US009868799B2 (12 ) United States Patent (10 ) Patent No. : US 9 ,868 , 799 B2 Siddiqui et al. (45 ) Date of Patent: Jan . 16 , 2018 ( 54 ) PROCATALYST FOR POLYMERIZATION OF 6 ,395 , 670 B1 5 / 2002 Morini et al. OLEFINS 9 , 663, 596 B2 5 / 2017 Taftaf et al. 9 , 688 , 790 B2 6 / 2017 Taftaf et al . 2010 /0130709 A1 5 / 2010 Chen et al. @(71 ) Applicants : SAUDI BASIC INDUSTRIES 2016 / 0311946 Al 10 /2016 Zuideveld et al. CORPORATION , Riyadh (SA ) ; 2016 / 0311950 A1 10 / 2016 Batinas- Geurts et al . SABIC GLOBAL TECHNOLOGIES 2016 /0326280 AL 11 /2016 Batinas -Geurts et al . B . V ., Bergen op Zoom (NL ) 2016 /0333121 AL 11 /2016 Batinas -Geurts et al . 2016 / 0340293 Al 11 /2016 Taftaf et al . @( 72 ) Inventors : Inaamul Haq Siddiqui, Riyadh (SA ) ; Khalid Abdullah Al- Bahily , Riyadh FOREIGN PATENT DOCUMENTS (SA ) ; Khalid Mohammed Al- Gahtani , EP 398698 A2 11 / 1990 Riyadh (SA ) EP 1086961 AL 5 / 2001 1283222 AL 2 / 2003 @(73 ) Assignees : SAUDI BASIC INDUSTRIES EP 1538167 AL 6 /2005 CORPORATION , Riyadh ( SA ) ; 1783145 Al 5 / 2007 EP 1222214 B1 7 / 2007 SABIC GLOBAL TECHNOLOGIES EP 1862480 A1 12 / 2007 B . V . , Bergen op Zoom (NL ) EP 1838741 B1 4 / 2011 WO 9632426 Al 10 / 1996 @( * ) Notice : Subject to any disclaimer, the term of this WO 9632427 Al 10 / 1996 patent is extended or adjusted under 35 WO 0123441 A1 4 /2001 WO 2006010414 Al 2 / 2006 U . S . C . 154 (b ) by 0 days . WO 2006056338 A1 6 / 2006 WO 2007134851 A1 11 / 2007 @(21 ) Appl. No. : 15 /104 ,808 wo 2008 -077770 A1 7 / 2008 WO 2011106494 Al 9 / 2011 ( 22 ) PCT Filed : Dec . 19 , 2014 WO 2011106497 A1 9 / 2011 WO 2011106500 A1 9 / 2011 ( 86 ) PCT No .: PCT/ EP2014 / 078798 WO 2014001257 Al 1 / 2014 $ 371 (c ) ( 1 ) , ( 2 ) Date : Jun . 15 , 2016 OTHER PUBLICATIONS International Search Report for PCT/ EP2014 / 078798 dated Mar. 12 , (87 ) PCT Pub. No. : W02015 /091984 2015 , 4 pages . Pullukat, Thomas and Hoff, Raymond E ., “ Silica - Based Ziegler PCT Pub. Date : Jun . 25 , 2015 Natta Catalysts : A Patent Review ” , Catal. Rev, Sci. Eng . 41( 3 & 4 ) , (65 ) Prior Publication Data 389 - 428 ( 1999 ) . Written Opinion of the International Searching Authority for PCT/ US 2016 /0311945 A1 Oct 27, 2016 EP2014 /078798 dated Mar. 12 , 2015 , 6 pages . International Search Report Authority for PCT/ EP2014 /078790 Related U . S . Application Data dated Mar. 17 , 2015 , 4 pages. Written Opinion of the International Searching Authority for PCT / (60 ) Provisional application No . 61/ 935 ,070 , filed on Feb . EP2014 /078790 dated Mar. 17 , 2015 , 4 pages . 3 , 2014 . “ Periodic System of the Elements ,” Handbook of Chemistry and Foreign Application Priority Data Physics , CRC Press; 1989 -1990 , 70th Edition . ( 30 ) ( Continued ) Dec . 20 , 2013 (EP ) . .. .. .. 13199166 Jun . 2 , 2014 ( EP ) . .. 14170827 Primary Examiner — Catherine S Branch (51 ) Int. Cl. ( 74 ) Attorney, Agent, or Firm — Cantor Colburn LLP C08F 110 / 06 ( 2006 .01 ) (52 ) U . S . Cl. CPC .. CO8F 110/ 06 ( 2013 . 01 ) (57 ) ABSTRACT ( 58 ) Field of Classification Search The invention relates to a procatalyst for polymerization of CPC . .. CO8F 110/ 06 olefins. The invention also relates to a process for preparing See application file for complete search history . said procatalyst . Furthermore, the invention is directed to a catalyst system for polymerization of olefins comprising the (56 ) References Cited said procatalyst , a co -catalyst and optionally an external U . S . PATENT DOCUMENTS electron donor; a process of preparing polyolefins by con tacting an olefin with said catalyst system and to polyolefins 4 , 384 ,087 A 5 / 1983 Capshew obtained or obtainable by said process . The invention also 4 , 399 , 054 A 8 / 1983 Ferraris et al . 4 ,414 , 132 A 11/ 1983 Goodall et al. relates to the use of said procatalyst in the polymerization of 4 , 472 , 524 A 9 / 1984 Albizzati olefins. 5 , 077 , 357 A 12 / 1991 Job 5 , 106 , 806 A 4 / 1992 Job 5 .556 ,820 A 9 / 1996 Funabashi et al. 9 Claims, No Drawings US 9 ,868 ,799 B2 Page 2 ( 56 ) References Cited OTHER PUBLICATIONS Bartoli et al . “ Convenient Procedure for the Reduction of p -Enamino Ketones : Synthesis of y - Amino Alcohols and Tetrahydro - I , 3 - oxazines” Journal of the Chemical Society , Perkin Transactions 1 , 1994 ; 537 - 543 . Emil White “ Deamination of Amines. 2 - Phenylethyl Benzoate Via the Nitrosoamide Decomposition ” Organic Syntheses , 1967 , 47 , 44 . Non - Final Office Action dated Jul. 6 , 2017 ; U . S . Appl. No . 15 / 104 , 822 , filed Jun . 15 , 2016 . Pasouini, N . ( ed . ) “ Polypropylene handbook , ” Carl Hanser Verlag Munich ; 2005 , 11 Pages, 2nd edition , Chapter 6 . 2 . S . van der Ven , Polypropylene and other Polyolefins, Elsevier 1990 , pp . 8 - 10 . US 9 , 868 , 799 B2 PROCATALYST FOR POLYMERIZATION OF In a first aspect, the present invention relates to a process OLEFINS for preparing a procatalyst suitable for preparing a catalyst composition for olefin polymerization , said process com This application is a national stage application of PCT/ prising the steps of : EP2014 /078798 filed Dec . 19 , 2014 , which claims priority 5 i ) contacting a compound R * ,MgX - 2 - z with an alkoxy - or to European Application EP14170827. 1 filed Jun . 2 , 2014 , aryloxy - containing silane compound to give a first U . S . Provisional Application 61/ 935 ,070 filed Feb . 3 , 2014 , intermediate reaction product, being a solid and European Application EP13199166 . 3 filed Dec . 20 , Mg (OR ) , X ' 2 - x , wherein : R4 is the same as Rl being a 2013 , all of which are hereby incorporated by reference in linear , branched or cyclic hydrocarbyl group indepen their entirety . 10 dently selected e . g . from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more BACKGROUND OF THE INVENTION combinations thereof; wherein said hydrocarbyl group may be substituted or unsubstituted , may contain one or The invention relates to a procatalyst for polymerization more heteroatoms and preferably has from 1 to 20 of olefins. The invention also relates to a process for 15 carbon atoms; X and X are each independently preparing said procatalyst . Furthermore , the invention is selected from the group of consisting of fluoride ( F ) , directed to a catalyst system for polymerization of olefins chloride (C1 — ) , bromide (Br — ) or iodide ( 1 – ) , pref comprising the said procatalyst , a co -catalyst and optionally erably chloride ; z is in a range of larger than 0 and an external electron donor; a process of preparing polyole smaller than 2 , being O < z < 2 ; fins by contacting an olefin with said catalyst system . The 20 ii ) optionally contacting the solid Mg( OR ), X ' 2 . invention also relates to the use of said procatalyst in the obtained in step i ) with at least one activating com polymerization of olefins . pound selected from the group formed by activating Catalyst systems and their components that are suitable electron donors and metal alkoxide compounds of for preparing a polyolefin are generally known . One type of formula M (ORP ) v - „ (OR ) w or MP( OR ) - „ (Rº ) w , to such catalysts are generally referred to as Ziegler -Natta 25 obtain a second intermediate reaction product ; wherein : catalysts . The term “ Ziegler -Natta ” is known in the art and M is a metal selected from the group consisting of Ti , it typically refers to catalyst systems comprising a transition Zr, Hf, Al or Si; M² is a metal being Si; v is the valency metal - containing solid catalyst compound ( also typically of M or M ; R2 and R3 are each a linear, branched or referred to as a procatalyst ); an organometallic compound cyclic hydrocarbyl group independently selected e . g . ( also typically referred to as a co - catalyst) and optionally 30 from alkyl , alkenyl, aryl, aralkyl, alkoxycarbonyl or one or more electron donor compounds ( e . g . external elec alkylaryl groups , and one or more combinations tron donors ) . thereof; wherein said hydrocarbyl group may be sub The transition metal- containing solid catalyst compound stituted or unsubstituted , may contain one or more comprises a transition metal halide ( e . g . titanium halide , heteroatoms, and preferably has from 1 to 20 carbon chromium halide , hafnium halide , zirconium halide, vana - 35 atoms; dium halide ) supported on a metal or metalloid compound iii ) contacting the first or second intermediate reaction ( e . g . a magnesium compound or a silica compound ) . An product obtained in step i) or ii ) respectively , with a overview of such catalyst types is for example given by T . halogen - containing titanium compound and either an Pullukat and R . Hoff in Catal. Rev . Sci . Eng . 41, vol . 3 and activator or an internal electron donor to obtain a third 4 , 389 -438 , 1999 . The preparation of such a procatalyst is for 40 intermediate reaction product ; example disclosed in WO96 /32427 Al and EP 1 086 961. iv ) modifying the third intermediate reaction product There is , however, an on - going need in industry for obtained in step iii ) with a modifier having the formula catalysts showing better performance , especially better yield MX3, wherein Mis a metal selected from the Group 13 and higher polymer bulk density . metals and transition metals of the IUPAC periodic It is thus an object of the invention to provide a procata - 45 table of elements , and wherein X is a halide , to yield a lyst for polymerization of olefins and a process to prepare modified intermediate reaction product ; such a procatalyst . It is a further object of the present v ) contacting said modified intermediate reaction product invention is to provide a procatalyst which shows better obtained in step iv ) with a halogen - containing titanium performance, especially higher yield and higher polymer compound and in the case that in step iii ) an activator bulk density . 50 was used an internal donor to obtain the procatalyst , wherein preferably step v ) is carried out at least two SUMMARY OF THE PRESENT INVENTION times .