EP0000371B1 - Dispersions de poudres dans des polyesters insaturés ne contenant pas de monomère et leur utilisation comme véhicules dans les polyesters insaturés réticulables - Google Patents

Dispersions de poudres dans des polyesters insaturés ne contenant pas de monomère et leur utilisation comme véhicules dans les polyesters insaturés réticulables Download PDF

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Publication number
EP0000371B1
EP0000371B1 EP78100307A EP78100307A EP0000371B1 EP 0000371 B1 EP0000371 B1 EP 0000371B1 EP 78100307 A EP78100307 A EP 78100307A EP 78100307 A EP78100307 A EP 78100307A EP 0000371 B1 EP0000371 B1 EP 0000371B1
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EP
European Patent Office
Prior art keywords
acid
polyester
unsaturated polyesters
und
parts
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
EP78100307A
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German (de)
English (en)
Other versions
EP0000371A1 (fr
Inventor
Hansjochen Dr. Schulz-Walz
Bernhard Dr. Hess
Johannes Beckers
Werner Dr. Klöker
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/06—Unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers

Definitions

  • the present invention relates to dispersions of powdery substances in unsaturated polyesters which are free from copolymerizable monomers. These dispersions according to the invention are an excellent form in which thickeners, pigments, fillers and other solid auxiliaries can be mixed in finely divided form with unsaturated polyester resins.
  • DT-OS 2 223 989 discloses mixtures of inorganic thickeners, that is to say preferably oxides and hydroxides of the elements of the 2nd and 3rd main groups (groups 11 a and III a) of the periodic table, and a polyester with acid numbers from 5 to 50 and hydroxyl numbers known from 100 to 300.
  • this polyester has a relatively low viscosity, so that it is suitable for absorbing considerable amounts of inorganic thickeners and can serve as the basis for a thickening paste. Since its viscosity hardly increases when thickening agents are added, the thickening pastes made from it can be stored for a long time.
  • the pigments have hitherto also been rubbed into the polyester resin used, while other, smaller amounts of solid additives, such as, for example, thickeners, release agents or thixotropic agents, are added as powders.
  • solid additives such as, for example, thickeners, release agents or thixotropic agents
  • Such pastes are often combined in one or two mixed pastes, since it is easier to precisely dose larger amounts of a paste than small amounts of different pastes.
  • These technical requirements mean that the amount of paste base supplied is greater than previously customary. Quantities of 10-15 parts by weight per 100 parts by weight of the polyester resin used are often required. Because of this large amount, customary liquid plasticizers are eliminated, except for the reasons already mentioned, primarily because they do not polymerize when the polyester resin is cured and, as a result, tend to exude. In addition, the mechanical, thermal and electrical properties of the hardening products deteriorate considerably.
  • the laminate In the case of molded parts which are produced by one of the customary lamination processes, for example in boats, the laminate is generally covered with a colored fine layer. If articles with frequently changing colors are produced in this way, or if colors have to be tinted by adding small amounts of other pigments, it is advantageous to use pigment pastes. Plasticizers or styrene-containing polyesters are not suitable as a paste base for the reasons already described. Even polyester in accordance with DT-OS 2223 989 cannot be used, since they impair the water absorption of a fine layer in such a way that bubbles and cracks occur after the laminate has been briefly stored in water.
  • Another object of the invention is the use of the dispersions according to the invention as auxiliaries for (f, ⁇ -ethylenically unsaturated polyester resins.
  • ⁇ , ⁇ -ethylenically unsaturated polyesters are the usual condensation products of at least one ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid with generally 4 or 5 carbon atoms or their ester-forming derivatives, if appropriate in a mixture with up to 100 mol% , based on the unsaturated acid component, at least one aliphatic saturated with 4-10 C atoms or an aromatic or cycloaliphatic dicarboxylic acid with 8-10 C atoms or their ester-forming derivatives with at least one polyhydroxy compound, in particular dihydroxy compound, with 2-8 C atoms - So polyester, as described in J. Björksen et al, "Polyesters and their Applicants", Reinhold Publishing Corp., New York 1956.
  • Examples of preferred unsaturated dicarboxylic acids or their derivatives are maleic anhydride and fumaric acid. However, mesaconic acid, citraconic acid, itaconic acid or chloromaleic acid can also be used, for example.
  • Examples of the aliphatic saturated, aromatic and cycloaliphatic dicarboxylic acids or their derivatives to be used are phthalic acid or phthalic anhydride, isophthalic acid, terephthalic acid, hexa- or tetrahydrophthalic acid or their anhydrides, endomethylene tetrahydrophthalic acid or their anhydride and succinic acid, succinic acid or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succ
  • hexachlorodomethylene tetrahydrophthalic acid hetic acid
  • tetrachlorophthalic acid tetrabromophthalic acid
  • Polyesters to be used preferably contain maleic acid residues which can be replaced by phthalic acid or isophthalic acid residues up to 25 mol /%.
  • Ethylene glycol propanediol-1,2, propanediol - 1,3, diethylene glycol, dipropylene glycol, butanediol-1,2-1,3, -1,4, -2,3, neopentyl glycol, hexanediol-1,6, 2,2-bis (4-hydroxycyclohexyl) propane, bis-oxyalkylated bisphenol A, perhydrobisphenol and others can be used.
  • Oligomers of ethylene oxide, propylene oxide and butene oxide in particular diethylene glycol, triethylene glycol, tetraethylene glycol and dipropylene glycol, tripropylene glycol and corresponding oligomers of the different butene oxides are preferably used.
  • Suitable monohydric alcohols are aliphatic, cycloaliphatic, aromatic and alkylaromatic alcohols with 1-18 C atoms, e.g. Methanol, ethanol, n- or isopropanol, n-, iso- or tert-butanol, the pentanols, hexanols, heptanols, octanols such as, for example, ⁇ -ethylhexanoI, up to long-chain, such as, for example, stearyl alcohol.
  • An example of aromatic, monohydric alcohols is benzyl alcohol. Cyclohexanol may be mentioned as an example of cycloaliphatic, monohydric alcohols. Unsaturated monoalcohols, such as allyl alcohol or croton alcohol, can also be used.
  • the number average molecular weights of the polyester B should be between 250 and 3000 (measured by vapor pressure osmometry in dioxane and acetone, the lower is considered correct if the values differ), the viscosities of the polyester B between 200 and 1000 cP.
  • Powdery substances A include inorganic or organic pigments, thixotropic agents, inorganic thickeners, fillers, etc.
  • magnesium hydroxide In addition to magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, zinc oxide, aluminates, titanates, aluminum oxides and their mixed oxides and mixtures of the products mentioned, and Portland cement are also suitable as inorganic thickeners.
  • the dispersions according to the invention can contain further additives, e.g. contain those that affect sedimentation and thixotropy.
  • the thixotropy and sedimentation mainly affect inorganic thixotropic agents, such as highly disperse silicas, products with an asbestos-like SiHcat structure, bentones or organic thixotropic agents, such as hydrogenated castor oil fatty acids, preferably organic compounds containing CONH or OCONH groups.
  • organic thixotropic agents which are preferably to be used, can be mixed into the dispersions according to the invention or else incorporated into the polyester B.
  • the thixotropic agents can be admixed simply in the preparation of the dispersion according to the invention, but if desired also by condensing with the starting components of the unsaturated polyester B during the preparation thereof or condensed onto the latter after the preparation thereof.
  • thixotropic polyesters are e.g. Reaction products which are made from unsaturated polyesters containing hydroxyl groups and have a hydroxyl number of 10-80 and an acid number of 1-50 and predominantly a free isocyanate group-containing reaction products made from polyisocyanates and monohydroxyl compounds.
  • Suitable polyesters B are the isocycanates. Specifically, aliphatic, cycloaliphatic and aromatic monoisocyanates with at least 4 carbon atoms, such as dodecyl isocyanate, phenyl isocyanate, naphthyl isocyanate, cyclohexyl isocyanate and the C 1 -C 4 alkyl derivatives of the isocyanates mentioned, diisocyanates such as 1,6-hexamethylene diisocyanate, Isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1-methyl-cyclohexane-2,4-and -2,6-diisocyanate and the mixtures of these isomers, 2,4- and 2,6-tolylene diisocyanate and the mixtures of these isomers, naphthylene 1,5-diisocyanate,
  • diisocyanates and polyisocyanates are preferred, the functionality of which is achieved by conversion with Zerewitinoff-H-acidic, monofunctional compounds, e.g. monofunctional alcohols and / or acids can be reduced to 2 or 1.
  • Thixotropic agents are generally used in amounts of 0.1-10, preferably 1-5% by weight, based on polyester resin.
  • the dispersions according to the invention can contain organic and / or inorganic fillers in fibrous and / or powdery form, e.g. Kaolin, magnesium and calcium carbonate, quartz flour, asbestos flour, thermoplastic powder, e.g. Polyethylene powder and other macromolecular cross-linked and non-cross-linked products in powder form.
  • Crosslinked macromolecular substances include e.g. considered: ground thermoset plastics, e.g. hardened unsaturated polyester resin, hardened melamine and urea-formaldehyde resin.
  • Fibrous fillers are e.g. Glass fiber sections, asbestos fibers, "organic chemical fibers" and natural fibers.
  • the preferred field of application of the mixtures according to the invention is the use for thickening unsaturated polyester solutions in copolymerizable monomers for the production of resin mats and molding compounds. Since such batches must contain peroxides, preferably organic peroxides, in order to be able to process them into molded parts, it may be expedient to incorporate the organic peroxides into the dispersions according to the invention.
  • Peroxides for resin mats and molding compounds are, for example: benzoyl peroxide, tert-butyl perbenzoate, perketals, etc. The perketals are particularly advantageous. They show the greatest storage stability in the presence of basic products.
  • the dispersions according to the invention can be mixed with the unsaturated polyester resins to be modified in amounts of 1-30% by weight, based on unsaturated unmodified polyester resin. If the dispersions according to the invention contain inorganic thickeners, the amounts are chosen such that 0.1-10% by weight, preferably 0.5-2.5% by weight, based on unsaturated unmodified polyester resin, of inorganic thickeners are added to the unsaturated polyester resins will.
  • the unsaturated polyesters of those polyester resins for the modification of which the dispersions according to the invention can be used can be prepared from the components listed above for the production of polyester B.
  • the acid numbers of the polyesters should be between 10 and 100, preferably between 10 and 40, the OH numbers between 10 and 150, preferably between 20 and 100, and the number average molecular weights between about 500 and 5000, preferably between about 1000 and 3,000 (measured by vapor pressure osmometry in dioxane and acetone; if the values differ, the lower one is considered the correct one).
  • Suitable copolymerizable vinyl and vinylidene compounds for the modified polyester resins are unsaturated compounds customary in polyester technology, which preferably carry a-substituted vinyl groups or ⁇ -substituted allyl groups, preferably styrene; but also, for example, nuclear chlorinated and alkylated or alkenylated styrenes, where the alkyl groups can contain 1-4 carbon atoms, such as Vinyl toluene, divinylbenzene, a-methylstyrene, tert-butylstyrene, chlorostyrenes; Vinyl esters of carboxylic acids with 2-6 carbon atoms, preferably vinyl acetate; Vinyl pyridine, vinyl naphthalene, vinyl cyclohexane, acyl acid and methacrylic acid and / or their esters (preferably vinyl, allyl and methallyl esters) with 1-4 carbon atoms in the alcohol component, their amines and nit
  • insoluble is intended to mean that when heated to 80 ° C. for 30 minutes in polyester B, less than 1% by weight of the substance in question goes into solution.
  • Resin 1 (comparison according to DT-OS 2 223 989)
  • a mixture of 2536 parts of a-ethylhexanoic acid, 5706 parts of dipropylene glycol and 1738 parts of maleic anhydride, according to a molar composition from 1.0: 2.4: 1.0 are heated in 8 hours to 200 ° C. while passing nitrogen through and at this temperature until an acid number of 22 and a viscosity of 380 mPa.s. (measured at 20 ° C) kept.
  • the product obtained has a hydroxyl number of 200.
  • a mixture of 2187 parts of benzyl alcohol, 2633 parts of 2-ethylhexanol-1, 3453 parts of maleic anhydride and 2360 parts of dipropylene glycol, corresponding to a molar ratio of 1.15: 1.15: 2.20: 1.00, are passed through with nitrogen in 14 Heated to 210 ° C and held at this temperature until an acid number of 21 and a viscosity of 320 mPa.s (measured at 20 ° C) was reached. The hydroxyl number is then 40.
  • Resins 1-4 were mixed with a commercially available polyester resin mixture, which is typical for use in fine layers, according to the following recipe: Casting plates (3 mm thick) were produced from the resin mixture, which were hardened at 75 ° C. for 3 hours and annealed at 100 ° C. for 15 hours. Test specimens (50 ⁇ 50 mm 2 ) were cut from these casting plates and were stored in distilled water at room temperature for 50 days. The water absorption was then determined in accordance with DIN 53 475.
  • Test specimens (30 ⁇ 100 mm 2 ) were produced from the plates produced according to test A and were stored in distilled water at room temperature for 5 months. The appearance was then assessed.
  • a resin mat base was produced according to the following recipe:
  • the batch was poured into 3 mm plate molds and allowed to thicken for four days.
  • the plates were then cured in a water bath at 75 ° C. for 3 hours and then tempered at 100 ° C. for 15 hours.
  • Test specimens 50 x 50 mm 2 ) were cut from the plates and the water absorption was determined according to DIN 53 475. Sheets from a batch containing 100 parts of polyester resin Z without addition of resin served as a comparison.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (2)

1. Dispersions, qui sont exemptes de monomères copolymérisables, consistant en
A) 10 à 80, de préférence 30 à 60, % en poids de substances insolubles dans B, et
B) 90 à 20, de préférence 70 à 40, % en poids d'un polyester α,β-éthylénique dérivé d'acides dicarboxyliques et d'alcools monoet divalents,
les pourcentages étant chaque fois rapportés à la somme des composants A et B,

caractérisées en ce que
le polyester insaturé B possède des indices d'acide de 1-50 et des indices d'hydroxyle de 10-80 et en ce que
l'on a utilisé pour sa préparation, par mole de diol, 1,5-2,5 moles d'acides dicarboxyliques et 1,5-2,5 moles d'alcools monovalents.
2. Utilisation des dispersions selon la revendication 1 comme agents auxiliares pour les résines de polyester α,β-éthyléniques.
EP78100307A 1977-07-12 1978-07-05 Dispersions de poudres dans des polyesters insaturés ne contenant pas de monomère et leur utilisation comme véhicules dans les polyesters insaturés réticulables Expired EP0000371B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2731320 1977-07-12
DE19772731320 DE2731320A1 (de) 1977-07-12 1977-07-12 Dispersionen von pulvern in ungesaettigten polyestern

Publications (2)

Publication Number Publication Date
EP0000371A1 EP0000371A1 (fr) 1979-01-24
EP0000371B1 true EP0000371B1 (fr) 1980-06-25

Family

ID=6013677

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100307A Expired EP0000371B1 (fr) 1977-07-12 1978-07-05 Dispersions de poudres dans des polyesters insaturés ne contenant pas de monomère et leur utilisation comme véhicules dans les polyesters insaturés réticulables

Country Status (5)

Country Link
US (1) US4222927A (fr)
EP (1) EP0000371B1 (fr)
DE (2) DE2731320A1 (fr)
ES (1) ES471653A1 (fr)
IT (1) IT1105747B (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3126862A1 (de) * 1981-07-08 1983-01-27 Chemische Werke Hüls AG, 4370 Marl Eindickungspasten zur herstellung von in der hitze haertbaren, auf ungesaettigten polyesterharzen basierenden formmassen
US5244985A (en) * 1991-03-29 1993-09-14 New Japan Chemical Co., Ltd. Epoxidized polyesters and method of production thereof
GB9601589D0 (en) * 1996-01-26 1996-03-27 Queensway Expert Developments Polyol compositions for polyurethanes
GB2340838B (en) 1998-08-21 2002-02-13 Cray Valley Ltd Resins and composites containing them
US7572755B2 (en) * 2000-12-29 2009-08-11 Halliburton Energy Services, Inc. Drilling fluid comprising a vinyl neodecanoate polymer and method for enhanced suspension
US6887832B2 (en) * 2000-12-29 2005-05-03 Halliburton Energy Service,S Inc. Method of formulating and using a drilling mud with fragile gels
US7456135B2 (en) * 2000-12-29 2008-11-25 Halliburton Energy Services, Inc. Methods of drilling using flat rheology drilling fluids

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2407479A (en) * 1939-10-31 1946-09-10 Gen Electric Interpolymerization products
US2388319A (en) * 1941-07-11 1945-11-06 Bell Telephone Labor Inc Cross-linked polyesters and electrical conductors containing them
US2628209A (en) * 1947-10-28 1953-02-10 Us Rubber Co Process for increasing viscosity of uncured alkyd copolymer resinous mixtures and product
US2623025A (en) * 1949-02-11 1952-12-23 Libbey Owens Ford Glass Co Production of stable thermosetting compositions
US3361705A (en) * 1965-08-03 1968-01-02 Pfizer & Co C Masterbatch compositions
DE2223989C3 (de) * 1972-05-17 1981-08-06 Bayer Ag, 5090 Leverkusen Kolloid-disperse Gemische
US3795650A (en) * 1972-10-16 1974-03-05 Engelhard Min & Chem Clay thixotrope for polyester resins and use thereof
JPS4992377A (fr) * 1972-11-29 1974-09-03

Also Published As

Publication number Publication date
EP0000371A1 (fr) 1979-01-24
IT7850226A0 (it) 1978-07-10
ES471653A1 (es) 1979-10-01
DE2731320A1 (de) 1979-01-25
IT1105747B (it) 1985-11-04
DE2860028D1 (en) 1980-10-30
US4222927A (en) 1980-09-16

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