PROCESS FOR PREPARATION OF ETHYLENE AND PROPYLENE IONOMER

Abstract

The present invention relates to an ethylene and propylene ionomer and a process for the preparation of an ethylene and propylene ionomer.

Claims

1. A process for the manufacture of an ethylene and propylene ionomer comprising the steps of: a1) copolymerizing ethylene, propylene and at least one masked functionalized olefin monomer in the presence of a catalyst system, 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 Brnsted acid solution capable to abstract the residue derived from the masking agent from the functionalized ethylene and propylene copolymer of step a1) to obtain the functionalized ethylene and propylene copolymer, 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 in step a1) the ethylene to propylene weight ratio is from 20:80 to 70:30.

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 0.01 to 30 mol %, with respect to the total molar amount of ethylene, propylene 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 Brnsted acid solution used in step a2) comprises inorganic and/or organic acids.

9. An ethylene and propylene ionomer obtained by the process of claim 1.

10. The ethylene propylene ionomer of claim 9 wherein, the ethylene to propylene weight ratio in the polymer is from 20:80 to 70:30, and 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.

11. The ethylene and propylene ionomer of claim 9 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.

12. The ethylene and propylene ionomer of claim 9, wherein the content of functionalized olefin monomer is between 0.01 and 30 mol %, with respect to the total of the olefin monomers and the functionalized olefin monomers in the copolymer.

13. The ethylene and propylene ionomer according to claim 9 comprising between 0.1 and 100 mol. 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 ethylene and propylene ionomer according to claim 9 comprising at least one or two types of reversible cross-links.

15. 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 and 10-undecenoic acid.

16. The process according to claim 1, wherein the monofunctional amine is NH.sub.3, Me.sub.2NH, NMe.sub.3, EtNH.sub.2, Et.sub.3N, or BuNH.sub.2.

17. The process according to 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.+.

18. The process according to claim 1, 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

[0127] The ethylene content and percentage of functionalization was determined by .sup.13C and .sup.1H NMR analysis carried out at 125 C. The samples were dissolved at 130 C. in deuterated tetrachloroethane (TCE-D2) containing butylated hydroxytoluene (BHT) as stabilizer. The spectra were recorded in 5 mm tubes on a Bruker Avance 500 spectrometer equipped with a cryogenically cooled probe head operating at 125 C.

[0128] Chemical shifts are reported in ppm versus tetramethylsilane and were determined by reference to the residual solvent protons.

Differential Scanning Calorimetry (DSC)

[0129] Thermal analysis was carried out on a DSC Q100 from TA Instruments at a heating rate of 5 C.-min-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.-min-1. 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

[0130] The copolymerization reaction of propylene, ethylene, and TiBA-pacified 10-undecenoic acid (entry 4, Table 1) was carried out in a stainless steel autoclave (2.2 L). The reactor, equipped with a mechanical stirrer interMIG, was operated at 900 rpm. The reactor was first flushed with a mixture of ethylene and propylene at set flows for 30 minutes. Pentamethyl heptane diluent (300 mL), solutions of TiBA solution (1.0 M solution in toluene, 4.0 mmol), TiBA-pacified 10-undecenoic acid (TiBA:10-undecenoic acid=2:1, 1.0 M, 15 mmol) and MAO (30 wt % solution in toluene, 6.0 mmol) were added. Pentamethyl heptane was added to bring the total volume to 1 L. The reactor was then heated to 85 C. and the overall pressure was brought to 9 bar with a propylene/ethylene mixture (feed rate ratio=80/20) and kept at this pressure using a set ethylene and propylene flow and a bleeding valve set at 9 bar. A solution of rac-Me.sub.2Si(2-Me-4-Ph-Ind).sub.2ZrCl.sub.2 catalyst precursor prepared in a glovebox by dissolving 3 mg of solid precatalyst in 5 mL toluene (5 mol) was injected into the reactor applying an over pressure of nitrogen. The reactor temperature was kept at 853 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, 1.0 mmol) and the resulting suspension was filtered, washed with demineralized water (2500 mL) and dried at 60 C. in vacuo overnight (yield 68.3 g). The product was analyzed by DSC and ICP-MS.

[0131] About 20 g of this product was dispersed in toluene (400 mL) containing hydrochloric acid (5.0 M, 2.5 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 (2500 mL) and dried at 60 C. in vacuo overnight. The resulting product was analyzed by DSC to determine the crystallinity, .sup.1H and .sup.13C NMR to determine the percentage of functionalization and ethylene content.

Example 2

[0132] The copolymerization reaction of propylene, ethylene and TiBA-pacified 10-undecen-1-ol (entry 6, Table 2) was carried out in a stainless steel Bchi 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 mol) and of TiBA-pacified 10-undecen-1-ol comonomer (TiBA:10-undecen-1-ol=1:1; 1.0 M, 15 mmol) were prepared in a glovebox. Pentamethyl heptane (120 mL), 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 a propylene/ethylene mixture flow rate ratio=70/30) and stirred for 10 minutes followed by the addition of TiBA-pacified 10-undecen-1-ol (1.0 M, 15 mmol) and catalyst precursor solution (0.4 mol). Then the reactor was pressurized to the desired set point (6 bar) and the pressure was maintained constant for 20 min using a set ethylene and propylene flow and a bleeding valve set at 6 bar. 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). The resulting suspension was filtered, washed with demineralized water (2300 mL) and dried at 60 C. in vacuo overnight (yield 5.6 g). The product was analyzed by DSC and ICP-MS.

[0133] About 2 g of this product was dispersed in toluene (100 mL) containing hydrochloric acid (5.0 M, 2.5 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 (2100 mL) and dried at 60 C. in vacuo overnight. The resulting product was analyzed by DSC to determine the crystallinity, NMR to determine the percentage of functionalization and ethylene content.

Example 3

[0134] The same polymerization procedure as described in example 1 was applied to produce a poly(propylene-co-ethylene-co-undecenoic acid)-based ionomer (entry 7, Table 1). At the end of reaction, the obtained polymer was transferred under N.sub.2 atmosphere using a bottom drain valve into a glass flask containing 1.0 L 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 (Product A, 75.3 g). The ionomer product obtained was analyzed by DSC and ICP-MS.

Example 4

[0135] Part of the polyolefinic ionomer product of Example 3 (about 15 g) was dispersed in toluene (200 mL) 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 and filtered. The obtained solid was washed with demineralized water (2200 mL), iPrOH (2200 mL) and dried at 60 C. in vacuo overnight (Product B). The poly(propylene-co-ethylene-co-undecenoic acid) was analyzed by DSC and ICP-MS.

Example 5

[0136] A fraction of the acid functionalized olefin copolymer product of example 4 (8.5 g) was dispersed in toluene (100 mL) and heated until a clear solution was obtained. Et.sub.3N/toluene (10 wt. %, 60 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. The poly(propylene-co-ethylene-co-undecenoic acid)-based ammonium ionomer was analyzed by DSC.

Example 6

[0137] A copolymer sample as described in experiment 1 (Table 1, entry 3, 5 g) was dispersed in toluene (400 mL) and heated until a nearly clear solution was obtained. Then solid NaH (0.1 g dispersed in 5 mL toluene) was added and the mixture was stirred for 1 h. Then water (1 mL) was added and the solvent was distilled of and all volatiles were removed in vacuum, to yield the poly(ethylene-co-propylene-co-sodium undecenoate) ionomer.

TABLE-US-00001 TABLE 1 Copolymerizations of propylene with 10-undecenoic acid using rac-Me.sub.2Si(2-Me-4-Ph-Ind).sub.2ZrCl.sub.2/MAO catalyst. .sup.a TiBA:10- undecenoic C.sub.2.sup.=/C.sub.3.sup.= Com. acid b feed ratio Yield .sup.c incorp. M.sub.n Entry # (mmol) (wt.) (g) (mol. %).sup.d (kg .Math. mol.sup.1) D M (wt. %) 1 20:80 65.2 n.a 44.3 2.6 <0.1 (Al, Na) 2 30:70 62.4 n.a 33.1 3.4 <0.1 (Al, Na) 3 10 20:80 59.6 0.9 46.2 2.3 0.4 (Al) 4 15 20:80 51.3 0.9 42.0 2.9 0.4 (Al) 5 20 20:80 54.2 1.2 50.5 3.2 0.7 (Al) 6 10 30:70 46.3 0.6 32.3 2.6 0.4 (Al) 7 20 30:70 35.7 0.8 46.5 2.4 0.6 (Na), 0.3 (Al) .sup.[a] Conditions: rac-Me.sub.2Si(2-Me-4-Ph-Ind).sub.2ZrCl.sub.2 catalyst precursor (5.0 mol), TiBA (1.0 M solution in toluene) 4 mL, MAO (30 wt % solution in toluene) = 6.0 mmol, C.sub.3.sup.=/C.sub.2.sup.= feed = 9 bar, pentamethyl heptane diluent 1 L, reaction temperature 85 C., reaction time 20 min. [b] Comonomer 10-undecenoic acid (1.0 M solution in toluene, TiBA:10-undecenoic acid 2:1). .sup.[c] 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.dTo determine the percentage of functionalization and ethylene content, a fraction of the product was dispersed in toluene (about 300 mL) containing glacial acetic acid 10 v % and hydrochloric acid (5 M, 2.5 v %) and heated until a clear solution was obtained. The resulting mixture was cooled down and precipitated in an excess iPrOH, filtered, washed with demineralized water, dried at 60 C. in vacuo overnight and analysed by NMR.

TABLE-US-00002 TABLE 2 Copolymerization of propylene with 10-undecenol using rac-Me.sub.2Si(2-Me-4-Ph-Ind).sub.2ZrCl.sub.2/MAO catalyst. .sup.a TiBA:10- C.sub.2.sup.=/C.sub.3.sup.= Com. undecenol .sup.b feed ratio Yield incorp..sup.d Entry # (mmol) (wt.) (g) .sup.c (mol. %) Al (wt %) 1 20:80 4.9 n.a. <0.1 2 30:70 5.8 n.a. <0.1 3 10 20:80 3.1 1.0 1.20 4 15 20:80 4.3 1.2 0.82 5 10 30:70 4.7 0.9 0.64 6 15 30:70 5.6 1.1 0.95 .sup.a Conditions: rac-Me.sub.2Si(2-Me-4-Ph-Ind).sub.2ZrCl.sub.2 catalyst precursor (0.4 mol), MAO (30 wt % solution in toluene) Al/Zr~1000, C3.sup.=/C2.sup.= feed = 6 bar. pentamethyl heptane 120 mL, reaction temperature 40 C., reaction time 20 min. .sup.b TiBA-pacified 10-undecen-1-ol comonomer solution (TIBA:10-undecen-1-ol = 1:1; 1.0M). .sup.c 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.dTo determine the percentage of functionalization and ethylene content, a fraction of the product was dispersed in toluene (100 mL) containing glacial acetic acid 10 v % and hydrochloric acid (5M, 2.5 v %) and heated until a clear solution was obtained. The resulting mixture was cooled down and precipitated in an excess iPrOH, filtered, washed with demineralized water, dried at 60 C. in vacuo overnight and analysed by NMR.