Liquid hydrocarbon-based copolymers bearing two cyclocarbonate ester end groups

Abstract

1) Hydrocarbon-based copolymer comprising two end groups preceded by an ester function and chosen from a 2-oxo-1,3-dioxolan-4-yl (or cyclocarbonate), a dithiocyclocarbonate, an exo-vinylene cyclocarbonate and a 2-oxo-1,3-dioxolen-4-yl, the main chain of which comprises units (I) and (II) ##STR00001## in which R.sup.0 is notably a methyl radical; and the number-average molecular mass Mn of which is between 400 and 100 000 g/mol. 2) Process for preparing said copolymer, comprising: (i) a step of heating a statistical bipolymer A chosen from a poly(butadiene-isoprene), a poly(butadiene-myrcene) and a poly(butadiene-farnesene); and then (ii) a step of heating the product formed, in the presence of a chain-transfer agent. 3) Use as adhesive, as a mixture with an amine compound comprising at least two amine groups.

Claims

1. A hydrocarbon-based copolymer P comprising two cyclocarbonate or dithiocyclocarbonate end groups F.sup.1 and F.sup.2 having the respective formulae: ##STR00128## in which: g and d, which may be identical or different, represent an integer equal to 0, 1, 2 or 3; and G and D are two monovalent radicals such that the pair (G, D) is as follows: (G1, D1) of formulae: ##STR00129## in which A.sup.1 is an alkylene group of 1 to 9 carbon atoms; (G2, D2) of formulae: ##STR00130## in which A.sup.2 is an alkylene group of 1 to 9 carbon atoms; (G3, D3) of formulae: ##STR00131## in which: A.sup.3 is an alkylene group of 1 to 9 carbon atoms; A.sup.4, A.sup.5 and A.sup.6, which may be identical or different, each represent a hydrogen atom, a linear or branched alkyl radical of 1 to 6 carbon atoms, a cycloalkyl radical of 5 or 6 carbon atoms, a phenyl radical or an alkylphenyl group, the alkyl chain of which has 1 to 4 carbon atoms; (G4, D4) of respective formulae: ##STR00132## in which: A.sup.8 represents a hydrogen atom or a linear or branched alkyl radical of 1 to 9 carbon atoms, A.sup.7 is an alkylene group of 1 to 9 carbon atoms or else a divalent radical of 1 to 20 carbon atoms and which may be linear or branched, cyclic or heterocyclic with one or more oxygen or sulfur heteroatoms; (G5, D5) of respective formulae: ##STR00133## in which: A.sup.9 and A.sup.10, which may be identical or different, each represent a hydrogen atom, a linear or branched alkyl radical of 1 to 6 carbon atoms, a cycloalkyl radical of 5 or 6 carbon atoms, a phenyl radical or an alkylphenyl group, the alkyl chain of which has 1 to 4 carbon atoms; A.sup.9 and A.sup.10 also possibly being bonded together to form a group —(CH.sub.2—).sub.q— in which q is an integer ranging from 3 to 5; wherein the main chain of said copolymer P comprises: a unit (I) of formula (I) repeated p times, p being an integer other than 0: ##STR00134## and a unit (II) of formula (II) repeated n times, n being an integer other than 0: ##STR00135## in which R.sup.0 represents a methyl radical or one of the three radicals having the following formula: ##STR00136## and, optionally, a unit (Ill) of formula (III) repeated m times, m being an integer greater than or equal to 0: ##STR00137## in which: R.sup.1, R.sup.2, R.sup.3 and R.sup.4, which may be identical or different, represent: a hydrogen or halogen atom; or a radical of 1 to 22 carbon atoms which is alkyl, alkenyl, alkoxycarbonyl, alkenyloxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy or alkylcarbonyloxyalkyl, the hydrocarbon-based chain of said radical possibly being optionally interrupted with at least one oxygen atom or one sulfur atom; in addition: at least one of the groups R.sup.1 to R.sup.4 can form, with at least one other of the groups R.sup.1 to R.sup.4 and with the carbon atom or atoms to which said groups are linked, a 3- to 10-membered, optionally substituted, saturated or unsaturated hydrocarbon-based ring or heterocycle; and at least one of the pairs (R.sup.1, R.sup.2) and (R.sup.3, R.sup.4) can form, with the carbon atom to which said pair is linked, a group of two carbon atoms linked by a double bond: C═C, the other carbon atom of which bears two substituents that are a hydrogen atom or a C.sub.1-C.sub.4 alkyl radical; and the carbon atom bearing one of the groups of the pair (R.sup.1, R.sup.2) may be linked to the carbon atom bearing one of the groups of the pair (R.sup.3, R.sup.4) by a double bond, it being understood that, in accordance with the valency rules, only one of the groups of each of these two pairs is then present; R.sup.5 represents: an oxygen or sulfur atom, or a divalent radical —CH.sub.2—, —C(═O)— or —NR.sup.6— in which R.sup.6 is an alkyl or alkenyl radical of 1 to 22 carbon atoms; it also being pointed out that: the bond represents a single bond or a double bond; F.sup.1 and F.sup.2 are each linked to one of the two ends of the main chain and to a unit (I); and n, p and m are such that the number-average molecular mass Mn of the copolymer P is within a range extending from 400 to 100 000 g/mol and its polydispersity index is within a range extending from 1.5 to 3.0.

2. The copolymer P according to claim 1, wherein its main chain consists essentially of the repeating unit (I) of formula (I), of the repeating unit (II) of formula (II) and, optionally, of the repeating unit (III) of formula (III), and in that the number p of units (I) and the number n of units (II) are such that: p/(n+p) is between 45% and 95%, and n/(n+p) is between 5% and 55%.

3. The copolymer P according to claim 1, wherein its main chain is such that: the unit (I) also has the formula (I′): ##STR00138## the unit (II) also has the formula (II′): ##STR00139## in which R.sup.0 represents a methyl radical or one of the three radicals having the following formula: ##STR00140## and, optionally, the unit (III) also has the formula (III′): ##STR00141## it being pointed out that, in the above formulae, the bond is a single bond geometrically oriented on one side or the other relative to the double bond (cis or trans).

4. The copolymer P according to claim 3, wherein its main chain is such that: on the p units of formula (I′), p″ also correspond to formula (I″), p″ being an integer other than 0, less than p and such that p″/p is greater than 0.8: ##STR00142## and on the n units of formula (II′), n″ also correspond to formula (II″), n″ being an integer other than 0, less than n and such that n″/n is greater than 0.9: ##STR00143##

5. The copolymer P according to claim 1, wherein the radical R.sup.0 of the unit (II) represents a methyl radical.

6. The copolymer P according to claim 1, wherein F.sup.1 and F.sup.2 have the respective formulae: ##STR00144## in which: A.sup.1 is a methylene group; and g and d are identical and equal to 0 or 1.

7. The copolymer P according to claim 1, wherein F.sup.1 and F.sup.2 have the respective formulae: ##STR00145## in which: A.sup.2 is a methylene group; and g and d are identical and equal to 0 or 1.

8. The copolymer P according to claim 1, wherein F.sup.1 and F.sup.2 have the respective formulae: ##STR00146## in which: A.sup.3 is a —(CH.sub.2).sub.2— group; A.sup.4 is a hydrogen atom; A.sup.5 and A.sup.6 are each a methyl; and g and d are identical and equal to 0 or 1.

9. The copolymer P according to claim 1, wherein F.sup.1 and F.sup.2 have the respective formulae: ##STR00147## in which: A.sup.7 is a propylene group; A.sup.8 is a methyl; and g and d are identical and equal to 0 or 1.

10. The copolymer P according to claim 1, wherein F.sup.1 and F.sup.2 have the respective formulae: ##STR00148## in which: A.sup.9 is a hydrogen atom; A.sup.10 is a methyl; and g and d are identical and equal to 0 or 1.

11. A process for preparing the hydrocarbon-based copolymer P as defined in claim 1, said process comprising: (i) heating at a temperature ranging from 30° C. to 80° C.: (a) of a statistical bipolymer A chosen from a poly(butadiene-isoprene), a poly(butadiene-myrcene) and a poly(butadiene-farnesene); and (b) optionally in the presence of a compound B of formula (B): ##STR00149## and then (ii) heating the product formed in (i) to a temperature in a range from 20 to 60° C., in the presence of a chain-transfer agent (also referred to as CTA), it being pointed out that: (c) when said hydrocarbon-based copolymer P is such that the pair (G, D) is (G1, D1), (G3, D3), (G4, D4) or (G5, D5), then said CTA is a compound of formula (C1) or (C2): ##STR00150## in which: F.sup.1 and F.sup.2 are such that the pair (G, D) corresponds to the corresponding definition (G1, D1), (G3, D3), (G4, D4) or (G5, D5); the bond is a carbon-carbon single bond geometrically oriented on one side or the other relative to the double bond (cis or trans); and (d) when said hydrocarbon-based copolymer P is such that the pair (G, D) is (G2, D2), then said CTA is the diepoxy compound of formula (C′1) or (C′2): ##STR00151## in which: F′.sup.1e and F′.sup.2e are monovalent radicals of formulae (G′) and (D′): ##STR00152## the bond is a carbon/carbon single bond geometrically oriented on one side or the other relative to the double bond (cis or trans); it also being pointed out that each of the steps (i) and (ii) is performed in the presence of a metathesis catalyst and of a solvent; and then (iii) when said hydrocarbon-based copolymer P is such that the pair (G, D) is (G2, D2), a step of dithiocarbonation of the polymer obtained in step (ii), by reaction with carbon disulfide (CS.sub.2) in the presence of a halogenated lithium compound, at a temperature ranging from 10 to 45° C.

12. The process according to claim 11, wherein the bipolymer A used in (i) is a poly(butadiene-isoprene), preferably comprising from 45% to 95% by number of butadiene-based units and from 5% to 55% by number of isoprene-based units, said percentages being expressed on the basis of the total number of constituent units of the poly(butadiene-isoprene) chain.

13. The process according to claim 11, wherein the chain of the poly(butadiene-isoprene) used in (i) comprises: less than 5% by number of vinyl-1,2 butadiene units on the basis of the number of butadiene-based units, and less than 5% of the total number of vinyl-1,2 isoprene units and of vinyl-3,4 isoprene units on the basis of the number of isoprene-based units.

14. The process according to claim 11, wherein the chain of the poly(butadiene-isoprene) used in (i) comprises: at least 80% by number of cis-1,4 butadiene units on the basis of the number of butadiene-based units, and at least 90% by number of cis-1,4 isoprene units on the basis of the number of isoprene-based units.

15. A mixture functional as an adhesive comprising the hydrocarbon-based polymer as defined in claim 1 and an amine compound comprising at least two amine groups.

16. A process for assembling two substrates by bonding, comprising: coating at least one of the two substrates to be assembled with a liquid adhesive composition obtained by mixing an amine compound comprising at least two amine groups with the hydrocarbon-based polymer as defined in claim 1; and then actually bringing the two substrates into contact.

Description

EXAMPLE 1

Depolymerization/Cyclization by Heating a Poly(Butadiene-Isoprene), Followed by Hot Cross-Metathesis in the Presence of CTA.SUP.1 .(Monofunctional CTA Route) and Production of a Copolymer P Such That (G, D) is (G1, D1)

(1) Kuraprene® LIR-390 as defined previously is used as liquid poly(butadiene-isoprene), and, as chain-transfer agent, the CTA.sup.1 having the formula:

(2) ##STR00083##

(3) Step (i):

(4) The poly(butadiene-isoprene) (81.00 mmol), benzoquinone (0.54 mmol) and dry CH.sub.2Cl.sub.2 (9 ml) are introduced into a 20 ml round-bottomed flask in which was also placed a Teflon®-coated magnetic stirring bar. The flask and its contents are subsequently placed under argon.

(5) The catalyst G2 defined previously (9.6 μmol) dissolved in CH.sub.2Cl.sub.2 (2 ml) is then added using a cannula.

(6) This mixture is heated in an oil bath for 3 hours at 40° C. with stirring until the Kuraprene® LIR-390 has disappeared and a mixture of macrocyclic cooligomers O has formed, as attested to by size exclusion chromatography.

(7) Step (ii):

(8) The compound CTA.sup.1 (0.27 mmol) is added by syringe and with stirring to the mixture contained in the flask from step (i) and heating is continued at a temperature of 40° C.

(9) The ratio r, as defined previously, is: 0.27/81.00, i.e. 0.003

(10) After 8 hours, with effect from the addition of the CTA.sup.1, the product present in the flask is extracted after evaporation of the solvent under vacuum. This product is then recovered in the form of a colourless liquid, after precipitating from methanol, filtering and drying at 23° C. under vacuum, in a yield of greater than 90%.

(11) Analysis by 1H/13C NMR gives the following results:

(12) .sup.1H NMR (CDCl.sub.3, 500 MHz, 298 K): δ (ppm) repeating unit 1.09 (s, CH.sub.3 isoprene unit), 2.06 and 2.11 (m, CH.sub.2/isoprene and butadiene units), 5.41 and 5.45 (m, CH═CH cis and trans/butadiene unit), 4.95 and 4.99 (m, CH═C(CH.sub.3) cis and trans/isoprene unit), end group=2.25 (m, O—C(O)—O—CH—CH.sub.2—O—C(O)—CH═CH—CH.sub.2), 2.90 (d, O—C(O)—O—CH—CH.sub.2—O—C(O)—CH═CH—CH.sub.2), 4.30 and 4.63 (m, O—C(O)—O—CH.sub.2—CH—CH.sub.2—O—C(O)—CH═CH), 4.96 (m, O—C(O)—O—CH—CH.sub.2—O—C(O)—CH═CH), 5.87 (m, O—C(O)—O—CH—CH.sub.2—O—C(O)—CH═CH—), 7.02 (m, O—C(O)—O—CH—CH.sub.2—O—C(O)—CH═CH).

(13) .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K): δ (ppm) repeating unit 20.0, 27.4, 32.7, 37.4, 41.8, 124.2, 126.2, 131.4, end group=62.80 and 66.0 O—C(O)—O—CH.sub.2—CH—CH.sub.2—O—C(O)—CH═CH, 74.1 O—C(O)—O—CH—CH.sub.2—O—C(O)—CH═CH, 122.2 O—C(O)—OCH—CH.sub.2—O—C(O)—CH═CH, 50.9 O—C(O)—O—CH—CH.sub.2—O—C(O)—CH═CH, 154.7 O—C(O)—O—CH—CH.sub.2—O—C(O)—CH═CH, 166.5 O—C(O)—O—CH—CH.sub.2—O—C(O)—CH═CH.

(14) These values confirm that the product obtained is a copolymer comprising two cyclocarbonate end groups, the main chain of which consists essentially: of unit (I) of formula:

(15) ##STR00084##
and of unit (II) of formula:

(16) ##STR00085##
and

(17) of which two units (I) are each connected to one of the two end groups of formulae:

(18) ##STR00086##

(19) The number-average molecular mass Mn and the polydispersity index are, respectively, 17 020 g/mol and 2.7.

EXAMPLE 2

Depolymerization/Cyclization by Heating a Poly(Butadiene-Isoprene), Followed by Cross-Metathesis in the Presence of CTA.SUP.2 .(Difunctional CTA Route) and Production of a Copolymer P Such That (G, D) is (G1, D1)

(20) Example 1 is repeated, without adding benzoquinone in step (i), and replacing in step (ii), as chain-transfer agent, CTA.sup.1 with CTA.sup.2 of formula:

(21) ##STR00087##

(22) A polymer is also recovered, in a yield of greater than 90%, in the form of a colourless liquid, the .sup.1H/.sup.13C NMR analysis of which gives the following values:

(23) .sup.1H NMR (CDCl.sub.3, 500 MHz, 298 K): δ (ppm) repeating unit 1.09 (s, CH.sub.3 isoprene unit), 2.06 and 2.11 (m, CH.sub.2/isoprene and butadiene units), 5.41 and 5.45 (m, CH═CH cis and trans/butadiene unit), 4.95 and 4.99 (m, CH═C(CH.sub.3) cis and trans/isoprene unit), end group=3.08 (d, O—C(O)—O—CH—CH.sub.2—O—C(O)CH.sub.2CH═CH), 4.36 (d, O—C(O)—O—CH—CH.sub.2—O—C(O)—CH.sub.2CH═CH), 4.53 (dd, O—C(O)—O—CH.sub.2CHCH.sub.2—O—C(O)—CH.sub.2CH═CH), 4.66 (m, O—(O)—O—CH—CH.sub.2—O—C(O)—CH.sub.2CH═CH), 5.44 (m, O—C(O)—O—CH—CH.sub.2—O—C(O)—CH.sub.2—CH═CH—).

(24) .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K): δ (ppm) repeating unit 20.0, 27.4, 32.7, 37.4, 41.8, 124.2, 126.2, 131.4, end group=37.4 O—C(O)—O—CH—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 62.80 and 66.0 O—C(O)—O—CH.sub.2—CH—CH.sub.2—O—C(O)—CH.sub.2CH═CH, 74.1 O—C(O)—O—CH—CH.sub.2—O—C(O)CH.sub.2CH═CH, 124.1 O—C(O)—O—CH—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 130.8 O—C(O)—O—CH—CH.sub.2—O—C(O)CH.sub.2—CH═CH, 154.7 O—C(O)—O—CH—CH.sub.2—O—C(O)—CH.sub.2CH═CH, 171.2 O—C(O)—O—CH—CH.sub.2—O—C(O)—CH.sub.2—CH═CH.

(25) These values confirm that the product obtained is a copolymer comprising two cyclocarbonate end groups, the main chain of which consists essentially: of unit (I) of formula:

(26) ##STR00088##
and of unit (II) of formula:

(27) ##STR00089##
and

(28) of which two units (I) are each connected to one of the two end groups of formulae:

(29) ##STR00090##

(30) The number-average molecular mass Mn and the polydispersity index are, respectively, 16 990 g/mol and 2.7.

EXAMPLE 3

Depolymerization/Cyclization by Heating a Poly(Butadiene-Isoprene), Followed by Cross-Metathesis in the Presence of CTA.SUP.9 .(Monofunctional CTA Route) and then Dithiocarbonation, and Production of a Copolymer P Such That (G, D) is (G2, D2)

(31) Steps (i) and (ii):

(32) Example 1 is repeated, replacing, as chain-transfer agent, CTA.sup.1 with CTA.sup.9 of formula:

(33) ##STR00091##
Step (iii):

(34) The isolated product, derived from steps (i) and (ii), lithium bromide (10.00 mmol) and dry THF (10 ml) were placed in a 20 ml round-bottomed flask in which was also placed a Teflon®-coated magnetic stirring bar. The flask and its contents were then placed under argon. Carbon sulfide (20.00 mmol) was then introduced dropwise by syringe into the flask. The flask was then immersed in an oil bath at 40° C. for 17 hours. A product was recovered after precipitating from methanol (20 ml), filtering and drying at 23° C. under vacuum.

(35) A polymer is also recovered in liquid form, the .sup.1H NMR/.sup.13C NMR analysis of which gives the following values:

(36) .sup.1H NMR (CDCl.sub.3, 500 MHz, 298 K): δ (ppm) repeating unit 1.09 (s, CH.sub.3 isoprene unit), 2.06 and 2.11 (m, CH.sub.2/isoprene and butadiene units), 5.41 and 5.45 (m, CH═CH cis and trans/butadiene unit), 4.95 and 4.99 (m, CH═C(CH.sub.3) cis and trans/isoprene unit), end group=2.25 (m, O—C(O)—O—CH—CH.sub.2—O—C(O)—CH═CH—CH.sub.2), 3.62 (d, O—C(S)—S—CH.sub.2—CH—CH.sub.2—O—C(O)—CH═CH), 2.86 (dd, O—C(S)—S—CH.sub.2—CH—CH.sub.2—O—C(O)—CH═CH), 5.39 (m, S—C(S)—O—CH—CH.sub.2—O—C(O)—CH═CH), 5.87 (m, S—C(S)—O—CH—CH.sub.2—O—C(O)—CH═CH), 7.07 (m, S—C(S)—O—CH—CH.sub.2—O—C(O)—CH═CH).

(37) .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K): δ (ppm) repeating unit 20.0, 27.4, 32.7, 37.4, 41.8, 124.2, 126.2, 131.4, end group=34.0 O—C(S)—S—CH.sub.2—CH—CH.sub.2—O—C(O)—CH═CH, 66.7 O—C(S)—S—CH.sub.2—CH—CH.sub.2—O—C(O)—CH═CH, 83.9 S—C(S)—O—CH—CH.sub.2—O—C(O)—CH═CH, 122.2 S—C(S)—O—CH—CH.sub.2—O—C(O)—CH═CH, 150.9 S—C(S)—O—CH—CH.sub.2—O—C(O)—CH═CH, 166.5 S—C(S)—O—CH—CH.sub.2—O—C(O)—CH═CH, 205.1 S—C(S)—O—CH—CH.sub.2—O—C(O)—CH═CH.

(38) These values confirm that the product obtained is a copolymer comprising two dithiocyclocarbonate end groups, the main chain of which consists essentially: of unit (I) of formula:

(39) ##STR00092##
and of unit (II) of formula:

(40) ##STR00093##
and

(41) of which two units (I) are each connected to one of the two end groups of formulae:

(42) ##STR00094##

(43) The number-average molecular mass Mn and the polydispersity index are, respectively, 17,090 g/mol and 2.80.

EXAMPLE 4

Depolymerization/Cyclization by Heating a Poly(Butadiene-Isoprene), Followed by Cross-Metathesis in the Presence of CTA.SUP.19 .(Difunctional CTA Route) and then Dithiocarbonation, and Production of a Copolymer P Such That (G, D) is (G2, D2)

(44) Example 3 is repeated, without adding benzoquinone in step (i), and replacing in step (ii), as chain-transfer agent, CTA.sup.9 with CTA.sup.10 of formula:

(45) ##STR00095##

(46) A polymer in the form of a colourless liquid is also recovered on conclusion of step (iii) (i.e. after reaction of CS.sub.2 with the unsaturated liquid polyolefin bearing epoxy end groups obtained from step (ii)), in a yield of greater than 90%, the .sup.1H/.sup.13C NMR analysis of which polymer gives the following values:

(47) .sup.1H NMR (CDCl.sub.3, 500 MHz, 298 K): δ (ppm) repeating unit 1.09 (s, CH.sub.3 isoprene unit), 2.06 and 2.11 (m, CH.sub.2/isoprene and butadiene units), 5.41 and 5.45 (m, CH═CH cis and trans/butadiene unit), 4.95 and 4.99 (m, CH═C(CH.sub.3) cis and trans/isoprene unit), end group=3.04 (d, S—C(S)—O—CH—CH.sub.2—O—C(O)—CH.sub.2—CH═CH), 3.69 (dd, O—C(S)—S—CH.sub.2—CH—CH.sub.2—O—C(O)—CH.sub.2—CH═CH), 4.37 (dd, O—C(S)—S—CH.sub.2—CH—CH.sub.2—O—C(O)—CH.sub.2—CH═CH), 4.51 (m, S—C(S)—O—CH—CH.sub.2—O—C(O)—CH.sub.2CH═CH), 5.44 (m, S—C(S)—O—CH—CH.sub.2—O—C(O)—CH.sub.2CH═CH).

(48) .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K): δ (ppm) repeating unit 20.0, 27.4, 32.7, 37.4, 41.8, 124.2, 126.2, 131.4, end group=34.0 O—C(S)—S—CH.sub.2—CH—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 37.4 S—C(S)—O—CH—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 34.0 O—C(S)—S—CH.sub.2CH—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 66.7 O—C(S)—S—CH.sub.2—CH—CH.sub.2—O—C(O)—CH.sub.2CH═CH, 83.9 S—C(S)—O—CH—CH.sub.2—O—C(O)—CH.sub.2CH═CH, 124.1 S—C(S)—O—CH—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 130.8 S—C(S)—O—CH—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 205.1 S—C(S)—O—CH—CH.sub.2—O—C(O)—CH.sub.2CH═CH, 171.2 S—C(S)—O—CH—CH.sub.2—O—C(O)—CH.sub.2—CH═CH.

(49) These values confirm that the product obtained is a copolymer comprising two dithiocyclocarbonate end groups, the main chain of which consists essentially: of unit (I) of formula:

(50) ##STR00096##
and of unit (II) of formula:

(51) ##STR00097##
and

(52) of which two units (I) are each connected to one of the two end groups of formulae:

(53) ##STR00098##

(54) The number-average molecular mass Mn and the polydispersity index are, respectively, 17110 g/mol and 2.80.

EXAMPLE 5

Depolymerization/Cyclization by Heating a Poly(Butadiene-Isoprene), Followed by Cross-Metathesis in the Presence of CTA.SUP.3 .(Monofunctional CTA Route) and Production of a Copolymer P Such That (G, D) is (G3, D3)

(55) Example 1 is repeated, replacing, as chain-transfer agent, CTA.sup.1 with CTA.sup.3 of formula:

(56) ##STR00099##

(57) A polymer is also recovered in liquid form, the .sup.1H NMR/.sup.13C NMR analysis of which gives the following values:

(58) .sup.1H NMR (CDCl.sub.3, 500 MHz, 298 K): δ (ppm) repeating unit 1.09 (s, CH.sub.3 isoprene unit), 2.06 and 2.11 (m, CH.sub.2/isoprene and butadiene units), 5.41 and 5.45 (m, CH═CH cis and trans/butadiene unit), 4.95 and 4.99 (m, CH═C(CH.sub.3) cis and trans/isoprene unit), end group=1.39 (s, O—C(O)—O—C(CH.sub.3).sub.2—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH═CH), 2.25 (m, O—C(O)—O—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH—CH.sub.2), 4.43 (dd, O—C(O)—O—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2CH═CH), 2.45 (m, O—C(O)—O—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH), 5.90 (m, O—C(O)—O—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH). 7.02 (m, O—C(O)—O—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH═CH),

(59) .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K): δ (ppm) repeating unit 20.0, 27.4, 32.7, 37.4, 41.8, 124.2, 126.2, 131.4, end group=26.9 O—C(O)—O—C(CH.sub.3).sub.2—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH═CH, 30.9 O—C(O)—O—C(CH.sub.3).sub.2—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH═CH, 64.2 O—C(O)—O—C(CH.sub.3).sub.2—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH═CH, 79.4 O—C(O)—O—C(CH.sub.3).sub.2—C═CH—CH.sub.2CH.sub.2—O—C(O)—CH═CH, 107.2 O—C(O)—O—C═CH—CH.sub.2CH.sub.2—O—C(O)—CH═CH, 122.2 O—C(O)—O—C═CH—CH.sub.2—CH.sub.2O—C(O)—CH═CH, 150.9 O—C(O)—O—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH═CH, 152.7 O—C(O)—O—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH═CH, 155.7 O—C(O)—O—C(CH.sub.3).sub.2—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH═CH, 166.5 O—C(O)—O—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH═CH.

(60) These values confirm that the product obtained is a copolymer comprising two cyclocarbonate end groups, the main chain of which consists essentially: of unit (I) of formula:

(61) ##STR00100##
and of unit (II) of formula:

(62) ##STR00101##
and

(63) of which two units (I) are each connected to one of the two end groups of formula:

(64) ##STR00102##

(65) The number-average molecular mass Mn and the polydispersity index are, respectively, 17080 g/mol and 2.80.

EXAMPLE 6

Depolymerization/Cyclization by Heating a Poly(Butadiene-Isoprene), Followed by Cross-Metathesis in the Presence of CTA.SUP.4 .(Difunctional CTA Route) and Production of a Copolymer P Such That (G, D) is (G3, D3)

(66) Example 2 is repeated, replacing the CTA.sup.2 with CTA.sup.4 of formula:

(67) ##STR00103##

(68) A polymer is also recovered in the form of a colourless liquid, in a yield of greater than 90%, the .sup.1H/.sup.13C NMR analysis of which gives the following values:

(69) .sup.1H NMR (CDCl.sub.3, 500 MHz, 298 K): δ (ppm) repeating unit 1.09 (s, CH.sub.3 isoprene unit), 2.06 and 2.11 (m, CH.sub.2/isoprene and butadiene units), 5.41 and 5.45 (m, CH═CH cis and trans/butadiene unit), 4.95 and 4.99 (m, CH═C(CH.sub.3) cis and trans/isoprene unit), end group=1.39 (s, O—C(O)—O—C(CH.sub.3).sub.2—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH), 2.59 (m, O—C(O)—O—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2CH═CH), 3.08 (d, O—C(O)—O—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH), 4.43 (dd, O—C(O)—O—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH), 5.44 (m, O—C(O)—O—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH—), 6.13 (dd, O—C(O)—O—C═CH—O—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH).

(70) .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K): δ (ppm) repeating unit 20.0, 27.4, 32.7, 37.4, 41.8, 124.2, 126.2, 131.4, end group=26.9 O—C(O)—O—C(CH.sub.3).sub.2—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 30.9 O—C(O)—O—C(CH.sub.3).sub.2—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 37.4 O—C(O)—O—C(CH.sub.3).sub.2—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 64.2 O—C(O)—O—C(CH.sub.3).sub.2—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 107.2 O—C(O)—O—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 79.4 O—C(O)—O—C(CH.sub.3).sub.2—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 124.1 O—C(O)—O—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 130.8 O—C(O)—O—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 152.7 O—C(O)—O—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 155.7 O—C(O)—O—C(CH.sub.3).sub.2—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH═CH, 171.2 O—C(O)—O—C═CH—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH.

(71) These values confirm that the product obtained is a copolymer comprising two cyclocarbonate end groups, the main chain of which consists essentially: of unit (I) of formula:

(72) ##STR00104##
and of unit (II) of formula:

(73) ##STR00105##
and

(74) of which two units (I) are each connected to one of the two end groups of formulae:

(75) ##STR00106##

(76) The number-average molecular mass Mn and the polydispersity index are, respectively, 17100 g/mol and 2.80.

EXAMPLE 7

Depolymerization/Cyclization by Heating a Poly(Butadiene-Isoprene), Followed by Cross-Metathesis in the Presence of CTA.SUP.5 .(Monofunctional CTA Route) and Production of a Copolymer P Such That (G, D) is (G4, D4)

(77) Example 1 is repeated, replacing, as chain-transfer agent, CTA.sup.1 with CTA.sup.5 of formula:

(78) ##STR00107##

(79) A polymer is also recovered in liquid form, the .sup.1H NMR/.sup.13C NMR analysis of which gives the following values:

(80) .sup.1H NMR (CDCl.sub.3, 500 MHz, 298 K): δ (ppm) repeating unit 1.09 (s, CH.sub.3 isoprene unit), 2.06 and 2.11 (m, CH.sub.2/isoprene and butadiene units), 5.41 and 5.45 (m, CH═CH cis and trans/butadiene unit), 4.95 and 4.99 (m, CH═C(CH.sub.3) cis and trans/isoprene unit), end group=1.49 (s, O—C(O)—O—CH(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH═CH), 1.69 (d, O—C(O)—O—C(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH═CH), 2.25 (m, O—C(O)—O—CH(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH═CH—CH.sub.2), 1.93 (m, O—C(O)—O—C(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH═CH), 4.20 (dd, O—C(O)—O—C(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH═CH), 5.31 and 5.61 (d, O—C(O)—O—C(═CH.sub.2)—C(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH═CH), 5.90 (m, O—C(O)—O—C(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH═CH), 7.02 (m, O—C(O)—O—C(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH═CH).

(81) .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K): δ (ppm) repeating unit 20.0, 27.4, 32.7, 37.4, 41.8, 124.2, 126.2, 131.4, end group=150.9 O—C(O)—O—C(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH═CH, 122.2 O—C(O)—O—C(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH═CH, 24.9 O—C(O)—O—CH(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—O(O)—CH═CH, 28.9 O—C(O)—O—CH(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—O(O)—CH═CH, 35.9 O—C(O)—O—CH(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH═CH), 65.3 O—C(O)—O—CH(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—O(O)—CH═CH, 79.3 O—C(O)—O—C(═CH.sub.2)—C(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH═CH, 122.2 O—C(O)—O—CH(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH═CH), 150.9 O—C(O)—O—CH(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH═CH, 152.7 O—C(O)—O—CH(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH═CH, 161.6 O—C(O)—O—C(═CH.sub.2)—C(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH═CH, 166.5 O—C(O)—O—CH(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH═CH).

(82) These values confirm that the product obtained is a copolymer comprising two cyclocarbonate end groups, the main chain of which consists essentially: of unit (I) of formula:

(83) ##STR00108##
and of unit (II) of formula:

(84) ##STR00109##
and

(85) of which two units (I) are each connected to one of the two end groups of formula:

(86) ##STR00110##

(87) The number-average molecular mass Mn and the polydispersity index are, respectively, 17070 g/mol and 2.80.

EXAMPLE 8

Depolymerization/Cyclization by Heating a Poly(Butadiene-Isoprene), Followed by Cross-Metathesis in the Presence of CTA.SUP.6 .(Difunctional CTA Route) and Production of a Copolymer P Such That (G, D) is (G4, D4)

(88) Example 2 is repeated, replacing the CTA.sup.2 with CTA.sup.6 of formula:

(89) ##STR00111##

(90) A polymer is also recovered in the form of a colourless liquid, in a yield of greater than 90%, the .sup.1H/.sup.13C NMR analysis of which gives the following values:

(91) .sup.1H NMR (CDCl.sub.3, 500 MHz, 298 K): δ (ppm) repeating unit 1.09 (s, CH.sub.3 isoprene unit), 2.06 and 2.11 (m, CH.sub.2/isoprene and butadiene units), 5.41 and 5.45 (m, CH═CH cis and trans/butadiene unit), 4.95 and 4.99 (m, CH═C(CH.sub.3) cis and trans/isoprene unit), end group=1.49 (s, O—C(O)—O—C(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH), 1.69 (d, O—C(O)—O—C(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH), 1.93 (m, O—C(O)—O—C(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH), 3.08 O—C(O)—C(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 4.22 (dd, O—C(O)—O—C(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH), 5.44 (m, O—C(O)—O—O—C(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH).

(92) .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K): δ (ppm) repeating unit 20.0, 27.4, 32.7, 37.4, 41.8, 124.2, 126.2, 131.4, end group=24.9 O—C(O)—O—C(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH), 28.9 O—C(O)—O—C(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 35.9 O—C(O)—O—C(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 37.4 O—C(O)—O—C(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 65.3 O—C(O)—O—C(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH), 79.3 O—C(O)—O—C(═CH.sub.2)—CH.sub.2—C(CH.sub.3)—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 124.1 O—C(O)—O—C(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 130.8 O—C(O)—O—C(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 152.7 O—C(O)—O—C(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 161.6 O—C(O)—O—C(═CH.sub.2)—CH.sub.2—C(CH.sub.3)—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 171.2 O—C(O)—O—C(CH.sub.3)—CH.sub.2—CH.sub.2—CH.sub.2—O—C(O)—CH.sub.2—CH═CH.

(93) These values confirm that the product obtained is a copolymer comprising two cyclocarbonate end groups, the main chain of which consists essentially: of unit (I) of formula:

(94) ##STR00112##
and of unit (II) of formula:

(95) ##STR00113##
and

(96) of which two units (I) are each connected to one of the two end groups of formulae:

(97) ##STR00114##

(98) The number-average molecular mass Mn and the polydispersity index are, respectively, 17120 g/mol and 2.80.

EXAMPLE 9

Depolymerization/Cyclization by Heating a Poly(Butadiene-Isoprene), Followed by Cross-Metathesis in the Presence of CTA.SUP.7.(Monofunctional CTA Route) and Production of a Copolymer P Such That (G, D) is (G5, D5)

(99) Example 1 is repeated, replacing, as chain-transfer agent, CTA.sup.1 with CTA.sup.7 of formula:

(100) ##STR00115##

(101) A polymer is also recovered in liquid form, the .sup.1H NMR/.sup.13C NMR analysis of which gives the following values:

(102) .sup.1H NMR (CDCl.sub.3, 500 MHz, 298 K): δ (ppm) repeating unit 1.09 (s, CH.sub.3 isoprene unit), 2.06 and 2.11 (m, CH.sub.2/isoprene and butadiene units), 5.41 and 5.45 (m, CH═CH cis and trans/butadiene unit), 4.95 and 4.99 (m, CH═C(CH.sub.3) cis and trans/isoprene unit), end group=2.25 (m, O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH—CH.sub.2), 2.31 (s, O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH), 4.73 (s, O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH═CH), 5.87 (m, O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH═CH), 7.08 (m, O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH═CH).

(103) .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K): δ (ppm) repeating unit 20.0, 27.4, 32.7, 37.4, 41.8, 124.2, 126.2, 131.4, end group=10.5 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH═CH, 62.8 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH═CH, 144.3 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH═CH, 150.9 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH═CH, 122.4 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH═CH, 122.2 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH═CH, 153.0 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH═CH, 155.7 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH═CH, 166.5 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH═CH.

(104) These values confirm that the product obtained is a copolymer comprising two cyclocarbonate end groups, the main chain of which consists essentially: of unit (I) of formula:

(105) ##STR00116##
and of unit (II) of formula:

(106) ##STR00117##
and

(107) of which two units (I) are each connected to one of the two end groups of formula:

(108) ##STR00118##

(109) The number-average molecular mass Mn and the polydispersity index are, respectively, 17050 g/mol and 2.80.

EXAMPLE 10

Depolymerization/Cyclization by Heating a Poly(Butadiene-Isoprene), Followed by Cross-Metathesis in the Presence of CTA.SUP.8 .(Difunctional CTA Route) and Production of a Copolymer P Such That (G, D) is (G5, D5)

(110) Example 2 is repeated, replacing the CTA.sup.2 with CTA.sup.8 of formula:

(111) ##STR00119##

(112) A polymer is also recovered in the form of a colourless liquid, in a yield of greater than 90%, the .sup.1H/.sup.13C NMR analysis of which gives the following values:

(113) .sup.1H NMR (CDCl.sub.3, 500 MHz, 298 K): δ (ppm) repeating unit 1.09 (s, CH.sub.3 isoprene unit), 2.06 and 2.11 (m, CH.sub.2/isoprene and butadiene units), 5.41 and 5.45 (m, CH═CH cis and trans/butadiene unit), 4.95 and 4.99 (m, CH═C(CH.sub.3) cis and trans/isoprene unit), end group=2.18 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 3.08 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 4.83 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 5.44 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH.

(114) .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K): δ (ppm) repeating unit 20.0, 27.4, 32.7, 37.4, 41.8, 124.2, 126.2, 131.4, end group=10.5 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 37.4 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 62.8 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 116.2 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 122.4 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 124.1 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 130.8 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 144.3 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 147.4 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 155.7 O—C(O)—O—C(═C)—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 171.2 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH.

(115) These values confirm that the product obtained is a copolymer comprising two cyclocarbonate end groups, the main chain of which consists essentially: of unit (I) of formula:

(116) ##STR00120##
and of unit (II) of formula:

(117) ##STR00121##
and

(118) of which two units (I) are each connected to one of the two end groups of formulae:

(119) ##STR00122##

(120) The number-average molecular mass Mn and the polydispersity index are, respectively, 17080 g/mol and 2.80.

EXAMPLE 11

Depolymerization/Cyclization by Heating Poly(Butadiene-Isoprene) in the Presence of Norbornene, Followed by Cross-Metathesis in the Presence of CTA.SUP.8

(121) Example 10 is repeated, the 81.00 mmol of poly(butadiene-isoprene) being replaced in step (i) with a mixture of 41.00 mmol of poly(butadiene-isoprene) and of 40.00 mmol of norbornene, of formula:

(122) ##STR00123##

(123) available from the company Sigma-Aldrich.

(124) The ratio r of the reagents, as defined previously, is equal to 0.27 mmol divided by 41.00 mmol+40.00 mmol, i.e. 0.003.

(125) After 8 hours, with effect from the addition of the CTA.sup.8, the product present in the flask is extracted after evaporation of the solvent under vacuum. The product is then recovered in a form that is liquid at room temperature, after precipitating from methanol, filtering and drying at 23° C. under vacuum, in a yield of greater than 90%.

(126) A polymer is also recovered in liquid form, the .sup.1H NMR/.sup.13C NMR analysis of which gives the following values:

(127) .sup.1H NMR (CDCl.sub.3, 500 MHz, 298 K): δ (ppm) repeating unit 1.09 (s, CH.sub.3 isoprene unit), 2.06 and 2.11 (m, CH.sub.2/isoprene and butadiene units), 5.41 and 5.45 (m, CH═CH cis and trans/butadiene unit), 4.95 and 4.99 (m, CH═C(CH.sub.3) cis and trans/isoprene unit), end group=2.18 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2O—C(O)—CH.sub.2CH═CH, 3.08 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 4.83 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 5.50 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH—, 5.58 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH.

(128) .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K): δ (ppm) repeating unit: 27.4, 33.1, 42.1, 43.4, 130.3, 133.1, end group=9.5 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 38.4 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 53.6 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 116.2 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 120.0 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 122.4 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 133.4 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 147.4 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH, 165.9 O—C(O)—O—C(CH.sub.3)═C—CH.sub.2—O—C(O)—CH.sub.2—CH═CH.

(129) These values confirm that the polymer obtained is a copolymer comprising two cyclocarbonate-like end groups, the main chain of which consists essentially: of unit (I) of formula:

(130) ##STR00124## of unit (II) of formula:

(131) ##STR00125##
and of unit (III) of formula:

(132) ##STR00126##
and

(133) of which two units (I) are each connected to one of the two end groups of formula:

(134) ##STR00127##

(135) The number-average molecular mass Mn and the polydispersity index are, respectively, 22,450 g/mol and 2.80.

EXAMPLE 12

Synthesis of a Polyurethane Starting from the Liquid Unsaturated Polyolefin Bearing a Cyclocarbonate End Group of Example 2

(136) The polyolefin of Example 2 was reacted at 80° C., in a stoichiometric ratio, with a primary diamine of polyetherdiamine type (Jeffamine EDR 176, Huntsman), until complete disappearance of the infrared band characteristic of the (1,3-dioxolan-2-one-4-yl)methyl groups (at 1806 cm.sup.−1) and appearance of the bands characteristic of the carbamate bond (band at 1700 cm.sup.−1).

(137) The reaction time recorded for complete disappearance of the infrared band characteristic of the (1,3-dioxolan-2-one-4-yl)methyl groups was about 3 hours.

EXAMPLE 13

Synthesis of a Poly(Thio)Urethane Starting from the Liquid Unsaturated Polyolefin Bearing a Dithiocyclocarbonate End Group of Example 4

(138) The liquid unsaturated polyolefin bearing a dithiocyclocarbonate end group of Example 4 was reacted at 23° C., in a stoichiometric ratio, with a primary diamine of polyetherdiamine type (Jeffamine EDR 176, Huntsman), until total disappearance of the infrared band characteristic of the 2-thione-1,3-oxathiolan-4-yl groups (CS band at 1200 cm.sup.−1 in infrared) and appearance of the bands characteristic of the thiocarbamate bond (C═S band at 1530 cm.sup.−1 in infrared) and of the thiol and disulfide functions (SH band at 2500 cm.sup.−1 and SS band at 510 cm.sup.−1 in Raman).

(139) The reaction time was about 3 hours.

EXAMPLE 14

Synthesis of a Polyurethane Starting from the Liquid Unsaturated Polyolefin Bearing a 2-oxo-1,3-dioxolen-4-yl End Group of Example 10

(140) The liquid unsaturated polyolefin bearing a 2-oxo-1,3-dioxolen-4-yl end group of Example 10 was reacted at 23° C., in a stoichiometric ratio, until total disappearance of the infrared band characteristic of the 1,3-dioxolen-2-one groups (at 1800 cm.sup.−1) and appearance of the bands characteristic of the 2-oxazolidinone groups (band between 1770 and 1780 cm.sup.−1) resulting from rapid post-cyclization of the keto-carbamates obtained previously.

(141) The reaction time was about 3 hours.

EXAMPLE 15

Synthesis of a Polyurethane Starting from the Liquid Unsaturated Polyolefin Bearing a 2-oxo-1,3-dioxolen-4-yl End Group of Example 11

(142) Example 14 is repeated, replacing the polyolefin of Example 10 with the polyolefin bearing a 2-oxo-1,3-dioxolen-4-yl end group of Example 11.

(143) The same result is obtained.