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
  • 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
  • C08G65/04—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
  • C08G65/105—Onium 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
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4833—Polyethers containing oxyethylene units
  • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
  • C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/487—Polyethers containing cyclic groups
  • C08G18/4883—Polyethers containing cyclic groups containing cyclic groups having at least one oxygen atom in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
• • 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
  • 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
  • C08G2101/00—Manufacture of cellular products

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 500 g/mole and produced by alkoxylating a polyoxyethylene-contai ⁇ ing initiator with an alkylene oxide in the presence of a basic catalyst having at least one cation thereof chelated by the polyoxyethylene-containing initiator.
• PEGs polyethylene glycols
• the present invention expands upon those teachings by using a polyoxyethylene-containing initiator to act as a chelating agent in the base- catalyzed production of long-chain polyether polyols, thus eliminating the need for the addition of a polyoxyethylene-containing additive.
• the present invention provides a long-chain polyether polyol having a number average molecular weight of more than about 500 g/mole and produced by alkoxylating a polyoxyethylene-containing initiator with an alkylene oxide in the presence of a basic catalyst having at least one cation thereof chelated by the polyoxyethylene-containing initiator.
• 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 500 g/mole and produced by alkoxylating a polyoxyethylene-containing initiator with an alkylene oxide in the presence of a basic catalyst having at least one cation thereof chelated by the polyoxyethylene-containing initiator.
• the present invention further provides a process for producing a long- chain polyether polyol having a number average molecular weight of more than 500 g/mole involving alkoxylating a polyoxyethylene-containing initiator with an alkylene oxide in the presence of a basic catalyst having at least one cation thereof chelated by the polyoxyethylene-containing initiator.
• the present invention yet further provides a polyurethane foam made from the reaction product of at least one polyisocyanate and a long-chain polyether polyol having a number average molecular weight of more than 500 g/mole and produced by alkoxylating a polyoxyethylene-containing initiator with an alkylene oxide in the presence of a basic catalyst having at least one cation thereof chelated by the polyoxyethylene-containing initiator, optionally in the presence of at least one of blowing agents, surfactants, other cross- linking agents, extending agents, pigments, flame retardants, catalysts and fillers.
• the present invention still further provides a process for producing a polyurethane foam involving reacting at least one polyisocyanate with a long- chain polyether polyoi having a number average molecular weight of more than 500 g/mole produced by alkoxylating a polyoxyethylene-containing initiator with an alkylene oxide in the presence of a basic catalyst having at least one cation thereof chelated by the polyoxyethylene-containing initiator, optionally in the presence of at least one of blowing agents, surfactants, other cross-linking agents, extending agents, pigments, flame retardants, catalysts and fillers.
• long-chain polyether polyol the inventors herein mean a polyether polyol having a number average molecular weight of greater than 500 g/mole, preferably from 500 to 50,000 g/mole, more preferably from 1 ,000 to 30,000 g/mole, and most preferably from 1 ,000 to 8,000 g/mole.
• the molecular weight of the inventive long-chain polyether polyols may be in an amount ranging between any combination of these values, inclusive of the recited values.
• the long-chain polyether polyols 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.
• the polyoxyethylene-containing initiators useful in the present invention are polyoxyethylene-containing polyether polyols having a molecular weight of less than 500 g/mole prepared by alkoxylating (with either ethylene oxide or mixtures of oxides containing ethylene oxide) any of the low molecular weight alcohols, amines, diols, diamines, polyols or polyamines known to those skilled in the art to be useful as starters for polyether polyols.
• C 1 -C 30 monois, ethylene glycol, diethylene glycol, Methylene 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, trimethylolprapane, trimethylolethane, pentaerythritol, ⁇ -methylglucoside, sorbitol, mannitol, hydroxymethylglucoside, hydroxypropylglucoside, sucrose, N,N,N',N'- tetrakis[2-hydroxyethyl or 2-hydroxypropyl]ethylene diamine, 1 ,4- cyclohexanediol
• the polyoxyethylene-containing starters useful in the present invention may preferably be produced at the same molecular weight as current starters used to prepare the polyols.
• the polyoxyethylene-containing accelerator is built directly into the initiator. This approach eliminates the need for the addition of a polyoxyethylene-containing additive prior to the alkoxylation as is taught in the three commonly assigned applications mentioned hereinabove.
• These initiators contain sufficient polyoxyethylene to result in the long-chain polyether polyol having a polyoxyethylene content of from 0.5 to 20 wt.%, more preferably from 1 to 10 wt.% and most preferably from 2 to 7 wt.%, based on the weight of the long-chain polyether.
• the polyoxyethylene-containing starter may be included in an amount such that the final polyoxyethylene content provided by the initiator ranges 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, cyclohexene 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. 3,404,109, 3,538,043 and 5,145,883, the contents of which are herein incorporated in their entireties by reference thereto.
• inventive long-chain polyether polyols may preferably be reacted with a polyisocyanate, optionally in the presence of one or more of blowing agents, surfactants, cross-linking agents, extending agents, pigments, flame retardants, catalysts and fillers to produce flexible polyurethane foams.
• 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 Auslegeschrift 1 ,202,785 and U.S. Pat. No.
• 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.
• the use of 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, piasticizers, 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 homologues (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- dimethylcyclohexylamine, N.N-diethyl-benzylamine, bis-(N,N- diethylaminoethyl) a
• 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, dibutyitin 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, dibutyl
• 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.
• 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 initiator based on propoxylated glycerine having a hydroxyl number of 350 mg KOH/g, contains 4 wt. % KOH;
• Polyol B a polyether polyol initiator based on propoxylated sorbitol having a hydroxyl number of 200 mg KOH/g, contains 2.2 wt. % KOH;
• Polyol C a polyoxyethylene-containing polyether polyol initiator having a hydroxyl number of ⁇ 350 mg KOH/g, prepared by ethoxylating glycerine with approximately 8.8 moles of ethylene oxide per mole of glycerine, contains 4 wt. % KOH;
• Polyol D a polyoxyethylene-containing polyether polyol initiator having a hydroxyl number of -350 mg KOH/g, prepared by ethoxylating glycerine first with ethylene oxide ( ⁇ 4.4 moles ethylene oxide per mole of glycerine and subsequently with ⁇ 3.4 moles of propylene oxide per mole of glycerine, contains 4 wt. % KOH.
• the inventive concept was applied to the synthesis of an ethylene oxide-capped molded foam triol (a glycerin-sorbitol based polyether having a hydroxyl number of about 31.5 mg KOH/g that has 16% ethylene oxide cap).
• a start mixture having a hydroxyl number of 290 mg KOH/g was prepared from 60 % Polyol A (120 g) and 40 % Polyol B (80 g). This mixture was charged to a one-liter p ⁇ lyether polyol reactor and propoxylated in two stages to a final hydroxyl number of 37 mg KOH/g. In the first stage, the 200 g of start mixture were heated under vacuum ( ⁇ 0.5 psia) at 105 0 C, while allowing nitrogen to flow through the reactor. After thirty 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.) for the first stage of the propoxylation.
• the reaction mixture was allowed to continue stirring at 105 0 C, until the propylene oxide was consumed, as evidenced by the pressure reaching a steady state value.
• the contents of the reactor were withdrawn, and 200 g of this product was added back into the reactor.
• the time required to feed 322 g of propylene oxide to this material under the same conditions of temperature and pressure as detailed above, thus decreasing the hydroxyl number from 97 to 37 mg KOH/g was determined and similarly used to determine the oxide feed rate.
• Examples 2 and 3 The long-chain polyethers of Examples 2 and 3 were made according to the procedure given above for Example C-1 , except that Polyol A of the start mixture was replaced either by Polyol C (Example 2) or Polyol D (Example 3).
• the polyoxyethylene-containing polyether polyol initiators (Polyols C and D) were evaluated as starters on a larger scale.
• a start mixture was prepared from 60% Polyol A and 40% Polyol B. This start mixture (hydroxyl number of 290 mg KOH/g) was stripped under vacuum (-0.5 psia) at 105 0 C, while allowing nitrogen to flow through the reactor. After thirty minutes, the nitrogen feed was stopped, and the vacuum valve was closed, thus blocking the vacuum in the reactor.
• the mixture was propoxylated at 105 0 C in a single stage to a final hydroxyl number of 37 mg KOH/g,
• the propylene oxide was fed at a constant rate sufficient to give either a seven-hour feed (Example C-4) or five-hour feed Example C-5).
• the reactor pressure was monitored, and the peak pressure was recorded.

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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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Citations (3)

• 2005
  • 2005-12-22 US US11/315,667 patent/US20070149634A1/en not_active Abandoned
• 2006
  • 2006-12-18 WO PCT/US2006/048039 patent/WO2007075482A1/en not_active Ceased
  • 2006-12-18 BR BRPI0620171-7A patent/BRPI0620171A2/pt not_active IP Right Cessation
  • 2006-12-18 CN CNA2006800483392A patent/CN101341189A/zh active Pending
  • 2006-12-18 JP JP2008547365A patent/JP2009521555A/ja not_active Withdrawn
  • 2006-12-18 KR KR1020087014995A patent/KR20080075194A/ko not_active Withdrawn
  • 2006-12-18 CA CA002633704A patent/CA2633704A1/en not_active Abandoned
  • 2006-12-18 EP EP06845618A patent/EP1966275A1/en not_active Withdrawn
  • 2006-12-18 MX MX2008008033A patent/MX2008008033A/es unknown

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