Method of increasing bubble stability of a polyethylene resin

Patent metadata

Field	Value
Publication number	US-12330362-B2
Application number	US-202017754785-A
Country	US
Kind code	B2
Filing date	Oct 26, 2020
Priority date	Oct 28, 2019
Publication date	Jun 17, 2025
Grant date	Jun 17, 2025

Abstract

A method of increasing bubble stability of a needful high molecular weight bimodal high-density polyethylene resin in need thereof, the method comprising subjecting the needful high molecular weight bimodal high-density polyethylene resin to a determined amount of oxygen tailoring of the resin so as to independently increase both the resin's melt storage modulus G′ (at G″=3000 pascals) and complex viscosity ratio SH1000, and thereby make an oxygen-tailored high molecular weight bimodal high-density polyethylene resin having a targeted increase in bubble stability. The method uses a tailoring effective amount of molecular oxygen (O 2 ) to achieve the desired oxygen tailoring. The method uses these advanced rheological properties from dynamic mechanical spectroscopy, but analyzes the data in a different way that is more sensitive to changes in resin composition and properties, and yet achieves a resin regime having a targeted increase in bubble stability.

First claim

The invention claimed is:

1. A method of increasing bubble stability of a needful bimodal high-density polyethylene (HDPE) resin that comprises a higher molecular weight (HMW) polyethylene polymer constituent and a lower molecular weight (LMW) polyethylene polymer constituent and has an overall density from 0.935 to 0.970 gram per cubic centimeter (g/cm 3 ) and an overall weight-average molecular weight (M w ) from 200,000 to 450,000 grams per mole (g/mol), which needful bimodal HDPE resin is in need of increased bubble stability because the properties of the needful bimodal HDPE resin are different than those of a prior resin made in the same reactor due to change in reactor conditions and the needful bimodal HDPE resin has a first melt storage modulus G′ (at loss modulus G″=3000 pascals) of less than 1501 pascals and a first complex viscosity ratio SH1000 of from 33.0 to 49.0, the method comprising:
contacting under oxygen-tailoring conditions a melt of the needful bimodal HDPE resin with an oxygen-tailoring mixture consisting essentially of a tailoring effective amount of molecular oxygen gas (O 2 ) and one or more inert gases, and wherein during the contacting the melt is at a temperature from 235° to 251° C., so as to make an oxygen-tailored bimodal HDPE resin having a second melt storage modulus G′ (at G″=3000 pascals) of from 1565 to 1900 pascals and a second complex viscosity ratio SH1000 of from 38.0 to 50.0;
wherein density is measured according to ASTM D792-13, Method B;
wherein M w is measured according to the Gel Permeation Chromatography (GPC) Test Method;
wherein each melt storage modulus G′ (at G″=3000 pascals) is measured according to the Melt Storage Modulus Test Method; and
wherein each complex viscosity ratio SH1000 is equal to Eta*0.10/Eta*100, wherein Eta*0.10 is complex viscosity in pascal-seconds (Pa-s) measured at 0.10 radian per second (rad/s) and wherein Eta*100 is complex viscosity in Pa-s measured at 100 rad/s, both measured according to Dynamic Mechanical Analysis Test Method.

2. The method of claim 1 wherein the tailoring effective amount of the O 2 gas in the contacting step is as described by any one of limitations (i) to (ii): (i) an O 2 gas concentration of X volume percent (vol %) of the oxygen-tailoring mixture; and (ii) an amount of the O 2 gas is Y weight parts per 1 million weight parts of the needful bimodal HDPE resin (ppmw).

3. The method of claim 1 wherein the oxygen-tailoring mixture has an O 2 gas concentration of X volume percent (vol %), and wherein the oxygen-tailoring conditions comprise any one of limitations (i) to (iv): (i) the melt is at a temperature from 235° to 245° C.; (ii) the melt is at a temperature from 236° and 241° C.; (iii) the one or more inert gases of the oxygen-tailoring mixture is molecular nitrogen (N 2 ), argon, helium, CO 2 , one or more alkane(s), or a combination of any two or more thereof; and (iv) both (iii) and any one of (i) and (ii).

4. The method of claim 1 wherein the oxygen-tailored bimodal HDPE resin further has any one of limitations (i) to (iii): (i) the second melt storage modulus G′ (at G″=3000) is from 1565 to 1800 pascals; (ii) the second complex viscosity ratio SH1000 is from 40 to 49.4; (iii) both (i) and (ii).

5. The method of claim 1 wherein the oxygen-tailored bimodal HDPE resin passes a MLS350 bubble stability test determined according to the Bubble Stability Test Method.

6. The method of claim 1 wherein the needful bimodal HDPE resin has any one of limitations (i) to (vi): (i) the overall density is from 0.940 to 0.960 g/cm 3 ; (ii) the overall M w is from 250,000 to 400,000 g/mol; (iii) the first melt storage modulus G′ (at G″=3000 pascals) is from 1001 to 1300 pascals; (iv) the first complex viscosity ratio SH1000 is from 35.0 to 48.0; (v) an overall high-load melt index (HLMI or I 21.6 ) of from 8.0 to 10.0 grams per 10 minutes (g/10 min.); and (vi) an overall melt flow ratio-5 (MFR5 or I 21.6 /I 5.0 ) from 25 to 45; wherein the I 21.6 is measured according to ASTM D1238-13, using conditions of 190° C./21.6 kilograms (kg); and wherein the I 5.0 is measured according to ASTM D1238-13, using conditions of 190° C./5.0 kg.

7. The method of claim 1 further comprising preliminary steps (A) and (B) before the contacting step:
(A) determining a molecular weight spread of the needful bimodal HDPE resin, wherein the molecular weight spread is (a1) a ratio of weight-average molecular weight of the HMW polyethylene polymer constituent to weight-average molecular weight of the LMW polyethylene polymer constituent (M w-HMW /M w-LMW );
(B) determining the tailoring effective amount of molecular oxygen gas (O 2 ) that is effective in the contacting step as a function of the determined molecular weight spread of the needful bimodal HDPE resin.

8. The method of claim 7 wherein the needful bimodal HDPE resin further has any one of limitations (i) to (iii): (i) the molecular weight spread is (a1) the ratio M w-HMW /M w-LMW , wherein M w-HMW /M w-LMW is from 23 to 45; (ii) the molecular weight spread is (a2) a ratio of number-average molecular weight of the HMW polyethylene polymer constituent to number-average molecular weight of the LMW polyethylene polymer constituent (M n-HMW /M n-LMW ), wherein M n-HMW /M n-LMW is from 18 to 30; (iii) the molecular weight spread is (a3) a ratio of z-average molecular weight of the HMW polyethylene polymer constituent to z-average molecular weight of the LMW polyethylene polymer constituent (M z-HMW /M z-LMW ), wherein M z-HMW /M z-LMW is from 18 to 45; wherein M w , M n , and M z are measured according to the Gel Permeation Chromatography (GPC) Test Method.

9. An oxygen-tailored bimodal HDPE resin made by the method of claim 1 .

10. A blown film comprising the oxygen-tailored bimodal HDPE resin of claim 9 .

11. A method of determining whether a bimodal high-density polyethylene (HDPE) resin that comprises a higher molecular weight (HMW) polyethylene polymer constituent and a lower molecular weight (LMW) polyethylene polymer constituent and has an overall density from 0.935 to 0.970 gram per cubic centimeter (g/cm 3 ) and an overall weight-average molecular weight (M w ) from 200,000 to 450,000 grams per mole (g/mol), is in need of increased bubble stability, the method comprising measuring melt storage modulus G′ (at loss modulus G″=3000 pascals) and complex viscosity ratio (shear thinning) SH1000 of the needful bimodal HDPE resin, and determining the bimodal HDPE resin is a need of increased bubble stability if the melt storage modulus G′ (at loss modulus G″=3000 pascals) is less than 1501 pascals and the complex viscosity ratio (shear thinning) SH1000 is from 33.0 to 49.0; wherein density is measured according to ASTM D792-13, Method B; wherein Mw is measured according to the Gel Permeation Chromatography (GPC) Test Method; wherein each melt storage modulus G′ (at G″=3000 pascals) is measured according to the Melt Storage Modulus Test Method; and wherein each complex viscosity ratio SH1000 is equal to Eta*0.10/Eta*100, wherein Eta*0.10 is complex viscosity in pascal-seconds (Pa-s) measured at 0.10 radian per second (rad/s) and wherein Eta*100 is complex viscosity in Pa-s measured at 100 rad/s, both measured according to Dynamic Mechanical Analysis Test Method.

Assignees

• Univation Tech Llc

Inventors

• Liu Bo
• Wieliczko Joel D
• Bafna Ayush A
• Abe Daudi A

Classifications

• C08J2323/08

  Copolymers of ethene (C08J2323/16 takes precedence) · CPC title

• C08J5/18

  Manufacture of films or sheets · CPC title

• C08F2800/10

  as molar percentages · CPC title

• C08F210/16 Primary

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

• B29K2995/0088

  Molecular weight · CPC title