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WO1993005095A1 - Oligoesters insatures contenant des groupes alcadienyles - Google Patents

Oligoesters insatures contenant des groupes alcadienyles Download PDF

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Publication number
WO1993005095A1
WO1993005095A1 PCT/EP1992/001964 EP9201964W WO9305095A1 WO 1993005095 A1 WO1993005095 A1 WO 1993005095A1 EP 9201964 W EP9201964 W EP 9201964W WO 9305095 A1 WO9305095 A1 WO 9305095A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyols
groups
hydroxyl groups
polyol
hydroxyl
Prior art date
Application number
PCT/EP1992/001964
Other languages
German (de)
English (en)
Inventor
Bert Gruber
Ulrich Eicken
Herbert Fischer
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1993005095A1 publication Critical patent/WO1993005095A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • 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
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation

Definitions

  • the invention relates to unsaturated esters containing alkadienyl groups, which due to their low viscosity are used as air-drying lacquer binders, and to a process for producing the unsaturated polyesters containing alkadienyl groups.
  • Varnishes are usually applied by spraying, brushing or dipping. A certain viscosity must not be exceeded in order to ensure good flow and complete wetting on the materials to be coated. So far, the person skilled in the art has set the correct viscosity by adding organic solvents or diluents, which, however, from today's perspective are to be limited at least in terms of the amount. In order to achieve this, attempts have been made to produce new paint binders which have a lower viscosity, so that no or only small amounts of organic solvents are necessary to adjust the viscosity.
  • the European patent specification 167962 proposes unsaturated, low-viscosity polyesters modified with monofunctional alcohols from olefinically unsaturated monofunctional alcohols and di- and / or tricarboxylic acids and polyols with a functionality of more than 2 as air-drying paint binders to use.
  • unsaturated polyesters lead to hard coatings more quickly, but the unsaturated onofunctional alcohol is difficult to produce.
  • Oligoesters containing alkadienyl groups obtainable by a) partially reacting polyols with 2 to 6 hydroxyl groups with conjugated dienes in the presence of palladium catalysts, phosphines and optionally water and aliphatic monoalkanols, and b) free diol groups of the polyol partial ethers with di-, Tricarboxylic acids and / or their derivatives in a molar ratio of hydroxyl group: carboxylic acid group of 1: 2 to 1: 3 and c) the free carboxyl groups of the polyol ether partial esters are practically completely esterified with polyols with 2 to 6 hydroxyl groups.
  • Polyols are understood to mean compounds which have at least 2 hydroxyl groups.
  • Suitable diols are those with 2 to 25 carbon atoms, preferably saturated aliphatic diols and in particular the alpha, omega diols thereof.
  • Examples of these diols are ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol with average molecular weights from 300 to 15,000, propylene glycol, polypropylene glycols with average molecular weights from 300 to 15,000, 1,3-propanediol, 1,6-hexanediol, 1,12 -Dodecanediol, 1,16-hexanedecanediol and / or 1,18-octadecandiol.
  • polyols preference is given to aliphatic polyols having 3 to 6 hydroxyl groups and having 3 to 12 carbon atoms and in particular those selected from the group consisting of triethylolpropane, glycerol, pentaerythritol, diglycerin, dipentaerythritol, sorbitol, glucose, methylglucoside and sucrose.
  • polyols preference is given to aliphatic polyols having 3 to 6 hydroxyl groups and having 3 to 12 carbon atoms and in particular those selected from the group consisting of triethylolpropane, glycerol, pentaerythritol, diglycerin, dipentaerythritol, sorbitol, glucose, methylglucoside and sucrose.
  • the aliphatic, saturated, alpha.omega-diols having 2 to 25 carbon atoms are very particularly preferred.
  • telomerization The reaction of the polyols with conjugated dienes in the presence of palladium catalysts, phosphines and optionally water and aliphatic alcohols is the telomerization known per se, which is described in detail in international application WO 90/13531.
  • free hydroxyl groups of the polyols are etherified by the assembly of 2 molecules of conjugated dienes to form an alkadienyl group. Accordingly, the molar ratio between the hydroxyl groups of the polyols and the conjugated dienes is decisive for the number of alkadienyl groups which the polyols carry etherified.
  • the polyols should now only be partially reacted with the conjugated dienes, as a result of which polyol partial ethers are formed.
  • the hydroxyl groups of the polyols are only partially etherified with alkadienyl groups and at least one hydroxyl group remains free.
  • preferably only one hydroxyl group of the polyols is etherified by reaction with conjugated dienes to form an alkadienyl group. Since the telerization according to process step a) involves equilibrium reactions, it can happen that polyols completely etherified with alkadienyl groups are also obtained.
  • telomerization products of 1,6-hexanediol and butadiene with hydroxyl numbers in the range from 230 to 250 and / or the telomerization products of glycerol and butadiene with hydroxyl numbers in the range from 172 to 560 are suitable.
  • the reaction between the polyols and the conjugated dienes is carried out in such proportions that 1 to 10 mol conjugated dienes, preferably 2 to 4 and in particular 2 to 3 mol conjugated dienes, are used per hydroxyl group to be etherified.
  • the conjugated dienes are to be understood as aliphatic and / or cycloaliphatic hydrocarbon compounds which have 4 to 20 C atoms and two double bonds which are conjugated to one another.
  • Suitable dienes are 1,3-butadiene, dimethylbutadiene, isoprene, 1,3-pentadiene, 1,3- or 2,4-hexadiene and 1,3-cyclooctadiene.
  • 1,3-Butadiene is particularly preferred as the conjugated diene.
  • the telomerization in process step a) expediently takes place in the presence of 0.001 to 1% by weight, based on the polyol, of palladium catalysts, palladium preferably being in the oxidation state 0 and / or 2 in the form of a compound.
  • Suitable palladium catalysts are palladium (II) acetylacetonate, bis (allyl) palladium (II), bis (cyclooctadiene) palladium (II), palladium (II) chloride, palladium (II) acetate and / or allyl palladium (II) chloride.
  • the telomerization is expediently carried out in the presence of 0.001 to 1% by weight, based on the polyol, of palladium (II) acetylacetonate.
  • Alkylated and / or arylated phosphines in combination with the palladium catalysts are present as cocatalysts during the telomerization.
  • the reaction is advantageously carried out in the presence of 0.001 to 1% by weight, based on polyol, and in particular in the presence of 0.001 to 1% by weight of triphenylphosphine. If desired, the reaction can also take place in the presence of aliphatic monoalcohols and water.
  • Secondary and / or tertiary alcohols and in particular isopropanol are preferably used as monoalcohols.
  • the amounts of monoalcohols can be between 10 and 50% by weight, based on the reaction mixture.
  • the amount of water in the molar ratio to polyols can be in the range from 1: 1 to 10: 1.
  • the reaction is expediently carried out at temperatures in the range from 40 to 100 ° C., preferably 60 to 80 ° C.
  • the free hydroxyl groups of the polyol partial ethers are esterified with di-, tricarboxylic acids and / or their derivatives.
  • di-, tricarboxylic acids and / or their derivatives Unsaturated aliphatic and / or cycloaliphatic di- and / or tricarboxylic acids with 4 to 10 carbon atoms such as maleic acid, fumaric acid, tetrahydrophthalic acid and / or substituted tetrahydrophthalic acids are preferred.
  • the polyol partial ethers with the free hydroxyl groups are in a molar ratio with the di- and / or tricarboxylic acids of hydroxyl group: carboxylic acid group from 1: 2 to 1: 3, that is, polyol ether partial esters with free carboxyl groups are formed.
  • the free carboxyl groups of the polyol ether partial esters are then reacted with such amounts of polyols with 2 to 6 hydroxyl groups that oligoesters containing practically completely esterified alkadienyl groups are formed.
  • esterification of the free carboxyl groups of the polyether partial esters preference is given to using polyols having 3 to 6 hydroxyl groups and having 3 to 12 C atoms, which were already described in process step a) during the telomerization.
  • polyols with 3 hydroxyl groups such as glycerol and trimethylolpropane and / or polyols with 4 hydroxyl groups such as pentaerythritol, diglycerols and sorbitol and / or polyols with 6 hydroxyl groups such as dipentaerythritol are particularly suitable.
  • the term practically complete esterification is understood to mean that the esterification is carried out so long that the oligoesters containing alkadienyl groups on statistical average no longer carry any free hydroxyl group in the molecule. Complete esterification is of course desirable, but in practice this is often difficult to achieve, so low residual acid numbers are permitted.
  • Amounts of polyols are preferably used in process step c) such that a molar ratio of hydroxyl group: carboxyl group of 1: 1 to 1: 0.8 is present.
  • the present invention further provides a process for the preparation of oligoesters containing alkadienyl groups, characterized in that a) partially conjugated polyols with 2 to 6 hydroxyl groups in the presence of palladium catalysts, phosphines and optionally water and aliphatic monoalkanols Serves and b) the free hydroxyl groups of the polyol partial ethers with di-, tricarboxylic acids and / or their derivatives in a molar ratio of hydroxyl group: carboxylic acid group of 1: 2 to 1: 3 and c) the free carboxyl groups of the polyol ether partial esters are almost completely esterified with polyols having 2 to 6 hydroxyl groups.
  • Another object of the present invention is the use of the oligoesters of the type described containing alkadienyl groups as air-drying paint binders.
  • the unsaturated oligoesters according to the invention are preferably used for the production of air-drying alkyd resin lacquers.
  • they are mixed with the usual auxiliaries such as siccatives, fillers, pigments, skin-preventing agents, pigment dispersants and the like.
  • organic solvents can of course also be used.
  • the reaction mixture thus obtained has a hydroxyl number of 293.05 and an iodine number (determined according to DGF CV, 11 b) of 249.3 and an acid number of 0.3.
  • a clear lacquer was produced from 50 g of the polyester prepared according to Example II, 0.25 g of cobalt naphtenate with 6% by weight of cobalt, 1.25 g of zirconium naphtenate with a zirconium content of 6% by weight and 1.0 g of methyl - ethyl ketone oxime.
  • a film of this clear lacquer with a gap width of 100 ⁇ was drawn on a glass plate and the pendulum hardness was measured according to König (DIN 53157).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

Sont décrits des oligoesters renfermant des groupes alcadiényléther utiles comme liants de peinture séchant à l'air. Leur fabrication s'effectue (A) par la réaction de polyols avec des diènes conjugués en présence de catalyseurs au palladium, de phosphines et éventuellement d'eau et de monoalcools aliphatiques; (B) par la réaction de groupes hydroxyles libres des éthers partiels de polyol avec des acides polycarboxyliques ou leurs dérivés; et (C) par l'estérification pratiquement complète des groupes carboxyles du produit de l'étape B avec des polyols.
PCT/EP1992/001964 1991-09-05 1992-08-26 Oligoesters insatures contenant des groupes alcadienyles WO1993005095A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4129527.7 1991-09-05
DE19914129527 DE4129527A1 (de) 1991-09-05 1991-09-05 Alkadienylgruppen enthaltende ungesaettigte oligoester

Publications (1)

Publication Number Publication Date
WO1993005095A1 true WO1993005095A1 (fr) 1993-03-18

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PCT/EP1992/001964 WO1993005095A1 (fr) 1991-09-05 1992-08-26 Oligoesters insatures contenant des groupes alcadienyles

Country Status (2)

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DE (1) DE4129527A1 (fr)
WO (1) WO1993005095A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11506854B2 (en) 2013-02-05 2022-11-22 Commscope Technologies Llc Slidable telecommunications tray with cable slack management

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0167962A2 (fr) * 1984-07-09 1986-01-15 Henkel Kommanditgesellschaft auf Aktien Polyesters insaturés

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0167962A2 (fr) * 1984-07-09 1986-01-15 Henkel Kommanditgesellschaft auf Aktien Polyesters insaturés

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Chemical Abstracts, Band 79, Nr. 24, 17. Dezember 1973, (Columbus, Ohio, US), siehe Zusammenfassung Nr. 137968x, & JP,A,47045838 (MITSUBISHI CHEMICAL INDUSTRIES CO., LTD) 18. November 1972, siehe Zusammenfassung *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11506854B2 (en) 2013-02-05 2022-11-22 Commscope Technologies Llc Slidable telecommunications tray with cable slack management

Also Published As

Publication number Publication date
DE4129527A1 (de) 1993-03-11

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