Continuous process for preparing particulate microporous, open-celled polymer structures in a screw-type extruder

BACKGROUND OF THE INVENTION
Mechanical grinding methods for preparing polymers in particulate form are useful only with polymers that possess sufficient modulus or brittleness to be broken down into particulate forms. For certain polymers such as polyacrylates, polyethylene, polypropylene, or ionic copolymers, comminution is difficult and must be carried out under cryogenic conditions. The process of this invention provides a process for producing comminuted polymer structures without cryogenic "grinding".
The process of this invention is an improvement over the processes taught in U.S. Pat. Nos. 3,752,784 and 3,753,932. This patent application is related to "A Process For Preparing Particulate Microporous, Open-Celled Polymer Structures", coassigned, and filed concurrently herewith in the name of Francis Edward Jenkins, bearing U.S. Ser. No. 576,634. It is also related to "A Process For Preparing Microporous, Open-Celled Cellular Polyblend Structures", coassigned, and filed concurrently herewith in the name of Francis Edward Jenkins, bearing U.S. Ser. No. 576,631.
SUMMARY OF THE INVENTION
The invention herein concerns a process for making particulate structures without the need for employing surface active agents, and with zero or negligible amounts of cosolvents or water. The method of this invention permits rapid continuous preparation of fine, uniform polymer powders at a high ratio of polymer to chlorofluorocarbon feed. It has been found that polymer solution having a solids content of up to at least 50% can be prepared and processed into fine polymeric powders in a matter of minutes. Further, plasticizers or pigments required in the end use of the polymer powders can be directly incorporated into the powder during the process of this invention.
The invention concerns a continuous process for preparing particulate, microporous, open-celled polymer structures comprising
I. CONTINUOUSLY FEEDING FROM ABOUT 5 TO 50 PARTS BY WEIGHT OF A NORMALLY SOLID ORGANIC POLYMER AND FROM ABOUT 95 TO 50 PARTS BY WEIGHT OF A CHLOROFLUOROCARBON OR A MIXTURE OF CHLOROFLUOROCARBONS HAVING A BOILING POINT IN THE RANGE OF FROM ABOUT 10.degree. C. to 150.degree. C., a melting point in the range of about -40.degree. C. to 125.degree. C., an entropy of fusion of less than 10 calories/.degree.K./mole, a plastic flow index of at least 0.1 g/10 minutes at the reduced temperature of 0.96 to 0.99 and a solubility in water of less than 2 weight percent to a screw-type extruder having first and second temperature zones,
ii. nonrandomly milling said polymer and said chlorofluorocarbon in said first zone at a temperature equal to or above the melting point of the highest melting chlorofluorocarbon present to provide a uniformly milled mixture,
iii. passing said uniformly milled mixture to said second zone and nonrandomly milling said mixture and cooling said mixture to a temperature equal to or below the solidification temperature of the lowest melting chlorofluorocarbon present to form a frozen mass,
iv. extruding the frozen mass from the second zone as a snow-like mass, and
v. removing the chlorofluorocarbon from the snowlike mass at a temperature equal to or below the solidification temperature of the lowest melting chlorofluorocarbon present.
By "nonrandomly milling" as the term is employed herein is meant that each portion or element of the polymerchlorofluorocarbon mixture, no matter how viscous or concentrated is the mixture, receives essentially the same degree of sheer stress for essentially the same period of time at essentially the same temperature.
The normally solid organic polymers have a glass transition temperature (T.sub.g) or a crystalline melting point (T.sub.m) of at least 293.degree. K. As employed herein, the term "polymer" includes homopolymers and/or copolymers depending upon the context.
The chlorofluorocarbon solvent contemplated herein is selected from at least one member of the group consisting of
______________________________________ Melting Boiling Point Point .degree. C. .degree. C.______________________________________1,1,1,2,2-pentachloro-2-fluoroethane 100 1371,1,2,2-tetrachloro-1,2-difluoroethane 24 931,1,1,2-tetrachloro-2,2-difluoroethane 41 921,1,2-trichloro-1,2,2-trifluoroethane -37 481,1,1-trichloro-2,2,2-trifluoroethane 14 461,1,1,3-tetrafluoro-2,2,3,3-tetrachloropropane 42 1121,1,1,3,3-pentafluoro-2,2,3-trichloropropane -4 721,1,1,3,3,3-hexafluoro-2,2-dichloropropane 3 331,1,1,4,4,4-hexafluoro-2,2,3,3-tetrachlorobutane 86 131-1361,1,2,2-tetrachloroperfluorocyclobutane 85 1361,2-dichloroperfluorocyclobutane -15 601-chloroperfluorocyclobutane -39 271,2-dichloroperfluorocyclohexane 34 108______________________________________
In the list of chlorofluorocarbons, the melting points and boiling points have been given to the nearest whole degree. The preferred chlorofluorocarbon is 1,1,1,2-tetrachloro-2,2-difluoroethane. The preferred mixture is 1,1,1,2-tetrachloro-2,2-difluoroethane and 1,1,2,2-tetrachloro-1,2-difluoroethane.
Cosolvents can be employed herein at up to 9 volumes per volume of chlorofluorocarbon. Contemplated cosolvents include methanol, ethanol, isopropanol, t-butanol, dimethylformamide, dimethylacetamide, dioxane, trioxane, dimethyl sulfoxide, tetrahydrofuran, acetone, methyl ethyl ketone, hexamethylphosphoramide, acetic acid, butyrolactone, N-methylpyrrolidone, pyridine, morpholine, methyl "Cellosolve", ethyl "Cellosolve", propyl "Cellosolve" and mixtures thereof. Usually, the cosolvent is present, if at all, from at least about 0.1 volume per volume of solvent, and preferably at from about 0.5 to 1.5 volumes per volume.
Polymers useful in the process of this invention include
I. addition polymers such as
a. homopolymers such as polystyrene, polyisobutylene, polyethylene, polypropylene, polychloroprene, polybutadiene, polyisoprene, polyvinyl acetate, polyvinyl chloride, polymethyl methacrylate, polybutyl methacrylate, and the like;
b. copolymers such as those of styrene-butadiene, ethylene-propylene-diene, styrene-butadiene-isoprene, ethylenevinyl acetate, styrene-acrylonitrile-butadiene, ethylenemethacrylic acid, hexafluoropropylene-vinylidene fluoride, vinylidene fluoride-tetrafluoroethylene-vinyl butyrate, tetrafluoroethylene-isobutylene, methyl methacrylate-butyl methacrylate and the like;
Ii. condensation polymers such as polyurethane, polyamide, polycarbonate, polyester, polyvinyl butyral, polysulfone, polyepoxide, polyphenylene oxide and the like; and
Iii. cellulosic polymers such as ethyl cellulose, cellulose acetate, cellulose acetate-butyrate and the like.
It is highly desirable that the polymers employed in the novel process have either T.sub.g or T.sub.m of at least 293.degree. K. since those polymers which do not have said minimum T.sub.g or T.sub.m values will form powders which can coalesce at ambient temperatures to provide products which are not free-flowing powders.
Glass transition temperature (T.sub.g) and crystalline melting point (T.sub.m) are well-known terms in the polymer art. Glass transition temperature (T.sub.g) is the temperature at which the polymer abruptly changes from hard, brittle, and glassy to a softer, more flexible, and rubbery material. Crystalline melting point (T.sub.m) is the temperature at which the polymer crystalline phase disappears with a drastic change in the physical properties such as becoming a viscous liquid with discontinuous changes in density, refractive index, heat capacity and the like.
Some representative polymers and their T.sub.g and T.sub.m values as listed in "Polymer Handbook" by J. Brandrup and E. H. Immergut, Interscience Publishers, 1966, pp. III-1 to III-75 are listed below.
______________________________________ T.sub.g (.degree. K.) T.sub.m (.degree. K.)______________________________________polyethylene low pressure-linear 148 383polypropylene isotactic 263 449polymethylmethacrylate random 378 isotactic 318 433 syndiotactic 388 473polyvinyl chloride syndiotactic 354.sup.(1) 485.sup.(1)polystyrene isotactic 373 513(1,2)-poly-1,3-butadiene isotactic 269 393 syndiotactic 427(1,4)-poly-1,3-butadiene trans 255 373polyhexamethylene adipamide 330 538______________________________________ .sup.(1) T.sub.g and T.sub.m are highly dependent on polymerization temperature.

BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1a and 1b are schematic views illustrating the required temperature zones and alternate feeding schemes of the contemplated twin-screw processor.
FIG. 2 is a schematic side view of one screw of the twin-screw processor, showing the arrangement of elements mounted upon the shaft of the screw;
FIG. 3a is a sectional view taken on line 3a--3a of FIG. 2, looking toward the feed end of the twin-screw processor, showing the cross-section of the three-tip screw elements mounted in twin-bore barrels;
FIG. 3b is a sectional view taken on line 3b--3b of FIG. 2, looking toward the discharge end of the twin-screw processor, showing the cross-section of three-tipped kneading discs mounted in twin-bore barrels;
FIG. 3c is a sectional view taken on line 3c--3c of FIG. 2, looking toward the feed end of the twin-screw processor, showing the cross section of deep flighted screws mounted in twin-bore barrels;
FIG. 4a is a detailed side view of a three-tip screw element and three-tip kneading discs of the types shown in cross-section in FIGS. 3a and 3b, mounted together as schematically shown in FIG. 2;
FIG. 4b is a detailed side view of one of the deep-flighted screw elements shown in FIG. 3c.

DETAILS OF THE INVENTION
Referring to the Figures, the process of this invention is carried out in twin-screw devolatilizing processor 1. As shown schematically in FIGS. 1a and lb, the processor consists of three zones: feed zone A, melt zone B, and cooling and milling zone C. Cool fluid, such as cold water, is circulated in cold zones A and C through the jacketed twin bore barrel enclosing the co-rotating screws. Heat can be supplied to zone B by circulating hot fluid through the jacketed barrel; or alternatively, electric heating elements may be used to supply heat to zone B.
In one scheme, as shown in FIG. 1a, a premix of organic polymer pellets or granules plus unmelted chlorofluorocarbon is fed into feed zone A through feed port 2. Alternatively, as shown in FIG. 1b, polymer pellets alone are fed into feed zone A through feed port 2 and molten chlorofluorocarbon is injected downstream into melt zone B through injection port 3. In either scheme, polymer and chlorofluorocarbon are forcibly advanced to melt zone B and worked into a solution by the kneading action of the screws and kneading elements with the aid of the additional heat (if needed) supplied through the screw barrel.
The temperature of zone B is maintained equal to or higher than the melting point of the chlorofluorocarbon. The solution is then forcibly advanced to milling zone C where the solution is cooled to form a frozen mass and agitated vigorously. The temperature of zone C is maintained equal to or lower than the solidification temperature of the chlorofluorocarbon. The agitated mass exits the extruder from zone C in the form of a snow-like mass from which mass chlorofluorocarbon is easily removed by sublimation to leave a fine, uniform organic polymer powder.
The preferred arrangement of elements mounted upon the shaft of the screw 20 is illustrated in FIG. 2 and consists of: an initial section 21 of co-rotating, righthanded, self-wiping screw with a fine screw pitch upstream of the injection ports; a section 22 of co-rotating, righthanded, deep flighted, non-self-wiping screws with a relatively coarse screw pitch into which section the components of solution are fed through feed port 2; a pumping and transport section 23 of co-rotating, right-handed, self-wiping screws with a fine screw pitch; a homogenizing section 24 of co-rotating kneading discs, followed by a short section 25 of left-handed screw elements; a pumping and transport section 26 of co-rotating, right-handed self-wiping screws; two homogenizing sections 27 and 28 separated by a section 29 of co-rotating right-handed screws of fine screw pitch; and a final discharge section 30.
As shown in FIGS. 3a, 3b, and 3c, these screw sections are assembled by sliding bushings 14 and 14' on shafts 15 and 15' to form the twin screws 20 and 20'. Keys 16 and 16' prevent rotation of the bushings with respect to the axis and thereby maintain the desired surface configuration of the screw.
The screw elements of sections 21, 23, 26, 29 and 30 are bushings having three-tipped cross section 17 and 17' as illustrated in FIG. 3a with the cross sections being continuously rotated along the length of the axes of the bushings to evolve triple-threaded screw surfaces as illustrated in FIG. 4a. The pitch and fineness of the screw surfaces are regulated as desired, and the bushing-to-bushing and bushing-to-wall clearances are kept small so that the screw elements wipe one another and the wall as the shafts rotate together in the same direction.
The kneading elements of homogenizing sections 24, 27, and 28 are bushings having three-tipped cross sections 18 and 18' as illustrated in FIG. 3b which when rotated do not evolve a triple-threaded screw. These three-tipped bushings are placed on the shaft alternately at a 60.degree. angle and at a coincident angle to the preceding screw elements. The kneading elements are continuously self-wiping just as the screw elements are.
The deep flighted screw elements of section 22 are bushings having three-tipped cross sections 19 and 19' as shown in FIG. 3c with the cross section being continuously rotated along the length of the axis of the bushing to evolve triple-threaded screw surfaces as illustrated in FIG. 4b. However, the bushing-to-bushing clearances of the deep flighted screws are kept large and the screws are not self-wiping although the barrel walls are wiped.
The twin-screw processor described above is just one example of many possible configurations that could be used for this invention. The deep flighted screw elements of section 22 would probably not be required on processors with larger screw diameters. Similarly, monolithic screws machined into proper configurations could be used rather than separate sliding bushings on screw shafts.
Concerning the useful chlorofluorocarbons and their various characterizing features as described herein: boiling points, melting points, and solubilities have the usual meaning. Entropy of fusion is defined as .DELTA. H.sub.f /T.sub.f where .DELTA. H.sub.f is the heat of fusion in calories per mole and T.sub.f is the fusion temperature in .degree. K. (degree Kelvin). Plastic flow index is a measure of the rate of extrusion of solid chlorofluorocarbon as measured on a plastometer according to ASTM D1238-65T and the reduced temperature is defined as T/T.sub.f where T is the temperature at which the plastic flow index is determined and T.sub.f is the fusion temperature, both in .degree. K. It is to be noted that the plastic flow index is determined at a temperature below the melting point of the chlorofluorocarbon (reduced temperature less than 1).
Some representative entropy of fusion values and plastic flow index values are given below.
__________________________________________________________________________ Plastic Flow Index Entropy of Reduced Fusion Temp.Chlorofluorocarbon Cal./.degree. K./Mole g/10 Min. (T/T.sub.f)__________________________________________________________________________1,1,1,2,2-pentafluoro-2-fluoroethane 4.15 0.9 0.9771,1,2,2-tetrachloro-1,2-difluoroethane 3.0 0.4 0.9851,1,1-trichloro-2,2,2-trifluoroethane 1.61 1.1 0.9861,1,1,2-tetrachloro-2,2-difluoroethane 3.74 8.5 0.9931,1,1,4,4,4-hexafluoro-2,2,3,3-tetra- chlorobutane 2.43 0.5 0.9851,1,2,2-tetrachloroperfluorocyclo- butane 3.66 3.5 0.9811,2-dichloroperfluorocyclobutane 2.03 -- --__________________________________________________________________________
Below is shown the solidification temperature of mixtures of 1,1,2,2-tetrachloro-1,2-difluoroethane (CCl.sub.2 FCCl.sub.2 F) and 1,1,1,2-tetrachloro-2,2-difluoroethane (CCl.sub.3 CClF.sub.2) as a function of the CCl.sub.3 CClF.sub.2 content in the mixture.
______________________________________Freezing Points of Mixture of CCl.sub.2 FCCl.sub.2 Fand CCl.sub.3 CClF.sub.2Wt. % CCl.sub.3 CClF.sub.2 Freezing Point, .degree. C.______________________________________0 23.510 27.420 28.930 30.440 31.850 33.360 34.770 36.280 37.790 39.1100 40.6______________________________________
The polymer powder produced by the process of this invention contains particles in the range of from about 75 .mu. (micron) to about 1 mm, depending upon the polymer concentration and the degree of subdivision of solidified chlorofluorocarbon-polymer composition. Each powder particle is, however, of microporous, open-celled cellular structure containing a pore size of from 1 to 15 .mu. and a void content of from about 50% to 99%. The pore size and void content are dependent upon polymer concentration. Because of the cellular nature of the powder particles, only a very gentle grinding is required to provide even finer polymer powders of, say, 30- 40 .mu. size.
The cellular nature of the powder particles inherently provides lower bulk density than those powder particles prepared by conventional methods, such as by grinding or pulverizing of bulk polymer. The lower bulk density contributes to the ease of fluidization such as in fluidized bed powder coating process. The microporous, open-celled cellular structure of the powder particles permits post-blending of polymer additives without adversely affecting their fluidizability. Thus, polymer additives such as plasticizer, dyes, pigments or stabilizer can be blended in the conventional amounts with the polymer powder prepared by the present method without appreciably affecting their fluidizability.
Certain process versatilities characterize the novel process of this invention. For instance, "polyblend" powders can be prepared which are physical mixtures of at least two thoroughly mixed, normally incompatible organic polymers. Polyblends are being used increasingly in various industries because they provide characteristics such as greater strength, added toughness, greater flexibility, greater resistance to environmental influences and the like not present to a desirable degree in the individual polymer.
For additional disclosure concerning the process for making particulate (as well as coherent) polyblend structures consult coassigned patent application bearing U.S. Ser. No. 576,631, filed concurrently herewith, having the title "Process for Preparing Microporous, Open-Celled Cellular Polyblend Structures". Said additional disclosure provides a fuller explanation of the types of polyblend structures that can be made (in particulate form) by the process of the instant invention.
Polyblend powders are prepared according to the process of this invention by mixing separate solutions of polymers in chlorofluorocarbon, a mixture of chlorofluorocarbons or a homogeneous solvent blend of chlorofluorocarbon and a cosolvent, and by rapidly cooling the mixture under agitation to provide a snow-like mass of a mixture of polymers dissolved in, or intimately dispersed in, a solidified chlorofluorocarbon matrix. Removal of the chlorofluorocarbon by any known method provides microporous, open-celled, cellular polyblend powders. The successful use of the present process in preparing polyblend powders is based upon the unusually low heats of fusion of the useful chlorofluorocarbons such that the rate of solidification of the chlorofluorocarbon greatly exceeds the rate of polymer separation. Polyblend powders preparable by the present process include polyblend mixtures comprising those polymers which are mutually reactive and/or mutually immiscible in the molten state.
It has now also been found that a simple mixing of a liquid chlorofluorocarbon described herein with an aqueous dispersion of dyes or pigments (the dispersion can be a high-solids-content dispersion such as an aqueous filter press cake) will bring about an almost complete transfer of the dye or pigment into the chlorofluorocarbon phase as fine particles. Such "flushing" into the chlorofluorocarbon phase is equally effective when the aqueous dispersion is mixed with chlorofluorocarbon containing polymer dissolved therein. Thus, by mixing an aqueous dispersion of dye or pigment with a chlorofluorocarbon-polymer solution or its feed stock and proceeding with the process as described herein, colored polymer powders are obtained. The amount of color body incorporated into the polymer will be such that the colored polymer powder can be used as color concentrate for blending with further amounts of polymer powder or the colored polymer powder can be used directly.
The following Examples are meant to illustrate but not limit the scope of this invention. In each Example, the polymer powder produced was found to be a microporous, open-celled structure.
The Twin-Screw Extruder Processor
The twin-screw extruder processor apparatus was assembled in accordance with FIGS. 1-4 from commercially available equipment and screw elements (based on Model ZDS-K28 of Werner & Pfleiderer Maschinenfabrik, Stuttgart, W. Germany). The screws when assembled had a diameter of 27.9-28.0 mm with a radial clearance of 0.075-0.175 mm and total screw length 772 mm, the first 120 mm corresponding to feed zone A, the next 280 mm corresponding to melt zone B, and the next 350 mm corresponding to milling zone C. The screws protruded from the barrel for a distance of 22 mm.
The elements comprising the twin screw used were as follows:
______________________________________Length Element______________________________________48 mm Right-handed screw of 24 mm pitch90 mm Right-handed, deep flighted screw of 45 mm pitch90 mm Right-handed screw of 15 mm pitch40 mm Staggered kneading discs8 mm Left-handed screw of 24 mm pitch16 mm Right-handed screw of 24 mm pitch330 mm Right-handed screw of 30 mm pitch9 mm Staggered kneading discs48 mm Right-handed screw of 24 mm pitch13 mm Staggered kneading discs20 mm Right-handed screw of 30 mm pitch60 mm Right-handed screw of 15 mm pitch______________________________________
EXAMPLE 1
Ethylene/vinyl acetate copolymer pellets, pre-mixed with unmelted 1,1,1,2-tetrachloro-2,2-difluoroethane, were fed to the twin-screw processor described above at a point, 2, 55 mm from the upstream end of the screws at the indicated rate. Zone A was cooled by circulating water at a temperature of approximately 16.degree. C through the jackets of the barrels in the zone. The screws were operated together in clockwise direction viewed from the discharge end, at equal speeds in the range of 50 to 100 rpm.
The polymer-chlorofluorocarbon premix was rapidly transported in large chunks through the deep flighted screws in section 22 into melt zone B to homogenizing section 24 where the mixture was mechanically worked and melted. Zone B was heated by electric heating elements surrounding the barrels in the zone to a temperature of approximately 95.degree. C.
The molten mixture was next transported into the cooling and milling zone C where the mixture was agitated in homogenizing sections 27 and 28 to form a snow-like mass. Zone C was cooled by circulating water at a temperature of approximately 16.degree. C. through the jackets of the barrels in the zone. The polymer exited from the processor as fine powder dispersed in the fluorocarbon solvent. Polymer discharge in the form of an uncompacted snow-like mass was aided by the protrusion of the screws beyond the barrel end. The fluorocarbon solvent was easily removed by sublimation to leave a fine uniform organic powder. Powders were recovered and classified by means of an air elutriator. Particle sizes were determined by sieving. See the Table for data summary.
EXAMPLE 2
Ethylene/vinyl acetate polymer pellets were processed into fine powder in the same manner as described in Example 1 except that a small amount of ethanol was added through port 4 that was provided 320 mm from the upstream end of the screws, to aid in coagulation of the polymer. Data and results are listed in the Table.
EXAMPLE 3
Ethylene/methacrylic acid copolymer pellets premixed with unmelted 1,1,1,2-tetrachloro-2,2-difluoroethane were fed to the twin screw processor and fine powder was produced in the same manner as described in Example 1 except that no additional heat was provided through the jacketed barrel of Zone B. See the data and results summarized in the Table.
EXAMPLES 4 AND 5
The processes were operated generally in the same manner as in Example 1, except that a small amount of a coagulant (50/50, ethanol/water) was added to each mix through port 4, 320 mm from the upstream end of the screws. For these processes, the processor employed for the process of Example 1 was modified by omitting the short section 25 of left-handed screw elements and by replacing it with a right-handed screw section of 24 mm pitch. See the data and results summarized in the Table.
TABLE__________________________________________________________________________ Discharge Solids of Polymer Solvent Coag. Screw Con- Product Feed Feed Feed Speed tent Particle__________________________________________________________________________ SizeExample passedNo. lb/hr lb/hr lb/hr lb/hr RPM % % mesh__________________________________________________________________________1 Ethylene/Vinyl Acetate 15 7.5 7.5 -- 50 50 67 200 (74.mu.) (12% VA; melt index 20)2 Ethylene/Vinyl Acetate 15 7.5 7.5 0.5 75 50 67 325 (44.mu.) (12% VA; melt index 20)3 Ethylene/Methacrylic Acid 15 5 10 -- 150 33 50 200 (74.mu.) (11% MAA; melt index 100)4 Ethylene/Methacrylic Acid 15 5 10 0.5 75 33 75 325 (44.mu.) (11% MAA; melt index 100)5 Ethylene/Methacrylic Acid 15 7.5 7.5 0.5 75 50 75 325 (44.mu.) (10% MAA; melt index 500)__________________________________________________________________________
EXAMPLE 6
The process was operated in the same manner as Example 1. Polymethyl methacrylate (500 g) in pellet form premixed with 1400 g of 1,1,1,2-tetrachloro-2,2, difluoroethane and 200 g of plasticizer (133.7 g didecyl phthalate plus 66.7 g dioctyl phthalate) was fed to the twin screw processor. The screws were operated at equal speeds of 75 rpm. Zones A and C were cooled by circulating water at a temperature of approximately 16.degree. C. through the jackets of the barrels in the zone. Zone B was heated by electric heating elements surrounding the barrel in the zone to a temperature of about 71.degree. to 80.degree. C. Fine polymer powder with plasticizer incorporated therein was produced with particle sizes of less than 325 mesh.

Number	Name	Date
3308211	Plastridge	Mar 1967
3462337	Gorton	Aug 1969
3468986	Watanabe	Sep 1969
3752784	Jenkins	Aug 1973
3753932	Jenkins	Aug 1973
3812224	Smith et al.	May 1974
3936517	Thomas	Feb 1976

Continuous process for preparing particulate microporous, open-celled polymer structures in a screw-type extruder

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US Referenced Citations (7)

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Entry
Natta, Giulio "Progress in Five Years of Research in Stereospecific Polymerization," in SPE Journal, May 1959, pp. 373-382.
Brandrup, J. and E. H. Immergut, Editors, "Polymer Handbook," New York, Interscience, c1966, pp. III-33, 34, 37, 39, 42, 46, 48, 51, 52, 57, 64, 65, 68, 71, 72, 74, 85, 86, 87, 88.