WO1997042246A1 - Polyurethane composition useful for coating cylindrical parts - Google Patents

Polyurethane composition useful for coating cylindrical parts Download PDF

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Publication number
WO1997042246A1
WO1997042246A1 PCT/US1997/006050 US9706050W WO9742246A1 WO 1997042246 A1 WO1997042246 A1 WO 1997042246A1 US 9706050 W US9706050 W US 9706050W WO 9742246 A1 WO9742246 A1 WO 9742246A1
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WO
WIPO (PCT)
Prior art keywords
isocyanate
polyol
diamine
recited
polyurethane composition
Prior art date
Application number
PCT/US1997/006050
Other languages
French (fr)
Inventor
Vincent J. Gajewski
Original Assignee
Uniroyal Chemical Company, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Uniroyal Chemical Company, Inc. filed Critical Uniroyal Chemical Company, Inc.
Priority to AU24566/97A priority Critical patent/AU2456697A/en
Priority to AT97920347T priority patent/ATE189238T1/en
Priority to CA002253420A priority patent/CA2253420C/en
Priority to DE69701221T priority patent/DE69701221T2/en
Priority to DK97920347T priority patent/DK0897401T3/en
Priority to JP9539924A priority patent/JP3066084B2/en
Priority to EP97920347A priority patent/EP0897401B1/en
Publication of WO1997042246A1 publication Critical patent/WO1997042246A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3237—Polyamines aromatic
    • C08G18/324—Polyamines aromatic containing only one aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8012—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with diols

Definitions

  • the present invention is related to a polyurethane composition useful for coating cylindrical objects. More particularly, the present invention is related to a polyurethane composition comprising an isocyanate- terminated polyurethane prepolymer and a curative mixture.
  • a variety of elastomeric coverings can be used to coat rolls in applications in which the rolls require protection.
  • Polyurethane elastomers are used as roll coatings in applications where abrasion and tear resistance, good load bearings characteristics, high hardness, and solvent resistance are required.
  • U.S. Patent 4,571,798 describes a method wherein paper mill rolls are coated by spraying a quick-gelling polyurethane onto a core.
  • Ruprecht et al Polyurethanes World Congress 1991 (September 24-26, 1991) , 478-481, describe rotational casting techniques useful for producing roll coverings using fast-reacting polyurethane elastomer systems.
  • the polyurethane reaction mixture is metered through a movable mixing head which travels at constant speed in the axial direction along the rotating roll core, a short distance above its surface.
  • the polyurethane reaction mixture solidifies very quickly, in a matter of seconds, to produce a polyurethane coating with a thickness buildup of 4-5 mm.
  • Additional layers of the polyurethane reaction mixture are applied until the desired thickness of polyurethane coating is achieved. Rotational casting reduces the number of steps involved in roll coating. However, if the polyurethane reaction mixture gels too slowly, the polyurethane coating will drip off the roll. If the polyurethane reaction mixture is formulated to gel quicker, the polyurethane can gel in the head of the mixer or ridges can develop on the outer surface of the roll requiring machine finishing of the polyurethane coating on the surface of the roll .
  • Thickening agents such as fumed silica
  • Thickening agents can be added to the polyurethane reaction mixture in a rotational casting procedure, to thicken the coating and eliminate dripping.
  • the use of thickening agents alone can often result in the polyurethane reaction mixture becoming too thick to flow or in the polyurethane coating being applied in undesirable thicknesses.
  • This invention relates to a polyurethane composition
  • a polyurethane composition comprising: a) an isocyanate-terminated polyurethane prepolymer; and b) a curative agent comprising i) a polyol; ii) an aromatic diamine; iii) a thixotropic aliphatic amine; and iv) a thixotropic colloidal additive.
  • isocyanate-terminated polyurethane prepolymer means the reaction product formed when an excess of an organic diisocyanate monomer is reacted with a polyol.
  • a stoichiometric excess of the diisocyanate monomer is used.
  • a material is "thixotropic" if its addition to the polyurethane composition results in a composition whose viscosity lowers under shear and whose viscosity rises (thickens) in the absence of shear.
  • the organic diisocyanate monomer can be an aromatic or aliphatic diisocyanate.
  • Useful aromatic diisocyanates can include, for example, 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate (each generally referred to as TDI) , mixtures of the two TDI isomers, 4,4' -diisocyanato diphenylmethane (MDI) , p-phenylenediisocyanate (PPDI) , naphthalene-1, 5-diisocyanate, diphenyl-4, 4' -diisocyanate, dibenzyl-4,4' -diisocyanate, stilbene-4,4' -diisocyanate, benzophenone-4, 4 'diisocyanate, 1,3- and 1,4-xylene diisocyanates, and mixtures thereof.
  • MDI 4,4' -diisocyanato di
  • Preferred aromatic isocyanates for preparation of the polyurethane prepolymers of the present invention include MDI, TDI, and PPDI .
  • Useful aliphatic diisocyantes can include, for example, 1, 6-hexamethylene diisocyanate, 1, 3-cyclohexyl diisocyanate, 1, 4-cyclohexyl diisocyanate (CHDI) , the saturated diphenylmethane diisocyante (known as H(12)MDI) , isophorone diisocyanate (IPDI) , and the like.
  • a preferred aliphatic diisocyanate is CHDI.
  • High molecular weight (MW) polyols useful in the preparation of the isocyanate-terminated polyurethane prepolymer have a number average molecular weight of at least about 250, e.g., polyether polyols or polyester polyols .
  • the molecular weight of the polyol can be as high as, e.g., about 10,000 or as low as about 250.
  • a molecular weight of about 650 to 3000 is preferred, with a molecular weight of 1000 being the most preferred.
  • a preferred high MW polyol is a polyalkyleneether polyol having the general formula HO(RO) n H, wherein R is an alkylene radical and n is an integer large enough that the polyether polyol has a number average molecular weight of at least 250.
  • Such polyalkyleneether polyols are well-known and can be prepared by the polymerization of cyclic ethers such as alkylene oxides and glycols, dihydroxyethers, and the like, using methods known in the art .
  • polyester polyols can be prepared by reacting dibasic acids (usually adipic acid but other components such as sebacic or phthalic acid may be present) with diols such as ethylene glycol, 1, 2-propylene glycol, 1,4- butylene glycol and diethylene glycol, tetramethylene ether glycol, and the like. Polyols such as glycerol, trimethylol propane, pentaerthythritol, sorbitol, and the like, can be used if chain branching or ultimate cross-linking is desired. Some polyester polyols also employ caprolactone and dimerized unsaturated fatty acids in their manufacture. Another useful polyester polyol can be obtained by the addition polymerization of e-caprolactone in the presence of an initiator.
  • dibasic acids usually adipic acid but other components such as sebacic or phthalic acid may be present
  • diols such as ethylene glycol, 1, 2-propylene glycol, 1,4-
  • polystyrene resin examples include those that have at least two hydroxyl groups and whose basic backbone is obtained by polymerization or copolymerization of such monomers as butadiene and isoprene monomers.
  • the high MW polyols can be used in combination with low MW polyols, i.e., polyols with an average molecular weight of less than 250.
  • An aliphatic glycol is a preferred low MW polyol .
  • Suitable aliphatic polyols include ethylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1, 3-butanediol, 1,4-butanediol, and the like.
  • the amount of the low MW polyol should be no more than about 20% of the combination of high MW polyol and low MW polyol .
  • the amount of low MW polyol is between about 0 to about 15% of the combination.
  • Particularly preferred polyols useful in the preparation of the isocyanate-terminated polyurethane prepolymer of this invention include polytetramethylene ether glycol (PTMEG) , polypropylene glycol, and a dihydroxypolyester.
  • PTMEG polytetramethylene ether glycol
  • the isocyanate-terminated polyurethane prepolymer can be prepared by reacting the organic diisocyanate monomer with the polyol or polyol blend, in a mole ratio of organic diisocyanate monomer to polyol or polyol blend ranging from about 1.7:1 to about 12:1, depending on the diisocyanate monomer being used.
  • the preferred mole ratio of organic diisocyanate monomer to polyol is from about 1.7:1 to about 2.2:1.
  • the preferred mole ratio of organic diisocyanate monomer to polyol is from about 2.5:1 to about 4:1.
  • the curative agent of the present invention comprises: i) a polyol; ii) an aromatic diamine; iii) a thixotropic aliphatic amine; and iv) a thixotropic colloidal additive.
  • the polyol useful in the curative agent can be any of those described above and can be the same or different than the polyol used in the preparation of the isocyanate-terminated polyurethane prepolymer.
  • Preferred polyols for use in the curative agent include polytetramethylene ether glycol (PTMEG) , polypropylene glycol, and a dihydroxypolyester.
  • PTMEG polytetramethylene ether glycol
  • the polyol can be used in an amount from about 10 weight percent to about 90 weight percent of the total weight of the curative agent.
  • a preferred amount of polyol will range from about 30 to about 60 weight percent of the total weight of the curative agent.
  • the aromatic diamine useful in the curative agent can be any aromatic diamine useful as a curative for polyurethane, such as, for example, 4 , 4 ' -methylene-bis- (2-chloroaniline) , 2,2' , 5-trichloro-4, 4' - methylenediamines, naphthalene-1, 5-diamine, ortho, meta, and para-phenylene diamines, toluene-2, 4-diamine, dichlorobenzidine, diphenylether-4 ,4' -diamine, including their derivatives and mixtures.
  • aromatic diamine useful as a curative for polyurethane such as, for example, 4 , 4 ' -methylene-bis- (2-chloroaniline) , 2,2' , 5-trichloro-4, 4' - methylenediamines, naphthalene-1, 5-diamine, ortho, meta, and para-phenylene diamines, toluene-2, 4-di
  • Preferred aromatic diamines include 4 , 4 ' -methylene-bis- (3-chloro) aniline (MBCA) , 4 , 4 'methylene-bis- (3-chloro-2, 6-diethyl) aniline (MCDEA) , diethyl toluene diamine (DETDA) , tertiary butyl toluene diamine (TBTDA) , dimethylthio-toluene diamine (EthacureTM 300 from Ethyl Corporation) , trimethylene glycol di-p-aminobenzoate (PolacureTM 740 from Polaroid Corporation) , and 1, 2-bis (2-aminophenylthio) ethane
  • aromatic diamines include Ethacure 300 and similar compounds.
  • the aromatic amine is present in the curative agent in an amount ranging from about 10 weight percent to about 90 weight percent of the total weight of the curative agent. A more preferred range is from about 20 to about 80 weight percent.
  • the thixotropic aliphatic diamine can be any aliphatic diamine which reacts quickly with the isocyanate-terminated polyurethane prepolymer and produces thixotropy in si tu , in the polyurethane composition, such as, for example, alkyl diamines, ethylene polyamines, amine-terminated polyoxypropylenes, and amine-terminated polyoxyethylenes .
  • alkyl diamines ethylene polyamines
  • amine-terminated polyoxypropylenes amine-terminated polyoxyethylenes
  • aliphatic diamines include, for example, ethylene diamine, 1, 6-hexanediamine, and 1, 12-dodecanediamine.
  • the aliphatic diamine can also be a cycloaliphatic diamine such as, for example, 1, 4-cyclohexane diamine, isophorone diamine, and the like.
  • the aliphatic diamine can also include ethylene polyamines such as diethylene triamine and triethylene tetramine, xylene diamine, piperazine, and, preferably, amine-terminated polyoxypropylenes such as the Jeffamine series of compounds (available from Texaco, Inc.) .
  • the aliphatic diamine or mixture of aliphatic diamines is present in the curative agent in amounts ranging from about 0.1 weight percent to about 1.5 weight percent of the total weight of the curative agent . A more preferable range is from about 0.2 to 0.7 weight percent .
  • the thixotropic colloidal additive can be any thixotropic colloidal material which does not have deleterious effect on the polyurethane composition or on the composition's use as a coating material.
  • Useful thixotropic colloidal additives can include, for example, fumed silicas, clays, bentonites, talcs, and the like.
  • Clays are usually hydrated aluminum silicates.
  • Bentonite is a type of colloidal clay, composed chiefly of montmoriUonite.
  • Talcs are hydrous magnesium silicates, which are also referred to as steatites or soapstone .
  • Silica is a common name for silicon dioxide, Si0 2 , which occurs in nature as sand, quartz, flint, and diatomite.
  • a preferred thixotropic colloidal additive is a fumed silica sold under the trademark AEROSIL (Degussa, Inc.) .
  • the thixotropic colloidal additive can be present in the curative agent in an amount of from about 1.0 weight percent to about 10 weight percent, based on the total weight of the curative agent . A more preferred range is from about 2 to about 5 weight percent.
  • the synergistic combination of the thixotropic aliphatic amine and the thixotropic colloidal additive in the polyurethane composition results in a polyurethane composition which flows effectively and resists undesirable dripping when the composition is used for rotational casting.
  • the isocyanate-terminated polyurethane prepolymer can be mixed with the curative agent in amounts such that the total active hydrogen content of the curative agent is equal to about 80-115% of the total isocyanate content of the isocyanate-terminated polyurethane prepolymer. In a more preferred embodiment, the total active hydrogen content of the curative agent is equal to about 90-95% of the total isocyanate content of the isocyanate-terminated polyurethane prepolymer.
  • the polyurethane composition of this invention can be reacted, mixed, and applied at ambient temperatures and can be applied to the substrates to be coated without the need for molds.
  • Use of the polyurethane composition of this invention in rotational casting results in minimal dripping and ridging of the coating on the rolls covered.
  • compositions used in covering cylindrical objects with polyurethanes by rotational casting Details of the equipment types and process steps used in rotational casting of rolls are described in Ruprecht et al, supra.
  • the pot life, dripping, tolerance, and thickness/pass characteristics of the tested polyurethane compositions are shown in Table 1.
  • the physical properties of the tested polyurethane coatings on the rolls, including durometer, 100% modules, tensile strength, elongation, and tear strength, are shown in Table 2.
  • An isocyanate-terminated polyurethane prepolymer was prepared by reacting 3.5 moles of MDI with 1 mole of a
  • a curative agent was prepared by mixing, in a beaker at 25°C for 10 minutes, a) a PTMEG polyol of 650 MW; b) a blend of the aromatic amines DETDA and DMTDA, and the aliphatic amine JeffamineTM T-403 (JeffamineTM T-403 is an amine-terminated polyoxypropylene triol of 400 MW sold by Texaco Inc.) ; and c) the fumed silica Aerosil 200, in a weight ratio of 37.9 PTMEG to 38.2 DETDA to 21.1 DMTDA to 2.5 Aerosil to 0.3 Jeffamine.
  • the isocyanate-terminated polyurethane prepolymer prepared in Example 1 was mixed with the curative agent prepared in Example 2 at a temperature of 25°C, on a Mark X meter/mix machine at a weight ratio of 100 to 35, respectively, resulting in a mixture with an active hydrogen to isocyanate ratio of 95%. The mixture was then dispensed onto a rotating roll core.
  • Example 3 Use of the composition of Example 3 resulted in no dripping and a significantly improved thickness per pass compared to the compositions of the three Comparative Examples. Surprisingly, use of the fast-curing aliphatic amine JeffamineTM T-403 in the composition of Example 3 did not result in reduced pot life. Similarly, the 1- inch tolerance was not adversely effected by the addition in-situ of JeffamineTM T-403 and Aerosil 200 in the composition of Example 3, indicating the absence of the ridging problems often found in prior methods of roll coating.
  • Table 2 below compares the properties of the polyurethane prepared in Example 3 with the polyurethanes prepared in Comparative Examples A, B and C. As can be seen in Table 2, the physical properties of the polyurethane produced from the polyurethane composition of this invention was comparable to polyurethanes cured by conventional curatives.

Abstract

A polyurethane composition comprising: a) an isocyanate-termined polyurethane prepolymer; and b) a curative agent comprising i) a polyol; ii) an aromatic diamine; iii) a thixotropic aliphatic amine; and iv) a thixotropic colloidal additive. This composition is useful for coating cylindrical objects.

Description

POLYURETHANE COMPOSITION USEFUL FOR COATING CYLINDRICAL PARTS
Field of Invention
The present invention is related to a polyurethane composition useful for coating cylindrical objects. More particularly, the present invention is related to a polyurethane composition comprising an isocyanate- terminated polyurethane prepolymer and a curative mixture.
Background of the Invention A variety of elastomeric coverings can be used to coat rolls in applications in which the rolls require protection. Polyurethane elastomers are used as roll coatings in applications where abrasion and tear resistance, good load bearings characteristics, high hardness, and solvent resistance are required.
In steel mill applications, for example, large numbers of these rolls are used for guiding, tensioning, and otherwise engaging steel strip during rolling and pickling applications. The rolls are subjected to the strong chemical agents used for pickling and cleaning the strip. Similarly, in paper mills, polyurethane-coated metal rolls are used for supporting and conveying paper through high pressure nips of paper making machine assemblies such as press rolls, calendar stacks, and the like. The rolls used in paper mill operations require a protective cover whose thickness can be varied depending on the roll's anticipated use. Being able to control the thickness of the protective cover is, therefore, desirable. Different methods have been developed for applying coatings to metal rolls. U.S. Patents Nos. 3,520,747; 3,646,651; and 4,368,568 describe multistep methods for multilayer coating of rolls.
U.S. Patent 4,571,798 describes a method wherein paper mill rolls are coated by spraying a quick-gelling polyurethane onto a core. Ruprecht et al, Polyurethanes World Congress 1991 (September 24-26, 1991) , 478-481, describe rotational casting techniques useful for producing roll coverings using fast-reacting polyurethane elastomer systems. In these systems, the polyurethane reaction mixture is metered through a movable mixing head which travels at constant speed in the axial direction along the rotating roll core, a short distance above its surface. The polyurethane reaction mixture solidifies very quickly, in a matter of seconds, to produce a polyurethane coating with a thickness buildup of 4-5 mm. Additional layers of the polyurethane reaction mixture are applied until the desired thickness of polyurethane coating is achieved. Rotational casting reduces the number of steps involved in roll coating. However, if the polyurethane reaction mixture gels too slowly, the polyurethane coating will drip off the roll. If the polyurethane reaction mixture is formulated to gel quicker, the polyurethane can gel in the head of the mixer or ridges can develop on the outer surface of the roll requiring machine finishing of the polyurethane coating on the surface of the roll .
Thickening agents, such as fumed silica, can be added to the polyurethane reaction mixture in a rotational casting procedure, to thicken the coating and eliminate dripping. However, the use of thickening agents alone can often result in the polyurethane reaction mixture becoming too thick to flow or in the polyurethane coating being applied in undesirable thicknesses.
It is therefore an object of the present invention to provide a new polyurethane composition useful for coating cylindrical objects. It is a further object of this invention to provide a polyurethane compostion which can be used in a rotational casting process. Summary of the Invention
This invention relates to a polyurethane composition comprising: a) an isocyanate-terminated polyurethane prepolymer; and b) a curative agent comprising i) a polyol; ii) an aromatic diamine; iii) a thixotropic aliphatic amine; and iv) a thixotropic colloidal additive.
Detailed Description of the Invention
For the purposes of this invention, the term "isocyanate-terminated polyurethane prepolymer" means the reaction product formed when an excess of an organic diisocyanate monomer is reacted with a polyol. Preferably, a stoichiometric excess of the diisocyanate monomer (an NCO:OH ratio greater than 2:1) is used.
For the purposes of this invention, a material is "thixotropic" if its addition to the polyurethane composition results in a composition whose viscosity lowers under shear and whose viscosity rises (thickens) in the absence of shear.
The organic diisocyanate monomer can be an aromatic or aliphatic diisocyanate. Useful aromatic diisocyanates can include, for example, 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate (each generally referred to as TDI) , mixtures of the two TDI isomers, 4,4' -diisocyanato diphenylmethane (MDI) , p-phenylenediisocyanate (PPDI) , naphthalene-1, 5-diisocyanate, diphenyl-4, 4' -diisocyanate, dibenzyl-4,4' -diisocyanate, stilbene-4,4' -diisocyanate, benzophenone-4, 4 'diisocyanate, 1,3- and 1,4-xylene diisocyanates, and mixtures thereof. Preferred aromatic isocyanates for preparation of the polyurethane prepolymers of the present invention include MDI, TDI, and PPDI . Useful aliphatic diisocyantes can include, for example, 1, 6-hexamethylene diisocyanate, 1, 3-cyclohexyl diisocyanate, 1, 4-cyclohexyl diisocyanate (CHDI) , the saturated diphenylmethane diisocyante (known as H(12)MDI) , isophorone diisocyanate (IPDI) , and the like. A preferred aliphatic diisocyanate is CHDI. High molecular weight (MW) polyols useful in the preparation of the isocyanate-terminated polyurethane prepolymer have a number average molecular weight of at least about 250, e.g., polyether polyols or polyester polyols . The molecular weight of the polyol can be as high as, e.g., about 10,000 or as low as about 250. A molecular weight of about 650 to 3000 is preferred, with a molecular weight of 1000 being the most preferred.
A preferred high MW polyol is a polyalkyleneether polyol having the general formula HO(RO)nH, wherein R is an alkylene radical and n is an integer large enough that the polyether polyol has a number average molecular weight of at least 250. Such polyalkyleneether polyols are well-known and can be prepared by the polymerization of cyclic ethers such as alkylene oxides and glycols, dihydroxyethers, and the like, using methods known in the art .
Another preferred high MW polyol is a polyester polyol. Polyester polyols can be prepared by reacting dibasic acids (usually adipic acid but other components such as sebacic or phthalic acid may be present) with diols such as ethylene glycol, 1, 2-propylene glycol, 1,4- butylene glycol and diethylene glycol, tetramethylene ether glycol, and the like. Polyols such as glycerol, trimethylol propane, pentaerthythritol, sorbitol, and the like, can be used if chain branching or ultimate cross-linking is desired. Some polyester polyols also employ caprolactone and dimerized unsaturated fatty acids in their manufacture. Another useful polyester polyol can be obtained by the addition polymerization of e-caprolactone in the presence of an initiator.
Other useful high MW polyols are those that have at least two hydroxyl groups and whose basic backbone is obtained by polymerization or copolymerization of such monomers as butadiene and isoprene monomers.
The high MW polyols can be used in combination with low MW polyols, i.e., polyols with an average molecular weight of less than 250. An aliphatic glycol is a preferred low MW polyol . Suitable aliphatic polyols include ethylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1, 3-butanediol, 1,4-butanediol, and the like. In general, the amount of the low MW polyol should be no more than about 20% of the combination of high MW polyol and low MW polyol . Preferably, the amount of low MW polyol is between about 0 to about 15% of the combination. Particularly preferred polyols useful in the preparation of the isocyanate-terminated polyurethane prepolymer of this invention include polytetramethylene ether glycol (PTMEG) , polypropylene glycol, and a dihydroxypolyester. The isocyanate-terminated polyurethane prepolymer can be prepared by reacting the organic diisocyanate monomer with the polyol or polyol blend, in a mole ratio of organic diisocyanate monomer to polyol or polyol blend ranging from about 1.7:1 to about 12:1, depending on the diisocyanate monomer being used. For example, when the diisocyanate monomer is TDI, the preferred mole ratio of organic diisocyanate monomer to polyol is from about 1.7:1 to about 2.2:1. When the diisocyanate monomer is MDI, the preferred mole ratio of organic diisocyanate monomer to polyol is from about 2.5:1 to about 4:1. The curative agent of the present invention comprises: i) a polyol; ii) an aromatic diamine; iii) a thixotropic aliphatic amine; and iv) a thixotropic colloidal additive. The polyol useful in the curative agent can be any of those described above and can be the same or different than the polyol used in the preparation of the isocyanate-terminated polyurethane prepolymer. Preferred polyols for use in the curative agent include polytetramethylene ether glycol (PTMEG) , polypropylene glycol, and a dihydroxypolyester. The polyol can be used in an amount from about 10 weight percent to about 90 weight percent of the total weight of the curative agent. A preferred amount of polyol will range from about 30 to about 60 weight percent of the total weight of the curative agent.
The aromatic diamine useful in the curative agent can be any aromatic diamine useful as a curative for polyurethane, such as, for example, 4 , 4 ' -methylene-bis- (2-chloroaniline) , 2,2' , 5-trichloro-4, 4' - methylenediamines, naphthalene-1, 5-diamine, ortho, meta, and para-phenylene diamines, toluene-2, 4-diamine, dichlorobenzidine, diphenylether-4 ,4' -diamine, including their derivatives and mixtures. Preferred aromatic diamines include 4 , 4 ' -methylene-bis- (3-chloro) aniline (MBCA) , 4 , 4 'methylene-bis- (3-chloro-2, 6-diethyl) aniline (MCDEA) , diethyl toluene diamine (DETDA) , tertiary butyl toluene diamine (TBTDA) , dimethylthio-toluene diamine (Ethacure™ 300 from Ethyl Corporation) , trimethylene glycol di-p-aminobenzoate (Polacure™ 740 from Polaroid Corporation) , and 1, 2-bis (2-aminophenylthio) ethane
(Cyanacure from American Cyanamid Company) . Especially preferred aromatic diamines include Ethacure 300 and similar compounds. The aromatic amine is present in the curative agent in an amount ranging from about 10 weight percent to about 90 weight percent of the total weight of the curative agent. A more preferred range is from about 20 to about 80 weight percent.
The thixotropic aliphatic diamine can be any aliphatic diamine which reacts quickly with the isocyanate-terminated polyurethane prepolymer and produces thixotropy in si tu , in the polyurethane composition, such as, for example, alkyl diamines, ethylene polyamines, amine-terminated polyoxypropylenes, and amine-terminated polyoxyethylenes . Examples of aliphatic diamines include, for example, ethylene diamine, 1, 6-hexanediamine, and 1, 12-dodecanediamine. The aliphatic diamine can also be a cycloaliphatic diamine such as, for example, 1, 4-cyclohexane diamine, isophorone diamine, and the like. The aliphatic diamine can also include ethylene polyamines such as diethylene triamine and triethylene tetramine, xylene diamine, piperazine, and, preferably, amine-terminated polyoxypropylenes such as the Jeffamine series of compounds (available from Texaco, Inc.) . The aliphatic diamine or mixture of aliphatic diamines, is present in the curative agent in amounts ranging from about 0.1 weight percent to about 1.5 weight percent of the total weight of the curative agent . A more preferable range is from about 0.2 to 0.7 weight percent .
The thixotropic colloidal additive can be any thixotropic colloidal material which does not have deleterious effect on the polyurethane composition or on the composition's use as a coating material. Useful thixotropic colloidal additives can include, for example, fumed silicas, clays, bentonites, talcs, and the like. Clays are usually hydrated aluminum silicates. Bentonite is a type of colloidal clay, composed chiefly of montmoriUonite. Talcs are hydrous magnesium silicates, which are also referred to as steatites or soapstone . Silica is a common name for silicon dioxide, Si02, which occurs in nature as sand, quartz, flint, and diatomite. A preferred thixotropic colloidal additive is a fumed silica sold under the trademark AEROSIL (Degussa, Inc.) .
The thixotropic colloidal additive can be present in the curative agent in an amount of from about 1.0 weight percent to about 10 weight percent, based on the total weight of the curative agent . A more preferred range is from about 2 to about 5 weight percent.
The synergistic combination of the thixotropic aliphatic amine and the thixotropic colloidal additive in the polyurethane composition results in a polyurethane composition which flows effectively and resists undesirable dripping when the composition is used for rotational casting.
Preferably, the isocyanate-terminated polyurethane prepolymer can be mixed with the curative agent in amounts such that the total active hydrogen content of the curative agent is equal to about 80-115% of the total isocyanate content of the isocyanate-terminated polyurethane prepolymer. In a more preferred embodiment, the total active hydrogen content of the curative agent is equal to about 90-95% of the total isocyanate content of the isocyanate-terminated polyurethane prepolymer.
The polyurethane composition of this invention can be reacted, mixed, and applied at ambient temperatures and can be applied to the substrates to be coated without the need for molds. Use of the polyurethane composition of this invention in rotational casting results in minimal dripping and ridging of the coating on the rolls covered.
The examples that follow detail the compositions used in covering cylindrical objects with polyurethanes by rotational casting. Details of the equipment types and process steps used in rotational casting of rolls are described in Ruprecht et al, supra. The pot life, dripping, tolerance, and thickness/pass characteristics of the tested polyurethane compositions, are shown in Table 1. The physical properties of the tested polyurethane coatings on the rolls, including durometer, 100% modules, tensile strength, elongation, and tear strength, are shown in Table 2. EXAMPLES
The following Examples are provided to illustrate the present invention.
Ex-ample 1
Preparation of Isocyanate-Terminated Polyurethane Prepolymer:
An isocyanate-terminated polyurethane prepolymer was prepared by reacting 3.5 moles of MDI with 1 mole of a
1000 MW PTMEG polyol for three hours at 75°C in a 3 neck,
3 liter, round bottom flask equipped with a stirrer, nitrogen inlet, and heating mantel. The resulting isocyanate content was measured by the dibutylamine method as described in ASTM D1638, to be 11.25% by weight .
Example 2
Preparation of Curative Agent A curative agent was prepared by mixing, in a beaker at 25°C for 10 minutes, a) a PTMEG polyol of 650 MW; b) a blend of the aromatic amines DETDA and DMTDA, and the aliphatic amine Jeffamine™ T-403 (Jeffamine™ T-403 is an amine-terminated polyoxypropylene triol of 400 MW sold by Texaco Inc.) ; and c) the fumed silica Aerosil 200, in a weight ratio of 37.9 PTMEG to 38.2 DETDA to 21.1 DMTDA to 2.5 Aerosil to 0.3 Jeffamine.
Example 3 Preparation of the polyurethane composition suitable for rotational casting
The isocyanate-terminated polyurethane prepolymer prepared in Example 1 was mixed with the curative agent prepared in Example 2 at a temperature of 25°C, on a Mark X meter/mix machine at a weight ratio of 100 to 35, respectively, resulting in a mixture with an active hydrogen to isocyanate ratio of 95%. The mixture was then dispensed onto a rotating roll core.
Three different comparative curative agents were prepared and mixed with the prepolymer of Example 1 as described in Example 3. In Comparative Example A, the curative agent was prepared as described in Example 2 except that the Jeffamine™ T-403 was not included. In Comparative Example B, the curative agent was prepared as described in Example 2 except that the Aerosil 200 was not included. In Comparative Example C, the curative agent was prepared as described in Example 2 except that both Jeffamine™ T-403 and Aerosil 200 were not included.
TABLE 1
Figure imgf000012_0001
Use of the composition of Example 3 resulted in no dripping and a significantly improved thickness per pass compared to the compositions of the three Comparative Examples. Surprisingly, use of the fast-curing aliphatic amine Jeffamine™ T-403 in the composition of Example 3 did not result in reduced pot life. Similarly, the 1- inch tolerance was not adversely effected by the addition in-situ of Jeffamine™ T-403 and Aerosil 200 in the composition of Example 3, indicating the absence of the ridging problems often found in prior methods of roll coating.
Table 2 below compares the properties of the polyurethane prepared in Example 3 with the polyurethanes prepared in Comparative Examples A, B and C. As can be seen in Table 2, the physical properties of the polyurethane produced from the polyurethane composition of this invention was comparable to polyurethanes cured by conventional curatives.
TABLE 2
Figure imgf000013_0001

Claims

What is claimed is:
1. A polyurethane composition comprising: a) an isocyanate-terminated polyurethane prepolymer; and b) a curative agent comprising i) a polyol; ii) an aromatic diamine; iii) a thixotropic aliphatic amine; and iv) a thixotropic colloidal additive.
2. A polyurethane composition as recited in claim
1 wherein the isocyanate-terminated polyurethane prepolymer is a reaction product of a polyol and an organic diisocyanate monomer selected from the group consisting of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, mixtures of the two isomers (TDI) ,
4, 4 ' -diisocyanato diphenylmethane (MDI) , p-phenylene- diisocyanate (PPDI) , naphthalene-1, 5-diisocyanate, diphenyl-4 , 4' -diisocyanate, dibenzyl-4, 4' -diisocyante, stilbene-4 , 4' -diisocyanate, benzophenone-4 , 4' -di- isocyanate, 1, 3-diisocyanate, 1,4-xylene diisocyanate, 1, 6-hexamethylene diisocyanate, 1, 3-cyclohexyl diisocyanate, 1, 4-cyclohexyl diisocyanate (CHDI) , diphenylmethane diisocyante (H(12)MDI) , and isophorone diisocyanate (IPDI) .
3. A polyurethane composition as recited in claim
2 wherein the organic isocyanate monomer is selected from the group consisting of CHDI, MDI, TDI, and PPDI.
4. A polyurethane composition as recited in claim
1 wherein the isocyanate-terminated polyurethane prepolymer is a reaction product of an organic diisocyanate monomer and a polyol selected from the group consisting of ethylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1, 3-butanediol,
1,4-butanediol, polytetramethylene ether glycol (PTMEG) , polypropylene glycol, and a dihydroxypolyester.
5. A polyurethane composition as recited in claim 4 wherein the isocyanate-terminated polyurethane prepolymer is a reaction product of an organic diisocyanate monomer and PTMEG.
6. A polyurethane composition as recited in claim 1 wherein the curative agent comprises a polyol selected from the group ethylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1, 3-butanediol, 1,4-butanediol, polytetramethylene ether glycol (PTMEG) , polypropylene glycol, and a dihydroxypolyester.
7. A polyurethane composition as recited in claim
1 wherein the curative agent comprises an aromatic amine selected from the group consisting of 4, 4 ' -methylene-bis- (3-chloro) aniline (MBCA) , 4, 4 'methylene-bis- (3-chloro- 2, 6-diethyl) aniline (MCDEA) , diethyl toluene diamine (DETDA) , tertiary butyl toluene diamine (TBTDA) , dimethylthio-toluene diamine, trimethylene glycol di-p-aminobenzoate, 1, 2-bis (2-aminophenylthio) ethane, 4, 4' -methylene bis (2-chloroaniline) , 2, 2' , 5-trichloro- 4, 4' -methylene-diamine, naphthalene-1, 5-diamine, ortho- phenylene diamine, meta-phenylene diamine, para-phenylene diamine, toluene-2, 4-diamine, dichlorobenzidine, diphenylether-4, 4' -diamine, and mixtures thereof.
8. A polyurethane composition as recited in claim 1 wherein the curative agent comprises a thixotropic aliphatic amine selected from the group consisting of ethylene diamine, 1, 6-hexanediamine, 1, 12-dodecane diamine, 1, 4-cyclohexane diamine, isophorone diamine, diethylene triamine, triethylene tetramine, amine- terminated polyoxypropylenes, xylene diamine, and piperazine.
9. A polyurethane composition as recited in claim 1 wherein the curative agent comprises a thixotropic colloidal additive selected from the group consisting of fumed silica, clay, bentonite, and talc.
10. A polyurethane composition as recited in claim 1 wherein the isocyanate-terminated polyurethane prepolymer is prepared by reacting an organic diisocyanate monomer with a polyol, in a mole ratio of organic diisocyanate monomer to polyol ranging from about 1.7:1 to about 12:1.
11. A polyurethane composition as recited in claim 10 wherein the isocyanate-terminated polyurethane prepolymer is prepared by reacting TDI with a polyol in a mole ratio of TDI to polyol ranging from about 1.7:1 to about 2.2:1.
12. A polyurethane composition as recited in claim 10 wherein the isocyanate-terminated polyurethane prepolymer is prepared by reacting MDI with a polyol in a mole ratio of MDI to polyol ranging from about 2.5:1 to about 4:1.
13. A polyurethane composition as recited in claim
1 wherein the total active hydrogen content of the curative agent is equal to about 80-115% of the total isocyanate content of the isocyanate-terminated polyurethane prepolymer.
14. A polyurethane composition as recited in claim 13 wherein the total active hydrogen content of the curative agent is equal to about 90-95% of the total isocyanate content of the isocyanate-terminated polyurethane prepolymer.
15. A polyurethane composition as recited in claim 1 comprising a) an isocyanate-terminated polyurethane prepolymer prepared by reacting an organic diisocyanate monomer with a polyol, in a mole ratio of organic diisocyanate monomer to polyol ranging from about 1.7:1 to about 12:1; and b) a curative agent comprising i) about 10 weight percent to about 90 weight percent of a polyol; ii) about 10 weight percent to about 90 weight percent of an aromatic diamine; iii) about 0.1 weight percent to about 1.5 weight percent of a thixotropic aliphatic amine; and iv) about 1.0 weight percent to about 10 weight percent of a thixotropic colloidal additive, wherein the total active hydrogen content of the curative agent is equal to about 80-115% of the total isocyanate content of the isocyanate-terminated polyurethane prepolymer.
16. A polyurethane composition as recited in claim
15 comprising a) an isocyanate-terminated polyurethane prepolymer prepared by reacting an organic diisocyanate monomer with a polyol, in a mole ratio of organic diisocyanate monomer to polyol ranging from about 1.7:1 to about 4:1; and b) a curative agent comprising i) about 30 to about 60 weight percent of a polyol; ii) about 20 to about 80 weight percent of an aromatic diamine; iii) about 0.2 to 0.7 weight percent of a thixotropic aliphatic amine; and iv) about 2 to about 5 weight percent of a thixotropic colloidal additive, wherein the total active hydrogen content of the curative agent is equal to about 90-95% of the total isocyanate content of the isocyanate-terminated polyurethane prepolymer.
17. A method for coating a cylindrical object which comprises applying to the cylindrical object an effective amount of a polyurethane composition as recited in claim 1.
18. A method as recited in claim 17 wherein the polyurethane composition is applied to the cylindrical object by rotational casting.
PCT/US1997/006050 1996-05-06 1997-04-11 Polyurethane composition useful for coating cylindrical parts WO1997042246A1 (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998056841A1 (en) * 1997-06-11 1998-12-17 Stowe Woodward Company Castable polyurethane elastomers for industrial rollers
EP0982079A2 (en) * 1998-08-24 2000-03-01 UNIROYAL CHEMICAL COMPANY, Inc. Method for producing cylindrical objects with multilayer coatings having dissimilar compositions without interfaces
WO2000039185A1 (en) * 1998-12-23 2000-07-06 Bayer Corporation Thixotropic wood binder compositions
WO2002038859A1 (en) * 2000-11-10 2002-05-16 Yamauchi Corporation Belt for papermaking and process for producing papermaking belt
KR100558684B1 (en) * 1999-07-09 2006-03-10 주식회사 코오롱 A polyurethane polymer, and a process of preparing the same
WO2007128596A1 (en) * 2006-05-05 2007-11-15 Voith Patent Gmbh Pu roller
WO2009129206A3 (en) * 2008-04-17 2010-01-21 The Boeing Company Composition and method for corrosion protection of a structure
WO2013160358A1 (en) * 2012-04-27 2013-10-31 Voith Patent Gmbh Press roll with a roll cover consisting of polyurethane
IT201700109802A1 (en) * 2017-10-02 2019-04-02 Lanxess Solution Italia S R L Method and composition for rotational molding of a polyurethane coating layer

Families Citing this family (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3869022B2 (en) * 1997-11-11 2007-01-17 東海ゴム工業株式会社 Conductive roll
US6224526B1 (en) * 1997-12-19 2001-05-01 H.B. Fuller Licensing & Financing, Inc. Printing rollers
ES2229753T3 (en) * 1998-07-30 2005-04-16 Macdermid Printing Solutions, Llc PRINT HOSE AND METHODS TO PRODUCE THE SAME.
JP3605523B2 (en) * 1998-12-24 2004-12-22 日東工業株式会社 Developing roller
FI105584B (en) * 1999-03-30 2000-09-15 Valmet Corp Method for making a roll of a paper or board machine and a roll of a paper or board machine
DE19919482C2 (en) * 1999-04-29 2001-04-26 Byk Chemie Gmbh Process for the preparation of a thixotropic agent and its use
WO2001072864A1 (en) * 2000-03-27 2001-10-04 Uniroyal Chemical Company, Inc. Rotational casting method for coating a flexible substrate and resulting coated flexible article
WO2003039764A1 (en) * 2001-11-08 2003-05-15 Coldwater Resins, Inc. One pass polyurethane roll covering system and method
US20030203771A1 (en) * 2002-04-26 2003-10-30 Ronald Rosenberg Polyurethane elastomers from HDI prepolymers with reduced content of free HDI monomers
US6747117B2 (en) * 2002-06-14 2004-06-08 Crompton Corporation Polyurethane/urea composition for coating cylindrical parts
US20040014383A1 (en) * 2002-07-19 2004-01-22 Atsushi Ishino Belt for papermaking machine and manufacturing method therefor
US20040091617A1 (en) * 2002-11-11 2004-05-13 Crompton Corporation Method and device for applying a thick reactive coating on a body rotating about an axis
WO2004096569A2 (en) * 2003-05-02 2004-11-11 Hyperlast Limited Manufacture of gravure printing rollers
US20050037194A1 (en) * 2003-08-15 2005-02-17 Kimberly-Clark Worldwide, Inc. Thermoplastic polymers with thermally reversible and non-reversible linkages, and articles using same
US7270711B2 (en) * 2004-06-07 2007-09-18 Kastalon, Inc. Nozzle for use in rotational casting apparatus
US7041171B2 (en) * 2003-09-10 2006-05-09 Kastalon, Inc. Nozzle for use in rotational casting apparatus
US6989061B2 (en) * 2003-08-22 2006-01-24 Kastalon, Inc. Nozzle for use in rotational casting apparatus
DE10344380A1 (en) * 2003-09-23 2005-05-12 Mankiewicz Gebr & Co Two-component composition for the production of polyurethane gel coats for epoxy resin and vinyl ester resin composites
DE10344379B4 (en) * 2003-09-23 2008-09-11 Mankiewicz Gebr. & Co (Gmbh & Co Kg) Use of a two-component composition to make flexible polyurethane gel coats for resin composites, methods of making composites and composites
US10287731B2 (en) * 2005-11-08 2019-05-14 Stowe Woodward Licensco Llc Abrasion-resistant rubber roll cover with polyurethane coating
CN101657665A (en) * 2007-01-22 2010-02-24 约翰·弗雷德里克·奥尔森 Elastomer lined abrasion-proof pipe and preparation method
PL1958975T3 (en) * 2007-02-06 2011-12-30 Nolax Ag Dual component glue
KR101498308B1 (en) * 2007-03-19 2015-03-03 바스프 에스이 Polyurethane system for the production of polyurethane sandwich parts
US8206791B2 (en) 2007-05-15 2012-06-26 Texas Research International, Inc. Protective coatings for high strength steels
CA2710691A1 (en) * 2009-09-30 2011-03-30 Garry Machine Mfg. Inc. Process for refurbishing cylinder rolls and bases for printing machines
KR101051316B1 (en) * 2010-11-22 2011-07-22 한국수자원공사 Ozone resistant polyurethane composition and process of preparing same
US10208227B2 (en) * 2013-01-30 2019-02-19 Lanxess Solutions Us Inc. Low free MDI prepolymers for rotational casting
US20140309397A1 (en) * 2013-04-11 2014-10-16 Anderson Development Company Polyurethane Elastomers Based on TDI Prepolymers Enriched in the 2,6-TDI Isomer Cured with Trimethylene Glycol Di-(para Amino Benzoate)
JP6176455B2 (en) * 2014-08-07 2017-08-09 シンジーテック株式会社 Paper feed roll and manufacturing method thereof
MX2018002285A (en) * 2015-11-17 2018-05-28 Stowe Woodward Licensco Llc Polyurethane roll cover for calender roll for papermaking machine.
WO2019003190A1 (en) * 2017-06-30 2019-01-03 3M Innovative Properties Company Composition comprising high creep rupture strength and methods of coating drinking water pipelines
DE102017115592A1 (en) * 2017-07-12 2019-01-17 Voith Patent Gmbh press cover
EP3441410A1 (en) * 2017-08-07 2019-02-13 RAMPF Holding GmbH & Co. KG Polyurethane system and its use in printing technology
FI128303B (en) * 2017-11-28 2020-03-13 Valmet Technologies Oy Roll and its use
CN113105816B (en) * 2021-03-31 2022-03-29 华南理工大学 Side chain epoxy functionalized polyurethane coating and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0239870A2 (en) * 1986-03-29 1987-10-07 Bayer Ag Process for the preparation of thixotropic binders, the binders obtained as a result of this process and their use in the preparation of coatings and sealants
EP0503755A1 (en) * 1991-03-13 1992-09-16 Gencorp Inc. Adhesive composition
EP0650988A1 (en) * 1993-10-30 1995-05-03 Hüls Aktiengesellschaft Cold curing, poorinsolvent or solventless 2-components polyurethane-urea composition

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3520747A (en) * 1965-10-29 1970-07-14 Mccreary Tire & Rubber Co Method of making structural members of layers of corrosion resistant coatings and fibrous material
US3646651A (en) * 1965-10-29 1972-03-07 Mccreary Tire & Rubber Co Abrasion and corrosion resistant composite structural materials and the like
US3929730A (en) * 1973-12-28 1975-12-30 Inter Polymer Res Corp Process for preparing polyurethanes employing a mixture of butanediol and phenylene diethanolamine as a chain extender
US4267299A (en) * 1978-09-22 1981-05-12 Metalweld, Inc. Method of curing isocyanate-terminated polyurethane prepolymers for use in solventless spray applications
JPS5936133B2 (en) * 1979-08-10 1984-09-01 山内ゴム工業株式会社 Polyurethane rubber roll and its manufacturing method
ZA816854B (en) * 1980-10-14 1982-09-29 Uniroyal Inc Polyurethane spray composition containing viscosity modifier
US4571798A (en) * 1983-09-19 1986-02-25 Beloit Corporation Urethane covered paper machine roll
US5112933A (en) * 1991-04-16 1992-05-12 Otis Elevator Company Ether-based polyurethane elevator sheave liner-polyurethane-urea made from polyether urethane prepolymer chain extended with polyester/diamine blend
US5504145A (en) * 1993-08-31 1996-04-02 The Thompson Minwax Company Water-dispersible poly(urethane-urea) compositions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0239870A2 (en) * 1986-03-29 1987-10-07 Bayer Ag Process for the preparation of thixotropic binders, the binders obtained as a result of this process and their use in the preparation of coatings and sealants
EP0503755A1 (en) * 1991-03-13 1992-09-16 Gencorp Inc. Adhesive composition
EP0650988A1 (en) * 1993-10-30 1995-05-03 Hüls Aktiengesellschaft Cold curing, poorinsolvent or solventless 2-components polyurethane-urea composition

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5994466A (en) * 1996-06-12 1999-11-30 Stowe Woodward Company Castable polyurethane elastomers for industrial rollers
WO1998056841A1 (en) * 1997-06-11 1998-12-17 Stowe Woodward Company Castable polyurethane elastomers for industrial rollers
EP0982079A2 (en) * 1998-08-24 2000-03-01 UNIROYAL CHEMICAL COMPANY, Inc. Method for producing cylindrical objects with multilayer coatings having dissimilar compositions without interfaces
EP0982079A3 (en) * 1998-08-24 2003-01-22 UNIROYAL CHEMICAL COMPANY, Inc. Method for producing cylindrical objects with multilayer coatings having dissimilar compositions without interfaces
WO2000039185A1 (en) * 1998-12-23 2000-07-06 Bayer Corporation Thixotropic wood binder compositions
US6287495B1 (en) 1998-12-23 2001-09-11 Bayer Corporation Thixotropic wood binder compositions
KR100558684B1 (en) * 1999-07-09 2006-03-10 주식회사 코오롱 A polyurethane polymer, and a process of preparing the same
US7090747B2 (en) 2000-11-10 2006-08-15 Yamauchi Corporation Belt for papermarking and process for producing papermaking belt
WO2002038859A1 (en) * 2000-11-10 2002-05-16 Yamauchi Corporation Belt for papermaking and process for producing papermaking belt
US7374641B2 (en) 2000-11-10 2008-05-20 Yamauchi Corporation Papermaking belt and method of manufacturing papermaking belt
WO2007128596A1 (en) * 2006-05-05 2007-11-15 Voith Patent Gmbh Pu roller
WO2009129206A3 (en) * 2008-04-17 2010-01-21 The Boeing Company Composition and method for corrosion protection of a structure
US7906215B2 (en) 2008-04-17 2011-03-15 The Boeing Company Composition and method for corrosion protection of a structure
US8367791B2 (en) 2008-04-17 2013-02-05 The Boeing Company Composition and method for corrosion protection of a structure
WO2013160358A1 (en) * 2012-04-27 2013-10-31 Voith Patent Gmbh Press roll with a roll cover consisting of polyurethane
CN104334796A (en) * 2012-04-27 2015-02-04 福伊特专利公司 Press roll with a roll cover consisting of polyurethane
US9267235B2 (en) 2012-04-27 2016-02-23 Voith Patent Gmbh Roll
IT201700109802A1 (en) * 2017-10-02 2019-04-02 Lanxess Solution Italia S R L Method and composition for rotational molding of a polyurethane coating layer
WO2019068531A1 (en) * 2017-10-02 2019-04-11 Lanxess Solution Italia S.R.L. Method and composition for rotational casting of polyurethane coating layer

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DE69701221T2 (en) 2000-06-21
JPH11509264A (en) 1999-08-17
JP3066084B2 (en) 2000-07-17
US5895689A (en) 1999-04-20
CA2253420C (en) 2006-11-28
ATE189238T1 (en) 2000-02-15
ES2142677T3 (en) 2000-04-16
US5895806A (en) 1999-04-20
AU2456697A (en) 1997-11-26
CA2253420A1 (en) 1997-11-13
PT897401E (en) 2000-04-28
EP0897401B1 (en) 2000-01-26
DE69701221D1 (en) 2000-03-02
EP0897401A1 (en) 1999-02-24

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