Shaped polyethylene articles of intermediate molecular weight and high modulus

• US 4,663,101 A
• Filed: 01/11/1985
• Issued: 05/05/1987
• Est. Priority Date: 01/11/1985
• Status: Expired due to Term

• Current Assignee: Allied Corp. (Honeywell International Inc.)
• Original Assignee: Allied Corp. (Honeywell International Inc.)
• Inventors: Kavesh, Sheldon, Prevorsek, Dusan C.
• Primary Examiner(s): Silbaugh, Jan
• Assistant Examiner(s): Lorin, Hubert C.
• Application Number:
  US06/690,914
• Time in Patent Office: 844 Days
• Field of Search: 264/203, 264/204, 264/41, 264/210.7, 264/210.8, 264/178 F, 264/46.1, 428/364
• US Class Current: 264/178.00F
• CPC Class Codes: B29C 48/022 characterised by the choice of material
• CPC Class Codes: B29C 48/05 Filamentary, e.g. strands
• CPC Class Codes: B29C 48/08 flexible, e.g. films
• CPC Class Codes: B29K 2023/06 PE, i.e. polyethylene
• CPC Class Codes: B29K 2105/0061 Gel or sol
• CPC Class Codes: B29K 2223/06 PE, i.e. polyethylene
• CPC Class Codes: B29K 2995/0088 Molecular weight
• CPC Class Codes: C08J 2323/06 Polyethene
• CPC Class Codes: C08J 5/18 Manufacture of films or sheets
• CPC Class Codes: D01D 5/00 Formation of filaments, threads, or the like
• CPC Class Codes: D01F 6/04 from polyolefins
• CPC Class Codes: D07B 1/02 Ropes built-up from fibrous or filamentary material, e.g. of vegetable origin, of animal origin, regenerated cellulose, plastics
• CPC Class Codes: D07B 1/025 comprising high modulus, or high tenacity, polymer filaments or fibres, e.g. liquid-crystal polymers
• CPC Class Codes: D07B 2205/2014 High performance polyolefins, e.g. Dyneema or Spectra
• CPC Class Codes: D07B 2801/10 Smallest filamentary entity of a rope or strand, i.e. wire, filament, fiber or yarn
• CPC Class Codes: D10B 2321/0211 high-strength or high-molecular-weight polyethylene, e.g. ultra-high molecular weight polyethylene [UHMWPE]
• CPC Class Codes: Y10T 428/2913 Rod, strand, filament or fiber
• CPC Class Codes: Y10T 428/2967 Synthetic resin or polymer
• CPC Class Codes: Y10T 428/31855 Of addition polymer from unsaturated monomers

Abstract

Solutions of intermediate molecular weight polymers from about 200,000 to about 4,000,000, such as polyethylene, in a relatively non-volatile solvent are extruded through an aperture at constant concentration and thereafter stretched at a ratio of at least about 3:1 prior to cooling to form a first gel. The first gels are extracted with a volatile solvent to form a second gel, and the second gel is dried to form a low porosity xerogel. Stretching occurs with any one or more of the first gel, second gel or xerogel. The polyethylene products produced by our process include products having a molecular weight between about 200,000 and about 4,000,000 a tenacity of at least about 13 grams/denier, a modulus of at least about 350 gram/denier, a porosity of less than 10% by volume, a crystalline orientation function of at least about 0.95, and a main melting temperature of at least about 140° C.

Claims

1. A process for producing shaped polyethylene articles which comprises the steps of:

(a) forming a solution of polyethylene in a first solvent, said polyethylene having a weight average molecular weight between about 200,000 and 4,000,000 kilograms/kg mole;

(b) extruding said solution through an apertures to form a solution product;

(c) stretching the solution product above the temperature at which a gel will form, at a stretch ratio of at least about 3;

1;

(d) cooling the solution product to form a first gel containing first solvent;

(e) extracting the first solvent form the first gel with a second solvent to form a second gel containing second solvent, substantially free of the first solvent;

(f) drying the gel containing the second solvent to form a xerogel substantially free of solvent; and

,

(g) stretching at least one of the first gel,

the second gel, and the xerogel, the total stretch ratio being sufficient to produce a polyethylene article having a tenacity of at least about 13 grams/denier and a modulus of at least about 350 grams/denier.

2. The process of claim 1 wherein the solution ptoduct is stretched at a ratio of at least about 10:

1.

3. The process of claim 1 wherein the total stretch ratio is at least about 30:

1.

4. The process of claim 2 wherein the total stretch ratio is at least asbout 30:

1.

5. The process of claim 1 wherein the cocnentration of polyehtylene in the first solvent is between about 5 and about 25 percent by weight.

6. The process of claim 1 wherein the concentration of polyethylene in the first solvent is between about 6 and about 15 percent by weight.

7. The process of claim 1 wherein the concentration of polyethylene in the first solvent is between about 6 and about 10 percent by weight.

8. The process of claim 1 wherein the polyethylene has a weight average molecular weight between about 200,000 and about 800,000.

9. The process of claim 1 wherein the polyethylene has a weight average molecular weight between about 250,000 and about 750,000.

10. The process of claim 1 wherein the polyethylene has a weight average molecular weight between about 300,000 and about 700,000.

11. The process of claim 1 wherein the total stretch ratio is sufficient to produce a polyethylene article having a crystalline orientation function of at least about 0.95.

12. The process of claim 1 wherein stretching at least one of the first gel, second gel, and xerogel occurs in at least two stages.

13. The process of claim 1 wherein stretching at least one of the first gel, second gel, and xerogel comprises the steps of stretching the first gel or second gel, and the xerogel.

14. The process of claim 1 wherein stretching at least one of the first gel, second gel, and xerogel comprises the step of stretching the xerogel.

15. The process of claim 14 wherein stretching at least one of the first gel, second gel, and xerogel further comprises the step of stretching the xerogel in at least two stages.

16. The process of claim 14 further comprising the step of stretching the xerogel in a first stage at a ratio of at least about 2:

1 and stretching the xerogel in a second stage at a ratio of at least about 1.1;

1.

17. The process of claim 15 wherein the xerogel is stretched in a first stage at a temperature between about 115°

C. and about 135°

C. and the xerogel is stretched in the second stage at a temperature of between about 130°

C. and about 155°

C.

18. The process of claim 1 wherein cooling the solution product comprises quenching the solution product in a quench bath.

19. The process of claim 1 wherein cooling the solution product occurs at a rate greater that about 50°

C./min.

20. The process of claim 1 wherein the solvent is a liquid during the extracting step (e).