PROCESS FOR PREPARATION OF SEMI-CRYSTALLINE POLYOLEFINIC IONOMERS

Abstract

The present invention relates to a semi-crystalline polyolefinic ionomer and a process for the preparation of a semi-crystalline polyolefinic ionomer.

Claims

1. A process for the manufacture of a semi-crystalline 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.2═CHR.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).sub.n].sub.m is a polar functional group containing one or multiple heteroatom containing functionalities X—(R.sup.6).sub.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).sub.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 Brønsted acid solution capable to abstract the residue derived from the masking agent from the functionalized olefin copolymer of step a1) to obtain the semi-crystalline 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 of claim 1, wherein the 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 of 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 of 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 of 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 of 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.

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 of claim 1, wherein, the Brønsted acid solution used in step a2) comprises inorganic and/or organic acids.

9. The process of claim 1, wherein the at least one olefin monomer is a first and a second olefin monomer, wherein the first and second olefin monomer are different and wherein the amount of the first olefin monomer is at least 75 mol %, and the amount of second olefin monomer is at most 25 mol %, the mol % based on the total molar amount of first and second olefin monomer.

10. The composition of claim 9 wherein the first olefin is propylene and the second olefin is 1-hexene.

11. A semi-crystalline polyolefinic ionomer obtained by the process of claim 1.

12. The semi-crystalline polyolefinic ionomer of claim 11 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.

13. The semi-crystalline polyolefinic ionomer according to claim 11 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.

14. The process of claim 1, wherein the at least one olefin monomer is propylene, 1-hexene, or a combination thereof.

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

16. The process of 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.

17. The process of claim 1, the monofunctional amine is selected from NH.sub.3, Me.sub.2NH, NMe.sub.3, EtNH.sub.2, Et.sub.3N, BuNH.sub.2.

18. The process of claim 1, wherein the ammonium salt 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.3NH.sup.+, Bu.sub.4N.sup.+.

19. 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, polyethylenimine.

Description

EXAMPLES

.SUP.1.H NMR Characterization

[0130] 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.

High Temperature Size Exclusion Chromatography (HT-SEC)

[0131] 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 μm PLgel Olexis, 300×7.5 mm. 1,2-Dichlorobenzene (o-DCB) was used as eluent at a flow rate of 1 mL-min-1. The molecular weights and the corresponding PDIs were calculated from HT SEC analysis with respect to narrow polystyrene standards (PSS, Mainz, Germany).

Differential Scanning Calorimetry (DSC)

[0132] 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 heating up to 210° C. and cooling down to ca. −40° C. at a rate of 10° C..Math.min. All copolymers were found to be semi-crystalline as determined by DSC. The melting enthalpy was calculated as the area under the peak from the melting transition in DSC.

Example 1

[0133] The copolymerization reaction of propylene with 10-undecenoic acid (entry 1, Table 1) was carried out in a stainless steel autoclave (2.2 L). The reactor, equipped with a mechanical stirrer, was operated at 900 rpm. The reactor was first flushed with propylene for at least 30 minutes. Pentamethylheptane diluent (300 mL), solutions of TiBA-pacified 10-undecenoic acid (TiBA:10-undecenoic acid=2:1, 1.0 M, 25 mmol) and MAO (30 wt % solution in toluene, 9 mmol) were added followed by the introduction of an additional amount of TiBA solution (1.0 M solution in toluene, 4.0 mmol) and DEZ (1.0 M solution in toluene, 1 mmol). Pentamethylheptane was added to bring the total volume to 1 L. The reactor was then heated to 87° C. and the pressure was brought to 9 bar with propylene. A solution of rac-Me.sub.2Si(2-Me-4-Ph-Ind).sub.2ZrCl.sub.2 catalyst precursor prepared in a glovebox by dissolving 4 mg of solid precatalyst in 5 mL toluene (˜ 6.4 μmol) was injected into the reactor applying an over pressure of nitrogen. The reactor temperature was kept at 87±3° 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 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 (2×500 mL) and dried at 60° C. in vacuo overnight (yield 57 g). The resulting ionomer product was analyzed by DSC and ICP-MS.

[0134] 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 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 2

[0135] The copolymerization reaction of propylene, 1-hexene and TiBA-pacified 10-undecen-1-ol (entry 3, Table 2) was carried out in a stainless steel Büchi reactor (0.3 L). Toluene solutions of the catalyst precursor rac-Me.sub.2Si(2-Me-4-Ph-Ind).sub.2ZrCl.sub.2 (0.4 μmol) and of TiBA-pacified 10-undecen-1-ol comonomer (TIBA:10-undecen-1-ol=1:1; 1.0 M, 10 mmol) were prepared in a glove box. Pentamethylheptane (120 mL), 1-hexene (0.04 mol) and MAO (30 wt % solution in toluene, 0.4 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 10-undecen-1-ol (1.0 M, 10 mmol) and catalyst precursor solution (0.4 μmol). 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 mixture (50 wt. %, 300 mL) and Irganox 1010 (1.0 M, 0.5 mmol) and the resulting suspension was filtered, washed with demineralized water (2×300 mL) and dried at 60° C. in vacuo overnight (yield 5.9 g). The resulting ionomer product was analyzed by DSC and ICP-MS.

[0136] 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 poly(propylene-co-1-hexene-coundecenol) 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

[0137] The copolymerization reaction of propylene, 1-hexene and 10-undecenoic acid (entry 1, Table 3) was carried out in a stainless steel Büchi reactor (0.3 L). The reactor, equipped with a mechanical stirrer, was operated at 600 rpm. Heptane (120 mL), 1-hexene (0.04 mol) and a TiBA-pacified 10-undecenoic acid comonomer solution (TiBA:10-undecenoic acid=2:1; 1.0 M, 10 mmol) were added. The reactor was then heated to 40° C. and pressurized with propylene to 4 bar. Meanwhile a pre-activated catalyst solution was prepared in a glovebox by mixing a rac-Me.sub.2Si(2-Me-4-Ph-Ind).sub.2ZrCl.sub.2 precatalyst solution (0.8 μmol) with a MAO solution (30 wt. % solution in toluene, 0.8 mmol). The activated catalyst solution was injected into the reactor applying an over pressure of nitrogen. The reactor temperature was kept at 40±3° 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 water/isopropanol mixture (500 mL) and Irganox 1010 (1.0 M, 0.5 mmol) and the resulting suspension was filtered, washed with demineralized water (2×300 mL) and dried at 60° C. in vacuo overnight (yield 7.4 g). The resulting ionomer product was analyzed by DSC and ICP-MS.

Example 4

[0138] The same polymerization procedure as described in example 3 was applied With this difference that 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 (6.8 g). The ionomer product obtained was analyzed by DSC.

Example 5

[0139] Part of the polyolefinic ionomer product of Example 4 (2.0 g) was dispersed in toluene containing 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 (2×200 mL), iPrOH (2×200 mL) and dried at 60° C. in vacuo overnight (Product B). The poly(propylene-co-1-hexene-co-undecenoic acid) was analyzed by DSC and ICP-MS.

Example 6

[0140] The acid functionalized olefin copolymer product of Example 5 (1.7 g) was dispersed in toluene and heated until a clear solution was obtained. Et.sub.3N (1 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(propylene-co-1-hexene-co-undecenoic acid)-based ammonium ionomer was analyzed by DSC.

TABLE-US-00001 TABLE 1 Copolymerizations of propylene with 10-undecenoic acid or 10- undecen-1-ol using rac-Me.sub.2Si(2-Me-4-Ph-Ind).sub.2 ZrCl.sub.2/MAO catalyst. .sup.a TiBA:10- TiBA:10- Com. un- undecenoic Melting incorp. Al Entry decenol.sup.b acid .sup.c Yield .sup.d T.sub.m enthalpy (mol. (wt. # (mmol) (mmol) (g) (° C.) (J/g) %) %) 1 — 25 57 136 30 1.2 1.26 2 — 10 46 150 59 0.3 0.24 3 20 — 59 143 55 0.8 0.28 4 10 — 88 147 61 0.3 0.32 .sup.a Conditions: rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 catalyst precursor (6.4 μmol), TiBA (1.0M solution in toluene) 4 mL, MAO (30 wt % solution in toluene) 9 mmol, DEZ (1.0M solution in toluene) 1 mmol, C.sub.3.sup.= monomer 9 bar, Pentamethlheptane diluent 1 L, reaction temperature 87° C. .sup.bComonomer 10-undecenol (1.0M solution in toluene), TiBA:10-undecenol 1:1. .sup.c Comonomer 10-undecenoic acid (1.0M solution in toluene), TiBA:10-undecenoic acid 2:1. .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.

TABLE-US-00002 TABLE 2 Copolymerization of propylene with 10-undecenol and 1-hexene using rac-Me.sub.2Si(2-Me-4-Ph-Ind).sub.2ZrCl.sub.2/MAO catalyst. .sup.a Melting Com. Catalyst 1-hexene Yield T.sub.m enthalpy incorp. Al Entry # (μmol) (mol) (g) .sup.b (° C.) (J/g) (mol. %) (wt. %) 1 0.8 0.04 13.7 136 43 2.0 1.63 2 0.8 004 11.5 134 41 1.9 1.20 3 0.4 0.04 5.9 105 19 1.7 0.98 4 0.4 0.08 3.8 78 16 2.1 1.11 5 0.4 0.08 4.2 85 18 1.5 0.75 .sup.a Conditions: TiBA scavenger (1.0M solution in toluene) 1 mL, MAO (30 wt % solution in toluene) Al/Zr~1000, C.sub.3.sup.= monomer 4 bar, TiBA-pacified 10-undecen-1-ol comonomer solution (TiBA:10-undecen-1-ol = 1:1; 1.0M, 10 mmol), pentamethyl heptane 120 mL, reaction temperature 40° C., reaction time 20 min. .sup.b The yield was obtained under non-optimized conditions and was determined using the weight of polymer obtained after filtration and drying in vacuum oven overnight at 60° C. .sup.c DEZ (1.0M solution in toluene) 0.3 mL was added.

TABLE-US-00003 TABLE 3 Copolymerization of propylene with 10-undecenoic acid and 1-hexene using rac-Me.sub.2Si(2-Me-4-Ph-Ind).sub.2ZrCl.sub.2/MAO catalyst..sup.a Melting. Com. 1-hexene Yield Tm enthalpy incorp. Al Entry # (mol) (g) .sup.b (° C.) (J/g) (mol. %) (wt. %) 1 0.04 7.4 81 36 1.3 1.28 2 0.08 3.5 65 23 1.9 1.65 3 0.12 2.9 40 21 1.8 1.74 .sup.aConditions: rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 catalyst precursor (0.8 μmol), MAO (30 wt % solution in toluene) Al/Zr~1000, C.sub.3.sup.= monomer 4 bar, TiBA-pacified 10-undecenoic acid comonomer (TiBA: 10-undecenoic acid = 2:1, 1.0M, 10 mmol), heptane 120 mL, reaction temperature 40° C., reaction time 20 min. .sup.b The yield was obtained under non-optimized conditions and was determined using the weight of polymer obtained after filtration and drying in vacuum oven overnight at 60° C.