PROCESS FOR PREPARATION OF AMORPHOUS FUNCTIONALIZED OLEFIN COPOLYMER

Abstract

The present invention relates to an amorphous functionalized olefin copolymer composition and a process for the preparation of an amorphous functionalized olefin copolymer composition.

Claims

1. A process for the manufacture of an amorphous 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 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).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 from the functionalized olefin copolymer and combining the obtained amorphous 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.

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

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 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 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 amorphous functionalized olefin copolymer and the cross-linking enhancing agent.

8. 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.

9. 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.

10. The process according to claim 1, wherein said at least one olefin monomer is propylene and wherein polypropylene segments of the amorphous functionalized olefin copolymer are atactic polypropylene segments.

11. An amorphous functionalized olefin copolymer composition obtained by the process of claim 1.

12. An amorphous functionalized olefin copolymer composition comprising i) from 90-99.99 wt. % of an amorphous functionalized olefin copolymer of at least one olefin monomer 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 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; 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 amorphous functionalized olefin copolymer and the cross-linking enhancing agent.

13. The composition of claim 12 wherein the at least one olefin monomer is propylene and polypropylene segments of the amorphous functionalized olefin copolymer are atactic polypropylene segments.

14. The composition of claim 12 wherein the at least one olefin 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 from 20 to 80 mol % and the amount of second olefin monomer is from 80 to 20 mol %, the mol % based on the total molar amount of first and second olefin monomer.

15. The composition of claim 14 wherein the first olefin is propylene and the second olefin is 1-hexene.

16. The process according to 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 olefin monomers and the functionalized olefin monomers.

18. 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 amorphous functionalized olefin copolymer and the cross-linking enhancing agent.

19. The process according to claim 1, wherein at least one of the olefin monomers is propylene used in an amount of at least 60 wt. % with respect to the total weight of the olefin monomers and the functionalized olefin monomers.

Description

EXAMPLES

[0152] .sup.1H NMR Characterization

[0153] 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.

[0154] High Temperature Size Exclusion Chromatography (HT-SEC)

[0155] 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-min-1. The molecular weights and the corresponding PDIs were calculated from HT SEC analysis with respect to narrow polystyrene standards (PSS, Mainz, Germany).

[0156] Differential Scanning Calorimetry (DSC)

[0157] 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

[0158] 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 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

[0159] The copolymerization reaction of propylene and 10-undecenoic acid (entry 2, Table 2) was carried out in a stainless steel Bchi reactor (0.3 L). The reactor, equipped with a mechanical stirrer, was operated at 600 rpm. Pentamethyl heptane solvent (100 mL) and a TiBA-pacified 10-undecenoic acid comonomer solution (TIBA:10-undecenoic acid=1:1; 1.0 M, 0.1 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 [C.sub.5Me.sub.4SiMe.sub.2NtBu]TiCl.sub.2, precatalyst solution (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 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, 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 isopropanol/demineralized water (50 wt. %, 500 mL) 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. The crystallinity of all copolymers was 0% as determined by DSC.

Example 3

[0160] The same polymerization procedure as described in example 1 was applied to produce atactic poly(propylene-co-undecenol) (entry 9, Table 2) using [C.sub.5Me.sub.4CH.sub.2CH.sub.2NMe.sub.2]TiCl.sub.2 catalyst (6 mol) and a TiBA-pacified 10-undecen-1-ol comonomer solution (TIBA:10-undecen-1-ol=1:1; 1.0 M, 1.0 mmol). The resulting hydroxyl randomly functionalized atactic polypropylene (rubbery white solid) was analyzed by HT-SEC to determine the molecular weight and .sup.1H NMR to determine the percentage of functionalization. The crystallinity of this copolymer was 0% as determined by DSC.

Example 4

[0161] The copolymerization of 1-hexene and TIBA-pacified 10-undecenoic acid (entry 2, Table 3) 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 an oil bath at 40 C. Toluene solutions of TiBA-pacified 10-undecenoic acid comonomer (TiBA:10-undecenoic acid=1:1; 1.0 M, 1 mL, 1.0 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 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, 1-5 v %), heated and stirred until a clear solution was obtained. The resulting mixture was cooled down and precipitated in an excess iPrOH. The obtained product was washed with isopropanol/demineralized water (50 wt. %, 500 mL) and dried at 60 C. in vacuo overnight to leave a sticky transparent material (1.4 g). The carboxylic acid randomly functionalized polyhexene was analyzed by HT-SEC to determine the molecular weight and .sup.1H NMR to determine the percentage of functionalization. The crystallinity of these copolymers was 0% as determined by DSC.

Example 5

[0162] The copolymerization of 1-hexene and TiBA-pacified 10-undecen-1-ol (entry 6, Table 3) 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) and 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 an oil bath at 40 C. Toluene solutions of TiBA-pacified 10-undecen-1-ol (TiBA:10-undecen-1-ol=1:1; 0.86 M, 2.5 mmol) and rac-Me.sub.2Si(2-Me-4-Ph-Ind).sub.2ZrCl.sub.2 catalyst precursor (1.6 mol) were transferred into 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 acidified isopropanol (2.5 wt % HCl, 300 mL) and Irganox 1010 (1.0 M, 0.5 mmol. The product was filtered, washed with demineralized water (2400 mL) and dried at 60 C. in vacuo overnight (Yield: 1.4 g). The hydroxyl randomly functionalized polyhexene was analyzed by HT-SEC to determine the molecular weight and .sup.1H NMR to determine the percentage of functionalization. The crystallinity of these copolymers was 0% as determined by DSC.

Example 6

[0163] The copolymerization product of example 1 (5 g; Table 1, entry 3) was dispersed in toluene (150 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 analyzed by HT-SEC to determine the molecular weight and .sup.1H NMR to determine the glycerol content. The same procedure was repeated for samples obtained in experiments 2-5.

Example 7

[0164] The copolymerization reaction of propylene with 3-buten-1-ol was performed in the same way as described in example 1. 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, 500 mL) and Irganox 1010 (1.0 M, 0.5 mmol). The resulting mixture was stirred for 4 h, filtered and washed with demineralised water (4300 mL) and dried at 60 C. in vacuo overnight. The resulting product was analyzed by HT-SEC to determine the molecular weight and .sup.1H NMR to determine the glycerol content. The same procedure was repeated for samples obtained in experiments 3 and 5.

Example 8

[0165] The copolymerization product of example 1 (5 g; Table 1, entry 3) was dispersed in toluene (150 mL) and heated until a clear solution was obtained. Then a solution of branched polyethyleneimine (0.5 g; Mn=10,000 g/mol, Sigma-Aldrich) in ethanol (10 mL) was added and the mixture was stirred for 15 minutes. Then the solvent was distilled off and all remaining volatiles were removed in vacuo leaving the final product as a rubbery material. The product was analyzed by HT-SEC to determine the molecular weight. The same procedure was repeated for samples obtained in experiments 3 and 5.

Example 9

[0166] The copolymerization product of example 2 (1.5 g; Table 2, entry 6) was dispersed in toluene (100 mL) and heated until a clear solution was obtained. Then poly(ethylene glycol) dimethyl ether (0.1 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 analyzed by HT-SEC to determine the molecular weight and .sup.1H NMR to determine the poly(ethylene glycol) dimethyl ether content.

TABLE-US-00001 TABLE 1 Copolymerizations of propylene with 3-buten-1-ol..sup.[a] 3-buten-1-ol Yield .sup.b Com. 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 [a] Conditions: [C.sub.5Me.sub.4CH.sub.2CH.sub.2NMe.sub.2]TiC1.sub.2 = 14 mol, 9 bar propylene, 40 C., 30 min, solvent (1L), MAO (30 wt % solution in toluene) (Al:cat~1000), TiBA/C.sub.4OH = 1, additional amount of TiBA was added as scavenger. [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-undecen-1-ol or 10-undecenoic acid. C.sub.10COOH C.sub.11OH Activity Com. incorp. M.sub.w Entry (mmol) (mmol) (kg/mol.sub.cat .Math. h) .sup.[d] (mol %) (kg .Math. mol.sup.1) PDI 1.sup.[a] 0 0 1160 0 56.8 2.3 2.sup.[a] 0.10 0 450 0.09 74.3 2.4 3.sup.[a] 0.25 0 25 0.2 40.5 2.5 4.sup.[a] 1 0 4 0.4 63.1 2.7 5.sup.[b] 0 0 2533 0 56.5 2.5 6.sup.[b] 0.25 0 817 0.15 70.9 1.9 7.sup.[b] 1.0 0 183 0.50 68.0 2.4 8.sup.[b] 2.0 0 33 0.85 63.2 2.9 9.sup.[b] 0 1 2917 0.25 138.6 2.2 10.sup.[c] 0 0 1739 0 42.3 2.2 11.sup.[c] 5 0 1467 1.1 69.3 2.7 12.sup.[c] 10 0 1581 1.5 85.9 2.7 13.sup.[c] 15 0 2331 1.5 73.6 3.2 .sup.[a][C.sub.5Me.sub.4SiMe.sub.2NtBu]TiCl.sub.2 = 5 mol, propylene = 4 bar, 40 C., 30 min, PMH solvent = 100 mL, MAO (30 wt % solution in toluene) = 9 mmol, TiBA/C.sub.10COOH = 1. .sup.[b][C.sub.5Me.sub.4CH.sub.2CH.sub.2NMe.sub.2]TiCl.sub.2 = 6 mol, 2 bar propylene, 40 C., 30 min, PMH solvent = 100 mL, MAO (Al:cat = 1500) TiBA/C.sub.10COOH = 1, TiBA/C.sub.11OH = 1. .sup.[c][C.sub.5Me.sub.4CH.sub.2CH.sub.2NMe.sub.2]TiCl.sub.2 catalyst = 10.5 mol, propylene monomer = 5 bars, 50 C., PMH solvent = 100 mL, 30 min, MAO (30 wt % solution in toluene) = 9 mmol, TiBA/C.sub.10COOH = 2. .sup.[d] 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 1-hexene and TIBA-pacified 10-undecen-1-ol or 10-undecenoic acid..sup.[a] M.sub.n .sup.1H NMR .sup.[e] C.sub.10COOH .sup.[b] C.sub.11OH .sup.[c] TiBA:com. Yield (kg/mol) C.sub.10COOH/C.sub.11OH # (mmol) (mmol) Mol. ratio (g).sup.d (PDI) (mol %) 1 0 0 0 1.5 26.6 (2.2) 0 2 1 0 1 1.4 17.6 (2.6) 0.14 3 5 0 1 0 0 0 4 2.5 0 2 1.7 15.9 (2.2) 0.53 5 0 0.8 1 2.3 24.9 (2.3) 0.42 6 0 2.5 1 1.4 19.0 (2.2) 0.75 .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, 1-hexene = 0.04 mol. .sup.[b] C.sub.10COOH is 10-undecenoic acid (1.0M solution in toluene). .sup.[c] C.sub.11OH is 10-undecen-1-ol (0.86M solution in toluene). .sup.dThe 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 or 10-undecen-1-ol incorporation level as determined by .sup.1H NMR. All copolymers were as determined to be amorphous by DSC.