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WO1993012157A1 - Catalyseur a base de guanidine destine a la reaction entre les polymeres fonctionnels de carboxyle et les composes fonctionnels d'epoxy, en tant que base pour les revetements en poudre - Google Patents

Catalyseur a base de guanidine destine a la reaction entre les polymeres fonctionnels de carboxyle et les composes fonctionnels d'epoxy, en tant que base pour les revetements en poudre Download PDF

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Publication number
WO1993012157A1
WO1993012157A1 PCT/NL1992/000221 NL9200221W WO9312157A1 WO 1993012157 A1 WO1993012157 A1 WO 1993012157A1 NL 9200221 W NL9200221 W NL 9200221W WO 9312157 A1 WO9312157 A1 WO 9312157A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
reaction
acid
basis
guanidine
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/NL1992/000221
Other languages
English (en)
Inventor
Wilhelmus Henricus Hubertus Antonius Van Den Elshout
Heman Jelle Wories
Dirk Armand Wim Stanssens
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.)
Koninklijke DSM NV
Original Assignee
DSM NV
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 DSM NV filed Critical DSM NV
Publication of WO1993012157A1 publication Critical patent/WO1993012157A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
    • B01J31/0251—Guanidides (R2N-C(=NR)-NR2)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers

Definitions

  • the invention relates to a guanidine catalyst for the reaction between carboxyl functional polymers and epoxy functional compounds as the basis for powder coatings.
  • Such catalysts are disclosed in DE-C-3545061, which patent publication describes a powder coating based on a polymer containing carboxyl groups; a polyepoxide; customary additives; and 0.1-5 wt.% of a catalyst system containing both amidine and tertiary amine.
  • the invention is characterized in that the catalyst is blocked by an acyl group.
  • the acyl group can be applied by acylation of the catalyst with an acylating compound.
  • the catalyst according to the invention compares favourably to the catalyst system described in DE-C-3545061, because in the process according to the German patent publication the use of amines is essential.
  • the blocked catalyst is not or less toxic than the non-blocked catalyst.
  • the blocking agents used according to the invention are not toxically suspect either. Mechanical properties, such as impact strength, reverse impact strengt and flexibility are very good. Resulting coatings further have a very good outdoor durability, a good adhesion to substrates such as metal or woord and a good overbake resistance (resistance against yellowing at a too high cure temperature or after a too large cure time) .
  • the applied blocked catalysts are based on an unblocked guanidine base according to formula (I) or (II):
  • R 1 H or C ⁇ Cio )alkyl
  • R 2 H or (C ⁇ C ⁇ )alkyl
  • R 3 H or i C x -C 1 0 )alkyl
  • R 4 H or (Ci-C ⁇ )alkyl
  • R 1 and R 3 , R 1 and R 2 , R 3 and R 4 and R 2 and R 4 can form a ring with (2-10) carbon atoms;
  • the unblocked bases according to formula (I) or (II) preferably have a pK a > 11.
  • the acylating compound preferably is a compound with 1-15 carbon atoms.
  • Suitable acylating compounds are, for instance, anhydrides such as e.g. propionic acid anhydride, acetic acid anhydride, phthalic anhydride, chloroacetic acid anhydride, dichloroacetic acid anhydride, trichloroacetic acid anhydride, hexahydrophthalic acid anhydride, maleic acid anhydride, succinic acid anhydride, acyl chlorides such as e.g. acetyl chloride, adipoyl chloride, terephthaloyl chloride, benzoyl chloride, and carboxylic acid esters such as e.g. ethylacetate, ethylbenzoate, dimethylmaleate, dimethylphthalate, dimethyladipate, methylformate.
  • anhydrides such as e.g. propionic acid anhydride, acetic acid anhydride, phthalic anhydride, chloroacetic acid anhydride, dichloroacetic acid anhydride
  • acetyl-tetramethylguanidine As catalyst use is preferably made of acetyl-tetramethylguanidine (acetyl-TMG) , of which we believe the structure is as follows:
  • the blocked compound does not catalyze addition reactions at temperatures below 130°C since no free base is present in the system. As a result, the systems that are stable on storage at room temperature are obtained. In addition, due to the blocking no gelation takes place during processing of powder coatings.
  • SU BSTITUTESHEET has increased significantly over the past decade.
  • Important representatives of this group are powder coatings on the basis of polyesters.
  • One of these systems consists, for instance, of a carboxyl functional polyester and triglycidyl isocyanurate (TGIC) in a ratio of 93:7 and is used where good weather resistance i required (for instance in facade cladding, garden furniture, bicycles).
  • Another system consists of an acid polyester in combination with an epoxy resin on the basis of bisphenol-A and is suitable in particular for interior applications (fo instance refrigerators) , inter alia because of discolouration on exposure to outdoor light (UV).
  • EP-A-0,051,787 but in that publication the catalysts are blocked with isocyanates. That does not give an indication that it would have been possible and advantageous to block these type of catalysts by an acyl group.
  • the isocyanate blocked guanidine catalysts in EP-A-0,051,787 have the disadvantage that they can release volatile isocyanate components during cure, which is environmentally very undesirable.
  • the catalysts according to the invention are suitable for use as curing catalyst for the reaction between carboxyl functional polymers, preferably acid-terminated polyesters, and epoxy functional compounds as the basis for powder coatings.
  • carboxyl functional polymers preferably acid-terminated polyesters, and epoxy functional compounds as the basis for powder coatings.
  • suitable carboxyl functional polymers are carboxyl functional polyacrylates and polyurethanes.
  • Acid-terminated polyester resins can be mixed with a polyfunctional epoxide, pigments and other additives at a temperature of about 110-130°C, for instance by means of extrusion. After electrostatic spraying they are cured at
  • SUBSTITUTESHEET temperatures between, for instance, 160°C and 200°C with the aid of a catalyst.
  • the catalyst must guarantee rapid curing and yet be virtually inactive during mixing of the polyester and the epoxy compound.
  • the curing catalyst can be added during mixing of the carboxyl functional polymer, for instance the polyester, and the epoxy functional compound.
  • the catalysts are preferably used in amounts of between 0.01 wt.% and 2.0 wt.% with respect to the carboxyl functional polymer, preferably in amounts of between 0.03 and 0.7 wt.%.
  • Suitable polyesters can be obtained using customary preparation methods from essentially aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 3,6-dichloro- phthalic acid, tetrachlorophthalic acid and, where available, the anhydrides, acid chlorides or lower alkyl esters of these.
  • the carboxylic acid component often consists of at least 50 wt.%, preferably at least 70 mol%, of isophthalic acid and/or terephthalic acid.
  • SUBSTITUTESHEET glycol dipropylene glycol and 2,2-bis-[4-(2-hydroxy- ethoxy) ]-phenylpropane and smaller amounts of polyols such as glycerol, hexanetriol, pentaerythritol, sorbitol, trimethylol ethane, trimethylol propane and tris-(2- hydroxy)-alkylisocyanurate.
  • diols and polyols us may also be made of epoxy compounds.
  • the alcohol component preferably contains at least 50 mol% of neopentyl glycol and/or propylene glycol.
  • Polycarboxylic acids which can also be used are cycloaliphatic and/or acyclic polycarboxylic acids such as, for instance, cyclohexane dicarboxylic acid, tetrahydro- phthalic acid, hexahydro-endomethylene tetrahydrophthalic acid, azelaic acid, sebacic acid, decane dicarboxylic acid, dimer fatty acid, adipic acid, succinic acid, maleic acid, in amounts of at most 30 mol%, preferably at most 20 mol%, of the total amount of carboxylic acids.
  • cyclohexane dicarboxylic acid such as, for instance, cyclohexane dicarboxylic acid, tetrahydro- phthalic acid, hexahydro-endomethylene tetrahydrophthalic acid, azelaic acid, sebacic acid, decane dicarboxylic acid, dimer fatty acid, adipic
  • Use may also be made of hydroxy carboxylic acids and/or optionally of lactones, such as, for instance, 12-hydroxy- stearic acid, epsilon-caprolacton and hydroxypivalic acid ester of neopentyl glycol.
  • lactones such as, for instance, 12-hydroxy- stearic acid, epsilon-caprolacton and hydroxypivalic acid ester of neopentyl glycol.
  • monocarboxylic acids such as benzoic acid, tert. butyl benzoic acid, hexahydrobenzoic acid and saturated aliphatic monocarboxylic acids may be added during the preparation.
  • the polyesters are prepared by methods known per se, by esterification or trans-esterification, optionally in the presence of standard catalysts such as, for instance, dibutyltin oxide or tetrabutyl titanate.
  • COOH/OH ratio it is possible to obtain final products having an acid number between 5 and 150.
  • the epoxy functional compound which is used can be, for instance, triglycidyl isocyanurate (TGIC) or a related heterocyclic triepoxy compound such as, for instance, methyl-substituted triglycidyl isocyanurate or 1,2,4- triglycidyl triazolidine-3,5-dione or diglycidyl terephthalate or diglycidyl hexahydroterephthalate or an epoxy resin based on bisphenol-A and epichlorohydrin.
  • TGIC triglycidyl isocyanurate
  • a related heterocyclic triepoxy compound such as, for instance, methyl-substituted triglycidyl isocyanurate or 1,2,4- triglycidyl triazolidine-3,5-dione or diglycidyl terephthalate or diglycidyl hexahydroterephthalate or an epoxy resin based on bisphenol-A and
  • SUBSTITUTESHEET amount of epoxy functional compound which is used in the binder with, for instance, the polyester resin depends on the acid number and on the epoxy equivalent weight of the epoxy compound with which the polyester is combined and is often between 0.8 and 1.2 epoxy equivalent per carboxyl equivalent.
  • the weight ratio between carboxyl functional polymer and epoxy functional compound will generally be between 96:4 and 30:70, and preferably has a value of 93 : to 50 : 50.
  • Suitable pigments are, for instance, inorganic pigments, such as titanium dioxide, zinc sulphide, iron oxide and chromium oxide, and organic pigments, such as.azo compounds.
  • Suitable fillers are, for instance, metal oxides, silicates, carbonates and sulphates
  • Powder coatings according to the invention can be used, for instance, on wood or as coatings for, for instance, industrial finish coats for general purposes, finish coats on machinery and apparatus and in particular finish coats on metal, for instance for cans, domestic and other small equipment, cars and the like.
  • the coating film had the desired solvent resistant (> 100 acetone dubbelrubs), flow and reverse impact ASTM D2794 (160 inch pnd. )
  • the stability of the powder coating on storage at room temperature was higher than 6 months.

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

Abstract

Catalyseur à base de guanidine destiné à la réaction entre les polymères fonctionnels de carboxyle et les composés fonctionnels d'époxy, en tant que base pour les revêtements en poudre; et bloqué par un groupe acyle.
PCT/NL1992/000221 1991-12-18 1992-12-09 Catalyseur a base de guanidine destine a la reaction entre les polymeres fonctionnels de carboxyle et les composes fonctionnels d'epoxy, en tant que base pour les revetements en poudre Ceased WO1993012157A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL9102113 1991-12-18
NL9102113A NL9102113A (nl) 1991-12-18 1991-12-18 Katalysator voor de reaktie tussen carboxylfunctionele polymeren en epoxyfunctionele verbindingen als basis voor poedercoatings.

Publications (1)

Publication Number Publication Date
WO1993012157A1 true WO1993012157A1 (fr) 1993-06-24

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1992/000221 Ceased WO1993012157A1 (fr) 1991-12-18 1992-12-09 Catalyseur a base de guanidine destine a la reaction entre les polymeres fonctionnels de carboxyle et les composes fonctionnels d'epoxy, en tant que base pour les revetements en poudre

Country Status (4)

Country Link
CN (1) CN1074227A (fr)
AU (1) AU3268293A (fr)
NL (1) NL9102113A (fr)
WO (1) WO1993012157A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2929281A1 (fr) * 2008-03-28 2009-10-02 Polyrise Soc Par Actions Simpl Modification de la chimie de surface d'especes macromoleculaires en presence d'une guanidine conjuguee

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4400929A1 (de) * 1994-01-14 1995-07-20 Huels Chemische Werke Ag Verfahren zur Herstellung von matten Epoxidharzbeschichtungen

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3732286A (en) * 1971-11-01 1973-05-08 Goodrich Co B F Compositions comprising an epoxy resin, dicyaniamide and an acylguanidine
EP0051787A2 (fr) * 1980-11-06 1982-05-19 Bayer Ag Amidines et produits d'addition amidine/isocyanate, leurs procédés de préparation et leur utilisation comme catalyseurs pour le durcissement d'époxy-résines

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3732286A (en) * 1971-11-01 1973-05-08 Goodrich Co B F Compositions comprising an epoxy resin, dicyaniamide and an acylguanidine
EP0051787A2 (fr) * 1980-11-06 1982-05-19 Bayer Ag Amidines et produits d'addition amidine/isocyanate, leurs procédés de préparation et leur utilisation comme catalyseurs pour le durcissement d'époxy-résines

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2929281A1 (fr) * 2008-03-28 2009-10-02 Polyrise Soc Par Actions Simpl Modification de la chimie de surface d'especes macromoleculaires en presence d'une guanidine conjuguee
WO2009133264A3 (fr) * 2008-03-28 2009-12-23 Polyrise Modification de la chimie de surface d'espèces macromoléculaires en présence d'une guanidine conjuguée
US8530544B2 (en) 2008-03-28 2013-09-10 Polyrise Modification of the surface chemistry of macromolecular species in the presence of a conjugated guanidine

Also Published As

Publication number Publication date
NL9102113A (nl) 1993-07-16
CN1074227A (zh) 1993-07-14
AU3268293A (en) 1993-07-19

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