BR112017005753B1 - Sulfurized aromatic polyol compound - Google Patents

Abstract

SULFURIZED AROMATIC POLYOL COMPOUND. A sulfur aromatic polyol compound, usable in particular as a monomer for the synthesis of a polyurethane by polycondensation with a polyisocyanate, comprising the formula (I): HO - CH2 - (Z1)a - CH(OH) - CH2 - S - Z3 - S - CH2 - CH(OH) - (Z2)b - CH2 - OH in which: Z1 and Z2, identical or different, represent an optional, at least divalent, linking group comprising at least 1 carbon atom; a and b, identical or different, are equal to 0 or 1; Z3 represents an at least divalent aromatic linking group comprising at least 6 carbon atoms, each sulfur atom on either side of the Z3 group, being directly bonded to an aromatic nucleus of Z3.

Description

1. FIELD OF THE INVENTION

[0001] The present invention relates to monomers capable of being used for the synthesis of polymers with urethane units (or polyurethanes) notably intended for adhesive systems for bonding glass or metal to rubber.

[0002] It is more especially concerning monomers above the sulfur-type polyols, notably intended for the synthesis of polyurethanes used in metal/rubber-type composites for articles made of rubber such as tyres.

2. STATE OF THE TECHNIQUE

[0003] Metal/rubber type compositions, especially for tires, are well known. They are generally made up of a matrix made of sulfur crosslinkable, generally dienic, unsaturated rubber comprising metallic reinforcing elements (or "ribs") such as wires, films or cables made of carbon steel.

[0004] Subjected to very high stresses during the tire run-in, notably to repeated compressions, bending or variations in curvature, these composites must, in a known way, satisfy a large number of technical criteria, sometimes contradictory, such as uniformity, flexibility , flexural and compressive strength, tensile strength, wear and corrosion resistance, and maintain these performances at a very high level for as long as possible.

[0005] It is easily understood that the adhesive interface between rubber and reinforcements plays a preponderant role in the continuity of these performances. The traditional process for bonding rubber compositions with carbon steel consists of coating the surface of the steel with brass (copper-zinc sling), the bond between the steel and the rubber matrix being ensured by sulfuration of the brass during vulcanization or firing. of rubber. To improve adhesion, on the other hand, organic salts or metal complexes such as cobalt salts are generally used as adhesion promoting additives in such rubber compositions.

[0006] Now, it is known that the adhesion between the carbon steel and the rubber matrix is susceptible to weakening over time, due to the progressive evolution of the sulfides formed under the effect of the different stresses encountered, notably mechanical and/or thermal, the above degradation process can be accelerated in the presence of moisture.

[0007] On the other hand, the use of cobalt salts makes rubber compositions more sensitive to oxidation and aging, and significantly increases their cost, not to mention that it is desirable to eliminate the use of such cobalt salts over time. in rubber compositions, due to the recent evolution of European regulations on this type of metallic salts.

[0008] For all the reasons stated above, manufacturers of metal/rubber composites, especially tire manufacturers, are looking for new adhesive solutions to make metallic reinforcements stick to rubber compositions, while correcting, at least in part, the aforementioned drawbacks.

3. BRIEF DESCRIPTION OF THE INVENTION

[0009] However, in the course of their research, the Applicants found a new polyol compound, of the sulfur aromatic type, which allows the synthesis of a polyurethane that corresponds to such an objective.

na qual: Zi e Z2, idênticos ou diferentes, representam um grupamento de ligação opcional, pelo menos divalente, que compreende pelo menos um átomo de carbono; a e b, idênticos ou diferentes, são iguais a 0 ou i; Z3 representa um grupamento de ligação aromático pelo menos divalente que compreende pelo menos 6 átomos de carbono, cada átomo de enxofre de um lado e de outro do grupamento Z3 sendo ligado diretamente a um núcleo aromático de Z3.[0010] According to the invention, said sulfur aromatic polyol compound corresponds to the formula (I) below:

in which: Z1 and Z2, identical or different, represent an optional, at least divalent, linking group comprising at least one carbon atom; a and b, identical or different, are equal to 0 or i; Z3 represents an at least divalent aromatic linkage group comprising at least 6 carbon atoms, each sulfur atom on either side of the Z3 group being directly bonded to an aromatic nucleus of Z3.

[0011] Thanks to this very specific sulfur aromatic polyol (primary diol) compound, which comprises in particular, in addition to its two primary alcohol functions, on the one hand at least two secondary alcohol functions and on the other hand a thioether function (- S - ) in the alpha position of each of these two secondary alcohol functions, it was revealed that it was possible to prepare a polyurethane that, used as an adhesion primer on metallic reinforcements, gives these reinforcements the greater and unexpected advantage of being able to adhere to unsaturated rubber matrices using simple textile glues such as “RFL” glues (resorcinol-formaldehyde-latex) or other equivalent adhesive compositions, or even directly (that is, without using such glues) to these unsaturated rubber matrices when the latter contain, for example, appropriate functionalized unsaturated elastomers such as for example epoxidized elastomers.

[0012] The invention also relates to the use of a polyol compound according to the invention for the manufacture of a polyurethane, as well as any polyurethane derived from at least one polyol compound according to the invention.

[0013] The invention also relates to any process of synthesizing a polyurethane by polycondensation of at least one polyol compound according to the invention with a polyisocyanate compound.

[0014] The invention as well as its advantages will be easily understood in the light of the detailed description and the examples of embodiment that follow, as well as figures 1 to 3 relating to those examples which represent or schematize: - two examples of sulfur polyol compounds of according to the invention (M1 and M2 monomers noted), as well as a synthesis scheme usable to obtain each of these compounds (Fig. 1 and Fig. 2); - a detailed synthesis scheme usable, starting from the M1 monomer according to the invention and a diisocyanate monomer (M2 monomer, benzophenone blocked MDI), of a polyurethane polymer P1 according to the invention (Fig. 3).

4. DETAILED DESCRIPTION OF THE INVENTION

[0015] It will be recalled first here that a polyurethane is a polymer (by definition any homopolymer or copolymer, notably a block copolymer) comprising a plurality of urethane bonds (-O-CO-NH-) which results in a known manner from the reaction addition of a polyol having at least two primary alcohol functions, in a polyisocyanate (a compound bearing at least two isocyanate functions -NCO), notably in a diisocyanate in the case of a polyurethane of the linear type.

na qual: Zi e Z2, idênticos ou diferentes, representam um grupamento de ligação opcional, pelo menos divalente, que compreende pelo menos i átomo de carbono; a e b, idênticos ou diferentes, são iguais a 0 ou i (quer dizer que Zi e Z2 podem estar presentes ou não); Z3 representa um grupamento de ligação aromático pelo menos divalente que compreende pelo menos 6 átomos de carbono, cada átomo de enxofre de um lado e de outro do grupamento Z3 sendo ligado diretamente a um núcleo aromático de Z3.[0016] The polyol compound (primary diol) aromatic sulfur of the invention, notably usable for the synthesis of a polyurethane, therefore corresponds to formula (I):

in which: Z1 and Z2, identical or different, represent an optional, at least divalent, linking group comprising at least 1 carbon atom; a and b, identical or different, are equal to 0 or i (that is, Zi and Z2 may or may not be present); Z3 represents an at least divalent aromatic linkage group comprising at least 6 carbon atoms, each sulfur atom on either side of the Z3 group being directly bonded to an aromatic nucleus of Z3.

[0017] This sulfur aromatic polyol compound has, therefore, notably as an essential characteristic, that it comprises, on both sides of the central aromatic group - Z3 -, a secondary alcohol function (- CH (OH) -) and a thioether function (- S -) in position α (alpha, that is to say for remembrance and by convention, carried by a carbon adjacent to the carbon that carries the secondary alcohol function) of this secondary alcohol function. In other words, this polyol compound comprises an a-hydroxy-thioether motif on both sides of the Z3 group.

[0018] Zi, Z2 and Z3 are linking groups, spacing units, of the organic type, preferably hydrocarbons, also commonly called “separators” or “spacers” by the professional; they can be saturated or unsaturated.

[0019] According to a special embodiment, Z1 and Z2, identical or different, substituted or unsubstituted, represent an aliphatic linking group having from 1 to 20 atoms, more especially 1 to 12 carbon atoms, or cycloaliphatic having from 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms; more especially, it is an alkylene with C1-C10, notably with C1-C5.

[0020] According to another preferred embodiment, Z3 comprises from 6 to 30, more preferably from 6 to 20 carbon atoms. By definition, each sulfur atom on either side of Z3 is directly bonded to an aromatic nucleus, it being understood that the latter can be the same nucleus or a different nucleus for these two sulfur atoms. More preferably still, Z3 comprises at least one (especially one or two) phenylene group, the latter(s) being substituted or unsubstituted.

[0021] According to another preferred embodiment, at least one of the groups Z1, Z2 and Z3 comprises at least one (that is to say 1 or more) heteroatoms preferably chosen from O, S or N.

[0022] According to another preferred embodiment, at least one of the groups Z1, Z2 and Z3 comprises at least one (that is to say 1 or more) ether bond (-O -) or thioether bond (-S -), the latter may be present in the carbon chain itself (Z1, Z2 or Z3) or in a substituent of one of its carbon atoms.

[0023] According to a preferred embodiment, a and b are equal to zero; in other words, in such a case, the primary sulfur diol compound of the invention corresponds to formula (I'):

[0024] The formulas below (with an integer “n” ranging for example from 1 to 30, notably from 1 to 20, more especially from 1 to 10) illustrate, by way of example, different groups that correspond to the definition of the chain - S - Z3 - S - above:

[0025] In the attached figures 1 and 2 were represented, in the developed form, the formulas of two examples of sulfur aromatic polyol compounds, according to the invention, noted Monomers M1 and M2, as well as a synthesis scheme usable to obtain of each of these compounds.

[0026] The polyol compound (Monomer M1, also noted in the sequence Monomer A1) of figure 1 is 3-{4-[4-(2,3-dihydroxy-propylsulfanyl)-phenylsulfanyl]-phenylsulfanyl}-propane-1, 2-diol. It can be obtained, for example, by reacting 4,4'-thiobisbenzenethiol and liquid 3-chloro-1,2-propanediol, as shown in figure 1. Its synthesis will be described in more detail in the following embodiment examples (Assay 1 of paragraph 5.1).

[0027] The polyol compound (M2 monomer) of figure 2 is 3-(4-{4-[(2,3-dihydroxypropylsulfanyl)-phenyl]-6-phenyl-[1,3,5]triazin- 2-yl}-phenylsulfanyl)-propane-1,2-diol.

[0028] It can be obtained for example according to the process outlined in figure 2.

[0029] Under a stream of nitrogen, they are introduced into a 500 ml 4-necked flask (equipped with a coolant, a magnetic bar and a nitrogen inlet, previously dried under vacuum at a temperature above 100°C) , 5.70 g (ie 16.5 mmol) of 2,4-bis-(p-fluorophenyl)-[1,3,5]-s-triazine, 200 ml of anhydrous DMSO solvent, then potassium carbonate dry (6.03 g or 43.6 mmol); previously, the triazine compound and potassium carbonate were both dried under vacuum at 150°C overnight. The starting triazine compound was synthesized in a known manner, as taught in WO 2012/016777 (Assay V-1-A, Compound 1, Fig. 18 ). The system is then purified for 30 min under stirring and under a stream of nitrogen. 4.29 g (ie 39.6 mmol) of 1-thioglycerol are then introduced and then the suspension is heated at 100°C for 4.5 h under a stream of nitrogen and stirring. The reaction mixture is then cooled to room temperature (23°C) and the potassium carbonate is filtered off over filter paper; the salt is washed with an additional 50 ml of DMSO. The filtrate is then poured into 250 ml of ice water and thus precipitated. 100 ml of HCl solution (at 10%) and 1 liter of demineralized water are then added; the pH is adjusted to 1.0 with the aid of HCl solution (10%). The white precipitate (Monomer M2) thus obtained (8.6 g, yield about 100%) is isolated by filtration over filter paper, washed with demineralized water and dried overnight at 90°C under vacuum.

na qual, para esses exemplos: a e b são iguais a zero, em outros termos Z1 e Z2 estão ausentes; Z3 representa um grupamento de ligação aromático divalente que compreende pelo menos 6 átomos de carbono e por outro lado pelo menos um heteroátomo (S ou N), cada átomo de enxofre de um lado e de outro do grupamento Z3 sendo ligado diretamente a um núcleo aromático (grupo fenileno).[0030] The common feature of the two sulfur aromatic polyol compounds described above in figures 1 and 2 is that they all correspond to formula (I'):

in which, for these examples: a and b are equal to zero, in other terms Z1 and Z2 are absent; Z3 represents a divalent aromatic linking group comprising at least 6 carbon atoms and on the other hand at least one heteroatom (S or N), each sulfur atom on either side of the Z3 group being directly bonded to an aromatic nucleus (phenylene group).

[0031] The aromatic sulfur polyol compound according to the invention described above is preferably usable for the synthesis of a polyurethane of the linear type, and therefore essentially resulting from the addition of this polyol (primary diol) and a diisocyanate compound. The usable diisocyanate may be aromatic, aliphatic or cycloaliphatic; it can be a monomer, a prepolymer or quasi-polymer, and even a polymer.

[0032] According to a preferred embodiment, the diisocyanate from which the polymer of the invention is derived is chosen from the group consisting of the following aromatic compounds: diphenylmethane diisocyanate (in abbreviated "MDI"), toluene diisocyanate ("TDI"), naphthalene diisocyanate (“NDI”), 3,3-bitoluene diisocyanate (“TODI”), paraphenylene diisocyanate (“PPDI”), for their different isomers, and for the mixtures of these compounds and/or isomers.

[0033] More preferably, an MDI or a TDI is used, most preferably an MDI.

[0034] All MDI isomers (notably 2,2'-MDI, 2,4'-MDI, 4,4'-MDI) and their mixtures are usable, as well as the so-called polymeric MDI (or "PMDI") that comprise oligomers of the following formula (with p equal to or greater than 1):

[0035] Aliphatic-type diisocyanate compounds are also useful, such as, for example, 1,4-tetramethylene diisocyanate, 1,6-hexane-diisocyanate ("HDI"), 1,4-bis(isocyanatomethyl)-cyclohexane, 1,3 -bis(isocyanatomethyl)-cyclohexane, 1,3-bis(isocyanatomethyl)benzene, 1,4-bis(isocyanatomethyl)benzene, isophorone diisocyanate ("IPDI"), bis(4-isocyananthocyclohexyl)methane diisocyanate ("H12MDI" ), 4,4'-dicyclohexylmethane diisocyanate ("H13MDI").

ou, se vários diisocianatos são utilizados, constitui o diisocianato majoritário em peso, que representa de preferência no último caso mais de 50 % do peso total dos compostos diisocianatos.[0036] According to a particularly preferred embodiment, the diisocyanate used is 4,4'-MDI (4,4'-diphenylmethane diisocyanate) which has the formula:

or, if several diisocyanates are used, it constitutes the majority diisocyanate by weight, which preferably represents in the latter case more than 50% of the total weight of the diisocyanate compounds.

[0037] It will be possible to advantageously use a caprolactam blocked 4,4'-MDI (for example the product in solid form “Grilbond” IL-6 from the company EMS), with the formula:

[0038] The invention is not, however, limited to a polymer of the linear type (as a reminder, from a diisocyanate), it will also be possible to use it, notably with the aim of increasing the Tg of the polymer of the invention by forming a network three-dimensional, a triisocyanate compound such as for example a triazine-nucleated MDI trimer of the formula below:

na qual Z1, Z2 e Z3, a e b têm evidentemente as definições principais e preferenciais dadas precedentemente.[0039] The polyurethane from the polyol compound of the invention has, therefore, the characteristic of comprising, in addition to its base structural units with urethane units (-O-CH-NH-) brought in a well-known way by the polyisocyanate starting compound, additional units specific recurrent units brought by the polyol monomer according to the invention, these additional units comprising at least one motif of formula (II):

in which Z1, Z2 and Z3, a and b evidently have the main and preferred definitions given above.

[0040] The formula (III) below reproduces an example of a sequence (recurring structural unit) of polymers of the polyurethane type, this sequence comprising on the one hand a base unit (urethane) brought by a diisocyanate (here, of the formula OCN-Z -NCO), and on the other hand an additional unit brought by a polyol compound according to the invention, namely:

[0041] In the above formula (III), Z represents an at least divalent, saturated or unsaturated linking group; it is preferably an aliphatic, cycloaliphatic or aromatic group, the aliphatic group preferably comprising from 1 to 30 (more preferably from 1 to 20) carbon atoms, the cycloaliphatic group preferably comprising from 3 to 30 (more preferably from 3 to 30) 20) carbon atoms, the aromatic group, substituted or unsubstituted, preferably comprising from 6 to 30 (more preferably from 6 to 20) carbon atoms.

[0042] Figure 3 illustrates a possible synthesis process starting from the polyol monomer according to the invention (Monomer M1, also annotated A1) and from another monomer (Monomer A2), of a polymer according to the invention of the type polyurethane (Polymer P1), a process that will be described in detail later.

[0043] This example of Polymer P1 prepared according to the invention even comprises a recurring motif of formula (III) in which Z corresponds more especially to the divalent residue group of MDI, a and b are equal to 0 and Z3 represents an aromatic group bearing notably of a thioether bond (-S-).

[0044] It is well seen in Figure 3 that according to the invention Polymer P1 comprises, in addition to its urethane base units, additional units comprising two a-hydroxy-thioether functions (- CH(OH) - CH2 - S - ) on both sides of Z3.

[0045] The polyurethane synthesized from an aromatic sulfur polyol compound according to the invention may comprise from ten to several hundred, preferably from 20 to 200 recurring structural units as described above. Its glass transition temperature Tg, measured by DSC (differential scanning calorimeter), for example according to ASTM D3418, is preferably above 50°C, more preferably above 100°C, in particular between 130°C C and 250°C.

[0046] This polyurethane has a high flexibility, an important elongation at break, it has shown on the other hand hydrophobic properties and effective anticorrosion properties.

[0047] It is advantageously used as a hydrophobic coating on any type of substrate, especially made of metal or glass, or as an adhesion primer on any type of metallic reinforcement, such as, for example, a wire, a film, a plate. or a handle made of carbon steel, whether or not covered with brass, intended in particular to reinforce an unsaturated rubber matrix such as natural rubber.

5. EXAMPLES OF CARRYING OUT THE INVENTION

[0048] In the present application, unless expressly stated otherwise, all percentages (%) indicated are percentages by mass.

5.1. Assay 1 - A1 Monomer Synthesis

[0049] The monomer A1 (or M1) is 3-{4-[4-(2,3-dihydroxy-propylsulfanyl)-phenylsilphanyl]-phenylsulfanyl}-propane-1,2-diol, according to the invention. This monomer was synthesized according to the operating mode outlined in Figure 3, as detailed below.

[0050] In a 500 ml 4-necked flask previously dried under vacuum at more than 100°C, equipped with a condenser, thermometer and magnetic bar, 8.3 g of ( Compound 1) Solid 4,4'-thiobisbenzenethiol (ie 33.03 mmol) and then 10.0 g of potassium carbonate (ie 72.56 mmol), previously dried under vacuum at 150°C for 12 h). 200 ml of anhydrous DMSO are then poured in, the dispersion is purified under nitrogen for 30 min, and then 7.29 g of liquid (Compound 2) 3-chloro-1,2-propanediol (i.e. 66 .06 mmol). The reaction mixture is immediately heated at 100°C for 5 h, always under a stream of nitrogen. The solution obtained is then allowed to cool to room temperature, and the solid potassium carbonate (K2CO3) is recovered by filtering through filter paper. The filtrate is then washed with 50 ml of DMSO, and then the whole is poured into 250 ml of deionized water at 0°C (ice) to precipitate the target product.

[0051] To neutralize residual K2CO3, 10 ml of HCl (10%) and 1 liter of deionized water are then added. After drying under vacuum at 60°C overnight (12 h), the obtained precipitate (orange sticky solid) is poured into 500 ml of ethyl acetate, everything is heated to 40°C until complete dissolution. The solution obtained is cooled to room temperature (20°C) and then transferred to a separatory funnel, 50 ml of saturated (aqueous) NH4Cl are then added. After stirring, the organic phase is separated and then washed twice with 25 ml of deionized water, and then dried with dry sodium carbonate. After filtration and distillation of ethyl acetate on a rotary evaporator (“Rotavap”), the solid obtained is dried at 80°C.

[0052] The NMR and ESI analyzes confirm the structure of Monomer A1, with the formula:

[0053] 1H NMR analysis (500 MHz, DMSO-d6) of the product gave the following results: 2.89 (m, 2H), 3.11 (m, 2H), 3.40 (m, 4H), 3.61 (m, 2H), 4.67 (d, 2H), 4.99 (d, 2H), 7.227.24 (d, 4H), 7.31-7.33 (d, 4H).

[0054] Regarding the molecular mass measured by ESI mass spectrometry, in a mixture of ethyl acetate/methanol (1/1) (with traces of aqueous NaCl), it was evaluated in negative mode (anion [M + Cl ]-) at 433.3 (calculated theoretical value equal to 434.0), and in positive mode ([M + Na]+ cation) at 421.1 (calculated theoretical value equal to 420.6).

5.2. Assay 2 - Synthesis of Polymer P1 by reaction of Monomers A1 and A2

[0055] This assay describes in detail the synthesis of Polymer P1 according to the invention, starting from monomers A1 and A2 (caprolactam blocked MDI), according to the mode of operation outlined in Figure 3.

[0056] 280.0 mg of Monomer A1, 334.6 mg of Monomer A2 (“Grilbond” IL-6) and 8 ml of NMP solvent are placed inside a vial made of glass. The suspension is heated (under a stream of hot air) at 120°C until a clear solution is obtained. And then 3 ml of the solution thus obtained are placed on a plate made of polished brass (10 x 10 cm 2 ) which is then passed in an oven at 190°C for 15 min. A clear film of Polymer P1 is thus obtained, of which DSC analysis (second pass, -80°C to 200°C; 10°C/min) revealed a Tg of about 115°C. It is possible to note that a similar polymerization reaction, but conducted in a 1-methoxypropanol-2-acetate / sulfolane solvent mixture (3:1), led to a Tg of about 130°C.

5.3. Test 3 - Adhesion test of Polymer 1 in a metal/rubber composite

[0057] A thin film of Polymer P1 thus obtained was placed (at room temperature) evenly on the surface of a brass plate. And then everything was covered with a layer of conventional textile glue of the “RFL” type (resorcinol-formaldehyde-latex). After a 5 min pre-drying at 100°C, the assembly was then treated in the oven at 190°C for 10 min.

[0058] The plate made of brass thus coated with the film of Polymer P1 and glued with RFL was then disposed within a composition matrix (in the raw, unvulcanized state) of conventional rubber for touring tire belt armour, based on natural rubber, carbon black and silica as filler, and a vulcanization system (sulfur and sulfenamide accelerator); that composition being devoid of cobalt salt.

[0059] And then the metal/rubber composite beaker thus prepared was placed under a press and the whole was baked (vulcanized) at 165°C for 30 min under a pressure of 20 bars. After vulcanization of the rubber, an excellent bond was obtained between the rubber matrix and the metal plate despite the absence of cobalt salt in the rubber matrix: on the occasion of debonding tests carried out at the same time at room temperature (23°C ) and at high temperature (100°C), it was indeed found that the rupture occurred systematically in the rubber matrix itself and not in the interface between metal and rubber.

[0060] In conclusion, the sulfur aromatic polyol compounds of the invention make it possible to synthesize polyurethanes that are characterized by a high glass transition temperature, a high thermal and chemical stability, and an excellent adhesion to glass or metal.

[0061] Thanks to the invention, these polyurethanes, used as an adhesion primer on metal in metal/rubber composites, make it possible to quite advantageously then glue the metal to the rubber matrices using, for example, simple textile glues such as “RFL” glues ( resorcinol-formaldehyde-latex) or other equivalent adhesive compositions, or even directly (that is to say without using such glues) to such rubber matrices when the latter contain for example suitable functionalized unsaturated elastomers such as epoxidized elastomers.

[0062] Thus, cobalt salts (or other metallic salts) in rubber compositions intended to be bonded to brass-coated metallic reinforcements can be remarkably eliminated.

Claims (12)

1. Aromatic sulfur polyol compound, usable in particular as a monomer for the synthesis of a polyurethane by polycondensation with a polyisocyanate, said polyol compound characterized in that it responds to the formula:

in which: - Z1 and Z2, identical or different, represent an optional linking group, at least divalent, comprising at least one carbon atom; - a and b, identical or different, are equal to 0 or 1; - Z3 represents an at least divalent aromatic linking group comprising at least 6 carbon atoms, each sulfur atom on each side of the Z3 group being directly bonded to an aromatic nucleus of Z3, Z3 comprises at least one phenylene group, the latter being possibly replaced or not replaced. 2. Compound according to claim 1, characterized in that Z1 and Z2, identical or different, represent an aliphatic bond group comprising from 1 to 20, preferably from 1 to 12 carbon atoms, or a cycloaliphatic group comprising from 3 to 20, preferably from 3 to 12 carbon atoms. 3. Compound according to claim 2, characterized in that Z1 and Z2, identical or different, represent an alkylene group with C1C10, preferably with C1-C5. 4. Compound according to any one of claims 1 to 3, characterized in that Z3 represents an aromatic group comprising from 6 to 30, preferably from 6 to 20 carbon atoms. 5. Compound according to any one of claims 1 to 4, characterized in that at least one of the groups Z1, Z2 and Z3 comprises a heteroatom chosen from O, S or N. 6. Compound according to claim 5, characterized in that at least one of the groups Z1, Z2 and Z3 comprises an ether or thioether bond. 7. Compound according to any one of claims 1 to 6, characterized in that a and b are equal to 0. 8. Compound according to claim 7, characterized in that it corresponds to the formula:

9. Compound, according to claim 7, characterized in that it corresponds to the formula:

10. Polymer with urethane units derived from at least one sulfur aromatic polyol compound, of the type defined in any one of claims 1 to 9, said polymer characterized in that it comprises at least units comprising a motif of the formula:

Process for the synthesis of a polymer with urethane units, characterized in that it is by polycondensation of at least one sulfur aromatic polyol compound as defined in any one of claims 1 to 9, with a polyisocyanate compound. Use of an aromatic sulfur polyol compound of the type defined in any one of claims 1 to 9, characterized in that it is in the manufacture of a polymer with urethane units.

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