EP1030886A1 - Method for reinforcing thermosetting resins with isobornyl acrylate or methacrylate polymers - Google Patents

Method for reinforcing thermosetting resins with isobornyl acrylate or methacrylate polymers

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Publication number
EP1030886A1
EP1030886A1 EP99921994A EP99921994A EP1030886A1 EP 1030886 A1 EP1030886 A1 EP 1030886A1 EP 99921994 A EP99921994 A EP 99921994A EP 99921994 A EP99921994 A EP 99921994A EP 1030886 A1 EP1030886 A1 EP 1030886A1
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EP
European Patent Office
Prior art keywords
percent
thermosetting resin
isobornyl acrylate
thermosetting resins
resin
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EP99921994A
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German (de)
French (fr)
Inventor
Jean-Marie Ch. G. Liegeois
Nadia Tahir
Alexandre Baidak
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Universite de Liege
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Universite de Liege
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Publication of EP1030886A1 publication Critical patent/EP1030886A1/en
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    • 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

  • thermosetting resins and in particular thermosets with high deformation temperature under load are inherently fragile.
  • these resins thus modified acquire better resistance to cracking.
  • the context of this description is therefore that of materials whose properties remain governed by the thermosetting component which is also present in major proportion in the modified material.
  • thermosetting resins themselves of high toughness and having a deformation temperature under high load
  • polyethersulfone, polyetherimide and polyethercetone are effective for the reinforcement of thermosetting resins with high crosslinking rate without sacrificing the modulus of elasticity.
  • another way of increasing the impact resistance of thermosetting resins consists in producing a network of interpenetrating polymers as described in the patent of the United States of America 5,126,406.
  • the object of the present invention is to provide a reinforcement additive for thermosetting resins which can be added in proportion up to 20 percent and beyond without excessively increasing the viscosity of the mixture before baking.
  • Another object of the present invention is to have an additive for reinforcing thermosetting resins with high crosslinking rate which does not lead to a significant reduction in the modulus of elasticity both in the dry state and after saturation with humidity.
  • Another object of the present invention is to provide a process which allows the incorporation of a large quantity of modifying agent into a thermosetting resin without compromising the wetting of fibers if it is a composite application.
  • polymers comprising the repeating unit of isobornyl acrylate or methacrylate can play an effective reinforcing role, increasing with the content of modifier and in particular for contents inaccessible in prior know-how.
  • thermosetting resins which is the subject of the present invention does not result in a significant reduction in the modulus of elasticity up to a high temperature close to the temperature of use of the resin. parent and this modification reduces the sensitivity of the parent resin to water absorption which is also a factor in reducing rigidity.
  • the effect of the present invention is all the more surprising since the polymers used as reinforcement additives for thermosetting resins themselves have poor mechanical resistance properties and in particular the homopolymers of methacrylate or isobornyl acrylate.
  • the constituents of the resin are dissolved in a solution of the polymer comprising isobornyl acrylate or methacrylate.
  • the resin mixture is then brought to the cooking temperature after extraction of the solvent under vacuum and with stirring.
  • a second embodiment of the present invention consists in mixing with the constituents of the thermosetting resin, the precursor monomers of the modifying agent and an appropriate radical initiator chosen to be active at the curing temperature of the resin. If necessary, maximum conversion of the thermoplastic additive is obtained by post polymerization under radiation such as, for example, accelerated electrons.
  • a third embodiment of the present invention consists in dispersing in the constituents of the resin, the powder of the reinforcing polymer obtained for example, by drying an aqueous dispersion prepared by suspension or emulsion polymerization.
  • the reinforcing polymer added to the constituents of the thermosetting resin can therefore be synthesized during the curing of the resin just as it can be synthesized beforehand.
  • its composition comprises at least 25 percent of the isobornyl acrylate or methacrylate structural unit.
  • This polymer can be thermoplastic or partially crosslinked. This polymer can also contain functional groups resulting in grafting with the network of the resin during the baking thereof.
  • a copolymer was synthesized by charging a Grignard reactor with 700 g methyl ethyl ketone, 210 g methyl methacrylate, 90 g isobornyl methacrylate, 3 g AIBN, then stirring at 70 ° C for 24 hours. 1.5 g of AIBN were then added again and the mixture was kept stirring at 70 ° C. for 24 hours. The conversion to monomers was 98 percent.
  • the epoxy / acrylate alloys referenced 2 to 15 in the table of observed properties, and comprising from 10 to 30 percent of polyacrylate modifier, were prepared by simultaneous reaction in a cooking autoclave, thermostatically controlled by oil circulation. in the form of an isobornylacrylate or methacrylate homopolymer or in the form of a copolymer with glycidylmethacrylate.
  • Tert-butyl benzoate peroxide (AKZO Trigonox C) was used as the initiator at the rate of 1 percent of the acrylic monomers and was added to the low viscosity mixture of the other constituents.
  • the composition of the resin and the baking cycle were identical to those described in Example 1 by applying no vacuum to the bearing at 120 ° C.
  • An emulsion polymer was prepared by charging a stirred Grignard reactor at 60 ° C., with:
  • the latex was destabilized with liquid nitrogen and the powdered polymer was recovered after drying, grinding and sieving. It was incorporated at a rate of 15 percent in the DGEBA / DDS mixture comprising 33.2 phr of hardener.
  • the alloy obtained is referenced 16 in the table of observed properties.
  • An epoxy / acrylate alloy was prepared according to the procedure described in Example 4, in which the polymer is a methylmethacrylate homopolymer. This alloy is referenced 17 in the table of observed properties.
  • the preparations according to the present invention described in references 1 to 16 of the table, all have a morphology of segregated phases, the continuous phase being the phase rich in thermosetting resin and the discrete phase being the phase rich in addition polymer.

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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)
  • Graft Or Block Polymers (AREA)

Abstract

Thermosetting resins with high modulus and high glass transition temperature are intrinsically fragile, thereby making them unsuitable for certain applications in particular in the form of composites. The invention concerns mixtures with isobornyl acrylate or methacrylate polymers synthesised in situ or added in the form of a solution or added in the form of a powder resulting from drying polymer prepared in the form of an emulsion. Said novel alloys have enhanced tenacity while retaining a high deformation temperature and a high modulus.

Description

RENFORCEMENT DES RESINES THERMODURCISSABLES PAR DES POLYMERES A BASE DE METHACRYLATE OU ACRYLATE D'ISOBORNYLEREINFORCEMENT OF THERMOSETTING RESINS WITH METHACRYLATE OR ISOBORNYL ACRYLATE POLYMERS
Les résines thermodurcissables et en particulier les thermodurcissables à haute température de déformation sous charge sont intrinsèquement fragiles.Thermosetting resins and in particular thermosets with high deformation temperature under load are inherently fragile.
Par addition de certains autres constituants poly ériques spécifiques, ces résines ainsi modifiées acquièrent une meilleure résistance à la fissuration. Le contexte de la présente description est donc celui des matériaux dont les propriétés restent gouvernées par le constituant thermodurcissable lequel est aussi présent en proportion majeure dans le matériau modifié.By addition of certain other specific poly eric constituents, these resins thus modified acquire better resistance to cracking. The context of this description is therefore that of materials whose properties remain governed by the thermosetting component which is also present in major proportion in the modified material.
Ainsi, l'addition à une résine époxy, de 8 à 12 pour cent de certains caoutchoucs fonctionalisés permet d'accroître la ténacité. Cette modification n'est toutefois efficace que pour des résines ayant un taux de réticulation limité et présentant de ce fait une faible rigidité à température élevée. En outre, la présence du caoutchouc rend la résine cuite plus sensible à la prise d'humidité.Thus, the addition to an epoxy resin of 8 to 12 percent of certain functionalized rubbers increases the toughness. However, this modification is only effective for resins having a limited crosslinking rate and therefore having low rigidity at high temperature. In addition, the presence of rubber makes the baked resin more sensitive to moisture uptake.
Dans le savoir faire antérieur, on connaît aussi l'addition par dissolution de certains thermoplastiques eux-mêmes de haute ténacité et ayant une température de déformation sous charge élevée. Ainsi, le polyethersulfone, le polyetherimide et le polyethercetone sont efficaces pour le renforcement des résines thermodurcissables à haut taux de réticulation sans sacrifier le module d'élasticité. Toutefois, il est en pratique difficile d'incorporer des quantités élevées de ces additifs du fait de l'accroissement important de la viscosité du mélange. Cet inconvénient compromet aussi le mouillage de fibres par le mélange lorsqu'il s'agit d'une application composite. Enfin, une autre manière d'accroître la résistance à l'impact de résines thermodurcissables consiste à réaliser un réseau de polymères interpénétrés comme décrit dans le brevet des Etats-Unis d'Amérique 5,126,406. Comme il est montré par les exemples 6 à 14 dudit brevet, cette façon de faire entraîne cependant une diminution de la dureté, c'est à dire du module d'élasticité, d'autant plus grande que le gain en résistance à l'impact est élevé. C'est le résultat automatique d'une morphologie où chaque constituant forme un réseau continu.In the prior art, the addition by dissolution of certain thermoplastics, themselves of high toughness and having a deformation temperature under high load, is also known. Thus, polyethersulfone, polyetherimide and polyethercetone are effective for the reinforcement of thermosetting resins with high crosslinking rate without sacrificing the modulus of elasticity. However, it is in practice difficult to incorporate high amounts of these additives due to the significant increase in the viscosity of the mixture. This drawback also compromises the wetting of fibers by the mixture when it is a composite application. Finally, another way of increasing the impact resistance of thermosetting resins consists in producing a network of interpenetrating polymers as described in the patent of the United States of America 5,126,406. As shown by Examples 6 to 14 of said patent, this procedure however results in a reduction in hardness, that is to say in the modulus of elasticity, all the greater as the gain in impact resistance is high. It is the automatic result of a morphology where each constituent forms a continuous network.
L'objet de la présente invention est de disposer d'un additif de renforcement des résines thermodurcissables qui puisse être ajouté en proportion jusqu'à 20 pour cent et au- delà sans accroître exagérément la viscosité du mélange avant cuisson.The object of the present invention is to provide a reinforcement additive for thermosetting resins which can be added in proportion up to 20 percent and beyond without excessively increasing the viscosity of the mixture before baking.
Un autre objet de la présente invention est de disposer d'un additif de renforcement des résines thermodurcissables à haut taux de réticulation qui n'entraîne pas une réduction importante du module d'élasticité tant à l'état sec qu'après saturation par l'humidité.Another object of the present invention is to have an additive for reinforcing thermosetting resins with high crosslinking rate which does not lead to a significant reduction in the modulus of elasticity both in the dry state and after saturation with humidity.
Un autre objet de la présente invention est de disposer d'un procédé qui permette l'incorporation d'une quantité importante d'agent modifiant à une résine thermodurcissable sans compromettre le mouillage de fibres s'il s'agit d'une application composite.Another object of the present invention is to provide a process which allows the incorporation of a large quantity of modifying agent into a thermosetting resin without compromising the wetting of fibers if it is a composite application.
On a trouvé de façon inattendue que des polymères comprenant l'unité récurrente de l'isobornyl acrylate ou méthacrylate peuvent jouer un rôle efficace de renforcement, croissant avec la teneur en modifiant et en particulier pour des teneurs inaccessibles dans le savoir faire antérieur.It has been unexpectedly found that polymers comprising the repeating unit of isobornyl acrylate or methacrylate can play an effective reinforcing role, increasing with the content of modifier and in particular for contents inaccessible in prior know-how.
La modification des résines thermodurcissables qui fait l'objet de la présente invention n'entraîne pas de réduction significative du module d'élasticité jusqu'à une température élevée proche de la température d'utilisation de la résine parente et cette modification réduit la sensibilité de la résine parente à l'absorption d'eau qui est aussi un facteur de réduction de rigidité.The modification of the thermosetting resins which is the subject of the present invention does not result in a significant reduction in the modulus of elasticity up to a high temperature close to the temperature of use of the resin. parent and this modification reduces the sensitivity of the parent resin to water absorption which is also a factor in reducing rigidity.
L'effet de la présente invention est d'autant plus surprenant que les polymères utilisés comme additifs de renforcement des résines thermodurcissables ont eux-mêmes des propriétés de résistance mécanique médiocres et en particulier les homopolymères du méthacrylate ou de l'acrylate d ' isobornyle.The effect of the present invention is all the more surprising since the polymers used as reinforcement additives for thermosetting resins themselves have poor mechanical resistance properties and in particular the homopolymers of methacrylate or isobornyl acrylate.
Dans un premier mode d'exécution de la présente invention, on dissout les constituants de la résine dans une solution du polymère comprenant 1 ' isobornyl acrylate ou méthacrylate. Le mélange de résines est alors porté à la température de cuisson après extraction du solvant sous vide et sous agitation.In a first embodiment of the present invention, the constituents of the resin are dissolved in a solution of the polymer comprising isobornyl acrylate or methacrylate. The resin mixture is then brought to the cooking temperature after extraction of the solvent under vacuum and with stirring.
Un second mode d'exécution de la présente invention consiste à mélanger aux constituants de la résine thermodurcissable, les monomères précurseurs de l'agent modifiant et un initiateur radicalaire approprié choisi pour être actif à la température de cuisson de la résine. Le cas échéant, une conversion maximale de l'additif thermoplastique est obtenue par une post polymérisation sous rayonnement comme par exemple des électrons accélérés.A second embodiment of the present invention consists in mixing with the constituents of the thermosetting resin, the precursor monomers of the modifying agent and an appropriate radical initiator chosen to be active at the curing temperature of the resin. If necessary, maximum conversion of the thermoplastic additive is obtained by post polymerization under radiation such as, for example, accelerated electrons.
Un troisième mode d'exécution de la présente invention consiste à disperser dans les constituants de la résine, la poudre du polymère de renforcement obtenue par exemple, par séchage d'une dispersion aqueuse préparée par polymérisation en suspension ou en émulsion.A third embodiment of the present invention consists in dispersing in the constituents of the resin, the powder of the reinforcing polymer obtained for example, by drying an aqueous dispersion prepared by suspension or emulsion polymerization.
On a observé que ces trois modes d'exécution donnent lieu après cuisson de la résine aux améliorations recherchées alors que la morphologie de l'alliage varie de manière assez significative selon les cas: tantôt sous forme d'inclusions sphériques monodisperses, tantôt sous forme de nodules hétérodisperses, tantôt sous forme de phases interpénétrées. En revanche, si l'on applique la même technique de modification en utilisant le méthylméthacrylate homopolymere par exemple, on n'obtient pas d'amélioration importante de la ténacité.It has been observed that these three embodiments give rise to the desired improvements after curing the resin, while the morphology of the alloy varies quite significantly depending on the case: sometimes in the form of spherical monodisperse inclusions, sometimes in the form of heterodisperse nodules, sometimes in the form of interpenetrating phases. On the other hand, if the same modification technique is applied using the methyl methacrylate homopolymer for example, no significant improvement in toughness is obtained.
Le polymère de renforcement ajouté aux constituants de la résine thermodurcissable peut donc être synthétisé pendant la cuisson de la résine tout comme il peut être synthétisé au préalable. Dans les deux cas, sa composition comprend au moins 25 pour cent de l'unité structurale isobornyl acrylate ou méthacrylate. Ce polymère peut être thermoplastique ou partiellement réticulé. Ce polymère peut aussi contenir des groupes fonctionnels entraînant un greffage avec le réseau de la résine lors de la cuisson de celle-ci.The reinforcing polymer added to the constituents of the thermosetting resin can therefore be synthesized during the curing of the resin just as it can be synthesized beforehand. In both cases, its composition comprises at least 25 percent of the isobornyl acrylate or methacrylate structural unit. This polymer can be thermoplastic or partially crosslinked. This polymer can also contain functional groups resulting in grafting with the network of the resin during the baking thereof.
Exemples .Examples.
1. On a synthétisé un copolymere en chargeant un réacteur Grignard de 700 g méthyléthylcétone, 210 g méthylméthacrylate, 90 g isobornylméthacrylate, 3 g AIBN, puis en agitant à 70°C pendant 24 heures. On a alors ajouté à nouveau 1,5 g AIBN et on a maintenu sous agitation à 70°C pendant 24 heures. La conversion en monomères était de 98 pour cent. On a placé au bain d'huile à 125°C : 101,5 g de diglycidylether de bisphenol A (EPIKOTE 828) (DGEBA) et 50 g de la solution préparée. Le mélange a été maintenu sous agitation pendant 90 minutes pour évaporer le solvant. Le reste de solvant a été extrait sous cloche à vide pendant 30 minutes. Ensuite, 33,5 g de diaminodiphenylsulfone (CIBA HT976) (DDS) ont été ajouté au mélange par agitation à 120°C pendant 60 minutes. La préparation a été dégazée sous cloche à vide pendant 60 minutes. Le mélange ainsi préparé a fait l'objet du cycle de cuisson : 2°C/minute jusqu'à 120°C, mise sous vide relatif pendant 1 heure à 120°C, 3°C/minute jusqu'à 180°C, maintien à 180°C pendant 5 heures et refroidissement à 3°C/minute jusqu'à 30°C. L'alliage obtenu porte la référence 1 au tableau des propriétés observées .1. A copolymer was synthesized by charging a Grignard reactor with 700 g methyl ethyl ketone, 210 g methyl methacrylate, 90 g isobornyl methacrylate, 3 g AIBN, then stirring at 70 ° C for 24 hours. 1.5 g of AIBN were then added again and the mixture was kept stirring at 70 ° C. for 24 hours. The conversion to monomers was 98 percent. Was placed in an oil bath at 125 ° C: 101.5 g of diglycidylether bisphenol A (EPIKOTE 828) (DGEBA) and 50 g of the prepared solution. The mixture was kept stirring for 90 minutes to evaporate the solvent. The rest of the solvent was extracted under a vacuum bell for 30 minutes. Next, 33.5 g of diaminodiphenylsulfone (CIBA HT976) (DDS) was added to the mixture by stirring at 120 ° C for 60 minutes. The preparation was degassed under a vacuum bell for 60 minutes. The mixture thus prepared was subjected to the cooking cycle: 2 ° C / minute up to 120 ° C, placing under relative vacuum for 1 hour at 120 ° C, 3 ° C / minute up to 180 ° C, holding at 180 ° C for 5 hours and cooling at 3 ° C / minute to 30 ° C. The alloy obtained is given the reference 1 in the table of observed properties.
2. On a préparé par réaction simultanée à l'autoclave de cuisson, thermostatisé par circulation d'huile, les alliages époxy/acrylate référencés 2 à 15 au tableau des propriétés observées, et comprenant de 10 à 30 pour cent de modifiant polyacrylate, soit sous forme d'un homopolymere d' isobornylacrylate ou méthacrylate soit sous forme d'un copolymere avec le glycidylméthacrylate . Le peroxyde de tert-butyl benzoate (AKZO Trigonox C) a été utilisé comme initiateur à raison de 1 pour cent des monomères acryliques et a été ajouté au mélange de basse viscosité des autres constituants. La composition de la résine et le cycle de cuisson furent identiques à ceux décrits à l'exemple 1 en n'appliquant pas de vide au palier à 120°C.2. The epoxy / acrylate alloys referenced 2 to 15 in the table of observed properties, and comprising from 10 to 30 percent of polyacrylate modifier, were prepared by simultaneous reaction in a cooking autoclave, thermostatically controlled by oil circulation. in the form of an isobornylacrylate or methacrylate homopolymer or in the form of a copolymer with glycidylmethacrylate. Tert-butyl benzoate peroxide (AKZO Trigonox C) was used as the initiator at the rate of 1 percent of the acrylic monomers and was added to the low viscosity mixture of the other constituents. The composition of the resin and the baking cycle were identical to those described in Example 1 by applying no vacuum to the bearing at 120 ° C.
3. On a réalisé trois préparations d'alliage époxy/acrylate par réactions simultanées en suivant la procédure décrite à l'exemple 2, la composition de la résine étant celle de l'exemple 1, et on a suivi la prise de poids par absorption d'eau en immergeant des éprouvettes dans l'eau désionisée à 50°C. L'augmentation de poids s'arrête au- delà de 400 heures et atteint les valeurs suivantes : a) époxy non modifié : 3 pour cent b) modification avec 20 pour cent d' isobornylméthacrylate : 2,25 pour cent c) modification avec 20 pour cent de polyacrylate comprenant 80 pour cent d1 isobornylméthacrylate et 20 pour cent de glycidylméthacrylate : 2,5 pour cent3. Three epoxy / acrylate alloy preparations were made by simultaneous reactions following the procedure described in Example 2, the resin composition being that of Example 1, and the weight gain was monitored by absorption. of water by immersing test pieces in deionized water at 50 ° C. The increase in weight stops after 400 hours and reaches the following values: a) unmodified epoxy: 3 percent b) modification with 20 percent of isobornylmethacrylate: 2.25 percent c) modification with 20 percent polyacrylate comprising 80 percent of isobornylméthacrylate 1 and 20 percent of glycidyl methacrylate: 2.5 percent
4. On a préparé un polymère en émulsion en chargeant un réacteur Grignard agité à 60°C, de :4. An emulsion polymer was prepared by charging a stirred Grignard reactor at 60 ° C., with:
Eau : 68 partsWater: 68 parts
Isobornylméthacrylate : 31 partsIsobornylmethacrylate: 31 parts
Dodécylsulfate sodique :0,36 part Persulfate ammonique : 0,1 part Peroxyde de dicumyle : 0,5 partSodium dodecyl sulfate: 0.36 part Ammonic persulfate: 0.1 part Dicumyl peroxide: 0.5 part
Le latex a été déstabilisé à l'azote liquide et le polymère en poudre a été récupéré après séchage, broyage et tamisage. Il a été incorporé à raison de 15 pour cent dans le mélange DGEBA/DDS comprenant 33,2 phr de durcisseur.The latex was destabilized with liquid nitrogen and the powdered polymer was recovered after drying, grinding and sieving. It was incorporated at a rate of 15 percent in the DGEBA / DDS mixture comprising 33.2 phr of hardener.
La cuisson de la résine modifiée a suivi le cycle décrit à l'exemple 1 en omettant le palier de 60 minutes à 120°C.The baking of the modified resin followed the cycle described in Example 1, omitting the 60-minute plateau at 120 ° C.
L'alliage obtenu est référencé 16 au tableau des propriétés observées.The alloy obtained is referenced 16 in the table of observed properties.
5. On a préparé suivant la procédure décrite à l'exemple 4, un alliage époxy/acrylate où le polymère est un homopolymere de méthylméthacrylate. Cet alliage est référencé 17 au tableau des propriétés observées.5. An epoxy / acrylate alloy was prepared according to the procedure described in Example 4, in which the polymer is a methylmethacrylate homopolymer. This alloy is referenced 17 in the table of observed properties.
6. On a réalisé la cuisson d'un époxy non modifié suivant la composition décrite aux exemples 1 à 5 et en suivant le cycle de cuisson décrit à l'exemple 1. Cette résine porte la référence 18 au tableau des propriétés observées .6. An unmodified epoxy was baked according to the composition described in examples 1 to 5 and by following the baking cycle described in example 1. This resin bears the reference 18 to the table of properties observed.
Les préparations, selon la présente invention, décrites aux références 1 à 16 du tableau, ont toutes une morphologie de phases ségrégées, la phase continue étant la phase riche en résine thermodurcissable et la phase discrète étant la phase riche en polymère d'addition. The preparations according to the present invention, described in references 1 to 16 of the table, all have a morphology of segregated phases, the continuous phase being the phase rich in thermosetting resin and the discrete phase being the phase rich in addition polymer.
Tableau des propriétés observéesTable of observed properties
Symboles : P(M)A : l'ensemble du polymère d'additionSymbols: P (M) A: all of the addition polymer
IBA : isobornylacrylateIBA: isobornylacrylate
IBMA isobornylméthacrylateIBMA isobornylmethacrylate
PMMA polymethylmethacrylatePMMA polymethylmethacrylate
K1C : ténacité en mode I (géométrie Charpy)K1C: tenacity in mode I (Charpy geometry)
G : module d'élasticité au cisaillement n.r . pas enregistréG: modulus of elasticity in shear n.r. not registered
Réf. Mode P(M)A IBA IBMA K1C G(30°C) Total P(M)A P(M)A Ref. Mode P (M) A IBA IBMA K1C G (30 ° C) Total P (M) AP (M) A
% % % MPa*mè GPa%%% MPa * mè GPa
1 solution 10 -- 30 1,041 n.r.1 solution 10 - 30 1,041 n.r.
2 simultané 10 100 -- • 0,974 1,102 simultaneous 10 100 - • 0.974 1.10
3 simultané 10 87 -- 0,922 1,233 simultaneous 10 87 - 0.922 1.23
4 simultané 20 100 -- 1,094 1,084 simultaneous 20 100 - 1.094 1.08
5 simultané 20 85 -- 1,164 1,165 simultaneous 20 85 - 1.164 1.16
6 simultané 20 70 -- 1,324 1,146 simultaneous 20 70 - 1.324 1.14
7 simultané 30 100 -- 1,213 1,057 simultaneous 30 100 - 1.213 1.05
8 simultané 30 85 -- 1,260 1,128 simultaneous 30 85 - 1,260 1.12
9 simultané 30 75 -- 1,276 1,089 simultaneous 30 75 - 1.276 1.08
10 simultané 20 -- 100 1,236 1,1710 simultaneous 20 - 100 1,236 1.17
11 simultané 20 -- 85 1,211 1,1711 simultaneous 20 - 85 1,211 1.17
12 simultané 20 -- 70 1,188 1,2112 simultaneous 20 - 70 1,188 1,21
13 simultané 30 -- 100 1,391 1,1513 simultaneous 30 - 100 1,391 1,15
14 simultané 30 -- 85 1,250 1,1714 simultaneous 30 - 85 1,250 1.17
15 simultané 30 -- 75 1,193 1,21 16 dispersionl5 — 100 1,070 n.r.15 simultaneous 30 - 75 1,193 1,21 16 dispersionl5 - 100 1,070 nr
17 dispersion 10 (PMMA) 0,775 n.r, (comparaison)17 dispersion 10 (PMMA) 0.775 n.r, (comparison)
18 non modifié 0 0,658 1,11 (contrôle) 18 not changed 0 0.658 1.11 (control)

Claims

Revendications claims
1. Mélange comprenant de 95 à 60 pour cent de constituants d'une résine thermodurcissable et de 5 à 40 pour cent respectivement de monomères d'addition ou leur polymère lesquels comprennent au moins 25 pour cent de l'unité structurale de 1 ' isobornyl acrylate ou méthacrylate.1. Mixture comprising from 95 to 60 percent of constituents of a thermosetting resin and from 5 to 40 percent respectively of addition monomers or their polymer which comprise at least 25 percent of the structural unit of the isobornyl acrylate or methacrylate.
2. Mélange selon la revendication 1 où la résine thermodurcissable est un polyépoxy et son durcisseur.2. Mixture according to claim 1 wherein the thermosetting resin is a polyepoxy and its hardener.
3. Alliages de résine durcie basés sur des mélanges selon les revendications 1 ou 2.3. Hardened resin alloys based on mixtures according to claims 1 or 2.
4. Matériaux composites ayant pour matrice l'alliage selon la revendication 3.4. Composite materials having as matrix the alloy according to claim 3.
5. Procédé d'obtention de l'alliage décrit selon la revendication 3 tel que la formation du polymère d'addition se produit pendant la cuisson de la résine thermodurcissable .5. Method for obtaining the alloy described according to claim 3 such that the formation of the addition polymer occurs during the firing of the thermosetting resin.
6. Procédé d'obtention de l'alliage décrit selon la revendication 3 tel que la cuisson de la résine thermodurcissable a lieu en présence du polymère d'addition préalablement dissout.6. Method for obtaining the alloy described according to claim 3 such that the baking of the thermosetting resin takes place in the presence of the addition polymer previously dissolved.
7. Procédé d'obtention de l'alliage décrit selon la revendication 3 tel que la cuisson de la résine thermodurcissable a lieu en présence du polymère d'addition préalablement dispersé sous forme d'une poudre finement divisée. 7. A method of obtaining the alloy described according to claim 3 such that the baking of the thermosetting resin takes place in the presence of the addition polymer previously dispersed in the form of a finely divided powder.
EP99921994A 1998-05-13 1999-05-12 Method for reinforcing thermosetting resins with isobornyl acrylate or methacrylate polymers Withdrawn EP1030886A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
BE9800363 1998-05-13
BE9800363A BE1011910A7 (en) 1998-05-13 1998-05-13 STRENGTHENING THERMOSETTING RESINS BY POLYMERS BASED OR METHACRYLATE isobornyl acrylate.
PCT/BE1999/000060 WO1999058606A1 (en) 1998-05-13 1999-05-12 Method for reinforcing thermosetting resins with isobornyl acrylate or methacrylate polymers

Publications (1)

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EP1030886A1 true EP1030886A1 (en) 2000-08-30

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EP (1) EP1030886A1 (en)
BE (1) BE1011910A7 (en)
WO (1) WO1999058606A1 (en)

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JPS61203108A (en) * 1985-03-04 1986-09-09 Toyobo Co Ltd Photocurable flexible composition
JPS6420216A (en) * 1987-07-15 1989-01-24 Matsushita Electric Works Ltd Photocurable resin composition
JPH02223037A (en) * 1988-11-24 1990-09-05 Mitsui Petrochem Ind Ltd Information recording medium
JPH03255122A (en) * 1990-03-02 1991-11-14 Nippon Paint Co Ltd Thermosetting resin composition and thermosetting resin molding
JPH04272978A (en) * 1991-02-28 1992-09-29 Hitachi Chem Co Ltd Coating resin composition and resin composition for color filter protective film containing same
KR100317407B1 (en) * 1993-03-24 2002-02-28 스프레이그 로버트 월터 Sheet material with topographic features
JPH06279566A (en) * 1993-03-24 1994-10-04 Dainippon Ink & Chem Inc Actinic-ray-curable composition for poly
JPH09505095A (en) * 1993-11-10 1997-05-20 ミネソタ マイニング アンド マニュファクチャリング カンパニー Thermosetting pressure sensitive adhesive

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WO1999058606A1 (en) 1999-11-18
BE1011910A7 (en) 2000-02-01

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