Phenol polymer with 5,5′-biaryl bonds, method for preparing same, and uses thereof

Abstract

A phenol polymer is obtainable by oligomerization of one or more macropolyphenols serving as monomers, wherein the oligomerization step is catalyzed by an oxidase enzyme. The bonds between the macropolyphenol fragments in the polymer are exclusively 5,5-biaryl bonds. This polymer is useful as an antioxidant, chelating agent, plasticizing agent, or antimicrobial agent.

Claims

1. A phenol polymer obtained by oligomerization catalyzed by an enzyme of oxidase type, said phenol polymer comprising a plurality of monomers, said monomers being of one or more macropolyphenol(s), each macropolyphenol having a structure with at least two phenol rings corresponding to general formula (I): ##STR00014## wherein: p represents an integer between 1 and 30, R.sub.1, R.sub.1, R.sub.2, R.sub.2, R.sub.3 and R.sub.3, which may be identical or different, each represent a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom, or an alkyl, benzyl, Xalkyl, where appropriate substituted, Xbenzyl, where appropriate substituted, Xacyl, B(OR).sub.2, NHR, NO.sub.2, SRO or SO.sub.2R group, where X represents N, O, S or P and R represents an alkyl group or an aryl group, R.sub.1 and R.sub.1 do not represent a hydrogen atom, Y and Y, which may be identical or different, each represent: either an oxygen atom, a sulfur atom or a deconjugating group, said deconjugating group comprising neither an epoxide ring, nor an aziridine ring, nor a phenol group which is not substituted on all its carbon atoms, said deconjugating group not comprising a bond conjugated with the phenol ring to which said deconjugating group is bonded, or a group corresponding to formula (II): ##STR00015## wherein: q represents an integer between 1 and 8, Y.sub.1 represents an oxygen atom, a sulfur atom or a deconjugating group, said deconjugating group comprising neither an epoxide ring, nor an aziridine ring, nor a phenol group which is not substituted on all its carbon atoms, said deconjugating group not comprising a bond conjugated with the phenol ring of the group of formula (II), Z.sub.1 represents a heteroatom or a spacer group comprising neither an epoxide ring, nor an aziridine ring, nor a phenol group which is not substituted on all its carbon atoms, nor an alkenyl group, nor an alkynyl group, and Z represents: either a heteroatom or a spacer group comprising neither an epoxide ring, nor an aziridine ring, nor a phenol group which is not substituted on all its carbon atoms, nor an alkenyl group, nor an alkynyl group, or a group corresponding to formula (III): ##STR00016## wherein q represents an integer between 1 and 8, the bonds between the monomers of the one or more macropolyphenol(s) of general formula (I), within said polymer, being exclusively 5,5-biaryl bonds.

2. The polymer as claimed in claim 1, wherein R.sub.1 and/or R.sub.1 represent(s) a linear or branched, saturated hydrocarbon-based radical comprising from 1 to 5 carbon atoms, or an OR.sub.4 group, where R.sub.4 represents a linear or branched, saturated hydrocarbon-based radical comprising from 1 to 5 carbon atoms.

3. The polymer as claimed in claim 1, wherein R.sub.2, R.sub.3, R.sub.2 and/or R.sub.3 represent(s) a hydrogen atom.

4. The polymer as claimed in claim 1, wherein Y and/or Y represent(s) a group of general formula (V):
(CH.sub.2).sub.mX(V) wherein: m is between 1 and 5, and X represents an oxygen atom or a sulfur atom or a group selected from the group consisting of: ##STR00017## NR, NH and SO.sub.2, where R represents an alkyl group or an aryl group.

5. The polymer as claimed in claim 1, wherein Y and Y, and where appropriate Y.sub.1, each represent a group of general formula (VI): ##STR00018##

6. The polymer as claimed in claim 1, wherein Z represents a linear or branched, saturated hydrocarbon group, where appropriate substituted, comprising from 1 to 6 carbon atoms, which can comprise one or more heteroatoms, or a saturated cyclic hydrocarbon group, where appropriate substituted, comprising from 1 to 6 carbon atoms, which can comprise a single ring or several condensed rings, and which can comprise one or more heteroatoms.

7. The polymer as claimed in claim 1, corresponding to general formula (IV): ##STR00019## wherein n represents an integer between 2 and 100.

8. The polymer as claimed in claim 1, corresponding to one of formulae (IVa), (IVb), (IVc) and (IVd) ##STR00020## wherein n represents an integer between 2 and 100.

9. The polymer as claimed in claim 1, corresponding to general formula (VII): ##STR00021## wherein n represents an integer between 2 and 100.

10. A process for synthesizing a phenol polymer as claimed in claim 1, comprising a step of oligomerization of one or more macropolyphenol(s) each corresponding to general formula (I), catalyzed by an enzyme of oxidase type.

11. The process as claimed in claim 10, wherein said enzyme is a laccase.

12. The process as claimed in claim 10, wherein said oligomerization step is carried out in an aqueous solution at a temperature of between 0 and 75 C.

13. The process as claimed in claim 10, wherein said oligomerization step is carried out in an aqueous solution at a pH of between 3 and 8.

14. The process as claimed in claim 10, wherein said oligomerization step is carried out in an aqueous solution comprising from 0 to 80% (v/v) of an organic solvent.

15. The process as claimed in claim 10, wherein said oligomerization step is carried out in an ionic liquid.

16. A composition comprising a phenol polymer as claimed in claim 1.

17. A part having a surface which is coated with a layer made up of a polymer as claimed in claim 1.

Description

(1) The characteristics and advantages of the invention will emerge more clearly in the light of the exemplary embodiments below, provided by way of simple and in no way limiting illustration of the invention, with the support of FIGS. 1 to 14, wherein:

(2) FIG. 1a shows a chromatograph obtained by size exclusion chromatography for a polymer B1 formed by a synthesis process in accordance with the invention, with detection at 250 nm;

(3) FIG. 1b shows a chromatograph obtained by size exclusion chromatography for a polymer P1 formed by a synthesis process in accordance with the invention, with detection at 250 nm;

(4) FIG. 1c shows a chromatograph obtained by size exclusion chromatography for a polymer G1 formed by a synthesis process in accordance with the invention, with detection at 250 nm;

(5) FIG. 2a shows a .sup.13C NMR spectrum of a polymer B1 formed by a synthesis process in accordance with the invention;

(6) FIG. 2b shows a .sup.13C NMR spectrum of a polymer P1 formed by a synthesis process in accordance with the invention;

(7) FIG. 2c shows a .sup.13C NMR spectrum of a polymer G1 formed by a synthesis process in accordance with the invention;

(8) FIG. 2d shows a .sup.13C NMR spectrum of a polymer I1 formed by a synthesis process in accordance with the invention;

(9) FIG. 2e shows the .sup.13C NMR chemical shifts, in ppm, predicted by simulation using the ChemBiodrawUltra 13.0.2 software, for various types of bond between phenol units;

(10) FIG. 3 shows the results obtained by MALDI-TOF analysis of a polymer B1 formed by a synthesis process in accordance with the invention;

(11) FIG. 4 shows the evolution of the degree of conversion of the PDF monomer to linear polymer by means of a synthesis process in accordance with the invention, as a function of the % of ethyl acetate cosolvent in the aqueous reaction solution;

(12) FIG. 5 shows the evolution of the degree of conversion of the PDF monomer to linear polymer by means of a synthesis process in accordance with the invention, as a function of the pH of the aqueous reaction solution, with ethyl acetate as cosolvent;

(13) FIG. 6 shows the evolution of the degree of conversion of the PDF monomer to linear polymer by means of a synthesis process in accordance with the invention, as a function of the nature of the cosolvent in the aqueous reaction solution, the % of cosolvent in the latter being 30% (v/v);

(14) FIG. 7 shows a graph representing, as a function of the reaction time, the degree of conversion of the BDF monomer and the number-average molecular weight (Mn) of the linear polymer obtained by means of a synthesis process in accordance with the invention;

(15) FIG. 8 shows the spectra obtained by size exclusion chromatography for linear polymers formed from the BDF monomer by means of the synthesis processes in accordance with the invention, using various concentrations of monomer in the reaction medium;

(16) FIG. 9 shows a graph representing, as a function of the temperature applied, the degrees of conversion of the GDF monomer and the number-average molecular weights (Mn) of the linear polymers obtained by means of synthesis processes in accordance with the invention using, as cosolvent, respectively acetone and ethanol (EtOH);

(17) FIG. 10 shows a graph representing, as a function of the temperature applied, the degrees of conversion of the IDF monomer and the number-average molecular weights (Mn) of the linear polymers obtained by means of synthesis processes in accordance with the invention using, as cosolvent, respectively acetone and ethanol (EtOH);

(18) FIG. 11 shows a graph representing, as a function of the laccase load used, for each of the respective GDF and IDF monomers, the degree of conversion and the number-average molecular weight (Mn) of the linear polymer obtained by means of a synthesis process in accordance with the invention;

(19) FIG. 12 shows a graph representing, for macrobisphenols corresponding to formula (I), called respectively IDF, GDF, BDF and PDF, the % antagonist activity with respect to the activity of estradiol (E2) at 10 nM, as a function of the concentration of the macrobisphenol;

(20) FIG. 13 shows a .sup.13C NMR spectrum of a polymer formed by means of a synthesis process in accordance with the invention, from BDF and IDF macropolyphenols;

(21) and FIG. 14 shows a 2D NMR spectrum (.sup.1H/.sup.13C correlation) of the polymer of FIG. 13.

A/SYNTHESIS OF THE PHENOL POLYMERS

(22) A.1/Macrobisphenol Monomers

(23) The following monomers (Ia) (glycerol-3-di(dihydroferulate), termed GDF), (Ib) (butane-1,4-di(dihydroferulate), termed BDF), (Ic) (isosorbide-2,5-(dihydroferulate), termed IDF) and (Id) (propane-1,3-di(dihydroferulate), termed PDF) are used for the synthesis of phenol polymers in accordance with the invention:

(24) ##STR00012##

(25) The macrotrisphenol of general formula (Ie) below is also used as a monomer for the synthesis of phenol polymers in accordance with the invention:

(26) ##STR00013##

(27) These monomers are prepared according to the process described in the publication by Pion et al., 2013, by means of a lipase B, from ferulic acid and polyols.

(28) A.2/Polymer Synthesis Protocol

(29) The polymers are synthesized by oligomerization of the monomers above, by means of a laccase, which forms a radical on each phenol ring, thus enabling the oligomerization by radical-radical coupling.

(30) The general procedure is the following.

(31) The macrobisphenol or the macrotrisphenol is weighed into a round-bottomed flask and then dissolved in the cosolvent chosen, before adding thereto water, optionally buffered to obtain the desired pH, and then the laccase of Trametes versicolor, at a chosen load dissolved in water, optionally buffered to obtain the desired pH. The medium is vigorously magnetically stirred for a chosen time, at a chosen temperature and in the open air or under an oxygen atmosphere.

(32) When a solid is present at the end of the reaction, it is recovered and then dried. Otherwise, the reaction medium is taken up in a volume of dichloromethane or of ethyl acetate, equal to 3 times the reaction volume, so as to extract therefrom the organic compounds, i.e. the polymer formed and, where appropriate, the unreacted macrobisphenol or macrotrisphenol. The resulting organic phase is dried in the presence of anhydrous magnesium sulfate (MgSO.sub.4), filtered and concentrated under vacuum.

(33) Depending on the starting monomer, the respective polymers (IVa), (IVb), (IVc) and (IVd) described above are thus obtained, as is, starting from the macrotrisphenol of formula (Ie), a branched polymer comprising exclusively 5,5-biaryl bonds between the base macrotrisphenol fragments.

(34) Various experiments were thus carried out with, for each monomer, various combinations of the following reaction conditions: cosolvent chosen from: methanol, ethanol, isopropanol, tert-butanol, butanol, benzyl alcohol, ethylene glycol, hexane, heptane, dichloromethane, 1,4-dioxane, tetrahydrofuran, acetone, 4-methyl-2-pentanone, ethyl acetate (EtOAc), diethyl ether, 1,2-dimethyl ether, diethyl succinate, dimethylformamide, chloroform, pyridine, benzene, o-dichlorobenzene or acetonitrile; aqueous solution, for example of Milli-Q water, which is pure or buffered with a buffer chosen from phosphate buffers and sodium acetate buffers, for a pH of between 2 and 7, more precisely of 2.3, 2.9, 3.7, 3.9, 4.2 or 5.6; % of cosolvent in the aqueous solution of between 0 and 100% by volume, more particularly of 0, 20%, 25%, 29%, 30%, 40%, 45%, 60%, 80% or 100% (v/v); macrobisphenol concentration in the solution of between 3 and 50 g/l, more particularly equal to 3.2, 6.4, 6.5, 13, 16.6, 20, 25, 27, 33, 33.33, 43, 45 or 50 g/l; laccase load of between 2 and 1000 units per millimol of macrobisphenol, more particularly equal to 2, 10, 50, 100, 200 or 1000 u/mmol; temperature of between 0 and 80 C., more particularly equal to 5, 20, 40, 50, 60 or 80 C.; time of between 8 and 120 h, more particularly equal to 8, 18, 24, 48, 72, 96 or 120 h.

(35) By way of particular examples, the following polymers are formed under the conditions indicated in table 1 below:

(36) TABLE-US-00001 TABLE 1 Reaction conditions for obtaining polymers in accordance with the invention Solvent Monomer Laccase Temp. Time Polymer Monomer (% v/v) pH concentration (g/l) (u/mmol) ( C.) (h) P1 PDF EtOH 20 100 40 120 (30) B1 BDF Acetone 4.2 6.5 1000 20 120 (45) G1 GDF Acetone 4.2 25 10 40 96 (25) PDF PDF EtOAc 3.7 33.33 50 20 72 1000 (40) PDF PDF EtOAc 3.7 33.33 50 20 72 1500 (20)
A.3/Analysis of the Products Obtained According to the Operating Parameters

(37) For each experiment, a size exclusion chromatography (HPSEC) analysis is carried out in order to determine the degree of conversion, and the molecular weight distribution curve and to evaluate the average molecular weights of the products obtained, by means of a device comprising a Gilson 305 pump, an UltiMate 3000 ACC injector from Dionex, a PLgel 5 m 100, 6007.5 mm column and a PDA 3000 UV detector from Dionex.

(38) The vector used is tetrahydrofuran at a flow rate of 1 ml/min, and the detection is carried out at 250 nm.

(39) The calibration of the analytical device is carried out by means of Igepal standards.

(40) By way of example, the spectra obtained for the polymers in accordance with the present invention B1, formed from the BDF monomer, P1, formed from the PDF monomer, and G1, formed from the GDF monomer, as indicated above, are shown respectively in FIGS. 1a, 1b and 1c. A virtually total conversion of the monomer, a good dispersity of the HPSEC signal, and a relatively high degree of polymerization are observed therein, for each polymer in accordance with the invention. Each of the polymers according to the invention is largely predominant in the corresponding mixture obtained.

(41) The .sup.13C NMR spectra of each of these polymers in accordance with the invention were also produced (DMSO-d.sub.6 or CDCl.sub.3), and are shown respectively in FIGS. 2a, 2b and 2c for the polymers B1, P1 and G1.

(42) A .sup.13C NMR spectrum was also produced for a polymer, called I1, obtained in accordance with the invention with the IDF macrobisphenol as monomer. This spectrum is shown in FIG. 2d.

(43) All of these spectra were compared to the chemical shifts predicted by simulation using the ChemBiodrawUltra 13.0.2 software, for various types of bond between the phenol units, which are shown in FIG. 2e. This comparison clearly demonstrates that the bonds in the polymers B1, P1 and G1 are indeed of the 5,5-biaryl type. Indeed, there is, on the spectra of these polymers, no peak characteristic of a 1,5 bond, at 181.2 ppm, and no peak characteristic of a 4-O-5 bond, at 106.2 ppm.

(44) MALDI-TOF analyses were also carried out on the polymers in accordance with the invention B1, P1 and G1. The result obtained for the polymer B1 is shown in FIG. 3. A regular sequence and a maximum degree of polymerization equal to 8 are observed therein for this polymer. This result is representative of that obtained for the polymers P and G1, and also for all the polymers obtained by means of a synthesis process in accordance with the invention.

(45) All of the spectra obtained show that, for all the operating parameter combinations, a linear and homogeneous polymer, characterized by a single type of 5,5-biaryl bond between the macrobisphenol monomers, is very predominantly obtained.

(46) On the basis of the spectra obtained, the influence of the various operating parameters on the polymer formed was studied.

(47) Influence of the Solvent

(48) The degree of conversion of the base monomer to polymer in accordance with the invention was evaluated for the PDF monomer, by varying respectively in the % of cosolvent, the pH of the reaction medium and the nature of the cosolvent.

(49) The results are shown respectively in FIG. 4 (variation in the % of solvent, the operating conditions being the following: cosolvent EtOAc, temperature 20 C., pH 3.7, monomer concentration 1 g/30 ml), FIG. 5 (variation in the pH, the operating conditions being the following: cosolvent EtOAc at 30% v/v, temperature 20 C.) and FIG. 6 (variation in the nature of the cosolvent, the operating conditions being the following: 30% v/v of cosolvent, temperature 20 C., pH 3.7, time indicated on the graph after the name of the cosolvent). These results are representative of those obtained for all the other starting monomers, and all the operating conditions combinations. They demonstrate that the process of oligomerization catalyzed by the laccase can advantageously be carried out with a wide range of cosolvents, in a wide pH range, and both in a strict aqueous medium and in a mixed water/cosolvent medium, this being up to high proportions of cosolvent.

(50) Influence of the Reaction Time

(51) The influence of the reaction time was evaluated using the BDF monomer, under the following operating conditions: temperature of 20 C., laccase load of 50 u/mmol, pH of 4.2, acetone cosolvent at 60% (v/v), initial concentration of monomer of 6.4 g/l. Reaction times between 8 and 120 h were tested.

(52) The results obtained, in terms of degree of conversion of the monomer and of number-average molecular weight, as a function of the reaction time, are shown in FIG. 7. It is observed therein that the maximum degree of conversion is very rapidly reached during the reaction, whereas the number-average molecular weight increases continuously with the reaction time. This demonstrates that the dimerization of the BDF monomer is rapid, the oligomerization taking a little longer to be carried out. Controlling the reaction time thus makes it possible to control the degree of polymerization.

(53) These results are representative of those obtained for all the other starting monomers, and all the operating conditions combinations.

(54) Influence of the Dilution

(55) The influence of the dilution of the monomer in the reaction medium was analyzed for the BDF monomer, under the following operating conditions: temperature of 20 C., laccase load of 50 u/mmol, pH of 4.2, acetone cosolvent at 60% (v/v), reaction time of 5 days. Initial concentrations of monomer of 3.2, 6.4 and 12.8 g/l were tested.

(56) For each of the reactions, the spectra obtained by size exclusion chromatography are shown in FIG. 8. It is observed therein that the dilution has a negligible influence on the reaction product obtained. These results are representative of those obtained for all the other starting monomers, and all the operating condition combinations.

(57) Influence of the Temperature

(58) The influence of the temperature was analyzed using the GDF and IDF monomers, respectively, under the following operating conditions: monomer concentration of 28 g/l, laccase load of 50 u/mmol, pH of 4.2, acetone or ethanol (EtOH) cosolvent at 30% (v/v), reaction time of 5 days. Temperatures of between 20 and 80 C. were tested.

(59) The results obtained, in terms of degree of conversion of the monomer and of number-average molecular weight (Mn), as a function of the temperature and for each monomer and each solvent, are shown in FIG. 9 for the GDF monomer and in FIG. 10 for the IDF monomer. It is observed therein that the polymerization reaction occurs for temperatures up to approximately 75 C., with an optimal temperature range of between 20 and 60 C., and an optimal value of approximately 40 C.

(60) These results are representative of those obtained for all the other starting monomers, and all the operating conditions combinations.

(61) Influence of the Laccase Load

(62) The influence of the temperature was analyzed using the GDF and IDF monomers, respectively, under the following operating conditions: monomer concentration of 28 g/l, pH of 4.2, acetone cosolvent at 30% (v/v), reaction time of 5 days, temperature of 20 C. Laccase loads of between 0 and 1100 u/mmol were tested.

(63) The results obtained, in terms of degree of conversion of the monomer and of number-average molecular weight (Mn), as a function of the laccase load and for each monomer, are shown in FIG. 11. It is observed therein that the population of the peaks at high molecular weight increases rapidly with the enzyme load, at least for IDF. The minimum amount of laccase required for a degree of conversion greater than or equal to 70% is 2 u/mmol of macrobisphenol monomer.

(64) These results are representative of those obtained for all the other starting monomers, and all the operating conditions combinations.

(65) A.4/Synthesis of a Copolymer in Accordance with the Invention from Macrobisphenols

(66) A copolymer in accordance with the invention was prepared from the BDF and IDF macrobisphenols and according to the following procedure.

(67) The BDF (0.5 g) and IDF (0.5 g) macrobisphenols are weighed into a round-bottomed flask and then dissolved in 20 ml of acetonitrile, before adding thereto milli-Q water and then the laccase of Trametes versicolor (15.6 mg; 100 u/mmol.sub.substrate) dissolved in water, the cosolvent/milli-Q water final volume ratio being 3/7. The medium is vigorously magnetically stirred for 24 hours, at ambient temperature and in the open air. After 24 hours, a yellow oil formed at the bottom of the round-bottomed flask.

(68) The reaction medium is taken up in a volume of dichloromethane or of ethyl acetate equal to 3 times the reaction volume, so as to extract therefrom the organic compounds (oligomers formed and unreacted starting reagents). The resulting organic phase is dried in the presence of anhydrous magnesium sulfate (MgSO.sub.4), filtered and concentrated under vacuum. A beige solid is obtained.

(69) The .sup.13C NMR spectrum of the resulting copolymer was produced (DMSO-d.sub.6 or CDCl.sub.3), and is shown in FIG. 13. A peak at 124.47 ppm, indicated by an arrow in the figure, characteristic of 5,5-biaryl bonds, is observed therein.

(70) An analysis by two-dimensional NMR spectrometry (.sup.1H/.sup.13C correlation) was also carried out. The spectrum obtained is shown in FIG. 14. It is characteristic of phenol polymers of which the biaryl bonds are solely of the 5,5 type. The two signals representative of the two phenol CH of the aromatic rings forming the 5,5-biaryl bonds (corresponding to the 5,5 repeat unit shown in FIG. 2e) are in particular observed, in the box.

(71) These analysis results confirm the formation of a copolymer with exclusively 5,5-biaryl bonds.

(72) A.5/Synthesis of a Copolymer in Accordance with the Invention from a Macrobisphenol and from a Macrotrisphenol

(73) A copolymer in accordance with the invention was prepared from the PDF macrobisphenol and from the GTF macrotrisphenol according to the following procedure.

(74) The PDF macrobisphenol (0.5 g) and the GTF macrotrisphenol (0.5 g) are weighed into a round-bottomed flask and then dissolved in 10 ml of acetonitrile, before adding thereto milli-Q water, and then the laccase of Trametes versicolor (15.6 mg; 100 u/mmol.sub.substrate) dissolved in water, the cosolvent/milli-Q water final volume ratio being 3/7. The medium is vigorously magnetically stirred for 24 hours, at ambient temperature and in the open air. After 24 hours, the reaction medium turned dark brown.

(75) The reaction medium is taken up in a volume of dichloromethane or of ethyl acetate equal to 3 times the reaction volume, so as to extract therefrom the organic compounds (oligomers formed and unreacted starting reagents). The resulting organic phase is dried in the presence of anhydrous magnesium sulfate (MgSO.sub.4), filtered and concentrated under vacuum. A brown solid is obtained.

B/ANALYSIS OF THE ANTIOXIDANT POWER OF THE PHENOL POLYMERS

(76) The antioxidant power of the phenol polymers in accordance with the invention PDF 1000 and PDF 1500 was evaluated using the DPPH test, according to the protocol described in the publication by Brand-Williams et al., 1995 (Food Sci. Technol-Leb, 28, 25).

(77) By way of comparative examples, the antioxidant power of ferulic acid, and that of the compounds well known for their antioxidant power: butylhydroxyanisole (BHA), butylhydroxytoluene (BHT), gallic acid and gentisic acid, were tested under equivalent conditions.

(78) For each substance to be analyzed, concentrations between 0.12 and 0.0012510.sup.3 mol/l, in ethanol (77 l) as solvent, were tested in the presence of 3 ml of a solution in ethanol of DPPH (i.e. a DPPH concentration of 610.sup.5 mol/l). For each sample, the absorbance was measured as a function of time, and the % of DPPH remaining in solution was calculated.

(79) The results obtained after 435 min of reaction, i.e. until a stable value corresponding to a plateau is reached, are shown in table 2 below.

(80) TABLE-US-00002 TABLE 2 Values obtained in a DPPH test for phenol polymers in accordance with the invention Concentration Optical absorbance % of DPPH Polymer (10.sup.3 mol/l) of the DPPH remaining PDF 1000 0.03 0.5 13.88 0.01 0.16 22.71 0.005 0.083 46.53 0.0025 0.042 70.19 0.00125 0.021 85.33 PDF 1500 0.03 0.5 13.56 0.01 0.16 16.88 0.005 0.083 33.28 0.0025 0.042 59.46 0.00125 0.021 80.44

(81) The concentration of each compound making it possible to reduce by 50% the initial amount of DPPH (EC50) is deduced from the data obtained. This concentration is indicated in table 3 below.

(82) TABLE-US-00003 TABLE 3 EC50 concentrations measured using a DPPH test PDF PDF Ferulic Gallic Gentisic Compound 1000 1500 acid BHA BHT acid acid EC50 0.0865 0.069 0.38 0.24 0.24 0.08 0.09

(83) These results clearly show that the phenol polymer compounds in accordance with the invention PDF 1000 and PDF 1500 have an antioxidant power greater not only than ferulic acid, but also than the commonly used antioxidants BHA, BHT, gallic acid and gentisic acid.

C/PHENOL POLYMER TOXICITY TEST

(84) A test for toxicity with respect to estrogen receptors was carried out for the IDF, PDF, GDF and BDF macrobisphenols, according to the method set out in the publication by Molina-Molina et al., 2008 (Toxicol. Appl. Pharmacol., doi: 10.1016/j.taap.2008.07.017), on the HELN-ER cell line, described in the publication by Escande et al., 2006 (Biochemical Pharmacology, 71, 1459-1469).

(85) The results obtained, expressed as % of antagonist activity with respect to the activity of estradiol (E2) at 10 nM, as a function of the monomer concentration, are shown in FIG. 12. It is observed therein that the IDF, PDF, GDF and BDF macrobisphenols interact only very little with estrogen receptors. In comparison, the same experiment carried out for commercially available bisphenol A shows that the latter exhibits a percentage activity, at 10.sup.6 M, of 45%, and, at 10.sup.5 M, of 60%. The IDF, PDF, GDF and BDF macrobisphenols consequently exhibit an action that is much lower than bisphenol A, with respect to estrogen receptors.

(86) It can reasonably be deduced therefrom that the same is true for the polymers in accordance with the invention, of which these macrobisphenols constitute the base monomers.