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
  • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/10—Metal compounds
• • 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
  • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/08—Polyesters modified with higher fatty oils or their acids, or with resins or resin acids

Definitions

• This disclosure relates to catalysts for the auto-oxidative drying of polymers, in particular for polymers used in paints or inks, based on unsaturated fatty acids, mostly from vegetal origin
• Cobalt carboxylates are hitherto the principal and unavoidable constituents, at least if drying has to take place at room-temperature and within a reasonable time
• cobalt carboxylates, and in particular of cobalt octoates has indeed been widely described, and is common practice throughout the paint industry (e g J H Bieleman, in Additives for Coatings, Ed J H Bieleman, Wiley/VCH, Wemheim, 2000, p 202)
• a compound for use as a polymerisation agent in coatings, characterized in that it comprises a cobalt-bearing alkyd polymer, said polymer having a cobalt content of 05 to 6% by weight, a mean molecular weight of more than 3000, and compnsing cobalt carboxylate sequences
• a cobalt-bearing alkyd polymer said polymer having a cobalt content of 05 to 6% by weight, a mean molecular weight of more than 3000, and compnsing cobalt carboxylate sequences
• the alkyd polymer has a preferred cobalt content of 1 to 2 5% by weight and/or a mean molecular weight of more than 4 000
• the alkyd polymer is preferably unsaturated It is furthermore useful to avoid the presence of P, N and S in the polymer
• a further embodiment concerns a coating formulation comprising a cobalt-free polymer compound and the above-described cobalt-bearing compound
• a coating formulation comprising a cobalt-free polymer compound and the above-described cobalt-bearing compound
• Such a formulation preferably contains 0 02 to 0 10 % cobalt by weight on binder
• a first process comprises reacting a cobalt compound, preferably cobalt hydroxide, with a carboxylic acid functional polymer having a mean molecular weight of more than 2000
• the acid functional polymer is synthesised in a preliminary step according to a known process, typically starting from unsaturated fatty acids, polyols or polyacids, without limitation to the nature and amount of other co- reactants
• This polymer forming reaction is carried out at temperatures of about 200 to 250 0 C, with removal of reaction water and in presence of a suitable solvent, the latter also helping in the removal of reaction water
• the product is diluted to a workable viscosity with a solvent that is compatible with the application of the product
• a second process comprises reacting a sub-stoichiometric amount of a mineral cobalt compound, preferably cobalt hydroxide, with an unsaturated polymeric fatty acid whereafter further polymerisation is performed with polyols until a mean molecular weight of more than 3000 is obtained This further poly
• any polymer "for use as a polymerisation agent” has implicitly to be soluble, or even to be completely soluble, in the targeted paints or inks, which are typically based on organic compounds, in particular on oils such as vegetable oils Moreover, the cobalt carboxylate sequences, although being an integral part of the polymer chain, impart the full catalytic effect of cobalt to the polymer The water-solubility of cobalt is however greatly suppressed.
• a relationship can be established between the mean molecular weight and the viscosity as measured at a given solvent dilution, and temperature However, in the present case, the molecular weight was determined with GPC (gel permeation chromatography)
• GPC gel permeation chromatography
• a GPC model PL- GPC-50 from Polymer Laboratories® was used, with polystyrene gel column and standard Rl- detector
• a calibration curve was defined by injecting polystyrene standards having a mole
• the elements P, N, and S are generally to be avoided in the considered catalysts, as they bear a negative effect on the drying capacity of the paints or inks They may moreover generate noxious combustion gasses when the coated articles or materials are recycled
• the compounds described in this invention offer a catalytic activity similar to the products used in the actual state of art They are however significantly less toxic, thanks to their low water solubility Indeed, as the toxicity of cobalt compounds depends on the presence of the cobalt in its ionic form in e g lung tissue, the water solubility of the used compound is of prime importance
• the cobalt content of the polymerizing agent should exceed 0 5%, and preferably 1 % by weight Otherwise, too high relative amounts of this agent could be needed in the coating, leading to a potential degradation of its characteristics
• Cobalt contents exceeding 6% are on the other hand difficult to reconcile with a mean molecular weight of more than 3000 However, cobalt contents exceeding 2 5% could result in the qualification of the product as toxic or hazardous, even
• the mean molecular weight of at least 3000 is dictated by the need to limit the solubility of the cobalt Such relatively long polymers are indeed sufficiently hydrophobic to ensure a low solubility in water
• a mean molecular weight of more than 4000 is however preferred
• the preferred upper limit for the mean molecular weight is about 30000 Heavier molecules may be insoluble in the coating formulation, which would render them inappropriate for the envisaged application
• a mean molecular weight of less than 8000 is therefore preferred
• ExxsolTM D 40 which is a commercial aliphatic petroleum distillate with maximum 0 1 % aromatics and a flashpoint of 40 °C
• a product with a cobalt content of about 2 3 wt % is obtained, that is 3 3 % on the pure polymer
• the mean molecular weight of the polymer is between about 4000 and 6000
• Example 1 in a glass vessel are mixed 67 5 parts of the mixture obtained in Example 1 , first step, before thinning, with 12 5 parts of freshly precipitated cobalt abietate, - this mixture is kept at 160 0 C for one hour under nitrogen blanket,
• reaction vessel is switched to pressure setting and 20 parts of dicyclopentadiene is added slowly under total reflux,
• Valires ® RE570 06 which is a typical alkyd resin used in solvent borne air drying paints
• the mixing ratios are chosen so as to obtain a varnish with a metal content of 0 05 wt % Co, 0 2 wt % Ca and 0 1 wt % Zr, calculated on resin solids Valirex ® Zr 12 and Ca 5 were used as Ca and Zr sources respectively
• this varnish composition was also prepared using standard cobalt octoate drier instead of the invented cobalt-bearing resin
• Synthetic alveolar fluid was prepared dissolving 0 9 g sodium chloride in distilled water
• Cobalt concentrations of well below 50 mg/l are obtained This is an excellent result, as a figure of less than 100 mg/l is already considered as most adequate This contrasts with the 880 mg/l obtained using cobalt octoate (comparative Example) The latter figure corresponds in fact with a nearly complete dissolution of the cobalt contained in the octoate
• Example 6a The same synthesis as under Example 6a is conducted, but with 7 5% additional carboxylic acid as neodeca ⁇ oic acid (VersaticTM 10) compared to the total weight of mono- and polyacids This acid is not expected to participate to the ethe ⁇ fication reactions
• Example 6c The same synthesis as under Example 6a is conducted, but with 10% additional carboxylic acid
• aqueous solubility of cobalt from the products obtained in Examples 6a to 6d was determined using the OECD 105 guideline for testing of chemical substances The same procedure is used as in Example 5, however, distilled water was used instead of the ssynthetic alveolar fluid The aqueous phase was analyzed for cobalt using atomic absorption spectrometry
• Example 7 To the cobalt-bearing polymer as made in Example 6a, an amount of 20 wt% of VersaticTM was added and thoroughly mixed The product was then submitted to the same leaching test as in Example 7

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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)
• General Chemical & Material Sciences (AREA)
• Wood Science & Technology (AREA)
• Materials Engineering (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Paints Or Removers (AREA)
• Polyesters Or Polycarbonates (AREA)
• Polyurethanes Or Polyureas (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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