WO2000008087A1 - Composition de resines epoxy pouvant etre reticulees - Google Patents

Composition de resines epoxy pouvant etre reticulees Download PDF

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Publication number
WO2000008087A1
WO2000008087A1 PCT/EP1999/005673 EP9905673W WO0008087A1 WO 2000008087 A1 WO2000008087 A1 WO 2000008087A1 EP 9905673 W EP9905673 W EP 9905673W WO 0008087 A1 WO0008087 A1 WO 0008087A1
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WO
WIPO (PCT)
Prior art keywords
composition
composition according
epoxy resins
lanthanide
component
Prior art date
Application number
PCT/EP1999/005673
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English (en)
Inventor
Virginia Cadiz Deleito
Marina Galia Clua
Ana Mantecon Arranz
Jose Antonio Reina Lozano
Juan Carlos Ronda Bargallo
Angels Serra I Albet
Original Assignee
Universitat Rovira I Virgili
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 Universitat Rovira I Virgili filed Critical Universitat Rovira I Virgili
Priority to AU54201/99A priority Critical patent/AU5420199A/en
Publication of WO2000008087A1 publication Critical patent/WO2000008087A1/fr

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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
    • 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
    • C08G59/68—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 catalysts used

Definitions

  • this invention is related to compositions based on epoxy resins and, in particular, to the use of lanthanide triflates as curing agents for epoxy resin crosslinking and as accelerators in conventional curing processes of epoxy resins.
  • Epoxy resins are substances that contain epoxide groups which can be crosslinked by catalysts and curing agents, leading to polymers with high mechanical and thermal resistance. These resins are used as adhesives, in coatings, in the manufacture of laminates and in a wide variety of applications that require high performance materials.
  • An epoxy resin can be cured using Lewis acids such as aluminium trichloride, boron trifluoride, iron trichloride and titanium tetrachloride.
  • the Lewis acid catalyst coordinates with the epoxide oxygen and finally forms ether bonds through a cationic mechanism.
  • Lewis acids can catalyse the crosslinking of both glycidyl resins and cycloaliphatic epoxy resins and are active in a wide range of low concentrations.
  • Epoxy resins with high contents of hydroxyl groups normally have high percentages of water which means that when they are crosslinked with Lewis acids the epoxide groups can be hydrolysed. So they are consumed in side reactions and the crosslinking is reduced considerably.
  • the catalyst Because of the speed at which a Lewis acid cures an epoxy resin, the catalyst must be blocked, if storage of the coating composition is required. So, the blocked catalysts either do not react or only react slightly at room temperature, and require high temperatures to start the reaction. Using this procedure longer "pot-life" times are achieved.
  • An example of this catalyst is the use of complexes of boron trifluoride with ethers or amines as blocking agent. These initiators require a proportion of about three parts per hundred of resin (phr) and relatively high curing temperatures.
  • Epoxy resin compositions catalysed by the compounds are relatively stable at room temperature and cure rapidly when they are exposed to high temperatures.
  • these blocked catalysts have the disadvantage that not only the amine complexes are hygroscopic and hydrolyse with moist air, but additionally the physical and electrical properties of the resin will deteriorate at high temperatures and at high levels of moisture.
  • This invention provides a solution to the need of better crosslinking agents and accelerators for epoxy resin systems, using lanthanide triflates
  • the lanthanide triflates act as blocked catalysts and have various advantages. They are tolerant to water, stable at room temperature and highly soluble in organic compounds. The solubility or dispersability of the crosslinking or curing agent in the epoxy resin is an important advantage because normal heterogeneous dispersions cluster together during storage and show less reactivity. These catalysts also need to be soluble in the epoxy resin for the manufacture of prepegs. Additionally, the toxicity of lanthanide salts is much lower than the toxicity of other transition metals and similar to that of alkaline metals, which provides advantages in handling of this substances. DETAILED DESCRIPTION OF THE INVENTION
  • composition of the invention comprising: A) one or more epoxy resins
  • X is an additional organic or inorganic salt residue (anionic residue), z is a number lower than n or 0;
  • composition of the invention can be liquid or solid.
  • the composition of the invention may comprise the components A and B or it may comprise components A, B and C and optionally components D and E may be included.
  • One preferred embodiment of the invention is a composition which is suitable for powder coating applications. However, the compositions are also useful in liquid coating agents.
  • Another embodiment of the invention is the process of crosslinking compositions comprising components A and optionally components C, D and E by incorporation of lanthanide triflates (I) in the composition
  • epoxy resin includes any monomeric, dimeric, oligomeric or polymeric epoxy material which contains one or more functional epoxy groups, either liquid or solid.
  • component A may be: - an epoxy resin which is the result of the reaction of Bisphenol A [2,2-bis (4- hydroxyphenyl) propane] and the epichlorohydrine [l-chloro-2,3-epoxypropane];
  • an epoxy resin which is the result of the reaction between phenolformaldehyde resins of low molecular weight and epichlorohydrin; whereby these resins can be used by themselves or in combination with additional compounds such as phenylglycidylether, glycidyl acrylate, glycidyl methacrylate, styrene oxide, allyl glycidylether, etc., as reactive diluent, which can be used to modify the viscosity of the resin;
  • - modified epoxy resins which generally have epoxide functional groups at the end or lateral of their chains, such as epoxy siloxane, epoxy polyurethane, epoxy polyester, epoxy polyether, epoxy polyamine, etc. and - epoxy resins modified with carboxylic acids, alcohols, amines, phenols, thiols, etc. as long as they contain at least one or more reactive epoxide group per molecule.
  • the component A is selected from the group made up of Bisphenol A diglycidyl ether resin (DGEBA), 3,4-epoxycyclohexylmethyl resin, 3,4-epoxy- cyclohexanocarboxylate resin and dodecylen-N,N'-bis (epoxy nadimide) resin.
  • DGEBA Bisphenol A diglycidyl ether resin
  • Component A may consist of one epoxy resin or a mixture of different types of epoxy resins can be used . The mixture can be selected according to the desired properties of the composition, e.g. viscosity, reactivity, crosslinked network.
  • Component B is a lanthanide triflate of formula (I) described above.
  • lanthanide shall be selected out of lanthanum and each of the chemical elements whose atomic number is between 58 (cerium) and 71 (lutetium), inclusive.
  • all lanthanides function in a similar fashion, but due to their different cationic structure they lead to crosslinked products which are different in the amount of crosslinking and glass transition temperature (Tg) and which influence also the reaction conditions.
  • the lanthanide is selected from the group made up of lanthan, ytterbium and samarium.
  • Some lanthanide triflates (I) are commercial products or can be obtained by conventional, well-known methods [see, for example, M. EL. M. Hamidi, M. Hnach and H. Zineddine, J. Chim. Phys. (1997), 94, 1295-1303].
  • X other organic and/or inorganic salt residues can be used, e.g. anions such as Cl , Br , J , NO 3 " , HSO 4 , H 2 PO 3 -, HCO 3 , CH 3 COO , HjOO , C 6 H 5 COO which may form mixed salts with the lanthanide M.
  • Z is a number between 0 and n - 1, so that at least one triflate residue is included in component (I).
  • the component B consists of lanthanide triflates, wherein Z is 0 or 1, most preferably Z is 0.
  • the organic or inorganic salt residues shall be selected in a way that they do not disturb the homogenity of the mixture of components A, B and the optional components.
  • the component B may comprise one metall ion M, but it is also possible to use a mixture of two and more different metall ions.
  • the component B can be present in the composition in a very wide range, but normally a range between 0.1 and 7 phr is preferred.
  • the amount of component B may be varied to influence certain properties. When the proportion of the component B is about 0.2 phr the curing of the composition takes place at higher temperatures. If the amount of component B is about 5 phr the curing proceeds faster at lower temperature. According to the amount of compnent B specific properties of the coating composition can be adjusted according to the application purpose.
  • a composition of the invention can be prepared by mixing component A with an effective quantity of component B, the lanthanide triflate (I).
  • component B can be mixed directly into component A or it may be dissolved or dispersed in an organic solvent such as methylene chloride, methanol, etc. , which is useful for liquid coating materials to obtain a practically homogenous mixture.
  • component A is solid
  • the component B can be incorporated and mixed also by dry-grinding or by fusion mixing.
  • small amounts of auxiliary solvents may be used for dissolving or dispersing component B to facilitate the mixing process of this component in the solid resins. Additionally this process may be performed by application of elevated temperature to soften or melt the component A and subsequent homogenisation.
  • the composition of the invention may contain conventional crosslinking agents and substances, e.g. primary and tertiary amines, acid anhydrides, dicyandiamide(DICY) and its derivatives, imidazoles, imidazolines, ureas, amides, melamines, hydrazides, guanidines, thioureas and sulphonamides among other products which are habitually used in the curing of epoxy resins.
  • the crosslinking agent is present in the suitable stoichiometric or non-stoichiometric ratio. This composition can be obtained by mixing appropriate amounts of the various components.
  • composition of the invention comprises at least one epoxy resin (A), a lanthanide triflate (B) and a conventional crosslinking agent (C) .
  • the ratio between component B and the components A and C can vary considerably. However, good results are obtained when the quantity of component B used is between 0.2 and 5 phr of the total mixture.
  • the mixing process for liquid or solid compositions of components A and C together with component B may be performed as described above, and as mentioned above it is preferred to obtain a homogenous dispersion or solution of the three components.
  • the composition of the invention may, e.g. contain pigments, fillers , fibres and/or dyes.
  • Pigments are well known in the paint industry, and are organic or inorganic pigments e.g. titanium dioxide, carbon black, chromium titanium yellow, ferroxide red, effect pigments like metallic pigment flakes or iriodine pigments or organic pigments like phthalocyanin ⁇ , chinacridone or azopigments.
  • fillers e.g. barium sulphate, calcium sulfates, siliciumdioxide and /or kaolin may be used.
  • additonally fibres may be incorporated.
  • the component D shall be stable at the curing temperature e.g. up to 200 C.
  • the composition of the invention shall preferably contain colouring pigments and fillers.
  • component E other additives may be incorporated in the composition of the invention.
  • additives are surfactants, catalysts, matting agents, solvents, accelerators, plasticisers, agents for controlling viscosity, UN protectors, reinforcing agents, etc., which are well known to a skilled person and which may be selected according to the different field of use of the composition.
  • surfactants for liquid compositions solvents, reactive solvents, and other liquid additives may be used.
  • solid additives shall be used as component E.
  • the mixing process of the composition is known in principle, liquid materials may be dissolved or dispersed and then mixed, solid components may be mixed after heating and melting or they may be mixed by dry grinding. If necessary the pigments or fillers may be ground to an appropriate particle size.
  • Such manufacturing process may be selected according to the specific composition of the invention and the purpose of use of this material; such processes are known to a skilled person. For all operations it is necessary to keep the temperature below the start of a crosslinking reaction of the components.
  • the composition of the invention can be crosslinked by heating it to a temperature between 90 and 250 ° C for between 0,5 and 90 minutes.
  • the temperature shall be between 100 and 200 C and the period may vary between 1 to 60 minutes.
  • an increase in the amount of component B leads to lower curing temperatures.
  • Lanthanide triflates can be used according to the invention as catalyst or accelerator for epoxy resin systems and they do not have the well-known disadvantages of other catalysts or accelerators which are normally used in epoxy resin technology and which are discussed in the prior art.
  • compositions according to the invention have the advantage that their use results to lower heat evolved during the crosslinking reaction, which is advantageous for curing objects of large dimensions or large quantities of materials in reducing the problem of dissipating the heat produced during curing. In this case, however, the curing takes place at unexpectedly short curing times compared with smaller volumes of such materials.
  • component B Another advantage of the use of component B is that in other numerous formulations comparable reaction processes require catalysts, the residues of which lead after the curing to problems of oxidation, premature ageing of the materials, yellowing, etc. which can be avoided by the invention.
  • composition of the invention can be used in any application of epoxy resins, with or without a crosslinker, for example as liquid coating or as solid coating material, as adhesive, in the manufacture of laminates or composites and in other applications.
  • Example 1 illustrate particular ways of using the invention.
  • a crosslinking composition of epoxy resins was prepared by mixing 0.5 g of a Bisphenol A diglycidyl ether resin (DGEBA) of a molecular weight of 348 with 5 mg (1 phr) of ytterbium triflate and dissolving both in a minimum quantity of methanol with the aim of achieving a homogeneous mixture. The methanol was eliminated under vacuum. The mixture was heated to 130 ° C for 35 minutes, and the curing was total and produced a crosslinked epoxy resin with a glass transition temperature of 97 C.
  • DGEBA Bisphenol A diglycidyl ether resin
  • Example 2 A curing mixture was prepared by dissolving 0.5g of DGEBA of a molecular weight of
  • Example 2 The procedure in Example 2 was repeated but with 1 phr of lanthanum triflate. The material was totally cured by heating the evaporated mixture at 150 ° C for 30 minutes. It had a glass transition temperature of 84 ° C.
  • a homogeneous mixture was made of 0.5 g of 3,4-epoxycyclohexylmethyl-3,4-epoxy cyclohexanecarboxylate and 5 mg (1 phr) of ytterbium triflate dissolved in a minimum quantity of methanol and dried under vacuum. After heating for 30 minutes at 120 ° C, the product was totally crosslinked.
  • a homogeneous mixture was made of 0.5 g of dodecylen-N,N'-bis (epoxynad-imide) and 10 mg (2 phr) of ytterbium triflate. By heating the mixture at 150 ° C for 30 minutes the material becomes crosslinked and has a glass transition temperature of 76 C.
  • Example 6
  • a homogeneous mixture was made of 0.1 g of DGEBA with a molecular weight of 348 and 0.043 g of tetrahydrophthalic anhydride and 1.4 mg (1 phr) of ytterbium triflate by dissolving it in the minimum quantity of methylene chloride and methanol and drying under vacuum.
  • Example 9 Two homogeneous mixtures were made of 0.2 g of DGEBA with a molecular weight of
  • Example 10 Two homogeneous mixtures were made of 0.2 g of DGEBA with a molecular weight of

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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)
  • Epoxy Resins (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Composition de résines époxy pouvant être réticulées et contenant (A) une ou plusieurs résines époxy; (B) un ou plusieurs triflates de lanthanides représentés par la formule: M (OSO2CF3)n-z Xz dans laquelle M représente le cation provenant d'un lanthanide, n est la valence du lanthanide dans le composé, X est un résidu supplémentaire anionique organique ou inorganique, z est un nombre inférieur à n ou à zéro; (C) un ou plusieurs agents éventuels de réticulation de résines époxy; des pigments ou des charges éventuels; (E) d'autres additifs éventuels.
PCT/EP1999/005673 1998-08-06 1999-08-05 Composition de resines epoxy pouvant etre reticulees WO2000008087A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU54201/99A AU5420199A (en) 1998-08-06 1999-08-05 Composition of crosslinkable epoxy resins

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ES9801693A ES2154165B1 (es) 1998-08-06 1998-08-06 Composicion para el entrecruzamiento de resinas epoxi.
ESP9801693 1998-08-06

Publications (1)

Publication Number Publication Date
WO2000008087A1 true WO2000008087A1 (fr) 2000-02-17

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AU (1) AU5420199A (fr)
ES (1) ES2154165B1 (fr)
WO (1) WO2000008087A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6444745B1 (en) 2000-06-12 2002-09-03 General Electric Company Silicone polymer network compositions
US6531540B1 (en) 2001-05-16 2003-03-11 General Electric Company Polyether siloxane copolymer network compositions
US6538061B2 (en) 2001-05-16 2003-03-25 General Electric Company Cosmetic compositions using polyether siloxane copolymer network compositions
US7241835B2 (en) 2001-05-16 2007-07-10 General Electric Company Cosmetic compositions comprising silicone gels
WO2009141593A1 (fr) * 2008-05-23 2009-11-26 Qinetiq Limited Procédé de cuisson de polyéther
WO2014073429A1 (fr) * 2012-11-09 2014-05-15 株式会社ダイセル Composé époxy, son procédé de production, et composition de résine époxy durcissable
WO2016100118A1 (fr) 2014-12-16 2016-06-23 Momentive Performance Materials Inc. Composition cosmétique et procédé de préparation
WO2016100119A1 (fr) 2014-12-16 2016-06-23 Momentive Performance Materials Inc. Feuilles cosmétiques couvrant la peau et leur procédé de préparation
WO2016100121A1 (fr) 2014-12-16 2016-06-23 Momentive Peformance Materials Inc. Composition de soins personnels comprenant un réseau de silicone
US9744119B2 (en) 2014-12-16 2017-08-29 Momentive Performance Materials Inc. Cosmetic composition and method of preparation
US9839602B2 (en) 2014-12-16 2017-12-12 Momentive Performance Materials Inc. Personal care compositions containing crosslinked silicone polymer networks and their method of preparation
WO2022000088A1 (fr) * 2020-07-02 2022-01-06 Socpra Sciences Et Génie S.E.C. Catalyseurs de réticulation de résines époxy

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3842019A (en) * 1969-04-04 1974-10-15 Minnesota Mining & Mfg Use of sulfonic acid salts in cationic polymerization
EP0139042A2 (fr) * 1983-10-27 1985-05-02 Union Carbide Corporation Produits d'addition de basse viscosité d'un composé organique à hydrogènes actifs et d'un polyépoxyde
EP0493916A2 (fr) * 1990-12-18 1992-07-08 Ciba-Geigy Ag Préparation de composés
US5475069A (en) * 1994-10-31 1995-12-12 E. I. Du Pont De Nemours And Company Polymerization of vinyl ethers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3842019A (en) * 1969-04-04 1974-10-15 Minnesota Mining & Mfg Use of sulfonic acid salts in cationic polymerization
EP0139042A2 (fr) * 1983-10-27 1985-05-02 Union Carbide Corporation Produits d'addition de basse viscosité d'un composé organique à hydrogènes actifs et d'un polyépoxyde
EP0493916A2 (fr) * 1990-12-18 1992-07-08 Ciba-Geigy Ag Préparation de composés
US5475069A (en) * 1994-10-31 1995-12-12 E. I. Du Pont De Nemours And Company Polymerization of vinyl ethers

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6444745B1 (en) 2000-06-12 2002-09-03 General Electric Company Silicone polymer network compositions
US6531540B1 (en) 2001-05-16 2003-03-11 General Electric Company Polyether siloxane copolymer network compositions
US6538061B2 (en) 2001-05-16 2003-03-25 General Electric Company Cosmetic compositions using polyether siloxane copolymer network compositions
US6759479B2 (en) 2001-05-16 2004-07-06 General Electric Company Process for making cosmetic compositions using polyether siloxane copolymer network compositions
US7241835B2 (en) 2001-05-16 2007-07-10 General Electric Company Cosmetic compositions comprising silicone gels
US7381769B2 (en) 2001-05-16 2008-06-03 Momentive Performance Materials Inc. Cosmetic compositions using polyether siloxane copolymer network compositions
US9815933B2 (en) 2008-05-23 2017-11-14 Qinetiq Limited Curing method for polyether
WO2009141593A1 (fr) * 2008-05-23 2009-11-26 Qinetiq Limited Procédé de cuisson de polyéther
GB2462158B (en) * 2008-05-23 2010-10-13 Qinetiq Ltd Curing method of a crosslinked polyether polymer
US9340642B2 (en) 2008-05-23 2016-05-17 Qinetiq Limited Curing method for polyether
WO2014073429A1 (fr) * 2012-11-09 2014-05-15 株式会社ダイセル Composé époxy, son procédé de production, et composition de résine époxy durcissable
WO2016100119A1 (fr) 2014-12-16 2016-06-23 Momentive Performance Materials Inc. Feuilles cosmétiques couvrant la peau et leur procédé de préparation
WO2016100121A1 (fr) 2014-12-16 2016-06-23 Momentive Peformance Materials Inc. Composition de soins personnels comprenant un réseau de silicone
US9498409B2 (en) 2014-12-16 2016-11-22 Momentive Performance Materials Inc. Cosmetic skin covering sheets and their method of preparation
US9744119B2 (en) 2014-12-16 2017-08-29 Momentive Performance Materials Inc. Cosmetic composition and method of preparation
US9801805B2 (en) 2014-12-16 2017-10-31 Momentive Performance Materials Inc. Personal care composition comprising silicone network
WO2016100118A1 (fr) 2014-12-16 2016-06-23 Momentive Performance Materials Inc. Composition cosmétique et procédé de préparation
US9839602B2 (en) 2014-12-16 2017-12-12 Momentive Performance Materials Inc. Personal care compositions containing crosslinked silicone polymer networks and their method of preparation
WO2022000088A1 (fr) * 2020-07-02 2022-01-06 Socpra Sciences Et Génie S.E.C. Catalyseurs de réticulation de résines époxy

Also Published As

Publication number Publication date
ES2154165A1 (es) 2001-03-16
AU5420199A (en) 2000-02-28
ES2154165B1 (es) 2001-10-16

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