NEW HYDROCARBON POLYMERS WITH EXO-VINYLENE CYCLOCARBONATE END GROUPS

Abstract

1) Hydrocarbon polymer of formula (I):

##STR00001##

F.sup.1 and F.sup.2 are exo-vinylene cyclocarbonate monovalent radicals of formulas (IIa) and (IIb):

##STR00002## g and d 0, 1, 2 or 3; A C1-C6 alkyl; X an oxygen atom or NR.sup.17 with R.sup.17 C1-C6 alkyl; R.sup.14, R.sup.15 and R.sup.16 a hydrogen atom or C1-C6 alkyl; R.sup.1 to R.sup.12 H or C1-C14 alkyl; R.sup.13 O or CH.sub.2; x 1 and y 1; n1 and n2 an integer or zero; m an integer or zero; p1 and p2 an integer or zero of non-zero sum; n1, n2, m, p1 and p2 such that the molecular weight of said polymer is 400 to 100,000 g/mol; process of preparation by ring-opening metathesis polymerization; and use as an adhesive in a mixture with an amine compound having at least 2 amine groups.

Claims

1. A hydrocarbon polymer comprising two exo-vinylene cyclocarbonate end groups, said hydrocarbon polymer having formula (I): ##STR00065## wherein: F.sup.1 and F.sup.2 are the exo-vinylene cyclocarbonate monovalent radicals of the respective formulas (I1a) and (I1b): ##STR00066## wherein: g and d, identical or different, represent an integer equal to 0, 1, 2 or 3; A represents a C1-C6 alkylene divalent radical; X is an oxygen atom or a nitrogen group NR.sup.17 where R.sup.17 is a C1-C6 alkyl group; R.sup.14, R.sup.15 and R.sup.16, which may be identical or different, each represent a hydrogen atom, a C1-C6 alkyl group, a C5-C6 cycloalkyl group, a phenyl group or an alkylphenyl group with a C1-C4 alkyl chain; each carbon-carbon bond of the main chain of the polymer, denoted represents a double bond or a single bond, according to the valence 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, identical or different, represent: a hydrogen or halogen atom; or a radical comprising from 1 to 22 carbon atoms selected from alkyl, alkenyl, alkoxycarbonyl, alkenyloxycarbonyl, alkylcarbonyloxy and alkenylcarbonyloxy, the hydrocarbon chain of said radical possibly being interrupted by at least one oxygen atom or one sulphur atom; in addition: at least one of the groups R.sup.1 to R.sup.8 can form, with at least one other R.sup.1 to R.sup.8 group including the carbon atom (s) to which said groups are attached, a saturated or unsaturated, optionally substituted, hydrocarbon ring or heterocycle comprising between 3 to 10 links; 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 connected, a carbonyl group CO or a group of 2 carbon atoms connected by a double bond: CC, the other carbon atom carrying 2 substituents selected from a hydrogen atom or a C.sub.1-C.sub.4 alkyl radical; x and y are integers, identical or different, ranging from 0 to 6, the sum x+y ranging from 0 to 6; R.sup.9, R.sup.10, R.sup.11 and R.sup.12, identical or different, represent: a hydrogen or halogen atom; or a radical comprising from 1 to 22 carbon atoms and selected from alkyl, alkenyl, alkoxycarbonyl, alkenyloxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy and alkylcarbonyloxyalkyl, the hydrocarbon chain of said radical possibly being interrupted by at least one oxygen atom or one sulphur atom; in addition: at least one of the groups R.sup.9 to R.sup.12 can form, with at least one other R.sup.9 to R.sup.12 group including the carbon atom or atoms to which said groups are attached, a saturated or unsaturated, optionally substituted, hydrocarbon ring or heterocycle comprising from 3 to 10 links; 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 connected, a group of 2 carbon atoms connected by a double bond: CC, the other carbon atom carrying 2 substituents selected from a hydrogen atom or a radical 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), can be connected to the carbon atom bearing one of the groups of the pair (R.sup.11, R.sup.12) by a double bond, provided that, in accordance with valence rules, only one of the groups of each of these 2 pairs is present; R.sup.13 represents: an oxygen or sulphur atom, or a divalent radical CH.sub.2, C(O) or NR.sup.0 wherein R.sup.0 is an alkyl or alkenyl radical comprising from 1 to 22 carbon atoms; n1 and n2, which are identical or different, are each an integer or zero, whose sum is denoted by n; m is an integer greater than or equal to 0; p1 and p2, which are identical or different, are each an integer or zero, the sum p1+p2 of which is non-zero and satisfies the equation: p1+p2=qx (z+1) wherein: q is an integer greater than 0; and z is an integer ranging from 1 to 5; and n1, n2, m, p1 and p2 further being such that a number-average molecular weight Mn of the polymer of formula (I) is comprised in a range from 400 to 100,000 g/mol and its polymolecularity index is comprised in a range from 1.0 to 3.0; the said Mn and polymolecularity index being measured by steric exclusion chromatography with implementation of a PolyStyrene calibration.

2. Hydrocarbon polymer according to claim 1, characterized in that: g or d are equal to 0; A represents a C1-C3 alkylene divalent radical; X is an oxygen atom or a nitrogen group NR.sup.17 where R.sup.17 is a C1-C3 alkyl group; R.sup.14 is a hydrogen atom; R.sup.15 and R.sup.16, identical or different, each represent a C1-C3 alkyl group; 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 in a range from 0 to 2, the sum x+y ranging from 0 to 2; R.sup.9, R.sup.10, R.sup.1 and R.sup.12 represent a hydrogen atom or a radical the hydrocarbon portion of which comprises from 1 to 14 carbon atoms; z is an integer equal to 1 or 2; and/or the number-average molecular weight Mn ranges from 1000 to 50,000 g/mol, and the polydispersity index ranges from 1.4 to 2.0.

3. Hydrocarbon polymer according to claim 1, characterized in that: when m is non-zero and n1 and n2 are each equal to 0, then the ratio: m/(p1+p2+m) ranges from 30 to 70%; or when m is equal to 0 and the sum n1+n2 is non-zero, then at least one of the groups R, 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 ratio: (n1+n2)/(p1+p2+n1+n2) ranges from 30 to 70%; or when m is non-zero, the sum n1+n2 is non-zero and that 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 in the range of 30 to 70%; when m is equal to non-zero and 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, thus the ratio: (m+n1+n2)/(p1+p2+n1+n2+m) ranges from 30 to 70%.

4. Hydrocarbon polymer according to claim 1, characterised in that it has the following formula (I): ##STR00067##

5. Hydrocarbon polymer according to claim 1, characterised in that it has the following formula (II): ##STR00068##

6. Hydrocarbon polymer according to claim 5, characterized in that it has the following formula (II): ##STR00069##

7. Hydrocarbon polymer according to claim 1, characterized in that n1 and n2 are each equal to 0, the polymer having the following formula (III): ##STR00070##

8. Hydrocarbon polymer according to claim 7, characterised in that it has the following formula (III): ##STR00071##

9. Hydrocarbon polymer according to claim 1, characterised in that n1, n2 and m are each equal to 0, the polymer being of formula (IV) below: ##STR00072##

10. Hydrocarbon polymer according to claim 9, characterised in that it has the following formula (IV): ##STR00073##

11. Process for preparing a hydrocarbon polymer as defined in claim 1, said process comprising a ring-opening metathesis polymerization step, in the presence of: (a) a 2.sup.nd generation Grubbs ruthenium carbene metathesis catalyst; (b) a chain transfer agent selected from a mono or di-exo vinylene cyclocarbonate of the respective formula (B1) or (B2): ##STR00074## on condition that in the above formulas: the bond is a single carbon-carbon bond geometrically oriented on one end or the other in relation to the double bond; (c) a compound of formula (C): ##STR00075## (d) optionally a compound of formula (D): ##STR00076## and (e) optionally a compound of formula (E): ##STR00077## said polymerization step being further implemented: for a duration ranging from 2 to 24 hours and at a temperature ranging 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 it is the only reagent other than the CTA used in the reaction, or to the sum of the number of moles of the compound of formula (C) and the number of moles of compounds of formula (D) and/or (E), if the compounds of formula (D) and/or (E) are also implemented in the reaction, within a range of 0.0010 to 1.0.

12. A hydrocarbon polymer adhesive comprising a polymer as defined in claim 1, in a mixture with an amine compound comprising at least two amine groups.

13. A method of bonding two substrates comprising: coating on 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 hydrocarbon polymer as defined in claim 1; then the effective contact of the two substrates.

Description

EXAMPLE 1: POLYMERISATION OF 1,5-CYCLOOCTADIENE (CYCLOOLEFIN OF FORMULA (C)) IN THE PRESENCE OF CTA.SUP.1

[0204] Commercially available 1,5-cyclooctadiene (COD) is used and as a chain transfer agent, the CTA.sup.1 of the formula:

##STR00047##

[0205] 1,5-cyclooctadiene (10.8 mmol), benzoquinone (0.54 mmol) and dry CH.sub.2Cl.sub.2 (5 ml) are inserted into a 20 ml flask in which a Teflon coated magnetic stirring bar has also been placed. The flask and its contents are then put under argon.

[0206] The CTA.sup.1 compound (0.54 mmol) is then added while stirring to the flask using a syringe. Reagent ratios expressed in number of moles: CTA.sup.1/COD is 0.050.

[0207] The flask is then immersed in an oil bath at 40 C., and then we proceed immediately to the addition, via cannula, of G2 catalyst defined above (5.4 mol) solution in CH.sub.2Cl.sub.2 (2 ml).

[0208] The reaction mixture becomes very viscous within 2 minutes. The viscosity then slowly decreases for the next 10 minutes.

[0209] After 8 hours from the addition of the catalyst, the product present in the flask is removed after evaporation of the solvent under vacuum. The product is then recovered in the form of a colourless solid powder, after precipitation in methanol, filtration and drying at 20 C. under vacuum, with a yield greater than 90%.

[0210] NMR .sup.1H (CDCl.sub.3, 500 MHz, 25 C.) and .sup.13C (CDCl.sub.3, 125 MHz, 25 C.) analyses of said polymer confirm the following structure:

##STR00048##

[0211] This structure is well covered by formula (IV) defined above.

[0212] The number-average molecular weight Mn, measured by NMR, is 6800 g/mol.

[0213] The polymolecularity index equal to the Mw/Mn ratio (measured by polystyrene standard steric exclusion chromatography) is 1.60.

EXAMPLE 2: POLYMERIZATION OF 1,5,9-CYCLODODECATRIENE (CYCLOOLEFIN OF FORMULA (C)) IN THE PRESENCE OF CTA.SUP.2

[0214] Example 1 is repeated while replacing: [0215] COD by 1,5,9-cyclododecatriene (known as CDT) which is commercially available, for example from the Sigma Aldrich company; and [0216] CTA.sup.1 by CTA.sup.2 of formula:

##STR00049##

[0217] A polymer is also recovered in the form of a colourless solid powder whose NMR .sup.1H/.sup.13C analysis confirms the structure below:

##STR00050##

[0218] which is equally covered by formula (IV) defined above.

[0219] The number-average molecular weight Mn and the polydispersity index are, respectively, 6900 g/mol and 1.80.

EXAMPLE 3: POLYMERIZATION OF 1,5,9-CYCLODODECATRIENE (CYCLOOLEFIN OF FORMULA (C)) IN THE PRESENCE OF CTA.SUP.3

[0220] Example 2 is repeated by replacing the CTA as a chain transfer agent, CTA.sup.2 by the CTA.sup.3 of formula:

##STR00051##

[0221] and at the rate of 0.27 mmol CTA.sup.3.

[0222] Reagent ratios expressed in number of moles: CTA.sup.3/COD is 0.025.

[0223] A polymer is also recovered in the form of a colourless solid powder whose NMR .sup.1H/.sup.13C analysis confirms the structure below:

##STR00052##

[0224] This structure is well covered by formula (IV) defined above.

[0225] The number-average molecular weight Mn and the polydispersity index are, respectively, 6900 g/mol and 1.80.

EXAMPLE 4: POLYMERIZATION OF 1,5,9-CYCLODODECATRIENE (CYCLOOLEFIN OF FORMULA (C)) IN THE PRESENCE OF CTA.SUP.4

[0226] Example 3 is repeated by replacing the CTA as a chain transfer agent, CTA.sup.3, by the CTA.sup.4 of formula:

##STR00053##

[0227] A polymer is also recovered in the form of a colourless solid powder the NMR .sup.1H/.sup.13C analysis of which confirms a structure identical to that obtained for example 2.

EXAMPLE 5: POLYMERISATION OF CDT AND NORBORNENE (CYCLOOLEFIN OF FORMULA (E)) IN THE PRESENCE OF CTA.SUP.3

[0228] Example 3 is repeated while replacing the 10.8 mmol CDT with a mixture of 5.4 mmol CDT, 5.4 mmol norbornene, of the formula:

##STR00054##

[0229] and available from the Sigma Aldrich company.

[0230] Reagent ratios expressed in number of moles: CTA.sup.3/(CDT+norbornene) is 0.025.

[0231] A liquid copolymer is obtained the RMN (.sup.1H NMR and .sup.13C NMR analysis of which confirms the structure below:

##STR00055##

[0232] This structure is well covered by formula (III) defined above.

[0233] The number-average molecular weight Mn and the polydispersity index are, respectively, 5500 g/mol and 1.60.

EXAMPLE 6: POLYMERISATION OF CDT AND METHYL 5-NORBORNENE-2-CARBOXYLATE(CYCLOOLEFIN OF FORMULA (E)) IN THE PRESENCE OF CTA.SUP.3

[0234] Example 5 is repeated while replacing norbornene with methyl 5-norbornene-2-carboxylate, of formula:

##STR00056##

[0235] and available from Sigma Aldrich.

[0236] A copolymer which is liquid at room temperature is also obtained, the NMR analysis of which confirms the following structure:

##STR00057##

[0237] This structure is well covered by formula (III) defined above.

[0238] The number-average molecular weight Mn and the polydispersity index are, respectively, 6600 g/mol and 1.70.

EXAMPLE 7: POLYMERISATION OF CDT AND METHYL 5-OXANORBORNENE-2-CARBOXYLATE(CYCLOOLEFIN OF FORMULA (E)) IN THE PRESENCE OF CTA.SUP.3

[0239] Example 5 is repeated while replacing norbornene with methyl 5-oxanorbornene-2-carboxylate, of formula:

##STR00058##

[0240] and available from the Boc Sciences company.

[0241] A copolymer, liquid at room temperature, is also obtained, its NMR analysis confirms the structure:

##STR00059##

[0242] which is well covered by formula (III) defined above.

[0243] The number-average molecular weight Mn and the polydispersity index are, 6500 g/mol and 1.70 respectively.

EXAMPLE 8: POLYMERISATION OF CDT AND DICYCLOPENTADIENE(CYCLOOLEFIN OF FORMULA (E)) IN THE PRESENCE OF CTA.SUP.3

[0244] Example 5 is repeated while replacing norbornene with dicyclopentadiene, of formula:

##STR00060##

[0245] and available from the Sigma Aldrich company.

[0246] A copolymer which is liquid at room temperature is also obtained, the NMR analysis of which confirms the following structure:

##STR00061##

[0247] which is well covered by formula (III) defined above.

[0248] The number-average molecular weight Mn and the polydispersity index are, respectively, 6800 g/mol and 1.80.

EXAMPLE 9: POLYMERISATION OF CDT AND 5-N-HEXYLCYCLOOCTENE(CYCLOOLEFIN OF FORMULA (D)) IN THE PRESENCE OF CTA.SUP.3

[0249] The 5-n-hexyl-cyclooctene used in this example was synthesized according to the route indicated in the reaction diagram below (see compound n 5):

##STR00062##

[0250] Raw materials (especially 5,6-epoxycyclooctene), reactants and solvents used in these syntheses are commercial products from the Sigma Aldrich company. For further details, reference is made to the publication of A. Diallo et al. (Polymer Chemistry, Vol 5, Issue 7, Apr. 7, 2014, pp 2583-2591), or to Kobayashi et al J. Am. Chem. Soc. 2011, 133, pp 5794-5797).

[0251] Example 5 is repeated while replacing norbornene with 5-n-hexyl-cyclooctene.

[0252] A copolymer which is liquid at room temperature is also obtained, the NMR analysis of which confirms the following structure:

##STR00063##

which is well covered by formula (II) defined above.

[0253] The number-average molecular weight Mn and the polydispersity index are, respectively, 7000 g/mol and 1.80.

EXAMPLE 10: POLYMERISATION OF CDT, CYCLOOCTENE (CYCLOOLEFIN OF FORMULA (D)) AND NORBORNENE (CYCLOOLEFIN OF FORMULA (E)) IN THE PRESENCE OF CTA.SUP.3

[0254] Example 3 is repeated while replacing the 10.8 mmol CDT with a mixture of 3.6 mmol CDT, 3.6 mmol cyclooctene and 3.6 mmol norbornene.

[0255] Reagent ratios expressed in number of moles: CTA.sup.3/(CDT+cyclooctene+norbornene) is 0.025.

[0256] After 8 hours from the addition of the catalyst, the product in the flask is removed after evaporation of the solvent under vacuum. The product is then recovered in the form of a liquid at ambient temperature, after precipitation in methanol, filtration and drying at 20 C. under vacuum, with a yield greater than 90%.

[0257] The NMR analysis of the polymer obtained confirms the following structure:

##STR00064##

The number-average molecular weight Mn and the polydispersity index are, respectively, 6900 g/mol and 1.70.

EXAMPLE 11: SYNTHESIS OF A POLYURETHANE BY REACTION OF THE POLYMER OF EXAMPLE 1 WITH A DIAMINE AT 80 C.

[0258] A mixture of the polyolefin of example 1 (solid at room temperature) with a primary diamine of the polyether diamine type (JEFFAMINE EDR 176, Huntsman) in a stoichiometric ratio, is reacted at 80 C., and this during a duration corresponding to the complete disappearance of the infrared band which is a characteristic of the 1.3-dioxolan-2-one groups (at 1800 cm.sup.1), and the appearance of the characteristic bands of carbamate bond (band at 1700 cm.sup.1 in Infra-Red).

[0259] This reaction time is less than 3 hours.

EXAMPLE 12: SYNTHESIS OF A POLYURETHANE BY REACTION OF THE POLYMER OF EXAMPLE 5 WITH A DIAMINE AT 80 C.

[0260] Example 11 is repeated with the polyolefin of example 5 (in the form of a viscous liquid) by reacting the mixture at 80 C.

[0261] The reaction time is less than 3 hours.

EXAMPLE 13: SYNTHESIS OF A POLYURETHANE BY REACTION OF THE POLYMER OF EXAMPLE 9 WITH A DIAMINE AT 60 C.

[0262] Example 12 is repeated with the polyolefin of example 9 (in the form of a viscous liquid) by reacting the mixture at 60 C.

[0263] The reaction time is less than 3 hours.