Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4829—Polyethers containing 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic 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
  • C08G18/48—Polyethers
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
  • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
  • C08G65/08—Saturated oxiranes
  • C08G65/10—Saturated oxiranes characterised by the catalysts used
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
  • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
• • 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

Definitions

• the present invention relates in general to polyether polyols, and more specifically, to a long-chain polyether polyol having a number average molecular weight of more than about 1 ,200 g/mole and produced by alkoxylating an initiator in the presence of a basic catalyst having at least one cation thereof chelated with from about 0.5 wt.% to about 20 wt.% of a polyoxyethylene-containing compound having a molecular weight of less than about 10,000 g/mole.
• the present invention provides a long-chain polyether polyol having a number average molecular weight of more than about 1 ,200 g/mole and produced by alkoxylating an initiator with an alkylene oxide in the presence of a basic catalyst having at least one cation thereof chelated with from about 0.5 to about 20 wt.% of a polyoxyethylene-containing compound having a molecular weight of less than about 10,000 g/mole, wherein the weight percentage is based on the weight of the long-chain polyether polyol.
• the inventive polyols may be used to provide flexible polyurethane foams and non-cellular polyurethanes.
• the present invention will now be described for purposes of illustration and not limitation. Except in the operating examples, or where otherwise indicated, all numbers expressing quantities, percentages, OH numbers, functionalities and so forth in the specification are to be understood as being modified in all instances by the term "about.” Equivalent weights and molecular weights given herein are number average equivalent weights and number average molecular weights respectively, unless indicated otherwise.
• the present invention provides a long-chain polyether polyol having a number average molecular weight of more than 1 ,200 g/mole and produced by alkoxylating an initiator with an alkylene oxide in the presence of a basic catalyst having at least one cation thereof chelated with from 0.5 to 20 wt.
• the present invention further provides a process for producing a long chain polyether polyol having a number average molecular weight of more than 1 ,200 g/mole and involving alkoxylating an initiator with an alkylene oxide in the presence of a basic catalyst having at least one cation thereof chelated with from 0.5 to 20 wt. % of a polyoxyethylene-containing compound having a molecular weight of less than 10,000 g/mole, wherein the weight percentage is based on the weight of the long-chain polyether polyol.
• the present invention still further provides a flexible polyurethane foam made from the reaction product of at least one polyisocyanate and at least one long-chain polyether polyol having a number average molecular weight of more than 1,200 g/mole and produced by alkoxylating an initiator with an alkylene oxide in the presence of a basic catalyst having at least one cation thereof chelated with from 0.5 to 20 wt.
• % of a polyoxyethylene-containing compound having a molecular weight of less than 10,000 g/mole optionally in the presence of at least one of blowing agents, surfactants, cross-linking agents, extending agents, pigments, flame retardants, catalysts and fillers, wherein the weight percentage is based on the weight of the long-chain polyether polyol.
• the present invention also provides a process for producing a flexible polyurethane foam involving reacting at least one polyisocyanate and at least one long-chain polyether polyol having a number average molecular weight of more than 1,200 g/mole and produced by alkoxylating an initiator with an alkylene oxide in the presence of a basic catalyst having at least one cation thereof chelated with from 0.5 to 20 wt.
• % of a polyoxyethylene-containing compound having a molecular weight of less than 10,000 g/mole optionally in the presence of at least one of blowing agents, surfactants, cross-linking agents, extending agents, pigments, flame retardants, catalysts and fillers, wherein the weight percentage is based on the weight of the long-chain polyether polyol.
• long-chain polyether polyol the inventors herein mean a polyether polyol having a number average molecular weight of greater than 1 ,200 g/mole, preferably from 1 ,200 to 50,000 g/mole, more preferably from 1 ,200 to 30,000 g/mole, and most preferably from 1,200 to 8,000 g/mole.
• the molecular weight of the inventive poiyols may be in ah amount ranging between any combination of these values, inclusive of the recited values.
• the long chain polyether poiyols of the present invention are made by basic catalysis, the general conditions of which are familiar to those skilled in the art.
• the basic catalyst may be any basic catalyst known in the art, more preferably the basic catalyst is one of potassium hydroxide, sodium hydroxide, barium hydroxide and cesium hydroxide, most preferably the basic catalyst is potassium hydroxide.
• Suitable initiator (or starter) compounds include, but are not limited to, C-i-C- 30 monols, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1 ,3-propanediol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 1 ,4-butanediol, 1 ,2-butanediol, 2,3-butanediol, 1,3-butanediol, 1,6- hexanediol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritot, ⁇ - methylglucoside, sorbitol, mannitol, hydroxymethylglucoside, hydroxypropylglucoside, sucrose, N,N,N',N'-tetrakis[2-hydroxyethyl or 2- hydroxypropyl]ethylene diamine, 1 ,
• Nominal initiator functionality is from 1 to 8 or more, preferably from 1 to 6, and more preferably from 2 to 4.
• the functionality of the initiators useful in the present invention may be in an amount ranging between any combination of these values, inclusive of the recited values. Any mixtures of monomeric initiators or their oxyalkylated oligomers may also be utilized.
• a polyoxyethylene-containing compound such as a polyethylene glycol, is added to chelate at least one of the cations of the basic catalyst during the alkoxylation in the inventive long-chain polyether polyol production process.
• the hydroxy functionality of the polyoxyethylene- containing compound may be capped with alkyl, preferably methyl, groups as is known to those skilled in the art.
• This polyoxyethylene-containing compound is added to the initiator at a level resulting in 0.5 to 20 wt. %, based on the weight of the long-chain polyether polyol, more preferably from 3 wt.% to 9 wt.%.
• This polyoxyethylene-containing compound preferably has a molecular weight of less than 10,000, more preferably from less than 10,000 to 100 and most preferably from 300 to 1 ,000 g/mole.
• the poloxyethylene- containing compound may have a molecular . weight in an amount ranging between any combination of these values, inclusive of the recited values.
• alkylene oxides useful in alkoxylating the initiator to produce the inventive long-chain polyether polyols include, but are not limited to, ethylene oxide, propylene oxide, oxetane, 1 ,2- and 2,3-butylene oxide, isobutylene oxide, epichlorohydrin, cycl ⁇ hexene oxide, styrene oxide, and the higher alkylene oxides such as the C 5 - C 30 ⁇ -alkylene oxides.
• Propylene oxide alone or mixtures of propylene oxide with ethylene oxide or another alkylene oxide are preferred.
• Other polymerizable monomers may be used as well, e.g. anhydrides and other monomers as disclosed in U.S. Pat. Nos.
• inventive long-chain polyether polyols may preferably be reacted with a polyisocyanate, optionally in the presence of blowing agents, surfactants, cross-linking agents, extending agents, pigments, flame retardants, catalysts and fillers to produce flexible polyurethane foams or non- cellular polyurethanes.
• Suitable polyisocyanates are known to those skilled in the art and include unmodified isocyanates, modified polyisocyanates, and isocyanate prepolymers.
• Such organic polyisocyanates include aliphatic, cycloaliphatic, araliphatic, aromatic, and heterocyclic polyisocyanates of the type described, for example, by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136. Examples of such isocyanates include those represented by the formula
• Suitable isocyanates include ethylene diisocyanate; 1 ,4- tetramethylene diisocyanate; 1 ,6-hexamethylene diisocyanate; 1 ,12-dodecane diisocyanate; cyclobutane-1 ,3-diisocyanate; cyclohexane-1 ,3- and -1 ,4- diisocyanate, and mixtures of these isomers; 1-isocyanato-3,3,5-trimethyl-5- isocyanatomethylcyclohexane (isophorone diisocyanate;. German
• polyurethane foams of the present invention are 2,4- and 2,6-toluene diisocyanate and mixtures of these isomers (TDI).
• TDI 2,4- and 2,6-toluene diisocyanate and mixtures of these isomers
• Prepolymers may also be employed in the preparation of the inventive foams. Prepolymers may be prepared by reacting an excess of organic polyisocyanate or mixtures thereof with a minor amount of an active hydrogen-containing compound as determined by the well-known Zerewitinoff test, as described by Kohler in Journal of the American Chemical Society, 49, 3181(1927). These compounds and their methods of preparation are known to those skilled in the art.
• any one specific active hydrogen compound is not critical; any such compound can be employed in the practice of the present invention.
• Suitable additives optionally included in the polyurethane forming formulations of the present invention include, for example, stabilizers, catalysts, cell regulators, reaction inhibitors, plasticizers, fillers, crosslinking or extending agents, blowing agents, etc.
• Stabilizers which may be considered suitable for the inventive foam forming process include, for example, polyether siloxanes, and preferably those which are insoluble in water. Compounds such as these are generally of such a structure that a relatively short chain copolymer of ethylene oxide and propylene oxide is attached to a polydimethylsiloxane residue. Such stabilizers are described in, for example, U.S. Pat. Nos. 2,834,748, 2,917,480 and 3,629,308.
• Catalysts suitable for the foam forming process of the present invention include those which are known in the art. These catalysts include, for example, tertiary amines, such as triethylamine, tributylamine, N- methylmorpholine, N-ethylmorpholine, N.N.N'.N'-tetramethylethylenediamine, pentamethyl-diethylenetriamine and higher homoiogues (as described in, for example, DE-A 2,624,527 and 2,624,528), 1,4-diazabicyclo(2.2.2)octane, N- methyl-N'-dimethyl-aminoethylpiperazine, bis- (dimethylaminoalkyl)piperazines, N,N-dimethylbenzylamine, N 1 N- dimethylcyclqhexylamine, N,N-diethyl-ben ⁇ ylamine, bis-(N,N- diethylaminoethyl)
• Suitable catalysts which may be used in producing the inventive polyurethane foams include, for example, organometallic compounds, and particularly, organotin compounds.
• Organotin compounds which may be considered suitable include those organotin compounds containing sulfur.
• Such catalysts include, for example, di-n-octyltin mercaptide.
• organotin catalysts include, preferably tin(ll) salts of carboxylic acids such as, for example, tin(ll) acetate, tin(ll) octoate, tin(ll) ethylhexoate and/or tin(ll) laurate, and tin(IV) compounds such as, for example, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and/or dioctyltin diacetate.
• tin(ll) salts of carboxylic acids such as, for example, tin(ll) acetate, tin(ll) octoate, tin(ll) ethylhexoate and/or tin(ll) laurate
• tin(IV) compounds such as, for example, dibutyltin oxide, dibutylt
• Water is preferably used as the sole blowing agent in the foams made according to the present invention, although auxiliary blowing agents, such as, for example, carbon dioxide, can be used.
• Water functions as the blowing by reacting with the isocyanate component to chemically form carbon dioxide gas plus an amine moiety which reacts further with the polyisocyanate to form urea backbone groups.
• Water can be used in an amount up to 10% by weight. Preferably. 1 to 8% by weight, more preferably, 1 to 5% by weight, based on the total weight of the isocyanate-reactive mixture, of water is used in the present invention.
• suitable additives which may optionally be included in the flexible polyurethane foams of the present invention can be found in Kunststoff-Handbuch, volume VII, edited by Vieweg & Hochtlen, Carl Hanser Verlag, Kunststoff 1993, 3 rd Ed., pp. 104 to 127, for example. The relevant details concerning the use and mode of action of these additives are set forth therein.
• Polyol A a polyether polyol based on propoxylated glycerine having a hydroxy! number of 240 mg KOH/g
• Polyol B a polyether polyol initiator based on propoxylated glycerine having a hydroxyl number of 350 mg KOH/g, contains 4 wt.
• Polyol C a polyether polyol initiator based on propoxylated sorbitol having a hydroxyl number of 200 mg KOH/g, contains 2.2 wt. % KOH;
• PEG-400 a dihydroxy terminated 400 MW polyethylene glycol (Aldrich
• PEG-1000 a dihydroxy terminated 1000 MW polyethylene glycol
• PEG-500 dimethylether a dimethoxy terminated 500 MW polyethylene glycol (Aldrich Chemical Co.);
• PEG-1000 dimethylether a dimethoxy terminated 1000 MW polyethylene glycol (Aldrich Chemical Co.).
• Polyol A (see Table I for charge weight), 50 % aqueous KOH (4.68 g) and PEG-400 (see Table I for charge weight) were charged to a one-liter polyether polyol reactor.
• the mixture was stripped for 30 minutes under vacuum (-0.5 psia) with a nitrogen purge at 110 0 C to remove water.
• the nitrogen purge was stopped and vacuum valve to the reactor was closed, thus blocking the vacuum (0.5 psia) in the reactor.
• Propylene oxide 300 g was fed to the reactor using a pressure feed back loop to control feed rate to maintain 50 psia pressure in the reactor throughout the run.
• the time 0 required to add the propylene oxide was recorded and used to determine absolute feed rate (g/min).
• a start mixture having a hydroxyl number of 290 mg KOH/g was prepared from 60 % Polyol B (120 g) and 40 % Polyol C (80 g). This mixture was charged to a one-liter stainless steel polyether polyol reactor. The start mixture was heated under vacuum ( ⁇ 0.5 psia) at 105 0 C, while allowing nitrogen to flow through the reactor. After 30 minutes, the nitrogen feed was stopped, and the vacuum valve was closed, thus blocking the vacuum in the reactor ( ⁇ 0.5 psia). Propylene oxide (400 g) was fed into the reactor at a rate sufficient to maintain 40 psia reactor pressure. The time required to complete the PO feed was measured and used to calculate a feed rate (g/min.) for the standard propoxylation.
• Example C-5 A start mixture similar to that of Example C-5 was prepared, except a portion of Polyol B was replaced gram for gram with the indicated polyoxyethylene containing compound (see Table II). Sufficient KOH was added as a 50% aqueous mixture (3.76 g) to bring the total KOH level to the same as that of Example C-5. This mixture was charged to a one-liter stainless steel polyether polyol reactor. The start mixture was heated under vacuum (-0.5 psia) at 105 0 C, while allowing nitrogen to flow through the reactor. After 30 minutes, the nitrogen feed was stopped, and the vacuum valve was closed, thus blocking the vacuum in the reactor. Propylene oxide (400 g) was fed into the reactor at a rate sufficient to maintain 40 psia reactor pressure. The time required to complete the 400 g feed was measured and used to calculate a feed rate (g/min.)
• Example C-5 no polyoxythyelene-containing additive
• Examples 6-10 and C-11 with various polyoxyethylene containing compounds having different MW and end groups, are summarized in Table Il below.
• the inventors herein speculate that the high molecular weight PEG resides in a separate phase and carries with it some of the KOH catalyst resulting in overall slower propoxylation rate. Examining the products after the final propoxylation showed that the PEG-10,000 (Ex. 10) and PEG-100,000 (Ex. C- 11 ) containing products contained solids. The 1 ,000 and lower molecular weight PEGs, at the levels investigated, gave liquid products without evidence for any solids. Liquid polyether polyols that do not contain solids are generally easier to process into polyurethanes and are generally recognized as higher quality.

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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)
• Polyethers (AREA)

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• 2005
  • 2005-12-22 US US11/315,517 patent/US20070149631A1/en not_active Abandoned
• 2006
  • 2006-12-18 BR BRPI0620228-4A patent/BRPI0620228A2/pt not_active IP Right Cessation
  • 2006-12-18 KR KR1020087015118A patent/KR20080078007A/ko not_active Withdrawn
  • 2006-12-18 CA CA002633700A patent/CA2633700A1/en not_active Abandoned
  • 2006-12-18 JP JP2008547364A patent/JP2009521554A/ja not_active Withdrawn
  • 2006-12-18 CN CNA2006800483049A patent/CN101341187A/zh active Pending
  • 2006-12-18 WO PCT/US2006/048035 patent/WO2007075480A2/en not_active Ceased
  • 2006-12-18 EP EP06845616A patent/EP1966274A2/en not_active Withdrawn

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