WO2008137546A1 - Mélange de catalyseur d'amine utile dans la production d'articles de poly(uréthane) - Google Patents

Mélange de catalyseur d'amine utile dans la production d'articles de poly(uréthane) Download PDF

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Publication number
WO2008137546A1
WO2008137546A1 PCT/US2008/062219 US2008062219W WO2008137546A1 WO 2008137546 A1 WO2008137546 A1 WO 2008137546A1 US 2008062219 W US2008062219 W US 2008062219W WO 2008137546 A1 WO2008137546 A1 WO 2008137546A1
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WIPO (PCT)
Prior art keywords
component
blend
quaternary ammonium
catalyst
polyol
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PCT/US2008/062219
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English (en)
Inventor
Robert B. Moore
Robert A. Grigsby, Jr.
Ernest L. Rister, Jr.
Gene Wiltz, Jr.
Jennifer Koch Pratt
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Huntsman Petrochemical Corporation
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Publication of WO2008137546A1 publication Critical patent/WO2008137546A1/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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1875—Catalysts containing secondary or tertiary amines or salts thereof containing ammonium salts or mixtures of secondary of tertiary amines and acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
    • C08G18/2063—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having two nitrogen atoms in the condensed ring system
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers

Definitions

  • This disclosure in general, relates to amine catalyst blends and in particular, to amine catalyst blends useful in the production of polyurethane articles.
  • Polyurethanes comprise a versatile family of polymers that can be used in a variety of applications.
  • polyurethane can be used to form films, foams, paints, and polymer fibers, or can be used as adhesives.
  • polyurethane elastomeric foams can be used to form a variety of products including seat cushions and the soles of shoes.
  • a polyol is mixed with an isocyanate in the presence of catalyst.
  • a polyol and isocyanate may be mixed in the presence of a catalyst and a blowing agent.
  • the cost of the article is often influenced by the curing characteristics of the polyurethane used in the process. If the reaction is initiated too quickly, it may be difficult to fill a mold with a mix of the prepolymer components. On the other hand, if the reaction proceeds in a slow manner, product through put is slowed, resulting in increased cost.
  • a catalyst blend includes a triethylenediamine and a quaternary ammonium salt.
  • a catalyst blend in another exemplary embodiment, includes a triethylenediamine component, a quaternary ammonium component, and a solvent.
  • the ratio of the amount of the triethylenediamine component to the amount of the quaternary ammonium component is in a range between about 1 : 1 and about 30:1.
  • a method of forming a polyurethane includes blending a first polyol component, an isocyanate component, a triethylenediamine component, and a quaternary ammonium component to form a blend, and curing the blend to form the polyurethane.
  • polyurethane is formed from a blend of prepolymer components including a polyol component, an isocyanate component, and a catalyst blend component.
  • the prepolymer components may include one or more additional polyols.
  • the prepolymer components also may include a blowing agent, such as water.
  • the catalyst blend includes a triethylenediamine component and a quaternary ammonium (QA) component.
  • the catalyst blend also may include metal catalysts or additional amine catalysts.
  • the triethylenediamine (TEDA) component and the quaternary ammonium component are included in amounts in a ratio of about 1 : 1 to about 30: 1 TEDA:QA.
  • the polyurethane is an elastomeric foam polyurethane.
  • a method of forming a polyurethane includes blending a polyol component, a triethylenediamine (TEDA) component, a quaternary ammonium component, and an isocyanate component to form a blend.
  • the method further includes curing the blend to form a polyurethane.
  • the method also may include blending a blowing agent to form the blend.
  • the polyurethane is formed from a prepolymer mixture including an isocyanate component, a polyol component, and a catalyst blend.
  • the prepolymer mixture may include a blowing agent, additives, auxiliary agents, or any combination thereof.
  • the isocyanate component may include a diisocyanate monomer.
  • An exemplary diisocyanate monomer may include tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymethylenepolyphenyl diisocyanate, 3,3'-dimethyl-4,4'- biphenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3,3'- dichloro-4,4'-biphenylene diisocyanate or 1,5-naphthalene diisocyanate; their modified products, for instance, carbodiimide-modif ⁇ ed products; or the like, or any combination thereof.
  • Such diisocyanate monomers may be used alone or in admixture of at least two kinds.
  • 4,4'-diphenylmethane diisocyanate, and a combined use of 4,4'- diphenylmethane diisocyanate and its carbodiimide-modified product may be used to provide sufficient strength and wear resistance as a shoe sole.
  • the isocyanate component may be Suprasec® 2981, an aliphatic ester based quasi prepolymer formed from the reaction of an aliphatic polyester polyol and MDI, available from Huntsman.
  • the amount of isocyanate reactive compound used in the prepolymer components provides an Isocyanate Index of between about 80 and about 120, such as between about 95 and about 105.
  • the Isocyanate Index equals the actual amount of isocyanate used divided by the amount of isocyanate required to react all reactive species in the polyol component multiplied by 100.
  • the polyol may include a polyether polyol, a polyester polyol, a polymeric polyol, a low molecular weight polyol, or any combination thereof.
  • Suitable polyether polyols useful for production of the elastomers can be produced by polyinsertion via DMC catalysis of alkylene oxides, by anionic polymerization of alkylene oxides in the presence of alkali hydroxides or alkali alcoholates as catalysts and with the addition of at least one initiator molecule containing 2 to 6, preferably 2 to 4, reactive hydrogen atoms in bonded form, or by cationic polymerization of alkylene oxides in the presence of Lewis acids, such as antimony pentachloride or boron fluoride etherate.
  • Lewis acids such as antimony pentachloride or boron fluoride etherate.
  • Suitable alkylene oxides contain 2 to 4 carbon atoms in the alkylene radical.
  • An example includes tetrahydrofuran, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide; ethylene oxide, 1,2-propylene oxide, or any combination thereof.
  • the alkylene oxides can be used individually, in succession, or as a mixture. In particular, mixtures of 1 ,2-propylene oxide and ethylene oxide may be used, whereby the ethylene oxide is used in quantities of 10 to 50% as an ethylene oxide terminal block so that the resulting polyols display over 70% primary OH terminal groups.
  • An example of an initiator molecule includes water or dihydric or trihydric alcohols, such as ethylene glycol, 1,2-propanediol and 1,3 -propanediol, diethylene glycol, dipropylene glycol, ethane- 1,4-diol, glycerol, trimethylol propane, or any combination theroef.
  • water or dihydric or trihydric alcohols such as ethylene glycol, 1,2-propanediol and 1,3 -propanediol, diethylene glycol, dipropylene glycol, ethane- 1,4-diol, glycerol, trimethylol propane, or any combination theroef.
  • Suitable polyether polyols such as polyoxypropylene polyoxyethylene polyols, have average functionalities of 1.6 to 2.4, such as 1.8 to 2.4, and number-average molecular weights of 800 g/mol to 25,000 g/mol, such as 800 g/mol to 14,000 g/mol, particularly 2,000 g/mol to 9,000 g/mol.
  • Difunctional or trifunctional polyether polyols having a number-average molecular weight of 800 g/mol to 25,000 g/mol, such as 800 g/mol to 14,000 g/mol, or even 2,000 g/mol to 9,000 g/mol, may be used as polyol components.
  • suitable polyol components include polymer polyols, polyether polyols, polymer-modified polyether polyols, such as graft polyether polyols, or any combination thereof.
  • polyols based on styrene or acrylonitrile may be used.
  • a polyester polyol is derived from dibasic acids such as adipic, glutaric, fumaric, succinic or maleic acid, or anhydrides and di-functional alcohols, such as ethylene glycol, diethylene glycol, propylene glycol, di or tripropylene glycol, 1-4 butane diol, 1-6 hexane diol, or any combination.
  • dibasic acids such as adipic, glutaric, fumaric, succinic or maleic acid
  • di-functional alcohols such as ethylene glycol, diethylene glycol, propylene glycol, di or tripropylene glycol, 1-4 butane diol, 1-6 hexane diol, or any combination.
  • the polyester polyol may be formed by the condensation reaction of the glycol and the acid with the continuous removal of the water by-product.
  • a small amount of high functional alcohol such as glycerin, trimethanol propane, pentaerythritol, sucrose or sorbitol or polysaccarides may be used to increase branching of the polyester polyol.
  • the esters of simple alcohol and the acid may be used via an ester interchange reaction where the simple alcohols are removed continuously like the water and replaced by one or more of the glycols above.
  • polyester polyols may be produced from aromatic acids, such as terphthalic acid, phthalic acid, 1,3, 5 benzoic acid or their anhydrides, such as phthalic anhydride.
  • An exemplary polyester polyols may include Fomrez available from Witco Corporation.
  • Fomrez-53 is a 56-hydroxyl number diethylene glycol adipate manufactured by Witco Corporation.
  • a similar product is manufactured by Inolex under the brand name Lexorez 1102-56A.
  • the polyurethane may be prepared using both a high molecular weight polyol and one or more low molecular weight polyols.
  • the high molecular weight polyol may have a hydroxyl number not greater than about 60, such as a hydroxyl number of not greater than about 56.
  • the one or more low molecular weight polyols may have a hydroxyl number of at least about 800, such as at least about 900.
  • the prepolymer components may include an aliphatic polyester polyol and a low molecular weight polyol, such as 1 , 4 butane diol or ethylene glycol.
  • a high molecular weight polyol and a low molecular weight polyol may be used in a ratio of about 5:1 to about 10:1 High: Low, such as about 6.5:1 to about 9:1.
  • the catalyst blend used in the prepolymer mixture may include triethylenediamine (TEDA) and a quaternary ammonium salt catalyst.
  • the quaternary ammonium cation includes functional groups having one or more hydroxyl groups.
  • the quaternary ammonium salt may have the general formula:
  • Rl, R2, R3, or R4 may include an alkyl, a hydroxy alkyl group, an alkoxy group, hydrogen, a group including more than one hydroxyl groups, an alkylamine group, or any combination thereof.
  • one or more of Rl, R2, R3, or R4 includes a hydroxy alkyl group or a group including at least one hydroxyl group.
  • at least two, such as at least three, of Rl, R2, R3, or R4 may include a group including at least one hydroxyl group, such as a hydroxy alkyl group.
  • the anion A " may be derived from a Cl -Cl 6 carboxylic acid or dicarboxylic acid.
  • the anion A " may be a formate ion, an acetate ion, a lactate ion, or any combination thereof.
  • the anion A " may be a formate ion.
  • the quaternary ammonium salt may be the formic acid salt of methyldiethanolamine quaternary ammonium hydroxide.
  • the quaternary ammonium hydroxide may be formed from methyl diethanolamine and ethylene oxide.
  • the quaternary ammonium hydroxide may be further reacted with formic acid to form the salt.
  • such a quaternary ammonium hydroxide salt includes multiple hydroxyl groups that may react with the isocyanate as a chain extender and be bound into the polymer.
  • the quaternary ammonium hydroxide may not be available to leave the foam as an odor body or to stain vinyl or other components of the shoe. Additionally, since it is bound in the polymer, it does not emit malodorous fumes during the manufacturing process or storage of the finished article.
  • the TEDA and the quaternary ammonia (QA) component may be used in amounts in a ratio of about 1 :20 to about 50:1 TEDA:QA.
  • the ratio may be in a range of about 1 : 1 to about 30:1, such as a range of about 1 : 1 to about 25 : 1 , or a range of about 5 : 1 to about 25:1.
  • the TEDA and the quaternary ammonia salt may be included in a catalyst blend that also includes a solvent.
  • a solvent may include a chain extender.
  • the solvent may include a polyol, such as 1, 4 - butanediol or ethylene glycol.
  • the solvent is included in an amount of about 25 wt% to about 95 wt% of the catalyst blend, such as about 50 wt% to about 75 wt%.
  • the catalyst blend also may include additional catalysts, such as a metal catalyst, another amine catalyst, or a combination thereof.
  • a metal catalyst for example, may include a lithium carboxylate, an organic titanium, an organic zirconium, a bismuth carboxylate, or any combination thereof.
  • the additional amine catalyst may include a tertiary amine, such as tributylamine, N-methyl morpholine, N-ethyl morpholine, N,N,N',N'-tetramethyl ethylene diamine, pentamethyl diethylene triamine and higher homologues, l,4-diazabicyclo-[2,2 ,2]- octane, N-methyl-N'-dimethylaminoethyl piperazine, bis(dimethylaminoalkyl) piperazine, N,N-dimethyl benzylamine, N,N-dimethyl cyclohexylamine, N,N-diethyl benzylamine, bis(N,N-diethylaminoethyl) adipate, N,N,N',N'-tetramethyl- 1,3 -butane diamine, N,N-dimethyl- ⁇ -phenyl ethylamine
  • a catalyst component includes Mannich bases including secondary amines, such as dimethylamine, or aldehyde, such as formaldehyde, or ketone such as acetone, methyl ethyl ketone or cyclohexanone or phenol, such as phenol, nonyl phenol or bisphenol.
  • secondary amines such as dimethylamine, or aldehyde, such as formaldehyde, or ketone such as acetone, methyl ethyl ketone or cyclohexanone or phenol, such as phenol, nonyl phenol or bisphenol.
  • a catalyst in the form of a tertiary amine having hydrogen atoms that are active with respect to isocyanate groups may include triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyl diethanolamine, N,N-dimethyl ethanolamine, reaction products thereof with alkylene oxides such as propylene oxide or ethylene oxide, or secondary-tertiary amines, or any combination thereof.
  • Silamines with carbon-silicon bonds can also be used as catalysts, for example, 2,2,4-trimethyl-2-silamorpholine, 1,3 -diethyl aminomethyl tetramethyl disiloxane, or any combination thereof.
  • the additional amine catalyst is selected from a pentamethyl diethylene triamine, dimethylaminopropylamine, N 5 N' dimethylpiperazine and dimorpholinoethylether, N 3 N' dimethyl aminoethyl N-methyl piperazine, JEFFC AT®DM-70 (a mixture of N 5 N' dimethylpiperazine and dimorpholinoethylether), imadozoles, triazines, or any combination thereof.
  • a ratio of the amount of TEDA to the amount of the additional amine catalyst is in a range of about 10:1 to about 1 :10 TEDA: additional amine catalyst, such as a range of about 6:1 to about 2:1.
  • the catalyst blend may be useful in a range of about 0.03 wt% to about 10.0 wt% of the prepolymer mixture.
  • the catalyst blend may be used in an amount of about 0.1 wt% to about 4.0 wt% of the prepolymer mixture.
  • the prepolymer mixture also may include low molecular weight chain extenders, blowing agents, stabilizers, and other additives and auxiliary agents.
  • the prepolymer mixture may also include a low molecular weight chain extender having an average functionality of 1.8 to 2.1.
  • the low molecular weight chain extender may have an average functionality of about 2.
  • a suitable chain extender may include alkane diol, dialkylene glycol, polyalkylene polyols, or any combination thereof.
  • the prepolymer mixture may include trifunctional or tetrafunctional crosslinking agents or mixtures of chain extenders and crosslinking agents.
  • An exemplary crosslinking agent may including trihydric or tetrahydric alcohols or oligomeric polyalkylene polyols having an average functionality of 3 to 4 and a molecular weight of up to about 750 g/mol.
  • the crosslinking agent may have a molecular weight of about 18 g/mol to about 400 g/mol, such as about 60 g/mol to about 300 g/mol.
  • Alkane diols having 2 to 12, preferably 2, 4 or 6 carbon atoms such as ethanediol, 1 ,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9- nonanediol, 1,10-decanediol, or in particular, 1,4-butanediol, or dialkylene glycols having 4 to 8 carbon atoms, such as diethylene glycol and dipropylene glycol, as well as polyoxyalkylene glycols, or any combination thereof, may be used as chain extenders.
  • ethanediol 1 ,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9- nonanediol, 1,10-decanediol, or in particular, 1,4-butanediol, or dialkylene glyco
  • branched-chain or unsaturated alkane diols with no more than 12 carbon atoms such as 1 ,2-propanediol, 2 -methyl- 1,3 -propanediol, 2,2-dimethyl- 1,3 -propanediol, 2-butyl-2-ethyl- 1,3 -propanediol, 2-butene-l,4-diol or 2-butyne-l,4-diol, diesters of terephthalic acid with glycols having 2 to 4 carbon atoms, such as terephthalic acid-bis- ethylene glycol or terephthalic acid-bis- 1,4-butanediol, hydroxyalkylene ethers of hydroquinone or resorcinol, e.g., l,4-di( ⁇ -hydroxyethyl) hydroquinone or l,3-( ⁇ - hydroxy ethyl) re
  • the prepolymer mixture includes a blowing agent.
  • a blowing agent may include water, or a physical blowing agent, such as a low boiling alkane, partially or completely fluorinated hydrocarbons, or any combination thereof.
  • a suitable low boiling alkane includes acetone, pentane, hexane, cyclopentane, or any combination thereof.
  • An example of a suitable partially or completely fluorinated hydrocarbon includes HFC- 134a (1,1,1,2-tetrafluoroethane), HFC-245fa (1,1,1,3,3- pentafluoropropane), HFC-245ca (1,1, 2,2,3 -pentafluoropropane), HFC-236ca (1,1,1,2,3,3-hexafluoropropane), or any combination thereof.
  • Methylene chloride is also a suitable blowing agent.
  • the blowing agent includes water.
  • water may be used in a range of about 0.1 to about 2.0 parts per hundred parts of isocyanate reactive component.
  • the prepolymer mixture may include film stabilizers, such as silicone oils or emulsif ⁇ ers.
  • film stabilizer such as silicone oils or emulsif ⁇ ers.
  • the film stabilizer may be an organic silane or siloxane.
  • the silicone foam stabilizer may have the formula:
  • R is an alkyl group containing about 1 to about 4 carbon atoms; n is an integer of about 4 to about 8; m is an integer of about 20 to about 40; and the oxyalkylene groups are derived from propylene oxide or ethylene oxide.
  • an additive or an auxiliary agent may be selected from a cell regulator, a crosslinker, a flame retardant, a plasticizer, a filler, a pigment, or any combination thereof.
  • a polyurethane is formed by blending the components of the prepolymer mixture.
  • the polyurethane may be formed by blending a polyol component, an isocyanate component, TEDA component, and a quaternary ammonium component to form a blend.
  • the method includes curing the blend to form the polyurethane.
  • the method may further include blending a second polyol to form the blend.
  • the first polyol may have a hydroxyl number not greater than about 60, such as not greater than about 56, and the second polyol may have a hydroxyl number of at least about 800, such as at least about 900.
  • blending includes blending the catalyst components in a specific ratio.
  • the ratio of the amount of TEDA component to the amount of quaternary ammonium (QA) component may be in a range of about 1 :1 to about 30:1 TEDArQA.
  • the ratio may be about 1 : 1 to about 25: 1 , such as about 5: 1 to about 25:1.
  • the TEDA component and the quaternary ammonium component may be mixed with the polyol component to form a preblend prior to mixing the isocyanate component to form the blend. Further, the TEDA component and the quaternary ammonium component may be blended with a solvent to form a catalyst blend.
  • the catalyst blend may be used to blend with the polyol prior to blending with the isocyanate component, or concurrently with blending with the isocyanate component.
  • the method further may include filling a mold with the blend and allowing the polyurethane prepolymer mixture to at least partially cure to form the polyurethane.
  • the at least partially cured polyurethane may be removed from the mold prior to complete curing and allowed to cure to completion outside of the mold.
  • the catalyst blend has been described in the context of a prepolymer mixture configured to form a polyurethane, the catalyst blend also may be useful in reactions between isocyanate functionality and an active hydrogen containing compound.
  • the active hydrogen containing compound may include an alcohol, a polyol, an amine, water, or any combination thereof.
  • compositions disclosed above advantageously provide technical features desirable in polyurethane systems.
  • embodiments influence the cure parameters of polyurethane systems, such as cream time, gel time, rise time, tack free time, rebound pinch time, and rise height.
  • Cream time correlates with the initiation of the reaction within the prepolymer components. Cream time is determined when the mixture of prepolymer components becomes milky or forms air bubbles. Generally, it is desirable to have a moderate cream time, not too fast and not too slow, such as about 8 sec. to 10 sec.
  • the gel time is when the liquid has polymerised enough that on touching the liquid and pulling away, a thin polymer strand (or string) is seen. At this point the liquid is turning into a polymer gel.
  • the rise time is when the foamed polyurethane has reached the largest volume.
  • the rise time is the time for the foam to reach maximum height and stop rising.
  • the tack-free time is when the polyurethane foam has cured enough that it is no longer 'sticky' or 'tacky' to the touch.
  • the rebound pinch time is the time for the foam to cure enough that upon pinching, the foam rebounds to it original shape or shows little evidence of deformation caused by the pinching.
  • Rise height is the maximum height the foam rises when reacted in a controlled measuring cup.
  • the tack-free time and rebound pinch time are indicative of the back end of the reaction and the cream time and gel time are indicative of the front end of the reaction.
  • embodiments disclosed above exhibit improved back-end reaction characterstics, such as lower tack-free time and lower rebound pinch times, while exhibiting similar front end reaction characteristics, such as cream time and gel time, relative to other systems.
  • foam production involves the preparation of a pre- blend, which consists of the polyols and other ingredients, except for the isocyanate prepolymer and the catalysts.
  • the pre-blend is allowed to degas prior to foam production and is weighed into an appropriately sized mixing cup.
  • the individual amine catalysts are added in appropriate quantities into the measured amount of preblend and are mixed for 10 seconds in a paper cup, followed by the immediate addition of isocyanate with continued mixing for 5 seconds.
  • the reacting foam is immediately poured into the container.
  • the pre-blend and isocyanate prepolymer are used at 70-75 0 F
  • polyester systems the pre-blend and isocyanate are used at 105- 115°F.
  • Reactivity profiles are recorded during the reaction; the cream, top of cup, end of rise, tack-free, and rebound pinch times are recorded.
  • the rebound pinch time correlates with the demold time.
  • the mold for these experiments is 1 inch x 4 inch x 14 inch.
  • the mold temperature is 45°C and the demold time is 2 to 6 minutes.
  • Example prepolymer component blends are reacted to form polyurethane and are timed.
  • Examples 1 and 2 are comparative examples. The results are shown in Table 1.
  • addition of a small amount of JEFFCAT® TR-63 which includes diethylene glycol, quaternary ammonium formate salt formed from methyldiethanolamine and ethylene oxide, and the formate salt of methyldiethanol amine, significantly shortens the tack-free time with minimal effect on the front-end of the reaction.
  • the skin appearance is also improved with the addition of JEFFCAT® TR-63.
  • use of DABCO 1028 quarternary salt formed form triethylene diamine exhibits little change in tack free time.
  • a pre-blend of B-component is prepared as shown in Table 2.
  • the quantities listed in are parts by weight.
  • the aliphatic polyester polyol is made from adipic acid, diethylene glycol, and 1,4 butanediol. It is sold under the name of Daltorez P 716.
  • Dabco DC- 193 is a silicone surfactant manufactured by Dow Corning. Table 2 gives the preblended B-component for the examples. Table 2
  • Examples 6 and 7 are comparative examples. As illustrated in Table 3, using JEFF CAT® TR-63 improves the back end of the reaction. In this example, the front also is slowed using the catalyst blend of example 7.
  • Example 8 is a comparative example. As illustrated in Table 4, the use of JEFF CAT® TR-63 significantly improves the back-end of the reaction without affecting the cream time (front-end reactivity). The amount of TEDA catalyst used in Example 9 is reduced from 33% to 25% relative to example 8. Table 4

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

L'invention concerne un mélange de catalyseur qui comprend une triéthylènediamine et un sel d'ammonium quaternaire.
PCT/US2008/062219 2007-05-07 2008-05-01 Mélange de catalyseur d'amine utile dans la production d'articles de poly(uréthane) WO2008137546A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103333312A (zh) * 2013-06-08 2013-10-02 浙江大学 具有溶胶-凝胶转变特性的温敏型抗菌嵌段聚合物及其制备方法
CN111548475A (zh) * 2020-04-15 2020-08-18 上海抚佳精细化工有限公司 一种慢回弹记忆棉及其制备方法
WO2021067035A1 (fr) * 2019-10-02 2021-04-08 Huntsman Petrochemical Llc Mélange de résine de polyol destiné à être utilisé dans la production de composants de polyol stables

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US4785025A (en) * 1984-11-13 1988-11-15 Air Products And Chemicals, Inc. Quaternary triethylenediamine compositions and their combination with tertiary amines for delayed action/enhanced curing catalysts in polyurethane systems
US5690855A (en) * 1994-01-11 1997-11-25 Sealed Air Corporation Polyol blend, cellular polyurethane foam product made therefrom, and halogenated hydrocarbon-free process therefor

Patent Citations (3)

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US4785025A (en) * 1984-11-13 1988-11-15 Air Products And Chemicals, Inc. Quaternary triethylenediamine compositions and their combination with tertiary amines for delayed action/enhanced curing catalysts in polyurethane systems
US4904629A (en) * 1984-11-13 1990-02-27 Air Products And Chemicals, Inc. Quaternary triethylenediamine compositions and their combination with tertiary amines for delayed action/enhanced curing catalysts in polyurethane systems
US5690855A (en) * 1994-01-11 1997-11-25 Sealed Air Corporation Polyol blend, cellular polyurethane foam product made therefrom, and halogenated hydrocarbon-free process therefor

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103333312A (zh) * 2013-06-08 2013-10-02 浙江大学 具有溶胶-凝胶转变特性的温敏型抗菌嵌段聚合物及其制备方法
WO2021067035A1 (fr) * 2019-10-02 2021-04-08 Huntsman Petrochemical Llc Mélange de résine de polyol destiné à être utilisé dans la production de composants de polyol stables
CN111548475A (zh) * 2020-04-15 2020-08-18 上海抚佳精细化工有限公司 一种慢回弹记忆棉及其制备方法

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