PROCESS FOR PREPARATION OF AMORPHOUS POLYOLEFINIC IONOMERS

Abstract

The present invention relates to an amorphous polyolefinic ionomer and a process for the preparation of an amorphous polyolefinic ionomer.

Claims

1. A process for the manufacture of an amorphous polyolefinic ionomer comprising the steps of: a1) copolymerizing at least one olefin monomer and at least one masked functionalized olefin monomer in the presence of a catalyst system, wherein the olefin monomer is represented by CH.sub.2CHR.sup.1, wherein R.sup.1 is an alkyl group having 1 to 6 carbon atoms, wherein the masked functionalized olefin monomer is a reaction product of a functionalized olefin monomer represented by the structure according to Formula (I) and a masking agent: ##STR00004## wherein R.sup.2, R.sup.3, and R.sup.4 are each independently selected from the group consisting of H and hydrocarbyl with 1 to 16 carbon atoms, wherein R.sup.5[X(R.sup.6)n]m is a polar functional group containing one or multiple heteroatom containing functionalities X(R.sup.6)n wherein X is selected from O, S or CO.sub.2 and R.sup.6 is H, and n is 1, or X is N and R.sup.6 is each independently selected from the group consisting of H and a hydrocarbyl group with 1 to 16 carbon atoms, and n is 2, wherein R.sup.5 is either C(R.sup.7a)(R.sup.7b) or a plurality of C(R.sup.7a)(R.sup.7b) groups, wherein R.sup.7a, and R.sup.7b are each independently selected from the group consisting of H or hydrocarbyl with 1 to 16 carbon atoms and R.sup.5 comprises 1 to 10 carbon atoms, wherein R.sup.3 and R.sup.5 may together form a ring structure that is functionalized with one or multiple X(R.sup.6)n, where X is attached to either the main chain or side chain of R.sup.5, where m is an entire number between 1 and 10, and either b1) treating the product of step a1) with a protic solution containing metal salts, ammonium salts or amines to perform an exchange reaction, or a2) contacting the product of a1) with a Brnsted acid solution capable to abstract the residue derived from the masking agent from the functionalized olefin copolymer to obtain the amorphous functionalized olefin copolymer comprising the first olefin monomer and the functionalized olefin monomer, and either b2) treating the product of step a2) with a monovalent metal salt, a monocationic ammonium salt or a monofunctional amine, or b3) treating the product of step a2) with a multi-valent metal salt, a polycationic ammonium salt or a polyfunctional amine.

2. The process according to claim 1, wherein the at least one olefin monomer is selected from the group consisting of propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, vinyl cyclohexane, and 1-octene.

3. The process according to claim 1 wherein the at least one functionalized olefin monomer is selected from the group consisting of allyl alcohol, 3-buten-1-ol, 3-buten-2-ol, 3-buten-1,2-diol, 5-hexene-1-ol, 5-hexene-1,2-diol, 7-octen-1-ol, 7-octen-1,2-diol, 9-decen-1-ol, 10-undecene-1-ol, 5-norbornene-2-methanol, 3-butenoic acid, 4-pentenoic acid or 10-undecenoic acid.

4. The process according to claim 1, wherein the amount of the functionalized olefin monomers in step a1) is from 0.01 to 30 mol %, with respect to the total molar amount of the olefin monomers and the functionalized olefin monomers.

5. The process according to claim 1, wherein the masking agent is selected from trialkyl aluminum complexes, dialkyl magnesium complexes, dialkyl zinc complexes or trialkyl boron complexes.

6. The process according to claim 1, wherein in step b1) or b2) the metal salt is a fluoride, chloride, bromide, iodide, hydroxide, nitrite, nitrate, formate, acetate, bicarbonate, carbonate, sulfite, sulfate, chlorate, perchlorate, bromate or EDTA salt of a metal selected from one or more of lithium, sodium, potassium and silver and/or the monofunctional amine is selected from NH.sub.3, Me.sub.2NH, NMe.sub.3, EtNH.sub.2, Et.sub.3N, BuNH.sub.2.

7. The process according to claim 1 wherein in step b1) or b3) the multi-valent metal salt is a fluoride, chloride, bromide, iodide, hydroxide, nitrite, nitrate, formate, acetate, bicarbonate, carbonate, sulfite, sulfate, chlorate, perchlorate, bromate or EDTA salts of the magnesium, calcium, strontium, barium, zinc, copper, tin, silver, iron, chrome, aluminum or gallium.

8. The process according to claim 1, wherein the Brnsted acid solution used in step a2) comprises inorganic and/or organic acids.

9. The process according to claim 1 wherein a first and a second olefin monomer are used, wherein the first and second olefin monomer are different and wherein the amount of the first olefin monomer is from 20 to 80 mol % and the amount of second olefin monomer is from 80 to 20 mol %, based on the total molar amount of first and second olefin monomer.

10. The process according to claim 1 wherein at least one of the olefin monomers is propylene used in an amount of at least 50 wt. %, with respect to the total weight of the olefin monomers and the functionalized olefin monomers.

11. The process according to claim 1 wherein said at least one olefin monomer is propylene and wherein polypropylene segments of the amorphous polyolefinic ionomer are atactic polypropylene segments.

12. Amorphous polyolefinic ionomer obtainable by the process of claim 1.

13. Amorphous polyolefinic ionomer of claim 12 wherein, said at least one olefin monomer is selected from the group consisting of propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, vinyl cyclohexane and 1-octene, said at least one functionalized olefin monomer is selected from the group consisting of allyl alcohol, 3-buten-1-ol, 3-buten-2-ol, 3-buten-1,2-diol, 5-hexene-1-ol, 5-hexene-1,2-diol, 7-octen-1-ol, 7-octen-1,2-diol, 9-decen-1-ol, 10-undecene-1-ol, 5-norbornene-2-methanol, 3-butenoic acid, 4-pentenoic acid or 10-undecenoic acid, wherein the functionalized groups in the ionomer are cross-linked by means of one or more from the group consisting of monovalent metal ions, monocationic ammonium ions, monofunctional amines, multi-valent metal ions, polycationic ammonium ions and polyfunctional amines.

14. Amorphous polyolefinic ionomer according to claim 12 comprising between 0.1 and 10 molar equivalent, of a metal salt, an ammonium salt or an amine with respect to the mol % of functionalized olefin monomers incorporated in the copolymer.

15. Amorphous polyolefinic ionomer according to claim 12 wherein the amount of propylene in the amorphous polyolefinic ionomer is at least 50 wt %, with respect to the total of the olefin monomers and the functionalized olefin monomers in the copolymer and wherein polypropylene segments in the amorphous polyolefinic ionomer are atactic polypropylene segments.

16. The process according to claim 1, wherein the at least one olefin monomer is propylene and/or 1-hexene.

17. The process according to claim 1 wherein the at least one functionalized olefin monomer is 3-buten-1-ol, 3-buten-2-ol, 10-undecene-1-ol, 4-pentenoic acid, or 10-undecenoic acid.

18. The process according to claim 1, wherein the amount of the functionalized olefin monomers in step a1) is from 0.02 to 20 mol %, with respect to the total molar amount of the olefin monomers and the functionalized olefin monomers.

19. The process according to claim 1, wherein the ammonium salts is a fluoride, chloride, bromide, iodide, hydroxide, nitrite, nitrate, formate, acetate, bicarbonate, carbonate, sulfite, sulfate, chlorate, perchlorate or bromate salt of NH.sub.4.sup.+, Et.sub.3N.sup.+, or Bu.sub.4N.sup.+.

20. The process according to claim 1, wherein the polyfunctional amine is selected from ethylene diamine, N,N,N,N-tetramethyl ethylene diamine, 1,3-diaminopropane, hexamethylenediamine, piperazine, diethylene triamine, N,N,N,N,N-pentamethyl diethylene triamine, or polyethylenimine.

Description

EXAMPLES

[0177] .sup.1H NMR Characterization

[0178] The percentage of functionalization was determined by 1H NMR analysis carried out at 130 C. using deuterated tetrachloroethane (TCE-D2) as solvent and recorded in 5 mm tubes on a Varian Mercury spectrometer operating at a frequency of 400 MHz. Chemical shifts are reported in ppm versus tetramethylsilane and were determined by reference to the residual solvent protons.

[0179] High Temperature Size Exclusion Chromatography (HT-SEC)

[0180] The molecular weights, reported in kg/mol, and the PDI were determined by means of high temperature size exclusion chromatography, which was performed at 150 C. in a GPC-IR instrument equipped with an IR4 detector and a carbonyl sensor (PolymerChar, Valencia, Spain). Column set: three Polymer Laboratories 13 m PLgel Olexis, 3007.5 mm. 1,2-Dichlorobenzene (o-DCB) was used as eluent at a flow rate of 1 mL.Math.min-1. The molecular weights and the corresponding PDIs were calculated from HT SEC analysis with respect to narrow polystyrene standards (PSS, Mainz, Germany).

[0181] Differential Scanning Calorimetry (DSC)

[0182] Thermal analysis was carried out on a DSC Q100 from TA Instruments at a heating rate of 5 C..Math.min.sup.1. First and second runs were recorded after cooling down to ca. 40 C. All copolymers were found to be amorphous as determined by DSC.

Example 1

[0183] The copolymerization reaction of propylene with 3-buten-1-ol (entry 2, Table 1) was carried out in a stainless steel autoclave with an internal volume of 2.2 L. The reactor, equipped with a mechanical stirrer interMIG, was operated at 900 rpm. The reactor was first flushed with propylene for at least 30 minutes. Heptane diluent (300 mL) and TiBA-pacified 3-buten-1-ol comonomer solution (TiBA: 3-buten-1-ol=1:1, 1.0 M, 10 mmol) was added followed by the introduction of an additional amount of TiBA solution (1.0 M solution in toluene, 4.0 mL). Heptane was added to bring the total volume to 1 L. The reactor was then heated to 40 C. and the pressure was brought to 9 bar with propylene. Meanwhile a pre-activated [C.sub.5Me.sub.4CH.sub.2CH.sub.2NMe.sub.2]TiCl.sub.2 catalyst solution was prepared in a glovebox by dissolving 5.0 mg of solid precatalyst in 5 mL toluene (16 mol) in MAO solution (30 wt % solution in toluene, 18 mmol) and the mixture was injected into the reactor applying an over pressure of nitrogen. The reactor temperature was kept at 403 C. by cooling with an oil LAUDA system. At the end of the reaction, the mixture was collected via a bottom drain valve in a beaker containing acidified methanol (2.5% v/v HCl, 500 mL) and Irganox 1010 (1.0 M, 0.5 mmol). The resulting suspension was stirred for 4 h, filtered and washed with demineralized water/iPrOH (50 wt. %, 2500 mL). To remove the residual aluminum, the product was dispersed in toluene (300 mL) containing hydrochloric acid (5 M, 5 v %) and heated until a clear solution was obtained. The resulting mixture was cooled down and precipitated in an excess iPrOH. The obtained rubbery solid was washed with demineralized water and dried at 60 C. in vacuo overnight (35 g). The resulting hydroxyl randomly functionalized atactic polypropylene was analyzed by HT-SEC to determine the molecular weight and .sup.1H NMR to determine the percentage of functionalization. The crystallinity of all copolymers was 0% as determined by DSC.

Example 2

[0184] The copolymerization reaction of propylene and 10-undecenoic acid (entry 2, Table 2) was carried out in a stainless steel BCHI autoclave (0.3 L). The reactor, equipped with a mechanical stirrer, was operated at 600 rpm. Heptane (120 mL) and a TiBA-pacified 10-undecenoic acid comonomer solution (TIBA:10-undecenoic acid=2:1; 1.0 M, 5 mL, 5 mmol) were added. The reactor was then heated to 50 C. and pressurized with propylene to 4 bar. Meanwhile a pre-activated catalyst solution was prepared in a glovebox by mixing a [C.sub.5Me.sub.4CH.sub.2CH.sub.2NMe.sub.2]TiCl.sub.2 precatalyst solution (3.3 mg/5 mL toluene, 10.5 mol) with an MAO solution (30 wt % solution in toluene, 9.0 mmol). The activated catalyst solution was injected into the reactor applying an over pressure of nitrogen. The reactor temperature was kept at 403 C. by heating with a water LAUDA system and cooling by circulating cold water through an internal spiral-shaped stainless steel tubing inside the reactor. At the end of the reaction, the mixture was transferred into a beaker containing a water/isopropanol mixture and Irganox 1010 (1.0 M, 0.5 mmol) and the resulting suspension was filtered, washed with demineralized water (2300 mL) and dried at 60 C. in vacuo overnight (yield 7.7 g). The resulting carboxylate-ionomer functionalized atactic polypropylene was analyzed by DSC and ICP-MS.

[0185] To determine the molecular weight, polydispersity and functionalized comonomer incorporation in the polyolefinic ionomer, the product was dispersed in toluene containing hydrochloric acid (5 M, 1-5 v %) and heated until a clear solution was obtained. The resulting mixture was cooled down and precipitated in an excess iPrOH. The obtained solid was washed with demineralized water and dried at 60 C. in vacuo overnight. The resulting carboxylic acid randomly functionalized atactic polypropylene was analyzed by HT-SEC to determine the molecular weight, DSC to determine the T.sub.g and .sup.1H NMR to determine the percentage of functionalization.

Example 3

[0186] The same polymerization procedure as described in example 2 was applied to produce a poly(propylene-co-undecenoic acid)-based ionomer using higher amount of TiBA-pacified 10-undecenoic acid comonomer solution (1.0 M, 15 mL, 15 mmol). At the end of reaction, the produced polymer was transferred under N.sub.2 atmosphere using a bottom drain valve into a glass flask containing 0.5 L of saturated aqueous NaCl solution. Irganox 1010 (1.0 M, 0.5 mL) was added and the resulting mixture was stirred at 70 C. in an oil bath under N.sub.2 atmosphere for 2 h. The resulting suspension was filtered, washed with iPrOH (200 mL) and dried at 60 C. in vacuo over night (Product A, 3.5 g). The polymer obtained was analyzed by DSC and ICP-MS.

Example 4

[0187] The polyolefinic ionomer Product A of Example 3 (1.5 g) was dispersed in toluene containing glacial acetic acid 5 v. % and hydrochloric acid (5 M, 2.5 v. %) and heated until a clear solution was obtained. The resulting mixture was precipitated in an excess iPrOH. The solid was washed with demineralized water (2200 mL), iPrOH (2200 mL) and dried at 60 C. in vacuo overnight (Product B). The product was analyzed by DSC and ICP-MS.

Example 5

[0188] The acid functionalized olefin copolymer Product B of Example 4 (1.0 g) was dispersed in toluene and heated until a clear solution was obtained. Et.sub.3N/toluene (10 wt %, 30 mL) was added and the mixture was stirred at 90 C. for 3 h. Next, the product was precipitated in an excess iPrOH, filtered and dried at 60 C. in vacuo overnight (product C). The product was analyzed by DSC.

Example 6

[0189] The copolymerization reaction of propylene and TiBA-pacified 10-undecen-1-ol (entry 2, Table 3) was carried out in a stainless steel Bchi reactor (0.3 L). Toluene solutions of the catalyst precursor ([C.sub.5Me.sub.4SiMe.sub.2NtBu]TiCl.sub.2 (5 mg/5 mL toluene, 16 mol) and of TiBA-pacified 10-undecen-1-ol comonomer (TIBA:10-undecen-1-ol=1:1; 1.0 M, 10 mL, 10 mmol) were prepared in a glove box. The reactor was dried under vacuum at 40 C. and flushed with nitrogen prior to conducting the polymerization experiment. Heptane (120 mL) and MAO (30 wt % solution in toluene, 2 mL, 9 mmol) were injected into the reactor under a nitrogen atmosphere. The solution was then saturated with propylene and stirred for 10 minutes followed by the addition of TiBA-pacified comonomer (1.0 M, 10 mmol) and catalyst precursor solution (16 mol). Then the reactor was pressurized to the desired set point (4 bar) and the pressure was maintained constant for 20 min. The reaction was stopped by depressurizing the reactor followed by quenching by pouring the mixture into a beaker containing water/isopropanol (50 wt. %, 400 mL). Irganox 1010 (1.0 M, 0.5 mmol) was added and the resulting suspension was filtered, washed with demineralized water and dried at 60 C. in vacuo overnight (7.2 g).

Example 7

[0190] A sample of a copolymer prepared according to experiment 6 (Entry 4, Table 3, 4 g) was dispersed in toluene (150 mL) and heated until a clear solution was obtained. Then 0.1 g NaH (dispersed in toluene 2 mL) was added and the mixture was stirred at 80 C. overnight. Then the solution was decanted from the non-reacted NaH and all volatiles were removed in vacuum, leaving the poly(propylene-co-1-hexene-co-sodium undecenolate) ionomer.

Example 8

[0191] The copolymerization of 1-hexene and TIBA-pacified 10-undecenoic acid (entry 5, Table 4) was conducted in a round bottom flask using rac-Me.sub.2Si(2-Me-4-Ph-Ind).sub.2ZrCl.sub.2 as catalyst precursor. 1-hexene monomer (5 mL, 0.04 mol), MAO (30 wt % solution in toluene, 4.5 mmol) were transferred into a vial under inert nitrogen atmosphere in the glovebox. The flask was placed in oil bath at 40 C. Toluene solutions of TiBA-pacified 10-undecenoic acid comonomer (TiBA:10-undecenoic acid=2:1; 0.5 M, 1 mL, 0.5 mmol) and rac-Me.sub.2Si(2-Me-4-Ph-Ind).sub.2ZrCl.sub.2 catalyst precursor (1.6 mol) were added to the flask and the mixture was kept under rigorous stirring for 60 min. At the end of the reaction, the mixture was transferred into a beaker containing a water/isopropanol mixture and Irganox 1010 (1.0 M, 0.5 mmol) and the resulting suspension was filtered, washed with demineralized water (2200 mL) and dried at 60 C. in vacuo overnight (Yield: 1.7 g).

Example 9

[0192] The copolymerization of 1-hexene and TiBA-pacified 10-undecen-1-ol (entry 11, Table 4) was conducted in a round bottom flask using rac-Me.sub.2Si(2-Me-4-Ph-Ind).sub.2ZrCl.sub.2 as catalyst precursor. 1-hexene monomer (100 mL, 0.8 mol) and MAO (30 wt % solution in toluene, 18 mmol) were transferred into a vial under inert nitrogen atmosphere in the glovebox. The flask was placed in oil bath at 40 C. Toluene solutions of TiBA-pacified 10-undecen-1-ol (TiBA:10-undecen-1-ol=1:1; 0.86 M, 16 mmol) and rac-Me.sub.2Si(2-Me-4-Ph-Ind).sub.2ZrCl.sub.2 catalyst precursor (16 mop were transferred into the flask and the mixture was kept under rigorous stirring for 16 h. At the end of the reaction, the mixture was transferred into a beaker containing a water/isopropanol mixture (50 wt. %, 500 mL) and Irganox 1010 (1.0 M, 0.5 mmol) and the resulting suspension was filtered, washed with demineralized water (2400 mL) and dried at 60 C. in vacuo overnight (Yield: 19.8 g).

Example 10

[0193] The same polymerization procedure as described in example 8 (entry 12, Table 4) was applied to produce a poly(l-hexene-co-undecenoic acid)-based ionomer. At the end of reaction, the obtained polymer was poured under N.sub.2 atmosphere into a glass flask containing 150 mL of saturated aqueous NaCl solution. Irganox 1010 (1.0 M, 1.0 mL) was added and the resulting mixture was stirred at 70 C. in an oil bath under N.sub.2 atmosphere for about 4 h. The resulting suspension was filtered, washed with iPrOH (2300 mL) and dried at 60 C. in vacuo overnight. The ionomer product obtained was analyzed by DSC and ICP-MS.

Example 11

[0194] A sample of a copolymer obtained following example 8 (entry 12, Table 4, 5 g) was dispersed in toluene and heated until a clear solution was obtained. Then Et.sub.3N/toluene (10 wt. %, 60 mL) was added and the mixture was stirred at 90 C. for 1 h. Next, the product was precipitated in an excess iPrOH, filtered and dried at 60 C. in vacuo overnight. The poly(l-hexene-co-undecenoic acid)-based ammonium ionomer was analyzed by DSC.

TABLE-US-00001 TABLE 1 Copolymerizations of propylene with 3-buten-1-ol..sup.[a] Com. 3-buten-1-ol Yield .sup.b incorp. M.sub.n Entry Solvent (mmol) (g) (mol. %) (kg/mol) PDI 1 heptane 5 27 0.25 30.4 2.5 2 heptane 10 35 0.42 43.2 2.1 3 heptane 20 37 0.45 51.9 2.2 4 heptane 30 55 0.45 41.1 2.1 5 PMH 20 31 0.42 46.7 2.4 .sup.[a]Conditions: [C.sub.5Me.sub.4CH.sub.2CH.sub.2NMe.sub.2]TiCl.sub.2 = 16 mol, 9 bar propylene, 40 C., 30 min, solvent (1 L), MAO (30 wt % solution in toluene) (Al:cat ~1000), TiBA/C.sub.4.sup.=OH = 1, additional amount of TiBA was added as scavenger. .sup.b The yield determined using the weight of polymer obtained after filtration and drying in vacuum oven overnight at 60 C.

TABLE-US-00002 TABLE 2 Copolymerizations of propylene and 10-undecenoic acid..sup.[a] Com. M.sub.w C.sub.10.sup.=COOH Activity Yield incorp. (kg .Math. Entry (mmol) (kg/mol.sub.cat .Math. h) .sup.[b] (g) (mol %) mol.sup.1) PDI 1 0 1739 9.1 0 42.3 2.2 2 5 1467 7.7 1.1 69.3 2.7 3 10 1581 8.3 1.5 85.9 2.7 4 15 2331 12.2 1.5 73.6 3.2 .sup.[a][C.sub.5Me.sub.4CH.sub.2CH.sub.2NMe.sub.2]TiCl.sub.2 = 10.5 mol, 2 bar propylene, 50 C., 30 min, PMH solvent = 100 mL, MAO (Al:cat = 1500) TiBA/C.sub.10.sup.=COOH = 2, propylene monomer = 5 bars. .sup.[b] Activity calculated using the polymer yield determined using the weight of polymer obtained after filtration and drying in vacuum oven overnight at 60 C.

TABLE-US-00003 TABLE 3 Copolymerizations of propylene with 10-undecenol and 1-hexene using [C.sub.5Me.sub.4CH.sub.2CH.sub.2NMe.sub.2]TiCl.sub.2/MAO catalyst system..sup.[a] .sup.1H Al NMR .sup.[e] Entry C.sub.11.sup.=OH .sup.[b] 1-C.sub.6.sup.= .sup.[c] Yield T.sub.g (wt C.sub.11.sup.=OH # (mmol) (mmol) (g) .sup.[d] ( C.) %) (mol %) 1 5 8.2 n.a. 2 10 7.2 n.a. 3 15 7.2 2.1 n.a. 4 10 40 6.5 8.7 0.48 0.4 5 10 80 3.1 17.7 0.44 0.7 6 10 120 4.7 0.30 1.1 7 10 160 1.5 0.16 .sup.[a]Conditions: [C.sub.5Me.sub.4CH.sub.2CH.sub.2NMe.sub.2]TiCl.sub.2 16 mol, MAO (30 wt % solution in toluene) 9 mmol, C.sub.3.sup.= monomer 4 bar, heptane diluent 120 mL, reaction temperature 40 C., reaction time 20 min. .sup.[b] C.sub.10.sup.=OH is 10-undecen-1-ol. .sup.[c] 1-C.sub.6.sup.= is 1-hexene. .sup.[d] The yield was obtained under non-optimized conditions and determined using the weight of polymer obtained after filtration and drying in vacuum oven overnight at 60 C. .sup.[e] 10-undecenoic acid incorporation level as determined by .sup.1H NMR. All copolymers were as determined to be amorphous by DSC.

TABLE-US-00004 TABLE 4 Copolymerizations of 1-hexene and TIBA-pacified 10-undecen-1-ol or 10-undecenoic acid. M.sub.n .sup.1H NMR .sup.[g] 1-C.sub.6.sup.= .sup.[c] C.sub.10.sup.=COOH .sup.[d] C.sub.11.sup.=OH .sup.[e] TiBA:com. Yield (kg/mol) C.sub.10.sup.=COOH/C.sub.11.sup.=OH # (mmol) (mmol) (mmol) Mol. ratio (g).sup.f (PDI) (mol %) 1.sup.[a] 40 0 0 0 1.5 26.6 (2.2) 0 2.sup.[a] 40 1 0 1 1.4 17.6 (2.6) 0.14 3.sup.[a] 40 3 0 1 0.5 7.6 (2.5) 0.31 4.sup.[a] 40 5 0 1 0 0 0 5.sup.[a] 40 0.5 0 2 1.7 23.3 (2.4) 0.11 6.sup.[a] 40 1.5 0 2 1.8 13.3 (3.1) 0.45 7.sup.[a] 40 2.5 0 2 1.7 15.9 (2.2) 0.53 8.sup.[a] 40 0 0.8 1 2.3 24.9 (2.3) 0.42 9.sup.[a] 40 0 2.5 1 1.4 19.0 (2.2) 0.75 10.sup.[a] 40 0 4.1 1 1.5 17.6 (2.0) 11.sup.[b] 800 0 16.6 1 19.8 26.6 (2.6) 1.1 12.sup.[b] 800 20 0 2 27.5 29.5 (2.6) 0.85 13.sup.[b] 800 0 25.0 2 37.7 36.9 (1.8) 1.3 14.sup.[b] 800 30 0 2 43.8 29.6 (2.1) 0.95 .sup.[a]Conditions: rac-Me.sub.2Si(2-Me-4-Ph-Ind).sub.2ZrCl.sub.2 (1.6 mol), MAO (30 wt % solution in toluene) 4.5 mmol, reaction temperature 40 C., reaction time 60 min. .sup.[b]same as for .sup.[a] but at room temperature for 16 hours using 16 mol rac-Me.sub.2Si(2-Me-4-Ph-Ind).sub.2ZrCl.sub.2 catalyst. .sup.[c] 1-C.sub.6.sup.= is 1-hexene. .sup.[d] C.sub.10.sup.=COOH is 10-undecenoic acid (1M solution in toluene). .sup.[e] C.sub.11.sup.=OH is 10-undecen-1-ol (0.86M solution in toluene). .sup.fThe yield was obtained under non-optimized conditions and determined using the weight of polymer obtained after filtration and drying in vacuum oven overnight at 60 C. .sup.[g] 10-undecenoic acid or 10-undecen-1-ol incorporation level as determined by .sup.1H NMR. All copolymers were as determined to be amorphous by DSC.