates to a polyurethane foam obtainable by a process as described herein before.
  • the foam according to the present invention typically has an overall density in the range of from 10 to 800 kg/m ⁇ , preferably from 20 to 250 kg/rr , more preferably from 20 to 120 kg/m-3.
  • the adhesion of the foam according to the invention to polypropylene is typically more than 150 N/25cm2, as determined by the force required to unstick a flat polypropylene plate of 25 cm ⁇ from the foam.
  • the adhesion to polypropylene is more than 200 more preferably from 250 to cohesion failure of the foam itself .
  • the invention further relates to articles containing such polyurethane foam, as well as to composites of a polyolefin or block copolymers comprising more than 50% by weight of at least one polyolefin block, and such polyurethane foam.
  • the foams of the present invention are preferably used as insulating material (including noise insulating material) in household equipment, pipe insulation, automotive applications, e.g. in dashboards, and in the building industry.
  • Example 1 shows rigid and semi-rigid polyurethane foams in accordance with the present invention.
  • the examples are not intended to limit the present invention to specific embodiments although each example may support a separate claim which is asserted to be a patentable invention.
  • Example 1 shows rigid and semi-rigid polyurethane foams in accordance with the present invention. The examples are not intended to limit the present invention to specific embodiments although each example may support a separate claim which is asserted to be a patentable invention.
  • Example 1 shows rigid and semi-rigid polyurethane foams in accordance with the present invention. The examples are not intended to limit the present invention to specific embodiments although each example may support a separate claim which is asserted to be a patentable invention.
  • Example 1 shows rigid and semi-rigid polyurethane foams in accordance with the present invention. The examples are not intended to limit the present invention to specific embodiments although each example may support a separate claim which is asserted to be a patentable invention.
  • a polyol mixture was prepared for use in the preparation of a semi-rigid polyurethane foam.
  • the polyol mixture contained 50 parts by weight (pbw) of a polyetherpolyol having a hydroxyl value of 520 mg KOH/g and marketed under the tradename CARADOL 520-03, 45 pbw of a polyetherpolyol having a hydroxyl value of 36 mg KOH/g and marketed under the tradename CARADOL 36-03, and 5 pbw of a hydrogenated polybutadiene diol having a functionality of 1.9 and a hydroxyl equivalent weight of 1700.
  • polystyrene resin marketed under the tradename TEGOSTAB B8404
  • a silicone oil surfactant marketed under the tradename TEGOSTAB B8404
  • 0.8 pbw of a glyme-type catalyst marketed under the tradename DIME-6
  • 0.8 pbw of an amine-type catalyst marketed under the tradename DABCO 33LV.
  • the latter catalyst is a blend of 33% by weight triethylenediamine (TEDA) and 67% by weight dipropylene glycol.
  • polymeric MDI marketed under the tradename CARADATE 30, contained about 70 % by weight of diphenylmethane diisocyanate, the remainder being isomers, oligomers, and polymers thereof.
  • the NCO:OH molar ratio amounted to 1.05:1.
  • the reaction mixture was poured into a mould at the bottom of which a polyolefin plate had been placed.
  • the mould was closed and the blend was allowed to react without additional heating or cooling of the mould. After the reaction was complete and a foam had been produced, the mould containing the foam was allowed to cool for 60 minutes .
  • Example 1 The experiment as described in Example 1 was repeated a number of times, each time using a different type of polyolefin material in the mould.
  • the polyol mixture used was different from the mixture used in Example 1 in that it contained 15 pbw of the polybutadiene diol used in Example 1 and 35 pbw of CARADOL 36-03.
  • the force necessary to unstick the polyolefin plate from the foam was determined, the results are reported in Table 1. Comparative Example 3
  • Example 1 The experiment as described in Example 1 was repeated a number of times, each time using a different type of polyolefin material in the mould.
  • the polyol mixture used was different from the mixture used in
  • Example 1 in that it contained only 50 pbw of CARADOL 36-03 polyether polyol, and no polybutadiene diol. The force necessary to unstick the polyolefin plate from the foam was determined. The results are reported in Table 1. TABLE 1
  • Example 2 Comp . Ex . 3 plates (N/25cm 2 ) (N/25cm 2 ) (N/25cm 2 ) (N/25cm 2 )
  • MM17 is an intimate blend of PMMA and a polypropylene resin.
  • GXPA018 is a glass-fibre reinforced polypropylene, containing 30% by weight of glass fibres.
  • GXPA055 is a glass-fibre reinforced, impact modified polypropylene, containing 35% by weight of glass fibre.
  • GXPA064 is an impact-modified polypropylene containing 30% by weight of CaC ⁇ 3.
  • GXPA grades are marketed by Montell Polyolefins under the tradename HIVALLOY.
  • Example 1 Introducing the hydrogenated polybutadiene diol of Example 1 in rigid foam enhances the adhesion of the foam to the polyethylene. Moreover, the optimal level in the formulation is 3%. This level gives in most cases a foam cohesion failure rather than a foam/PE adhesion failure. For higher amounts this phenomenon is not seen. The foam looks good and cannot be distinguished from the reference formulation. Furthermore, other typical foam properties (mechanical and thermal properties, closed cell content) were measured and compared to the reference formulation. Foam quality stays good.
  • the samples were prepared as follows: mould and polyethylene plates were preheated at approximately 50°C plates were glued in the mould reaction mixtures was poured onto the plates, mould was closed filling density of the mould was approximately 50 g/1 mouldings were cut and tested few days afterwards
  • the reference formulation is based on CARADOL GB475- 01 and GB250-01 which are polyetherpolyols having hydroxyl values of 475 and 250, respectively.
  • Modified formulations contain 3%, 5%, or 10% (of polyol blend) of the hydrogenated polybutadiene diol, that is polyethylene/butylene diol (EB diol) .
  • EB diol polyethylene/butylene diol
  • the thermal conductivity aging behavior of the reference formulation was compared with the formulation containing 5% EB diol. Naked foams were conditioned at 50 °C and the thermal conductivity, Lambda, at 10°C was measured at several intervals. The polyethylene/butylene diol containing formulation apparently ages slightly faster, but the difference is small .

Abstract

L'invention concerne un mélange de polyols s'utilisant dans la préparation de mousses de polyuréthane, comprenant : (i) de 80 à 99 %, en poids d'au moins un polyol de polyéther et/ou au moins un polyol de polyester; et (ii) de 1 à 20 %, en poids d'au moins un polyol de polyoléfine. L'invention concerne également un procédé de préparation de mousses en polyuréthane au moyen du mélange considéré, des mousses en polyuréthane pouvant être obtenues à l'aide dudit procédé ainsi que des articles et composites renfermant lesdites mousses de polyuréthane.
PCT/EP1998/000545 1997-01-30 1998-01-29 Utilisation de melanges de polyols dans les mousses rigides et semi-rigides de polyurethane WO1998033832A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
PCT/EP1998/000545 WO1998033832A1 (fr) 1997-01-30 1998-01-29 Utilisation de melanges de polyols dans les mousses rigides et semi-rigides de polyurethane
DE69805162T DE69805162T2 (de) 1997-01-30 1998-01-29 Verwendung von polyolgemischen für polyurethan-(halb)hartschaumstoffe
EP98905386A EP0961796B1 (fr) 1997-01-30 1998-01-29 Utilisation de melanges de polyols dans les mousses rigides et semi-rigides de polyurethane
CA002278680A CA2278680A1 (fr) 1997-01-30 1998-01-29 Utilisation de melanges de polyols dans les mousses rigides et semi-rigides de polyurethane
BR9806728-1A BR9806728A (pt) 1997-01-30 1998-01-29 Uso de misturas de polióis em espumas rìgidas e semi-rìgidas de poliuretano.
JP53254898A JP2001509834A (ja) 1997-01-30 1998-01-29 硬質及び半硬質のポリウレタンフォーム中のポリオール混合物の使用

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP97300591.1 1997-01-30
PCT/EP1998/000545 WO1998033832A1 (fr) 1997-01-30 1998-01-29 Utilisation de melanges de polyols dans les mousses rigides et semi-rigides de polyurethane

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* Cited by examiner, † Cited by third party
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US8324290B2 (en) 2008-06-27 2012-12-04 Cardiac Pacemakers, Inc. Polyisobutylene urethane, urea and urethane/urea copolymers and medical devices containing the same
US8374704B2 (en) 2009-09-02 2013-02-12 Cardiac Pacemakers, Inc. Polyisobutylene urethane, urea and urethane/urea copolymers and medical leads containing the same
US8529934B2 (en) 2009-08-21 2013-09-10 Boston Scientific Scimed, Inc. Crosslinkable polyisobutylene-based polymers and medical devices containing the same
US8660663B2 (en) 2010-12-20 2014-02-25 Cardiac Pacemakers, Inc. Lead having a conductive polymer conductor
US8942823B2 (en) 2009-09-02 2015-01-27 Cardiac Pacemakers, Inc. Medical devices including polyisobutylene based polymers and derivatives thereof
US8962785B2 (en) 2009-01-12 2015-02-24 University Of Massachusetts Lowell Polyisobutylene-based polyurethanes
US20180051124A1 (en) * 2015-03-12 2018-02-22 Huntsman Advanced Materials Licensing (Switzerland) Gmbh Polyol component for the production of pur foams
US9926399B2 (en) 2012-11-21 2018-03-27 University Of Massachusetts High strength polyisobutylene polyurethanes
US10526429B2 (en) 2017-03-07 2020-01-07 Cardiac Pacemakers, Inc. Hydroboration/oxidation of allyl-terminated polyisobutylene
US10835638B2 (en) 2017-08-17 2020-11-17 Cardiac Pacemakers, Inc. Photocrosslinked polymers for enhanced durability
US11472911B2 (en) 2018-01-17 2022-10-18 Cardiac Pacemakers, Inc. End-capped polyisobutylene polyurethane
US11976157B2 (en) 2015-03-12 2024-05-07 HUNTSMAN ADVANCED MATERIALS (Switz Polyol component for the production of PUR foams

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EP0295640A2 (fr) * 1987-06-18 1988-12-21 Dai-Ichi Kogyo Seiyaku Co., Ltd. Composition de polyuréthane
DE3943080A1 (de) * 1989-12-27 1991-07-04 Henkel Kgaa Verwendung von polyesterpolyolen enthaltenden reaktionsmischungen bei der herstellung von massiven polyurethanwerkstoffen nach dem giessverfahren
EP0610714A2 (fr) * 1993-02-08 1994-08-17 Bayer Ag Polyuréthane dur Hydrophobe
EP0639596A1 (fr) * 1993-08-20 1995-02-22 Bridgestone Corporation Préparation d'une mousse de polyuréthane étanché

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EP0295640A2 (fr) * 1987-06-18 1988-12-21 Dai-Ichi Kogyo Seiyaku Co., Ltd. Composition de polyuréthane
US4752626A (en) * 1987-08-27 1988-06-21 General Motors Corporation Method of making low compression set urethane foams
DE3943080A1 (de) * 1989-12-27 1991-07-04 Henkel Kgaa Verwendung von polyesterpolyolen enthaltenden reaktionsmischungen bei der herstellung von massiven polyurethanwerkstoffen nach dem giessverfahren
EP0610714A2 (fr) * 1993-02-08 1994-08-17 Bayer Ag Polyuréthane dur Hydrophobe
EP0639596A1 (fr) * 1993-08-20 1995-02-22 Bridgestone Corporation Préparation d'une mousse de polyuréthane étanché

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8501831B2 (en) 2008-06-27 2013-08-06 Cardiac Pacemakers, Inc. Polyisobutylene urethane, urea and urethane/urea copolymers and medical devices containing the same
US8324290B2 (en) 2008-06-27 2012-12-04 Cardiac Pacemakers, Inc. Polyisobutylene urethane, urea and urethane/urea copolymers and medical devices containing the same
US8962785B2 (en) 2009-01-12 2015-02-24 University Of Massachusetts Lowell Polyisobutylene-based polyurethanes
US11174336B2 (en) 2009-01-12 2021-11-16 University Of Massachusetts Lowell Polyisobutylene-based polyurethanes
US10513576B2 (en) 2009-01-12 2019-12-24 University of Masschusetts Lowell Polyisobutylene-based polyurethanes
US9574043B2 (en) 2009-01-12 2017-02-21 University Of Massachusetts Lowell Polyisobutylene-based polyurethanes
US8529934B2 (en) 2009-08-21 2013-09-10 Boston Scientific Scimed, Inc. Crosslinkable polyisobutylene-based polymers and medical devices containing the same
US8927660B2 (en) 2009-08-21 2015-01-06 Cardiac Pacemakers Inc. Crosslinkable polyisobutylene-based polymers and medical devices containing the same
US8676344B2 (en) 2009-09-02 2014-03-18 Cardiac Pacemakers Inc. Polyisobutylene urethane, urea and urethane/urea copolymers and medical leads containing the same
US8942823B2 (en) 2009-09-02 2015-01-27 Cardiac Pacemakers, Inc. Medical devices including polyisobutylene based polymers and derivatives thereof
US8903507B2 (en) 2009-09-02 2014-12-02 Cardiac Pacemakers, Inc. Polyisobutylene urethane, urea and urethane/urea copolymers and medical leads containing the same
US8374704B2 (en) 2009-09-02 2013-02-12 Cardiac Pacemakers, Inc. Polyisobutylene urethane, urea and urethane/urea copolymers and medical leads containing the same
US8660663B2 (en) 2010-12-20 2014-02-25 Cardiac Pacemakers, Inc. Lead having a conductive polymer conductor
US9926399B2 (en) 2012-11-21 2018-03-27 University Of Massachusetts High strength polyisobutylene polyurethanes
US10562998B2 (en) 2012-11-21 2020-02-18 University Of Massachusetts High strength polyisobutylene polyurethanes
US20180051124A1 (en) * 2015-03-12 2018-02-22 Huntsman Advanced Materials Licensing (Switzerland) Gmbh Polyol component for the production of pur foams
US11976157B2 (en) 2015-03-12 2024-05-07 HUNTSMAN ADVANCED MATERIALS (Switz Polyol component for the production of PUR foams
US10526429B2 (en) 2017-03-07 2020-01-07 Cardiac Pacemakers, Inc. Hydroboration/oxidation of allyl-terminated polyisobutylene
US10835638B2 (en) 2017-08-17 2020-11-17 Cardiac Pacemakers, Inc. Photocrosslinked polymers for enhanced durability
US11472911B2 (en) 2018-01-17 2022-10-18 Cardiac Pacemakers, Inc. End-capped polyisobutylene polyurethane
US11851522B2 (en) 2018-01-17 2023-12-26 Cardiac Pacemakers, Inc. End-capped polyisobutylene polyurethane

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