PROCESS FOR PREPARATION OF FUNCTIONALIZED ETHYLENE AND PROPYLENE COPOLYMER

Abstract

The present invention relates to a process for the manufacture of a functionalized ethylene and propylene copolymer composition. The invention further relates to such functionalized ethylene and propylene copolymer composition.

Claims

1. A process for the manufacture of a functionalized ethylene and propylene copolymer composition comprising the steps of: a) 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 b) treating the product obtained by step a) with a Brnsted acid solution, optionally containing metal salts or ammonium salts, capable to abstract the residue derived from the masking agent and combining the obtained functionalized ethylene and propylene copolymer with a cross-linking enhancing agent selected from the group consisting of polyols, polyamines, polyacids, polyethers, polyesters, polycarbonates, polyamides, polyurethanes, polyureas, polysaccharides, polypeptides and combinations of at least two of said cross-linking enhancing agents, wherein said cross-linking enhancing agent has at least two functionalities.

2. The process according to claim 1, wherein in step a) the ethylene to propylene weight ratio is from 20:80 to 70:30.

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 a) is from 0.01 to 30 mol %, with respect to the total molar amount of the olefins 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 the cross-linking enhancing agent is selected from the group consisting of ethylene glycol, glycerol, pentaerythritol, mucic acid, galactaric acid, carbohydrates, ethylene diamine, diethylene triamine, tetramethyl ethylene diamine, pentamethyl diethylene triamine, polyethylenimine, maleic acid, succinic acid, tartaric acid, citric acid, polyacrylic acid, poly(ethylene-co-acrylic acid), polyvinyl acetate, poly(ethylene-co-vinyl acetate), polyvinyl alcohol, poly(ethylene-co-vinyl alcohol), polyethylene oxide, polypropylene oxide, poly(ethylene oxide-co-propylene oxide), poly(ethylene carbonate), poly(propylene carbonate), polycaprolactone, poly(ethylene brassylate), polylactide, polybutylene adipate, polybutylene adipate terephthalate, polyamide 6, polyamide 4,6, polyamide 6,6 and combinations of at least two of the foregoing cross-linking enhancing agents.

7. The process according to claim 1, wherein the amount of cross-linking enhancing agent is from 0.01 to 10 wt. %, based on the combined weight of the a functionalized ethylene and propylene copolymer and the cross-linking enhancing agent.

8. A functionalized ethylene and propylene copolymer composition obtained by the process of claim 1.

9. A functionalized ethylene and propylene copolymer composition comprising i) from 90-99.99 wt. % of a functionalized ethylene and propylene copolymer of ethylene, propylene and at least one functionalized olefin monomer 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, preferably 3-buten-1-ol, 3-buten-2-ol, 10-undecen-1-ol, 4-pentenoic acid and 10-undecenoic acid; and ii) from 0.01 to 10 wt. % of at least one cross-linking enhancing agent selected from the group consisting of polyols, polyamines, polyacids, polyethers, polyesters, polycarbonates, polyamides, polyurethanes, polyureas, polysaccharides, polypeptides, wherein said cross-linking enhancing agent has at least two functionalities, wherein the wt. % is based on the combined weight of the functionalized ethylene and propylene copolymer and the cross-linking enhancing agent.

10. The composition of claim 8, wherein the weight ratio of ethylene to propylene in the functionalized ethylene and propylene copolymer is from 20:80 to 70:30.

11. The composition of claim 8, wherein the melting enthalpy is between 5 J/g and 150 J/g, as measured by differential scanning calorimetry.

12. The composition of claim 8, wherein the functionalized ethylene and propylene copolymer comprises at least one or two types of reversible cross-links.

13. A thermoplastic composition comprising the functionalized ethylene and propylene copolymer composition of claim 8 and at least one further thermoplastic polymer.

14. The composition of claim 8, wherein the composition is a shape memory copolymer and/or self-healing copolymer.

15. The process according to claim 1, wherein in step a) the ethylene to propylene weight ratio is from 25:75 to 60:40.

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

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

18. The process according to claim 1, wherein the amount of the functionalized olefin monomers in step a) is from 0.05 to 10 mol % with respect to the total molar amount of the olefins and the functionalized olefin monomers.

19. The process according to claim 1, wherein the masking agent is triisobutylaluminum.

20. The process according to claim 1, wherein The process according to claim 1, wherein the amount of cross-linking enhancing agent is from 0.03 to 7 wt. %, based on the combined weight of the a functionalized ethylene and propylene copolymer and the cross-linking enhancing agent.

Description

EXAMPLES

[0139] .sup.1H and .sup.13C NMR Characterization

[0140] 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.

[0141] 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)

[0142] The molecular weights, reported in kg.Math.mol.sup.1, 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.sup.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)

[0143] 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

[0144] The copolymerization reaction of propylene, ethylene, and TiBA-pacified 10-undecenoic acid (entry 5, Table 1) was carried out in a stainless steel autoclave (2.2 L). The mechanical stirrer of the reactor was operated at 900 rpm. The reactor was first flushed with a mixture of ethylene and propylene at set flows for about 30 minutes. Pentamethyl heptane diluent (300 mL), solutions of TiBA (1.0 M solution in toluene, 4.0 mmol), TiBA-pacified 10-undecenoic acid (TiBA:10-undecenoic acid=2:1, 1.0 M, 10 mmol) and MAO (30 wt % solution in toluene, 3.5 mmol) were added. Pentamethyl heptane was added to bring the total volume to 1 L. The reactor was then heated to 80 C. and the overall pressure was brought to 9 bar with a propylene/ethylene mixture (feed rate ratio 70/30) 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 2 mg of solid precatalyst in 5 mL toluene (3.2 mol), was injected into the reactor applying an over pressure of nitrogen. The reactor temperature was kept at 803 C. by cooling with an oil LAUDA system.

[0145] At the end of the reaction, the mixture was collected via a bottom drain valve in a beaker. A mixture of acidified methanol (2.5% v/v HCl, 500 mL) and Irganox 1010 (1.0 M, 1.0 mL) was added and the resulting suspension was filtered. To remove residual aluminum, the crude product was dispersed in toluene (300 mL) containing 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. The obtained solid was washed with a solution containing a water/isopropanol mixture (50 wt. %, 500 mL) and Irganox 1010 (1.0 M, 1.0 mmol) and the resulting suspension was filtered and dried at 60 C. in vacuo overnight (yield 46.3 g). The resulting product was analyzed by HT-SEC to determine the molecular weight and molecular weight distribution (D), DSC to determine the crystallinity, .sup.1H and .sup.13C NMR to determine the percentage of functionalization and ethylene content.

Example 2

[0146] The copolymerization reaction of propylene, ethylene and TiBA-pacified 10-undecen-1-ol (entry 4, 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, 10 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 (feet rate ratio 70/30) 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 mol). Then the reactor was pressurized to the desired set point (6 bar) and the pressure was maintained constant for 20 min using a constant ethylene/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 a mixture of acidified methanol (2.5 v. % HCl, 300 mL) and Irganox 1010 (1.0 M, 0.5 mL). To remove residual aluminum, the crude product was dispersed in toluene (300 mL) containing 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. The obtained solid was washed with a solution containing a water/isopropanol mixture (50 wt. %, 2250 mL) and Irganox 1010 (1.0 M, 0.5 mmol) and the resulting suspension was filtered and dried at 60 C. in vacuo overnight (yield 3.7 g). The resulting product was analyzed by HT-SEC to determine the molecular weight and molecular weight distribution (0), DSC to determine the crystallinity, .sup.1H and .sup.13C NMR to determine the percentage of functionalization and ethylene content.

Example 3

[0147] The copolymerization product of example 1 (5 g; Table 1, entry 5) was dispersed in toluene (250 mL) and heated until a clear solution was obtained. Then poly(ethylene glycol) dimethyl ether (0.5 g; Mn=250 g/mol) was added and the mixture was stirred for 15 minutes. Then the solvent was distilled off and all volatiles were removed in vacuo and the thus obtained material was washed with demineralised water (220 mL) leaving the final product as a rubbery material. The product was analysed by HT-SEC, DSC and .sup.1H NMR.

Example 4

[0148] The copolymerization product of example 2 (2.5 g; Table 2, entry 4) was dispersed in toluene (200 mL) and heated until a clear solution was obtained. Then a solution of branched polyethyleneimine (0.2 g; Mn=10,000 g/mol, Sigma-Aldrich) was added and the mixture was stirred for 15 minutes. Then the solvent was distilled off and all volatiles were removed in vacuo leaving the final product as a rubbery material. The product was analyzed by HT-SEC, DSC and .sup.1H NMR.

Example 5

[0149] A sample of a copolymerization product obtained as described in example 2 (3 g; Table 2, entry 3) was dispersed in toluene (200 mL) and heated until a clear solution was obtained. Then glycerol (0.6 g) was added. Then the solvent was distilled off and all volatiles were removed in vacuo leaving the final product as a rubbery material. The product was analysed by HT-SEC, DSC and .sup.1H NMR.

Example 6

[0150] The copolymerization reaction of propylene with 10-undecen-1-ol was performed in the same way as described in example 2. At the end of the reaction, the mixture was collected via a bottom drain valve in a beaker containing an acidified glycerol solution (2.5% v/v HCl, 100 mL) and Irganox 1010 (1.0 M, 0.5 mmol). The resulting mixture was stirred for 2 h, filtered and washed with demineralised water (4200 mL) and dried at 60 C. in vacuo overnight. The product was analysed by HT-SEC, DSC and .sup.1H NMR.

TABLE-US-00001 TABLE 1 Copolymerizations of ethylene, propylene and 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. M.sub.n acid .sup.b feed ratio Yield .sup.c incorp. (kg .Math. Entry # (mmol) (%) (g) (mol. %) mol.sup.1) 1 20:80 65.2 n.a 44.3 2.6 2 10 20:80 59.6 0.9 46.2 2.3 3 20 20:80 54.2 1.2 50.5 3.2 4 30:70 62.4 n.a 33.1 3.4 5 10 30:70 46.3 0.6 32.3 2.6 6 20 30:70 35.7 0.8 46.5 2.4 .sup.a Conditions: rac-Me.sub.2Si(2-Me-4-Ph-Ind).sub.2ZrCl.sub.2 catalyst precursor (3.2 mol), TiBA (1.0M solution in toluene) 4 mL, MAO (30 wt % solution in toluene) = 3.5 mmol, C.sub.3.sup.=/C.sub.2.sup.= feed = 9 bar, TiBA-pacified 10-undecenoic acid comonomer solution (TIBA:10-undecenoic acid = 2:1), pentamethyl heptane diluent 1 L, reaction temperature 80 C., reaction time 20 min. .sup.b Comonomer 10-undecenoic acid (1.0M solution in toluene), TiBA:10-undecenoic acid 2:1. .sup.c The yield was obtained under non-optimised conditions. The ICP-MS revealed Al content 0.1 wt. %.

TABLE-US-00002 TABLE 2 Copolymerization of ethylene, propylene and 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. M.sub.n undecenol .sup.b feed ratio Yield incorp. (kg .Math. Entry # (mmol) (%) (g) .sup.b (mol. %) mol.sup.1) 1 20:80 5.4 n.a. 44.3 2.6 2 10 20:80 4.6 0.9 36.2 2.8 3 15 20:80 4.3 1.1 29.8 2.4 4 10 30:70 3.7 1.0 55.1 3.1 5 15 30:70 4.1 1.2 65.0 2.8 .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, C.sub.3.sup.=/C.sub.2.sup.= feed = 6 bar, TiBA-pacified 10-undecen-1-ol comonomer solution (TIBA:10-undecen-1-ol = 1:1), pentamethyl heptane 120 mL, reaction temperature 40 C., reaction time 20 min. .sup.b The yield was obtained under non-optimised conditions and was determined using the weight of polymer obtained after filtration and drying in vacuum oven overnight at 60 C. The ICP-MS revealed Al content 0.1 wt. %.