WO2024052459A1

WO2024052459A1 - Clear binder comprising particles of plastic waste, and uses thereof

Info

Publication number: WO2024052459A1
Application number: PCT/EP2023/074576
Authority: WO
Inventors: Ana Maria CENACCHI; Julie Prevost; Céline LAGOUTTE; Matthieu SEGUELA; Jean-Philippe Paillac
Original assignee: Totalenergies Onetech
Priority date: 2022-09-09
Filing date: 2023-09-07
Publication date: 2024-03-14
Also published as: FR3139577A1

Abstract

The invention relates to a clear-binder composition comprising (i) a plasticizer comprising at least one oil of plant origin comprising an ester compound derived from tall oil, (ii) a structuring agent comprising at least one resin of plant origin chosen from natural rosins, modified rosins, rosin esters, and any mixture thereof, (iii) at least one polymer based on conjugated diene units and on monovinyl aromatic hydrocarbon units, (iv) particles of plastic waste comprising a polymeric part comprising polypropylene, optionally in a mixture with polyethylene.

Description

CLEAR BINDER INCLUDING PLASTIC WASTE PARTICLES AND

ITS APPLICATIONS

Technical area

The present invention relates to a clear binder composition incorporating plastic particles, in particular recycled plastic particles. The invention also relates to a process for preparing a clear binder composition according to the invention. The invention also relates to different uses of a clear binder composition according to the invention for road and/or industrial applications, in particular for the production of colored surface coating compositions.

State of the prior art

The phenomenon of urban heat islands is defined as localized rises in temperatures, particularly maximum daytime and nighttime temperatures, recorded in urban areas, compared to neighboring rural or forest areas or compared to regional average temperatures. Significant differences in temperature can thus be noted depending on the nature of the land use (forest, bodies of water, suburbs, dense city, etc.), the relief, the exposure or even the season.

Urban heat islands have an environmental and meteorological impact but also on public health. These harmful effects are accentuated during periods of extreme heat.

The origins of this phenomenon are multiple. They are partly natural, directly linked to the geographical area in which the city is located and the associated climate (range of temperature, humidity, exposure to wind, precipitation, etc.). These increases in temperatures are also linked to human activities responsible for localized heat emissions (due in particular to the operation of cars, construction machinery, various household appliances such as air conditioners but also industrial activity), and On the other hand, there is the emission of greenhouse gases, notably carbon dioxide and methane, contributing to the phenomenon of global warming.

Another factor contributing to the phenomenon of urban heat islands is urbanization, due to the disappearance of natural soils in favor of industrial coverings or buildings. Part of the vegetation participating in thermal management is thus replaced by construction materials such as cement or coatings. These coverings are, however, waterproof and thus block natural cooling phenomena such as the evapotranspiration of water contained in soils and plants. Urban morphology, as such, is also an element essential: a dense city with tall, closely spaced buildings creates confinement zones reducing air circulation which could help with cooling. In addition, part of the solar radiation is reflected by buildings and returned to the city, thus contributing to a further increase in temperature. Finally, buildings absorb a significant amount of heat, much greater than that absorbed by natural environments. This stored energy is then retransmitted to the urban environment by thermal radiation.

There remains a need for construction materials, particularly for urban construction, capable of limiting and/or preventing the phenomenon of urban heat islands.

In particular, there remains a need for materials with improved thermal properties, so as to prevent and/or limit and/or reduce the increase in urban ambient temperature.

In particular, there remains a need for materials having reduced thermal emissivity and/or thermal capacity and/or thermal conductivity.

Urban surfaces, and in particular road surfaces, are today mainly prepared from bituminous binders or colored coatings, called clear binders. Due to the presence of asphaltenes, bituminous binders are black in color and are therefore difficult to color. Colored coatings are increasingly used because, among other things, they improve the safety of road users by clearly identifying specific lanes such as pedestrian lanes, cycle paths and bus lanes. They also make it possible to mark certain danger zones such as town entrances or dangerous bends. Colored coatings promote visibility in low light conditions, for example at night or in special sites such as tunnels. Finally, they simply improve the aesthetic appearance of urban roads and can be used for public squares, building and school courtyards, sidewalks, pedestrian streets, garden and park paths. , parking and rest areas.

Consequently, for all the aforementioned applications, it is preferred to use clear synthetic binders, which do not contain asphaltenes and which can be colored.

The clear binders of the prior art generally consist of a plasticizing agent, for example an oil of petroleum origin, a structuring agent, for example a hydrocarbon resin, and a polymer.

Application WO2018/046838 discloses a clear binder that is solid when cold. In particular, it describes a clear binder containing a synthetic oil from unit cuts of deasphalting (DAO) and a copolymer based on butadiene and styrene units, for example an SB or SBS copolymer.

Application WO2018/115729 discloses a cold solid binder composition. In particular, the composition can be a clear binder and the plasticizing agent is in particular an oil of petroleum origin. Application WO2018/115730 describes a similar composition for the preparation of mastic asphalts and the production of coatings.

Document US2002/052431 discloses aqueous emulsions comprising on the one hand a clear synthetic binder and on the other hand a latex. During manufacturing, and then in implementation, these binders are subject to different types of external factors which modify their structure and change their properties.

Clear binders with a reduced environmental footprint compared to the clear binders discussed above have also been developed by seeking to at least partially substitute the plasticizing agent and/or the structuring agent with constituents of plant origin.

Application EP3081599 describes in this sense a binder of plant origin based on modified tall oil pitch, a modified resin and possibly a polymer.

However, these clear binders are not entirely satisfactory.

None of these binders of plant origin has in fact shown itself capable of sufficiently limiting and/or preventing the phenomena of urban heat islands discussed above.

In addition, although they do have a reduced environmental footprint compared to traditional clear binders, these plant-based binders present sustainability issues. In fact, the clear binders currently available and incorporating a plasticizing agent and/or a structuring agent of plant origin have significantly reduced resistance to aging, compared to traditional clear binders prepared from products of petroleum origin. In particular, these binders prepared from compounds of plant origin have significantly reduced resistance to aging of cold properties, compared to traditional clear binders prepared from products of petroleum origin.

A more regular replacement of road surfaces is therefore to be expected, which significantly reduces their environmental benefit.

There thus remains a need for clear biosourced binders (prepared from at least one plasticizing agent of plant origin and/or at least one structuring agent of plant origin) with improved mechanical properties, compared to clear binders. existing biosourced products. In particular, there remains a need for biosourced clear binders (prepared from at least one plasticizing agent of plant origin and/or at least one structuring agent of plant origin) having properties equivalent to traditional clear binders prepared from oil and resin of petroleum origin.

There also remains a need for clear biosourced binders (prepared from at least one plasticizing agent of plant origin and/or at least one structuring agent of plant origin) capable of limiting and/or preventing the phenomenon of urban heat islands.

In particular, there remains a need for clear biosourced binders (prepared from at least one plasticizing agent of plant origin and/or at least one structuring agent of plant origin) presenting improved thermal properties, so as to limit and /or prevent and/or reduce the increase in urban ambient temperature.

In particular, there remains a need for clear biosourced binders (prepared from at least one plasticizing agent of plant origin and/or at least one structuring agent of plant origin) having a thermal emissivity and/or a capacity thermal and/or reduced thermal conductivity.

Surprisingly, it was found that the combination (i) of a vegetable oil comprising an ester derived from tall oil having a solidification temperature below 30°C and whose acidity index, determined according to the ASTM D465 method, is less than or equal to 150 mg KOH/g, (ii) of a resin of plant origin chosen from natural rosins, modified rosins, rosin esters, and mixtures thereof and whose index acidity, determined according to the ASTM D465 method, is less than 8 mg KOH/g, (iii) a polymer based on conjugated diene units and monovinyl aromatic hydrocarbon units, and (iv) particles of plastic waste comprising a polymer part chosen from polypropylene and a mixture of propylene and polyethylene, made it possible to obtain a clear biosourced binder capable of limiting and/or preventing urban heat island phenomena.

In particular, the clear binder according to the invention allows the preparation of an urban covering, in particular a road surface, making it possible to prevent and/or limit and/or reduce the increase in urban ambient temperature.

In addition, the clear binder according to the invention has properties similar to those of traditional clear binders, obtained from compounds of petroleum origin.

Summary of the invention

By “biosourced clear binder” is meant within the meaning of the invention a clear binder comprising at least one plasticizing agent of plant origin and/or at least one structuring agent of plant origin. By “urban ambient temperature” is meant for the purposes of the invention the average temperature measured in the exterior spaces of a city, in particular in the street.

For the purposes of the invention, “surface temperature” means the average temperature measured on the surface of a material present in an urban environment, in particular on the surface of a construction material such as asphalt.

In the remainder of the application, any reference to a standard (e.g. ASTM D1982) relates to the version of said standard in force on the date of filing of this application.

The invention firstly relates to a clear binder composition comprising:

(i) a plasticizing agent comprising at least one oil of vegetable origin comprising an ester compound derived from tall oil, said oil of vegetable origin having a solidification temperature, determined according to the ASTM D1982 method, less than 30° C and an acidity number, determined according to the ASTM D465 method, less than or equal to 150 mg KOH/g,

(ii) a structuring agent comprising at least one resin of plant origin chosen from natural rosins, modified rosins, rosin esters, and any of their mixtures, said resin of plant origin having an index of acidity, determined according to the ASTM D465 method, less than 8 mg KOH/g,

(iii) at least one polymer based on conjugated diene units and monovinyl aromatic hydrocarbon units,

(iv) particles of plastic waste comprising a polymeric part comprising polypropylene, optionally mixed with polyethylene, and

(v) possibly an adhesive boost.

Preferably, the ester compound is chosen from derivatives of a tall oil fatty acid.

More preferably, the ester compound is chosen from the group consisting of: trimethylolpropane tallates, ethylene glycol monomerates, neopentyl glycol monomerates, 2-ethylhexyl monomerates, glycerol monomerates, and any one of their mixtures.

Advantageously, the clear binder composition has a plasticizing agent content ranging from 1% to 40% by mass, relative to the total mass of the composition, preferably from 5% to 30% by mass, more preferably from 10% to 20% by mass.

Preferably, the resin of plant origin is chosen from natural rosin esters, more preferably from pentaerythritol esters of natural rosins, in particular among the pentaerythritol esters of tall oil rosins.

Advantageously, the clear binder composition has a structuring agent content ranging from 50% to 95% by mass, relative to the total mass of the composition, preferably from 60% to 90% by mass, more preferably from 75% to 90% by mass. 85% by mass.

Advantageously, the polymer is a copolymer of styrene and butadiene, preferably chosen from a styrene/butadiene/styrene block copolymer of radial structure, a butadiene/styrene block copolymer of radial structure and their mixtures.

According to a preferred embodiment, the particles of plastic waste (introduced into the clear binder composition) have:

- a thickness less than or equal to 1 mm, preferably ranging from 0.1 mm to 0.5 mm, and/or

- a length less than or equal to 10 cm, preferably ranging from 0.1 cm to 10 cm, and/or

- a surface area less than 20 cm ² , preferably ranging from 5 to 20 cm ² .

Preferably, the clear binder composition according to the invention has a content of plastic waste particles ranging from 0.1% to 5% by mass, relative to the total mass of the composition, preferably from 0.5% to 3% by mass, more preferably from 0.7% to 1.5% by mass.

According to one embodiment, the clear binder composition according to the invention has a biosourced carbon content, measured according to the ASTM D6668 standard, of at least 75%, preferably at least 80%, more preferably at least 80%. less 85%, advantageously at least 90%.

According to one embodiment, the clear binder composition of the invention is characterized in that it has an eco-material content of at least 70%, preferably at least 80%, preferably at least 90%, and more preferably at least 95%.

According to one embodiment, the clear binder composition of the invention has an aerobic biodegradability, measured according to the ISO 17556 standard, at least 2 times higher than the aerobic biodegradability of a clear binder composition prepared from a plasticizing agent of petroleum origin and a structuring agent of petroleum origin, preferably at least 3 times higher, more preferably at least 4 times higher, advantageously at least 5 times higher.

The invention also relates to a process for preparing a clear binder composition as defined above, comprising the steps: a) bringing the plasticizing agent and the structuring agent into contact, and heating to a temperature between 140°C and 200°C, b) mixing with stirring the plasticizing agent and the structuring agent at a temperature between 140°C and 200°C, c) adding the polymer, mixing and heating to a temperature ranging from 140°C to 200°C, d) adding the plastic waste particles, mixing and heating to a temperature ranging from 140°C to 200°C, e) adding any adhesive dope, mixing and heating to a temperature ranging from 140°C to 200°C.

The invention also relates to an emulsion comprising a clear binder composition as defined above and described in detail below, water, and an emulsifying agent.

The invention also relates to a coating comprising (i) a clear binder composition as defined above and described in detail below or an emulsion as defined above and described in detail below, (ii ) aggregates and/or mineral fillers, and optionally (iii) one or more pigments.

According to one embodiment, the coating according to the invention further comprises particles of plastic waste comprising a polymeric part made of polystyrene.

Preferably, the coating defined below and in detail below is a draining coating.

The invention also relates to the use of a clear binder composition as defined above and described in detail below, of an emulsion as defined above and described in detail below or 'a coating as defined above and described in detail below, for:

- limit and/or prevent and/or reduce an increase in urban ambient heat, and/or

- limit and/or prevent and/or reduce the surface temperature of construction materials used in urban areas.

The invention finally relates to the use of a clear binder composition according to the invention or of an emulsion according to the invention, to improve the eco-performance of a coating. Preferably, eco-performance is chosen from:

- increasing the durability of the coating, and/or

- reducing the environmental impact of the coating. detailed description

The essential constituents of a clear binder composition are:

- a plasticizing agent, for example an oil devoid of asphaltenes,

- a structuring agent,

- at least one polymer,

- where applicable, doping agents, or dopes, or adhesiveness dopes.

The clear binder of the invention is characterized by the combination of an oil of particular plant origin and a resin of specific plant origin. This selection of components makes it possible to obtain a clear binder with a reduced environmental footprint, compared to clear binders prepared from an oil of petroleum origin and a resin of petroleum origin, while having similar properties, particularly in terms of mechanical resistance.

According to one embodiment, the clear binder composition of the invention comprises a majority of biosourced materials, recycled or from waste. It can therefore have a high eco-material index. The eco-material index is defined by the following equation:

Eco-material index = 100% - [% of non-biosourced, non-biodegradable, non-recycled or non-waste materials].

According to one embodiment, the clear binder composition of the invention has an eco-material content of at least 70%, preferably at least 80%, preferably at least 90%, and more preferably 'at least 95%.

For the purposes of the invention, the terms “clear binder” and “clear binder base” are used equivalently.

The invention relates to a clear binder comprising:

(ii) a structuring agent comprising at least one resin of plant origin chosen from natural rosins, modified rosins, rosin esters, and any of their mixtures, said resin of plant origin having an index of acidity, determined according to the ASTM D465 method, less than 8 mg KOH/g

(iii) at least one polymer based on conjugated diene units and monovinyl aromatic hydrocarbon units, (iv) particles of plastic waste comprising a polymeric part chosen from polypropylene and a mixture of polypropylene and polyethylene, and (iv) optionally an adhesive boost.

The plasticizing agent

By “plasticizing agent”, within the meaning of the invention, is meant a chemical constituent making it possible to fluidize and reduce the viscosity and modulus of the binder in which it is incorporated.

According to the invention, the plasticizing agent comprises, preferably consists of, at least one oil of vegetable origin whose characteristics are stated above.

The oil of plant origin typically comprises at least one ester compound of plant origin derived from tall oil.

By “tall oil derivative”, within the meaning of the invention is meant a chemical compound obtained at least in part from one of the components of crude tall oil (or CTO for “Crude Tall OR”). in English). The components of crude tall oil include, for example, tall oil fatty acids (TOFA), tall oil heads, tall oil rosins, tall and tall oil pitch (also called tall oil pitch). Suitable tall oil derivatives suitable for the invention include acid-functional derivatives such as monomeric, dimeric and trimer acids made from tall oil fatty acids, dimerized rosin acids and acids. refined fats obtainable from tall oil.

The ester compound has a solidification temperature, determined according to the ASTM D1982 method, of less than 30°C.

Preferably, the ester compound is chosen from C4-C36 fatty acid esters, typically C8-C20.

In a known manner, an ester compound results from the reaction between a carboxylic acid and an alcohol with the elimination of water. In the remainder of the application, the ester compound of the invention is described from the carboxylic acid and the alcohol whose esterification reaction would lead to obtaining said ester.

According to one embodiment, the carboxylic acid is in a polymerized form, in particular in the form of dimerized fatty acids.

Preferably, the fatty acid is chosen from the group consisting of: oleic acid, linoleic acid, linolenic acid, palmitic acid and any of their mixtures.

According to a variant, the fatty acid is chosen from monomeric acids (defined below), dimeric acids, tall oil heads, and the like, and mixtures thereof. Alcohol can be primary, secondary or tertiary. In particular, it may be a monol, a diol or a polyol. Alcohol can also come from polyethers such as triethylene glycol or polyethylene glycols. Phenolate esters are also suitable.

Preferably, the alcohol is chosen from: methanol, ethanol, 1-propanol, isobutyl alcohol, 2-ethylhexanol, octanol, isodecyl alcohol, benzyl alcohol, cyclohexanol, ethylene glycol monobutyl ether, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol, sorbitol, sucrose and the like, and any mixtures thereof .

More preferably, the alcohol is chosen from alcohols comprising a quaternary carbon atom located in the beta position relative to the oxygen of any of their hydroxyl groups. By way of example, mention may in particular be made of trimethylolpropane, neopentyl glycol, trimethylolethane, pentaerythritol, dipentaerythritol, benzyl alcohols and others.

As noted above, the ester compound is a derivative of tall oil.

Preferably, it is obtained from a tall oil fatty acid (also called TOFA for “Tall Oil fatty acid”) or from a derivative of a tall oil fatty acid. tall, for example from a tall oil fatty acid dimer acid. The fatty acid of tall oil is obtained from crude tall oil (or CTO) by distillation. Crude tall oil is a byproduct of the process of converting wood into paper pulp, also called the Kraft process. The distillation of crude tall oil yields, in addition to the tall oil fatty acid, a more volatile and highly saturated fraction of long-chain fatty acids (mainly palmitic acid), called "heads". of tall oil". Tall oil fatty acid is the following cut, which mainly contains C and C20 fatty acids with varying degrees of unsaturation (for example, oleic acid, linoleic acid, linolenic acid and various isomers thereof) . Another cut, known as Distilled Tall Oil (or DTO), is a mixture composed primarily of tall oil fatty acids and a smaller proportion of rosin of tall oil. Tall oil rosin (or TOR for “Tall Oil Rosin”), subsequently isolated, consists largely of a C19-C20 tricyclic monocarboxylic acid. The lower cut of the distillation is known as tall oil pitch. In general, any cut which contains at least one tall oil fatty acid is preferred for the preparation of an ester compound suitable for the invention. As noted above, the polymerized fatty acids can be used to make the tall oil-derived ester compounds of the invention. Unsaturated fatty acids are generally polymerized using acidic clay catalysts. Fatty acids with high levels of mono- or polyunsaturation are preferred. In this high temperature process, unsaturated fatty acids undergo intermolecular addition reactions, for example the "Alder-ene reaction", to form polymerized fatty acids. The mechanism is complex and not well understood. However, the product primarily comprises dimerized fatty acids and a unique blend of monomeric fatty acids. Distillation makes it possible to obtain a fraction highly enriched in dimerized fatty acid, commonly called "dimer acid". These dimer acids can be used for the manufacture of ester-functional rejuvenating agents.

Distillation of polymerized tall oil fatty acid provides a fraction enriched in monomeric fatty acids, known as "Monomer" (with a capital "M") or "Monomer Acid". Monomer, a unique composition, is a preferred starting material for the preparation of the ester compound of the invention. While tall oil fatty acid derived from a natural source consists largely of linear C unsaturated carboxylic acids, primarily oleic and linoleic acids, the Monomer contains relatively small amounts of oleic and linoleic, and on the contrary contains significant quantities of branched and cyclic C acids, saturated and unsaturated, as well as elaidic acid. The more diverse and significantly branched composition of the Monomer results from the catalytic treatment performed on the tall oil fatty acid during polymerization. It is accepted that the reaction of Monomer with alcohols to make esters "Monomerates" will yield unique derivatives which differ from the corresponding tall oil fatty acid esters. CAS number 68955-98-6 has been assigned to “Monomer”. Examples of Monomer are Century® MO5 and MO6 fatty acids, produced by Arizona Chemical Company. More information on the composition of Monomer and its conversion to various esters is given in US Patent 7,256,162.

By “Monomerate of an alcohol”, within the meaning of the invention, is meant the product of the reaction between the “Monomer” (defined above) and said alcohol. More particularly, the “Monomerate of an alcohol” is obtained by esterification of the monomeric fatty acids obtained by distillation of the polymerized tall oil fatty acid and said alcohol.

Ester compounds of the invention include, for example, ethylene glycol tallate (i.e., ethylene glycol ester of tall oil fatty acid), propylene tallate glycol, trimethylolpropane tallate, neopentyl glycol tallate, methyl tallate, ethyl tallate, glycerol tallate, oleyl tallate, octyl tallate, Benzyl tallate, 2-ethylhexyl tallate, polyethylene glycol tallates, tall oil pitch esters, Ethylene glycol monomerate, Glycerol monomerate, Trimethylolpropane monomerate, Neopentyl glycol monomerate, 2-ethylhexyl monomerate , ethylene glycol dimerate, 2-ethylhexyl dimerate, 2-ethylhexyl trimerate, and their derivatives. Particularly preferred ester compounds are tallates and monomerates, including trimethylolpropane tallate, ethylene glycol monomerate, glycerol monomerate, and any mixtures thereof.

The ester compounds are typically non-crystalline, that is to say they have a solidification temperature, determined according to the ASTM D1982 method, lower than 30°C, preferably lower than 20°C, more preferably lower than 10 °C, and most preferably less than 0°C.

Preferably, the ester compounds have a cloud point below 0°C, more preferably below -10°C, even more preferably below -20°C, and most preferably below -25°C. The cloud point is determined by gradually cooling a pure, molten sample and observing the temperature at which the clear sample becomes just cloudy.

Preferably, the plasticizing agent has a Gardner color index, determined according to standard ASTM D6166, less than or equal to 10, more preferably less than or equal to 8.

Preferably, the plasticizing agent has a flash point, determined according to the ASTM D92 method, greater than or equal to 200°C, preferably greater than or equal to 250°C, even more preferably greater than or equal to 280°C.

Preferably, the plasticizing agent has an acidity index, determined according to the ASTM D465 method, less than or equal to 150 mg KOH/g, more preferably less than or equal to 100 mg KOH/g, even more preferably less than or equal to 50 mg KOH/g.

Advantageously, the plasticizing agent has an acidity index, determined according to the ASTM D465 method, less than or equal to 20 mg KOH/g, preferably less than or equal to 15 mg KOH/g, typically between 0.1 mg KOH/ g and 15 mg KOH/g.

Preferably, the plasticizing agent has a Cannon-Fenske kinematic viscosity at 40°C, measured according to the ASTM D445 method, greater than or equal to 30 cSt, more preferably between 30 cSt and 100 cSt, even more preferably between 35 cSt and 50 cSt .

Preferably, the plasticizing agent has a Cannon-Fenske kinematic viscosity at -20°C, measured according to the ASTM D445 method, greater than or equal to 1000 cSt, more preferably between 1000 cSt and 2000 cSt, even more preferably between 1500 cSt and 1800 cSt, typically 1600 cSt. Preferably, the plasticizing agent has a Cannon-Fenske kinematic viscosity at 0°C, measured according to the ASTM D445 method, greater than or equal to 200 cSt, more preferably between 200 cSt and 500 cSt, even more preferably between 300 cSt and 400 cSt , typically 350 cSt.

Preferably, the plasticizing agent has a Cannon-Fenske kinematic viscosity at 20°C, measured according to the ASTM D445 method, greater than or equal to 50 cSt, more preferably between 50 cSt and 200 cSt, even more preferably between 75 cSt and 150 cSt , typically 100 cSt.

Preferably, the plasticizing agent has a Cannon-Fenske kinematic viscosity at 40°C, measured according to the ASTM D445 method, greater than or equal to 10 cSt, more preferably between 10 cSt and 100 cSt, even more preferably between 15 cSt and 50 cSt , typically 40 cSt.

Preferably, the plasticizing agent has a Cannon-Fenske kinematic viscosity at 60°C, measured according to the ASTM D445 method, greater than or equal to 10 cSt, more preferably between 15 cSt and 50 cSt, even more preferably between 20 cSt and 30 cSt , typically 23 cSt.

Preferably, the plasticizing agent has a Cannon-Fenske kinematic viscosity at 100°C, measured according to the ASTM D445 method, greater than or equal to 5 cSt, more preferably between 5 cSt and 50 cSt, even more preferably between 5 cSt and 20 cSt , typically 10 cSt.

In particular, in a preferred embodiment, the plasticizing agent according to the invention consists solely of one or more ester compound(s) derived from tall oil.

For example, an oil usable in the clear binder compositions according to the invention may be a product marketed by the company KRATON under the name: SYLVAROAD® RP1000.

Advantageously, the clear binder of the invention has a plasticizing agent content ranging from 1% to 40% by mass, relative to the total mass of the clear binder, preferably from 5% to 30% by mass, more preferably from 10 % to 20% by mass, typically 14% to 17% by mass.

Advantageously, in the clear binder compositions of the invention, the oils of vegetable origin, as defined above, represent at least 90% by mass relative to the total mass of the plasticizing agent, of preferably at least 95%, even more advantageously at least 98%, and still advantageously at least 99%. The structuring agent

By “structuring agent” is meant any chemical constituent conferring mechanical properties and satisfactory cohesiveness to said binder.

The structuring agent used in the composition of the invention is a resin chosen from resins of plant origin.

Resins of plant origin can be called harvested, that is to say harvested from the living plant. They can be used as is, we then speak of natural resins, or they can be chemically transformed, we then speak of modified natural resins.

Harvest resins include natural rosins, modified rosins, and rosin esters. These can be taken alone or in a mixture. Among natural rosins, we can cite gem and wood rosins, in particular pine, and/or tall oil. These natural rosins can be taken alone or in a mixture.

Among the modified rosins, mention may be made of hydrogenated rosins, dismutated rosins, polymerized rosins and/or maleized rosins. These modified natural rosins can be taken alone or in a mixture, and undergo one or more disproportionation, polymerization and/or maleization treatments.

Preferably, the resin is chosen from rosin esters, optionally modified.

More preferably, the resin is chosen from modified rosin esters.

Even more preferably, the resin is chosen from tall oil rosin esters, optionally modified.

Advantageously, the resin is chosen from modified tall oil rosin esters.

Among the rosin esters, mention may be made of methyl esters of natural rosins, methyl esters of hydrogenated rosins, esters of glycerol and of natural rosins, esters of glycerol and of hydrogenated rosins, esters of glycerol and of dismutated rosins, esters of glycerol and polymerized rosins, esters of glycerol and maleized rosins, pentaerythritol esters of natural rosins and pentaerythritol esters of hydrogenated rosins. These rosin esters can be taken alone or in a mixture and come from rosins having undergone one or more disproportionation, polymerization and/or maleization treatments.

Advantageously, the resin is chosen from pentaerythritol esters of natural rosins, pentaerythritol esters of hydrogenated rosins and one any of their mixtures, more advantageously among pentaerythritol esters of natural rosins.

According to a preferred embodiment, the resin is chosen from pentaerythritol esters of tall oil rosins.

For more information on the resins of plant origin that can be used according to the invention, one can refer to article K340 by Bernard Delmond published in “Engineering Techniques”.

Preferably, the resin of plant origin has a softening temperature, determined according to the AQCM 003 method, of between 60°C and 200°C, preferably between 80°C and 150°C, more preferably between 90°C and 110°C.

Resin of plant origin typically has an acidity index, determined according to the ASTM D465 method, of less than 8 mg KOH/g.

Preferably, the resin of plant origin has an acidity index, determined according to the ASTM D465 method, of between 0.1 and 8 mg KOH/g, preferably between 0.2 and 7 mg KOH/g, more preferably between 0.5 mg and 6 mg KOH/g.

Advantageously, the resin of plant origin has an acidity index, determined according to the ASTM D465 method, less than or equal to 5 mg KOH/g.

Preferably, the resin has a Gardner color index, determined according to standard ASTM D6166, less than or equal to 10, more preferably less than or equal to 5, even more preferably less than or equal to 1, typically 0.9.

Preferably, the resin of plant origin has a glass transition temperature, measured according to the AQCM 218 method, of between 10°C and 80°C, preferably between 20°C and 60°C, more preferably between 40°C. and 50°C.

Preferably, the resin of plant origin has a Brookfield viscosity at 125°C, measured according to the AQCM 004 method, greater than or equal to 5,000 mPa.s, preferably between 7,500 mPa.s and 15,000 mPa.s, more preferably between 10,000 mPa.s and 11,000 mPa.s.

Preferably, the resin of plant origin has a Brookfield viscosity at 150°C, measured according to the AQCM 004 method, greater than or equal to 500 mPa.s, preferably between 750 mPa.s and 1500 mPa.s, more preferably between 900 mPa.s and 1000 mPa.s.

Preferably, the resin of plant origin has a Brookfield viscosity at 177°C, measured according to the AQCM 004 method, greater than or equal to 80 mPa.s, preferably between 100 mPa.s and 500 mPa.s, more preferably between 150 mPa.s and 200 mPa.s. For example, a resin usable in the clear binder compositions according to the invention may be a product marketed by the company KRATON under the name: SYLVALITE® 2100 Rosin Ester.

Preferably, the weight ratio between the structuring agent and the plasticizing agent used for the preparation of the clear binder composition according to the invention is between 2 and 10, for example between 4 and 6.

In a specific embodiment, the content of structuring agent in the clear binder composition of the invention ranges from 50% to 95% by mass, relative to the total mass of the composition, preferably from 60% to 90% by mass, more preferably from 75% to 85% by mass, typically from 76% to 83% by mass.

The polymer

The polymer used in the process for preparing the clear binder according to the invention is a copolymer based on conjugated diene units and monovinyl aromatic hydrocarbon units. The conjugated diene is preferably chosen from those containing 4 to 8 carbon atoms per monomer, for example butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3- butadiene, 1,3-pentadiene and 1,2-hexadiene, chloroprene, carboxylated butadiene, carboxylated isoprene, in particular butadiene and isoprene, and mixtures thereof.

The monovinyl aromatic hydrocarbon is preferably chosen from styrene, o-methyl styrene, p-methyl styrene, p-tert-butylstyrene, 2,3 dimethyl styrene, vinyl naphthalene, vinyl toluene, vinyl xylene, and analogues or mixtures thereof, in particular styrene.

Advantageously, the polymer is chosen from copolymers of styrene and conjugated diene. More particularly, the polymer consists of one or more copolymers chosen from block copolymers of styrene and butadiene, styrene and isoprene, styrene and chloroprene, styrene and carboxylated butadiene or even styrene and isoprene carboxylated. Preferably, the polymer consists of one or more copolymers chosen from copolymers of styrene and butadiene.

For example, the polymer may be chosen from one or more of the following copolymers: SB copolymers (styrene and butadiene block copolymers), SBS (styrene-butadiene-styrene block copolymers), SIS (styrene-isoprene-styrene), SBS* (styrene-butadiene-styrene star block copolymer), SBR (styrene-b-butadiene-rubber).

Advantageously, the polymer is chosen from block copolymers. A preferred polymer is a copolymer based on butadiene units and styrene units, in particular such as a styrene/butadiene block copolymer SB or a styrene/butadiene/styrene block copolymer SBS, or a mixture of such copolymers.

More preferably, the polymer is a mixture of a styrene/butadiene/styrene SBS block copolymer and a styrene/butadiene SB block copolymer.

Advantageously, the polymer is a mixture of a styrene/butadiene/styrene SBS block copolymer and a styrene/butadiene SB block copolymer in an SB/SBS mass ratio ranging from 0.1:99.9 to 30:70 , advantageously from 1:99 to 20:80, even more advantageously from 5:95 to 15:85.

The block copolymer of styrene and conjugated diene, in particular the copolymer of styrene and butadiene, advantageously has a weight content of styrene ranging from 5 to 50%, preferably from 20 to 40%, even better from 25 to 35%. .

The copolymer of styrene and conjugated diene, in particular the copolymer of styrene and butadiene, advantageously has a weight content of styrene ranging from 20 to 40%, preferably from 25 to 35% by weight relative to the total mass of the copolymer. .

According to one embodiment, the average molecular mass of the copolymer of styrene and conjugated diene, and in particular that of the copolymer of styrene and butadiene, can be comprised, for example, between 10,000 and 700,000, preferably between 50,000 and 500,000 and more preferably from 200,000 to 400,000 daltons.

According to a variant, the average molecular mass of the copolymer of styrene and conjugated diene, and in particular that of the copolymer of styrene and butadiene, can be comprised, for example, between 10,000 and 500,000, preferably between 20,000 and 100,000. , more preferably from 30,000 to 75,000 daltons, advantageously between 50,000 and 60,000.

The polymer can be of linear, branched or radial structure. Preferably, the copolymer of styrene and conjugated diene, in particular the copolymer of styrene and butadiene, used in the clear binder composition according to the invention, has a radial structure.

In a preferred embodiment, the total quantity of the polymer used in the process for preparing the clear binder of the invention is between 0.5 and 20% by mass, preferably between 1 and 10%, preferably between 1.5 and 7.5%, for example between 2.5% and 5%, even more preferably between 3.5% and 4.5% by mass relative to the total mass of the clear binder composition. Polypropylene-based plastic waste particles present in the clear binder composition

The clear binder according to the invention further comprises particles of plastic waste comprising a polymeric part comprising polypropylene.

The use of plastic waste particles in this composition makes it possible to recycle part of the polypropylene-based waste. These particles of plastic waste are taken into account when calculating the eco-material index. The plastic waste particles present in the clear binder composition comprise a polymeric portion.

The polymeric part of the plastic waste particles integrated into the clear binder typically represents at least 80% by mass of the total mass of the plastic waste particles, preferably at least 90% by mass, more preferably at least 95% by mass, advantageously at least 99% by mass.

Preferably, the polymeric part of the plastic waste particles integrated in the clear binder represents from 80% to 100% by mass of the total mass of the plastic waste particles, more preferably from 85% to 99.9% by mass, even more preferably from 90% to 99% by mass.

According to a first embodiment, the polymeric part of the plastic waste integrated into the clear binder consists solely of polypropylene.

According to a second embodiment, the polymeric part of the plastic waste integrated into the clear binder comprises a mixture of polypropylene and polyethylene.

Preferably, the polymeric part of the plastic waste integrated into the clear binder comprises, preferably consists of:

- from 95% to 99.9% by mass of polyethylene, and

- from 0.1% to 5% polypropylene.

Advantageously, the polymeric part of the plastic waste integrated into the clear binder comprises, preferably consists of, a mixture of polypropylene, low density polyethylene and halogenated polyethylene, in particular chlorinated polyethylene.

More advantageously, the polymeric part of the plastic waste integrated into the clear binder comprises, preferably consists of:

- from 90% to 99.8% by mass of low density polyethylene,

- from 0.1% to 5% polypropylene,

- from 0.1% to 5% by mass of halogenated polyethylene, in particular chlorinated polyethylene. Preferably, the plastic waste particles integrated into the clear binder have a thickness less than or equal to 1 mm, more preferably less than or equal to 0.5 mm.

More preferably, the particles of plastic waste integrated into the clear binder have a thickness ranging from 0.1 mm to 0.5 mm.

Preferably, the particles of plastic waste integrated into the clear binder have a length less than or equal to 10 cm, more preferably ranging from 1 mm to 10 cm.

Preferably, the particles of plastic waste integrated into the clear binder have a surface area less than or equal to 20 cm ² , more preferably ranging from 5 cm ² to 20 cm ² . Particle surface area is typically determined by multiplying the average particle length by the average particle width.

The size of the particles, in particular their thickness, their length and their width, is determined by simple measurement using a graduated ruler, in particular according to the ISO 7976-1 standard (“Methods of measurement of buildings and building products - Part 1: Methods and instruments).

Advantageously, the particles of plastic waste integrated into the clear binder have a glass transition temperature, measured by differential calorimetric analysis, below -80°C, preferably between -120°C and -90°C.

Advantageously, the plastic waste particles integrated into the clear binder have a melting temperature, measured by differential calorimetric analysis, greater than 50°C, preferably between 70°C and 150°C.

Advantageously, the particles of plastic waste integrated into the clear binder have a starting crystallization temperature, measured by differential calorimetric analysis, less than 150°C, preferably less than or equal to 130°C.

Advantageously, the content of plastic waste particles in the clear binder composition according to the invention ranges from 0.1% to 5% by mass, relative to the total mass of the composition, preferably from 0.5% to 3 % by mass, more preferably from 0.7% to 1.5% by mass. It is typically 1% by mass, relative to the total mass of the clear binder composition.

Adhesiveness boosts

To improve the reciprocal affinity between the binder and the aggregates and ensure their durability, adhesive additives can also be used. These are, for example, nitrogen-containing surfactant compounds derived from fatty acids (amines, polyamines, alkyl-polymanne, etc.). When added to the clear binder, the tackiness dopes generally represent between 0.05% and 0.5% by weight relative to the total weight of the clear binder composition. For example, in a specific embodiment, between 0.05% and 0.5% of amine will be added, preferably between 0.1% and 0.3% of amine, by weight relative to the total weight of the clear binder composition.

Coloring agents

The clear binder may also include one or more coloring agents, such as mineral pigments or organic dyes. The pigments are selected according to the shade, the color desired for the coating. For example, metal oxides such as iron oxides, chromium oxides, cobalt oxides and titanium oxides will be used to obtain the colors red, yellow, gray, green, blue or white. The pigments can be added either in the clear binder or in the coating (mixed with the aggregates for example) or in an emulsion of the clear binder.

Optional additive(s)

According to one embodiment, the clear binder composition of the invention further comprises at least one Fischer-Tropsch wax.

The waxes (or paraffins) used are synthetic waxes from the Fischer-Tropsch synthesis process. These Fischer-Tropsch waxes are generally prepared by reacting carbon monoxide with hydrogen, typically at high pressures over a metal catalyst.

The preferred Fischer-Tropsch waxes are the Fischer-Tropsch waxes described in application WO991 1737. The Fischer-Tropsch waxes described in this document are Fischer-Tropsch waxes comprising a mixture of paraffins. Fischer-Tropsch waxes comprise a majority of n-paraffins, often more than 90%, the remainder being made up of iso-paraffins.

The average length of the paraffin chains of Fischer-Tropsch waxes is between 30 and 15 carbon atoms, preferably between 40 and 100, more preferably between 60 and 90.

Fischer-Tropsch waxes have a melting point (freezing point) between 65 and 105°C, preferably between 68 and 100°C.

The Fischer-Tropsch waxes used in the invention can be partially oxidized or fully oxidized.

A preferred example of Fischer-Tropsch wax is that sold under the brand name Sasobit®, which has a freezing point of 100°C (ASTM D 938), penetrability at 25°C less than 1 1/10 mm (ASTM D 1321) and a penetrability at 65°C of 7 1/10 mm (ASTM 1321). Another type of Fischer-Tropsch waxes which can be used are the Fischer-Tropsch waxes described in patent EP1951818. These Fischer-Tropsch waxes include a slightly larger quantity of isomerized paraffins than conventional Fischer-Tropsch waxes. These Fischer-Tropsch waxes comprising more iso-paraffins are characterized by a freezing point (ISO 2207) between 85 and 120°C and a PEN value at 43°C, expressed in 0.1 mm, determined according to IP 376, greater than 5.

Preferably, when present, the quantity of Fischer-Tropsch waxes is between 0.1% and 10% by mass, relative to the total mass of the clear binder composition, preferably between 0.5% and 5%, more preferably between 1% and 3%.

Clear binder preparation process

The present invention also relates to a process for preparing the clear binder composition which has been described above. This process includes the following steps:

(a) bringing the plasticizing agent and the structuring agent into contact, and heating to a temperature between 140-200°C, for example from 10 minutes to 1 hour,

(b) mixing with stirring the plasticizing agent and the structuring agent at a temperature between 140°C and 200°C, for example from 30 minutes to 2 hours,

(c) adding the polymer, for example SB and/or SBS, mixing and heating at a temperature between 140-200°C, for example, from 60 minutes to 3 hours, preferably from 60 minutes to 2 hours,

(d) adding the plastic waste particles, mixing and heating at a temperature ranging from 140°C to 200°C, for example from 10 minutes to 60 minutes, and

(e) possible addition of an adhesive boost and/or Fischer-Tropsch waxes, mixing and heating at a temperature between 140-200°C, for example, from 5 minutes to 30 minutes.

Preferably, the process comprises between steps (d) and (e) an additional step of mixing with stirring at high shear (6000 rpm), for example from 5 to 30 minutes.

The order of steps (a) to (e) can be changed.

Clear binder composition

Advantageously, a clear binder composition according to the invention comprises, by weight relative to the total weight of clear binder, or better consists essentially of:

- from 1% to 40% by weight of plasticizing agent, in particular the ester compound derived from tall oil, preferably from 5% to 30% by weight, more preferably between 10% and 20% by weight, - from 50% to 90% by weight of structuring agent, in particular resin of plant origin, preferably from 60% to 85% by weight, more preferably from 70% to 85% by weight,

- from 0.5% to 20% by weight of polymer, in particular copolymer of styrene and butadiene, preferably from 1% to 10%, even better from 1.5% to 7.5%, advantageously from 2.5 % to 5% by weight,

- from 0.1% to 5% by mass, of plastic waste comprising a polymeric part comprising polypropylene, optionally mixed with polyethylene, preferably from 0.5% to 3% by mass, more preferably 0.7% at 1.5% by mass, and

- optionally, from 0.05% to 0.5% by weight of dope, preferably between 0.1% and 0.3% by weight of dope, for example a dope chosen from amines,

- optionally, from 0.1% to 10% by weight of Fischer-Tropsch wax(es), preferably from 0.5% to 5% by mass, more preferably from 1% to 3% by mass.

Preferably, the clear binder according to the invention has a penetrability at 25°C, measured according to standard NF EN 1426, of between 10 and 220 1/10 mm, preferably between 20 and 160 1/10 mm, more preferably between 30 and 100 1/10 mm. Those skilled in the art can modulate the penetrability of the clear binder in particular by judiciously choosing the weight ratio [structuring agent/plasticizing agent] in the composition of the clear binder. Indeed, it is known that an increase in this ratio makes it possible to reduce the penetrability at 25°C.

Advantageously, the clear binder according to the invention has a ball and ring softening temperature (TBA), measured according to the NF EN 1427 method, ranging from 40 to 80°C, advantageously from 45 to 70°C.

The clear binder composition of the invention is advantageous in that it has a significantly higher biosourced carbon content compared to the clear binder compositions of petroleum origin of the prior art.

By “biosourced carbon” we mean, in the sense of the invention, carbon provided by materials derived from renewable organic matter (or biomass), of plant or animal origin, preferably plant. Biosourced carbon is thus distinguished from fossil carbon present in the earth's crust, particularly in the form of coal, oil or even natural gas.

According to a preferred embodiment, the clear binder composition according to the invention has a biosourced carbon content, measured according to the ASTM D6668 standard, greater than or equal to 75%, preferably greater than or equal to 80%, more preferably greater than or equal to 80%. equal to 85%, advantageously greater than or equal to 90%. The clear binder composition of the invention is also advantageous in that it has biodegradability, in particular aerobic biodegradability, improved compared to the clear binder compositions of petroleum origin of the prior art.

For the purposes of the invention, “biodegradability” means the ability of a material to deteriorate once placed in a particular environment, in particular under the effect of microorganisms such as bacteria, fungi or even algae. Biodegradability can be measured in an aerobic environment, that is to say in the presence of oxygen, or in an anaerobic environment, that is to say in the absence of oxygen.

According to a preferred embodiment, the clear binder composition according to the invention has an aerobic biodegradability, measured according to the ISO 17556 standard, at least 2 times higher than the biodegradability of a clear binder composition of petroleum origin of the prior art, preferably at least 3 times higher, more preferably at least 4 times higher, advantageously at least 5 times higher.

Applications of clear binder

The clear binder composition according to the invention can be used and applied indifferently via so-called “hot”, “warm” techniques or so-called “cold” techniques well known to those skilled in the art.

By hot techniques we mean techniques in which the clear binder composition is brought to relatively high temperatures during its application. Hot techniques lead to coatings, asphalts and so-called “hot” mixes such as bitumen gravels, high modulus mixes, bitumen sands, semi-grained bituminous concretes (BBSG), concretes. high modulus bituminous concrete (BBME), flexible bituminous concretes (BBS), thin bituminous concretes (BBM), pervious bituminous concretes (BBDr), very thin bituminous concretes (BBTM), ultra-thin bituminous concretes (BBUM) . The clear binder composition according to the invention is suitable for the preparation of coatings, asphalts and coatings of all types, and in particular those mentioned above.

The invention therefore also relates to coatings comprising a clear binder composition according to the invention, aggregates, possibly fillers and possibly pigments.

According to a preferred embodiment, the coating according to the invention further comprises particles of plastic waste comprising a polymeric part made of polystyrene.

Plastic waste particles comprising a polystyrene polymer part are distinguished from polypropylene-based plastic waste particles defined above in the context of the clear binder composition. In this specific embodiment, the coating according to the invention thus comprises particles of plastic waste of two different natures. The coating according to the invention firstly comprises particles of plastic waste based on polypropylene, called “polypropylene-based waste particles” introduced into the binder composition. The coating according to the invention further comprises particles of polystyrene-based plastic waste, hereinafter referred to as “polystyrene-based waste particles” introduced into the coating, mixed with the aggregates.

Polystyrene-based waste particles typically comprise a polymeric part and an organic part, for example fillers.

Preferably, the polymeric part of the polystyrene-based waste particles represents from 50% to 99.9% by mass of the total mass of the polystyrene-based waste particles, more preferably from 75% to 99.5% by mass. , even more preferably from 80% to 99.5% by mass, advantageously from 90% to 99.5% by mass.

The organic part of polystyrene-based waste particles typically consists of inorganic fillers.

Preferably, the polystyrene-based waste particles have an average size, determined by sieving according to standard NF P 18-560, ranging from 1 mm to 20 mm, more preferably from 1.5 mm to 10 mm, typically 2 mm. at 6mm.

More preferably, at least 90% by mass of plastic waste based on polystyrene has an average size, determined by sieving according to standard NF P 18-560, between 2 mm and 6 mm, preferably at least 95% by mass.

Advantageously, the particles of plastic waste based on polystyrene have a glass transition temperature, measured by differential calorimetric analysis, of between 80°C and 120°C, preferably between 90°C and 100°C.

Advantageously, the particles of plastic waste based on polystyrene have a melting temperature, measured by differential calorimetric analysis, between 350°C and 500°C, preferably between 380°C and 465°C.

Advantageously, the particles of plastic waste based on polystyrene have a degradation temperature, measured by differential calorimetric analysis, greater than 300°C, preferably greater than 380°C.

Fillers (or fines) are particles with dimensions less than 0.063 mm. The aggregates include particles of dimensions 0/2 (sand), 2/4 (gravel), 4/6 and 6/10.

Preferably, the aggregates are chosen from granules of dimensions 0/2, 4/6, 6/10 and their mixtures. The coating generally comprises from 1 to 10% by weight of clear binder, relative to the total weight of the coating, preferably from 4 to 8% by mass, the remainder consisting of the aggregates, possibly the waste particles. polystyrene-based plastics and/or fillers and/or pigments. Usually, the pigments represent a quantity by weight of 0 to 1% of the coating, the fillers represent a quantity by weight of 0 to 2% of the coating.

Advantageously, the content of particles of plastic waste based on polystyrene in the coating ranges from 0% to 10% by mass, relative to the total mass of the coating, preferably from 0.1% to 10% by mass , more preferably from 0.5% to 8% by mass, advantageously from 1% to 7.5%. It is typically 5% by mass, relative to the total mass of the coating.

According to a preferred embodiment, the coating according to the invention is a draining coating.

Advantageously, the coating comprises, relative to the total mass of the coating:

- from 1% to 10% by weight of binder, preferably 4% to 8% by weight, more preferably from 3 to 6% by weight;

- from 80% to 98% by mass of aggregates, preferably from 84% to 97% by mass;

- from 0 to 2% by mass of fillers, preferably from 0.5 to 1.5% by mass; And

- 0.1% to 10% by mass of plastic waste based on polystyrene, preferably from 2.5% to 7.5 by mass.

Another subject of the invention is cast asphalts comprising a clear binder composition according to the invention, mineral fillers and possibly pigments. The asphalt comprises from 1 to 20% by weight of clear binder, relative to the total weight of the asphalt, preferably from 5 to 10% by weight, the remainder consisting of the fillers and possibly the pigments (the pigments representing a mass quantity of 0 to 1% of the asphalt).

By cold techniques we mean techniques based on the use of clear binder emulsions in the aqueous phase, at lower temperatures. Cold techniques lead to surface coatings, grouts, cold poured mixes, cold mixes, cold bituminous concretes, emulsion gravels, storable cold mixes. The clear binder composition according to the invention is suitable for the preparation of the products mentioned above.

The invention therefore also relates to a clear binder emulsion comprising a clear binder composition according to the invention, water and an emulsifying agent. The clear binder comprises at least one plasticizing agent, at least one structuring agent and at least one polymer, as defined above.

The invention therefore also relates to a process for preparing a clear binder emulsion comprising:

(i) the preparation of a clear binder composition by mixing at least one plasticizing agent, at least one structuring agent and at least one polymer, as defined above,

(ii) the preparation of an emulsifying solution by mixing water and the emulsifying agent,

(iii) dispersing the clear binder from step (i) in the emulsifying solution from step (ii).

The clear binder emulsion according to the invention preferably comprises from 50% to 80% by weight of the clear binder composition, preferably from 60% to 70%, relative to the total weight of the clear binder emulsion.

The invention further relates to the use of a clear binder composition, an emulsion or a coating according to the invention, to limit and/or prevent and/or reduce an increase in urban ambient heat.

By “increase in urban heat” is meant within the meaning of the invention the difference between the ambient temperatures recorded in an urban environment, in relation to neighboring rural or forest areas or in relation to regional average temperatures.

The invention further relates to the use of a clear binder composition, an emulsion or a coating according to the invention, to limit and/or prevent and/or reduce the surface temperature of materials of construction used in urban areas.

Finally, the subject of the invention is the use of a clear binder composition or a clear binder emulsion according to the invention to improve the eco-performance of a coating. Eco-performance can be chosen from:

- increasing the durability of the coating, and/or

- reducing the environmental impact of the coating.

The different embodiments, variants, preferences and advantages described above for the plasticizing agent, the structuring agent and the other components of the clear binder composition apply to the use according to the invention.

Surprisingly, in fact, it has been observed that the combination of an oil of vegetable origin comprising an ester compound derived from tall oil and a particular rosin resin in a clear binder composition allows, by comparison with other oils and resins of plant origin, to obtain improved properties of resistance to aging of cold properties. This improvement was observed by means of a standardized test called BBR for determining the modulus of rigidity in bending (NF EN14771: 2012), this test being carried out before and after an aging protocol applied to the sample. This better resistance to aging of cold properties makes it possible to formulate surface coatings, particularly in the field of roads, which degrade less under the effect of time and/or climatic conditions. This improves the durability of the coating and reduces the frequency of coating replacements.

The invention is illustrated by the following examples given without limitation.

Examples

In the examples below, parts and percentages are by weight unless otherwise noted.

Materials and methods:

Plasticizer: the oil available under the trade name SYLVAROAD® RP1000 from the company KRATON was used. It is an oil of vegetable origin obtained from tall oil.

Resin: the resin available under the trade name SYLVALITE® 2100 Rosin ester from the company KRATON was used. It is a plant-based resin comprising a blend of tall oil rosin pentaerythritol esters.

Copolymer of styrene and butadiene: a mixture of SB and SBS block copolymers, thermoplastics, having a content of constituent units derived from 70/30 Butadiene/Styrene monomers, of radial structure, obtained by solution polymerization, of mass was used. molecular weight of approximately 330,000 daltons polystyrene equivalent (PS), available commercially under the name Calprene 41 1 from the company Dynasol.

Plastic waste particles integrated into the binder (A particles): plastic waste particles comprising at least 80% by mass of low density polyethylene, at least 0.5% by mass of chlorinated polyethylene and at least 0.5% by mass polypropylene . The particles have a thickness of less than 0.5 mm, a length of less than 10 cm and a surface area of less than 20 cm ² . The glass transition temperature of the particles is between -120°C and -90°C. The melting temperature of the particles is between 70°C and 150°C. The crystallization temperature is below 130°C.

Particles of plastic waste integrated into the coating (mixed with the aggregates, particles B): particles of plastic waste comprising at least 90% by mass of polystyrene and between 0.5% and 10% by mass of inorganic fillers. THE particles have an average size ranging from 2 mm to 6 mm. The glass transition temperature of the particles is between 90°C and 100°C. The melting temperature of the particles is between 380°C and 465°C. The degradation temperature is above 380°C.

Aggregates for asphalt: mixtures comprising 13% by mass of sand (dimensions 0/2), 86% by mass of gravel (dimensions 6/10) and 1% by mass of fillers.

1) Preparation of a clear binder composition according to the invention (C1)

The clear binder is prepared according to the following process:

The oil and the resin are brought into contact and the whole is heated to a temperature of 175°C;

- The oil and the resin heated for 2 hours are mixed with a stirring speed of 200 rpm, while maintaining the mixture at a temperature of 175°C;

- The copolymer based on styrene and butadiene, in powder form, is added and mixed for 1 hour at 180°C with a stirring speed of 250 rpm.

- We add the plastic waste particles gradually, then we apply a mixture at high shear (6000 rpm) for 15 minutes

- The stirring is reduced to 250 rpm and the mixing is continued at 180°C for 4 hours.

Methods for determining the properties of clear binder compositions

Table 1

Clear binder compositions

The clear binder composition according to the invention C1 is prepared according to the protocol described in the previous paragraph with the constituents and proportions (in percentage by weight relative to the total weight of clear binder) reported in Table 2. Table 2

The composition is formulated at a grade of 50/70.

Results

It can be seen that the composition according to the invention C1 has good mechanical properties, suitable for use as a clear binder both for road applications and for industrial applications.

2) Preparation of a coating comprising a clear binder composition according to the invention (C2)

The C2 coating is prepared according to the following protocol:

The aggregates are previously heated to a mixing temperature equal to 170°C;

Separately, the clear binder composition is heated to a mixing temperature equal to 170°C;

The hot aggregates are then introduced into a mixer, set at 170°C, and mixed for a few minutes:

The following two steps are then carried out, the order of the steps may change:

A) The clear binder is added hot to the mixer and mixed with the aggregates for 90 seconds;

B) The polystyrene waste particles, not previously heated, are added and the final mixture is left stirring for 30 seconds at 170°C. Methods for determining asphalt properties

Table 3

Coated

The C2 coating is prepared according to the protocol described in the previous paragraph with the constituents and proportions (in percentage by weight relative to the total weight of coating) reported in table 4.

Table 4

Results

It can be seen that the C2 coating according to the invention has crushing resistance values suitable for use as an urban covering (low traffic). These values are higher (more than 2 times higher) than the conventional values for coatings based on clear binders known to those skilled in the art.

The i/C ratio values close to 70% are satisfactory for a level 0 coating, that is to say suitable for low-traffic roads. The C2 coating is also advantageous in that it has a low density.

Finally, the void content of the material (equal to 23.5%) testifies to the draining nature of the coating.

2) Evaluation of the thermal properties of the C2 coating

The thermal properties of the C2 mix prepared below were evaluated and compared to those of a conventional bituminous mix (bitumen-based) according to the following protocol:

The C2 coating according to the invention was applied to an exterior plot of 30 m ² (plot A according to the invention).

A reference bituminous coating (called “black coating”), prepared from the same aggregates as those used for the C2 coating but from a bitumen type binder, was then applied to a plot B. Parcel B was located right next to plot A and had the same dimensions as plot A (same width, same length and same thickness).

Different thermal sensors were placed on the different plots in order to measure:

- the air temperature overlooking the two plots at a height of 40 cm and 120 cm relative to the surface of the coating,

- the surface temperature of the coating, measured at ground level,

- the temperature at a depth of 5 cm (inside the coating), and

- the temperature at a depth of 20 cm (basement temperature).

The measurements were carried out over a period of 34 days, during the summer period. During this period, the maximum temperature was below 25°C for 3 days only. Cumulative precipitation was 92.8 mm of water.

The following results were thus obtained:

Despite small variations, the air temperature measured above the two plots is similar. The surface temperature of the C2 coating according to the invention is generally lower than that of the black coating. In particular, a surface temperature up to 4°C lower was measured during the day for the C2 coating, compared to that of the black coating. It is also noted that the C2 coating according to the invention has a lower inertia than the black coating: at night, when the exposure and the temperature decrease, the temperature of the C2 coating according to the invention decreases faster than that of the black coating. The C2 coating according to the invention therefore stores less heat, which allows it to drop lower in temperature during the night and to cool more quickly during a storm.

At a depth of 5 cm, while the plots are in full sun, the temperature of the C2 coating according to the invention is up to 8°C lower than that of the black coating.

At a depth of 20 cm, the temperature of the C2 coating according to the invention is up to

5.6°C lower than that of the black coating.

Claims

1. Clear binder composition comprising:

(v) possibly an adhesive boost.

2. Composition according to claim 1, in which the ester compound is chosen from derivatives of a tall oil fatty acid.

3. Composition according to claim 2, in which the ester compound is chosen from the group consisting of: trimethylolpropane tallates, ethylene glycol monomerates, neopentyl glycol monomerates, 2-ethylhexyl monomerates, glycerol monomerates , and any of their mixtures.

4. Composition according to any one of claims 1 to 3, in which the content of plasticizing agent ranges from 1% to 40% by mass, relative to the total mass of the composition, preferably from 5% to 30% by weight. mass, more preferably from 10% to 20% by mass.

5. Composition according to any one of the preceding claims, in which the resin of plant origin is chosen from esters of natural rosins, more preferably from pentaerythritol esters of natural rosins, in particular from pentaerythritol esters of natural rosins. tall oil.

6. Composition according to any one of the preceding claims, in which the content of structuring agent ranges from 50% to 95% by mass, relative to the total mass of the composition, preferably from 60% to 90% by mass, more preferably from 75% to 85% by mass.

7. Composition according to any one of the preceding claims, in which the polymer is a copolymer of styrene and butadiene, preferably is chosen from a styrene/butadiene/styrene block copolymer of radial structure, a butadiene/styrene block copolymer of structure radial and their mixtures.

8. Composition according to any one of the preceding claims in which the particles of plastic waste present:

- a surface area less than 20 cm ² , preferably ranging from 5 to 20 cm ² .

9. Composition according to any one of the preceding claims, in which the content of plastic waste particles ranges from 0.1% to 5% by mass, relative to the total mass of the composition, preferably 0.5%. at 3% by mass, more preferably from 0.7% to 1.5% by mass.

10. Composition according to any one of the preceding claims, having a biosourced carbon content, measured according to the ASTM D6668 standard, of at least 75%, preferably at least 80%, more preferably at least 85%. , advantageously at least 90%.

11. Composition according to any one of the preceding claims, characterized in that it has an eco-material content of at least 70%, preferably at least 80%, preferably at least 90%, and more preferably at least 95%.

12. Composition according to any one of the preceding claims, having an aerobic biodegradability, measured according to the ISO 17556 standard, at least 2 times higher than the aerobic biodegradability of a clear binder composition prepared from a plasticizing agent of petroleum origin and a structuring agent of petroleum origin, preferably at least 3 times higher, more preferably at least 4 times higher, advantageously at least 5 times higher

13. Process for preparing a clear binder composition according to any one of the preceding claims, comprising the steps: a) bringing the plasticizing agent and the structuring agent into contact, and heating to a temperature between 140 °C and 200°C, b) mixing with stirring the plasticizing agent and the structuring agent at a temperature between 140°C and 200°C, c) adding the polymer, mixing and heating at a temperature ranging from 140°C to 200°C, d) adding the plastic waste particles, mixing and heating at a temperature ranging from 140°C at 200°C, e) adding any adhesive dope, mixing and heating to a temperature ranging from 140°C to 200°C.

14. Emulsion comprising a clear binder composition according to any one of claims 1 to 12, water, and an emulsifying agent.

15. Coating comprising (i) a clear binder composition according to any one of claims 1 to 12 or an emulsion according to claim 14, (ii) aggregates and/or mineral fillers, and optionally (iii) one or more pigments.

16. Coating according to claim 15, further comprising particles of plastic waste comprising a polymeric part made of polystyrene.

17. Coating according to claim 15 or according to claim 16, which is a draining coating.

18. Use of a clear binder composition according to any one of claims 1 to 12, of an emulsion according to claim 14 or of a coating according to one of claims 15, 16 and 17, to limit and/ or prevent and/or reduce an increase in urban ambient heat and/or to limit and/or prevent and/or reduce the surface temperature of construction materials used in an urban environment.

19. Use of a clear binder composition according to any one of claims 1 to 12 or of an emulsion according to claim 14, to improve the eco-performance of a coating.

20. Use according to claim 19, in which the eco-performance is chosen from:

- increasing the durability of the coating, and/or

- reducing the environmental impact of the coating.