EP0000941B1 - Résines de polyesters insaturés durcissables, peu volatiles et susceptibles d'être laminées - Google Patents

Résines de polyesters insaturés durcissables, peu volatiles et susceptibles d'être laminées Download PDF

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Publication number
EP0000941B1
EP0000941B1 EP78100727A EP78100727A EP0000941B1 EP 0000941 B1 EP0000941 B1 EP 0000941B1 EP 78100727 A EP78100727 A EP 78100727A EP 78100727 A EP78100727 A EP 78100727A EP 0000941 B1 EP0000941 B1 EP 0000941B1
Authority
EP
European Patent Office
Prior art keywords
acid
unsaturated
polyester resins
paraffin
unsaturated polyester
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.)
Expired
Application number
EP78100727A
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German (de)
English (en)
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EP0000941A1 (fr
Inventor
Walter Gramlich
Wolfgang Dr. Koser
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.)
BASF SE
Original Assignee
BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0000941A1 publication Critical patent/EP0000941A1/fr
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Classifications

    • 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
    • C08L67/06—Unsaturated polyesters
    • 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
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
    • 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
    • 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

Definitions

  • the invention relates to low-evaporation, curable in the presence of conventional polymerization initiators, highly overlaminable unsaturated polyester resins composed of an ethylenically unsaturated polyester, a copolymerizable, ethylenically unsaturated monomeric compound and optionally further structural components and auxiliaries which contain paraffin mixtures to reduce monomer evaporation and to improve the ability to be laminated.
  • Molding and molding compounds made from unsaturated polyester resins usually contain, apart from unsaturated polyesters and monomeric vinyl compounds copolymerizable therewith, polymerization initiators and inhibitors, and often powdery fillers and glass fibers or flat glass fiber structures.
  • Low-shrinkable molding compositions also contain up to 30 percent by weight of thermoplastic polymers.
  • small amounts of finely divided alkaline earth oxides are added to the polyester molding compounds before they are mixed with fillers. Thickening takes place due to salt formation with the carboxyl end groups of the unsaturated polyester and complex formation.
  • DE-OS 1 956376 it is proposed to apply a wax-like substance, its dispersion or solution in a thin layer to a paint polyester resin shortly before curing, gasoline hydrocarbons and aromatics being mentioned as solvents for these barrier layer formers, which are preferably sprayed on.
  • a disadvantage of this process is that the barrier layer formers are dissolved in large quantities of solvents - usually 1% by weight solutions of the wax-like substances are used - and the solutions have to be applied to the films of the unsaturated paint polyester resins in a separate operation.
  • polyester resin If only one layer of polyester resin is cured in one operation, such as when painting, then you can achieve as low a styrene loss as possible by adding paraffin. Paraffins have the disadvantage, however, that they also act as release agents. This means that polyester resin layers cured in the presence of paraffins have a cloudy, inert surface. If further unsaturated polyester resin is applied to such a surface and cured, an inadequate bond is obtained and the two cured resin layers can be separated relatively easily from one another. The better the substrate is hardened, the worse the adhesion.
  • DE-AS 1 156 230 describes curable molding compositions which contain unsaturated polyesters, polymerizable compounds, customary auxiliaries and a mixture of waxes. This mixture contains waxes with a melting point above 75 ° C and those with a melting point below 75 ° C. None of the waxes mentioned in the description melt below 50 ° C. The overlaminability of unsaturated polyester resins cannot be improved with such wax mixtures.
  • the laminability of unsaturated polyester resins can be increased by adding water-in-oil or oil-in-water emulsifiers with an HBL of 1.5 to 15 or by Addition of liquid alkanes or their mixtures to waxy substances can be improved.
  • a disadvantage of the two methods is that the adhesion between two laminate layers is still not completely satisfactory and that the polyester resins can only be produced with insufficient reproducibility.
  • the object of the present invention was to develop unsaturated curable polyester resins, in which the ethylenically un did not or only to a minor extent evaporate saturated monomers during processing without impairing overlaminability.
  • polyester resins according to the invention surprisingly have the advantage that the release agent effect is eliminated by the special composition of the paraffin mixture without increasing the monomer evaporation.
  • the low-evaporation, easily over-aminable, curable, unsaturated polyester resins according to the invention are prepared in a manner known per se by mixing the paraffin mixture with the polyester resin components (a) - (d). It has proven to be expedient to dissolve the paraffin mixture in an ethylenically unsaturated monomer, preferably styrene, and to meter the monomer solution obtained into the polyester resin.
  • Suitable polyhydric, in particular dihydric, optionally unsaturated alcohols are the customary, in particular acyclic, cyclic groups and also alkanediols and oxalkanediols containing both types of groups, such as Ethylene glycol, propylene glycol 1,2, propanediol 1,3, butylene glycol 1,3, butanediol 1,4, hexanediol 1,6 2,2-dimethylene propanediol 1,3, diethylene glycol, triethylene glycol, polyethylene glycol, cyclohexanediol-1 , 2, 2,2-bis (p-hydroxycyclohexyl) propane, 1,4-bismethylolcyclohexane,, vinyl glycol,. Trimethylolpropane monoallyl ether or 1,4-butenediol.
  • one-, three- or higher-hydric alcohols such as ethylhexanol, fatty alcohols, benzyl alcohols, 1,2-di (allyl l oxy) propanol (-3), glycerol, pentaerythritol or trimethylol propane, are co-used in minor amounts.
  • the polyhydric, especially dihydric alcohols are generally reacted in stoichiometric or approximately stoichiometric amounts with polybasic, in particular dibasic carboxylic acids or their condensable derivatives.
  • Suitable carboxylic acids or their derivatives are dibasic olefinically unsaturated, preferably, a, ⁇ -olefinically unsaturated carboxylic acids, e.g. Maleic acid, fumaric acid, iltaconic acid, citraconic acid, methylene glutaric acid and mesaconic acid or their esters or preferably their anhydrides.
  • Other modifying dibasic, unsaturated and / or saturated and aromatic carboxylic acids or derivatives such as e.g.
  • Succinic acid glutaric acid, a-methylglutaric acid, adipic acid, sebacic acid, pimelic acid, phthalic anhydride, o-phthalic acid, isophthalic acid, terephthalic acid, dihydrophthalic acid, tetrahydrophthalic acid, tetrachlorophthalic acid, 3,6-endomethylene-1,2,3-methylene chloride, tetrachlorophthalic acid, 3,6-endomethylene-1,2,3-methylene chloride, , be condensed, further mono-, tri- and higher basic carboxylic acids, such as Ethylhexanoic acid, fatty acids, methacrylic acid, propionic acid, benzoic acid, 1,2,4-benzenetricarboxylic acid or 1,2,4,5-benzenetetracarboxylic acid.
  • the unsaturated polyesters are generally prepared from their components by melt condensation or condensation under azeotropic conditions. Amorphous and optionally crystallizable unsaturated polyesters can be used for the process according to the invention.
  • the unsaturated polyesters have an acid number of 10 to 100, preferably 25 to 60, and an average molecular weight of about 600 to 4,000, preferably 800 to 3,000.
  • thickeners are: alkaline earth metal oxides or hydroxides, such as calcium oxide, calcium hydroxide, magnesium hydroxide and preferably magnesium oxide, and mixtures of these oxides and / or hydroxides.
  • the alkaline earth oxides can also be partially replaced by zinc oxide.
  • the content of thickeners in the polyester resins is generally 0.5 to 5, preferably 1 to 3 percent by weight, based on the mixture of components (a) and (b).
  • the usual inhibitors come into question, e.g. Hydroquinone, tert-butyl catechol, p-benzoquinone, chloranil, nitrobenzenes, such as m-dinitrobenzene, thiodiphenylamine or salts of N-nitroso-N-cyclohexylhydroxylamine and mixtures thereof.
  • the inhibitors are generally present in the polyester resins in an amount of 0.005 to 0.2, preferably 0.01 to 0.1 percent by weight, based on components a) and b).
  • Suitable fillers are e.g. Usual fine powdery or granular inorganic or organic fillers, such as chalk, kaolin, quartz powder, dolomite, heavy spar, metal powder, cement, talc, diatomaceous earth, wood powder, wood chips, pigments and the like.
  • Suitable reinforcing agents are inorganic or organic fibers or flat structures, optionally woven therefrom, e.g. those made of glass, asbestos, cellulose and synthetic organic high polymers, such as polyesters and polyamides.
  • the fillers and reinforcing materials can be used in amounts of 5 to 200 percent by weight, based on components a) and b).
  • inert solvents include ketones, esters, hydrocarbons in amounts of up to 100 percent by weight, based on component a).
  • the unsaturated polyester resins can be pre-accelerated.
  • Possible polymerization accelerators are, for example, heavy metal salts such as cobalt and vanadium salts, tertiary aromatic amines, 1,3-diketone compounds such as acetylacetone, ⁇ -keto esters such as ethyl acetoacetate and ⁇ -keto amides such as ethyl acetoacetic acid and combinations of these compounds.
  • Contrast-reducing additives that can also be used are, for example, thermoplastic polymers such as polystyrene, styrene copolymers and polyvinyl acetate and / or poly (meth) acrylates.
  • Thermoplastic polymers which contain carboxyl groups in amounts of 1 to 5 percent by weight, based on the total weight, bound in the polymer chain are preferably used.
  • the shrinkage-reducing additives are usually used in amounts of 1 to 30, preferably 8 to 15 percent by weight, based on the weight of components (a) and (b).
  • the individual components (a) to (d) can be mixed and the paraffin mixtures mixed in using conventional mixing units, for example with an agitator or a roller mill.
  • Unsaturated polyester resins produced in this way can be cured with polymerization initiators, such as peroxides, azo compounds, etc., possibly in the presence of polymerization accelerators or co-accelerators or promoters, or by irradiation, for example with light, by UV radiation or accelerated electron beams, possibly in the presence of light initiators and sensitizers .
  • the unsaturated polyester resins according to the invention are suitable for the production of coatings, fine layers and molded materials with and without reinforcing materials and optionally fillers.
  • Polyester resin A is a 66% styrenic solution of an unsaturated polyester with an acid number of 50, stabilized with 0.01% hydroquinone, which by melt condensation at 190 to 210 ° C in the presence of an inert gas atmosphere of maleic acid, o-phthalic acid and 1,2-propylene glycol was produced in a molar ratio of 1: 2: 3. The degree of isomerization of maleic acid - fumaric acid was 95%.
  • Polyester resin B is produced analogously to the specifications of polyester resin A, but the starting components maleic acid, o-phthalic acid and 1,2-propylene glycol are condensed in a molar ratio of 1: 0.5: 1.5 to produce the unsaturated polyester.
  • the degree of isomerization was 95%.
  • Polyester resin C is produced analogously to the specifications of polyester resin A, but the starting components maleic acid, isophthalic acid and neopentyl glycol are condensed in a molar ratio of 1: 1: 2 to produce the unsaturated polyester.
  • the degree of isomerization was 90%.
  • Polyester resin D is produced analogously to the specifications of polyester resin A, but the starting components maleic acid, tetrahydrophthalic acid, phthalic acid, diethylene glycol, propylene glycol are condensed in a molar ratio of 1: 0.5: 0.5: 1.0: 1.0 to produce the unsaturated polyester.
  • the degree of isomerization was 95%.
  • Polyester resin E is produced analogously to the specifications for polyester resin A, but the starting components maleic acid, isophthalic acid, diethylene glycol, propylene glycol are condensed in a molar ratio of 1: 1: 1: 1 to produce the unsaturated polyester. The degree of isomerization was 95%.
  • polyester resin is distributed so that a uniform 2 mm thick layer is created.
  • the weight loss is determined within one hour at 23 ⁇ 1 ° C.
  • a 3 mm thick glass fiber reinforced unsaturated polyester resin layer consisting of 3 layers of glass fiber mat is made using 1% methyl ethyl ketone peroxide (50% in dimethyl phthalate) and 0.2 to 0.5% 1% cobalt octoate solution in styrene (1% cobalt content) Room temperature hardened from 23 ⁇ 1 ° C.
  • polyester resins A and B were mixed with paraffins, whose softening range was between 32 ° C and 96 ° C.
  • paraffins used and the amounts added in percent by weight, based on the weight of polyester resin are summarized in the following table.
  • the comparative tests a, b, d and e which are not produced according to the invention have good layer adhesion, but high styrene evaporation and the comparison tests c and f have low styrene evaporation and poor layer adhesion.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Claims (1)

  1. Résines durcissables de polyesters insaturés, contenant
    a) au moins un polyester copolymérisable insaturé éthyléniquement,
    b) au moins un composé monomère copolymérisable insaturé éthyléniquement,
    c) des substances cireuses et, le cas échéant,
    d) d'autres éléments constitutifs et agents auxiliaires usuels caractérisées en ce qu'elles contiennent, en tant que substances cireuses, un mélange de paraffines qui se compose de 0,01 à 0,5 % en poids d'au moins une paraffine dont le point de fusion se situe entre 25°C et 50°C et de 0,01 à 0,5 % en poids d'une paraffine dont le point de fusion est compris entre 51 °C et 100°C, ces pourcentages se rapportant au poids total des éléments a) et b).
EP78100727A 1977-08-29 1978-08-23 Résines de polyesters insaturés durcissables, peu volatiles et susceptibles d'être laminées Expired EP0000941B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19772738805 DE2738805A1 (de) 1977-08-29 1977-08-29 Verdunstungsarme, gut ueberlaminierbare, haertbare ungesaettigte polyesterharze
DE2738805 1977-08-29

Publications (2)

Publication Number Publication Date
EP0000941A1 EP0000941A1 (fr) 1979-03-07
EP0000941B1 true EP0000941B1 (fr) 1980-07-23

Family

ID=6017531

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100727A Expired EP0000941B1 (fr) 1977-08-29 1978-08-23 Résines de polyesters insaturés durcissables, peu volatiles et susceptibles d'être laminées

Country Status (4)

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EP (1) EP0000941B1 (fr)
DE (2) DE2738805A1 (fr)
DK (1) DK378278A (fr)
NO (1) NO782921L (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL125545B1 (en) * 1980-02-11 1983-05-31 Inst Chemii Przemyslowej Method of manufacture of unsaturated polyester resins of diminished monomer vaporization
DE3933656A1 (de) * 1989-10-09 1991-04-11 Basf Ag Verdunstungsarme polyesterharze
US5378743A (en) * 1989-11-08 1995-01-03 The Dow Chemical Company Stable low styrene emission vinyl ester and unsaturated polyester resin composition
DK195190D0 (da) * 1990-08-16 1990-08-16 Keld Jakobsen Slidstaerk maling
US5206077A (en) * 1991-11-25 1993-04-27 The Dow Chemical Company Low vaporizable ethylenically unsaturated monomer emission vinyl ester and polyester resin compositions

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1007449A (en) * 1961-07-27 1965-10-13 British Titan Products Titanium dioxide pigment
DE1592956A1 (de) * 1966-06-27 1971-02-11 Du Pont Verfahren zur Herstellung von ueberzogenen Titandioxyd-Pigmenten
DE2948334A1 (de) * 1978-11-30 1980-06-19 Du Pont Lichtbestaendige titandioxidpigmentzusammensetzung
DE2223524C2 (fr) * 1972-05-13 1987-01-02 Kronos Titan-Gmbh, 5090 Leverkusen, De

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE538294A (fr) * 1953-10-09
DE1156230B (de) * 1961-01-02 1963-10-24 Jaeger Fabrik Chem Ernst Verfahren zum Herstellen von Formteilen oder UEberzuegen aus Polyester-Formmassen, die Wachse enthalten
DE2554930A1 (de) * 1975-12-06 1977-06-16 Basf Ag Verdunstungsarme, haertbare, ungesaettigte polyesterharze

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1007449A (en) * 1961-07-27 1965-10-13 British Titan Products Titanium dioxide pigment
DE1592956A1 (de) * 1966-06-27 1971-02-11 Du Pont Verfahren zur Herstellung von ueberzogenen Titandioxyd-Pigmenten
DE2223524C2 (fr) * 1972-05-13 1987-01-02 Kronos Titan-Gmbh, 5090 Leverkusen, De
DE2948334A1 (de) * 1978-11-30 1980-06-19 Du Pont Lichtbestaendige titandioxidpigmentzusammensetzung

Also Published As

Publication number Publication date
NO782921L (no) 1979-03-01
EP0000941A1 (fr) 1979-03-07
DK378278A (da) 1979-03-01
DE2738805A1 (de) 1979-03-08
DE2860076D1 (en) 1980-11-13

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