WO2006032034A2 - Polymere polyurethanne-polyuree - Google Patents

Polymere polyurethanne-polyuree Download PDF

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Publication number
WO2006032034A2
WO2006032034A2 PCT/US2005/033209 US2005033209W WO2006032034A2 WO 2006032034 A2 WO2006032034 A2 WO 2006032034A2 US 2005033209 W US2005033209 W US 2005033209W WO 2006032034 A2 WO2006032034 A2 WO 2006032034A2
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WIPO (PCT)
Prior art keywords
component
reactive component
isocyanate
polymer
polyisocyanate
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PCT/US2005/033209
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English (en)
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WO2006032034A3 (fr
Inventor
Michael Cork
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Specialty Products, Inc.
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Publication date
Priority claimed from US10/980,217 external-priority patent/US7655309B2/en
Priority claimed from US10/980,456 external-priority patent/US20060058492A1/en
Application filed by Specialty Products, Inc. filed Critical Specialty Products, Inc.
Publication of WO2006032034A2 publication Critical patent/WO2006032034A2/fr
Publication of WO2006032034A3 publication Critical patent/WO2006032034A3/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
    • C08G18/08—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
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • 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
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6453—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having sulfur
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/725—Combination of polyisocyanates of C08G18/78 with other polyisocyanates
    • 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
    • C08G2150/00—Compositions for coatings
    • C08G2150/50—Compositions for coatings applied by spraying at least two streams of reaction components

Definitions

  • This invention relates, in general, to polyurethane-polyurea polymers and, in particular, to a polyisocyanate prepolymer component that reacts with an isocyanate-reactive component to synthesize a polyurethane-polyurea polymer.
  • Polyurethanes and related polyureas are used in a wide variety of applications, including fibers (particularly the elastic type), adhesives, coatings, elastomers, and flexible and rigid foams.
  • a number of methods have been employed to prepare polyurethanes and polyureas.
  • polyurethane-polyurea polymers are typically synthesized by the condensation reaction of a polyisocyanate, such as diphenylmethane diisocyanate, and a resin that includes a hydroxyl-containing material. Resins may also include linear polyesters, polyethers containing hydroxyl groups, amine-substituted aromatics, and aliphatic amines.
  • the resulting polyurethane-polyurea polymer provides resistance to abrasion, weathering, and organic solvents and may be utilized in a variety of industrial applications as a sealant, caulking agent, or lining, for example.
  • the existing polyurethane-polyurea polymers are not necessarily successful in aggressive environments.
  • the existing polyurethane-polyurea polymers exhibit insufficient chemical and/or permeability resistance when placed into prolonged contact with organic reagents such as fuels and organic solvents. Accordingly, further improvements are warranted in the preparation of polyurethane-polyurea polymers.
  • a polyisocyanate prepolymer component that reacts with an isocyanate- reactive component in the preparation of a polyurethane-polyurea polymer.
  • the polyisocyanate prepolymer component includes mercaptan functional moieties.
  • the isocyanate-reactive component or both the polyisocyanate prepolymer and isocyanate-reactive components include mercaptan functional moieties.
  • the polyurethane-polyurea polymer may be formulated as an A-side, which may be referred to as a polyisocyanate prepolymer or polyisocyanate prepol component, and a B-side, which may be referred to as a resin or isocyanate-reactive component.
  • the polyurethane- polyurea polymer is synthesized using a high-pressure impingement mixing technique wherein a metered amount of the polyisocyanate prepolymer component and a metered amount of the isocyanate-reactive component are sprayed or impinged into each other in the mix head of a high-pressure impingement mixing machine using pressures between 2,000 psi and 3,000 psi and temperatures in the range of about 145°F to about 19O 0 F (about 63 0 C to about 88 0 C).
  • the mixed formulation immediately exits the mix head into a mold to form a cast polyurethane- polyurea elastomer or as a spray to form a polyurethane-polyurea polymer coating on a substrate.
  • the polyisocyanate component and the isocyanate- reactive component may be mixed in ratios other than 1 :1.
  • the mixing ratios between the polyisocyanate component and the isocyanate-reactive component may range from 1 :10 to 10:1.
  • various types of plural component spray equipment may be employed in the preparation of the polyurethane-polyurea polymer.
  • the overall synthesis of the polyurethane-polyurea polymer is very fast and the pot lives of successful formulations and tack free time are short compared to coating formulations that are applied as powders and then heated to melt the powders into coatings.
  • the polyisocyanate prepolymer component has an NCO group content of about 3% to about 50% and an average functionality of about 2 to about 3.
  • the polyisocyanate prepolymer component has an NCO group content of about 13% to about 24%.
  • the polyisocyanate component may be either a liquid polyisocyanate or a polyisocyanate prepolymer.
  • the polyisocyanate prepolymer comprises the reaction product of a ⁇ poiyii(!eyWate : » ⁇ ilM' ⁇ iyybtive component.
  • the polyisocyanate and the reactive component are agitated in the presence of an amine catalyst or organometallic catalyst.
  • Suitable polyisocyanates which are compounds with two or more isocyanate groups in the molecule, include polyisocyanates having aliphatic, cycloaliphatic, or aromatic molecular backbones.
  • suitable aliphatic polyisocyanates include aralkyl diisocyanates, such as the tetramethylxylyl diisocyanates, and polymethylene isocyanates, such as 1,4- tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, hexamethylene diisocyanates (HDIs or HMDIs), 1,6-HDI, 1 ,7-heptamethylene diisocyanate, 2,2,4-and 2,4,4- trimethylhexamethylene diisocyanate, 1,10-decamethylene diisocyanate and 2-methyl-l,5- pentamethylene diisocyanate.
  • HDIs or HMDIs hexamethylene diisocyanates
  • Suitable aliphatic polyisocyanates include 3- isocyanatomethyl-3,5,5-trimethylcyclohexl isocyanate, bis(4-isocyanatocyclohexyl)methane, S ⁇ S-trimethyl-S-isocyanato-methyl-cyclohexyl isocyanate, which is isophorone diisocyanate (IPDI), 1 ,4-cyclohexane diisocyanate, m-tetramethylxylene diisocyanate, 4,4'- dicyclohexlmethane diisocyanate, and hydrogenated materials such as cyclohexylene diisocyanate and 4,4'-methylenedicyclohexyl diisocyanate (H12MDI).
  • Suitable aliphatic isocyanates also include ethylene diisocyanate and 1,12-dodecane diisocyanate.
  • Cycloaliphatic isocyanates that are suitable include cyclohexane-l,4-diisocyanate, cyclobutane-1 ,3-diisocyanate, cyclohexane-1 ,3-diisocyanate, 1 -isocyanato-2-isocyanatomethyl cyclopentane, l-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane, 2,4'- dicyclohexylmethane diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate.
  • Aromatic polyisocyanates that are suitable include phenylene diisocyanate, toluene diisocyanate (TDI), xylene diisocyanate, 1,5 -naphthalene diisocyanate, chlorophenylene 2,4- diisocyanate, bitoluene diisocyanate, dianisidine diisocyanate, tolidine diisocyanate, and alkylated benzene diisocyanates generally.
  • TDI toluene diisocyanate
  • xylene diisocyanate 1,5 -naphthalene diisocyanate
  • chlorophenylene 2,4- diisocyanate chlorophenylene 2,4- diisocyanate
  • bitoluene diisocyanate dianisidine diisocyanate
  • tolidine diisocyanate tolidine diisocyanate
  • alkylated benzene diisocyanates generally.
  • Methylene-interrupted aromatic diisocyanates such as diphenylmethane diisocyanate (MDI), especially the 4,4'-isomer including alkylated analogs such as 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate and polymeric methylenediphenyl diisocyanate are also suitable.
  • MDI diphenylmethane diisocyanate
  • 4,4'-isomer including alkylated analogs such as 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate and polymeric methylenediphenyl diisocyanate are also suitable.
  • Suitable aromatic diisocyanates which may also be used include 3,3'-dimethoxy-4,4'-bisphenylenediisocyanate, 3,3'-diphenyl-4,4'-biphenylenediisocyanate, 4,4'- biphenylene diisocyanate, 4-chloro-l ,3-phenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, and 1,5-naphthalene diisocyanate.
  • polyisocyanate component includes MDI.
  • polyisocyanate or polyisocyanates influences the flexibility of the polyurethane-polyurea polymer.
  • flexibility can be increased with minimum impact to chemical resistance by selecting a polyisocyanate that includes a blend of TDI, caprolactone, and MDI wherein the greater the amounts of TDI and caprolactone, the greater the flexibility.
  • Desmodur ® W aliphatic diisocyanate from Bayer Corporation may be utilized to increase the flexibility of the polyurethane- polyurea polymer.
  • the reactive component includes from about 20% to about 100% by weight, based on 100% by weight of the reactive component, of at least one organic compound having a mercaptan functional moiety.
  • the reactive component may include polyols, glycols, amine-substituted aromatics, and aliphatic amines, for example.
  • an excess of polyisocarnae is reacted with the reactive component such that the polyisocyanate prepolymer includes reactive NCO groups for the reaction with the isocyanate-reactive component.
  • a polyisocyanate prepolymer component including mercaptan functional moieties in the synthesis of a polyurethane-polyurea polymer results in a polymer having excellent tensile properties and tear strength properties, substantially no volatile organic compounds (VOCs), abrasion and weathering resistance, and electrical resistance. Additionally, the incorporation of the sulfur into the synthesized polyurethane-polyurea polymer imparts improved chemical resistance and/or reduced permeability.
  • the polyurethane-polyurea polymer has a mercaptan content of about 0.5% to about 5.0%. In another implementation, the polyurethane-polyurea polymer has a mercaptan content of about 1.2% to about 2.4%.
  • the organic compound having a mercaptan functional moiety is preferably a polysulfide.
  • the polysulfide is a thiol having the following general formula:
  • the polysulfide will include two or more sulfur atoms and contain reactive mercaptan end-groups according to the following general formula: HS-R'(SS-R") n -SH
  • Suitable polysulfides include aliphatic polysulfides (ALIPS) and polymercaptans.
  • ALIPS aliphatic polysulfides
  • the formation of ALIPS occurs by way of an equilibrating polycondensation reaction from bifunctional organic compounds such as dihalogen alkanes or dihalogen ether and alkali metal polysulfide solution.
  • Suitable ALIPS include THIOPLASTTM polysulfides manufactured by Akzo Nobel Inc. (Chicago, IL) and THIOKOL ® polysulfides manufactured by Toray Industries, Inc. (Tokyo, Japan).
  • THIOPLASTTM polysulfides which are the most preferable polysulfides, result from the polycondensation of bis-(2-chloroethyl-)formal with alkali polysulfide. This reaction generates long-chain macromolecules which are cut to the required chain length by reductive splitting with sodium dithionite.
  • the disulfide groups are at the same converted into reactive thiol terminal groups.
  • a trifunctional component e.g., 1 ,2,3-trichloropropane
  • Tables I-III provide a survey of the chemical properties of suitable THIOPLASTTM polysulfides.
  • THIOKOL ® polysulfides are also suitable ALIPS.
  • Tables IV-VI provide a survey of the chemical properties of suitable THIOKOL ® polysulfides.
  • polymercaptans are also suitable polysulfides.
  • Polymercaptans are formed from aliphatic, cyclo-aliphatic, or aromatic molecular segments, which can also contain individual sulfur atoms, e.g., in the form of thioether or similar compounds, but which have no disulfide bridges and which have reactive mercaptan groups according to the general formula:
  • the polymercaptans may include hydroxyl end-groups, -griuj ⁇ sfMII ⁇ lysilyl end-groups, or alkyl end-groups, for example.
  • suitable polymercaptans may include hydroxyl end-groups, -griuj ⁇ sfMII ⁇ lysilyl end-groups, or alkyl end-groups, for example.
  • BAYTHIOL ® is a mercaptan-terminated polyurethane from Bayer AG (Leverkusen, Germany).
  • HYCAR ® MTA is a mercaptan-terminated acrylate-polymerisate from B. F. Goodrich
  • HYCAR ® MTB is a mercaptan-terminated butadiene-polymerisate from B. F. Goodrich Chemical Corporation (Cleveland, OH).
  • HYCAR ® MTBN (1300 x 10) is a mercaptan-terminated butadiene-acrylnitrile-co- polymerisate from B. F. Goodrich Chemical Corporation (Cleveland, OH).
  • PERMAPOL ® P-2 is a mercaptan-terminated liquid polymer from Product Research Corporation (Glendale, CA).
  • PERMAPOL ® P-3 is a mercaptan-terminated liquid polymer from Product Research Corporation (Glendale, CA).
  • PERMAPOL ® P-5 is a chemically-modified ALIPS from Product Research Corporation
  • PM ® polymer is a mercaptan-terminated liquid polymer from Philips Chemical Corporation (Bartlesville, OK).
  • the reactive component may include from about 0% to about 80%, based upon 100% by weight of the reactive component, of other organic compounds such as polyols, glycols, amine-substituted aromatics, and aliphatic amines, for example.
  • Suitable polyols for use in the reactive component consist essentially of polyether or polyester polyols of nominal functionality 2 to 3 that have molecular weights (number averaged) of from 100 g/mol to 8000 g/mol.
  • Suitable polyether or polyester diols which can be utilized in the reactive component include those which are prepared by reacting alkylene oxides, halogen-substituted or aromatic-substituted alkylene oxides or mixtures thereof with an active hydrogen-containing initiator compound.
  • Suitable oxides include, for example, ethylene oxide, propylene oxide, 1 ,2- butylene oxide, styrene oxide, epichlorohydrin, epibromohydrin, and mixtures thereof.
  • the reactive component includes relatively low molecular weight species containing two active hydrogen atoms, ethylene glycol, propylene glycol, 1 ,4-butandiol, butenediol, butynediol, hexanediol, bisphenols, diethylene glycol, dipropylene glycol, tripropylene glycol, triethylene glycol, mixtures of these, and like difunctional active hydrogen species.
  • U ⁇ i aromatic diols such as hydroquinone di(beta-hydroxyethyl) ether, or hydrazines, such as hydroxyethylhydrazine (HEH) are utilized in the prepolymer synthesis.
  • hydrazine such as hydrazides (e.g., adipic dihydrazide (ADH)), hydrazones, or triazoles may also be utilized.
  • the reactive component may include aliphatic amines and amine- substituted aromatics.
  • suitable compounds include diethylthtoluenediamine, diaminodiphenylmethane, polyoxypropylenediamine, secondary aliphatic diamines, cycloaliphatic diamines, and mixtures and reaction products thereof.
  • Suitable secondary aliphatic diamines include polyaspartic ester compounds such as the Desmophen ® polyaspartic esters from Bayer AG (Leverkusen, Germany).
  • Sulfur diamines such as di-(methylthio)toluenediamine are suitable as well. Diethyltoluenediamine, diaminodiphenylmethane, and di-(methylthio)toluenediamine are preferred intermediate resin components.
  • a caprolactone such as a tri-functional polycaprolactone, is utilized as the reactive component in preparing the polyurethane-polyurea prepolymer formulations. More preferably, a blend of tri-functional compounds are utilized as the reactive component.
  • the reactive component may include additives such as non-primary components, fillers, anti-aging agents, or coloring agents, for example.
  • a catalyst such as an amine catalyst or organometallic catalyst may be utilized. The selection of catalysts can influence the shelf life of the final product. In implementations where a long shelf life is desirable, an organometallic catalyst or heat (approximately 140°F) is preferable to an amine catalyst.
  • the isocyanate-reactive component includes chain extenders and initiators that react with the NCO groups in the polyisocyanate prepolymer component to synthesize the polyurethane-polyurea polymer.
  • the isocyanate-reactive component may include organic compounds such as polyols, glycols, amine-substituted aromatics, and aliphatic amines, for example.
  • the isocyanate-reactive component may include organic compounds similar to those described in connection with the reactive component hereinabove.
  • the isocyanate reactive component may include diethyltoluenediamine and an aromatic diamine.
  • the isocyanate reactive component may include diethyltoluenediamine, a primary polyether triamine, and polyoxypropylenediamine. ./ LJ f;M " b!Ee./er-i3HicS(i£M ⁇ iiiE
  • the isocyanate-reactive component includes from about 20% to about 90% by weight, based on 100% by weight of the isocyanate-reactive component, of at least one organic compound having a mercaptan functional moiety.
  • the isocyanate-reactive component includes from about 10% to about 80%, based on 100% by weight of the isocyanate-reactive component, of an intermediate resin component.
  • the use of an isocyanate-reactive component including mercaptan functional moieties in the synthesis of a polyurethane-polyurea polymer results in a polymer having excellent tensile properties and tear strength properties, substantially no volatile organic compounds (VOCs), abrasion and weathering resistance, and electrical resistance. Additionally, the incorporation of the sulfur into the synthesized polyurethane-polyurea polymer imparts improved chemical resistance and/or reduced permeability.
  • the polyurethane-polyurea polymer has a mercaptan content of about 0.5% to about 5.0%. In another implementation, the polyurethane-polyurea polymer has a mercaptan content of about 1.2% to about 2.4%.
  • the organic compounds having mercaptan functional moieties used in the preparation of the isocyanate-reactive component are substantially similar to the organic compounds having mercaptan functional moieties discussed hereinabove with respect to the polyisocyanate prepolymer component.
  • the intermediate resin component may include suitable initiator compounds comprising relatively low molecular weight species containing two active hydrogen atoms, ethylene glycol, propylene glycol, 1 ,4-butandiol, butenediol, butynediol, hexanediol, bisphenols, diethylene glycol, dipropylene glycol, tripropylene glycol, triethylene glycol, mixtures of these, and like difunctional active hydrogen species. Additionally, the intermediate resin component may include aliphatic amines and amine-substituted aromatics.
  • suitable intermediate resin components include diethylthtoluenediamine, diaminodiphenylmethane, polyoxypropylenediamine, secondary aliphatic diamines, cycloaliphatic diamines, and mixtures and reaction products thereof.
  • Suitable secondary aliphatic diamines include polyaspartic ester compounds such as the Desmophen ® polyaspartic esters from Bayer AG (Leverkusen, Germany). Sulfur diamines such as di-(methylthio)toluenediamine are suitable as well.
  • Diethyltoluenediamine, diaminodiphenylmethane, and di-(methylthio)toluenediamine are preferred intermediate resin components.
  • the polysulf ⁇ de and intermediate resin component are mixed together to create the isocyanate- reactive component.
  • additives such as non-primary components, filleref coloring agents, as well as catalysts, may be utilized in the preparation of the isocyanate-reactive component.
  • the polyisocyanate prepolymer component and the isocyanate-reactive component are reacted together to create the polyurethane-polyurea polymer component.
  • the polyisocyanate prepolymer component and/or the isocyanate-reactive component may include mercaptan functional moieties.
  • C AP A ® 3091 polyol is a 900 g/mol molecular weight caprolactone polyol from Solvay
  • Castor oil is derived from the seeds of the castor bean, Ricinus communis, and is readily available.
  • DESMODUR ® Z 4470 BA IPDI is an IPDI trimer from Bayer Corporation (Pittsburgh,
  • ETHACURE ® 100 curing agent is diethyltoluenediamine (DETA) from Albemarle Corporation (Baton Rouge, LA).
  • ETHACURE ® 300 curing agent is di-(methylthio)toluenediamine (DMTDA) from Albermarle Corporation (Baton Rouge, LA).
  • DMTDA di-(methylthio)toluenediamine
  • GLYMOTM silane is 3-glycidoxypropyl trimethoxysilane from Degussa AG (Frankfort, Germany).
  • JEFFAMINE ® D-2000 polyoxypropylenediamine is a difunctional primary amine having an average molecular weight of 2000 g/mol from Huntsman LLC (Salt Lake City, UT).
  • JEFFAMINE ® T-5000 polyol is a primary polyether triamine of approximately 5000 g/mol molecular weight from Huntsman LLC (Salt Lake City, UT).
  • JEFFCAT ® ZF-10 amine catalyst is N,N,N'-trimethyl-N'-hydroxyethyl- bisaminoethylether from Huntsman LLC (Salt Lake City, UT). ' U S 1 JMf 'FtiS ⁇ K ' ⁇ 7 ! W :; liamine is a bis(secondary amine) cycloaliphatic diamine from Huntsman LLC (Salt Lake City, UT).
  • JEFFOX ® PPG-230 glycol is a 230 g/mol molecular weight polyoxyalkylene glycol from Huntsman LLC (Salt Lake City, UT).
  • JEFFSOL ® propylene carbonate is a propylene carbonate from Huntsman LLC (Salt Lake City, UT).
  • JP-7 Fuel Oil is jet propellant-7 fuel oil manufactured in accordance with the MIL-DTL- 38219 specification from special blending stocks to produce a very clean hydrocarbon mixture that is low in aromatics and nearly void of sulfur, nitrogen, and oxygen impurities found in other fuels.
  • K-KAT ® XC-6212 organometallic catalyst is a zirconium complex reactive diluent from King Industries, Inc. (Norwalk, CT).
  • METACURE ® T- 12 catalyst is a dibutyltin dilaurate catalyst from Air Products and Chemicals, Inc. (Allentown, PA).
  • MONDUR ® ML MDI is an isomer mixture of MDI from Bayer Corporation (Pittsburgh,
  • PA that contains a high percentage of the 2'4 MDI isomer.
  • POLY-T ® 309 polyol is a 900 g/mol molecular weight tri-functional polycaprolactone from Arch Chemicals, Inc. (Norwalk, CT).
  • PPG-2000TM polymer is a 2000 g/mol molecular weight polymer of propylene oxide from The Dow Chemical Company (Midland, Michigan).
  • RUBINATE ® M MDI is a polymeric MDI from Huntsman LLC (Salt Lake City, UT) which is prepared by the phosgenation of mixed aromatic amines obtained from the condensation of aniline with formaldehyde.
  • THIOPLASTTM G4 polysulfide is a less than 1000 g/mol molecular weight polysulfide from Akzo Nobel Inc. (Chicago, IL).
  • THIOPLASTTM G22 polysulfide is a 2400-3100 g/mol molecular weight polysulfide from Akzo Nobel Inc. (Chicago, IL).
  • TOLONATE ® HDT-LV2 isocyanate is a tri-functional 1 ,6-hexamethylene diisocyanate- based polyisocyanate from Rhodia Inc. (Cranbury, NJ).
  • TMXD ITM isocyanate is tetramethylenexylene diisocyanate from Cytec Industries, Inc.
  • UNILINKTM 4200 diamine is a 310 g/mol molecular weight 2-functional aromatic diamine from Dorf Ketal Chemicals, LLC (Stafford, TX) (formerly from UOP Molecular Sieves (Des Plaines, Illinois)).
  • U S ifti ⁇ pl B ⁇ hil-iide prepolymer is made by reacting 201O g of DESMODUR ® Z 4470 BA IPDI with 900 g of POLY-T ® 309 polyol and 160 g of TMXDITM isocyanate. The ingredients are mixed vigorously for 5 minutes at a speed that is short of forming a vortex.
  • a B-side resin is formed by mixing 1295 g of JEFFLINK ® 754 diamine with 740 g of THIOPLASTTM G22 polysulfide and 1665 g of THIOPLASTTM G4 polysulfide. The ingredients are stirred at ambient conditions until well mixed. A tertiary type amine catalyst may be utilized to increase the rate of the reaction. The B-side resin formation is then complete. The A-Side and the B-side are then loaded into a GX-7 spray gun, which is manufactured by Gusmer Corporation (Lakewood, NJ), and impinged into each other at a 1 : 1 ratio at 2500 psi and 17O 0 F (77 0 C).
  • Example IL The polyurethane-polyurea polymer was prepared substantially according to the procedures presented in Example I with the components noted in Table VII. The resulting polyurethane-polyurea polymer has a mercaptan content between 1.2% and 1.9%.
  • additives e.g., color control additives
  • Example III The polyurethane-polyurea polymer was prepared substantially according to the procedures presented in Example I with the components noted in Table VIII. The resulting polyurethane-polyurea polymer has a mercaptan content between 1.2% and 2.0%. IJ S UJH 1 ? ⁇ 3 ⁇ r ⁇ i p ,pB m $ r Formation (Example III)
  • Example IV The polyurethane-polyurea polymer was prepared substantially according io to the procedures presented in Example I with the components noted in Table IX. The resulting polyurethane-polyurea polymer has a mercaptan content between 1.4% and 2.3%.
  • Example V The polyurethane-polyurea polymer was prepared substantially according 20 to the procedures presented in Example I with the components noted in Table X. The resulting polyurethane-polyurea polymer has a mercaptan content between 1.9% and 3.3%.
  • Example VI The polyurethane-polyurea polymer was prepared substantially according 30 to the procedures presented in Example I with the components noted in Table XI. The resulting polyurethane-polyurea polymer has a mercaptan content between 2.1% and 3.5%. ⁇ u ij ⁇ mation (Example VI)
  • Example VII The polyurethane-polyurea polymer was prepared substantially according to the procedures presented in Example I with the components noted in Table XII. The resulting polyurethane-polyurea polymer has a mercaptan content between 2.1% and 3.5%.
  • Example VIII The polyurethane-polyurea polymer was prepared substantially according to the procedures presented in Example I with the components noted in Table XIII.
  • Tables XV-XVII provide a survey of the mercaptan content of the polymers synthesized in accordance with Examples I-IX.
  • Test Method I A polyurethane-polyurea polymer of the present invention synthesized in accordance with Example V (Ex. V Polymer) and the HTS-SP were tested according to the standard test method for tensile properties of plastics prescribed in American Society for Testing and Materials (ASTM) D638. This test method covers the determination of the tensile properties of unreinforced and reinforced plastics in the form of standard dumbbell-shaped test specimens when tested under defined conditions of pretreatment, temperature, humidity, and testing machine speed. Table XIX depicts the ASTM D638 test results for the Ex. V Polymer and the HTS-SP.
  • Test Method II The Ex. V Polymer and the HTS-SP were tested according to the standard test method for water transmission of materials prescribed in ASTM E96. This test method covers the determination of water vapor transmission of materials through which the passage of water vapor may be of importance. Table XX depicts the ASTM E96 test results for the Ex. V Polymer and the HTS-SP.
  • a polyurethane-polyurea polymer of the present invention synthesized in accordance with Example III (Ex. Ill Polymer), the HTS-SP, and a conventional s polyurea were tested to evaluate resistance to chemical reagents and, in particular, resistance to gasoline, xylene, and diesel fuel.
  • Each of polymers under evaluation was sealed in a glass receptacle containing one of the three test fluids for 30 days at ambient conditions. At the end of the 30 days, change in weight was recorded.
  • Table XXII depicts the Chemical Resistance test results, i.e., percent weight increase, for the Ex. Ill Polymer, the HTS-SP, and the o conventional polyurea (CP).
  • Ex. I-II and IV-IX Polymers exhibited chemical resistance with respect to gasoline, xylene, and diesel fuel substantially equivalent to the Ex. Ill Polymer. ICTiesti ⁇ gl! Me ⁇ BicCd ⁇ lV.
  • the Ex. IX Polymer under evaluation was sealed in a glass receptacle containing 30% JP-7 Jet Fuel Oil and 70% toluene. Periodically changes in weight and dimension were recorded.
  • Table XXIII depicts the Chemical Resistance test results, i.e., percent weight increase and percent dimension increase, for the Ex. IX Polymer.
  • the Ex. I- VIII Polymers exhibited jet fuel oil/toluene resistance substantially equivalent to the Ex. IX Polymer. Accordingly, the results of Testing Methods I-V illustrate that the polyurethane-polyurea polymers having the mercaptan functional moieties in accordance with the teachings presented herein exhibit physical properties that are equivalent 20 or better than those of existing polyurethane-polyurea polymers. Further, the polyurethane- polyurea polymers synthesized according to the teachings presented herein exhibit chemical resistance at least an order of magnitude better than existing polyurethane-polyurea polymers.

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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)

Abstract

L'invention concerne un composant prépolymère de polyisocyanate qui réagit avec un composant réactif à l'isocyanate dans la préparation d'un polymère polyuréthanne-polyurée. Le composant prépolymère et/ou le composant réactif à l'isocyanate comprennent au moins un composé organique présentant une fraction fonctionnelle de mercaptan.
PCT/US2005/033209 2004-09-15 2005-09-15 Polymere polyurethanne-polyuree WO2006032034A2 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US61112404P 2004-09-15 2004-09-15
US60/611,124 2004-09-15
US10/980,217 US7655309B2 (en) 2004-09-15 2004-11-03 Isocyanate-reactive component for preparing a polyurethane-polyurea polymer
US10/980,456 US20060058492A1 (en) 2004-09-15 2004-11-03 Polyisocyanate prepolymer component for preparing a polyurethane-polyurea polymer
US10/980,456 2004-11-03
US10/980,217 2004-11-03

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007137608A1 (fr) * 2006-05-31 2007-12-06 Pirelli Tyre S.P.A. Pneu à surface revêtue
WO2009095739A1 (fr) * 2008-01-29 2009-08-06 Le Joint Francais Composition de produit d'étanchéité à base de copolymères séquencés segmentés de polymères fonctionnalisés par mercapto et de prépolymères à terminaison isocyanate
US7655309B2 (en) 2004-09-15 2010-02-02 Specialty Products, Inc. Isocyanate-reactive component for preparing a polyurethane-polyurea polymer
WO2015195197A1 (fr) * 2014-06-18 2015-12-23 Ppg Industries Ohio, Inc. Compositions de revêtement élastique formant barrière à gaz

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5679756A (en) * 1995-12-22 1997-10-21 Optima Inc. Optical thermoplastic thiourethane-urethane copolymers

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5679756A (en) * 1995-12-22 1997-10-21 Optima Inc. Optical thermoplastic thiourethane-urethane copolymers

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7655309B2 (en) 2004-09-15 2010-02-02 Specialty Products, Inc. Isocyanate-reactive component for preparing a polyurethane-polyurea polymer
WO2007137608A1 (fr) * 2006-05-31 2007-12-06 Pirelli Tyre S.P.A. Pneu à surface revêtue
US8196627B2 (en) 2006-05-31 2012-06-12 Pirelli Tyre S.P.A. Tire having a coated surface
WO2009095739A1 (fr) * 2008-01-29 2009-08-06 Le Joint Francais Composition de produit d'étanchéité à base de copolymères séquencés segmentés de polymères fonctionnalisés par mercapto et de prépolymères à terminaison isocyanate
WO2015195197A1 (fr) * 2014-06-18 2015-12-23 Ppg Industries Ohio, Inc. Compositions de revêtement élastique formant barrière à gaz
US10752806B2 (en) 2014-06-18 2020-08-25 Ppg Industries Ohio, Inc. Elastic gas barrier coating compositions

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