NEW PHENOLIC POLYMERS AND PREPARATION PROCESSES THEREOF

Abstract

The present invention concerns the use of a compound having the following formula (I), for the preparation of a polymer. The present invention also concerns the polymers obtained from polymerization of compound of formula (I), and their processes of preparation.

##STR00001##

Claims

1. A process for the preparation of a polymer, comprising a step of polymerizing a compound having the following formula (I): ##STR00087## wherein: R.sub.1 is H or a OR.sub.7 group, R.sub.7 being H, a (C.sub.1-C.sub.10)alkyl group or a (C.sub.2-C.sub.6)alkenyl group; R.sub.2 is a (C.sub.1-C.sub.6)alkoxy group; R.sub.3 is H or a radical of formula (II) ##STR00088## k being an integer varying from 1 to 6; R.sub.4 is a (C.sub.1-C.sub.6)alkoxy group or a radical X chosen from the group consisting of: (C.sub.2-C.sub.6)alkenyl groups, (C.sub.1-C.sub.10)alkyl group, —CHO, —COOH, —CH.sub.2OH, and —COOR.sub.a, R.sub.a being a (C.sub.1-C.sub.6)alkyl group or a (C.sub.2-C.sub.12)alkenyl group; and wherein: when R.sub.1 is H, then R.sub.3 is a group of formula (II) and R.sub.4 is a (C.sub.1-C.sub.6)alkoxy group, and when R.sub.1 is a OR.sub.7 group, then R.sub.3 is H and R.sub.4 is X as defined above.

2. A compound susceptible to be obtained by polymerization of the compound of formula (I) as defined in claim 1, and of a monomer chosen from the group consisting of: diacids, diesters, diamines, and epoxy compounds.

3. A compound susceptible to be obtained by polymerization of the compound of formula (I) as defined in claim 1, comprising at least one repetitive unit U, wherein said unit U comprises a moiety having the following formula (III): ##STR00089## wherein: R.sub.1 represents OR.sub.7 group, R.sub.7 being H or a (C.sub.1-C.sub.10)alkyl group; R.sub.2 represents a (C.sub.1-C.sub.6)alkoxy group.

4. The compound of claim 2, having the following formula (IV): ##STR00090## wherein: A.sub.1 is chosen from the group consisting of: a (C.sub.2-C.sub.10)alkylene radical; a (C.sub.3-C.sub.12)cycloalkylene radical, optionally substituted by at least one (C.sub.1-C.sub.10)alkyl group; a (C.sub.2-C.sub.30)alkenylene radical; an arylene radical comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with a (C.sub.1-C.sub.10)alkyl group; a heteroarylene radical comprising from 5 to 14 carbon atoms and at least one heteroatom chosen from O, S and N, optionally substituted in ortho, meta or para with a (C.sub.1-C.sub.10)alkyl group; and a radical of formula —B.sub.1—B.sub.2—B.sub.3— wherein: B.sub.2 is a (C.sub.3-C.sub.12)cycloalkylene radical, in which one or more carbon atom(s) is optionally substituted by at least one (C.sub.1-C.sub.10)alkyl group, and B.sub.1 and B.sub.3, identical or different, are chosen from the (C.sub.2-C.sub.15)alkylene radicals; a radical of formula —B.sub.4—B.sub.5—, wherein B.sub.4 and B.sub.5, identical or different, are chosen from the arylene radicals comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with one or several substituents chosen from the (C.sub.1-C.sub.6)alkoxy groups; R.sub.2 is a (C.sub.1-C.sub.6)alkoxy group; R.sub.6 is (C.sub.1-C.sub.6)alkyl group; and n is an integer varying from 1 to 130.

5. A process for preparing a compound according to claim 4, comprising at least one step of polymerization of: a compound having the following formula (I-1): ##STR00091## wherein R.sub.2 and R.sub.6 are as defined in claim 4, and a compound of formula (V) R.sub.bOOC-A.sub.1-COOR.sub.b, wherein A.sub.1 is as defined in claim 4, and R.sub.b is H or a (C.sub.1-C.sub.6)alkyl group.

6. The process of claim 5, wherein the polymerization step is carried out in the presence of a catalyst chosen from the group consisting of: 5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), zinc acetate (ZnAc), Ti(OBu).sub.4, dibutyl tin oxide (DBTO), and mixtures thereof.

7. The compound of claim 2, having the following formula (IV-bis): ##STR00092## wherein: A.sub.4 is a (C.sub.2-C.sub.10)alkylene radical; R.sub.2 is a (C.sub.1-C.sub.6)alkoxy group; R.sub.6 is (C.sub.1-C.sub.6)alkyl group; and n is an integer varying from 1 to 40.

8. A process for preparing a compound according to claim 7, comprising at least one step of polymerization of: a compound having the following formula (I-2): ##STR00093## wherein R.sub.2 and R.sub.6 are as defined in claim 7, and a compound of formula (VIII):
HO-A.sub.4-OH  (VIII) wherein A.sub.4 is as defined in claim 7.

9. The process of claim 8, wherein the polymerization step is carried out in the presence of a catalyst chosen from the group consisting of: 5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), zinc acetate (ZnAc), Ti(OBu).sub.4, dibutyl tin oxide (DBTO), and mixtures thereof.

10. The compound of claim 2, having the following formula (VI): ##STR00094## wherein: A.sub.2 is chosen from the group consisting of: a (C.sub.2-C.sub.10)alkylene radical; a (C.sub.3-C.sub.12)cycloalkylene radical, optionally substituted by at least one (C.sub.1-C.sub.10)alkyl group; a (C.sub.2-C.sub.30)alkenylene radical; an arylene radical comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with a (C.sub.1-C.sub.10)alkyl group; a heteroarylene radical comprising from 5 to 14 carbon atoms and at least one heteroatom chosen from O, S, and N, optionally substituted in ortho, meta or para with a (C.sub.1-C.sub.10)alkyl group; and a radical of formula —B′.sub.1—B′.sub.2—B′.sub.3— wherein: B′.sub.2 is a (C.sub.1-C.sub.10)alkylene radical, and B′.sub.1 and B′.sub.3, identical or different, are chosen from the arylene radicals comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with a (C.sub.1-C.sub.10)alkyl group; R.sub.2 is a (C.sub.1-C.sub.6)alkoxy group; R.sub.6 is (C.sub.1-C.sub.6)alkyl group; and n is an integer varying from 1 to 100.

11. A process for preparing a compound according to claim 10, comprising at least one step of polymerization of: a compound having the following formula (I-3): ##STR00095## wherein R.sub.2 and R.sub.6 are as defined in claim 10, and a diamine of formula (VII) H.sub.2N-A.sub.2-NH.sub.2, A.sub.2 being as defined in claim 10.

12. A process for preparing a compound according to claim 2, comprising at least one step of polymerization of: a compound having the following formula (I-4): ##STR00096## wherein: R.sub.2 is a (C.sub.1-C.sub.6)alkoxy group, k is an integer varying from 1 to 6, R′ being a (C.sub.1-C.sub.6)alkoxy group; and a diamine of formula (X) H.sub.2N-A.sub.3-NH.sub.2, A.sub.3 being a radical of formula —B″.sub.1—B″.sub.2— wherein: B″.sub.1 is a (C.sub.3-C.sub.12)cycloalkylene radical, in which one or more carbon atom(s) is optionally substituted by at least one (C.sub.1-C.sub.10)alkyl group, and B″.sub.2 is a (C.sub.1-C.sub.10)alkylene radical.

13. The compound of claim 3, having the following formula (XI-A) or (XI-B): ##STR00097## wherein: R.sub.2 is a (C.sub.1-C.sub.6)alkoxy group; R.sub.6 is a (C.sub.1-C.sub.10)alkyl group, Y is chosen from the group consisting of: a bond, a (C.sub.1-C.sub.10)alkylene radical, a radical —C(O)O—R.sub.c— and —R.sub.c—O(O)C—, R.sub.c being a (C.sub.1-C.sub.10)alkylene radical; R.sub.8 is a (C.sub.1-C.sub.6)alkoxy group or a (C.sub.1-C.sub.10)alkyl group; and n is an integer varying from 10 to 120.

14. A process for preparing a compound according to claim 13, comprising at least one step of polymerization of a compound having the following formula (I-5): ##STR00098## wherein: R.sub.2 is as defined in claim 13; R′.sub.7 is chosen from the group consisting of: (C.sub.1-C.sub.10)alkyl groups and (C.sub.2-C.sub.6)alkenyl groups, and R.sub.9 is chosen from the group consisting of: (C.sub.1-C.sub.10)alkyl groups, (C.sub.2-C.sub.6)alkenyl groups, and —COOR.sub.a groups, R.sub.a being a (C.sub.2-C.sub.12)alkenyl group, wherein, when R.sub.7 is an alkyl group, then R.sub.9 is chosen from the (C.sub.2-C.sub.6)alkenyl groups and —COOR.sub.a groups, and when R.sub.7 is an alkenyl group, then R.sub.9 is an alkyl group.

15. The process of claim 14, wherein the polymerization step is carried out in the presence of a Grubbs catalyst.

16. The compound of claim 2, having the following formula (XII): ##STR00099## wherein: A.sub.2 is chosen from the group consisting of: a (C.sub.2-C.sub.10)alkylene radical; a (C.sub.3-C.sub.12)cycloalkylene radical, optionally substituted by at least one (C.sub.1-C.sub.10)alkyl group; a (C.sub.2-C.sub.30)alkenylene radical; an arylene radical comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with a (C.sub.1-C.sub.10)alkyl group; a heteroarylene radical comprising from 5 to 14 carbon atoms and at least one heteroatom chosen from O, S, and N, optionally substituted in ortho, meta or para with a (C.sub.1-C.sub.10)alkyl group; and a radical of formula —B′.sub.1—B′.sub.2—B′.sub.3— wherein: B′.sub.2 is a (C.sub.1-C.sub.10)alkylene radical, and B′.sub.1 and B′.sub.3, identical or different, are chosen from the arylene radicals comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with a (C.sub.1-C.sub.10)alkyl group; R.sub.2 is a (C.sub.1-C.sub.6)alkoxy group; R.sub.7 is H, a (C.sub.1-C.sub.10)alkyl group or a (C.sub.2-C.sub.6)alkenyl group; and n is an integer varying from 1 to 100.

17. A process for preparing a compound according to claim 16, comprising at least one step of polymerization of: a compound having the following formula (I-6): ##STR00100## wherein R.sub.2 and R.sub.7 are as defined in claim 16, and a diamine of formula (VII) H.sub.2N-A.sub.2-NH.sub.2, A.sub.2 being as defined in claim 16.

Description

EXAMPLES

[0241] Suppliers

[0242] Triazobycyclodecene, Zinc acetate, Dibutyltin oxide, Titanium butoxide, Grubbs 1.sup.st generation catalyst, Grubbs 2.sup.nd generation catalyst, Hoveyda Grubbs 1.sup.st generation catalyst, Hoveyda Grubbs 2.sup.nd generation catalyst, Succinic acid, Dimethyl succinate, Dimethyl terephthalate, 4,4′-methylenedianiline were purchased at Sigmal Aldrich. Sebacic acid and 1,6-diaminohexane were bought at Alfa Aesar. 2,5-furandicarboxylic acid, 1,1-diaminodecane and dimethylsebacate were supplied by TCI. Polarclean (methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate) and Pripol were respectively supplied at Solvay and Croda. Maleic acid, terephtalic acid and Isophorone diamine were respectively purchased at Merck, Prolabo and Fisher.

Example 1: Preparation of Polyesters (P1 to P8) by Esterification

[0243] General Procedure

[0244] Diol (1 equivalent) and diester (or diacid) (1 equivalent) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 0.5 mol % of titanium butoxide

[0245] The following polymers were prepared according to this procedure:

##STR00050## ##STR00051##

P1 synthesis

[0246] 0.5 g of methylated divanillyl diol (1.39 mmol) and 0.28 g of sebacid acid (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide 0.5 mol %.

[0247] P2 Synthesis

[0248] 0.5 g of methylated divanillyl diol (1.39 mmol) and 0.75 g of Pripol (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide 0.5 mol %.

[0249] P3 Synthesis

[0250] 0.5 g of methylated divanillyl diol (1.39 mmol) and 0.51 g of C22 diacid (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide 0.5 mol %.

[0251] P4 Synthesis

[0252] 0.5 g of methylated divanillyl diol (1.39 mmol) and 0.16 g of succinic acid (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide 0.5 mol %.

[0253] P5 synthesis

[0254] 0.5 g of methylated divanillyl diol (1.39 mmol) and 0.16 g of maleic acid (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide 0.5 mol %.

[0255] P6 Synthesis

[0256] 0.5 g of methylated divanillyl diol (1.39 mmol) and 0.23 g of terephtalic acid (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide 0.5 mol %.

[0257] P7 Synthesis

[0258] 0.5 g of methylated divanillyl diol (1.39 mmol) and 0.18 g of 2,5-furandicarboxylic acid (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide 0.5 mol %.

TABLE-US-00001 TABLE 1 Thermomechanical properties of polymers from methylated divanillyl diol and different diacids T.sub.g TD5% Diol Diacid Catalyst (° C.).sup.a (° C.).sup.b Polymer [00052] [00053] TiOBu.sub.4 0, 5%  19 297 P1 [00054] −5  284 P2 [00055]  13 260 P3 [00056]  90 270 P4 [00057]  97 240 P5 [00058] 113 260 P6 [00059] 140 260 P7 .sup.aT.sub.g (glass transition temperature) determined by DSC second heating cycle .sup.bTD5% .sup.(Temperature of 5% degradation) determined by TGA.

[0259] Differential Scanning Calorimetry (DSC) measurements were performed on DSC Q100 (TA Instruments). The sample was heated from −70° C. to 200° C. at a rate of 10° C. min.sup.−1. Consecutive cooling and second heating run were also performed at 10° C. min.sup.−1. The glass transition temperatures (Tg) were calculated from the second heating run.

[0260] Thermogravimetric analyses (TGA) were performed on TGA-Q50 system from TA instruments at a heating rate of 10° C. min.sup.−1 under air between 20° C. and 800° C. TD5%=Temperature at which 5% of the material is degraded.

Example 2: Preparation of Polyester P1 by Transesterification

[0261] General Procedures

[0262] Methylated divanillic diol (1 equivalent) and dimethyl sebacate (1 equivalent) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2 mol % of catalyst (titanium butoxide, zinc acetate or dibutyltin oxide) or in the presence of 0.5 mol % of titanium butoxide.

[0263] According to another variant, methylated divanillic diol (1 equivalent) and dimethyl sebacate (1 equivalent) were stirred at 120° C. for 24 h in the presence of 10 mol % of TBD.

[0264] Polymers from Methylated Divanillyl Diol and Methyl Sebacate (P1) Using Different Catalysts (See Table 2 Below)

[0265] TBD10%

[0266] 0.5 g of methylated divanillyl diol (1.39 mmol) and 0.32 g of dimethyl sebacate (1.39 mmol) were stirred at 120° C. for 24 h in the presence of 19.3 mg of TBD −5% mol per ester function)

[0267] TiOBu.sub.4 0.5%

[0268] 0.5 g of methylated divanillyl diol (1.39 mmol) and 0.32 g of dimethyl sebacate (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide (0.25 mol % catalyst relative per ester function).

[0269] TiOBu.sub.4 2%

[0270] 0.5 g of methylated divanillyl diol (1.39 mmol) and 0.32 g of dimethyl sebacate (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 9.6 mg of Titanium butoxide (1 mol % catalyst relative per ester function).

[0271] ZnAc 2%

[0272] 0.5 g of methylated divanillyl diol (1.39 mmol) and 0.32 g of dimethyl sebacate (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 6 mg of ZnAc (1 mol % catalyst relative per ester function).

[0273] DBTO 2%

[0274] 0.5 g of methylated divanillyl diol (1.39 mmol) and 0.32 g of dimethyl sebacate (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 6.9 mg of DBTO (1 mol % catalyst relative per ester function).

TABLE-US-00002 TABLE 2 Properties of polymers from methylated divanillyl diol and methyl sebacate using different catalysts Catalyst T.sub.g TD5% M.sub.n.sup.b Diol Methylsebacate (diester) (% by mol) (° C.).sup.a (° C.).sup.c (g/mol).sup.b [00060] [00061] TBD 10% 14 299 33000 1.6 TiOBu.sub.4 0, 5% 34 319 65000 2.1 TiOBu.sub.4 2% 36 301 30000 2 ZnAc 2% 45 311 43000 1.8 DBTO 2% 25 319 44000 1.9 .sup.adetermined by DSC second heating cycle .sup.bdetermined by SEC in DMF/DMSO 80/20 .sup.cdetermined by TGA. (TD5%: Temperature of 5% degradation)

[0275] Size exclusion chromatography (SEC) analysis was performed at room temperature in DMF/DMSO using simultaneous UV and refraction index detections. The elution times were converted to molar mass using a calibration curve based on low dispersity (=M.sub.n/M.sub.w) polystyrene (PS) standards.

[0276] Differential Scanning Calorimetry (DSC) measurements were performed on DSC Q100 (TA Instruments). The sample was heated from −70° C. to 200° C. at a rate of 10° C. min.sup.−1. Consecutive cooling and second heating run were also performed at 10° C. min.sup.−1. The glass transition temperatures (Tg) were calculated from the second heating run.

[0277] Thermogravimetric analyses (TGA) were performed on TGA-Q50 system from TA instruments at a heating rate of 10° C. min-1 under air between 20° C. and 800° C. TD5%=Temperature of 5% degradation.

Example 3: Preparation of Polyester P9 by Transesterification

[0278] General Procedure

[0279] Methylated dimethyl vanillate (1 equivalent) and 1,10-decanediol (1 equivalent) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2 mol % of catalyst (titanium butoxide, zinc acetate or dibutyltin oxide) or in the presence of 0.5 mol % of titanium butoxide.

[0280] According to another variant, methylated dimethyl vanillate (1 equivalent) and 1,10-decanediol (1 equivalent) were stirred at 120° C. for 24 h in the presence of 10 mol % of TBD.

##STR00062##

[0281] Polymers Obtained from Methylated Dimethylvanillate and Decanediol Using Different Catalysts

[0282] TiOBu.sub.4 2%

[0283] 0.5 g methylated dimethyldivanillate (1.28 mmol) and 0.23 g of 1,10-decanediol (1.28 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 8.7 mg of Titanium butoxide (1 mol % catalyst relative per ester function).

[0284] DBTO 2%

[0285] 0.5 g methylated dimethyldivanillate (1.28 mmol) and 0.23 g of 1,10-decanediol (1.28 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 6.3 mg of DBTO (1 mol % catalyst relative per ester function).

[0286] TBD 10%

[0287] 0.5 g methylated dimethyldivanillate (1.28 mmol) and 0.23 g of 1,10-decanediol (1.28 mmol) (1.39 mmol) were stirred at 120° C. for 24 h in the presence of 17.8 mg of TBD −5% mol per ester function)

[0288] ZnAc 2%

[0289] 0.5 g methylated dimethyldivanillate (1.28 mmol) and 0.23 g of 1,10-decanediol (1.28 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 4.7 mg of ZnAc (1 mol % catalyst relative per ester function).

[0290] TiOBu.sub.4 0.5%

[0291] 0.5 g methylated dimethyldivanillate (1.28 mmol) and 0.23 g of 1,10-decanediol (1.28 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.2 mg of Titanium butoxide (0.25 mol % catalyst relative per ester function).

TABLE-US-00003 TABLE 3 Properties of polymers obtained from methylated dimethylvanillate and decanediol using different catalysts Methylated Catalyst T.sub.g TD5% M.sub.n dimethyldivanilate Decanediol (mol %) (° C.).sup.a (° C.).sup.c (g/mol).sup.b [00063] [00064] TiOBu.sub.4 2% 38 273 11000 1.3 DBTO 2% 43 319 12000 1.6 TBD 10% 36 253  3000 1.2 ZnAc 2% 13 205  3000 1.0 TiOBu.sub.4 0, 5% 32 300 20000 1.7 .sup.adetermined by DSC second heating cycle .sup.bdetermined by SEC in DMF/DMSO 80/20 .sup.cdetermined by TGA. Temperature of 5% degradation

[0292] Differential Scanning Calorimetry (DSC) measurements were performed on DSC Q100 (TA Instruments). The sample was heated from −70° C. to 200° C. at a rate of 10° C. min.sup.−1. Consecutive cooling and second heating run were also performed at 10° C. min.sup.−1. The glass transition temperatures (Tg) were calculated from the second heating run.

[0293] Thermogravimetric analyses (TGA) were performed on TGA-Q50 system from TA instruments at a heating rate of 10° C. min.sup.−1 under air between 20° C. and 800° C. TD5%=Temperature of 5% degradation.

[0294] Size exclusion chromatography (SEC) analysis was performed at room temperature in DMF/DMSO using simultaneous UV and refraction index detections. The elution times were converted to molar mass using a calibration curve based on low dispersity (=M.sub.n/M.sub.w) polystyrene (PS) standards.

Example 4: Preparation of Polyester P1 to P′8 by Transesterification

[0295] The general procedure is identical to example 1.

[0296] The polymers P′1 to P′8 possess a structure similar to the one of polymers P1 to P8, except that the value of the repetitive units (n) differs, leading to polymers with various properties.

[0297] P′1 Synthesis

[0298] 0.5 g of methylated divanillyl diol (1.39 mmol) and 0.32 g of dimethyl sebacate (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide (0.25 mol % catalyst relative per ester function).

[0299] P2 Synthesis

[0300] 0.5 g of methylated divanillyl diol (1.39 mmol) and 0.79 g of Pripol ester (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide (0.25 mol % catalyst relative per ester function).

[0301] P′3 Synthesis

[0302] 0.5 g of methylated divanillyl diol (1.39 mmol) and 0.54 g of C22 diester (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide (0.25 mol % catalyst relative per ester function).

[0303] P′4 Synthesis

[0304] 0.5 g of methylated divanillyl diol (1.39 mmol) and 0.20 g of dimethyl succinate (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide (0.25 mol % catalyst relative per ester function).

[0305] P′6 Synthesis

[0306] 0.5 g of methylated divanillyl diol (1.39 mmol) and 0.27 g of dimethyl terephtalate (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide (0.25 mol % catalyst relative per ester function).

[0307] P′7 Synthesis

[0308] 0.5 g of methylated divanillyl diol (1.39 mmol) and 0.26 g of 2,5-furandicarboxylic acid (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide (0.25 mol % catalyst relative per ester function).

[0309] P′8 Synthesis

[0310] 0.5 g of methylated divanillyl diol (1.39 mmol) and 0.54 g of methylated dimethyldivanillate (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide (0.25 mol % catalyst relative per ester function).

TABLE-US-00004 TABLE 4 Thermomechanical properties of polymers from of methylated divanillyl diol and different methyldiesters (with catalyst TiOBu.sub.4 0.5%) T.sub.g TD5% E′ Diester (° C.).sup.a (° C.).sup.c (GPa).sup.b Polymers [00065]  5 308 2.0 P3′ [00066] 101 310 2.0 P6′ [00067]  68 302 5.1 P4′ [00068] −5 347 0.1 P2′ [00069] 140 342 1.4 P7′ [00070]  38 319 8.1 P1′ [00071] 102 305 1.3 P8′ .sup.aDetermined by DSC second heating cycle .sup.bDetermined by DMA 3 points flexion .sup.cDetermined by TGA. Temperature of 5% degradation

[0311] Differential Scanning Calorimetry (DSC) measurements were performed on DSC Q100 (TA Instruments). The sample was heated from −70° C. to 200° C. at a rate of 10° C. min.sup.−1. Consecutive cooling and second heating run were also performed at 10° C. min.sup.−1. The glass transition temperatures (Tg) were calculated from the second heating run.

[0312] Thermogravimetric analyses (TGA) were performed on TGA-Q50 system from TA instruments at a heating rate of 10° C. min.sup.−1 under air between 20° C. and 800° C. TD5%=Temperature of 5% degradation.

[0313] The mechanical properties were measured with a dynamic mechanical thermal analyzer DMA RSA 3 (TA instrument). The sample temperature was modulated from −80° C. to 220° C., depending on the sample at a heating rate of 5° C./min. The measurements were performed in a 3-point bending mode at a frequency of 1 Hz, an initial static force varying between 0.1 and 0.5 N and a strain sweep of 0.1%.

Example 5: Preparation of Polyamides P10 to P12

[0314] General Procedure

[0315] Equimolar amount of diacids and diamines were dissolved in ethanol and the mixture was stirred slowly for 30 min at 80° C. to allow the formation of ammonium salt. The salt was obtained as a fine powder after elimination of the solvent and dried under vacuum. The salt was warmed at 230° C. for 4 h.

[0316] The following polyamides were synthesized:

##STR00072##

TABLE-US-00005 TABLE 5 Thermomechanical properties of polyamides synthesized from methylated divanillic diacid and different diamines Tg Diacid Diamine (° C.).sup.a Name [00073] [00074] 124 P10 [00075] 136 P11 [00076] 157 P12 .sup.aDetermined by DSC second heating cycle

[0317] Differential Scanning Calorimetry (DSC) measurements were performed on DSC Q100 (TA Instruments). The sample was heated from −70° C. to 200° C. at a rate of 10° C. min.sup.−1. Consecutive cooling and second heating run were also performed at 10° C. min.sup.−1. The glass transition temperatures (Tg) were calculated from the second heating run.

Example 6: Preparation of Epoxy Resin Synthesis

[0318] General Procedure

[0319] Bisepoxide and diamine were mixed together in ethanol. After evaporation of the solvent the mixture is poured into a matrix and warmed at 80° C. for 4 h.

TABLE-US-00006 TABLE 6 Thermomechanical properties of Epoxy resins Ratio Epoxy group/H of amine = 1 E′ Tα Tg.sup.b (GPa) TD5% TD30% Bisepoxy Diamine (° C.).sup.a (° C.) 25° C..sup.b (° C.) (° C.) [00077] [00078] 112 126 1.1 312 337 .sup.aobtained from DMA .sup.bobtained from DSC

[0320] DMA RSA 3 (TA instrument). The sample temperature was modulated from −80° C. to 220° C., depending on the sample at a heating rate of 5° C./min. The measurements were performed in a 3-point bending mode at a frequency of 1 Hz, an initial static force varying between 0.1 and 0.5 N and a strain sweep of 0.1%.

[0321] Differential Scanning Calorimetry (DSC) measurements were performed on DSC Q100 (TA Instruments). The sample was heated from −70° C. to 200° C. at a rate of 10° C. min.sup.−1. Consecutive cooling and second heating run were also performed at 10° C. min.sup.−1. The glass transition temperatures (Tg) were calculated from the second heating run.

[0322] Thermogravimetric analyses (TGA) were performed on TGA-Q50 system from TA instruments at a heating rate of 10° C. min.sup.−1 under air between 20° C. and 800° C. TD5%=Temperature of 5% degradation.

Example 7: Preparation of Unsaturated Polyesters

[0323] General Procedure

[0324] Unsaturated dimer (0.22 mmol) was dissolved in 1 mL of Polarclean. Grubbs catalyst (2% mol) was added to the flask. The flask was heated at 80° C. under vacuum for 18 h. Then 1 mL of ethyl vinyl ether was introduced to the flask to quench the reaction. The final polymer was diffolved into 1 mL of THF and reprecipitated in cold methanol.

[0325] The following polymers were synthesized:

##STR00079##

TABLE-US-00007 TABLE 7 Thermomechanical properties of polyesters by ADMET resins M.sub.n T.sub.g TD5% Monomer Catalyst (g/mol) (° C.).sup.a (° C.) Polymer [00080] HG1  7000 1.1 17 250 P14 [00081] HG2 40000 1.7 50.4 330 P15 [00082] HG2 29000 1.7 160 380 P16 [00083] HG2 10000 1.6 4.0 310 P17

[0326] The catalysts mentioned in table 7 are the following:

##STR00084## ##STR00085##

[0327] Differential Scanning Calorimetry (DSC) measurements were performed on DSC Q100 (TA Instruments). The sample was heated from −70° C. to 200° C. at a rate of 10° C. min.sup.−1. Consecutive cooling and second heating run were also performed at 10° C. min.sup.−1. The glass transition temperatures (Tg) were calculated from the second heating run.

[0328] Thermogravimetric analyses (TGA) were performed on TGA-Q50 system from TA instruments at a heating rate of 10° C. min.sup.−1 under air between 20° C. and 800° C. TD5%=Temperature of 5% degradation.

[0329] Size exclusion chromatography (SEC) analysis was performed at room temperature in DMF/DMSO using simultaneous UV and refraction index detections. The elution times were converted to molar mass using a calibration curve based on low dispersity (=M.sub.n/M.sub.w) polystyrene (PS) standards.

Example 8: Preparation of Polyimines

[0330] The polyimines of formula (XII) as mentioned above are prepared by reacting divanilline with a diamine.

[0331] The monomers are mixed in stoichiometric amounts in the presence of a solvent (toluene, CH.sub.3Cl) (5 mg/mL). The mixture of the monomers in the solvent is heated at reflux for 3 days in a Dean-Stark apparatus.

[0332] Then, the polymer thus obtained is washed with methanol and fractionated with a Soxhlet extractor.

[0333] The following reaction is carried out:

##STR00086##

[0334] R being H.

[0335] The polymer thus obtained has a Mn of 3 525 g.Math.mol.sup.−1 and =1.4.

[0336] The same method could be carried out by using microwaves.