# US 7,745,538 B2 · Polymer composite, film thereof and separation membrane made therefrom

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- Number: US 7,745,538 B2
- Document ID: US7745538B2
- Status: Granted
- Kind: B2
- Application number: 10/591,057
- Filed: 2005-02-16
- Published: 2007-08-09
- Granted: 2010-06-29
- Earliest claimed: 2004-10-26
- Inventors: Yongsok Seo
- Web page: https://patentgrep.com/patent/US7745538B2

## CPC

- C08J 5/2275: {Heterogeneous membranes}
- B01D 53/228: {characterised by specific membranes}
- B01D 67/002: {from melts}
- B01D 69/1411: {containing dispersed material in a continuous matrix}
- B01D 69/148: {Organic/inorganic mixed matrix membranes}
- B01D 71/281: {Polystyrene}
- B01D 71/403: {Polymers based on the polymerisation of maleic acid or derivatives thereof}
- B01D 71/5222: {Polyetherketone, polyetheretherketone, or polyaryletherketone}
- C08J 5/18: Manufacture of films or sheets
- C08L 71/12: Polyphenylene oxides
- B01D 71/56: Polyamides, e.g. polyester-amides
- B01D 71/80: Block polymers
- B01D 2323/12: Specific ratios of components used
- B01D 2325/20: Specific permeability or cut-off range
- C08J 2371/12: Polyphenylene oxides
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

Polymer composite including a compatibilizer and having selective permeability to chemical permeants due to interaction differences between the compatibilizer and the chemical permeants, includes 50-99 wt % of an amorphous thermoplastic resin selected from the group polyethylenepropylendienterpolymer, poly(1-(trimethylsilyl)-1-propyne), amorphous nylon, polystyrene and polycarbonate; 0.9-50 wt % of a semi-crystalline polymer selected from the group polyamide (nylons), polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, polyetheretherketone, polyvinylidene fluoride, polytetrafluoroethylene, polyphenylene sulfide, and thermotropic or lyotropic liquid crystal polymer, and dispersed in the amorphous thermoplastic resin to provide a dispersed phase having an interface with the amorphous thermoplastic resin; and 0.1-10 wt % of a compatibilizer positioned at the interface of the dispersed phase with the amorphous thermoplastic resin and having different interactions with different chemical permeants so that the selective permeability of the polymer composite is affected.

## Claims

### Claim 1

Polymer composite including a compatibilizer and having selective permeability to chemical permeants due to interaction differences between the compatibilizer and the chemical permeants, the polymer composite comprising:
50-99 wt % of an amorphous (or low crystalline) thermoplastic resin as a matrix resin selected from the group consisting of polyethylenepropylendienterpolymer, poly(1-(trimethylsilyl)-1-propyne), -amorphous nylon, polystyrene and polycarbonate;
0.9-50 wt % of a semi-crystalline polymer selected from the group consisting of polyamide (nylons), polyethylene terephthalate, polybuthylene terephthalate, polyethylene, polypropylene, polyetheretherketone, polyvinylidene fluoride, polytetrafluoroethylene, polyphenylene sulfide, thermotropic liquid crystal polymer, and lyotropic liquid crystal polymer, and dispersed in the amorphous thermoplastic resin to provide a dispersed phase having an interface with the amorphous thermoplastic resin; and
0.1-10 wt % of a compatibilizer consisting of a block copolymer or a graft copolymer having compatibility or compatibility generated by interfacial reaction, being selected from the group consisting of poly(styrene-co-maleic anhydride), random or block copolymer of styrene and maleic, polystyrene whose oxazoline group is substituted, amorphous polymer added with a maleic anhydride group, polycarbonate having a reaction group, and polystyrene having a reaction group, and positioned at the interface of the dispersed phase with the amorphous thermoplastic resin, and having different interactions with different chemical permeants so that the selective permeability of the polymer composite is affected.

### Claim 2 (depends on 1)

The polymer composite according to claim 1, wherein the amorphous thermoplastic resin is present in an amount of 75-95 wt %, the semi-crystalline polymer is present in an amount of 4.9-25 wt %, and the compatibilizer is present in an amount of 0.1-5 wt %.

### Claim 3 (depends on 1)

The polymer composite according to claim 1, wherein the semi-crystalline polymer has low gas permeability irrespective of degree of crystallinity and is selected from the group consisting of polyamide (nylons), polyethylene terephthalate, polyethylene, polypropylene, polyetheretherketone, polyvinylidene fluoride, polytetrafluoroethylene, polyphenylene sulfide, thermotropic liquid crystal polymer, and lyotropic liquid crystal polymer.

### Claim 4 (depends on 1)

The polymer composite according to claim 1, wherein the compatibilizer is positioned at the interface between the amorphous thermoplastic resin and the semi-crystalline polymer to lower interfacial tension there between so that dispersion is improved, interfacial adhesion is strengthened, and interaction with diffusing gas molecules varies to vary respective gas diffusion rates.

### Claim 5 (depends on 1)

A method for preparing a film from the polymer composite claimed in claim 1, comprising the step of:
a. forming a melt blend by mixing the thermoplastic resin, the semi-crystalline polymer and the compatibilizer; and
b. axially drawing the melt blend obtained from step (a) using an extension apparatus or film blowing apparatus connected to an extrusion die to fabricate a film,
wherein the semi-crystalline polymer has a phase having a stripe shape in the film due to non-equal biaxial drawing, so that the film has greater extension in the vertical direction than in the horizontal direction.

### Claim 6 (depends on 5)

A film prepared by the method claimed in claim 5.

### Claim 7 (depends on 5)

The method according to claim 5, wherein the extrusion die has a dual mandrel of which inside and outside are rotated in opposite directions, so that a morphologically modified semi-crystalline phase is formed in a net shape.

### Claim 8 (depends on 7)

A film prepared by the method claimed in claim 7.

### Claim 9 (depends on 5)

The method according to claim 5, wherein the extrusion die is a multiple coextrusion dye, wherein the film is a multilayer film composed of a plurality of layers that is fabricated by using the multiple coextrusion die.

### Claim 10 (depends on 9)

A film prepared by the method claimed in claim 9.

### Claim 11 (depends on 1)

A gas separation method, comprising:
providing a gas separation membrane comprised of the polymer composite of claim 1; and
using the gas separation membrane to separate gases.

### Claim 12 (depends on 1)

The polymer composite according to claim 1, wherein the amorphous crystalline polymer of the matrix resin has a higher melting point than that of the semi-crystalline polymer at the processing temperature.

### Claim 13 (depends on 12)

An oriented film prepared from the polymer composite of claim 12.

### Claim 14 (depends on 13)

Gas separation method, comprising:
providing the oriented film of claim 13; and
using the oriented film as a gas separation membrane.

### Claim 15 (depends on 1)

The polymer composite according to claim 1, wherein the semi-crystalline polymer consists of one or more of said semi-crystalline polymer selected from the group consisting of polyamide (nylons), polyethylene terephthalate polybuthylene terephthalate, polyethylene, polypropylene, polyetherketone, polyvinylidene fluoride, polytetrafluoroethylene, polyphenylene sulfide, thermotropic liquid crystal polymer and lyotropic liquid crystal polymer.

### Claim 16 (depends on 15)

A thin film that is a one layer thin film or a multilayer thin film comprising the polymer composite of claim 15.

### Claim 17 (depends on 16)

A method of preparing the thin film of claim 16, comprising the step of:
a. forming a melt blend by mixing thermoplastic resin, the semi-crystalline polymer and the compatibilizer; and
b. axially drawing the melt blend obtained from step (a) using an extension apparatus or film blowing apparatus connected to an extrusion die to fabricate a film,
wherein the semi-crystalline polymer has a phase having a stripe shape in the film due to non-equal biaxial drawing, so that the film has greater extension in the vertical direction than in the horizontal direction.

### Claim 18 (depends on 17)

The method according to the claim 17, wherein the extrusion die has a dual mandrel of which inside and outside are rotated in opposite directions, so that a morphologically modified semi-crystalline phase is formed in a net shape.

### Claim 19 (depends on 15)

The polymer composite according to claim 15, wherein the amorphous crystalline polymer of the matrix resin has a higher melting point than that of the semi-crystalline polymer at the processing temperature.

### Claim 20 (depends on 17)

An oriented film prepared by the method of claim 17.

### Claim 21 (depends on 20)

Gas separation method, comprising:
providing the oriented film of claim 20; and
using the oriented film as a gas separation membrane by passing gases through the oriented film to cause separation of the gases.

### Claim 22 (depends on 1)

A polymer composite film for gas separation, wherein the semi-crystalline polymer of claim 1 has a thickness in nanometers.

### Claim 23 (depends on 6, 13)

A film according to claim 6 or 13, wherein the dispersed phase is composed of at least one inorganic material and the film includes a compatibilizer for the matrix resin and the dispersed phase.

### Claim 24 (depends on 23)

Gas separation method, comprising:
providing the film of claim 23; and
using the film as a gas separation membrane by passing gases through the film to cause separation of the gases.

### Claim 25 (depends on 1, 2)

The polymer composite according to claim 1 or 2, wherein the compatibilizer is positioned at the interface by reaction with the matrix resin or the dispersed phase to form a copolymer.

### Claim 26 (depends on 1)

A polymer composite gas separation membrane according to the claim 1, wherein the compatibilizer is positioned at the interface by reaction with the matrix resin or the dispersed phase to form a copolymer.

### Claim 27 (depends on 20, 23)

A film according to claim 20 or 23, wherein, when the matrix resin is PPO (poly(2,6-dimethyl-1,4-phenylene oxide) and the dispersed phase is polyamides, the compatibilizer is a random copolymer or a block copolymer of styrene and maleic anhydride.