EP0000587B1 - Compositions de résines époxydes et leurs applications - Google Patents

Compositions de résines époxydes et leurs applications Download PDF

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Publication number
EP0000587B1
EP0000587B1 EP19780100540 EP78100540A EP0000587B1 EP 0000587 B1 EP0000587 B1 EP 0000587B1 EP 19780100540 EP19780100540 EP 19780100540 EP 78100540 A EP78100540 A EP 78100540A EP 0000587 B1 EP0000587 B1 EP 0000587B1
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Prior art keywords
base
weight
mixture
mixing
hardener
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Expired
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EP19780100540
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German (de)
English (en)
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EP0000587A1 (fr
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Margaret L. Elliott
Mary J. Wright
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    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/226—Mixtures of di-epoxy compounds
    • 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/145—Compounds containing one epoxy group
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • This invention relates to amine-hardened epoxy resin compositions based on epichlorohydrin/bisphenol A and their uses.
  • the field of the application of the invention is that of durable surface materials for concrete or asphalt roads, pavements, floors and other structures subjected to heavy wear during use.
  • Epoxy resins adhere well to many surfaces, cure easily, exhibit low shrinkage, are chemically inert, heat and moisture resistant and hard, and have a marked flexibility and impact resistance.
  • Resins of this type contain the epoxy group, in which an atom of oxygen is linked to both of two adjacent carbon atoms of a carbon chain in the same way as it is in the ethylene oxide molecule:
  • Olefinic material may be converted to simple epoxy (oxirane) compounds by a variety of methods, such as direct oxidation in the presence of silver catalysts, dehydrochlorination of chlorohydrins and, commonly, reaction with peracids. Depending on the peracid used and the conditions, the reaction may proceed further, with the reactive epoxy group forming hydroxyacyloxy compounds or glycols, as shown by the following equation:
  • Epoxy resins are formed by condensation reactions of epoxy compounds, for example, of epichlorohydrin with bisphenol A to form low molecular weight chains which have various lengths and still contain active epoxy groups. By interaction with amino and phenolic resins or reaction of curing agents such as polyamines, polyamides or polysulphides, cross-linking and extension of the chains occurs. During hardening to the solid state no volatile products are formed and the reaction occurs with only minimal shrinkage of the resin.
  • curable epoxy resins having various physical properties, e.g. viscosities, are commercially available for various applications, together with recommended flexibilizers, plasticizers, diluents, curing agents and hardeners.
  • Various kinds of fillers, colouring materials and other additives may also be employed.
  • the available compositions fall short of the requirements.
  • the shrinkage of the known compositions during curing is low, it is still excessive when these are used to cover large areas of surface, when cracking is apt to occur.
  • the presently available epoxy materials also tend to loose their initial flexibility in the course of aging, thus exhibiting a phenomenon similar to that of the loss of strength of concrete with passage of time.
  • amidoamine adduct hardened epoxy resin composition based on epichlorohydrin/bisphenol A, the composition being produced by the process of
  • ester preferably used in forming the base resin is available under the name CARDURA (registered trade mark) E (Shell Chemical Company, One Shell Plaza, Box 2463, Houston, Texas 77001, USA).
  • This product may be regarded in general as a fatty acid monoglyceride anhydride of the formula having a boiling point of 275°C.
  • the a-carbon atom is sterically hindered by 3 saturated carbon chains.
  • a first resin used in forming the base resin has an epoxide equivalent weight in the range 182 to 194, preferably 184 to 194 and, most preferably, 187 to 191.
  • a suitable resin is available under the name GENEPOXY (registered trade mark) 190 (General Mills Chemicals Inc., 4620 West 77th Street, Minneapolis, Minn. 55435, USA) and has a viscosity of 11.0 to 14.0 Pas/25°C and a specific gravity of 1.18.
  • EPON registered trade mark
  • EPIKOTE registered trade mark
  • GENEPOXY registered trade mark
  • a suitable plasticizer, usable in forming the base resin is available under the name CARDO-LITE (registered trade mark) Epoxy Resin Flexibilizer and Reactive Diluent NC-513 (3M Company 3M Center, St. Paul, Minnesota 55101, USA).
  • a suitable second resin preferably used in forming the base resin, is available under the name EPON (registered trade mark) 871 (Shell Chemical Company, USA) or under the name EPIKOTE (registered trade mark) 871 (Deutsche Shell Chemie GmbH, Germany) and has a viscosity of 0.4 to 0.9 Pas/25°C and a specific gravity of 0.988. This material has also been available as a solid resin.
  • a suitable co-reactant, preferably used in forming the base hardener, is available under the name GENAMID (registered trade mark) 250 and has a viscosity of 0.5 of 1.0 Pas/25°C.
  • a suitable phenol, preferably used in forming the base hardener is 2, 4, 6-tri(dimethylaminomethyl) phenol.
  • This product is available, for example, under the name DMP-30 (registered trade mark) (Rohm and Haas Company, Indepence Mall West, Philadelphia, Pennsylvania 19105, USA) or under the name DION (registered trade mark) Hardener EH-30 (Diamond Shamrock Chemical Company, 300 Union Commerce Building, Cleveland, Ohio 44115, USA).
  • the pine oil component of the base hardener is added primarily to modify the odour of the resin composition, but it also acts as an additional plasticizer.
  • the starting materials are selected from the above specified commercial products.
  • the base resin and the base hardener are mixed together preferably in a proportion of equal parts by weight (50% : 50%), although the mixing ratio may vary by 50% or even more.
  • the base resin and the base hardener of the present invention have an indefinite shelf life prior to mixing and are water-soluble.
  • the mixture has a pot life of about one hour and can be applied over damp surfaces and trace amounts of grease and oil. It may include organic or mineral colouring materials.
  • the mixture will set below freezing point. At ordinary temperatures it sets within a few hours, although higher temperatures accelerate the process.
  • the cured composition adheres to asphalt as well as to concrete and will not become tacky under the action of heat.
  • the basic epoxy composition described above may be used directly as a flexible molding material and its surface may be shaped to form patterns of very fine and intricate detail.
  • the base resin and the base hardener, as formed in the present invention may be supplemented with fillers and other additives in order to yield desirable characteristics of the final composition for other applications. Preferred embodiments are described hereunder.
  • An epoxy resin composition of the present invention is produced by:
  • the silica flour as used above, consists of equal parts by weight of 140, 200, and 325 mesh (according to ASTM E 11-58 T, coresponding to mesh apertures of 0.105, 0.074, and 0.044 mm, respectively) silica flour and acts as an inert filler which keeps the resin composition from becoming brittle. It also acts as a heat absorbent during the reaction between the base resin mixture and the base hardener mixture.
  • the colouring agent serves to identify the base resin mixture in order to distinguish it from other materials during its application by the end user.
  • the colloid used in preparing the base hardener mixture serves as a thickener, extender or suspension agent.
  • a suitable material is very fine Si0 2 powder.
  • a preferred colloid is available commercially under the name Cab-o-Sil (registered trade mark) (Cabot Inc., Boston Massachusetts, USA) and consists of fine white Si0 2 powder having a density of 2.1 g/cm 3 and a particle size of 0.015 to 0.020 ⁇ m.
  • the colloid increases the viscosity of the base hardener mixture and prevents the silica flour from settling out during the reaction period.
  • Epoximide E-12 is a flexible epoxy resin composition suitable for the repair of spalling, cracking, pitting and other damage to concrete and asphalt. It can be used to join concrete to asphalt and to resurface concrete floors, tanks and water reservoirs. Wood and metal surfaces may also be coated with this composition.
  • Another preferred epoxy composition of the present invention is produced by:
  • the synthetic rubber as used above, consists preferably of equal parts by weight of polybutadiene, oil extended butadiene-styrene copolymer, polychloroprene, polyisobutyrene and polysulphide rubber, whilst the silica flour is preferably the same as that used in preparing the epoxy composition E-12. Whilst the silica flour again acts as an inert filler, the synthetic rubber additives participate in the reactions between the base resin mixture and the base hardener mixture and undergo chemical change during the process. The colouring agent is again employed in order to distinguish the material during use in the field.
  • the epoxy resin composition produced in the above-described manner is designated LA-15.
  • This epoxy resin composition is suitable for use as a heavy-duty paving material and has been formulated specifically for use as a cable- barrier inlay or cable-arrester inlay as fitted to the deck of an aircraft carrier.
  • the material is inlayed to a minimum depth of 5 cm covering the impact area. It bonds extremely well to cut- away concrete and metal surfaces, is chemically resistant to jet fuels, liquid oxygen, grease, acids and cleaning solvents, and is an unusually tough and resilient material.
  • Another preferred epoxy resin composition of the present invention is produced by:
  • the synthetic rubber additives are the same as those previously described and they function in the same way in both cases.
  • the base epoxy resin composition produced as described above is designated LA-40.
  • the epoxy resin composition LA-40 is a modification of the base epoxy resin composition, adapted for use as a filler in concrete or asphalt joints, where flexibility and adhesion are of primary importance.
  • This composition with its high content of synthetic rubber materials is highly flexible and also resistant to jet fuel, liquid oxygen, grease, acid and cleaning solvents, so that it may be utilized in a wide variety of structures.
  • a further preferred epoxy resin composition of the present invention is produced by:
  • the base hardener employed in forming this composition is the same base hardener which is used in forming the basic epoxy resin composition E-12.
  • the silica flour is preferably the same as that described above.
  • This particular epoxy resin composition is designated LA-5.
  • the epoxy resin composition LA-5 is a flexible, highly adherent and durable material, which is ideally suited for use as a paint for distinguishing traffic lanes on highways or work and safety zones on factory floors, or similar applications.
  • the colouring agent may be selected as appropriate for the particular application.
  • a base resin 11 is formed from 10% of an ester of 13, 79% of a first resin 14, 6% of a first resin 14, 6% of a plasticizer 15 and 5% of a second resin 16, and a base hardener 12 is formed from 80% of a coreactant 17, 5% of a phenol 18 and 15% of pine oil 19, the individual constituents being as previously defined and the percentages being by weight.
  • the base resin 11 and the base hardener 12 are stored separately until the final composition is required for application, when they are mixed together in suitable proportions, the curing being more rapid with higher proportions of the hardener.
  • equal parts by weight of the base resin 11 and the base hardener 12 are mixed together to give a curable base epoxy resin composition 10.
  • a base resin mixture E-12A is formed from 27% of the base resin 11, 72% of silica flour 21 and 1% of a colouring agent 22, and a base hardener E-12B is formed from 20% of the base hardener 12, 2% of a colloid 23 and 78% of silica flour 24, the individual constituents being as previously defined and the percentages being by weight.
  • the base resin mixture E12A and the base hardener mixture E-12B are again stored separately until the final composition is required, when equal parts of each are mixed together to give the curable epoxy resin composition E-12.
  • a base resin mixture LA-1 5A is formed from 50% of the base resin 11, 34% of synthetic rubber 25, 14.5% of silica flour 26 and 1.5% of a colouring agent 27, and a base hardener mixture LA-1 5A is formed from 54% of the base hardener 12, 31% of synthetic rubber 28 and 15% of silica flour 29, the individual constituents being as previously defined and the percentages being by weight.
  • the base resin mixture LA-1 5A and the base hardener mixture LA-1 5B are again stored separately until the final composition is required for application, when equal parts of each are mixed together to give the curable epoxy resin composition LA-1 5.
  • a base resin mixture LA--40A is formed from 60% of the base resin 11 and 40% of synthetic rubber 31, and a base hardener mixture LA-40B is formed from 55% of the base hardener 12 and 45% of synthetic rubber 32, the individual constituents being as previously defined and the percentages being by weight.
  • the base resin mixture LA-40A and the base hardener mixture LA-40B are again stored separately until the final composition is required for application, when equal parts of each are mixed together to give the curable epoxy resin composition LA-40.
  • a base resin mixture LA-5A is formed from 27% (wt.) of the base resin 11, 69% of silica flour 33 and 4% of a colouring agent 34.
  • a mixture is prepared of equal parts by weight of the base resin mixture LA-5A and a base hardener LA-5B, this base hardener being identical with the base hardener 12 as prepared in Figure 1, to give the curable epoxy resin composition LA-5.
  • the silica flour is as defined previously.
  • ALI of the final epoxy resin compositions described including the base epoxy resin composition 10 and the epoxy resin compositions E-12, LA-15, LA-40 and LA-5 as well as other modified forms of the base constituents not described are of high durable stability, mechanical strength and resilience and exhibit low shrinkage and resistance to reaction of chemicals.
  • the component materials are non-toxic, non-irritating, non-combustible and they contain no volatile solvents. They may be applied at virtually any temperature, although the rate of curing is very slow below freezing point.
  • a layer of the curable epoxy resin composition of the present invention of 5 cm thickness will cure in about 8 hours at 10°C and in about 6 hours at 21 °C. Curing is accelerated at higher temperatures, for example, 60°C.
  • a solid resin is used as the second resin, consideration should be given to the melting point of the solid resin.
  • the solid resin selected is that available under the name EPON (registered trade mark) 1001 or EPIKOTE (registered trade mark) 1001
  • curing should be made above 70°C.
  • Equipment used may be cleaned with soap and water or with steam.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (10)

1. Composition de résine époxy, durcue par un produit d'addition amidoamine, à base d'épi- chlorhydrine/bisphénol A, caractérisée en ce qu'elle est obtenue par le procédé consistant à:
a) mélanger environ 10% en poids d'un ester glycidique (13) d'un acide carboxylique tertiaire à chaîne carbonée saturée substituée, présentant un poids équivalent époxyde de 240 à 250, environ 79% en poids d'une première résine (14) qui est une résine liquide à base d'épichlorohydrine/bisphénol A présentant un poids équivalent époxyde compris entre 182 et 194, environ 6% en poids d'un plastifiant (15) qui est un mélange des dérivés éthers mono- glycidiques des phénols aicoylés en C'5 obtenus à partir du liquide de la noix de cajou, présentant un poids équivalent époxyde d'environ 490, et environ 5% en poids d'une seconde résine (16) qui est une résine liquide ou solide à base d'épichlorohydrine/bisphénol A, présentant un poids équivalent époxyde de 390 à 500, afin d'obtenir une résine de base (11);
b) mélanger environ 80% en poids d'un réactif complémentaire (17) qui est une résine amidoamine présentant une valeur d'amine d'environ 450 et une viscosité de 0,5 à 1,0 pas/25°C, environ 5% en poids d'un tri(di- méthylaminométhyl) phénol (18) et environ 15% en poids d'huile de pin afin d'obtenir un durcisseur de base (12); et
c) mélanger la résine de base et le durcisseur de base et permettre au mélange de subir une réticulation.
2. Composition de résine époxy suivant la revendication 1, caractérisée en ce qu'elle est obtenue en mélangeant la résine de base et le durcisseur de base dans des proportions égales en poids.
3. Composition de résine époxy suivant la revendication 1 caractérisée en ce qu'elle est obtenue en procédant comme suit:
a) mélanger la résine de base (11) avec de la silice en poudre (21) et en colorant (22) respectivement dans des proportions de 27:72:1 % en poids de façon à obtenir un mélange de résine de base;
b) mélanger le durcisseur de base (12) avec de la silice en poudre (24) et en colloîde (23) respectivement dans des proportions de 20:78:2% en poids de façon à obtenir un mèlange de durcisseur de base; et
c) mélanger le mélange de résine de base avec le mélange de durcisseur de base dans un rapport de 50:50% en poids.
4. Composition de résine époxy suivant la revendication 1, caractérisée en ce qu'elle est obtenue en procédant comme suit:
a) mélanger la résine de base (11) avec du caoutchouc synthétique (25), de la silice en poudre (26) et un colorant (27) respectivement dans un rapport de 50:34:14,5 et 1,5% en poids de façon à former un mélange de résine de base;
b) mélanger le durcisseur de base (12) avec du caoutchouc synthétique (28) et de la silice en poudre (29) respectivement dans un rapport de 54:31:15% en poids de façon à former un mélange de durcisseur de base; et
c) mélanger le mélange de résine de base et le mélange de durcisseur de base dans un rapport de 50:50% en poids.
5. Composition de résine époxy suivant la revendication 1, caractérisée en ce qu'elle est obtenue en procédant comme suit:
a) mélanger la résine de base (11) avec du caoutchouc synthétique (31) respectivement dans un rapport de 60:40% en poids de façon à former un mélange de résine de base;
b) mélanger le durcisseur de base (12) avec du caoutchouc synthétique (32) respectivement dans un rapport de 55:45% en poids de façon à former un mélange de durcisseur de base; et
c) mélanger le mélange de résine de base avec le mélange de durcisseur de base dans un rapport de 50:50% en poids.
6. Composition de résine époxy suivant la revendication 1, caractérisée en ce qu'elle est obtenue en procédant comme suit:
a) mélanger la résine de base (11) avec de la silice en poudre (33) et un colorant (34) respectivement dans un rapport de 27:69:4% en poids de façon à former un mélange de résine de base; et
b) mélanger le mélange de résine de base avec le durcisseur de base dans un rapport de 50:50% en poids.
7. Utilisation de la composition de résine époxy suivant la revendication 3 pour réparer et refaire le revêtement d'ouvrages en béton ou en asphalte.
8. Utilisation de la composition de résine époxy suivant la revendication 4 en tant que matière de revêtement résistant à des conditions de service sévères.
9. Utilisation de la composition de résine époxy suivant la revendication 5 en tant que remplissage de joints entre des parties en asphalte ou en béton.
10. Utilisation de la composition de résine époxy suivant la revendication 6 en tant que peinture durable pour autoroutes, grandes routes, sols, chemins et surfaces analogues.
EP19780100540 1977-07-29 1978-07-28 Compositions de résines époxydes et leurs applications Expired EP0000587B1 (fr)

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Application Number Priority Date Filing Date Title
US82016877A 1977-07-29 1977-07-29
US820168 1977-07-29

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EP0000587A1 EP0000587A1 (fr) 1979-02-07
EP0000587B1 true EP0000587B1 (fr) 1981-12-09

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL1006958C2 (nl) * 1997-09-05 1999-03-11 Hollandsche Betongroep Nv Evenementen-bouwwerk met verplaatsbaar veld.
NL2002363C2 (en) * 2008-12-22 2010-06-23 Jacobus Petrus Johannes Bisseling Werkwijze en epoxymortel voor het herstellen van een aangetaste houtconstructie.
CN102276962A (zh) * 2011-08-02 2011-12-14 南京路德金友新材料科技有限公司 一种环氧沥青桥面快速冷修补用树脂及其制备方法

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Publication number Priority date Publication date Assignee Title
NL232051A (fr) * 1957-10-07 1900-01-01
US3007888A (en) * 1958-12-31 1961-11-07 Electric Storage Battery Co Epoxy resin base protective surfaces
NL257277A (fr) * 1959-10-29
FR1275869A (fr) * 1960-12-09 1961-11-10 Cie De Prod Chim Produit résistant à l'abrasion pour le revêtement d'ouvrages et en particulier des surfaces de circulation
US3649583A (en) * 1970-04-10 1972-03-14 Dexter Corp Water cleanable epoxy adhesive

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DE2861433D1 (en) 1982-02-04
EP0000587A1 (fr) 1979-02-07

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