WO2016083746A1 - Elastomer compositions containing at least one plasticiser formed by an unsaturated, preferably monounsaturated, fatty diacid ester - Google Patents

Elastomer compositions containing at least one plasticiser formed by an unsaturated, preferably monounsaturated, fatty diacid ester Download PDF

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Publication number
WO2016083746A1
WO2016083746A1 PCT/FR2015/053223 FR2015053223W WO2016083746A1 WO 2016083746 A1 WO2016083746 A1 WO 2016083746A1 FR 2015053223 W FR2015053223 W FR 2015053223W WO 2016083746 A1 WO2016083746 A1 WO 2016083746A1
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ester
elastomer
carbon atoms
weight
diacid
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PCT/FR2015/053223
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French (fr)
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Jean-Luc Dubois
Jean-Luc Couturier
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Arkema France
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Publication of WO2016083746A1 publication Critical patent/WO2016083746A1/en

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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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/315—Compounds containing carbon-to-nitrogen triple bonds

Definitions

  • the invention relates to natural or synthetic elastomeric compositions containing at least one plasticizer formed by an unsaturated fatty acid ester, preferably monounsaturated.
  • Elastomers whether natural (NR for natural rubber) or synthetic, require the addition of a series of adjuvants, called plasticizers, to provide the properties required by the finished product and / or to allow / facilitate the setting implementation of their treatment prior to vulcanization.
  • plasticizers a series of adjuvants
  • plasticizer is meant a whole range of compounds which are intended to confer on polymers the plastic or more generally physical properties so as to adapt these polymers to the desired end use.
  • a broad overview of the types of plasticizers suitable for some 50 polymers is described in an article by Georges Wypych entitled Plasticizers Use and Selection for Specifies Polymers, Chapter 11 (pp 273-379) of the Handbook of Plasticizers (2004).
  • Synthetic elastomers fall into a few broad categories among which NBRs (Nitrile Butadiene Rubber), CR (Chloroprene Rubber), SBR (Styrene Butadiene Rubber) can be mentioned.
  • NBR and CR are rather polymers with technical applications, while SBRs are widely used in the tire industry.
  • the plasticizer is a generally liquid, low-volatility substance which, incorporated in a polymer (plastic) makes it possible in particular to lower the softening interval, to lower its glass transition temperature, to facilitate its implementation, especially by reducing the viscosity of the polymer in the molten state and increase its flexibility.
  • This plasticizer can be used alone to bring its intrinsic properties to the reaction mixture and the final product, but it can also be associated with another agent, in particular a plasticizer, which improves the performance of the first plasticizer by, if appropriate, adding its own properties.
  • one or the other of primary plasticizer or secondary plasticizer is qualified or, according to the properties conferred by this second agent, is referred to as "extender” or "process aids".
  • esters of short-chain aliphatic fatty acids which chain has a number of carbon atoms of less than 1 1, such as adipates, sebacates and azelates; polyesters, such as poly-glycol adipates, for example poly (1,3-butylene glycol adipate (Drapex 429) or polydiethylene glycol adipate, of low molecular weight;
  • the compounds di-esters obtained by reacting a mono-alcohol with a diacid or a mono-acid with a diol, such as glycol benzoate or / 'sobutyrate trimethyl-2,2, 4 pentane diol 1, 3;
  • aromatic diesters such as phthalates
  • chlorinated paraffins long-chain fatty acid mono-esters, a chain whose number of carbon atoms is greater than 10 carbon atoms, such as oleates, palmitates, etc .; tri- or polyesters such as trimellitates, citrates and pentaerythrates
  • epoxides such as epoxidized soybean oil, octyl epoxy stearates and epoxyallates; etc.
  • plasticizers Today, the most widely used plasticizers by industry are phthalates. Mention may be made in this connection of the most common phthalates, namely diisooctyl phthalate (DIOP), dioctyl phthalate (DOP), bis (2-ethylhexyl phthalate (DEHP), diisodecyl phthalate (DIDP), diisononyl phthalate (DINP), the dibutyl phthalate (DBP), benzyl butyl phthalate (BBP), diisodecyl phthalate (DIDP).
  • DIOP diisooctyl phthalate
  • DOP dioctyl phthalate
  • DEHP 2,2-ethylhexyl phthalate
  • DIDP diisodecyl phthalate
  • esters are, for example, esters of an optionally unsaturated fatty acid comprising from 1 to 21 carbon atoms with a linear or branched alcohol containing from 1 to 12 carbon atoms. These esters may also be di-esters or poly-esters resulting from the reaction of a fatty acid with a polyol such as pentaerythritol.
  • Patent document WO 03/095550 filed May 9, 2003 discloses an elastomer composition consisting of a natural and / or synthetic elastomer containing in addition to an adhesive resin, a plasticizer consisting of an ester of a saturated C3-C24 fatty acid, or unsaturated compound having 1 to 6 double bonds, with a linear or branched alcohol, - a di-ester of a fatty diacid having a saturated linear chain of 3 to 24 carbon atoms with one (or two) linear alcohol (s) ( s) or branched (s), saturated (s) or unsaturated (s), a cyclic di-ester of a dimer of the fatty acid or, a bi-cyclic tri-ester of a trimer of the
  • the chain of the acid (mono-acid) is linear (unconnected) and liable to be unsaturated, for example with oleic acid; in the case of the diester, the diacid chain is saturated.
  • US Pat. No. 5,252,650 describes a process for preparing elastomer compositions consisting of adding to the elastomer, as plasticizer, a mixture of C12-C22 fatty esters which contributes to improving the effectiveness of an anti-ozonant contained in the composition. elastomer, while ensuring excellent physical properties to the vulcanizate from the process.
  • No. 4,737,535 discloses an elastomer composition for tires based on SBR-type polymers and containing, as plasticizer, a short-chain diacid ester such as sebacic and adipic acids or an oleate fatty acid ester.
  • This plasticizer gives the elastomer composition an improvement in its cold resistance.
  • the technical problem to be solved by the present invention is to find new plasticizers that can replace phthalates in terms of performance, but part of a sustainable approach that is to say, synthesized from natural and renewable raw materials.
  • the plasticizers used in the elastomer manufacturing processes must simultaneously have certain indispensable properties. They must indeed have an effective plasticizing action, a good compatibility with the polymer and the compounds of the mixture in order to avoid a rejection, a longevity in the plasticizing action in order to maintain performances compatible with the service life of the finished product and therefore correlatively good resistance to various thermal, oxidizing or UV aggressions.
  • the invention therefore relates to an elastomeric composition
  • R 1 and R 2 which are identical or different, are linear or branched alkyl or alkenyl radicals comprising from 1 to 24 carbon atoms, preferably from 4 to 21 carbon atoms, and more preferably from 6 to 18 carbon atoms.
  • the elastomers used in the composition of the invention are either natural and therefore of the polyisoprene type, or synthetic.
  • the synthetic elastomers are either homopolymers of conjugated dienes or copolymers of these dienes conjugated with vinyl compounds.
  • conjugated dienes are, for example, isoprene, butadiene, chloroprene (2-chloro-1,3-butadiene), etc., leading to homopolymers, polyisoprene (IR), polybutadiene (BR), chloroprene (CR) etc ...
  • styrene acrylonitrile
  • vinyl pyridine vinyl compounds
  • acrylic acids and their esters to yield elastomeric copolymers such as styrene-butadiene (SBR), styrene-butadiene-styrene (SBS), acrylonitrile-butadiene (NBR), (meth) acrylic-butadiene acid or elastomeric terpolymers such as acrylonitrile-butadiene-styrene (ABS) ...
  • SBR styrene-butadiene
  • SBS styrene-butadiene-styrene
  • NBR acrylonitrile-butadiene
  • ABS acrylonitrile-butadiene-styrene
  • plasticizer esters of the invention are well suited to technical elastomers such as NBR and CR.
  • the di-esters are formed from monounsaturated diacids which comprise either 18 carbon atoms per molecule (octadecenedioic acids) or 20 carbon atoms per molecule (eicosenedioic acids).
  • the di-esters used in the context of the invention will be either symmetrical, the alcohol used for the esterification being the same for the two acid functions, or asymmetric with two different alcohols. In the latter case, the initial di-ester, generally symmetrical, will be subjected to trans-esterification.
  • the esterification of the diacid or the transesterification of the diester it is possible to use light alcohols, such as methanol, ethanol or propanol, but it is preferable to use heavy alcohols having a number of carbon atoms of at least 4 (butanols). and higher). These heavy alcohols advantageously have one or more branches and, where appropriate, one or more double bonds.
  • the diacid esters used in the context of the invention comprise at least one radical R 1 or R 2 comprising at least 4 carbon atoms, and preferably branched.
  • the choice of the alcohol depends on the type of action desired vis-à-vis the elastomer and the reaction mixture prior to vulcanization. Indeed, the choice of the diacid ester is according to the constraints related to the intended application.
  • a first constraint (C1) is that the ester must be compatible with the polymer and the reaction medium of the vulcanization operation.
  • the ester must be soluble in the reaction medium and the elastomer in order to ensure its homogeneous diffusion within said medium and therefore the elastomer.
  • a second constraint (C2) is that the ester must remain incorporated within the matrix of the polymer.
  • a third constraint (C3) is that the molecular weight of the ester must be large enough to avoid salting out during the vulcanization process. This molecular weight is preferably in the range of 350 to 1200 g / mol and preferably 400 to 600 g / mol.
  • a fourth constraint (C4) is that at the time of introduction into the reaction medium containing the elastomer, the ester must be in the liquid state.
  • the ester can be further mixed with other compounds of lower melting point as long as they are also compatible with the elastomer and do not harm the action. plasticizer of the ester.
  • the ester of the diacid has a melting point below 40 ° C., preferably below 20 ° C. and preferably in the range -50 to -10 ° C. at a pressure of 760 mm Hg. Its boiling point under the same pressure conditions is above 200 ° C and preferably in the range of 300 to 400 ° C.
  • the amount of plasticizing diacid ester added to the reaction medium is adapted according to the performances targeted for the final elastomer composition, but it is preferably in the range of 1 to 15% by weight of ester on the weight of elastomer (elastomer alone) and preferably in the range of 2 and 10% by weight of ester on the weight of elastomer (for 100% elastomer alone).
  • esters of the invention with respect to phthalates is that it is possible to synthesize them from natural renewable raw materials. This is true for both diacid and alcohol. Another advantage is that the diacid ester has good biodegradability. Finally, the esters of the invention often make it possible to dispense with the use of a secondary plasticizer.
  • esters of long chain fatty acids are not currently available on the market at acceptable prices for the plasticizer application. It is essential, in the context of industrial development, to have a sustainable and competitive source of supply.
  • the applicant has carried out important work in the field of the valorization of fatty chains with a view to using them as raw material for the synthesis of di-functional compounds which may in particular constitute monomers for the specialty polyamide industry, such as les amino acids C1 1 or C12.
  • the Applicant has in particular designed a process (and filed patents) for the synthesis of oo-amino acids C1 1 with a variant for C12 from natural fatty esters of C18 (oleic ester and / or ricinoleic). These processes comprise a step during which a ester-unsaturated fatty ester having, according to the variant, 10 or 11 carbon atoms is formed. This fatty ester is then subjected to a cross-metathesis reaction with acrylonitrile to obtain unsaturated nitrile-esters which are the precursors of the ⁇ -amino acids C1 or C12.
  • This metathesis step leads in parallel to an unsaturated C18 or C 20 diester; in fact, the metathesis reactions being balanced, cross metathesis is always accompanied by a homo-metathesis of the reagents present in the medium, here the ⁇ -unsaturated acids in C1 1 or C12, and thus the formation of a unsaturated diester.
  • This type of process is described in patent applications WO2014 / 106724 and WO201 1/138051.
  • the residue is fractionated between a light product cut (essentially C10 to C1 1) and a heavy diester fraction (C18 to C20). .
  • nitrile-ester C1 1 or C12
  • the di-ester fraction may also comprise traces of C15 to C18 monounsaturated esters resulting from an incomplete reaction during the first stage of synthesis of ⁇ -decenoic or ⁇ -undecenoic acid and remaining in the reaction medium during the second step.
  • the purity of the diester fraction depends on the manner in which the two reaction stages are carried out, in particular with the conversion degrees, and on the other hand the purification / extraction treatments applied during the two stages of the process.
  • the impurity content can be up to 10% by weight relative to the total weight of heavy diester fraction.
  • the ester fraction of the diacid consists of a mixture of compounds: ester of the target diacid, nitrile-esters, esters of fatty diacids of neighboring structure (C17, C19 or C20), fatty mono acid esters.
  • the main constituents of the mixture are the diacid ester of formula (I) and the nitrile-ester C 1 or C 12.
  • the nitrile-ester content of the diester fraction depends mainly on the performance of its extraction from the reaction medium; it is generally in the range of 1% by weight in the case of 40% by weight extraction under stress under low stress extraction, on the total weight of the diester fraction.
  • the diester fraction constitutes a "pure” compound since 95% of the molecules of the mixture correspond to formula (I).
  • the invention also relates to a process for producing elastomer compositions in which a mixture of 55 to 95% by weight of diacid ester (s) of formula (I) and 1 to 40% by weight of plasticizer is used as plasticizer.
  • a nitrile-ester of formula CN-CH CH-R'-COORi in which R 'is an alkylene radical having 7 or 8 carbon atoms and R 1 has the same meaning as in formula (I).
  • the mixture of the diester fraction derived from the nitrile-ester synthesis process, comprising both the diester and the diester is preferably used as the plasticizer raw material for the production of the elastomer compositions of the invention.
  • by-products of the process dinitrile, unsaturated fatty diesters of chain length C 17, C 19, C 21 and / or unsaturated fatty monoesters of slightly lower C 15 to C 18 chain length.
  • the presence, with the diester, of a small amount of nitrile-ester or unsaturated dinitrile such as that contained in the diester fraction above, does not affect the effectiveness of the plasticizer action for the elastomer .
  • the subject of the present invention is also the use of a diacid ester of formula (I) in an elastomer to give it a plasticizing effect, and in particular to improve its resistance to aging, in which the elastomer composition conforms to those defined more according to the invention.
  • the reference mixtures A (comparative) and B according to the invention are made from the following raw materials.
  • Perbunan ® 3945, NBR copolymer (acrylonitrile content 39% by weight) is a product of Lanxess.
  • Zinc oxide, "ZnO Active”, is a commercial product of Grillo Zinkoxid.
  • Black charges, Corax ® N660 and MT-N-900 are available at Evonik.
  • Rhenogran ® MBTS-80, TBzTD-70, S-80, (vulcanization accelerators) are available from Rhein Chemie.
  • Elastomeric mixtures (without crosslinking agent or accelerator) are prepared in a Haake Rheodrive laboratory mixer, with a rotation speed of 1 revolution per second and for 10 minutes.
  • the other components, crosslinking agent and accelerator, are added in a second mixing step in a roller mixer (roll diameter of 20 cm and width of 55 cm).
  • the mixture samples thus obtained are vulcanized in a hydraulic press operating at 200 bar.
  • composition of the mixtures A and B is the following expressed in parts.
  • Perbunan ® 100; ZnO Active: 5; Stearic acid: 1; Corax® N660: 65; MTN900: 15; Rhenogan® MBTS-80: 3.1; Rhenogan® TBzTD70: 2.1; Rhenogan® S80: 0.5.
  • composition A further contains 3 parts of dioctyl phthalate (DOP), while composition B according to the invention contains 3 parts of methyl 9-octadecenodioate.
  • DOP dioctyl phthalate
  • the samples of composition A and B differ on the plasticizer effect measurements after accelerated aging for 96 hours at room temperature in the isooctane, where sample A shows a loss of mass of 0.2% by bleeding, while sample B shows no measurable loss.
  • sample A shows a loss of mass of 0.2% by bleeding
  • sample B shows no measurable loss.
  • the plasticizer of A is dibutyl sebacate.
  • the plasticizer of B is an iso-oleonitrile at 87% by weight, which is a mixture of 11-octadecenenitrile and 12-octadecenenitrile containing 12% by weight of stearic nitrile.
  • the plasticizer of C is dimethyl 9-octadecenedioate at 97% by weight.
  • the plasticizer of D is dimethyl 9-octadecenedioate at 88% by weight, containing a C1-nitrile ester.
  • the plasticizer of E is 2-ethylhexyl 9-octadecenedioate at 97% by weight, obtained by trans-esterification of the plasticizer of C.
  • NBR Krynac 4450F comes from Lanxess and contains 45% acrylonitrile monomers.
  • the preparation of the mixtures is carried out in two stages.
  • the first one which aims at the preparation of elastomeric (unvulcanized) mixtures, is carried out in an internal Rhéomix mixer (300 cm 3 ) during which Krynac, ZnO and stearic acid are introduced in a first phase at room temperature. 30 seconds then, in a second phase, we add
  • the second stage dedicated to accelerating the process towards the vulcanization of the mixtures resulting from the first stage, is carried out with a mixer with cooled rolls, whose rotational speeds are set at 18 and 24 rpm.
  • the sulfur and the accelerators MTBS and TBzTD are added for 2 minutes and the vulcanization is then carried out until a temperature of 170 ° C. is reached.
  • a plate mixture approximately 2 mm thick is obtained.
  • the physical (mechanical) properties of the mixtures were measured according to the standards.
  • the Shore A hardness was evaluated according to standard NF ISO 7619-1 and the various tensile measurements: elongation at break, tensile stress and stress at 100% elongation measured according to standard NF ISO 37. The results obtained are shown in Table 3.
  • the first test is the measurement of physical properties after aging in air at 100 ° C. The results obtained are shown in Table 4. In each line is below the measured value, the observed variation from that of Table 3 (initial state of the mixture).
  • Variation volume (%) -5,77 -5,70 -2,19 -3,10 +0,12 It can be observed that the three mixtures according to the invention (C, D and E) have better results than those of the reference mixture (A). We can note the hardness which increases little, the increase of the stresses to elongation and to the break which is less and especially the variations in mass and in volume which are of less amplitude, thus marking a better stability of the mixtures according to the invention.
  • the mixtures according to the invention and more particularly E are distinguished by their resistance to the extractability of plasticizers. This observation has already been made in the previous tests on aging in air at 100 ° C.

Abstract

The invention relates to an elastomer composition comprising a natural or synthetic elastomer or a mixture of the two and at least one diacid ester compound of formula R1OOC-R-COOR2 (I) wherein R is an alkenyl radical comprising between 6 and 18 carbon atoms and at least one double bond, and R1and R2, which are the same or different, are linear or branched alkyl radicals comprising between 1 and 24 carbon atoms, preferably between 4 and 21 carbon atoms, and even more preferably between 6 and 18 carbon atoms.

Description

COMPOSITIONS ELASTOMERES CONTENANT AU MOINS UN PLASTIFIANT FORME PAR UN ESTER DE DIACIDE GRAS INSATURE, DE PREFERENCE MONO- ELASTOMERIC COMPOSITIONS CONTAINING AT LEAST ONE PLASTICIZER FORMED BY AN UNSATURATED FATTY DIACIDE ESTER, PREFERABLY MONO-
INSATURE UNSATURATED
DOMAINE DE L'INVENTION FIELD OF THE INVENTION
L'invention concerne des compositions élastomères naturelles ou synthétiques contenant au moins un plastifiant formé par un ester de diacide gras insaturé, de préférence mono-insaturé. The invention relates to natural or synthetic elastomeric compositions containing at least one plasticizer formed by an unsaturated fatty acid ester, preferably monounsaturated.
ARRIERE-PLAN TECHNIQUE TECHNICAL BACKGROUND
Les élastomères, qu'ils soient naturels (NR pour natural rubber) ou synthétiques, nécessitent l'addition de toute une série d'adjuvants, appelés plastifiants, pour leur apporter les propriétés requises par le produit fini et/ou permettre/faciliter la mise en œuvre de leur traitement préalablement à la vulcanisation. Elastomers, whether natural (NR for natural rubber) or synthetic, require the addition of a series of adjuvants, called plasticizers, to provide the properties required by the finished product and / or to allow / facilitate the setting implementation of their treatment prior to vulcanization.
Par plastifiant on entend toute une gamme de composés qui sont destinés à conférer aux polymères les propriétés plastiques ou plus généralement physiques de manière à adapter ces polymères à l'utilisation finale recherchée. Un large panorama des types de plastifiants adaptés à quelque 50 polymères est décrit dans un article de Georges Wypych intitulé Plasticizers Use and Sélection for Spécifie Polymers, chapitre 1 1 (pp 273-379) du Handbook of Plasticizers (2004). Les élastomères synthétiques relèvent de quelques grandes catégories parmi lesquelles on peut notamment citer les NBR (Nitrile Butadiène Rubber), les CR (Chloroprène Rubber), les SBR (Styrène Butadiène Rubber). Les NBR et CR sont plutôt des polymères à applications techniques tandis que les SBR sont, eux, largement utilisés dans l'industrie du pneumatique. Le plastifiant est une substance généralement liquide, peu volatile qui, incorporée à un polymère (plastique) permet notamment d'en abaisser l'intervalle de ramollissement, d'abaisser sa température de transition vitreuse, de faciliter sa mise en œuvre, notamment par réduction de la viscosité du polymère à l'état fondu et d'augmenter sa flexibilité. Ce plastifiant peut être utilisé seul pour apporter ses propriétés intrinsèques au mélange réactionnel et au produit final, mais il peut également être associé à un autre agent notamment plastifiant qui améliore la performance du premier plastifiant en y apportant le cas échéant ses propriétés propres. Dans cette hypothèse on qualifie l'un ou l'autre de plastifiant primaire ou de plastifiant secondaire ou, selon les propriétés conférées par ce second agent, on parle d' « extendeur » ou de « facilitateur de procédé » (processing aids). By plasticizer is meant a whole range of compounds which are intended to confer on polymers the plastic or more generally physical properties so as to adapt these polymers to the desired end use. A broad overview of the types of plasticizers suitable for some 50 polymers is described in an article by Georges Wypych entitled Plasticizers Use and Selection for Specifies Polymers, Chapter 11 (pp 273-379) of the Handbook of Plasticizers (2004). Synthetic elastomers fall into a few broad categories among which NBRs (Nitrile Butadiene Rubber), CR (Chloroprene Rubber), SBR (Styrene Butadiene Rubber) can be mentioned. NBR and CR are rather polymers with technical applications, while SBRs are widely used in the tire industry. The plasticizer is a generally liquid, low-volatility substance which, incorporated in a polymer (plastic) makes it possible in particular to lower the softening interval, to lower its glass transition temperature, to facilitate its implementation, especially by reducing the viscosity of the polymer in the molten state and increase its flexibility. This plasticizer can be used alone to bring its intrinsic properties to the reaction mixture and the final product, but it can also be associated with another agent, in particular a plasticizer, which improves the performance of the first plasticizer by, if appropriate, adding its own properties. In this case, one or the other of primary plasticizer or secondary plasticizer is qualified or, according to the properties conferred by this second agent, is referred to as "extender" or "process aids".
Parmi les plastifiants connus on peut citer : les esters de diacides gras aliphatiques à chaîne courte, chaîne dont le nombre d'atomes de carbone est inférieur à 1 1 , tels que les adipates, sébaçates, azélates..; - les polyesters, tels que les poly-glycol adipates, par exemple le poly(1 ,3- butylene glycol adipate (Drapex 429) ou le polydiéthylèneglycol adipate, de faibles masses moléculaires ; Among the known plasticizers, mention may be made of: esters of short-chain aliphatic fatty acids, which chain has a number of carbon atoms of less than 1 1, such as adipates, sebacates and azelates; polyesters, such as poly-glycol adipates, for example poly (1,3-butylene glycol adipate (Drapex 429) or polydiethylene glycol adipate, of low molecular weight;
- les composés de type di-esters obtenus par réaction d'un mono-alcool sur un diacide ou d'un mono-acide sur un diol, par exemple le benzoate de glycol ou l'/'sobutyrate du triméthyl-2,2,4 pentane diol 1 ,3 ; - the compounds di-esters obtained by reacting a mono-alcohol with a diacid or a mono-acid with a diol, such as glycol benzoate or / 'sobutyrate trimethyl-2,2, 4 pentane diol 1, 3;
- les diesters aromatiques tels que les phtalates ; aromatic diesters such as phthalates;
- les paraffines chlorées, les mono-esters d'acide gras à longue chaîne, chaîne dont le nombre d'atomes de carbone est supérieur à 10 atomes de carbone, tels que les oléates, palmitates...; les tri- ou polyesters tels que les trimellitates, les citrates et les pentaerythrates chlorinated paraffins, long-chain fatty acid mono-esters, a chain whose number of carbon atoms is greater than 10 carbon atoms, such as oleates, palmitates, etc .; tri- or polyesters such as trimellitates, citrates and pentaerythrates
- les huiles végétales ; - vegetable oils;
- les époxydes tels que l'huile de soja époxydée, les époxy-stéarates et époxy- tallates d'octyle ; etc .. Aujourd'hui, les plastifiants de loin les plus utilisés industriellement sont les phtalates. On peut citer à ce propos les phtalates les plus courants à savoir, le phtalate de diisooctyle (DIOP), le phtalate de dioctyle (DOP), phtalate de bis(2-éthylehexyle (DEHP), le phtalate de diisodécyle (DIDP), le phtalate de diisononyle (DINP), le phtalate de dibutyle (DBP), le phtalate de benzyle-butyle (BBP), le phtalate de diisodécyle (DIDP). epoxides such as epoxidized soybean oil, octyl epoxy stearates and epoxyallates; etc. Today, the most widely used plasticizers by industry are phthalates. Mention may be made in this connection of the most common phthalates, namely diisooctyl phthalate (DIOP), dioctyl phthalate (DOP), bis (2-ethylhexyl phthalate (DEHP), diisodecyl phthalate (DIDP), diisononyl phthalate (DINP), the dibutyl phthalate (DBP), benzyl butyl phthalate (BBP), diisodecyl phthalate (DIDP).
S'il est incontestable que les phtalates et notamment les DEHP (DiEthylHexylPhtalates) et DBP (DiButylePhtalates) dominent actuellement le marché des plastifiants, l'avenir de leur utilisation est remis en cause par la Directive 2005/84/EC de l'Union Européenne du 14 décembre 2005 qui les considère comme des substances dangereuses. While it is indisputable that phthalates and especially DEHP (DiethylHexylPhtalates) and DBP (DiButylPhtalates) currently dominate the plasticizer market, the future of their use is challenged by Directive 2005/84 / EC of the European Union. December 14, 2005, which considers them hazardous substances.
Les industriels s'intéressent donc aux solutions alternatives et notamment à l'utilisation d'esters gras et de di-esters. Industrialists are therefore interested in alternative solutions, particularly the use of fatty esters and di-esters.
Le document de brevet US 2013/0323449 déposée le 10 mai 2013 décrit l'utilisation de divers esters comme agents plastifiants dans la synthèse de produits élastomères à partir d'élastomères type NBR et CR. Ces esters sont par exemple des esters d'un acide gras éventuellement insaturé comportant de 1 1 à 21 atomes de carbone avec un alcool linéaire ou ramifié comportant de 1 à 12 atomes de carbone. Ces esters peuvent aussi être des di-esters ou poly-esters résultant de la réaction d'un acide gras avec un polyol tel que le penta-erythritol. Ce document établit au moyen d'exemples comparatifs que les esters gras permettent d'atteindre des performances comme plastifiant, agissant sur les propriétés mécaniques de l'élastomère, au moins égales à celles obtenues avec des phtalates de dibutyle ou de di/'sononyle. Le document de brevet WO 03/095550 déposée le 9 mai 2003 décrit une composition élastomère constitué d'un élastomère naturel et/ou synthétique contenant outre une résine adhésive, un plastifiant constitué par un ester d'un acide gras C3-C24 saturé, ou insaturé comprenant de 1 à 6 doubles liaisons, avec un alcool linéaire ou branché, - un di-ester d'un diacide gras comportant une chaîne linéaire saturée de 3 à 24 atomes de carbone avec un (ou deux) alcool(s) linéaire(s) ou ramifié(s), saturé(s) ou insaturé(s), un di-ester cyclique d'un dimère de l'acide gras ou, un tri-ester bi-cyclique d'un trimère de l'acide gras. Il est mentionné dans la description de ce document que le plastifiant joue un rôle de promotion de l'action de l'adhésif entre les deux substrats métal-élastomère. The patent document US 2013/0323449 filed May 10, 2013 describes the use of various esters as plasticizers in the synthesis of elastomeric products from elastomers type NBR and CR. These esters are, for example, esters of an optionally unsaturated fatty acid comprising from 1 to 21 carbon atoms with a linear or branched alcohol containing from 1 to 12 carbon atoms. These esters may also be di-esters or poly-esters resulting from the reaction of a fatty acid with a polyol such as pentaerythritol. This document sets by means of comparative examples as fatty esters can achieve performance as a plasticizer, acting on the mechanical properties of the elastomer, at least equal to those obtained with dibutyl phthalate or di / 'sononyle. Patent document WO 03/095550 filed May 9, 2003 discloses an elastomer composition consisting of a natural and / or synthetic elastomer containing in addition to an adhesive resin, a plasticizer consisting of an ester of a saturated C3-C24 fatty acid, or unsaturated compound having 1 to 6 double bonds, with a linear or branched alcohol, - a di-ester of a fatty diacid having a saturated linear chain of 3 to 24 carbon atoms with one (or two) linear alcohol (s) ( s) or branched (s), saturated (s) or unsaturated (s), a cyclic di-ester of a dimer of the fatty acid or, a bi-cyclic tri-ester of a trimer of the fatty acid . It is mentioned in the description of this document that the plasticizer plays a role in promoting the action of the adhesive between the two metal-elastomer substrates.
D'après ce document, dans le cas du mono-ester la chaîne de l'acide (mono-acide) est linéaire (non branchée) et susceptible d'être insaturée, par exemple avec l'acide oléique ; dans le cas du diester, la chaîne du diacide est quant à elle saturée. According to this document, in the case of the mono-ester the chain of the acid (mono-acid) is linear (unconnected) and liable to be unsaturated, for example with oleic acid; in the case of the diester, the diacid chain is saturated.
Le brevet US 5,252,650 décrit un procédé de préparation de compositions élastomères consistant à ajouter à l'élastomère, comme plastifiant, un mélange d'esters gras en C12-C22 qui contribue à améliorer l'efficacité d'un anti-ozonant contenu dans la composition élastomère, tout en assurant d'excellentes propriétés physiques au vulcanisât issu du procédé. US Pat. No. 5,252,650 describes a process for preparing elastomer compositions consisting of adding to the elastomer, as plasticizer, a mixture of C12-C22 fatty esters which contributes to improving the effectiveness of an anti-ozonant contained in the composition. elastomer, while ensuring excellent physical properties to the vulcanizate from the process.
Le brevet US 4,737,535 décrit une composition élastomère pour pneumatiques à base de polymères de type SBR et contenant comme plastifiant un ester de diacides à chaîne courte tels que les acides sébacique et adipique ou un ester d'acide gras de type oléate. Ce plastifiant apporte à la composition élastomère une amélioration de sa tenue à froid. No. 4,737,535 discloses an elastomer composition for tires based on SBR-type polymers and containing, as plasticizer, a short-chain diacid ester such as sebacic and adipic acids or an oleate fatty acid ester. This plasticizer gives the elastomer composition an improvement in its cold resistance.
Le problème technique à résoudre par la présente invention est de trouver de nouveaux plastifiants pouvant se substituer aux phtalates en termes de performances, mais s'inscrivant dans une démarche durable c'est-à-dire synthétisés à partir de matières premières naturelles et renouvelables. Les plastifiants utilisés dans les procédés de fabrication des élastomères doivent présenter simultanément certaines propriétés indispensables. Ils doivent en effet avoir une action plastifiante efficace, une bonne compatibilité avec le polymère et les composés du mélange afin d'éviter un rejet, une longévité dans l'action plastifiante afin de maintenir des performances compatibles avec la durée de vie du produit fini et donc corrélativement une bonne résistance aux diverses agressions thermiques, oxydantes ou UV. The technical problem to be solved by the present invention is to find new plasticizers that can replace phthalates in terms of performance, but part of a sustainable approach that is to say, synthesized from natural and renewable raw materials. The plasticizers used in the elastomer manufacturing processes must simultaneously have certain indispensable properties. They must indeed have an effective plasticizing action, a good compatibility with the polymer and the compounds of the mixture in order to avoid a rejection, a longevity in the plasticizing action in order to maintain performances compatible with the service life of the finished product and therefore correlatively good resistance to various thermal, oxidizing or UV aggressions.
L'invention a donc pour objet une composition élastomère comprenant un élastomère naturel ou synthétique ou un mélange des deux et au moins un composé ester de diacide de formule R1OOC- R-COOR2 (I) dans laquelle - R est un radical alcènyle comportant de 16 à 18 atomes de carbone et au moins une double liaison, de préférence une seule double liaison ; Ri et R2 , identiques ou différents, sont des radicaux alkyles ou alcényles linéaires ou branchés comportant de 1 à 24 atomes de carbone, de préférence de 4 à 21 atomes de carbone, et de manière plus préférée de 6 à 18 atomes de carbone. The invention therefore relates to an elastomeric composition comprising a natural or synthetic elastomer or a mixture of both and at least one diacid ester compound of formula R1OOC-R-COOR2 (I) in which - R is an alkenyl radical having 16 to 18 carbon atoms and at least one double bond, preferably only one double bond; R 1 and R 2, which are identical or different, are linear or branched alkyl or alkenyl radicals comprising from 1 to 24 carbon atoms, preferably from 4 to 21 carbon atoms, and more preferably from 6 to 18 carbon atoms.
Les élastomères entrant dans la composition de l'invention sont soit naturels et donc de type poly-isoprène, soit synthétiques. Les élastomères synthétiques sont soit des homopolymères de diènes conjugués, soit des copolymères de ces diènes conjugués avec des composés de type vinyle. The elastomers used in the composition of the invention are either natural and therefore of the polyisoprene type, or synthetic. The synthetic elastomers are either homopolymers of conjugated dienes or copolymers of these dienes conjugated with vinyl compounds.
Ces diènes conjugués seront par exemple l'isoprène, le butadiène, le chloroprène (2- chloro-1 ,3-butadiène) etc .. conduisant à des homo-polymères, poly-isoprène (IR), polybutadiène (BR), poly-chloroprène (CR) etc...Ils pourront aussi être copolymérisés avec des composés vinyliques tels que le styrène, l'acrylonitrile, le vinyle pyridine, les acides (meth)acryliques et leurs esters pour conduire à des copolymères élastomères tels que styrène-butadiène (SBR), styrène-butadiène-styrène (SBS), acrylonitrile- butadiène (NBR), acide (meth)acrylique-butadiène ou à des ter-polymères élastomères tels que acrylonitrile-butadiène-styrène (ABS)... These conjugated dienes are, for example, isoprene, butadiene, chloroprene (2-chloro-1,3-butadiene), etc., leading to homopolymers, polyisoprene (IR), polybutadiene (BR), chloroprene (CR) etc ... They may also be copolymerized with vinyl compounds such as styrene, acrylonitrile, vinyl pyridine, (meth) acrylic acids and their esters to yield elastomeric copolymers such as styrene-butadiene (SBR), styrene-butadiene-styrene (SBS), acrylonitrile-butadiene (NBR), (meth) acrylic-butadiene acid or elastomeric terpolymers such as acrylonitrile-butadiene-styrene (ABS) ...
Les esters plastifiants de l'invention conviennent bien aux élastomères techniques tels que les NBR et CR. The plasticizer esters of the invention are well suited to technical elastomers such as NBR and CR.
Les di-esters sont formés à partir de diacides mono-insaturés qui comportent soit 18 atomes de carbone par molécule (acides octadécènedioïques), soit 20 atomes de carbones par molécule (acides eicosénedioïques). The di-esters are formed from monounsaturated diacids which comprise either 18 carbon atoms per molecule (octadecenedioic acids) or 20 carbon atoms per molecule (eicosenedioic acids).
Les di-esters utilisés dans le cadre de l'invention seront soit symétriques, l'alcool utilisé pour l'estérification étant le même pour les deux fonctions acides, soit dissymétriques avec deux alcools différents. Dans ce dernier cas, le di-ester initial, en général symétrique, sera soumis à une trans-estérification. The di-esters used in the context of the invention will be either symmetrical, the alcohol used for the esterification being the same for the two acid functions, or asymmetric with two different alcohols. In the latter case, the initial di-ester, generally symmetrical, will be subjected to trans-esterification.
Pour l'estérification du diacide ou la transestérification du diester, on peut utiliser les alcools légers, tels que méthanol, éthanol ou propanol, mais on utilise de préférence des alcools lourds ayant un nombre d'atomes de carbone au moins égal à 4 (butanols et supérieurs). Ces alcools lourds présentent avantageusement une ou plusieurs ramifications, et le cas échéant une ou plusieurs doubles liaisons. A titre d'exemples de tels alcools on peut citer l'isobutanol, le 2-ethylebutanol, le n- ou iso-octanol, le 2- ethylehexanol, le 2-propyleheptanol, le dodécanol, le tridécanol, le tetradécanol, le pentadécanol, l'hexadécanol, l'heptadécanol, l'octadécanol..., les alcools de Guerbet (dimères d'alcools linéaires), le farnesol éventuellement hydrogéné. For the esterification of the diacid or the transesterification of the diester, it is possible to use light alcohols, such as methanol, ethanol or propanol, but it is preferable to use heavy alcohols having a number of carbon atoms of at least 4 (butanols). and higher). These heavy alcohols advantageously have one or more branches and, where appropriate, one or more double bonds. As examples of such alcohols, mention may be made of isobutanol, 2-ethylbutanol, n- or iso-octanol, 2-ethylhexanol, 2-propylheptanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol ..., Guerbet alcohols (linear alcohol dimer), and possibly hydrogenated farnesol.
Les esters de diacides utilisés dans le cadre de l'invention comportent au moins un radical Ri ou R2 comprenant au moins 4 atomes de carbone, et de préférence ramifié. Le choix de l'alcool dépend du type d'action recherchée vis-à-vis de l'élastomère et du mélange réactionnel préalable à la vulcanisation. En effet, le choix de l'ester de diacide se fait en fonction des contraintes liées à l'application visée. The diacid esters used in the context of the invention comprise at least one radical R 1 or R 2 comprising at least 4 carbon atoms, and preferably branched. The choice of the alcohol depends on the type of action desired vis-à-vis the elastomer and the reaction mixture prior to vulcanization. Indeed, the choice of the diacid ester is according to the constraints related to the intended application.
Une première contrainte (C1 ) est que l'ester doit être compatible avec le polymère et le milieu réactionnel de l'opération de vulcanisation. L'ester doit être soluble dans le milieu réactionnel et l'élastomère afin d'assurer sa diffusion homogène au sein dudit milieu et donc ensuite de l'élastomère. A first constraint (C1) is that the ester must be compatible with the polymer and the reaction medium of the vulcanization operation. The ester must be soluble in the reaction medium and the elastomer in order to ensure its homogeneous diffusion within said medium and therefore the elastomer.
Une deuxième contrainte (C2) est que l'ester doit rester incorporé au sein de la matrice du polymère. A second constraint (C2) is that the ester must remain incorporated within the matrix of the polymer.
Le respect de ces deux contraintes (C1 et C2) est grandement facilité dans le cas où l'ester est susceptible de se fixer au milieu par exemple par le biais de liaisons radicalaires entre des sites de l'ester et de l'élastomère ou par réticulation par exemple via la double liaison localisée au sein de la chaîne du diacide. Respect for these two constraints (C1 and C2) is greatly facilitated in the case where the ester is capable of binding to the medium for example by means of radical bonds between sites of the ester and the elastomer or by crosslinking for example via the localized double bond within the diacid chain.
Une troisième contrainte (C3) est que la masse moléculaire de l'ester doit être suffisamment importante pour éviter un relargage en cours d'opération de vulcanisation. Cette masse moléculaire est de préférence comprise dans la gamme de 350 à 1200 g/mole et de préférence de 400 à 600 g/mole. A third constraint (C3) is that the molecular weight of the ester must be large enough to avoid salting out during the vulcanization process. This molecular weight is preferably in the range of 350 to 1200 g / mol and preferably 400 to 600 g / mol.
Une quatrième contrainte (C4) est qu'au moment de l'introduction dans le milieu réactionnel contenant l'élastomère, l'ester doit se trouver à l'état liquide. Pour respecter cette contrainte, il est avantageux d'utiliser des alcools ramifiés et/ou insaturés selon l'invention pour obtenir, à masse moléculaire équivalente, un point de fusion de l'ester aussi bas que possible. Afin d'obtenir un bas point de fusion, on peut en outre mélanger l'ester avec d'autres composés de point de fusion plus bas dès lors qu'ils sont également compatibles avec l'élastomère et ne portent pas préjudice à l'action plastifiante de l'ester. Avantageusement, l'ester du diacide présente un point de fusion inférieur à 40°C, de préférence inférieur à 20°C et de préférence compris dans la gamme -50 à -10°C sous une pression de 760 mm Hg. Son point d'ébullition aux mêmes conditions de pression est supérieur à 200°C et de préférence compris dans la gamme de 300 à 400 °C. A fourth constraint (C4) is that at the time of introduction into the reaction medium containing the elastomer, the ester must be in the liquid state. To respect this constraint, it is advantageous to use branched and / or unsaturated alcohols according to the invention to obtain, at equivalent molecular mass, a melting point of the ester as low as possible. In order to obtain a low melting point, the ester can be further mixed with other compounds of lower melting point as long as they are also compatible with the elastomer and do not harm the action. plasticizer of the ester. Advantageously, the ester of the diacid has a melting point below 40 ° C., preferably below 20 ° C. and preferably in the range -50 to -10 ° C. at a pressure of 760 mm Hg. Its boiling point under the same pressure conditions is above 200 ° C and preferably in the range of 300 to 400 ° C.
La quantité d'ester de diacide plastifiant ajouté au milieu réactionnel est adaptée en fonction des performances visées pour la composition élastomère finale, mais elle est de préférence comprise dans la gamme de 1 à 15 % en poids d'ester sur le poids d'élastomère (élastomère seul) et de préférence dans la gamme de 2 et 10 % en poids d'ester sur le poids d'élastomère (pour 100% d'élastomère seul). The amount of plasticizing diacid ester added to the reaction medium is adapted according to the performances targeted for the final elastomer composition, but it is preferably in the range of 1 to 15% by weight of ester on the weight of elastomer (elastomer alone) and preferably in the range of 2 and 10% by weight of ester on the weight of elastomer (for 100% elastomer alone).
L'avantage des esters de l'invention en regard des phtalates est qu'il est possible de les synthétiser à partir de matières premières naturelles renouvelables. Ceci est vrai aussi bien pour le diacide que pour l'alcool. Un autre avantage est que l'ester du diacide présente une bonne biodégradabilité. Enfin, les esters de l'invention permettent souvent de s'affranchir de l'utilisation d'un plastifiant secondaire. The advantage of the esters of the invention with respect to phthalates is that it is possible to synthesize them from natural renewable raw materials. This is true for both diacid and alcohol. Another advantage is that the diacid ester has good biodegradability. Finally, the esters of the invention often make it possible to dispense with the use of a secondary plasticizer.
Les esters de diacides gras longue chaîne ne sont pas aujourd'hui disponibles sur le marché à des prix acceptables pour l'application plastifiant. Il est indispensable, dans l'optique d'un développement industriel, de disposer d'une source d'approvisionnement durable et compétitive. The esters of long chain fatty acids are not currently available on the market at acceptable prices for the plasticizer application. It is essential, in the context of industrial development, to have a sustainable and competitive source of supply.
La demanderesse a conduit des travaux importants dans le domaine de la valorisation des chaînes grasses en vue de les utiliser comme matière première pour la synthèse de composés di-fonctionnels pouvant notamment constituer des monomères pour l'industrie des polyamides de spécialités, tels que les ω-amino-acides en C1 1 ou C12. The applicant has carried out important work in the field of the valorization of fatty chains with a view to using them as raw material for the synthesis of di-functional compounds which may in particular constitute monomers for the specialty polyamide industry, such as les amino acids C1 1 or C12.
La Demanderesse a notamment conçu un procédé (et déposé des brevets) de synthèse d'oo-aminoacides en C1 1 avec une variante pour le C12 à partir d'esters gras naturels en C18 (ester oléique et/ou ricinoléique). Ces procédés comportent une étape au cours de laquelle on forme un ester gras ω-insaturé comportant, selon la variante, 10 ou 1 1 atomes de carbone. Cet ester gras est soumis ensuite à une réaction de métathèse croisée avec l'acrylonitrile pour obtenir des nitrile-esters insaturés qui sont les précurseurs des ω-aminoacides en C1 1 ou C12. Cette étape de métathèse conduit en parallèle à un diester insaturé en C18 ou C 20 ; en effet, les réactions de métathèse étant équilibrées, la métathèse croisée s'accompagne toujours d'une homo-métathèse des réactifs présents dans le milieu, ici les acides ω-insaturés en C1 1 ou C12, et donc de la formation d'un diester insaturé. Ce type de procédé est décrit dans les demandes de brevet WO2014/106724 et WO201 1/138051 . Après l'extraction du nitrile-ester produit principal de la réaction de l'étape de métathèse croisée, le résidu est fractionné entre une coupe de produits légers (essentiellement C10 à C1 1 ) et une fraction « diester » lourde (C18 à C20). Cette dernière coupe est en pratique « polluée » par le produit des réactions de métathèse parasites ayant conduit à la formation de nitrile-ester (C1 1 ou C12). On peut avoir dans cette coupe des di-esters insaturés de longueurs de chaîne différentes, issus de réactions d'isomérisation de la double liaison, par exemple des di-esters en C17, C19 ou C21 ainsi que des nitriles esters incomplètement récupérés et qui contaminent les di-esters ciblés. Enfin, la fraction di-ester pourra comporter également des traces d'esters mono-insaturés en C15 à C18 résultant d'une réaction incomplète lors de la première étape de synthèse de l'acide ω-décènoïque ou ω-undécènoïque et subsistant dans le milieu réactionnel lors de la deuxième étape. The Applicant has in particular designed a process (and filed patents) for the synthesis of oo-amino acids C1 1 with a variant for C12 from natural fatty esters of C18 (oleic ester and / or ricinoleic). These processes comprise a step during which a ester-unsaturated fatty ester having, according to the variant, 10 or 11 carbon atoms is formed. This fatty ester is then subjected to a cross-metathesis reaction with acrylonitrile to obtain unsaturated nitrile-esters which are the precursors of the ω-amino acids C1 or C12. This metathesis step leads in parallel to an unsaturated C18 or C 20 diester; in fact, the metathesis reactions being balanced, cross metathesis is always accompanied by a homo-metathesis of the reagents present in the medium, here the ω-unsaturated acids in C1 1 or C12, and thus the formation of a unsaturated diester. This type of process is described in patent applications WO2014 / 106724 and WO201 1/138051. After extraction of the main product nitrile ester from the reaction of the cross metathesis step, the residue is fractionated between a light product cut (essentially C10 to C1 1) and a heavy diester fraction (C18 to C20). . This last cut is in practice "polluted" by the product of the parasitic metathesis reactions which led to the formation of nitrile-ester (C1 1 or C12). In this section it is possible to have unsaturated diesters of different chain lengths resulting from isomerization reactions of the double bond, for example C17, C19 or C21 di-esters, as well as incompletely recovered ester nitriles which contaminate the targeted di-esters. Finally, the di-ester fraction may also comprise traces of C15 to C18 monounsaturated esters resulting from an incomplete reaction during the first stage of synthesis of ω-decenoic or ω-undecenoic acid and remaining in the reaction medium during the second step.
La pureté de la fraction diester dépend de la manière dont sont conduits d'une part les deux étapes réactionnelles avec notamment les degrés de conversion, et d'autre part les traitements de purification/extraction appliqués au cours des deux étapes du procédé. La teneur en impuretés peut atteindre 10 % en poids sur le poids total de fraction diester lourde. The purity of the diester fraction depends on the manner in which the two reaction stages are carried out, in particular with the conversion degrees, and on the other hand the purification / extraction treatments applied during the two stages of the process. The impurity content can be up to 10% by weight relative to the total weight of heavy diester fraction.
C'est ainsi que, quel que soit le mode opératoire du procédé, la fraction ester du diacide est constituée d'un mélange de composés : ester du diacide cible, nitrile-esters, esters de diacides gras de structure voisine (C17, C19 ou C20), esters de monoacides gras. Les principaux constituants du mélange sont l'ester de diacide de formule (I) et le nitrile-ester en C1 1 ou C12. La teneur en nitrile-ester de la fraction diester dépend principalement de la performance de son extraction du milieu réactionnel ; elle est généralement comprise dans la gamme de 1 % en poids en cas d'extraction sous contrainte profonde à 40% poids en cas d'extraction sous faible contrainte, sur le poids total de la fraction diester. Thus, whatever the procedure of the process, the ester fraction of the diacid consists of a mixture of compounds: ester of the target diacid, nitrile-esters, esters of fatty diacids of neighboring structure (C17, C19 or C20), fatty mono acid esters. The main constituents of the mixture are the diacid ester of formula (I) and the nitrile-ester C 1 or C 12. The nitrile-ester content of the diester fraction depends mainly on the performance of its extraction from the reaction medium; it is generally in the range of 1% by weight in the case of 40% by weight extraction under stress under low stress extraction, on the total weight of the diester fraction.
On considère généralement que la fraction diester constitue un composé « pur » dès lors que 95 % des molécules du mélange répondent à la formule (I). It is generally considered that the diester fraction constitutes a "pure" compound since 95% of the molecules of the mixture correspond to formula (I).
L'invention vise également un procédé de fabrication de compositions élastomères dans lequel on utilise comme agent plastifiant un mélange de 55 à 95% en poids d'ester(s) de diacide de formule (I) et de 1 à 40 % poids d'un nitrile-ester de formule CN-CH=CH-R'-COORi dans laquelle R' est un radical alkylène comportant 7 ou 8 atomes de carbone et Ri a la même signification que dans la formule (I). Pour des raisons pratiques on utilise de préférence comme matière première d'agent plastifiant pour la fabrication des compositions élastomères de l'invention, directement le mélange de la fraction diester issue du procédé de synthèse des nitrile-esters, comportant à la fois le diester et des sous-produits du procédé : dinitrile, di-esters gras insaturés de longueur de chaîne voisine C 17, C 19, C 21 et/ou mono-esters gras insaturés de longueur de chaîne légèrement inférieure de C 15 à C 18. The invention also relates to a process for producing elastomer compositions in which a mixture of 55 to 95% by weight of diacid ester (s) of formula (I) and 1 to 40% by weight of plasticizer is used as plasticizer. a nitrile-ester of formula CN-CH =CH-R'-COORi in which R 'is an alkylene radical having 7 or 8 carbon atoms and R 1 has the same meaning as in formula (I). For practical reasons, the mixture of the diester fraction derived from the nitrile-ester synthesis process, comprising both the diester and the diester, is preferably used as the plasticizer raw material for the production of the elastomer compositions of the invention. by-products of the process: dinitrile, unsaturated fatty diesters of chain length C 17, C 19, C 21 and / or unsaturated fatty monoesters of slightly lower C 15 to C 18 chain length.
La présence, avec le diester, d'une faible quantité de nitrile-ester ou de dinitrile insaturé telle que celle contenue dans la fraction diester ci-dessus, ne porte pas préjudice à l'efficacité de l'action de plastifiant pour l'élastomère. La présente invention a également pour objet l'utilisation d'un ester de diacide de formule (I) dans un élastomère pour lui apporter un effet plastifiant, et notamment améliorer sa résistance au vieillissement, dans laquelle la composition élastomère est conforme à celles définies plus haut selon l'invention. The presence, with the diester, of a small amount of nitrile-ester or unsaturated dinitrile such as that contained in the diester fraction above, does not affect the effectiveness of the plasticizer action for the elastomer . The subject of the present invention is also the use of a diacid ester of formula (I) in an elastomer to give it a plasticizing effect, and in particular to improve its resistance to aging, in which the elastomer composition conforms to those defined more according to the invention.
L'invention est illustrée par les exemples suivants. The invention is illustrated by the following examples.
Exemples Examples
Première série d'exemples First series of examples
Dans les exemples ci-après, les mélanges A de référence (comparatif) et B selon l'invention, sont fabriqués à partir des matières premières suivantes. Le Perbunan ® 3945, copolymère NBR (teneur acrylonitrile de 39 % poids) est un produit de Lanxess. L'oxyde de zinc, « ZnO Active », est un produit commercial de Grillo Zinkoxid. Les charges noires, Corax ® N660 et le MT-N-900 sont disponibles chez Evonik. Les produits Rhenogran ® MBTS-80, TBzTD-70, S-80, (accélérateurs de vulcanisation) sont disponibles chez Rhein Chemie. In the examples below, the reference mixtures A (comparative) and B according to the invention are made from the following raw materials. Perbunan ® 3945, NBR copolymer (acrylonitrile content 39% by weight) is a product of Lanxess. Zinc oxide, "ZnO Active", is a commercial product of Grillo Zinkoxid. Black charges, Corax ® N660 and MT-N-900 are available at Evonik. Rhenogran ® MBTS-80, TBzTD-70, S-80, (vulcanization accelerators) are available from Rhein Chemie.
Des mélanges élastomères (sans agent de réticulation ni accélérateur) sont préparés dans un mélangeur de laboratoire de type Haake Rheodrive, avec une vitesse de rotation de 1 tour par seconde et pendant 10 minutes. Les autres composants, agent de réticulation et accélérateur, sont ajoutés dans une seconde étape de mélange dans un mélangeur à rouleaux (diamètre des rouleaux de 20 cm et largeur de 55 cm). Les échantillons de mélange ainsi obtenu sont vulcanisés dans une presse hydraulique fonctionnant sous 200 bars. Elastomeric mixtures (without crosslinking agent or accelerator) are prepared in a Haake Rheodrive laboratory mixer, with a rotation speed of 1 revolution per second and for 10 minutes. The other components, crosslinking agent and accelerator, are added in a second mixing step in a roller mixer (roll diameter of 20 cm and width of 55 cm). The mixture samples thus obtained are vulcanized in a hydraulic press operating at 200 bar.
La composition des mélanges A et B est la suivante exprimée en parties. The composition of the mixtures A and B is the following expressed in parts.
Perbunan ® :100 ; ZnO Active : 5 ; Acide stéarique : 1 ; Corax® N660 : 65 ; MTN900 : 15 ; Rhenogan® MBTS-80 : 3,1 ; Rhenogan® TBzTD70 : 2,1 ; Rhenogan® S80 : 0,5. Perbunan ®: 100; ZnO Active: 5; Stearic acid: 1; Corax® N660: 65; MTN900: 15; Rhenogan® MBTS-80: 3.1; Rhenogan® TBzTD70: 2.1; Rhenogan® S80: 0.5.
La composition A de référence contient en outre 3 parties de dioctylphtalate (DOP), alors que la composition B selon l'invention contient 3 parties de 9-octadécénodioate de méthyle. Reference composition A further contains 3 parts of dioctyl phthalate (DOP), while composition B according to the invention contains 3 parts of methyl 9-octadecenodioate.
Différentes propriétés ont été mesurées sur les deux échantillons qui donnent des valeurs équivalentes pour les échantillons non vulcanisés (viscosité, vitesse de réticulation). En ce qui concerne les mesures sur les échantillons vulcanisés, la dureté mesurée est équivalente, tout comme la résilience de rebondissement. L'effet plastifiant pour ces propriétés est donc équivalent. Different properties were measured on both samples which give equivalent values for uncured samples (viscosity, crosslinking rate). With regard to the measurements on the vulcanized samples, the hardness measured is equivalent, as is the rebound resilience. The plasticizing effect for these properties is therefore equivalent.
En revanche, les échantillons de composition A et B se différencient sur les mesures d'effet plastifiant après vieillissement accéléré pendant 96 heures à température ambiante dans l'isooctane, où l'échantillon A fait apparaître une perte de masse de 0,2 % par ressuage, alors que l'échantillon B ne présente pas de perte mesurable. Lorsque le test est effectué à 100 °C dans une huile minérale hydrogénée ayant un « flash point » supérieur à 163 °C et une température d'auto-inflammation supérieure à 343 °C, l'échantillon de composition A montre une perte de masse de 1 % alors que l'échantillon de composition B montre une perte de masse de 0,5 % seulement. On the other hand, the samples of composition A and B differ on the plasticizer effect measurements after accelerated aging for 96 hours at room temperature in the isooctane, where sample A shows a loss of mass of 0.2% by bleeding, while sample B shows no measurable loss. When the test is carried out at 100 ° C. in a hydrogenated mineral oil having a flash point greater than 163 ° C. and a self-ignition temperature greater than 343 ° C., the sample of composition A shows a loss of mass. of 1% whereas the sample of composition B shows a loss of mass of only 0.5%.
Deuxième série d'exemples Second series of examples
Les exemples ci-après illustrent les performances obtenues avec trois mélanges d'élastomères NBR : C, D et E comprenant comme plastifiant un diester gras insaturé conforme à l'invention en les comparant avec celles de deux mélanges : d'une part A, où le plastifiant de l'élastomère est un diacide gras représentatif de l'art antérieur et d'autre part B, où le plastifiant est un mono-acide gras sous forme nitrile. The following examples illustrate the performances obtained with three mixtures of elastomers NBR: C, D and E comprising as plasticizer an unsaturated fatty diester according to the invention by comparing them with those of two mixtures: firstly A, where the plasticizer of the elastomer is a fatty diacid representative of the prior art and on the other hand B, where the plasticizer is a mono-fatty acid in nitrile form.
Le plastifiant de A est le dibutyl sébaçate. The plasticizer of A is dibutyl sebacate.
Le plastifiant de B est un iso-oléonitrile à 87% poids, qui est un mélange de 1 1 - octadécènenitrile et de 12-octadécènenitrile contenant 12% poids de nitrile stéarique. The plasticizer of B is an iso-oleonitrile at 87% by weight, which is a mixture of 11-octadecenenitrile and 12-octadecenenitrile containing 12% by weight of stearic nitrile.
Le plastifiant de C est le 9-octadécènedioate de diméthyle à 97% poids. The plasticizer of C is dimethyl 9-octadecenedioate at 97% by weight.
Le plastifiant de D est le 9-octadécènedioate de diméthyle à 88% poids, contenant un nitrile-ester en C1 1 . The plasticizer of D is dimethyl 9-octadecenedioate at 88% by weight, containing a C1-nitrile ester.
Le plastifiant de E est le 9-octadécènedioate de 2-éthylhexyle à 97% poids, obtenu par trans-estérification du plastifiant de C. The plasticizer of E is 2-ethylhexyl 9-octadecenedioate at 97% by weight, obtained by trans-esterification of the plasticizer of C.
Les différentes formulations sont précisées dans le tableau 1 suivant. The different formulations are specified in the following Table 1.
Tableau 1 Table 1
Figure imgf000013_0001
Figure imgf000013_0001
Les quantités des divers composants sont exprimées en parties (poids) en référence au NBR. Le NBR Krynac 4450F vient de chez Lanxess et contient 45% de monomères acrylonitriles. The amounts of the various components are expressed in parts (weight) with reference to the NBR. NBR Krynac 4450F comes from Lanxess and contains 45% acrylonitrile monomers.
La préparation des mélanges s'effectue par en deux étapes. The preparation of the mixtures is carried out in two stages.
La première, qui vise la préparation de mélanges élastomères (non vulcanisés), est conduite dans un mélangeur interne Rhéomix (300cm3)au cours de laquelle on introduit dans une première phase à température ambiante, le Krynac, ZnO et l'acide stéarique pendant 30 secondes puis, dans une deuxième phase, on ajoute The first one, which aims at the preparation of elastomeric (unvulcanized) mixtures, is carried out in an internal Rhéomix mixer (300 cm 3 ) during which Krynac, ZnO and stearic acid are introduced in a first phase at room temperature. 30 seconds then, in a second phase, we add
successivement le noir de carbone et l'huile grasse (plastifiant) d'une part et les agents protecteurs, TMQ et 6PPD d'autre part. Le mélange est chauffé progressivement et on recueille la tombée des mélanges vers 95-104°C et entre 6 et 8 minutes selon les mélanges. successively the carbon black and the fatty oil (plasticizer) on the one hand and the protective agents, TMQ and 6PPD on the other hand. The mixture is gradually heated and the mixture is collected at about 95 ° -104 ° C. and between 6 and 8 minutes depending on the mixtures.
La seconde étape, dédiée l'accélération du processus vers la vulcanisation des mélanges issus de la première étape, est réalisée avec un mélangeur à cylindres refroidis, dont les vitesses de rotation sont fixées à 18 et 24 tours/min. Au cours de la première phase de cette étape, on ajoute le soufre et les accélérateurs MTBS et TBzTD pendant 2 min puis on conduit la vulcanisation jusqu'à atteindre une température de 170°C. On obtient à la sortie de la compression un mélange en plaque d'environ 2mm d'épaisseur. The second stage, dedicated to accelerating the process towards the vulcanization of the mixtures resulting from the first stage, is carried out with a mixer with cooled rolls, whose rotational speeds are set at 18 and 24 rpm. During the first phase of this step, the sulfur and the accelerators MTBS and TBzTD are added for 2 minutes and the vulcanization is then carried out until a temperature of 170 ° C. is reached. At the exit of the compression, a plate mixture approximately 2 mm thick is obtained.
Propriété rhéométriques Les propriétés rhéométriques de ces divers mélanges ont été déterminés Rheometric properties The rheometric properties of these various mixtures have been determined
conformément aux normes, à savoir temps de grillage (ts2), NF ISO 289, temps de vulcanisation à 170°C (¾»), NF ISO 6502, viscosité Mooney à 100°C (ML (1 +4), NF ISO 289, temps de prévulcanisation à 125°C (MLt5), NF ISO 6502, qui sont réunies dans le tableau 2. Tableau 2 according to the standards, namely toasting times (ts 2 ), NF ISO 289, vulcanization time at 170 ° C (¾ "), NF ISO 6502, Mooney viscosity at 100 ° C (ML (1 + 4), NF ISO 289, prevulcanization time at 125 ° C (MLt 5 ), NF ISO 6502, which are shown in Table 2. Table 2
Figure imgf000015_0001
Figure imgf000015_0001
*Unités Mooney Propriétés physiques * Mooney Units Physical Properties
Les propriétés physiques (mécaniques) des mélanges ont été mesurées conformément aux normes. La dureté Shore A a été évaluée selon la norme NF ISO 7619-1 et les différentes mesures de traction : allongement à la rupture, contrainte à la rupture et contrainte à 100% d'allongement mesurées selon la norme NF ISO 37. Les résultats obtenus sont réunis dans le tableau 3. The physical (mechanical) properties of the mixtures were measured according to the standards. The Shore A hardness was evaluated according to standard NF ISO 7619-1 and the various tensile measurements: elongation at break, tensile stress and stress at 100% elongation measured according to standard NF ISO 37. The results obtained are shown in Table 3.
Tableau 3 Table 3
Figure imgf000015_0002
Figure imgf000015_0002
*en points Les divers mélanges ont été soumis ensuite à une série de tests destinés à évaluer la contribution des divers plastifiants à leur stabilité dans le temps et les conditions d'utilisation. * in points The various mixtures were then subjected to a series of tests intended to evaluate the contribution of the various plasticizers to their stability over time and the conditions of use.
Vieillissement dans l'air Le premier test est la mesure des propriétés physiques après vieillissement dans l'air à 100°C. Les résultats obtenus sont réunis dans le tableau 4. Dans chacune des lignes figure en dessous de la valeur mesurée, la variation observée par rapport à celle du tableau 3 (état initial du mélange). Aging in air The first test is the measurement of physical properties after aging in air at 100 ° C. The results obtained are shown in Table 4. In each line is below the measured value, the observed variation from that of Table 3 (initial state of the mixture).
Tableau 4 Table 4
Mélanges A B C D E Mixtures A B C D E
Propriétés properties
Dureté shore A * 78 77 70 73 73 Hardness shore A * 78 77 70 73 73
Variation +9 + 14 +5 +8 +2 Variation +9 + 14 +5 +8 +2
Allongement à la 353 491 455 415 326 rupture (%) Lengthening to 353 491 455 415 326 break (%)
Variation (%) Variation (%)
-19 -22 -23 -24 -23  -19 -22 -23 -24 -23
Contrainte à la 17,9 16 ,0 16,5 16,4 14,0 rupture (MPa) Constraint at 17.9 16, 0 16.5 16.4 14.0 rupture (MPa)
Variation (%) Variation (%)
+ 10,8 + 12,3 +6,9 +6,6 + 1 ,6  + 10.8 + 12.3 +6.9 +6.6 + 1, 6
Contrainte à 100% 7,20 5,12 4,82 5,33 5,36 d'allongement (MPa) 100% stress 7,20 5,12 4,82 5,33 5,36 elongation (MPa)
Variation (%) Variation (%)
+63,9 +77,7 +48,0 +56,4 +24,4  +63.9 +77.7 +48.0 +56.4 +24.4
Variation masse (%) -4,48 -4,00 -1 ,75 -2,43 +0,12 Mass variation (%) -4,48 -4,00 -1, 75 -2,43 +0,12
Variation volume (%) -5,77 -5,70 -2,19 -3,10 +0,12 On peut observer que les trois mélanges selon l'invention (C,D et E) présentent des résultats meilleurs que ceux du mélange de référence (A). On peut noter la dureté qui augmente peu, l'augmentation des contraintes à l'allongement et à la rupture qui est moindre et surtout les variations en masse et en volume qui sont de moindre amplitude, marquant ainsi une meilleure stabilité des mélanges selon l'invention. Variation volume (%) -5,77 -5,70 -2,19 -3,10 +0,12 It can be observed that the three mixtures according to the invention (C, D and E) have better results than those of the reference mixture (A). We can note the hardness which increases little, the increase of the stresses to elongation and to the break which is less and especially the variations in mass and in volume which are of less amplitude, thus marking a better stability of the mixtures according to the invention.
Extractibilté Extractibilté
La mesure de l'extractibilité des plastifiants par la température en présence de charbon actif (24 h à 70°C) a été réalisée par référence à la norme NF EN ISO 176 pour les plastiques. Les résultats sont réunis dans le tableau 5. The measurement of the extractability of the plasticizers by the temperature in the presence of activated carbon (24 h at 70 ° C.) was carried out with reference to the NF EN ISO 176 standard for plastics. The results are shown in Table 5.
Tableau 5 Table 5
Figure imgf000017_0001
Figure imgf000017_0001
Les mélanges selon l'invention et plus particulièrement E se distinguent par leur résistance à l'extractibilité des plastifiants. Cette observation a déjà été faite dans les tests précédents sur le vieillissement à l'air à 100°C. The mixtures according to the invention and more particularly E are distinguished by their resistance to the extractability of plasticizers. This observation has already been made in the previous tests on aging in air at 100 ° C.
Vieillissement dans l'huile Aging in the oil
Les propriétés physiques des formulations après vieillissement dans l'huile IRM 903 de SUNOCO (simulant les huiles moteur) à 100°C pendant 70 h sont données dans le tableau 6. The physical properties of the formulations after aging in SUNOCO MRI 903 oil (simulating motor oils) at 100 ° C for 70 h are given in Table 6.
Tableau 6 Table 6
A B C D E A B C D E
Dureté Shore A (points) 75 72 71 72 71 Hardness Shore A (points) 75 72 71 72 71
Variation +6 +9 +6 +7 0 Variation +6 +9 +6 +7 0
Variation de masse (%) -2,84 -2,45 -2,28 -2,58 0,67 Mass change (%) -2.84 -2.45 -2.28 -2.58 0.67
Variation de volume (%) -3,22 -3,39 -2,15 -2,46 -1 ,43 Les variations relevées font référence aux valeurs mesurées sur les mélanges à l'état initial (tableau 3). Volume change (%) -3.22 -3.39 -2.15 -2.46 -1, 43 The variations noted refer to the values measured on mixtures in the initial state (Table 3).
Les variations des propriétés après vieillissement dans l'huile IRM 903 des trois mélanges selon l'invention font apparaître des performances au moins égales en dureté Shore avec une très bonne résistance de la formulation E, les pertes en masse et en volume étant nettement moindres que celles du mélange de référence (A). The variations of the properties after aging in the IRM 903 oil of the three mixtures according to the invention show at least equal performances in Shore hardness with a very good resistance of the formulation E, the losses in mass and in volume being considerably less than those of the reference mixture (A).
Chacune des valeurs portées dans les tableaux 2 à 6 sont le résultat des moyennes obtenues avec au moins 3 essais. Each of the values given in Tables 2 to 6 are the result of averages obtained with at least 3 trials.

Claims

Revendications claims
1 ) Composition élastomère comprenant un élastomère naturel ou synthétique ou un mélange des deux et au moins un composé ester de diacide de formule R-iOOC- R-COOR2 (I) dans laquelle R est un radical alcényle comportant de 16 à 18 atomes de carbone et au moins une double liaison, Ri et R2 identiques ou différents sont des radicaux alkyles ou alcényles linéaires ou branchés comportant de 1 à 24 atomes de carbone, de préférence de 4 à 21 atomes de carbone, et de manière encore plus préférée de 6 à 18 atomes de carbone. 1) An elastomeric composition comprising a natural or synthetic elastomer or a mixture of both and at least one diacid ester compound of formula R-iOOC-R-COOR 2 (I) in which R is an alkenyl radical containing from 16 to 18 carbon atoms and at least one double bond, R 1 and R 2, which are identical or different, are linear or branched alkyl or alkenyl radicals comprising from 1 to 24 carbon atoms, preferably from 4 to 21 carbon atoms, and still more preferably from 6 to 18 carbon atoms.
2) Composition selon la revendication 1 , caractérisée en ce que l'élastomère est choisi parmi le poly-isoprène (IR), polybutadiène (BR), poly- chloroprène (CR) styrène-butadiène (SBR), styrène-butadiène-styrène (SBS), acrylonitrile-butadiène (NBR), acide (meth)acrylique-butadiène ou acrylonitrile-butadiène-styrène (ABS). 2) Composition according to claim 1, characterized in that the elastomer is chosen from poly-isoprene (IR), polybutadiene (BR), polychloroprene (CR) styrene-butadiene (SBR), styrene-butadiene-styrene ( SBS), acrylonitrile-butadiene (NBR), (meth) acrylic-butadiene or acrylonitrile-butadiene-styrene (ABS) acid.
3) Composition selon la revendication 1 ou 2, caractérisée en ce que les esters de diacide comportent au moins un radical Ri ou R2, comprenant au moins 4 atomes de carbone, et de préférence ramifié. 3) Composition according to claim 1 or 2, characterized in that the diacid esters comprise at least one radical R 1 or R 2, comprising at least 4 carbon atoms, and preferably branched.
4) Composition selon l'une des revendications 1 à 3, caractérisée en ce que Γ ester de diacide présente un point de fusion inférieur à 40°C, de préférence inférieur à 20°C, et de manière encore plus préférée compris dans la gamme de -50 à -10 °C sous une pression de 760 mm Hg et un point d'ébullition, aux mêmes conditions de pression, supérieur à 200 °C, de préférence compris dans la gamme de 300 et 400 °C. 5) Composition selon l'une des revendications 1 à 4, caractérisée en ce que la teneur en ester de diacide est comprise dans la gamme de 1 à 15 % en poids d'ester sur le poids 100% d'élastomère seul, de préférence dans la gamme de 2 et 10 % en poids d'ester sur le poids d'élastomère seul. 4) Composition according to one of claims 1 to 3, characterized in that Γ diacid ester has a melting point of less than 40 ° C, preferably less than 20 ° C, and even more preferably included in the range from -50 to -10 ° C under a pressure of 760 mm Hg and a boiling point, under the same pressure conditions, greater than 200 ° C, preferably in the range of 300 and 400 ° C. 5) Composition according to one of claims 1 to 4, characterized in that the diacid ester content is in the range of 1 to 15% by weight of ester on the weight of 100% elastomer alone, preferably in the range of 2 and 10% by weight of ester on the weight of elastomer alone.
6) Procédé de fabrication de compositions élastomères selon les revendications 1 à 5, caractérisé en ce qu'on utilise comme agent plastifiant un mélange de 55 à 95 % poids d'ester de diacide de formule (I) et de 1 à 40 % poids d'un nitrile-ester de formule CN-CH=CH-R'-COORi dans laquelle R' est un radical alkylène comportant 7 ou 8 atomes de carbone et Ri a la même signification que dans la formule (I). 6) A method of manufacturing elastomeric compositions according to claims 1 to 5, characterized in that a plasticizer used a mixture of 55 to 95% by weight of diacid ester of formula (I) and 1 to 40% by weight a nitrile-ester of formula CN-CH = CH-R'-COORi in which R 'is an alkylene radical having 7 or 8 carbon atoms and R 1 has the same meaning as in formula (I).
7) Compositions élastomères fabriquées selon le procédé de la revendication 6. 8) Utilisation d'un ester de diacide de formule (I) dans un élastomère pour lui apporter un effet plastifiant, et notamment améliorer sa résistance au vieillissement, dans laquelle la composition élastomère ainsi obtenue est conforme à celle définie dans les revendications 1 à 5 et 7. 7) elastomer compositions manufactured according to the process of claim 6. 8) using a diacid ester of formula (I) in an elastomer to provide a plasticizing effect, and in particular to improve its resistance to aging, wherein the elastomer composition thus obtained is in accordance with that defined in claims 1 to 5 and 7.
PCT/FR2015/053223 2014-11-27 2015-11-26 Elastomer compositions containing at least one plasticiser formed by an unsaturated, preferably monounsaturated, fatty diacid ester WO2016083746A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3483233A1 (en) 2017-11-10 2019-05-15 Arkema France Lubricant base oil compositions of mono-unsaturated dibasic acid esters with branched alcohols

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4737535A (en) 1984-04-20 1988-04-12 Sumitomo Rubber Industries, Ltd. Rubber composition for tire tread
US5252650A (en) 1992-08-24 1993-10-12 The Goodyear Tire & Rubber Company Rubber compounds containing alkyl (C12 -C22) esters of a mixture of fatty acids
WO2003095550A1 (en) 2002-05-09 2003-11-20 The C.P. Hall Company Adhesion promoter for cord-reinforced rubber and metal or polymer substrate/rubber composites
WO2011138051A1 (en) 2010-05-07 2011-11-10 Arkema France Process for preparing saturated amino acids or saturated amino esters comprising a metathesis step
US20130289182A1 (en) * 2010-12-20 2013-10-31 Novamont S.P.A. Vegetable oil derivatives as extender oils for elastomer compositions
US20130323449A1 (en) 2010-11-12 2013-12-05 H&R Ölwerke Schindler Gmbh Oxygen Compounds as Plasticizers for Rubbers
US20140187808A1 (en) * 2011-08-01 2014-07-03 Arkema France Method for synthesizing an omega-amino acid or ester from a monounsaturated fatty acid or ester
WO2014106724A1 (en) 2013-01-07 2014-07-10 Arkema France Cross metathesis process

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4737535A (en) 1984-04-20 1988-04-12 Sumitomo Rubber Industries, Ltd. Rubber composition for tire tread
US5252650A (en) 1992-08-24 1993-10-12 The Goodyear Tire & Rubber Company Rubber compounds containing alkyl (C12 -C22) esters of a mixture of fatty acids
WO2003095550A1 (en) 2002-05-09 2003-11-20 The C.P. Hall Company Adhesion promoter for cord-reinforced rubber and metal or polymer substrate/rubber composites
US20040002563A1 (en) * 2002-05-09 2004-01-01 Gary Wentworth Liquid adhesion promoter for cord-reinforced rubber and metal or polymer substrate/rubber composites
WO2011138051A1 (en) 2010-05-07 2011-11-10 Arkema France Process for preparing saturated amino acids or saturated amino esters comprising a metathesis step
US20130323449A1 (en) 2010-11-12 2013-12-05 H&R Ölwerke Schindler Gmbh Oxygen Compounds as Plasticizers for Rubbers
US20130289182A1 (en) * 2010-12-20 2013-10-31 Novamont S.P.A. Vegetable oil derivatives as extender oils for elastomer compositions
US20140187808A1 (en) * 2011-08-01 2014-07-03 Arkema France Method for synthesizing an omega-amino acid or ester from a monounsaturated fatty acid or ester
WO2014106724A1 (en) 2013-01-07 2014-07-10 Arkema France Cross metathesis process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
GEORGES WYPYCH: "Handbook of Plasticizers", 2004, article "Plasticizers Use and Selection for Specific Polymers", pages: 273 - 379

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3483233A1 (en) 2017-11-10 2019-05-15 Arkema France Lubricant base oil compositions of mono-unsaturated dibasic acid esters with branched alcohols
WO2019091786A1 (en) 2017-11-10 2019-05-16 Arkema France Lubricant base oil compositions of mono-unsaturated dibasic acid esters with branched alcohols

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