Elastic substantially linear olefin polymers

• US 5,272,236 A
• Filed: 10/15/1991
• Issued: 12/21/1993
• Est. Priority Date: 10/15/1991
• Status: Expired due to Term

• Current Assignee: The Dow Chemical Company (Dow, Inc.)
• Original Assignee: The Dow Chemical Company (Dow, Inc.)
• Inventors: Lai, Shih-Yaw, Wilson, John R., Stevens, James C., Chum, Pak-Wing S., Knight, George W.
• Primary Examiner(s): Schofer, Joseph L.
• Assistant Examiner(s): WU, DAVID WEI HSIUNG
• Application Number:
  US07/776,130
• Time in Patent Office: 798 Days
• Field of Search: 526/160, 526/170, 526/127, 526/348, 526/348.2, 526/348.4, 526/348.5, 526/348.6
• US Class Current: 526/348.5
• CPC Class Codes: B29C 48/00 Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor extrusion blow-moulding B29C49/04
• CPC Class Codes: B29C 48/022 characterised by the choice of material
• CPC Class Codes: B29C 48/10 flexible, e.g. blown foils
• CPC Class Codes: B29C 48/15 incorporating preformed parts or layers, e.g. extrusion moulding around inserts
• CPC Class Codes: B29C 65/00 Joining or sealing of preformed parts , e.g. welding of plastics materials; Apparatus therefor general aspects of processes or apparatus for joining preformed parts B29C66/00; using porous material formed by internal pressure generated therein for joining preformed parts B29C44/1228, B29C44/326
• CPC Class Codes: B29C 65/8207 by mechanical methods
• CPC Class Codes: B29C 65/8223 Peel tests
• CPC Class Codes: B29C 66/71 characterised by the composition of the plastics material of the parts to be joined welding bar compositions B29C65/125
• CPC Class Codes: B29K 2995/0022 Bright, glossy or shiny surface
• CPC Class Codes: B32B 2250/03 3 layers
• CPC Class Codes: B32B 2250/246 All polymers belonging to those covered by groups B32B27/32 and B32B27/30
• CPC Class Codes: B32B 2270/00 Resin or rubber layer containing a blend of at least two different polymers
• CPC Class Codes: B32B 2307/7244 Oxygen barrier
• CPC Class Codes: B32B 2439/70 Food packaging
• CPC Class Codes: B32B 27/08 of synthetic resin
• CPC Class Codes: B32B 27/306 comprising vinyl acetate or vinyl alcohol (co)polymers
• CPC Class Codes: B32B 27/308 comprising acrylic (co)polymers
• CPC Class Codes: B32B 27/32 comprising polyolefins comprising vinyl (co)polymers or acrylic (co)polymers B32B27/30
• CPC Class Codes: B32B 27/322 comprising halogenated polyolefins, e.g. PTFE
• 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 10/02 : Ethene
• CPC Class Codes: C08F 110/00 : Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 110/02 : Ethene
• CPC Class Codes: C08F 210/00 : Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 210/14 : Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 210/16 : Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 216/14 : Monomers containing only one unsaturated aliphatic radical
• CPC Class Codes: C08F 2500/03 : Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 2500/05 : Bimodal or multimodal molecular weight distribution
• CPC Class Codes: C08F 2500/07 : High density, i.e. > 0.95 g/cm3
• CPC Class Codes: C08F 2500/08 : Low density, i.e. < 0.91 g/cm3
• CPC Class Codes: C08F 2500/09 : Long chain branches
• CPC Class Codes: C08F 2500/11 : Melt tension or melt strength
• CPC Class Codes: C08F 2500/12 : Melt flow index or melt flow ratio
• CPC Class Codes: C08F 2500/17 : Viscosity
• CPC Class Codes: C08F 2500/19 : Shear ratio or shear ratio index
• CPC Class Codes: C08F 2500/26 : Use as polymer for film forming
• CPC Class Codes: C08F 4/65908 : in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• CPC Class Codes: C08F 4/6592 : containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
• CPC Class Codes: C08G 83/003 : Dendrimers
• CPC Class Codes: C08J 2303/08 : Ethers
• CPC Class Codes: C08J 2323/08 : Copolymers of ethene C08J2323/16 takes precedence
• CPC Class Codes: C08J 5/18 : Manufacture of films or sheets
• CPC Class Codes: C08L 2205/02 : containing two or more polymers of the same C08L -group
• CPC Class Codes: C08L 23/02 : not modified by chemical after-treatment
• CPC Class Codes: C08L 23/04 : Homopolymers or copolymers of ethene
• CPC Class Codes: C08L 23/06 : Polyethene
• CPC Class Codes: C08L 23/0815 : Copolymers of ethene with aliphatic 1-olefins
• CPC Class Codes: C08L 23/16 : Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
• CPC Class Codes: C08L 2314/06 : Metallocene or single site catalysts
• CPC Class Codes: C08L 2666/04 : Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: Y10S 526/943 : Polymerization with metallocene catalysts

Abstract

Substantially linear olefin polymers having a melt flow ratio, I₁₀ /I₂, ≧5.63, a molecular weight distribution, M_w /M_n, defined by the equation: M_w /M_n ≦(I₁₀ /I₂)-4.63, and a critical shear stress at onset of gross melt fracture of greater than about 4×10⁶ dyne/cm² and their method of manufacture are disclosed. The substantially linear olefin polymers preferably have at least about 0.01 long chain branches/1000 carbons and a molecular weight distribution from about 1.5 to about 2.5. The new polymers have improved processability over conventional olefin polymers and are useful in producing fabricated articles such as fibers, films, and molded parts.

Claims

1. A substantially linear olefin polymer characterized as having:

a) a melt flow ratio, I₁₀ /I₂, ≧

5.63,

b) a molecular weight distribution, M_w /M_n, defined by the equation;

space="preserve" listing-type="equation">M.sub.w /M.sub.n ≦

(I.sub.10 /I.sub.2)-4.63, and

c) a critical shear stress at onset of gross melt fracture of greater than about 4×

10⁶ dyne/cm²,

wherein the olefin polymer is further characterized as a copolymer of ethylene with a C₃ -C₂₀ alpha-olefin.

2. The polymer of claim 1 wherein the M_w /M_n is less than about 3.5.

3. The polymer of claim 1 wherein the M_w /M_n is from about 1.5 to about 2.5.

4. The polymer of claim 1 wherein the polymer has about 0.01 to about 3 long chain branches/1000 carbons along the polymer backbone.

5. The polymer of claim 4 having at least about 0.1 long chain branches/1000 carbons along the polymer backbone.

6. The polymer of claim 4 having at least about 0.3 long chain branches/1000 carbons along the polymer backbone.

21. The substantially linear olefin polymer of claim 1, wherein the polymer is a copolymer of ethylene and 1-octene.

22. The substantially linear olefin polymer of claim 1, wherein the polymer is a copolymer of ethylene and 1-hexene.

23. The substantially linear olefin polymer of claim 1, wherein the polymer is a copolymer of ethylene and 1-butene.

24. The substantially linear olefin polymer of claim 1, wherein the polymer is a copolymer of ethylene and 4-methyl-1-pentene.

7. A composition comprising a substantially linear olefin polymer, wherein the polymer is characterized as having:

a) a melt flow ratio, I₁₀ /I₂, ≧

5.63,

b) a molecular weight distribution, M_w /M_n, defined by the equation;

space="preserve" listing-type="equation">M.sub.w /M.sub.n ≦

(I.sub.10 /I.sub.2)-4.63, and

c) a critical shear stress at onset of gross melt fracture of greater than about 4×

10⁶ dyne/cm²,

and at least one other natural or synthetic polymer, wherein the substantially linear olefin polymer is further characterized as a copolymer of ethylene with a C₃ -C₂₀ alpha-olefin.

8. The composition of claim 7 wherein the substantially linear olefin polymer has a I₁₀ /I₂ up to about 20.

9. The composition of claim 7 wherein the substantially linear olefin polymer has a M_w /M_n less than about 3.5.

10. The composition of claim 7 wherein the substantially linear olefin polymer has a M_w /M_n from about 1.5 to about 2.5.

11. The composition of claim 7 wherein the synthetic polymer is a conventional ethylene homopolymer or copolymer.

25. The composition of claim 7, wherein the substantially linear olefin polymer is a copolymer of ethylene and 1-octene.

26. The composition of claim 7, wherein the substantially linear olefin polymer is a copolymer of ethylene and 1-hexene.

27. The composition of claim 7, wherein the substantially linear olefin polymer is a copolymer of ethylene and 1-butene.

28. The composition of claim 7, wherein the substantially linear olefin polymer is a copolymer of ethylene and 4-methyl-1-pentene.

12. A substantially linear olefin polymer having a melt flow ratio, I₁₀ /I₂, ≦

5.63, and a molecular weight distribution, M_w /M_n, defined by the equation;

space="preserve" listing-type="equation">M.sub.w /M.sub.n ≦

(I.sub.10 /I.sub.2)-4.63,

produced by continuously contacting ethylene and a C₃ -C₂₀ alpha-olefin with a catalyst composition under polymerization conditions, wherein said catalyst composition is characterized as;

a) a metal coordination complex comprising a metal atom of groups 3-10 or the Lanthanide series of the Periodic Table of the Elements and a delocalized π

-bonded moiety substituted with a constrain inducing moiety,

said complex having a constrained geometry about the metal atom such that the angle at the metal atom between the centroid of the delocalized, substituted π

-bonded moiety and the center of at least one remaining substituent is less than such angle in a similar complex containing a similar π

-bonded moiety lacking in such constrain-inducing substituent,

and provided further that for such complexes comprising more than one delocalized, substituted π

-bonded moiety, only one thereof for each metal atom of the complex is a cyclic, delocalized, substituted π

-bonded moiety, and

b) an activating cocatalyst.

38. The substantially linear olefin polymer of claim 12 wherein (a) is an amidosilane- or amidoalkanediyl- compound corresponding to the formula:

##STR8## wherein;

M is titanium, zirconium or hafnium, bound in an η

⁵ bonding mode to the cyclopentadienyl group;

R'"'"' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl and combinations thereof having up to 10 carbon or silicon atoms;

E is silicon or carbon;

X independently each occurrence is hydride, halo, alkyl, or aryl, of up to 20 carbons; and

m is 1 or 2.

13. A substantially linear olefin polymer characterized as having:

a) a melt flow ratio, I₁₀ /I₂, ≧

7,

b) a molecular weight distribution, M_w /M_n, of from about 1.5 to about 2.5,

wherein the substantially linear olefin polymer is further characterized as a copolymer of ethylene with a C₃ -C₂₀ alpha-olefin.

14. The polymer of claim 13 wherein the I₁₀ /I₂ is at least about 8.

15. The polymer of claim 13 wherein the I₁₀ /I₂ is at least about 9.

16. The polymer of claim 13 wherein the substantially linear olefin polymer is an ethylene/alpha-olefin copolymer.

29. The substantially linear olefin polymer of claim 13, wherein the polymer is a copolymer of ethylene and 1-octene.

30. The substantially linear olefin polymer of claim 13, wherein the polymer is a copolymer of ethylene and 1-hexene.

31. The substantially linear olefin polymer of claim 13, wherein the polymer is a copolymer of ethylene and 1-butene.

32. The substantially linear olefin polymer of claim 13, wherein the polymer is a copolymer of ethylene and 4-methyl-1-pentene.

17. A substantially linear olefin polymer having:

(a) from about 0.01 to about 3 long chain branches/1000 carbons along the polymer backbone and

(b) a critical shear stress at onset of gross melt fracture of greater than about 4×

10⁶ dyne/cm²,

wherein the substantially linear olefin polymer is further characterized as a copolymer of ethylene with a C₃ -C₂₀ alpha-olefin.

18. The polymer of claim 17 having at least about 0.1 long chain branches/1000 carbons along the polymer backbone.

19. The polymer of claim 17 having at least about 0.3 long chain branches/1000 carbons along the polymer backbone.

20. The polymer of claim 17 wherein the polymer has a I₁₀ /I₂ of at least about 16.

33. The substantially linear olefin polymer of claim 17, wherein the polymer is a copolymer of ethylene and 1-octene.

34. The substantially linear olefin polymer of claim 17, wherein the polymer is a copolymer of ethylene and 1-hexene.

35. The substantially linear olefin polymer of claim 17, wherein the polymer is a copolymer of ethylene and 1-butene.

36. The substantially linear olefin polymer of claim 17, wherein the polymer is a copolymer of ethylene and 4-methyl-1-pentene.

37. A composition comprising:

(i) a substantially linear olefin polymer, wherein the substantially linear olefin polymer is characterized as having;

a) from about 0.01 to about 3 long chain branches/1000 carbons along the polymer backbone and

b) a critical shear stress at onset of gross melt fracture of greater than about 4×

10⁶ dyne/cm², and

(ii) at least one other natural or synthetic polymer, wherein the substantially linear olefin polymer is further characterized as a copolymer of ethylene with a C₃ -C₂₀ alpha-olefin.