The present invention relates to the field of associative nitrogen molecules comprising at least one unit making them capable of associating with one another or with a load by noncovalent bonds, and comprising a function capable of reacting with a polymer containing unsaturation to form a covalent bond with said polymer.

More specifically, the present invention relates to carrier molecules of a nitrile oxide function and a function imidazolidinone. The application also relates to a method for synthesizing such molecules.

In the industrial field, with loads polymer blends are often used. For such mixtures have good properties, continuously is searching for ways to improve filler dispersion within the polymers. One way to achieve this is the use of coupling agents able to establish interaction between the polymer and filler.

Coupling agents of a polymer with a feed comprising nitrogen dipoles are described in papers published under the US7186845B2 and JP2008208163 numbers.

These documents describe the modification of polymers comprising diene units by nitrogen dipolar compounds further comprising a heterocycle, said heterocycle itself comprising a nitrogen atom and an atom of oxygen and / or sulfur.

More particularly, the disclosed compounds are carriers of nitrones function oxazoline, thiazoline such as the ((2-oxazolyl) -phenyl-N-methylnitrone):

When diene polymers are reacted with such compounds, polymers resulting carry the oxazoline or thiazoline cycles.

These rings present on the polymer may react in turn with fillers of surface features, such as carbon black or silica, with which the polymers are blended. This reaction led to the establishment of covalent bonds between the polymer modified with the coupling agent and the load due to the opening of the oxazoline or thiazoline ring. Indeed, as is disclosed in US7186845B2, oxazolines cycles and / or thioazolines are likely to open in the presence of a nucleophile which may for example be present on the surface of the load.

The establishment of such covalent bonds nevertheless has disadvantages when preparing mixtures comprising these polymers modified with coupling agents with loads. In particular, the existence of these early established covalent bonds, between the polymer and fillers, makes these mixtures highly viscous in the uncured state, making it difficult all operations prior to crosslinking (vulcanization) based formulations rubber, including the preparation of mixtures of components, and their formatting. These disadvantages have a strong impact on industrial productivity.

It is therefore desirable to provide new compounds not having the above drawbacks, that is to say molecules which are capable upon reaction with a polymer and mixing with a filler, not form covalent bonds with the load and therefore does not cause excessive increase in the viscosity of the mixture.

Thus, patent application WO 2012/007684 relates to a compound comprising at least one group Q and at least one A moiety linked together by at least one and preferably a spacer group Sp wherein:

- Q comprises a dipole containing at least one and preferably a nitrogen atom;

- A comprises an associative group comprising at least one nitrogen atom;

- Sp is an atom or an atomic group forming a bond between Q and A.

When a polymer grafted with a compound as defined above is mixed with fillers, it establishes that labile bonds with the loads, thereby to ensure good interaction polymer - filler, beneficial for final properties of the polymer, but without the disadvantages that too much interaction polymer - load could cause.

An example of such a compound is the oxide of 2- [2- (2-oxoimidazolidin-1-yl) ethoxy] benzonitrile:

Furthermore, in WO 2016/207263, various compounds are exemplified, including the 2,4,6-trimethyl-3- [2- (2-oxoimida1zolidin-1-yl) ethoxy] benzonitrile:

It turns out that the rubber compositions used in particular for the manufacture of tires, including this molecule have interesting properties in terms of rigidity, tensile strength or hysteresis. Nevertheless, there remains a continuing need for rubber compositions having improved properties.

In this context, we have discovered that a particular compound polyaromatic, once integrated into the rubber compositions used in particular for the manufacture of tires, leading to obtaining excellent stiffness properties, tensile strength and hysteresis.

The invention therefore relates to a compound of formula (I):

in which :

- PAr denotes a polyaromatic group containing at least two aromatic condensed rings, each said fused aromatic rings being optionally substituted by one or more carbon chains, which are identical or different, independent of each other, aliphatic or aromatic, linear, branched or cyclic, optionally substituted or interrupted by one or more heteroatoms;

- Sp represents an atom or group of atoms.

Another object of the invention is a method of synthesizing the compound of formula (I) according to the invention.

Refers in the sense of the present invention, "hydrocarbon chain" means a chain comprising one or more carbon atoms.

In the present description, unless expressly indicated otherwise, all percentages (%) indicated are mass%. Furthermore, any range of values ​​denoted by the expression "between a and b" represents the range of values ​​of from greater than a to less than b (that is to say terminals a and b excluded), whereas any range ofvalues ​​denoted by the expression "from a to b" means the range of values ​​from a to b (that is to say including the strict limits a and b).

The invention and its advantages will be readily understood in the light of the description and examples that follow achievements.

The compounds mentioned in the description can be fossil or bio-based. In the latter case, they may be partially or completely, from biomass or obtained from renewable raw materials derived from biomass.

According to the formula (I), the compound according to the invention comprises a group PAr designating a polyaromatic group containing at least two aromatic rings fused.

Refers in the sense of the present invention, "aromatic hydrocarbon ring" an aromatic ring whose backbone consists of carbon atoms. In other words, there is no hetero atom in the backbone of the cycle.

Refers in the sense of the present invention, "at least two aromatic hydrocarbon rings fused to" two or more aromatic rings having in common at least two successive carbon atoms.

Said at least two aromatic condensed rings may be ortho-fused or ortho- and peri-condensed.

Advantageously, the polyaromatic group comprising at least two aromatic rings condensed is selected from a group consisting of two fused aromatic rings in a rectilinear arrangement and a group of three fused aromatic rings in a rectilinear arrangement, preferably a group consisting of two rings aromatic condensed in a rectilinear arrangement. These structures are similar to naphthalene compounds and anthracene.

According to the formula (I), the polyaromatic group comprising at least two aromatic rings

condensed is at least substituted by nitrile oxide group and the group Sp. In other words, the first cycle of said at least two aromatic rings is at least substituted by nitrile oxide function, said first ring or the second ring of said at least two aromatic rings being substituted by at least Sp group, said group Sp for connecting the imidazolidinone according to at least one of said at least two aromatic rings.

Advantageously, each of the fused aromatic hydrocarbon rings is optionally substituted with one or more carbon chains, which are identical or different, aliphatic or aromatic, linear, branched or cyclic, optionally substituted or interrupted by one or more heteroatoms, and inert vis-à-vis one or other of the functions that are the imidazolidinone nitrile function and oxide function.

Refers in the sense of the present invention, "inert carbon chain vis-à-vis one or other of the functions that are the imidazolidinone function and nitrile oxide group" means a carbon chain which does not react with the either of these functions. Whereby said carbon chain inert vis-à-vis the one or the other of these functions is for example a carbon chain which does not exhibit functions alkenyl or alkynyl group capable of reacting with the nitrile oxide function.

Preferably, said carbon chains are saturated.

Preferably, each of the fused aromatic hydrocarbon rings is optionally substituted with one or more carbon chains, which are identical or different, saturated, more preferably one or more alkyl groups, which are identical or different, preferably one or more alkyl groups, the same or different C 1 -C 12 , more preferably C 1 -C 6 , more preferably C 1 -C 4 , or a group chosen from -OR ', -NHR', -SR ', R' being an alkyl group, preferably a alkyl C 1 -C 12 , more preferably C 1 -C 6, More preferably C 1 -C 4 .

Still more preferably, each of the condensed aromatic rings is optionally substituted with one or more groups, identical or different methyl, ethyl or one or more groups OCH 3 .

The group Sp is preferably a hydrocarbon chain C 1 -C 24 linear, branched, or cyclic, may contain one or more aromatic radicals, and / or one or more heteroatoms. Said chain may optionally be substituted, provided the substituents do not react with either of the functions that are the imidazolidinone nitrile function and oxide function.

Refers in the sense of the present invention, "hydrocarbon chain" means a chain comprising one or more carbon atoms and one or more hydrogen atoms.

meaning means of the present invention, "hydrocarbon chain can contain one or more heteroatoms" in that the chain may be substituted or interrupted by one or more heteroatoms. When the chain is interrupted by a heteroatom, it may be at the chain end or mid-chain.

Advantageously, the Sp group is a linear or branched alkylene chain in C 1 -C 24 , preferably C 1 -C 10 , more preferably C 1 -C 6 , optionally interrupted by one or more atoms of nitrogen, sulfur or oxygen.

Preferably, the Sp group contains a pattern selected from - 1

and y and 3 representing, independently of each other, an integer ranging from 1 to 6, and x 1 and x 2 representing, independently of one another, an integer from 1 to 4.

Preferably, the compound of formula (I) according to the invention is of formula (II):

in which :

- a group selected from R 1 to R 7 denotes the group of formula (III):

wherein Sp is as defined above,

the other six groups, identical or different, representing independently of each other, a hydrogen atom or a carbon chain, aliphatic or aromatic, linear, branched or cyclic, optionally substituted or interrupted by one or more heteroatoms.

Advantageously, said carbon chain is inert vis-à-vis one or other of the functions that are the imidazolidinone nitrile function and oxide function.

Preferably, said carbon chain is saturated.

Said carbon chain may be an alkyl group of C 1 -C 12 , more preferably C 1 -C 6 , more preferably C 1 -C 4 , or a group chosen from -OR ', -NHR', -SR ' , R 'being an alkyl group, preferably alkyl C 1 -C 12 , more preferably C 1 -C 6 , more preferably C 1 -C 4 .

Preferably, R 1 or R 7 denotes the group of formula

(III).

According to a particular embodiment, Ri is the group of formula (III) and R 2 to R 7 represent a hydrogen atom.

According to another particular embodiment, R 7 denotes the group of formula (III) and R 1 to R 6 represent a hydrogen atom.

Preferably, the Sp group refers to -O-CH 2 -CH 2 -.

According to a particular embodiment, the compound of formula (I) according to the invention is selected from a compound of formula (IV):

and a compound of formula (V):

preferably the compound of formula (IV).

The invention also relates to a method of synthesizing the compound of formula (I) according to the invention, comprising the following successive steps:

(B1) reacting a compound of formula (VI):

wherein PAr is as previously defined and Y represents a nucleophilic group,

with a compound of formula (VII):

wherein Sp is as defined above and Z is a nucleofugic group;

in the presence of at least one polar solvent S 1 , of at least one base, at a temperature T 1 ranging from 70 to 150 ° C,

to form a compound of formula (VIII):

(b2) reacting said compound of formula (VIII) with an aqueous solution of hydroxylamine to a temperature T 2 of from 30 to 70 ° C to obtain an oxime compound of formula (IX):

(C) a step of recovering said oxime compound of formula

(IX) ;

(D) a step of oxidizing oxime compound of formula (IX) with an oxidizing agent in the presence of at least one organic solvent

S2.

Refers in the sense of the present invention, "polar solvent" means a solvent having a dielectric constant greater than 2.2.

Refers in the sense of the present invention "by leaving group" a leaving group which carries its binding pair.

Refers in the sense of the present invention "nucleophilic group" means a compound comprising at least one lone pair of a carrier atom or a negatively charged atom.

As explained above, the method for synthesizing the compound of formula (I) according to the invention includes the sequential steps (b1) and (b2).

According to a particular embodiment, the two steps (b1) and (b2) are separated by a step of isolation and purification of the compound of formula (VIII).

According to another embodiment, the two steps (b1) and (b2) are performed in a one-pot synthesis, that is to say that the steps (b1) and (b2) are "one pot" (synthetic method pot two step) or without isolating the compound of formula (VIII) intermediate.

The method according to the invention comprises a step (b1) reacting a compound of formula (VI), as mentioned above, bearing a group Y, with a compound of formula (VII), as mentioned above, bearing a group Z.

Preferably, the group Y is selected from hydroxyl, thiol and primary or secondary amine.

The Z group may be selected from chlorine, bromine, iodine, mesylate group, tosylate group, acetate group and trifluoromethylsulfonate group.

Said step (b1) of the method according to the invention is carried out in the presence of at least one polar solvent S 1 , and at least one base, at a temperature T 1 ranging from 70 to 150 ° C.

According to a particular embodiment of the invention, the polar solvent S 1 is a water-miscible polar solvent in water, préférentiellementun solvantprotique.

Dimethylformamide (DMF), dimethylsulfoxide (DMSO), 1,3-dimethyl-2-imidazolidinone (DMI), 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone ( DMPU), isopropanol, acetonitrile, ethanol, n-butanol and n-propanol are examples of solvents S 1 used in the process according to the invention.

Preferably the solvantprotique is an alcoholic.

Advantageously, the compound of formula (VI) is from 5 to 40% by weight, preferably 10 to 30% by weight, based on the solvent weight.

The base can be selected from alkali alcoholates, alkali carbonates, alkaline earth carbonates, alkali hydroxides, alkaline earth hydroxides and mixtures thereof.

Advantageously, estpossible added:

- one or more catalysts selected from a catalyst of silver (I) salt, a quaternary ammonium phase-transfer catalyst, and mixtures thereof;

- a ouplusieurs ionic liquids.

Preferably, the base is selected from sodium methoxide, potassium carbonate and sodium hydroxide, more preferably potassium carbonate.

According to a particular embodiment of the invention, the molar amount of base is from 1.5 to 8 molar equivalents, preferably 2 to 6 molar equivalents, relative to the molar amount of compound of formula (VI).

As explained above, the step (b1) of the method according to the invention is carried out at a temperature T ranging from 70 to 150 ° C.

Preferably, the temperature T1 is a temperature of from 70 to 120 ° C, more preferably from 80 to 110 ° C.

As explained above, the step (b1) of the method according to the invention is followed by the step (b2) adding to the reaction medium containing the compound of formula (VIII) to an aqueous solution of hydroxylamine a temperature T 2 of from 30 to 70 ° C.

Preferably, the addition of the aqueous hydroxylamine solution is carried out when the conversion of the compound of formula (VI) is at least 70% by weight.

Advantageously, the temperature T 2 ranges from 40 to 60 ° C.

The method according to the invention also comprises a step (c) recovery, as mentioned above, the oxime compound of formula (IX).

Preferably, the oxime compound of formula (IX) is recovered by precipitation with water, optionally followed by washing with water.

The method according to the invention also comprises a step (d) oxidation of the oxime compound of formula (IX) with an oxidizing agent in the presence of at least one organic solvent S 2 .

Preferably, said oxidizing agent is selected from sodium hypochlorite, N-bromosuccinimide in the presence of a base, N-chlorosuccinimide in the presence of a base and hydrogen peroxide in the presence of a catalyst, preferably sodium hypochlorite.

Advantageously, the amount of oxidizing agent is from 1 to 5 molar equivalents, preferably 1 to 2 molar equivalents, relative to the molar amount of oxime compound of formula (IX).

Preferably, the organic solvent S 2 is an organic solvent selected from chlorinated solvents and ester, ether and alcohol, more preferably selected from dichloromethane, ethyl acetate, butyl acetate, diethyl ether, isopropanol and ethanol, more preferably selected from ethyl acetate and butyl acetate.

Preferably, the oxime compound of formula (IX) is from 1 to 30% by weight, preferably 1 to 20% by weight, based on the total weight of the assembly comprising said oxime compound of formula (IX), said organic solvent S 2 and said oxidizing agent.

Preferably, the method according to the invention comprises, after step (d), a step (e) recovering the compound of formula (I) ·

According to a particular embodiment of the invention, the method of the invention comprises a step (a2) for producing the compound of formula (VII) prior to step (b1) by reacting a compound of formula (X):

wherein Sp is as defined above,

with an agent for forming the leaving group Z. Preferably, said agent is thionyl chloride. Preferably, step (a2) is carried out in the absence or in the presence of at least one solvent S 4 , preferably a chlorinated solvent, more preferably dichloromethane.

Advantageously, step (a2) is immediately followed by a step (a3) ​​recovering the compound of formula (VII), preferably by purification with toluene, more preferably by crystallization of compound of formula (VII) in toluene.

As explained above, the compound of formula (I) can be incorporated into rubber compositions used in particular for the manufacture of tires. These rubber compositions can be based on at least one diene elastomer, a reinforcing filler and a chemical crosslinking agent.

In the following text, the term "base composition" a composition comprising the mixture and / or reaction product of the various constituents used, some of these base constituents being liable to, or intended to react together, at least in part, during the various stages of manufacture of the composition, in particular during its crosslinking or vulcanization.

Elastomer (or rubber indiscriminately) a diene elastomer, whether natural or synthetic, should be understood in known manner, an elastomer consisting at least in part (ie, a homopolymer or a copolymer) from diene monomer units (monomers bearing two double of carbon-carbon bonds, whether conjugated or not).

The compound of formula (I) can be used to graft one or more diene elastomer (s) present in the rubber composition. The diene elastomer may be grafted with the compound of formula (I) prior to its introduction into the rubber composition, or may be grafted by reaction with the compound of formula (I) in the manufacture of the composition.

The rubber composition can be included in the tire can therefore contain a single diene elastomer grafted with the compound of formula (I) (or graft prior to its introduction into the composition, either grafted by reaction with the compound of formula (I) for the manufacture of the composition), or a mixture of several diene elastomers grafted all or some of which are grafted and some do not.

The grafted diene elastomers may be used in combination with any type of synthetic elastomer other than a diene elastomer, or even with polymers other than elastomers.

The rubber composition may also include a reinforcing filler.

The reinforcing filler may be of any type as said reinforcing filler, known for its ability to reinforce a rubber composition usable for manufacturing tires, for example an organic filler such as carbon black, a reinforcing inorganic filler such as the silica with which is associated in a known manner a coupling agent, or a mixture of these two types of load.

Such reinforcing filler typically consists of nanoparticles having an average size (by mass) is less than one micrometer, typically less than 500 nm, usually between 20 and 200 nm, in particular, and more preferably between 20 and 150 nm.

Another rubber composition component, as mentioned previously, is the chemical crosslinking agent.

The crosslinking agent allows the formation of covalent bonds between the elastomer chains, which gives them elastic properties. The crosslinking agent can be based either on sulfur or sulfur donors and / or peroxide and / or bismaleimide compounds, preferably sulfur based.

The rubber composition as mentioned above may also comprise all or some of the conventional additives usually used in elastomer compositions for the manufacture of tires, especially treads, such as plasticizers, pigments, protective agents such as antioxidants, non-reinforcing fillers.

The present invention is further illustrated by the following nonlimiting examples.

EXAMPLES

molecules

Structural analysis and the determination of the molar purities syntheses molecules are carried out by NMR analysis. The spectra are acquired on a spectrometer Avance 3400 MHzBruker equipped with a probe "broadband" BBFO-zgrad 5 mm.

The NMR experiment 1 quantitative H, uses a simple pulse sequence 30 ° and a repeating time of 3 seconds between each 64 acquisitions. The samples are dissolved in a deuterated solvent, deuterated dimethyl sulfoxide (DMSO) unless otherwise stated. Deuterated solvent is also used for the lock signal. For example, the calibration is performed on the proton signal of the deuterated DMSO at 2.44 ppm relative to TMS at 0ppm reference.

The NMR spectrum 1 H coupled HSQC experiments 2D 1 H / 13 C HMBC and 1 H / 13 C allow structural determination molecules (see tables assignments). The molar quantifications are formed from the 1D NMR spectrum 1 quantitative H.

Analysis by mass spectrometry is performed by direct injection mode electrospray ionization (ID / ESI). Analyzes were performed on a Bruker HCT (flow 600 .mu.l / min Nebulizer gas pressure 10 psi, flow rate of the nebulizer gas 4

L / min).

grafted molecule on SBR or IR

Determining the molar ratio of the oxide of 2- [2- (2-oxoimidazolidin-1-yl) ethoxy] -1-naphthonitrile grafted onto SBR (styrene-butadiene rubber), IR (isoprene rubber) is performed by an analysis NMR. The spectra were acquired on a Bruker 500 MHz spectrometer equipped with a "cryoprobe BBFO-zgrad-5 mm." The NMR experiment 1 quantitative Η, uses a simple pulse sequence 30 ° and a repeating time of 5 seconds between each acquisition. Samples are dissolved in deuterated chloroform (CDCI 3 ) to obtain a signal of "lock". 2D NMR experiments have verified the nature of the graft pattern through the chemical shifts of the carbon atoms and protons.

Testing traction

These tensile tests to determine the elasticity stresses and the properties at break. Unless indicated otherwise, theyare performed in accordance with French standard NF T 46-002 of September 1988.

Stress at break (in MPa) and elongations at break (in base 100) are measured at 23 ° C ± 2 ° C and at 100 ° C ± 2 ° C, according to standard NF T 46-002.

dynamic properties

The dynamic properties .DELTA.G * and tan (δ) max are measured on a viscosity analyzer (Metravib VA4000), according to ASTM D 5992-96. The response of a sample of vulcanized composition (cylindrical test piece of 4 mm thick and 400 mm 2section), subjected to a sinusoidal stress in simple alternating shear frequency of 10 Hz, under normal temperature (23 ° C) according to ASTM D 1349-99, or depending on the case at a different temperature (100 ° C). Is swept strain amplitude of 0, 1% to 100% (outward cycle), then to 100%) at 0, 1%) (return cycle). The results exploited are the complex dynamic shear modulus (G *) and the loss factor tan (δ). For the return cycle, the maximum value of tan (δ) observed, denoted tan (δ) max.

I. Synthesis of 2-oxide [2- (2-oxoimidazolidin-1-yl) ethoxy] -1-naphthonitrile

The oxide of 2- [2- (2-oxoimidazolidin-1-yl) -ethoxy] -1-naphthonitrile was synthesized in six steps, called step a1, step a2, step b1, step b2, step c and step d.

The step a1 is performed according to Protocol 1, step a2 according to protocol 2, Step b1 according to the protocol 3. The steps b2 and c are carried out according to the protocol 4. The step is performed according to the protocol

5.

Step Al: Preparation of 2-hydroxy-1-naphthaldehyde

Protocol 1:

This compound can be obtained from naphthol by a formylation reaction according to the protocol of said Reimer-Tiemann described in Organic Syntheses, 22, 63-4; 1942 by Russell and Alfred Lockhart, Luther B. or Organic Reactions (Hoboken, NJ, USA), 28, 1982 Wynberg, Hans and Meijer, W. Egbert, or as described by Casiraghi Giovanni et al. in Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), (9), 1862-5, 1980 or by a Vilsmeier reaction described by Jones and Gurnos Stanforth, Stephen P. in Organic Reactions (Hoboken, NJ, USA), 49, 1997.

The 2-hydroxy-1-napthaldéhyde is commercial. It can for example be obtained from Aldrich (CAS 708-06-5).

Step a2: Preparation of 1- (2-chloroethyl) imidazolidin-2-one

Protocol 2:

This compound can be obtained according to a protocol described in the patent application WO 2012/007684.

Step b1: Preparation of 2- (2- (2-oxoimidazolidin-1-yl) ethoxy) -1-naphthaldehyde

Protocol 3:

A mixture of 2-hydroxy-1-naphthaldehyde (20.0 g, 0.116 mol), potassium carbonate (24.08 g, 0.174 mol), and 1- (2-chloroethyl) imidazolidin-2-one (25 , 9 g, 0.174 mol) in DMF (20 mL) was heated at 75 ° C (T bath ) for 3.0-3.5 hours. Then a second portion of 1- (2-chloroethyl) imidazolidin-2-one (17.26 g, 0.116 mol) was added and the reaction mixture is stirred for 9-10 hours at 75 ° C (T bath ). After unretour at 40-45 ° C, the reaction medium is poured into sodium hydroxide solution (10g, 0.25 mol) in water (700 mL). The mixture is stirred for 10 to 15 minutes. The precipitate is filtered and washed on the filter with water (3 times 400 mL).

A gray solid (31,51g, mass yield of 95%) is obtained.

The molar purity is greater than 85% (NMR 1 Η).

Solvent: CDCl 3

Steps b2 and c: preparation of the oxime of 2- (2- (2-oxoimidazolidin-1-yl) ethoxy) -1-naphthaldehyde

The product isolated following the protocol 3 is used in the following 4 protocol.

Protocol 4:

To a solution of 2- (2- (2-oxoimidazolidin-1-yl) ethoxy) -1-naphthaldehyde (6.3 g, 22.2 mmol) in ethanol (30 mL) at 45 ° C (T bath ) is added a solution of hydroxylamine (2.05 g, 31.0 mmol, 50% in water, Aldrich) in ethanol (5 mL). The reaction medium is stirred for 4 hours at 55 ° C (T bath ). After a return to 40 ° C, ethyl acetate (30 mL) was added dropwise over 15 minutes. The precipitate is filtered, washed on the filter with ethanol / ethyl acetate.

A white solid (4,00g, 60% mass yield) is obtained.

The molar purity estimated by NMR 1 H is greater than 95%. TLC: Rf = 0, 10 (SiO 2 ; EtOAc); visualization by UV and I 2 .

Solvent: MeOH

Step d: Preparation of 2- oxide [2- (2-oxoimidazolidin-1-yl) ethoxy] -1-naphthonitrile

Protocol 5:

To a solution of oxime of 2- (2- (2-oxoimidazolidin-1-yl) ethoxy) -1-naphthaldehyde (7.5 g, 25.06 mmol) in dichloromethane (300 mL) cooled to 4 ° C ( T bath = 0 ° C) is added dropwise an aqueous solution of NaOCl (78% Cl g / L, 35 mL) for 15 minutes. The reaction medium is stirred for 60 to 70 minutes at a temperature of 4-5 ° C. The organic phase was separated. The aqueous phase is extracted with dichloromethane (25 mL). The combined organic solutions are washed with water (2 times 25 mL). The solvent was evaporated under reduced pressure to 40-50 mL. Petroleum ether 40/60 (60 mL) was added for crystallization. The precipitate obtained is filtered and washed with 40/60 petroleum ether (2 times 30 mL).

A white solid (6.46 g, weight yield 87%) was obtained.

The molar purity estimated by NMR 1 H is greater than 99%.

Solvent: CDCl 3

II. Manufacturing a SBR grafted with oxide 2- [2- (2- oxoimidazolidin-1-yl) ethoxy] -1-naphthonitrile

The oxide of 2- [2- (2-oxoimidazolidin-1-yl) ethoxy] -1- naphthonitrile obtained above (following the protocol 5) is used.

It incorporates the oxide 2- [2- (2-oxoimidazolidin-1-yl) ethoxy] -1-naphthonitrile (0.88 g; 2.97 mmol) in 20g of SBR (containing 26.5% by weight styrene and 25% by weight of 1,2-butadiene unit, Mn = 150000 g / mol and Ip = 1.84) on an open mill (external mixer at 23 ° C). The mixture is homogenized in 15 portfolio assists. The mixing phase is followed by treatment Heat at 120 ° C for 10 minutes in a press at 10 bar pressure.

The NMR 1 H demonstrated a molar grafting rate of 0.81% with a molar yield of grafting 80%>.

(*) 1 H nonequivalent: protons carried by the same carbon atom does not have the same chemical shift 1 H.

III. Producing a grafted with IR oxide 2- [2- (2- oxoimidazolidin-1-yl) ethoxy] -1-naphthonitrile

The oxide of 2- [2- (2-oxoimidazolidin-1-yl) ethoxy] -1- naphthonitrile obtained above (following the protocol 5) is used.

It incorporates the oxide 2- [2- (2-oxoimidazolidin-1-yl) ethoxy] -1-naphthonitrile (0.26 g; 0,8`mmol) 20 g IR (containing 98% by weight isoprene-1,4 cis unit and Mn = 375000 g / mol and Ip = 3.6) on an open mill (external mixer at 23 ° C). The mixture is homogenized in 15 portfolio assists. The mixing phase is followed by a heat treatment at 120 ° C for 10 minutes in a press at 10 bar pressure.

The NMR 1 H demonstrated a molar grafting rate of 0.26% with a molar yield of grafting 90%>.

IV. rubber compositions

1) Preparation of rubber compositions

Four rubber compositions are prepared.

Rubber compositions comprising SBR or IR grafted with oxide 2- [2- (2-oxoimidazolidin-1-yl) ethoxy] -1-naphthonitrile (Compound of formula (IV) according to the invention, called as compound A) are prepared. rubber compositions comprising SBR or IR grafted with 2,4,6-trimethyl-3- [2-(2-oxoimidazolidin-1-yl) ethoxy [benzonitrile (hereinafter referred to as compound B, comparative compound) were also prepared.

The procedure for the following tests as follows in two cases:

- Case A: is introduced into an internal mixer Polylab 85cm 3 , filled to 70% and with an initial chamber temperature was about 110 ° C, the grafted diene elastomers as described in Section II or point III.

- Case B: is introduced into an internal mixer Polylab 85cm 3 , filled to 70% and with an initial chamber temperature was about 110 ° C, or the ungrafted diene elastomers. For mixtures for compound A and compound B, compound A or compound B is introduced together with the diene elastomer and thermomechanical working is conducted from one minute to 120 ° C.

Then, for each of the four compositions is introduced or reinforcing any charges, the eventual coupling agent and then, after one to two minutes of mixing, the various other ingredients except for the vulcanization system. Is then performed thermomechanical working (non-productive phase) in one step (total kneading time equal to about 5 minutes), until a maximum temperature "dropping" of 160 ° C. Recovering the thus obtained mixture, cooled and then the vulcanization system (sulfur) in an external mixer (homo-finisher) at 25 ° C, mixing the (productive phase) for about 5 to 6 minutes.

The compositions thus obtained are subsequently calendered, either in the form of plates (2 to 3 mm thick) or sheets fine rubber for the measurement of their physical or mechanical properties, or in the form of usable profiles directly after cutting and / or assembling to the desired dimensions, for example as semi-finished products for tires, in particular as treads for tires.

a) Rubber compositions SBR

The rubber compositions for SBR are given in Table 1. The rubber composition comprising the grafted SBR by the compound A according to the invention is referred to as composition 1. The rubber composition comprising the SBR grafted with the comparative compound B is called 2. composition contents are expressed in phr. The molar ratio of grafted compound on the SBR was 0.3% for both the SBR-gA as SBR-gB. Thus, there are 0.3 mole of grafted compound per 100 moles of the polymer units (moles of monomer units constituting the polymer, including those bearing the graft compound).

Table 1

(1) SBR-grafted Compound A

(2) SBR grafted compound B

(3) Silica "Zeosil 1165 MP" - Rhodia in the form of microbeads (BET and CTAB of about 150-160 m 2 / g)

(4) TESPT ( "S169" - Degussa)

(5) Carbon Black N234

(6) Antioxidant "Santoflex 6PPD" - Solutia

(7) 2,2,4-trimethyl-1,2-dihydroquinoline - Company Flexys

(8) Paraffin

(9) Zinc oxide (grade industrial - Umicore Company)

(10) Stearin ( "Pristerene 4031" - Uniqema Company)

(11) CBS : N-cyclohexyl-2-benzothiazyl-sulfénamide

( "CBS Santocure» - Société Flexys)

b) Rubber compositions IR

The rubber compositions for the IR spectra are given in Table 2. The rubber composition comprising the IR grafted with the compound A according to the invention is called composition 3. The rubber composition comprising the graft by IR Compound B is called comparative composition 4. the rubber composition comprising the IR grafted with oxide 2- [2- (2-oxoimidazolidin-1-yl) ethoxy] benzonitrile (hereinafter referred to as compound C) is called composition 5, prepared according to a procedure identical to the case B if except using the comparative compound C. Both compounds B and C are described in WO 2016/207263. The contents are expressed in phr. The molar ratio of grafted compound on the IR was 0.6% for both IR-gA the IR-gB and gC-IR. Thus, there are 0,

Table 2

(1) IR grafted compound A

(2) IR grafted compound B

(3) IR grafted with the compound C

(4) Silica "Zeosil 1165 MP" - Rhodia in the form of microbeads (BET and CTAB of about 150-160 m 2 / g)

(5) TESPT ( "S169" - Degussa)

(6) Carbon Black N234

(7) Antioxidant "Santoflex 6PPD" - Solutia

(8) 2,2,4-triméthyl-1,2-dihydroquinoline

(9) Paraffin

(10) Zinc oxide (industrial grade - Umicore Company) (11) Stearin ( "Pristerene 4031" - Uniqema Company)

(12) CBS: N-cyclohexyl-2-benzothiazyl sulfenamide ( "CBS Santocure" - Flexys Company)

2) characterization tests - Results

When the results are shown in base 100 relative to a control, the value specified for a composition is the ratio between the measured value on the composition and the measured value of the control composition.

a) Rubber compositions SBR

The properties of the compositions 1 and 2 are compared. The results are reported in Table 3:

Table 3

The composition 1 is at 100 ° C greater tensile strength than the composition 2. Moreover, the composition 1 shows better rigidity than the composition 2, accompanied by a conservation hysteresis properties.

The composition comprising the compound according to the invention thus has improved properties compared to the comparative composition comprising a compound.

b) Rubber compositions IR

The properties of compositions 3 and 4 are compared. The results are reported in Table 4:

Table 4

Composition 3 has greater tensile strength than the composition 4, accompanied by a conservation properties of rigidity and hysteresis, regardless of the temperature.

The properties of compositions 3 and 5 are compared. The results are reported in Table 5:

Table 5

The composition 3 shows at 100 ° C a much better breaking stress that the composition 5, accompanied by a conservation stiffness properties and hysteresis.

The composition comprising the compound according to the invention thus has improved properties compared to the comparative composition comprising a compound.

CLAIMS

1. A compound of formula (I):

in which :

- PAr denotes a polyaromatic group containing at least two aromatic condensed rings, each said fused aromatic rings being optionally substituted by one or more carbon chains, which are identical or different, independent of each other, aliphatic or aromatic, linear, branched or cyclic, optionally substituted or interrupted by one or more heteroatoms;

- Sp represents an atom or group of atoms.

2. A compound according to claim 1, characterized in that the Sp group is a linear or branched alkylene chain in C 1 -C 24 , preferably C 1 -C 10 , more preferably C 1 -C 6 , optionally interrupted by an or more atoms of nitrogen, sulfur or oxygen.

3. A compound according to claim 1 or 2, characterized in that it is of formula (II):

in which :

- a group selected from R 1 to R 7 denotes the group of formula (III):

wherein Sp is as defined in claim 1 or 2, the remaining six groups, identical or different, representing independently of each other, a hydrogen atom or a carbon chain, aliphatic or aromatic, linear, branched or cyclic optionally substituted or interrupted by one or more heteroatoms.

4. A compound according to any one of the preceding claims, characterized in that it is selected from a compound of formula (IV):

and a compound of formula (V):

preferably the compound of formula (IV).

5. A method for synthesizing the compound of formula (I) as defined in any one of the preceding claims, comprising the following successive steps:

(B1) reacting a compound of formula (VI):

wherein PAr is as defined in claim 1 and Y represents a nucleophilic group,

with a compound of formula (VII):

wherein Sp is as defined in claim 1 or 2, and Z is a nucleofugic group;

in the presence of at least one polar solvent S 1 , of at least one base, at a temperature T 1 ranging from 70 to 150 ° C,

to form a compound of formula (VIII):

(b2) reacting said compound of formula (VIII) with an aqueous solution of hydroxylamine to a temperature T 2 of from 30 to 70 ° C to obtain an oxime compound of formula (IX):

(C) a step of recovering said oxime compound of formula

(IX) ;

(D) a step of oxidizing oxime compound of formula (IX) with an oxidizing agent in the presence of at least one organic solvent

S2.

6. The method of claim 5, wherein both steps (b1) and (b2) are separated by a step of isolation and purification of the compound of formula (VIII).

7. The method of claim 5, wherein both steps (b1) and (b2) are performed in a one-pot synthesis.

8. A method according to any one of claims 5 to 7, wherein the group Y is selected from hydroxyl, thiol and primary or secondary amine.

9. A method according to any one of claims 5 to 8, wherein the Z group is selected from chlorine, bromine, iodine, mesylate, tosylate group, acetate group and trifluoromethylsulfonate group.

10. A method according to any one of claims 5 to 9, wherein the polar solvent S 1 is a water-miscible polar solvent in water, preferably a protic solvent, more preferably an alcoholic protic solvent.

11. A method according to any one of claims 5 to 10, wherein the compound of formula (VI) is from 5 to 40% by weight, preferably 10 to 30% by weight, based on the weight of the solvent.

12. A method according to any one of claims 5 to 11, wherein the base is selected from alkali alcoholates, alkali carbonates, alkaline earth carbonates, alkali hydroxides, alkaline earth hydroxides and mixtures thereof.

13. A method according to any one of claims 5 to 12, wherein the base is selected from sodium methoxide, potassium carbonate and sodium hydroxide, preferably potassium carbonate.

14. A method according to any one of claims 5 to 13, wherein the molar amount of base is from 1, 5 to 8 molar equivalents, preferably 2 to 6 molar equivalents, relative to the molar amount of compound of formula (VI).

15. A method according to any one of claims 5 to 14, wherein the addition of the aqueous hydroxylamine solution is carried out when the conversion of the compound of formula (VI) is at least 70% by weight.

16. A method according to any one of claims 5 to 15, wherein the oxidizing agent is selected from sodium hypochlorite, N-bromosuccinimide in the presence of a base, N-chlorosuccinimide in the presence of a base , and hydrogen peroxide in the presence of a catalyst, preferably sodium hypochlorite.

17. A method according to any one of claims 5 to 16, wherein the organic solvent S 2 is an organic solvent selected from chlorinated solvents and ester, ether and alcohol, morepreferably selected from dichloromethane, ethyl acetate, butyl acetate, diethyl ether, isopropanol and ethanol, more preferably selected from ethyl acetate and butyl acetate.

18. A method according to any one of claims 5 to 17, comprising a step (a2) for producing the compound of formula (VII) prior to step (b1) by reacting a compound of formula ( X):

wherein Sp is as defined in claim 1 or 2, with an agent for forming the leaving group Z.

19. Method according to the preceding claim, wherein said agent is thionyl chloride.

20. The method of claim 18 or 19, wherein step (a2) is carried out in the absence or in the presence of at least one solvent S 4 , preferably a chlorinated solvent, more preferably dichloromethane.

21. A method according to any one of claims 18 to 20, wherein step (a2) is immediately followed by a step (a3) ​​recovering the compound of formula (VII), preferably by purification with toluene, more preferably by crystallization of compound of formula (VII) in toluene.