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WO1998042766A1 - Resines epoxy cycloaliphatiques - Google Patents

Resines epoxy cycloaliphatiques Download PDF

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Publication number
WO1998042766A1
WO1998042766A1 PCT/EP1998/001609 EP9801609W WO9842766A1 WO 1998042766 A1 WO1998042766 A1 WO 1998042766A1 EP 9801609 W EP9801609 W EP 9801609W WO 9842766 A1 WO9842766 A1 WO 9842766A1
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WO
WIPO (PCT)
Prior art keywords
group
reacting
groups
polyester resin
composition according
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/EP1998/001609
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English (en)
Inventor
Carlo Fumagalli
Roberto Pirola
Silvestro Farronato
Sergio Gazzea
Robertino Chinellato
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.)
Polynt SpA
Vianova Resins SpA
Original Assignee
Polynt SpA
Vianova Resins SpA
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 Polynt SpA, Vianova Resins SpA filed Critical Polynt SpA
Priority to EP98917014A priority Critical patent/EP0971967A1/fr
Priority to AU70383/98A priority patent/AU7038398A/en
Publication of WO1998042766A1 publication Critical patent/WO1998042766A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/918—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • 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
    • C09D163/08—Epoxidised polymerised polyenes
    • 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 relates to novel solid cycloaliphatic epoxy resins with improved properties and their use in thermoset powder coatings.
  • Cycloaliphatic epoxy resins find use in important fields like electric/electronic equipment and appliances, filament winding and coatings.
  • cycloaliphatic epoxy resins are used mainly in coatings for high performance outdoor applications, due to their very high resistance to atmospheric agents and ultraviolet radiation.
  • thermoset powder coatings epoxy resins are used as crosslinking agents in conjunction with carboxyl-terr-iinated polyester resins.
  • the most widely used epoxy crosslinking agent is triglycidyl isocyanurate (TGIC; compare, for exam- pie, EP-A 0 107 888). This compound, which is a solid with a softening point in the
  • These solid epoxidized polyester resins comprise at least one epoxidized ester which contains, per molecule, two or more dicarboxylic cycloaliphatic moieties of the general formula
  • R , ⁇ ' and R are independently selected from the group consisting of hydrogen and methyl or R 1 and R together are methylene,
  • R and R are independently selected from the group consisting of hydrogen and methyl.
  • the dicarboxylic cycloaliphatic moieties are bonded by their open valencies to moieties independently selected from the group consisting of hydrogen, linear or branched C ⁇ g alky Is, linear or branched linking C 2 _ 8 alkanediyls, linear or branched (cross-) linking C 3 _ 8 alkanetriyls, linear or branched (cross-) linking C ⁇ _ 8 alkanetetrayls and linking or crosslinking moieties of the general formula X(Y-) friendship wherein n is an integer from 2 to 4, X is a di-, tri- or tetravalent group containing at least one isocyclic or heterocyclic ring and Y is a direct bond or a -(CH 2 ) m - group wherein m is an integer from 1 to 4.
  • open valence means any valence of a moiety that is (formally) available for engaging in a bond to another moiety. In the molecule as a whole, there are of course no open valencies.
  • the epoxidized esters contain at least two cycloaliphatic moieties, they comprise "terminal" carboxylate functions which are bonded to C ] _ 8 alkyl or hydrogen, forming a C]_ 8 alkylester or a free carbox- ylic acid function, respectively, and "inner" carboxylate functions which are linked or cross- linked by the above-mentioned diyls, triyls, tetrayls or di-, tri- or tetravalent moieties.
  • linear or branched C,_ 8 alkyl means any alkyl group having up to 8 carbon atoms and any possible number of branches, for example methyl, ethyl, propyl, isopropyl, butyl, isobu- tyl, sec-butyl, tert-butyl, pentyl, 3-methylbutyl (isoamyl), tert-pentyl, neopentyl, hexyl, octyl or 2-ethylhexyl.
  • linear or branched C 2 _ 8 alkanediyl means any alkanediyl group having 2 to 8 carbon atoms and any possible number of branches, except those having two open valences at the same carbon atom, for example 1,2-ethanediyl, 1 ,2-propanediyl, 1,3-pro- panediyl, 1,2-butanediyl, 1,3-butanediyl, 1 ,4-butanediyl, 2,3-butanediyl, 2-methyl-l,3-pro- panediyl, 3-methyl-l,3-butanediyl, 1,2-hexanediyl, 1,6-hexanediyl or 2,2-dimethyl-l,3-pro- panediyl.
  • linear or branched C 3 _ g alkanetriyl means any alkanetriyl group having 3 to 8 carbon atoms and any possible number of branches, except those having two or three open valences at the same carbon atom, for example 1,2,3-propanetriyl or 2,2-dimethylbutane- l, ,l"-triyl.
  • linear or branched C ⁇ g alkanetetrayl means any alkanetetrayl group having 4 to 8 carbon atoms and any possible number of branches, except those having two or three open valences at the same carbon atom, for example 1,2,3,4-butanetetrayl and 2,2-di- methylpropane-l, ,l",3-tetrayl.
  • the term "di-, tri- or tetravalent group containing at least one isocyclic or heterocyclic ring” means any organic moiety having 2 to 4 open valencies and containing any number of isocyclic or heterocyclic rings, for example triazine rings.
  • the epoxidized polyester resins are essentially free of monomeric products.
  • monomeric products are compounds containing only one cycloaliphatic moiety of the type defined above, especially those wherein both open valencies are bound to hydrogen or C ⁇ _ 8 alkyl, and any hydroxy c ⁇ rpounds from the synthesis of the polyester resin.
  • "Essentially free of monomeric products” is to be understood as containing less than 5 wt %, preferably less than 3 wt % of those products.
  • one of the substituents R 1 to R is hydrogen or a methyl group and the remaining of R l to R 4 are hydrogens.
  • the compounds according to this embodiment are derived from tet- rahydrophthalic and methyltetrahydrophthalic acids. H
  • resins wherein R 1 and R 4 together are methylene, one of R 2 and R 3 is hydrogen or methyl and the other one is hydrogen.
  • R 1 and R 4 together are methylene, one of R 2 and R 3 is hydrogen or methyl and the other one is hydrogen.
  • the C ⁇ _ 8 alkyls are preferably selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl and 2-ethylhexyl. Most preferably, isobutyl is employed as Cj_ 8 alkyl.
  • the linking C 2 _ 8 al- kanediyls are preferably selected from 1,2-ethanediyl, 1,2-propanediyl, 1,3-pro- panediyl, 1 ,2-butanediyl, 1,3-butanediyl, 1 ,4-butanediyl, 2,3-butanediyl, 3 -methyl- 1,3 -bu- tanediyl, 1,2-hexanediyl, 1 ,6-hexanediyl and 2,2-dimethyl-l,3-propanediyl.
  • the (cross-) link- ing C 3 _ 8 alkanetriyls are preferably selected from 1,2,3-propanetriyl and 2,2-di- methylbutane-l, ,l"-triyl.
  • the (cross-) linking C 4 _ 8 alkanetetrayls, if present, are preferably selected from 1,2,3,4-butanetetrayl and 2,2-dimethylpropane-l, ,l",3-tetrayl.
  • linking or crosslinking moieties of the general formula X(Y-) if present, isocyanurate groups of the formula
  • the solid epoxidized polyester resin according to the invention has an acid number of not more than 2 mg KOH/g, more preferably, not more than 1 mg KOH/g. This means that essentially no free carboxyl groups are present.
  • the (weight-averaged) molecular weight, as determined by gel permeation chromatography, is typically between about 500 and 10000, preferably between 1000 and 5000.
  • the solid epoxidized polyester resins may be prepared by i) reacting an unsaturated dicarboxylic acid or acid derivative of the general formula
  • R 1 to R 4 are as defined above and Q and Q are independently selected from the group consisting of hydroxy and C ! _g alkoxy or Q and Q together are -0-, with at least one hydroxy compound selected from the group consisting of linear or branched C 2 _ g alkanediols, linear or branched C ⁇ g alkanetriols, linear or branched C ⁇ g alkanetetraols and hydroxy co - pounds of the general formula X(Y-OH) bear wherein n is an integer from 2 to 4, X is a di-, tri- or tetravalent group containing at least one isocyclic or heterocyclic ring and each Y is a direct bond or a -(CH ⁇ - group wherein m is an integer from 1 to 4; and a linear or branched C[_g alkanol, ii) removing essentially all monomeric byproducts, and i ⁇ ) epoxidizing the resulting unsaturated polyester.
  • the first step is a direct esterification if an acid or an- anhydride is employed, and a transesterification if a dialkyl ester is used as starting material.
  • the linear or branched C ⁇ _ 8 alkanol is required to esterify the "terminal" carboxylic functions of the resulting polyester.
  • Another process for preparing the solid epoxidi zed polyester resins accord ⁇ ing to the invention comprises the steps of i) reacting an unsaturated dicarboxylic acid ester of the general forr ⁇ ula
  • R to R are as defined in claim 1 and Q and Q are C ⁇ g alkoxy groups, with at least one hydroxy compound selected from the group consistmg of linear or branched C 2 _ 8 alkane- diols, linear or branched C 3 _ 8 alkanetriols, linear or branched C 4 _ 8 alkanetraols and hydroxy compounds of the general formula X(Y-OH) law wherein n is an integer from 2 to 4, X is a di-, tri- or tetravalent group containing at least one isocyclic or heterocyclic ring and each Y is a direct bond or a -(CH 2 ) m - group wherein m is an integer from 1 to 4, ii) removing essentially all monomeric byproducts, and iii) epoxidizing the resulting unsaturated polyester by reacting it with a peroxy compound.
  • X(Y-OH) wherein n is an integer from 2 to 4
  • X is a
  • dialkyl esters are used as starting materials and therefore only transesterification reactions are required in the first step.
  • the "terminal" carboxylic functions still carry the alkyl groups that had been present in the starting dialkyl ester.
  • the preferred methyl, ethyl, propyl, isopropyl, butyl, isobutyl and 2-ethylhexyl groups are introduced by using methanol, efhanol, propanol, isopropyl alcohol, butanol, isobutyl alcohol (especially preferred) and 2-ethylhexanol, respectively.
  • the preferred 1 ,2-ethanediyl, 1,2-pro- panediyl, 1,3-propanediyl, 1,2-butanediyl, 1,3-butanediyl, 1,4-butanediyl, 2,3-butanediyl, 3-methyl-l,3-butanediyl, 1,2-hexanediyl, 1 ,6-hexanediyl and 2,2-dimethyl-l,3-propanediyl groups are introduced by using ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-bu- tanediol, 1,3-butanediol, 1 ,4-butanediol, 2,3-butanediol, 3-methyl-l,3-butanediol, 1,2-hexane- diol and 2,2-dimethyl-l,3-propanediol
  • 1,2,3-propanetriyl and 2,2-d.methylbutane-l,r,l"-triyl groups are introduced by using glyc- erol and trimethylolpropane, respectively.
  • the preferred 1,2,3,4-butanetetrayl and 2,2-di- methylpropane-l,l,l,3-tetrayl groups are introduced by using threitol/erythritol and penta- erythritol, respectively.
  • the molecular mass distribution of the crude polyester is modified by eliminating the molecules with lower mo- lecular mass, e. g., the monomeric dialkyl esters.
  • the molecules with lower molecular mass are removed by distillation.
  • This distillation is advantageously performed under high vacuum.
  • the residue has a relatively narrow molecular mass distribution.
  • Other possible methods for eliminating the low molecular mass products are, for example, liquid chromatography or membrane separa- tion processes such as ultrafiltration.
  • the unsaturated ester precursor with a narrow molecular weight distribution is epoxidized by reacting it with a peroxy compound.
  • peroxy compound both organic and inorganic peroxy compounds may be used.
  • Prefera- bly peroxycarboxylic acids such as peracetic acid or m-chloroperbenzoic acid are used as peroxy compounds.
  • Monoperphthalic acid is especially preferred.
  • Hydrogen peroxide is also a preferred peroxy compound.
  • a phase transfer catalyst may be used.
  • suitable phase transfer catalysts are de- scribed in J Polym. Sci., Part A: Polym. Chem. 1993, 31, 1825-1838.
  • the epoxidation reaction is advantageously carried out in an inert solvent.
  • Suitable inert solvents are, for example, alkyl alkanoates, halogenated hydrocarbons, cycloaliphatic hydrocarbons, aromatic hydrocarbons or alcohols.
  • the coating powder usually comprises a thermosetting binder composition and further ingredients such as catalysts, pigments, fillers and auxiliary materials.
  • the thermosetting binder composition may be a one-component binder composition which can be used as such or a two-component binder composition which comprises a hardener and a reactive polymer.
  • the terms "one-component” and "two-component” in this context are independent of the actual chemical composition, i. e., a one-component binder composition may consist of several compounds. In addition, each component of a two-component binder composition may consist of several compounds.
  • compositions which are suitable for both one-component binder compositions and, as hardener component, two-component binder compositions comprise at least one solid epoxidized polyester resin according to the invention and, optionally, a catalyst.
  • Suitable catalysts for this type of composition are, for example, Lewis acids such as boron trifluoride complexes or Lewis bases such as tertiary amines.
  • the solid epoxidized polyester compounds according to the invention are used in compositions further comprising at least one polymer capable of reacting with epoxy groups.
  • polymers capable of reacting with epoxy groups preferably polymers containing carboxy groups, polymers containing anhydride groups, polymers containing hydroxy groups, polymers containing amino and/or amido groups or (other) polymers containing epoxy groups are employed.
  • Especially preferred polymers capable of reacting with epoxy groups are polymers based on polyesters, polyacrylates or polyethers which are modified so as to contain the above func- tional groups.
  • suitable catalysts known in the art may be used to expedite the curing process.
  • Particularly preferred as polymers capable of reacting with epoxy groups are carboxylated polyesters with an acid number of 10 to 70 mg KOH/g resin and a glass transition temperature T g of 50 to 70 °C.
  • Resins of this type are available from Vianova Resins, a company of the Hoechst Group, under the trademark Alftalat .
  • compositions comprising at least one solid epoxidized polyester resin according to the in- vention and at least one polymer capable of reacting with epoxy groups may be blends with no substantial degree of crosslinking between the epoxidized polyester resin and the other polymer. These blends are often called masterbatches.
  • compositions are pre-polymerized, i. e., crosslinking has taken place to some extent, but without considerably impairing the thermosetting properties of the composition. Accordingly, these compositions are often called prepolymer compositions.
  • the masterbatch compositions may be prepared by — separately or together — melting the solid epoxidized polyester resin and the polymer capable of reacting with epoxy groups, mix- ing the melts thoroughly, solidifying and comminuting the composition. Especially the mixing should be performed at a temperature where no substantial crosslinking occurs.
  • the prepolymer compositions may be prepared by — separately or together — melting the solid epoxidized polyester resin and the polymer capable of reacting with epoxy groups, mix- ing the melts thoroughly, keeping the mixture at a temperature where crosslinking is possible for a time sufficient to achieve the desired degree of crosslinking, solidifying the mixture and comminuting it.
  • Both the solid epoxidized polyester resins as such and the above compositions may be used in thermosetting one-component binder compositions suitable for powder coating.
  • the solid ep- oxidized polyester compounds according to the invention yield homopolymerized epoxy resins on curing.
  • both the solid epoxidized polyester resins as such and the above compositions may be used as hardener components in thermosetting two-component binder compositions suitable for powder coating which comprise a hardener component, a reactive polymer component which comprises at least one reactive polymer capable of reacting with epoxy groups and, optionally, a catalyst. If masterbatch or prepolymer compositions are employed as hardener components, the reactive polymer in the second component may be the same as that comprised in the hardener or a different one.
  • preferred polymers capable of reacting with epoxy groups are polymers containing carboxy groups, polymers containing anhydride groups, polymers containing hydroxy groups, polymers containing amino and or amido groups or (other) polymers containing epoxy groups.
  • Especially preferred polymers capable of reacting with epoxy groups are polymers based on polyesters, polyacrylates or polyethers which are modified so as to contain the above functional groups.
  • Particularly preferred as polymers capable of reacting with epoxy groups are carboxylated polyesters with an acid number of 10 to 70 mg KOH/g resin and a glass transition temperature g of 50 to 70 °C.
  • Resins of this type are available from Vianova Resins, a company of the Hoechst Group, under the trademark Alftalat .
  • powder coating compositions comprising a one- component or two-component binder composition as described above and one or more substance ⁇ ) such as pigments, catalysts, curing agents, including polymers capable of reacting with epoxy groups, fillers, and auxiliary materials.
  • substance ⁇ such as pigments, catalysts, curing agents, including polymers capable of reacting with epoxy groups, fillers, and auxiliary materials.
  • auxiliary materials include materials such as flow improvers, antioxidants etc.
  • the powder coating compositions may be prepared by methods known in the art, for example by mixing and extruding the components in a heated extruder and subsequently comminuting the solid extrudate to a particle size suitable for the usual coating techniques.
  • the coating process may be carried out by applying the powder coating composition on a substrate, for example by electrostatic spraying or another known method, and curing the coating by subjecting it to heat for a sufficient time at a suitable temperature to obtain a completely cured coating.
  • the invention will be further described based on the following non-limiting examples.
  • the molecular masses have been determined by gel permeation chromatography (GPC).
  • the relative peak areas refer to the resolved peaks (at high retention times) only, whereas the averaged molecular masses have been determined from the complete elution diagrams.
  • THPA 1,2,3,6-tetrahydrophthalic anhydride
  • the mixture was heated and the temperature was gradually raised to 230 °C.
  • the esterification reaction was carried out distilling off the water formed until the acid number of the mixture was 15 mg KOH/g. Then 0.5 g of stannous oxide was added. After ca. 12 h, the xylene and
  • Solid monoperphthalic acid (95%> purity, 100 g, 0.52 mol) was added portionwise during 1 h. By immersing the reaction flask in cold water the temperature of the stirred reaction mixture was maintained at 50 °C. When the exothermic reaction ceased, the flask was immersed in a warm bath and the reaction mixture was allowed to stand at 50 °C for another 2 h. After cool- ing to room temperature, the reaction mixture was filtered and the filtrate washed with aqueous sodium carbonate and then with water. The organic layer was concentrated in vacuum and dried at 80 °C/13 mbar to give 103.3 g of solid epoxy resin with a softening point of about 80 °C.
  • THPA 1,2,3, 6-tetrahydrophthalic anhydride
  • Example 12 Epoxidation of the polyester obtained in Example 11
  • Example 13 Preparation of a pre-polymer binder/hardener from the epoxy ester of Example 2 and a carboxylated polyester
  • Example 14 Preparation of a pre-polymer binder/hardener from the epoxy ester of Example 4 and a carboxylated polyester
  • Example 13 The procedure of Example 13 was repeated with the epoxidized polyester of Example 4 using the same ratio of epoxide to Alftalat 01634.
  • Example 15 The procedure of Example 15 was repeated using the epoxidized polyester resin of Example 12 and the same ratio of epoxide to Alftalat ® 01634.
  • Example 17 Powder compositions for coating and coating tests performed therewith
  • Each composition comprises a two-component binder which in turn comprises a reactive polyester resin ("Polyester”) and a epoxy-containig hardener (“Hardener”).
  • Polyter reactive polyester resin
  • Hardener epoxy-containig hardener
  • the compound or composition used as hardener is identified by the corresponding Example No. in parentheses.
  • compositions were:
  • Alftalat 01634 carboxylated polyester resin, acid number ⁇ 35 mg KOH/g, T ⁇ 65 °C Alftalat ® AN 989: carboxylated polyester resin, acid number - 35 mg KOH/g, T % ⁇ 60 °C Alftalat ® AN 770: carboxylated polyester resin, acid number ⁇ 35 mg KOH/g, T ⁇ ⁇ 50 °C Alftalat ® AN 995: carboxylated polyester resin, acid number ⁇ 25 mg KOH/g, T g ⁇ 55 °C Alftalat ® VAN 997: carboxylated polyester resin, acid number ⁇ 35 mg KOH/g, T ⁇ 55 °C Additol ® XL 496: flow promoting agent
  • Polyester Alftalat ® AN 989 569
  • Polyester Alftalat ® AN 770 465
  • Polyester Alftalat 13 AN 770 465
  • Polyester Alftalat ® AN 770 465 Hardener (Ex. 15) 155 Additol ® XL 496 30 Benzoin 5
  • Polyester Alftalat ® AN 770 496
  • Polyester Alftalat ® VAN 995 496 Hardener (Ex. 8) 124
  • Polyester Alftalar AN 989 496
  • Polyester Alftalat ® AN 770 465
  • Polyester Alftalat ® AN 770 496 Hardener (Ex. 12) 124
  • Polyester Alftalat ® AN 770 496
  • Ratio polyester/hardener 80/20 The powders of the above mentioned compositions were extruded using the following conditions: Twin screw extruder.
  • the extrudate was cooled, micronized and sieved ( ⁇ 125 ⁇ m).
  • the powder compositions thus obtained were used for the painting tests.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Epoxy Resins (AREA)

Abstract

Résines solides cycloaliphatiques époxydées de polyester contenant, par molécule, au moins deux fractions cycloaliphatiques représentées par la formule générale (I): dans laquelle R1 et R4 représentent hydrogène ou méthyle ou R1 et R4 ensemble représentent méthylène et R2 et R3 représentent hydrogène ou méthyle. Ces fractions cycloaliphatiques sont reliées ou réticulées par des groupes di-, tri- ou tétravalents, tandis que les fonctions terminales carboxyliques sont liées à des groupes alkyle C¿1?-C8. Ces résines cycloaliphatiques époxydées de polyester sont essentiellement exemptes de composés monomères et particulièrement appropriées pour réaliser des revêtements en poudre.
PCT/EP1998/001609 1997-03-21 1998-03-19 Resines epoxy cycloaliphatiques Ceased WO1998042766A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP98917014A EP0971967A1 (fr) 1997-03-21 1998-03-19 Resines epoxy cycloaliphatiques
AU70383/98A AU7038398A (en) 1997-03-21 1998-03-19 Cycloaliphatic epoxy resins

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI970669 IT1290432B1 (it) 1997-03-21 1997-03-21 Resine epossidiche cicloalifatiche
ITMI97A000669 1997-03-21

Publications (1)

Publication Number Publication Date
WO1998042766A1 true WO1998042766A1 (fr) 1998-10-01

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AU (1) AU7038398A (fr)
IT (1) IT1290432B1 (fr)
WO (1) WO1998042766A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002062867A1 (fr) * 2001-02-09 2002-08-15 Solutia Italy S.R.L. Résines solides d'hydroxylate cycloaliphatique époxidé, procédé d'élaboration, et compositions de peintures durcissables à base de poudre contenant ces résines
EP2163950A1 (fr) * 2008-09-10 2010-03-17 Xerox Corporation Toner contenant des polyesters epoxidés et procédé de production
CN111116879A (zh) * 2019-12-09 2020-05-08 广东盈骅新材料科技有限公司 不饱和聚酯树脂及其制备方法和应用

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US8278020B2 (en) 2008-09-10 2012-10-02 Xerox Corporation Polyester synthesis
CN111116879A (zh) * 2019-12-09 2020-05-08 广东盈骅新材料科技有限公司 不饱和聚酯树脂及其制备方法和应用
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ITMI970669A1 (it) 1998-09-21
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EP0971967A1 (fr) 2000-01-19

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