WO1996023035A1 - Vehicule polymere servant a former des compositions de revetement sans solvant - Google Patents

Vehicule polymere servant a former des compositions de revetement sans solvant Download PDF

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Publication number
WO1996023035A1
WO1996023035A1 PCT/US1996/001141 US9601141W WO9623035A1 WO 1996023035 A1 WO1996023035 A1 WO 1996023035A1 US 9601141 W US9601141 W US 9601141W WO 9623035 A1 WO9623035 A1 WO 9623035A1
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WO
WIPO (PCT)
Prior art keywords
polymeric vehicle
crosslinker
recited
viscosity
oligoester diol
Prior art date
Application number
PCT/US1996/001141
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English (en)
Other versions
WO1996023035A9 (fr
Inventor
Frank Jones
Shou-Kuan Fu
Xiaouying Yuan
Jun Hua
Original Assignee
Eastern Michigan University
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
Priority claimed from PCT/US1995/001053 external-priority patent/WO1995019997A1/fr
Application filed by Eastern Michigan University filed Critical Eastern Michigan University
Priority to AU49058/96A priority Critical patent/AU718881B2/en
Priority to JP8523036A priority patent/JPH10501582A/ja
Priority to KR1019960705325A priority patent/KR970702336A/ko
Priority to EP96905248A priority patent/EP0751979A1/fr
Publication of WO1996023035A1 publication Critical patent/WO1996023035A1/fr
Publication of WO1996023035A9 publication Critical patent/WO1996023035A9/fr

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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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • 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
    • C09D175/06—Polyurethanes from polyesters

Definitions

  • the present invention relates to a blend of ingredients which is effective for providing a formulated coating composition without the addition of organic solvent to provide a composition which may be applied to a substrate as a protective paint by existing commercial application equipment. More particularly, this invention is directed to a polymeric vehicle which is a blend of a linear oligoester diol having a number average molecular weight in the range of from about 275 to about 1200 and a crosslinker, a solventless formulated coating composition made from the polymeric vehicle, a coating binder made from the solventless formulated coating composition and a method of controlling the viscosities of the polymeric vehicle and formulated coating composition.
  • Film forming components of liquid paint include resins which have required organic solvents to provide the resins with suitable viscosities such that the paint can be applied by existing commercial application equipment.
  • Use of organic solvents raises at least two problems. In the past and potentially in the future, petrochemical shortages mitigate against the use of organic solvent in great volumes. Second, environmental concern mitigates against the use of organic solvents.
  • compositions which are applied and used by industry and by the consuming public are not only often unpleasant, but also contribute to photochemical smog.
  • Governments have established regulations setting forth guidelines relating to volatile organic compounds (VOCs) which may be released to the atmosphere.
  • VOCs volatile organic compounds
  • the U.S. Environmental Protection Agency (EPA) has established guidelines limiting the amount of VOCs released to the atmosphere, such guidelines being scheduled for adoption or having been adopted by various states of the United States.
  • VOCs such as those of the EPA, and environmental concerns. are particularly pertinent to the paint and industrial coating industry which uses organic solvents which are emitted into the atmosphere.
  • compositions and powdered coating compositions are liquid and are designed to minimize solvents.
  • Powdered coating compositions are solid powders and generally eliminate solvents. While each have advantages, each coating composition has disadvantages.
  • Coating compositions which include high solids polymeric vehicles based upon polyesters have become popular. In high solid polyesters as opposed to
  • the resultant polymers typically exhibit 70-80% solids-weight when reacted stoichiometrically with isocyanate crosslinkers, but frequently yield empirical solids up to 12% lower, when crosslinked with melamine resins.
  • high solids polyester coating compositions could be produced on the same equipment and be employed in many of the same applications as lower solids "conventional" polyester coating compositions.
  • high solids polyester coating compositions have enjoyed spectacular growth in manufacture and use. They still require organic solvents, however, and are a source of VOCs.
  • Powder coatings and UV-curable coatings are desirable ultrahigh or 100% solids coatings.
  • the viscosity of polymers in the liquid state depends mainly on the average molecular weight and the temperature, so it is desirable to reduce average molecular weight for solventless polyester coating.
  • the major factor controlling molecular weight (M n ) of a polyester is the mole ratio of dibasic acid/diol or polyol. A dibasic acid to diol or polyol ratio of the order of 2:3 is typical. However, loss of polyol during the production of the polyester can result in a
  • the low molecular weight fraction of resin may be volatile enough to evaporate when a thin film is baked. Such loss has to be counted as part of the VOC emissions.
  • the number of functional groups per molecule also affects the viscosity because of hydrogen bonding. Most oligomers or polymers require high functionality to achieve a highly crosslinked film and reasonable Tgs to have adequate film properties for most applications. The high functionality tends to increase the viscosity significantly.
  • composition for application of the formulated coating composition for application of the formulated coating composition.
  • Another object of this invention is to provide polymeric vehicles which are not only low in VOCs and effective in providing solventless formulated coating compositions, but which provide coating binders with good film properties such as hardness and impact resistance.
  • Yet another object of this invention is to control the viscosity to low levels at a specific
  • the invention provides a liquid polymeric vehicle which is effective for providing a formulated coating composition which does not require the addition of organic solvent to obtain a viscosity such that the formulated coating composition may be applied by existing commercial application equipment.
  • the invention also provides a way of controlling the viscosity of the polymeric vehicle at a specific shear rate using linear oligoester diols having a number average molecular weight within controlled limits of a polydispersity index, a linearity and a molecular weight limitation which are effective for controlling the viscosity of the polymeric vehicle.
  • the invention provides a polymeric vehicle which has at least about 92 weight percent solids and which comprises at least one linear oligoester diol having a number average molecular weight in the range of from about 275 to about 1200 which is effective for reaction with a crosslinker.
  • the linear oligoester diol and/or mixture of such diols has a polydispersity index (M w /M n ) of less than about 2.6, preferably less than 2.2, preferably in the range of from about 1.4 to about 1.8, and most preferably less than about 1.4, and a viscosity in the range of from about 0.1 to about 1.2 Pa.s at a temperature in the range of from about 20°C to about 50°C as measured on a Brookfield thermocell viscometer model DV-II+ using a SC4-31 spindle at 6 rpm.
  • M w /M n polydispersity index
  • a linear oligoester or mixture of such oligoesters in the polymeric vehicle is important because it has a low viscosity and has a sufficiently low evaporation rate such that the oligoester has at least about 93 weight percent solids when tested by ASTM test D-2369-92. This minimizes the VOC content of the oligoester since only a small fraction of the material will evaporate upon baking. Generally, when the crosslinker is added even a lower fraction of the oligomer will evaporate during baking because part of the volatile material reacts with the crosslinker.
  • the crosslinker may be a solid, but generally is a liquid. In either circumstance, the crosslinker is miscible or soluble in a blend of oligoester diol and crosslinker without raising the viscosity of the blend of the oligoester diol/crosslinker or the formulated coating composition above the range of from about 0.1 to about 20 Pa.s at about 20 to about 60°C at a shear rate of at least 1000 sec. -1 without organic solvent.
  • the crosslinker has an average functionality of greater than about 2.4, and preferably greater than about 2.9, a viscosity of less than about 3.0 Pa.s at about 25°C when it is a liquid, preferably is a liquid at about 10°C, and a has functionality which is reactive with the hydroxyl groups of the oligoester.
  • the polymeric vehicle comprises at least about a stoichiometric amount of crosslinker which will react with the hydroxyls of the linear oligoester diol.
  • a catalyst such as a soluble tin compound for polyisocyanates or an acid for amino resins generally should be used in an amount effective to effect the reaction between the oligoester diol and the
  • the invention is effective for providing a polymeric vehicle which will have at least about 80, preferably about 88 to about 90 and most preferably at least about 92 weight percent solids. Since no solvent is added, the volatile material comprises primarily crosslinking reaction by-products and traces of volatile materials and impurities present in the resinous and other components of the formulation.
  • the crosslinking reaction does not evolve volatile by-products, for example the aspect of the invention which includes a polyisocyanate as a crosslinking agent, the invention is effective for providing a polymeric vehicle which will have at least about 97 weight percent solids and typically about 99 weight percent solids.
  • the crosslinking reaction does not evolve volatile by-products
  • the aspect of the invention which includes a polyisocyanate as a crosslinking agent
  • the invention is effective for providing a polymeric vehicle which will have at least about 97 weight percent solids and typically about 99 weight percent solids.
  • aforedescribed polymeric vehicles, and formulated coating compositions based thereon may be less than 100 weight percent solids without the addition of organic solvents because low molecular weight fractions of the oligoester which forms the polymeric vehicle may evaporate or otherwise originate from the polymeric vehicle and become a VOC with the application of heat for a thermoset into a coating binder.
  • the crosslinker blended with the linear oligoester diol is a polyisocyanate or is a blend which comprises a polyisocyanate and melamine in amounts effective to achieve desired hardnesses, impact resistance and
  • the polymeric vehicle has a viscosity of not more than about 1.2 Pa.s at the temperature of application, which is usually not more than about 50°C and is preferably about 25°C.
  • the polymeric vehicle preferably has a viscosity of not more than about 0.8 Pa.s at 25°C to provide a coating binder having a pencil hardness of at least about B. DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • Olemer means a compound that is a polymer, but has a number average weight not greater than about 10,000 with or without repeating monomeric units.
  • Crosslinking agent means a di- or polyfunctional substance containing functional groups that are capable of forming covalent bonds with hydroxyl groups that are present on the oligoester diol.
  • the crosslinking agent may be a blend; hence, there may be more than one substance which forms a blend of substances which form covalent bonds with the hydroxyl groups of the oligoester diol.
  • Amino resins and polyisocyanates are members of this class.
  • Polymeric vehicle means polymeric and resinous components in the formulated coating, i.e., before film formation,
  • Coating binder means the polymeric part of the film of the coating after solvent has evaporated and after crosslinking.
  • Formated coating composition means the polymeric vehicle and optional solvents, as well as pigments, catalysts and additives which may optionally be added to impart
  • VOC volatile organic
  • Dial is a compound or oligomer with two hydroxyl groups.
  • Polyol is a compound or oligomer with two or more hydroxyl groups.
  • solvent means an organic solvent
  • Organic solvent means a liquid which includes but is not limited to carbon and hydrogen and has a boiling point in the range of from about 30°C to about 300°C at about one atmosphere pressure.
  • Dissolved in respect to a polymeric vehicle, formulated coating composition or components thereof means that the material which is dissolved does not exist in a liquid in particulate form having at least about 5 weight percent particles having diameters greater than about 30nM which are as measured by dynamic light
  • Soluble means a liquid dissolved in a liquid or a solid dissolved in a liquid.
  • Distible means a liquid which is dissolved or is soluble in a liquid.
  • Volatile organic compounds are defined by the U.S. Environmental Protection Agency at 40 C.F.R. 51.000 of the Federal Regulations of the United States of
  • chlorodifluoromethane CFC-22
  • trifluoromethane FC-23
  • 1,2-dichloro-1,1,2,2-tetrafluoroethane CFC-114
  • chloropentafluoroethane CFC-115; 1,1,1-trifluoro 2,2-dichloroethane (HCFC-123); 1,1,1,2-tetrafluoroethane (HF-134a); 1,1-dichloro 1-fluoroethane (HCFC-141b); 1-chloro 1,1-difluoroethane (HCFC-142b); 2-chloro-1,1,1,2- tetrafluoroethane (HCFC-124); pentafluoroethane (HFC-125); 1,1,2,2-tetrafluoroethane (HFC-134); 1,1,1-trifluoroethane (HFC-143a); 1,1-difluoroethane (HFC-152a); and perfluorocarbon compounds which fall into these classes:
  • a "film” is formed by application of the formulated coating composition to a base or substrate, evaporation of solvent, if present, and crosslinking.
  • the liquid polymeric vehicle has at least about 80 to about 92 weight percent solids and comprises at least one linear oligoester diol having a number average molecular weight in the range of from about 275 to about 1200 which is effective for reaction with a crosslinker.
  • the polymeric vehicle is thermosetting with the thermoset being
  • the reaction of the linear oligoester diol and crosslinker with the application of heat provides a coating binder of a paint coating.
  • the oligoester diol may be liquid or solid at about 25°C, but if it is a solid it has a melting point of below about 50°C, preferably below about 40°C. The melting point is most preferably below about 10°C.
  • the melting point of the oligoester diol is usually reduced after it is mixed with the crosslinker. Even so, it may be necessary in some cases to heat the coating composition to melt crystalline oligomers before its application. Control of the viscosity of the oligoester diol comes from at least two sources.
  • the linear longitudinal chain of the oligomer is substantially without any side chain or group. This linearity reduces the viscosity of the oligoester relative to an oligomer even with relatively small amounts of branching.
  • the number average molecular weight of the oligoester is controlled such that the oligoester has at most a small low molecular weight fraction which will be a source for evaporation or VOCs upon the
  • the linear oligoester diol has a polydispersity index (M w / M n ) of less than 2.6, preferably less than about 2.2 and preferably in the range of from about 1.4 to about 1.8, and most preferably less than about 1.4.
  • M w / M n polydispersity index
  • Relative to its molecular weight the oligoester diol has a low viscosity (about 0.1 to about 1.2 Pa.s as set forth above) on the Brookfield viscometer which produces a shear rate of about 2 sec. -1 .
  • oligoester and the polymeric vehicle are sufficiently low to permit a formulated coating composition with a useable viscosity that permits its application without the addition of organic solvents.
  • oligoester may be obtained by synthesizing the oligomer through a direct catalyzed esterification reaction, a catalyzed transesterification reaction or by a catalyzed esterification reaction using reactants such as
  • DCC dicyclohexyl-carbodiimide
  • polydispersity index as low as 1.4.
  • the polydispersity index may be lowered to levels below 1.4 by purification of the oligoester product such as by extraction of the volatile low molecular weight fractions or by vacuum stripping of such fractions. Using these techniques a polydispersity index of 1.1 or even lower may be
  • Typical oligoester diols include the reaction products of linear aliphatic dicarboxcylic acids having not more than about 16 carbon atoms or esters thereof such as azelaic acid, glutaric acid, adipic acid,
  • decanedioic acid dodecanedioic acid
  • succinic acid dimethyl azeleate
  • dimethyl glutarate dimethyl
  • linear diol means a diol with segments having the structures -CH 2 - and -O- terminated with -OH. Mixtures of the acids or esters thereof and diols may be
  • cotransesterified and may be used to achieve certain melting points and molecular weights.
  • examples of such mixtures include a cotransesterified mixture of dimethyl azeleate with equal weights of 1,4-butanediol and 1,6-hexanediol which provides a product having a viscosity of 0.65 Pa.s at 30°C; a cotransesterified mixture of
  • Typical linear oligoesters which may be used in the invention have the general formulas :
  • the oligoester diol may be a mixture of the chemically same or different oligoester diols which have differing number average molecular weights and which number average molecular weights are in the range of from about 275 to about 1200.
  • oligoester diols having the same chemical formula, but with differing number average molecular weights, are mixed to provide a polymeric vehicle according to the invention. Such mixtures may be used to improve the properties of the coating binder or the polymeric
  • oligoester diols having the same formulas, but for number average molecular weight, when mixed to provide a blend of oligomers comprising 20 weight percent of an oligomer having an M n of about 500 and 80 weight percent of an oligomer having an M n of about 300 improves the impact resistance of a coating binder over a coating binder which is made using exclusively an oligomer which has an M n of about 300.
  • Such blends of oligomers increase the PDI of the oligomeric diol such that the oligomeric blend used in a polymeric vehicle may approach 2.6.
  • PDI of the oligoester diol used in the polymeric vehicles according to the invention should not have a PDI of more than about 2 .2 . Further, the lower the PDI while
  • the crosslinker has a functionality which is reactive with active hydrogens such as the hydroxyl groups of the oligoester.
  • the crosslinker may be a polyisocyanate which generally is not blocked because blocking generally will raise the viscosity of the isocyanate such that it will not be functional or useful in the practice of the invention. Liquid blocked isocyanates may be used if the viscosity of the crosslinker or blend of crosslinkers is less than 3.0 Pa.s as described herein.
  • Two useful polyisocyanate crosslinking agents which may be used in the invention include hexamethylene diisocyanate which has the structure shown below (HDI and sold commercially as Desmodur N-3200)
  • Amino resins (usually made from amidines, ureas or amides by reaction with formaldehyde and subsequently usually with an alcohol) also may be used as a crosslinker which will react with the hydroxyls of the linear oligoester.
  • Melamine resins are a subclass of amino resins and may also be referred to as "melamine-formaldehyde resin” or "alcoholated melamine-formaldehyde resin.” Melamine resin amounts should be adjusted according to the
  • molecular weight of the oligoester diol increases the equivalent weight ratio of melamine resin to total diol should be adjusted from about 1:1 to about 1.5:1 to about 1.7:1 and possibly higher to achieve desired film
  • Suitable amino crosslinkers include, but are not limited to melamine formaldehyde types such as hexakis (methoxymethyl) melamine resin (HMMM) (sold as “Cymel 303" and “Resimene-747”) and other amino resins as described in Wicks, Jones and Pappas "Organic Coatings: Science and Technology” PP 83-103, Wiley Interscience, 1992. Additionally, the crosslinker may be solid under certain conditions as long as it is soluble in the oligoester diol/crosslinker blend and does not increase the viscosity of the oligoester diol/crosslinker blend or formulated coating composition above the rages described herein. These crosslinkers include a hexakis
  • HMMM (methoxymethyl) melamine
  • HMMM resin appears as a waxy solid with a melting point in the range of about 30°C and is sold by Cytec Chemical Company under the name Cymel 300.
  • Cymel 300 A similar melamine resin which sometimes appears to be a solid at about 25°C and which can be used in the
  • HM-2612 is a highly monomeric, highly methylolated hexamethylolated melamine formaldehyde resin which is sold by Monsanto Chemical Company under the designation HM-2612.
  • composition of the coating binders resulting from the use of amino resin crosslinkers may be improved with hardeners additional to the aforedescribed crosslinkers.
  • additional hardeners include
  • K-FLEX UD320-100 is a 100% polyurethane-diol with hydroxyl equivalent weight 160, viscosity 7.0 Pa.s at 50°C. Its structure is thought to be HO (CH 2 ) 6 OCONH(CH 2 ) 6 NHCOO(CH 2 ) 6 OH.
  • K-FLEX UD-320W has the same structure as K-FLEX UD320-100, is a polyurethane-diol contained about 10% by weight of water with hydroxyl equivalent weight 178, viscosity 8.0 Pa.s at 25°C. Both may be obtained from King
  • TECA 1,3,5-tri(hydroxyethyl) cyanuric acid
  • AY-1 Mesogenic polyols, diesters of neopentyl glycol and parahydroxybenzoic acid which diesters are hereinafter referred to as AY-1, a preferred AY-1 diester having the structural formula
  • PHEAs phenolic ester alcohols
  • M n or number average molecular weight for a PHEA is in the range of about 250 to about 1200.
  • mesogenic polyols see published PCT application no. US95/01058.
  • additional hardeners are especially useful if small amounts of organic solvents are used in the formulated coating composition.
  • a useful PHEA has two ester groups, a phenolic hydroxy (which extends from the aromatic group), an aliphatic hydroxy and has the structural formula:
  • Amino resins by themselves without additives such as hardeners may not give desired film properties.
  • additional hardeners especially PHEAs
  • polymeric vehicles which include amino resins where each of the components are in amounts effective for providing a polymeric vehicle with the aforedescribed viscosity range and effective for providing a coating binder with a pencil hardness of at least about B at a thickness of about 1 mil dry.
  • Isocyanates provide excellent film properties but may shorten the pot life of the polymeric vehicle or formulated coating composition.
  • a particularly useful crosslinker blend in the invention is a melamine sold as Cymel 1135 (a 50/50 methylated/butylated melamine with 70% monomeric;
  • the crosslinker has an average functionality reactive with the hydroxyls of the
  • oligoester of greater than about 2.4, a viscosity of less than about 3.0 Pa.s at about 25°C, and in an important aspect, is liquid at about 10°C and is miscible with the oligoester.
  • the reaction between the oligoester and the crosslinker which provides the coating binder generally is a catalyzed reaction.
  • a catalyst is not required for some isocyanate crosslinkers, typical catalysts for isocyanate crosslinking reactions include soluble zinc or tin catalysts such as dibutyl tin
  • catalysts for the amino resin crosslinking reactions include para toluene sulfonic acid (p-TSA) , dodecyl benzene sulfonic acid and dinonyl nathphalene disulfonic acid.
  • p-TSA para toluene sulfonic acid
  • the catalyst comprises from about 0.03 to about 0.5 weight percent of the blend of oligoester and crosslinker, based upon the weight of the oligoester, crosslinker and catalyst.
  • the polymeric vehicle comprises at least about a stoichiometric amount of crosslinker which will react with the hydroxyl groups of the oligoester.
  • the polymeric vehicle comprises an oligoester diol and a crosslinker in an equivalent ratio in the range of from about 1.0:0.93 to about 1:2.5, diol to crosslinker.
  • the polymeric vehicle will have a viscosity of not more than about 1.2 Pa.s at the
  • the polymeric vehicle and formulated coating composition provide a coating binder having a pencil hardness of at least about B when applied to a substrate at a thickness of about 1 mil dry.
  • polydispersity index of less than about 2.6, preferably less than 2.2, preferably in the range of from about 1.4 to about 1.8 and most preferably less than 1.4 and mixing the oligoester with a crosslinking agent with the
  • the formulated coating compositions are made by mixing the polymeric vehicle with pigments, catalysts and additives such as defoamers, pigment dispersants,
  • formulated coating compositions have a viscosity of not more than about 1.2 at about 50°C or less at shear rates which may range from about 1 sec. -1 to about 100,000 sec. -1 depending upon the method of application.
  • the formulated coating composition may be applied to a substrate by spraying (which has very high shear rates), dipping
  • the formulated coating compositions will have less than 140 g/L VOCs under ASTM Test D-3960-93.
  • A is synthesized from dimethyl azeleate with
  • a 500-mL, 4-neck flask is equipped with a mechanical stirrer, Dean-Stark trap, condenser,
  • thermometer and nitrogen inlet Dimethyl azeleate (86.4 g, 0.4 mol), 1,4-butanediol (54 g, 0.6 mol) and zinc acetate dihydrate (0.2% of total wt.) are placed into the flask and gradually heated by an electrothermal heating mantle with controller from 130°C to 170°C during 3 hours. Nitrogen is bubbled through the solution to facilitate methanol removal. The temperature is then raised to 200oC and maintained for one hour, as methanol is collected in the Dean-Stark trap. 94% Of the
  • the NMR spectra indicate that the M n is about 570. A significant NMR signal at 3.85 ppm for residual methyl group remaining in the oligomer solution is observed. The results in Table 1 describe the viscosity of A 1 .
  • Table 2 describes the formulation of A 1 and coatings based on A 1 . As shown in Table 2 , solvent
  • Resimene 747 was 7 to 3 and was very good for the
  • Resimene 747 is a fully methylated monomeric melamine resin in which hexakis (methoxymethyl) melamine is a representative structure (obtained from Monsanto Chemical Company). Other properties are shown in Table 2.
  • transesterification reaction is done in the following way:
  • a 500-mL, 4-neck flask is equipped with a mechanical stirrer, Dean-Stark trap, condenser,
  • thermometer and nitrogen inlet Dimethyl azeleate (130 g, 0.6 mol), 1, 4-butanediol (108 g, 1.2 mol) and zinc acetate dihydrate (1.2% of total wt.) are placed into the flask and are gradually heated by an electrothermal heating mantle with controller from 130°C to 170°C during 3 hours. The temperature then is raised to 200°C and maintained for one hour, as methanol is collected in the Dean-Stark trap. Nitrogen is fed slowly through the solution to help methanol removal, and 91% of the
  • the temperature is raised to 210°C and the flow rate of nitrogen is increased to help 1,4-butanediol
  • the degree of polymerization and M n were measured by NMR spectra.
  • the average number of repeating units x in the oligoester can be calculated from the NMR peak area ratio of the methylene connected with the ester group (-CH 2 -O-CO-) at 4.0 ppm to the methylene connected with the hydroxy group (-CH 2 -OH) at 3.5 ppm.
  • x is the repeating unit in the oligomer.
  • M n for A can be calculated by the following equation:
  • MW(diacid) and MW(diol) are the molecular weights of the monomers, azelaic acid and 1,4-butanediol, respectively.
  • M n of the fractions of A 2 are listed in Table 3.
  • the viscosities of the oligomers are listed in Table 4. It was found that the viscosity of the
  • oligomers was directly affected by their molecular weights and increased quickly as the molecular weight increased. Since some oligomers with increased molecular weights crystallize at room temperature (25°C), all oligomers were warmed first and cooled down to room temperature right before viscosity measurements.
  • the mechanical properties of coatings of oligoester A 2 are shown in Table 5 for Formulation I and in Table 6 for Formulation II. Comparing properties of the two formulations, it can been seen that the film hardness and MEK solvent resistance of Formulation II were better than that of Formulation I.
  • the film of the oligomers with low M n was harder than that with higher M n , because the oligomer of low molecular weight may give relatively high crosslinking densities in a crosslinked network. It was noted that all coating films had poor adhesion on untreated steel panels, but they have generally good adhesion on primed or pretreated steel panels.
  • Non-linear oligoester diol derived from 2,2-dimethyl-1,3-propanediol with dimethyl azeleate.
  • the reaction to make the non-linear oligoester diol, which will be labeled PA, is shown below.
  • a 500-mL, 4-neck flask is equipped with a mechanical stirrer, Dean-Stark trap, condenser,
  • oligoester diol with methyl side chain such as PA with linear oligoester diol (A 2 ) with M n of 695, the M n of the above non-linear diol was controlled at 718, close to 695.
  • Degree of polymerization, M n , and NVW of PA are shown in Table 7.
  • the dimethyl azeleate used in these experiments was a redistilled, commercial (Aldrich) product having a composition, as determined by gas chromatography/mass spectroscopy, of the dimethyl esters of heptanedioic
  • DBE-3 and DBE- 5" are products of the duPont Company; they are said to be mixtures of the dimethyl esters of succinic (SA), glutaric (GA) and adipic (AA) acids in the following proportions: DBE-3: SA, ⁇ 1%; GA, 5-15%; AA, 85-95%.
  • DBE-5 is said to be >98.5% pure dimethyl glutarate.
  • the products are liquid at 25°C and are solids at 0°C.
  • the crosslinker is stated to have a viscosity of
  • oligoester IV-2 The M. of oligoester IV-2 is reported at >608 because the molecular weight cannot be exactly calculated from end group analysis without knowing the proportions of the two diols incorporated in the product. It is probably only slightly above 608.
  • An oligoester was made by reacting 1,4- butanediol with a mixture of dimethyl esters of
  • Example V (a) The oligoester diol described in Example V (a) was mixed with titanium dioxide and crosslinked with a melamine formaldehyde resin.
  • the film properties were studied as described in Table 13 below:
  • An oligoester diol was made by reacting 1,4- butanediol and a mixture of dimethyl esters of
  • the number average weight (MJ was 520, and the oligoester had a viscosity of 0.64 Pa.s at 25°C and had 98.7% solids as measured under ASTM D-2369.
  • the film properties of the oligoester (M n 520) crosslinked with a melamine formaldehyde resin were studied as described in Table 14 below.
  • Example VI (a) crosslinked with a Melamine
  • Example VI (a) The oligoester diol described in Example VI (a) was mixed with TiO 2 and crosslinked with a mixture of melamine formaldehyde and polyisocyanate crosslinkers in weight ratios of 2.0/0.65 to 2.0/0.22 (melamine
  • K-FLEX UD320-100 was a 100% polyurethane-diol with hydroxyl equivalent weight 160 and viscosity 7.0 Pa.s at 50°C. Its structure is HO(CH 2 ) 6 OCONH(CH 2 ) 6 NHCOO(CH 2 ) 6 OH.
  • K-FLEX UD-320W having the same structure as K-FLEX UD320-100, was a
  • polyurethane-diol containing about 10% by weight of water with hydroxyl equivalent weight 178, viscosity 8.0 Pa.s at 25°C. Both were obtained from King Industries.
  • Cymel 1135 a 50/50 methylated/butylated melamine, with 70% monomeric content, was obtained from Cytec Co.
  • Resimene 797 a modified methylated melamine resin, and Resimene HM2612, 100% methylated melamine with > 90% monomeric content, were obtained from Monsanto Chemical Company.
  • DNNDSA dinonyl naphthalene disulfonic acid
  • Defoamers BYK-077 and leveling additive BYK-358 were obtained from BYK Chemie.
  • the formulations were prepared by blending oligoester-diol, crosslinker, catalyst, and additive together.
  • Films were prepared by casting the blended solution on a panel by a 26# wire - wound draw bar and baking in an oven at 150°C for 30 minutes unless
  • Pencil hardness was measured according to ASTM D3364-74 standard test method for film hardness by pencil test. Impact resistance, either direct or reverse impact, was measured according to the ASTM D2794-84 standard test method for resistance of organic coatings to the effects of rapid deformation (Impact). Resistance to methyl-ethyl-ketone (MEK) was measured by double rubbing with MEK saturated non-woven paper ("Kim-Wipe"). The non-woven paper was kept saturated by MEK during the measurement. Dry film thickness was measured by an
  • Aromatic oligoester diol 6GT and 10GT were synthesized with the following structure. 1,3,5-Tri (hydroxyethyl) cyanuric acid (THECA)
  • PHBA parahydroxybenzoic acid
  • Dispersant Solsperse 24000 a
  • polyester/polyamine copolymer with m.p. of 47.5oC, was obtained from United Color Technology, Inc.
  • Hardeners were dissolved in the oligoester-diol - melamine resin blend at 150°C along with a
  • Tables 19-20 describe formulation of the oligoester-diols of Example III with varying molecular weights with hardeners, polyurethane diol and melamine,
  • Tables 21-23 describe formulation of oligoester-diols in combination with hardeners and mixtures of crosslinkers.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
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Abstract

Cette invention se rapporte à un véhicule polymère qui réduit ou élimine les composés organiques volatils dans des compositions de revêtement en permettant de former une composition de revêtement formulée qui ne nécessite pas de solvant organique en vue de son application sur un substrat. Ce véhicule polymère comprend au moins un diol d'oligoester linéaire propre à entrer en réticulation avec un agent réticulant et possédant un poids moléculaire moyen en nombre compris dans des limites contrôlées d'un indice de polydispersion propre à contrôler la viscosité du véhicule polymère.
PCT/US1996/001141 1994-01-25 1996-01-24 Vehicule polymere servant a former des compositions de revetement sans solvant WO1996023035A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AU49058/96A AU718881B2 (en) 1995-01-24 1996-01-24 Polymeric vehicle effective for providing solventless coating compositions
JP8523036A JPH10501582A (ja) 1995-01-24 1996-01-24 無溶剤被覆組成物を得るのに有効なポリマービヒクル
KR1019960705325A KR970702336A (ko) 1994-01-25 1996-01-24 무용매 코팅 조성물을 제공하는데 효과적인 중합체성 담체(polymeric vehicle effective for providing solventless coating compositions)
EP96905248A EP0751979A1 (fr) 1995-01-24 1996-01-24 Vehicule polymere servant a former des compositions de revetement sans solvant

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
USPCT/US95/01053 1995-01-24
PCT/US1995/001053 WO1995019997A1 (fr) 1994-01-25 1995-01-24 Vehicule polymere formant des compositions de revetement sans solvant
US08/487,962 1995-06-07
US08/487,962 US5587428A (en) 1994-01-25 1995-06-07 Polymeric vehicle effective for providing solventless coating compositions

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WO1996023035A1 true WO1996023035A1 (fr) 1996-08-01
WO1996023035A9 WO1996023035A9 (fr) 1996-11-21

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JP (1) JPH10501582A (fr)
AU (1) AU718881B2 (fr)
CA (1) CA2185454A1 (fr)
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5910563A (en) * 1994-01-25 1999-06-08 Exxon Chemical Patents, Inc. Water thinned polymeric vehicle for coating compositions with low amounts of volatile organic compounds
US5955550A (en) * 1994-01-25 1999-09-21 Exxon Chemical Patents, Inc. Polymeric vehicle for providing solventless coating compositions
US5969085A (en) * 1994-01-25 1999-10-19 Exxon Chemical Patents, Inc. Polymeric vehicle for high solids coatings
US5976706A (en) * 1995-10-10 1999-11-02 Exxon Chemical Patents Inc. Low viscosity, high solids polyesterdiols and compositions containing same
US6087464A (en) * 1995-04-19 2000-07-11 Exxon Chemical Patents, Inc. Polymeric vehicles which include a polyol, a phenolic ester alcohol and isocyanate compound
US6103826A (en) * 1995-04-19 2000-08-15 Eastern Michigan University Clearcoat compositions containing phenolic ester compounds
US6541594B2 (en) 2000-12-19 2003-04-01 Basf Corporation Coating compositions containing crosslinkable monomeric difunctional compounds having at least thirty carbon atoms
US6740706B2 (en) 2001-12-07 2004-05-25 Basf Corporation Method for obtaining coating compositions having reduced VOC
US6812316B2 (en) 2000-12-19 2004-11-02 Basf Corporation Powder coating compositions and powder slurry coating compositions containing monomeric difunctional compounds
US7163984B2 (en) 2000-12-19 2007-01-16 Basf Corporation Waterborne coating compositions containing monomeric difunctional compounds
US7205029B2 (en) 2000-12-19 2007-04-17 Basf Corporation Method of providing cured coating films free of popping defects
US7321013B2 (en) 2000-12-19 2008-01-22 Basf Corporation Method for obtaining coating compositions having reduced VOC
US7368501B2 (en) 2000-12-19 2008-05-06 Basf Corporation Method for improving environmental durability of materials
US7696285B2 (en) 2000-12-19 2010-04-13 Basf Coatings Ag Carbamate functional reactive polymer composition

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2185456A1 (fr) * 1995-01-24 1996-08-01 Frank Jones Vehicule polymere pour revetements a haute teneur en matieres solides

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2185662A1 (fr) * 1972-05-24 1974-01-04 Dulux Australia Ltd
US3994851A (en) * 1972-10-26 1976-11-30 Ppg Industries, Inc. High solids polyester coating composition
US4459401A (en) * 1983-05-04 1984-07-10 Desoto, Inc. Polyester oligomer and high solids thermosetting coatings

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2185662A1 (fr) * 1972-05-24 1974-01-04 Dulux Australia Ltd
US3994851A (en) * 1972-10-26 1976-11-30 Ppg Industries, Inc. High solids polyester coating composition
US4459401A (en) * 1983-05-04 1984-07-10 Desoto, Inc. Polyester oligomer and high solids thermosetting coatings

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5910563A (en) * 1994-01-25 1999-06-08 Exxon Chemical Patents, Inc. Water thinned polymeric vehicle for coating compositions with low amounts of volatile organic compounds
US5955550A (en) * 1994-01-25 1999-09-21 Exxon Chemical Patents, Inc. Polymeric vehicle for providing solventless coating compositions
US5969085A (en) * 1994-01-25 1999-10-19 Exxon Chemical Patents, Inc. Polymeric vehicle for high solids coatings
US6087464A (en) * 1995-04-19 2000-07-11 Exxon Chemical Patents, Inc. Polymeric vehicles which include a polyol, a phenolic ester alcohol and isocyanate compound
US6103826A (en) * 1995-04-19 2000-08-15 Eastern Michigan University Clearcoat compositions containing phenolic ester compounds
US5976706A (en) * 1995-10-10 1999-11-02 Exxon Chemical Patents Inc. Low viscosity, high solids polyesterdiols and compositions containing same
US6812316B2 (en) 2000-12-19 2004-11-02 Basf Corporation Powder coating compositions and powder slurry coating compositions containing monomeric difunctional compounds
US6541594B2 (en) 2000-12-19 2003-04-01 Basf Corporation Coating compositions containing crosslinkable monomeric difunctional compounds having at least thirty carbon atoms
US6962730B2 (en) 2000-12-19 2005-11-08 Basf Corporation Coating composition containing crosslinkable monomeric difunctional compounds having at least thirty carbon atoms
US7163984B2 (en) 2000-12-19 2007-01-16 Basf Corporation Waterborne coating compositions containing monomeric difunctional compounds
US7205029B2 (en) 2000-12-19 2007-04-17 Basf Corporation Method of providing cured coating films free of popping defects
US7321013B2 (en) 2000-12-19 2008-01-22 Basf Corporation Method for obtaining coating compositions having reduced VOC
US7368501B2 (en) 2000-12-19 2008-05-06 Basf Corporation Method for improving environmental durability of materials
US7691951B2 (en) 2000-12-19 2010-04-06 Basf Corporation Method for obtaining coating compositions having reduced VOC
US7696285B2 (en) 2000-12-19 2010-04-13 Basf Coatings Ag Carbamate functional reactive polymer composition
US6740706B2 (en) 2001-12-07 2004-05-25 Basf Corporation Method for obtaining coating compositions having reduced VOC

Also Published As

Publication number Publication date
CA2185454A1 (fr) 1996-08-01
AU718881B2 (en) 2000-04-20
JPH10501582A (ja) 1998-02-10
AU4905896A (en) 1996-08-14
EP0751979A1 (fr) 1997-01-08

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