Hydrocarbon-based polymers bearing dithiocyclocarbonate end groups

Abstract

1) Hydrocarbon-based polymer of formula (I): ##STR00001## in which F.sup.1 and F.sup.2 have the respective formulae (IIa) and (IIb) or (IIa) and (IIb): ##STR00002## a process for its preparation, and use as an adhesive.

Claims

1. Hydrocarbon-based polymer comprising two dithiocyclocarbonate end groups, said hydrocarbon-based polymer having the formula (I): ##STR00086## in which: F.sup.1 and F.sup.2 are monovalent radicals of respective formulae (IIa) and (IIb): ##STR00087## or alternatively F.sup.1 and F.sup.2 are monovalent radicals of respective formulae (IIa) and (IIb): ##STR00088## in which: g1 and d1, which may be identical or different, represent an integer equal to 0, 1, 2 or 3; g2 and d2, which may be identical or different, represent an integer equal to 1, 2 or 3; A represents a divalent C.sub.1-C.sub.9 alkylene radical; Z is such that: the divalent group A-Z is the group -A-C(O)O and the divalent group Z-A- is the group OC(O)-A- with the proviso that g1 and d1 are each other than 0; or alternatively the divalent group A-Z is the group -A-OC(O) and the divalent group Z-A- is the group C(O)O-A-; each carbon-carbon bond of the main chain of the polymer, denoted , represents a double bond or a single bond, in accordance with the valency rules of organic chemistry; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8, which may be identical or different, represent: a hydrogen or halogen atom; or a radical comprising from 1 to 22 carbon atoms chosen from alkyl, alkenyl, alkoxycarbonyl, alkenyloxycarbonyl, alkylcarbonyloxy or alkenylcarbonyloxy, it being possible for the hydrocarbon-based chain of said radical to be optionally interrupted with at least one oxygen atom or one sulfur atom; in addition: at least one of the R.sup.1 to R.sup.8 groups can form, with at least one other of the R.sup.1 to R.sup.8 groups 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), (R.sup.3, R.sup.4), (R.sup.5, R.sup.6) and (R.sup.7, R.sup.8) can form, with the carbon atom to which said pair is linked, a carbonyl group CO or a group of two carbon atoms linked by a double bond: CC, the other carbon atom of which bears two substituents chosen from a hydrogen atom and a C.sub.1-C.sub.4 alkyl radical; x and y are integers, which may be identical or different, within a range extending from 0 to 4, the sum x+y being within a range extending from 0 to 4; R.sup.9, R.sup.10, R.sup.11 and R.sup.12, which may be identical or different, represent: a hydrogen or halogen atom; or a radical comprising from 1 to 22 carbon atoms which is chosen from alkyl, alkenyl, alkoxycarbonyl, alkenyloxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy and alkylcarbonyloxyalkyl, it being possible for the hydrocarbon-based chain of said radical to be optionally interrupted with at least one oxygen atom or one sulfur atom; in addition: at least one of the R.sup.9 to R.sup.12 groups can form, with at least one other of the R.sup.9 to R.sup.12 groups 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.9, R.sup.10) and (R.sup.11, R.sup.12) can form, with the carbon atom to which said pair is linked, a group of two carbon atoms linked by a double bond: CC, the other carbon atom of which bears two substituents chosen from a hydrogen atom and a C.sub.1-C.sub.4 alkyl radical; and the carbon atom bearing one of the groups of the pair (R.sup.9, R.sup.10) may be linked to the carbon atom bearing one of the groups of the pair (R.sup.11, R.sup.12) 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.13 represents: an oxygen or sulfur atom, or a divalent radical CH.sub.2, C(O) or NR.sup.0 in which R.sup.0 is an alkyl or alkenyl radical comprising from 1 to 22 carbon atoms; n1 and n2, which may be identical or different, are each an integer or equal to 0, the sum of which is denoted by n; m is an integer greater than or equal to 0; p1 and p2, which may be identical or different, are each an integer or equal to 0, the sum p1+p2 of which is non-zero and adheres to the equation:
p1+p2=q(z+1) in which: q is an integer greater than 0; and z is an integer ranging from 1 to 5; and n1, n2, m, p1 and p2 also being such that the number-average molecular mass Mn of the polymer of formula (I) is within a range extending from 400 to 100 000 g/mol and its polydispersity index is within a range extending from 1.0 to 3.0.

2. Hydrocarbon-based polymer according to claim 1, characterized in that: R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 represent a hydrogen atom or an alkyl radical comprising from 1 to 14 carbon atoms; the integers x and y are within a range extending from 0 to 2, the sum x+y being within a range extending from 0 to 2; x is equal to 1 and y is equal to 1; R.sup.9, R.sup.10, R.sup.11 and R.sup.12 represent a hydrogen atom or a radical, the hydrocarbon-based part of which comprises from 1 to 14 carbon atoms; z is an integer equal to 1 or 2; and/or the number-average molecular mass Mn is within a range extending from 1000 to 50 000 g/mol.

3. Hydrocarbon-based polymer according to claim 1, characterized in that: when m is non-zero and when n1 and n2 are each equal to 0, then the ratio: m/(p1+p2+m) is within the interval ranging from 30 to 70%; or when m is equal to 0 and when the sum n1+n2 is non-zero, then at least one of the groups R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 is other than a hydrogen atom, and the ratio: (n1+n2)/(p1+p2+n1+n2) is within the interval ranging from 30 to 70%; or when m is non-zero, when the sum n1+n2 is non-zero and when each of the groups R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 is a hydrogen atom, then the ratio: m/(p1+p2+n1+n2+m) is within the interval ranging from 30 to 70%; or when m is non-zero, when the sum n1+n2 is non-zero and when at least one of the groups R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 is other than a hydrogen atom, then the ratio: (m+n1+n2)/(p1+p2+n1+n2+m) is within the interval ranging from 30 to 70%.

4. Hydrocarbon-based polymer according to claim 1, characterized in that it has the formula (I) below: ##STR00089## in which the bond is a bond geometrically oriented on one side or the other relative to the double bond.

5. Hydrocarbon-based polymer according to claim 1, characterized in that m is equal to 0, the polymer being of formula (II) below: ##STR00090##

6. Hydrocarbon-based polymer according to claim 5, characterized in that it has the formula (II) below: ##STR00091##

7. Hydrocarbon-based polymer according to claim 1, characterized in that n1 and n2 are each equal to 0, the polymer being of formula (III) below: ##STR00092##

8. Hydrocarbon-based polymer according to claim 7, characterized in that it has the formula (III) below: ##STR00093##

9. Hydrocarbon-based polymer according to claim 1, characterized in that n1, n2 and m are each equal to 0, the polymer being of formula (IV) below: ##STR00094##

10. Hydrocarbon-based polymer according to claim 9, characterized in that it has the formula (IV) below: ##STR00095##

11. Hydrocarbon-based polymer according to claim 1, characterized in that the radical A represents a methylene radical; and/or Z is such that the divalent group -A-Z is the group -A-OC(O) and the divalent group Z-A- is the group C(O)O-A-.

12. Hydrocarbon-based polymer according to claim 1, characterized in that g1=d1=0 or g2=d2=1.

13. Process for preparing a hydrocarbon-based polymer as defined in claim 1, said process comprising at least: (i) one step of ring-opening metathesis polymerization in the presence of: (a) a metathesis catalyst; (b) a chain-transfer agent which is: when F.sup.1 and F.sup.2 are the monovalent radicals having the respective formulae (IIa) and (IIb): a mono- or diepoxide compound having the respective formulae (E1) and (E2): ##STR00096## in which F.sup.1e and F.sup.2e are the monovalent radicals having the respective formulae (IIea) and (IIeb): ##STR00097## and when F.sup.1 and F.sup.2 are the monovalent radicals having the respective formulae (IIa) and (IIb): a diepoxide compound of formula (E2): ##STR00098## in which F.sup.1e and F.sup.2e are the monovalent radicals having the respective formulae (IIea) and (IIeb): ##STR00099## it being understood that, in the above formulae, the bond is a carbon-carbon single bond geometrically oriented on one side or the other relative to the double bond; (c) a compound of formula (C): ##STR00100## (d) optionally a compound of formula (D): ##STR00101## and (e) optionally a compound of formula (E): ##STR00102## said polymerization step leading to the formation of a polymer bearing epoxide end groups of formula (V): ##STR00103## or (V): ##STR00104## in which F.sup.1e, F.sup.2e, F.sup.1e and F.sup.2e are as defined previously, and, in the case where the CTA of formula (E1) is implemented: F.sup.1e=F.sup.2e; said polymerization step also being performed: for a time ranging from 2 to 24 hours and at a temperature within an interval from 20 to 60 C.; and with a ratio r equal to the ratio of the number of moles of said CTA: to the number of moles of the compound of formula (C), if the latter is the only reagent other than the CTA implemented in the reaction, or to the sum of the number of moles of the compound of formula (C) and of the number of moles of the compounds of formulae (D) and/or (E), if the compounds of formulae (D) and/or (E) are also implemented in the reaction, within an interval ranging from 0.0010 to 1.0; and then (ii) a step of dithiocarbonation of the polymer of formula (V) or (V) obtained in the preceding step, 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.

14. An adhesive comprising the hydrocarbon-based polymer as defined in claim 1, as a mixture with an amine compound comprising at least two amine groups.

15. 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; then actually bringing the two substrates into contact.

Description

EXAMPLE 1: SYNTHESIS OF A POLYMER COMPRISING TWO (2-THIONE-1,3-OXATHIOLAN-4-YL)-METHYLENE-ESTER END GROUPS WITH A STEP OF POLYMERIZATION OF COD IN THE PRESENCE OF CTA1

(1) Step (i):

(2) Commercially available 1,5-cyclooctadiene (known as COD) is used, and, as chain-transfer agent, CTA.sup.1:

(3) ##STR00063##

(4) 1,5-Cyclooctadiene (10.8 mmol), benzoquinone (0.54 mmol) and dry CH.sub.2Cl.sub.2 (5 ml) are introduced into a 20 ml round-bottomed flask in which was also placed a Teflon-coated magnetic stirring bar. The round-bottomed flask and its contents are subsequently placed under argon.

(5) The compound CTA.sup.1 (0.54 mmol) is subsequently added with stirring to the round-bottomed flask via a syringe. The ratio of the reagents, expressed as number of moles: CTA.sup.1/COD is 0.050.

(6) The round-bottomed flask is then immersed in an oil bath at 40 C. and the catalyst G2 defined previously (5.4 mol) in solution in CH.sub.2Cl.sub.2 (2 ml) is then immediately added using a cannula.

(7) The reaction mixture becomes very viscous within the space of 2 minutes. The viscosity subsequently slowly decreases over the following 10 minutes.

(8) After 8 hours, counting from the addition of the catalyst, the product present in the round-bottomed flask is extracted after evaporation of the solvent under vacuum. The product is then recovered in the form of a colourless solid powder, after precipitating from methanol, filtering and drying at 20 C. under vacuum, in a yield of greater than 90%.

(9) Step (ii):

(10) The product isolated above (10.00 mmol), 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 round-bottomed flask and its contents were subsequently placed under argon. Carbon sulfide (20.00 mmol) was then introduced dropwise by syringe into the round-bottomed flask. The round-bottomed 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.

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

(12) .sup.1H NMR (CDCl.sub.3, 500 MHz, 25 C.) and .sup.13C NMR (CDCl.sub.3, 125 MHz, 25 C.) analyses of said polymer give the following values:

(13) .sup.1H NMR: (ppm) repeating unit 2.10 (4H*n), 5.43 (2H*n), end group=3.60 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 4.49 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 5.39 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 5.85 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 7.08 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH.

(14) .sup.13C NMR: (ppm) repeating unit 27.4, 32.7, 131.4, end group=36.1 OC(S)SCH.sub.2CHCH.sub.2OC(O), 62.7 OC(S)SCH.sub.2CHCH.sub.2OC(O), 87.7 OC(S)SCH.sub.2CHCH.sub.2OC(O), 119.9 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 152.1 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 166.2 OC(S)SCH.sub.2CHCH.sub.2OC(O), 210.2 OC(S)SCH.sub.2CHCH.sub.2OC(O).

(15) These values confirm the structure below:

(16) ##STR00064##

(17) This structure is indeed covered by formula (IV) defined previously.

(18) The number-average molecular mass Mn, measured by NMR, is 4700 g/mol.

(19) The polydispersity index, equal to the ratio Mw/Mn (measured by size exclusion chromatography with polystyrene standard), is 1.60.

EXAMPLE 2: SYNTHESIS OF A POLYMER COMPRISING TWO (2-THIONE-1,3-OXATHIOLAN-4-YL)-METHYLENE-ESTER END GROUPS WITH A STEP OF POLYMERIZATION OF CDT IN THE PRESENCE OF CTA2

(20) Example 1 is repeated, replacing in step (i): the COD with 1,5,9-cyclododecatriene (referred to hereinbelow as CDT), which is commercially available, for example from the company Sigma-Aldrich; the 0.54 mmol of CTA.sup.1 with 0.27 mmol of the compound CTA.sup.2 of formula:

(21) ##STR00065##

(22) such that the ratio of the reagents, expressed as number of moles: CTA.sup.2/CDT is 0.025, and without introducing benzoquinone.

(23) At the end of step (ii), a polymer is also recovered in the form of a colourless solid powder, the .sup.1H NMR/.sup.13C NMR analysis of which is identical to the polymer of Example 1, thus confirming the structure below:

(24) ##STR00066##

(25) which is thus also covered by formula (IV) defined previously.

(26) The number-average molecular mass Mn and the polydispersity index are, respectively, 6900 g/mol and 1.80.

EXAMPLE 3: SYNTHESIS OF A POLYMER COMPRISING TWO (2-THIONE-1,3-OXATHIOLAN-4-YL)-METHYLENE-ETHER END GROUPS WITH A STEP OF POLYMERIZATION OF CDT IN THE PRESENCE OF CTA2

(27) Example 2 is repeated, replacing, as chain-transfer agent, CTA.sup.2 with CTA.sup.2 of formula:

(28) ##STR00067##

(29) At the end of step (ii), a polymer is also recovered in the form of a colourless solid powder, the .sup.1H NMR/.sup.13C NMR analysis of which gives the following values:

(30) .sup.1H NMR: (ppm) repeating unit 2.10 (4H*n), 5.43 (2H*n), end group=3.60 OC(S)SCH.sub.2CHCH.sub.2O, 4.04 OC(S)SCH.sub.2CHCH.sub.2OCH.sub.2, 4.49 OC(S)SCH.sub.2CHCH.sub.2O, 5.39 OC(S)SCH.sub.2CHCH.sub.2O.

(31) .sup.13C NMR: (ppm) repeating unit 27.4, 32.7, 131.4, end group=41.5 OC(S)SCH.sub.2CHCH.sub.2O, 69.1 OC(S)SCH.sub.2CHCH.sub.2OCH.sub.2, 73.9 OC(S)SCH.sub.2CHCH.sub.2O, 88.3 OC(S)SCH.sub.2CHCH.sub.2O, 210.2 OC(S)SCH.sub.2CHCH.sub.2O.

(32) These values confirm the structure below:

(33) ##STR00068##

(34) This structure is indeed covered by formula (IV) defined previously.

(35) The number-average molecular mass Mn and the polydispersity index are, respectively, 6800 g/mol and 1.80.

EXAMPLE 4: SYNTHESIS OF A POLYMER COMPRISING TWO (2-THIONE-1,3-OXATHIOLAN-4-YL)-METHYLENE-ESTER END GROUPS WITH A STEP OF POLYMERIZATION OF CDT AND NORBORNENE (CYCLOOLEFIN OF FORMULA (E)) IN THE PRESENCE OF CTA2

(36) Example 2 is repeated, the 10.8 mmol of CDT being replaced with a mixture of 5.4 mmol of CDT and of 5.4 mmol of norbornene, of formula:

(37) ##STR00069##

(38) available from the company Sigma-Aldrich.

(39) The ratio of the reagents, expressed as number of moles: CTA.sup.2/(CDT+norbornene), is 0.025.

(40) At the end of step (ii), a liquid copolymer is obtained, NMR analysis of which gives the following values:

(41) .sup.1H NMR: (ppm) repeating unit trans: 1.08 (2H*n), 1.39 (4H*n), 2.07 (4H*n), 2.47 (2H*n trans), 5.24-5.44 (4H*n trans), repeating unit cis: 1.82-1.91 (6H*n), 2.07 (4H*n), 2.82 (2H*n cis), 5.24-5.44 (4H*n cis), end group=3.60 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 4.49 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 5.39 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 5.85 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 7.08 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH.

(42) .sup.13C NMR: (ppm) repeating unit: 27.4, 33.1, 42.1, 43.4, 130.3, 133.1, end group=36.1 OC(S)SCH.sub.2CHCH.sub.2OC(O), 62.7 OC(S)SCH.sub.2CHCH.sub.2OC(O), 87.7 OC(S)SCH.sub.2CHCH.sub.2OC(O), 119.9 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 152.1 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 166.2 OC(S)SCH.sub.2CHCH.sub.2OC(O), 210.2 OC(S)SCH.sub.2CHCH.sub.2OC(O).

(43) These values confirm the structure below:

(44) ##STR00070##

(45) This structure is indeed covered by the formula (III) defined above.

(46) The number-average molecular mass Mn and the polydispersity index are respectively 5500 g/mol and 1.60.

EXAMPLE 5: SYNTHESIS OF A POLYMER COMPRISING TWO (2-THIONE-1,3-OXATHIOLAN-4-YL)-METHYLENE-ETHER END GROUPS WITH A STEP OF POLYMERIZATION OF CDT AND NORBORNENE IN THE PRESENCE OF CTA2

(47) Example 4 is repeated, replacing the CTA.sup.2 with CTA.sup.2.

(48) At the end of step (ii), a liquid copolymer is obtained, NMR analysis of which gives the following values:

(49) .sup.1H NMR: (ppm) repeating unit trans: 1.08 (2H*n), 1.39 (4H*n), 2.07 (4H*n), 2.47 (2H*n trans), 5.24-5.44 (4H*n trans), repeating unit cis: 1.82-1.91 (6H*n), 2.07 (4H*n), 2.82 (2H*n cis), 5.24-5.44 (4H*n cis), end group=3.60 OC(S)SCH.sub.2CHCH.sub.2O, 4.04 OC(S)SCH.sub.2CHCH.sub.2OCH.sub.2, 4.49 OC(S)SCH.sub.2CHCH.sub.2O, 5.39 OC(S)SCH.sub.2CHCH.sub.2O.

(50) .sup.13C NMR: (ppm) repeating unit: 27.4, 33.1, 42.1, 43.4, 130.3, 133.1, end group=41.5 OC(S)SCH.sub.2CHCH.sub.2O, 69.1 OC(S)SCH.sub.2CHCH.sub.2OCH.sub.2, 73.9 OC(S)SCH.sub.2CHCH.sub.2O, 88.3 OC(S)SCH.sub.2CHCH.sub.2O, 210.2 OC(S)SCH.sub.2CHCH.sub.2O.

(51) These values confirm the structure below:

(52) ##STR00071##
This structure is indeed covered by formula (III) defined previously.

(53) The number-average molecular mass Mn and the polydispersity index are, respectively, 5400 g/mol and 1.60.

EXAMPLE 6: SYNTHESIS OF A POLYMER COMPRISING TWO (2-THIONE-1,3-OXATHIOLAN-4-YL)-METHYLENE-ESTER END GROUPS WITH A STEP OF POLYMERIZATION OF CDT AND METHYL 5-NORBORNENE-2-CARBOXYLATE (CYCLOOLEFIN OF FORMULA (E)) IN THE PRESENCE OF CTA2

(54) Example 4 is repeated, replacing the norbornene with methyl 5-norbornene-2-carboxylate, of formula:

(55) ##STR00072##

(56) available from the company Sigma-Aldrich.

(57) A copolymer that is liquid at room temperature is also obtained, NMR analysis of which gives the following values:

(58) .sup.1H NMR: (ppm) repeating unit 1.08-1.26 (1H*n), 1.56-1.99 (3H*n), 2.07 (4H*n), 2.44-3.02 (3H*n), 5.13-5.29 (4H*n), end group=3.60 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 4.49 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 5.39 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 5.85 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 7.08 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH.

(59) .sup.13C NMR: (ppm) repeating unit: 27.4, 33.1, 36.1-42.9, 130.3, 133.1, end group=36.1 OC(S)SCH.sub.2CHCH.sub.2OC(O), 62.7 OC(S)SCH.sub.2CHCH.sub.2OC(O), 87.7 OC(S)SCH.sub.2CHCH.sub.2OC(O), 119.9 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 152.1 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 166.2 OC(S)SCH.sub.2CHCH.sub.2OC(O), 210.2 OC(S)SCH.sub.2CHCH.sub.2OC(O).

(60) These values confirm the structure:

(61) ##STR00073##

(62) This structure is indeed covered by formula (III) defined previously.

(63) The number-average molecular mass Mn and the polydispersity index are, respectively, 6600 g/mol and 1.70.

EXAMPLE 7: SYNTHESIS OF A POLYMER COMPRISING TWO (2-THIONE-1,3-OXATHIOLAN-4-YL)-METHYLENE-ETHER END GROUPS WITH A STEP OF POLYMERIZATION OF CDT AND METHYL 5-NORBORNENE-2-CARBOXYLATE (CYCLOOLEFIN OF FORMULA (E)) IN THE PRESENCE OF CTA2

(64) Example 6 is repeated, replacing the CTA.sup.2 with CTA.sup.2.

(65) At the end of step (ii), a liquid copolymer is obtained, NMR analysis of which gives the following values:

(66) .sup.1H NMR: (ppm) repeating unit 1.08-1.26 (1H*n), 1.56-1.99 (3H*n), 2.07 (4H*n), 2.44-3.02 (3H*n), 5.13-5.29 (4H*n), end group=3.60 OC(S)SCH.sub.2CHCH.sub.2O, 4.04 OC(S)SCH.sub.2CHCH.sub.2OCH.sub.2, 4.49 OC(S)SCH.sub.2CHCH.sub.2O, 5.39 OC(S)SCH.sub.2CHCH.sub.2O.

(67) .sup.13C NMR: (ppm) repeating unit: 27.4, 33.1, 36.1-42.9, 130.3, 133.1, end group=41.5 OC(S)SCH.sub.2CHCH.sub.2O, 69.1 OC(S)SCH.sub.2CHCH.sub.2OCH.sub.2, 73.9 OC(S)SCH.sub.2CHCH.sub.2O, 88.3 OC(S)SCH.sub.2CHCH.sub.2O, 210.2 OC(S)SCH.sub.2CHCH.sub.2O.

(68) These values confirm the structure:

(69) ##STR00074##

(70) This structure is indeed covered by formula (III) defined previously.

(71) The number-average molecular mass Mn and the polydispersity index are, respectively, 6600 g/mol and 1.60.

EXAMPLE 8: SYNTHESIS OF A POLYMER COMPRISING TWO (2-THIONE-1,3-OXATHIOLAN-4-YL)-METHYLENE-ESTER END GROUPS WITH A STEP OF POLYMERIZATION OF CDT AND METHYL 5-OXANORBORNENE-2-CARBOXYLATE (CYCLOOLEFIN OF FORMULA (E)) IN THE PRESENCE OF CTA2

(72) Example 4 is repeated, replacing the norbornene with methyl 5-oxanorbornene-2-carboxylate, of formula:

(73) ##STR00075##

(74) available from the company Boc Sciences.

(75) A copolymer that is liquid at room temperature is also obtained, NMR analysis of which gives the following values:

(76) .sup.1H NMR: (ppm) repeating unit 2.07 (4H*n), 2.16-2.36 (2H*n), 2.79 (1H*n), 4.44-4.74 (2H*n), 5.60-5.77 (4H*n), end group=3.60 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 4.49 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 5.39 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 5.85 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 7.08 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH.

(77) .sup.13C NMR: (ppm) repeating unit: 27.4, 33.1, 36.23, 49.4-53.5, 78.8, 81.7, 130.3, 133.1, end group=36.1 OC(S)SCH.sub.2CHCH.sub.2OC(O), 62.7 OC(S)SCH.sub.2CHCH.sub.2OC(O), 87.7 OC(S)SCH.sub.2CHCH.sub.2OC(O), 119.9 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 152.1 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 166.2 OC(S)SCH.sub.2CHCH.sub.2OC(O), 210.2 OC(S)SCH.sub.2CHCH.sub.2OC(O).

(78) These values confirm the structure:

(79) ##STR00076##

(80) which is indeed covered by formula (III) defined previously.

(81) The number-average molecular mass Mn and the polydispersity index are, respectively, 6600 g/mol and 1.70.

EXAMPLE 9: SYNTHESIS OF A POLYMER COMPRISING TWO (2-THIONE-1,3-OXATHIOLAN-4-YL)-METHYLENE-ETHER END GROUPS WITH A STEP OF POLYMERIZATION OF CDT AND METHYL 5-OXANORBORNENE-2-CARBOXYLATE IN THE PRESENCE OF CTA2

(82) Example 8 is repeated, replacing the CTA.sup.2 with CTA.sup.2.

(83) At the end of step (ii), a liquid copolymer is obtained, NMR analysis of which gives the following values:

(84) .sup.1H NMR: (ppm) repeating unit 2.07 (4H*n), 2.16-2.36 (2H*n), 2.79 (1H*n), 4.44-4.74 (2H*n), 5.60-5.77 (4H*n), end group=3.60 OC(S)SCH.sub.2CHCH.sub.2O, 4.04 OC(S)SCH.sub.2CHCH.sub.2OCH.sub.2, 4.49 OC(S)SCH.sub.2CHCH.sub.2O, 5.39 OC(S)SCH.sub.2CHCH.sub.2O.

(85) .sup.13C NMR: (ppm) repeating unit: 27.4, 33.1, 36.23, 49.4-53.5, 78.8, 81.7, 130.3, 133.1, end group=41.5 OC(S)SCH.sub.2CHCH.sub.2O, 69.1 OC(S)SCH.sub.2CHCH.sub.2OCH.sub.2, 73.9 OC(S)SCH.sub.2CHCH.sub.2O, 88.3 OC(S)SCH.sub.2CHCH.sub.2O, 210.2 OC(S)SCH.sub.2CHCH.sub.2O.

(86) These values confirm the structure:

(87) ##STR00077##
which is indeed covered by formula (III) defined previously.

(88) The number-average molecular mass Mn and the polydispersity index are respectively 6500 g/mol and 1.80.

EXAMPLE 10: SYNTHESIS OF A POLYMER COMPRISING TWO (2-THIONE-1,3-OXATHIOLAN-4-YL)-METHYLENE-ESTER END GROUPS WITH A STEP OF POLYMERIZATION OF CDT AND DICYCLOPENTADIENE (CYCLOOLEFIN OF FORMULA (E)) IN THE PRESENCE OF CTA2

(89) Example 4 is repeated, replacing the norbornene with dicyclopentadiene, of formula:

(90) ##STR00078##

(91) available from the company Sigma-Aldrich.

(92) A copolymer that is liquid at room temperature is also obtained, NMR analysis of which gives the following values:

(93) .sup.1H NMR (CDCl.sub.3, 500 MHz, 298 K): (ppm) repeating unit 1.24 (1H*n), 1.59 (1H*n), 2.07 (4H*n), 2.26 (2H*n), 2.62 (1H*n), 2.85 (2H*n), 3.24 (1H*n), 5.36-5.68 (4H*n), end group=3.60 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 4.49 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 5.39 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 5.85 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 7.08 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH.

(94) .sup.13C NMR (CDCl.sub.3, 125 MHz, 298 K): (ppm) repeating unit 27.4, 33.1, 35.1, 38.0, 42.3, 46.0, 47.0, 55.4, 130.5, end group=36.1 OC(S)SCH.sub.2CHCH.sub.2OC(O), 62.7 OC(S)SCH.sub.2CHCH.sub.2OC(O), 87.7 OC(S)SCH.sub.2CHCH.sub.2OC(O), 119.9 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 152.1 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 166.2 OC(S)SCH.sub.2CHCH.sub.2OC(O), 210.2 OC(S)SCH.sub.2CHCH.sub.2OC(O).

(95) These values confirm the structure:

(96) ##STR00079##

(97) This structure is indeed covered by the formula (III) defined above.

(98) The number-average molecular mass Mn and the polydispersity index are respectively 6300 g/mol and 2.00.

EXAMPLE 11: SYNTHESIS OF A POLYMER COMPRISING TWO (2-THIONE-1,3-OXATHIOLAN-4-YL)-METHYLENE-ETHER END GROUPS WITH A STEP OF POLYMERIZATION OF CDT AND DICYCLOPENTADIENE IN THE PRESENCE OF CTA2

(99) Example 10 is repeated, replacing the CTA.sup.2 with CTA.sup.2.

(100) At the end of step (ii), a liquid copolymer is obtained, NMR analysis of which gives the following values:

(101) .sup.1H NMR: (ppm) repeating unit 1.24 (1H*n), 1.59 (1H*n), 2.07 (4H*n), 2.26 (2H*n), 2.62 (1H*n), 2.85 (2H*n), 3.24 (1H*n), 5.36-5.68 (4H*n), end group=3.60 OC(S)SCH.sub.2CHCH.sub.2O, 4.04 OC(S)SCH.sub.2CHCH.sub.2OCH.sub.2, 4.49 OC(S)SCH.sub.2CHCH.sub.2O, 5.39 OC(S)SCH.sub.2CHCH.sub.2O.

(102) .sup.13C NMR: (ppm) repeating unit 27.4, 33.1, 35.1, 38.0, 42.3, 46.0, 47.0, 55.4, 130.5, end group=41.5 OC(S)SCH.sub.2CHCH.sub.2O, 69.1 OC(S)SCH.sub.2CHCH.sub.2OCH.sub.2, 73.9 OC(S)SCH.sub.2CHCH.sub.2O, 88.3 OC(S)SCH.sub.2CHCH.sub.2O, 210.2 OC(S)SCH.sub.2CHCH.sub.2O.

(103) These values confirm the structure:

(104) ##STR00080##
which is indeed covered by formula (III) defined previously.

(105) The number-average molecular mass Mn and the polydispersity index are respectively 6300 g/mol and 1.90.

EXAMPLE 12: SYNTHESIS OF A POLYMER COMPRISING TWO (2-THIONE-1,3-OXATHIOLAN-4-YL)-METHYLENE-ESTER END GROUPS WITH A STEP OF POLYMERIZATION OF CDT AND 5-N-HEXYLCYCLOOCTENE (CYCLOOLEFIN OF FORMULA (D)) IN THE PRESENCE OF CTA2

(106) The 5-n-hexylcyclooctene used in this example was synthesized via the route indicated in the reaction scheme below (cf. compound 5):

(107) ##STR00081##

(108) The starting materials (especially 5,6-epoxycyclooctene), reagents and solvents used during these syntheses are commercial products from the company Sigma-Aldrich. For further details, reference is made to the publication by A. Diallo et al. (Polymer Chemistry, Vol. 5, Issue 7, 7 Apr. 2014, pages 2583-2591), or else to the reference Kobayashi et al, J. Am. Chem. Soc. 2011, 133, pages 5794-5797).

(109) Example 4 is repeated, replacing the norbornene with 5-n-hexylcyclooctene.

(110) A copolymer that is liquid at room temperature is also obtained, NMR analysis of which gives the following values:

(111) .sup.1H NMR: (ppm) repeating unit 0.83 (3H*n), 1.27 (16H*n), 2.07 (4H*n), 2.17 (5H*n), 5.37 (2H*n), end group=3.60 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 4.49 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 5.39 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 5.85 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 7.08 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH.

(112) .sup.13C NMR: (ppm) repeating unit 14.1, 22.7, 27.4, 29.6, 31.8, 32.4, 33.1, 33.8, 40.6, 130.5, end group=36.1 OC(S)SCH.sub.2CHCH.sub.2OC(O), 62.7 OC(S)SCH.sub.2CHCH.sub.2OC(O), 87.7 OC(S)SCH.sub.2CHCH.sub.2OC(O), 119.9 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 152.1 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 166.2 OC(S)SCH.sub.2CHCH.sub.2OC(O), 210.2 OC(S)SCH.sub.2CHCH.sub.2OC(O).

(113) These values confirm the structure:

(114) ##STR00082##

(115) which is indeed covered by formula (II) defined previously.

(116) The number-average molecular mass Mn and the polydispersity index are, respectively, 7500 g/mol and 1.80.

EXAMPLE 13: SYNTHESIS OF A POLYMER COMPRISING TWO (2-THIONE-1,3-OXATHIOLAN-4-YL)-METHYLENE-ETHER END GROUPS WITH A STEP OF POLYMERIZATION OF CDT AND 5-N-HEXYLCYCLOOCTENE, IN THE PRESENCE OF CTA2

(117) Example 12 is repeated, replacing the CTA.sup.2 with CTA.sup.2.

(118) At the end of step (ii), a liquid copolymer is obtained, NMR analysis of which gives the following values:

(119) .sup.1H NMR: (ppm) repeating unit 0.83 (3H*n), 1.27 (16H*n), 2.07 (4H*n), 2.17 (5H*n), 5.37 (2H*n), end group=3.60 OC(S)SCH.sub.2CHCH.sub.2O, 4.04 OC(S)SCH.sub.2CHCH.sub.2OCH.sub.2, 4.49 OC(S)SCH.sub.2CHCH.sub.2O, 5.39 OC(S)SCH.sub.2CHCH.sub.2O.

(120) .sup.13C NMR: (ppm) repeating unit 14.1, 22.7, 27.4, 29.6, 31.8, 32.4, 33.1, 33.8, 40.6, 130.5, end group=41.5 OC(S)SCH.sub.2CHCH.sub.2O, 69.1 OC(S)SCH.sub.2CHCH.sub.2OCH.sub.2, 73.9 OC(S)SCH.sub.2CHCH.sub.2O, 88.3 OC(S)SCH.sub.2CHCH.sub.2O, 210.2 OC(S)SCH.sub.2CHCH.sub.2O.

(121) These values confirm the structure:

(122) ##STR00083##

(123) which is indeed covered by formula (II) defined previously.

(124) The number-average molecular mass Mn and the polydispersity index are, respectively, 7600 g/mol and 1.80.

EXAMPLE 14: SYNTHESIS OF A POLYMER COMPRISING TWO (2-THIONE-1,3-OXATHIOLAN-4-YL)-METHYLENE-ESTER END GROUPS WITH A STEP OF POLYMERIZATION OF CDT AND CYCLOOCTENE AND NORBORNENE IN THE PRESENCE OF CTA2

(125) Example 2 is repeated, the 10.8 mmol of COD being replaced with a mixture of 3.6 mmol of CDT, 3.6 mmol of cyclooctene and 3.6 mmol of norbornene.

(126) The ratio of the reagents, expressed as number of moles: CTA.sup.2/(CDT+cyclooctene+norbornene), is 0.025.

(127) A copolymer that is liquid at room temperature is also obtained, NMR analysis of which gives the following values:

(128) .sup.1H NMR: (ppm) repeating unit trans: 1.08 (2H*n), 1.26 (8H*n), 1.39 (4H*n), 2.00 (4H*n), 2.07 (4H*n), 2.47 (2H*n trans), 5.24-5.44 (6H*n trans), repeating unit cis: 1.26 (8H*n), 1.82-1.91 (6H*n), 2.00 (4H*n), 2.07 (4H*n), 2.82 (2H*n cis), 5.24-5.44 (6H*n cis), end group=3.60 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 4.49 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 5.39 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 5.85 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 7.08 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH.

(129) .sup.13C NMR: (ppm) repeating unit 27.4, 28.5, 32.5, 33.1, 42.1, 43.4, 130.3, 133.1, end group=36.1 OC(S)SCH.sub.2CHCH.sub.2OC(O), 62.7 OC(S)SCH.sub.2CHCH.sub.2OC(O), 87.7 OC(S)SCH.sub.2CHCH.sub.2OC(O), 119.9 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 152.1 OC(S)SCH.sub.2CHCH.sub.2OC(O)CHCH, 166.2 OC(S)SCH.sub.2CHCH.sub.2OC(O), 210.2 OC(S)SCH.sub.2CHCH.sub.2OC(O).

(130) These values confirm the structure:

(131) ##STR00084##
This structure is indeed covered by formula (I) defined previously.

(132) The number-average molecular mass Mn and the polydispersity index are respectively 5800 g/mol and 1.90.

EXAMPLE 15: SYNTHESIS OF A POLYMER COMPRISING TWO (2-THIONE-1,3-OXATHIOLAN-4-YL)-METHYLENE-ETHER END GROUPS WITH A STEP OF POLYMERIZATION OF CDT, CYCLOOCTENE AND NORBORNENE, IN THE PRESENCE OF CTA2

(133) Example 14 is repeated, replacing the CTA.sup.2 with CTA.sup.2.

(134) At the end of step (ii), a liquid copolymer is obtained, NMR analysis of which gives the following values:

(135) .sup.1H NMR: (ppm) repeating unit trans: 1.08 (2H*n), 1.26 (8H*n), 1.39 (4H*n), 2.00 (4H*n), 2.07 (4H*n), 2.47 (2H*n trans), 5.24-5.44 (6H*n trans), repeating unit cis: 1.26 (8H*n), 1.82-1.91 (6H*n), 2.00 (4H*n), 2.07 (4H*n), 2.82 (2H*n cis), 5.24-5.44 (6H*n cis), end group=3.60 OC(S)SCH.sub.2CHCH.sub.2O, 4.04 OC(S)SCH.sub.2CHCH.sub.2OCH.sub.2, 4.49 OC(S)SCH.sub.2CHCH.sub.2O, 5.39 OC(S)SCH.sub.2CHCH.sub.2O.

(136) .sup.13C NMR: (ppm) repeating unit 27.4, 28.5, 32.5, 33.1, 42.1, 43.4, 130.3, 133.1, end group=41.5 OC(S)SCH.sub.2CHCH.sub.2O, 69.1 OC(S)SCH.sub.2CHCH.sub.2OCH.sub.2, 73.9 OC(S)SCH.sub.2CHCH.sub.2O, 88.3 OC(S)SCH.sub.2CHCH.sub.2O, 210.2 OC(S)SCH.sub.2CHCH.sub.2O.

(137) These values confirm the structure:

(138) ##STR00085##
This structure is indeed covered by formula (I) defined previously.

(139) The number-average molecular mass Mn and the polydispersity index are respectively 5800 g/mol and 1.80.

EXAMPLE 16: SYNTHESIS OF A POLY(THIO)URETHANE BY REACTING THE POLYMER OF EXAMPLE 2 WITH A DIAMINE AT 80 C.

(140) A mixture of the polyolefin (2-thione-1,3-oxathiolan-4-yl)-methylene-ester of Example 2 (solid at room temperature) is reacted at 80 C., in a stoichiometric ratio, with a primary diamine of polyetherdiamine type (Jeffamine EDR 176, Huntsman), for a time corresponding to the 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 to the appearance of the bands characteristic of the thiocarbamate bond (CS 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).

(141) This reaction time is less than 3 hours.

EXAMPLE 17: SYNTHESIS OF A POLY(THIO)URETHANE BY REACTING THE POLYMER OF EXAMPLE 4 WITH A DIAMINE AT 23 C.

(142) Example 16 is repeated with the liquid polyolefin (2-thione-1,3-oxathiolan-4-yl)-methylene-ester of Example 6, the mixture being reacted at room temperature (23 C.).

(143) The reaction time is less than 3 hours.

EXAMPLE 18: SYNTHESIS OF A POLY(THIO)URETHANE BY REACTING THE POLYMER OF EXAMPLE 3 WITH A DIAMINE AT 80 C.

(144) Example 16 is repeated with the solid polyolefin (2-thione-1,3-oxathiolan-4-yl)-methylene-ether of Example 3.

(145) The reaction time is less than 3 hours.

EXAMPLE 19: SYNTHESIS OF A POLY(THIO)URETHANE BY REACTING THE POLYMER OF EXAMPLE 7 WITH A DIAMINE AT 23 C.

(146) Example 17 is repeated with the viscous liquid polyolefin (2-thione-1,3-oxathiolan-4-yl)-methylene-ether of Example 7. The reaction time is less than 3 hours.

(147) The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.

(148) From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.