Process for preparation of semi-crystalline functionalized olefin copolymer

Abstract

The present invention relates to a semi-crystalline functionalized olefin copolymer composition and a process for the preparation of a semi-crystalline functionalized olefin copolymer composition.

Claims

1. A process for the manufacture of a semicrystalline functionalized olefin copolymer composition comprising the steps of: a) copolymerizing at least one olefin monomer and at least one masked functionalized olefin monomer in the presence of a catalyst system, wherein the at least one 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 b) treating the product obtained by step a) with a Brønsted acid solution capable to abstract the residue derived from the masking agent from the functionalized olefin copolymer, and combining the obtained semi- crystalline functionalized olefin 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, wherein the amount of cross-linking enhancing agent is from 0.01 to 10 wt. %, based on the combined weight of the semi-crystalline functionalized olefin copolymer and the cross-linking enhancing agent.

2. The process of 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 or wherein the at least one olefin monomer is propylene and/or 1-hexene.

3. The process of claim 1 wherein the 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 a) 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. (Previously Presented Previously Presented) The process of 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 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.

8. The process of claim 7 wherein the first olefin monomer is propylene and the second olefin monomer is 1-hexene.

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

10. The process of 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 olefin monomers and the functionalized olefin monomers.

11. The process of claim 1 wherein the amount of cross-linking enhancing agent is from 0.03 to 7 wt. %, based on the combined weight of the semi-crystalline functionalized olefin copolymer and the cross-linking enhancing agent.

12. The process of claim 8, wherein the amount of the first olefin monomer is at least 85 mol %, and the amount of second olefin monomer is at most 15 mol %, the mol % based on the total molar amount of first and second olefin monomer.

13. The process of claim 1, wherein the Brønsted acid solution comprises metal salts or ammonium salts.

Description

EXAMPLES

(1) .sup.1H NMR Characterisation

(2) The percentage of functionalisation 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.

(3) High Temperature Size Exclusion Chromatography (HT-SEC)

(4) 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.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).

(5) Differential Scanning Calorimetry (DSC)

(6) 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.

(7) Dynamic Mechanical Thermal Analysis (DMTA)

(8) The dynamic mechanical thermal analysis (DMA) studies were conducted in a tensile mode using model Q800 DMA (TA Instruments). The DMA curves were obtained in a controlled force mode. The ramp stress was 0.03 MPa/min until the sample strain was 50%. The heating and cooling rate was 5° C./min. Representative example is given in FIG. 1.

Example 1

(9) The copolymerization reaction of propylene with 10-undecen-1-ol (entry 3, 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-undecen-1-ol comonomer (TiBA: 10-undecen-1-ol=1:1, 1.0 M, 20 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 acidified isopropanol (2.5% v/v HCl, 500 mL) and Irganox 1010 (1.0 M, 0.5 mmol). The resulting suspension was stirred for about 4 h, filtered and washed with demineralized water/iPrOH (50 wt. %, 2×500 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 and precipitated in an excess iPrOH. The obtained solid was washed with demineralized water and dried at 60° C. in vacuo overnight (30 g). The resulting hydroxyl functionalized isotactic poly(propylene-co-10-undecen-1-ol) was analyzed by HT-SEC to determine the molecular weight and .sup.1H NMR to determine the percentage of functionalization and DSC to determine the crystallinity.

Example 2

(10) The copolymerization reaction of propylene, 1-hexene and TiBA-pacified 10-undecen-1-ol (entry 5, 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 (0.08 mol) and MAO (30 wt % solution in toluene, 0.4 mmol) were injected into the reactor under a nitrogen atmosphere. The reactor was then heated to 40° C. and 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 acidified isopropanol (2.5 wt % HCl, 300 mL) and Irganox 1010 (1.0 M, 0.5 mmol). The mixture was stirred for 4 h, filtered and the resulting product was dispersed in toluene 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, washed with isopropanol/demineralized water (50 wt. %, 500 mL) and dried at 60° C. in vacuo overnight (4.6 g). The resulting hydroxyl randomly functionalized isotactic poly(propylene-co-1-hexene-co-10-undecen-1-ol) was analyzed by HT-SEC to determine the molecular weight, DSC to determine the T.sub.m and .sup.1H NMR to determine the percentage of functionalization.

Example 3

(11) 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=1:1; 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 an 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 acidified isopropanol (2.5 wt % HCl, 300 mL) and Irganox 1010 (1.0 M, 0.5 mmol). The suspension was stirred for 4 h, filtered and the resulting product was dispersed in toluene 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 isopropanol/demineralized water (50 wt. %, 500 mL) and dried at 60° C. in vacuo overnight (6.5 g). The resulting carboxylic acid randomly functionalized isotactic poly(propylene-co-1-hexene-co-10-undececoinc acid) was analyzed by HT-SEC to determine the molecular weight, DSC to determine the T.sub.m and the crystallinity and .sup.1H NMR to determine the percentage of functionalization.

Example 4

(12) A copolymerization product obtained as described in example 2 (5 g; Table 2, entry 3) was dispersed in toluene (200 mL) and heated until a clear solution was obtained. Then glycerol (1 g) 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 analysed by HT-SEC, DSC and .sup.1H NMR.

Example 5

(13) The copolymerization reaction of propylene, 1-hexene and 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 (2.5% v/v HCl, 100 mL) and Irganox 1010 (1.0 M, 0.5 mmol). The resulting mixture was stirred for 4 h, filtered and washed with demineralized water (4×200 mL) and dried at 60° C. in vacuo overnight. The resulting product was analysed by HT-SEC, DSC and .sup.1H NMR.

Example 6

(14) A copolymerization product obtained as described in example 2 (3 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 (1 g; Mn=10,000 g/mol, Sigma-Aldrich) in ethanol (50:50 wt %) 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 analysed by HT-SEC, DSC and .sup.1H NMR.

Example 7

(15) The copolymerization product of example 3 (5 g; Table 3, entry 1) was dispersed in toluene (400 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 (2×20 mL) leaving the final product as a rubbery material. The product was analysed by HT-SEC, DSC and .sup.1H NMR.

(16) TABLE-US-00001 TABLE 1 Copolymerizations of propylene with 10-undecenol using rac-Me.sub.2Si(2-Me-4-Ph-Ind).sub.2ZrCl.sub.2/MAO catalyst. .sup.a Com. TiBA:10- Enthal- incorp. M.sub.n Entry undecenol .sup.b Yield .sup.c T.sub.m py (mol. (kg/ # (mmol) (g) (° C.) (J/g) %) mol) Ð 1 10 52 147.2 67 0.4 53.6 2.0 2 10 51 147.5 65 0.6 47.6 1.9 3 20 30 143.1 52 0.9 50.4 1.9 4 20 35 142.4 48 0.9 51.1 2.1 .sup.a Conditions: rac-Me.sub.2Si(2-Me-4-Ph-Ind).sub.2ZrCl.sub.2 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, pentamethylheptane diluent 1 L, reaction temperature 87° C. .sup.b Comonomer 10-undecenol (1.0M solution in toluene) 1.0 mL. .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.

(17) 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 Com. 1- Enthal- incorp. M.sub.n Entry Catalyst hexene Yield T.sub.m py (mol. (kg/ # (μmol) (mol) (g) .sup.b (° C.) (J/g) %) mol) Ð 1 1.6 0.04 18.1 132 39 2.8 53.2 3.3 2 0.8 0.04 14.1 132 34 2.5 44.0 3.0 3 0.4 0.04 7.3 94 29 2.6 65.3 3.9 4 0.4 0.04 5.7 99 28 2.0 112.2  3.2 5 0.4 0.08 4.6 52 12 1.9 36.6 3.5 6 0.4 0.08 4.9 44 8 2.6 46.3 4.2 7 0.4 0.08 4.5 80 18 n.d n.d n.d 8 0.4 0.08 3.9 85 21 2.9 n.d n.d .sup.a Conditions: rac-Me.sub.2Si(2-Me-4-Ph-Ind).sub.2ZrCl.sub.2 catalyst precursor, 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), pentamethylheptane 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.

(18) 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 Com. 1- Enthal- incorp. M.sub.n Entry hexene Yield T.sub.m py (mol. (kg/ # (mol) (g) .sup.b (° C.) (J/g) %) mol) Ð 1 0.04 6.5 80 26 1.2 39.9 2.9 2 0.04 7.4 78 25 1.4 46.3 3.3 3 0.08 4.3 50 18 1.7 n.d n.d 4 0.12 3.9 40 14 1.9 53.5 2.6 .sup.aConditions: rac-Me.sub.2Si(2-Me-4-Ph-Ind).sub.2ZrCl.sub.2 catalyst precursor (0.8 μmol), 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-undecenoic acid comonomer (TiBA:10-undecenoic acid = 1:1; 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.

(19) The FIGURE shows the shape memory properties, by means of DMTA, of the material of Entry 1, Table 3.