EP0646149A1 - Revetement et materiau d'etancheite contenant du polyurethane - Google Patents

Revetement et materiau d'etancheite contenant du polyurethane

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Publication number
EP0646149A1
EP0646149A1 EP92917303A EP92917303A EP0646149A1 EP 0646149 A1 EP0646149 A1 EP 0646149A1 EP 92917303 A EP92917303 A EP 92917303A EP 92917303 A EP92917303 A EP 92917303A EP 0646149 A1 EP0646149 A1 EP 0646149A1
Authority
EP
European Patent Office
Prior art keywords
composition according
coating composition
uud
latices
applying
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP92917303A
Other languages
German (de)
English (en)
Other versions
EP0646149A4 (fr
Inventor
Robert M. Evans
Han X. Xiao
Kurt C. Frisch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ROBERT M EVANS ASSOCIATES Inc
Original Assignee
ROBERT M EVANS ASSOCIATES Inc
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Application filed by ROBERT M EVANS ASSOCIATES Inc filed Critical ROBERT M EVANS ASSOCIATES Inc
Publication of EP0646149A4 publication Critical patent/EP0646149A4/fr
Publication of EP0646149A1 publication Critical patent/EP0646149A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
    • C08L95/005—Aqueous compositions, e.g. emulsions
    • 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

Definitions

  • compositions and methods providing improved sealing and coating properties.
  • Such compositions and methods are particularly useful in sealing and/or coating aging, chalky, rough or powdery surfaces which are typically difficult to seal or coat and maintain good adhesion, such as roofs or driveways. They are also particularly useful in coating flexible surfaces (or surfaces undergo thermal expansion/contraction) and require the associated coating to flex without significant loss of its sealing properties.
  • compositions and methods of the present invention relate to waterborne sealing or coating compositions which employ urethane-urea dispersions. They also relate to compositions which include urethane-urea dispersions ("UUD") and which also employ asphalt, natural and/or synthetic latex, or mixtures of all three, and may additionally employ other select additives or components. These other additives or components include other polymers or polymer-like material (e.g., in addition to latices and asphalt emulsions); pigments; fillers; biocides; antioxidants; and the like.
  • UUD urethane-urea dispersions
  • compositions and methods are known in the art; however, none of the art-disclosed compositions or methods provide the same combination of unique properties and advantages as the compositions and methods of the present invention.
  • Warach in "Polyurethane Dispersions - Waterbased High
  • the primary coating substances may include one or more of the mentioned classes of compound such as a polymethyl methacrylate latex in which particles of polystyrene or a prepolymer of the urethane type are dispersed together with bitumen particles and/or a natural or synthetic (ABS-type) rubber.
  • ABS-type natural or synthetic
  • the patentee discloses specific latex materials and, more specifically, water-dispersible polyurethane products from stable latices of select chain-extended quaternized polyurethane ureas.
  • a specific latex is made from a quaternized isocyanate terminated prepolymer. These materials are disclosed as being useful as adhesives and "skin-coat” films and do not require heat for "drying.”
  • U. S. Patent Nos. 3,873,484 issued to Bluestein et al. on March 25, 1975; and 3,758,427 issued to Katsibas on September 11, 1973; are directed to additional water- dispersible polyurethanes. Both of these patents are expressly incorporated herein by reference.
  • U. S. Patent No. 4,186,118, issued to Reischl et al. on January 29, 1980, discloses a process for preparing modified aqueous synthetic resin dispersions which includes introducing organic diisocyanates (which are liquid at room temperature) into polyurethane-containing, non-sedimenting, aqueous synthetic resin dispersions.
  • aqueous dispersions so modified are described as containing latex particles which are enveloped with polyurea formed from the diisocyanates.
  • the resulting compositions are described as being useful as water-resistant surface coatings.
  • aqueous dispersions of non-polyurethane polymerization products may be mixed with the polyurethane dispersion before the process described by the patentee is carried out.
  • Polymer latices can be made from, among other materials: natural or synthetic rubber; butadiene-methacrylate copolymers; polyacrylic acid esters; PVC; and others. See, without limitation, Col. 2, lines 34-44.
  • U. S. Patent No. 3,988,278 issued to D. C. Bartizal on October 26, 1976 discloses self-emulsified polyurethane polyurethane-polyurea latices formed by chain extending (in water) a prepolymer which contains about two isocyanates group (per molecule) at the ends of a chain. Attached to some of these prepolymer chains is a pendant group; at the end of the pendant group is either a "salt-forming" group or a hydrophilic group. It is the patentee's contention that it is the inclusion of these latter groups which produces the resulting self-emulsified characteristics.
  • exemplary coating or sealing compositions of the present invention comprise dispersions or suspensions preferably employing: (a) a select urethane-urea dispersion at a level of up to about 90% by weight of solids of the final compositions (wherein said UUD is preferably a chain-extended anionic, cationic and nonionic polyurethane-urea dispersion and is optionally a UUD modified latex) wherein the UUD preferably has an average particle size of less than about 0.1 microns, more preferably less than about 0.65 and still more preferably about 0.02 to about 0.06 microns; and (b) up to about 90%, by weight of solids of the final composition, of a bituminous material, preferably as asphalt added as an asphalt emulsion or natural latex.
  • compositions of the present invention also comprise (a) about 3% to about 40%, by weight of solids, of a urethane-urea dispersions having a select average particle size; (b) about 3% to about 30% of a natural or synthetic latex material; and (c) about 10% to about 94% of a bituminous material (preferably an asphalt emulsion) wherein said composition cures without application of heat.
  • a bituminous material preferably an asphalt emulsion
  • the methods of the present invention also include the application of a composition comprising a blend of a urethane-urea dispersion (UUD) with a select average particle size.
  • the methods further include the application of a natural or synthetic latex (e.g., an acrylic) modified by the inclusion of a UUD.
  • the methods still further include the application of an asphalt modified by a UUD or UUD latex or UUD ⁇ atex/asphalt composition to a roof or driveway, preferably with the addition of a pigment, filler, or the like.
  • the methods of the present invention also relate to the preparation of these materials and the application of these compositions to a surface in need of coating or sealing.
  • Urethane-urea dispersions based upon or which employ aromatic isocyanates, aliphatic isocyanates (including cyclic aliphatics), trimeric isocyanates, or mixtures there of, are useful in the compositions and methods of the present invention.
  • Aliphatic-based materials and more particularly cyclic aliphatic-based materials, are highly preferred.
  • Such art-disclosed teachings of these compositions are included in Waterborne Polyurethanes, J. W. Rosthauser and K. demokamp, published as part of a collection in
  • anionic, cationic or nonionic urethane-urea is modified by the inclusion or addition of a latex.
  • these urethane-urea dispersions useful in the present invention are prepared by fully reacting urethane polymers in an aqueous system. They may be cationic, anionic or nonionic, depending upon the selection of the functional diol employed.
  • a polyol, a diisocyanate, a functional diol, a neutralizing agent (if necessary), a chain extender, and water are employed; the resulting products are fully reacted. While anionic, cationic and nonionic materials are useful, anionic materials are presently highly preferred.
  • the NCO-terminated anionic, cationic or nonionic prepolymer is dispersed in water to provide a dispersion of an NCO-terminated prepolymer.
  • the polyurethane dispersion further reacts with an amine -reactive reagent to form the desired chain extended polymeric product having a higher molecular weight.
  • the amine- reactive reagent is added substantially together with the water.
  • Liquid polymers based on butadiene and containing a controlled number of hydroxyl functional groups can be utilized for the preparation of the prepolymer used in the present invention.
  • a hydroxylated polybutadiene having a functionality of about 2.1 is used.
  • the polyol or mixture of polyols utilized for the preparation of such a prepolymer for use in the present invention preferably has a hydroxyl number in the range of from about 10 to about 200, most preferably in the range of from about 20 to about
  • the polyol can also comprise, alternatively, a hydroxyl or polyhydroxy- containing polyester.
  • a hydroxyl or polyhydroxy- containing polyester preferably comprises a dihydroxy or a trihydroxy compound and, optimally, the dihydroxy polyester polyol is utilized.
  • Polyether type polyols are most commonly derived from simple alkane diols, polymerized by reaction with an alkylene oxide, for example, to form the corresponding polyoxyalkylene polyether polyols.
  • the preferred polyol monomers can be selected from among the glycols, such as neopentylglycol, ethyleneglycol, diethyleneglycol, hexamethyleneglycol, 1,4- and 1,3-butyleneglycols, 1,3- and 1,2-propyleneglycols, and the corresponding dipropyleneglycols.
  • the most useful monomeric triols include the alkyl triols, such as trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, 1,2,6-hexanetriol, glycerol, and triethanolamine.
  • Aromatic polyols can also be used, such as trihydroxymethyl benzene.
  • the alkylene oxides used in preparing the polyether polyols are preferably those which contain from two to about four carbon atoms, including, for example, ethylene oxide, 1,2-propylene oxide and 1,2-butylene oxide, and homopolymers and copolymers thereof.
  • the polyhydric, polyalkylene ether can also be prepared from reagents such as glycidol and cyclic ethers, such as tetramethylene ethers, and the epihalohydrins, e.g., epichlorohydrin.
  • the polyaralkylene ether polyols are derived from the corresponding aralkylene oxides, such as, for example, styrene oxide, alone or mixed with alkylene oxide. Generally, 1,2-propylene oxide, and mixtures of 1,2-propylene oxide and ethylene oxide, are preferred for the preparation of the polyether polyol reactant.
  • the polyether polyols are useful in the present invention preferably at a molecular weight of from about 500 to about 8,000, most preferably from 1,000 to about 6,500, and optimally not greater than about 5,000, and are preferably characterized by a hydroxy functionality of at least about 1.5 up to about 8, and more preferably an average hydroxy functionality of from about 2 to about 5. Mixtures of all of the above may also be employed.
  • the polyester polyol compounds useful for preparing the prepolymer in accordance with the present invention can be prepared by, for example, the reaction of a polyhydric alcohol with a polycarboxylic acid, generally each containing from about two to twenty carbon atoms.
  • the polycarboxylic acid can be not only the free carboxylic acid, but such acid precursors as the corresponding acid anhydrides or acid halides or even, for example, alkyl esters.
  • the preferred acids are the dicarboxylic acids containing from about 4 to about 12 carbon atoms.
  • Examples of the preferred carboxylic acid components include, for example, aromatic acids such as phthalic acid, terephthalic acid, isophthalic acid, tetrachlorophthalic acid; cycloaliphatic acids, such as dimerized Iinoleic acid, maleated and fumarated rosin acids, and cyclohexane-l,4-diacetic acid; but preferably include the aliphatic acids, such as oxydipropionic, succinic, glutaric, adipic, azelaic, suberic, and sebacic acids, or mixtures of such acids.
  • aromatic acids such as phthalic acid, terephthalic acid, isophthalic acid, tetrachlorophthalic acid
  • cycloaliphatic acids such as dimerized Iinoleic acid, maleated and fumarated rosin acids, and cyclohexane-l,4-diacetic acid
  • aliphatic acids such as oxydipropionic
  • Lactones which can be used in place of the polyester polyols include those derived from gamma-butyrolactone, or epsilon-caprolactones.
  • the glycols which can be utilized in the preparation of the prepolymer polyesters include any of those set forth above for the preparation of the polyether polyols. Generally, however, a dihydric polyol is preferred when preparing the polyester even more than when preparing the polyether polyol.
  • the polyester polyol reactants preferably have a molecular weight of at least about 500 and optimally between about 2,000 and 6,000.
  • the maximum molecular weight for both the polyether and the polyester polyols is limited primarily by the difficulty of mixing such materials with the other ingredients in the procedure.
  • the higher molecular weight ingredients are useful, but because of the difficulty of working with them, they are not considered economical or practical and, therefore, are less preferred.
  • An efficient mixing apparatus must be provided when dealing with such high molecular weight materials.
  • polystyrene resin examples include polyethylene glycol dimethacrylate resin, polypropylene glycol dimethacrylate resin, polyethylene glycol dimethacrylate resin, polypropylene glycol dimethacrylate resin, polymethyl methacrylate resin, polymethyl methacrylate resin, polymethyl methacrylate resin, polymethyl methacrylate resin, polymethyl methacrylate resin, polymethyl methacrylate resin, polymethyl methacrylate resin, polystyrene, polys modified by grafting styrene and an acrylonitrile, such as Pluracol 637; Pluracol 1002; or Pluracol 1028 (all available from BASF Corp.) can also be employed in the preparation of a UUD.
  • Pluracol 637 examples include Pluracol 1002; or Pluracol 1028 (all available from BASF Corp.
  • the organic polyisocyanates useful in preparing the prepolymer compound in accordance with the present invention include those which contain at least two isocyanate groups per molecule, and may contain two or three isocyanate groups.
  • the useful isocyanates include, aromatic, aliphatic, cycloaliphatic, and trimeric isocyanates. Most preferably a diisocyanate is utilized.
  • Suitable organic polyisocyanates include, for example, n-butylene diisocyanate, methylene diisocyanate, m-xylylene diisocyanate, p- xylylene diisocyanate, cyclohexyl-l,4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3-(alphaisocyanatoethyl)-phenyl isocyanate, 2,6-diethylbenzene-l,4-diisocyanate, diphenyl-dimethylmethane-4,4'- diisocyanate, ethylidene diisocyanate, propylene-l,2-diisocyanate, cyclohexylene-1,2- diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene
  • the aromatic, aliphatic diisocyanates and the cyclocaliphatic diisocyanates are preferred.
  • the diisocyanates which have been found most useful in the preparation of the prepolymers are, specifically, cyclocaliphatic isocyanates, such as dicyclohexyl methane 4,4' diisocyanate (H 12 MDI), isophorone diisocyanate (IPDI), and aromatic isocyanates including toluene diisocyanate (TDI), and diphenyl methane diisocyanate.
  • IPDI based UUD's tend to have different characteristics than H 1 MDI based UUD's. For example, IPDI-based materials appear to demonstrate improved elongation and adhesion with the H 12 MDI-ba_ed materials appear to demonstrate better tensile strength.
  • the polyol and polyisocyanate are preferably reacted with an acid functional diol to form a pendant acid-containing NCO- terminated prepolymer.
  • the preferred acid-containing diols may be of the formula (HO)-R(COOH) y or (HO)_R(SO 3 H) y where R represents a straight or branched chain hydrocarbon radical having from 1 to about 20 carbon atoms, and preferably about 2 to about 5 carbon atoms; x represents a value of from 1 to about 5, and preferably about 2 to 3; and y represents a value of from 1 to about 4, and preferably 1 to about 3.
  • acid containing diols When such acid containing diols are employed, they may be neutralized (the pendent group) with organic or inorganic bases such as ammonium hydroxide, sodium hydroxide, potassium hydroxide, triethylamine, dimethylethylamine, and the like.
  • organic or inorganic bases such as ammonium hydroxide, sodium hydroxide, potassium hydroxide, triethylamine, dimethylethylamine, and the like.
  • hydrophilic- group containing materials are preferably ethoxylated materials of the formula III or IV
  • R represents a straight or branched chained hydrocarbon radical containing 1 to about 20 carbon atoms, and preferably about 2 to about 5 carbon atoms; n represents a value of from 1 to about 5, and preferably about 2 to about 3; m represents a value of about 1 to about 50, and preferably 2 to about 20, and even more preferably about 2 to about 10; R 2 represents a straight or branched hydrocarbon radical containing 1 to about 5 carbon atoms, preferably 1 to about 3; and R j represents either an aromatic or aliphatic hydrocarbon, e.g., H 12 MDI, IPDI, etc.
  • the nonionic UUD can also be formed by reacting the prepolymer with diamines such as hydrazine and ethylene diamine, among others.
  • diamines such as hydrazine and ethylene diamine, among others.
  • R 3 is an aromatic or aliphatic hydrocarbon, preferably H 12 MDI or IPDI; and R 4 is (CH 2 ) X wherein x is O to about 4. Continued chain growth then proceeds.
  • a neutralization step typically required with the preparation of an anionic or cationic (quaternized) material, is not required with the preparation of a nonionic UUD.
  • the only significant groups in the reactant compounds are the isocyanate groups and the hydroxyl groups which are reactive therewith.
  • Any other group can be present in the reactants or in the final urethane polymer, so long as the group does not adversely interfere with, and is preferably inert to, the desired isocyanate/hydroxyl reaction as well as the optional neutralizing reaction and the subsequent chain-extending reactions between the prepolymer and the a ine -reactive reagent.
  • acyclic, alicyclic, aromatic and heterocyclic groups can all be present on any of the reactive compounds as long as they do not adversely interfere.
  • inert substituent groups such as certain halogens
  • inert substituent groups can be present as long as they do not interfere with any of these reactions.
  • any suitable monofunctional quatemizing agent can be utilized in preparing a prepolymer.
  • a di(loweralkyl) sulphate is preferred.
  • the lower alkyl groups most preferably contain up to about 6 carbon atoms each and include, for example methyl, ethyl, n-propyl, isopropyl, etc. Dimethylsulphate is most preferred because of its ready availability and low cost.
  • a catalyst is generally preferably present to increase the rate of reaction, especially between the polyisocyanate and the polyol.
  • Catalysts which are useful for this reaction are well known in the art and include, for example, metal catalysts such as tin compounds and bismuth compounds, as well as other metal compounds, such as compounds of cobalt, lead, and, vanadium.
  • metal catalysts such as tin compounds and bismuth compounds
  • other metal compounds such as compounds of cobalt, lead, and, vanadium.
  • the tin compounds which include the stannous salts, e.g. stannous octoate, stannous acetate, and stannous oleate, the stannic salts, e.g.
  • stannic diacetate, and stannic di-octoate and also the covalently- linked, so-called organotin compounds, such as the dialkyltin dicarboxylate salts, including, for example, dibutylin diactate, and dibutylin dilaurate, and tributyltin oxide.
  • organotin compounds such as the dialkyltin dicarboxylate salts, including, for example, dibutylin diactate, and dibutylin dilaurate, and tributyltin oxide.
  • the preparation of the prepolymer and the anionic, cationic or nonionic isocyanate terminated prepolymer, as described above, is conventional in the art, and the various materials useful for forming such a prepolymer are generally described in the literature, for example, in the text Advances in Polyurethane Science and Technology, Vol. 10, Roshauser and Nachcamp; published by Technomic Publishing, (1987); also see Warrach as well as U. S. Patent Nos. 3,873,484, 4,046,729, 4,160,065, 4,403,083, 4,501,852, and 4,472,550, all mentioned supra and incorporated herein by reference.
  • the prepolymer is generally prepared in an anhydrous medium, and can include the presence of an inert diluent or solvent medium.
  • solvent is optional, and can be avoided if the viscosity (if liquid) of the various reagents permits. Generally, not more than about 10% of an organic solvent is utilized, if any. Any suitable inert organic solvent can be utilized, and the term "inert" in this context refers to an ingredient which does not enter into, nor interfere with, the course of the prepolymerizing or quaternizating reactions.
  • Useful such solvents include, preferably, n-methyl pyrrolidone, acetone and other water-soluble materials.
  • Other useful solvents include, for example, tetrahydrofuran, dimethylformamide, ethylacetate, benzene, dioxane, and the like.
  • the solvent most preferably has a boiling point in the range of from about 40° to about 90°C, in order to facilitate separation of the solvent from water.
  • the proportions of the polyisocyanate reactant to the polyhydric alcohol reactant, including one or more polyols, can be varied to achieve desired results by varying the NCO/OH ratios in order to obtain different concentrations of soft and hard segments.
  • the total isocyanate (— NCO) equivalent-to-total hydroxy equivalent should be such as to provide from about 1.6 to about 2.4 equivalents of the hydroxy to about 3 to about 7 equivalents of the isocyanate, the preferred ratio being approximately 1.4 hydroxy equivalents to 2.1 isocyanate equivalents.
  • the proportions of the major reagents in the cationic prepolymer reaction mixture would be as follows:
  • the isocyanate terminated prepolymer in accordance with the present invention, comprises a terminal isocyanate group ( ⁇ NCO) group content within the range of from about 0.5% to about 10% by weight, and most preferably in the range from about 1.4% to about 3.5% by weight of the isocyanate group.
  • ⁇ NCO terminal isocyanate group
  • the prepolymer is generally prepared in anhydrous medium.
  • the addition of a solvent is optional and depends upon the viscosity and state of the various reagents utilized and the apparatus which is available for carrying out the process.
  • the reaction is generally carried out at a temperature above typical room temperatures, as the result of the reaction exotherm. However, the reaction can be carried out at a temperature of from about a typical room temperature (or even lower) up to the natural exotherm temperature of the reaction, which should generally be maintained at or below about 125°C, and preferably at no greater than about 85°C. Higher temperatures can be utilized but are not preferred because of possible concurrent side reactions at higher temperatures.
  • the reaction is generally initiated by admixing the polymeric polyol, such as the polyether polyol or polyester polyol, with an acid functional diol or tertiary alkanolamine or hydrophilic group containing diol and the polyisocyanate. Following substantial completion of this reaction, and cooling to almost room temperature, the prepolymer is by the addition of the neutralizing agent, for example, the triethylamine.
  • the neutralizing agent for example, the triethylamine.
  • a diol such as a polyoxyalkylene glycol
  • a diol such as a polyoxyalkylene glycol
  • an acid functional diol or N-alkyl dialkanolamine, or hydrophilic group- containing diol
  • an organic polyisocyanate most preferably, a diisocyanate.
  • the resultant reaction mixture is then neutralized (if desired) with about 0.5 equivalent of a neutralizing agent, such as triethylamine.
  • the resulting anionic, nonionic or cationic (quaternized) prepolymer as finally prepared, generally has an average molecular weight in the range of from about 500 to about 100.000; however, the molecular weight of the prepolymer is estimated and does not form a critical part of the present invention. It is prepared such that the typical or average particle size is in the range of from about less than 1 micron; more preferably less than about 0.8 microns; still more preferably less than about 0.65 microns, and still more less than about 0.4 microns. In one highly preferred embodiment, the average particle size is in the range of about 0.02 to about 0.06 microns.
  • the resulting UUD may then be employed to coat and/or seal an aging, chalky, rough and/or powdery surface. It is particularly useful in coating pavement or roofing surfaces. It is also useful in coating metal and plastic surfaces;
  • the UUD may also be used to modify a waterborne latex-containing composition, or water-borne asphalt-containing composition; it may also be used to modify a latex-containing composition which is then employed to in turn modify a water-borne asphalt-containing composition.
  • These compositions are likewise useful in coating and/or sealing an aging, chalky, rough, powdery and/or flexible surface in need of such coating or sealing, particularly roofing and pavement surfaces.
  • An asphalt emulsion which can be anionic, cationic or nonionic, is added to the UUD prepared as described above to prepare the UUD/asphalt compositions of the present invention.
  • the asphalt can be added to the waterborne urethane-urea systems described above (with or without modification with latex) by any conventional manner.
  • a number of commercial asphalt emulsions on the market may be employed to prepare such composition.
  • the pH should be adjusted with a base material such as triethanolamine or ammonium hydroxide to increase the pH value to greater than 7, and preferably between about 8 and 10 before addition. If the asphalt is anionic the pH must generally be higher than 7.
  • a "neutral" asphalt emulsion generally has a pH of about 7. Both high penetration and low penetration asphalt may be employed.
  • the asphalt be added in the following method.
  • the asphalt emulsion is slowly added to a container to which the UUD (or UUD/latex blend as described below) has been previously added.
  • the mixing is carried out under a medium agitation until the addition of asphalt emulsion is finished and a homogeneous mixture is formed.
  • the weight ratios of the UUD (or UUD/latex blend) to the added asphalt emulsion is preferably from about 5% to about 95%, more preferably about 5% to about 50%; still more preferably about 5% to about 30%; and still more preferably about 10% to about 30%; by weight of total solids; but again, lower levels of the UUD or UUD/latex blend may be employed, e.g., as low as one-half (1/2) to one percent (1%) weight by total solids.
  • 'A defoamer may be employed at a level of 0.1% to about 5% and preferably about 0.3% to about 2%, based upon total solids.
  • asphalt includes all useful bituminous materials; useful material can be substantially any pyrogennous distallate or tars composed mainly of hydrocarbons with small or trace amounts of heterocyclic compounds containing sulfur, nitrogen, oxygen, and the like. Such materials may be selected from the group consisting of straight run asphalt, air-blown asphalt, cracked asphalt, and mixtures thereof. Particularly preferred are asphalt emulsions manufactured by Koch Material Companv under the tradename 5980; other similar materials are useful.
  • a typical formula for an anionic asphalt emulsion with a medium setting rate which would be used as a topcoat according to the present invention is as follows:
  • a fast setting grade would have the following formula:
  • the tall oil is added to a sodium hydroxide solution in the water.
  • the mixture is heated with agitation until the tall oil dissolves in the sodium hydroxide solution to form the soap.
  • the asphalt is then heated until its viscosity is less than 300 seconds Saybolt Furol.
  • the two phases the heated asphalt and the soap solutions — are added to the face of the mill.
  • the emulsion is formed in the mill by the high shearing forces. Particle size will be approximately 4 microns.
  • UUD modified asphalt emulsions The more important properties of UUD modified asphalt emulsions are tensile strength, elongation, and retention of elongation at low temperatures. It has been observed that if tensile strength of the UUD/asphalt emulsion composition is important, a UUD with a high hard segments percentage should be employed. Conversely, if elongation is more important, a UUD with a low hard segments percentage should be employed.
  • the UUD can be used to prepare some additional novel compounds, in which UUD will be blended, preferably prior to the addition of asphalt, with various vinylic latices in a container equipped with an electrical stirrer at room temperature.
  • a range of different ratios may be employed.
  • 1 to 90, and preferably 10 to 90 parts of an anionic, cationic or nonionic UUD may be blended with 90 to 10 parts of various vinylic latices. More preferably, a ratio of about 30 parts to about 50 parts of UUD (by weight of solids) is employed.
  • the pH value of the UUD modified latices added should be higher than 7, and preferably between about 8 and 10.
  • the mixing process is carried out in a suitable container until a homogenous uniform blend is formed.
  • the final composition can be characterized and evaluated by solids content, viscosity, tensile strength, elongation, glass transition temperature, or low temperature flexibility properties.
  • the asphalt emulsion is then added to the UUD modified latex as described above for the UUD.
  • UUD modified latex compositions as described above or when used to further modify an asphalt composition, are particularly useful in the treatment or coatings of roofs and/or pavement surfaces, by employing the additives disclosed herein, such as surfactants, pigments, fillers, wetting, agents, anti-oxidants, defoamers, adhesion promoters, u.v. stabilizers, thickening agents, biocides, anti-microbials, and the like.
  • the additives disclosed herein such as surfactants, pigments, fillers, wetting, agents, anti-oxidants, defoamers, adhesion promoters, u.v. stabilizers, thickening agents, biocides, anti-microbials, and the like.
  • the polyurethane-urea dispersion may also employ other latices.
  • the composition may employ many types of acrylics; synthetic and natural rubbers; neoprenes; nitrile rubber; butyl rubber; polybutadiene; styrene-acrylic; styrene- butadiene; acrylonitrile; styrene-butadiene or styrene -isoprene block copolymers (e.g., "Kraton” by Shell Chemical); and chlorosulfonated polyethylene (“Hypalon” by duPont).
  • compositions of the present invention are often desirable for ease of application to thicken the compositions of the present invention, particularly those employing a latex; in short, it may be necessary or desirable to increase its viscosity.
  • Useful thickeners for use in the compositions and methods of the present invention include, for example, urea copolymers of polyvinyl pyrrolidone, polyacrylates, polyacrylamides, .polesterpolyols, polyether polyols, silicates, synthetic cellulose derivatives and preferably the cellulose ether derivatives, such as, for example, hydroxypropyl methylcellulose, e.g., Methocel.
  • the thickening can also be attained by the utilization of solid filler materials, such as calcium carbonates, fumed silica, clays, mica, aluminum pastes, aluminum flakes, polyolefins.
  • solid filler materials such as calcium carbonates, fumed silica, clays, mica, aluminum pastes, aluminum flakes, polyolefins.
  • Materials such as the calcined clays or hydrated alumina, which are very fine particulate powders, are compatible at up to 50% by weight of the total latex solids. At the higher concentrations of such filler materials, a mastic may be formed.
  • Certain of the filler materials are useful as pigments and include, for example, carbon black and other conventional pigments which provide a white or other color to the final resin film. For use as a pigment, generally only from about 0.5 to about 15% by weight is necessary.
  • the pigments or fillers are preferably added as dispersions, either in aqueous or non-aqueous systems.
  • the non-aqueous systems are generally, preferably, at least partially miscible in water.
  • the particulate material can be added directly as a powder.
  • Stabilizers against discoloration and aging such as any of the well known antioxidants and ultraviolet screening materials can also be employed in the compositions and methods of the present invention as desired for the particular purpose for which a film is to be used.
  • Plasticizing agents can also be utilized, such as the phosphate esters, which, in addition to their plasticizing activity also act as emulsifiers, especially in combination with the alkoxylated alkylphenols. Biocides and/or antimicrobials may also be employed.
  • the final UUD preferably contains from about 25 to 70% by weight of solids in water and most preferably from about 30% to about 65% by weight of solids.
  • the preferred average particle size for UUD's of the present invention is as express about, i.e., less than one micron; in one highly preferred embodiment the preferred average particle size are in the range of between about 0.02 and about 0.06 microns. This relatively small particle size (less than one micron) is important in that, among other benefits, it gives rise to dramatically better performance, especially when used as a modifier of asphalt and/or latex, chalky and/or flexible surfaces.
  • the latices which are obtained in accordance with the present invention are generally stable at ambient temperatures, and can be used to produce films, for instance, which have reproducible, consistent properties, including especially water resistance and adhesion.
  • the following are examples of the products and the processes for preparing said products according to this invention. The examples are not intended to be exclusive of the full scope of this invention, but merely set out certain preferred embodiments thereof.
  • Poly(oxypropylene)glycol (PPG, MW 2000) 100 parts (by wt.), demoistured at 80°-90°C under vacuum for about 10 hours, is added in a reaction kettle equipped with electrical stirrer, thermometer, dry nitrogen inlet and heating jacket.
  • Dimethylolpropionic acid (DMPA) 6.7, N-methylpyrrolidone (NMP) 14.6 and dibutyltin dilaurate (T12) 0.05% (based on the total weight of prepolymer) is then added to above reaction kettle and heated to 60° ⁇ 5°C with stirring under dry nitrogen for about 5-10 min. until a uniform mixture was formed.
  • DMPA dimethylolpropionic acid
  • NMP N-methylpyrrolidone
  • T12 dibutyltin dilaurate
  • Biscyclohexylmethane-4, 4'diisocyanate (H ⁇ 2 MDI) 39.3g is then added and the reaction of preparing the pendant carboxylic acid - containing polyurethane (PU) prepolymer was carried out at 85° - 90°C for 3-4 hr. with stirring under dry nitrogen until the NCO content of the prepolymer was close to the theoretical calculation according to the titration of n-dibutylamine.
  • the temperature is decreased to about 70°C and triethylamine (TEA) lO.lg is added.
  • the neutralization between the pendant carboxylic acid of PU prepolymer and the tertiary amine of TEA is carried out at about 70°C for 30-40 min.
  • a certain amount of distilled water (based on about 35% solids) is added under vigorous agitation to carry out the dispersion of the neutralized PU prepolymer in water.
  • the chain extension is carried out at room temperature under vigorous agitation by adding hydrazine (HZ) 1.6g or ethylenediamine (EDA) 3.0g, which is diluted with water to about 50% solids, in the neutralized prepolymer dispersion.
  • HZ hydrazine
  • EDA ethylenediamine
  • the dispersion is cast in a glass mold which is coated with a release agent at room temperature ("RT'). After the dried film is formed at RT it is put in oven at 50-60°C overnight before testing the properties.
  • RT' room temperature
  • PU transparent polyurethane
  • the PU prepolymer 146.1g is added to a container which contains both water and TEA(lO.lg) at room temperature under vigorous agitation to carry out both neutralization and dispersion.
  • Hyrazine (HZ, 1.6g) diluted with water is slowly added in the above neutralized prepolymer dispersion under vigorous agitation to carry out the chain extension at room temperature.
  • Method 1 The prepolymer is neutralized with TEA at first and then dispersed in water containing HZ to carry out both dispersion and chain extension.
  • Method 2. The prepolymer is neutralized and dispersed in water containing TEA. HZ is then added to carry out chain extension.
  • Method 3. The prepolymer is neutralized, dispersed and chain- extended in water containing TEA and HZ.
  • Example A-4 Dried films are then prepared for testing purposes.
  • the mechanical properties of this UUD are better than one's of Example A-4.
  • the UUD of Example A-4 may also be blended with this UUD at various ratios.
  • Example A-2 The UUD of Example A-2 is blended with various acrylic dispersions at
  • the dispersion blends are cast in the release agent coated mold at room temperature and the film after being dried at room temperature is kept in oven at 50 - 60°C for about 15 hrs. until water or some co-solvent is completely removed from the film.
  • the sample films are aged at room temperature for one or two days before testing the properties.
  • the appropriate curing condition for the sample films is typically room temperature for one week and 80°C for one day.
  • a ratio of about 30 parts to about 50 parts of UUD (by weight of solids) is employed.
  • UUD modified acrylic dispersions exhibit very good adhesion to chalky surfaces of weathered PIB (polyisobutylene rubber).
  • UUD-Modified styrene-acrylic dispersions The UUD of Example 2 is blended with a highly preferred styrene-acrylic dispersion RES 1019 or 10526 (by Unocal Polymers) by using same procedure as that described in Example B-l.
  • the blends from RES 1019 typically have better properties than one from RES 10526.
  • Tensile strength, elongation and retention of elongation properties at low temperatures are very important: Tensile strength, elongation and retention of elongation properties at low temperatures. In the examples below, to be satisfactory, the elongation capacity should be greater than 80%; tensile strength should exceed 200 psi.
  • EXAMPLE C-l Mixtures of an anionic asphalt and a UUD from Example A-2 are made as follows. The asphalt emulsion is added relatively slowly, with agitation, to the required amount of UUD. Mixtures are made slowly, and a number of samples are prepared with increasing percentages of UUD from 0 to 50%, or the desired percentage. It is important to add the asphalt to the UUD. They are then applied at a thickness of about 0.010 inches to silicone coated release paper, allowed to cure at room temperature for two days and then at 60°C for two days. Then tensile properties of the dried film are determined.
  • EXAMPLE C-2 Mixtures are made using the higher elongation UUD of Example A-6. Mixing, curing and testing were the same as Example C-1. The 180° bend test results show that at 20, 30 and 50% UUD satisfactory results are obtained. At 20, 30 and 50% UUD, the results are also satisfactory. With this UUD, 20% is the preferred ratio.
  • EXAMPLE C-3 Mixtures using a UUD made with a TDI base (Example A-4) are prepared. Mixing procedures, coating, curing and testing procedures are the same as those shown in Example C-1 (absent the bend test). Mixtures from 10 to 100% UUD are tested. It is found that levels as low as 10% UUD gave good elongation, while 20%-30% would be the preferred UUD concentration.
  • a test can be run to determine the wetting properties and resistance to rutting of pavements made with the addition of UUDs as compared with an unmodified asphalt emulsion, even when employed at very low levels.
  • the UUD is made with IPDI (example No. A-3).
  • the asphalt emulsion can be made with high penetratic asphalt for use with chip seal pavements.
  • a mixture of graded aggregates is mixed with 8% by weight of: a mixture of UUD (1.6%) and an asphalt emulsion (6.4%) The mixtures are compacted in a cylinder required for the split tensile and Marshall tests. The mixed material is much better wetted than the asphalt only.
  • the addition of the UUD (1.6%)/asphalt emulsion (6.4%) wets the aggregate more thoroughly.
  • the cylinders are then aged 2 days at 50°C and force is applied to the warm cylinders. The results are shown in the table that follows:
  • A UUD, parts by weight of solids B: Latex, parts by weight of solids C: Asphalt emulsion, parts by weight of solids
  • UUD with natural latex (NR) 3. UUD, acrylic and natural latex (NR)
  • the blending process was carried out at room temperature by using a stirrer with variable speed for about 10 min. until a homogeneous mixture was formed.
  • the UUD used is from Example A-l unless otherwise noted.
  • Table 1 shows the properties of UUD-acrylic latex (1019) with various blending ratios.
  • the UUD is made by using IPDI and the results indicate that the tensile strength of blends is generally increased with an increasing concentration of UUD. However, the elongation of blends did not change except for the 80/20 ratio. All blends with different ratios are homogeneous. The results imply that one can change tensile strength without affecting elongation of blends.
  • Table 2 shows the properties of blends which are made by using UUD and acrylic 1019.
  • the UUD is made by H 12 MDI and dipropylene glycol monoether acetate (DPMA) as a replacement of "NMP".
  • DPMA dipropylene glycol monoether acetate
  • UUD-NR blends Some general properties of UUD-NR blends are shown in Table 3. Three types of natural latex (“NR”) are used and the properties of both NR and blends before and after heating age are shown. Both tensile strength and elongation of blends with 50/50 ratios (on solids) increase by introducing UUD, compared to the properties of NR itself. Elongation of blends decrease about 10% after heating age. This suggests that an antioxidant should be introduced to avoid the oxidation of NR. TABLE 4 IPDI based UUD is blended with NR at various ratios as shown in Table 4. The results indicate that the tensile strength of the blends decrease with increasing NR. Elongation also decreases except for 60/40 ratio.
  • NR natural latex
  • Asphalt A is a hard type with a low penetration degree and asphalt B apparently is a soft type with a high penetration degree.
  • the acidic clay inside asphalt B resulted in a compatibility problem with UUD.
  • a pretreatment of asphalt B with triethanolamine (TEAL) is carried out to improve both tensile strength and elongation (see Table 5. 70/30 ratio). With increasing amounts of TEAL elongation increases but tensile strength decreases (see Table 5 80/20 ratio). Both tensile strength and elongation of UUD modified asphalt emulsion increase with increasing amounts of UUD.
  • NR/UUD (50/50) exhibits higher tensile strength but lower elongation compared to NR/UUD/1019 (30/40/30).
  • NR/UUD (50/50) exhibits higher tensile strength but lower elongation compared to NR/UUD/1019 (30/40/30).
  • Asphalt emulsion from Hy-Grade Corp. is modified by UUD, NR, UUD NR and
  • UUD/acrylic latex/1019 as shown in Table 13. After heat aging, both modified asphalt emulsion based on NR and UUD/NR result in very poor elongation because of oxidation of NR. However, both modified asphalt emulsions based on UUD and UUD/acrylic latex/1019 exhibit good properties after heat aging, in particular UUD/acrylic latex/1019.
  • Asphalt emulsion with a low penetration degree (harder than Hy-Grade asphalt emulsion) is modified by UUD, NR, 1019, UUD/NR and UUD/1019 as shown in Table
  • Solids content is 50% for 1019 and 28.6% for IPDI based UUD.
  • the blending ratios are based on solids.
  • Solids content is 50% for 1019 and 36.7% for DPMA (dipropylene glycol monoether acetate) based UUD.
  • the blending ratios are based on solids.
  • Table 3 Effect of various natural latices and blends of natural latices with UUD on the mechanical properties before and after heat aging.
  • UUD:UUD was prepared by using DPMA as solvent.
  • the aluminum panel with modified asphalt was immersed in a -20°C cold bath for 5 min. before 180° bending.
  • the modified asphalt emulsion is coated on a standard steel panel by using a doctor blade. After one week at RT the sample panel is immersed into a dry ice/acetone/water bath for 5 to 10 min. The sample panel is then taken out to carry out 180° bending test immediately.
  • Tables 17 and 18 demonstrate the importance of particle size of the UUD in the compositions and methods of the present invention.
  • the IPDI based UUD modified natural latex (NR) or asphalt emulsions exhibited better properties tensile strength (T t ) and elongation (E) than H 12 MDI based UUD modified NR or asphalt. This is due to the fact that the particle size of the UUD plays an important role in the fixed property of UUD modified latex or asphalt.
  • the modified asphalt emulsion was based on the following basic formula (on solids):

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  • Polymers & Plastics (AREA)
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Abstract

Cette invention concerne des compositions de revêtement à base d'eau, des procédés permettant de préparer des compositions de ce type et des procédés permettant de les appliquer. Plus spécifiquement, mais sans restriction, deux compositions selon cette invention comprennent des dispersions, des suspensions ou des émulsions contenant de l'eau. Pour les produire, on utilise soit (a) environ 10 % à environ 90 % en poids des compositions finales d'une dispersion sélectionnée uréthane-urée, soit (b) environ 10 % à environ 90 % en poids de la composition finale, d'un matériau bitumineux tel qu'un asphalte, soit (c) environ 10 % à environ 90 % en poids de la composition finale, d'un matériau latex (vinylique). Une autre dispersion, suspension ou émulsion contenant de l'eau est présentée sans limitation, dans laquelle on utilise (a) environ 5 % à environ 10 % en poids de la composition finale d'une dispersion uréthane-urée; (b) environ 5 % à environ 30 % en poids de la composition finale d'un matériau latex (vinylique); et (c) environ 10 % à environ 90 % en poids de la composition finale, d'un matériau bitumineux, de préférence de l'asphalte.
EP92917303A 1991-04-12 1992-04-10 Revetement et materiau d'etancheite contenant du polyurethane Withdrawn EP0646149A1 (fr)

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US68423191A 1991-04-12 1991-04-12
US684231 1991-04-12
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CN110003851A (zh) * 2019-04-03 2019-07-12 辽宁新发展公路科技养护有限公司 一种道路工程粘结层用改性乳化沥青及其制备方法

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AU6096096A (en) * 1995-06-07 1996-12-30 Sherwin-Williams Company, The Penetrating stains and sealants from polyurethane dispersion s
US6191213B1 (en) 1996-06-06 2001-02-20 The Sherwin-Williams Company Penetrating stains and sealants from polyurethane dispersions
JP3996009B2 (ja) * 2002-07-31 2007-10-24 東亜道路工業株式会社 ２液系止水材組成物
US8277949B2 (en) 2009-05-22 2012-10-02 Garland Industries, Inc. Use of thermoplastic polyurethanes in rubber modified bitumen roofing membranes
ITBA20130038A1 (it) * 2013-05-14 2014-11-15 Gennaro Fabio Di "adesivo sigillante, impermeabilizzante, poliuretanico"
CN109457567A (zh) * 2017-09-06 2019-03-12 上海同济检测技术有限公司 道路局部破损的快速修复方法
CN115160913A (zh) * 2022-06-24 2022-10-11 重庆科顺新材料科技有限公司 一种液体防水卷材及其制备方法和使用方法

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US3909474A (en) * 1971-09-27 1975-09-30 Atlantic Richfield Co Road surface stabilization
FR2438069A1 (fr) * 1978-10-02 1980-04-30 Wilmington Chem Corp Dispersions de polyurethanne reticule et leur procede de production
EP0161479A1 (fr) * 1984-04-19 1985-11-21 Bayer Ag Procédé pour la préparation de revêtements de surfaces résistant aux produits chimiques
EP0219399A1 (fr) * 1985-09-30 1987-04-22 Screg Routes Et Travaux Publics Procédé de préparation d'une composition d'émulsion aqueuse de bitume-polyuréthanne
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CA2108015A1 (fr) 1992-10-13

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