Method for producing temperature-stable polyalkenylenes

Abstract

The polymerization of cycloalkenamer is stopped by adding an alkyl vinyl derivative. Subsequently compound A is added, wherein compound A has at least one of the features i) or ii): i) at least one functional group or ii) at least one saturated or unsaturated aliphatic or aromatic heterocyclic ring having 3 to 14 ring atoms, wherein the ring atoms contain at least one carbon atom and at least one atom selected from oxygen, nitrogen and sulfur. A membrane filtration is subsequently carried out. This type of production produces polyalkenamers which are temperature-stable at 180° C.

Claims

1. A process for producing a polyalkenamer-containing composition, the process comprising: a) reacting at least one cycloalkene by ring-opening metathesis polymerization in at least one organic solvent to obtain a polyalkenamer-containing product mixture, wherein the polymerization is performed in the presence of at least one metal-containing catalyst, wherein a metal of the at least one metal-containing catalyst is selected from the group consisting of rhenium, ruthenium, osmium and mixtures thereof, wherein the at least one cycloalkene is selected from the group consisting of cyclobutene, cyclopentene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cyclododecene, cycloocta-1,5-diene, 1,5-dimethylcycloocta-1,5-diene, cyclodecadiene, norbomadiene, cyclododeca-1,5,9-triene, trimethylcyclododeca-1,5,9-triene, norbomene (bicy-clo[2.2.1]hept-2-ene), 5-(3′-cyclohexenyl)-2-norbomene, 5-ethyl-2-norbomene, 5-vinyl-2-norbomene, 5-ethylidene-2-norbomene, dicyclopentadiene and mixtures thereof, b) adding at least one alkyl vinyl derivative selected from the group consisting of C.sub.1- to C.sub.12-alkyl vinyl ethers, C.sub.1- to C.sub.12-alkyl vinyl sulfides and mixtures thereof after the polymerization, wherein an amount of the at least one alkyl vinyl derivative is at least equal to an amount of the at least one metal-containing catalyst, c) adding at least one compound A after addition of the at least one alkyl vinyl derivative, wherein an amount of the at least one compound A is at least equal to the amount of the at least one-metal containing catalyst, wherein the at least one compound A has at least one of the features i) or ii): i) at least one functional group selected from the group consisting of primary amino groups, secondary amino groups, tertiary amino groups, thiol groups, ester groups, carbonate ester groups, acetal groups, aldehyde groups, carbonyl groups, carboxamido groups, imido groups, oxime groups, thioester groups, nitrile groups, thiocyanate groups, primary ketimino groups, secondary ketimino groups, primary aldimino groups, secondary aldimino groups, sulfinyl groups, amino oxide groups, carboxyl groups, phosphino groups, phosphane oxide groups, and phosphono groups, ii) at least one saturated or unsaturated aliphatic or aromatic heterocyclic ring having 3 to 14 ring atoms, wherein ring atoms of the heterocyclic ring contain at least one carbon atom and at least one atom selected from the group consisting of oxygen, nitrogen and sulfur, and d) working up the product mixture to remove the at least one metal-containing catalyst to obtain the polyalkenamer-containing composition, wherein the working up is carried out by membrane filtration in at least one organic solvent, wherein the polyalkenamer is dissolved during the membrane filtration.

2. The process according to claim 1, wherein ethyl vinyl ether, butyl vinyl ether or mixtures thereof are added as the at least one alkyl vinyl ether.

3. The process according to claim 1, wherein methyl vinyl sulfide, ethyl vinyl sulfide, propyl vinyl sulfide, butyl vinyl sulfide or mixtures thereof are added as the at least one alkyl vinyl sulfide.

4. The process according to claim 1, wherein the at least one compound A has the feature (i) and wherein the at least one functional group i) is selected from the group consisting of primary amino groups, secondary amino groups, carboxamido groups, nitrile groups, primary ketimino groups, secondary ketimino groups, primary aldimino groups, secondary aldimino groups, carbonyl groups, amino oxide groups, sulfinyl groups, phosphino groups and phosphane oxide groups.

5. The process according to claim 1, wherein the at least one compound A comprises at least one saturated or unsaturated aliphatic heterocyclic ring having 3 to 14 ring atoms or at least one aromatic heterocyclic ring having 5 to 14 ring atoms.

6. The process according to claim 1, wherein the at least one compound A comprises a nitrogen-containing aromatic ring.

7. The process according to claim 1, wherein a membrane of the membrane filtration has a separation-active layer selected from the group consisting of polymers, glass, metal, ceramic and mixtures thereof.

8. The process according to claim 1, wherein the at least one cycloalkene is selected from the group consisting of cyclopentene, cycloheptene, cyclooctene, cyclododecene and mixtures thereof.

9. The process according to claim 1, wherein the polymerization is performed in a nonpolar aromatic or aliphatic solvent.

10. The process according to claim 1, wherein the polymerization and the membrane filtration are performed in a solvent and the same solvent is used for the polymerization and the membrane filtration.

11. The process according to claim 1, wherein the metal of the at least one metal-containing catalyst is ruthenium.

12. The process according to claim 1, wherein the reaction of the at least one cycloalkene is carried out in the presence of a chain transfer agent.

13. The process according to claim 1, wherein the reaction of the at least one cycloalkene is carried out in the presence of an acyclic alkene as chain transfer agent having one or more non-conjugated double bonds, or a cyclic compound having a double bond in a side chain.

Description

EXAMPLES

(1) Methods of Determination

(2) Weight-Average Molecular Weight

(3) Determination of molecular weight was carried out by gel permeation chromatography (GPC) as per DIN 55672-1:2016-03. Measurements were performed with a GPC system from Knauer Wissenschaftliche Geräte GmbH. The polymer was measured as a solution in tetrahydrofuran (c=5 g/L, injection volume 100 μL) on an SDV column (30 cm, 5 μm, linear) with pre-column (SDV 5 cm, 5 μm, 100 Å) at 23° C. and a flow rate of 1 mL/min. Calculation of the average molar masses was carried out by means of the strip method against polystyrene standards. WinGPC UniOhrom (Build 5350) software from PSS Polymer Standards Service GmbH was employed for evaluation.

(4) Melting Point and Melting Enthalpy

(5) Determination of melting point and melting enthalpy was carried out by differential scanning calorimetry (DSC). Polymer samples between 5 and 10 mg were measured. Measurements were performed on a PerkinElmer DSC-7 instrument with 20 mL/min of nitrogen 5.0 as purging gas. The measurement program contained a first heating from −90° C. to 80° C. (heating rate 20 K/min), a cooling from 80° C. to −90° C. (cooling rate 20 K/min) and a second heating from −90° C. to 80° C. (heating rate 20 K/min). The melting point and the melting enthalpy of the polyalkenamers was determined using the second heating.

(6) Trace Elemental Analysis

(7) Determination of trace elements from the catalyst in the polyalkenamer were performed quantitatively by ICP-MS. 0.1-0.2 g of sample were digested in 10 ml of 65% by weight HNO.sub.3 and 2 mL of water at not more than 130 bar of pressure and not more than 300° C. The digestate was evaporated in a closed system at not more than about 95° C., dissolved with 0.5 mL of HNO.sub.3 and made up to 20 mL with water. The content of various elements in the solution was determined quantitatively with a Thermo Fisher “ICAP Q” quadrupole ICPMS.

Example 1A: Synthesis of Polyoctenamer in Heptane with Tungsten/Aluminium Catalyst System

(8) 585 mL of heptane, 100 g of cyclooctene (COE) and 0.34 g of vinyl cyclohexene (VCH) were charged into a dry 2 L glass reactor fitted with a mechanical stirrer under argon. The reaction mixture was heated to 50° C. and 0.4 mL of a solution of ethylaluminium dichloride (20% by weight) in heptane was added. Subsequently, 1 mL of a solution of tungsten hexachloride/propylene oxide (1/3 mol/mol) in toluene (2.8% by weight of tungsten) were added slowly.

(9) A temperature increase of 5° C. was observed and the reaction mixture became markedly more viscous. The contents of the reactor were then discharged and a solution of 20% by weight of polyoctenamer in heptane was obtained.

Example 1B (Comparative Example): Membrane Purification of Polyoctenamer in Heptane with Tungsten/Aluminium Catalyst System

(10) 1.25 L of the solution of 20% by weight of polyoctenamer in heptane (produced as per example 1A) was further diluted to 5% by weight with 3.75 L of heptane. The obtained 5 L of polymer solution was recirculated for 3 hours at 50° C. and then purified by diafiltration through a PuraMem® UF (cut-off about 35 000 Da) ultrafiltration polymer membrane from Evonik Resource Efficiency GmbH. This was carried out using a crossflow filtration system with an 1812 membrane module (membrane area about 0.14 m.sup.2). In a diafiltration the membrane is used as a semipermeable barrier, the large molecules (polymer) being retained and the small molecules (impurities) being washed out through the membrane by solvent addition. The addition of fresh solvent was synchronized with the permeate flow so that the fill level in the feed container remained constant. The experiment was performed at 50° C. and 3 bar and altogether 25 L of fresh heptane were added (5 washing volumes in relation to the starting volume of the polymer solution). 5 L of polymer solution were obtained as retentate after this purification. 25 L of permeate solution were also obtained.

(11) Heat Treatment at 180° C.

(12) For analytical purposes 10 mL of the retentate (purified polymer solution) were dried in an aluminium dish in a vacuum drying cabinet over 20 h at 180° C. and a vacuum of 1 mbar after inertization with nitrogen. 1.5 g of white solid were obtained. The NMR spectrum of the solid corresponded to the expected structure of a polyoctenamer which contained 0.25 mol % of vinyl end groups and 0.30 mol % of cyclohexane end groups.

(13) .sup.1H NMR (CDCl.sub.3, 500 MHz, 30° C.) δ (ppm): polyoctenamer: 5.38, 5.34, 2.01, 1.96, 1.30; end groups: 5.81 (m, 1H, —CH2=CH—CH2-), 5.66 (d, 2H, CH2-CH═CH—CH2), 5.38-5.34 (m, 2H, —CH—CH═CH—CH2), 4.95 (m, 2H, CH2=CH—CH2-). Cis/trans double bond ratio: 22/78

(14) Melting point: 54° C.

(15) Melting enthalpy: 75 J/g

(16) Molar mass M.sub.w: 135 000 g/mol

(17) Oligomer proportion (M<3000 g/mol): 3.8%

(18) A trace elemental analysis showed that the polymer contained 250 ppm of tungsten, 125 ppm of aluminium and 110 ppm of chlorine.

Example 2A: Synthesis of Polyoctenamer in Heptane with Ru Catalyst

(19) 1 L of heptane, 300 g of cyclooctene (COE) and 1.03 g of vinyl cyclohexene (VCH) were charged into a dry 2 L glass reactor fitted with a mechanical stirrer under argon. The reaction mixture was heated to 70° C. and a solution of 14.4 mg of tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dimethylimidazol-2-ylidene](2-thienylmethyliden)ruthenium(II) dichloride (catalyst C3) in 3.27 mL of toluene was added. A temperature increase of 16° C. was observed and the reaction mixture became markedly more viscous. The contents of the reactor were then discharged and a solution of 30% by weight of polyoctenamer in heptane was obtained.

Example 2B (Comparative Example): Membrane Purification of Polyoctenamer in Heptane with Ru Catalyst

(20) 0.8 L of the solution of 30% by weight of polyoctenamer in heptane (produced as per example 2A) was further diluted to 5% by weight with 4.2 L of heptane. The obtained 5 L of polymer solution was recirculated for 3 hours at 50° C. and then purified by diafiltration through a PuraMem® UF (cut-off about 35 000 Da) ultrafiltration polymer membrane from Evonik Resource Efficiency GmbH. This was carried out using a crossflow filtration system with an 1812 membrane module (membrane area about 0.14 m.sup.2). The addition of fresh solvent was synchronized with the permeate flow so that the fill level in the feed container remained constant. The experiment was performed at 50° C. and 3 bar and altogether 25 L of fresh heptane were added (5 washing volumes in relation to the starting volume of the polymer solution), 5 L of polymer solution were obtained as retentate after this purification. 25 L of permeate solution were also obtained.

(21) Heat Treatment at 80° C.

(22) For analytical purposes 10 mL of this solution were dried in an aluminium dish in a vacuum drying cabinet over 3 h at 80° C. and a vacuum of 1 mbar after inertization with nitrogen. 2 g of white solid were obtained. The NMR spectrum of the solid corresponded to the expected structure of a polyoctenamer which contained 0.30 mol % of vinyl end groups and 0.32 mol % of cyclohexene end groups. Cis/trans double bond ratio: 22/78

(23) .sup.1H NMR (CDCl.sub.3, 500 MHz, 30° C.) δ (ppm): polyoctenamer: 5.38, 5.34, 2.01, 1.96, 1.30; end groups: 5.81 (m, 1H, —CH2=CH—CH2-), 5.66 (d, 2H, CH2-CH═CH—CH2), 5.38-5.34 (m, 2H, —CH—CH═CH—CH2), 4.95 (m, 2H, CH2=CH—CH2-).

(24) Melting point: 57° C.

(25) Melting enthalpy: 78 J/g

(26) Molar mass M.sub.w: 115 000 g/mol

(27) Oligomer proportion (M<3000 g/mol): 7%

(28) Heat Treatment at 180° C.

(29) For analytical purposes 10 mL of this solution were dried in an aluminium dish in a vacuum drying cabinet over 20 h at 180° C. and a vacuum of 1 mbar after inertization with nitrogen. 2 g of white solid were obtained. The NMR spectrum of the solid partly corresponded to the expected structure of a polyoctenamer (see above) but the end groups (vinyl and cyclohexene end groups) were absent and unknown signals were observed in the olefin region. Cis/trans double bond ratio: 20/80

(30) Melting point: 30° C.

(31) Melting enthalpy: 58 J/g

(32) The markedly lower melting point and melting enthalpy values compared to drying at 80° C. showed that the polymer was unstable at a temperature of 180° C. The polymer solution contained fine grey particles that blocked the membrane so that further use thereof was not possible. The grey particles were presumably inorganic ruthenium-containing compounds which were insoluble and remained in the polymer after drying.

Example 2C (Comparative Example): Membrane Purification of Polyoctenamer in Heptane with Ru Catalyst and Addition of Butyl Vinyl Ether (No Addition of Compound A)

(33) 1 L of heptane, 300 g of cyclooctene (COE) and 1.03 g of vinyl cyclohexene (VCH) were charged into a dry 2 L glass reactor fitted with a mechanical stirrer under argon. The reaction mixture was heated to 50° C. and a solution of 24 mg of tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dimethylimidazol-2-ylidene](2-thienylmethyliden)ruthenium(II) dichloride (catalyst C3) in 5.4 mL of toluene was added. A temperature increase of 19° C. was observed and the reaction mixture became markedly more viscous. 2.7 g of butyl vinyl ether were added 15 min after catalyst addition. After 30 min at 50° C. the contents of the reactor were discharged and a solution of 30% by weight of polyoctenamer in heptane was obtained.

(34) 0.8 L of the solution of 30% by weight of polyoctenamer in heptane were further diluted to 5% by weight with 4.2 L of heptane. The obtained 5 L of polymer solution were recirculated for 3 hours at 50° C. and then purified by diafiltration through a PuraMem® UF (cut-off about 35 000 Da) ultrafiltration polymer membrane from Evonik Resource Efficiency GmbH. This was carried out using a crossflow filtration system with a 1812 membrane module (membrane area about 0.14 m.sup.2). The addition of fresh solvent was synchronized with the permeate flow so that the fill level in the feed container remained constant. The experiment was performed at 50° C. and 3 bar and altogether 25 L of fresh heptane were added (5 washing volumes in relation to the starting volume of the polymer solution). 5 L of polymer solution were obtained as retentate after this purification. 25 L of permeate solution were also obtained.

(35) Heat Treatment at 80° C.

(36) For analytical purposes 10 mL of this solution were dried in an aluminium dish in a vacuum drying cabinet over 3 h at 80° C. and a vacuum of 1 mbar after ineilization with nitrogen. 2 g of white solid were obtained. The NMR spectrum of the solid corresponded to the expected structure of a polyoctenamer which contained 0.30 mol % of vinyl end groups and 0.32 mol % of cyclohexene end groups. Cis/trans double bond ratio: 21/79

(37) .sup.1H NMR (CDCl.sub.3, 500 MHz, 30° C.) δ (ppm): Polyoctenamer: 5.38, 5.34, 2.01, 1.96, 1.30; End groups: 5.81 (m, 1H, —CH2=CH—CH2-), 5.66 (d, 2H, CH2-CH═CH—CH2), 5.38-5.34 (m, 2H, —CH—CH═CH—CH2), 4.95 (m, 2H, CH2=CH—CH2-).

(38) Melting point: 57° C.

(39) Melting enthalpy: 83 J/g

(40) Molar mass M.sub.w: 100 000 g/mol

(41) Oligomer proportion (M<3000 g/mol): 10%

(42) Heat Treatment at 180° C.

(43) For analytical purposes 10 mL of this solution were dried in an aluminium dish in a vacuum drying cabinet over 20 h at 180° C. and a vacuum of 1 mbar after inertization with nitrogen. 2 g of white solid were obtained. The NMR spectrum of the solid partly corresponded to the expected structure of a polyoctenamer (see above) but the end groups (vinyl and cyclohexene end groups) were absent and unknown signals were observed in the olefin region. Cis/trans double bond ratio: 22/78

(44) Melting point: 49° C.

(45) Melting enthalpy: 71 J/g

(46) The lower melting point and melting enthalpy compared to drying at 80° C. showed that the polymer was unstable at a temperature of 180° C. A trace elemental analysis showed that the polymer contained 3.5 ppm of ruthenium.

(47) The ruthenium-containing catalyst was only partially removed. The addition of butyl vinyl ether was apparently not sufficient to stabilize the catalyst during the 3 hours prior to the membrane filtration: presumably insoluble inorganic ruthenium-containing compounds were formed and remained in the polymer after drying.

Example 3A (Comparative Example): Synthesis of Polyoctenamer in Heptane with Ru Catalyst and Addition of Butyl Vinyl Ether then 2-aminophenol

(48) 1 L of heptane, 300 g of cyclooctene (COE) and 1.03 g of vinyl cyclohexene (VCH) were charged into a dry 2 L glass reactor fitted with a mechanical stirrer under argon. The reaction mixture was heated to 50° C. and a solution of 24 mg of tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dimethylimidazol-2-ylidene](2-thienylmethyliden)ruthenium(II) dichloride (catalyst C3) in 5.4 mL of toluene was added. A temperature increase of 19° C. was observed and the reaction mixture became markedly more viscous. 2.7 g of butyl vinyl ether were added 15 min after catalyst addition. The reaction mixture was stirred for a further 15 min and 0.3 g of 2-aminophenol (dissolved in 10 ml of ethanol) was added. After 30 min at 50° C. the contents of the reactor were discharged and a solution of 30% by weight of polyoctenamer in heptane was obtained.

(49) Heat Treatment at 80° C.

(50) For analytical purposes 10 mL of this solution were dried in an aluminium dish in a vacuum drying cabinet over 3 h at 80° C. and a vacuum of 1 mbar after inertization with nitrogen. 2 g of white solid were obtained. The NMR spectrum of the solid corresponded to the expected structure of a polyoctenamer which contained 0.30 mol % of vinyl end groups and 0.28 mol % of cyclohexene end groups. Cis/trans ratio double bond ratio: 21/79

(51) .sup.1H NMR (CDCl.sub.3, 500 MHz, 30° C.) δ (ppm): Polyoctenamer: 5.38, 5.34, 2.01, 1.96, 1.30; end groups; 5.81 (m, 1H, —CH2=CH—CH2-), 5.66 (d, 2H, CH2-CH═CH—CH2), 5.38-5.34 (m, 2H, —CH—CH═CH—CH2), 4.95 (m, 2H, CH2=CH—CH2-).

(52) Melting point: 60° C.

(53) Melting enthalpy: 82 J/g

(54) Molar mass M.sub.w: 104 000 g/mol

(55) Oligomer proportion (M<3000 g/mol): 2.5%

(56) Heat Treatment at 180° C.

(57) For analytical purposes 10 mL of this solution were dried in an aluminium dish in a vacuum drying cabinet over 20 h at 180° C. and a vacuum of 1 mbar after inertization with nitrogen, 2 g of white solid were obtained. The NMR spectrum of the solid partly corresponded to the expected structure of a polyoctenamer (see above) but the end groups (vinyl and cyclohexene end groups) were absent and unknown signals were observed in the olefin region. Cis/trans double bond ratio: 25/75

(58) Melting point: 29° C.

(59) Melting enthalpy: 65 J/g

(60) The markedly lower melting point and melting enthalpy compared to drying at 80° C. showed that the polymer was unstable at a temperature of 180° C. A trace elemental analysis showed that the polymer contained 8.6 ppm of ruthenium.

Example 3B (Inventive): Membrane Purification of Polyoctenamer in Heptane with Ru Catalyst and Addition of Butyl Vinyl Ether then 2-aminophenol

(61) 0.8 L of the solution of 30% by weight of polyoctenamer in heptane (produced as per example 3A) was further diluted to 5% by weight with 4.2 L of heptane. The obtained 5 L of polymer solution was recirculated for 3 hours at 50° C. and then purified by diafiltration through a PuraMem® UF (cut-off about 35 000 Da) ultrafiltration polymer membrane from Evonik Resource Efficiency GmbH. This was carried out using a crossflow filtration system with an 1812 membrane module (membrane area about 0.14 m.sup.2). The addition of fresh solvent was synchronized with the permeate flow so that the fill level in the feed container remained constant. The experiment was performed at 50° C. and 3 bar and altogether 25 L of fresh heptane were added (5 washing volumes in relation to the starting volume of the polymer solution). 5 L of polymer solution were obtained as retentate after this purification. 25 L of permeate solution were also obtained.

(62) Heat Treatment at 180° C.

(63) For analytical purposes 10 mL of the retentate (purified polymer solution) were dried in an aluminium dish in a vacuum drying cabinet over 20 h at 180° C. and a vacuum of 1 mbar after inertization with nitrogen, 2 g of white solid were obtained. The NMR spectrum of the solid corresponded to the expected structure of a polyoctenamer which contained 0.29 mol % of vinyl end groups and 0.26 mol % of cyclohexene end groups. Cis/trans double bond ratio: 21/79

(64) .sup.1H NMR (CDCl.sub.3, 500 MHz, 30° C.) δ (ppm): Polyoctenamer: 5.38, 5.34, 2.01, 1.96, 1.30; end groups: 5.81 (m, 1H, —CH2=CH—CH2-), 5.66 (d, 2H, CH2-CH═CH—CH2), 5.38-5.34 (m, 2H, —CH—CH═CH—CH2), 4.95 (m, 2H, CH2=CH—CH2-).

(65) Melting point: 59° C.

(66) Melting enthalpy: 81 J/g

(67) Molar mass M.sub.w: 111 000 g/mol

(68) Oligomer proportion (M<3000 g/mol): 0.8%

(69) The high melting point (>56° C.) and the high melting enthalpy (>75 J/g) showed that the purified polyoctenamer was stable under the temperature conditions at 180° C.

(70) The reduction in the oligomer proportion in the GPC compared to the starting solution (see example 3A) showed that this purification by ultrafiltration allowed separation of oligomers. A trace elemental analysis showed that the polymer contained only 0.2 ppm of ruthenium. In addition, no insoluble particles in the polymer solution were observed.

Example 4A (Comparative Example): Synthesis of Polyoctenamer in Heptane with Ru Catalyst and Addition of Butyl Vinyl Ether then N-methylimidazole

(71) 1 L of heptane, 300 g of cyclooctene (COE) and 1.03 g of vinyl cyclohexene (VCH) were charged into a dry 2 L glass reactor fitted with a mechanical stirrer under argon. The reaction mixture was heated to 50° C. and a solution of 24 mg of tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dimethylimidazol-2-ylidene](2-thienylmethyliden)ruthenium(II) dichloride (catalyst C3) in 5.4 mL of toluene was added. A temperature increase of 15° C. was observed and the reaction mixture became markedly more viscous. 2.7 g of butyl vinyl ether were added 15 min after catalyst addition. The reaction mixture was stirred for a further 15 min and 0.22 g of N-methylimidazole was added. After 30 min at 50° C. the contents of the reactor were discharged and a solution of 30% by weight of polyoctenamer in heptane was obtained.

(72) Heat Treatment at 80° C.

(73) For analytical purposes 10 mL of this solution were dried in an aluminium dish in a vacuum drying cabinet over 3 h at 80° C. and a vacuum of 1 mbar after inertization with nitrogen. 2 g of white solid were obtained. The NMR spectrum of the solid corresponded to the expected structure of a polyoctenamer which contained 0.31 mol % of vinyl end groups and 0.28 mol % of cyclohexene end groups. Cis/trans double bond ratio: 21/79

(74) .sup.1H NMR (CDCl.sub.3, 500 MHz, 30° C.) δ (ppm); Polyoctenamer: 5.38, 5.34, 2.01, 1.96, 1.30; end groups; 5.81 (m, 1H, —CH2=CH—CH2-), 5.66 (d, 2H, CH2-CH═CH—CH2), 5.38-5.34 (m, 2H, —CH—CH═CH—CH2), 4.95 (m, 2H, CH2=CH—CH2-).

(75) Melting point: 57° C.

(76) Melting enthalpy: 78 J/g

(77) Molar mass M.sub.w: 99 900 g/mol

(78) Oligomer proportion (M<3000 g/mol): 2%

(79) Heat Treatment at 180° C.

(80) For analytical purposes 10 mL of this solution were dried in an aluminium dish in a vacuum drying cabinet over 20 h at 180° C. and a vacuum of 1 mbar after inertization with nitrogen. 2 g of white solid were obtained. The NMR spectrum of the solid partly corresponded to the expected structure of a polyoctenamer (see above) but the end groups (vinyl and cyclohexene end groups) were absent and unknown signals were observed in the olefin region, Cis/trans double bond ratio: 24/76

(81) Melting point: 49° C.

(82) Melting enthalpy: 70 J/g

(83) The markedly lower melting point and melting enthalpy compared to drying at 80° C. showed that the polymer was unstable at a temperature of 180° C. A trace elemental analysis showed that the polymer contained 8.4 ppm of ruthenium.

Example 4B (Inventive): Membrane Purification of Polyoctenamer in Heptane with Ru Catalyst and Addition of Butyl Vinyl Ether then N-methylimidazole

(84) 0.8 L of the solution of 30% by weight of polyoctenamer in heptane (produced as per example 4A) was further diluted to 5% by weight with 4.2 L of heptane. The obtained 5 L of polymer solution was pumped recirculated 3 hours at 50° C. and then purified by diafiltration through a PuraMem® UF (cut-off about 35 000 Da) ultrafiltration polymer membrane from Evonik Resource Efficiency GmbH. This was carried out using a crossflow filtration system with an 1812 membrane module (membrane area about 0.14 m.sup.2). The addition of fresh solvent was synchronized with the permeate flow so that the fill level in the feed container remained constant. The experiment was performed at 50° C. and 3 bar and altogether 15 L of fresh heptane were added (3 washing volumes in relation to the starting volume of the polymer solution). 5 L of polymer solution were obtained as retentate after this purification. 15 L of permeate solution were also obtained.

(85) Heat Treatment at 180° C.

(86) For analytical purposes 10 mL of the retentate (purified polymer solution) were dried in an aluminium dish in a vacuum drying cabinet over 20 h at 180° C. and a vacuum of 1 mbar after inertization with nitrogen. 2 g of white solid were obtained. The NMR spectrum of the solid corresponded to the expected structure of a polyoctenamer which contained 0.30 mol % of vinyl end groups and 0.26 mol % of cyclohexene end groups. Cis/trans double bond ratio: 22/78

(87) .sup.1H NMR (CDCl.sub.3, 500 MHz, 30° C.) δ (ppm): Polyoctenamer: 5.38, 5.34, 2.01, 1.96, 1.30; end groups: 5.81 (m, 1H, —CH2=CH—CH2-), 5.66 (d, 2H, CH2-CH═CH—CH2), 5.38-5.34 (m, 2H, —CH—CH═CH—CH2), 4.95 (m, 2H, CH2=CH—CH2-).

(88) Melting point: 57° C.

(89) Melting enthalpy: 78 J/g

(90) Molar mass M.sub.w: 104 400 g/mol

(91) Oligomer proportion (M<3000 g/mol): 0.7%

(92) The high melting point (>56° C.) and the high melting enthalpy (>75 J/g) showed that the purified polyoctenamer was stable under the temperature conditions at 180° C.

(93) The reduction in the oligomer proportion in the GPC compared to the starting solution (see example 3A) showed that this purification by ultrafiltration allowed separation of oligomers. A trace elemental analysis showed that the polymer contained only 0.3 ppm of ruthenium. In addition, no insoluble particles in the polymer solution were observed.

Example 5A (Comparative Example): Synthesis of Polyoctenamer in Toluene with Ru Catalyst and Addition of Butyl Vinyl Ether then Acetonitrile

(94) 800 mL of toluene, 300 g of cyclooctene (COE) and 1.03 g of vinyl cyclohexene (VCH) were charged into a dry 2 L glass reactor fitted with a mechanical stirrer under argon. The reaction mixture was heated to 50° C. and a solution of 24 mg of tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dimethylimidazol-2-ylidene](2-thienylmethyliden)ruthenium(II) dichloride (catalyst C3) in 5.4 of toluene was added. A temperature increase of 19° C. was observed and the reaction mixture became markedly more viscous. 2.7 g of butyl vinyl ether were added 15 min after catalyst addition. The reaction mixture was stirred for a further 15 min and 0.11 g of acetonitrile was added. After 30 min at 50° C. the contents of the reactor were discharged and a solution of 30% by weight of polyoctenamer in toluene was obtained.

(95) Heat Treatment at 80° C.

(96) For analytical purposes 10 mL of this solution were dried in an aluminium dish in a vacuum drying cabinet over 3 h at 80° C. and a vacuum of 1 mbar after inertization with nitrogen. 2 g of white solid were obtained. The NMR spectrum of the solid corresponded to the expected structure of a polyoctenamer which contained 0.29 mol % of vinyl end groups and 0.36 mol % of cyclohexene end groups. Cis/trans double bond ratio: 21/79

(97) .sup.1H NMR (CDCl.sub.3, 500 MHz, 30° C.) δ (ppm): Polyoctenamer: 5.38, 5.34, 2.01, 1.96, 1.30; end groups: 5.81 (m, 1H, —CH2=CH—CH2-), 5.66 (d, 2H, CH2-CH═CH—CH2), 5.38-5.34 (m, 2H, —CH—CH═CH—CH2), 4.95 (m, 2H, CH2=CH—CH2-).

(98) Melting point: 57° C.

(99) Melting enthalpy: 78 J/g

(100) Molar mass M.sub.w: 105 000 g/mol

(101) Oligomer proportion (M<3000 g/mol): 3%

(102) Heat Treatment at 180° C.

(103) For analytical purposes 10 mL of this solution were dried in an aluminium dish in a vacuum drying cabinet over 20 h at 180° C. and a vacuum of 1 mbar after inertization with nitrogen. 2 g of white solid were obtained. The NMR spectrum of the solid partly corresponded to the expected structure of a polyoctenamer (see above) but the end groups (vinyl and cyclohexene end groups) were absent and unknown signals were observed in the olefin region. Cis/trans double bond ratio: 25/75

(104) Melting point: 35° C.

(105) Melting enthalpy: 63 J/g

(106) The markedly lower melting point and melting enthalpy compared to drying at 80° C. showed that the polymer was unstable at a temperature of 180° C. A trace elemental analysis showed that the polymer contained 8.5 ppm of ruthenium.

Example 5B (Inventive): Membrane Purification of Polyoctenamer in Toluene with Ru Catalyst and Addition of Butyl Vinyl Ether then Acetonitrile

(107) 0.8 L of the solution of 30% by weight of polyoctenamer in toluene (produced as per example 5A) was further diluted to 5% by weight with 4.2 L of toluene. The obtained 5 L of polymer solution was recirculated for 3 hours at 50° C. and then purified by diafiltration through a PuraMem® UF (cut-off about 35 000 Da) ultrafiltration polymer membrane from Evonik Resource Efficiency GmbH. This was carried out using a crossflow filtration system with an 1812 membrane module (membrane area about 0.14 m.sup.2). The addition of fresh solvent was synchronized with the permeate flow so that the fill level in the feed container remained constant. The experiment was performed at 50° C. and 3 bar and altogether 15 L of fresh toluene were added (3 washing volumes in relation to the starting volume of the polymer solution). 5 L of polymer solution were obtained as retentate after this purification. 15 L of permeate solution were also obtained.

(108) Heat Treatment at 180° C.

(109) For analytical purposes 10 mL of the retentate (purified polymer solution) were dried in an aluminium dish in a vacuum drying cabinet over 20 h at 180° C. and a vacuum of 1 mbar after inertization with nitrogen. 2 g of white solid were obtained. The NMR spectrum of the solid corresponded to the expected structure of a polyoctenamer which contained 0.26 mol % of vinyl end groups and 0.34 mol % of cyclohexene end groups, Cis/trans double bond ratio: 21/79

(110) .sup.1H NMR (CDCl.sub.3, 500 MHz, 30° C.) δ (ppm); Polyoctenamer: 5.38, 5.34, 2.01, 1.96, 1.30; end groups; 5.81 (m, 1H, —CH2=CH—CH2-), 5.66 (d, 2H, CH2-CH═CH—CH2), 5.38-5.34 (m, 2H, —CH—CH═CH—CH2), 4.95 (m, 2H, CH2=CH—CH2-).

(111) Melting point: 57° C.

(112) Melting enthalpy: 78 J/g

(113) Molar mass M.sub.w: 111 000 g/mol

(114) Oligomer proportion (M<3000 g/mol): 0.95%

(115) The high melting point (>56° C.) and the high melting enthalpy (>75 J/g) showed that the purified polyoctenamer was stable under the temperature conditions at 180° C.

(116) The reduction in the oligomer proportion in the GPC compared to the starting solution (see example 3A) showed that this purification by ultrafiltration allowed separation of oligomers. A trace elemental analysis showed that the polymer contained only 2.1 ppm of ruthenium. In addition, no insoluble particles in the polymer solution were observed.

Example 6A (Comparative Example): Synthesis of Polyoctenamer in Toluene with Ru Catalyst and Addition of Butyl Vinyl Ether then 2-aminophenol

(117) 800 mL of toluene, 300 g of cyclooctene (COE) and 1.03 g of vinyl cyclohexene (VCH) were charged into a dry 2 L glass reactor fitted with a mechanical stirrer under argon. The reaction mixture was heated to 50° C. and a solution of 24 mg of tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dimethylimidazol-2-ylidene](2-thienylmethyliden)ruthenium(II) dichloride (catalyst C3) in 5.4 mL of toluene was added. A temperature increase of 22° C. was observed and the reaction mixture became markedly more viscous. 2.7 g of butyl vinyl ether were added 15 min after catalyst addition. The reaction mixture was stirred for a further 15 min and 0.3 g of 2-aminophenol (dissolved in 10 ml of ethanol) was added. After 30 min at 50° C. the contents of the reactor were discharged and a solution of 30% by weight of polyoctenamer in toluene was obtained.

(118) Heat Treatment at 80° C.

(119) For analytical purposes 10 mL of this solution were dried in an aluminium dish in a vacuum drying cabinet over 3 h at 80° C. and a vacuum of 1 mbar after inertization with nitrogen. 2 g of white solid were obtained. The NMR spectrum of the solid corresponded to the expected structure of a polyoctenamer which contained 0.26 mol % of vinyl end groups and 0.28 mol % of cyclohexene end groups. Cis/trans double bond ratio: 22/78

(120) .sup.1H NMR (CDCl.sub.3, 500 MHz, 30° C.) δ (ppm): Polyoctenamer: 5.38, 5.34, 2.01, 1.96, 1.30; end groups: 5.81 (m, 1H, —CH2=CH—CH2-). 5.66 (d, 2H, CH2-CH═CH—CH2), 5.38-5.34 (m, 2H, —CH—CH═CH—CH2), 4.95 (m, 2H, CH2=CH—CH2-).

(121) Melting point: 59° C.

(122) Melting enthalpy: 80 J/g

(123) Molar mass M.sub.w: 103 600 g/mol

(124) Oligomer proportion (M<3000 g/mol): 1.7%

(125) Heat Treatment at 180° C.

(126) For analytical purposes 10 mL of this solution were dried in an aluminium dish in a vacuum drying cabinet over 20 h at 180° C. and a vacuum of 1 mbar after inertization with nitrogen. 2 g of white solid were obtained. The NMR spectrum of the solid partly corresponded to the expected structure of a polyoctenamer (see above) but the end groups (vinyl and cyclohexene end groups) were absent and unknown signals were observed in the olefin region. Cis/trans double bond ratio: 25/75

(127) Melting point: 30° C.

(128) Melting enthalpy: 67 J/g

(129) The markedly lower melting point and melting enthalpy compared to drying at 80° C. showed that the polymer was unstable at a temperature of 180° C. A trace elemental analysis showed that the polymer contained 8.5 ppm of ruthenium.

Example 6B (Inventive): Membrane Purification of Polyoctenamer in Toluene with Ru Catalyst and Addition of Butyl Vinyl Ether then N-methylimidazole

(130) 0.8 L of the solution of 30% by weight of polyoctenamer in toluene (produced as per example 6A) was further diluted to 5% by weight with 4.2 L of toluene, The obtained 5 L of polymer solution was recirculated for 3 hours at 50° C. and then purified by diafiltration through a PuraMem® UF (cut-off about 35 000 Da) ultrafiltration polymer membrane from Evonik Resource Efficiency GmbH. This was carried out using a crossflow filtration system with an 1812 membrane module (membrane area about 0.14 m.sup.2). The addition of fresh solvent was synchronized with the permeate flow so that the fill level in the feed container remained constant. The experiment was performed at 50° C. and 3 bar and altogether 15 L of fresh toluene were added (3 washing volumes in relation to the starting volume of the polymer solution). 5 L of polymer solution were obtained as retentate after this purification. 15 L of permeate solution were also obtained.

(131) Heat Treatment at 180° C.

(132) For analytical purposes 10 mL of the retentate (purified polymer solution) were dried in an aluminium dish in a vacuum drying cabinet over 20 h at 180° C. and a vacuum of 1 mbar after inertization with nitrogen. 2 g of white solid were obtained. The NMR spectrum of the solid corresponded to the expected structure of a polyoctenamer which contained 0.25 mol % of vinyl end groups and 0.26 mol % of cyclohexene end groups. Cis/trans double bond ratio: 21/79

(133) .sup.1H NMR (CDCl.sub.3, 500 MHz, 30° C.) δ (ppm): Polyoctenamer: 5.38, 5.34, 2.01, 1.96, 1.30; end groups: 5.81 (m, 1H, —CH2=CH—CH2-). 5.66 (d, 2H, CH2-CH═CH—CH2), 5.38-5.34 (m, 2H, —CH—CH═CH—CH2), 4.95 (m, 2H, CH2=CH—CH2-).

(134) Melting point: 59° C.

(135) Melting enthalpy: 81 J/g

(136) Molar mass M.sub.w: 109 000 g/mol

(137) Oligomer proportion (M<3000 g/mol): 0.5%

(138) The high melting point (>56° C.) and the high melting enthalpy (>75 J/g) showed that the purified polyoctenamer was stable under the temperature conditions at 180° C.

(139) The reduction in the oligomer proportion in the GPC compared to the starting solution (see example 3A) showed that this purification by ultrafiltration allowed separation of oligomers. A trace elemental analysis showed that the polymer contained only 0.7 ppm of ruthenium. In addition, no insoluble particles in the polymer solution were observed.

Example 7A (Comparative Example): Synthesis of Polyoctenamer in Toluene with Ru Catalyst and Addition of Butyl Vinyl Ether then N-methylimidazole

(140) 800 mL of toluene, 300 g of cyclooctene (COE) and 1.03 g of vinyl cyclohexene (VCH) were charged into a dry 2 L glass reactor fitted with a mechanical stirrer under argon. The reaction mixture was heated to 50° C. and a solution of 24 mg of tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dimethylimidazol-2-ylidene](2-thienylmethyliden)ruthenium(II) dichloride (catalyst C3) in 5.4 mL of toluene was added. A temperature increase of 20° C. was observed and the reaction mixture became markedly more viscous. 2.7 g of butyl vinyl ether were added 15 min after catalyst addition. The reaction mixture was stirred for a further 15 min and 0.22 g of N-methylimidazole was added. After 30 min at 50° C. the contents of the reactor were discharged and a solution of 30% by weight of polyoctenamer in toluene was obtained.

(141) Heat Treatment at 80° C.

(142) For analytical purposes 10 mL of this solution were dried in an aluminium dish in a vacuum drying cabinet over 3 h at 80° C. and a vacuum of 1 mbar after inertization with nitrogen. 2 g of white solid were obtained. The NMR spectrum of the solid corresponded to the expected structure of a polyoctenamer which contained 0.32 mol % of vinyl end groups and 0.32 mol % of cyclohexene end groups. Cis/trans double bond ratio: 21/79

(143) .sup.1H NMR (CDCl.sub.3, 500 MHz, 30° C.) δ (ppm): Polyoctenamer: 5.38, 5.34, 2.01, 1.96, 1.30; end groups: 5.81 (m, 1H, —CH2=CH—CH2-). 5.66 (d, 2H, CH2-CH═CH—CH2), 5.38-5.34 (m, 2H, —CH—CH═CH—CH2), 4.95 (m, 2H, CH2=CH—CH2-).

(144) Melting point: 59° C.

(145) Melting enthalpy: 80 J/g

(146) Molar mass M.sub.w: 107 500 g/mol

(147) Oligomer proportion (M<3000 g/mol): 2%

(148) Heat Treatment at 180° C.

(149) For analytical purposes 10 mL of this solution were dried in an aluminium dish in a vacuum drying cabinet over 20 h at 180° C. and a vacuum of 1 mbar after inertization with nitrogen. 2 g of white solid were obtained. The NMR spectrum of the solid partly corresponded to the expected structure of a polyoctenamer (see above) but the end groups (vinyl and cyclohexene end groups) were absent and unknown signals were observed in the olefin region. Cis/trans double bond ratio: 24/76

(150) Melting point: 47° C.

(151) Melting enthalpy: 66 J/g

(152) The markedly lower melting point and melting enthalpy compared to drying at 80° C. showed that the polymer was unstable at a temperature of 180° C. A trace elemental analysis showed that the polymer contained 8.8 ppm of ruthenium.

Example 7B (Inventive): Membrane Purification of Polyoctenamer in Toluene with Ru Catalyst and Addition of Butyl Vinyl Ether then N-methylimidazole

(153) 0.8 L of the solution of 30% by weight of polyoctenamer in toluene (produced as per example 7A) was further diluted to 5% by weight with 4.2 L of toluene. The obtained 5 L of polymer solution was recirculated for 3 hours at 50° C. and then purified by diafiltration through a PuraMem® UF (cut-off about 35 000 Da) ultrafiltration polymer membrane from Evonik Resource Efficiency GmbH. This was carried out using a crossflow filtration system with an 1812 membrane module (membrane area about 0.14 m.sup.2). The addition of fresh solvent was synchronized with the permeate flow so that the fill level in the feed container remained constant. The experiment was performed at 50° C. and 3 bar and altogether 15 L of fresh toluene were added (3 washing volumes in relation to the starting volume of the polymer solution). 5 L of polymer solution were obtained as retentate after this purification. 15 L of permeate solution were also obtained.

(154) Heat treatment at 180° C.

(155) For analytical purposes 10 mL of the retentate (purified polymer solution) were dried in an aluminium dish in a vacuum drying cabinet over 20 h at 180° C. and a vacuum of 1 mbar after inertization with nitrogen. 2 g of white solid were obtained. The NMR spectrum of the solid corresponded to the expected structure of a polyoctenamer which contained 0.30 mol % of vinyl end groups and 0.29 mol % of cyclohexene end groups. Cis/trans double bond ratio: 21/79

(156) .sup.1H NMR (CDCl.sub.3, 500 MHz, 30° C.) δ (ppm): Polyoctenamer: 5.38, 5.34, 2.01, 1.96, 1.30; end groups: 5.81 (m, 1H, —CH2=CH—CH2-), 5.66 (d, 2H, CH2-CH=CH—CH2), 5.38-5.34 (m, 2H, —CH—CH═CH—CH2), 4.95 (m, 2H, CH2=CH—CH2-).

(157) Melting point: 60° C.

(158) Melting enthalpy: 81 J/g

(159) Molar mass M.sub.w: 113 000 g/mol

(160) Oligomer proportion (M<3000 g/mol): 0.5%

(161) The high melting point (>56° C.) and the high melting enthalpy (>75 J/g) showed that the purified polyoctenamer was stable under the temperature conditions at 180° C.

(162) The reduction in the oligomer proportion in the GPC compared to the starting solution (see example 3A) showed that this purification by ultrafiltration allowed separation of oligomers. A trace elemental analysis showed that the polymer contained only 0.3 ppm of ruthenium. In addition, no insoluble particles in the polymer solution were observed.

Example 8A (Comparative Example): Synthesis of Polyoctenamer in Toluene with Ru Catalyst and Addition of Ethyl Vinyl Sulfide then N-methylimidazole

(163) 800 mL of toluene, 300 g of cyclooctene (COE) and 1.03 g of vinyl cyclohexene (VCH) were charged into a dry 2 L glass reactor fitted with a mechanical stirrer under argon. The reaction mixture was heated to 50° C. and a solution of 24 mg of tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl-4,5-dimethylimidazol-2-ylidene](2-thienylmethyliden)ruthenium(II) dichloride (catalyst C3) in 5.4 mL of toluene was added. A temperature increase of 21° C. was observed and the reaction mixture became markedly more viscous. 2.4 g of ethyl vinyl sulfide were added 15 min after catalyst addition. The reaction mixture was stirred for a further 15 min and 0.22 g of N-methylimidazole was added. After 30 min at 50° C. the contents of the reactor were discharged and a solution of 30% by weight of polyoctenamer in toluene was obtained.

(164) Heat Treatment at 80° C.

(165) For analytical purposes 10 mL of this solution were dried in an aluminium dish in a vacuum drying cabinet over 3 h at 80° C. and a vacuum of 1 mbar after inertization with nitrogen. 2 g of white solid were obtained. The NMR spectrum of the solid corresponded to the expected structure of a polyoctenamer which contained 0.33 mol % of vinyl end groups and 0.29 mol % of cyclohexene end groups. Cis/trans double bond ratio: 21/79

(166) .sup.1H NMR (CDCl.sub.3, 500 MHz, 30° C.) δ (ppm): Polyoctenamer: 5.38, 5.34, 2.01, 1.96, 1.30; end groups: 5.81 (m, 1H, —CH2=CH—CH2-), 5.66 (d, 2H, CH2-CH═CH—CH2), 5.38-5.34 (m, 2H, —CH—CH═CH—CH2), 4.95 (m, 2H, CH2=CH—CH2-).

(167) Melting point: 59° C.

(168) Melting enthalpy: 81 J/g

(169) Molar mass M.sub.w: 114 700 g/mol

(170) Oligomer proportion (M<3000 g/mol): 1.2%

(171) Heat Treatment at 180° C.

(172) For analytical purposes 10 mL of this solution were dried in an aluminium dish in a vacuum drying cabinet over 20 h at 180° C. and a vacuum of 1 mbar after inertization with nitrogen. 2 g of white solid were obtained. The NMR spectrum of the solid partly corresponded to the expected structure of a polyoctenamer (see above) but the end groups (vinyl and cyclohexene end groups) were absent and unknown signals were observed in the olefin region. Cis/trans double bond ratio: 22/78

(173) Melting point: 50° C.

(174) Melting enthalpy: 72 J/g

(175) The markedly lower melting point and melting enthalpy compared to drying at 80° C. showed that the polymer was unstable at a temperature of 180° C. A trace elemental analysis showed that the polymer contained 8.6 ppm of ruthenium.

Example 8B (Inventive): Membrane Purification of Polyoctenamer in Toluene with Ru Catalyst and Addition of Ethyl Vinyl Sulfide then N-methylimidazole

(176) 0.8 L of the solution of 30% by weight of polyoctenamer in toluene (produced as per example 8A) was further diluted to 5% by weight with 4.2 L of toluene. The obtained 5 L of polymer solution was recirculated for 3 hours at 50° C. and then purified by diafiltration through a PuraMem® UF (cut-off about 35 000 Da) ultrafiltration polymer membrane from Evonik Resource Efficiency Gmbh. This was carried out using a crossflow filtration system with an 1812 membrane module (membrane area about 0.14 m.sup.2). The addition of fresh solvent was synchronized with the permeate flow so that the fill level in the feed container remained constant. The experiment was performed at 50° C. and 3 bar and altogether 15 L of fresh toluene were added (3 washing volumes in relation to the starting volume of the polymer solution), 5 L of polymer solution were obtained as retentate after this purification. 15 L of permeate solution were also obtained.

(177) Heat Treatment at 180° C.

(178) For analytical purposes 10 mL of the retentate (purified polymer solution) were dried in an aluminium dish in a vacuum drying cabinet over 20 h at 180° C. and a vacuum of 1 mbar after inertization with nitrogen. 2 g of white solid were obtained. The NMR spectrum of the solid corresponded to the expected structure of a polyoctenamer which contained 0.32 mol % of vinyl end groups and 0.28 mol % of cyclohexene end groups. Cis/trans double bond ratio: 21/79

(179) .sup.1H NMR (CDCl.sub.3, 500 MHz, 30° C.) δ (ppm): Polyoctenamer: 5.38, 5.34, 2.01, 1.96, 1.30; end groups: 5.81 (m, 1H, —CH2=CH—CH2-), 5.66 (d, 2H, CH2-CH═CH—CH2), 5.38-5.34 (m, 2H, —CH—CH═CH—CH2), 4.95 (m, 2H, CH2=CH—CH2-).

(180) Melting point: 59° C.

(181) Melting enthalpy: 81 J/g

(182) Molar mass M.sub.w: 113 800 g/mol

(183) Oligomer proportion (M<3000 g/mol): 0.4%

(184) The high melting point (>56° C.) and the high melting enthalpy (>75 J/g) showed that the purified polyoctenamer was stable under the temperature conditions at 180° C.

(185) The reduction in the oligomer proportion in the GPC compared to the starting solution (see example 3A) showed that this purification by ultrafiltration allowed separation of oligomers. A trace elemental analysis showed that the polymer contained only 1.2 ppm of ruthenium. In addition, no insoluble particles in the polymer solution were observed.

Example 9A (Comparative Example): Synthesis of Polyoctenamer in Toluene with Ru Catalyst and Addition of Butyl Vinyl Ether then Pyridine

(186) 800 mL of toluene, 300 g of cyclooctene (COE) and 1.03 g of vinyl cyclohexene (VCH) were charged into a dry 2 L glass reactor fitted with a mechanical stirrer under argon. The reaction mixture was heated to 50° C. and a solution of 24 mg of tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dimethylimidazol-2-ylidene](2-thienylmethyliden)ruthenium(II) dichloride (catalyst C3) in 5.4 mL of toluene was added. A temperature increase of 18° C. was observed and the reaction mixture became markedly more viscous. 2.7 g of butyl vinyl ether were added 15 min after catalyst addition. The reaction mixture was stirred for a further 15 min and 0.22 g of pyridine was added. After 30 min at 50° C. the contents of the reactor were discharged and a solution of 30% by weight of polyoctenamer in toluene was obtained.

(187) Heat Treatment at 80° C.

(188) For analytical purposes 10 mL of this solution were dried in an aluminium dish in a vacuum drying cabinet over 3 h at 80° C. and a vacuum of 1 mbar after inertization with nitrogen. 2 g of white solid were obtained. The NMR spectrum of the solid corresponded to the expected structure of a polyoctenamer which contained 0.28 mol % of vinyl end groups and 0.30 mol % of cyclohexene end groups. Cis/trans double bond ratio: 22/78

(189) .sup.1H NMR (CDCl.sub.3, 500 MHz, 30° C.) δ (ppm): Polyoctenamer: end 5.38, 5.34, 2.01, 1.96, 1.30; end groups: 5.81 (m, 1H, —CH2=CH—CH2-), 5.66 (d, 2H, CH2-CH═CH—CH2), 5.38-5.34 (m, 2H, —CH—CH═CH—CH2), 4.95 (m. 2H, CH2=CH—CH2-).

(190) Melting point: 57° C.

(191) Melting enthalpy: 78 Jig

(192) Molar mass M.sub.w: 108 000 g/mol

(193) Oligomer proportion (M<3000 g/mol): 1.7%

(194) Heat Treatment at 180° C.

(195) For analytical purposes 10 mL of this solution were dried in an aluminium dish in a vacuum drying cabinet over 20 h at 180° C. and a vacuum of 1 mbar after inertization with nitrogen. 2 g of white solid were obtained. The NMR spectrum of the solid partly corresponded to the expected structure of a polyoctenamer (see above) but the end groups (vinyl and cyclohexene end groups) were absent and unknown signals were observed in the olefin region. Cis/trans double bond ratio: 25/75

(196) Melting point: 29° C.

(197) Melting enthalpy: 59 J/g

(198) The markedly lower melting point and melting enthalpy compared to drying at 80° C. showed that the polymer was unstable at a temperature of 180° C. A trace elemental analysis showed that the polymer contained 8.4 ppm of ruthenium.

Example 9B (Inventive): Membrane Purification of Polyoctenamer in Toluene with Ru Catalyst and Addition of Butyl Vinyl Ether then Pyridine

(199) 0.8 L of the solution of 30% by weight of polyoctenamer in toluene (produced as per example 9A) was further diluted to 5% by weight with 4.2 L of toluene. The obtained 5 L of polymer solution was recirculated for 3 hours at 50° C. and then purified by diafiltration through a PuraMem® UF (cut-off about 35 000 Da) ultrafiltration polymer membrane from Evonik Resource Efficiency GmbH. This was carried out using a crossflow filtration system with an 1812 membrane module (membrane area about 0.14 m.sup.2). The addition of fresh solvent was synchronized with the permeate flow so that the fill level in the feed container remained constant. The experiment was performed at 50° C. and 3 bar and altogether 15 L of fresh toluene were added (3 washing volumes in relation to the starting volume of the polymer solution). 5 L of polymer solution were obtained as retentate after this purification. 15 L of permeate solution were also obtained.

(200) Heat Treatment at 180° C.

(201) For analytical purposes 10 mL of the retentate (purified polymer solution) were dried in an aluminium dish in a vacuum drying cabinet over 20 h at 180° C. and a vacuum of 1 mbar after inertization with nitrogen. 2 g of white solid were obtained. The NMR spectrum of the solid corresponded to the expected structure of a polyoctenamer which contained 0.26 mol % of vinyl end groups and 0.28 mol % of cyclohexene end groups, Cis/trans double bond ratio: 22/78

(202) .sup.1H NMR (CDCl.sub.3, 500 MHz, 30° C.) δ (ppm); polyoctenamer: 5.38, 5.34, 2.01, 1.96, 1.30; end groups: 5.81 (m, 1H, —CH2=CH—CH2-), 5.66 (d, 2H, CH2-CH═CH—CH2), 5.38-5.34 (m, 2H, —CH—CH═CH—CH2), 4.95 (m, 2H, CH2=CH—CH2-).

(203) Melting point: 57° C.

(204) Melting enthalpy: 78 J/g

(205) Molar mass M.sub.w: 120 000 g/mol

(206) Oligomer proportion (M<3000 g/mol): 0.5%

(207) The high melting point (>56° C.) and the high melting enthalpy (>75 J/g) showed that the purified polyoctenamer was stable under the temperature conditions at 180° C.

(208) The reduction in the oligomer proportion in the GPC compared to the starting solution (see example 3A) showed that this purification by ultrafiltration allowed separation of oligomers. A trace elemental analysis showed that the polymer contained only 1.0 ppm of ruthenium. In addition, no insoluble particles in the polymer solution were observed.

Example 10A: Synthesis of Polyoctenamer in Heptane with Tungsten/Aluminium Catalyst System and Addition of Butyl Vinyl Ether Followed by N-methylimidazole

(209) 585 mL of heptane, 100 g of cyclooctene (COE) and 0.34 g of vinyl cyclohexene (VCH) were charged into a dry 2 L glass reactor fitted with a mechanical stirrer under argon. The reaction mixture was heated to 50° C. and 0.4 mL of a solution of ethylaluminium dichloride (20% by weight) in heptane was added. Subsequently, 1 mL of a solution of tungsten hexachlorideipropylene oxide (1/3 mol/mol) in toluene (2.8% by weight of tungsten) were added slowly. 30 min after the catalyst addition 0.73 g of butyl vinyl ether were added and the mixture was stirred at 50° C. over 2 h. A temperature increase of 5° C. was observed and the reaction mixture became markedly more viscous. 0.91 g of butyl vinyl ether were added 15 min after catalyst addition. The reaction mixture was stirred for a further 15 min and 0.07 g of N-methylimidazole was added. After 30 min at 50° C. the contents of the reactor were discharged and a solution of 20% by weight of polyoctenamer in heptane was obtained.

Example 10B (Comparative Example): Membrane Purification of Polyoctenamer in Heptane with Tungsten/Aluminium Catalyst System and Addition of Butyl Vinyl Ether Followed by N-methylimidazole

(210) 1.25 L of the solution of 20% by weight of polyoctenamer in heptane (produced as per example 5A) was further diluted to 5% by weight with 3.75 L of heptane. The obtained 5 L of polymer solution was recirculated for 3 hours at 50° C. and then purified by diafiltration through a PuraMem® UF (cut-off about 35 000 Da) ultrafiltration polymer membrane from Evonik Resource Efficiency GmbH. This was carried out using a crossflow filtration system with an 1812 membrane module (membrane area about 0.14 m.sup.2). The addition of fresh solvent was synchronized with the permeate flow so that the fill level in the feed container remained constant. The experiment was performed at 50° C. and 3 bar and altogether 25 L of fresh heptane were added (5 washing volumes in relation to the starting volume of the polymer solution). 5 L of polymer solution were obtained as retentate after this purification. 25 L of permeate solution were also obtained.

(211) Heat Treatment at 180° C.

(212) For analytical purposes 10 mL of the retentate (purified polymer solution) were dried in an aluminium dish in a vacuum drying cabinet over 20 h at 180° C. and a vacuum of 1 mbar after inertization with nitrogen. 1.5 g of white solid were obtained. The NMR spectrum of the solid corresponded to the expected structure of a polyoctenamer which contained 0.25 mol % of vinyl end groups and 0.30 mol % of cyclohexene end groups, Cis/trans double bond ratio: 22/78

(213) .sup.1H NMR (CDCl.sub.3, 500 MHz, 30° C.) δ (ppm): Polyoctenamer: 5.38, 5.34, 2.01, 1.96, 1.30; end groups: 5.81 (m, 1H, —CH2=CH—CH2-), 5.66 (d, 2H, CH2-CH═CH—CH2), 5.38-5.34 (m, 2H, —CH—CH═CH—CH2), 4.95 (m, 2H, CH2=CH—CH2-).

(214) Melting point: 54° C.

(215) Melting enthalpy: 75 J/g

(216) Molar mass M.sub.w: 135 000 g/mol

(217) Oligomer proportion (M<3000 g/mol): 3.8%

(218) A trace elemental analysis showed that the polymer contained 250 ppm of tungsten, 125 ppm of aluminium and 110 ppm of chlorine.

(219) TABLE-US-00001 Summary Results after Addition after Membrane 180° C. heat Example Catalyst Solvent reaction filtration treatment  1A EADC/WCl.sub.6 heptane none no m.p. 54° C., 250 ppm W, 125 ppm Al, 110 ppm Cl  1B EADC/WCl.sub.6 heptane none 5 washing m.p. 54° C., volumes 250 ppm W, 125 ppm Al, 110 ppm Cl  2A C3 heptane none no m.p. 30° C., 10 ppm Ru  2B C3 heptane none 5 washing m.p. 30° C., volumes precipitation of grey particles  2C C3 heptane butyl vinyl ether 5 washing m.p. 49° C., volumes 3.5 ppm Ru  3A C3 heptane butyl vinyl ether no m.p. 29° C., then 2-amino-phenol 8.6 ppm Ru  3B* C3 heptane butyl vinyl ether 5 washing m.p. 59° C., then 2-amino-phenol volumes 0.2 ppm Ru  4A C3 heptane butyl vinyl ether then no m.p. 49° C., N-methylimidazole 8.4 ppm Ru  4B* C3 heptane butyl vinyl ether then 3 washing m.p. 57° C., N-methylimidazole volumes 0.3 ppm Ru  5A C3 toluene butyl vinyl ether no m.p. 35° C., then acetonitrile 8.5 ppm Ru  5B* C3 toluene butyl vinyl ether 3 washing m.p. 57° C., then acetonitrile volumes 2.1 ppm Ru  6A C3 toluene butyl vinyl ether no m.p. 30° C., then 2-amino-phenol 8.5 ppm Ru  6B* C3 toluene butyl vinyl ether 3 washing m.p. 59° C., then 2-amino-phenol volumes 0.7 ppm Ru  7A C3 toluene butyl vinyl ether then no m.p. 47° C., N-methylimidazole 8.8 ppm Ru  7B* C3 toluene butyl vinyl ether then 3 washing m.p. 60° C., N-methylimidazole volumes 0.3 ppm Ru  8A C3 toluene ethyl vinyl sulfide then no m.p. 50° C., N-methylimidazole 8.6 ppm Ru  8B* C3 toluene ethyl vinyl sulfide then 3 washing m.p. 59° C., N-methylimidazole volumes 1.2 ppm Ru  9A C3 toluene butyl vinyl ether no m.p. 29° C., then pyridine 8.4 ppm Ru  9B* C3 toluene butyl vinyl ether 3 washing m.p. 57° C., then pyridine volumes 1.0 ppm Ru 10B EADC/WCl.sub.6 heptane butyl vinyl ether then 5 washing m.p. 54° C., N-methylimidazole volumes 250 ppm W. 125 ppm Al, 110 ppm Cl *inventive EADC = Ethylaluminium dichloride, m.p. = melting point

(220) Polyoctenamer synthesized with tungsten catalyst and subsequently subjected to a membrane filtration showed a melting point below 57° C. High chlorine and metal proportions were also present (cf. example 1B). An addition of an alkyl vinyl ether and a compound A (example 10B) did not show any change in melting point and metal proportions.

(221) In the ruthenium-catalyzed production of polyoctenamer a membrane filtration without alkyl vinyl ether resulted in a precipitation of grey particles and in a very low melting point of the polyoctenamer of 30° C. (example 2B). When alkyl vinyl ether or alkyl vinyl sulfide was added without performing a membrane filtration the polymers were not thermally stable at 180° C. (melting point in examples 3A, 4A, 5A, 6A, 7A, 8A, 9A between 29° C. and 50° C.) and the metal proportion in the polymer was much higher.

(222) The combination of ruthenium catalyst, alkyl vinyl ether addition, compound A addition and membrane filtration resulted in a polyoctenamer which is thermally stable at 180° C. and has a high melting point of 57° C. to 60° C. and a low residual metal proportion.