Hydrocarbon polymers comprising two exo-vinylene cyclic carbonate terminal groups

Abstract

The invention relates to a hydrocarbon polymer comprising two exo-vinylene cyclic carbonate terminal groups, of formula (1), production method thereof and use of same for the production of coating, mastic and adhesive compositions.

Claims

1. A hydrocarbon-based polymer comprising two exo-vinylene cyclocarbonate end groups, said hydrocarbon-based polymer being of formula (1) below: ##STR00041## wherein: each bond noted is a carbon-carbon single bond geometrically oriented on one side or the other relative to the double bond to which it is bonded; the groups R1, R2, R3, R4, R5, R6, R7 and R8, which may be identical or different, are selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a heteroalkyl group, an alkoxycarbonyl group and a heteroalkoxycarbonyl group; at least one of the groups R1 to R8 optionally forms part of the same saturated or unsaturated hydrocarbon-based ring or heterocycle, with at least one other of the groups R1 to R8; at least one of the pairs (R1,R2), (R3,R4), (R5,R6) and (R7,R8) optionally is an oxo group; x and y, which may be identical or different, are integers within a range from 0 to 5; the groups R13, R14, R15 and R16, which may be identical or different, are selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a heteroalkyl group, an alkoxycarbonyl group and a heteroalkoxycarbonyl group; at least one of the groups R13 to R16 optionally forms part of the same saturated or unsaturated hydrocarbon-based ring or heterocycle, with at least one other of the groups R13 to R16; the group R17 comprises CH.sub.2, O, S, C(O) or NR.sub.0, R.sub.0 being an alkyl group comprising from 1 to 22 carbon atoms; and n comprises an integer greater than or equal to 2 and m comprises an integer greater than or equal to 0, wherein the mole ratio m/n is within a range from 0/100 to 90/10; n and m are also such that the number-average molar mass Mn of the hydrocarbon-based polymer of formula (1) is within a range from 400 to 50 000 g/mol; F1 is represented by the following formula: ##STR00042## and F2 is represented by the following formula: ##STR00043## wherein: p1 and p2, which may be identical or different, each represent an integer equal to 0, 1, 2 or 3; X is an oxygen atom or a nitrogenous group NR12 in which R12 is a C1-C6 alkyl group; A is a C1-C6 alkylene group; R9 comprises a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkyl group oxyalkylenated with one or more C1-C6 oxyalkylene groups, a C5-C6 cycloalkyl group, a phenyl group or an alkylphenyl group with a C1-C4 alkyl chain; and R10 and R11, which may be identical or different, each comprise a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkyl group oxyalkylenated with one or more C1-C6 oxyalkylene groups, a C5-C6 cycloalkyl group, a phenyl group or an alkylphenyl group with a C1-C4 alkyl chain.

2. The hydrocarbon-based polymer comprising two exo-vinylene cyclocarbonate end groups as claimed in claim 1, wherein m is equal to 0, the polymer being of formula (2) below: ##STR00044## wherein: x, y, n, F1, F2, R1, R2, R3, R4, R5, R6, R7 and R8 are as defined in claim 1.

3. The hydrocarbon-based polymer comprising two exo-vinylene cyclocarbonate end groups as claimed in claim 1, wherein X is an oxygen atom.

4. The hydrocarbon-based polymer comprising two exo-vinylene cyclocarbonate end groups as claimed in claim 1, wherein X is a group NR12 wherein R12 is as defined in claim 1.

5. The hydrocarbon-based polymer comprising two exo-vinylene cyclocarbonate end groups as claimed in claim 1, wherein R12 is a methyl group.

6. The hydrocarbon-based polymer comprising two exo-vinylene cyclocarbonate end groups as claimed in claim 1, wherein R9 is a hydrogen atom, R10 and R11 are methyl groups, and p1=0 or p2=0.

7. The hydrocarbon-based polymer comprising two exo-vinylene cyclocarbonate end groups as claimed in claim 1, wherein p1=p2=0.

8. A process for preparing at least one hydrocarbon-based polymer comprising two exo-vinylene cyclocarbonate end groups as claimed in claim 1, said process comprising at least one step of ring-opening metathesis polymerization, in the presence of: at least one metathesis catalyst, at least one mono- or di-exo-vinylene cyclocarbonate chain-transfer agent of formula (C1) or (C2), respectively, below: ##STR00045## wherein: F1 and F2 are as defined in claim 1, and the bond is a carbon-carbon single bond geometrically oriented on one side or the other relative to the double bond in formula (C2); at least one compound of formula (A) below: ##STR00046## wherein the groups R1, R2, R3, R4, R5, R6, R7 and R8, and x and y are as defined in claim 1; and optionally, at least one compound of formula (B): ##STR00047## wherein the groups R13, R14, R15 and R16 are as defined in claim 1; for a reaction time ranging from 2 to 24 hours and at a temperature within a range from 20 to 60 C.

9. The preparation process as claimed in claim 8, said process being such that the mole ratio of the CTA of formula (C1) to the compound of formula (A), or to the sum of the compounds of formulae (A) and (B), if the compound of formula (B) is present, is within a range from 110.sup.3 to 1.0 or the mole ratio of the CTA of formula (2) to the compound of formula (A), or to the sum of the compounds of formulae (A) and (B), if the compound of formula (B) is present, is within a range from 0.510.sup.3 to 0.5.

10. A process for preparing polyurethane, comprising the reaction of at least one hydrocarbon-based polymer of formula (1) as claimed in claim 1 with at least one compound comprising at least one amine group.

Description

EXAMPLES

(1) The examples that follow illustrate the invention without, however, limiting its scope.

I) Examples 1 to 9: Synthesis of a Polymer Bearing Exo-Vinylene Cyclocarbonate End Groups According to the Invention

(2) The hydrocarbon-based polymers bearing exo-vinylene cyclocarbonate end groups of Examples 1 to 9 were obtained by means of the following steps:

(3) 1a step of synthesis of the cycloolefin(s) of formulae (A) and/or (B),

(4) 2a step of synthesis of the transfer agent (CTA) of formula (C1) or (C2),

(5) 3a step of ring-opening metathesis polymerization of a cycloolefin of formula (A) and optionally of a compound of formula (B) in the presence of a Grubbs catalyst and of the transfer agent, step 1 preferably being optional when the cycloolefin(s) of formulae (A) and (B) are commercially available.

(6) The ring-opening metathesis polymerization reactions performed in Examples 1 to 9 are represented by the general schemes (3) and (4), using, respectively, a monofunctional CTA (C1) and a difunctional CTA (C2), and will be explained in each individual case in the examples.

(7) ##STR00020##

(8) ##STR00021##

(9) In these schemes (3) and (4): 1 equiv. means one equivalent and corresponds to the amount of metathesis catalyst used; DCM means dichloromethane; (A) and (B) are the cycloolefins corresponding, respectively, to formulae (A) and (B) defined previously; (C1) and (C2) are the transfer agents corresponding, respectively, to formulae (C1) and (C2) defined previously; the bond is a carbon-carbon single bond geometrically oriented on one side or the other relative to the double bond (cis or trans) for (C2); G2 is the metathesis catalyst of formula (G2) as defined previously; F1 and F2 are identical and both correspond: either to the group of ester type below:

(10) ##STR00022## or to the group of amide type:

(11) ##STR00023## in which: p=p1 or p2, and A, R9, R10 and R11 are as defined previously; n is the number of moles of cycloolefin(s) of formula (A); m is the number of moles of cycloolefin(s) of formula (B); q is the number of moles of CTA of formula (C1) or (C2).

(12) The number of monomer units in the polymer obtained on conclusion of the polymerization reaction is equal to n+m.

(13) In each of the Examples 1 to 9 described below, the reaction lasts 24 hours (h) at a temperature of 40 C.

(14) All the polymerizations were performed in a similar manner. The only differences lie in the nature and the initial concentration of the chain-transfer agent(s) (CTA) of type (C1) or (C2) used.

(15) The CTAs used in Examples 1 to 9 are the following:

[(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene)propyl] acrylate (noted CTA.SUP.1.)

(16) ##STR00024##
(which corresponds to a CTA of formula (C1) in which: p1=0, X is an oxygen atom, A is an ethylene group CH2-CH2-, R9 is a hydrogen atom, R10 and R11 are methyl groups);

[N-methyl(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene)propyl]acrylamide (noted CTA.SUP.2.)

(17) ##STR00025##
(which corresponds to a CTA of formula (C1) in which: p1=0, X is an NCH3 group with R12 being a methyl group, A is an ethylene group CH2-CH2-, R9 is a hydrogen atom, R10 is a methyl group, R11 and R12 are methyl groups);

bis[(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene)propyl] fumarate (noted CTA.SUP.3.)

(18) ##STR00026##
(which corresponds to a CTA of formula (C2) in which: p1=p2=0, X is an oxygen atom, A is an ethylene group CH2-CH2-, R9 is a hydrogen atom, R10 and R11 are methyl groups); and

bis[(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene)propyl]fumaramide (noted CTA.SUP.4.)

(19) ##STR00027##
(which corresponds to a CTA of formula (C2) in which: p1=p2=0, X is an NCH3 group with R12 being a methyl group, A is an ethylene group CH2-CH2-, R9 is a hydrogen atom, R10 and R11 are methyl groups).

(20) Two reaction possibilities (i and ii) exist, depending on whether the cycloolefin of formula (A) is used alone (Examples 1 to 7) or depending on whether the cycloolefins of formulae (A) and (B) are used as a mixture (Examples 8 and 9).

iExamples 1 to 7: Polymerization of the Cycloolefins of Formula (A)

(21) The cycloolefins of formula (A) used in Examples 1 to 7 are as follows:

(22) ##STR00028##

(23) Cyclooctene (COE) and 5,6-epoxycyclooctene (5-epoxyCOE) are commercial products from the company Sigma-Aldrich.

(24) 5-Oxocyclooctene (5-O=COE) and 5-n-hexylcyclooctene (5-hexyl-COE) may be synthesized from 5,6-epoxycyclooctene (5-epoxy-COE) according to the route indicated in reaction scheme (5) below:

(25) ##STR00029##

(26) 5-Oxocyclooctene (5-O=COE, referenced 2 in scheme (5) above) was synthesized according to the procedure indicated in the publication by A. Diallo et al., Polymer Chemistry, Vol. 5, Issue 7, 7 Apr. 2014, pages 2583-2591 (which referred to Hillmyer et al., Macromolecules, 1995, 28, pages 6311-6316).

(27) 5-Hexylcyclooctene (5-hexyl-COE referenced 5 in scheme (5) above) was synthesized according to the procedure indicated in the abovementioned publication by A. Diallo et al., Polymer Chemistry (which referred to Kobayashi et al., J. Am. Chem. Soc., 2011, 133, pages 5794-5797).

(28) The starting materials, reagents and solvents used for the synthesis of these cycloolefins of formula (A) are commercially available from the company Sigma-Aldrich.

(29) In the examples that follow: the NMR spectra were recorded on Brker AM-500 and Brker AM-400 spectrometers, at 298 K in CDCl.sub.3. The chemical shifts were referenced with respect to tetramethylsilane (TMS) using the (.sup.1H) or (.sup.13C) resonance of the deuterated solvents. the number-average and weight-average molar masses (M.sub.n and M.sub.w) and the polydispersity PDI (M.sub.w/M.sub.n) of the polymers were determined by size exclusion chromatography (SEC), with PS calibration using a Polymer Laboratories PL-GPC 50 machine.

Example 1: Synthesis of a Polymer Comprising Two [(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene)propyl] ester End Groups Starting with cyclooctene (COE) and [(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene)propyl] acrylate (CTA.SUP.1.)

(30) The reaction was performed according to scheme (6) below, in a mole ratio m/n equal to 0/100 and according to the procedure described below:

(31) ##STR00030##
Procedure:

(32) The cycloolefin of formula (A) (108.00 mmol), hydroquinone (0.54 mmol) and dry CH.sub.2Cl.sub.2 (50 mL) were mixed in a 1000 mL round-bottomed flask. The round-bottomed flask and its contents were then placed under argon. The CTA (10.80 mmol) of type (C1) was introduced into the round-bottomed flask using a syringe. The round-bottomed flask was then immersed in an oil bath at 40 C. and the catalyst G2 (54.00 mol) in solution in CH.sub.2Cl.sub.2 (20 mL) was then immediately added using a cannula. 24 hours after the addition of the catalyst, the product is extracted from the round-bottomed flask after evaporating off the solvent under vacuum. The product is then recovered after precipitating from methanol, filtering and drying at 20 C. under vacuum.

(33) Results:

(34) The polymer obtained is solid at room temperature.

(35) The degree of conversion of the cycloolefin of formula (A) determined by NMR (expressed in %), the number-average molar mass of the polymer obtained (expressed in grams per mol) and the polydispersity (PDI) of said polymer, determined by SEC, gave the following results:

(36) TABLE-US-00001 TABLE 1 Conversion Mn.sub.SEC Test no. [A]/[CTA.sup.1]/[Ru] (mol/mol) A (%) (g/mol) PDI 1 2 000/200/1 100 4 600 1.53 The .sup.1H (CDCl.sub.3, 500 MHz, 298 K) and .sup.13C (CDCl.sub.3, 100 MHz, 298 K) NMR analyses for the polymer obtained for this test confirmed the structure of the expected polymer as represented in scheme (6).

Example 2: Synthesis of a Polymer Comprising Two [N-methyl(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene)propyl]amide End Groups Starting with cyclooctene (COE) and [N-methyl(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene)propyl]acrylamide (CTA.SUP.2.)

(37) The reaction was performed according to scheme (7) below, in a mole ratio m/n equal to 0/100 and according to the procedure of Example 1:

(38) ##STR00031##
Results:

(39) The polymer obtained is solid at room temperature.

(40) The degree of conversion of the cycloolefin of formula (A) determined by NMR (expressed in %), the number-average molar mass of the polymer obtained (expressed in grams per mol) and the polydispersity (PDI) of said polymer, determined by SEC, gave the following results:

(41) TABLE-US-00002 TABLE 2 Conversion Mn.sub.SEC Test no. [A]/[CTA.sup.2]/[Ru] (mol/mol) A (%) (g/mol) PDI 2 2 000/200/1 100 4 900 1.49 The .sup.1H (CDCl.sub.3, 500 MHz, 298 K) and .sup.13C (CDCl.sub.3, 100 MHz, 298 K) NMR analyses for the polymer obtained for this test confirmed the structure of the expected polymer as represented in scheme (7).

Example 3: Synthesis of a Polymer Comprising Two [(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene)propyl] ester End Groups Starting with cyclooctene (COE) and bis[(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene)propyl] fumarate (CTA.SUP.3.)

(42) The reaction was performed according to scheme (8) below, in a mole ratio m/n equal to 0/100 and according to the procedure described below:

(43) ##STR00032##
Procedure:

(44) The cycloolefin of formula (A) (108.00 mmol), hydroquinone (0.54 mmol) and dry CH.sub.2Cl.sub.2 (50 mL) were mixed in a 1000 mL round-bottomed flask. The round-bottomed flask and its contents were subsequently placed under argon. The CTA (5.40 mmol) of type (C2) was introduced into the round-bottomed flask using a syringe. The round-bottomed flask was then immersed in an oil bath at 40 C., and the catalyst G2 (54.00 mol) in solution in CH.sub.2Cl.sub.2 (20 mL) was then immediately added using a cannula. 24 hours after the addition of the catalyst, the product is extracted from the round-bottomed flask after evaporating off the solvent under vacuum. The product is then recovered after precipitating from methanol, filtering and drying at 20 C. under vacuum.

(45) Results:

(46) The polymer obtained is solid at room temperature.

(47) The results for the degree of conversion of the cycloolefin of formula (A) determined by NMR (expressed in %), the number-average molar mass of the polymer obtained (expressed in grams per mol) and the polydispersity (PDI) of said polymer, determined by SEC, are given in table 3 below.

(48) The .sup.1H (CDCl.sub.3, 500 MHz, 298 K) and .sup.13C (CDCl.sub.3, 100 MHz, 298 K) NMR analyses for the polymer obtained for this test confirmed the structure of the expected polymer as represented in scheme (8).

Example 4: Synthesis of a Polymer Comprising Two [(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene)propyl]amide End Groups Starting with cyclooctene (COE) and bis[(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene)propyl]fumaramide (CTA.SUP.4.)

(49) The reaction was performed according to scheme (9) below, in a mole ratio m/n equal to 0/100 and according to the procedure of Example 3:

(50) ##STR00033##
Results:

(51) The polymer obtained is solid at room temperature.

(52) The results for the degree of conversion of the cycloolefin of formula (A) determined by NMR (expressed in %), the number-average molar mass of the polymer obtained (expressed in grams per mol) and the polydispersity (PDI) of said polymer, determined by SEC, are given in table 3 below.

(53) The .sup.1H (CDCl.sub.3, 500 MHz, 298 K) and .sup.13C (CDCl.sub.3, 100 MHz, 298 K) NMR analyses for the polymer obtained for this test confirmed the structure of the expected polymer as represented in scheme (9).

Example 5: Synthesis of a Polymer Comprising Two [(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene)propyl] ester End Groups Starting with cyclooctene monoepoxide (5-Epoxy-COE) and bis[(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene)propyl] fumarate (CTA.SUP.3.)

(54) The reaction was performed according to scheme (10) below, in a mole ratio m/n equal to 0/100 and according to the procedure of Example 3:

(55) ##STR00034##
Results:

(56) The polymer obtained is liquid at room temperature.

(57) The results for the degree of conversion of the cycloolefin of formula (A) determined by NMR (expressed in %), the number-average molar mass of the polymer obtained (expressed in grams per mol) and the polydispersity (PDI) of said polymer, determined by SEC, are given in table 3 below.

(58) The .sup.1H (CDCl.sub.3, 500 MHz, 298 K) and .sup.13C (CDCl.sub.3, 100 MHz, 298 K) NMR analyses for the polymer obtained for this test confirmed the structure of the expected polymer as represented in scheme (10).

Example 6: Synthesis of a Polymer Comprising Two [(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene)propyl] ester End Groups Starting with 5-oxocyclooctene (5-O=COE) and bis[(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene)propyl] fumarate (CTA.SUP.3.)

(59) The reaction was performed according to scheme (11) below, in a mole ratio m/n equal to 0/100 and according to the procedure of Example 3:

(60) ##STR00035##
Results:

(61) The polymer obtained is solid at room temperature.

(62) The results for the degree of conversion of the cycloolefin of formula (A) determined by NMR (expressed in %), the number-average molar mass of the polymer obtained (expressed in grams per mol) and the polydispersity (PDI) of said polymer, determined by SEC, are given in table 3 below.

(63) The .sup.1H (CDCl.sub.3, 500 MHz, 298 K) and .sup.13C (CDCl.sub.3, 100 MHz, 298 K) NMR analyses for the polymer obtained for this test confirmed the structure of the expected polymer as represented in scheme (11).

Example 7: Synthesis of a Polymer Comprising Two [(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene)propyl] ester End Groups Starting with 5-hexylcyclooctene (5-Hexyl-COE) and bis[(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene)propyl] fumarate (CTA.SUP.3.)

(64) The reaction was performed according to scheme (12) below, in a mole ratio m/n equal to 0/100 and according to the procedure of Example 3:

(65) ##STR00036##
Results:

(66) The polymer obtained is liquid at room temperature.

(67) The results for the degree of conversion of the cycloolefin of formula (A) determined by NMR (expressed in %), the number-average molar mass of the polymer obtained (expressed in grams per mol) and the polydispersity (PDI) of said polymer, determined by SEC, are given in table 3 below.

(68) TABLE-US-00003 TABLE 3 Conversion Mn.sub.SEC Test no. [A]/[CTA.sup.3]/[Ru] (mol/mol) A (%) (g/mol) PDI 3 2 000/100/1 100 5 100 1.53 4 2 000/100/1 100 5 200 1.47 5 2 000/100/1 100 4 800 1.50 6 2 000/100/1 100 5 000 1.51 7 2 000/100/1 100 5 300 1.52 The .sup.1H (CDCl.sub.3, 500 MHz, 298 K) and .sup.13C (CDCl.sub.3, 100 MHz, 298 K) NMR analyses for the polymer obtained for this test confirmed the structure of the expected polymer as represented in scheme (12).

ii) Examples 8 to 9Polymerization of a Mixture of Cycloolefins of Formulae (A) and (B)

(69) The cycloolefins of formulae (A) and (B) used in Examples 8 and 9 are, respectively, as follows:

(70) ##STR00037##

(71) Cyclooctene (COE) with a purity of greater than 95% and norbornene (NBN) with a purity of greater than 99% are commercially available from the company Sigma-Aldrich. These products were distilled beforehand over CaH.sub.2, before being used in Examples 8 and 9.

Example 8: Synthesis of a Polymer Comprising Two Exo-Vinylene Cyclocarbonate End Groups Starting with Cyclooctene (COE), Norbornene (NBN) and bis[(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene)propyl] fumarate (CTA.SUP.3.)

(72) The reaction was performed according to scheme (13) below, in a mole ratio m/n equal to 50/50 and according to the procedure described below:

(73) ##STR00038##
Procedure:

(74) The cycloolefins of formulae (A) and (B), corresponding to COE (54.00 mmol) and NBN (54.00 mmol), respectively, hydroquinone (0.54 mmol) and dry CH.sub.2Cl.sub.2 (50 mL) were mixed in a 1000 mL round-bottomed flask. The round-bottomed flask and its contents were subsequently placed under argon. The CTA (5.40 mmol) of type (C2) was then introduced into the round-bottomed flask using a syringe. The round-bottomed flask was then immersed in an oil bath at 40 C. and the catalyst G2 (54 mol) in solution in CH.sub.2Cl.sub.2 (20 mL) was then immediately added using a cannula. 24 hours after the addition of the catalyst, the product was extracted from the round-bottomed flask after evaporating off the solvent under vacuum. The product was then recovered after precipitating from methanol, filtering and drying at 20 C. under vacuum.

(75) Results:

(76) The polymer obtained is liquid at room temperature.

(77) The degrees of conversion of the cycloolefins of formulae (A) and (B) determined by NMR (expressed in %), the number-average molar mass of the polymer obtained (expressed in grams per mol) and the polydispersity (PDI) of the polymer, determined by SEC. The results are given in table 4 below.

(78) TABLE-US-00004 TABLE 4 Conversion Mn.sub.SEC Test no. [A]/[B]/[CTA.sup.1]/[Ru] (mol/mol) (%) (g/mol) PDI 8 1 000/1 000/100/1 100 5 000 1.60 The .sup.1H (CDCl.sub.3, 500 MHz, 298 K) and .sup.13C (CDCl.sub.3, 100 MHz, 298 K) NMR analyses for the polymer obtained confirmed the structure of the expected polymer as represented in scheme (13).

Example 9: Synthesis of a Polymer Comprising Two Exo-Vinylene Cyclocarbonate End Groups Starting with Cyclooctene (COE), Norbornene (NBN) and bis[(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene)propyl]fumaramide (CTA.SUP.4.)

(79) The reaction was performed according to scheme (14) below, in a mole ratio m/n equal to 50/50 and according to the same procedure as Example 8:

(80) ##STR00039##
Results:

(81) The polymer obtained is liquid at room temperature.

(82) The degrees of conversion of the cycloolefins of formulae (A) and (B) determined by NMR (expressed in %), the number-average molar mass of the polymer obtained (expressed in grams per mol) and the polydispersity (PDI) of the polymer, determined by SEC. The results are given in table 5 below.

(83) TABLE-US-00005 TABLE 5 Conversion Mn.sub.SEC Test no. [A]/[B]/[CTA.sup.3]/[Ru] (mol/mol) (%) (g/mol) PDI 9 1 000/1 000/100/1 100 5 300 1.58 The .sup.1H (CDCl.sub.3, 500 MHz, 298 K) and .sup.13C (CDCl.sub.3, 100 MHz, 298 K) NMR analyses for the polymer obtained confirmed the structure of the expected polymer as represented in scheme (14).

IIComparative Example 10: Synthesis of a Polymer Comprising Two methylene cyclocarbonate End Groups Starting with cyclooctene (COE) and bis[(2-oxo-1,3-dioxolan-4-yl)methyl] fumarate (CTA.SUP.5.)

(84) The reaction was performed according to scheme (15) below, in a mole ratio m/n equal to 0/100 and according to the same procedure as Example 3:

(85) ##STR00040##
Results:

(86) The polymer obtained is solid at room temperature.

(87) The results for the degree of conversion of the cycloolefin of formula (A) determined by NMR (expressed in %), the number-average molar mass of the polymer obtained (expressed in grams per mol) and the polydispersity (PDI) of said polymer, determined by SEC, are given in table 6 below:

(88) TABLE-US-00006 TABLE 6 Conversion Mn.sub.SEC Test no. [A]/[B]/[CTA.sup.1]/[Ru] (mol/mol) (%) (g/mol) PDI 8 1 000/1 000/100/1 100 5 000 1.60 The .sup.1H (CDCl.sub.3, 500 MHz, 298 K) and .sup.13C (CDCl.sub.3, 125 MHz, 298 K) NMR analyses for the polymer obtained for this test confirmed the structure of the expected polymer as represented in scheme (15).

IIIExamples 11 to 13: Syntheses of polyurethanes Starting with the Unsaturated polyolefins of Examples 10, 3 and 8, Respectively

Comparative Example 11: Synthesis of a polyurethane Starting with the Solid Unsaturated polyolefin of Comparative Example 10

(89) The polyolefin of Comparative Example 10 was reacted at 80 C., separately and in a stoichiometric ratio, with a primary diamine of polyetherdiamine type (Jeffamine EDR 148, Huntsman), until complete disappearance of the infrared band characteristic of the 1,3-dioxolan-2-one groups (at 1800 cm.sup.1) and appearance of the bands characteristic of the carbamate bond (band at 1700 cm.sup.1).

(90) The reaction time recorded for complete disappearance of the infrared band characteristic of the 1,3-dioxolan-2-one groups was about 12 hours at 80 C.

Example 12: Synthesis of a polyurethane Starting with the Solid Unsaturated polyolefin of Example 3 According to the Invention

(91) Example 11 was reproduced, replacing the polyolefin of Example 10 with the polyolefin of Example 3.

(92) The reaction time recorded for complete disappearance of the infrared band characteristic of the 1,3-dioxolan-2-one groups was less than 3 hours at 80 C.

Example 13: Synthesis of a polyurethane Starting with the Liquid Unsaturated polyolefin of Example 8 According to the Invention

(93) Example 11 was reproduced, replacing the polyolefin of Example 3 with the polyolefin of Example 8 and performing the reaction at room temperature (23 C.). The reaction time recorded for complete disappearance of the infrared band characteristic of the 1,3-dioxolan-2-one groups was less than 3 hours at 23 C.

(94) In each case, the products of Examples 12 and 13 were able to be formulated in the form of a two-pack mixture with satisfactory adhesive properties.