Catalyst system for polymerization of an olefin

Patent metadata

Field	Value
Publication number	US-2016333121-A1
Application number	US-201415105873-A
Country	US
Kind code	A1
Filing date	Dec 19, 2014
Priority date	Dec 20, 2013
Publication date	Nov 17, 2016
Grant date	—

Abstract

The present invention relates to a process for the preparation of a catalyst system suitable for olefin polymerization wherein the external electron donor is n-propyltriethoxysilane, and a catalyst system obtained or obtainable by said process. The invention also relates to a process for preparing a polyolefin using said catalyst system. The invention further relates to a polyolefin, in particular polyprolyene, obtainable by such a process, and shaped articles manufactured from such a polymer. The polymers produced using the catalyst system exhibit low volatiles and therefore have a reduced environmental and health impact.

First claim

1 . A process for the preparation of a catalyst system suitable for olefin polymerization, said process comprising:
providing a magnesium-based support; optionally activating said magnesium-based support; contacting said magnesium-based support with a Ziegler-Natta type catalytic species, and optionally one or more internal electron donors to yield a procatalyst, and contacting said procatalyst with a co-catalyst and at least one external donor; wherein the at least one external electron donor is n-propyltriethoxysilane.

2 . The process according to claim 1 , wherein the process comprises:
i) preparing a magnesium-based support by heating a carbonated magnesium compound of the formula MgR′R″xCO 2 wherein R′ is an alkoxide or aryloxide group, R″ is an alkoxide group, aryloxide group or halogen, and x has a value between about 0.1 and 2.0 to a temperature above 100° C. for a period of time sufficient to cause complete loss of CO 2 ; ii) contacting the resulting product with a halide of tetravalent titanium as the Ziegler-Natta type catalytic species in the presence of a halohydrocarbon and an internal electron donor; and iii) contacting the resulting halogenated product with a tetravalent titanium halide; and contacting said product obtained with a co-catalyst and at least one external donor; wherein the at least one external electron donor is n-propyltriethoxysilane.

3 . The process according to claim 1 , wherein the process comprises preparing a magnesium-based support by
halogenating a magnesium compound of the formula MgR′R″, wherein R′ and R″ are alkoxide groups containing from 1 to 8 carbon atoms, with titanium tetrachloride, in the presence of: 1) an aromatic halohydrocarbon containing from 6 to 12 carbon atoms and from 1 to 2 halogen atoms and; 2) a polycarboxylic acid ester derived from a branched or 4 of 12 unbranched monohydric alcohol containing from 1 to 12 carbon atoms, and 3) a monocyclic or polycyclic aromatic compound containing from 8 to 20 carbon atoms and two carboxyl groups which are attached to ortho carbon atoms of the ring structure and contacting the product obtained with a co-catalyst and at least one external donor; wherein the at least one external electron donor is n-propyltriethoxysilane.

4 . The process according to claim 1 , wherein the process comprises:
preparing the magnesium-based support by forming a solution of a magnesium-containing species from a magnesium carbonate or a magnesium carboxylate, precipitating solid particles from such magnesium-containing solution by treatment with a transition metal halide and an organosilane having a formula: RnSiR′ 4 ″n, wherein n=0 to 4 and wherein R is hydrogen or an alkyl, a haloalkyl or aryl radical containing one to about ten carbon atoms or a halosilyl radical or haloalkylsilyl radical containing one to about eight carbon atoms, and R′ is OR or a halogen, reprecipitating such solid particles from a mixture containing a cyclic ether, and contacting the product obtained with a co-catalyst and at least one external donor; wherein the at least one external electron donor is n-propyltriethoxysilane.

5 . The process according to claim 1 , wherein the process comprises:
A) providing said procatalyst obtainable via a process comprising:
i) contacting a compound R 4 z MgX 4 2-z with an alkoxy- or aryloxy-containing silane compound to give a first intermediate reaction product, being a solid Mg(OR′) x X 1 2-x , wherein: R 4 is the same as R 1 being a linear, branched or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof; wherein said hydrocarbyl group is substituted or unsubstituted, optionally comprises one or more heteroatoms and has between 1 and 20 carbon atoms; X 4 and X 1 are each independently selected from fluoride (F − ), chloride (Cl − ), bromide (Br − ) or iodide (I − ); z is in a range of larger than 0 and smaller than 2, being 0<z<2;
ii) optionally contacting the solid Mg(OR 1 ) x X 2-x obtained in step i) with at least one activating compound selected from activating electron donor compounds and metal alkoxide compounds of formula M 1 (OR 2 ) v-w (OR 3 ) w or M 2 (OR 2 ) v-w (R 3 ) w , to obtain a second intermediate product; wherein M 1 is a metal selected from Ti, Zr, Hf, Al or Si; M 2 is a metal being Si; v is the valency of M 1 or M 2 ; R 2 and R 3 are each a linear, branched or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof; wherein said hydrocarbyl group substituted or unsubstituted, optionally comprises one or more heteroatoms, and has between 1 and 20 carbon atoms;
iii) contacting the first or second intermediate reaction product, obtained respectively in step i) or ii), with a halogen-containing Ti-compound and optionally an internal electron donor to obtain said procatalyst;
B) contacting said procatalyst with a co-catalyst and at least one external electron donor being n-propyltriethoxysilane.

6 . The process according to claim 1 , wherein the process is essentially phthalate free.

7 . The process according to claim 1 , wherein an internal donor is selected from aminobenzoates represented by Formula XI:

wherein:
R 80 , R 81 , R 82 , R 83 , R 84 , R 85 , and R 86 are independently selected from hydrogen, C 1 -C 10 straight and branched alkyl; C 3 -C 10 cycloalkyl; C 6 -C 10 aryl; and C 7 -C 10 alkaryl and aralkyl group;

wherein R 81 and R 82 is each a hydrogen atom and R 83 , R 84 , R 85 and R 86 are independently selected from a group consisting of C 1 -C 10 straight and branched alkyl; C 3 -C 10 cycloalkyl; C 6 -C 10 aryl; and C 7 -C 10 alkaryl and aralkyl group;
wherein when one of R 83 and R 84 and one of R 85 and R 86 has at least one carbon atom, then the other one of R 83 and R 84 and of R 85 and R 86 is each a hydrogen atom;
wherein R 87 is selected from a group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, phenyl, benzyl, substituted benzyl and halophenyl group; and
wherein R 88 is selected from the group consisting of C 6 -C 10 aryl; and C 7 -C 10 alkaryl and aralkyl group.

8 . Process according to claim 1 , wherein the internal electron donor is selected from 4-[benzoyl(methyl)amino]pentan-2-yl benzoate; 2,2,6,6-tetramethyl-5-(methylamino)heptan-3-ol dibenzoate; 4-[benzoyl (ethyl)amino]pentan-2-yl benzoate, 4-(methylamino)pentan-2-yl bis (4-methoxy)benzoate); 3-[benzoyl(cyclohexyl)amino]-1-phenylbutyl benzoate; 3-[benzoyl(propan-2-yl)amino]-1-phenylbutyl; 4-[benzoyl(methyl)amino]-1,1,1-trifluoropentan-2-yl; 3-(methylamino)-1,3-diphenylpropan-1-ol dibenzoate; 3-(methyl)amino-propan-1-ol dibenzoate; 3-(methyl)amino-2,2-dimethylpropan-1-ol dibenzoate, and 4-(methylamino)pentan-2-yl bis-(4-methoxy)benzoate).

9 . Process according to claim 1 , wherein the internal electron donor is activated by an activator.

10 . A catalyst system obtained by the process of claim 1 .

11 . A process for preparing a polyolefin, comprising contacting at least one olefin with the catalyst system of claim 10 .

12 . A polyolefin obtained by the process of claim 11 .

13 . A propylene homopolymer, a propylene-olefin copolymer, or a heterophasic propylene copolymer characterized by:
having a melt flow index in the range from 30 to 1000 as determined according to ISO 1133: 2005 at 230° C. with 2.16 kg load; a ratio of an oligomer con

Assignees

• Batinas-Geurts Aurora Alexandra
• Zuideveld Martin Alexander
• Saudi Basic Ind Corp
• Sabic Global Technologies Bv

Inventors

• Batinas-Geurts Aurora Alexandra
• Zuideveld Martin Alexander

Classifications

• C08L23/12

  Polypropene · CPC title

• C08F10/06 Primary

  Propene · CPC title

• C08F210/16 Primary

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F2410/01

  Additive used together with the catalyst, excluding compounds containing Al or B · CPC title

• C08F2500/12

  Melt flow index or melt flow ratio · CPC title