BULKPOLYMERISATION PROCESS FOR THE PREPARATION OF POLYDIENES

Abstract

The present invention is directed at a bulkpolymerisation process for the preparation of a polymer (P) comprising the steps of: (i) providing at least one diene monomer (DM) and optionally at least one comonomer (COM); (ii) contacting the at least one diene monomer (DM) and optionally the at least one comonomer (COM) with a catalyst system (CS) forming a reaction mixture (RM); (iii) polymerizing the reaction mixture (RM) comprising the at least one diene monomer (DM) and optionally the at least one comonomer (COM) in at least one reactor vessel (RV); (iv) isolating the polymer (P) obtained from the at least one reactor vessel (RV); wherein the reaction mixture (RM) comprises solvent, diluent and/or dispersant in an amount of 10 wt.-%, based on the weight of the reaction mixture (RM); and wherein the conversion rate of the diene monomer (DM) and optionally the comonomer (COM) is 80%.

Claims

1. Bulkpolymerisation process for the preparation of a polymer (P) comprising the steps of: (i) providing at least one diene monomer (DM) and optionally at least one comonomer (COM); (ii) contacting the at least one diene monomer (DM) and optionally the at least one comonomer (COM) with a catalyst system (CS) forming a reaction mixture (RM); (iii) polymerizing the reaction mixture (RM) comprising the at least one diene monomer (DM) and optionally the at least one comonomer (COM) in at least one reactor vessel (RV); (iv) isolating the polymer (P) obtained from the at least one reactor vessel (RV); wherein the reaction mixture (RM) comprises solvent, diluent and/or dispersant in an amount of 10 wt.-%, based on the weight of the reaction mixture (RM); wherein the conversion rate of the diene monomer (DM) and optionally the comonomer (COM) is 80%; and wherein the reaction mixture (RM) comprises the at least one diene monomer (DM) in an amount of 50.0 wt.-%.

2. Bulkpolymerisation process according to claim 1, wherein the diene monomer (DM) is a conjugated diene selected from 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, 1,3-heptadiene; 2,4-heptadiene, 2-methyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, and mixtures thereof.

3. Bulkpolymerisation process according to claim 1 or 2, wherein the comonomer (COM) is selected from ethylene, propylene, isobutene, styrene, -methyl styrene, 4-methyl styrene, acrylate, methacrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, maleic acid anhydride, acrylonitrile, and mixtures thereof.

4. Bulkpolymerisation process according to any one of preceding claims, wherein the catalyst system (CS) comprises a coordination catalyst component (CC) and optionally a co-catalyst component (Co), and wherein the coordination catalyst component (CC) is based on a transition metal of the groups 4 to 10 of the periodic table and/or rare earth metals, preferably the coordination catalyst component (CC) is based on titanium, chromium, vanadium, cobalt, nickel, zirconium, neodymium, gadolinium, or mixtures thereof.

5. Bulkpolymerisation process according to any one of preceding claims, wherein the catalyst system (CS) comprises an anionic initiator (AI) and optionally activating and/or regulating compounds (ARC), and wherein the anionic initiator (AI) is a mono- or polyfunctional organic metal compound, preferably a mono- or polyfunctional organic alkali metal compound, more preferably a mono-lithium compound represented by the formula RLi, wherein R is selected from alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkoxy, heteroalkyl, heteroalkenyl, heteroalkynyl, arylalkyl, arylalkenyl, aryl, aryloxy, and mixtures thereof.

6. Bulkpolymerisation process according to any one of preceding claims, wherein the preparation of a polymer is conducted in absence of the at least one comonomer (COM), and wherein the reaction mixture (RM) comprises the at least one diene monomer (DM) in an amount of 59.0 wt.-%, preferably 70.0 wt.-%, more preferably 90.0 wt.-%, even more preferably 95.0 wt.-%, yet even more preferably 98.0 wt.-%, based on the weight of the reaction mixture (RM).

7. Bulkpolymerisation process according to any one of preceding claims, wherein the preparation of a polymer is conducted in presence of the at least one comonomer (COM), and wherein the reaction mixture (RM) comprises the at least one diene monomer (DM) in an amount of 59.0 wt.-%, preferably 60.0 wt.%, more preferably 70.0 wt.-%, even more preferably 75.0 wt.-%, based on the weight of the reaction mixture (RM), and wherein the reaction mixture (RM) comprises the at least one comonomer (COM) in an amount of 50.0 wt.-%, preferably 40.0 wt.%, more preferably 30.0 wt.-%, even more preferably 25.0 wt.-%, based on the weight of the reaction mixture (RM).

8. Bulkpolymerisation process according to any one of the preceding claims, wherein the polymer (P) isolated from the reactor vessel (RV) has a weight average molecular weight (Mw) in the range of 1.000 to 1.500.000, preferably in the range of 100.000 to 1.500.000, more preferably in the range of 300.000 to 900.000.

9. Bulkpolymerisation process according to any one of the preceding claims, wherein the polymer (P) isolated from the reactor vessel (RV) has a ratio of weight average molecular weight to numerical average molecular weight (M.sub.w/M.sub.n) in the range of 1.0 to 30.0, preferably in the range of 1.0 to 10.0, more preferably in the range of 1.0 to 5.0, even more preferably in the range of 1.0 to 4.0.

10. Bulkpolymerisation process according to any one of the preceding claims, wherein the polymer (P) isolated from the reactor vessel (RV) has a molar ratio of cis-1,4 units of 90.0%, preferably 95.0%, more preferably 98.0%, even more preferably 99.0%, like in the range of 90.0 to 100.0%, preferably in the range of 95.0 to 100.0%, more preferably in the range of 98.0 to 100.0%, even more preferably in the range of 99.0 to 100.0%.

11. Bulkpolymerisation process according to any one of the preceding claims, wherein the polymer (P) isolated from the reactor vessel (RV) has a molar ratio of cis-1,4 units of 50.0%, preferably 30.0%, more preferably 15.0%, even more preferably 10.0%, yet even more preferably 5.0%, like in the range of 0.0 to 50.0%, preferably in the range of 0.0 to 30.0%, more preferably in the range of 0.0 to 15.0%, even more preferably in the range of 0.0 to 10.0%, yet even more preferably in the range of 0.0 to 5.0%.

12. Bulkpolymerisation process according to any one of the preceding claims, wherein the polymer (P) isolated from the reactor vessel (RV) has a molar ratio of cis-1,4 units in the range of 10.0 to 50.0%, preferably in the range of 20.0 to 40.0%.

13. Bulkpolymerisation process according to any one of the preceding claims, wherein the reactor vessel (RV), is equipped with a dynamic mixing device (MD) comprising at least two mixing units (MU), wherein the at least two mixing units (MU) are movable relative to each other to conduct a shearing motion.

14. Bulkpolymerisation process according to any one of the preceding claims, wherein the reactor vessel (RV), is equipped with a dynamic mixing device (MD) comprising at least two mixing units (MU) movable relative to each other to conduct a shearing motion, wherein the mixing device (MD) comprises at least one first mixing unit (1MU) and at least one second mixing unit (2MU), and wherein and the shearing motion occurs between the at least one first mixing unit (1MU) and the at least one second mixing unit (2MU).

15. Bulkpolymerisation process according to any one of the preceding claims, wherein the reactor vessel (RV) includes at least one condenser (CON) to control the temperature in the reactor vessel (RV) during the bulkpolymerisation process, and wherein the diene monomer (DM) and/or optionally the comonomer (COM) is evaporated during the bulkpolymerisation process and liquefied in the condenser (CON)

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0165] FIG. 1 shows a reactor vessel (1) with a mixing device comprising a first mixing unit (22), which is provided with a first mixing element (222), and a second mixing unit (33), which is provided with a second mixing element, wherein the first mixing unit (22) is mounted on a first drive shaft (4) and the second mixing unit (33) is mounted on a second drive shaft (5).

[0166] FIG. 2 shows a sectional view (A-A) of the reactor vessel (1) with a first mixing unit (22), which is provided with the first mixing element (222), mounted on the first drive shaft (4).

[0167] FIG. 3 shows a sectional view (C-C) of the reactor vessel (1) with the second mixing unit (33), which is provided with the second mixing element (333), mounted on the second drive shaft (5).

PREFERRED EMBODIMENTS

[0168] In the following paragraphs preferred embodiments of the bulkpolymerisation process are disclosed:

[0169] Paragraph 1: Bulkpolymerisation process for the preparation of a polymer (P) comprising the steps of: [0170] (i) providing at least one diene monomer (DM) and optionally at least one comonomer (COM); [0171] (ii) contacting the at least one diene monomer (DM) and optionally the at least one comonomer (COM) with a catalyst system (CS) forming a reaction mixture (RM); [0172] (iii) polymerizing the reaction mixture (RM) comprising the at least one diene monomer (DM) and optionally the at least one comonomer (COM) in at least one reactor vessel (RV); [0173] (iv) isolating the polymer (P) obtained from the at least one reactor vessel (RV); [0174] wherein the reaction mixture (RM) comprises solvent, diluent and/or dispersant in an amount of 10 wt.-%, based on the weight of the reaction mixture (RM); and [0175] wherein the conversion rate of the diene monomer (DM) and optionally the comonomer (COM) is 80%.

[0176] Paragraph 2: Bulkpolymerisation process according to paragraph 1, wherein the diene monomer (DM) is a conjugated diene selected from 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, 1,3-heptadiene; 2,4-heptadiene, 2-methyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, and mixtures thereof

[0177] Paragraph 3: Bulkpolymerisation process according to paragraphs 1 or 2, wherein the comonomer (COM) is selected from ethylene, propylene, isobutene, styrene, -methyl styrene, 4-methyl styrene, acrylate, methacrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, maleic acid anhydride, acrylonitrile, and mixtures thereof.

[0178] Paragraph 4: Bulkpolymerisation process according to any one of preceding paragraphs, wherein the catalyst system (CS) comprises a coordination catalyst component (CC) and optionally a co-catalyst component (Co), and wherein the coordination catalyst component (CC) is based on a transition metal of the groups 4 to 10 of the periodic table and/or rare earth metals, preferably the coordination catalyst component (CC) is based on titanium, chromium, vanadium, cobalt, nickel, zirconium, neodymium, gadolinium, or mixtures thereof.

[0179] Paragraph 5: Bulkpolymerisation process according to any one of preceding paragraphs, wherein the catalyst system (CS) comprises an anionic initiator (AI) and optionally activating and/or regulating compounds (ARC), and wherein the anionic initiator (AI) is a mono- or polyfunctional organic metal compound, preferably a mono- or polyfunctional organic alkali metal compound, more preferably a mono-lithium compound represented by the formula RLi, wherein R is selected from alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkoxy, heteroalkyl, heteroalkenyl, heteroalkynyl, arylalkyl, arylalkenyl, aryl, aryloxy, and mixtures thereof.

[0180] Paragraph 6: Bulkpolymerisation process according to any one of preceding paragraphs, wherein the preparation of a polymer is conducted in absence of the at least one comonomer (COM), and wherein the reaction mixture (RM) comprises the at least one diene monomer (DM) in an amount of 50.0 wt.-%, preferably 70.0 wt.-%, more preferably 90.0 wt.-%, even more preferably 95.0 wt.-%, yet even more preferably 98.0 wt.-%, based on the weight of the reaction mixture (RM).

[0181] Paragraph 7: Bulkpolymerisation process according to any one of preceding paragraphs, wherein the preparation of a polymer is conducted in presence of the at least one comonomer (COM), and wherein the reaction mixture (RM) comprises the at least one diene monomer (DM) in an amount of 50.0 wt.-%, preferably 60.0 wt.%, more preferably 70.0 wt.-%, even more preferably 75.0 wt.-%, based on the weight of the reaction mixture (RM), and wherein the reaction mixture (RM) comprises the at least one comonomer (COM) in an amount of 50.0 wt.-%, preferably 40.0 wt.%, more preferably 30.0 wt.-%, even more preferably 25.0 wt.-%, based on the weight of the reaction mixture (RM).

[0182] Paragraph 8: Bulkpolymerisation process according to any one of the preceding paragraphs, wherein the polymer (P) isolated from the reactor vessel (RV) has a weight average molecular weight (Mw) in the range of 1.000 to 1.500.000, preferably in the range of 100.000 to 1.500.000, more preferably in the range of 300.000 to 900.000.

[0183] Paragraph 9: Bulkpolymerisation process according to any one of the preceding paragraphs, wherein the polymer (P) isolated from the reactor vessel (RV) has a ratio of weight average molecular weight to numerical average molecular weight (M.sub.w/M.sub.n) in the range of 1.0 to 30.0, preferably in the range of 1.0 to 10.0, more preferably in the range of 1.0 to 5.0, even more preferably in the range of 1.0 to 4.0.

[0184] Paragraph 10: Bulkpolymerisation process according to any one of the preceding paragraphs, wherein the polymer (P) isolated from the reactor vessel (RV) has a molar ratio of cis-1,4 units of 90.0%, preferably 95.0%, more preferably 98.0%, even more preferably 99.0%, like in the range of 90.0 to 100.0%, preferably in the range of 95.0 to 100.0%, more preferably in the range of 98.0 to 100.0%, even more preferably in the range of 99.0 to 100.0%.

[0185] Paragraph 11: Bulkpolymerisation process according to any one of the preceding paragraphs, wherein the polymer (P) isolated from the reactor vessel (RV) has a molar ratio of cis-1,4 units of 50.0%, preferably 30.0%, more preferably 15.0%, even more preferably 10.0%, yet even more preferably 5.0%, like in the range of 0.0 to 50.0%, preferably in the range of 0.0 to 30.0%, more preferably in the range of 0.0 to 15.0%, even more preferably in the range of 0.0 to 10.0%, yet even more preferably in the range of 0.0 to 5.0%.

[0186] Paragraph 12: Bulkpolymerisation process according to any one of the preceding paragraphs, wherein the polymer (P) isolated from the reactor vessel (RV) has a molar ratio of cis-1,4 units in the range of 10.0 to 50.0%, preferably in the range of 20.0 to 40.0%.

[0187] Paragraph 13: Bulkpolymerisation process according to any one of the preceding paragraphs, wherein the reactor vessel (RV), is equipped with a dynamic kneading device (KD) comprising at least two kneading units (KU), wherein the at least two kneading units (KU) are movable relative to each other to conduct a shearing motion.

[0188] Paragraph 14: Bulkpolymerisation process according to any one of the preceding paragraphs, wherein the reactor vessel (RV), is equipped with a dynamic kneading device (KD) comprising at least two kneading units (KU) movable relative to each other to conduct a shearing motion, wherein the kneading device (KD) comprises at least one first kneading unit (1KU) and at least one second kneading unit (2KU), and wherein and the shearing motion occurs between the at least one first kneading unit (1KU) and the at least one second kneading unit (2KU).

[0189] Paragraph 15: Bulkpolymerisation process according to any one of the preceding paragraphs, wherein the reactor vessel (RV) includes at least one condenser (CON) to control the temperature in the reactor vessel (RV) during the bulkpolymerisation process, and wherein the diene monomer (DM) and/or optionally the comonomer (COM) is evaporated during the bulkpolymerisation process and liquefied in the condenser (CON).

[0190] The present invention will now be described in further detail by the examples provided below.

EXAMPLES

A. Measuring Methods

[0191] The following definitions of terms and determination methods apply for the above general description of the invention as well as to the below examples unless otherwise defined.

[0192] Mooney Viscosity (ML1+4, 100 C.) [MU] is determined in accordance with ASTM D 1646 (2004) with a Monsanto Mooney viscometer (MV 2000) with a one-minute warm-up time, and a four-minute running time.

[0193] The Conversion Rate [%] is determined according to Formula (I):

[00002]$\mathrm{CR}=\frac{1}{1+w_m}$ [0194] wherein [0195] CR is the conversion rate; and [0196] w.sub.m is the weight of residual monomer in wt.-% present in the polymer obtained from the reactor vessel, based on the total weight of the polymer.

[0197] The Weight Average Molecular Weight (Mw) [g/mol] and the Number Average Molecular Weight (Mn) [g/mol] are determined according to by Gel Permeation Chromatography (GPC) according to ISO 16014-4:2003 and ASTM D 6474-99. A PolymerChar GPC instrument, equipped with refraction index (RI) detector was used with 2 columns from PSS and THF as solvent at 30 C. and at a constant flow rate of 1 mL/min 200 L of sample solution were injected per analysis. The column set was calibrated using calibration with at least 9 narrow MWD polybutadiene standards in the range of 0.8 kg/mol to 1049 kg/mol. All samples were prepared by dissolving 2.9-3.1 mg of polymer in 3 mL (at ambient Temperature) for 24 hours. The Glass Transition Temperature (Tg) [ C.] is determined by differential scanning calorimetry. The measurements are done between 120 C. and +100 C. with a heating rate of 2.0 K/min and 4.0 K/min.

[0198] The 1,4-Cis Molar Ratio [%] the 1,4-Trans Molar Ratio [%] and the 1,2-Vinyl Molar Ratio [%] are determined by proton nuclear magnetic resonance spectroscopy for the ratio of 1,2-vinyl to 1,4-tans and 1,4-cis, in total and carbon nuclear magnetic resonance spectroscopy for the ratio of 1,4-trans to 1,4-cis content, in deuterated chloroform (CDCl.sub.3) as solvent.

[0199] The Styrene Weight Ratio [%] Is determined by using proton nuclear magnetic resonance spectroscopy the ratio to tetramethylsilane (TMS) with a fixed concentration (0.03 wt.-%) in the solvent, deuterated chloroform (CDCl.sub.3).

B. Examples

Example 1

[0200] The reactor vessel (RV) equipped with a thermostat (Proline P5 of Lauda GmbH & Co. KG, Germany), a rotary vane pump (322002 P4Z of Ilmvac GmbH, Germany), a temperature control jacket (TCJ) and a condenser (CON) is heated to a temperature of 90 C. The reactor is evacuated to 0.01 mbar and flushed with argon (grade 5.0) up to a pressure of 1.2 bar. This procedure is repeated 30 times. The reactor is evacuated to 0.01 bar and cooled to a temperature of 10 C. 127.5 g 1,3-butadiene and 65.94 mg di-isobutylaluminiumhydride (19% in hexane, 1.0 mol/L) are added and the reactor vessel (RV) is heated to a temperature of 60 C. 32.97 mg di-isobutylaluminiumhydride (19% in hexane, 1.0 mol/L), 145 mg catalyst system (CS) NdV3/Al.sub.3Et.sub.3Cl.sub.3/Al(i-bu).sub.2H (COMCAT Nd-FC/20, Comar Chemicals (Pty) Ltd., SA) and 2,36 g n-hexane are added. The polymerisation is conducted for 60 min and the temperature is adjusted with the temperature control jacket (TCJ) and the condenser (CON) to maintain a temperature of 60 C.

[0201] Table 1 provides the conversion rate and the properties of the polymer obtained according to Example 1.

TABLE-US-00001 TABLE 1 Conversion rate and properties of the polymer obtained Time CR Mn Mw Mooney 1,4-Cis 1,4- 1,2- T.sub.g [min] [%] [g/mol] [g/mol] PDI [MU] [%] Trans Vinyl [ C.] 1 6.95 214000 577000 2.69 2 20.65 224000 596000 2.66 3 32.83 225000 615000 2.73 4 44.97 232000 625000 2.70 5 63.74 210000 605000 2.88 6 72.04 216000 591000 2.74 60 99.60 233000 517000 2.22 39.5 99.12 0.15 0.73 109.3 CR is the conversion rate in [%] Mn is the number average molecular weight in [g/mol] Mw is the weight average molecular weight in [g/mol] PDI is the polydispersity (Mw/Mn) Mooney is the Mooney Viscosity (ML.sub.1+4, 100 C.) in [MU] 1,4-Cis is the 1,4-cis molar ratio in [%] 1,4-Trans is the 1,4-trans molar ratio in [%] 1,2-Vinyl is the 1,2-vinyl molar ratio in [%] T.sub.g is the glass transition temperature in [ C.]

Example 2

[0202] The reactor vessel (RV) equipped with a thermostat (Proline P5 of Lauda GmbH & Co. KG, Germany), a rotary vane pump (322002 P4Z of Ilmvac GmbH, Germany), a temperature control jacket (TCJ) and a condenser (CON) is heated to a temperature of 90 C. The reactor is evacuated to 0.01 mbar and flushed with argon (grade 5.0) up to a pressure of 1.2 bar. This procedure is repeated 30 times. The reactor is evacuated to 0.01 bar and cooled to a temperature of 10 C. 912.5 g 1,3-butadiene and 462.22 mg di-isobutylaluminiumhydride (19% in hexane, 1.0 mol/L) are added and the reactor vessel (RV) is heated to a temperature of 60 C. 1074 mg catalyst system (CS) NdV.sub.3/Al.sub.2Et.sub.3Cl.sub.3/Al(i-bu).sub.2H (COMCAT Nd-FC/20, Comar Chemicals (Pty) Ltd., SA) and 16.4 g n-hexane are added. The polymerisation is conducted for 60 min and the temperature is adjusted with the temperature control jacket (TCJ) and the condenser (CON) to maintain a temperature of 60 C.

[0203] Table 2 provides the conversion rate and the properties of the polymer obtained according to Example 2.

TABLE-US-00002 TABLE 2 Conversion rate and properties of the polymer obtained Time CR Mn Mw Mooney 1,4-cis T.sub.g [min] [%] [g/mol] [g/mol] PDI [MU] [%] 1,4-trans 1,2-vinyl [ C.] 0.5 7.12 333000 682000 2.05 1 20.82 360000 726000 2.02 2 41.33 385000 801000 2.08 60 99.99 371000 822000 2.22 71.9 99.32 0.07 0.61 109.4 CR is the conversion rate in [%] Mn is the number average molecular weight in [g/mol] Mw is the weight average molecular weight in [g/mol] PDI is the polydispersity (Mw/Mn) Mooney is the Mooney Viscosity (ML.sub.1+4, 100 C.) in [MU] 1,4-Cis is the 1,4-cis molar ratio in [%] 1,4-Trans is the 1,4-trans molar ratio in [%] 1,2-Vinyl is the 1,2-vinyl molar ratio in [%] T.sub.g is the glass transition temperature in [ C.]

Example 3

[0204] The reactor vessel (RV) equipped with a thermostat (Proline P5 of Lauda GmbH & Co. KG, Germany), a rotary vane pump (322002 P4Z of Ilmvac GmbH, Germany), a temperature control jacket (TCJ) and a condenser (CON) is heated to a temperature of 90 C. The reactor is evacuated to 0.01 mbar and flushed with argon (grade 5.0) up to a pressure of 1.2 bar. This procedure is repeated 30 times. The reactor is evacuated to 0.01 bar and cooled to a temperature of 10 C. 650.7 g 1,3-butadiene and 1.77 g diisobutylaluminiumhydride (19% in hexane, 1.0 mol/L) are added and the reactor vessel (RV) is heated to a temperature of 60 C. 489 mg catalyst system (CS) NdV.sub.3/Al.sub.2Et.sub.3Cl.sub.3/Al(i-bu).sub.2H (COMCAT Nd-FC/20, Comar Chemicals (Pty) Ltd., SA) and 7.47 g (86.62 mmol) n-hexane are added. The polymerisation is conducted for 60 min and the temperature is adjusted with the temperature control jacket (TCJ) and the condenser (CON) to maintain a temperature of 60 C.

[0205] Table 3 provides the conversion rate and the properties of the polymer obtained according to Example 3.

TABLE-US-00003 TABLE 3 Conversion rate and properties of the polymer obtained Time CR Mn Mw Mooney 1,4-cis T.sub.g [min] [%] [g/mol] [g/mol] PDI [MU] [%] 1,4-trans 1,2-vinyl [ C.] 60 99.8 105000 405000 3.87 34.68 99.21 0.00 0.79 108.2 CR is the conversion rate in [%] Mn is the number average molecular weight in [g/mol] Mw is the weight average molecular weight in [g/mol] PDI is the polydispersity (Mw/Mn) Mooney is the Mooney Viscosity (ML.sub.1+4, 100 C.) in [MU] 1,4-Cis is the 1,4-cis molar ratio in [%] 1,4-Trans is the 1,4-trans molar ratio in [%] 1,2-Vinyl is the 1,2-vinyl molar ratio in [%] T.sub.g is the glass transition temperature in [ C.]

Example 4

[0206] The reactor vessel (RV) equipped with a thermostat (Proline P5 of Lauda GmbH & Co. KG, Germany), a rotary vane pump (322002 P4Z of Ilmvac GmbH, Germany), a temperature control jacket (TCJ) and a condenser (CON) is heated to a temperature of 90 C. The reactor is evacuated to 0.01 mbar and flushed with argon (grade 5.0) up to a pressure of 1.2 bar. This procedure is repeated 30 times. The reactor is evacuated to 0.01 bar and cooled to a temperature of 10 C. 903.0 g 1,3-butadiene and 0.96 g tetraethylenediamine are added and the reactor vessel (RV) is heated to a temperature of 40 C. 0.26 g n-buthyllithium and 3.01 g cyclohexane are added. The polymerisation is conducted for 30 min and the temperature is adjusted with the temperature control jacket (TCJ) and the condenser (CON) to maintain a temperature of 60 C.

[0207] Table 4 provides the conversion rate and the properties of the polymer obtained according to Example 4.

TABLE-US-00004 TABLE 4 Conversion rate and properties of the polymer obtained Time CR Mn Mw Mooney 1,4-cis T.sub.g [min] [%] [g/mol] [g/mol] PDI [MU] [%] 1,4-trans 1,2-vinyl [ C.] 5 46.24 103000 131000 1.27 30 99.98 222000 321000 1.45 72.1 7.68 17.46 74.86 24.18 CR is the conversion rate in [%] Mn is the number average molecular weight in [g/mol] Mw is the weight average molecular weight in [g/mol] PDI is the polydispersity (Mw/Mn) Mooney is the Mooney Viscosity (ML.sub.1+4, 100 C.) in [MU] 1,4-Cis is the 1,4-cis molar ratio in [%] 1,4-Trans is the 1,4-trans molar ratio in [%] 1,2-Vinyl is the 1,2-vinyl molar ratio in [%] T.sub.g is the glass transition temperature in [ C.]

Example 5

[0208] The reactor vessel (RV) equipped with a thermostat (Proline P5 of Lauda GmbH & Co. KG Germany), a rotary vane pump (322002 P4Z of Ilmvac GmbH, Germany), a temperature control jacket (TCJ) and a condenser (CON) is heated to a temperature of 90 C. The reactor is evacuated to 0.01 mbar and flushed with argon (grade 5.0) up to a pressure of 1.2 bar. This procedure is repeated 30 times. The reactor is evacuated to 0.01 bar and cooled to a temperature of 10 C. 699.0 g 1,3-butadiene, 166.45 g styrene and 1.1 g tetraethylenediamine are added and the reactor vessel (RV) is heated to a temperature of 40 C. 0.26 g n-buthyllithium and 3.01 g cyclohexane are added. The polymerisation is conducted for 30 min and the temperature is adjusted with the temperature control jacket (TCJ) and the condenser (CON) to maintain a temperature of 60 C.

[0209] Table 5 provides the conversion rate and the properties of the polymer obtained according to Example 5.

TABLE-US-00005 TABLE 5 Conversion rate and properties of the polymer obtained 1,4- Time CR Mn Mw Mooney cis 1,4- 1,2- T.sub.g [min] [%] [g/mol] [g/mol] PDI [MU] [%] trans vinyl Styrene [ C.] 0.5 4.42 11200 13200 1.17 1 8.55 21700 26600 1.23 10.4 10.7 47.3 31.6 2 15.42 39200 50900 1.30 10.3 10.6 50.0 29.1 5 34.01 86500 127000 1.47 10.8 11.0 51.1 27.1 40 99.99 254000 460000 1.81 86.2 12.0 12.0 52.6 23.6 24.18 CR is the conversion rate in [%] Mn is the number average molecular weight in [g/mol] Mw is the weight average molecular weight in [g/mol] PDI is the polydispersity (Mw/Mn) Mooney is the Mooney Viscosity (ML.sub.1+4, 100 C.) in [MU] T.sub.g is the glass transition temperature in [ C.] 1,4-Cis is the 1,4-cis molar ratio in [%] 1,4-Trans is the 1,4-trans molar ratio in [%] 1,2-Vinyl is the 1,2-vinyl molar ratio in [%] Styrene is the styrene weight ratio in [%]