HUE033236T2

HUE033236T2 - Telekelikus poliolefin és eljárás elõállítására

Info

Publication number: HUE033236T2
Application number: HUE12762631A
Authority: HU
Inventors: Christophe Boisson; Franck D'agosto; Ian German
Original assignee: Univ Claude Bernard Lyon; Centre Nat Rech Scient; Cpe Lyon Formation Continue Et Rech
Priority date: 2012-03-12
Filing date: 2012-09-27
Publication date: 2017-11-28
Also published as: JP6131279B2; FR2987838B1; DK2825573T3; EP2825573B1; ES2624134T3; CN104254548A; CA2864742A1; WO2013135314A1; FR2987838A1; PL2825573T3; PT2825573T; US9598510B2; US20150038647A1; JP2015510018A; CN104254548B; EP2825573A1

Description

(12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C08F 8122 <2006 01> C08F 8134 <200601> 19.04.2017 Bulletin 2017/16 C07F 3I02<2006 01> (21) Application number: 12762631.5 (86) International application number: PCT/EP2012/069110 (22) Date of filing: 27.09.2012 (87) International publication number: WO 2013/135314 (19.09.2013 Gazette 2013/38)

(54) TELECHELIC POLYOLEFIN AND PREPARATION THEREOF

TELECHELES POLYOLEFIN UND HERSTELLUNG DAVON POLYOLEFINE TELECHELIQUE ET SA PREPARATION (84) Designated Contracting States: · D’AGOSTO, Franck AL AT BE BG CH CY CZ DE DK EE ES FI FR GB F-69100 Villeurbanne (FR) GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO · GERMAN, Ian PL PT RO RS SE SI SK SM TR Bromsgrove

Worcestershire B60 2HP (GB) (30) Priority: 12.03.2012 FR 1252191 (74) Representative: Cabinet Laurent & Charras (43) Date of publication of application: Le Contemporain 21.01.2015 Bulletin 2015/04 50 Chemin de la Bruyere 69574 Dardilly Cedex (FR) (73) Proprietors: • Universite Claude Bernard Lyon 1 (56) References cited: 69622 Villeurbanne, Cedex (FR) US-A1- 2004 030 048 US-A1- 2007 010 639 • Centre National de la Recherche Scientifique 75794 Paris Cedex 16 (FR) · MIZZOLINI J. ET AL.: "Catalyzed chain growth • CPE Lyon Formation Continue et Recherche (CCG) on a main group metal: an efficient tool to

69622 Villeurbanne Cedex (FR) functionalize polyethylene", POLYMER C HEMISTRY, vol. 1,22 January 2010 (2010-01-22), (72) Inventors: pages 793-800, XP002680073, DOI: • BOISSON, Christophe 10.1039/B9PY00353C F-01390 Tramoyes (FR)

Description

FIELD OF THE INVENTION

[0001] The invention described herein concerns a telechelic polyolefin presenting a reactive group at eachpolymer chain-end. This type of polymer can serve as a precursor for the incorporation of the polymer into e.g. a hydrophilic or hydrophobic environment, or organic, inorganic, hybrid or composite materials.

STATE OF THE ART

[0002] In general, a polymer able to undergo a subsequent polymerization or reaction in light of the reactivity of its chain-ends is known as a "telechelic polymer". In this class of molecule, the reactive groups located at the chain-ends do not originate from the monomers.

[0003] The prior art includes mono-functionalized polyethylene (see for instance Mazzonlini et al. Polymer Chemistry, 2010, 1, 793-800). There is no evident chemistry to obtain telechelic polyethylene from these mono-functionalized polyethylenes.

[0004] Many synthetic routes to telechelic polymers have been described in the literature. However, regarding the synthesis of telechelic polyolefin synthesis, three principle methods have been developed: (i) The first concerns the synthesis of a hydroxyl-telechelic polybutadiene by an anionic pathway. The butadiene is first polymerized before a hydrogenation step of the unsaturated groups of the polymer chain. The telechelic polyethylene thus obtained features identical chain-ends and is also branched due to the presence of ethyl groups resulting from 1,2-butadiene enchainment. This type of polymer is commercially available under the trade name Kraton® L2203.

Document US 2004/0030048 describes a polymer having chain-end groups such as OH, SH or an amine. It does not concern bi-functionalized polyethylene polymers. (ii) Another synthetic pathway concerns the polymerization of cyclooctadiene by ring-opening metathesis polymerization (ROMP). The polymer obtained is then hydrogenated to give a hydroxyl-telechelic polyolefin (Hillmyer et al.

Macromolecules 1995, 28, 7256-7261). (iii) Finally living ethylene polymerization has also been demonstrated in the presence of a palladium complex. This complex not only initiates the living polymerization of ethylene, but also acts as a chain-end functionalization reagent. The branched, telechelic polyethylene obtained features chain-end functions of either identical ester groups, or those of one ester function and one ketone function (Brookhart, Macromolecules 2003, 36, 3085). In the same vein, the document US2007/0010639 describes the three-step synthesis of telechelic polypropylene featuring polar chain-ends. Olefinic monomers containing protected functional groups are used at the start of the polymerization to create a short segment with orthogonal functional groups. The (co)polymerization of polypropylene is then undertaken. Following that, a functional monomer is again used to form a second short sequence containing lateral functional groups. The polymers thus prepared are free from vinyl groups at the chain-end.

[0005] With the term "living polymerization" we denote a chain-growth polymerization that does not include transfer reactions or chain-termination reactions. Living polymerizations of olefins allow the preparation of polymers that are functional atone or two chain-ends. In the field of olefin polymerization however, living polymerization is limited by the fact that only one chain may be produced per transition metal complex, which poses a problem in terms of production cost. Catalytic polymerization presents the advantage of producing a large number of chains per transition metal. There is therefore a need to establish a system permitting the preparation of telechelic polyolefins, particularly polyethylene, in true polymerization conditions by coordination catalysis.

[0006] The problem proposed to be solved by the invention described herein concerns the preparation of a polymer, in particular telechelic polyolefin of which the two principal chain-ends are either identical or non-identical.

[0007] In contrast to the literature procedures, the procedure of this invention permits the catalytic polymerization of an olefin (mono-olefin) by a mechanism that results in a large number of chains produced per catalyst molecule; and that polymerization proceeds in a controlled fashion in the sense that the distribution of molecular weight of the polymer chains produced is narrow (Mw/Mn <1.5) and that molecular weight increases with productivity.

[0008] This process for polymerization and functionalization can be implemented in situ. It is not necessary to isolate an intermediate to ensure the functionalization of the chain-ends.

SUMMARY OF THE INVENTION

[0009] The applicant has developed a polyolefin of which the two chain-ends each feature a functional group. It is a polyolefin in which at least one of the chain-ends is readily reacted to facilitate the incorporation of the described polyolefin into e.g. a hydrophilic or hydrophobic environment, or into organic, inorganic, hybrid or composite materials.

[0010] The telechelic polyolefin according to the invention is preferably linear. It includes, advantageously, two distinct chain-ends, able to react selectively due to their different reactivity.

[0011] More specifically, the subject matter of the present invention concerns a telechelic polyolefin of formula (I) and its derivatives: CH2=CH-(CH2)p-A-Z (I) wherein: A represents a (co)polymer comprising at least 95 mol % of (CH2-CH2) units, Z is a functional group selected from the group comprising halogens; thiols and their derivatives; azides; amines; alcohols; carboxylic acid function; isocyanates; silanes; phosphorous derivatives; dithioesters; dithiocarbamates; dithiocarbonates; trithiocarbonates; alkoxyamines; vinyl function; dienes; and the group A-(CH2)p-CH=CH2; p is a whole number between 1 and 20, preferably between 6 and 9.

[0012] The term ’derivatives of the telechelic polyolefin’ of formula (I) is defined as all polyolefins resulting from the functionalization of at least one of the chain-ends of the telechelic polyolefin of formula (I). Derivatives are therefore the products obtained from the modification of at least one of the vinyl function or the group Z, and preferentially of the vinyl function according to reactions known to the skilled man in the art.

[0013] The units (CH2-CH2) of the (co)polymer A originate from the polymerization of ethylene.

[0014] Generally, polymer A is a linear polyethylene or a linear copolymer of ethylene with at least one alpha-olefin containing at least one unsaturated bond. As previously described, this (co)polymer is comprised of at least 95% by mole fraction of (CH2-CH2) units.

[0015] However, according to a preferred embodiment, polymer A is a linear polyethylene, i.e. a homopolymer of ethylene of formula (CH2-CH2)n, n being a whole number between 7 and 3600, advantageously between 17 and 360.

[0016] The (co)polymer A has preferably an average molar mass of between 200 g/mol and 100 000 g/mol, most advantageously between 500 g/mol and 10 000 g/mol.

[0017] According to a particularly preferred embodiment, group Z in the telechelic polyolefin of formula (I) is a halogen - preferably an iodine atom - or a dithiocarbamate group. The principal chain-ends of the telechelic polyolefin of formula (I) may feature two groups, in this case vinyl and Z, of which the respective reactivity of one is significantly different from the other.

[0018] Consequently, according to a particularly preferred embodiment, the telechelic polyolefin is of the formula Ql—l2=CH-(CH2) -A-Z, Z being an iodine atom or dithiocarbamate group and p being a whole number between 6 and 9. Advantageously, the(co) polymer A is polyethylene, (CH2-CH2)n, n being a whole number between 7 and 3600, preferably between 17 and 360.

[0019] The present invention also concerns a process for preparing a telechelic polyolefin of formula (I), CH2=CH-(CH2)p-A-Z, and its derivatives. This procedure is characterized in that it comprises in particular the following steps: - preparation of a compound of formula (II) : Y(A-(CH2)p-CH=CH2)m, (II) in which when m = 2, Y is an alkaline earth atom, preferentially magnesium, or zinc; and when m = 3, Y is an element of group 13, preferably aluminium cleavage of the bond(s) between Y and A-(CH2)p-CH=CH2, and functionalization of A-(CH2)p-CH=CH2 with Z.

[0020] The preparation of the molecule of composition of formula (II) is effected in the presence of a complex of a transition metal or a lanthanide, and a transfer agent of composition described by formula (III): Y((CH2)p-CH=CH2)m (III) [0021] As previously described, the group Z may be chosen from a selection including halogens, thiols and their derivatives, azides, amines, alcohols, carboxylic acid function, isocyanates, silanes, phosphorous derivatives, dithioesters, dithiocarbamates, dithiocarbonates, trithiocarbonates, alkoxyamines, vinyl function, dienes and the group A-(CH2)p-CH=CH2.

According to a preferred embodiment, the group Z is an iodine atom or a dithiocarbamate group, such as diethyldithio-carbamate (S-C(=S)-N(Et)2.

[0022] The complex of a transition metal or a lanthanide is preferably a metallocene, selected from the group comprising compounds of which the formula contains the base structure: (Cp1)(Cp2)M or E(Cp1)(Cp2)M.

[0023] This complex allows the implementation of catalytic olefin polymerization by coordination-insertion, with a large number of chains produced per catalyst molecule.

[0024] Generally, M is a metal from group 3 or 4, or a lanthanide.

[0025] Furthermore, Cp1, Cp2 are cyclopentadienyl, fluorenyl or indenyl groups, which may be substituted.

[0026] Group E is a bridge between the Cp1 and Cp2 ligands, and can be represented by the formula M’R1 R2 in which M’ is an element from group 14; R1 and R2 are either identical or non-identical and chosen from the group comprising alkyl and aryl groups having between 1 and 20 carbon atoms. Group E may, for example, be -C(CH3)2-,-CH2-CH2-, or -Si(CH3)2-.

[0027] The transition metal or lanthanide complex may also be of a non-metallocene structure, such as those described in the review of V.C. Gibson and S.K. Spitzmesser (Chem. Rev. 2003,103, 283-315).

[0028] Where appropriate, particularly when the complex does not include a lanthanide or group 3 metal, a co-catalyst may be used in combination with the complex. The skilled man in the art will be able to choose the appropriate co-catalyst.

[0029] According to particularly preferred embodiment, the metallocene complex is of the formula (C5Me5)2MX2Li(OEt2)2, M being a lanthanide or group 3 metal and X being preferentially a halogen. It is preferably a lanthanide complex, most advantageously one of Nd, and notably of the structure (C5Me5)2NdCI2Li(OEt2)2.

[0030] In the second step of the procedure of the invention, the functionalization with Z can be effected by the addition of a compound which may notably be chosen from the group comprising iodine; sulfur - S8; oxygen; nitroxyl radicals; C02; chlorosilanes, such as CISiR2H or CI2SiRH (R being an alkyl group containing between 1 and 20 carbon atoms); isobutene; alkyl halides, aryl halides and vinyl halides; CS2; and disulfides such as tetraethylthiuram disulfide.

[0031] The functionalization step is preferably carried out by addition of iodine l2, sulfur S8 or tetraethylthiuram disulfide.

[0032] The second step of the procedure consists in introducing the Z group by cleavage of the Y-A bond, of the intermediate complex of formula (II), formed during the olefin polymerization in the presence of the transfer agent and the transition metal or lanthanide complex.

[0033] Consequently, the polyolefin of formula CH2=CH-(CH2)p-A-l may serve as a precursor to new polyolefins, for example polyolefins including a Z group of the type azide (N3) or amine (NH2).

[0034] According to a particular embodiment, the functionalization step with Z may proceed via oxidative coupling, to obtain a polyolefin of the formula CH2=CH-(CH2)p-A-A-(CH2)p-CH=CH2, i.e. a polyolefin where the group Z has the structure -A-(CH2)p-CH=CH2.

[0035] This oxidative coupling reaction can be implemented by the reaction of the intermediate complex Y(A-(CH2)p-CH=CH2)m, notably in the presence of a silver tosylate catalyst. This is particularly the case when Y = Mg.

[0036] One of the advantages of the process that is the subject matter of the invention is that all steps may be performed in situ. Unlike procedures outlined in the prior art that concern telechelic polyolefins, the procedure described herein eliminates the separation steps for intermediate compounds in that the second step can be carried out in situ. The polymerization and functionalization can therefore be advantageously achieved in the same reactor.

[0037] Furthermore, the polymerization displays pseudo-living characteristics which permits the control of the polymer molar mass and provides for a relatively narrow polymer molecular weight distribution, advantageously with Mw/Mn<1.5.

[0038] Generally, the experimental conditions allow control of the molar mass of the telechelic polyolefin of formula (I), in addition to the level of chain-end functionalization of (I) with the groups vinyl and Z. The level of functionalization is approximated using %F: %F = 100 x [number of vinyl chain-end groups per chain] x [number of Z chain-end groups per chain], with the maximum number of vinyl chain-ends per chain being fixed at 1.

[0039] The number of vinyl and/or Z chain-ends present are determined by NMR (nuclear magnetic resonance) spectroscopy, according to techniques known to the skilled man in the art.

[0040] The level of functionalization can thus be advantageously greater than 70% and most advantageously greater than 90%. In short, the process according to the invention allows the advantageous production of at least 90% telechelic polyolefins.

[0041] Furthermore, this procedure allows the direct polymerization of ethylene, a monomer considerably less expensive than butadiene or cyclooctadiene, monomers featured in prior art routes to telechelic polyolefins.

[0042] The chain transfer agent of formula (III) (preferably when m = 2 and Y = alkaline earth metal) and its usage (when m = 2 or 3) in a process for the preparation of telechelic polyethylene also fall under the invention described herein.

[0043] As previously outlined, according to a particular embodiment, the telechelic polyolefin which is the subject matter of the invention is of the formula CH2=CH-(CH2)p-(CH2-CH2)n I, I being an iodine atom, p being a whole number between 6 and 9, and n being a whole number between 17 and 360. This polymer can advantageously be obtained according to the procedure comprising the following steps: preparation of the compound of formula (II) (with Z = I; p = 9; n = 17 to 360) by polymerization of ethylene, CH2=CH2, in the presence of (C5Me5)2NdX2Li(OEt2)2, X being a halogen, and the transfer agent Mg((CH2)9-CH=CH2)2; functionalization by the addition of iodine in order to obtain the telechelic polyolefin CH2=CH-(CH2)9-(CH2-CH2)n-l· [0044] The derivatives of the telechelic polyolefin of formula (I) may, as previously outlined, be obtained by the above procedure, notably by the modification of at least one chain-end of the telechelic polyolefin in a step subsequent to functionalization with Z. At least one of the chain-ends of the telechelic polyolefin can therefore be modified by reaction of the vinyl function and/or of the Z group.

[0045] With regard to the vinyl and Z groups of the telechelic polyolefin of formula (I), the two groups may later be readily modified by organic chemistry to introduce new groups, whether by transformation of the Z group or of the vinyl group, as has been detailed for monofunctional polyethylene by D’Agosto and Boisson et al. (R. Briquel, J. Mazzolini, T. Le Bris, O. Boyron, F. Boisson, F. Delolme, F. D’Agosto, C. Boisson, R. Spitz Angew. Chem. Int. Eng. Ed., 47, 9311-9313 (2008); J. Mazzolini, R. Briquel, I. Mokthari, O. Boyron, V. Monteil, F. Delolme, D. Gigmes, D. Bertin, F. D’Agosto, C. Boisson Macromolecules 43, 7495-7503 (2010); M. Unterlass, E. Espinosa, F. Boisson, F. D’Agosto, C. Boisson, K. Ariga, I. Khalakhan, R. Charvet, JP. Hill Chem. Commun. 47, 7057-7059 (2011); Mazzolini, O. Boyron, V. Monteil, D. Gigmes, D. Bertin, F. D’Agosto, C. Boisson Macromolecules44, 3381-3387 (2011); E. Espinosa, M. Glassner, C. Boisson, C. Barner Kowollik, F. D’Agosto Macromol. Rapid Commun. 32, 1447-1453 (2011)).

[0046] The telechelic polyolefin of formula (I), CH2=CH-(CH2)p-A-Z, can therefore be later modified. The skilled man in the art will be able to selectively modify the vinyl function. One could, in particular, although not limitatively, refer to the reactions described in the document Macromolecules 44, 3381-3387 (2011).

[0047] The present invention therefore also concerns the derivatives of the telechelic polyolefin of formula (I). Additionally, the present invention concerns the utilization of telechelic polyolefins and their derivatives as additive(s) for the modification of organic, inorganic, hybrid or composite materials, or as reactive synthon(s) for polymerization reactions in the role of initiator, monomer, transfer agent, deactivation/termination agent, control agent or crosslinking agent.

[0048] The fields of interest for the present invention concern in particular, yet are not limited to, cosmetics, adhesives, inks, waxes and coatings.

[0049] The telechelic polyolefins of the invention and their derivatives may be applied within the framework of the preparation of architectures or of original materials based on polyethylene in particular.

[0050] The invention, and the benefits which result from it, is best described by the following examples, given to illustrate the invention and which are not limitative of the scope of the invention.

FIGURES

[0051]

Figure 1 is the 1H NMR (nuclear magnetic resonance) spectrum of the telechelic polyethylene according to the invention, CH2=CH-(CH2)g-PE-l, where PE = (CH2-CH2)n·

Figure 2 is the 1H NMR (nuclear magnetic resonance) spectrum of the telechelic polyethylene according to the invention, CH2=CH-(CH2)9-PE-S-C(=S)-N(Et)2, where PE = (CH2-CH2)n·

Figure 3 is the 1H NMR (nuclear magnetic resonance) spectrum of the telechelic polyethylene according to the invention, CH2=CH-(CH2)9-PE-N3, where PE = (CH2-CH2)n·

Figure 4 is the 1H NMR (nuclear magnetic resonance) spectrum of the telechelic polyethylene according to the invention, CH2=CH-(CH2)g-PE-NH2, where PE = (CH2-CH2)n·

Figure 5 is the 1H NMR (nuclear magnetic resonance) spectrum of the telechelic polyethylene according to the invention, CH2=CH-(CH2)9-PE-(CH2)9-CH=CH2, where PE = (CH2-CH2)n·

EXAMPLES

[0052] The following examples concern the preparation: of a transfer agent of formula (III) of an intermediate compound of formula (II); oftelechelic polyolefins of formula (I).

Synthesis of the transfer agent bis(10-undecenyl)magnesium, Mg((CH2)9(CH=CH2)2 [0053] 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, 49mmol) dropwise at 0°C. The reaction mixture was stirred at 0°C for 1h 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 2h and then filtered, to obtain a solution of Mg((CH2)9CH=CH2)2 in di-n-butyl ether. Aliquots from the solution were taken for concentration determination by titration using i) pyrene-1-acetic acid and ii) HCI(aq) then NaOH(aq) solutions.

[0054] A further sample of the recovered solution was taken and the solvent removed under reduced pressure for NMR analysis.

Characterization by 1H NMR (THF-d8, 300 MHz, 300K) δ: 5.81 (m, CH2=CH-CH2-), 4.89-5.02 (m, CH2=CH-CH2-), 2.06 (q, J = 7 Hz, CH2=CH-CH2-), 1.56 (quin, J = 7 Hz, , CH2=CH-CH2-C«2-), 1.32 (br, -(CH2)6-), -0.63 (m, -CH2-Mg) ppm.

General polymerization procedure for the preparation of the intermediate CH2=CH-(CH2)g-PE-Mg-PE-(CH2)g-CH=CH2 (PE = CH2-CH2)n) [0055] A solution of bis(10-undecenyl)magnesium in dibutyl ether (0.24 mol.L-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*2NdCI2Li(OEt2)2 (10.7 mg, 16.7 μηιοΙ) 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 CH2=CH-(CH2)g-PE-l (PE = (CH2-CH2)n) [0056] After the polymerization step described above, the reaction mixture containing the intermediate CH2=CH-(CH2)9-PE-Mg-PE-(CH2)g-CH=CH2 (PE = (CH2-CH2)n) was cooled to 10°C.

[0057] A solution of iodine (2.54 g, 10 mmol) in 50 mL of THF was added, and the suspension stirred for 3 hours.

[0058] The reactor contents were then added to methanol (200 mL) and the solution filtered. The solids recovered were washed with methanol (3 x 100 mL) then dried.

Characterization: 1H NMR(figure 1) (2/1 v/v TCE/C6D6, 400 MHz, 363K) δ ppm = 5.70 (m, CH2=CH-CH2-), 4.83-4.93 (m, CH2=CH-CH2-), 2.94 (t, J= 7 Hz, -CH2l),1.96(q, J=7Hz,CH2=CH-CH2-), 1.66 (quin, J=7Hz,-CH2CH2l),1.24(br,(CH2CH2)n). 13C NMR (2/1 v/v TCE/C6D6, 101 MHz, 363K) δ ppm = 138.90, 114.20, 33.98, 30.78, 30.00 ((CH2CH2)n), 29.90, 29..82, 29.80, 29.69, 29.44, 29.32, 28.82, 4.96.

Mn = 1500 g.mol'1, MJMn= 1.1, F = 95%.

Synthesis of the telechelic polyolefin CH9=CH-CH?)Q-PE-S-C(=S)-N(Et)2 (PE = CH2-CH2)n [0059] After the polymerization step described above, the reaction mixture containing the intermediate CH2=CH-(CH2)9-PE-Mg-PE-(CH2)9-CH=CH2 (PE = (CH2-CH2)n) was heated to 80°C.

[0060] A solution of W,W,A/’,/V-tetraethylthiuram disulfide (1.85 g, 6.25 mmol) in toluene (50 mL) was then added and the resulting solution stirred for 3 hours.

[0061] The reaction mixture was cooled to ambient temperature before being added to methanol (200 mL), then the resulting suspension filtered.

[0062] The solids recovered from filtration were washed three times with methanol (3 x 100 mL) then dried. Characterization: 1H NMR (figure 2) (2/1 v/v TCE/C6D6, 400 MHz, 363K) δ ppm = 5.70 (m, CH2=CH-CH2-), 4.83-4.93 (m, CH2=CH-CH2-), 3.68 (br, -N-CH2-CH3), 3.23 (t, J= 7 Hz, -CH2-S-C(S)-), 1.96 (q, J = 7 Hz, CH2-CH-CH2-), 1.63 (quin, J-7 Hz, -CH2CH2-S-C(S)-) 1.24 (br, (CH2CH2)n), 1.08 (t, J = 7 Hz, -N-CH2-CH3). 13CNMR(2/1 v/vTCE/C6D6, 101 MHz, 363K)6ppm = 195.98,138.90,114.20,47.74,37.38,33.98,30.0((CH2CH2)n), 29.90, 29.83, 29.80, 29.54, 29.44, 29.35, 29.32, 29.23, 12.25.

Mn = 1550 g.mol-1, MJMn = 1.14, F = 87%

Synthesis of the telechelic polyolefin CH2=CH-(CH2)g-PE-SH (PE - (CH2-CH2)n) [0063] A suspension of lithium aluminium hydride (0.61 g, 16 mmol) in tetrahydrofuran (200mL) was added to a solution of CH2=CH-(CH2)9-PE-S-C(=S)-NEt2 (Mn =1550 g.mol-1, F = 87%; 3.0 g) in toluene (200 mL) at 100°C.

[0064] The suspension obtained was stirred under argon in reflux conditions (90°C) for 15 hours.

[0065] The reaction mixture was then cooled to ambient temperature, at which point methanol (20 mL) was slowly added.

[0066] The resultant suspension was then heated to 95°C and filtered.

[0067] The filtrate was cooled and added to methanol (200 mL).

[0068] The suspension produced was then filtered and the solids recovered were washed with methanol (3 x 100 mL) and dried under vacuum.

Yield = 2.5 g.

Characterization: 1H NMR (2/1 v/v TCE/C6D6, 400 MHz, 363K) : δ ppm = 5.70 (m, CH2=CH-CH2-), 4.83-4.93 (m, CH2=CH-CH2-), 2.32 (t, J= 7 Hz, -CH2SH), 1.96 (q, J= 7 Hz, CH2=CH-CH2-), 1.24 (br, (CH2CH2)n), 1.05 (t, J= 7 Hz, -CH2SH). F = 70 %

Synthesis of the telechelic polyolefin CH2=CH-(CH2)g-PE-N3 PE = CH2-CH2)n) [0069] To a suspension of CH2=CH-(CH2)9-PE-I (PE = (CH2-CH2)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.

[0070] The reactor contents were then added to methanol (200 mL) and the resultant suspension filtered.

[0071] The solids recovered were washed with methanol (3 x 100 mL) and dried. Characterization: 1H NMR (figure 3) (2/1 v/v TCE/C6D6, 400 MHz, 363K) δ ppm = 5.70 (m, CH2=CH-CH2-), 4.83-4.93 (m, CH2=CH-CH2-), 3.00 (t, J = 7 Hz, -CH2N3), 1.96 (q, J = 7 Hz, CH2=CH-CHT), 1.72(quin, J = 7 Hz, -CH2CH2N3), 1.24 (br, (CH2CH2)n).

Synthesis 1: Mn = 1080 g.moM, MJMn = 1.1, F = 94%. For this synthesis, 3 g of CH2=CH-(CH2)9-PE-I (Mn - 1080 g.mol"1, F = 94%) were used.

Synthesis 2: Mn = 1750 g.mol"1, MJMn = 1.2, F = 89%. For this synthesis, 3 g of CH2=CH-(CH2)9-PE-I (Mn = 1750 g.mol-1, F = 90%) were used.

Synthesis of the telechelic polyolefin CH2=CH-(CH2)9-PE-NH2 PE = (CH2-CH2)n) [0072] To a suspension of CH2=CH-(CH2)9-PE-N3 (PE = (CH2-CH2)n) (1.5 g, Mn = 1750 g.mol"1, F = 89%) in 100 mL of toluene was added a solution of lithium aluminium hydride (LiAIH4, 10 equivalents) in 50 mL of THF. The suspension was stirred at 100°C for 6 hours.

[0073] The reactor contents were then added to methanol (200 mL) and the suspension obtained was filtered.

[0074] The solids recovered were washed with methanol (3 x 100 mL) and dried. Characterization: 1H NMR (figure 4) (2/1 v/v TCE/C6D6, 400 MHz, 363K) δ ppm = 5.70 (m, CH2=CH-CH2-), 4.83-4.93 (m, CH2=CH-CH2-), 2.55 (t, J = 7 Hz, -CH2NH2), 1.96 (q, J = 7 Hz, CH2=CH-CHT), 1.47(quin, J = 7 Hz, -CH2CH2NH2), 1.24 (br, (CH2CH2)n).

Synthesis 1: Mn = 1750 g.mol-1, MJMn = 1.2, F = 85%.

Synthesis of the telechelic polyolefin CH2=CH-(CH2)9-PE-(CH2)9-CH=CH2 (PE = (CH2-CH2)n) by oxidative homo-coupling [0075] Afterthe general polymerization procedure described above, the temperature of the reaction mixture containing the intermediate CH2=CH-(CH2)9-PE-Mg-PE-(CH2)9-CH=CH2 was maintained at 80°C.

[0076] A solution of silver tosylate (2 mol% with respect to CH2=CH-(CH2)9-PE-Mg-PE-(CH2)9-CH=CH2 (PE = (CH2-CH2)n) and 1,2-dibromoethane (2,4 equivalents with respect to CH2=CH-(CH2)9-PE-Mg-PE-(CH2)9-CH=CH2 (PE = (CH2-CH2)n) in THF (40 mL) was added to the post-polymerization reaction mixture. The resultant suspension was stirred for 16 hours.

[0077] The reactor contents were then added to methanol (200 mL) and the suspension obtained was filtered.

[0078] The solids recovered were washed with methanol (3 x 100 mL) and dried.

Characterization: 1H NMR (figure 5) (2/1 v/v TCE/C6D6, 400 MHz, 363K) δ ppm = 5.70 (m, CH2=CH-CH2-), 4.83-4.93 (m, CH2=CH-CH2-), 1.96 (q, J= 7 Hz, CH2=CH-CH2-), 1.24 (br, (CH2CH2)n).

Synthesis 1: Mn = 1630 g.mol-1, =1.27, F = 75%.

Claims 1. Telechelic polyolefin of formula (1) and derivatives thereof: CH2=CH-(CH2)p-A-Z (I) wherein: - A represents a (co)polymer comprising at least 95 mol % of (CH2-CH2) 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; dithio- carbonates; trithiocarbonates; alkoxyamines; the vinyl function; dienes; and the group -A-(CH2)p-CH=CH2; - p is a whole number between 1 and 20, advantageously between 6 and 9. 2. Telechelic polyolefin and its derivatives according to claim 1, characterized in that A is a linear polyethylene of formula (CH2-CH2)n, n being a whole number between 7 and 3600. 3. Telechelic polyolefin and its derivatives described in one of the preceding claims, characterized in that the telechelic polyolefin is represented by the formula CH2=CH-(CH2)p-(CH2-CH2)n-l, I being an iodine atom, p being a whole number between 6 and 9, and n being a whole number between 17 and 360. 4. Process for preparing the telechelic polyolefin and its derivatives of any of the preceding claims, comprising the following steps: - preparation of a compound of formula (II): Y(A-(CH2)p-CH=CH2)m, (II) wherein when m = 2, Y is an alkaline earth metal, preferably magnesium, or zinc; and when m = 3, Y is an element of group 13, preferably aluminium; - cleavage of the bond between Y and A-(CH2)p-CH=CH2, and functionalization of A-(CH2)p-CH=CH2 with Z. 5. Process according to claim 4, characterized in that the preparation of 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((CH2)p-CH=CH2)m (III) 6. Process according to claim 5, characterized in that the transition metal or lanthanide complex is a metallocene selected from the group comprising compounds of which the formula contains the base structure: (Cp1)(Cp2)M or E(Cp1)(Cp2)M; - M being a group 3 or 4 metal, or a lanthanide; and - Cp1, Cp2 being cyclopentadienyl, fluorenyl or indenyl groups or those groups featuring additional substituents; - E being a bridge between the Cp1 and Cp2 ligands, of the formula M’R1R2, M’ being a group 14 element, and R1 and R2 being alkyl or aryl groups having 1 to 20 carbon atoms. 7. Process according to claim 6, characterized in that the complex is a lanthanide metallocene, advantageously of the formula (C5Me5)2MX2Li(OEt2)2, M being a group 3 metal or lanthanide and X being a halogen. 8. Process according to claim 4, characterized in that the functionalization step with Z comprises the addition of a compound selected from the group comprising iodine l2, sulfur S8 and tetraethylthiuram disulfide. 9. Process according to claim 4, characterized in that the functionalization step with Z is an oxidative coupling when Z = -A-(CH2)p-CH=CH2. 10. Process according to claim 4 including a step, subsequent to the functionalization with Z, consisting in modifying at least one of the chain-ends of the telechelic polyolefin by reaction of the vinyl function and/or of the Z group. 11. Transfer agents of formula (III): Y((CH2)p-CH=CH2)m (III) wherein m = 2 when Y is an alkaline earth metal. 12. Transfer agent according to claim 11, of the formula Mg((CH2)g-CH=CH2)2. 13. Use of a transfer agent according to claim 11 or 12 in a process for preparing a telechelic polyolefin. 14. Use of the telechelic polyolefin, and its derivatives according to claim 1 as additive(s) for the modification of organic, inorganic, hybrid or composite materials, or as a reactive synthon(s) for polymerization reactions.

Patentansprüche 1. Telecheles Polyolefin der Formel (I) und seine Derivate: CH2 =CH-(CH2)p-A-Z (I) worin: - A ein (Co-) Polymer repräsentiert, das mindestens 95 mol % (CH2 - CH2) Einheiten enthält, - Z wird aus der Gruppe ausgewählt, die aus Halogenen, Thiolen und deren Derivaten, Aziden, Aminen, Alkoholen, der Carbonsäurefunktion, Isocyanaten, Silanen, Phosphor- Derivaten, Dithioestern, Dithiocarbamaten, Dithiocarbonaten, Trithiocarbonaten, Alkoxyaminen, die Vinylfunktion, Dienen und der Gruppe -A-(CH2)9- CH= CH2 besteht; - p ist eine ganze Zahl zwischen 1 und 20, am besten zwischen 6 und 9. 2. Telecheles Polyolefin und seine Derivate gemäß Anspruch 1, dadurch gekennzeichnet, dass A ein lineares Polyethylen der Formel (CH2 - CH2)n ist, wobei n eine ganze Zahl zwischen 7 und 3600 ist. 3. Telecheles Polyolefin und seine Derivate, beschrieben in einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das telechele Polyolefin dargestellt wird durch die Formel CH2 =CH-(CH2)p-(CH2 - CH2)n -I, wobei I ein Jod-Atom ist, p eine ganze Zahl zwischen 6 und 9 ist und n eine ganze Zahl zwischen 17 und 360 ist. 4. Verfahren zur Herstellung des telechelen Polyolefins und seiner Derivate nach einem der vorhergehenden Ansprüche, umfassend die folgenden Schritte: - Herstellung einer Verbindung der Formel (II): Y (A-(CH2)p-CH= CH2)m (II) in der wenn m = 2, Y ein Erdalkaliatom ist, vorzugsweise Magnesium oder Zink; und wenn m = 3 ist Y ein Element der Gruppe 13, vorzugsweise Aluminium; - Spaltung der Bindung zwischen Y und A-(CH2)p-CH= CH2 und Funktionalisierung von A-(CH2)p-CH- CH2 mit Z. 5. Verfahren gemäß Anspruch 4 dadurch gekennzeichnet, dass die Herstellung der Zusammensetzung der Formel (II) in Anwesenheit eines Komplexes eines Übergangsmetalls odereines Lanthanoids geschieht und eines Ubertragungsmittels der Formel (III): Y((CH2)p-CH= CH2)m (Hl) 6. Verfahren gemäß Anspruch 5 dadurch gekennzeichnet, dass der Übergangsmetall- oder Lanthanoid - Komplex ein Metallocene ist, das aus der Gruppe ausgewählt wird, die Verbindungen, bei denen die Formel die folgende Basisstruktur enthält: (Cp1)(Cp2)M oder E(Cp1)(Cp2)M umfasst; - M ist dabei ein Gruppe 3 oder 4 Metall, oder ein Lanthanoid; und - Cp1, Cp2 sind Cyclopentadienyl-, Fluorenyl- oder Indenyl - Gruppen, oder solche Gruppen, die zusätzliche Substituenten aufweisen; - E ist eine Brücke zwischen den Cp1 und Cp2 Liganden, mit der Formel M’R1R2, in der M’ ein Gruppe 14 -Element ist, und R1 und R2 sind Alkyl- und ArylGruppen, die zwischen 1 und 20 Kohlenstoffatomen haben. 7. Verfahren gemäß Anspruch 6 dadurch gekennzeichnet, dass der Komplex ein Lanthanoid-Metallocene, vorteilhafterweise mit der Formel (C5Me5)2MX2Li(OEt2)2, ist, wobei M dabei ein Gruppe 3 - Metall oder Lanthanoid ist und X vorzugsweise ein Halogen ist. 8. Verfahren gemäß Anspruch 4 dadurch gekennzeichnet, dass der Schritt der Funktionalisierung mit Z die Zugabe einer Verbindung umfasst, die aus der Gruppe ausgewählt wird, die aus Jod 12, Schwefel S8 und Tetraethylthi-uramdisulfid besteht. 9. Verfahren gemäß Anspruch 4, dadurch gekennzeichnet, dass der Schritt der Funktionalisierung mit Zeine oxidative Bindung ist, wenn Z = -A-(CH2)P-CH=CH2. 10. Verfahren gemäß Anspruch 4, umfassend einen auf die Funktionalisierung m it Z folgenden Schritt, der darin besteht, mindestens eine der Kettenenden des telechelen Polyolefins durch Reaktion der Vinylfunktion und/ oder der Z-Gruppe zu modifizieren. 11. - Übertragungsmittel mit der Formel (III): Y ((CH2)p-CH=CH2)m (III) wobei m = 2 wenn Y ein Erdalkalimetall ist. 12. Übertragungsmittel gemäß Anspruch 11 mit der Formel Mg((CH2)9-CH=CH2)2. 13. Verwendung eines Übertragungsmittels gemäß Anspruch 11 oder 12 in einem Verfahren zur Herstellung eines telechelen Polyolefins. 14. Verwendung eines telechelen Polyolefins und seiner Derivate gemäß Anspruch 1, als Zusatz(Zusätze) zur Modifizierung von organischem, anorganischem, hybridem oder Verbundmaterialen, oder als reaktive(s) Synthon(e) für Polymerisationsreaktionen.

Revendications 1. Polyoléfine téléchélique de formule (I) et ses dérivés : CH2=CH-(CH2)p-A-Z (I) dans laquelle : - A représente un (co)polymère comprenant au moins 95% molaire de motifs (CH2-CH2) ; - Z est choisi dans le groupe comprenant les halogènes, les thiols et leurs dérivés, les azotures, les amines, les alcools, la fonction acide carboxylique, les isocyanates, les silanes, les dérivés phosphorés, les dithioesters, lesdithiocarbamates, lesdithiocarbonates, lestrithiocarbonates, les alkoxyamines, la fonction vinyle, lesdiènes et le groupement -A-(CH2)p-CH=CH2 ; - p est un nombre entier compris entre 1 et 20, avantageusement compris entre 6 et 9. 2. Polyoléfine téléchélique et ses dérivés selon la revendication 1, caractérisée en ce que A est un polyéthylène linéaire de formule (CH2-CH2)n, n étant un nombre entier compris entre 7 et 3600. 3. Polyoléfine téléchélique et ses dérivés selon l’une des revendications précédentes, caractérisée en ce que la polyoléfine téléchélique est de formule CH2=CH-(CH2)p-(CH2-CH2)n-l, I étant un atome d iode, p étant un nombre entier compris entre 6 et 9, et n étant un nombre entier compris entre 17 et 360. 4. Procédé de préparation de la polyoléfine téléchélique et ses dérivés selon l’une des revendications précédentes, comprenant les étapes suivantes : - préparation d’un composé de formule (II) : Y(A-(CH2)p-CH=CH2)m, (II) dans laquelle lorsque m = 2, Y est un alcalino terreux, de préférence le magnésium , ou le zinc , et lorsque m = 3, Y est un élément du groupe 13, de préférence l’aluminium ; - clivage de la liaison entre Y et A-(CH2)p-CH=CH2, et fonctionnalisation de A-(CH2)p-CH=CH2 par Z. 5. Procédé selon la revendication 4, caractérisée en ce que la préparation du composé de formule (II) est effectuée en présence d’un complexe à base d’un métal de transition ou d’un lanthanide, et d un agent de transfert de formule (III): Y ((CH2)p-CH=CH2)m (III) 6. Procédé selon la revendication 5, caractérisée en ce que le complexe à base d’un métal de transition ou d un lanthanide est un métallocène choisi dans le groupe comprenant les composés dont la formule contient la structure de base : (Cp1)(Cp2)M ou E(Cp1)(Cp2)M ; - M étant un métal du groupe 3, ou 4 ou un lanthanide ; et - Cp1, Cp2 étant des groupements cyclopentadiényle, fluorényle ou indényle ou ces groupes présentant des substituants additionnels ; - E étant un pont entre les ligands Cp1 et Cp2, de formule M’R1R2, M’ étant un élément du groupe 14 et R1 et R2 étant des groupes alkyles ou aryles ayant de 1 à 20 atomes de carbones. 7. Procédé selon la revendication 6, caractérisée en ce que le complexe est un métallocène de lanthanide, avantageusement de formule (C5Me5)2MX2Li(OEt2)2, M étant un métal du groupe 3 ou un lanthanide etX étant un halogène. 8. Procédé selon la revendication 4, caractérisée en ce que l’étape de fonctionnalisation par Z comprend l’addition d’un composé choisi dans le groupe comprenant l’iode l2, le soufre S8 et le disulfure de tétraéthylthiuram. 9. Procédé selon la revendication 4, caractérisée en ce que l’étape de fonctionnalisation par Z est un couplage oxydant quand Z = -A-(CH2)p-CH=CH2. 10. Procédé selon la revendication 4, comprenant une étape ultérieure à la fonctionnalisation par Z, consistant à modifier au moins une des extrémités de la polyoléfine téléchélique par réaction de la fonction vinyle et/ou du groupement Z. 11. Agent de transfert de formule (III) : Y((CH2)p-CH=CH2)m (III) dans laquelle m = 2, lorsque Y est un métal alcalino terreux. 12. Agent de transfert selon la revendication 11, de formule Mg((CH2)g-CH=CH2)2 13. Utilisation de l’agent de transfert selon la revendication 11 ou 12 dans un procédé de préparation d’une polyoléfine téléchélique. 14. Utilisation de la polyolefine telechelique et ses derives selon la revendication 1, en tant qu’additif(s) pour la modification de materiaux organiques, inorganiques, hybrides ou composites, ou en tant que synthon(s) reactif(s) pour des reactions de polymerisation.

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

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Non-patent literature cited in the description • MAZZONLINI et al. Polymer Chemistry, 2010, vol. · M. UNTERLASS ; E. ESPINOSA ; F. BOISSON ; F. 1,793-800 [0003] D’AGOSTO ; C. BOISSON; K. ARIGA; I. • HILLMYER et al. Macromolecules, 1995, vol. 28, KHALAKHAN ; R. CHARVET ; JP. HILL. Chem. 7256-7261 [0004] Commun., 2011, vol. 47, 7057-7059 [0045] • BROOKHART. Macromolecules, 2003, vol. 36, 3085 · MAZZOLINI, O. BOYRON ; V. MONTEIL ; D.

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Claims

igénypontok •í, kiplgíl iejekeilkus poliolefin és származékai; CH^ClKCthvV/ih AhÉ; > á: jelembe legalább 9$ mól {M> ft'Hz-CH?) egységes t,tilalmazó (kojpoiicncr, »Z. jelentéséi az alábbiakat tartalmazó csoportból válaszunk: halogének; dőlök és ezek párnppékaí; aztdok; ami nők; alkoholok; karbonsav funkció; izodaoátoh; &/üőnok; ibsx-ipsiárnmzékok; dltioészterek: áitiokarbamáiok; ditíokarbonátok; triiiokárbonátok; ab ko.sbammok; xind Inakéin, sídnek; és -A-tCkhgM ΉΗΉ: csoport; - p libáké 1 és 20 közöld, előnyösen 6 és 9 közöld, egész szám, 2, ki mons pont unt ni trLUhkus tokomon e* szomunckm azzal $dlemez"**\ hogy A jelentése (Clb-CH >}ss képlett lineáris polietilén,« értéke 7 és 36ÖÖ közötti égé#! szám. :k Az előző igénypontok bármelyike szerinti teiekelíkus pdmbíin I# Siánnazékal, azzal JMléttezve, hogy a teIekciik«K:}mÍk*léÍ«.ÓIf“€H<Öfi1V^^^feW képettl I jetoté-ae jáiaimtt, p értéke 6 és b közötti egész szám, és n értéke 1 ? és 36b közötti egész szám. 4; Épzás az előző igénypontok Mnnélyske gzerlötllélekélikns pölioléBn is Mlrmm zokni elöállílására, amely az alábbi· lépéseket fögldíjá magában; - őül képiéin segsélei ekvdhno e Y{A-(CH^rCH-Cli,^ííí) ahol amikor m2, Y jelentése alkáliiÖkl“fémí előnyösen magnézium vagy eink; és amikor m:::: 3, Y jelentése egy 13- csoportbeli elem, előnyösen alumínium; \ és v:(' ~t II CH kö'öttxk nv^Xts^asa,es Vidbi -t Η Π1 ookuonalua rsa / 'd A 4, Igébypöpt szerinti eljárás, azzal jellemezve;, hogy n f ii) képiéin vegyitlet H:n vagyláotanida komplex, és egy Ippr, Yí(cii2}roi-ci Éímcm} jelenlétében végezzük, ö. Az i, igénypont szerinti eljárás, gazai Jellemezve* hogy az átmeneti lem vagy iiptanlöa kompfey így metallocén. amelyet olyan vevőietek csoportjából yiksztüök* mnefvek képlete mémmm a tCp!KCp2)M vgp B(Í^s ÍGps)M álap szerkezetet; - Ól jéléüiélé 3. vagy 4, esoportbaMtozé llm, vagy egy lantanida; és -öp^ Q$f Mfnlése eiklopenmdleM!% Éooremk vagy Inda: besöpört vagy olyan ésbpormte umeRck Unahh smbsnboonsekkd rendelkeznek, ·· I-, a smtesr MR 4’ kMv n mé t 4 e Γρ hganfervk k>np M lYet"* <^s t4. eső-rnubeh ele u es R u'l' s e ücso 1 '1 széna te nos „ hd x«ev mdcsopoü ?. A 6. igénypont szerinti eljárás, azzal jellemezve,htW ή kompiek egy tanlhasnea nmtalhven, előnyösen oAMexyMXd itt H'pp képiem, M mentése k csoportbeli lem tagv kan tétnek; ea X jelentése halogén. g. Λ 4. igénypont szerint? elírás, azzal jellemeze, hogy u / -ve! értene; tuokeü'na·' luáiási lépés tartalmazza egy atáhl lakat tartalmast» csoportból választott vegyülő t; jód !.\ kán $% és tetcaeUiíuu'ánvdiozulftd, addieieiat. 4. Λ 4 ,^ηνροηι .veriati oltár *,v azzal jellem ózva, Ita^ «;ΐδ*νβΙ történő fűnkéit ma* L <éo \ \S\ v « \ P\ kopt. ό as >«" vx ' VtOfelm Ji-CIIz. 10. A 4. igénypont szerinti eljárás. amely a 72vel történő íimkcionaiisáíásl lépés mm: n tclekritki* polí olefin legalább egy lánc végét módosító lépést tartalmaz a vhtil IriiWó édvagy a Z csoport reakciójává!, 11. pl|l kép leid imstkZ&r Igen se YtíCH-.VCH::!CH-jk(IH) ahol m'2 amikor V jelentése alkáltffc ki-lem, 12. Λ 1 L igénypont szénáit NignCH»t, el Í~C! i As képiéit tnm$s ‘ef ágens,
13. All, vagy 12. ígérő pont szerinti trans/ier ágens alkalmazása teíekelikus gólisles Un * délhúsa oltam» tktn
14. Az 1. igénypont szénné teleks-iikits poholefin & vzánnazákat aduin? azasa adut»·· tn^ek'íkení ?όη\ - v? tettet , ívénd %<tg\ kampó a magok mádoriUsau. \»$> teaktív vm- ion(ok.)kém polimerizációs reakciókhoz. A meghstat mázott: