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(12) U11l16(I S1316S P316111 (10) Patent No.: US 7,531,602 B2 Hoang et al. (45) Date of Patent: May 12, 2009 (54) POLYMER BLENDS 5,434,116 A 7/1995 Sone et al. ................ .. 502/103 5,554,775 A 9/1996 Krishnamurti et al. ....... .. 556/7 (75) Inventors, Peter Phung Minh H0ang’ Calgary 5,637,659 A 6/1997 Krishnamurti et al. .... .. 526/133 (CA); Cliff Robert Baar, Calgary (CA) i ii; [eeebsen ete1~ 502/124 , , acobsen et al. 502/152 (73) Assignee: Nova Chemicals (International) S.A. $1 g3‘i.ri1:he1:iiet (CH) 6,346,575 B1 2/2002 Debras et al. 525/191 * _ _ _ _ _ 7,064,096 B1 * 6/2006 Hoang et al. .. 502/103 ( ) Notice: S11b]6C1i1O any disclaimer, the term ofthis 7,321,015 B2 1 1/2008 Hoang ei 21‘ __ 526/73 Patent 15 extended Or editlsted under 35 2002/0077431 A1 6/2002 Whiteker .................. .. 526/113 U.S.C. 154(b) by 270 days. OTHER PUBLICATIONS (21) APPI N05 I1/244-1351 Corwin Hansch et al., A Survey of Hammett Substituent Constants and Resonance and Field Perameters, Chem Rev. 1991. 91, 165-195; (22) Filedi 061- 5, 2005 1991 American Chemical Society. Peri et al., The Surface Structure of Silica Gel, J . Phys. Chem 72(8) (65) Prior Publication Data 2926, 1968. Noshay, A. et al., Transition Metal Catalyzed Polymerizations, pp. Us 2007/0078223 A1 Apr‘ 3’ 2007 396-416, Cambridge University Press, 1988. (51) Int C]_ * cited by examiner C081‘ 23/04 (200601) _ _ _ Primary Examiner—Rober‘t D. Harlan (52) U.S. Cl. .................... .. 525/240, 428/34.1, 526/172, (74) Attorney Agent] Oi, Fl-i,m_Kenneih H Johnson 526/73; 526/113; 526/114; 526/118; 526/119; 502/152; 502/155; 502/167 (57) ABSTRACT (58) Field of Classification Search ............... .. 525/240; _ _ _ 526/172, 73, 113, 114, 113, 119; 423/34_1; A blend ofpolymers comprising from 5 to 95 weight ofa 502/152, 15 5, 167 polymer having a high molecular weight made using a single See application file for complete search history. 511e IYPe eaIaIY5I and Rem 95 I0 5 Welt‘-5111 % OI 3 Pelymer _ having a lower molecular weight made using a catalyst con(56) References Clted taining a phenoxide, preferably a salicylaldimine ligand, has
4,530,914 A 7/1985 Ewen et al. ............... .. 502/113 4,719,193 A 1/1988 Levine et al. ............. .. 502/107
an excellent toughness and would be suitable for use in applications such as polyolefin pipes.
13 Claims, 2 Drawing Sheets
U.S. Patent May 12, 2009 Sheet 1 0f2 US 7,531,602 B2
- BrF#(No correction) E25
0 BrF#(2 Methyl correction) j
O BrF#(1 Methyl correction) I
0.5 - 15
0 1 T 1 1 1 1 1 1 I‘ 0
2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7
- BrF#(No correction) I 25
O BrF#(2 Methyl correction) :
O BrF#(1 Methyl correction) 5 20
0 1 - I 17 1 1 1 1 1 1 1 0
2 2.5 3 3.5 4 4.5 5 5.5 6 6.5
Branch Freq. (Branches/1000 C)
Branch Freq. (Branches/1000 C)
U.S. Patent May 12, 2009 Sheet 2 0f2 US 7,531,602 B2
0 BrF#(2 Methyl correction)
O BrF#(1 Methyl correction)
520 0.5- 515 E10 gs 01 51* §0 2 2.5 7
Branch Freq. (Branches/1000 C)
The present invention relates to blends of polymers one of which is made using a single site type catalyst (e.g. representative catalysts containing at least one cyclopentadienyl ligand) and the other of which is made by a catalyst containing a phenoxy, preferably a salicylaldimine, ligand. The polymer made using the single site type catalyst provides a higher molecular weight polymer component and the polymer made using the phenoxy ligand containing catalyst provides a lower molecular weight component. The copolymer incorporation in either component or the resulting blend may be nonnal (e.g. more comonomer in the lower molecular weight component) or reverse (e.g. more comonomer in the higher molecular weight component) or unifonn.
U.S. Pat. No. 4,530,914 issued Jul. 23, 1985 to Ewen et al., assigned to EXXON Research & Engineering Co. teaches the use in the same reactor of two metallocene catalysts each having different propagation and tennination rate constants for ethylene polymerizations. The patent does not teach the polymers prepared in the presence of a phenoxide ligand containing catalyst of the present invention.
U.S. Pat. No. 6,346,575, issued Feb. 12, 2002 to Debras et al., assigned to Fina Research S.A. teaches a method to make a bimodal blended polymer by polymerizing monomers in a first reactor in the presence of a metallocene type catalyst and them moving the resulting polymer to a second reactor and polymerizing additional monomer in the prior formed polymer. The patent does not teach using a catalyst having a phenoxide ligand as required in the present patent. Further the patent teaches away from physical blending as required by the present invention.
U.S. Pat. No. 6,309,997 issued Oct. 30, 2001 teaches an olefin polymerization catalyst using a phenoxide (preferably a salicylaldimine) ligand for use in the polymerization of olefins. The patent does not teach blending such resins with a resin made using a single site catalyst (representative catalysts contain at least one cyclopentadienyl type ligand).
U.S. patent application 2002/0077431 published Jun. 20, 2002 in the name of Whiteker discloses a process for the polymerization and oligomerization of olefins in the presence of a mixed catalyst system in a single reactor. The catalyst system as disclosed comprises a first component similar to the catalyst containing the phenoxide component of the present invention except that at least one of substituents R3, R4, R3, R8, R9 and R10 must have a Hammett op value (Hansch et al., Chem Rev. 1991,91,165) greater than 0.2 (i.e. at least one of these substituents needs to be a sufliciently electron withdrawing group, (e.g. CF3, Br, etc.)). In the present invention, in the catalyst containing the phenoxide ligand, all of R3, R4, R3 , R8, R9 and R10 are hydrocarbyl substituents which have a
Hammett value of less than 0.2. Furthermore, the reference teaches away from the blending approach of the present invention.
The present invention seeks to provide a polymer blend (physical blend) having good physical properties which would make it suitable for numerous applications including pipe applications.
The present invention provides a post reactor polyolefin blend comprising:
(a) from 5 to 95 weight % of a polymer having a weight average molecular weight greater than 5,000, typically from 10,000 to 140,000, preferably from about 15,000 to about 100,000, comprising from 80 to 100 weight % of ethylene and from 20 to 0 weight % of one or more C3_3 alpha olefins which are unsubstituted or substituted by up to two C1_6 alkyl radicals, having a density greater than 0.930, preferably from 0.940 to 0.965 g/cm3, said copolymer being prepared in the presence of a supported catalyst of the fonnula:
wherein M is a group 4 transition metal; R1 and R6 are independently selected from the group consisting of C1_6 alkyl or C6_1O aryl radicals; R2 and R7 are independently selected from the group consisting of C3_3 secondary or tertiary alkyl radicals; R3, R4, R3, R8, R9 and R10 are independently selected from the group consisting of a hydrogen atom, C1_4 alkyl radicals, C6_1O aryl radicals, C1-C4 alkoxy radicals which substituents have a Hammett op value of less than 0.2; and X and X' are selected from the group consisting of a halogen atom, C1_4 alkyl radicals, C7_12 arylalkyl radicals, C6_1O phenoxy radicals, amido radicals which may be substituted by up to two C1_4 alkyl radicals and C1_4 alkoxy radicals, and an activator; and
(b) from 95 to 5 weight % of a polymer having a weight average molecular weight greater than 100,000, preferably from 140,000 to 1,000,000, most preferably from 140,000 to 600,000, comprising from 60 to 100 weight % of ethylene and from 40 to 0 weight % of one or more C3_3 alpha olefins which are unsubstituted or substituted by up to two C1_6 alkyl radicals, having a density from 0.890 to 0.950, preferably from 0.910 to 0.940 g/cm3, said copolymer being prepared in the presence of a supported catalyst of the fonnula: