EP3212685A1 - Mit funktionellen polyestern härtbare resolphenolharze - Google Patents

Mit funktionellen polyestern härtbare resolphenolharze

Info

Publication number
EP3212685A1
EP3212685A1 EP15791849.1A EP15791849A EP3212685A1 EP 3212685 A1 EP3212685 A1 EP 3212685A1 EP 15791849 A EP15791849 A EP 15791849A EP 3212685 A1 EP3212685 A1 EP 3212685A1
Authority
EP
European Patent Office
Prior art keywords
phenol
resole
mole
weight
phenolic resin
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.)
Pending
Application number
EP15791849.1A
Other languages
English (en)
French (fr)
Inventor
Thauming Kuo
Junjia LIU
Phillip Bryan Hall
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.)
Eastman Chemical Co
Original Assignee
Eastman 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
Priority claimed from US14/524,509 external-priority patent/US9487619B2/en
Priority claimed from US14/524,514 external-priority patent/US9650539B2/en
Priority claimed from US14/540,490 external-priority patent/US9598602B2/en
Priority claimed from US14/683,278 external-priority patent/US20160115345A1/en
Priority claimed from US14/922,846 external-priority patent/US20160115347A1/en
Application filed by Eastman Chemical Co filed Critical Eastman Chemical Co
Publication of EP3212685A1 publication Critical patent/EP3212685A1/de
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/24Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28Chemically modified polycondensates
    • C08G8/36Chemically modified polycondensates by etherifying
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D167/00Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D167/00Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/02Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • This invention pertains to resole curable phenolic resins based on m-substituted phenol that are soluble and curable with polyesters having a variety of functionalities.
  • the resole phenolic resins can be formulated with functional polyesters for thermoset applications.
  • the thermosetting compositions of the invention can have utility in solvent-based coatings as well as waterborne coatings.
  • Metal containers are commonly used for food and beverage packaging.
  • the containers are typically made of steel or aluminum.
  • a prolonged contact between the metal and the filled product can lead to corrosion of the container.
  • a coating is typically applied to the interior of the food and beverage cans. In order to be effective, such a coating must have adequate properties that are needed for protecting the packaged products, such as adhesion, corrosion resistance, chemical resistance, flexibility, stain
  • the coating must be able to withstand processing conditions during can fabrication and food sterilization.
  • Coatings based on a combination of epoxy and phenolic resins are known to be able to provide a good balance of the required properties and are most widely used.
  • BPA bisphenol A
  • BADGE bisphenol A diglycidyl ether
  • Polyesters have been of particular interest to the coating industry to be used as a replacement for epoxy resin because of their comparable properties such as flexibility and adhesion.
  • Crosslinking between polyester and common phenolic resin generally is too poor to provide adequate properties for use in interior can coatings.
  • conventional phenolic resin generally is too poor to provide adequate properties for use in interior can coatings.
  • polyesters having hydroxyl functionalities are generally not reactive enough with commercially available phenolic resins under curing conditions to provide adequate cross-linking density, resulting in a coating that lacks good solvent resistance and other desirable properties.
  • This invention provides polyesters that have functionality that is capable of reacting with aromatic hydroxyl group.
  • this invention provides a resole phenolic phenolic resin comprising the residues of (a) from about 50 to 1 00 mole % of a meta-substituted phenol
  • said resole phenolic resin is soluble in an organic solvent and curable with a functional polyester.
  • thermosetting composition comprising :
  • the curable polyester resin useful in the invention can comprise the residues of
  • polyhydroxyl compounds other than TACD ii) polyhydroxyl compounds other than TACD, and b) polycarboxyl compounds comprising:
  • curable polyester resin has an acid number ranging from about 20 to about 120 mg KOH/g, a hydroxyl number ranging from greater than 0 to about 100 mg KOH/g, and an acid numbenhydroxyl (AN:OH) number ratio of at least 0.5:1 .
  • the curable polyester resin useful in the invention comprise the residues of:
  • TACD 2,2,4,4-tetraalkylcyclobutane-1 ,3-diol
  • a polycarboxylic acid a derivative of polycarboxyl ic acid compound (other than bii)), or a combination thereof in an amount ranging from 70 to 95 mole %, based on the total moles of (b), and
  • polyester has an acid number ranging from about 30 to about 100 mg KOH/g and a hydroxyl number ranging from 3 to about 80 mg KOH/g.
  • this polyester can have an acid numbenhydroxyl number ratio of at least 0.5:1 .
  • reaction mixture in a first stage, combining the polyhydroxyl compounds and polycarboxylic acid compounds to form a reaction mixture, and reacting the reaction mixture in a reactor at a temperature from 180-250 °C, optionally in the presence of an acid catalyst until the reaction mixture has an acid number of 0 to 20 mg KOH/g, and
  • a second stage for forming a curable polyester composition by reacting a polycarboxylic anhydride with the reaction mixture at a temperature of 140 °C to 1 80 °C to thereby obtain a polyester composition having an acid number of greater than 20 mg KOH/g.
  • the meta-substituted phenol useful in the resole phenolic resin useful in the present disclosure can be selected from at least one from the group comprising m-cresol, m-ethylphenol, m-propylphenol, m-butylphenol, m-octylphenol, m-alkylphenol, m-phenylphenol, m-alkoxyphenol, 3,5-xylenol, 3,5-diethyl phenol, 3,5-dibutyl phenol, 3,5-dialkylphenol, 3,5-dialkoxyphenol, 3,5-dicyclohexyl phenol, 3,5-dimethoxy phenol, and 3-alkyl-5-alkyoxy phenol.
  • the meta-substituted phenol useful in the resole phenolic resin useful in the present disclosure can be m-cresol.
  • Phenolic component (b) useful in the present disclosure can be ortho- substituted, para-substituted, or unsubstituted phenol, or a mixture thereof.
  • Phenolic component (b) useful in the present disclosure can be ortho- substituted, or para-substituted phenol, or a mixture thereof.
  • Phenolic component (b) useful in the present disclosure can be selected from one or more selected from the group comprising o-cresol, o- ethylphenol, o-propylphenol, o-n-butylphenol, o-t-butyl phenol, o-octylphenol, o-phenylphenol, p-cresol, p-ethylphenol, p-propylphenol, p-n-butylphenol, p-t- butyl phenol, p-octylphenol, p-phenylphenol, 2,3-xylenol, 2,3-diethyl phenol, 2,3-dibutyl phenol, 2,5-xylenol, 2,5-diethyl phenol, 2,5-dibutyl phenol, 3,4- xylenol, 3,4-diethyl phenol, and 3,4-dibutyl phenol.
  • Phenolic component (b) useful in the present disclosure can be selected from o-cresol, p-cresol, and a mixture thereof.
  • the aldehyde useful in the resole phenolic resin of the present disclosure can be selected from formaldehyde, acetaldehyde,
  • the aldehyde useful in the resole phenolic resin of the present disclosure cab be formaldehyde.
  • the resole phenolic resin of the present disclosure can be soluble in one or more organic solvents selected from the group comprising xylene, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, methyl isoamyl ketone, n-butyl acetate, isobutyl acetate, t-butyl acetate, n-propyl acetate, isopropyl acetate, ethyl acetate, methyl acetate, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, ethylene glycol monobutyl ether, propylene glycol n-butyl ether, propylene glycol methyl ether, propylene glycol monopropyl ether, dipropylene glycol methyl ether, dipropylene
  • the resole phenolic resin comprises the meta- substituted phenol (a) in an amount of from 70 to 1 00 mole % and the phenolic component (b) in an amount of from 0 to 30 mole %.
  • the resole phenolic resin comprises the meta- substituted phenol (a) in an amount of from 90 to 1 00 mole % and the phenolic component (b) in an amount of from 0 to 1 0 mole %.
  • the resole phenolic resin comprises the meta- substituted phenol (a) in the amount of 1 00 mole %.
  • the resole phenolic resin comprises at least one aldehyde in the amount of from 1 70 to 270 mole % of an aldehyde, based on the total moles of phenolic components, (a) and (b).
  • the resole phenolic resin can contain an average of at least 0.5 or 0.7 methylol groups (including either or both of -- CH 2 OH and ⁇ CH 2 OR) per one phenolic hydroxyl group.
  • the resole phenolic resin comprises a functional polyester having a functionality selected from hydroxyl, carboxyl, ⁇ , ⁇ -unsaturated dicarboxylate, beta-ketoacetate, carbamate, phenol, amino, maleimide, or a combination thereof.
  • thermosetting composition comprising :
  • a curable polyester which has one or more functionalities selected from the group comprising hydroxyl, carboxyl, ⁇ , ⁇ - unsaturated dicarboxylate, beta-ketoacetate, carbamate, phenol, amino, and maleimide groups.
  • thermosetting composition of the present disclosure can further comprise one or more acid catalysts selected from the group comprising p- toluenesulfonic acid, dinonylnaphthaiene disuifonic acid,
  • dodecylbenzenesulfonic acid and phosphoric acid.
  • thermosetting composition of the present disclosure can further comprise phosphoric acid catalyst.
  • thermosetting composition of the present disclosure can further comprise phosphoric acid catalyst in an amount ranging from 0.8 to 1 .2 weight% based on the total weight of the resole phenolic resin (I) and the curable polyester (I I).
  • thermosetting composition of the present disclosure can contain the resole phenolic resin (I) in an amount from 20 to 50 weight% and the curable polyester (II) in an amount from 50 to 80 weight% based on the total weight of (I) and (II).
  • thermosetting composition of the present disclosure can contain at least one curable polyester having a cumulative hydroxyl number and an acid number in a range of 3 to 280 mg KOH/g.
  • thermosetting composition of the present disclosure can contain at least one curable polyester having a cumulative hydroxyl number and acid number in a range of 30 to 1 50 mg KOH/g. [0036] In one embodiment, the thermosetting composition of the present disclosure can contain at least one curable polyester having a hydroxyl number ranging from 30 to 1 50 mg KOH/g.
  • thermosetting composition of the present disclosure can contain at least one curable polyester having functionalities comprising ⁇ , ⁇ -unsaturated dicarboxylate group.
  • thermosetting composition of the present disclosure can contain at least one curable polyester having functionalities comprising beta-ketoacetate group.
  • thermosetting composition of the present disclosure can contain at least one curable polyester having functionalities comprising carbamate group.
  • thermosetting composition of the present disclosure can contain at least one curable polyester having functionalities comprising at least one phenol group.
  • thermosetting composition of the present disclosure can contain at least one curable polyester having functionalities comprising at least one amino group.
  • thermosetting composition of the present disclosure can contain at least one curable polyester having functionalities comprising at least one maleimide group.
  • thermosetting composition of the present disclosure can contain at least one curable polyester comprising the residues of :
  • mole % is based on 1 00% of all moles of polyhydroxyl compounds a) ; and b) polycarboxyl compounds comprising polycarboxylic acid compounds, derivatives of polycarboxylic acid compounds, the anhydrides of polycarboxylic acids, or combinations thereof.
  • thermosetting composition of the present disclosure can further comprise one or more organic solvents selected from the group comprising xylene, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, methyl isoamyl ketone, n-butyl acetate, isobutyl acetate, t-butyl acetate, n-propyl acetate, isopropyl acetate, ethyl acetate, methyl acetate, ethanol, n-propanol, isopropanol, n-butanol, sec- butanol, isobutanol, ethylene glycol monobutyl ether, propylene glycol n-butyl ether, propylene glycol methyl ether, propylene glycol monopropyl ether, dipropylene glycol methyl ether, diethylene glycol monobutyl ether,
  • the present disclosure further provides a resole aqueous
  • the neutralizing agent can be selected from ammonium hydroxide, triethylamine, ⁇ , ⁇ -dimethylethanolamine, 2-amino-2-methyl-1 -propanol, and a mixture thereof.
  • the present disclosure also provides a waterborne thermosetting composition
  • a waterborne thermosetting composition comprising
  • TACD 2,2,4,4- tetraalkylcyclobutane-1 ,3-diol
  • TMCD 2,2,4,4- tetramethylcyclobutane-1 ,3-diol
  • thermosetting composition of present disclosure there is provided a coating made from the thermosetting composition of present disclosure.
  • thermosetting composition can further comprise aminoplast crosslinker, isocyanate crosslinker, and/or epoxy crosslinker.
  • step (a) wherein said steps are sequential in the order listed and begin with step (a).
  • the pH in step (b) can be from 9.6 to 1 0.2
  • the temperature in step (c) can be from 58 °C to about 62 °C
  • the reaction time in step (d) can be two to five hours.
  • the curable polyester resins of the present disclosure can be used in several end-use applications as may be apparent to one of ordinary skill in the art. Some examples of these end-use applications are water borne coatings, solvent borne coatings, or powder coatings. Such coatings can be used in automotive OEM, auto refinish, transportation, aerospace,
  • a range stated to be 0 to 10 is intended to disclose all whole numbers between 0 and 10 such as, for example 1 , 2, 3, 4, etc., all fractional numbers between 0 and 10, for example 1 .5, 2.3, 4.57, 6.1 1 13, etc., and the endpoints 0 and 10.
  • a range associated with chemical substituent groups such as, for example, "Ci to C 5 alkyl groups” is intended to specifically include and disclose Ci and C 5 alkyl groups as well as C 2 , C 3 , and C 4 alkyl groups.
  • Phenolic resins having methylol (--CH 2 OH) functionalities on the phenolic rings are referred to as resole type phenolic resins.
  • resole type phenolic resins Phenolic resins having methylol (--CH 2 OH) functionalities on the phenolic rings
  • a resole resin is an oligomeric material containing phenolic rings linked predominantly by either methylene or methylene ether group. Because the linkages can be of different type and be on either ortho, para, or both, and the number of phenolic rings can vary, the resole resin is a mixture of numerous small molecules and oligomers having, for example, one to four rings or more. Possible structures of resoles based on cresol and phenol are reported in the reference -Biedermann, M., & Grab, K. "Phenolic resins for can coatings: I I.
  • Resoles based on cresol/phenol mixtures or tert-butyl phenol LWT— Food Science and Technology 39 (2006) 647-659 (Elsevier).
  • the resole samples are reported to be based on predominantly o- or p- cresol and phenol ; they are found to contain molecules with one to four rings at a ratio of about 2/3 with the rest being higher molecular weight molecules.
  • the resole type phenolic resin is prepared by the reaction of a phenol compound including substituted and unsubstituted phenols) and an aldehyde at an aldehyde:phenol molar ratio of greater than 1 :1 , for example 1 .5:1 .0, 2.0:1 .0, or 3.0:1 .0. Said molar ratio can greatly affect the properties of the resulting resole resin, such as solubility and the number of methylol functionality.
  • Unsubstituted phenol is suitable for making resole phenolic resin, but it is not desirable for interior can coating applications since its resulting resole resin can contain bisphenol F (BPF) residue, which is a health concern.
  • BPF bisphenol F
  • Meta- substituted phenol is desirable as compared to ortho- or para- substituted since it can provide three reaction sites for methylol formation ; however, it can also lead to poor solubility or gelation during preparation.
  • the alkyl or alkoxy substituents on the meta-substituted phenol can enhance the reactivity of phenol. Such reactivity-enhancing substituents coupled with three reactive sites often lead to difficulty in synthesis and yield products that cannot be formulated into coating compositions. Because of all these obstacles in working out a soluble resole phenolic resin that is crosslinkable with functional polyesters, there remains a need in the industry for a novel resole resin that is free of BPF.
  • this invention provides a resole phenolic resin comprising the residues of
  • said resole phenolic resin is soluble in an organic solvent and curable with a functional polyester.
  • meta-substituted phenols (a) include m-cresol, m- ethylphenol, m-propylphenol, m-butylphenol, m-octylphenol, m-alkylphenol, m-phenylphenol, m-alkoxyphenol, 3,5-xylenol, 3,5-diethyl phenol, 3,5-dibutyl phenol, 3,5-dialkylphenol, 3,5-dialkoxyphenol, 3,5-dicyclohexyl phenol, 3,5- dimethoxy phenol, 3-alkyl-5-alkyoxy phenol, and the like.
  • Said unsubstituted phenol can be phenol compound itself without any substituents (C 6 H 5 OH), or dihydroxybenzenes such as resorcinol and catechol, or trihydroxybenzenes such as hydroxyquinol and phloroglucinol.
  • Said o- substituted phenols include o-cresol, o-ethylphenol, o-propylphenol, o-n- butylphenol, o-t-butyl phenol, o-octylphenol, o-alkylphenol, o-phenylphenol, o- alkoxyphenol, 2,3-xylenol, 2,3-diethyl phenol, 2,3-dibutyl phenol, 2,3- dialkylphenol, 2,3-dialkoxyphenol, 2,3-dicyclohexyl phenol, 2,3-dimethoxy phenol, 2-alkyl-3-alkoxy phenol, 2,5-xylenol, 2,5-diethyl phenol, 2,5-dibutyl phenol, 2,5-dialkylphenol, 2,5-dialkoxyphenol, 2,5-dicyclohexyl phenol, 2,5- dimethoxy phenol, 2-alkyl-5-alkoxy phenol, and
  • Said p-substituted phenols include p-cresol, p-ethylphenol, p-propylphenol, p-n-butylphenol, p-t- butyl phenol, p-octylphenol, p-alkylphenol, p-phenylphenol, p-alkoxyphenol, 3,4-xylenol, 3,4-diethyl phenol, 3,4-dibutyl phenol, 3,4-dialkylphenol, 3,4- dialkoxyphenol, 3,4-dicyclohexyl phenol, 3,4-dimethoxy phenol, 3-alkyl-4- alkyoxy phenol, and the like.
  • the at least one aldehyde of component (c) can have the general formula RCHO, where R is hydrogen or a hydrocarbon group having 1 to 8 carbon atoms. Specific examples include formaldehyde, acetaldehyde, propionaldehyde, furfuraldehyde, or benzaldehyde. In one embodiment, the aldehyde can be formaldehyde.
  • the mole % of m-substituted phenol (a) can be from about 50 to 100 mole % based on the total moles of phenolic components (a) and (b), or from 55 to 100, or from 60 to 100, or from 65 to 100, or from 70 to 100, or from 75 to 100, or from 80 to 100, or from 85 to 100, or from 90 to 100, or from 95 to 100 mole %.
  • the mole % of phenolic component (b) can be from 0 to about 50 mole % based on the total moles of phenolic components (a) and (b), or from 0 to 45, or from 0 to 40, or from 0 to 35, or from 0 to 30, or from 0 to 25, or from 0 to 20, or from 0 to 1 5, or from 0 to 1 0, or from 0 to 5 mole %.
  • the mole % of aldehyde (c) based on the total moles of the phenolic compounds, (a) and (b), can be from about 150 to about 300, or from about 1 60 to about 280, or from about 1 70 to about 270, or from about 1 75 to about 265, or from about 180 to about 260, or from about 200 to about 255, or from about 230 to about 250.
  • the resole phenolic resin of this disclosure has methylol ( ⁇ CH 2 OH) functionality available for crosslinking.
  • the methylol group may be etherated with an alcohol and present as ⁇ CH 2 OR, wherein R is C1 -C8 alkyl group, in order to improve resin properties such as storage stability, solubility, and compatibility.
  • methylol used herein includes both ⁇ CH 2 OH and ⁇ CH 2 OR.
  • the resole resin desirably contains an average of at least 0.5 methylol groups per one phenolic hydroxyl (Ar-OH) group, more desirably at least 0.7 methylol groups, and most desirably at least 0.8 methylol groups.
  • the resole phenolic resin of the present disclosure can be heat curable.
  • the resole phenolic resin is not made by the addition of bisphenol A, F, or S (collectively "BPA").
  • the resole resin can be liquid at 25 °C.
  • the resole resin can have a number average molecular weight of from 300 to 1500.
  • the resole resin of the present invention is soluble in one or more organic solvents selected from the group comprising benzene, xylene, mineral spirits, naptha, toluene, acetone, methyl ethyl ketone, methyl isobuty! ketone, methyl n-amyl ketone, methyl isoamyl ketone, n-butyl acetate, isobuty!
  • a resin when a resin is soluble in a solvent, if forms a solution with the solvent which is substantially free of insoluble substance. It is within the scope of this invention if less than 20%, or less than 15%, or less than 10%, or less than 5%, or less than 4%, or less than 3%, or less than 2%, or less than 1 %, or less than 0.5%, or less than 0.1 %, of the resin remains insoluble in the solvent. In one embodiment, less than 5%, or less than 4%, or less than 3%, or less than 2%, or less than 1 %, or less than 0.5%, or less than 0.1 %, by weight of the resin remains insoluble in the solvent. For the purposes of clarify, for a resin having less than 1 % by weight of solubility in a solvent, there is less than 1 g resin per 100 g of solvent. In one embodiment, the resulting solution can be visually clear.
  • the resole phenolic resin of the invention can be prepared by a process comprising the steps of
  • the pH in step (II) can be from 9.6 to 10.2 or from 9.7 to 10.0;
  • the temperature in step (Hi) can be 58 °C to about 62°C;
  • reaction time in step (IV) can be two to five hours.
  • the resole resin of the present disclosure can be crosslinkabie with polyesters having a variety of functionalities. Such polyesters are also referred to as "functional polyesters" throughout the description of this invention. Below is a schematic diagram depicting the reaction of resole phenolic resin and hydroxyl-functional polyester through a reactive quinone methide intermediate. Polyesters having other functionalities described herein can also undergo crossiinking reaction through the quinone methide intermediate.
  • thermosetting composition comprising:
  • curable polyester which has one or more functionalities selected from the group comprising hydroxyl, carboxyl, ⁇ , ⁇ -unsaturated dicarboxylate, beta-ketoacetate, carbamate, phenol, amino, and maleimide groups.
  • the resole phenolic resin (I) can be present in an amount from about 10 to about 90 wt.% based on the total weight of (I) and (II), or from 20 to 80 wt.%, or from 30 to 70 wt.%, from 40 to 60 wt.%, from 20 to 50 wt.%, from 20 to 40 wt.%, or from 20 to 30 wt.%.
  • the curable polyester can be present in an amount from about 10 to about 90 wt.% based on the total weight of (I) and (II), or from 20 to 80 wt.%, or from 30 to 70 wt.%, from 40 to 60 wt.%, from 50 to 80 wt.%, from 60 to 80 wt.%, or from 70 to 80 wt.%.
  • the curable polyester (II) can have a functionality of hydroxyl, carboxyl, ⁇ , ⁇ -unsaturated dicarboxylate, beta-ketoacetate, carbamate, phenol, amino, and/or maleimide. Desirably, the functionality is hydroxyl, carboxyl, ⁇ , ⁇ -unsaturated dicarboxylate, or beta-ketoacetate. Hydroxyl and carboxyl groups are commonly present in said curable polyester.
  • the functional polyesters described in this invention are either modified from a conventional hydroxyl- or carboxyl- functional polyester or synthesized with a monomer having the desirable functionality.
  • beta-ketoacetate - and maleimide- functional polyester can be synthesized by modifying from a hydroxyl functional polyester, the carbamate functional polyester from either a carboxyl functional or a hydroxyl functional polyester, and the amino functional polyester from an unsaturated polyester, whereas the a, ⁇ -unsaturated dicarboxylate functional polyester can be synthesized by incorporating a functional monomer such as, for example, maleic anhydride.
  • Polyesters having hydroxyl and/or carboxyl functionalities can be prepared by reacting a polyhydroxyl compound with a polycarboxyl compound.
  • a polyester suitable for this invention comprises the residues of
  • diol compounds in an amount of 70 mole % to 100 mole % and polyhydroxyl compounds having 3 or more hydroxyl groups in an amount of 0 to 30 mole %,
  • polycarboxyl compounds comprising polycarboxylic acid compounds, derivatives of polycarboxylic acid compounds, the anhydrides of
  • polyhydroxyl compounds For purposes of calculating quantities, all compounds having at least one hydroxyl group are counted as polyhydroxyl compounds (a).
  • Such compounds include, but are not limited to, mono-ols, diols, polyhydroxyl compounds having 3 or more hydroxyl groups, and for each of the foregoing, can be hydrocarbons of any chain length optionally containing ether groups such as polyether polyols, ester groups such as polyesters polyols, and amide groups.
  • the diols (a)(i) have two hydroxyl groups and can be branched or linear, saturated or unsaturated, aliphatic or cycloaliphatic C 2 -C 2 o compounds, the hydroxyl groups being primary, secondary, and/or tertiary. Desirably, the polyhydroxyl compounds are hydrocarbons and do not contain atoms other than hydrogen, carbon and oxygen.
  • Examples of diols (a)(i) include 2,2,4,4- tetraalkylcyclobutane-1 ,3-diol (TACD), 2,2-dimethyl-1 ,3-propanediol
  • the TACD compound can be represented by the general structure (1 ) :
  • R ; R 2 , R3, and R 4 each independently represent an alkyl radical, for example, a lower alkyl radical having 1 to 8 carbon atoms; or 1 to 6 carbon atoms, or 1 to 5 carbon atoms, or 1 to 4 carbon atoms, or 1 to 3 carbon atoms, or 1 to 2 carbon atoms, or 1 carbon atom.
  • the alkyl radicals may be linear, branched, or a combination of linear and branched alkyl radicals.
  • TACD examples include 2,2,4,4-tetramethylcyclobutane-1 ,3-diol (TMCD), 2,2,4,4-tetraethylcyclobutane-1 ,3-diol, 2,2,4,4-tetra-n-propylcyclobutane-1 ,3- diol, 2,2,4,4-tetra-n-butylcyclobutane-1 ,3-diol, 2,2,4,4-tetra-n- pentylcyclobutane-1 ,3-diol, 2,2,4,4-tetra-n-hexylcyclobutane-1 ,3-diol, 2,2,4,4- tetra-n-heptylcyclobutane-1 ,3-diol, 2,2,4,4-tetra-n-octylcyclobutane-1 ,3-diol, 2,2-dimethyl-4,4-diethylcyclobut
  • the diol (a)(i) is 2,2,4,4-tetramethylcyclobutane-1 ,3-diol (TMCD), 2,2-dimethyl-1 ,3-propanediol (neopentyl glycol), 1 ,2- cyclohexanedimethanol, 1 ,3-cyclohexanedimethanol, 1 ,4- cyclohexanedimethanol, 2,2,4-trimethyl-1 ,3-pentanediol, hydroxypivalyl hydroxypivalate, 2-methyl-1 ,3-propanediol, 2-butyl-2-ethyl-1 ,3-propanediol, 1 ,4-butanediol, and 1 ,6-hexanediol or mixtures thereof.
  • at least one of the diols (a)(i) is TMCD.
  • the diols (a)(i) are desirably present in an amount of at least 70 mole%, or at least 75 mole%, or at least 80 mole%, or at least 85 mole%, or at least 87 mole%, or at least 90 mole%, or at least 92 mole%, based on 1 00 mole% of all polyhydroxyl compounds. Additionally or in the alternative, the diols (a)(i) can be present in an amount of up to 1 00 mole%, or up to 98 mole%, or up to 96 mole%, or up to 95 mole%, or up to 93 mole%, or up to 90 mole%, based on 1 00 mole% of all polyhydroxyl compounds.
  • Suitable ranges include, in mole% based on 1 00 mole% of all polyhydroxyl compounds (a), 70-1 00, or 75-1 00, or 80-1 00, or 85-1 00, or 87-100, or 90-100, or 92-1 00, or 95-100, or 96-100, or 70-98, or 75-98, or 80-98, or 85-98, or 87-98, or 90- 98, or 92-98, or 95-93, or 96-93, or 70-93, or 75-93, or 80-93, or 85-93, or 87- 93, or 90-93, or 92-93, or 70-90, or 75-90, or 80-90, or 85-90, or 87-90.
  • the polyhydroxyl compounds (a)(ii) having three or more hydroxyl groups can be branched or linear, saturated or unsaturated, aliphatic or cycloaliphatic C 2 -C 2 o compounds, the hydroxyl groups being primary, secondary, and/or tertiary, and desirably at least two of the hydroxyl groups are primary.
  • the polyhydroxyl compounds are hydrocarbons and do not contain atoms other than hydrogen, carbon and oxygen.
  • polyhydroxyl compounds (a)(ii) examples include 1 , 1 , 1 -trimethylol propane, 1 , 1 , 1 - trimethylolethane, glycerin, pentaerythritol, erythritol, threitol, dipentaerythritol, sorbitol, mixtures thereof, and the like.
  • the polyhydroxyl compounds (a)(ii), if present, can be present in an amount of at least 1 mole%, or at least 2 mole%, or at least 5 mole%, or at least 8 mole%, or at least 1 0 mole%, based on 1 00 mole% of all polyhydroxyl compounds (a). Additionally or in the alternative, the polyhydroxyl compounds (a)(ii) can be present in an amount of up to 30 mole%, or up to 25 mole%, or up to 20 mole%, or up to 15 mole%, or up to 1 3 mole%, or up to 1 0 mole%, or up to 8 mole%, based on 1 00 mole% of all polyhydroxyl
  • Suitable ranges of the polyhydroxyl compounds (a)(ii) include, in mole% based on 100 mole% of all polyhydroxyl compounds (a), 1 - 30, or 2-30, or 5-30, or 8-30, or 10-30, or 1 -25, or 2-25, or 5-25, or 8-25, or 1 0-25, or 1 -20, or 2-20, or 5-20, or 8-20, or 1 0-20, or 1 -1 5, or 2-1 5, or 5-1 5, or 8-1 5, or 1 0-15, or 1 -1 3, or 2-1 3, or 5-1 3, or 8-1 3, or 1 0-13, or 1 -1 0, or 2-1 0, or 5-1 0, or 8-1 0, or 1 -8, or 2-8, or 5-8.
  • the mole % of the diol (a)(i) is desirably from 70 to 1 00, 80 to 97, or 85 to 95, and the mole% of the polyhydroxyl compound (a)(ii) is desirably from 0 to 30, 3 to 20, or 5 to 1 5.
  • all of the polyhydroxyl compounds (a) used to react with the polycarboxylic compounds (b) are hydrocarbons, meaning that they contain only oxygen, carbon, and hydrogen.
  • none of the polyhydroxyl compounds (a) contain any ester, carboxyl (-COO-), and/or anhydride groups.
  • none of the polyhydroxyl compounds (a) have any carbonyl groups (-CO-).
  • the compounds (a) contain any ether groups.
  • the polyhydroxyl compounds (a) have from 2 to 20, or 2 to 1 6, or 2 to 1 2, or 2 to 1 0 carbon atoms.
  • the polycarboxyl compounds (b) contain at least polycarboxylic acid compounds, derivatives of polycarboxylic acid compounds, the
  • Suitable polycarboxylic acid compounds include compounds having at least two carboxylic acid groups.
  • the polycarboxylic acid compounds are capable of forming ester linkages with polyhydroxyl compounds.
  • a polyester can be synthesized by using a polyhydroxyl compound and a dicarboxylic acid or a derivative of a dicarboxylic acid such as, for example, dimethyl ester or other dialkyl esters of the diacid, or diacid chloride or other diacid halides, or acid anhydride.
  • the polycarboxylic acid compounds (b) can be a combination of aromatic polycarboxylic acid compounds and either or both of aliphatic or cycloaliphatic polycarboxylic acid compounds.
  • aromatic polycarboxylic acid compounds can be a combination of aromatic polycarboxylic acid compounds and either or both of aliphatic or cycloaliphatic polycarboxylic acid compounds.
  • polycarboxylic acid compounds (b) can include aromatic polycarboxylic acid compounds and aliphatic polycarboxylic acids compounds having 2 to 22 carbon atoms; or aromatic polycarboxylic acid compounds and cycloaliphatic polycarboxylic acids compounds having 2 to 22 carbon atoms; or aromatic polycarboxylic acid compounds, aliphatic polycarboxylic acids compounds having 2 to 22 carbon atoms; and cycloaliphatic polycarboxylic acids compounds having 2 to 22 carbon atoms.
  • Examples of such polycarboxylic compounds (b) that form the polycarboxylic (b) residues in the curable polyester include those having two or more, desirably only two, carboxylic acid functional groups or their esters.
  • Examples of these compounds include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, derivatives of each, or mixtures of two or more of these acids, or the C C 4 ester derivatives thereof.
  • Suitable dicarboxylic acids include, but are not limited to, isophthalic acid (or dimethyl isophthalate), terephthalic acid (or dimethyl terephthalate), phthalic acid, phthalic anhydride, 1 ,4-cyclohexanedicarboxylic acid,
  • tetrahydrophthalic anhydride tetrachlorophthalic anhydride, dodecanedioic acid, sebacic acid, azelaic acid, succinic anhydride, succinic acid, adipic acid, 2,6-naphthalenedicarboxylic acid, glutaric acid, diglycolic acid; 2,5- norbornanedicarboxylic acid; 1 ,4-naphthalenedicarboxylic acid; 2,5- naphthalenedicarboxylic acid; diphenic acid; 4,4'-oxydibenzoic acid; 4,4'- sulfonyidibenzoic acid, and mixtures thereof.
  • Anhydride analogs to each of the polycarboxyl compounds (b) described above can be used. This would include the anhydrides of polycarboxylic acids having at least two acyl groups bonded to the same oxygen atom.
  • the anhydrides can be symmetrical or unsymmetrical (mixed) anhydrides.
  • the anhydrides have at least one anhydride group, and can include two, three, four, or more anhydride groups.
  • anhydrides of the dicarboxylic acids include, but are not limited to, maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid, aconitic acid, aconitic anahydride, oxalocitraconic acid and its anhydride, mesaconic acid or its anhydride, beta- acylacrylic acid, phenyl maleic acid or its anhydride, t-butyl maleic acid or its anhydride, monomethyl fumarate, monobutyl fumarate, methyl maleic acid or its anhydride, or mixtures thereof.
  • the polycarboxylic component (b) includes isophthalic acid (or dimethyl isophthalate), terephthalic acid (or dimethyl terephthalate), phthalic acid, phthalic anhydride, 1 ,4-cyclohexanedicarboxylic acid,
  • the curable polyester of the invention has a cumulative hydroxyl number and acid number in a range of 0 to 300 mgKOH/g, or 3 to 280, or 1 0 to 250, or 20 to 200, or 30 to 1 50, or 40 to 1 20, or 50 to 100.
  • the hydroxyl number desirably is from about 30 to about 1 50 mg KOH/g.
  • the acid number of the hydroxyl functional polyester is not particularly limited. The acid number may range from 0 to about 1 20 mgKOH/g. The acid number may vary depending on the application. For example, the desirable acid number for waterborne coating application is about 50 to about 1 00 to impart sufficient water dispersibility after neutralization, whereas the desired acid number for solvent-based coating application is 0 to about 10 for better solubility and lower solution viscosity.
  • the acid number of the hydroxyl functional polyester for solvent-based coating application is not more than 30, or not more than 25, or not more than 20, or not more than 15, or not more than 1 0, or not more than 8, or not more than 5 mgKOH/g .
  • Acid and hydroxy! numbers are determined by titration and are reported herein as mg KOH consumed for each gram of polyester. The acid number can be measured by ASTM D1 639-90 test method. The hydroxyl numbers can be measured by the ASTM D4274-1 1 test method.
  • the glass transition temperature (Tg) of the polyester of the present invention may be from -40 °C to 1 20 °C, from -1 0 °C to 1 00 ° C, from 10 °C to 80 °C, from 1 0 °C to 60 ° C, from 1 0 °C to 50 °C, from 1 0°C to 45 ° C, from 1 0 °C to 40 °C, from 20 °C to 80 °C, from 20 °C to 60 ° C, from 20 °C to 50 ° C, from 30 °C to 80 ° C, from 30 °C to 70 ° C, from 30 °C to 60 ° C, from 30 °C to 50 ° C, or from 35 °C to 60 ° C.
  • the Tg is measured on the dry polymer using standard techniques, such as differential scanning calorimetry ("DSC"), well known to persons skilled in the art.
  • DSC differential scanning calorimetry
  • the Tg measurements of the polyesters are conducted using a "dry polymer,” that is, a polymer sample in which
  • adventitious or absorbed water is driven off by heating to polymer to a temperature of about 200°C and allowing the sample to return to room temperature.
  • the polyester is dried in the DSC apparatus by conducting a first thermal scan in which the sample is heated to a temperature above the water vaporization temperature, holding the sample at that temperature until the vaporization of the water absorbed in the polymer is complete (as indicated by an a large, broad endotherm), cooling the sample to room temperature, and then conducting a second thermal scan to obtain the Tg measurement.
  • the number average molecular weight (Mn) of the polyester of the present invention is not limited, and may be from 1 ,000 to 20,000, from 1 ,000 to 15,000, from 1 ,000 to 1 2,500, from 1 ,000 to 1 0,000, from 1 ,000 to 8,000, from 1 ,000 to 6,000, from 1 ,000 to 5,000, from 1 ,000 to 4000, from 1 ,000 to 3,000, from 1 ,000 to 2,500, from 1 ,000 to 2,250, or from 1 ,000 to 2,000, in each case g/mole.
  • the Mn is measured by gel permeation chromatography (GPC) using polystyrene equivalent molecular weight.
  • the weight average molecular weight (Mw) of the polyester can be from 1 ,000 to 1 00,000; from 1 ,500 to 50,000; and desirably from 2,000 to 20,000 or from 2,500 to 1 0,000 g/mole.
  • the polyester may be linear or branched.
  • the (a)(i) diol includes 2, 2-dimethyl-1 ,3-propanediol (neopentyl glycol) ; 1 ,2- cyclohexanedimethanol ; 1 ,3-cyclohexanedimethanol ;
  • the (a)(ii) polyhydroxyl compound having 3 or more hydroxyl groups include 1 ,1 , 1 - trimethylol propane, 1 ,1 , 1 -trimethylolethane, glycerin, pentaerythritol, or combinations thereof.
  • the (b) compounds include isophthalic acid (or dimethyl isophthalate),
  • the hydroxyl or carboxyl functional polyester can be prepared by any conventional process for the preparation of polyesters.
  • the polyester resin can be prepared by combining polyhydroxyl compounds (a) with the polycarboxyl compounds (b) in a reaction vessel under heat to form a reaction mixture comprising the polyester in a batch or continuous process and in one or more stages, optionally with the continuous removal of distillates and applied vacuum during at least part of the residence time.
  • Polyhydroxyl compounds (a) and polycarboxyl compounds (b) are combined and reacted in at least one reactor at a temperature from 1 80-250 °C, optionally in the presence of an acid catalyst. Desirably, a distillate is removed from the reactor.
  • carboxyl functional polyester can also be prepared by reacting a hydroxy! functional polyester with a polycarboxylic anhydride to generate the desired number of carboxyl functionalities.
  • the hydroxy! functional polyester is first prepared at a temperature of 180 to 250 °C, and then the temperature is reduced and a polycarboxylic anhydride added for further reaction at a temperature of 140 to 180 °C.
  • Suitable polycarboxylic anhydride includes trimellitic anhydride, hexahydrophthalic anhydride, maleic anhydride, and succinic anhydride. Desirable acid numbers of such carboxyl functional polyesters can be from about 30 to about 1 00.
  • the beta-ketoacetate functionaly polyesters suitable for this invention include acetoacetate functional polyester, which may be prepared by reacting a polyester containing hydroxyl groups, for example, a polymer having a hydroxyl number of at least 5, preferably about 30 to 200, with an alkyl acetoacetate or diketene.
  • acetoacefy!ated polyester coating resins have been described by Witzeman et ai. in the Journal of Coatings Technology, Vol. 82, No. 789, pp. 101 -1 12 (1990).
  • Suitable alkyl acetoacetates for the reaction with (esterification of) a hydroxyl-containing polyester include t-butyi acetoacetate, ethyl acetoacetate, methyl acetoacetate, isobutyl acetoacetate, isopropyl acetoacetate, n-propyl acetoacetate, and n-butyl acetoacetate.
  • t-Butyl acetoacetate is preferred.
  • the carbamate functional polyester suitable for this invention is a polyester having the functionality below (2):
  • R H or alkyl
  • a non-limiting example for preparing such a polyester is to react a carboxyl-functional polyester with hydroxyalkyl carbamate, for example, hydroxypropyl carbamate available from Huntsman as CARBALINK ® HPC. It can also be prepared by reacting a hydroxyl-functional polyester with urea or an alkyl carbamate such as, for example, methyl carbamate.
  • hydroxyalkyl carbamate for example, hydroxypropyl carbamate available from Huntsman as CARBALINK ® HPC. It can also be prepared by reacting a hydroxyl-functional polyester with urea or an alkyl carbamate such as, for example, methyl carbamate.
  • the amino functional polyester suitable for this invention can be prepared by reacting an unsaturated polyester with ammonium or a primary amine as illustrated below.
  • the preparation of such polyesters is disclosed in Canadian Patent Application CA21 1 1927 (A1 ), the content of which is incorporated in its entirety by reference.
  • the phenol functional polyester suitable for the invention can be prepared by reacting a hydroxyl functional polyester with p-hydroxylbenzoic acid (PHBA) or its ester such as methyl 4-hydroxybenzoate (MHB). It can also be prepared by using PHBA, MHB, or 5-hydroxyisophthalic acid as one of the monomers for polycondensation reaction.
  • PHBA p-hydroxylbenzoic acid
  • MHB methyl 4-hydroxybenzoate
  • the ⁇ , ⁇ -unsaturated dicarboxylate functional polyester suitable for this invention is a polyester comprising the following structure residue (3).
  • Such a polyester can be prepared by incorporating an ⁇ , ⁇ - ethylenically unsaturated carboxyl compound as a carboxylic acid component for polyester synthesis.
  • carboxylic acid component for polyester synthesis.
  • Such components include, but are not limited to, maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid, acrylic acid, and methacrylic acid.
  • the preferred are maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, and itaconic acid.
  • the maleimide functional polyester suitable for this invention is a polyester having the functionality below (4):
  • a non-limiting example for preparing such a polyester is to react a hydroxyl functional polyester (6) with a maleimide compound having carboxyl functionality (5), which in turned can be prepared by reacting 4- aminobenzoic acid with maleic anhydride.
  • the reaction scheme is shown below:
  • the thermosetting composition can further comprise one or more organic solvents selected from the group comprising benzene, xylene, mineral spirits, naptha, toluene, acetone, methyl ethyl ketone, methyl n-amyl ketone, methyl isoamyl ketone, n-butyl acetate, isobutyl acetate, t-butyl acetate, n-propyl acetate, isopropyl acetate, ethyl acetate, methyl acetate, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, ethylene glycol monobutyl ether, propylene glycol n-butyl ether, propylene glycol methyl ether, propylene glycol monopropyl ether, dipropylene glycol methyl ether, diethylene glycol monobutyl ether, ethylene
  • the organic solvent can be present in an amount from 30 to 85 wt.% based on the total weight of resole and polyester, (I) and (I I), or from 40 to 80 wt. %, or from 50 to 75 wt.%, or from 55 to 70 wt.%, or 60 to 65 wt.%.
  • the phenolic hydroxyl group of the resole of the invention is acidic and thus can be neutralized with a base for waterborne applications.
  • this invention further provides a resole aqueous dispersion comprising the resole phenolic resin of the present invention, a neutralizing agent, and water.
  • the neutralizing agent may be an amine such as ammonium hydroxide, triethylamine, ⁇ , ⁇ -dimethylethanolamine, 2-amino-2-methyl-1 -propanol, and the like, or an inorganic base such as sodium hydroxide, potassium
  • this invention provides a waterborne thermosetting composition
  • a waterborne thermosetting composition comprising said resole aqueous dispersion and a waterborne curable polyester which has one or more functionalities selected from the groups comprising hydroxyl, carboxyl, ⁇ , ⁇ -unsaturated dicarboxylate, beta-ketoacetate, carbamate, phenol, amino, and maleimide groups.
  • Said waterborne curable polyester may be amine neutralized polyester or polyester containing the residues of one or more hydrophilic monomers such as 5- sodiosulfoisophthalic acid, polyetheylene glycol, or YmerTM N120 (available from Perstorp) to provide water dispersibility.
  • the waterbome thermosetting composition of this disclosure may further comprise an organic co-solvent.
  • Suitable co-solvents include ethanol, n-propanol, isopropanoi, n-butano!, sec-butano!, isobutanoL ethylene glycol monobutyi ether, propylene glycol n-butyl ether, propylene glycol methyl ether, propylene glycol monopropyl ether, dipropyiene glycol methyl ether, diacetone alcohol, and other water-miscibie solvents.
  • the polyesters used for waterborne thermosetting compositions comprise TMCD in the polyester compositions, it has been found that TMCD based polyesters exhibit superior water dispersibility over polyesters based on other diols such as NPG and CHDM.
  • thermosetting composition of the present invention can further comprise an acid or base catalyst in an amount ranging from 0.1 to 10 weight %, or 0.1 to 9 weight %, or 0.1 to 8 weight %, or 0.1 to 7 weight %, or 0.1 to 6 weight %, or 0.1 to 5 weight %, or 0.1 to 4 weight %, or 0.1 to 3 weight %, or 0.1 to 2 weight %, or 0.1 to 1 .5 weight %, or 0.1 to 1 .2 weight %, or 0.1 to 1 weight %, or 0.1 to 0.9 weight %,or 0.1 to 0.8 weight %, or 0.1 to 0.7 weight %, or 0.1 to 0.8 weight %, or 0.1 to 0.5 weight %, or 0.2 to 10 weight %, or 0.2 to 9 weight %, or 0.2 to 8 weight %, or 0.2 to 7 weight %, or 0.2 to 6 weight %, or 0.2 to 5 weight %, or 0.2 to 4 weight %, or 0.2 to %,
  • acid catalyst examples include protonic acids such as p-toiuenesuifonic acid, dinonyinaphthaiene disuifonic acid, dodecylbenzenesulfonic acid, phosphoric acid, and the like.
  • protonic acids such as p-toiuenesuifonic acid, dinonyinaphthaiene disuifonic acid, dodecylbenzenesulfonic acid, phosphoric acid, and the like.
  • the commercial phosphoric acid catalyst is CYCAT XK406N (9% active) (available from Allnex).
  • the desirable amount can be from about 0.3 to about 0.7 weight %, or from about 0.4 to about 0.6 weight %, or about 0.5 weight %, based on the total weight of the resins (polyester and phenolic resin).
  • the desirable amount can be from about 0.8 to about 1 .2, or from about 0.9 to about 1 , or about 1 weight %, based on the total weight of the resins (polyester and phenolic resin).
  • the acid catalyst may also be Lewis acid or amine-blocked acid catalyst.
  • base catalyst include amine such as ammonium hydroxide, triethylamine, N,N- dimethylethanolamine, and the like, and inorganic base such as sodium hydroxide, potassium hydroxide, and the like.
  • thermosetting composition of this disclosure can further comprise a conventional crosslinker known in the art, such as, for example, aminoplast, isocyanate, and epoxy crosslinkers.
  • a conventional crosslinker known in the art, such as, for example, aminoplast, isocyanate, and epoxy crosslinkers.
  • thermosetting composition of this disclosure can be a coating composition.
  • thermosetting resin [00122] In addition to coating applications, the thermosetting resin
  • composition can also be used for other applications, such as adhesive, plastic molding, rubber compounding, where forming a polymeric network is
  • thermosetting composition of this invention can further comprise natural rubber, synthetic rubber, or a combination thereof.
  • a coating composition as described above further comprising one or more leveling, rheo!ogy, and flow control agents such as silicones, iluorocarbons or cellulosics; flatting agents; pigment wetting and dispersing agents; surfactants; ultraviolet (UV) absorbers; UV light stabilizers; tinting pigments; defoaming and antifoaming agents; anti-settling, anti-sag and bodying agents; anti- skinning agents; anti-fSooding and anti-floating agents; fungicides and mildewicides; corrosion inhibitors; thickening agents; and/or coalescing agents.
  • one or more leveling, rheo!ogy, and flow control agents such as silicones, iluorocarbons or cellulosics; flatting agents; pigment wetting and dispersing agents; surfactants; ultraviolet (UV) absorbers; UV light stabilizers; tinting pigments; defoaming and antifoaming agents; anti-settling, anti
  • the coating composition can be applied to a substrate or article.
  • a further aspect of the present disclosure is a shaped or formed article that has been coated with the coating compositions of the present disclosure.
  • the substrate can be any common substrate such as paper; polymer films such as polyethylene or polypropylene; wood; metals such as aluminum, fin, steel or galvanized sheeting; glass; urethane elastomers; primed (painted) substrates; and the like.
  • the coating can be any common substrate such as paper; polymer films such as polyethylene or polypropylene; wood; metals such as aluminum, fin, steel or galvanized sheeting; glass; urethane elastomers; primed (painted) substrates; and the like.
  • the coating can be cured by heating to a temperature of about 150°C to about 230 °C, or desirably from 160 °C to 200 °C, for a time period that typically ranges about 10 seconds to about 90 minutes and allowed to cool.
  • MEK double rub test was carried out according to ASTM method D4752 by using an automatic rub machine equipped with a hemispherical hammer having a weight of 720 gram. A 16-fold cheesecloth was wrapped around the hammer end and soaked with methyl ethyl ketone (MEK). The coated test panel was placed underneath the wrapped hammer and rubbed back and forth until the main body of the film was first exposing the metal, discounting the effect on the end of the rubbed film. One back and forth movement is counted as one double rub.
  • MEK methyl ethyl ketone
  • Wedge bend test was carried out using Gardner Impact tester PF-1 125 equipped with a steel rod for bending. A 10cm x 3.8cm coated panel was cut and bent in half over the 3 mm rod with the coating on the outside of the bend. The folded panel was then inserted in the wedge mandrel. A metal weight was raised to the 40 in-lb mark and dropped; the cylindrical fold in the panel was squeezed into a conical shape. The edge of the coated panel as rubbed with a solution of copper sulfate (mixture of deionized water (69 g), copper sulfate (40 g), HCI (20 g), and Dowfax 2A1 (2 g, available from Dow). Dark spots appeared where the coating had been cracked. The length of the failure was then measured and expressed as % failure over the length of the panel.
  • copper sulfate mixture of deionized water (69 g), copper sulfate (40 g), HCI (20 g), and Dowfax 2A1 (2 g, available from Dow
  • n-Butanol 150 ml_ was then added to dissolve the resin at 40 °C, which was filtered by suction filtration to remove the insoluble solid particles to afford a resole phenolic resin solution.
  • the solvent, n-butanol was subsequently removed using a rotary evaporator under reduced pressure to yield a viscous yellow-red unetherified resole phenolic resin.
  • Example 3 Synthesis of Etherified (Butylated) Resole Phenolic Resin Based on m-Cresol (Resole 3)
  • An unetherified resole resin was first synthesized according to Example 2. To this resole resin (74 g) were added n-butanol (84 ml_) and toluene (7 ml_) to form a solution. The pH of the solution was adjusted to about 6 by gradual addition of phosphoric acid in ethanol. The resole resin solution thus prepared was added to a round-bottom flask equipped with a Dean-Stark adaptor and a water-jacketed condenser. The solution was stirred and allowed to reflux at 1 20 °C for 4.5 hours.
  • a 2-L kettle with a four-neck lid was equipped with a mechanical stirrer, a thermocouple, a heated partial condenser (107°C), a Dean-Stark trap, and a chilled condenser (1 5 °C).
  • TMCD 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol
  • MPDiol 2-methyl-1 ,3-propanediol
  • TMP trimethylolpropane
  • I PA isophthalic acid
  • Fascat-41 00 Analogous metallocate
  • the reaction was allowed to react under a nitrogen blanket. The temperature was ramped up from room temperature to 1 50 °C over 90 minutes.
  • the temperature was increased from 1 50 to 230 °C over 3 hours.
  • the reaction was allowed to continue until the theoretical distillate (about 1 50 g) was collected.
  • the resin was then sampled for acid number analysis with a target of ⁇ 5 mgKOH/g. After achieving an acid number of 2.6, the resin was allowed to cool to 1 90 °C before being poured into aluminum pans. The resin was cooled and a solid product collected.
  • solvent-based formulations were prepared by using the polyesters, PE-1 , PE-2, and PE-3, and the resole phenolic resins, Resole 1 , Resole 2, and Resole 3.
  • Polyester solutions (35% solids) were first prepared by dissolving the polyester in methyl amyl ketone (MAK).
  • MAK methyl amyl ketone
  • Formulations were then prepared by mixing respectively the polyester solution with a resole phenolic resin (100 %) in the presence of an acid catalyst, p- toluenesulfonic acid (pTSA).
  • pTSA p- toluenesulfonic acid
  • Formulations 1 -9 prepared in Example 5 were drawn down respectively on electrolytic tin test panels (10 cm x 30 cm) using a draw-down bar and subsequently baked in an oven at 205 °C for 1 0 minutes.
  • the thickness of the coating films was about 1 0 ⁇ .
  • the degree of crosslinking of the cured films was determined by their solvent resistance using MEK Double Rub Method (ASTM D4752). In the test, the rubbing was stopped when the main body of the film was first exposing the metal, discounting the effect on the end of the rubbed film. The results are collected in Table 4.
  • TMCD 2,2,4,4-tetramethyl-1 3- cyclobutanediol
  • TMP trimethylolpropane
  • CHDA 1 ,4- cyclohexanedicarboxylic acid
  • I PA isophthalic acid
  • Fascat-41 00 Arkema Inc.
  • the reaction was allowed to react under nitrogen at 1 80 °C for 25 min., at 200 °C for 60 min., at 220 °C for 1 25 min., and at 230 °C for about 2.5 hours to yield a clear, viscous mixture. A total of 1 2 ml_ of distillate was collected in the Dean-Stark trap. The reaction mixture was then allowed to cool to 1 50°C, followed by the addition of trimellitic anhydride (TMA) (14.06g). After the addition of TMA, the temperature was increased to 1 70 °C and the mixture allowed to react for about 1 .5 hours. The resulting mixture was allowed to cool to room temperature and subsequently placed in dry ice to chill for ease to break and collect the solid product (1 33 g). The polyester was analyzed to have the properties: Tg, 89.6 °C; Mn 1 659, Mw 5470; acid number 58; and hydroxyl number 97.
  • solvent-based formulations were prepared by using polyester, PE-4, and various cresol based phenolic resins, m-
  • Cresol/HCHO, o-Cresol/HCHO, and p-Cresol/HCHO prepared in Example 8 and Comparative Examples 1 and 2.
  • Polyester solution (35% solids) was first prepared by dissolving the polyester (PE-4) in methyl amyl ketone (MAK). Three formulations were then prepared by mixing respectively the polyester solution with a phenolic resin (m-Cresol/HCHO, o-Cresol/HCHO, and p- Cresol/HCHO) in the presence of an acid catalyst, p-toluenesu!fonic acid (pTSA).
  • Formulations 1 0-1 2 prepared in Example 9 were drawn down respectively on cold-rolled steel test panels (ACT 3x9x032 from Advanced Coating Technologies) using a draw-down bar and subsequently baked in an oven at 205 °C for 10 minutes.
  • the thickness of the coating films was about 20 to 25 ⁇ .
  • the degree of crosslinking of the cured films was determined by their solvent resistance using MEK Double Rub Method (ASTM D4752). The results are collected in Table 6.
  • a Parr reactor was used for the preparation of the resin dispersion.
  • Polyester resin, PE-4 was first ground to about 6mm pellets.
  • the resin pellets (42. Og) was then placed in the reaction vessel along with distilled water (78. Og) and ammonia aqueous solution (30%, 2.46 g) for neutralization.
  • the amount of ammonia added for neutralization (1 00%) is calculated according to the measured acid number of the resin.
  • the Parr reactor was then assembled and heated first to 95 °C and then to 1 10 °C. The stirring was allowed to continue at 1 1 0 °C for 45 min. and subsequently allowed to cool to 50 °C.
  • the resulting dispersion (35% solids) was filtered with a standard paint filter and collected.
  • Particle size (MV) of the dispersion was determined to be 14 nm using Nanotrac (Microtrac Inc.). The particle size, MV, represents the mean diameter in nanometer (nm) of the volume distribution.
  • An aqueous dispersion was prepared by mixing the phenolic resin, m-cresol/HCHO (Example 8) (3 g) sequentially with ethylene glycol monobutyl ether (EB) (1 .3 g), ⁇ , ⁇ -dimethylethanolamine (DMEA) (0.7 g), and water (1 .5 g) to yield a clear resole dispersion (46% solids).
  • a waterborne formulation was then prepared by mixing the resole dispersion (0.98 g), the aqueous polyester dispersion (Example 1 1 ) (35%, 3 g), and the pTSA catalyst (5% in isopropanol, 0.15 g).
  • Example 13 Evaluation of Cured Films by MEK Double Rub Test
  • Example 1 2 The formulation prepared in Example 1 2 was drawn down on cold-rol!ed steel test panels (ACT 3x9x032 from Advanced Coating
  • the thickness of the coating films was about 20 to 25 ⁇ .
  • the cured film was determined to have 50 MEK double rubs.
  • Butanol (200 ml_) was added to dissolve the crude product, and the pH of the mixture was adjusted to around 5.5 by careful addition of phosphoric acid in ethanol (prepared by approximately 1 :1 volume ratio of phosphoric acid and ethanol). Toluene (20ml_) was then added. To a round- bottom flask equipped with a Dean-Stark adaptor and a water-jacketed condenser was added the above resole resin solution. The mixture was then allowed to reflux (at 130 °C oil bath) for 2 hours. After cooling down, the mixture was subjected to rotary evaporation under reduced pressure to remove the solvent. Butanol (150 ml_) was added to dissolve the mixture.
  • Butanol (1 00 ml_) was added to dissolve the crude product, and 1 0 ml_ toluene was added. After suction filtration, another 50 ml_ butanol was added. The pH of the mixture was adjusted to around 5.5 by careful addition of phosphoric acid in ethanol. To a round-bottom flask equipped with a Dean- Stark adaptor and a water-jacketed condenser was added the above resole resin solution. The mixture was then allowed to reflux (at 130 °C oil bath) for 4 hours. After cooling down, the mixture was subjected to rotary evaporation under reduced pressure to remove the solvent. Butanol (1 50 ml_) was added to dissolve the mixture. After suction filtration, the mixture was concentrated using rotary evaporator under reduced pressure to give 1 00 g of the final resin.
  • Butanol (200 ml_) was added to dissolve the crude product, and the pH of the mixture was adjusted to around 5.5 by careful addition of phosphoric acid in ethanol. Toluene (20 ml_) was subsequently added. To a round-bottom flask equipped with a Dean-Stark adaptor and a water-jacketed condenser was added the above resole resin solution. The mixture was then allowed to reflux (1 30 °C bath) for 2 hours. After cooling down, the mixture was subjected to rotary evaporation under reduced pressure to remove the solvent. Butanol (150 ml_) was added to dissolve the mixture. After suction filtration, the mixture was concentrated using rotary evaporator under reduced pressure to give the final resin.
  • Example 17 Synthesis of Hydroxyl Functional Polyester (PE- 4)
  • a 2-L kettle with a four-neck lid was equipped with a mechanical stirrer, a thermocouple, a heated partial condenser (107°C), a Dean-Stark trap, and a chilled condenser (1 5 °C).
  • TMCD 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol
  • MPDiol 2-methyl-1 ,3-propanediol
  • TMP trimethylolpropane
  • I PA isophthalic acid
  • Fascat-41 00 Analog Cat-41 00
  • the reaction was allowed to continue until the theoretical distillate (about 1 50 g) was collected.
  • the resin was then sampled for acid number analysis with a target of ⁇ 5 mgKOH/g. After achieving an acid number of 6.7, the resin was allowed to cool to 1 90 °C before being poured into aluminum pans. The resin was cooled and a solid product collected.
  • solvent-based formulations were prepared by using the polyesters, PE-4, PE-5, and PE-6, and the resole phenolic resins, Resole 4, Resole 5, Resole 6, and Resole 7.
  • Polyester solutions (35% solids) were first prepared by dissolving the polyester in methyl amyl ketone (MAK).
  • MAK methyl amyl ketone
  • Formulations were then prepared by mixing respectively the polyester solution with a resole phenolic resin (100 %) in the presence of an acid catalyst, p-toiuenesulfonic acid (pTSA).
  • pTSA p-toiuenesulfonic acid
  • Example 19 Evaluation of Cured Films by MEK Double Rub Test
  • Formulations 1 3-24 prepared in Example 1 8 were drawn down respectively on electrolytic tin test panels (10 cm x 30 cm) using a draw-down bar and subsequently baked in an oven at 205 °C for 1 0 minutes.
  • the thickness of the coating films was about 1 0 ⁇ .
  • the degree of crosslinking of the cured films was determined by their solvent resistance using MEK Double Rub Method (ASTM D4752).
  • ASTM D4752 MEK Double Rub Method
  • the rubbing was stopped when the main body of the film was first exposing the metal, discounting the effect on the end of the rubbed film.
  • the results are collected in Table 1 0.
  • Typically a result of >30 is considered acceptable and >100 is preferred.
  • the results indicate those based on Resole 5 (formulations 1 6, 1 7, and 1 8) are not cured adequately as the MEK double rubs are significantly lower than others.
  • a 2-L kettle with a four-neck lid was equipped with a mechanical stirrer, a thermocouple, a heated partial condenser (107°C), a Dean-Stark trap, and a chilled condenser (1 5 °C).
  • TMCD 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol
  • MPDiol 2-methyl-1 ,3-propanediol
  • TMP trimethylolpropane
  • I PA isophthalic acid
  • Fascat-41 00 Analog Cat-41 00
  • the reaction was allowed to react under a nitrogen blanket. The temperature was ramped up from room temperature to 1 50 °C over 90 minutes.
  • the temperature was increased from 1 50 to 230 °C over 3 hours.
  • the reaction was allowed to continue until the theoretical distillate (about 1 50 g) was collected.
  • the resin was then sampled for acid number analysis with a target of ⁇ 5 mgKOH/g. After achieving an acid number of 6.4, the resin was allowed to cool to 1 90 °C before being poured into aluminum pans. The resin was cooled and a solid product collected.
  • polyesters were prepared by using the polyesters, PE-7 and PE-8, and the resole phenolic resins, Resole 4.
  • Polyester solutions (35% solids) were first prepared by dissolving the polyester in methyl amyl ketone (MAK).
  • MAK methyl amyl ketone
  • Formulations were then prepared by mixing respectively the polyester solution with a resole phenolic resin (100 %) in the presence of an acid catalyst, p-toluenesulfonic acid (pTSA).
  • pTSA p-toluenesulfonic acid
  • Formulations 25 and 26 contained 0.5 phr (parts per hundred of resin) pTSA, whereas Formulations 27 and 28 contained 1 .0 phr.
  • Formulations 25-28 prepared in Example 21 were drawn down respectively on electrolytic tin test panels (10 cm x 30 cm) using a draw-down bar and subsequently baked in an oven at 205 °C for 1 0 minutes.
  • the thickness of the coating films was about 1 0 ⁇ .
  • the degree of crosslinking of the cured films was determined by their solvent resistance using EK Double Rub Method (ASTM D4752). In the test, the rubbing was stopped when the main body of the film was first exposing the metal, discounting the effect on the end of the rubbed film.
  • the results are collected in Table 14. The results indicate that increasing the amount of pTSA from 0.5 phr to 1 .0 phr does not improve coating properties in general.
  • Example 21 and 22 were repeated by replacing the pTSA acid catalyst with a phosphoric acid catalyst, CYCAT XK406N (9% active) (available from Allnex) to see its effect on the coating properties.
  • Formulations 29-32 prepared in Example 23 were drawn down respectively on electrolytic tin test panels (10 cm x 30 cm) using a draw-down bar and subsequently baked in an oven at 205 °C for 1 0 minutes.
  • the thickness of the coating films was about 1 0 ⁇ .
  • the degree of crosslinking of the cured films was determined by their solvent resistance using EK Double Rub Method (ASTM D4752). In the test, the rubbing was stopped when the main body of the film was first exposing the metal, discounting the effect on the end of the rubbed film.
  • the results are collected in Table 1 8. The results indicate that formulations (31 and 32) based on 1 .0 phr phosphoric acid catalyst exhibit significantly better water- and acid- retort resistances than those based on 0.5 phr (29 and 30).
  • a 2-L kettle with a four-neck lid was equipped with a mechanical stirrer, a thermocouple, a heated partial condenser (107°C), a Dean-Stark trap, and a chilled condenser (1 5 °C).
  • TMCD 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol
  • MPDiol 2-methyl-1 ,3-propanediol
  • TMP trimethylolpropane
  • I PA isophthalic acid
  • CHDA 1 ,4-cyclohexanedicarboxylic acid
  • Fascat-41 00 Analog to Chemical Vapor Deposition
  • the reaction was allowed to react under a nitrogen blanket. The temperature was ramped up from room temperature to 1 50 °C over 90 minutes. Once reaching the meltdown temperature of 1 50 °C, the temperature was increased from 1 50 to 230 °C over
  • polyesters were prepared by using the polyesters, PE-9, PE-10, and PE-7, and the resole phenolic resins, Resole 10.
  • Polyester solutions (35% solids) were first prepared by dissolving the polyester in methyl amyl ketone (MAK). Formulations were then prepared by mixing respectively the polyester solution with a resole phenolic resin (100 %) in the presence of a phosphoric acid acid catalyst, CYCAT XK408N (9% active).
  • Formulations 33-35 prepared in Example 29 were drawn down respectively on electrolytic tin test panels (10 cm x 30 cm) using a draw-down bar and subsequently baked in an oven at 205 °C for 10 minutes.
  • the thickness of the coating films was about 10 ⁇ .
  • the degree of crosslinking of the cured films was determined by their solvent resistance using EK Double Rub Method (ASTM D4752). In the test, the rubbing was stopped when the main body of the film was first exposing the metal, discounting the effect on the end of the rubbed film. The results are collected in Table 20.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
EP15791849.1A 2014-10-27 2015-10-27 Mit funktionellen polyestern härtbare resolphenolharze Pending EP3212685A1 (de)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US14/524,509 US9487619B2 (en) 2014-10-27 2014-10-27 Carboxyl functional curable polyesters containing tetra-alkyl cyclobutanediol
US14/524,514 US9650539B2 (en) 2014-10-27 2014-10-27 Thermosetting compositions based on unsaturated polyesters and phenolic resins
US14/540,490 US9598602B2 (en) 2014-11-13 2014-11-13 Thermosetting compositions based on phenolic resins and curable poleyester resins made with diketene or beta-ketoacetate containing compounds
US14/683,278 US20160115345A1 (en) 2014-10-27 2015-04-10 Curable polyesters and thermosetting compostions containing resole phenolic resins
US14/922,846 US20160115347A1 (en) 2015-04-10 2015-10-26 Resole phenolic resins curable with functional polyesters
PCT/US2015/057529 WO2016069572A1 (en) 2014-10-27 2015-10-27 Resole phenolic resins curable with functional polyesters

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EP18191066.2A Active EP3428231B1 (de) 2014-10-27 2015-10-27 Härtbare polyester und wärmehärtende zusammensetzungen mit resolphenolharzen
EP15793972.9A Active EP3212686B1 (de) 2014-10-27 2015-10-27 Wärmehärtende zusammensetzungen enthaltend härtbare polyester und resolphenolharzen
EP18191065.4A Active EP3431547B1 (de) 2014-10-27 2015-10-27 Wässrige dispersion enthaltend härtbare polyester, resolphenolharze und wasser

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CN110684517B (zh) * 2019-10-23 2021-11-26 四川捷贝通能源科技有限公司 一种自聚固结抗压增渗耐温防砂剂
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WO2016069567A3 (en) 2016-08-04
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EP3431547B1 (de) 2023-10-25
CN107148433A (zh) 2017-09-08
WO2016069567A2 (en) 2016-05-06
EP3431547A1 (de) 2019-01-23
CN107001772A (zh) 2017-08-01
WO2016069572A1 (en) 2016-05-06
CN111500024A (zh) 2020-08-07
EP3428231B1 (de) 2023-08-30
CN111500024B (zh) 2023-03-10
EP3212686A2 (de) 2017-09-06
EP3428231A1 (de) 2019-01-16

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