WO1998038249A1 - Dispersions aqueuses de polymeres polyurethannes et ethyleniques - Google Patents

Dispersions aqueuses de polymeres polyurethannes et ethyleniques Download PDF

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Publication number
WO1998038249A1
WO1998038249A1 PCT/US1998/003440 US9803440W WO9838249A1 WO 1998038249 A1 WO1998038249 A1 WO 1998038249A1 US 9803440 W US9803440 W US 9803440W WO 9838249 A1 WO9838249 A1 WO 9838249A1
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WO
WIPO (PCT)
Prior art keywords
prepolymer
dispersion
composition
carbon atoms
group
Prior art date
Application number
PCT/US1998/003440
Other languages
English (en)
Inventor
Rodney M. Weston
Konstantinos A. Arvanitis
Original Assignee
Witco Corporation
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 Witco Corporation filed Critical Witco Corporation
Priority to AU61806/98A priority Critical patent/AU6180698A/en
Publication of WO1998038249A1 publication Critical patent/WO1998038249A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • 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
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to aqueous dispersions containing both polyurethane polymers, and ethylenic polymers.
  • Polyurethanes find use in a variety of applications, including coatings, paints, adhesives, and the manufacture of fibers and solid articles.
  • Polyurethanes are typically soluble in organic solvents, and exhibit little if any solubility in aqueous solvents or in systems in which water and a second water-soluble solvent are employed.
  • Organic solvent-based resin solutions have thus typically been the vehicle of choice for use in forming coatings and the like of polyurethanes.
  • many organic solvents commonly used in conjunction with such resins present environmental problems associated with their toxicity.
  • U.S. Patent No. 4,318,833 discloses that a urethane/acrylic dispersion could be made by adding an ethylenic monomer to a fully reacted polyurethane dispersion and then polymerizing the monomer by free radical initiation.
  • U.S. Patents No. 4,644,030 and No. 5,169,895 describe a process in which a urethane prepolymer is prepared as a solution in an ethylenic monomer. This mixture is dispersed in water, the prepolymer is chain extended and the monomer is then polymerized by free radical initiation.
  • European Patent Application No. 0 510 572 A2 discloses the preparation of urethane/vinyl polymer dispersions by the addition of ethylenic monomers to a completely reacted urethane prepolymer to give a solution which is dispersed in water. The monomer is then polymerized by free radical initiation and the prepolymer is chain extended.
  • the present invention is thus directed to an improved technique for forming aqueous dispersions containing both polyurethane, which technique affords improved ease of operation, more satisfactory yields, and offers a greater variety in the selection of reactants and in the range of properties of the products that can be obtained.
  • the present invention is directed to a process for producing an aqueous dispersion of polyurethane and polyethylenic polymers, comprising
  • the present invention also includes the stable aqueous dispersions resulting from the foregoing method of this invention, the use of such dispersions for application in a film- forming amount to a substrate with subsequent drying thereon, and the resulting dried, cured and hardened films which may be permanently coated on the substrate or made self- supporting involving use of a substrate with a release surface.
  • the dispersions of the invention may also be used in the above manner or otherwise as impregnants and sizing for paper, textiles and other foraminous materials, as pigment binders and adhesives, and for making cross -linked brittle polymeric products when the dispersion contains non-elastomeric, non-film polyurethanes .
  • the method of this invention yields several unexpected improvements relative to the method disclosed in U.S. Patent No. 4,318,833 which produces a different type of aqueous dispersion containing polyurethanes and polymerized ethylenically unsaturated monomers.
  • the necessity of using an organic solvent medium (with its attendant disadvantages) in the reaction for producing the fully chain-extended polyurethane is eliminated.
  • the ethylenic polymer becomes intimately, homogeneously and/or molecularly intermixed with the polyurethane prepolymer in the reaction medium, so the subsequent chain extension of the prepolymer provides thereby a true, more thorough in situ dispersion.
  • the resulting aqueous dispersions of this invention thereby yield films and other products with unexpectedly improved properties with respect to rapidity of curing and hardening, resistance to water, organic solvents and environmental conditions, tensile strength, modulus of elasticity, and/or elongation and the like.
  • the products formed in accordance exhibit a single glass transition temperature (Tg) . This characteristic confirms that the products are distinct from mere mixtures of polyurethanes and polyethylenic polymers, which would exhibit at least two glass transition temperatures.
  • the prepolymer is terminated with preferably an average of at least two isocyanate (-NC0) groups per molecule.
  • NCO- terminated polyurethane prepolymers are commonly produced by reacting organic material containing an average of at least about 2 active hydrogen atoms per molecule, usually a diol and preferably a polyester polyol, with a stoichiometric excess of an organic diisocyanate, preferably methylene bis (isocyanato cyclohexane) .
  • a suitable proportion of the said organic material also contains anionic substituent groups for providing water dispersibility to the prepolymer, such as at least one comparatively unreactive pendant carboxylic or sulfonate group, in salt form or preferably neutralized with a suitable basic material to salt form during or after the prepolymer formation or during the formation of the dispersion.
  • anionic substituent groups for providing water dispersibility to the prepolymer such as at least one comparatively unreactive pendant carboxylic or sulfonate group, in salt form or preferably neutralized with a suitable basic material to salt form during or after the prepolymer formation or during the formation of the dispersion.
  • Any organic polyisocyanates may be used in the process according to the invention. It is preferred to use polyisocyanates of the formula
  • Q represents an aliphatic hydrocarbon group containing from 4 to 12 carbon atoms, a cycloaliphatic hydrocarbon group containing from 6 to 15 carbon atoms, an aromatic hydrocarbon group containing from 6 to 15 carbon atoms or an araliphatic hydrocarbon group containing from 7 to 15 carbon atoms.
  • the most preferred diisocyanate is isophorone diisocyanate.
  • diisocyanates tetramethylene- diisocyanate, hexamethylene diisocyanate, dodecamethylene- diisocyanate, 1 , 4 -diisocyanato- cyclohexane, 1- isocyanato- 3 , 3, 5 - trimethyl - 5 - isocyanatomethyl cyclohexane, 4,4' -diisocyanatodicyclohexylemethane, 4,4' - diisocyanato -dicyclohexyl -propane- (2,2); 1,4- diisocyanato-benzene, 2 , 4 -diiocyanatotoluene, 2,6- diisocyanatotoluene, 4 , 4 ' -diisocyanatodiphenylmethane, 4,4' -diisocyanatodiphenyl -propane- (2,2)
  • Reaction of the diisocyanate and the polyol or polyol polymer can be carried out at moderately elevated temperatures, e.g. 50°C.-100°C.
  • the reaction is generally carried out in an inert solvent or without a solvent.
  • One preferred solvent is N-methyl pyrrolidone.
  • Other suitable solvents include acetone, methyl ethyl ketone, toluene, dimethyl formamide, ethyl acetate, tetrahydro furan, and dioxane.
  • Suitable polyol reactants preferably have a molecular weight (M.W.) of about 400 to 5000, and an average OH value of about 10 to about 1,000, preferably about 30 to about 150, as determined by ASTM E222-67, Method B.
  • M.W. molecular weight
  • other polyols or mixtures thereof may be employed such as poly-caprolactone, polycarbonate and polybutadiene resins (hydroxyl terminated homopolymers of butadiene) , polyethers based on ethylene oxide, propylene oxide and tetrahydrofuran, and the like.
  • isocyanate reactant which, in addition to or instead of the preferred organic diisocyanate may include organic materials containing an average of more than two isocyanate groups.
  • suitable commercially available polyisocyanates include Mondur CB (adduct of 3 moles toluene diisocyanate with 1 mole trimethylol propane, Bayer) , Desmodur-N,
  • the NCO- terminated polyurethane prepolymers employed in this invention are preferably rendered water dispersible by including in the prepolymer chain an effective water -dispersing amount of pendant carboxylic or cationic salt groups such as sulfonate groups. Such amount is typically about 0.5 to about 10 wt.% of such groups.
  • the monomer - containing prepolymer may be devoid of such groups in which case it is then dispersed in water with the aid of a dispersing agent, preferably a nonionic ethoxameric surfactant.
  • the polyurethane chain in known manner contains about 1 to abut 5 wt.% of units derived from melamine, thereby providing films produced from the present aqueous dispersions with improved resistance to organic solvents.
  • the polyurethane is provided in known manner with cross - linking, curable, hardening groups activated to self condensation and cross - linking upon drying of the film on a substrate under ambient conditions, such groups comprising about 2 to about 10 wt.% of N-methylol hydrazide terminii or end caps.
  • homopolymers are contemplated as are copolymers of two (or more) different ethylenically unsaturated monomers .
  • Such monomers include butadiene, isoprene, styrene, alpha-methyl styrene and the like; substituted styrenes such as chlorostyrene, dichlorostyrene, bromostyrene, p-vinylphenyl phenyl oxide and the like; the acrylic and substituted acrylic monomers such as acrylic acid, methacrylic acid, cyclohexyl acrylate and methacrylate, benzyl acrylate and methacrylate, the C ⁇ .
  • alkyl acrylates and methacrylates such as methyl , ethyl and butyl acrylate and methacrylate, phenyl acrylate, phenyl methacrylate, alphachloroacrylonitrile and the like; the vinyl esters and vinyl ethers such as vinyl acetate, vinyl acrylate, vinyl methacrylate, vinyl propyl ethers, vinyl butyl ethers and the like; other water soluble monomers, especially hydroxy -C 1 -C 6 - alkyl esters such as hydroxy ethyl acrylate or methacrylate, hydroxy propyl acrylate or methacrylate and the like.
  • Any of the known polymerizable monomers can be used and the compounds listed above are illustrative and not restrictive of the monomers suitable for use in this invention.
  • the ethylenically unsaturated monomers which are preferred in the practice of this invention include the (meth) acrylic and substituted (meth) acrylic monomers as well as styrene.
  • the aqueous dispersion used in the present invention is preferably prepared by emulsion polymerization of the monomers or comonomers in an aqueous system.
  • the reagents necessary for emulsion polymerization are those conventionally employed, including a free radical initiator (typically a peroxy compound) and a surfactant (typically an anionic surfactant, such as alkyl sulfonates, alkyl aryl sulfonates, or alkyl aryl polyalkoxy sulfonates) .
  • the conditions for carrying out the emulsion polymerization are likewise those conventionally employed, and are familiar to those of ordinary skill in this art.
  • the polyurethane prepolymer which is preferably free of ethylenically unsaturated monomeric compounds, is next combined with the aqueous dispersion of the polyethylenic polymer.
  • the ratio by weight of the polyurethane to the polyethylenic polymer should be in the range of 10:90 to 90:10 and more preferably 70:30 to 30:70.
  • the polyurethane prepolymer and the polyethylenic polymer dispersion are preferably combined by dispersing the polyurethane prepolymer into the dispersion of the polyethylenic polymer. This can be accomplished by providing the polyethylenic polymer dispersion in a vessel and then adding thereto the prepolymer while the vessel contents are being subjected to high shear agitation. The presence of the surfactant (s) used in the emulsion polymerization step assists in formation of a stable aqueous dispersion of the prepolymer and the polyethylenic polymer.
  • the prepolymer is next reacted with a suitable chain extender, which reacts with the isocyanate groups.
  • suitable chain extenders include diamines such as hydrazine, and alkyl and aromatic polyols, especially diols, and alkyl and aromatic diamines and triamines, wherein the alkyl compounds contain a table of 2 to 12 carbon atoms or the aromatic moiety contains 6 to 10 carbon atoms.
  • chain extenders include ethylene diamine, diethylene triamine, 1, 2 -diaminopropane, 1,3- diaminopropane, 1 , 4 -diaminobutane, and 3,3,5- trimethyl - 5 -aminomethyl cyclohexylamine; and ethylene glycol, 1 , 2 -dihydroxypropane, 1 , 6-dihydroxyhexane, and the polyols described herein as useful reactants to make the polyester.
  • the product of reaction with the chain extender is a dispersion of polymeric polyurethane together with the polyethylenic polymer.
  • This dispersion exhibits functional properties superior to those exhibited by mixtures obtained by forming the polyurethane and polyethylenic polymers separately and then mixing them together.
  • aqueous dispersions of this invention are advantageously employed as coating compositions, for which purpose they may be further diluted with water and/or organic solvents, or they may be supplied in more concentrated form by evaporation of water and/or organic components of the liquid medium.
  • coating compositions they may be applied to any substrate including wood, metals, glass, cloth, plastics, foam and the like, by any conventional method including brushing, dipping, flow coating, spraying, and the like.
  • the compositions may contain other conventional ingredients including organic solvents, pigments, dyes, emulsifiers, surfactants, thickeners, heat stabilizers, leveling agents, anticratering agents, fillers, sedimentation inhibitors, UV absorbers, antioxidants and the like introduced at any stage of the production process or subsequently.
  • dispersions are preferably applied to substrates in effective film- forming amounts depending on the solids content, temperature and other conditions, the type of substrate, product desired, etc.
  • the film coating on the substrate may simply be protective, decorative, and/or intelligence imparting or the like or serve as an adhesive or other function.
  • Self-supporting thin or thick films or sheets may be produced by application to a substrate with a release surface from which the cured, hardened film can be removed. Hardening and curing on the substrate is generally accomplished by simply drying under ambient conditions, which may if desired by expedited and/or facilitated by concurrent heating, subsequent baking, etc.
  • the dispersions of this invention have good storage storage- stability and yield films and coatings with improved properties such as resistance to water, organic solvents and environmental conditions, flexibility, elasticity and/or tensile strength, and the like.
  • the mixture in the flask was heated under dry air for 4 hours at 80°C-85°C, until the residual isocyanate content was 4.1% (theoretical isocyanate content was 4.1%) , then 6. was added and mixed for 30 minutes. The result was a NCO- terminated prepolymer.
  • Triton X-200 (alkyl aryl EO sulfonate) 96.00 3. Methyl methacrylate 792.00
  • a purely physical blend of the polyurethane and the acrylic dispersion was prepared by making a water-borne polyurethane dispersion by the method shown below and blending this with the acrylic dispersion described earlier.
  • Films were prepared from this blend. These were air -dried overnight and annealed in an oven at 130°C for 2 hours. The films had the following properties :
  • the physical properties of the film prepared from the blended dispersions were inferior to those of the film prepared from urethane/acrylic dispersion of the present invention.
  • the film from the blend also exhibited three T g values, unlike the dispersion of the present invention; which showed a single T .
  • a comparison of the chemical resistance tests carried out on the blend and the dispersion of the present invention also showed the inferiority of the physical blend (see table below) :
  • the resulting dispersion had the following physical properties:
  • the prepolymer was prepared using the same ingredients and same procedure as in Example 2.
  • the NCO- terminated prepolymer as described in Example 2. was dispersed in 2692 g of the poly (butyl acrylate- methacrylic acid) dispersion and chain extended as in Example 2.
  • the physical properties of the resulting dispersion were:
  • the resulting NCO- terminated prepolymer had a theoretical % NCO of 2.88.
  • the NCO- terminated prepolymer was added, with high speed stirring, to 1070 g of the poly (butyl acrylate-methacrylic acid) dispersion containing 7.9 g of triethylamine and 71 g of a nonionic nonyl phenol surfactant.
  • the dispersion temperature was maintained below 35°C during the prepolymer addition.
  • 21.5 g of a 35% solution of hydrazine was added and an exotherm of 5°-10°C occurred.
  • the physical properties of the dispersion were :
  • Viscosity (Brookfield LVF) , cps 1100

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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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

On fabrique des dispersions homogènes de polymères polyuréthannes et polyéthyléniques en dispersant un prépolymère isocyanate dans une dispersion aqueuse de polymère polyéthylénique, et en allongeant la chaîne du prépolymère. La dispersion résultante présente une température de transition vitreuse unique.
PCT/US1998/003440 1997-02-28 1998-02-23 Dispersions aqueuses de polymeres polyurethannes et ethyleniques WO1998038249A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU61806/98A AU6180698A (en) 1997-02-28 1998-02-23 Waterborne dispersions of polyurethane and ethylenic polymers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US80811297A 1997-02-28 1997-02-28
US08/808,112 1997-02-28

Publications (1)

Publication Number Publication Date
WO1998038249A1 true WO1998038249A1 (fr) 1998-09-03

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7238391B2 (en) 2000-11-01 2007-07-03 Valspar Sourcing, Inc. Abrasion resistant coating for stacks of fiber cement siding
EP2210908A1 (fr) 2006-07-31 2010-07-28 Lubrizol Advanced Materials, Inc. Dispersions aqueuses de compositions de polyuréthane avec une cétone-hydrazide
WO2012058534A1 (fr) 2010-10-29 2012-05-03 Lubrizol Advanced Materials, Inc. Dispersions aqueuses cationiques de polyuréthanne

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4927876A (en) * 1987-09-14 1990-05-22 Ici Americas Inc. Aqueous dispersions
US5011881A (en) * 1989-01-18 1991-04-30 Kansai Paint Company, Limited Aqueous thermoplastic coating composition for plastics materials and coating method using same
US5227422A (en) * 1990-08-22 1993-07-13 Kansai Paint Company, Limited Aqueous coating composition and coating
US5541251A (en) * 1994-01-14 1996-07-30 U C B S.A. Aqueous polyurethane compositions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4927876A (en) * 1987-09-14 1990-05-22 Ici Americas Inc. Aqueous dispersions
US5011881A (en) * 1989-01-18 1991-04-30 Kansai Paint Company, Limited Aqueous thermoplastic coating composition for plastics materials and coating method using same
US5227422A (en) * 1990-08-22 1993-07-13 Kansai Paint Company, Limited Aqueous coating composition and coating
US5541251A (en) * 1994-01-14 1996-07-30 U C B S.A. Aqueous polyurethane compositions

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7238391B2 (en) 2000-11-01 2007-07-03 Valspar Sourcing, Inc. Abrasion resistant coating for stacks of fiber cement siding
US7442416B2 (en) 2000-11-01 2008-10-28 Valspar Sourcing, Inc. Method using abrasion resistant coating for stacks of fiber cement siding
EP2210908A1 (fr) 2006-07-31 2010-07-28 Lubrizol Advanced Materials, Inc. Dispersions aqueuses de compositions de polyuréthane avec une cétone-hydrazide
WO2012058534A1 (fr) 2010-10-29 2012-05-03 Lubrizol Advanced Materials, Inc. Dispersions aqueuses cationiques de polyuréthanne

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Publication number Publication date
AU6180698A (en) 1998-09-18

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