Process for the preparation of a copolymer of ethylene

Abstract

A process for the preparation of an elastomeric polymer of ethylene which comprises polymerizing, in suspension, a mixture of monomers comprising ethylene, at least one a-olefin having from 3 to 12 carbon atoms, possibly at least one non-conjugated diene having from 4 to 20 carbon atoms, in the presence of a catalytic system comprising: a suspension in oil of at least one catalyst selected from compounds containing vanadium; at least one co-catalyst, as such, selected from compounds containing aluminum; at least one activator, as such, selected from compounds containing chlorine.

Claims

1. A process for the preparation of an elastomeric polymer of ethylene which comprises polymerizing, in suspension, a mixture of monomers comprising ethylene, at least one -olefin having from 3 to 12 carbon atoms, optionally at least one non-conjugated diene having from 4 to 20 carbon atoms, in the presence of a catalytic system comprising: an oil suspension of at least one catalyst selected from compounds containing vanadium; at least one co-catalyst in the absence of organic solvents, selected from compounds containing aluminium; at least one activator in the absence of organic solvents, selected from compounds containing chlorine.

2. The process for the preparation of an elastomeric polymer of ethylene according to claim 1, wherein said -olefin having from 3 to 12 carbon atoms is selected from: propylene, 1-butene, iso-butene, 1-pentene, 1-hexene, 1-octene, styrene, -methylstyrene; or mixtures thereof.

3. The process for the preparation of an elastomeric polymer of ethylene according to claim 1, wherein said non-conjugated diene having from 4 to 20 carbon atoms is selected from: linear non-conjugated dienes; branched non-conjugated dienes; non-conjugated dienes containing an alicyclic ring; non-conjugated dienes containing several alicyclic rings, condensed or bridged; and mixtures thereof.

4. The process for the preparation of an elastomeric polymer of ethylene according to claim 1, wherein said elastomeric polymer comprises: (a) from 40% by weight to 80% by weight of ethylene; (b) from 20% by weight to 60% by weight of at least one -olefin; (c) from 0% by weight to 15% by weight of at least one non-conjugated diene; the sum of (a)+(b)+(c) being equal to 100.

5. The process for the preparation of an elastomeric polymer of ethylene according to claim 1, wherein said oil is selected from: paraffinic oil, naphthene oils, polybutene-based oils, polypropylene-based oils, or mixtures thereof.

6. The process for the preparation of an elastomeric polymer of ethylene according to claim 1, wherein said catalyst is present in said oil suspension in a catalytic amount ranging from 3% by weight to 20% by weight with respect to the total weight of said oil suspension.

7. The process for the preparation of an elastomeric polymer of ethylene according to claim 1, wherein said catalyst is selected from vanadium compounds in oxidation state +3 to +5; vanadyl alkoxyhalides or vanadyl alkoxides having formula VOCl.sub.x(OR).sub.3-x wherein R represents a linear or branched C.sub.1-C.sub.20 alkyl group and x is an integer ranging from 0 to 3; vanadium and vanadyl acetylacetonates; complexes between vanadium halides and Lewis bases; or mixtures thereof.

8. The process for the preparation of an elastomeric polymer of ethylene according to claim 7, wherein said catalyst is selected from vanadium triacetylacetonate [V(acac).sub.3] and vanadyl acetylacetonate [VO(acac).sub.2].

9. The process for the preparation of an elastomeric polymer of ethylene according to claim 1, wherein said co-catalyst is selected from compounds containing aluminium having general formula (I):
(R.sub.1).sub.3-nAlY.sub.n(I) wherein: R.sub.1 represents a linear or branched C.sub.1-C.sub.20 alkyl group; Y represents a halogen atom; or a linear or branched C.sub.1-C.sub.20 alkoxyalkyl group; n represents an integer ranging from 0 to 2.

10. The process for the preparation of an elastomeric polymer of ethylene according to claim 9, wherein said co-catalyst is diethyl aluminium chloride (DEAC).

11. The process for the preparation of an elastomeric polymer of ethylene according to claim 1, wherein the molar ratio between the aluminium present in the co-catalyst and the vanadium present in the catalyst ranges from 1 to 200.

12. The process for the preparation of an elastomeric polymer of ethylene according to claim 1, wherein said activator is selected from compounds containing chlorine having general formula (II): ##STR00003## wherein: R.sub.2 represents a linear or branched C.sub.1-C.sub.20 alkyl group, optionally substituted; a C.sub.5-C.sub.20 aryl group, optionally substituted; a C.sub.3-C.sub.20 cycloalkyl group, optionally substituted; with the proviso that the group C(O)OR.sub.2 can be substituted with a derivative of carbonic acid, a keto group or a nitrile group; R.sub.3, R.sub.4 and R.sub.5, the same or different, are selected from: (a) R.sub.2; (b) halogens; (c) hydrogen; (d) linear or branched C.sub.1-C.sub.20 alkyl groups, optionally substituted; (e) C.sub.3-C.sub.20 cycloalkyl groups, optionally substituted; (f) C.sub.5-C.sub.20 aryl groups, optionally substituted; (g) C.sub.1-C.sub.20 alkyloxyl groups, optionally substituted; (h) C.sub.5-C.sub.20 aryloxyl groups, optionally substituted; (i) C(O)OR.sub.6 groups wherein R.sub.6 is a C.sub.1-C.sub.20 hydrocarbon group; with the proviso that: (i) at least one of R.sub.3, R.sub.4 and R.sub.5 is selected from halogens, and (ii) in the activator having formula (II), all the following conditions are not satisfied: R.sub.2 is a C.sub.1-C.sub.6 alkyl group, R.sub.3 is a C.sub.1-C.sub.6 alkyl group or a C.sub.1-C.sub.6 alkoxyl group, R.sub.4 is chlorine, bromine or hydrogen, R.sub.5 is chlorine or bromine.

13. The process for the preparation of an elastomeric polymer of ethylene according to claim 12, wherein said activator is ethyl trichloride acetate (ETA) or dichlorophenyl ethyl acetate (DCPAE).

14. The process for the preparation of an elastomeric polymer of ethylene according to claim 1, wherein the molar ratio between the activator and the vanadium present in the catalyst ranges from 0.5 to 10.

15. The process for the preparation of an elastomeric polymer of ethylene according to claim 1, wherein said process is carried out in the presence of at least one molecular weight regulator selected from hydrogen, or from compounds having general formula (III):
M(R.sub.7).sub.n(III) wherein: M represents a metal selected from group 2 or group 12 of the Periodic Table of Elements; R.sub.7 represents a linear or branched C.sub.1-C.sub.12 alkyl group; n represents the valence number of the metal M.

16. The process for the preparation of an elastomeric polymer of ethylene according to claim 1, wherein said process is carried out at a temperature ranging from 0 C. to 100 C.

17. The process for the preparation of an elastomeric polymer of ethylene according to claim 1, wherein said process is carried out at a pressure ranging from 0 bar to 50 bar.

18. The process for the preparation of an elastomeric polymer of ethylene according to claim 1, wherein said process is carried out for a time ranging from 10 minutes to 4 hours.

Description

EXAMPLES

(1) The characterization and analysis techniques listed hereunder were used:

(2) Composition of the Elastomeric Polymer

(3) The composition of the elastomeric polymer was determined by means of FTIR infrared spectroscopy (Fourier Transform Infra Red), using a method based on the standard ASTM D3900. For this purpose, a film of the elastomeric polymer was prepared by pressing at 150 C. and the relative spectra were registered.

(4) The propylene content (weight %) was determined by integration of the absorption peaks at 720 cm.sup.1 and at 1155 cm.sup.1, and effecting the calculation using relations obtained empirically.

(5) The content of 5-ethylidene-2-norbornene (ENB) (weight %) was determined by means of FTIR infrared spectroscopy (Fourier Transform Infra Red), using a method based on the standard ASTM D6047.

(6) Viscosity of the Polymer

(7) The Mooney viscosity (ML 1+4 @ 125 C.) was determined according to the standard ASTM D1646.

Examples 1-4

(8) Two ethylene-propylene polymers and two ethylene-propylene-5-ethylidene-2-norbornene (ENB) polymers were prepared, operating as described hereunder.

(9) The polymerization reaction in suspension, was carried out, in continuous, in a 40 l reactor, equipped with rotating blades, an anchor scraper and discharge from the bottom.

(10) Said reactor was fed with: liquid propane (inert diluent) (Lyondelbasell); liquid propylene (monomer) (Polimeri Europa); gaseous ethylene (monomer) (Polimeri Europa); liquid 5-ethylidene-2-norbornene (ENB) (monomer) (Ineos); gaseous hydrogen (molecular-weight regulator) (Sapio); a suspension of vanadium acetylacetonate V(acac).sub.3 (Reactana) in paraffinic oil (8% by weight of vanadium acetylacetonate with respect to the total weight of the suspension) (catalyst); diethylaluminium chloride (DEAC) (as such; purity degree 98.5%; molar ratio Al/Cl: 1; Albemarle) (co-catalyst); dichlorophenyl ethyl acetate (DCPAE) (as such; purity degree 97%; Chem Solutions) (activator).

(11) Table 1 indicates the operative conditions used: feeding of the compounds to the reactor, temperature and pressure.

(12) The average residence time of the compounds in the reactor was 1.5 hours. The suspension of elastomeric polymer obtained was discharged from the bottom of the reactor and sent, in continuous, to the strippers filled with water at 120 C., to which steam was also sent, thus obtaining the evaporation of the hydrogen, propane and non-reacted monomers (propylene and ethylene).

(13) The non-reacted diethyl aluminium chloride (DEAC) and dichlorophenyl ethyl acetate (DCPAE), were also neutralized and decomposed in the above strippers, with a solution of sodium hydroxide (NaOH) and with the consequent formation of aluminium hydroxide/aluminium oxide [Al(OH).sub.3/Al.sub.2O.sub.3], acetic acid/acetic anhydride [CH.sub.3COOH/(CH.sub.3CO).sub.2O] and sodium chloride (NaCl).

(14) The water leaving the strippers, which also contains traces of non-reacted vanadium, was collected and sent for water treatment.

(15) The elastomeric polymer obtained was subjected to the characterizations described above and the results obtained are indicated in Table 1.

(16) TABLE-US-00001 TABLE 1 Example 1 Example 2 Example 3 Example 4 Temperature ( C.) 20.0 22.5 18.0 24.0 Pressure (bar) 10.0 10.0 9.5 10.5 Propylene.sup.(1) (kg//h) 6.4 11.2 5.6 10.8 Propane.sup.(2) (kg/h) 12.5 6.3 11.0 9.0 Ethylene.sup.(3) (kg/h) 0.80 0.35 0.60 0.50 ENB.sup.(4) (ml/h) 250.0 180.0 Hydrogen.sup.(5) (g/h) 2.80 0.20 2.34 0.02 Purge.sup.(6) (kg/h) 1.60 1.60 1.60 1.60 V(acac).sub.3.sup.(7) (mmol/h) 0.083 0.181 0.107 0.259 DEAC.sup.(8) (mmol/h) 7.45 10.85 9.65 7.75 Molar ratio Al/V.sup.(9) 90 60 90 30 DCPAE.sup.(10) (mmol/h) 0.50 1.0 0.53 1.53 Molar ratio DCPAE/V.sup.(12) 6 6 5 5 Propylene Content 29.5 49.0 35.0 40.0 (% by weight) ENB content 2.1 4.1 (% by weight) Mooney Viscosity 60.0 77.0 58.0 75.0 .sup.(1)liquid propylene (monomer); .sup.(2)liquid propane (inert diluent); .sup.(3)gaseous ethylene (monomer); .sup.(4)liquid 5-ethylidene-2-norbornene (monomer); .sup.(5)gaseous hydrogen (molecular-weight regulator); .sup.(6)purge of the gas phase; .sup.(7)suspension of vanadium acetylacetonate V(acac).sub.3 in paraffinic oil (8% by weight of vanadium acetylacetonate with respect to the total weight of the suspension) (catalyst); .sup.(8)diethyl aluminium chloride (as such; degree of purity 98.5%) (co-catalyst); .sup.(9)molar ratio between the aluminium present in the co-catalyst and the vanadium present in the catalyst; .sup.(10)dichlorophenyl ethyl acetate (as such; degree of purity 97%) (activator); .sup.(11)molar ratio between the activator and vanadium present in the catalyst.