Hydrophilic microporous polyolefin membrane

• US 5,209,849 A
• Filed: 04/24/1992
• Issued: 05/11/1993
• Est. Priority Date: 04/24/1992
• Status: Expired due to Term

• Current Assignee: Pall Corporation (Danaher Corporation)
• Original Assignee: Gelman Sciences, Inc. (Danaher Corporation)
• Inventors: Cai, Zhihua, Hu, Hopin
• Primary Examiner(s): SPEAR JR, FRANK
• Application Number:
  US07/874,480
• Time in Patent Office: 382 Days
• Field of Search: 427/245, 427/246, 427/44, 427/53.1, 264/22, 210/490, 210/500.35
• US Class Current: 210/490
• CPC Class Codes: B01D 2323/385 involving radiation
• CPC Class Codes: B01D 67/0093 Chemical modification
• CPC Class Codes: B01D 67/00931 by introduction of specific groups after membrane formation, e.g. by grafting
• CPC Class Codes: C08J 2323/02 not modified by chemical after treatment
• CPC Class Codes: C08J 2327/12 containing fluorine atoms
• CPC Class Codes: C08J 9/405 with polymerisable compounds

Abstract

A hydrophilic microporous membrane, is provided comprising a hydrophobic membrane substrate exemplified by a polyolefin or partially fluorinated polyolefin membrane. A process is also provided for preparing a hydrophilic membrane by grafting a water soluble polymer to the hydrophobic membrane substrate surface by irradiation means, e.g., ultraviolet irradiation. The invention further concerns a method for making the membrane and process means for filtering a fluid through such membrane.

Claims

1. A composite microporous membrane structure comprising:

a hydrophobic polyolefin microporous precursor membrane having external surfaces and having pores with internal pore surfaces; and

a water soluble hydrophilic polymer comprising polyethylene glycol diacrylate co-extensively applied to said surfaces in a thin liquid coating that is permanently photografted in solid state form onto the internal pore surfaces of the precursor membrane so that the thus grafted membrane structure is hydrophilic, essentially retains the same microporosity as the precursor membrane and is water wettable, and non-leachable.

2. The membrane structure of claim 1 wherein the hydrophilic polymer comprises polyethylene glycol dimethacrylate.

3. The membrane structure of claim 1 wherein the hydrophilic polymer comprises polyethylene glycol di(lower alkyl)acrylate.

4. The membrane structure of claim 1 wherein the polyolefin precursor membrane is a polypropylene membrane.

5. The membrane structure of claim 1 wherein the polyolefin precursor membrane is a partially fluorinated polyolefin membrane.

6. The membrane structure of claim 1 wherein the polyolefin precursor membrane is a polyvinylidene difluoride membrane.

7. A method of making a hydrophilic microporous membrane comprising:

forming a composite porous membrane formed from a microporous hydrophobic membrane substrate having external surfaces and pores with internal pore surfaces formed of a first polymer comprising polyolefin, said substrate being directly coated over its entire surfaces with a second polymer comprising polyethylene glycol-dialkylacrylate, said composite porous membrane having essentially the same porous configuration as said porous membrane substrate;

by contacting said porous membrane substrate with a photografting solution of said second polymer and a photoinitiator in ethylene glycol, and exposing said second polymer to radiation ray treatment to graft said second polymer in situ over the entire surfaces of said substrate under conditions such that the thus grafted membrane is hydrophilic, essentially retains the same microporosity as the membrane substrate and is water wettable and non-leachable, while avoiding plugging of said pores.

8. A method according to claim 7 where the precursor membrane substrate is formed of polypropylene.

9. A method according to claim 7 where the second polymer comprises polyethylene glycol dimethacrylate.

10. A method according to claim 7 where said photografting solution comprises polyethylene glycol dimethacrylate, a photoinitiator, a low surface tension liquid, and ethylene glycol.

11. A method according to claim 10 where the photoinitiator comprises a hydroxyalkylphenone having the formula ##STR4## where R₁ represents hydrogen, or a C_1-4 alkyl or alkoxy group or halogen, and R₂ and R₃ independently represent C_1-4 alkyl or alkoxy groups.

12. A method according to claim 7 wherein the amount of water soluble polymer concentration in the solution is such that the resulting grafted membrane structure retains microporosity and is readily wettable in water and is non-leachable.

13. A method according to claim 7 wherein the radiation ray treatment comprises:

wetting the hydrophobic membrane substrate completely in the photografting solution;

removing excess solution from the thus wetted membrane substrate, and

exposing the resulting residually wet membrane in a UV chamber under inert gas for about 10 to about 50 seconds at a UV intensity of about 140 mW/cm² to graft the polyethylene glycol dialkylacrylate to the membrane substrate.

14. A method according to claim 13 comprising:

soaking the thus grafted membrane substrate in a water soluble solvent for a time sufficient to remove photografting contaminants from the membrane substrate; and

washing the thus soaked membrane substrate with water and drying the washed substrate.