Nova Patents
EP1539841B1

Polymer production at supercritical conditions

Abstract

This record has no abstract on file.

EP1539841B1, drawing sheet 1
Sheet 1 of 38

Term

Term ended

Expired 22 September 2023, 3 years ago.

  1. Priority
  2. Filed
  3. Granted
  4. Expired
  5. Today

17 claims: 10 independent, 7 dependent

  1. 1
    A process to polymerize olefins comprising contacting, in a polymerization system comprising propylene, any comonomer present, any diluent or solvent present, and the polymer product:1) a catalyst system of (i) a metallocene catalyst compound, a bisamide catalyst compound and/or a bisimide catalyst compound, and (ii) an activator, 2) propylene in an amount of 50 wt % or more of the polymerization system, 3) optionally comonomer, and 4) optionally a diluent and/or solvent, at a temperature above the cloud point temperature of the polymerization system up to 210 °C and a pressure of between 10 and 120 MPa and above the cloud point pressure of the polymerization system to provide a propylene derived polymer, which is a homopolymer of propylene or a copolymer of propylene comprising less than 30 wt% of ethylene, having a melting point of 70 to 165 °C. between
  2. 2
    Process according to Claim 1 wherein the pressure of the polymerization system is between 15 and 50 MPa.
  3. 3
    Process according to Claim 1 or Claim 2 wherein solvent and/or diluent is present in the polymerization system at 0 to 25 wt %.
  4. 4
    Process according to any of the preceding claims wherein the propylene is present in the polymerization system at 55 wt % or more.
  5. 5
    Process according to any of the preceding claims wherein the polymerization medium of the monomer, comonomers, solvents and diluents comprises from 55-100 wt% propylene monomer and from 0 to 45 wt% of comonomer comprising at least one comonomer selected from ethylene, but-1-ene, hex-1-ene, 4-methylpent-1-ene and 1-octene.
  6. 6
    Process according to Claim 1 wherein the catalyst compound comprises a metallocene catalyst compound and the pressure of the polymerization system is less than 100 MPa, and/or the temperature is between 140 to 180°C.
  7. 7
    Process according to Claim 1 wherein the polymerization temperature is 105 to 150 °C.
  8. 8
    Process according to any of the preceding claims wherein the catalyst compound is represented by the formula:where M 1 is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten;R 1 and R 2 are identical or different and are selected from hydrogen atoms, C 1 -C 10 alkyl groups, C 1 -C 10 alkoxy groups, C 6 -C 10 aryl groups, C 6 -C 10 aryloxy groups, C 2 -C 10 alkenyl groups, C 2 -C 40 alkenyl groups, C 7 -C 40 arylalkyl groups, C 7 -C 40 alkylaryl groups, C 8 -C 40 arylalkenyl groups, OH groups or halogen atoms;or conjugated dienes that are optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl groups or hydrocarbyl tri(hydrocarbyl)silylhydrocarbyl groups;R 3 -R 12 are the same or different and are selected from hydrogen atoms, halogen atoms, C 1 -C 10 halogenated or unhalogenated alkyl groups, C 6 -C 10 halogenated or unhalogenated aryl groups, C 2 -C 10 halogenated or unhalogenated alkenyl groups, C 7 -C 40 halogenated or unhalogenated arylalkyl groups, C 7 -C 40 halogenated or unhalogenated alkylaryl groups, C 8 -C 40 halogenated or unhalogenated arylalkenyl groups, -NR' 2 , -SR', -OR', -OSiR' 3 or -PR' 2 radicals in which R' is one of a halogen atom, a C 1 -C 10 alkyl group, or a C 6 -C 10 aryl group;or two or more adjacent radicals R 5 to R 7 together with the atoms connecting them can form one or more rings;R 13 is selected from -B(R 14 )-, -Al(R 14 )-, -Ge-, -Sn-, -O-, -S-, -SO-, -SO 2 -, -N(R 14 )-, -CO-, -P(R 14 )- -P(O)(R 14 )-, - B(NR 14 R 15 )- and -B[N(SiR 14 R 15 R 16 ) 2 ]-, R 14 , R 15 and R 16 are each independently selected from hydrogen, halogen, C 1 -C 20 alkyl groups, C 6 -C 30 aryl groups, C 1 -C 20 alkoxy groups, C 2 -C 20 alkenyl groups, C 7 -C 40 arylalkyl groups, C 8 -C 40 arylalkenyl groups and C 7 -C 40 alkylaryl groups, or R 14 and R 15 , together with the atom(s) connecting them, form a ring;and M 3 is selected from carbon, silicon, germanium and tin, or R 13 is represented by the formula: wherein R 17 to R 24 are as defined for R 1 and R 2 , or two or more adjacent radicals R 17 to R 24 , including R 20 and R 21 , together with the atoms connecting them form one or more rings;M 2 is carbon, silicon, germanium, or tin.
  9. 9
    Process according to any of the preceding claims wherein the metallocene catalyst compound comprises µ-dimethyl silylbis(-2-methyl, 4-phenylindenyl) zirconium dichloride or dimethyl.
  10. 10
    Process according to any of the preceding claims wherein the activator comprises alumoxane or a modified alumoxane or a non-coordinating anion.
  11. 11
    Process according to any of claims 1 to 10 wherein the polymerization takes place in a tubular reactor having a length-to-diameter ratios of 4:1 to 20:1 and the reactor contains up to six different injection positions.
  12. 12
    Process according to any of claims 1 to 10 wherein the polymerization takes place in an autoclave reactor.
  13. 13
    Process according to Claim 12 wherein the process comprises (a) continuously feeding olefin monomers, catalyst compound, and activator to the autoclave reactor;(b) continuously polymerizing the monomers in a polymerization zone reactor under elevated pressure;(c) continuously removing the polymer/monomer mixture from the reactor, (d) continuously separating monomer from molten polymer;(e) reducing pressure to form a monomer-rich and a polymer-rich phase;and (f) separating monomer from the polymer.
  14. 14
    Process according to any of Claims 1 to 10 wherein the polymerization takes place in a loop reactor.
  15. 16
    Process according to any of Claim 11 to 15 wherein the polymerization takes place in multiple reactors which may be a combination of a tubular reactor and then an autoclave reactor or a combination of a tubular reactor and then a loop reactor.
  16. 17
    Process according to any of the preceding claims wherein the propylene derived polymer has:a) a 1,3 regio defect population of greater than 5 per 10,000 monomer units;b) a melting point of 140-165 °C;c) branching index of 0.97 or less, and d) weight average molecular weight of from 20,000-1,000,000.
Independent claims16