SUPERIOR C2C3C4 TERPOLYMER BASED BLOWN FILM AND C2C3C4 TERPOLYMER

Abstract

Blown film made from terpolymers, and terpolymers containing units derived from propylene, ethylene and 1-butene.

Claims

1. A blown film made from an ethylene-propylene-1-butene terpolymer including a) units derived from ethylene in an amount of 0.8 to 2.8 mol-% with respect the total terpolymer; and b) units derived from propylene in an amount of 91.6 to 95.8 mol-% with respect the total terpolymer; and c) units derived from 1-butene in an amount of 3.4 to 5.6 mol-% with respect the total terpolymer, d) wherein the units derived from ethylene, propylene and 1-butene add up to 100 mol-% and e) a total amount of units derived from ethylene and 1-butene of 4.5 to 8.0 mol-%, and f) a molar ratio of units derived from 1-butene versus units derived from ethylene of 1.5 to 5.0; and g) 2.1 regioinversions in an amount of 0.20 to 0.45 mol-% as determined by .sup.13C-NMR analysis (as described in the experimental part); and h) a melt flow rate MFR.sub.2 (230? C./2.16 kg) measured according to ISO 1133 in the range from 1.5 to 4.5 g/10 min, and i) a melting temperature Tm measured by differential scanning calorimetry (DSC) following the equation
Tm<[150?1.6*(defects)?0.14*(defects).sup.2]? C., wherein defects denote the sum of units derived from ethylene, units derived from 1-butene and 2.1 regioinversions, all values in mol-%, and wherein the blown film has a sealing initiation temperature (SIT) (as determined by a method described in the experimental part) below 117? C.

2. The blown film according to claim 1, wherein the ethylene-propylene-1-butene terpolymer has units derived from ethylene in an amount of 1.3 to 2.4 mol-% with respect the total terpolymer.

3. The blown film according to claim 1, wherein the ethylene-propylene- 1 -butene terpolymer has units derived from 1-butene in an amount of 4.6 to 5.4 mol-% with respect the total terpolymer.

4. The blown film according to claim 1, wherein the ethylene-propylene-1-butene terpolymer has a total amount of units derived from ethylene and 1-butene of 5.8 to 7.5 mol-%.

5. The blown film according to claim 1, wherein the molar ratio of units derived from 1-butene versus units derived from ethylene is within the range of 1.6 to 4.5.

6. The blown film according to claim 1, wherein the ethylene-propylene-1-butene terpolymer has 2.1 regioinversions in an amount of 0.20 to 0.40 mol-% as determined by .sup.13C-NMR analysis (as described in the experimental part).

7. The blown film according to claim 1, wherein the ethylene-propylene-1-butene terpolymer includes a) units derived from ethylene in an amount of 1.3 to 2.4 mol-% with respect the total terpolymer; and b) units derived from propylene in an amount of 92.2 to 94.1 mol-% with respect the total terpolymer; and c) units derived from 1-butene in an amount of 4.6 to 5.4 mol-% with respect the total terpolymer, d) wherein the units derived from ethylene, propylene and 1-butene add up to 100 mol-% and e) a total amount of units derived from ethylene and 1-butene of 5.8 to 7.5 mol-%, and f) a molar ratio of units derived from 1-butene versus units derived from ethylene of 1.6 to 4.5; and g) 2.1 regioinversions in an amount of 0.20 to 0.40 mol-% as determined by .sup.13C-NMR analysis (as described in the experimental part); and h) a melt flow rate MFR.sub.2 (230? C./2.16 kg) measured according to ISO 1133 in the range from 1.5 to 4.5 g/10 min, and i) a melting temperature Tm measured by differential scanning calorimetry (DSC) following the equation
Tm<[150?1.6*(defects)?0.14*(defects).sup.2]? C., wherein defects denote the sum of units derived from ethylene, units derived from 1-butene and 2.1 regioinversions, all values in mol-% wherein the film has a sealing initiation temperature (SIT) (as determined by a method described in the experimental part) below 112? C.

8. The blown film according to claim 1, wherein the ethylene-propylene-1-butene terpolymer has a flexural modulus of 600 to 900 MPa measured according to ISO 178.

9. The blown film according to claim 1, wherein the ethylene-propylene-1 -butene terpolymer is bimodal as to the butene content and/or is bimodal as to the molecular weight.

10. An ethylene-propylene-1-butene terpolymer including a) units derived from ethylene in an amount of 0.8 to 2.8 mol-% with respect the total terpolymer; and b) units derived from propylene in an amount of 91.6 to 95.8 mol-% with respect the total terpolymer; and c) units derived from 1-butene in an amount of 3.4 to 5.6 mol-% with respect the total terpolymer, d) wherein the units derived from ethylene, propylene and 1-butene add up to 100 mol-%, and e) a total amount of units derived from ethylene and 1-butene of 4.5 to 8.0 mol-%, and f) a molar ratio of the units derived from 1-butene versus units derived from ethylene within the range of 1.5 to 5.0; and g) 2.1 regioinversions in an amount of 0.20 to 0.45 mol-%, as determined by .sup.13C-NMR analysis (as described in the experimental part); and h) a melt flow rate MFR.sub.2 (230? C./2.16 kg) measured according to ISO 1133 in the range from 1.5 to 4.5 g/10 min, and i) a melting temperature Tm measured by differential scanning calorimetry (DSC) following the equation
Tm<[150?1.6*(defects)?0.14*(defects).sup.2]? C., wherein defects denote the sum of units derived from ethylene, units derived from 1-butene and 2.1 regioinversions, all values in mol.-%.

11. The ethylene-propylene-1-butene terpolymer according claim 10 having a) units derived from ethylene in an amount of 1.3 to 2.4 mol-% with respect the total terpolymer; and b) units derived from propylene in an amount of 92.2 to 94.1 mol-% with respect the total terpolymer; and c) units derived from 1-butene in an amount of 4.6 to 5.4 mol-% with respect the total terpolymer, d) wherein the units derived from ethylene, propylene and 1-butene add up to 100 mol-% and e) a total amount of units derived from ethylene and 1-butene of 5.8 to 7.5 mol-%, and f) a molar ratio of units derived from 1-butene versus units derived from ethylene of 1.6 to 4.5; and g) 2.1 regioinversions in an amount of 0.20 to 0.40 mol-% as determined by .sup.13C-NMR analysis (as described in the experimental part); and h) a melt flow rate MFR.sub.2 (230? C./2.16 kg) measured according to ISO 1133 in the range from 1.5 to 4.5 g/10 min, and i) a melting temperature Tm measured by differential scanning calorimetry (DSC) following the equation
Tm<[150?1.6*(defects)?0.14*(defects).sup.2]? C., wherein defects denote the sum of units derived from ethylene, units derived from 1-butene and 2.1 regioinversions, all values in mol-%

12. The composition including the ethylene-propylene-1-butene terpolymer according to claim 10 in an amount of at least 97 wt.-% with respect to the total composition.

13. The composition including the ethylene-propylene-1-butene terpolymer according to claim 10 in an amount of at least 97 wt.-% with respect to the total composition wherein the composition, consists of the ethylene-propylene-1-butene terpolymer according to claim 10 and additives.

14. The blown film according to claim 1, wherein the ethylene-propylene-1 -butene terpolymer has units derived from ethylene in an amount of 1.3 to 2.4 mol-% with respect the total terpolymer; and wherein the ethylene-propylene-1-butene terpolymer has units derived from 1-butene in an amount of 4.6 to 5.4 mol-% with respect the total terpolymer.

15. The blown film according to claim 1, wherein the ethylene-propylene- 1 -butene terpolymer has units derived from ethylene in an amount of 1.3 to 2.4 mol-% with respect the total terpolymer; and wherein the ethylene-propylene-1-butene terpolymer has units derived from 1-butene in an amount of 4.6 to 5.4 mol-% with respect the total terpolymer and wherein the ethylene-propylene-1-butene terpolymer has a total amount of units derived from ethylene and 1-butene of 5.8 to 7.5 mol-%.

Description

B. EXAMPLES

Preparation of the First Catalyst System (#1)

[0277] The metallocene (MC1) (rac-anti-dimethylsilandiyl(2-methyl-4-phenyl-5-methoxy-6-tert-butyl-indenyl)(2-methyl-4-(4-tert-butylphenyl)indenyl)zirconium dichloride) has been synthesized as described in WO 2013/007650.

Preparation of MAO-Silica Support

[0278] A steel reactor equipped with a mechanical stirrer and a filter net was flushed with nitrogen and the reactor temperature was set to 20? C. Next silica grade DM-L-303 from AGC Si-Tech Co, pre-calcined at 600? C. (7.4 kg) was added from a feeding drum followed by careful pressuring and depressurising with nitrogen using manual valves. Then toluene (32 kg) was added. The mixture was stirred for 15 min. Next 30 wt % solution of MAO in toluene (17.5 kg) from Lanxess was added via feed line on the top of the reactor within 70 min. The reaction mixture was then heated up to 90? C. and stirred at 90? C. for additional two hours. The slurry was allowed to settle and the mother liquor was filtered off. The MAO treated support was washed twice with toluene (32 kg) at 90? C., following by settling and filtration. The reactor was cooled off to 60? C. and the solid was washed with heptane (32.2 kg). Finally MAO treated SiO2 was dried at 60? under nitrogen flow for 2 hours and then for 5 hours under vacuum (-0.5 barg) with stirring. MAO treated support was collected as a free-flowing white powder found to contain 12.6% Al by weight.

Catalyst System Preparation

[0279] 30 wt % MAO in toluene (2.2 kg) was added into a steel nitrogen blanked reactor via a burette at 20? C. Toluene (7 kg) was then added under stirring. Metallocene MC1 (286 g) was added from a metal cylinder followed by flushing with 1 kg toluene. The mixture was stirred for 60 minutes at 20? C. Trityl tetrakis(pentafluorophenyl) borate (336 g) was then added from a metal cylinder followed by a flush with 1 kg of toluene. The mixture was stirred for 1 h at room temperature. The resulting solution was added to a stirred cake of MAO-silica support prepared as described above over 1 hour. The cake was allowed to stay for 12 hours, followed by drying under N2 flow at 60? C. for 2 h and additionally for 5 h under vacuum (?0.5 barg) under stirring. Dried catalyst was sampled in the form of pink free flowing powder containing 13.9 wt % Al and 0.26wt % Zr.

Preparation of the Second Catalyst System (#2)

[0280] The catalyst used was Anti-dimethylsilanediyl[2-methyl-4,8-di(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl] zirconium dichloride.

[0281] The metallocene complex has been produced as described in WO 2019/179959 for MC-2.

##STR00020##

Preparation of MAO-Silica Support

[0282] A steel reactor equipped with a mechanical stirrer and a filter net was flushed with nitrogen and the reactor temperature was set to 20? C. Next silica grade DM-L-303 from AGC Si-Tech Co, pre-calcined at 600? C. (5.0 kg) was added from a feeding drum followed by careful pressurising and depressurising with nitrogen using manual valves. Then toluene (22 kg) was added. The mixture was stirred for 15 min. Next 30 wt.-% solution of MAO in toluene (9.0 kg) from Lanxess was added via feed line on the top of the reactor within 70 min. The reaction mixture was then heated up to 90? C. and stirred at 90? C. for additional two hours. The slurry was allowed to settle and the mother liquor was filtered off. The catalyst was washed twice with toluene (22 kg) at 90? C., following by settling and filtration. The reactor was cooled off to 60? C. and the solid was washed with heptane (22.2 kg). Finally MAO treated SiO2 was dried at 60? under nitrogen flow for 2 hours and then for 5 hours under vacuum (?0.5 barg) with stirring. MAO treated support was collected as a free-flowing white powder found to contain 12.2% Al by weight.

Catalyst Preparation

[0283] 30 wt.-% MAO in toluene (0.7 kg) was added into a steel nitrogen blanked reactor via a burette at 20? C. Toluene (5.4 kg) was then added under stirring. The catalyst as cited above (93 g) was added from a metal cylinder followed by flushing with 1 kg toluene. The mixture was stirred for 60 minutes at 20? C. Trityl tetrakis(pentafluorophenyl) borate (91 g) was then added from a metal cylinder followed by a flush with 1 kg of toluene. The mixture was stirred for 1 h at room temperature. The resulting solution was added to a stirred cake of MAO-silica support prepared as described above over 1 hour. The cake was allowed to stay for 12 hours, followed by drying under N2 flow at 60? C. for 2 h and additionally for 5 h under vacuum (?0.5 barg) under stirring. Dried catalyst was sampled in the form of pink free flowing powder containing 13.9% Al and 0.11% Zr.

Preparation of the Third Catalyst System (#3)

[0284] First, 0.1 mol of MgCl.sub.2?3 EtOH was suspended under inert conditions in 250 ml of decane in a reactor at atmospheric pressure. The solution was cooled to the temperature of ?15? C. and 300 ml of cold TiCl.sub.4 was added while maintaining the temperature at said level. Then, the temperature of the slurry was increased slowly to 20? C. At this temperature, 0.02 mol of dioctylphthalate (DOP) was added to the slurry. After the addition of the phthalate, the temperature was raised to 135? C. during 90 minutes and the slurry was allowed to stand for 60 minutes. Then, another 300 ml of TiCl.sub.4 was added and the temperature was kept at 135? C. for 120 minutes. After this, the catalyst was filtered from the liquid and washed six times with 300 ml heptane at 80? C. Then, the solid catalyst component was filtered and dried. Catalyst and its preparation concept is described in general e.g. in patent publications EP491566, EP591224 and EP586390. The catalyst was used with triethyl-aluminium (TEAL) as co-catalyst and dicyclo pentyl dimethoxy silane (D-donor) as donor.

Polymerization and Pelletization

[0285] Terpolymers IE1-IE4 were produced in a Borstar pilot plant comprising a prepolymerization reactor, one loop reactor and a gas phase reactor coupled in series. The polymerization conditions as well as the results of polymer characterization are indicated in Table 1. IE1-IE3 were made with catalyst system number one (#1) as described above, and 1E4 was made with the catalyst system number two (#2).

[0286] All examples were compounded in a co-rotating twin-screw extruder Coperion ZSK 57 at 220? C. with with 0.1 wt.-% antiblocking agent (synthetic silica; CAS-no. 7631-86-9); 0.05 wt.-% antioxidant (Irgafos 168FF, CAS-no. 31570-04-4, BASF AG); 0.1 wt.-% of a sterical hindered phenol (Irganox 1010FF, CAS-no. 6683-19-8, BASF AG); 0.04 wt.-% of DHT-4A (CAS-no. 11097-59-9, Kisuma Chemicals).

TABLE-US-00003 TABLE 1 Polymerization process conditions for IEs and CEs. IE1 IE2 IE3 IE4 CE1 CE2 * Prepoly reactor Temp. (? C.) 20 20 20 20 20 28 Catalyst #1 #1 #1 #2 #1 #3 Teal/Ti (mol/mol) 0 0 0 0 0 120 Teal/donor (wt.-%/wt.-%) 0 0 0 0 0 3 Press. (kPa) 4948 5258 4973 4956 4911 3500 Loop reactor Temp. (? C.) 70 70 70 70 75 65 Press. (kPa) 4799 5138 4864 4839 4828 3500 H2/C3 ratio (mol/kmol) 0.1 0.1 0.1 0.05 0.1 1.5 C4/C3 ratio (mol/kmol) 29.8 30.3 25.4 40.0 30 210 C2/C3 ratio (mol/kmol) 10.6 17.8 16.1 17.1 1.2 21.3 C4 content (loop) (wt.-%) 5.5 5.5 5.2 5.3 5.5 9.0 C2 content (loop) (wt.-%) 0.6 0.8 0.7 1.0 n.d. 1.1 MFR loop (g/10 min) 2 2 2 2.2 2 1.5 Split loop (wt.-%) 43 47 41 40 54 100 GPR1 Temp. (? C.) 75 75 75 80 75 Press. (kPa) 2480 2480 2441 2498 2480 H2/C3 ratio (mol/kmol) 1.2 1.5 1.5 2.1 1.1 C4/C3 ratio (mol/kmol) 51 59 61 47 52 C2/C3 ratio (mol/kmol) 70.3 120.7 120.8 107 33.6 Split GPR 1 (wt.-%) 57 57 59 60 46 Comp Pellets IE1 IE2 IE3 IE4 CE1 CE2 5*/6* MFR2 (g/10 min) 2.1 2.6 2.2 3.4 2 1.5 5.1 C2 (mol-%) 1.2 2.2 2.2 1.3 0.4 1.5 0.5 C4 (mol-%) 4.5 4.8 5.0 4.7 4.5 6.9 6.3 2.1 (mol-%) 0.37 0.32 0.26 0.35 0.51 0 0.32 C2 + C4 (mol-%) 5.7 7.0 7.2 6.0 4.9 8.4 6.8 C4/C2 (mol/mol) 3.8 2.2 2.3 3.6 11.3 4.6 11.6 Tm (? C.) 133 129 129 131 139 131 132 Inequation cl. 135 131 130 134 137 127 131 1 right side Inequation met? yes yes yes yes no no no XCS (wt.-%) 1.1 15.2 17.1 16.9 0.7 7 n.d. Tc (? C.) 98 92.5 91 95 102 91 n.d. Flexural mod. (MPa) 866 693 672 789 985 nd n.d. C6 (FDA) 0.47 0.56 0.57 0.52 0.46 3.0 nd *from U.S. Pat. No. 6,388,040

[0287] It can be seen that carefully tailoring the amount of units derived from ethylene, the total amount of units derived from ethylene and butene, as well as the ratio of units from butene versus ethylene together with control of 2.1 regioinversions results in relatively low melting temperature for a given amount of total defects.

[0288] Simultaneously the hexane solubility is also very low. CE2 was excluded from the further evaluation due to inacceptable high hexane solubility (FDA).

[0289] The characteristics of the blown films made from the terpolymers are provided below in Table 2.

TABLE-US-00004 TABLE 2 Characteristics of the polymer compositions and the results of the blown film IE1 IE2 IE3 IE4 CE1 Film type blown blown blown blown blown SIT (? C.) 116 111 110 110 122 TM(MD) 993 828 807 696 1115 (MPa) TM(TD) 795 810 807 671 1005 (MPa) DDI (g) 44 50 54 60 31 Haze (%) 5.69 4.36 3.83 5.74 6.18 Hot tack 3.47 2.98 2.86 n.m. 3.82 force (N) OMA, TD 7679 9495 11378 7275 5593 OMA, MD 6148 9289 11378 7014 5041

[0290] It can be gathered that the inventive blown films had relatively low sealing initiation temperature, good impact-tensile-haze balance (OMA) as well as reasonable hot tack force. Compared to CE1 (0.4 mol-% C2; ratio C4/C2 of 11.3), the inventive examples had significantly better DDI, better haze, and significantly better SIT.