Process for the preparation of porous polymers and polymers obtainable thereof

• US 7,183,332 B2
• Filed: 12/21/2001
• Issued: 02/27/2007
• Est. Priority Date: 12/22/2000
• Status: Expired due to Fees

• Current Assignee: Basell Poliolefine Italia Srl (Lyondellbasell Industries NV)
• Original Assignee: Basell Poliolefine Italia Srl (Lyondellbasell Industries NV)
• Inventors: Fusco, Ofelia, Baruzzi, Giovanni, Ferraro, Angelo, Stewart, Constantine A.
• Primary Examiner(s): ZEMEL, IRINA SOPJIA
• Application Number:
  US10/450,603
• Publication Number:
  US 20040092615A1
• Time in Patent Office: 1,894 Days
• Field of Search: 521/143, 521/144, 521/142, 526/160, 526/346, 526/348.6, 526/351, 526/943
• US Class Current: 521/142
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 10/06 Propene
• CPC Class Codes: C08F 110/06 Propene
• CPC Class Codes: C08F 2/001 Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer C08F295/00, C08F297/00 take precedence
• CPC Class Codes: C08F 2500/17 Viscosity
• CPC Class Codes: C08F 2500/18 Bulk density
• CPC Class Codes: C08F 2500/24 Polymer with special particle form or size
• CPC Class Codes: C08F 4/027 Polymers
• CPC Class Codes: Y10S 526/943 Polymerization with metallocene catalysts

Abstract

A process for preparing porous olefin polymers comprising bringing into contact in a polymerization reactor, at a temperature T¹, one or more olefins of the formula (I) CH₂═CHR¹, R¹ being hydrogen, a C₁–C₂₀-alkyl or a C₆–C₁₂-aryl group, with a catalyst obtained by reacting a solid catalyst component in the form of spheroidal particles comprising a compound of Ti or V not containing metal-π bonds and a Mg halide, optionally containing one or more electron donor compounds, with an aluminum-alkyl (Al-alkyl) compound, then raising the temperature up to the polymerization temperature, said process being characterized in that: a) if the temperature T¹ is lower than 40° C., the temperature is raised up to the polymerization temperature is such a way that, for a time of at least one minute after the introduction temperature in such a way that, for a time of at least one minute after the introduction of the catalyst system into the reactor, the temperature of the reaction T² fulfills the following condition of formula (II) wherein m is the time expressed in minutes employed for reaching the temperature T²; or b) if temperature T¹ is 40° C. or higher, the reactor is maintained for a time of at least one minute at a temperature of at least 40° C.

Claims

1. A process for preparing porous olefin polymers, having a porosity of greater than 0.54 cc/g, comprising putting into contact in a polymerization reactor having a reactor temperature initially at a temperature T¹, one or more olefins of formula CH₂═

CHR¹, R¹ being hydrogen, a C₁–

C₂₀-alkyl or a C₆–

C₁₂-aryl group with a catalyst obtained by reacting a solid catalyst component in the form of spheroidal particles comprising a compound of Ti or V not containing metal -π

bonds and a Mg halide, optionally containing one or more electron donor compounds, with an aluminum-alkyl (Al-alkyl) compound, then raising the reactor temperature up to a polymerization temperature, wherein

(I) if the temperature T¹ is lower than 40°

C., the reactor temperature is raised up to the polymerization temperature in such a way that, for a time of at least one minute after the introduction of the catalyst system into the reactor, the reactor temperature is raised up to T² under the following condition;

2. The process according to claim 1 wherein T¹ ranges from 28°

C. to the polymerization temperature.

3. The process according to claim 1 wherein m is between 1 and 5 minutes.

4. The process according to claim 1 wherein polymerization is carried out at a temperature ranging generally between 40°

and 150°

C.

5. The process of claim 1 wherein under (II) the reactor temperature is maintained for a time of between 1 and 5 minutes at a temperature ranging from 45°

C. to 65°

C.

6. A solid catalyst system obtained by contacting in any order:

(A) a porous polymer, having a porosity of greater than 0.54 cc/g, obtained in a process comprising putting into contact in a polymerization reactor having a reactor temperature initially at a temperature T¹, one or more olef ins of formula CH₂═

CHR¹, R¹ being hydrogen, a C₁–

C₂₀-alkyl or a C₆–

C₁₂-aryl group with a catalyst obtained by reacting the solid catalyst component in the form of spheroidal particles comprising a compound of Ti or V not containing metal-π

bonds and a Mg halide, optionally containing one or more electron donor compounds, with an aluminum-alkyl (Al-alkyl) compound, then raising the reactor temperature up to a polymerization temperature, wherein

(I) if the temperature T¹ is lower than 40°

C., the reactor temperature is raised up to the polymerization temperature in such a way that, for a time of at least one minute after the introduction of the catalyst system into the reactor, the reactor temperature is raised up to T₂ under the following condition;

7. The solid catalyst system according to claim 6 wherein the suitable catalyst component is selected from compounds of a transition metal M selected from the Groups 3 to 10 of the Periodic Table of the Elements (new IUPAC version).

8. The solid catalyst system according to claim 7 wherein the suitable catalyst component is selected from the group consisting of:

(a) compounds of Ti or V not containing a metal-π

bond;

(b) compounds of transition metal M containing at least a M-π

bond having a general formula (I)

QL_lZMX¹_p  

 

(I)

wherein Q is selected from substituted or unsubstituted cyclopentadienyl radicals, which can carry one or more condensed cycles, which can contain one or more heteroatoms belonging to Groups 13–

17 of the Periodic Table of the Elements;

Z has the same meaning of Q or it can also be ═

NR⁶, —

O—

, —

S— and

═

PR⁶, R⁶ being selected from hydrogen, a C₁–

C₂₀-alkyl, C₃–

C₂₀-cycloalkyl, C₂–

C₂₀-alkenyl, C₆–

C₂₀-aryl, C₇–

C₂₀-alkylaryl or C₇–

C₂₀-arylalkyl radical which can contain one or more heteroatoms belonging to Groups 13 –

17 of the Periodic Table of the Elements;

L is a divalent bridge connecting the moieties Q and Z;

M is an atom of transition metal selected from the Groups 3 to 10 or the lanthanide or actinide groups of the Periodic Table of the Elements (new TUPAC version);

X¹, same or different, is a ligand selected from hydrogen, a halogen, R⁹, OR⁹, OSO₂CF₃, OCOR⁹, SR⁹, NR⁹₂ or PR⁹₂ group, wherein R⁹ is selected from hydrogen, a C₁–

C₂₀-alkyl, C₃–

C₂₀-cycloalkyl, C₂–

C₂₀-alkenyl, C₆–

C₂₀-aryl, C₇–

C₂₀-alkylaryl or C₇–

C₂₀-arylalkyl radical, optionally containing one or more heteroatoms belonging to Groups 13–

17 of the Periodic Table of the Elements;

p is an integer of from 0 to 3;

1 is 0 or 1; and

(c) a late transition metal complex of formula (II) or (III);

L^aM^aX^a_p′

X^a′

_s′

 

 

(II)

L^aM^aA^a  

 

(III)

wherein M^a is a metal belonging to Group 8, 9, 10 or 11 of the Periodic Table of the Elements (new IUPAC notation);

L^a is a bidentate or tridentate ligand of formula (VI);

9. The solid catalyst system according to claim 6 wherein the suitable co-catalyst comprises at least one of Al-alkyl compounds, alumoxanes and a compound that forms an alkylmetallocene cation.

10. A process for polymerization of one or more olef ins of formula CH₂═

CHR¹, R¹ being hydrogen, a C₁–

C₂₀-alkyl or a C₆–

C₁₂-aryl group, comprising the following steps;

(A) polymerizing said olefin CH₂═

CHR¹, in one or more reactors, by a process comprising putting into contact in a polymerization reactor having a reactor temperature initially at a temperature T¹, one or more olef ins of formula CH₂═

CHR¹, R¹ being hydrogen, a C₁–

C₂₀-alkyl or a C₆–

C₁₂-aryl group with a catalyst obtained by reacting a solid catalyst component in the form of spheroidal particles comprising a compound of Ti or V not containing metal-π

bonds and a Mg halide, optionally containing one or more electron donor compounds, with an aluminum-alkyl (Al-alkyl) compound, then raising the reactor temperature up to a polymerization temperature, wherein

(I) if the temperature T¹ is lower than 40°

C., the reactor temperature is raised up to the polymerization temperature in such a way that, for a time of at least one minute after the introduction of the catalyst system into the reactor, the reactor temperature is raised up to T² under the following condition;

11. A process for polymerizing a heterophasic copolymer of propylene comprising the following steps:

(A) polymerizing, in at least one reactor, propylene or its mixtures with one or more olefins CH₂═

CHR⁴, R⁴ being hydrogen, a C₂–

C₂₀-alkyl or a C₆–

C₁₂-aryl group, by a process comprising putting into contact in a polymerization reactor having a reactor temperature initially at a temperature T¹, one or more olefins of formula CH₂═

CHR¹, R¹ being hydrogen, a C₁–

C₂₀-alkyl or a C₆–

C₁₂-aryl group with a catalyst obtained by reacting a solid catalyst component in the form of spheroidal particles comprising a compound of Ti or V not containing metal- π

bonds and a Mg halide, optionally containing one or more electron donor compounds, with an aluminum-alkyl (Al-alkyl) compound, then raising the reactor temperature up to a polymerization temperature, wherein

(I) if the temperature T¹ is lower than 40°

C., the reactor temperature is raised up to the polymerization temperature in such a way that, for a time of at least one minute after the introduction of the catalyst system into the reactor, the reactor temperature is raised up to T² under the following condition;

12. The process according to claim 11 wherein in step (C) ethylene is copolymerized with propylene and optionally with polyene.