WO2013093242A1 - Stabilized composition based on a chlorinated thermoplastic material - Google Patents
Stabilized composition based on a chlorinated thermoplastic material Download PDFInfo
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- WO2013093242A1 WO2013093242A1 PCT/FR2012/000538 FR2012000538W WO2013093242A1 WO 2013093242 A1 WO2013093242 A1 WO 2013093242A1 FR 2012000538 W FR2012000538 W FR 2012000538W WO 2013093242 A1 WO2013093242 A1 WO 2013093242A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
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- the present invention relates to a composition based on a chlorinated thermoplastic material stabilized with a zinc-derived additive.
- Halogenated polymers and more particularly polyvinyl chloride (PVC) are widely used polymers in many different and varied fields.
- Pure PVC is a rigid, mechanically strong material that is relatively resistant to weather, water and chemicals. It is electrically insulating but quite unstable to heat and light. Thus, under the influence of heat, PVC undergoes a deep degradation, accompanied by a characteristic coloration.
- Degradation mechanisms have been widely studied and it is recognized that the induction of thermal degradation of PVC is caused by the presence of "labile chlorine atoms" causing a dehydrochlorination reaction giving rise to conjugated double bond sequences, responsible for parasitic staining, this reaction being itself catalyzed by free hydrochloric acid.
- the PVC then takes a brown color which turns with time to black. In addition to these coloring phenomena, parasitic crosslinking also affects the physical properties of the material.
- thermal stabilizers have been developed for PVC.
- the function of the thermal stabilizers of PVC is to slow the spread of the dehydrochlorination chain and eliminate the hydrochloric acid released by this reaction.
- organotins organotins
- tin carboxylates which are of two types:
- the essential objective of the present invention is therefore to find new substitution stabilizers for lead or tin derivatives which have been widely used, especially for the stabilization of chlorinated thermoplastics such as for example PVC.
- Another essential objective of the present invention is to propose new articles prepared from a composition containing a chlorinated thermoplastic material additive with the new stabilizers according to the invention.
- composition comprising:
- thermal stabilizer A which is a zinc complex of formula chosen from the group consisting of the following complexes (4) to (6):
- compositions according to the invention have a better thermal stability than chlorinated thermoplastic resins not additive with the stabilizer according to the invention. Thus, these compositions have a viable alternative to formulations using lead or tin derivatives.
- complex or metal salt includes any oligomeric form or the like of said complex or metal salt.
- the stabilizer A according to the invention can be used in the composition according to the invention in amounts ranging from 0.1 to 50 parts by weight, preferably from 0.1 to 20 parts and even more preferentially from 0.1 to 10 parts. parts by weight per 100 parts by weight of the chlorinated thermoplastic material M.
- the composition according to the invention comprises:
- a complex or metal salt chosen from the group consisting of the following complexes (4) to (6) is preferably used as heat stabilizer A:
- the thermal stabilizer A according to the invention is bis (2,2,7-trimethyl-3,5-octanedion) (6):
- the chlorinated thermoplastic material M may especially consist of a chlorinated resin selected from the group consisting of homopolymers of vinyl chloride which may be optionally superchlorinated and optionally grafted copolymers, which result from the co-polymerization of vinyl chloride with one or more ethylenically comonomers. unsaturated.
- comonomers include vinylidene halides such as vinylidene chloride or fluoride, vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylic and methacrylic acids.
- nitriles, amides and alkyl esters derived therefrom in particular acrylonitrile, acrylamide, methacrylamide, methyl methacrylate, methyl acrylate, butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, vinylaromatic derivatives.
- styrenes such as, for example, styrenes
- vinyl naphthalenes such as bicyclo (2.2.1) hep-2-ene, bicyclo (2.2.1) hepta-2,5-diene, ethylene, propene and butene-1.
- olefins such as bicyclo (2.2.1) hep-2-ene, bicyclo (2.2.1) hepta-2,5-diene, ethylene, propene and butene-1.
- the chlorinated thermoplastic material M is chosen from the group consisting of: a homopolymer of vinyl chloride, a copolymer of vinyl chloride with unsaturated comonomers and their mixtures
- the chlorinated thermoplastic material M is chosen from the group consisting of: a polyvinyl chloride resin, a plastisol obtained by mixing a polyvinyl chloride resin in a liquid plasticizer and their mixtures.
- compositions according to the invention may furthermore contain, depending on
- one or more additives chosen from the group consisting of: a lubricating agent, a plasticizer, a filler, a coloring aid, an anti-oxidizing agent, an antistatic additive, a fungicidal additive, a blowing additive, a sun-protective additive, a processing-aids additive for improving the gelling of the ready-to-use mixture, and mixtures thereof.
- the thermal stabilizer A according to the present invention may be incorporated, at the same time and / or before the additives mentioned above when it is used. According to a particularly preferred embodiment, this operation is carried out in a slow or fast mixer and the thermoplastic resin, the stabilizer according to the invention and then the additives and / or fillers are successively introduced so as to obtain a mixture in the form of a dry powder. or in the form of paste. In a manner known per se, this operation can be carried out at room temperature or at a higher temperature due to the heat generated by this operation.
- the heat-stabilizing action and the light of the stabilizer A according to the invention can for example be demonstrated for the articles transformed by standard tests and well known by those skilled in the art such as static thermal stability test at oven.
- compositions according to the invention in particular those based on PVC, can be injection molded, rotational molded, calendered and then thermoformed, extruded, coextruded, pressed in the form of articles such as lines, window profiles, sheets, tubes. or, in the case of flexible resin formulations of the plastisol type, implemented by coating or dipping processes and transformed into articles such as interior and exterior coatings, in particular coated fabrics for the building industry, leather goods, etc.
- the transformed articles can be rigid or flexible, compact or expanded.
- the invention also relates to an article obtained by extrusion, extrusion blow molding, calendering, injection and intrusion, or thermoforming of the composition according to the invention and as described herein.
- a last object of the invention consists in the use of the composition according to the invention and as described herein or the article according to the invention for the fields of building, packaging, electricity, electronics, medical, consumer goods and transportation.
- a solution of 100 mmol of 97% sodium methylate (6.12 g) in 100 ml of isopropanol is concentrated by distillation of 20%, then 100 mmol of 95% isopropyl acetoacetate (15.93 g) are added and the solution is heated at 80 ° C for 1 h to obtain a homogeneous orange solution.
- a solution of zinc chloride (50 mmol, 7 g) in 50 ml of isopropanol is then added at 70 ° C over 1 hour. The heating is maintained between 80 and 90 ° C for 3:30 and then the sodium chloride formed is filtered after cooling.
- the alcoholic solution is evaporated to dryness to yield 25.3 g of a paste which is redissolved in 200 ml of ethanol. After hot filtration and evaporation to dryness, 17.2 g of a white solid are obtained (yield 98%).
- Thermal stabilizer (6) zinc bis (2,2,7-trimethyl-3,5-octanedionate) of formula
Abstract
The invention relates to a stabilized composition based on a chlorinated thermoplastic material and a zinc-based additive.
Description
COMPOSITION STABILISEE A BASE D'UNE MATIERE THERMOPLASTIQUE STABILIZED COMPOSITION BASED ON THERMOPLASTIC MATERIAL
CHLOREE CHLORINATED
La présente invention a pour objet une composition à base d'une matière thermoplastique chlorée stabilisée par un additif dérivé du zinc. The present invention relates to a composition based on a chlorinated thermoplastic material stabilized with a zinc-derived additive.
Les polymères halogénés et plus particulièrement le polychlorure de vinyle (PVC) sont des polymères très utilisés dans de nombreux domaines divers et variés. Le PVC pur est un matériau rigide, mécaniquement solide, qui résiste relativement bien aux intempéries, à l'eau et aux produits chimiques. Il est électriquement isolant mais assez instable à la chaleur et à la lumière. Ainsi, sous l'influence de la chaleur, le PVC subit une dégradation profonde, accompagnée d'une coloration caractéristique. Les mécanismes de dégradation ont été largement étudiés et il est admit que l'induction de la dégradation thermique du PVC est causée par la présence « d'atomes de chlore labiles » provoquant une réaction de déshydrochloruration donnant naissance à des séquences de doubles liaisons conjuguées, responsables de colorations parasites, cette réaction étant elle-même catalysée par l'acide chlorhydrique libre. Le PVC prend alors une coloration brune qui vire avec le temps au noir. A ces phénomènes de coloration s'ajoutent aussi des réticulations parasites qui altèrent les propriétés physiques du matériau. Halogenated polymers and more particularly polyvinyl chloride (PVC) are widely used polymers in many different and varied fields. Pure PVC is a rigid, mechanically strong material that is relatively resistant to weather, water and chemicals. It is electrically insulating but quite unstable to heat and light. Thus, under the influence of heat, PVC undergoes a deep degradation, accompanied by a characteristic coloration. Degradation mechanisms have been widely studied and it is recognized that the induction of thermal degradation of PVC is caused by the presence of "labile chlorine atoms" causing a dehydrochlorination reaction giving rise to conjugated double bond sequences, responsible for parasitic staining, this reaction being itself catalyzed by free hydrochloric acid. The PVC then takes a brown color which turns with time to black. In addition to these coloring phenomena, parasitic crosslinking also affects the physical properties of the material.
C'est pour cette raison que de nombreux stabilisants thermiques ont été développés pour le PVC. Cependant, Il est encore impossible d'agir sur l'induction de la dégradation thermique du PVC qui est inhérente à la structure même de ce polymère. Ainsi, la fonction des stabilisants thermique du PVC consiste à ralentir la propagation de la déshydrochloruration en chaîne et à éliminer l'acide chlorhydrique libéré par cette réaction. It is for this reason that many thermal stabilizers have been developed for PVC. However, it is still impossible to act on the induction of thermal degradation of PVC which is inherent in the very structure of this polymer. Thus, the function of the thermal stabilizers of PVC is to slow the spread of the dehydrochlorination chain and eliminate the hydrochloric acid released by this reaction.
Parmi les stabilisants utilisés, les stabilisants au plomb sont les plus anciens mais du fait d'une très forte pression environnementale, on observe un bannissement progressif de part le monde. Les organoétains (organostanniques) sont aussi très utilisés. Différents types d'organoétains, en particulier des mélanges de composés mono- et diorganostanniques, sont utilisés comme stabilisants, essentiellement pour produire des films d'emballage rigides, des bouteilles, des revêtements pour toitures et des panneaux de construction rigides clairs. Parmi les plus utiles on peut citer les carboxylates d'étain qui sont de deux types : Among the stabilizers used, lead stabilizers are the oldest but due to very strong environmental pressure, there is a gradual ban in the world. Organotins (organotins) are also widely used. Various types of organotins, particularly mixtures of mono- and diorganotin compounds, are used as stabilizers, essentially for producing rigid packaging films, bottles, roof coatings and clear rigid building boards. Among the most useful are tin carboxylates which are of two types:
- les savons tels que le dilaurate de dibutylétain, et - soaps such as dibutyltin dilaurate, and
- les maléates.
Cependant, ces dérivés à base d'alkylétain, bien que très efficaces, présentent l'inconvénient d'être toxiques (CMR2 toxiques pour la reproduction). Ainsi, pour un développement durable, il apparaît donc nécessaire de développer des stabilisants pour les matières thermoplastiques chlorés non toxiques. - the maleates. However, these alkyltin derivatives, although very effective, have the disadvantage of being toxic (CMR2 toxic for reproduction). Thus, for sustainable development, it therefore appears necessary to develop stabilizers for non-toxic chlorinated thermoplastics.
L'objectif essentiel de la présente invention est donc de trouver de nouveaux stabilisants de substitution aux dérivés de plomb ou de l'étain qui ont largement été utilisé, notamment pour la stabilisation des matières thermoplastiques chlorés telles que par exemple le PVC. The essential objective of the present invention is therefore to find new substitution stabilizers for lead or tin derivatives which have been widely used, especially for the stabilization of chlorinated thermoplastics such as for example PVC.
Un autre objectif essentiel de la présente invention est de proposer de nouveaux articles préparés à partir de composition renfermant une matière thermoplastique chlorée additivée avec les nouveaux stabilisants selon l'invention. Another essential objective of the present invention is to propose new articles prepared from a composition containing a chlorinated thermoplastic material additive with the new stabilizers according to the invention.
Ces objectifs, parmi d'autres, sont atteints par la présente invention qui concerne tout d'abord une composition comprenant: These and other objects are achieved by the present invention which firstly relates to a composition comprising:
a) au moins une matière thermoplastique chlorée M, et a) at least one chlorinated thermoplastic material M, and
b) au moins un stabilisant thermique A qui est un complexe de zinc de formule choisi parmi le groupe constitué par les complexes (4) à (6) suivants: b) at least one thermal stabilizer A which is a zinc complex of formula chosen from the group consisting of the following complexes (4) to (6):
(4) : [Zn (EAA)2] avec EAA = Fanion éthyle acétoacétato ou l'anion énolate de l'éthyle acétoacétate, (4): [Zn (EAA) 2 ] with EAA = ethyl acetate acetoacetate or the enolate anion of ethyl acetoacetate,
(5) : [Zn (iPr-AA)2] avec iPr-AA = l'anion isopropyle acétoacétato ou l'anion (5): [Zn (iPr-AA) 2 ] with iPr-AA = isopropylacetoacetate anion or anion
et and
Les compositions selon l'invention présentent une meilleure stabilité thermique que les résines thermoplastiques chlorées non additivées avec le stabilisant selon l'invention. Ainsi, ces compositions présentent une alternative viable aux formulations utilisant les dérivés au plomb ou à l'étain. The compositions according to the invention have a better thermal stability than chlorinated thermoplastic resins not additive with the stabilizer according to the invention. Thus, these compositions have a viable alternative to formulations using lead or tin derivatives.
Il est du mérite des inventeurs d'avoir trouvé, de manière tout à fait surprenante et inattendue, qu'il convient d'utiliser des complexes métalliques de zinc spécifiques pour obtenir d'excellents stabilisants thermiques pour les matières thermoplastiques chlorées telles que le PVC.
La définition des ligands est tirée de l'ouvrage « Chimie Organométallique » de Didier Astruc, publié en 2000 par EDP Sciences, Cf. notamment Chapitre 1 , « Les complexes monométalliques », pages 31 et suivantes. It is the merit of the inventors to have found, quite surprisingly and unexpectedly, that it is appropriate to use specific zinc metal complexes to obtain excellent thermal stabilizers for chlorinated thermoplastics such as PVC. The definition of ligands is taken from the book "Organometallic Chemistry" by Didier Astruc, published in 2000 by EDP Sciences, see in particular Chapter 1, "The monometallic complexes", pages 31 and following.
II est entendu que par "complexe ou sel métallique", cette définition inclut toute forme oligomérique ou analogue dudit complexe ou sel métallique. It is understood that by "complex or metal salt", this definition includes any oligomeric form or the like of said complex or metal salt.
Le stabilisant A selon l'invention peut être utilisé dans la composition selon l'invention en des quantités allant de 0,1 à 50 parties en poids, de préférence de 0,1 à 20 parties et encore plus préférentiellement de 0,1 à 10 parties en poids pour 100 parties en poids de la matière thermoplastique chlorée M. Ainsi la composition selon l'invention comprend: The stabilizer A according to the invention can be used in the composition according to the invention in amounts ranging from 0.1 to 50 parts by weight, preferably from 0.1 to 20 parts and even more preferentially from 0.1 to 10 parts. parts by weight per 100 parts by weight of the chlorinated thermoplastic material M. Thus the composition according to the invention comprises:
a) pour 100 parties poids d'au moins une matière thermoplastique chlorée M, et b) de 0,1 à 50 parties poids d'au moins un stabilisant thermique A selon l'invention et tel que décrit dans le présent mémoire, et de préférence de 0,1 à 20 parties poids et encore plus préférentiellement de 0,1 à 10 parties poids. a) per 100 weight parts of at least one chlorinated thermoplastic material M, and b) from 0.1 to 50 weight parts of at least one thermal stabilizer A according to the invention and as described herein, and preferably from 0.1 to 20 parts by weight and even more preferably from 0.1 to 10 parts by weight.
Pour la réalisation de l'invention, on utilise de préférence comme stabilisant thermique A un complexe ou sel métallique choisi parmi le groupe constitué par les complexes (4) à (6) suivants: For carrying out the invention, a complex or metal salt chosen from the group consisting of the following complexes (4) to (6) is preferably used as heat stabilizer A:
(4) : [Zn {EAA)2] avec EAA = l'anion éthyle acétoacétato ou l'anion énolate de l'éthyle acétoacétate, (4): [Zn (EAA) 2 ] with EAA = ethyl anion acetoacetate or enolate anion of ethyl acetoacetate,
(5) : [Zn {iPr-AA)2] avec iPr-AA = l'anion isopropyle acétoacétato ou l'anion énolate de l'isopropyle acétoacétate, et (5): [Zn (iPr-AA) 2 ] with iPr-AA = the isopropyl acetoacetate anion or the enolate anion of isopropyl acetoacetate, and
Selon un mode de réalisation préféré, le stabilisant thermique A selon l'invention est le bis(2,2,7-triméthyl-3,5-octanedion le (6):suivante: According to a preferred embodiment, the thermal stabilizer A according to the invention is bis (2,2,7-trimethyl-3,5-octanedion) (6):
(6)
Ce composé présente l'avantage d'être liquide à température ambiante (25°C) et soluble dans des solvants organiques tels que des alcanes. La matière thermoplastique chlorée M peut notamment consister en une résine chlorée choisie dans le groupe constitué par les homopolymères du chlorure de vinyle qui peuvent être éventuellement surchlorés et les copolymères éventuellement greffés, qui résultent de la copolynnérisation du chlorure de vinyle avec un ou plusieurs comonomères éthyléniquement insaturés. A titre d'exemple de comonomères on peut notamment citer les halogénures de vinylidène comme le chlorure ou le fluorure de vinylidène, les carboxylate de vinyle comme l'acétate de vinyle, le propionate de vinyle, le butyrate de vinyle, les acides acrylique et méthacrylique ainsi que les nitriles, amides et ester d'alkyle qui en dérivent, notamment acrylonitrile, acrylamide, méthacrylamide, méthacrylate de méthyle, acrylate de méthyle, acrylate de butyle, acrylate d'éthyle, acrylate d'éthyle-2 hexyle, les dérivés vinylaromatiques tels que par exemple les styrènes, les (6) This compound has the advantage of being liquid at room temperature (25 ° C.) and soluble in organic solvents such as alkanes. The chlorinated thermoplastic material M may especially consist of a chlorinated resin selected from the group consisting of homopolymers of vinyl chloride which may be optionally superchlorinated and optionally grafted copolymers, which result from the co-polymerization of vinyl chloride with one or more ethylenically comonomers. unsaturated. Examples of comonomers that may be mentioned include vinylidene halides such as vinylidene chloride or fluoride, vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylic and methacrylic acids. as well as the nitriles, amides and alkyl esters derived therefrom, in particular acrylonitrile, acrylamide, methacrylamide, methyl methacrylate, methyl acrylate, butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, vinylaromatic derivatives. such as, for example, styrenes,
vinylnaphtalènes, les oléfines telles que bicyclo(2.2.1)hep-2-ène, bicyclo(2.2.1)hepta-2,5- diène, éthylène, propène et butène-1. vinyl naphthalenes, olefins such as bicyclo (2.2.1) hep-2-ene, bicyclo (2.2.1) hepta-2,5-diene, ethylene, propene and butene-1.
Selon un mode de réalisation préféré, la matière thermoplastique chlorée M est choisi parmi le groupe constitué par: un homopolymère du chlorure de vinyle, un copolymère du chlorure de vinyle avec des co-monomères insaturés et leurs mélanges According to a preferred embodiment, the chlorinated thermoplastic material M is chosen from the group consisting of: a homopolymer of vinyl chloride, a copolymer of vinyl chloride with unsaturated comonomers and their mixtures
Selon un mode de réalisation préféré, la matière thermoplastique chlorée M est choisi parmi le groupe constitué par : une résine de poly(chlorure de vinyle), un plastisol obtenue par mélange d'une résine poly(chlorure de vinyle) dans un plastifiant liquide et leurs mélanges. According to a preferred embodiment, the chlorinated thermoplastic material M is chosen from the group consisting of: a polyvinyl chloride resin, a plastisol obtained by mixing a polyvinyl chloride resin in a liquid plasticizer and their mixtures.
Les compositions selon l'invention peuvent renfermer en outre, en fonction The compositions according to the invention may furthermore contain, depending
notamment des conditions de mise en œuvre, de transformation et/ou des applications auxquelles elles sont destinées, un ou plusieurs additifs choisi parmi le groupe constitué par : un agent lubrifiant , un agent plastifiant, une charge, un adjuvant de coloration, un agent anti-choc, un additif antistatique, un additif fongicide, un additif gonflant, un additif protecteur contre le rayonnement solaire, un additif « processing-aids » pour améliorer la gélification du mélange prêt à l'emploi et leurs mélanges. in particular the conditions of implementation, transformation and / or the applications for which they are intended, one or more additives chosen from the group consisting of: a lubricating agent, a plasticizer, a filler, a coloring aid, an anti-oxidizing agent, an antistatic additive, a fungicidal additive, a blowing additive, a sun-protective additive, a processing-aids additive for improving the gelling of the ready-to-use mixture, and mixtures thereof.
Le stabilisant thermique A selon la présente invention peut être incorporé, en même temps et/ou avant les additifs mentionnés précédemment lorsqu'il en est fait usage.
Selon une mise en particulièrement préférée, on effectue cette opération dans un mélangeur lent ou rapide et on introduit successivement la résine thermoplastique, le stabilisant selon l'invention puis les additifs et/ou charges, de façon à obtenir un mélange sous forme de poudre sec ou sous forme de pâte. De manière connue en soi, cette opération peut s'effectuer à température ambiante ou à une température supérieure due à la chaleur dégagée par cette opération. The thermal stabilizer A according to the present invention may be incorporated, at the same time and / or before the additives mentioned above when it is used. According to a particularly preferred embodiment, this operation is carried out in a slow or fast mixer and the thermoplastic resin, the stabilizer according to the invention and then the additives and / or fillers are successively introduced so as to obtain a mixture in the form of a dry powder. or in the form of paste. In a manner known per se, this operation can be carried out at room temperature or at a higher temperature due to the heat generated by this operation.
L'action stabilisante à la chaleur et la lumière du stabilisant A selon l'invention peut par exemple être mise en évidence pour les articles transformés par des tests standards et bien connus par l'homme du métier tels que des test de stabilité thermique statique au four. The heat-stabilizing action and the light of the stabilizer A according to the invention can for example be demonstrated for the articles transformed by standard tests and well known by those skilled in the art such as static thermal stability test at oven.
Les compositions selon l'invention, notamment celles à base de PVC, peuvent être moulées par injection, moulées par rotation, calandrées puis thermoformées, extrudées, coextrudées, pressées sous forme d'articles tels qu'huisseries, profilés de fenêtres, feuilles, tubes ou, dans le cas de formulations de résines flexibles de type plastisols, mises en œuvre selon les procédés d'enduction ou de trempage et transformées en articles tels que revêtements intérieurs et extérieurs, notamment des tissus enduits pour le bâtiment, la maroquinerie, etc. Les articles transformés peuvent être rigides ou souples, compacts ou expansés. The compositions according to the invention, in particular those based on PVC, can be injection molded, rotational molded, calendered and then thermoformed, extruded, coextruded, pressed in the form of articles such as lines, window profiles, sheets, tubes. or, in the case of flexible resin formulations of the plastisol type, implemented by coating or dipping processes and transformed into articles such as interior and exterior coatings, in particular coated fabrics for the building industry, leather goods, etc. The transformed articles can be rigid or flexible, compact or expanded.
L'invention concerne aussi un article obtenu par extrusion, extrusion-soufflage, calandrage, injection et intrusion, ou thermoformage de la composition selon l'invention et telle que décrite dans le présent mémoire. The invention also relates to an article obtained by extrusion, extrusion blow molding, calendering, injection and intrusion, or thermoforming of the composition according to the invention and as described herein.
Enfin, un dernier objet de l'invention consiste en l'utilisation de la composition selon l'invention et telle que décrite dans le présent mémoire ou de l'article selon l'invention pour les domaines du bâtiment, de l'emballage, de l'électricité, de l'électronique, médical, des biens de consommation et du transport. Finally, a last object of the invention consists in the use of the composition according to the invention and as described herein or the article according to the invention for the fields of building, packaging, electricity, electronics, medical, consumer goods and transportation.
D'autres avantages et caractéristiques de la présente invention apparaîtront à la lecture des exemples suivants donnés à titre illustratif nullement limitatif.
EXEMPLES Other advantages and features of the present invention will appear on reading the following examples given by way of non-limiting illustration. EXAMPLES
EXEMPLE 1 : Synthèse des stabilisants thermiques (5) et (6) selon l'invention EXAMPLE 1 Synthesis of Thermal Stabilizers (5) and (6) According to the Invention
a) Synthèse du composé (5V. a) Synthesis of the compound (5V.
[Zn (isopropyle acétoacétato)2] ou [Zn (iPr-AA)2] avec iPr-AA = l'anion isopropyle acétoacétato ou l'anion énolate de l'isopropyle acétoacétate, [Zn (isopropylacetoacetato) 2 ] or [Zn (iPr-AA) 2 ] with iPr-AA = the isopropylacetoacetato anion or the enolate anion of isopropylacetoacetate,
Une solution de 100 mmol de méthylate de sodium à 97 % (6.12 g) dans 100 ml d'isopropanol est concentrée par distillation de 20 %, puis 100 mmol d'isopropyle acétoacétate à 95 % (15.93 g) sont ajoutés et la solution est chauffée à 80°C pendant 1 h pour obtenir une solution homogène orange. Une solution de chlorure de zinc (50 mmol, 7 g) dans 50 ml d'isopropanol est alors ajoutée à 70°C en 1 h. Le chauffage est maintenu entre 80 et 90°C pendant 3h30 puis le chlorure de sodium formé est filtré après refroidissement. La solution alcoolique est évaporée à sec pour conduire à 25.3 g d'une pâte qui est redissoute dans 200 ml d'éthanol. Après filtration à chaud et évaporation à sec, sont obtenus 17.2 g d'un solide blanc (rendement 98%). A solution of 100 mmol of 97% sodium methylate (6.12 g) in 100 ml of isopropanol is concentrated by distillation of 20%, then 100 mmol of 95% isopropyl acetoacetate (15.93 g) are added and the solution is heated at 80 ° C for 1 h to obtain a homogeneous orange solution. A solution of zinc chloride (50 mmol, 7 g) in 50 ml of isopropanol is then added at 70 ° C over 1 hour. The heating is maintained between 80 and 90 ° C for 3:30 and then the sodium chloride formed is filtered after cooling. The alcoholic solution is evaporated to dryness to yield 25.3 g of a paste which is redissolved in 200 ml of ethanol. After hot filtration and evaporation to dryness, 17.2 g of a white solid are obtained (yield 98%).
Teneur en Zn calculée : 18.59 %, teneur en Zn dosée (ICP) : 18.57 % Zn content calculated: 18.59%, assayed Zn content (ICP): 18.57%
Analyse IR (nm): 2989, 1617, 1514, 1246, 1170. IR (nm) analysis: 2989, 1617, 1514, 1246, 1170.
(6) (6)
0.86 g d'hydroxyde de sodium (21 mmol) sont dissous dans 10 ml d'éthanol absolu, puis 4 g de 2,2,7-triméthyl-3,5-octanedione (21 mmol) sont ajoutés à la solution obtenue. Une solution de 1.55 g de chlorure de zinc (11 mmol) dans 10 ml d'éthanol absolu est ajoutée en 5 min à la solution jaune pâle de l'énolate de sodium. Le mélange est agité 3h à 20°C puis 10 ml de toluène sont ajoutés. La suspension de chlorure de sodium est refroidie à 10°C sous agitation puis filtrée. Le filtrat est évaporé sous vide pour donner 4 g d'une huile épaisse limpide (rendement 90%). 0.86 g of sodium hydroxide (21 mmol) are dissolved in 10 ml of absolute ethanol and then 4 g of 2,2,7-trimethyl-3,5-octanedione (21 mmol) are added to the solution obtained. A solution of 1.55 g of zinc chloride (11 mmol) in 10 ml of absolute ethanol is added over 5 min to the pale yellow solution of sodium enolate. The mixture is stirred for 3 h at 20 ° C. and then 10 ml of toluene are added. The suspension of sodium chloride is cooled to 10 ° C. with stirring and then filtered. The filtrate is evaporated under vacuum to give 4 g of a clear thick oil (yield 90%).
L'analyse RMN du proton dans le diméthylsulfoxyde (DMSO) montre que la structure du complexe ainsi formé est sous la forme d'un seul isomère : Déplacements chimiques : 0.87 (12H, doublet), 1.05 (18H, singulet), 1.95 (6H, massif), 5.33 (2H, singulet). Proton NMR analysis in dimethylsulfoxide (DMSO) shows that the structure of the complex thus formed is in the form of a single isomer: Chemical displacements: 0.87 (12H, doublet), 1.05 (18H, singlet), 1.95 (6H , massive), 5.33 (2H, singlet).
Teneur en Zn calculée : 15.1 %, teneur en Zn dosée : (ICP) 14.9 %
EXEMPLE 2 : Préparation d'une composition à base de PVC de type simplifiée et contenant les stabilisants (4) à (6) selon l'invention. Zn content calculated: 15.1%, Zn content assayed: (ICP) 14.9% EXAMPLE 2 Preparation of a Composition Based on PVC of Simplified Type Containing the Stabilizers (4) to (6) According to the Invention
- Stabilisant thermique (4): [Zn (EAA)2] avec EAA = l'anion éthyle acétoacétato ou l'anion énolate de l'éthyle acétoacétate, Thermal stabilizer (4): [Zn (EAA) 2 ] with EAA = the ethyl anion acetoacetate or the enolate anion of ethyl acetoacetate,
- Stabilisant thermique (5): [Zn (iPr-AA)2] avec iPr-AA = l'anion isopropyle - Thermal Stabilizer (5): [Zn (iPr-AA) 2 ] with iPr-AA = isopropyl anion
acétoacétato ou l'anion énolate de l'isopropyle acétoacétate, et acetoacetato or the enolate anion of isopropyl acetoacetate, and
- Stabilisant thermique(6): bis(2,2,7-triméthyl-3,5-octanedionate) de zinc de formule Thermal stabilizer (6): zinc bis (2,2,7-trimethyl-3,5-octanedionate) of formula
(6) (6)
Protocole opératoire: On introduit dans un mélangeur 100 parties en poids d'une résine PVC. Après agitation (>3000 tours/mn), on observe une élévation de température. A 60°C, on introduit alors des quantités variables (= de 1 à 40 parties) d'un stabilisant selon l'invention, puis ensuite les additifs usuels (pigment tel que le TiO2, agent plastifiant). Lorsque la température atteind 110°C environ, la formulation PVC est refroidie en réduisant l'agitation et en refroidissant le réacteur. Operating Procedure: 100 parts by weight of a PVC resin are introduced into a mixer. After stirring (> 3000 rpm), a rise in temperature is observed. At 60 ° C., variable amounts (= 1 to 40 parts) of a stabilizer according to the invention are then introduced, followed by the usual additives (pigment such as TiO 2, plasticizer). When the temperature reaches about 110 ° C, the PVC formulation is cooled by reducing stirring and cooling the reactor.
EXEMPLE 3 EXAMPLE 3
Environ 10 g de chacune des compositions préparées selon le protocole décrit dans l'Exemple 2 sont versés sur un support papier avant d'être introduite dans un four porté à une température de 190°C environ. Des échantillons sont prélevés sur la feuille About 10 g of each of the compositions prepared according to the protocol described in Example 2 are poured onto a paper support before being introduced into an oven heated to a temperature of about 190 ° C. Samples are taken from the sheet
d'enduction à intervalles de temps réguliers en notant leur coloration. Sur les échantillons prélevés, on mesure la stabilité résiduelle, exprimée en min, et mesurée à l'aide d'un banc de déhydrochloruration (DHC) selon la norme ISO 182-2. Les bons résultats de stabilité résiduelle selon le test de DHC mettent en évidence les bonnes propriétés de stabilisation thermique des stabilisants selon l'invention.
coating at regular time intervals by noting their coloring. On the samples taken, the residual stability, expressed in min, is measured and measured using a dehydrochlorination bench (DHC) according to the ISO 182-2 standard. The good results of residual stability according to the DHC test highlight the good thermal stabilization properties of the stabilizers according to the invention.
Claims
REVENDICATIONS
1 - Composition comprenant: 1 - Composition comprising:
a) au moins une matière thermoplastique chlorée M, et a) at least one chlorinated thermoplastic material M, and
b) au moins un stabilisant thermique A qui est un complexe de zinc de formule choisi parmi le groupe constitué par les complexes (4) à (6) suivants: b) at least one thermal stabilizer A which is a zinc complex of formula chosen from the group consisting of the following complexes (4) to (6):
(4): [Zn [EAA)2] avec EAA = fanion éthyle acétoacétato ou l'anion énolate de l'éthyle acétoacétate, (4): [Zn [EAA] 2 ] with EAA = ethyl acetoacetate pennant or the enolate anion of ethyl acetoacetate,
(5): [Zn (iPr-AA)2] avec iPr-AA = l'anion isopropyle acétoacétato ou l'anion énolate de et (5): [Zn (iPr-AA) 2 ] with iPr-AA = the isopropyl acetoacetate anion or the enolate anion of and
2 - Composition selon la revendication 1 comprenant: 2 - Composition according to claim 1 comprising:
a) pour 100 parties poids d'au moins une matière thermoplastique chlorée M, et b) de 0,1 à 50 parties poids d'au moins un stabilisant thermique A tel que décrit selon la revendication 1 , et de préférence de 0,1 à 20 parties poids et encore plus préférentiellement de 0,1 à 10 parties poids. a) per 100 parts by weight of at least one chlorinated thermoplastic material M, and b) from 0.1 to 50 parts by weight of at least one thermal stabilizer A as described in claim 1, and preferably of 0.1 at 20 weight parts and even more preferably from 0.1 to 10 weight parts.
3 - Composition selon la revendication 1 dans laquelle la matière thermoplastique chlorée M est choisi parmi le groupe constitué par : un homopolymère du chlorure de vinyle, un copolymère du chlorure de vinyle avec des co-monomères insaturés et leurs mélanges. 3 - The composition of claim 1 wherein the chlorinated thermoplastic material M is selected from the group consisting of: a homopolymer of vinyl chloride, a copolymer of vinyl chloride with unsaturated comonomers and mixtures thereof.
4 - Composition selon la revendication 1 dans laquelle la matière thermoplastique chlorée M est choisi parmi le groupe constitué par : une résine de poly(chlorure de vinyle), un plastisol obtenue par mélange d'une résine poly(chlorure de vinyle) dans un plastifiant liquide et leurs mélanges. 4 - The composition of claim 1 wherein the chlorinated thermoplastic material M is selected from the group consisting of: a polyvinyl chloride resin, a plastisol obtained by mixing a polyvinyl chloride resin in a plasticizer liquid and their mixtures.
5- Composition selon l'une quelconque des revendications précédentes dans laquelle la composition comprend en outre au moins un additif choisi parmi le groupe constitué par
un agent lubrifiant , un agent plastifiant, une charge, un adjuvant de coloration, un agent anti-choc, un additif antistatique, un additif fongicide, un additif gonflant, un additif protecteur contre le rayonnement solaire, un additif « processing-aids » pour améliorer la gélification du mélange prêt à l'emploi et leurs mélanges. 5. The composition according to claim 1, wherein the composition further comprises at least one additive selected from the group consisting of a lubricating agent, a plasticizer, a filler, a coloring aid, an anti-shock agent, an antistatic additive, a fungicidal additive, a blowing additive, a sun-protective additive, a processing-aids additive for to improve the gelling of the ready-to-use mixture and their mixtures.
5 - Article obtenu par extrusion, extrusion-soufflage, calandrage, injection et l'intrusion, ou thermoformage de la composition telle que décrite selon l'une quelconque des revendications précédentes. 5 - Article obtained by extrusion, extrusion blow molding, calendering, injection and intrusion, or thermoforming of the composition as described in any one of the preceding claims.
6 - Utilisation de la composition telle que décrite selon l'une quelconque des revendications 1 à 5 ou de l'article tel que décrit selon la revendication 5 pour les domaines du bâtiment, de l'emballage, de l'électricité, de l'électronique, médical, des biens de consommation et du transport.
6 - Use of the composition as described according to any one of claims 1 to 5 or the article as described according to claim 5 for the fields of building, packaging, electricity, the electronic, medical, consumer goods and transportation.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1104061 | 2011-12-23 | ||
| FR11/04061 | 2011-12-23 |
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| WO2013093242A1 true WO2013093242A1 (en) | 2013-06-27 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016015616A1 (en) * | 2014-07-28 | 2016-02-04 | 天津合智化工有限责任公司 | Β-keto ester complex and application thereof |
| CN107236210A (en) * | 2017-06-13 | 2017-10-10 | 浙江工业大学 | A kind of application of glucaric acid zinc coordination polymer in heat stabilizer is prepared |
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| EP0040286A2 (en) * | 1980-01-14 | 1981-11-25 | Phoenix Chemical Corporation | Polyvinyl halide resin compositions containing 1,3 Dicarbonyl compounds |
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| WO2016015616A1 (en) * | 2014-07-28 | 2016-02-04 | 天津合智化工有限责任公司 | Β-keto ester complex and application thereof |
| CN107236210A (en) * | 2017-06-13 | 2017-10-10 | 浙江工业大学 | A kind of application of glucaric acid zinc coordination polymer in heat stabilizer is prepared |
| CN107236210B (en) * | 2017-06-13 | 2019-06-14 | 浙江工业大学 | A kind of glucaric acid zinc coordination polymer is preparing the application in heat stabilizer |
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