Patent Application
20250206935
This application claims priority from French Patent Application No. FR2314522 filed on Dec. 19, 2023. The French Patent Application is hereby expressly incorporated by reference herein in its entirety.
The invention relates to a rubber composition based on at least one elastomer that can be used to form in the crosslinked state at least one layer of a hose, and a hose in which at least one layer is made up of this composition. The invention applies to a single layer or multilayer hose for conveying a fluid under pressure, preferably a multilayer hose conveying a fluid at a pressure equal to or over 2×105 Pa, the fluid may be a liquid (e.g. water or cooling liquid), a supercritical gas or fluid (e.g. in an air conditioning circuit), a gas mixture (e.g. air in an air intake circuit), or a fuel. The invention applies generally to any hose for transfer of a fluid for a thermal engine, an electric motor or for a fuel cell (e.g. hydrogen) for an automobile, rail, aquatic, aeronautic or spatial vehicle, and also for any industrial facility or residence conveying a pressurized fluid.
As is well known, a rubber hose for an automobile vehicle cooling circuit usually comprises an inner layer designed to be in contact with the conveyed cooling liquid, at least one reinforcing structure on top of the inner layer (typically a reinforcement formed of knitted, twisted or braided yarn, for example PET, aramid or rayon), and an outer layer on top of the reinforcement and exposed to the air surrounding the hose. These inner and outer layers are typically made of a rubber composition reinforced with a filler comprising carbon black of fossil origin and reinforcing grade (i.e. conventional carbon black usually described as “virgin,” generally obtained by thermal decomposition or incomplete combustion of hydrocarbons), possibly coupled or replaced with a mineral reinforcing inorganic filler, such as silica or kaolin, for example.
Over recent years there has been a search to couple such a carbon black with another reinforcing filler of neither fossil nor mineral origin, i.e. a biosourced filler (coming from biomass), like for example lignin, in order to reduce the portion of fossil or mineral ingredients in the composition and in exchange increase the portion of biosourced ingredients. The following patent documents relating to rubber compositions for hoses comprising a partially biosourced reinforcing filler may in particular be mentioned.
WO 2023/025808 A1 has a rubber composition crosslinked by peroxide for example for a hose, which comprises:
EP 4,059,996 A1 has a rubber composition crosslinked by sulfur for example for a hose, which comprises:
A disadvantage of the rubber compositions tested in these examples from WO 2023/025808 A1 and EP 4,059,996 A1, which use a virgin carbon black and a modified lignin as reinforcing filler, resides in their reduced sustainable mass fraction which is at most 22% in said examples.
The goal of the present invention is to propose a rubber composition usable to form in the crosslinked state at least one layer of a hose, where the composition remediates in particular the aforementioned disadvantage from the prior art, while also being suitability for use in the crosslinkable state and having properties from the crosslinked state which are both satisfactory for said layer of the hose.
This goal is achieved in that the Applicant just discovered that if, in a composition of rubber crosslinkable with sulfur or peroxide, a mixed-reinforcing filler is used comprising:
In other words, a rubber composition according to the invention, which is based on at least one elastomer, can be used to form in the crosslinked state at least one layer of a hose and comprises a reinforcing filler and a crosslinking system comprising sulfur and/or a peroxide, and as such that the reinforcing filler comprises:
The expression “a rubber composition usable to form in the crosslinked state at least one layer of a hose” is understood to mean a rubber composition for hose, based on at least one elastomer.
The expression “based on” is understood to mean in the present description that the composition or ingredient considered comprises by weight mostly the constituent in question, i.e. at a fraction by mass over 50%, preferably over 75% and which may range up to 100%.
“At least one recycled carbon black coming from shredding and thermal decomposition of used rubber-based articles” is understood to mean that said or each recycled carbon black (i.e. non-virgin carbon black, also called “recovered carbon black”) is essentially obtained by shredding, and then by high temperature decomposition of the shreds (such as pyrolysis, (vapor) thermolysis or de-vulcanization) of a used article made of at least one rubber or else mostly made up of at least one rubber (such as a tire, hose, joint, belt or any other rubber industrial product). “Shredding” and “shred” are understood generically in the present description to mean respectively breaking possibly supplemented by shredding of the used rubber-based article, and the product of the successive operations of breaking and possibly shredding applied to the used articles.
“Functionalized lignin” in the present description is understood to mean a carbon lignin which is modified by thermal hydrolysis or by another method for modification/purification, with which to get a purified lignin extract. As is well known, lignin is a major component of lignocellulosic biomass, made up of a phenolic-polymer type branched macromolecule comprising in particular carbonyl (C═O), aliphatic hydroxyl and phenolic hydroxyl functional groups. The functionalized lignin usable in the invention may have in particular all or part of these functional groups.
According to implementation examples from the invention, the functionalized lignin in powder form comprises:
Note that the combination of said at least one recycled carbon black and the functionalized lignin serves to confer to the crosslinked composition according to the invention (both with sulfur and with peroxide) physical properties (e.g. density, hardness, volume resistivity) and mechanical properties (e.g. M100 secant modulus at 100% deformation, elongation and stress at break, compression set) which are each sufficient for the hose according to the invention, for which at least one layer is made up of this composition, and have properties for use and functional properties (e.g. pressure resistance, dynamic performance and aging resistance) equivalent to those of the hose incorporating said “control” composition (which is distinguished from the invention composition only in that the carbon black coupled to the same functionalized lignin is virgin).
Advantageously, said at least one recycled carbon black may have reinforcement properties of the composition analogous to those of reinforcing-grade virgin carbon black selected from the ASTM N300, N400, N500, N600 and N700 series, for example analogous to those of carbon black from N500 or N600 series (e.g. analogous to those of an N550 or N660 black, nonlimiting).
According to another aspect of the invention, the composition comprises, in addition to said at least one elastomer, the crosslinking system and the functionalized lignin in powdered form:
Advantageously, the recycled pulverulent mixture may comprise said at least one recycled carbon black according to a fraction by mass included between 80% and 99%, and inorganic substances at a fraction by mass included between 1% and 20%, comprising in particular silicon oxides and/or zinc compounds, where the recycled pulverulent mixture in micronized form comes for example from pyrolysis of used tires.
In the present description “reinforcing filler” is understood to mean a filler comprising individual reinforcing grade fillers for said at least one elastomer which are homogeneously dispersed in the composition, with it specified that the reinforcing filler may further comprise:
According to a preferential embodiment of the invention which may include any one of the aforementioned characteristics, the reinforcing filler may further comprise at least one virgin (i.e. not recycled) carbon black having for example a BET specific surface area measured according to the ASTM D 6556 standard which is included between 10 and 50 m2/g and for example from 15 to 30 m2/g, such as a carbon black from N500 or N600 series (e.g. N550 or M660, without limitation).
According to another general characteristic of the invention which may include any one of the aforementioned characteristics, the composition may comprise 10-120 PCE of said at least one recycled carbon black and 2-90 PCE of the functionalized lignin (PCE: parts by weight for 100 parts of elastomer(s)).
Note that the incorporation of the functionalized lignin in the reinforcing filler is not contrary to the use of a large quantity of carbon black in the composition, serving to give it satisfactory mechanical properties.
According to another general characteristic of the invention which may include any one of the aforementioned characteristics, said at least one elastomer may be selected from the ethylene-propylene-diene terpolymers (EPDM), the isobutylene-isoprene copolymers (IIR), the halogen isobutylene-isoprene copolymers (XIIR), the silicone rubbers, the fluoro silicone rubbers, the acrylic rubbers such as polyacrylate (ACM) and ethylene polyacrylate (AEM), and the bromine copolymers of isobutylene-para-methylstyrene. According to an embodiment, said at least one elastomer may be selected from the ethylene-propylene-diene terpolymers (EPDM) and acrylic rubbers such as polyacrylate (ACM) and ethylene polyacrylate (AEM).
It will however be noted that other rubbers than those aforementioned can be used in the composition according to the invention, as a function of the property sought for the or each layer of the hose.
According to a specific embodiment of the invention:
Preferably, said at least one EPDM, not oil-extended, has:
to another general aspect of the invention which may relate to any one of the aforementioned characteristics, the composition of the invention, for example based on at least one EPDM, comprises:
Still more preferably, according to another general aspect of the invention which may relate to any one of the aforementioned characteristics, the sum of the quantities of said at least one virgin carbon black and said at least one recycled carbon black in the composition according to the invention, for example based on at least one EPDM, is 70-100 PCE, and
Also preferred, the reinforcing filler comprises:
According to another general aspect of the invention which may relate to any one of the aforementioned characteristics, the composition according to the invention, for example based on at least one EPDM or at least acrylic rubber such as (ACM) or (AEM), may advantageously have in the crosslinked state a resistivity per unit volume over 106 Ohm·cm, preferably over 108 Ohm·cm and still more preferably over 1012 Ohm·cm, measured according to IEC 62631 3 standard.
Note that these compositions according to the invention, for example based on at least one EPDM or at least acrylic rubber such as (ACM) or (AEM), thus have a high resistivity because of said functionalized lignin, despite the use of a large quantity of carbon black which is known to penalize this resistivity (by increasing the electrical conductivity). This high resistivity serves in particular to minimize the electrochemical breakdown of the inner layer of the hose in contact with the fluid that it conveys, when this fluid is a cooling liquid for example of glycolated-water type, without penalizing the resistance of the hose to the outside environment thereof.
Note that the use of a recycled carbon black allows for a better resistivity compared to a composition comprising a virgin carbon black.
Further, note that the aforementioned quantities used for said at least one recycled carbon black, the functionalized lignin and optionally said at least one virgin carbon black combined with the use of a suited plasticizer system serve to limit the Mooney ML (1+4) viscosity at 100° C. for the crosslinkable composition (whatever the elastomer matrix used) all while opposing the premature crosslinking (scorch) thereof, thus making the composition from the invention suited for being used by mixing then extrusion.
As a plasticizer system for the composition according to the invention, at least one plasticizer oil and/or at least one plasticizer resin may be used, with it specified that the plasticizer system according to the invention preferably comprises at least one oil selected from mineral oils, oils coming from the biomass (including modified or unmodified vegetable oils), and mixtures thereof.
Still more preferred, as a plasticizer system, at least one oil is used selected from paraffinic, naphthenic and aromatic mineral oils, for example an at least partial naphthenic mineral oil (which may comprise both paraffinic, naphthenic and aromatic functions).
Concerning said crosslinking system, it serves to chemically crosslink the rubber composition by subsequent vulcanization of the hose comprising the or each layer made up of the composition, at a temperature for example included between 16° and 200° C. This crosslinking system, if it uses peroxide, may comprise an organic peroxide and a crosslinking co-agent, for example, selected from triallyl cyanurate (TAC) and triallyl isocyanurate (TAIC).
According to another general aspect of the invention which may relate to any one of the aforementioned characteristics, the composition may have a fraction by mass of sustainable ingredients (i.e. biosourced and recycled), in which sustainable ingredients include said at least one recycled carbon black and said functionalized lignin, that is over 10%, preferably over 20 or 25%, more preferably over 30%, for example equal to or greater than 40%.
Note that said sustainable ingredients, present in the composition according to more than 25%, 30% even 40%, may be made up of said at least one recycled carbon black and said functionalized lignin, or else as a variant further include one or more sustainable ingredients.
According to another general aspect of the invention, the crosslinkable rubber compositions from the invention are prepared by using a method essentially comprising the following successive steps:
As a variant, the crosslinking system may be added during step b) of thermomechanical work with a control of the maximum temperature at 120° C., for example, or else during a second introduction in the internal mixer following cooling of the precursor mix resulting from the first step.
As the results shown in the following examples attest, the physical properties (e.g. density, hardness, volume resistivity) and mechanical properties (e.g. M100 at 100% deformation, elongation and stress at break, compression set) of the crosslinked compositions according to the invention are globally sufficient so that hoses incorporating them convey with a good dynamic strength a fluid at a pressure of at least 2×105 Pa, even after thermal-oxidizing aging at 150° C. for 168 hours.
A hose according to an embodiment of the invention for transferring a liquid, gaseous or supercritical fluid for thermal or electric motor, or for fuel cell for an automobile, rail, aquatic, aerial or spatial vehicle, the hose comprising a radially inner tube of rubber, at least one reinforcing layer and one cover layer of rubber is suited for conveying the fluid at a pressure equal to or over 2×105 Pa.
A hose according to this embodiment of the invention is such that one at least of the inner tube and the covering layer is made up of a rubber composition in the crosslinked state such as defined above.
Note that the hose according to this embodiment may further comprise a barrier layer of a plastic based on at least one thermoplastic polymer. This barrier layer may form the most radially inward layer of the hose, or else an “insulating layer” between the inner tube and a reinforcing layer or between the inner tube and a rubber intermediate layer.
According to another general aspect of the invention which may relate to any one of the aforementioned characteristics, the rubber composition for hose, based on at least one elastomer, comprises a reinforcing filler and a crosslinking system comprising sulfur and/or a peroxide,
According to another general aspect of the invention which may relate to any one of the aforementioned characteristics, the recycled pulverulent mixture is micronized, and comprises the product of a thermal decomposition reaction by thermolysis, pyrolysis applied to shreds of used rubber-based articles.
According to another general aspect of the invention which may relate to any one of the aforementioned characteristics, the recycled pulverulent mixture is from pyrolysis of used tires.
Other features, advantages and details of the invention will emerge upon reading the following description of several examples of implementation of the invention, given for illustration in connection with the attached drawings, among which:
The multilayer hose 10 from
As explained above, the tube 11 and the cover layer 13 may, as a variant, each be based on at least one IIR or XIIR (halobutyl rubber, e.g. chlorinated or brominated), at least one silicon rubber optionally with fluorine (e.g. MQ, PMQ, PVMQ, VMQ or FMQ, FVMQ) or at least one brominated copolymer of isobutylene-p-methylstyrene (e.g. Exxpro® tradename).
The reinforcement layer 12 may comprise, without limitation, a knit, twist or braid based on multifilament yarn made of one or more textile material(s), for example a polyamide (e.g. aramid), polyester (e.g. PET) or rayon (where the term “yarn” designates as usual both a thread based on a multitude of elementary small-diameter filaments which are twisted together and a plied obtained by torsion of several threads).
The multilayer hose 20 from
The multilayer hose 30 from
The multilayer hose 40 from
Note that a multilayer hose according to the invention could comprise an arrangement of layers different from those shown in
The control rubber composition C1, the rubber compositions not conforming to the invention C2-C6 and the rubber compositions according to the invention I1-I8, were prepared essentially by making use of the following method.
The ingredients for each composition, except for the crosslinking system, were added to a Banbury® type internal mixer. Then, thermomechanical work was done in one step (mixing length: 30 s to 2 min.), until reaching a maximum “dropping” temperature of about 125° C.
The resulting mixture was recovered, cooled, then the crosslinking system was added in an outer mixer with cylinders at 100° C., while mixing everything for about 2 min., in a mechanical work step.
The resulting crosslinkable rubber compositions C1-C6 and I1-I8 were then shaped as cylindrical test pieces for undergoing measurement of properties in the non-crosslinked state (Mooney viscosity and scorch time), and as dumbbell-shaped test pieces for performing measurements of mechanical properties in the crosslinked state after vulcanization of the test piece at 180° C. (hardness, M100 secant modulus at 100% deformation and properties at break).
For each cylindrical type crosslinkable test piece, the Mooney ML (1+4) viscosity at 100° C. was measured according to the ISO 289-1 standard and the scorch time t5 without premature crosslinking was measured at 135° C. according to the ISO 289-2 standard.
Further, for each dumbbell type crosslinked test piece, the following were measured:
Each test piece made up of the rubber compositions C1-C6 and I1-I8 was subject to a thermal-oxidizing aging under hot air for 168 hours at 150° C., then the hardness, and stress and elongation at break were measured again as specified in b) and d) above.
The following Table 1 gives the formulations of the compositions C1-C3 and I1-I5 prepared as indicated above.
The following Table 2 gives the formulations of the compositions C4-C6 and I6-I8 prepared as indicated above
The ingredients used for these compositions identified in Tables 1 and 2 by the * sign have the following characteristics:
Table 3 below shows the essential rheological properties of the resulting compositions C1-C3 and I1-I5, including for each of them:
Table 4 below shows the physical and mechanical properties of the resulting crosslinked compositions C1-C3 and I1-I5 measured as indicated above on dumbbell type test pieces.
The set of properties obtained in Tables 3-4 for the compositions I1-I5 according to the invention show, in comparison with the control composition C1 (comprising a mixture of 50% of the same virgin carbon black and 50% of the same lignin as reinforcing filler):
The resulting properties for the compositions I1-I5 according to the invention show, in comparison with the composition C2 not complying with the invention (comprising 100% of the same virgin carbon black as reinforcing filler):
The resulting properties for the compositions I1-I5 according to the invention show, in comparison with the composition C3 not complying with the invention (comprising 100% of the same lignin as reinforcing filler):
Table 5 below shows the essential rheological properties of the resulting compositions C4-C6 and I6-I8, including for each of them:
Table 6 below shows the physical and mechanical properties of the resulting crosslinked compositions C4-C6 and I6-I8 measured as indicated above on dumbbell type test pieces.
The resulting properties for the compositions I6-I8 according to the invention show, in comparison with compositions C4-C6 not complying with the invention:
In conclusion, these examples show that:
These examples also show that the compositions according to the invention I1, I2, I3, I5, I6, I7 and I8 advantageously have a fraction by mass of sustainable ingredients (i.e. biosourced and recycled) which is over 10% (composition I7), over 20% (composition I6), over 25% (composition I8), even over 30% (compositions I2, I3 and I5) and even over 40% (composition I3).
These examples also show that the replacement of at least one part of the virgin carbon black by recycled carbon black makes it possible to improve the resistivity of the composition.
| Number | Date | Country | Kind |
|---|---|---|---|
| FR2314522 | Dec 2023 | FR | national |
