Telechelic polyolefin and preparation thereof

Abstract

Telechelic polyolefin of formula(I) and its derivatives:
CH.sub.2CH(CH.sub.2).sub.p-A-Z(I)
wherein: A represents a (co)polymer comprising at least 95 mol % of (CH.sub.2CH.sub.2) units; Z is selected from the group comprising halogens, thiols and their derivatives, azides, amines, alcohols, the carboxylic acid function, isocyanates, silanes, phosphorous derivatives, dithioesters, dithiocarbamates, dithiocarbonates, trithiocarbonates, alkoxyamines, the vinyl function, dienes, and the group -A-(CH.sub.2).sub.pCHCH.sub.2; p is a whole number between 1 and 20, most advantageously between 6 and 9.

Claims

1. A process for preparing a telechelic polyolefin of formula (I):
CH.sub.2CH(CH.sub.2).sub.p-A-Z(I) wherein: A represents a (co)polymer comprising at least 95 mol % of (CH.sub.2CH.sub.2) units; Z is selected from the group consisting of halogens; thiols and their derivatives; azides; amines; alcohols; the carboxylic acid function; isocyanates; silanes; phosphorous derivatives; dithioesters; dithiocarbamates; dithiocarbonates; trithiocarbonates; alkoxyamines; the vinyl function; dienes; and the group -A-(CH.sub.2).sub.pCHCH.sub.2; and p is a whole number between 1 and 20, said process comprising the following steps: preparing a compound of formula (II):
Y(A-(CH.sub.2).sub.pCHCH.sub.2).sub.m(II) wherein m is 2 or 3; and when m=2, Y is an alkaline earth metal; and when m=3, Y is an element of group 13; and cleaving the bond between Y and A-(CH.sub.2).sub.pCHCH.sub.2, and functionalizing A-(CH.sub.2).sub.pCHCH.sub.2 with Z.

2. A process according to claim 1, wherein the preparing the compound of formula (II) is achieved in the presence of a transition metal or lanthanide complex, and a transfer agent of formula (III):
Y((CH.sub.2).sub.pCHCH.sub.2).sub.m(III).

3. A process according to claim 2, wherein the transition metal or lanthanide complex is a metallocene selected from the group consisting of compounds of which the formula contains the base structure: (Cp.sup.1)(Cp.sup.2)M or E(Cp.sup.1)(Cp.sup.2)M; M being a group 3 or 4 metal, or a lanthanide; and Cp.sup.1, Cp.sup.2 being cyclopentadienyl, fluorenyl or indenyl groups or those groups featuring additional substituents; E being a bridge between the Cp.sup.1 and Cp.sup.2 ligands, of the formula MR.sup.1R.sup.2, M being a group 14 element, and R.sup.1 and R.sup.2 being alkyl or aryl groups having 1 to 20 carbon atoms.

4. A process according to claim 3, wherein the complex is a metallocene of the formula (C.sub.5Me.sub.5).sub.2MX.sub.2Li(OEt.sub.2).sub.2, M being a group 3 metal or lanthanide and X being a halogen.

5. A process according to claim 4, wherein M is a lanthanide.

6. A process according to claim 2, wherein the telechelic polyolefin is represented by the formula CH.sub.2CH(CH.sub.2).sub.p(CH.sub.2CH.sub.2).sub.nI, I being an iodine atom, p being a whole number between 6 and 9, and n being a whole number between 17 and 360.

7. A process according to claim 1, wherein the functionalizing step with Z comprises the addition of a compound selected from the group consisting of iodine I.sub.2, sulfur S.sub.8 and tetraethylthiuram disulfide.

8. A process according to claim 1, wherein the functionalizing step with Z is an oxidative coupling when Z=-A-(CH.sub.2).sub.pCHCH.sub.2.

9. A process according to claim 1, further comprising, subsequent to the functionalizing with Z, modifying at least one of the chain-ends of the telechelic polyolefin by reaction of the vinyl function and/or of the Z group.

10. A process according to claim 1, wherein, when m=2, Y is magnesium or zinc, and when m=3, Y is aluminum.

11. A process according to claim 1, wherein p is a whole number between 6 and 9.

12. A process according to claim 1, wherein the telechelic polyolefin is represented by the formula CH.sub.2CH(CH.sub.2).sub.p(CH.sub.2CH.sub.2).sub.nI, I being an iodine atom, p being a whole number between 6 and 9, and n being a whole number between 17 and 360.

13. A telechelic polyolefin of formula (I):
CH.sub.2CH(CH.sub.2).sub.p-A-Z(I) wherein: A represents a (co)polymer comprising at least 95 mol % of (CH.sub.2CH.sub.2) units; Z is selected from the group consisting of halogens; thiols and their derivatives; azides; amines; alcohols; the carboxylic acid function; isocyanates; silanes; phosphorous derivatives; dithioesters; dithiocarbamates; dithiocarbonates; trithiocarbonates; alkoxyamines; and dienes; and p is a whole number between 1 and 20.

14. A telechelic polyolefin according to claim 13, wherein the CH.sub.2CH(CH.sub.2).sub.p group of formula (I) originates from a transfer agent of formula Y((CH.sub.2).sub.pCHCH.sub.2).sub.m, wherein m is 2 or 3; and when m=2, Y is an alkaline earth metal; and when m=3, Y is an element of group 13.

15. A telechelic polyolefin according to claim 13, wherein A is a linear polyethylene of formula (CH.sub.2CH.sub.2).sub.n, n being a whole number between 7 and 3600.

16. A telechelic polyolefin according to claim 13, wherein the telechelic polyolefin is represented by the formula CH.sub.2CH(CH.sub.2).sub.p(CH.sub.2CH.sub.2).sub.nI, I being an iodine atom, p being a whole number between 6 and 9, and n being a whole number between 17 and 360.

17. A telechelic polyolefin according to claim 13 wherein p is a whole number between 6 and 9.

Description

FIGURES

(1) FIG. 1 is the .sup.1H NMR (nuclear magnetic resonance) spectrum of the telechelic polyethylene according to the invention, CH.sub.2CH(CH.sub.2).sub.9-PE-I, where PE=(CH.sub.2CH.sub.2).

(2) FIG. 2 is the .sup.1H NMR (nuclear magnetic resonance) spectrum of the telechelic polyethylene according to the invention, CH.sub.2CH(CH.sub.2).sub.9-PE-SC(S)N(Et).sub.2, where PE=(CH.sub.2CH.sub.2).

(3) FIG. 3 is the .sup.1H NMR (nuclear magnetic resonance) spectrum of the telechelic polyethylene according to the invention, CH.sub.2CH(CH.sub.2).sub.9-PE-N.sub.3, where PE=(CH.sub.2CH.sub.2).

(4) FIG. 4 is the .sup.1H NMR (nuclear magnetic resonance) spectrum of the telechelic polyethylene according to the invention, CH.sub.2CH(CH.sub.2).sub.9-PE-NH.sub.2, where PE=(CH.sub.2CH.sub.2).

(5) FIG. 5 is the .sup.1H NMR (nuclear magnetic resonance) spectrum of the telechelic polyethylene according to the invention, CH.sub.2CH(CH.sub.2).sub.9-PE-(CH.sub.2).sub.9CHCH.sub.2, where PE=(CH.sub.2CH.sub.2).

EXAMPLES

(6) The following examples concern the preparation: of a transfer agent of formula (III) of an intermediate compound of formula (II); of telechelic polyolefins of formula (I).

Synthesis of the Transfer Agent bis(10-undecenyl)magnesium, Mg((CH2)9CHCH2)2

(7) To a suspension of magnesium (2.38 g, 98 mmol) in di-n-butyl ether (100 ml) was added 11-bromo-1-undecene (11.3 ml, 49 mmol) dropwise at 0 C. The reaction mixture was stirred at 0 C. for 1 h and then allowed to return to room temperature. The resulting suspension was filtered to remove excess magnesium. To the filtrate was added dioxane (5.0 ml, 59 mmol), whereupon a white precipitate was immediately formed. The suspension was stirred for 2 h and then filtered, to obtain a solution of Mg((CH.sub.2).sub.9CHCH.sub.2).sub.2 in di-n-butyl ether.

(8) Aliquots from the solution were taken for concentration determination by titration using i) pyrene-1-acetic acid and ii) HCl.sub.(aq) then NaOH.sub.(aq) solutions.

(9) A further sample of the recovered solution was taken and the solvent removed under reduced pressure for NMR analysis.

(10) Characterization by .sup.1H NMR (THF-d.sub.8, 300 MHz, 300K) : 5.81 (m, CH.sub.2CHCH.sub.2), 4.89-5.02 (m, CH.sub.2CHCH.sub.2), 2.06 (q, J=7 Hz, CH.sub.2CHCH.sub.2), 1.56 (quin, J=7 Hz, 1.32 (br, (CH.sub.2).sub.6), 0.63 (m, CH.sub.2Mg) ppm.

(11) General Polymerization Procedure for the Preparation of the Intermediate CH.sub.2CH(CH.sub.2).sub.9-PE-Mg-PE-(CH.sub.2).sub.9CHCH.sub.2(PE=(CH.sub.2CH.sub.2).sub.n)

(12) A solution of bis(10-undecenyl)magnesium in dibutyl ether (0.24 mol.Math.L.sup.1, 10.4 ml, 2.5 mmol) was diluted with toluene (400 mL). The resulting solution was transferred to a reactor under an argon atmosphere. The reactor was heated to 75 C. and then charged with an ethylene atmosphere at a pressure of 3 bars. A precatalyst suspension of Cp*.sub.2NdCl.sub.2Li(OEt.sub.2).sub.2 (10.7 mg, 16.7 mol) in toluene (10 ml) was then added to the reactor and the consumption of ethylene monitored. After the desired consumption the ethylene atmosphere was replaced with argon.

Synthesis of the telechelic polyolefin CH2CH(CH2)9-PE-I (PE=(CH2CH2)n)

(13) After the polymerization step described above, the reaction mixture containing the intermediate CH.sub.2CH(CH.sub.2).sub.9-PE-Mg-PE-(CH.sub.2).sub.9CHCH.sub.2 (PE=(CH.sub.2CH.sub.2).sub.n) was cooled to 10 C.

(14) A solution of iodine (2.54 g, 10 mmol) in 50 mL of THF was added, and the suspension stirred for 3 hours.

(15) The reactor contents were then added to methanol (200 mL) and the solution filtered. The solids recovered were washed with methanol (3100 mL) then dried.

(16) Characterization:

(17) .sup.1H NMR (FIG. 1) (2/1 v/v TCE/C.sub.6D.sub.6, 400 MHz, 363K) ppm=5.70 (m, CH.sub.2CHCH.sub.2), 4.83-4.93 (m, CH.sub.2CHCH.sub.2), 2.94 (t, J=7 Hz, CH.sub.2I), 1.96 (q, J=7 Hz, CH.sub.2CHCH.sub.2), 1.66 (quin, J=7 Hz, CH.sub.2CH.sub.2I), 1.24 (br, (CH.sub.2CH.sub.2).sub.n).

(18) .sup.13C NMR (2/1 v/v TCE/C.sub.6D.sub.6, 101 MHz, 363K) ppm=138.90, 114.20, 33.98, 30.78, 30.00 ((CH.sub.2CH.sub.2).sub.n), 29.90, 29.82, 29.80, 29.69, 29.44, 29.32, 28.82, 4.96.

(19) M.sub.n=1500 g.Math.mol.sup.1, M.sub.w/M.sub.n=1.1, F=95%.

Synthesis of the Telechelic Polyolefin CH2CH(CH9-PE-SC(S)N(Et)2 (PE=(CH2CH2)n)

(20) After the polymerization step described above, the reaction mixture containing the intermediate CH.sub.2CH(CH.sub.2).sub.9-PE-Mg-PE-(CH.sub.2).sub.9CHCH.sub.2 (PE=(CH.sub.2CH.sub.2).sub.n) was heated to 80 C.

(21) A solution of N,N,N,N-tetraethylthiuram disulfide (1.85 g, 6.25 mmol) in toluene (50 mL) was then added and the resulting solution stirred for 3 hours.

(22) The reaction mixture was cooled to ambient temperature before being added to methanol (200 mL), then the resulting suspension filtered.

(23) The solids recovered from filtration were washed three times with methanol (3100 mL) then dried.

(24) Characterization:

(25) .sup.1H NMR (FIG. 2) (2/1 v/v TCE/C.sub.6D.sub.6, 400 MHz, 363K) ppm=5.70 (m, CH.sub.2CHCH.sub.2), 4.83-4.93 (m, CH.sub.2CHCH.sub.2), 3.68 (br, NCH.sub.2CH.sub.3), 3.23 (t, J=7 Hz, CH.sub.2SC(S)), 1.96 (q, J=7 Hz, CH.sub.2CHCH.sub.2), 1.63 (quin, J=7 Hz, CH.sub.2CH.sub.2SC(S)) 1.24 (br, (CH.sub.2CH.sub.2).sub.n), 1.08 (t, J=7 Hz, NCH.sub.2CH.sub.3).

(26) .sup.13C NMR (2/1 v/v TCE/C.sub.6D.sub.6, 101 MHz, 363K) ppm=195.98, 138.90, 114.20, 47.74, 37.38, 33.98, 30.0 ((CH.sub.2CH.sub.2).sub.n), 29.90, 29.83, 29.80, 29.54, 29.44, 29.35, 29.32, 29.23, 12.25.

(27) M.sub.n=1550 g.Math.mol.sup.1, M.sub.w/M.sub.n=1.14, F=87%

Synthesis of the Telechelic Polyolefin CH2CH(CH2)9-PE-SH (PE=(CH2CH2)n)

(28) A suspension of lithium aluminium hydride (0.61 g, 16 mmol) in tetrahydrofuran (200 mL) was added to a solution of CH.sub.2CH(CH.sub.2).sub.9-PE-SC(S)NEt.sub.2 (M.sub.n=1550 g.Math.mol.sup.1, F=87%; 3.0 g) in toluene (200 mL) at 100 C.

(29) The suspension obtained was stirred under argon in reflux conditions (90 C.) for 15 hours.

(30) The reaction mixture was then cooled to ambient temperature, at which point methanol (20 mL) was slowly added.

(31) The resultant suspension was then heated to 95 C. and filtered.

(32) The filtrate was cooled and added to methanol (200 mL).

(33) The suspension produced was then filtered and the solids recovered were washed with methanol (3100 mL) and dried under vacuum.

(34) Yield=2.5 g.

(35) Characterization:

(36) .sup.1H NMR (2/1 v/v TCE/C.sub.6D.sub.6, 400 MHz, 363K): ppm=5.70 (m, CH.sub.2CHCH.sub.2), 4.83-4.93 (m, CH.sub.2CHCH.sub.2), 2.32 (t, J=7 Hz, CH.sub.2SH), 1.96 (q, J=7 Hz, CH.sub.2CHCH.sub.2), 1.24 (br, (CH.sub.2CH.sub.2).sub.n), 1.05 (t, J=7 Hz, CH.sub.2SH).

(37) F=70%

Synthesis of the Telechelic Polyolefin CH2CH(CH2)9-PE-N3 (PE=(CH2CH2)n)

(38) To a suspension of CH.sub.2CH(CH.sub.2).sub.9-PE-I (PE=(CH.sub.2CH.sub.2).sub.n) in toluene was added sodium azide (1,2 equivalents). A mixture of toluene and DMF was added, then the reaction mixture heated to 120 C. and stirred for 3 hours.

(39) The reactor contents were then added to methanol (200 mL) and the resultant suspension filtered.

(40) The solids recovered were washed with methanol (3100 mL) and dried.

(41) Characterization:

(42) .sup.1H NMR (FIG. 3) (2/1 v/v TCE/C.sub.6D.sub.6, 400 MHz, 363K) ppm=5.70 (m, CH.sub.2CHCH.sub.2), 4.83-4.93 (m, CH.sub.2CHCH.sub.2), 3.00 (t, J=7 Hz, CH.sub.2N.sub.3), 1.96 (q, J=7 Hz, CH.sub.2CHCH.sub.2), 1.72 (quin, J=7 Hz, CH.sub.2CH.sub.2N.sub.3), 1.24 (br, (CH.sub.2CH.sub.2).sub.n)

(43) Synthesis 1: M.sub.n=1080 g.Math.mol.sup.1, M.sub.w/M.sub.n=1.1, F=94%. For this synthesis, 3 g of CH.sub.2CH(CH.sub.2).sub.9-PE-I (M.sub.n=1080 g.Math.mol.sup.1, F=94%) were used.

(44) Synthesis 2: M.sub.n=1750 g.Math.mol.sup.1, M.sub.w/M.sub.n=1.2, F=89%. For this synthesis, 3 g of CH.sub.2CH(CH.sub.2).sub.9-PE-I (M.sub.n=1750 g.Math.mol.sup.1, F=90%) were used.

Synthesis of the Telechelic Polyolefin CH2CH(CH2)9-PE-NH2 (PE=(CH2CH2)n)

(45) To a suspension of CH.sub.2CH(CH.sub.2).sub.9-PE-N.sub.3 (PE=(CH.sub.2CH.sub.2).sub.n) (1.5 g, M.sub.n=1750 g.Math.mol.sup.1, F=89%) in 100 mL of toluene was added a solution of lithium aluminium hydride (LiAlH.sub.4, 10 equivalents) in 50 mL of THF. The suspension was stirred at 100 C. for 6 hours.

(46) The reactor contents were then added to methanol (200 mL) and the suspension obtained was filtered.

(47) The solids recovered were washed with methanol (3100 mL) and dried.

(48) Characterization:

(49) .sup.1H NMR (FIG. 4) (2/1 v/v TCE/C.sub.6D.sub.6, 400 MHz, 363K) ppm=5.70 (m, CH.sub.2CHCH.sub.2), 4.83-4.93 (m, CH.sub.2CHCH.sub.2), 2.55 (t, J=7 Hz, CH.sub.2NH.sub.2), 1.96 (q, J=7 Hz, CH.sub.2CHCH.sub.2), 1.47 (quin, J=7 Hz, CH.sub.2CH.sub.2NH.sub.2), 1.24 (br, (CH.sub.2CH.sub.2).sub.n).

(50) Synthesis 1: M.sub.n=1750 g.Math.mol.sup.1, M.sub.w/M.sub.n=1.2, F=85%.

Synthesis of the Telechelic Polyolefin CH2CH(CH2)9-PE-(CH2)9CHCH7 (PE=(CH2CH2)n) by Oxidative Homo-Coupling

(51) After the general polymerization procedure described above, the temperature of the reaction mixture containing the intermediate CH.sub.2CH(CH.sub.2).sub.9-PE-Mg-PE-(CH.sub.2).sub.9CHCH.sub.2 was maintained at 80 C.

(52) A solution of silver tosylate (2 mol % with respect to CH.sub.2CH(CH.sub.2).sub.9-PE-Mg-PE-(CH.sub.2).sub.9CHCH.sub.2(PE=(CH.sub.2CH.sub.2).sub.n) and 1,2-dibromoethane (2,4 equivalents with respect to CH.sub.2CH(CH.sub.2).sub.9-PE-Mg-PE-(CH.sub.2).sub.9CHCH.sub.2 (PE=(CH.sub.2CH.sub.2).sub.n) in THF (40 mL) was added to the post-polymerization reaction mixture. The resultant suspension was stirred for 16 hours.

(53) The reactor contents were then added to methanol (200 mL) and the suspension obtained was filtered.

(54) The solids recovered were washed with methanol (3100 mL) and dried.

(55) Characterization:

(56) .sup.1H NMR (FIG. 5) (2/1 v/v TCE/C.sub.6D.sub.6, 400 MHz, 363K) ppm=5.70 (m, CH.sub.2CHCH.sub.2), 4.83-4.93 (m, CH.sub.2CHCH.sub.2), 1.96 (q, J=7 Hz, CH.sub.2CHCH.sub.2), 1.24 (br, (CH.sub.2CH.sub.2).sub.n).

(57) Synthesis 1: M.sub.n=1630 g.Math.mol.sup.1, M.sub.w/M.sub.n=1.27, F=75%.