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Elastomeric polyurethanes with improved properties based on crystallizable polyols in combination with low monol polyoxpropylene polyols

Assignee: Lyondell Chemical Technology LP
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Filing: 1995-12-22
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Granted: 1997-07-15
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Expires: 2015-12-22
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Abstract

Abstract Polyurethane elastomers of improved elongation, tensile strength and other physical properties are prepared from a polyol component containing a crystallizable polyol and from 5 to 35 equivalent percent of a low monol polyoxypropylene polyol by one-shot, quasiprepolymer, and preferably, by prepolymer techniques involving chain extension with an aliphatic diol or aromatic amine.

Inventors

  • 👤 Stephen D. Seneker
  • 👤 Nigel Barksby
  • 👤 Bruce D. Lawrey

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-29 04:30
CPC Classifications
C; C08; C08G; C08G18/00; C08G18/06; C08G18/28; C08G18/40; C08G18/48; C08G18/4866; C08G18/08; C08G18/10; C08G18/4009; C08G18/4018; C08G18/4804; C08G18/4808; C08G2250/00

Claims Analysis

Total Claims: 49
Claim 1
Independent Claim 156 words
A polyurethane elastomer comprising the reaction product of a chain extender with an isocyanate-terminated prepolymer prepared by reacting a stoichiometric excess of one or more di- or polyisocyanates with a polyol component comprising from 65 to about 95 equivalent percent based on the weight of the polyol component of a crystallizable polyol having a number average equivalent weight of between about 500 Da and 6000 Da and from about 5 to about 35 equivalent percent based on the weight of the polyol component of a low monol polyoxyalkylene diol containing in excess of 70 weight percent oxypropylene moieties, a number average equivalent weight of from about 1000 Da to about 6000 Da, and a level of unsaturation of less than about 0.02 meq/g, said prepolymer having an NCO group content of from about 3 to less than 14 weight percent based on the weight of the prepolymer, at an isocyanate index between about 70 and 130.
Claim 2
Dependent Claim 156 words
A polyurethane elastomer comprising the reaction product of a chain extender with an isocyanate-terminated prepolymer prepared by reacting a stoichiometric excess of one or more di- or polyisocyanates with a polyol component comprising from 65 to about 95 equivalent percent based on the weight of the polyol component of a crystallizable polyol having a number average equivalent weight of between about 500 Da and 6000 Da and from about 5 to about 35 equivalent percent based on the weight of the polyol component of a low monol polyoxyalkylene diol containing in excess of 70 weight percent oxypropylene moieties, a number average equivalent weight of from about 1000 Da to about 6000 Da, and a level of unsaturation of less than about 0.02 meq/g, said prepolymer having an NCO group content of from about 3 to less than 14 weight percent based on the weight of the prepolymer, at an isocyanate index between about 70 and 130.
Claim 3
Dependent Claim 24 words
The elastomer of claim 1 wherein said crystallizable polyol comprises a polyoxyethylene glycol, a polytetramethylene ether glycol or a polyester diol, or mixtures thereof.
Claim 4
Dependent Claim 27 words
The elastomer of claim 1 wherein said crystallizable polyol comprises a polytetramethylene ether glycol having an equivalent weight of from about 800 Da to about 2000 Da.
Claim 5
Dependent Claim 13 words
The elastomer of claim 2 wherein said polyester diol is a polycaprolactone diol.
Claim 6
Dependent Claim 19 words
The elastomer of claim 2 wherein said low monol polyoxypropylene diol has an unsaturation of less than 0.010 meq/g.
Claim 7
Dependent Claim 76 words
The elastomer of claim 1 wherein said crystallizable polyol comprises a polytetramethylene ether glycol having an equivalent weight of from about 800 Da to about 2000 Da, and wherein said low monol polyoxypropylene polyol comprises in major part one or more polyoxypropylene diols containing no more than about 20 weight percent oxyethylene moieties and having an equivalent weight of from about 1250 Da to about 4000 Da, and an unsaturation of about 0.010 meq/g or less.
Claim 8
Dependent Claim 37 words
The elastomer of claim 6 wherein said low monol polyoxypropylene polyol further comprises a polyoxypropylene diol having an unsaturation greater than 0.02 meq/g, such that the average unsaturation of said polyol component is less than 0.02 meq/g.
Claim 9
Dependent Claim 24 words
The elastomer of claim 1 wherein said crystallizable polyol comprises a polytetramethylene ether glycol and said elastomer has an elongation greater than about 800%.
Claim 10
Dependent Claim 25 words
The elastomer of claim 1 wherein said low monol polyoxypropylene diol comprises about 5 equivalent percent to about 25 equivalent percent of said polyol component.
Claim 11
Dependent Claim 75 words
The elastomer of claim 9 wherein said crystallizable polyol comprises a polytetramethylene ether glycol having an equivalent weight of from about 800 Da to about 2000 Da, and wherein said low monol polyoxypropylene polyol comprises in major part one or more polyoxypropylene diols containing no more than about 20 weight percent oxyethylene moieties having an equivalent weight of from about 1250 Da to about 4000 Da, and an unsaturation of about 0.010 meq/g or less.
Claim 12
Dependent Claim 14 words
The elastomer of claim 1 wherein said chain extender comprises a diol chain extender.
Claim 13
Dependent Claim 15 words
The elastomer of claim 1 wherein said chain extender comprises an aromatic diamine chain extender.
Claim 14
Dependent Claim 13 words
The elastomer of claim 12 wherein said aromatic diamine chain extender comprises 4,4'-methylenebis(3-chloro-2,6-diethylaniline).
Claim 15
Dependent Claim 40 words
The elastomer of claim 1 wherein said reacting takes place in the present of an amount of a blowing agent effective to produce a microcellular elastomer having a density of from about 0.15 g/cm 3 to 0.8 g/cm 3 .
Claim 16
Dependent Claim 152 words
An isocyanate-terminated prepolymer or quasiprepolymer suitable for the preparation of polyurethane elastomers, said prepolymer of quasiprepolymer comprising the reaction product of a stoichiometric excess of one or more di- or polyisocyanates with a polyol component comprising from 25 to about 95 equivalent percent based on the weight of the polyol component of a crystallizable polyol having a number average equivalent weight of between about 500 Da and 6000 Da and from about 5 to about 35 equivalent percent based on the weight of the polyol component of a low monol polyoxyalkylene diol containing in excess of 70 weight percent oxypropylene moieties, having a number average equivalent weight of from about 1000 Da to about 6000 De, and a level of unsaturation of less than about 0.02 meq/g, said prepolymer having an NCO group content of from about 3 to about 20 weight percent based on the weight of the prepolymer or quasiprepolymer.
Claim 17
Dependent Claim 152 words
An isocyanate-terminated prepolymer or quasiprepolymer suitable for the preparation of polyurethane elastomers, said prepolymer of quasiprepolymer comprising the reaction product of a stoichiometric excess of one or more di- or polyisocyanates with a polyol component comprising from 25 to about 95 equivalent percent based on the weight of the polyol component of a crystallizable polyol having a number average equivalent weight of between about 500 Da and 6000 Da and from about 5 to about 35 equivalent percent based on the weight of the polyol component of a low monol polyoxyalkylene diol containing in excess of 70 weight percent oxypropylene moieties, having a number average equivalent weight of from about 1000 Da to about 6000 De, and a level of unsaturation of less than about 0.02 meq/g, said prepolymer having an NCO group content of from about 3 to about 20 weight percent based on the weight of the prepolymer or quasiprepolymer.
Claim 18
Dependent Claim 26 words
The isocyanate-terminated prepolymer or quasiprepolymer of claim 15 wherein said crystallizable polyol comprises a polyoxyethylene glycol, a polytetramethylene ether glycol, a polyester diol, or mixtures thereof.
Claim 19
Dependent Claim 30 words
The isocyanate-terminated prepolymer or quasiprepolymer of claim 15 wherein said crystallizable polyol comprises a polytetramethylene ether glycol having an equivalent weight of from about 800 Da to about 2000 Da.
Claim 20
Dependent Claim 16 words
The isocyanate-terminated prepolymer or quasiprepolymer of claim 16 wherein said polyester diol is a polycaprolactone diol.
Claim 21
Dependent Claim 22 words
The isocyanate-terminated prepolymer or quasiprepolymer of claim 15 wherein said low monol polyoxypropylene diol has an unsaturation of less than 0.010 meq/g.
Claim 22
Dependent Claim 78 words
The isocyanate-terminated prepolymer or quasiprepolymer of claim 15 wherein said crystallizable polyol comprises a polytetramethylene ether glycol having an equivalent weight of from about 800 Da to about 2000 Da, and wherein said low monol polyoxypropylene polyol comprises in major part one or more polyoxypropylene diols containing no more than about 20 weight percent oxyethylene moieties, having an equivalent weight of from about 1250 Da to about 4000 Da, and an unsaturation of about 0.010 meq/g or less.
Claim 23
Dependent Claim 40 words
The isocyanate-terminated prepolymer or quasiprepolymer of claim 20 wherein said low monol polyoxypropylene polyol further comprises a polyoxypropylene diol having an unsaturation greater than 0.02 meq/g, such that the average unsaturation of said polyol component is less than 0.02 meq/g.
Claim 24
Dependent Claim 27 words
The isocyanate-terminated prepolymer or quasiprepolymer of claim 20 wherein said crystallizable polyol comprises a polytetramethylene ether glycol and said elastomer has an elongation greater than about 800%.
Claim 25
Dependent Claim 28 words
The isocyanate-terminated prepolymer or quasiprepolymer of claim 20 wherein said low monol polyoxypropylene diol comprises about 5 equivalent percent to about 25 equivalent percent of said polyol component.
Claim 26
Dependent Claim 76 words
The isocyanate-terminated prepolymer of claim 20 wherein said crystallizable polyol comprises a polytetramethylene ether glycol having an equivalent weight of from about 800 Da to about 2000 Da, and wherein said low monol polyoxypropylene polyol comprises in major part one or more polyoxypropylene diols containing no more than about 20 weight percent oxyethylene moieties having an equivalent weight of from about 1250 Da to about 4000 Da, and an unsaturation of about 0.010 meq/g or less.
Claim 27
Independent Claim 65 words
A method of increasing the physical properties of a chain-extended polyurethane elastomer prepared by the reaction of an isocyanate with a polyol component comprising a crystallizable polyol, said method comprising: adding to said polyol component, from 5 equivalent percent to about 35 equivalent percent based on the weight of said polyol component of a polyoxypropylene polyol having an unsaturation of less than about 0.02 meq/g.
Claim 28
Independent Claim 65 words
A method of increasing the physical properties of a chain-extended polyurethane elastomer prepared by the reaction of an isocyanate with a polyol component comprising a crystallizable polyol, said method comprising: adding to said polyol component, from 5 equivalent percent to about 35 equivalent percent based on the weight of said polyol component of a polyoxypropylene polyol having an unsaturation of less than about 0.02 meq/g.
Claim 29
Dependent Claim 11 words
The method of claim 25 wherein said crystallizable polyol comprises PTMEG.
Claim 30
Dependent Claim 30 words
The method of claim 26 wherein said PTMEG has an equivalent weight of from about 800 Da to 2000 Da, and wherein said unsaturation is less than about 0.010 meq/g.
Claim 31
Dependent Claim 158 words
A polyurethane elastomer comprising the reaction product of a chain extender and polyoxyalkylene polyol with an isocyanate-terminated quasiprepolymer prepared by reacting a stoichiometric excess of one or more di- or polyisocyanates with a polyol component comprising from 65 to about 95 equivalent percent based on the weight of the polyol component of a crystallizable polyol having a number average equivalent weight of between about 500 Da and 6000 Da and from about 5 to about 35 equivalent percent based on the weight of the polyol component of a low monol polyoxyalkylene diol containing in excess of 70 weight percent oxypropylene moieties, a number average equivalent weight of from about 1000 Da to about 6000 Da, and a level of unsaturation of less than about 0.02 meq/g, said quasiprepolymer having an NCO group content of from about 14 to about 20 weight percent based on the weight of the quasiprepolymer, at an isocyanate index between about 70 and 130.
Claim 32
Dependent Claim 158 words
A polyurethane elastomer comprising the reaction product of a chain extender and polyoxyalkylene polyol with an isocyanate-terminated quasiprepolymer prepared by reacting a stoichiometric excess of one or more di- or polyisocyanates with a polyol component comprising from 65 to about 95 equivalent percent based on the weight of the polyol component of a crystallizable polyol having a number average equivalent weight of between about 500 Da and 6000 Da and from about 5 to about 35 equivalent percent based on the weight of the polyol component of a low monol polyoxyalkylene diol containing in excess of 70 weight percent oxypropylene moieties, a number average equivalent weight of from about 1000 Da to about 6000 Da, and a level of unsaturation of less than about 0.02 meq/g, said quasiprepolymer having an NCO group content of from about 14 to about 20 weight percent based on the weight of the quasiprepolymer, at an isocyanate index between about 70 and 130.
Claim 33
Dependent Claim 79 words
The elastomer of claim 26 wherein said polyoxyalkylene polyol is a mixture comprising a crystallizable polyol having a number average equivalent weight of from about 500 Da to 6000 Da and from about 5 to about 35 equivalent percent of a low monol polyoxyalkylene diol containing in excess of 70 weight percent oxypropylene moieties, a number average equivalent weight of from about 1000 Da to about 6000 Da, and a level of unsaturation of less than about 0.02 meq/g.
Claim 34
Dependent Claim 14 words
The elastomer of claim 28 wherein said crystallizable polyol is a polytetramethylene ether glycol.
Claim 35
Dependent Claim 29 words
The elastomer of claim 30 wherein said chain extender is selected from the group consisting of aliphatic diols having molecular weights below 300 Da, aromatic diamines, and mixtures thereof.
Claim 36
Dependent Claim 11 words
The elastomer of claim 31 wherein said aromatic diamine comprises 4,4'-methylenebis(3-chloro-2,6-diethylaniline).
Claim 37
Dependent Claim 42 words
The elastomer of claim 28 wherein said reaction product is prepared in the presence of an amount of a blowing agent effective to provide a microcellular elastomer having a density of from about 0.015 g/cm 3 to about 0.8 g/cm 3 .
Claim 38
Dependent Claim 126 words
A one-shot polyurethane elastomer prepared by reacting one or more di- or polyisocyanates, with an isocyanate-reactive component comprising in substantial part by weight a polyol component comprising from 65 to about 95 equivalent percent based on the weight of the polyol component of a crystallizable polyol having a number average equivalent weight of between about 500 Da and 6000 Da and from about 5 to about 35 equivalent percent based on the weight of the polyol component of a low monol polyoxyalkylene diol containing in excess of 70 weight percent oxypropylene moieties, a number average equivalent weight of from about 1000 Da to about 6000 Da, and a level of unsaturation of less than about 0.02 meq/g, at an isocyanate index between about 70 and 130.
Claim 39
Dependent Claim 126 words
A one-shot polyurethane elastomer prepared by reacting one or more di- or polyisocyanates, with an isocyanate-reactive component comprising in substantial part by weight a polyol component comprising from 65 to about 95 equivalent percent based on the weight of the polyol component of a crystallizable polyol having a number average equivalent weight of between about 500 Da and 6000 Da and from about 5 to about 35 equivalent percent based on the weight of the polyol component of a low monol polyoxyalkylene diol containing in excess of 70 weight percent oxypropylene moieties, a number average equivalent weight of from about 1000 Da to about 6000 Da, and a level of unsaturation of less than about 0.02 meq/g, at an isocyanate index between about 70 and 130.
Claim 40
Dependent Claim 22 words
The elastomer of claim 34 wherein at least a portion of said low monol polyoxyalkylene diol comprises an oxyethylene capped polyoxyalkylene diol.
Claim 41
Dependent Claim 25 words
The elastomer of claim 35 wherein said oxyethylene capped polyoxyalkylene diol has a primary hydroxyl content of between 35 mol percent and 90 mol percent.
Claim 42
Dependent Claim 25 words
The elastomer of claim 35 wherein said oxyethylene capped polyoxyalkylene diol has a primary hydroxyl content of between 70 mol percent and 90 mol percent.
Claim 43
Dependent Claim 13 words
The elastomer of claim 34 wherein said crystallizable polyol comprises polytetramethylene ether glycol.
Claim 44
Dependent Claim 35 words
The elastomer of claim 34 wherein said isocyanate reactive component further comprises a chain extender selected from the group consisting of aliphatic diols having molecular weights lower than 300 Da, aromatic diamines, and mixtures thereof.
Claim 45
Dependent Claim 41 words
The elastomer of claim 34 wherein said elastomer is prepared in the presence of an amount of a blowing agent effective to produce a microcellular elastomer having a density of from about 0.15 g/cm 3 to about 0.8 g/cm 3 .
Claim 46
Dependent Claim 171 words
A polyurethane elastomer comprising the reaction product of a B-side comprising a chain extender and a crystallizable polyol having a number average molecular weight of between 500 Da and 6000 Da with an A-side comprising an isocyanate-terminated quasiprepolymer having a NCO group content of from about 14 to about 20 weight percent based on the weight of the quasiprepolymer, said quasiprepolymer prepared by the reaction of a stoichiometric excess of one or more di- or polyisocyanates with a low monol polyoxyalkylene diol containing in excess of 70 mol percent oxypropylene moieties, a number average equivalent weight of from about 1000 Da to 6000 Da and a level of unsaturation of less than about 0.02 meq/g and optionally an amount of said crystallizable polyol, wherein said elastomer contains from about 5 to about 35 equivalent percent low monol polyoxyalkylene diol-derived moieties and from about 65 to about 95 equivalent percent crystallizable polyol-derived moieties, said equivalent percents relative to the sum of said low monol polyoxyalkylene diol-derived moieties and said crystallizable polyol-derived moieties.
Claim 47
Dependent Claim 171 words
A polyurethane elastomer comprising the reaction product of a B-side comprising a chain extender and a crystallizable polyol having a number average molecular weight of between 500 Da and 6000 Da with an A-side comprising an isocyanate-terminated quasiprepolymer having a NCO group content of from about 14 to about 20 weight percent based on the weight of the quasiprepolymer, said quasiprepolymer prepared by the reaction of a stoichiometric excess of one or more di- or polyisocyanates with a low monol polyoxyalkylene diol containing in excess of 70 mol percent oxypropylene moieties, a number average equivalent weight of from about 1000 Da to 6000 Da and a level of unsaturation of less than about 0.02 meq/g and optionally an amount of said crystallizable polyol, wherein said elastomer contains from about 5 to about 35 equivalent percent low monol polyoxyalkylene diol-derived moieties and from about 65 to about 95 equivalent percent crystallizable polyol-derived moieties, said equivalent percents relative to the sum of said low monol polyoxyalkylene diol-derived moieties and said crystallizable polyol-derived moieties.
Claim 48
Dependent Claim 13 words
The elastomer of claim 41 wherein said crystallizable polyol comprises polytetramethylene ether glycol.
Claim 49
Dependent Claim 16 words
The elastomer of claim 41 wherein all of said crystallizable polyol is contained in said B-side.

References Cited (Backward Citations)

US3980606A Cited
US5026815A Cited
US5185420A Cited
US5470813A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 2000-07-14 2001-01-13 2001-07-15 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 2004-07-14 2005-01-13 2005-07-15 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 2008-07-14 2009-01-13 2009-07-15 $7700.00 Window Closed / Lapsed

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