Hydrocarbon polymers having two azlactone end groups

Abstract

1) Hydrocarbon polymer having two azlactone end groups ##STR00001##
F.sup.1 is formula (IIa) and F.sup.2 is formula (IIb): ##STR00002## g and d are 0, 1, 2 or 3; R.sup.14 and R.sup.15 are C.sub.1-C.sub.4 or a cyclohexyl radical; R.sup.1 to R.sup.12 represents hydrogen or alkyl with 1 to 22 carbon atoms; x and y are integers, x+y is 0 to 2; R.sup.13 is oxygen or sulphur or divalent CH.sub.2 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 preparation of the polymer; and use as adhesive in mixture with an amino compound with at least two amine groups.

Claims

1. Hydrocarbon polymer comprising two azlactone end groups, the said hydrocarbon polymer having the formula (I): ##STR00054## in which: F.sup.1 represents a radical of formula (IIa) and F.sup.2 represents a radical of formula (IIb): ##STR00055## in which: g and d, which are identical or different, represent an integer equal to 0, 1, 2 or 3; R.sup.14 and R.sup.15, which are identical or different, represent a hydrogen atom or an aromatic or linear or branched aliphatic hydrocarbon group comprising from 1 to 20 carbon atoms which can be interrupted by one or more oxygen or sulphur atoms; in addition, the R.sup.14 and R.sup.15 groups can form, with the carbon atom to which they are connected, a hydrocarbon ring comprising from 4 to 10 ring members and optionally one or more heteroatoms chosen from oxygen and sulphur; each carboncarbon 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: the R.sup.14and R.sup.15 radicals represent a C.sub.1-C.sub.4 alkyl radical or else form, with the carbon atom to which they are connected, a cyclohexyl radical; g and d represent 0 or 1; 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; 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; 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; R.sup.13 represents the divalent CH.sub.2 radical; z is an integer equal to 1 or 2; and the number-average molecular weight Mn is within a range extending from 3000 to 50 000 g/mol.

3. 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%.

4. Hydrocarbon polymer according to claim 1, characterized in that it has the following formula (I): ##STR00056## in which the bond is a bond geometrically oriented on one side or the other with respect to the double bond.

5. Hydrocarbon polymer according to claim 1, characterized in that it has the following formula (II): ##STR00057##

6. Hydrocarbon polymer according to claim 1, characterized in that it has the following formula (III): ##STR00058##

7. Process for the preparation of a hydrocarbon polymer comprising two azlactone end groups of formula (I) as defined in claim 1, the said process 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 2 azlactone groups, of following formula (B): ##STR00059## 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): ##STR00060## the compound of formula (C2): ##STR00061## and the compound of formula (C3): ##STR00062## the said polymerization reaction being 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.

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

9. 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 as defined in claim 1; then actually bringing the two substrates into contact.

Description

(1) The following examples are given purely by way of illustration of the invention and should not be interpreted in order to limit the scope thereof.

(2) Examples 1 to 5 describe the preparation of polymers comprising 2 azlactone end groups by means of a ring-opening metathesis polymerization.

EXAMPLE 1

Polymerization of Cyclooctene (Compound C of Formula (C2)) In The Presence Of CTA Azl2

(3) Use is made of commercially available cyclooctene (denoted below as COE) and of CTA Azl.sub.2 of formula:

(4) ##STR00045##

(5) 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.

(6) The compound CTA Azl.sub.2 (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 Azl.sub.2/COE, is 0.020.

(7) 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.

(8) The reaction mixture becomes very viscous in the space of 10 minutes. The viscosity subsequently slowly decreases over the following hours.

(9) 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%.

(10) The .sup.1H/.sup.13C NMR analysis of the polymer obtained gives the following values:

(11) .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: 1.53 OC(O)C(CH3)2NCCH, 5.30 OC(O)C(CH3)2NCCHCH, 5.79OC(O)C(CH3)2NCCHCH.

(12) .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K) (ppm)=repeat unit: 29.8 (4C*n), 33.7 (2C*n), 130.1 (2C*n); end group: 24.3 OC(O)C(CH3)2NCCH, 70.4 OC(O)C(CH3)2NCCH, 121.3OC(O)C(CH3)2NCCH, 161.4OC(O)C(CH3)2NCCH, 181.1OC(O)C(CH3)2NCCH;

(13) These values confirm the following structure:

(14) ##STR00046##

(15) This structure is indeed covered by the formula (II) defined above.

(16) The number-average molecular weight Mn, measured by NMR, is 6900 g/mol.

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

EXAMPLE 2

Polymerization of COE in the Presence of CTA di-CH2-Azl

(18) Example 1 is repeated, CTA Azl.sub.2 being replaced with CTA di-CH.sub.2-Azl of formula:

(19) ##STR00047##

(20) A polymer in the form of a colourless solid powder is also recovered, but with a degree of conversion of the CTA of 100%, the .sup.1H/.sup.13C NMR analysis of which gives the following values:

(21) .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: 1.42 (s, 12H) OC(O)C(CH3)2NCCH2CH, 3.17 (m, 4H) OC(O)C(CH3)2NCCH2CH.

(22) .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K) (ppm)=repeat unit: 29.8 (4C*n), 33.7 (2C*n), 130.1 (2C*n); end group: 25.0 OC(O)C(CH3)2NCCH2CH, 40.6 OC(O)C(CH3)2NCCH2CH, 57.4OC(O)C(CH3)2NCCH2CH, 131.2 OC(O)C(CH3)2NCCH2CH, 173.1OC(O)C(CH3)2NCCH2CH, 176.0 OC(O)C(CH3)2NCCH2CH;

(23) These values confirm the structure below, also covered by the formula (II):

(24) ##STR00048##

(25) The number-average molecular weight Mn and the polydispersity index are respectively 6000 g/mol and 1.3.

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 di-CH2-Azl

(26) Example 2 is repeated, the 10.8 mmol of COE 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:

(27) ##STR00049##

(28) available from Sigma-Aldrich.

(29) The ratio of the reactants, expressed as number of moles: CTA di-CH.sub.2-Azl/(CDT+norbornene), is 0.020.

(30) 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:

(31) .sup.1H NMR: (ppm) repeat 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), 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=1.42 (s, 12H) OC(O)C(CH3)2NCCH2CH, 3.17 (m, 4H) OC(O)C(CH3)2NCCH2CH.

(32) .sup.13C NMR: (ppm) repeat unit: 27.4, 33.1, 42.1, 43.4, 130.3, 133.1, end group=25.0 OC(O)C(CH3)2NCCH2CH, 40.6OC(O)C(CH3)2NCCH2CH, 57.4 OC(O)C(CH3)2NCCH2CH, 131.2OC(O)C(CH3)2NCCH2CH, 173.1OC(O)C(CH3)2NCCH2CH, 176.0OC(O)C(CH3)2NCCH2CH.

(33) These values confirm the structure below:

(34) ##STR00050##

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

(36) The number-average molecular weight Mn and the polydispersity index are respectively 6900 g/mol and 1.5.

EXAMPLE 4

Polymerization pf COE in the Presence of CTA di-CH2-HexAzl

(37) Example 1 is repeated, CTA Azl.sub.2 being replaced with CTA di-CH.sub.2-HexAzl of formula:

(38) ##STR00051##

(39) A polymer in the form of a colourless solid powder is also recovered, but with a degree of conversion of the CTA of 100%, the .sup.1H/.sup.13C NMR analysis of which gives the following values:

(40) .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 1.42-1.62 (m, 20H) OC(O)C(C5H10)NCCH2CH, 3.25 (m, 4H) OC(O)C(C5H10)NCCH2CH, 5.65 (s, 2H) OC(O)C(C5H10)NCCH2CH;

(41) .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K) (ppm)=repeat unit: 29.8 (4C*n), 33.7 (2C*n), 130.1 (2C*n); end group: 20.7, 24.45, 32.8 OC(O)C(C5H10)NCCH2CH, 29.9OC(O)C(C5H10)NCCH2CH, 68.2 OC(O)C(C5H10)NCCH2CH, 120.5OC(O)C(C5H10)NCCH2CH, 162.4 OC(O)C(C5H10)NCCH2CH, 182.6OC(O)C(C5H10)NCCH2CH;

(42) These values confirm the structure below:

(43) ##STR00052##

(44) This structure is indeed covered by the formula (II) defined above.

(45) The number-average molecular weight Mn and the polydispersity index are respectively 5500 g/mol and 1.3.

EXAMPLE 5

Polymerization of CDT and Norbornene in the Presence of CTA di-CH2-HexAzl

(46) Example 3 is repeated, CTA di-CH.sub.2-Azl being replaced with CTA di-CH.sub.2-HexAzl.

(47) A copolymer in the form of a colourless viscous liquid is also obtained, with a degree of conversion of the CTA of 100%, the .sup.1H/.sup.13C NMR analysis of which gives the following values:

(48) .sup.1H NMR: (ppm) repeat 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), 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=1.42-1.62 (m, 20H) OC(O)C(C5H10)NCCH2CH, 3.25 (m, 4H) OC(O)C(C5H10)NCCH2CH;

(49) .sup.13C NMR: (ppm) repeat unit: 27.4, 33.1, 42.1, 43.4, 130.3, 133.1, end group=20.7, 24.45, 32.8OC(O)C(C5H10)NCCH2CH, 29.9 OC(O)C(C5H10)NCCH2CH, 68.3OC(O)C(C5H10)NCCH2CH, 131.7 OC(O)C(C5H10)NCCH2CH, 162.2OC(O)C(C5H10)NCCH2CH, 181.0 OC(O)C(C5H10) NCCH2CH;

(50) These values confirm the structure:

(51) ##STR00053##

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

(53) The number-average molecular weight Mn and the polydispersity index are respectively 6600 g/mol and 1.6.

EXAMPLE 6

Synthesis of Polyamide from the Unsaturated Polyolefin Comprising Two Azlactone End Groups of Example 5

(54) A stoichiometric mixture in methyl ethyl ketone of the polyolefin comprising two azlactone groups obtained in Example 5 with a primary diamine of polyether diamine type (Jeffamine EDR 176, Huntsman) was left at ambient temperature, until complete disappearance of the infrared band characteristic of the azlactone groups (at 1815 cm.sup.1) and appearance of the bands characteristic of the amide bond (bands at 1550 and 1530 cm.sup.1). The duration of the reaction is approximately 1 hour.

(55) The product thus synthesized resulted in the formation of polyamide which, appropriately formulated, made it possible to obtain adhesive properties.

(56) 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.

(57) 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.