[go: up one dir, main page]

WO1993004122A1 - Compositions de polyester contenant des composes de phosphonium - Google Patents

Compositions de polyester contenant des composes de phosphonium Download PDF

Info

Publication number
WO1993004122A1
WO1993004122A1 PCT/US1992/007130 US9207130W WO9304122A1 WO 1993004122 A1 WO1993004122 A1 WO 1993004122A1 US 9207130 W US9207130 W US 9207130W WO 9304122 A1 WO9304122 A1 WO 9304122A1
Authority
WO
WIPO (PCT)
Prior art keywords
tri
benzyl
tolylphosphonium
polyester
iodide
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.)
Ceased
Application number
PCT/US1992/007130
Other languages
English (en)
Inventor
John Michael Beckerdite
Peter Charles Rooney
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.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Publication of WO1993004122A1 publication Critical patent/WO1993004122A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/688—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing phosphorus
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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

Definitions

  • the present invention pertains to the polyester compositions containing phosphonium salts as low-temperature or accelerated cure catalysts for the reaction of carboxyl-terminated polyesters with epoxy compounds to form thermosetting powder coatings.
  • the invention also pertains to curable compositions comprising carboxyl- terminated polyesters, epoxy-containing compounds and phosphonium salts as well as powder coating compositions containing said curable compositions.
  • Polyester powder coatings are a well-known type of thermosetting coatings.
  • Carboxyl-group bearing polyesters are typically formulated with epoxide compounds to yield powders which can be applied to various substrates by electrostatic spraying orfluidized bed and then cured by baking.
  • triglycidylisocyanurate Various cure catalysts are known to the art for the reaction of carboxyl- terminated polyesters with epoxides for use in powder coatings. Accelerators include choline chloride, benzyl trimethyl ammonium chloride, imidazole, 1-methylimidazole, 2- methyiimidazole and benzotriazoles as discussed in by Worles et al. in EP 395,185, by Heater in U.S. Patent 4,370,452, by Goring in U.S. Patent 4,507,441 , and by McLafferty et al. in U.S. Patent 4,910,287.
  • Accelerators include choline chloride, benzyl trimethyl ammonium chloride, imidazole, 1-methylimidazole, 2- methyiimidazole and benzotriazoles as discussed in by Worles et al. in EP 395,185, by Heater in U.S. Patent 4,370,452,
  • McLafferty et al. in U.S. Patent No. 4,910,287, mentioned above, discloses the use of triphenylphosphine as a cure catalyst for a carboxyl-terminated polyester with triglycidyl isocyanurate for the low-temperature or accelerated cure of carboxyl- terminated polyesters with epoxides suitable for powder coatings. This disclosure by McLafferty et al.
  • tetrabutylphosphonium chloride and other phosphorous-containing compounds for the direct esterification of terephthalic acid with an alkylene glycol.
  • Brady in U.S. Patent No. 3,600,365 discloses the use of phosphines and quaternary phosphonium salts for the preparation of poly carboxylic acids from organic polyhalides and salts of polycarboxylic acids.
  • Craun in U.S. Patent No. 4,742,096 and Craun et al. in U.S. Patent No. 4,749,728 disclose the use of phosphonium salts as transesterification catalysts for hydroxyl- functional materials with carboxylic esters.
  • phosphonium salts can be used for the low- temperature or accelerated cure of carboxyl-terminated thermosettable polyesters with epoxy compounds such as triglycidyl isocyanurate (TGIC).
  • the cure catalyst may be added to the polyester at any stage of the synthesis or can be added with the epoxy agent during the formulation, with additives if desired, before mixing or extrusion (melt- mixing) or after extrusion.
  • the phosphonium salt is added to a liquid melt of the polyester towards the end of the polyester synthesis but can be added at the beginning of the polyester synthesis if desired.
  • the present invention pertains to a polyester composition
  • a polyester composition comprising (1) a carboxyl-containing thermosettable polyester, and (2) a phosphonium compound .
  • the present invention also pertains to a curable polyester composition
  • a curable polyester composition comprising (1) a carboxyl-containing thermosettable polyester, (2) a phosphonium compound as a catalyst for the reaction between (1) and (3), and (3) a compound containing an average of more than one vicinal epoxy group per molecule as a curing agent for the polyester.
  • the present invention also pertains to a powder coating composition containing (A) a curable polyester composition comprising (1) a carboxyl-containing thermosettable polyester, (2) a phosphonium compound as a catalyst for the reaction between (1) and (3), and (3) a compound containing an average of more than one vicinal epoxy group per molecule as a curing agent for the polyester; and (B) at least one member selected from the group consisting of fillers, pigments, flow control agents, any combination thereof.
  • A a curable polyester composition comprising (1) a carboxyl-containing thermosettable polyester, (2) a phosphonium compound as a catalyst for the reaction between (1) and (3), and (3) a compound containing an average of more than one vicinal epoxy group per molecule as a curing agent for the polyester
  • B at least one member selected from the group consisting of fillers, pigments, flow control agents, any combination thereof.
  • the amount of the phosphonium catalyst to be employed depends upon the reactants used and the particular phosphonium catalyst used. In any event, an amount sufficient to produce the desired reaction is used.
  • the amount of phosphonium compound which can be employed in the present invention is from 0.0005 to 1.0, preferably from 0.005 to 0.5, more preferably from 0.05 to 0.2, percent by weight based upon the weight of the thermosettable polyester.
  • the rate of the cure of the thermosettable polyester with the epoxy compound may be too slow to suit industrial needs.
  • the rate of cure may be too fast. That is, the thermosettable polyester/epoxy system may cure upon storage, during extrusion and/or melt mixing or may cure too fast to form a coating with poor properties such as adhesion, impact, gloss, solvent resistance combinations thereof.
  • Suitable phosphonium compounds which can be employed herein include, but are not limited to those represented by formulas RRRP+X- or -XRRRP + -Z- P + RRRX- wherein each R is independently a hydrocarbyl or inertly substituted hydrocarbyl group, Z is a hydrocarbyl or inertly substituted hydrocarbyl group and X is any suitable anion.
  • hydrocarbyl as employed herein means any aliphatic, cycloaliphatic, aromatic, or aliphatic or cycloaliphatic substituted aromatic groups.
  • the aliphatic groups can be saturated or unsaturated.
  • Those R groups which are not aromatic contain from 1 to 20, preferably from 1 to 10, more preferably from 1 to 4 carbon atoms.
  • inertly substituted hydrocarbyl group means that the hydrocarbyl group can contain one or more substituent groups that does not enter into the reaction and does not interfere with the reaction between the epoxy compound and the polyester.
  • substituent groups include for example, NO 2 , Br, Cl, I, F.
  • Suitable anions include, for example, any of those described by Dante et al. in U.S. Patent No. 3,477,990, by Perry in U. S. Patent No. 3,948,855, by Tyler, Jr. et al. in U.S. Patent No. 4,366,295, by Marshall in U.S. Patent No. 4,634,757 and by Pham et al. in U.S. Patent No. 4,933,420.
  • Particularly suitable anions include the halides such as, for example, chloride, bromide, iodide and the carboxylates as well as the carboxylic acid complexes thereof, such as formate, acetate, propionate, oxalate, trifluoroacetate, formate ⁇ formic acid complex, acetate ⁇ acetic acid complex, propionate ⁇ propionic acid complex, oxalate ⁇ oxalic acid complex, trifluoroacetate ⁇ trifluoroacetic acid complex.
  • halides such as, for example, chloride, bromide, iodide and the carboxylates as well as the carboxylic acid complexes thereof, such as formate, acetate, propionate, oxalate, trifluoroacetate, formate ⁇ formic acid complex, acetate ⁇ acetic acid complex, propionate ⁇ propionic acid complex, oxalate ⁇ oxalic acid complex, trifluoroacetate ⁇ trifluoroacetic acid complex.
  • Suitable anions include, for example, phosphate, and the conjugate bases of inorganic acids, such as, for example, bicarbonate, phosphate, tetrafluoroborate or biphosphate and conjugate bases of phenol, such as, for example phenate or an anion derived from bisphenol A.
  • inorganic acids such as, for example, bicarbonate, phosphate, tetrafluoroborate or biphosphate
  • conjugate bases of phenol such as, for example phenate or an anion derived from bisphenol A.
  • methyltriphenyiphosphonium acetate-acetic acid complex ethyltriphenylphosphonium acetate ⁇ acetic acid complex, propyrtriphenylphosphonium acetate ⁇ acetic acid complex, tetrabutylphosphonium acetate-acetic acid complex, methyltriphenyiphosphonium bromide, ethyltriphenylphosphonium bromide, propyitriphenylphosphonium bromide, tetrabutylphosphonium bromide, ethyltriphenylphosphonium phosphate, benzyl-tri- para-tolylphosphonium chloride, benzyl-tri-para-tolylphosphonium bromide, benzyl-tri- para-tolylphosphonium iodide, benzyl-tri-meta-tolylphosphonium chloride, benzyl-tri- meta-tolylphosphonium bromide, benzyl-tri-meta-
  • Particularly suitable phosphonium compounds which can be employed herein include, for example, methyltriphenyiphosphonium iodide,
  • methyltriphenyiphosphonium acetate-acetic acid complex ethyrtriphenyiphosphonium acetate-acetic acid complex, tetrabutylphosphonium acetate-acetic acid complex, methyltriphenyiphosphonium bromide, ethyltriphenylphosphonium bromide, tetrabutylphosphonium bromide, ethyltriphenylphosphonium phosphate, benzyl-tri- para-tolylphosphonium chloride, benzyl-tri-para-tolylphosphonium bromide, benzyl-tri- para-tolylphosphonium iodide, benzyl-tri-meta-to ⁇ ylphosphonium chloride, benzyl-tri- meta-tolylphosphoniurn bromide, benzyl-tri-meta-toiylphosphonium iodide, benzyl-tri- ortho-tolylphosphonium chlor
  • the phosphonium compouds can be employed as is or they may be dissolved or dispersed in an organic carrier such as, for example, alcohols such as methanol, ethanol, propanol, glycol ethers such as, for example, ethylene glycol methyl ether, ethylene glycol n-butyl ether, propylene glycol methyl ether or any combination thereof.
  • an organic carrier such as, for example, alcohols such as methanol, ethanol, propanol, glycol ethers such as, for example, ethylene glycol methyl ether, ethylene glycol n-butyl ether, propylene glycol methyl ether or any combination thereof.
  • a solvent or diluent when employed, it can be employed in amounts such that the concentration of the phosphonium compound in the diluent is from 0.01 to 99.99, preferably from 25 to 99.99, more preferably from 50 to 99.99, percent by weight.
  • the phosphonium compounds can be added to the polyesters after they have been prepared or they can be added at the beginning of their preparation or they can be added at any point during their preparation.
  • the polyesters useful in the practice of the present invention are thermosettable carboxyl-terminated and are any of those suitable for the formulation of thermosetting powder coatings with epoxide group bearing compounds. This implies that the polyesters have a sufficiently high glass transition temperature to resist clumping when in powder form and subjected to normally encountered field conditions. It is preferred that the polyesters have a DSC obtained glass transition temperature (Tg) of at least 45°C, wherein the glass transition temperature is obtained by differential scanning calorimetry employing a heat-up rate of 10°C per minute in a nitrogen atmosphere.
  • Thermosettable carboxyl-terminated polyesters having lower glass transition temperatures can be used, but special handling and/or additives may be required to resist the above-mentioned clumping.
  • the thermosettable carboxyl- terminated polyester can have an acid number of 20-100, preferably from 20 to 60, more preferably from 20 to 40. It is preferred that they have a hydroxy! number less than 20, preferably less than 10, more preferably less
  • Suitable organic dicarboxylic acids which can be employed to prepare the thermosettable polyesters used herein include, for example, aliphatic, cycloaliphatic or aromatic diacids having from 2 to 20 carbon atoms. These diacids can be either saturated or unsaturated. Also suitable are the anhydrides thereof. Such diacids or anhydrides include, but are not limited to, adipic acid, terephthalic acid, oxalic acid, succinic acid, sebacic acid, fumaric acid, azelaic acid, suberic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, succinic anhydride, phthalic anhydride or any combination thereof. Particularly suitable such acids or anhydrides include, for example, terephthalic acid, isophthalic acid, adipic acid or any combination thereof.
  • esters of any of the aforementioned dicarboxylic acids.
  • esters include, for example, the methyl, ethyl or propyl mono and diesters of adipic acid, terephthalic acid, oxalic acid, succinic acid, sebacic acis, fumaric acid, azelaic acid, suberic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, or any combination thereof.
  • DIOL COMPOUNDS the methyl, ethyl or propyl mono and diesters of adipic acid, terephthalic acid, oxalic acid, succinic acid, sebacic acis, fumaric acid, azelaic acid, suberic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, or any combination thereof.
  • Suitable diols (compounds containing two hydroxyl groups per molecule) which can be employed to prepare the polyesters used herein.include, for example, aliphatic, cycloaliphatic or aromatic diols which can be either saturated or unsaturated. These diols can have from 2 to 20, preferably from 2 to 12, more preferably from 2 to 8, carbon atoms per molecule.
  • Such diols include, but are not limited to, ethylene glycol, propylene glycol, 1 ,4-butanediol, 1 ,3-butanediol, 1 ,2-butanediol, pentanediol, hexanediol, heptanediol, neopentyl glycol, nonanediol, decanediol, 2,2,4- trimethyl-1 ,3-pentanediol, diethylene glycol, dipropylene glycol,
  • diols include, for example, neopentyl glycol, ethylene glycol, cyclohexanedimethanol or any combination thereof.
  • a tri- or poly-functional reactant is introduced into the reaction mixture.
  • This tri- or poly-functional reactant can be either hydroxyl or acid or anhydride functional.
  • Particularly suitable tri- or poly-functional reactants which can be employed herein include, for example, trimellitic anhydride, trimethylolpropane, glycerin, triethylolpropane, pentaerythritol or any combination thereof.
  • Suitable such monofunctional reactants include, for example, benzoic acid, tert-butylbenzoic acid, phenylbenzoic acid, stearic acid, tert-butylphenol, benzyl alcohol, or any combination thereof.
  • These monofunctional compounds are employed in amounts of from 0.01 to 10, preferably from 1 to 8, more preferably from 2 to 5, weight percent based upon the total weight of reactants.
  • the process for preparing polyesters can be conducted in the presence of a suitable solvent such as, for example, aromatic hydrocarbons, ethers, sulfones, chlorinated aromatic hydrocarbons, sulfolanes, sulfoxides or any combination thereof.
  • a suitable solvent such as, for example, aromatic hydrocarbons, ethers, sulfones, chlorinated aromatic hydrocarbons, sulfolanes, sulfoxides or any combination thereof.
  • Particularly suitable such solvents include, for example, toiuene, xylene, diphenyl ether, dimethyl sulfolane or any combination thereof.
  • the solvent can be employed in amounts of from 40 to 95, preferably from 45 to 90, more preferably from 50 to 90, percent by weight based upon the weight of the reactants.
  • the diol, dicarboxylic acid and, when employed, the tri- or poly-functional compound and monofunctional compound, when employed, are employed in quantities and the reaction conducted such that the resultant acid terminated polyester contains the desired acid number.
  • the desired acid number is less than 100, preferably less than 60, more preferably less than 40.
  • the acid terminated polyesters are usually prepared at temperatures usually employed in the preparation of polyester resins. Such temperatures are from 150°C to 270°C, preferably from 170°C to 270°C, more preferably from 180°C to 250°C.
  • the reaction is conducted for a time sufficient to bring the reaction to the desired degree of completion.
  • the reaction is usually considered complete when the acid number of the reaction mixture is below 100, preferably below 60, more preferably below 40.
  • the polyester may become colored and/or by-product formation such as ethers may result.
  • the reaction is conveniently conducted at pressures from 700 mm
  • reaction temperature and pressure are balanced such that the water or low-boiling alcohol of reaction is removed as quickly as possible while not distilling the low-boiling reactants, generally glycols, from the reaction. It is generally advantageous to finish the reaction at reduced pressure, generally below 100 mm Hg, preferably below 50 mm Hg, more preferably below 10 mm Hg.
  • the time required to achieve the desired degree of reaction depends upon many factors, such as heating and cooling capacity, reaction vessel size, particular reactants and catalyst,. Generally, for lab scale reactions up to 2 liters, the reaction is usually complete in less than 12 hours, preferably in less than 10 hours, more preferably in less than 8 hours.
  • the time to essentially complete the reaction is less than 36 hours, preferably less than 30 hours, more preferably less than 24 hours.
  • the polyester resins are prepared in the presence of a suitable catalyst such as, for example, organotin compounds such as dibutyltin oxide, dimethyltin oxide, dibutyltin dilaurate, butylchlorotin dihydroxide, organotitanium compounds such as tetramethyl titanate, tetrabutyl titanate, vanadyl alcoholates such as vanadyl isopropylate and vanadyl isobutylate or any combination thereof.
  • organotin compounds such as dibutyltin oxide, dimethyltin oxide, dibutyltin dilaurate, butylchlorotin dihydroxide, organotitanium compounds such as tetramethyl titanate, tetrabutyl titanate, vanadyl alcoholates such as vanadyl isopropylate and vanadyl isobutylate or any combination thereof.
  • a catalyst composition comprising (1) at least one organotin salt of a carboxylic acid, and (2) either (a) at least one organotin oxide, or (b) at least one organostannoic acid, or (c) a combination of (a) and (b).
  • Suitable organotin salts of a carboxylic acid which can be employed herein include, for example, those represented by the following formulas R-Sn(O 2 CR'), R 2 Sn(O 2 R') 2 , R 2 Sn(O 2 CR')(OCR'), R-Sn(O 2 CR') 3 or
  • R-Sn(O 2 CR') 2 Y wherein each R is the same or different and is an alkyl group having from
  • R groups can be saturated or unsaturated and can be substituted or unsubstituted with such substituent groups as alkyl, aryl or cycloalkyl groups having from 1 to 20 carbon atoms, halogen, preferably chlorine or bromine, -NO 2 ,; and Y is a halogen, preferably chlorine or bromine.
  • organotin salts of carboxylic acids include, for example, dibutyltin diacetate, dibutyltin dilaurate, stannous octoate, dioctyltin dilaurate or any combination thereof.
  • organotin oxides which can be employed herein include, for example, those represented by the formula R 2 SnO wherein R is as defined above.
  • organotin oxides include, but are not limited to bis(carbomethoxyethyl) tin oxide, diallyitin oxide, dibenzyltin oxide, dibutyltin oxide, dicyclohexyltin oxide, dilauryltin oxide, dimethyltin oxide, di-1-naphthyrtin oxide, dioctyltin oxide, diphenyltin oxide, divinyltin oxide, or any combination thereof.
  • Particularly suitable organotin oxides include, for example, dibutyltin oxide, dimethyltin oxide or any combination thereof.
  • organostannoic acids which can be employed herein include, for example, those represented by the formula R-SnOOH or their corresponding anhydrides represented by the formula (R-SnO) 2 O wherein R is as defined above.
  • organostannoic acids or anhydrides thereof include, but are not limited to
  • methylstannoic acid 1-naphthylstannoic acid, butylstannoic acid, octyistannoic acid, their anhydrides, or any combination thereof.
  • Particularly suitable organostannoic acids or anhydrides include, for example, butylstannoic acid, methylstannoic acid or any combination thereof.
  • tin catalysts which can be employed herein are employed in an amount which provides a total amount of catalyst of from 0.00 i to abut 3, preferably from 0.01 to 1.0, more preferably from 0.05 to 0.2 weight percent based upon the weight of the reactants.
  • the organotin salt of a carboxylic acid catalyst (component 1) is employed in an amount of from 0.01 to 99.99, preferably from 0.01 to 60, more preferably from 0.01 to 30 mole percent based upon the total amount of catalyst; and the organotin oxide and/or organostannoic acid catalyst (component 2) is employed in an amount of from 0.01 to 99.99, preferably from 50 to 99.99, more preferably from 70 to 99.99 mole percent based upon the total amount of catalyst.
  • the epoxy curing agent can be any epoxy that results in a thermosettable coating with acceptable properties.
  • suitable epoxides include for example, triglycidyl isocyanurate or a related heterocyclic triepoxy compound such as methyl-substituted triglycidyl isocyanurate, 1 ,2,4-triglycidyl triazolidine-3,5-dione or diglycidylterephthalate or diglycidylhexahydroterephthalate or diglycidyl ethers of polyhydric phenols such as, for example, resorcinol, catecol and hydroquinone, the diglycidyl ethers of bisphenol and bisphenols such as, for example, bisphenol A, bisphenol F, bisphenol K, bisphenol S as well as the alkyl and halogen derivatives thereof such as the C-1 to C-4 alkyl, chlorine or bromine derivatives.
  • polyglycidyl ethers of the novalac resins prepared by reacting a phenol or alkyl or halogen substituted phenol with an aldehyde such as formaldehyde.
  • the epoxide containing compounds are triglycidyl isocyanurate and the diglycidyl ethers of dihydroxyl containing compounds represented by the formulas I, II, III, IV or V wherein each A is independently a divalent hydrocarbyl group having from 1 to 12, more suitably from 1 to 8, most suitably from 1 to 4 carbon atoms; each A' is independently a divalent saturated or unsaturated aliphatic or cycloaliphatic group having grom 1 to 10, preferably from 1 to 6, more preferably from 1 to 4, carbon atoms; each R is independently hydrogen or an alkyl group having from 1 to 4 carbon atoms, preferably hydrogen or methyl, most preferably hydrogen; each X is independently hydrogen or a hydrocarbyl or hydrocarbyloxy group having from 1 to 12, preferably from 1 to 6, more preferably from 1 to 4, carbon atoms or a halogen, preferably chlorine or bromine; Z is a glycidyl group or an alkyl substituted
  • the quantity of the epoxy compound used in the binding agent with the thermosettable polyester resin depends on the acid number of the polyester resin and on the epoxy equivalent weight of the epoxy compound with which the polyester is combined, and is in general between from 0.80 to 1.30, preferably from 0.90 to 1.10, more preferably from 0.95 to 1.05 epoxy equivalents per carboxyl equivalent and is particularly preferred to approach stoichiometry, that is, one epoxy group per carboxyl group.
  • the powder coating compositions of the present invention comprise the curable compositions and one or more additives such as, for example, fillers, pigments, flow control agents, any combination thereof.
  • the amounts of the additive compounds are those which provides the composition with the desired result. That is in the instance of pigments, they are added in amounts which provides the powder coating with the desired color. Usually, the amount is from 0.01 to 40, preferably from 0.01 to 15, more preferably from 0.1 to 10, percent by weight based upon the weight of the binder (combined weight of polyester resin plus curing agent).
  • Suitable pigments include, for example, carbon black, titanium dioxide, iron oxide, zinc sulfide, zinc oxide, lead chromate, phthalocyanine blue, chromium oxide or any combination thereof.
  • the fillers are employed in amounts which provide the powder coating with the desired cost, hardness, volume, surface texture, corrosion resistance or the like. However, the fillers are usually employed in amounts of from 0 to 80, preferably from 2 to 75, more preferably from 5 to 50, percent by weight based upon the weight of the binder.
  • Suitable flow control agents include, for example, polyacrylate oligomers, silicones, teflon, benzoin or any combination thereof.
  • TGIC is triglycidylisocyanurate.
  • MEK is methylethyl ketone.
  • A-1 is ethyltriphenylphosphonium acetate ⁇ acetic acid (70 wt. percent in methanol).
  • P-1 is ethyltriphenylphosphonium phosphate (30 wt. percent in methanol).
  • Uralac P-5400 is a saturated carboxylated polyester resin (commercially available from Dutch State Mines) having an acid number of 34 (acid equivalent weight of 1650) and a melt viscosity of 120 poise at 175°C.
  • Ruco 106 is a saturated hydroxyl-terminated polyester resin having a hydroxyl number of 44 (hydroxyl equivalent weight of 1275), commercially available from Ruco Polymer Corporation.
  • Pioester 4140 is a saturated hydroxyl-terminated polyester resin having a hydroxyl number of 41 (hydroxyl equivalent weight of 1368), commercially available from Pioneer Plastics.
  • Pioester 4248 is a saturated carboxylated polyester resin having an acid number of 27 (acid equivalent weight of 2078), commercially available from Pioneer Plastics.
  • Acid numbers were determined by dissolving 0.5-1 g of resin in 30mL dimethyl formamide (DMF) and titrating with 0.1 N KOH (in methanol) using
  • APHA color was measured on a Hellige Aqua Tester (Hellige Inc., Garden City, N.Y.) using 5g of sample and 45g of tetrahydrofuran (THF) and comparing the color of the solution (after sonication to fully dissolve the polyester) with color disk standards. The higher the APHA number, the darker the solution.
  • Methyl ethyl ketone (MEK. double rubs, which is an indication of solvent resistance, was determined by imparting double rubs on the coating side of the panel with a Q-tip that was rewetted every 50 double rubs with fresh MEK. The number of double rubs to metal is recorded. Gel times were measured at 180°C on a Thomas Electric Company (Cleveland, Ohio) Cure Plate using 1/4 teaspoon (0.7g) of the formulated powder. The powder was stroked with a wooden craft stick until the mixture gells. EXAMPLE 1
  • the dry-mixed formulation is then extruded in a Buss-Condux PLK 46 single screw extruder (equipped with a 46mm diameter kneader screw operated at 100rpm) with Zone 1 at 55°C and Zone 2 at 110°C.
  • the extrudate is passed through Buss-Condux Chill Rolls (6.5 in., 165.1 mm diameter), cooled and crushed.
  • the crushed extrudate is then fine ground in a Brinkman ZM-1 Centrifugal Grinding Mill utilizing the 12-tooth grinding attachment and 0.75mm screen.
  • the finely ground extrudate is sieved through a No.140 (150 mesh, 100um) standard test sieves (wire cloth).
  • Portions of the -150 mesh powder coating formulation were applied via electrostatic spray with a Wagner EPM200 unit (set at 80-90kV) connected to a Wagner G-100 electrostatic Spray-O-Round sprayer onto 4" x 12" x 20 gauge (101.6mm x 304.8mm x 0.529mm) cold rolled steel, clean treatment Parker test panels (Parker Division, Hooker Chemicals and Plastics Corp.).
  • the electrostatically coated panels were set in a Blue M Touchmatic convection-type oven and cured. After removal from the oven the panels were evaluated via the following test methods: coating thickness is determined per ASTM D1186 by utilizing a Fisher Model 650C film thickness tester.
  • Example 1 was heated to 180°C whereupon 1.2 g of I-1 was added. The polyester was raised to 200°C (in 10 min) and the polyester/l-1 was stirred at 200°C for an additional 30 min whereupon the mixture was poured onto aluminum foil. The APHA color, measured using 10 wt % resin in THF, of the Uralac P-5400 polyester was 60 before heating and was 80 after heating in the presence of I-1 catalyst. EXAMPLE 4
  • Uralac P-5400 polyester and I-1 catalyst containing Uralac P-5400 polyester described in Example 3 were used in this comparison evaluation.
  • the polyester (837g, 0.505 equivalents), TGIC (63g, 0.636 equivalents), TiO 2 (450g) and
  • Resiflow P-67 (a flow modifier; 13.5g) were placed in a plastic bag, sealed and dry mixed to provide a homogeneous dry blend which was further processed and evaluated using the method of Example 2. The are given in Table II.
  • Tetrabutyl phosphonium acetate ⁇ acetic acid complex catalyst (A-2) was tested for its ability to shorten the gel time of the uncatalyzed formulated polyester powder described in Example 4.
  • the A-2 catalyst was first dispensed via a 10 ⁇ L syringe onto the gel plate which was maintained at 180°C.
  • the formulated polyester powder was immediately placed on the gel plate and, with stirring, the time taken for the powder to gel at 180°C was recorded. The results are given in Table III.
  • I-1 catalyst Use of l-1 catalyst in Formulated Uralac P-5400 Powder I-1 catalyst was tested for its ability to shorten the gel time of the uncatalyzed formulated polyester powder described in Example 4. The following amounts of I-1 were combined with 5.00 ⁇ 0.01g of the formulated Uralac P-5400 powder in a 2 ounce(59mL) jar. The were mixed on a mechanical shaker for 1 hour to facilitate mixing. One quarter tablespoon (0.7g) of the formulated polyester powder was placed on the gel plate maintained at 180°C and the time taken for the powder to gel was recorded. The are given in Table IV.
  • Uralac P-5400 polyester described in Example 1 was used in this comparison evaluation.
  • the polyester (837g, 0.507 equivalents), TGIC (63g, 0.636 equivalents), TiO2 (450g) and Resiflow P-67 (a flow modifier; 13.5g) were placed in a plastic bag, sealed and dry mixed to provide a homogeneous dry blend which was further processed and evaluated using the method of Example 2.
  • the results are given in Table V.
  • the storage stability of formulated Uralac P-5400 powder was compared to the storage stability of tetrabutyl phosphonium acetate»acetic acid complex (A-2) catalyzed Uralac P-5400 powder described in Example 2 and to the storage stability of I-1 catalyzed Uralac P-5400 powder described in Example 4.
  • A-2 tetrabutyl phosphonium acetate»acetic acid complex
  • I-1 I-1 catalyzed Uralac P-5400 powder described in Example 4.
  • approximately 1 inch (25.4 mm) of powder was placed into 25 x 200 mm test tubes and then a 100 ⁇ 0.5 g weight was placed on top of the powder.
  • the powders were heated in an air oven for 24 hours at 110°F (43.3°C).
  • the powders were removed from the test tubes and cooled for 30 min.
  • the powders were then graded on a scale of 1 -10 with 1 being poor and 10 being excellent.
  • EXAMPLE 9 Use of various phosphonium salts to accelerate the cure of a formulated carboxyl- terminated polyester.
  • the polyester used in this study was prepared in a 10 gallon reactor equipped with a heating jacket, temperature controller, agitator and a column packed with stainless steel wire mesh. To this reactor was charged:
  • This mixture was heated to 230°C and monitored periodically by measuring the acid number and viscosity using an I.C.I. cone and plate viscometer. After a viscosity of 72 poise at 175°C and an acid number of 5.5 was obtained isophthalic acid (2937g, 17.68 moles) was added. Vacuum was applied slowly until a final acid number of 36.5 and a 175°C viscosity of 189 was obtained. The resin was discharged from the reactor at this point.
  • Formulated powder was prepared, by dry mixing polyester resin (930g, 0.605 equivalents), TGIC (70g, 0.707 equivalents) TiO 2 (500g) and Resiflow P-67 (a flow modifying agent, 15g were placed in a plastic bag, sealed and dry mixed to provide a homogeneous dry blend which was processed using the method of Example 2.
  • liquid catalysts tetrabutylphosphonium acetate ⁇ acetic acid complex (A-2, 70 wt % in MeOH) and ethyltriphenylphosphonium phosphate (P-1 , 30 wt % in MeOH)
  • A-2 70 wt % in MeOH
  • P-1 ethyltriphenylphosphonium phosphate
  • the gel time of the uncatalyzed powder was 285 sec.
  • Polyester resin described in Example 9 (1200 g) was heated to 200°C in a 2 liter flask equipped with a heating mantle, thermometer, stirrer and a nitrogen inlet and outlet. To this molten resin was added either triphenyl phosphine (2.65 g) or tetrabutylphosphonium acetate ⁇ acetic acid complex (A-2) catalyst (3.7g). The resin was heated for an additional 30 min at 200°C and the polyester was then poured onto aluminum foil.
  • triphenyl phosphine (2.65 g)
  • A-2 tetrabutylphosphonium acetate ⁇ acetic acid complex
  • Polyester resin (930 g, 0.605 equivalents) was formulated with TGIC (70 g, 0.707 equivalents), TiO 2 and Resiflow P-67 as described in Example 9 and then placed in a plastic bag, sealed and dry mixed to provide a homogeneous dry blend which was further processed and evaluated using the method of Example 2. In this case, the panels were cured in the oven at 180°C for 15 min. The results are given in Table VI.
  • Example 9 APHA color results of the polyester described in Example 9 plus various agents compared with commercially available DSM P2400 polyester (Dutch State Mines).
  • the polyester was melted at 200°C and the agents shown were added.
  • Ten grams of each resin was placed in an aluminum pan in an air oven set at 220°C for 6 hours.
  • APHA color was measured on a Hellige Aqua Tester (Hellige Inc.) using 5 g of sample and 45 g of tetrahydrofuran (THF) and comparing the color of the solutions with color disk standards. Higher APHA numbers correspond to darker solution colors.
  • Table VII The results are given in Table VII.
  • Example 9C Use of Example 9C for cure at 149°C.
  • DSM P-5400 polyester described in Examplel , was heated to 200°C in a 5 liter flask equipped with a heating mantle, stirrer, thermometer, nitrogen inlet and outlet.
  • Tetrabutylphosphonium acetate ⁇ acetic acid complex (A-2) catalyst (15.0g) was added at 200°C , the resin was stirred at this temperature for 30 min and then poured onto aluminum foil.
  • the catalyzed resin and a control of P-5400 polyester were formulated accordingly:
  • the mixture was heated to 250°C and monitored periodically by measuring the acid number and viscosity using a cone and plate viscometer. After a viscosity of 10 poise at 175°C and an acid number of 14 was obtained, the temperature was lowered to 200°C. Succinic anhydride (113 g, 1.13 moles) was added and the temperature then was slowly increased to 230°C. When an acid number of 37 was obtained, triphenyiphosphite (2.4 g, 0.15 wt. percent) was added. No color change occured. The resin was poured onto aluminum foil 15 minutes after addition of the triphenyiphosphite. APHA color of the poured resin was 15. EXAMPLE 15
  • triphenylphosphonium was used at concentrations of 0.28, 0.72, 1.38, 1.86 and 3.34 mg catalyst per gram of Pioester 4140 powder, there was no sign of cure up to 900 seconds.
  • ethyl triparatolylphosphonium was used (70 wt. % in methanol) at concentrations of 2.07, 10.36, 15.54 and 20.72 mg catalyst per gram of Pioester 4140 powder, there was no sign of cure up to 900 seconds.
  • the A-2 catalyst was first dispensed via a 10 ⁇ L syringe onto the gel plate which was maintained at 180°C.
  • the formulated polyester powder was immediately placed on the gel plate and, with stirring, the time taken for the powder to gel at 180°C was recorded.
  • Table XV The results are given in Table XV.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Paints Or Removers (AREA)

Abstract

On décrit des polyesters à terminaison d'acide contenant des composés de phosphonium, et qui, lorsqu'ils sont mélangés avec un agent de polymérisation époxy, peuvent être utilisés dans des revêtements en poudre.
PCT/US1992/007130 1991-08-27 1992-08-24 Compositions de polyester contenant des composes de phosphonium Ceased WO1993004122A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US75067491A 1991-08-27 1991-08-27
US750,674 1991-08-27

Publications (1)

Publication Number Publication Date
WO1993004122A1 true WO1993004122A1 (fr) 1993-03-04

Family

ID=25018787

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1992/007130 Ceased WO1993004122A1 (fr) 1991-08-27 1992-08-24 Compositions de polyester contenant des composes de phosphonium

Country Status (4)

Country Link
CN (1) CN1072193A (fr)
AU (1) AU2568492A (fr)
MX (1) MX9204933A (fr)
WO (1) WO1993004122A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996017026A1 (fr) * 1994-11-28 1996-06-06 Nissan Chemical Industries, Ltd. Composition de resine pour poudrage
US5637654A (en) * 1996-08-12 1997-06-10 Mcwhorter Technologies Low temperature cure carboxyl terminated polyesters
WO2000034391A1 (fr) * 1998-12-10 2000-06-15 Institut Für Polymerforschung Dresden E.V. Matiere durcissable et son procede de production et de traitement
US6084035A (en) * 1996-05-20 2000-07-04 Nissan Chemical Industries, Ltd. Weather-resistant resin composition for powder coating
WO2001094463A1 (fr) * 2000-06-02 2001-12-13 Sartomer Technology Company, Inc. Revetement en poudre fait d'une resine epoxy, d'un polyester a terminaison acide carboxylique, et d'une resine de styrene anhydride maleique
WO2003082996A3 (fr) * 2002-03-29 2004-03-11 Dsm Ip Assets Bv Composition de revetement moins sensible a des defauts superficiels
JP2010229418A (ja) * 2002-05-31 2010-10-14 Grace Gmbh & Co Kg エステル−アミド縮合生成物および粉末コーティングマット化剤
WO2014123534A1 (fr) * 2013-02-08 2014-08-14 Valspar Sourcing, Inc. Revêtement en poudre à température de durcissement ultra-basse
EP2688944B2 (fr) † 2011-03-25 2017-12-20 DSM IP Assets B.V. Compositions de résine pour les compositions de revêtement en poudre thermodurcissable

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105176169A (zh) * 2015-10-31 2015-12-23 安徽神剑新材料股份有限公司 一种环氧端基粉末涂料固化剂及其合成方法
CN111187559B (zh) * 2020-03-10 2021-07-27 镇江牛盾新材料科技有限公司 基于海因树脂的固化剂及其制备方法和应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2336436A1 (fr) * 1975-12-24 1977-07-22 Celanese Corp Procede d'obtention de polymeres thermoplastiques ameliores pour l'extrusion, et produits obtenus
US4910287A (en) * 1989-01-06 1990-03-20 Ruco Polymer Corporation 1-methyl imidazole catalyzed carboxyl terminated polyester

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2336436A1 (fr) * 1975-12-24 1977-07-22 Celanese Corp Procede d'obtention de polymeres thermoplastiques ameliores pour l'extrusion, et produits obtenus
US4910287A (en) * 1989-01-06 1990-03-20 Ruco Polymer Corporation 1-methyl imidazole catalyzed carboxyl terminated polyester

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6303706B1 (en) 1994-11-28 2001-10-16 Nissan Chemical Industries, Ltd. Resin composition for powder coating
KR100385599B1 (ko) * 1994-11-28 2005-02-24 닛산 가가쿠 고교 가부시키 가이샤 분말도료용수지조성물
AU701183B2 (en) * 1994-11-28 1999-01-21 Nissan Chemical Industries Ltd. Resin composition for powder coating
CN1073603C (zh) * 1994-11-28 2001-10-24 日产化学工业株式会社 用于粉末涂料的树脂组合物
WO1996017026A1 (fr) * 1994-11-28 1996-06-06 Nissan Chemical Industries, Ltd. Composition de resine pour poudrage
US6084035A (en) * 1996-05-20 2000-07-04 Nissan Chemical Industries, Ltd. Weather-resistant resin composition for powder coating
EP0906941A4 (fr) * 1996-05-20 2001-05-02 Nissan Chemical Ind Ltd Composition de resine resistant aux intemperies pour revetements pulverises
EP0918810A4 (fr) * 1996-08-12 2001-05-16 Mcwhorter Technologies Inc Polyesters a terminaison carboxyle durcissant a faible temperature
US5637654A (en) * 1996-08-12 1997-06-10 Mcwhorter Technologies Low temperature cure carboxyl terminated polyesters
WO2000034391A1 (fr) * 1998-12-10 2000-06-15 Institut Für Polymerforschung Dresden E.V. Matiere durcissable et son procede de production et de traitement
WO2001094463A1 (fr) * 2000-06-02 2001-12-13 Sartomer Technology Company, Inc. Revetement en poudre fait d'une resine epoxy, d'un polyester a terminaison acide carboxylique, et d'une resine de styrene anhydride maleique
WO2003082996A3 (fr) * 2002-03-29 2004-03-11 Dsm Ip Assets Bv Composition de revetement moins sensible a des defauts superficiels
JP2010229418A (ja) * 2002-05-31 2010-10-14 Grace Gmbh & Co Kg エステル−アミド縮合生成物および粉末コーティングマット化剤
EP2688944B2 (fr) † 2011-03-25 2017-12-20 DSM IP Assets B.V. Compositions de résine pour les compositions de revêtement en poudre thermodurcissable
US10179867B2 (en) 2011-03-25 2019-01-15 Dsm Ip Assets B.V. Resin compositions for thermosetting powder coating compositions
WO2014123534A1 (fr) * 2013-02-08 2014-08-14 Valspar Sourcing, Inc. Revêtement en poudre à température de durcissement ultra-basse
RU2629288C2 (ru) * 2013-02-08 2017-08-28 Вэлспар Сорсинг, Инк. Порошковое покрытие с ультранизкой температурой отверждения

Also Published As

Publication number Publication date
MX9204933A (es) 1993-02-01
CN1072193A (zh) 1993-05-19
AU2568492A (en) 1993-03-16

Similar Documents

Publication Publication Date Title
US4401774A (en) Thermosetting resinous binder compositions, their preparation, and use as coating materials
EP0040867B1 (fr) Compositions de liants résineux thermodurcissables, leur préparation et leur utilisation comme matériaux de revêtement
US4997907A (en) Curable powder mixtures
US4140728A (en) Heat hardenable powder coatings based on polyester resins containing carboxyl groups
CN1073585C (zh) 带酸官能团及环氧官能团的聚酯树脂
JP3341215B2 (ja) １５００未満の分子量を持つポリグリシジル化合物の固体組成物
WO1993004122A1 (fr) Compositions de polyester contenant des composes de phosphonium
US5869191A (en) Acid functional and epoxy functional polyster resins
EP0634434A2 (fr) Procédé pour la préparation d'une résine de polyester à fonctionalité acide
CA1188038A (fr) Liants a base de resines thermodurcissables, leur preparation et leur utilisation comme produit d'enduction
US4405763A (en) Thermosetting resinous binder compositions, their preparation, and use as coating materials
EP0656023B1 (fr) Revetement en poudre et utilisation de polyesters termines par un ester de glycidyle dans la preparation de revetements en poudre
US4130601A (en) Resin composition for powder paint
EP0751970B1 (fr) Compositions pour revetements exterieurs durables a base de poudre
US6451929B1 (en) Glycidyl ester by reacting COOH polyester with epihalohydrin
US5276071A (en) Phenol-terminated oxyalkylated or (cyclo)aliphatic diglycidyl ethers
KR20010080961A (ko) 증가한 분자량을 가지는 에폭시 작용성 폴리에스테르수지, 이의 제조방법 및 이를 포함하는 옥외 내구성 코팅조성물
EP0375801A1 (fr) Résines epoxy bloquées au moyen de monoisocyanate
AU1384000A (en) Epoxy functional polyester resins, process for their preparation, and outdoor durable coating compositions comprising them
JPS6135232B2 (fr)
JPH0372579A (ja) 金属プライマーのためのバインダーとしてのポリエステル／エポキシブロックコポリマー
US5003040A (en) Modified epoxy resins
JPS62950B2 (fr)
JP2001279171A (ja) 耐衝撃性の向上した粉体塗料用樹脂組成物
JPH1171452A (ja) 第三級カルボキシル官能性ポリエステル樹脂、その製造法およびそれから得られるポリグリシジルエステル、並びにそれを含有する粉体塗料組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AT AU BB BG BR CA CH CS DE DK ES FI GB HU JP KP KR LK LU MG MN MW NL NO PL RO RU SD SE

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL SE BF BJ CF CG CI CM GA GN ML MR SN TD TG

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

NENP Non-entry into the national phase

Ref country code: CA

122 Ep: pct application non-entry in european phase