United States Patent [19]

' Lopatin et al.

[54] MICROPOROUS MEMBRANES FROM
POLYPROPYLENE

[11] Patent Number:

[45]
[56]
3,713,875

4,874,567
Oct. 17 , 1989

Date of Patent:
References Cited

U.S. PATENT DOCUMENTS

1/1973 Beyer et al. .................. .. 210/490 X

[75] Inventors: George Lopatin, Newton Centre; Larry Y, Yen, Tewksbury;Randa11 R,

Rogers Binerica an of Mass_

4,214,020 7/1980 Ward et a1. 4,406,673 9/1983 Yamada et a1.

4,519,909 5/1985 Castro . . . . . . . . . . .

210/490 X 264/451 X
. . . .. 210/ 500.27

4,539,256

9/1925

Shipman

..... .. 264/41 X

4,726,989

2/1988

Mrozinski .................. .. 264/2888 X

[73] Assignee: Millipore Corporation, Bedford,

Mas-5'

Ian-ma), Examiner~prank spear

Attorney, Agent, or Firm-Andrew T. Karnakis; Paul J. Cook

[21] Appl. No.: 42,138

22 FH d: A . 24 1987 [ 1 e pr _ [51] Int. Cl.4 ............................................ .. B29D 27/04 [52] U.S. Cl. ................................. .. 264/45.1; 210/490;

[57]

ABSTRACI

Microporous polypropylene membrane or hollow ?bers

is formed from a melt blend of 5 to 20 weight percent polypropylene and a solvent. The melt blend is shaped and cooled to effect solid phase separation of the poly propylene from the blend. The solvent is separated from the polypropylene by extraction and the porous poly

210/500,36; 264/288.8
[58] Field of Search ............ .. 210/490, 500.13, 500.36,

propylene is dried under restraint to prevent shrinkage.

210/41, 49; 264/451, 288.8; 428/3155

8 Claims, 3 Drawing Sheets

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US. Patent

Oct. 17,1989

Sheet 1 of3

4,874,567

mm Ow

1
MICROPOROUS MEMBRANES FROM

4,874,567

eliminates the need for stretching of the product during

formation so that the product can be deposited directly
upon a suitable substrate such as a porous woven or

POLYPROPYLENE

unwoven substrate which cannot be stretched. If such a

BACKGROUND OF THE INVENTION 5 process were available, the membrane could be formed onto the porous substrate directly in order to produce This invention relates to a process for producing

microporous polypropylene membranes and to the membrane so-produced.

Microporous membranes include thin sheets and hol

laminates having the increased mechanical strength

which would permit their use in a wide variety of ?ltra tion environments.
SUMMARY OF THE INVENTION

low ?bers generally formed from synthetic thermoplas

tic materials and having a substantially continuous ma trix structure containing open pores or conduits of small size. The size range for pores of microporous mem branes is not precisely de?ned in the art, but it is gener ally understood to extend from about 0.05 microns to about 10 microns. It is disclosed in US. Pat. Nos. 4,247,498 and 4,519,909 as well as in European Patent Application No.

In accordance with this invention, microporous

membranes are formed from polypropylene having an open pore structure which is permeable to both liquids
and gases and can be used as ?ltration media. A mixture

is formed comprising between about 5 and 20 weight

percent polypropylene and the remainder a solvent

which permits solid (crystalline)-liquid separation. The

8330665l.7 and 833066525 that polypropylene micro mixture is heated and extruded to form a ?lm or hollow porous membranes can be formed by casting under 20 ?bers which then is quenched to effect phase separation conditions to effect a thermally induced phase separa of the polypropylene from the solvent. The solvent is tion. A mixture of polypropylene and an initially incom separated from the polypropylene by extraction and the patible liquid is heated to form a homogeneous solution resultant polypropylene membrane is dried under re
' which is then cooled under non equilibrium thermody

namic conditions to initiate liquid-liquid phase separa tion. The polypropylene is solidi?ed by further cooling and the liquid dispersed within the solid matrix is re
moved by extraction to form a microporous structure. It is disclosed that different microporous structures can

straint in order to minimize or prevent membrane

shrinkage and collapse. In addition, the present inven tion provides laminate products wherein a porous poly

propylene membrane sheet produced by the process of

this invention is adhered directly to a porous sheet sub
strate on one or both surfaces of the membrane without the use of an adhesive.

be formed by varying the cooling rate. A slow cooling

rate produces a cellular microstructure whereas a rapid cooling rate results in a lacey noncellular structure. It is disclosed that the choice of solvents is critical and only

BRIEF DESCRIPTION OF THE FIGURES

those which will result in liquid-liquid phase separation are useful. The solvents which exhibit solid (crystal
line)-liquid separation behavior are not useful in pro

FIG. 1 is a flow diagram depicting the process of this

invention. '

FIG. 2 shows the melt and crystallization curves for

FIG. 3 shows the melt and crystallization curves for phthalate is speci?cally disclosed as being a nonuseful polypropylene and mineral oil. solvent in these processes. US. Pat. No. 4,539,256 and 4,519,909 also discloses a method for forming micropo 40 DESCRIPTION OF SPECIFIC EMBODIMENTS rous membranes from polypropylene at column 13, lines In accordance with this invention, it has been found 17-28. In the process, between 30 and 80 weight percent that membranes having a desired porosity and strength of a polymer is mixed with a solvent at an elevated can be formed from a melt blend of polypropylene and temperature high enough to dissolve the polypropyl a solvent which permits solid (crystalline)-liquid phase ene. Thereafter the mixture is cooled to effect crystalli separation wherein the polypropylene comprises be zation of the polypropylene and a shaped article such as tween about 5 and about 20 percent weight percent of a ?lm is formed during the cooling. The article is subse the blend. If a proportion of polypropylene greater than quently subjected to stretching (orientation) in order to about 20 weight percent in the blend is employed, the produce the desired product. The resultant product is resulting membrane will have an undesirably low poros microporous characterized by a multiplicity of spaced, ity while membranes formed from melt blends having a randomly dispersed non-uniform shaped, nonporous concentration of polypropylene less than about 5 per particles of the polypropylene. Adjacent particles cent are too weak for use in a ?ltration environment. throughout the material are separated from one another The use of this type of solvent also has been found to be to provide micropores and which particles are con essential in the process of this invention. In contrast, if nected to each other by a plurality of ?brils consisting a solvent which effects liquid-liquid phase separation of the polypropylene. Suitable solvents include mineral such as dibutyl phthalate is utilized as the solvent or oil and dioctyl phthalate. Since this product must be porogen, the resultant membrane may form closed cells oriented or highly stretched during its formation, it and is not suitable for ?ltration. cannot be deposited directly on a substrate which can In the ?rst step of this invention a melt blend of poly not be highly stretched such as a woven, nonwoven or 60 propylene and solvent is prepared which contains be knitted substrate. tween about 5 and 20 percent of polypropylene based It would be desirable to provide a process for produc upon the total weight of the blend. The-melt blend of ing microporous polypropylene membranes which per mit the use of solvents which effect a solid (crystalline) polypropylene and solvent is formed by heating to at liquid phase separation since it would promote solubili 65 least the melting temperature of the polypropylene and zation of the polymer in the solvent. In addition, it usually between about 180 and about 220 C. In the would be desirable to provide such a process which formation of the melt blend, the polypropylene and the

ducing microporous structure. In particular, dioctyl

polypropylene and dioctyl phthalate.

produces a product having uniform porosity and which

solvent are mixed such as in the mixing barrel of a con

3
mixture is heated during mixing.

4,874,567

ventional twin screw extruding apparatus wherein the

The melt blend is passed from the extrusion zone
through a slot die or a hollow ?ber die to form molten ?lm or molten hollow ?bers. The molten ?lm or hollow

through conduit 18 and into die 20 from which a sheet membrane 22 exits through ori?ce 24. Extrudate ?lm 22 passes over chill roll 26 where the extrudate ?lm 22 is cooled to a temperature for effecting microphase sepa ration of the polypropylene and the solvent into a gel
membrane 23. The gel membrane 23 then passes over

?bers then is quenched such as by being passed through

a quench bath comprising water or the like at a tempera

the guide rolls 28 and then through the bath 30 contain

ture below the phase separation temperature of the

polypropylene to form gel ?lm or hollow ?ber. Alterna
tively, the extruded molten membrane or ?bers can be

ing a liquid extractant for the solvent. Membrane 23

then passes out of the bath 30 into an enclosed heating zone 32 wherein the edges of the membrane 23 are

quenched by being passed over cooled rollers at the appropriate temperature in order to effect phase separa
tion of the polypropylene to form a gel-like membrane or ?bers. The gel membrane or ?bers then is immersed

restrained while the polypropylene membrane is option

ally heated in order to dry the membrane. The mem brane 23 then passes over guide rollers 34 and 36 into heat-setting zone 38 wherein the membrane 23 is heat set by heating. The membrane 23 passes out of the heat
setting zone 38 onto wind up roller 40. In an alternative

into a liquid bath which selectively imbibes the solvent

thereby removing it from the polypropylene matrix without substantially softening or dissolving the poly propylene. The imbibing extraction liquid can also func
tion as a quench medium such that the molten ?lm or hollow ?bers can be extruded directly into it. In this

embodiment of this invention, a porous sheet substrate

42 which is housed on roller 44 can be directed to the chill roll 26 in order to contact the extrudate ?lm 22 and be adhered to it without the use of an adhesive. This
' porous sheet can either be inserted between extrudate

case, the quench and extraction steps take place in the same bath. Suitable imbibing liquids include haloethanes

including 1,l,1-trichloroethane, 1,1 dichloro-2-fluoroe

about 50 C. in order to maximize solvent extraction

thane, Freons or methanol or the like. Extraction can be surface. Another embodiment will be to form a three effected at a temperature between about 20 C. and 25

?lm 22 and chill roll 26, or alternatively be placed in contact with ?lm 22 on the air side opposite to chill roll

layer laminate by sandwiching extrudate ?lm 22 be

while not softening the polypropylene. The polypropyl

ene then is dried at a temperature usually between about

tween two porous sheets. Since the substrate is porous, it will have little adverse affect on the liquid extraction

20 C. and about 70 C. and, during drying, the polypro

pylene membrane is restrained in order to prevent

steps, the drying step or the heat-setting step which are downstream. of the chill roll 26.

shrinkage. Optionally, the dry polypropylene can be

heat-set by heating it to a temperature between about 125 C. and about 150 C. in order to further set the characteristic of the membrane. The membrane then
can be rolled onto a core for storage.

The following examples illustrate the present inven

tion and are not intended to limit the same.

As set forth below, the polypropylene/dioctyl

35

phthalate (PP/DOP) and polypropylene/mineral oil (PP/MO) solutions used for making microporous PP
membranes exhibit solid (crystalline)-liquid phase sepa

ration behavior. The crystallization and melt temperatures for PP in the presence of DOP and MO (heavy white mineral oil) were measured by using the Perkin-Elmer DSC-2 dif ferential scanning calorimeter (DSC). Data were ob substrate such as a woven fabric, knitted or non-woven tained as a function of polymer concentration for each fabric, e.g. spun bonded or melt blown, or the like in of the systems. order to adhere the heated polypropylene to the sub At each concentration, a mixture of polymer and strate. This embodiment can be effected since the ex truded polypropylene of this invention is not stretched 45 solvent was prepared directly in the DSC sample pan and heated to above the melting temperature at 20 during subsequent processing. The direct deposition of C./min. heating rate. The mixture was kept at 200 C. the membrane of this invention onto a porous substrate

Representation of suitable solvents include dioctyl

phthalate, mineral oil, hexatriacontane, octadecane,

hexadecane, dodecane and decane. In one embodiment of this invention, the extruded membrane, while hot, can be deposited onto a porous

provides advantages over prior art methods for forming

laminates in that no adhesive is required. Also, the de position can be effected as a single step with the normal

processing of the membrane by threading the porous

substrate so it contacts the membrane being processed over the rollers normally utilized in extrusion process ing. In addition, since no stretching step is utilized in the process of this invention, the porosity and mechanical properties of the resulting laminate product can be

for about 10 mins. It was then cooled at 20 C./min cooling rate to a temperature below the crystallization peak. The crystallization temperature was taken as the temperature corresponding to the onset of crystalliza
tion. The mixture was then reheated at 20 C./min rate

above the melting peak. The melting temperature was

taken at the end of the peak, corresponding to the melt

ing of the highest melting crystallites.

The melt and crystallization curves for each of the PP/DOP and PP/MO systems are shown in FIGS. 2 and 3 respectively. In both systems, the melt and crys tallization temperatures increase as a function of poly mer concentration. No constancy in temperature is
observed over any concentration range. These results demonstrate both PP/DOP and PP/MO systems ex

made essentially isotropic. The polypropylene microporous product of this in

vention is characterized by open pores of an average size of between about 0.1 and about 1 micron.

A typical process useful for producing the membrane product of this invention is depicting in FIG. 1. An

hibit crystalline (solid)/liquid phase separation behavior extruder 10 is provided which is connected to a hopper on cooling, and both solvents are thermodynamically 12 from which polypropylene is introduced into the extruder 10. A tank 14 and conduit 16 are provided for 65 good solvents for PP. A constancy in temperature over introducing the solvent into the extruder 10 for admix a portion of the concentration range would have dem ture with the polypropylene. The melt blend of poly onstrated liquid-liquid phase separation behavior. A propylene and solvent is removed from extruder 10 solvent exhibiting such behavior is a thermodynami

5
EXAMPLE 1

4,874,567

cally poorer solvent than dioctyl phthalate (DOP) or mineral oil (MO).

The removal of MO from the quenched PP/MO ?lm was performed similarly as in Example 2 with the ex
ception that the ?nal membrane was dried from water rather than Freon. The Freon in the membrane after
5 extraction was exchanged with water via an intermedi

A 15% by weight polypropylene (PP) (Himont 6824

PM powder) slurry in DOP was prepared at room tem perature. It was pumped into a heated Werner and

ate isopropyl alcohol exchange. The drying from water allowed the restrained membrane to remain intact with
out breaking. The drying and heat set temperature were the same as in Example 1. The properties of this mem
TABLE II

P?eiderer ZSK 30 co-rotating twin-screw extruder (L/D=27). The feed rate was approx. 40 lbs/hr with

the screws rotating at 310 rpm. The screws in the ex- 10 brane are given in Table II.
Microporous Polypropylene Membrane from Examnle 2
Chill Roll

Quench Temp. (C.)

30

Final Membrane Thickness (um)

85

Porosity (a) %
43

Iso-Propyl Alcohol (b) Bubble Point (psi)

20

Water Flow (c) Rate (ml/min/cmz)

9.2

truder consist of interchangeable conveying and kneadWe claim: ing disc elements of varying pro?les to allow for melt- 20 1. A process for forming a microporous polypropyl ing, mixing and conveying of the blend. A Zenith gear ene membrane which comprises the following steps in sequence: pump, a Koch static mixer (1.5 diameter, 14" length) and a 16" wide ?lm die were used downstream of the (a) forming a melt-blend consisting essentially of extruder. The temperature at various zones of the extru polypropylene and a solvent capable of effecting
sion line ranged from 165 C. to 210 C. N; purge in the

solid liquid phase separations of polypropylene

therefrom containing between about 5 and 20

extruder was employed during the operation. The PP/DOP solution was extruded from the ?lm die (die gap=0.33 mm) and quenched on a rotating chrome plated chill roll. The temperature of the chill roll was

weight percent polypropylene based upon the weight of the blend,

(b) shaping said melt-blend to form a shaped precur
sor to said membrane,

maintained by circulating thermostated liquid through

its core. The extruded ?lm after quench was about 75
um in thickness and was rolled up with a motorized

(0) cooling said shaped precursor to a temperature at which said solvent separates from polypropylene

wind-up unit.
To remove the DOP from the quenched PP/DOP ?lm, a section of the ?lm was restrained on a rectangu lar metal frame and placed in an excess volume of Freon

TF (1, l, 2-trichlorotri?uoroethane) solvent, which is

miscible with DOP and practically inert to PP. The extraction time used was approximately two hours, with one Freon change during this time. The restrained sample was then removed from the Freon bath and, still restrained, allowed to dry at 70 C. After drying, the white rnicroporous membrane was further heat-set with restraint at 148 C. for 10 mins. The properties of the membranes prepared at various chill roll quench tem
peratures are given in Table I.
. . 45

by solid-liquid phase separation to form a gel ?lm, (d) selectively extracting said solvent formed from said gel ?lm in step (c) to form a microporous polypropylene membrane and (e) drying said membrane from step (d) while said
membrane is restrained to prevent said membrane

from shrinking.
2. The process of claim 1 wherein said shaped precur
sor is contacted with a porous sheet substrate to adhere

said precursor to said sheet substrate prior to cooling

said shaped precursor.

3. The process of claim 1 wherein said dried mem brane is heat-set.
4. The process of claim 2 wherein said dried mem
. . . .

TABLE I
Microporous Polypropylene Membrane from Example 1
Chill Roll

Quench Temp. (C.)

39

Final Membrane Thickness (pm)

42

Porosity (a) %
52

Iso-Propyl Alcohol (b) Bubble Point (psi)

44

Water Flow (0) Rate (ml/min/cm2)

3.1 -

49 59 69 79 84

49 52 63 71 76

60 66 70 74 77

32 21 18 15 10

5.4 12.0 14.9 19.5 39.0

(a) Percent void volume in sample (1:) ASTM 5128-61 (0) ASTM F3l7-72 sample prewet with iso-propyl alcohol

60 brane is heat-set.

5. The process of any one of claim 2 or 4 wherein said

EXAMPLE 2

substrate is a woven fabric.

6. The process of any one of claim 2 or 4 wherein said

substrate is a non-woven fabric.
65

A 20% by weight of PP (Himont 6824 PM powder) slurry in MO (ARCO prime 350) was used for extrusion and preparation of microporous PP membrane. The
slurry feed rate was about 35 lbs./hr. The temperature
of the chill roll was maintained at 30 C. and the

7. The process of any one of claims 1, 2, 3 or 4

wherein said solvent is dioctyl phthalate.

8. The process of any one of claims 1, 2, 3 or 4

wherein said solvent is mineral oil.

* * * * *

quenched ?lm was about 130 microns thick.