HYDROCARBON POLYMERS HAVING TWO 2-OXO-1,3-DIOXOLANE-4-CARBOXYLATE END GROUPS

Abstract

Hydrocarbon polymer having two 2-oxo-1,3-dioxolane-4-carboxylate end groups of formula (I):

##STR00001## F.sup.1 has formula (IIa) and F.sup.2 has formula (IIb):

##STR00002## in which g and d, which are identical or different, represent an integer equal to 1, 2 or 3; R.sup.1 to R.sup.12 represent a hydrogen atom or an alkyl radical of 1 to 22 carbon atoms; x and y are integers such that the sum x+y is 0 to 2; R.sup.13 is an oxygen or sulphur atom or a divalent CH.sub.2 radical; n1, n2, m, p1 and p2 are an integer or equal to 0 and such that the molecular weight Mn of the polymer of formula (I) is between 400 and 100 000 g/mol, a process for the preparation of the polymer by ring-opening metathesis polymerization, and use as adhesive in mixture with an amino compound having at least two amine groups.

Claims

1. Hydrocarbon polymer comprising two 2-oxo-1,3-dioxolane-4-carboxylate end groups, the said hydrocarbon polymer having the formula (I): ##STR00049## in which: F.sup.1 represents a radical of formula (IIa) and F.sup.2 represents a radical of formula (IIb): ##STR00050## in which g and d, which are identical or different, represent an integer equal to 1, 2 or 3; 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 are 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 chain of the said radical to be optionally interrupted by at least one oxygen atom or one sulphur 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 the said groups are connected, a saturated or unsaturated hydrocarbon ring or heterocycle which is optionally substituted and which comprises from 3 to 10 ring members; 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 the said pair is connected, a carbonyl CO group or a group of 2 carbon atoms connected by a double bond: CC, the other carbon atom of which carries 2 substituents chosen from a hydrogen atom or a C.sub.1-C.sub.4 alkyl radical; x and y are integers, which are identical or different, within a range extending from 0 to 6, the sum x+y being within a range extending from 0 to 6; R.sup.9, R.sup.10, R.sup.11 and R.sup.12, which are 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 or alkylcarbonyloxyalkyl, it being possible for the hydrocarbon chain of the said radical to be optionally interrupted by at least one oxygen atom or one sulphur 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 the said groups are connected, a saturated or unsaturated hydrocarbon ring or heterocycle which is optionally substituted and which comprises from 3 to 10 ring members; 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 the said pair is connected, a group of 2 carbon atoms connected by a double bond: CC, the other carbon atom of which carries 2 substituents chosen from a hydrogen atom or a C.sub.1-C.sub.4 alkyl radical; and the carbon atom carrying one of the groups of the pair (R.sup.9, R.sup.10) can be connected to the carbon atom carrying 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, just one of the groups of each of these 2 pairs is then present; R.sup.13 represents: an oxygen or sulphur atom, or a divalent CH.sub.2, C(O) or NR.sup.0 radical in which 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 equal to 0, the sum of which is denoted by n; m is an integer or equal to 0; p1 and p2, which are identical or different, are each an integer or equal to 0, the sum p1+p2 of which adheres to the equation: p1+p2=q(z+1) in which: q is an integer or equal to 0; and z is an integer ranging from 1 to 5; and n1, n2, m, p1 and p2 additionally being such that the number-average molecular weight 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 polymer according to claim 1, characterized in that: g and d included in the definition of F.sup.1 and F.sup.2 are identical; 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 part of which comprises from 1 to 14 carbon atoms and more preferably still from 1 to 8; R.sup.13 represents the divalent CH.sub.2 radical; z is an integer equal to 1 or 2; and/or the number-average molecular weight Mn is within a range extending from 3000 to 50 000 g/mol and the polydispersity index is within a range extending from 1.4 to 2.0.

3. Hydrocarbon polymer according to claim 1, characterized in that the meaning of q is other than 0.

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

5. Hydrocarbon polymer according to claim 1, characterized in that it has the formula (I): ##STR00051## in which the bond is a bond geometrically oriented on one side or the other with respect to the double bond.

6. Hydrocarbon polymer according to claim 1, characterized in that it has the formula (II): ##STR00052##

7. Hydrocarbon polymer according to claim 1, characterized in that it has the formula (III): ##STR00053##

8. Process for the preparation of a hydrocarbon polymer comprising two 2-oxo-1,3-dioxolane-4-carboxylate end groups of formula (I) as defined in claim 1, comprising at least one ring-opening metathesis polymerization reaction, in the presence: (a) of a metathesis catalyst; (b) of a chain transfer agent (or CTA) comprising two 2-oxo-1,3-dioxolane-4-carboxylate groups, of following formula (B): ##STR00054## in which the bond is a bond geometrically oriented on one side or the other with respect to the double bond; and (c) of at least one compound C chosen from: the compound of formula (C1): ##STR00055## the compound of formula (C2): ##STR00056## and the compound of formula (C3): ##STR00057## the said polymerization reaction being in addition carried out: for a time ranging from 2 to 24 hours and at a temperature within an interval from 20 to 70 C.; and with a ratio r, equal to the ratio of the number of moles of the said CTA to the total number of moles of the compound C, within an interval ranging from 0.0010 to 1.0.

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

10. Process for assembling two substrates by adhesive bonding, comprising: coating, on at least one of the two substrates to be assembled, with a liquid adhesive composition obtained by mixing an amino compound comprising at least two amine groups with the hydrocarbon polymer comprising two 2-oxo-1,3-dioxolane-4-carboxylate end groups as is defined in claim 1; then actually bringing the two substrates into contact.

Description

EXAMPLE 1: POLYMERIZATION OF CYCLOOCTENE (COMPOUND C OF FORMULA (C2)) IN THE PRESENCE OF CTA

[0165] Use is made of commercially available cyclooctene (denoted below as COE) and of CTA of formula:

##STR00043##

[0166] The COE (10.8 mmol) and dry 1,2-dichloroethane (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.

[0167] The compound CTA (0.216 mmol) is subsequently added with stirring to the round-bottomed flask via a syringe. The ratio of the reactants, expressed as number of moles: CTA/COE, is 0.020.

[0168] The round-bottomed flask is then immersed in an oil bath at 60 C. and then the catalyst G2 defined above (5.4 mol) in solution in 1,2-dichloroethane (2 ml) is immediately added using a hollow needle.

[0169] The reaction mixture becomes very viscous in the space of 10 minutes. The viscosity subsequently slowly decreases over the following hours.

[0170] 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 precipitation from methanol, filtering and drying at 20 C. under vacuum, with a degree of conversion of the CTA of 50%.

[0171] The .sup.1H/.sup.13C NMR analysis of the polymer obtained gives the following values:

[0172] .sup.1H NMR (CDCl.sub.3, 400 MHz, 298 K) (ppm)=repeat unit: 1.29 (8H*n), 1.96 (4H*n), 5.39 (2H*n); end group=5.0 (dd, O(O)CCHO-1,3-dioxolan-2-one), 4.6-4.5 (m, CH2O 1,3-dioxolan-2-one), 4.7 (s, CH2-O(O)C), 5.5 (m, CHCHCH.sub.2O(O)C), 5.6 (m, CHCHCH.sub.2O(O)C)

[0173] .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K) (ppm)=repeat unit: 130.34 (trans), 129.88 (cis), 32.63, 29.77, 29.69, 29.24, 29.20, 29.07, 27.26; end group=171.5 (CHC(O)CH2- ester), 154.81 (C(O) cyclocarbonate), 74.16 (CHC(O)O), 68.39 (CH2-CHC(O)O), 64.04 (C(O)OCH2-CHCH)

[0174] These values confirm the following structure:

##STR00044##

[0175] This structure is indeed covered by the formula (II) defined above.

[0176] The number-average molecular weight Mn, measured by NMR, is 5900 g/mol.

[0177] The polydispersity index, equal to the ratio Mw/Mn (measured by size exclusion chromatography with polystyrene standard), is 1.4.

EXAMPLE 2: POLYMERIZATION OF 1,5,9-CYCLODODECATRIENE (COMPOUND C OF FORMULA (C1)) IN THE PRESENCE OF THE CTA

[0178] Example 1 is repeated, the 10.8 mmol of COE being replaced with 10.8 mmol of 1,5,9-cyclododecatriene (also known as CDT), of formula:

##STR00045##

[0179] available from Sigma Aldrich.

[0180] The ratio of the reactants, expressed as number of moles: CTA/(CDT+norbornene), is 0.020.

[0181] A polymer in the form of a solid is also recovered, with a degree of conversion of the CTA of 100%, the .sup.1H/.sup.13C NMR analysis of which gives the following values:

[0182] .sup.1H NMR (CDCl.sub.3, 400 MHz, 298 K) (ppm)=repeat unit: 1.29 (8H*n), 1.96 (4H*n), 5.39 (2H*n); end group=5.0 (dd, O(O)CCHO-1,3-dioxolan-2-one), 4.6-4.5 (m, CH2O 1,3-dioxolan-2-one), 4.7 (s, CH2-O(O)C), 5.5 (m, CHCHCH.sub.2O(O)C), 5.6 (m, CHCHCH.sub.2O(O)C)

[0183] .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K): (ppm)=repeat unit 27.4, 32.7, 131.4, end group=171.5 (CHC(O)CH2- ester), 154.81 (C(O) cyclocarbonate), 74.16 (CHC(O)O), 68.39 (CH2-CHC(O)O), 64.04 (C(O)OCH2-CHCH)

[0184] These values confirm the structure below:

##STR00046##

[0185] This structure is indeed covered by the formula (III) defined above.

[0186] The number-average molecular weight Mn and the polydispersity index are respectively 8400 g/mol and 1.5.

EXAMPLE 3: POLYMERIZATION OF 1,5,9-CYCLODODECATRIENE (COMPOUND C OF FORMULA (C1)) AND OF NORBORNENE (COMPOUND C OF FORMULA (C3)) IN THE PRESENCE OF CTA

[0187] Example 2 is repeated, the 10.8 mmol of CDT being replaced with a mixture of 5.4 mmol of 1,5,9-cyclododecatriene (also denoted CDT) and of 5.4 mmol of norbornene, of formula:

##STR00047##

[0188] available from Sigma-Aldrich.

[0189] The ratio of the reactants, expressed as number of moles: CTA/(CDT+norbornene), is 0.020.

[0190] A polymer in the form of a colourless viscous liquid is also recovered, with a degree of conversion of the CTA of 100%, the .sup.1H/.sup.13C NMR analysis of which gives the following values:

[0191] .sup.1H NMR (CDCl.sub.3, 400 MHz, 298 K) (ppm)=repeat unit: 1.29 (8H*n), 1.96 (4H*n), 5.39 (2H*n); end group=5.0 (dd, O(O)CCHO 1,3-dioxolan-2-one), 4.6-4.5 (m, CH2O 1,3-dioxolan-2-one), 4.7 (s, CH2-O(O)C), 5.5 (m, CHCHCH.sub.2O(O)C), 5.6 (m, CHCHCH.sub.2O(O)C)

[0192] .sup.13C NMR: (ppm)=repeat unit: 27.4, 33.1, 42.1, 43.4, 130.4, 133.1, end group=171.5 (CHC(O)CH2- ester), 154.81 (C(O) cyclocarbonate), 74.16 (CHC(O)O), 68.39 (CH2-CHC(O)O), 64.04 (C(O)OCH2-CHCH)

[0193] These values confirm the structure below:

##STR00048##

[0194] This structure is indeed covered by the formula (III) defined above.

[0195] The number-average molecular weight Mn and the polydispersity index are respectively 6700 g/mol and 1.5.

EXAMPLE 4: SYNTHESIS OF A POLYURETHANE FROM THE SOLID UNSATURATED POLYOLEFIN OF EXAMPLE 1

[0196] The polyolefin of Example 1 was reacted at 80 C., in a stoichiometric ratio, with a primary diamine of polyether diamine type (Jeffamine EDR 176, Huntsman), until complete disappearance of the infrared band characteristic of the 1,3-dioxolan-2-one groups (at 1800 cm.sup.1) and appearance of the bands characteristic of the carbamate bond (band at 1700 cm.sup.1).

[0197] The duration of the reaction recorded during the complete disappearance of the infrared band characteristic of the 1,3-dioxolan-2-one groups was approximately 3 hours at 80 C.