FUNCTIONAL OR TELECHELIC POLYOLEFIN, DERIVATIVES THEREOF, AND PROCESS FOR PREPARING SAME

Abstract

The invention herein pertains to a telechelic polyolefin of formula (III) or (IV) and to a process for its preparation,

Z-A-(CH.sub.2).sub.p—B′  (III)

Z-A-(CH.sub.2).sub.p—B  (IV) A being a polymer chain obtained by homopolymerization of ethylene or by copolymerization of ethylene and an alpha-monoolefin; B′ being selected from the group consisting of N(SiMe.sub.3).sub.2; N(SiMe.sub.2CH.sub.2CH.sub.2SiMe.sub.2); para-C.sub.6H.sub.4(NMe.sub.2); para-C.sub.6H.sub.4(OMe); C.sub.6H.sub.4(N(SiMe.sub.3).sub.2); ortho-CH.sub.2—C.sub.6H.sub.4NMe.sub.2; ortho-CH.sub.2—C.sub.6H.sub.4OMe; C.sub.6F.sub.5; C.sub.3F.sub.7; C.sub.6F.sub.13; CH(OCH.sub.2CH.sub.2O); B being the function B′ or a function derived from B′; p being an integer from 0 to 50, advantageously from 0 to 11; Z being a function selected from the group consisting of halogens; thiols; thiol derivatives; azides; amines; alcohols; carboxylic acid function; isocyanates; silanes; phosphorus derivatives; dithioesters; dithiocarbamates; dithiocarbonates; trithiocarbonates; alkoxyamines; vinyl function; dienes; and the group -A-(CH.sub.2).sub.p—B′.

Claims

1. A method for preparing a polyolefin having at least one functionalized chain end, the method comprising the following step (a): (a) preparation of a compound of formula (I) by homopolymerization of ethylene, or by copolymerization of ethylene and an alpha-monoolefin in the presence of a transfer agent of formula (II):
Y(A-(CH.sub.2).sub.p—B′).sub.m  (I)
Y((CH.sub.2).sub.pB′).sub.m  (II) wherein: when m is 2, Y is an alkaline earth metal or zinc, and when m is 3, Y is aluminum; A is a polymer chain obtained by homopolymerization of ethylene, or by copolymerization of ethylene and an alpha-mono-olefin; B′ is selected from the group consisting of N(SiMe.sub.3).sub.2, N(SiMe.sub.2CH.sub.2CH.sub.2SiMe.sub.2), para-C.sub.6H.sub.4(NMe.sub.2), para-C.sub.6H.sub.4(OMe), C.sub.6H.sub.4(N(SiMe.sub.3).sub.2), ortho-CH.sub.2—C.sub.6H.sub.4NMe.sub.2, ortho-CH.sub.2—C.sub.6H.sub.4OMe, C.sub.6F.sub.5, C.sub.3F.sub.7, C.sub.6F.sub.13, and CH(OCH.sub.2CH.sub.2O); and p is an integer from 0 to 50.

2. The method according to claim 1, wherein A is a polymer of 70 to 100 mol % of ethylene and 0 to 30 mol % of an alpha-monoolefin selected from the group consisting of styrene, styrene derivatives, and olefins of the formula: CH.sub.2═CH—C.sub.xH.sub.2x+1, wherein x is an integer from 1 to 6.

3. The method according to claim 1, wherein the transfer agent is Mg [(CH.sub.2).sub.p—N(SiMe.sub.2CH.sub.2CH.sub.2SiMe.sub.2)].sub.2 or Mg [(CH.sub.2).sub.p—N(SiMe.sub.3).sub.2].sub.2; wherein p is an integer from 1 to 11.

4. The method according to claim 1, wherein the preparation of the compound of formula (I) is carried out in the presence of a catalyst based on a transition metal or a lanthanide.

5. The method according to claim 4, wherein the catalyst is of the formula: (Cp.sup.1)(Cp.sup.2)M or E(Cp.sup.1)(Cp.sup.2)M, wherein: M is a group 3 or 4 metal or a lanthanide; Cp.sup.1 is a cyclopentadienyl, fluorenyl, or substituted or unsubstituted indenyl group; Cp.sup.2 is a cyclopentadienyl, fluorenyl, or substituted or unsubstituted indenyl group; and the group E is a group bridging the two groups Cp.sup.1 and Cp.sup.2.

6. The method according to claim 4, wherein the catalyst is obtained from the compound (C.sub.5Me.sub.5).sub.2NdCl.sub.2Li(OEt.sub.2).sub.2 or a metallocene borohydride compound of a lanthanide.

7. The method according to claim 1, wherein step (a) is followed by a step (b) that includes reacting the compound of formula (I) with a chain terminating agent.

8. The method according to claim 7, wherein step (b) is a Z-functionalization step that is performed: by successive addition of B(OR).sub.3 and NMe.sub.3O, wherein R is a C.sub.1-C.sub.4 alkyl; or by adding a compound selected from the group consisting of iodine, sulfur, oxygen, nitroxyl radicals, carbon dioxide, the chlorosilanes, isobutene, alkoxysilanes, alkyl halides, aryl halides, vinyl halides, and disulfides.

9. The method according to claim 8, wherein the polyolefin is of formula (III) or (IV):
Z-A-(CH.sub.2).sub.p—B′  (III)
Z-A-(CH.sub.2).sub.p—B  (IV), wherein: Z is a group selected from the group consisting of hydrogen halogens, thiols, thiol derivatives, azides, amines, alcohols, carboxylic acids, isocyanates, silanes, phosphorus derivatives, dithioesters, dithiocarbamates, dithiocarbonates, trithiocarbonates, alkoxyamines, vinyl groups, dienes; and the group -A-(CH.sub.2).sub.p—B′, wherein B is the group B′, or a group derived from B′.

10. A telechelic polyolefin of formula (III) or (IV):
Z-A-(CH.sub.2).sub.p—B′  (III)
Z-A-(CH.sub.2).sub.p—B  (IV), wherein: A is a polymer chain obtained by homopolymerization of ethylene or by copolymerization of ethylene and an alpha-mono-olefin; B′ is selected from the group consisting of N(SiMe.sub.3).sub.2, N(SiMe.sub.2CH.sub.2CH.sub.2SiMe.sub.2), para-C.sub.6H.sub.4(NMe.sub.2), para-C.sub.6H.sub.4(OMe), C.sub.6H.sub.4(N(SiMe.sub.3).sub.2), ortho-CH.sub.2—C.sub.6H.sub.4NMe.sub.2, ortho-CH.sub.2—C.sub.6H.sub.4OMe, C.sub.6F.sub.5, C.sub.3F.sub.7, C.sub.6F.sub.13, and CH(OCH.sub.2CH.sub.2O); B is the group B′, or a group derived from B′; P is an integer from 0 to 50; and Z is selected from the group consisting of halogens, thiols, thiol derivatives, azides, amines, alcohols, carboxylic acids, isocyanates, silanes, phosphorus derivatives, dithioesters, dithiocarbamates, dithiocarbonates, trithiocarbonates, alkoxyamines, vinyl groups, dienes; and the group -A-(CH.sub.2).sub.p—B′.

11. The telechelic polyolefin of claim 10, wherein the polyolefin is of formula (IV); B is NH.sub.3Cl; A a polyethylene chain with an average molar mass of between 500 and 100,000 g/mol; p is greater than or equal to 1 and less than or equal to 11; Y is Mg; and Z is I.

12. The method according to claim 1, wherein p is an integer from 0 to 11.

13. The method according to claim 6, wherein the catalyst is obtained from a compound selected from the group consisting of {(Me.sub.2Si(C.sub.13H.sub.8).sub.2)Nd(μ-BH.sub.4)[(μ-BH.sub.4)Li(THF)]}.sub.2, Me.sub.2Si(C.sub.13H.sub.8).sub.2)Nd(BH.sub.4)(THF), (Me.sub.2Si(2,7-tBu.sub.2-C.sub.13H.sub.6).sub.2)Nd(BH.sub.4)(μ-BH.sub.4)Li(ether).sub.3, Me.sub.2Si(3-Me.sub.3Si—C.sub.5H.sub.3).sub.2NdBH.sub.4(THF).sub.2, {Me.sub.2Si(3-Me.sub.3Si—C.sub.5H.sub.3).sub.2NdCl}, {Me.sub.2Si(C.sub.5H.sub.4)(C.sub.13H.sub.8)NdCl}, and [Me.sub.2Si(C.sub.5H.sub.4)(C.sub.13H.sub.8)Nd(BH.sub.4).sub.2][Li(THF)].

14. The telechelic polyolefin of claim 10, wherein p is an integer from 0 to 11.

15. The method according to claim 2, wherein the transfer agent is Mg [(CH.sub.2).sub.p—N(SiMe.sub.2CH.sub.2CH.sub.2SiMe.sub.2)].sub.2 or Mg [(CH.sub.2).sub.p—N(SiMe.sub.3).sub.2].sub.2; wherein p is an integer from 1 to 11.

16. The method according to claim 2, wherein the preparation of the compound of formula (I) is carried out in the presence of a catalyst based on a transition metal or a lanthanide.

17. The method according to claim 16, wherein the catalyst is obtained from the compound (C.sub.5Me.sub.5).sub.2NdCl.sub.2Li(OEt.sub.2).sub.2 or a metallocene borohydride compound of a lanthanide.

18. The method according to claim 17, wherein the catalyst is obtained from a compound selected from the group consisting of {(Me.sub.2Si(C.sub.13H.sub.8).sub.2)Nd(μ-BH.sub.4)[(μ-BH.sub.4)Li(THF)]}.sub.2, Me.sub.2Si(C.sub.13H.sub.8).sub.2)Nd(BH.sub.4)(THF), (Me.sub.2Si(2,7-tBu.sub.2-C.sub.13H.sub.6).sub.2)Nd(BH.sub.4)(μ-BH.sub.4)Li(ether).sub.3, Me.sub.2Si(3-Me.sub.3Si—C.sub.5H.sub.3).sub.2NdBH.sub.4(THF).sub.2, {Me.sub.2Si(3-Me.sub.3Si—C.sub.5H.sub.3).sub.2NdCl}, {Me.sub.2Si(C.sub.5H.sub.4)(C.sub.13H.sub.8)NdCl}, and [Me.sub.2Si(C.sub.5H.sub.4)(C.sub.13H.sub.8)Nd(BH.sub.4).sub.2][Li(THF)].

19. The method according to claim 2, wherein step (a) is followed by a step (b) that includes reacting the compound of formula (I) with a chain terminating agent.

20. The method according to claim 19, wherein step (b) is a Z-functionalization step that is performed: by successive addition of B(OR).sub.3 and NMe.sub.3O, wherein R is a C.sub.1-C.sub.4 alkyl; or by adding a compound selected from the group consisting of iodine, sulfur, oxygen, nitroxyl radicals, carbon dioxide, the chlorosilanes, isobutene, alkoxysilanes, alkyl halides, aryl halides. vinyl halides, and disulfides.

Description

EXAMPLES OF IMPLEMENTATION OF THE INVENTION

[0120] Polyethylenes of formula (IV) have been prepared from the transfer agent MgR.sub.2 (R=(CH.sub.2).sub.3—N(SiMe.sub.2CH.sub.2CH.sub.2SiMe.sub.2) or (CH.sub.2).sub.3—N(SiMe.sub.3).sub.2) described hereinafter.

[0121] Nuclear Magnetic Resonance (NMR)

[0122] High-resolution NMR spectroscopy has been performed on a Bruker DRX 400 spectrometer operating at 400 MHz for the proton. The acquisitions were made at 363 K, using a 5 mm QNP probe. The samples were analyzed at a concentration of 5-15% by mass. A mixture of tetrachlorethylene (TCE) and deuterated benzene (C.sub.6D.sub.6) (2/1 v/v) was used as the solvent. The chemical shifts are stated in ppm units, relative to tetramethylsilane as internal reference.

[0123] Steric Exclusion Chromatography (SEC)

[0124] High-temperature steric exclusion chromatography (HT-SEC) analyses were carried out using a Viscotek appliance (from Malvern Instruments) equipped with 3 columns (PLgel Olexis 300 mm×7 mm I. D. from Agilent Technologies) and 3 detectors (refractometer, viscometer and light scattering). 200 μL of a solution of the sample, at a concentration of 5 mg.Math.mL.sup.−1 was eluted in 1,2,4-trichlorobenzene using a flow rate of 1 mL min at 150° C. The mobile phase was stabilized with 2,6-di(tert-butyl)-4-methylphenol (200 mg L.sup.−1). OmniSEC software was used for data acquisition and analysis. The molar masses are calculated using a calibration curve obtained from standard polyethylenes (M.sub.p: 170, 395, 750, 1,110, 2,155, 25,000, 77,500, 126,000 g.Math.mol.sup.−1) from Polymer Standard Service (Mainz).

Example 1

Preparation of the Transfer Agent MgR.SUB.2 .(R=1-propyl-2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane=(CH.SUB.2.).SUB.3.—N(SiMe.SUB.2.CH.SUB.2.CH.SUB.2.SiMe.SUB.2.))

[0125] 2.6 g (2 equivalents) of magnesium and then 50 ml of dry dibutyl ether is inserted into a 100 mL flask under an argon inert atmosphere.

[0126] The flask is placed in a cold bath at 0° C., and 13.3 mL (15 g, 1 equivalent) of 1-(3-bromopropyl)-2,2,5,5-tetramethyl-1 aza-2,5-disilacyclopentane is then added. The solution is allowed to gradually return to ambient temperature, with magnetic stirring.

[0127] The solution of 1-(3-bromopropyl)-2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane magnesium is then recovered by canulation in a Schlenk under argon to eliminate magnesium, which does not react.

[0128] To this solution, 5.5 ml (1.2 equivalents) of dioxane is added to displace the Schlenk equilibrium, to form the compound MgR.sub.2 (R=1-propyl-2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane) and precipitate MgBr.sub.2.

[0129] This solution is then filtered under argon on celite, to recover MgR.sub.2 in solution in dibutyl ether.

Example 2

Preparation of the Transfer Agent MgR.SUB.2 .(R=1-propyl-2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane=(CH.SUB.2.).SUB.3.—N(SiMe.SUB.2.CH.SUB.2.CH.SUB.2.SiMe.SUB.2.))

[0130] 2.6 g (2 equivalents) of magnesium and then 50 mL of dry THF is inserted into a 100 mL flask under an argon inert atmosphere.

[0131] 13.3 ml (15 g, 1 equivalent) of 1-(3-bromopropyl)-2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane are then added dropwise at ambient temperature. The solution is left under magnetic stirring for one hour.

[0132] The solution of 1-(3-bromopropyl)-2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane magnesium is then recovered by canulation in a Schlenk under argon to eliminate magnesium, which does not react.

[0133] To this solution, 5.5 ml (1.2 equivalents) of dioxane is added to displace the Schlenk equilibrium, to form the compound MgR.sub.2 (R=1-propyl-2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane) and precipitate MgBr.sub.2.

[0134] This solution is then filtered under argon on celite, to recover MgR.sub.2 in solution in the THF.

[0135] The THF is then distilled under vacuum at ambient temperature and the MgR.sub.2 is then dissolved in dibutyl ether.

[0136] .sup.1H NMR (THF-d8—400 MHz—298K) δ: ppm=2.63 (m, —CH.sub.2—N), 1.60 (m, —CH.sub.2—CH.sub.2—N), 0.64 (s, N—Si(CH.sub.3).sub.2—CH.sub.2—), 0.01 (s, N—Si(CH.sub.3).sub.2—CH.sub.2—), −0.78 (Mg—CH.sub.2—)

Example 3

Preparation of the Polyolefin Z-A-(CH.SUB.2.).SUB.3.—B (with Z=H; A=(CH.SUB.2.—CH.SUB.2.).SUB.n., and B=NH.SUB.3.Cl)

[0137] 21.7 ml (4.77 mmol) of MgR.sub.2 prepared according to example 2 (0.22 M in dibutyl ether) are inserted in a flask containing 400 ml of dry toluene.

[0138] The solution is transferred under an argon atmosphere into a 500 mL reactor.

[0139] A solution of 20.7 mg of compound (C.sub.5 Me.sub.5).sub.2 NdCl.sub.2 Li. (OEt.sub.2).sub.2(32 μmol).

[0140] The argon is then removed under vacuum, and the reactor is pressurized to 3 bar of ethylene at 70° C. The pressure is kept constant in the reactor during polymerization, by means of a reservoir.

[0141] When the desired amount of ethylene has been consumed, the reactor is degassed and the temperature is brought back to 20° C.

[0142] A methanol/HCl solution is added, and the medium is stirred for 1 hour.

[0143] The polymer is then filtered, washed with methanol and then dried.

[0144] 15.3 g of polyethylene CH.sub.3—(CH.sub.2CH.sub.2).sub.n—(CH.sub.2).sub.3NH.sub.3Cl (82% functionality, Mn=1850 g.Math.mol.sup.−1 by NMR) are recovered.

[0145] .sup.1H NMR (2/1 v/v TCE/C.sub.6D.sub.6, 400 MHz, 363K) δ ppm=8.29 (broad, —NH.sub.3Cl), 2.87 (t, J=7 Hz, —CH.sub.2—NH.sub.3Cl), 1.73 (quin, J=7 Hz, —CH.sub.2CH.sub.2NH.sub.3Cl) 1.24 (broad, (CH.sub.2CH.sub.2).sub.n), 0.83 (t, J=7 Hz, —CH.sub.2—CH.sub.3).

[0146] .sup.13C NMR (2/1 v/v TCE/C.sub.6D.sub.6, 101 MHz, 363K) δ ppm=39.72, 32.21 30.00 ((CH.sub.2CH.sub.2).sub.n), 29.61, 29.25, 27.80, 26.85, 22.90, 14.04.

Example 4

Preparation of Polyolefin ZA-(CH.SUB.2.).SUB.3.—B (with Z=H; A=(CH.SUB.2.—CH.SUB.2.).SUB.n .and B=NH.SUB.2.)

[0147] 21.7 mL (4.77 mmol) of MgR.sub.2 prepared according to example 2 (0.22 M in dibutyl ether) is inserted into a flask containing 400 mL of dry toluene.

[0148] The solution is transferred under an argon atmosphere into a 500 mL reactor.

[0149] A solution of 21.4 mg of compound (C.sub.5Me.sub.5).sub.2 NdCl.sub.2Li.(OEt.sub.2).sub.2(33 μmol).

[0150] The argon is then removed under vacuum, and the reactor is pressurized to 3 bar of ethylene at 70° C. The pressure is kept constant in the reactor during polymerization, by means of a reservoir.

[0151] When the desired amount of ethylene has been consumed, the reactor is degassed and the temperature is brought back to 20° C.

[0152] A methanol/HCl solution is added, and the medium is stirred for 1 hour.

[0153] The resulting suspension is poured into IM methanol/NaOH solution and stirred for 1 hour.

[0154] The polymer is then filtered, washed with methanol and then dried.

[0155] 15.0 g of polyethylene CH.sub.3—(CH.sub.2CH.sub.2).sub.n—(CH.sub.2).sub.3NH.sub.2 (functionality 80%, Mn=1820 g.Math.mol.sup.−1 by NMR) are recovered.

[0156] .sup.1H NMR (2/1 v/v TCE/C.sub.6D.sub.6, 400 MHz, 363K) δ ppm=2.53 (broad, CH.sub.2—NH.sub.2), 1.24 (broad, (CH.sub.2CH.sub.2).sub.n), 0.83 (t, J=7 Hz, —CH.sub.2—CH.sub.3).

[0157] .sup.13C NMR (2/1 v/v TCE/C.sub.6D.sub.6, 101 MHz, 363K) δ ppm=42.55, 34.44, 32.21, 30.00 ((CH.sub.2CH.sub.2)), 29.61, 27.25, 22.90, 14.04.

Example 5

Preparation of the Telechelic Polyolefin ZA-(CH.SUB.2.).SUB.3.—B (with Z=I; A=(CH.SUB.2.—CH.SUB.2.).SUB.n .and B=NH.SUB.3.C)

[0158] 8.4 ml of MgR.sub.2 prepared according to example 2 (in solution in 0.3 M of dibutyl ether) are inserted into a flask containing 400 ml of dry toluene.

[0159] The solution is transferred under an argon atmosphere into a 500 mL reactor.

[0160] A solution of 10.7 mg of compound (C.sub.5Me.sub.5).sub.2 NdCl.sub.2Li (OEt.sub.2).sub.2 (molar ratio Mg/Nd=150) is then transferred.

[0161] The argon is then removed under vacuum, and the reactor is pressurized to 3 bar of ethylene at 70° C. The pressure is kept constant in the reactor during polymerization, by means of a reservoir.

[0162] When the desired amount of ethylene has been consumed, the reactor is degassed and the temperature is brought back to 20° C.

[0163] A solution of 2.5 g of iodine in THF (molar ratio I/Mg=4) is added, and the medium is stirred for 2 hours.

[0164] A methanol/HCl solution is added, and the medium is stirred for 1 hour.

[0165] The resulting suspension is poured into methanol and then the polymer is filtered, washed with methanol and then dried.

[0166] 4.5 g of telechelic polyethylene I—(CH.sub.2CH.sub.2).sub.n—(CH.sub.2).sub.3 NH.sub.3Cl (100% functionality, Mn=1350 g.Math.mol.sup.−1 by NMR) are recovered.

[0167] .sup.1H NMR (2/1 v/v TCE/C.sub.6D.sub.6, 400 MHz, 363K) δ ppm=8.29 (broad, —NH.sub.3Cl), 2.94 (t, J=7 Hz, —CH.sub.2I), 2.87 (t, J=7 Hz, —CH.sub.2—NH.sub.3Cl), 1.73 (quin, J=7 Hz, —CH.sub.2CH.sub.2NH.sub.3Cl), 1.66 (quin, J=7 Hz, —CH.sub.2CH.sub.2I), 1.24 (broad, (CH.sub.2CH.sub.2).sub.n).

[0168] .sup.13C NMR (2/1 v/v TCE/C.sub.6D.sub.6, 101 MHz, 363K) δ ppm=39.72, 30.77, 30.00 ((CH.sub.2CH.sub.2).sub.n), 29.68, 29.25, 28.81, 27.80, 26.85, 4.91.

Example 6

Preparation of the Transfer Agent MgR.SUB.2 .(R=N, N-bis (trimethylsilyl) propan-1-amine=(CH.SUB.2.).SUB.3.—N(SiMe.SUB.3.)

[0169] 2.6 g (2 equivalents) of magnesium and then 50 mL of dry THF is inserted into a 100 mL flask under an argon inert atmosphere.

[0170] 15 g (1 equivalent) of 3-bromo-N, N-bis (trimethylsilyl) propan-1-amine are then added dropwise, at room temperature. The solution is left under magnetic stirring for one hour.

[0171] The solution of 3-bromo-N, N-bis (trimethylsilyl) propan-1-amine magnesium is then recovered by canulating in a Schlenk under argon, to remove the unreacted magnesium.

[0172] To this solution, 5.5 ml (1.2 equivalents) of dioxane is added to displace the Schlenk equilibrium, to form the compound MgR.sub.2 (R=N, N-bis (trimethylsilyl) propan-1-amine) and Precipitate MgBr.sub.2.

[0173] This solution is then filtered under argon on celite, to recover MgR.sub.2 in solution in the THF.

[0174] The THF is then distilled under vacuum at ambient temperature, and the MgR.sub.2 is then dissolved in dibutyl ether to obtain a 0.40 M solution.

Example 7

Preparation of the Polyolefin Z-A-(CH.SUB.2.).SUB.3.—B (with Z=H; A=(CH.SUB.2.—CH.SUB.2.).SUB.n., and B=NH.SUB.3.Cl)

[0175] 6.3 ml (2.52 mmol) of MgR.sub.2 prepared according to example 6 (0.40 M in dibutyl ether) are inserted in a flask containing 400 ml of dry toluene.

[0176] The solution is transferred under an argon atmosphere into a 500 mL reactor.

[0177] A solution of 10.7 mg of compound (C.sub.5Me.sub.5).sub.2 NdCl.sub.2Li.(OEt.sub.2).sub.2(16 μmol).

[0178] The argon is then removed under vacuum, and the reactor is pressurized to 3 bar of ethylene at 70° C. The pressure is kept constant in the reactor during polymerization, by means of a reservoir.

[0179] When the desired amount of ethylene has been consumed, the reactor is degassed and the temperature is brought back to 20° C.

[0180] A methanol/HCl solution is added, and the medium is stirred for 1 hour.

[0181] The polymer is then filtered, washed with methanol and then dried.

[0182] 5.3 g of polyethylene CH.sub.3—(CH.sub.2CH.sub.2).sub.n—(CH.sub.2).sub.3NH.sub.3Cl (84% functionality, Mn=1440 g.Math.mol.sup.−1 by NMR) are recovered.

[0183] 1H NMR (2/1 v/v TCE/C.sub.6D.sub.6, 400 MHz, 363K) δ ppm=8.62 (broad, —NH.sub.3Cl), 2.86 (—CH.sub.2—NH.sub.3Cl), 1.75 (quin, J=7 Hz, —CH.sub.2CH.sub.2NH.sub.3Cl) 1.29 (broad, (CH.sub.2CH.sub.2).sub.n), 0.86 (t, J=7 Hz, —CH.sub.2—CH.sub.3).

Example 8

Preparation of Polyolefin Z-A-(CH.SUB.2.).SUB.3.—B (with Z=H; A=(CH.SUB.2.—CH.SUB.2.) and B=NH.SUB.2.)

[0184] 6.3 ml (2.52 mmol) of MgR.sub.2 prepared according to example 6 (0.40 M in dibutyl ether) are inserted in a flask containing 400 ml of dry toluene.

[0185] The solution is transferred under an argon atmosphere into a 500 mL reactor.

[0186] A solution of 10.7 mg of compound (C.sub.5Me.sub.5).sub.2 NdCl.sub.2Li.(OEt.sub.2).sub.2(16 μmol).

[0187] The argon is then removed under vacuum, and the reactor is pressurized to 3 bar of ethylene at 70° C. The pressure is kept constant in the reactor during polymerization, by means of a reservoir.

[0188] When the desired amount of ethylene has been consumed, the reactor is degassed and the temperature is brought back to 20° C.

[0189] A methanol/HCl solution is added, and the medium is stirred for 1 hour.

[0190] The resulting suspension is poured into IM methanol/NaOH solution and stirred for 1 hour.

[0191] The polymer is then filtered, washed with methanol and then dried.

[0192] 5.0 g of polyethylene CH.sub.3—(CH.sub.2CH.sub.2).sub.n—(CH.sub.2).sub.3NH.sub.2 (functionality 84%, Mn=1440 g.Math.mol.sup.−1 by NMR) are recovered.

[0193] .sup.1H NMR (2/1 v/v TCE/C.sub.6D.sub.6, 400 MHz, 363K) δ ppm=2.53 (broad, CH.sub.2—NH.sub.2), 1.24 (broad, (CH.sub.2CH.sub.2).sub.n), 0.83 (t, J=7 Hz, —CH.sub.2—CH.sub.3).

Example 9

Preparation of Polyolefin ZA-(CH.SUB.2.).SUB.3.—B (with Z=OH; A=(CH.SUB.2.—CH.SUB.2.).SUB.n .and B=NH.SUB.3.Cl)

[0194] 6.3 ml (2.52 mmol) of MgR.sub.2 prepared according to example 6 (0.40 M in dibutyl ether) are inserted a flask containing 400 ml of dry toluene.

[0195] The solution is transferred under an argon atmosphere into a 500 mL reactor.

[0196] A solution of 10.7 mg of compound (C.sub.5Me.sub.5).sub.2 NdCl.sub.2Li.(OEt.sub.2).sub.2(16 μmol).

[0197] The argon is then removed under vacuum, and the reactor is pressurized to 3 bar of ethylene at 70° C. The pressure is kept constant in the reactor during polymerization, by means of a reservoir.

[0198] When the desired amount of ethylene has consumed, the reactor is degassed and a solution of triethyl borate B(OEt).sub.3 (2.55 mL in 10 mL of toluene B/Mg=6) is added under argon. The medium is stirred for 2 hours, and then a solution of trimethylamine N oxide TAO (2.5 g in 20 mL of DMF TAO/B=1.5) is added under argon.

[0199] The medium is stirred for 2 hours, and then the temperature is brought to 20° C.

[0200] A methanol/HCl solution is added, and the medium is stirred for 1 hour.

[0201] The polymer is then filtered, washed with methanol and then dried.

[0202] 6.3 g of polyethylene HO—CH.sub.2—(CH.sub.2CH.sub.2).sub.n—(CH.sub.2).sub.3NH.sub.3Cl (70% functionality, Mn=1940 g.Math.mol.sup.−1 by NMR) are recovered.

[0203] .sup.1H NMR (2/1 v/v TCE/C.sub.6D.sub.6, 400 MHz, 363K) δ ppm=8.63 (broad, —NH.sub.3Cl), 3.40 (t, J=7 Hz, HO—CH.sub.2—) 2.86 (broad, —CH.sub.2—NH.sub.3Cl), 1.75 (quin, J=7 Hz, —CH.sub.2CH.sub.2NH.sub.3Cl) 1.29 (broad, (CH.sub.2CH.sub.2).sub.n).

Example 10

Preparation of the Polyolefin Z-A-(CH.SUB.2.).SUB.3.—B (with Z=S—(C═S)—N(CH.SUB.2.—CH.SUB.3.).SUB.2.; A=(CH.SUB.2.—CH.SUB.2.).SUB.n., and B=NH.SUB.3.Cl)

[0204] 6.3 ml (2.52 mmol) of MgR.sub.2 prepared according to example 6 (0.40 M in dibutyl ether) are inserted a flask containing 400 ml of dry toluene.

[0205] The solution is transferred under an argon atmosphere into a 500 mL reactor.

[0206] A solution of 10.7 mg of compound (C.sub.5Me.sub.5).sub.2 NdCl.sub.2Li.(OEt.sub.2).sub.2(16 μmol).

[0207] The argon is then removed under vacuum, and the reactor is pressurized to 3 bar of ethylene at 70° C. The pressure is kept constant in the reactor during polymerization, by means of a reservoir.

[0208] When the desired amount of ethylene has been consumed, the reactor is degassed and a solution of tetraethylthiuram disulfide (1.5 g, 2 equivalents in 20 mL of toluene) is added under argon.

[0209] The medium is stirred for 2 hours, and then the temperature is brought to 20° C.

[0210] A methanol/HCl solution is added, and the medium is stirred for 1 hour.

[0211] The polymer is then filtered, washed with methanol and then dried.

[0212] 5.6 g of polyethylene (CH.sub.3—CH.sub.2).sub.2N—(CH.sub.2CH.sub.3).sub.n—(CH.sub.2).sub.3NH.sub.3Cl (functionality 100%; Mn=1480 g.Math.mol.sup.−1 by NMR).

[0213] .sup.1H NMR (2/1 v/v TCE/C.sub.6D.sub.6, 400 MHz, 363K) δ ppm=8.59 (broad, —NH.sub.3Cl), 3.64 (q, J=7 Hz (CH.sub.3—CH.sub.2).sub.2N—(S═C)—S), 3.30 (t, J=7 Hz, (CH.sub.3—CH.sub.2).sub.2N—(S═C)—S—CH.sub.2—) 2.88 (broad, —CH.sub.2—NH.sub.3Cl), 1.77 (broad, —CH.sub.2CH.sub.2NH.sub.3Cl), 1.67 (quin, J=7 Hz, (CH.sub.3—CH.sub.2).sub.2N—(S═C)—S—CH.sub.2—CH.sub.2—), 1.29 (broad, (CH.sub.2CH.sub.2).sub.n), 1.04 (t, J=7 Hz (CH.sub.3—CH.sub.2).sub.2N—(S═C)—S).

Example 11

Preparation of the telechelic Polyolefin ZA-(CH.SUB.2.).SUB.3.—B (with Z=I; A=(CH.SUB.2.—CH.SUB.2.).SUB.n .and B=NH.SUB.3.Cl)

[0214] 6.3 ml (2.52 mmol) of MgR.sub.2 prepared according to example 6 (0.40 M in dibutyl ether) are inserted a flask containing 400 ml of dry toluene.

[0215] The solution is transferred under an argon atmosphere into a 500 mL reactor.

[0216] A solution of 10.7 mg of compound (C.sub.5 Me.sub.5).sub.2 NdCl.sub.2 Li. (OEt.sub.2).sub.2(16 μmol).

[0217] The argon is then removed under vacuum, and the reactor is pressurized to 3 bar of ethylene at 70° C. The pressure is kept constant in the reactor during polymerization, by means of a reservoir.

[0218] When the desired amount of ethylene has been consumed, the reactor is degassed and the temperature is brought back to 20° C.

[0219] A solution of 2.5 g of iodine in THF (molar ratio I/Mg=4) is added, and the medium is stirred for 2 hours.

[0220] A methanol/HCl solution is added, and the medium is stirred for 1 hour.

[0221] The resulting suspension is poured into methanol and then the polymer is filtered, washed with methanol and then dried.

[0222] 6.3 g of telechelic polyethylene I—(CH.sub.2CH.sub.2).sub.n—(CH.sub.2).sub.3 NH.sub.3Cl (100% functionality, Mn=1300 g.Math.mol.sup.−1 by NMR) are recovered.

[0223] .sup.1H NMR (2/1 v/v TCE/C.sub.6D.sub.6, 400 MHz, 363K) δ ppm=8.30 (broad, —NH.sub.3Cl), 2.91 (t, J=7 Hz, —CH.sub.2I), 2.86 (t, J=7 Hz, —CH.sub.2—NH.sub.3Cl), 1.73 (quin, J=7 Hz, —CH.sub.2CH.sub.2NH.sub.3Cl), 1.63 (quin, J=7 Hz, —CH.sub.2CH.sub.2I), 1.26 (broad, (CH.sub.2CH.sub.2).sub.n).