DD140052A5 - MICROPOROESE POLYMER STRUCTURES AND METHOD OF PREPARING THEM - Google Patents

Description

Microporous polymer structures and process for their preparation

Field of application of the invention

The invention relates to porous polymer structures and a process for their preparation. In particular, the invention relates to microporous structures that are easy to produce and characterized by a relatively homogeneous, three-dimensional microcellular structure, as well as to a novel, easily performed process for producing microporous polymer structures.

Characteristic of the known technical solutions

For the production of microporous polymer structures, a variety of methods have been proposed · They range from what the expert calls classical phase inversion, on the nuclear bombardment for the storage of microporous solid particles in a substrate, from which they are then v / ieder removed, up to Zu -Binter sintering of microporous particles. Earlier. Attempts in this area have led to further techniques and innumerable variations of these classical or basic methods.

The interest in microporous polymer products derives from the multitude of poten ti eil * possible uses for ma

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These potential applications are well known, ranging from stamp pads or the like to leather-like breathable fabrics and filters. But despite this potential, commercial use has remained relatively low. In addition, the previously commercially exploited Teohniken certain constraints that did not allow _s to obtain the required versatility for the evaluation of the use and penetration of the potential market for microporous products are subject.

As already mentioned, some microporous P _o commercially offered are lymerprodukte by bombardment with atomic nuclei produced. Such a technique can achieve a very narrow distribution of pore size; the pore volume, however, must be relatively low (ie less than about 10 % void space) to ensure that the polymer does not disintegrate during manufacture. Many polymers can not be used for such a process because of their lack of etchability. In addition, the process requires a relatively thin sheet _or polymer film and considerable experience is needed to perform the process to avoid "double shots" which would result in the formation of oversized pores. "

The classical phase inversion has also been used commercially to produce microporous polymers of cellulose acetate and certain other polymers. "Classical phase inversion has been described in detail by RE Kesting in SYNTHETIC POLYMERIC MEMBRIES, McGraw-Hill, 1971." Publication is expressly noted. ₉ that classical phase inversion requires the use of at least three components

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requires, a polymer, a solvent for this polymer and a non-solvent this polymer.

It can also be found on US patent N _r . 3,945,926 which teaches the formation of polycarbonate resin membranes from a casting containing the resin, a solvent and a swelling agent and / or a non-solvent. In lines 42-27, column 15 of this patent, it is said that in the complete absence of a swelling agent, generally no phase inversion occurs, and that at low concentration of the swelling agent, closed cell structures are encountered.

From the above discussion, it is clear that the classical phase inversion requires the use of a solvent at room temperature, so that many other useful polymers can not be substituted for such polymers as cellulose acetate. Also contemplated by the process point of view, the method of the classical phase inversion generally is limited ax the formation of films, since large amounts of solvents are required for the preparation of the solutions, which must then be re-extracted. It is further apparent that classical phase inversion requires a relatively high degree of process control to yield structures of the desired configuration. Thus, the relative concentration of solvent, solvent and swelling agent must be controlled within critical limits, as described in column 14-16 of U.S. Patent No. 3,945,926, on the other hand, to change the number, size and homogeneity of the resulting structure , experimentally alter the aforementioned parameters.

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Other commercially available microporous polymers are made by sintering microporous polymer particles ranging from high density polyethylene to polyvinylidene fluoride. However, such a technique makes it difficult to produce a product with the narrow pore size distribution required for many applications.

Highly one more general method in which considerable effort has been invested in previous attempts involves heating a polymer with various liquids to produce a dispersion or solution followed by cooling, after which the liquid is removed with a solvent or the like The method is presented in the following US patents, the list of which is by way of example only and not exhaustive

3,607,793 3,378,507 3,310,505 3,748,287 3,536,796 3,308,073 and 3,812,224

We do not believe that the process described above has ever, if ever, been carried out to a commercially significant extent, probably because of the lack of economic feasibility of the processes developed on this line. In addition, the pre-processes do not permit the production of microporous polymers having relatively homogeneous pore size microcellular structures and pore distribution, as typically

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wisely requires.

With regard to the microporous polymers which have been obtained by the prior art, no previously known method was able to produce isotropic olefin or oxidation polymers in which the largest T _e il of the pore size in the range of about 0.1 to about 5 Micron is, while the distribution of the pore size is relatively narrow and thus have a high degree of pore uniformity in a material sample. Some earlier known

Olefin or oxidation polymers presumably had pore size in the aforementioned range, but without the relatively narrow distribution, so that these materials remained without significant value in applications such as e.g. require filtration, a high degree of selectivity. Furthermore, prior microporous olefin or oxidation polymers, which may be considered to be relatively narrowly limited in pore size distribution, had a pore size outside the aforementioned range, usually having much smaller pore sizes, ζ. Β. for use in ultrafiltration. Finally, although some olefin polymers of the known art had a pore size in the aforementioned range and a size distribution to be regarded as relatively narrowly limited, these materials were prepared by methods, e.g. the extension, which communicates a high orientation to the anisotropic material thus prepared, making it unsuitable for many applications. Thus, there has been a demand for microporous olefin and oxidation polymers having a pore size ranging from about 0.1 to about 5 microns, characterized by a relatively narrow isotropic pore size distribution. ,

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A major disadvantage of many previously available microporous polymers was the low flow rate of these polymers in structures such as microfiltration membranes. One of the main reasons for this low throughput rate is the typically low void volume of many of these polymers. 20 % of the polymer structure or less "hollow" space through which the filtrate can flow, the remainder of 80 % of the structure being the polymer resin forming the microporous structure. Thus, there was also a need for microporous polymers with a high content of cavity, in particular for olefin polymers.

The present also Castro and S ^ oil! -Registration which has already been mentioned above _t describes a highly advantageous process for the conversion of a certain type of a liquid amine anti-static agent in a material that behaves like a Peststoff. The benefits of processing that result from this are real and significant. It would be of the same utility ^ \? F you also other useful functional fluids such as * flame retardants and the like, could turn into materials that behave as solids.

Object of the invention.

Accordingly, it is an object of the present invention to produce microporous polymeric products characterized by relative homogeneity and narrow distribution of pore size.

Another object is a simple process which allowed the economical production of microporous polymers

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Yet another object is to provide a process for producing microporous products which can be applied to a large number of useful thermoplastic polymers. A related and more specific object is a process which makes microporous polymers of any synthetic thermoplastic polymers, such as polyolefins, condensation polymers and oxidation polymers, without difficulty.

Another object of the invention is the preparation of microporous polymers in structures from thin shapes to relatively thick blocks. Related to this is the possibility of producing microporous polymers in complex forms.

Furthermore, the conversion of functional fluids is sought in materials which have the properties of a solid.

Dealing with the nature of the invention

It has been found that any synthetic thermoplastic polymers can be rendered microporous by heating these polymers and a compatible liquid, discussed below, until such time as a homogeneous solution is formed. The solution thus formed is brought into the desired shape and allowed to cool in this form so quickly and so far that a thermodynamic unequal weight liquid / liquid phase separation begins. While the solution cools down in the desired shape, no mixing or other shear forces are applied * Cooling will continue so far.

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This pesticide needs only sufficient mechanical integrity to handle it without physical degradation. Finally, at least a substantial portion of the compatible liquid is removed from the resulting solid to form the desired microporous polymer.

Certain novel microporous olefin and oxidation polymers of this invention are characterized by a narrow pore size distribution, as measured by mercury intrusion porosimetry. The narrow pore size distribution can be expressed analytically with the sharpness function ⁿ S ⁿ , which is explained in more detail below. The "S ⁿ " yrs of the olefin and oxidation polymer of the invention range from 1 to about 10. Moreover, these polymers of the invention are characterized by average pore sizes between about 0 _f 10 and about 5 microns, with a size of about 0.2 Further, these microporous products are substantially isotropic and have substantially the same cross-sectional configuration when viewed at any spatial level.

In a further aspect of the present inventive process for producing microporous polymers is a mixture of a synthetic thermoplastic polymer, in particular a polyolefin, an ethylene-acrylic acid copolymer, a polyphenylene oxide-polystyrene mixture or a mixture of one or more of these polymers, and a compatible liquid heated until a homogeneous solution results. The solution is then cooled down so that essentially the same

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early results in a plurality of liquid droplets of the same size. The cooling is then continued to solidify the polymer? an at least substantial portion of the liquid is then removed from the resulting solid to form the desired cell structure.

The process described above results in microporous polymer products characterized by a cellular, three-dimensional microvoid structure, i. a series of entrapped cells - of substantially spherical shape and pores or passageways between these cells. The basic structure is relatively homogeneous and the cells are evenly distributed over all three dimensions, while the connecting pores have a diameter which, when measured by mercury intrusion, has a narrow size distribution. For better understanding, microporous polymers of this structure are referred to as "cell structures."

A related aspect of the invention relates to novel microporous polymeric products which behave as solids and contain relatively large quantities of functionally useful liquids, e.g. Polymer additives including flame retardants and the like. In this way, useful liquids can · take on the processing advantages of solids that are directly, e.g. v.on a stock, can be used. Such products can be prepared directly by using a functional liquid as a compatible liquid and refraining from removal of the compatible liquid, or indirectly either by later replenishment of the microporous polymer after removal of the compatible liquid.

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or by displacement of the compatible liquid, the functional fluid.

The pictures are explained in more detail below

Figure 1 is the plot of temperature: concentration for a hypothetical polymer "fluid system with binodial and spinodal curves and" illustrates the concentration required to obtain the microporous polymers and to carry out the method of the invention.

Fig. 1A is the representation of temperature ϊ concentration similar to Fig. 1, but also shows the curve of the solidification point depression phase;

Fig. 2i, is an x-ray photo magnified 55 times, showing the macrostructure of a microporous polypropylene polymer of the invention having about 75 % void space;

Fig. 3-5 are photomicrographs of polypropylene microporous structure according to the Figure 2 _e in 550, 2200 and 550Ofacher magnification and illustrate a homogeneous cell structure%

Figures 6 to 10 are photomicrographs in 1325, 1550, 1620, 1450 and 1250 magnifications of other microporous polypropylene structures showing the changes in structure; when the voids are reduced from 90 to 70, GO, 40 and 20 % ;

Figures 11 to 13 are photomicrographs. in 2000, 2050 and 1950x magnification of yet another invention, polypropylene structure and showing the decreasing pore size /

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if the polypropylene content of 10% by weight in FIG. 11 is increased to 20 or 30 % in FIGS. 12 and 13, respectively.

Figs. 14-17 are photomicrographs of 250, 2500, 2500 and 2475X magnifications of microporous low density polyethylene structures of the invention, Figs. 14 and 15 showing the macro and microstructure of a microporous polymer with 20 weight percent polyethylene and Figs 16 and 17 represent the microstructure at 40 and 70 % polyethylene.

Figs. 18 and 19 are photomicrographs of 2100 and 2000f8 magnifications of high density microporous polyethylene structures of the present invention showing the structures at 30 and 70 weight percent polyethylene, respectively.

Figures 20 and 21 are photomicrographs in .2500 and 2575 magnifications of microporous SBR polymers of the invention showing a homogeneous cell structure.

The Abbe 22 is a photomicrograph at 2400x magnification of a microporous myptype I pt ion.

Figures 23 and 24 are photomicrographs at 255 and 255X magnification, respectively, of a microporous ethylene-acrylic acid copolymer.

Figure 25 is a photomicrograph at 2500x magnification of a microporous polymer formed from a polyphenylene oxide / polystyrene blend.

Fig. 26 is a microfoto at 205x magnification showing a microporous polystyrene polymer.

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The Abbe 27 is a microfoto at 200X magnification showing a microporous polyvinyl chloride polymer.

Fig, 28 and 29 are photomicrographs in 200Ofacher magnification of microporous Polyäthylenpolymeren a lower density and show the partial covering of the G _1, undstruktur by a ^"M ~ foliage-like structure?

Figures 30 and 33 are mercury virus curves of microporous structures of the present invention and illustrate the narrow distribution of pore diameters characteristic of the polymers of this invention

Figures 34 to 40 show mercury intrusion curves of commercial microporous products such as "Celgard" polypropylene (Figure 34), "Amerace A20" and "Amerace A30" polyvinyl chloride (Figures 35 and 36), "Porex" polypropylene (Fig 37), "Millipore BDWP 29300 ^ Cellulose Acetate (Fig. 38)," Gelman TCM-200 "Cellulose Triacetate, and" Gelman'Acropor WA "Acrylonitrile-Polyvinyl Chloride Copolymer (Figs. 39 and 40).

Figures 41 to 43 are mercury intrusion curves of microporous structures according to U.S. Patent 3,378,507 of polyethylene (Figures 41 and 42) and polypropylene, respectively (Figure 43). FIG. 44 shows a mercury intrusion curve for a microporous polyethylene material according to US Pat. No. 3,310,505.

Fig. 45 and 46 are photomicrographs of a porous Polyäthylenproduktes, which was the B _e ispiel 2 of U.S. Patent 3,378,507 followed, using the injection molding technique _and wherein Figure "45 (in 24Ofacher magnification) shows the macro-structure and Figure 46 (in. 240x magnification) the microstructure.

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Fig. 47 and 48 are Mikrofotoö a porous polyethylene product, which was 2 refinished of U.S. Patent 3,378,507 using the Pormpreßtechnik the B _e ispiel, wherein Figure "47 (in 195facher magnification) shows the macrostructure, and Fig. 48 (in 200X magnification) the I.Iikrostruktur.

Fig. 49 and 50 are photomicrographs of a porous Polyäthylenproduktes, which was the example 2 of US-P _a tent 3378 followed, using the injection molding technique, wherein Fig. 49 (in 195facher magnification) shows the macrostructure, and Fig. 50 (in 200Ofacher Magnification) the microstructure.

Fig. 51 and 52 are photomicrographs of a porous Polyäthylenproduktes, which was the example 2 of US-P _a tent 3378 refinished using the Preßformtechnik, wherein Fig. 51 (in 206facher magnification) shows the macrostructure, and Fig. 52 (in 2000X Magnification) the microstructure, and

Figs. 53 and 54 are photomicrographs of a porous polyethylene product following Example 2 of U.S. Patent 3,310,505, Fig. 53 (at 205X magnification) showing the macrostructure and Fig. 54 (at 20X magnification) showing the microstructure ,

Fig. 55 shows an S _c hmelskurve and a crystallization curve of a polypropylene and Chinolinpolymer / FlUssigkeitssystem. '

Fig. 56 shows a melting curve and a plurality of K _r istallisationskurven for a polypropylene and Ii, lT-bis (2-hydroxy-

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- 14''-. 'äthy1) = tallowamine (tallowamine) polymer / liquid si s t s.

Figure 57 shows a melting curve and a crystallization curve for a polypropylene and dioctyl phthalate polymer / liquid system, i.e., a system which does not fall within the scope of the present invention.

The 'Fig. "58 shows the phase diagram for a low molecular weight polyethylene and Diphenvläther polymer / liquid" · systeaij that was created when cooling and heating in speeds of i ° C / min _ö

The figure "59 is more melting and K _r istallisationskur-" ven a niedrigmolelcuiares polyethylene and Diphfenyläther polymer / liquid system ''

Fig. 60 shows a glass transition tangential curve for a low molecular weight polystyrene and 1-dodecanol polymer / solute system.

The Abbe 61 is a microfoto in 5000x magnification of a 70 % voids microporous cell structure of the invention made from polymethylmethacrylate

Fig. 62 shows smelting and crystallization curves for. a nylon 11 and tetramethylenesulfone polymer / oil system «·

FIG. ₉ is a photomicrograph at 200 × magnification of a microporous cell structure according to the invention, made from Hylon .11 _; 'with 70 % cavities ». ·.

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Fig. 64 is a microfoto at 200x magnification for a microporous cell structure made of polycarbonate with 70 % cavities according to the invention.

Fig · 65 is a photomicrograph enlargement in 200Ofacher for an inventive microporous cell structure from PoIyphenylenoxid 70 ¹ ^ cavities.

FIGS. 66 and 67 are photomicrographs in 200 × magnifications of microporous non-cellular structures according to the invention made of polypropylene with 60 or 75 % cavities.

Figures 68 and 69 are mercury intrusion curves for noncellular microporous polypropylene structures within the scope of the present invention having 60 and 75 % voids, respectively.

Fig. 70 is a graphical representation of the novel microporous cell structures of the present invention compared to certain compositions of previously described methods.

The process according to the invention can be carried out in various forms and variants. The following description deals in detail with the preferred embodiments. However, this is not intended to limit the invention in any way to those specifically described herein. On the contrary, it is intended to embrace all modifications and alternative forms which fall within the scope of the invention process according to the appended claims.

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Roughly speaking, carrying out the process of the invention involves heating the desired polymer with a suitable compatible liquid to form a solution, cooling this solution in a suitable manner to form a solid and then extracting the liquid to obtain a microporous material. The at the. Carrying out the method according to the invention will be described in detail below.

Selection of polyglygene

As already indicated, the process according to the invention surprisingly represents a technique by which any thermoplastic polymer can be rendered microporous. Thus, the process according to the invention for olefin, condensation and oxidation polymers «

Illustrative of the useful non-acrylic polyolefins are low density polyethylenes. High pressure polyethylene, polypropylene, polystyrene, polyvinyl chloride, acrylonitrile. Butadiene-styrene polymers, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, poly (4-methyl-pentene-1), polybutylene, polyvinylidene chlorides, polyvinyl butyral, chlorinated polyethylene, ethylene-vinyl acetate copolymers, polyvinyl acetate and polyvinyl alcohol *

Useful acrylic polyolefins include poly (methyl methacrylate, polymethyl acrylate, ethylene acrylate copolymers, and xylene-acrylic acid metal salt copolymers

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Polyphenylene oxide is exemplary of the usable oxidation polymers. The useful condensation polymers include polyethylene terephthalate, polybutylene terephthalate, nylon 6, nylon 11, nylon 13, nylon 66, polycarbonates and polysulfones

Selection of compatible liquid

To carry out the process according to the invention one must

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-ftf- Berlin; el, 27 .'9 »1978 AP C E8J / .200810

first select a synthetic thermoplastic polymer which should be made microporous after selecting the polymer _? The next step is to select the appropriate compatible liquid and quantity ratios

Of course, mixtures of one or more polymers can also be used to carry out the process according to the invention. Polymer and liquid are heated with stirring to the temperature required for the formation of a clear, homogeneous solution. If a solution can not be obtained at any liquid concentration, the liquid is unsuitable and can not be used together with this polymer ν, / erdena. Because of the selectivity, it is absolutely safe to predict the practical usefulness of a particular liquid in combination with one certain polymers possible However, it can not werden- been some useful general guidelines "If the polymer used for _s B _s is non-polar _t is non-polar liquids with similar solubility parameters should probably more suitable _e at the solution temperature If such parameters are not known, one can Similarly, polar organic liquids with similar solubility parameters should be tested for use with polar polymers. In addition, the relative polarity or non-polarity of the liquid should be kept at a constant temperature e to adjust the relative polarity or "non-polarity of the polymer". In the case of hydrophobic polymers, the useful liquids typically show little or no water-solubility. On the other hand, polymers ₉ which are more hydrophilic require "generally a liquid with a certain solubility in water",

Concerning the suitable liquids one has determined _f dal? Certain types of different types of organic compounds are useful _? such as Z ₀ B ₀ aliphatic and aromatic

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However, it should be noted that the concept is quite selective For example, not all saturated aliphatic acids are suitable; and not all liquids useful for high density polyethylene are necessarily also useful for polystyrene. "

It will be understood that the proper proportions of polymer and liquid for any given system can be readily deduced from a consideration of the parameters discussed below.

However, where mixtures of one or more polymers are used, the fluid must understandably be suitable for all polymers used. However, it may be possible for a polymer blend to have properties that do not necessarily require that the fluid be compatible with all the polymers employed. By way of example, if one or more polymeric constituents are present in relatively small amounts such that they have no significant effect on the properties of the mixture, then the liquid employed need only be in harmony with the main polymer (s).

While most suitable materials are liquids that are liquid at room temperature, materials that are solid at room temperature can also be used, as long as they can form solutions with the polymer at elevated temperatures and the material does not form the microporous ones Structure obstructs "In particular, a solid may be used as long as the phase separation is due to separation of liquid and liquid rather than separation of liquid and solid.

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The amount of liquid used may generally be between about 10 and about 90%. lie",

As said, any of synthetic // may thermoplastic polymers can be used _for as long as the selected fluid with this polymer forms a solution and the concentration at separation during the cooling, a continuous polymer phase yields j As will be described in more detail "For a better overview of the range of appropriate polymer and liquid crystal systems, a short summary of some of these systems may be useful »

For the preparation of microporous polymers of polypropylene, alcohols, such as 2-benzylamino-1-propanol and 3-hydroxy-1-propanol, have aldehydes, such as salicyldehyde amides, such as N, N-diethyl-m-toluamido amines such as N "Hexyldiäthänolamin, K ~ Diphenyldiäthanolamin, N-coco diethanolamine, benzylamine, N _s K" bii3- »ß ~ hydroxyathj ^ _1} lcyclohexylaminj diphenylamine and 12-diaininäode" Kanj esters such as methyl benzoate, benzyl benzoate _t, Phenylsalizylat, methyl salicylate and dibutyl phthalate; 2 | |, and ethers such as diphenyl ether, 4-bromo ~ diphenyl ether and dibenzyl suitable proven addition, halohydrocarbons _s as 1J1 may 2 ~ Tetrabromäthani and hydrocarbons, such as Transstiiben _s and other alkyl / aryl phosphites as well as ketones such as methyl nonyl>

For the formation of high density polyethylene microporous polymers, saturated aliphatic acids, such as decanoic acid, have primary saturated alcohols, such as decyl alcohol and isodecanol secondary alcohols, such as 2-undecane and 6-undecanol ethoxylated amines such as N-aromatic Lauryldiäthanolamini 'amines wio N _f N-diethylaniline; Diesters such as dibutyl sebacate and dihexyl _f and ethers such as diphenyl ether and benzyl ether, proved to be suitable "V / urther useful

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Liquids are e.g. halogenated compounds such as octabromodiphenyl, hexabromobenzene and hexabromocyclodecane; Hydrocarbons such as 1-hexadecane, diphenylmethane and naphthalene; aromatic compounds such as acetophenone, and other organic compounds such as alkyl aryl phosphites, and quinoline and ketones such as methyl nonyl ketone.

For the formation of microporous polymers of low density polyethylene, the following liquids have been found to be useful? saturated aliphatic acids such as hexanoic acid, caprylic acid, "decanoic acid, undecanoic acid, lauric acid, myristic ', palmitic acid and stearic acid; unsaturated aliphatic ^ acids _$ such as oleic acid and erucic acid, aromatic acids such as benzoic acid, phenylstearic acid, polystearic and Xylylbehensäure, as well as other acids such as branched carboxylic acids having an average chain length of 6, 9 and 11 carbon atoms, tall oil acids and rosin acid, primary saturated alcohols, such as 1-octanol, nonyl alcohol, decyl alcohol 1-decanol, 1-dodecanol, tridecyl alcohol, cetyl alcohol and 1-heptadecanol; primary unsaturated alcohols such as undecylenyl alcohol and olelyl alcohol; secondary alcohols such as 2-octanol-2-undecanol, dinonylcarbinol and diundecylcarbinol; and aromatic alcohols such as 1-phenylethanol, 1-phenyl-1-pentanol, nonylphenol, phenylstearyl alcohol and 1-naphthol. Other useful hydroxyl containing compounds are polyoxyethylene ethers of Olelyl alcohol and a polypropylene glycol having a number average molecular weight of about 400. Also useful liquids are cyclic alcohols such as 4-t-butylcyclohex: anole and menthol; Aldehydes such as salicylaldehyde; primary amines such as octylamine, tetradecylamine and hexadecylamine; secondary amines such as bis (1-ethyl-3-methylpentyl) amine and ethoxylated amines such as N-lauryl diethanolamine, N-tallow diethanolamine, N-stearyl diethanolamine and N -Cocodiäthanolaminc

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Other useful liquids are ζ, Β "aromatic amines such as N-sec-batylanilin, Dodecylaniline, N _f N-dimethyl aniline" N. _s N "diethylaniline _$ p" Toluiäin _$ N lthyl-o-tölaidin, diphenylamine and Aminodipheny! methane \ diamines, such as N "erucyl" -1,3-pro- pandiamine and 1,8 "diamino-p""niethan; other amines, such as branched tetramines and cyclododecylamine amides, such as. Cocoamide, hydrogenated tallow fatty amides, octadecylamide, eruciamide, ITjN-diethyltoluamide and N-trimethylolpropane stearamide; saturated aliphatic esters such as methyl caprylate, Äthylläorat, isopropyl myristate, Äthylpalmitat _s IsopropylpaliD-itat, - methyl stearate _s isobutyl and Tridecylstearati unsaturated esters such as butyl and Stearylao.rylat.j ecylenat and butyl oleate; Alkoxyester _f . such as butoxyethyl stearate and butoxyethyl oleate; aromatic esters, 'as Viny! phenyl st ear at, Isobutylphenylstearat, Tride »» oylphenylstearatj methyl benzoate, ethyl benzoate, butyl benzoate, -Benzylbenzoat, phenyl laurate _s PhenylsaIizylat, methyl salicylate and benzyl acetate and diesters such as Dimethylphenylendistearat, Diäthylphthalatf dibutyl _phthalate? 'Capryladipat di-iso-ootylphthalaty di-, dibutyl sebacate, dihexyl sebacate, di ~ isO'-octylsebaoat, Dicaprylsebacat and dioctyl _e Other suitable liquids are, for _{fi e} B Polyäthylenglykolester as PoIyäthylenglykol (having an average Molgev; layer of etrwa 400) Diphenylstearat Polyhydrozyl esters, such as castor oil (triglyceride), glycerol monostearate, glycerol monooleate, glyceryl distearate, glycerol dioleate and trimethylolpropane monophenylsteacate? Ethers such as diphenyl ether and benzyl ether halogenated. Compounds such as hexachlorocyclopentadiene, ootabromobiphenyl, deoabromodiphenyl oxide and 4-bromodiphenyl ether, hydrocarbons such as i-ionones, 2-nonene, 2-indium, 2-heptadecone _? 2-nonadecenes, 3 «= · Εΐοο sen, 9 ~ nonadecenes _? Dipheny! Methane _? Tr ipheny! Methane and trans Stilbenj aliphatic "ketones such as 2-heptanone, methyl nonyl, 6" ünäecanon, Metb.ylundecylketon _s 6 ~ tridecanone _s 8-Pentadecanonj H pentadecanone, 2 »heptadecanone, 8 ~ Heptadecanons Methylheptadecylketon, and Dinonylketon Distearyl ketone aromatic ketones, such as acetophenone and benzophenone and others ~ -

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Berlin, d.27.9.1973 AP C 08J / 200 810

ketones, like xanthone. Also useful liquids are phosphorus compounds such as trixylenyl phosphate, polysiloxanes, Muget, Hyazinth (An Merigenaebler, Inc.), Terpineol Prime No ₀ I (Givaudan-Delawanna Inc.), Bath Oil Aroma No. 5864 K (International Flavor & Fragrance Inc.), Phosclere P3150 (organophosphite), Phosclere P576 (organophosphite), styrenated nonylphenol, quinoline and quinolidines

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To produce microporous polymer product © polystyrene following liquids are useful * tris-halogenated propyl! Phosphate, aryl / alkyl ~ phosphites, 1,1, 2, 2 ~ Tatrsbroraäthan, Tr their oia-neopsn ty I alcohol, 40% Voranol CP. 30% Polyol, tri-bromo-nopentyl alcohol 60%, Tris-β-chloroethyl phosphate,. Tris (1, S-dichloroisopropyl) phosphate, tri - (dichloropropyl) phosphate, dichlorobisole and 1 "-dodecanol.

For the preparation of polyvinyl chloride microporous polymeric products, usable as liquids are aromatic ©

Alcohol © including MsthoKybensyl alcohol, 2-B © nsylasino ~ 1-propanol «ad other hydroxyl-containing © liquids, including 1,3-dichloro-2-propanol. Arider © usable liquids on halogenated compounds. Including Firexsester T33P (tetrabromophthalic acid diester) as well as aromatic © Kohlenf. ©, including trans-arrows.

According to the invention, microporous products can also be made from other polymers, copolymers and blends. There are each use certain liquids au, for example

for styrene-butadiene copolymer

Dacyl alcohol, N-tallow-fat diethanolamine, N-coconut fat diethanolamine and diphenylamine

for ethylene-acrylic acid-copolyinsrQ

Salse, including N-tallow fat diethanolamine, N-coconut fat diethanolamine. Dibutyl phthalate and diphenyl ether %

for high-impact polystyrene

Kexabroiabiphenyl and Alky! - / Jiryl ~ phosphites?

for * HQryl ^e -Polyphenylene Oxide PGlystyryl Mixtures (General Electric Comp)

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A3AM13475 DT

N-coconut fat diethanolamine, N-tallow fat diethanolamine, Diphenyi & rain, dibutyl phthalate and hexabromophenol;

for mixtures of low density polyethylene (high density polyethylene) and chlorinated polyethylene

1-dodecanol, diphenyl ether and N-tallow diethanolamine

With 1-dodecanol as liquids, various microporous polymeric products can be made, for example, those from blends of polypropylene-chlorinated polyethylene, high density polyethylene (low density poly- &thetav; @) polyvinyl chloride, high density acrylonitrile-butadiene-styrene terpolymer polyethylene.

For the production of microporous products from polymethyl and acrylate, 1, 4-butanediol and lauric acid have been found suitable.

Microporous nylon 11 can be prepared using ethylene carbonate, 1,2-propylene carbonate or tetramethylene sulfone as liquids.

Menthol can be used to process polycarbonates into microporous products. ,

Selection of concentrations for polymers and liquids,.

The determination of the addition amount of the liquid to be used is carried out by means of the binodial and spinodal curves of the respective system, as shown in FIG. (Fig. 010). As can be seen, T ^ is the maximum temperature in the binodial curve (ie, the maximum temperature of the System®,

: - 36- A3AM13475 DT

where binodial decomposition occurs) _f T __ is the upper critical temperature (ie, the maximum temperature at which sinusoidal decomposition occurs), 0 indicates the polymer concentration at T, g indicates the critical concentration, and 0 the polymer concentration of the system, ie required to form the unique microporous polymer structures according to the invention. Theoretically, 0 and 0 should actually be identical. However, it is known that owing to the molecular weight distribution of a commercially available polymer, O is about 5% by weight greater than the fourth for zero. To form a microporous polymer product according to the invention, the polymer concentration used for a system 0 / polymer concentration greater than 0. Inasmuch as the polymer concentration is less than 0, phase drowning will occur when the system is cooled, with the liquid being the continuous, the polymer the discontinuous phase. However, by complying with the prescribed polymer concentration, it is ensured that upon cooling to the phase separation membrane the polymer forms the continuous phase, as is essential if one wishes to prepare a uniform microsellular structure according to the invention. Similarly, to achieve a continuous polymer phase, it is imperative that a solution be first formed. Unless the procedures of the invention are followed and a dispersion is first formed, the resulting microporous product resembles that which is obtained in co-sintering of polymer particles.

Accordingly, it is important to note that the concentration of polymark to be maintained and the amount of solvent used varies with each system. The number of phase diagraemuls has already been recorded. Where no corresponding curves are available, they can easily yield

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usual methods are created. Thus, a corresponding method, for example, in "Sxaolders, van Aartsen and Steenbergen, Kolloid Z. u. Z. Polymere / 243/14 (1971) explained.

A general representation of a temperature / concentration curve for a hypothetical polymer-liquid system is shown in FIG. 1A. The section ¥ ~ d. shows the thermo-dynaic weight-loss curve of liquid-liquid phase separation, that of the liquid-solid phase separation section, which is usually regarded as the melting point despression curve of a hypothetical liquid-Polymar system. The upper shaded area represents an upper liquid-liquid immiscibility that may occur in some systems. The dashed line shows the lowering of the crystallization temperature as a result of the cooling with sufficient to achieve the thermodynamic liquid-liquid imbalance weight phase separation rate. The flat portion of the crystallization / composition curve defines a useful compositional range as a function of the applied cooling as will be described in more detail below.

Thus, for any given rate of cooling, one can apply the crystallization temperature to the percentage of resin or miscible liquid, and thus determine the liquid / polymer concentration ranges that result in the desired microporous structure at the given cooling rate. For crystalline polymers, determination of the useful concentration range by applying the aforementioned crystallization curve represents a viable alternative to providing a phase diagonal random as shown in Fig. 1. As an example of the above,

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Reference may be made to Figure 55, which shows the dependence of temperature on the polymer-liquid concentration, namely the lath curve at a heating rate of 16 ° C per minute and the crystallization curve for polypropylene and quinoline over a wide range of conversion. As can be deduced from the crystallization curve, for a cooling of 16 ° C. per minute, the p & sseads reaction liquid is between .20 to 70% polypropylene.

Figure 56 is a diagraxaza in which di® temperature versus polyhydric liquid S 'composition for polypropylene and N, N-bis- (2-hydroxyethyl) tallow fat ajmin plot for an upper curve, the enamel curve, are plotted for a heating rate of 16 ° C per minute. The lower. Curves are crystallization curves taken in descending order for cooling rates of 8 ° C, .16 ° C, 32 ° C and 64 ° C per minute. The curves show two competing phenomena that occur as the cooling rate increases. First, the flat portion of the curve indicates that the crystallization temperature _t, which is quite stable over a broad range of concentrations, decreases with increasing cooling rate, from which it can be deduced that the higher the cooling rate, the lower the respective crystallization temperature.

The second phenomenon that can be seen is the change in the slope of the crystallization curve Ei.it with the change in the cooling rate. It appears that the flat portion of the crystallization curves increases as this cooling rate increases. Accordingly, one can assume that by increasing the Ahkühlgeschwindlgkeit sul & seigen Kon ^ entrationsbereich for erfindungsgemäSa production

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expand microporous structures. From the above, it will be apparent that in order to determine the useful concentration range for a given system, only a few representative concentrations of polymer / liquid need to be prepared and then cooled at a desired rate. After application of the crystallization temperatures, the permissible concentration range is easily recognizable.

Fig; Figure 57 is the plot of temperature versus polymer-liquid concentration for polypropylene and dioctyl phthalate. The upper curve is the melting curve for the system over a concentration range and the lower curve represents the crystallization dependency in the same concentration range. Since the crystallization curve does not have a flat section within which the crystallization temperature would remain substantially constant for a certain concentration range, it can be assumed that the polypropylene / dioctylphthalate system is unsuitable for the production of microporous structures - and this is indeed the case.

For evidence of the excellent correlation between the "phase diagram method" for determining the useful concentration range for polymers and liquids and the "crystallization method", reference may be made to Figs. Figure 58 is a phase diagram for the low molecular weight polyethylene diphenyl ether system determined by the conventional light scattering technique using a thermally controlled vessel. It can be seen from the phase diagram in FIG. 58 that T is approximately at 135 ° C. and 0 is approximately 7% polymer. It also shows that at about 45% polymer concentration, the cloud point curve

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the melting point cut-off curve intersects indicating a permissible concentration range of about 7% polymer to about 45% polymer.

The consensus range determined from curve 58 can be compared with that from FIG. 59. Fig. 5S shows the melting curves of the same system

speeds of 8 ° C and 16 ° C per minute and the di crystallization curves at cooling rates of also 8 ° C and 16 ° C per minute. From the crystallization curves it can be seen that the substantially flat section extends between 10% to about 42-45% polymer, depending on the cooling rate. Thus, on the other hand, the results from the crystallization curves on the one hand and the cloud point phasing on the other agree surprisingly well.

For non-crystalline polymers, it is believed that one can use the temperature / concentration dependence of the glass transition temperature as an alternative to the phase diagram of Figure 1. Fig. 60 shows the temperature / concentration curve for the 2nd order transition temperatures for the low molecular weight polystyrene system / manufactured by Pennsylvania Industrial Chemical Corporation under the name "Piccolastlc D-125" and 1-dodecanol in various concentration ranges.

From Fig. 60 it can be seen that from about 8 % polymer to about 50% polymer, the 2nd order transition temperature for polystyrene / 1-dodecanol ira is substantially constant »It was therefore assumed that the concentrations in the range of ira substantially flat Curve section would be useful for the inventive method, according to the

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shallow sections of the previously discussed crystallization curves. From this it can be seen that as a valid alternative to the determination of the phase diagram for non-crystalline Polymsre system © the determination of the transformation temperatures 2, order can be considered, and that one can work in the region of the flat portion of such curves.

For all the figures discussed above, the crystallization temperatures were determined using a Perkin-Elmer "DSC differential scanning calorimeter" or similar equipment.

Further influences of the cooling rate on the practice of the present invention will be discussed below.

After having selected the desired synthetic thermoplastic polymer, a compatible liquid and the potentially useful concentration range, one must still select the actual concentration of polymer and liquid to be used. In addition to assessing the theoretically possible concentration range, other considerations must be added to tune the proportions of a particular system. For example, as far as the maximum amount of liquid that can be used is concerned, the desired strength properties must be taken into account; or more specifically, the addition of liquid used should allow for the creation of a microporous structure having sufficient 'processing strength' ^{1 to} avoid collapse of the microporous or cellular structure. On the other hand, selection of the maximum amount of resin or viscosity limits by a particular processing device may dictate the tolerable maximum polymer or resin content.

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Furthermore, the proportion of polymers should not be so great that © s results in the formation of closed cells or other microporous areas.

The relative amount of liquid also affects the desired effective pore size to the extent that it is on the goi-iissexn. di © special cell or pore size required for later use. For example, the mean © pore or cell size with st @ ing @ ra liquid content su.

In any case, the usefulness of a liquid and its procedurally permissible concentration of the bestinsate polymer can easily be determined by experimentally determining the liquid in the manner explained above.

However, the parameters discussed above must be adhered to. Mixtures of two or more liquids may also be used; The usefulness of certain mixtures can easily be tested. It may happen that a particular mixture of liquids is useful, although one or more of the liquids may be unusable.

It must be emphasized that a particular addition of a liquid can often be dictated by the particular end use of the product. For example, from high density polyethylene and Ν, Ν-bis (2-hydroxyethyl) tallow fat amine, a useful microporous product can be made using 30 to 90%, preferably 30-70% of the amine. For low density polyethylene and the same amine, the proportion of liquid at 20-90 % _{t may} preferably be between

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20 and ΘΟ% are. In contrast, when diphenyl ether is used as the liquid, the addition to low-density polyethylene is allowed to be not more than about 80%, with a maximum amount of 60% being preferred. If 1-hexadecane is used together with low-density polyethylene, the additives can be up to 90 S and more. In the case of polypropylene and the above-described tallow fatty amine, the amine additive is about 10 to 90%, with a jtexia addition amount of about 85% being preferred. In the system polystyrene-1-Dod © - canol, the alcohol concentration can vary between 20 and about 90%, preferably between 30 and 70%. When using styrene-butadiene copolymers (e.g., SBR), the liquid content may be between 40 to 90%; in the case of diphenylamine as a liquid, a range between 50 and 80% is useful. Kenn microporous structures of the said amine and an ethylene-acrylic acid Copolymaren to be produced, the liquid content can be between 30 and 70%. ' lie; with diphenyl ether, it can vary between 10 and 90%. This also applies when dibutyl phthalate is used as a liquid.

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Äusformung the homogeneous n Flü LIQUID.

From the formation of the solution it follows that it can then be processed to achieve any desired shape or form. Ii general and depending on the respective system can thereby di © thickness of the produced article from a thin film of about 1 sail. (about 25.4 px &) oä®x less to su a -relatively thick block with a thickness of about 2 1/2 inches (about 63.5 cm) or even more vary. The ability to form blocks allows this orphan to be placed in any desired, even difficult, form, such as by extrusion, injection molding, or other related techniques. Practical considerations in determining the range of thicknesses applicable to a best-rated system include the rate of viscosity build-up as the system cools. In general, the higher the viscosity, the thicker the structure can be. Accordingly, the structure may be of any thickness as long as coarse phase separation does not occur, ie how not two distinguishable layers become visible *

It can be seen that complete separation into two distinct layers occurs when liquid-liquid phase separation can take place under thermodynamic equilibrium conditions. A layer consists of molten polymer, which still contains the soluble portion em liquid, dia other from the liquid phase, which contains the soluble in the liquid portion of polymers! contains. This condition is represented by the binodial line in the phase disparity of FIGS. 1 and 1a. The realizable size or thickness of the fabricated structure can be seen

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determined by the thermal conduction characteristics of the composition; if the object is thick enough and the heat conduction is poor enough, the cooling rate inside the object may be slow enough for the solution to approach equilibrium conditions, resulting in a distinct layered phase separation corresponding to that described above.

Increased thicknesses can also be achieved by adding smaller amounts of theseotropic substances. Thus, e.g. the addition of commercially available colloidal silicone compounds prior to cooling clearly exceeds the range of useful thicknesses without, however, affecting the characteristic microporous structure. The particular required or appropriate specific quantities can easily be determined by experiment.

Cooling of the homogeneous solution

As is apparent from the foregoing, regardless of the type of processing (i.e., casting into a film or the like), the solution must be cooled to obtain a shape that looks and behaves like a solid body. The resulting material should have sufficient strength and integrity so that it does not crumble when handled, such as when you pick it up. Another way to determine if the resulting system has the desired structure is to use a substance that is a solvent for the fluid used but not for the polymer. If the material falls in the process, the system could not meet the criteria to be demanded.

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The cooling rate of the solution can be within wide limits JUsxt% ¨derderx. In fact, no cooling is usually required by © Ben Ben. For example, it may suffice _for example to film by casting the hot fluidity system on a surface which is sensitive to stretching the filsis. letīe temperature © rhitst is ^ produce? alternatively be carried k & nsi since © forms a block, ind m @ issn di © poured heiß® solution vmter übiicheB conditions' on ein® corresponding unterlag®.

The cooling rate, as we have already mentioned, must be large and small; So Plüsslg-Flttsßlg-Phasantremmng under theriBodyn ami see Gleichgewlchtsbedingvingen not take place. Moreover, the cooling can have a significant influence on the resulting microporous structure. For many polymer / fit system, if the cooling gas velocity is still sufficiently slow but satisfying the aforementioned conditions, the liquid-liquid phase separation can be about the same time by forming a plurality of liquid droplets of substantially equal size Lm . If the decarburization rate is such that these liquid droplets are formed, the resulting microporous polymer will exhibit the previously defined cell-forming microstructure, as long as all of the other conditions mentioned are also satisfied.

Generally, it will be appreciated that the structures of the present invention are obtained by cooling the liquid system to a temperature below the binodial curve, as shown in Fig. 1, so that the liquid-liquid phase separation is excited , In

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At this stage, germs or cells begin to form, consisting mainly of pure solvent. When the cooling gas velocity is adjusted to produce the cellular microstructure, each seed is believed to be surrounded by a polymer enriched zone as it continues to grow, increasing in thickness as it is deprived of liquid. Finally, this Polymar-enriched zone resembles a skin or film that encloses the growing solvent droplets. As the polymar-enriched zone thickens, diffusion of further solvent through the skin decreases. Accordingly, the growth of the liquid droplets also decreases until finally it practically ceases; the liquid droplet has reached its maximum size. At this point, the formation of a new core (new ropes) is more likely than the further growth of the already large solvent droplets. However, in order to achieve this type of growth, it is necessary that nucleation or nucleation be excited by spinodal rather than binodal decomposition.

The cooling is thus carried out so that a plurality of liquid droplets of substantially the same size in a homogeneous (continuous) polymer phase are formed at substantially the same time. If this type of separation does not take place, then the cellular structure can not arise. It is generally achieved by applying such conditions as prevent the onset of thermodynamic equilibrium at least until nucleation bsw. the droplet growth started.

By the way, this can be achieved by allowing the systam to cool, without resorting to mixing or other shearing.

A3AM13475

subjugate forces. The time parameter may also be important where relatively thick blocks are to be formed, since in such cases faster cooling may be desirable.

There is general evidence that within the range in which the cooling of the formation of a large number of liquid droplets leads, the size of the resulting solids can be influenced by the cooling rate in the orphan, that as the cooling rate increases, the hulls become clain , In this regard, it has been observed that an increase in the cooling rate of about 8 ° C / in obviously has the effect of reducing the cell size in half for a microporous polypropylene polymer. Accordingly, external cooling may be used if desired to control the final cell and pore size, as further described below. '

The way in which the interconnections or pores are formed in the cellular structure can not be fully explained. However, without the applicant's wishing to be bound by any particular theory, there are several possible mechanisms that may be used to explain this phenomenon; each of them can be reconciled with the idea described here. The formation of the pores may occur, for example, as a result of thermal shrinkage of the polymeric phase on cooling, the liquid droplets behaving as incompressible beads when the solvent has a lower coefficient of expansion than the polymer. On the other hand, and as already indicated _f contains itself

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After the solvent droplets have reached their maximum size, the polymer-enriched phase still has some residual solvent and vice versa. Accordingly, as the system continues to cool, it is possible for additional phase separation to occur. The residual solvent in the polymer-rich skin may therefore diffuse toward the solvent droplets, thereby reducing the volume of the polymer-rich skin and enlarging the solvent droplet. It is conceivable that this may weaken the polymer skin, while increasing the volume of the solvent or liquid phase results in the build-up of an internal pressure which eventually suffices to break the polymer skin and bond adjacent solvent droplets. Based on this mechanism last described, the polymer may possibly return to a more compact state just as the residual liquid migrates out of the polymer skin, -] for example, by crystallization, if such permitting of the polymer is involved. This would probably shrink the polymar skin and have defects or holes, which are likely to be found in the areas of particularly low strength. These weak areas may be found between adjacent liquid droplets, so that the j

Form holes between adjacent liquid droplets and would lead to the connection of the solvent droplets. However that may be, irrespective of the actual process, the connecting pores are formed when the process has been carried out as described.

A possible explanation for the formation of the pores can "be established; this · is in" on the ^w Harangoni Marangoni effect, C.Nuovo Cimanto (2) 5-6239 (1871); (3), 3, 97, 193 (1878)

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and Marangoni, C _e , Note _o Phys _e Lpc _e (1871), 14-3, 337} "The Marangoni effect was intended to explain the phenomenon that occurs when alcoholic beverages spontaneously flow back from the sides of drinking glasses, in particular when a condensed droplet flows back into the mass of the liquid. "The droplet liquid first enters the liquid mass, but then a rapid retraction of some of the liquid back into the droplet occurs." It could be said that the liquid droplets are similar. As a result of the liquid-liquid phase separation, one droplet may collide with another and the liquid of one may first penetrate into that of the other, followed by a rapid separation of the two droplets, with perhaps a portion of the liquid. Do not get stuck between the two droplets, these connecting, and possibly the verbin A recent discussion of the Marangoni effect can be found in "Charles & Mason, J, Colloid, 15, p. 236 to 267

When the homogeneous solution is cooled at a sufficiently high rate, liquid phase liquid separation can take place under conditions which are not in equilibrium with the thermodynamics, but the solidification of the polymer occurs so rapidly that effectively no formation of cells or nuclei followed by growth takes place _e 'In such a case there will be no formation of droplets of the liquid "," the polymer entstehende.mikroporöse consequently do not have the defined cell structure "

Thus, under certain conditions, it is possible to achieve various microporous structures by extremely high cooling rates.

ί- /.Ο ill, ki / U * Υ 'j OO 9 · ί

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cellular microstructure when a solution of 75 parts of an N, N-bis-U-hydroxyethyl tallow fatty amine and 25 parts of a polypropylene at rates between about 5 ° C / min and about 135 ° C / min. is cooled. The different cooling rates mainly affect the change in the absolute cell size. Where cooling rates of about 2OOO ° C / min are applied, the microstructures assume, for example, a fine filigree or gazeartiga (lacey) non-cellular form. When a solution of 60 parts of N, N-bia- (2-hydroxyethyl) tallow fatty amine and 40 parts of polypropylene is treated in the same manner, cooling rates above 2OOO ° C / min must be applied before the filigree non-cellular structure is achieved.

In order to examine the effect of the cooling rate on the cell size of the cellular structure and the transition from the cellular structure to one not having any particular cells, various concentrations of polypropylene and N, N-bis- (2-hydroxyethyl) tallow fatty amine were used Homogeneous solution prepared. To complete the study, the previously discussed DSC-2 was used in conjunction with standard x-ray equipment and a scanning electron microscope. Since the DSC-2 can provide a maximum cooling rate of about 80 ° C / min, a kind of Kofier (thermal gradient bar) bank was used. This was a brass rod or bench which could have a temperature gradient of more than 2000 C over its one meter length and provided the opportunity to arrange samples.

An Infrsxot Kemera was used to determine the temperatures of the samples by first placing the camera on a dish

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focussed, which was placed at the temperature of 110 C, frozen with a thermocouple, nearest to the picking point of the Keizbank. The camera was then set up so that its temperature reading coincided with that of the thermocouple. "

7, mIn each case, the camera was aimed at the location where a tube should be cooled with a solution sample. Dia dish. -With the sample was then put on the Kofier bench for 2 min. Simultaneously with the transfer of the bowl from the heating bench into the camera's recording field, a stopwatch was set in motion. As soon as the camera showed a cup temperature of 110 C, the stopwatch was stopped and the required tent was held. It was used to determine the respective cooling rate, which thus resulted from the time it took for the sample to cool over a temperature range of about 100 ° C.fV '''

It was found that the possibilities for controlling the cooling rates were not significantly influenced by the specific amount of each material to be cooled. Rather, it was found that the silicone oil used to improve conductivity between bowl and hot tap had a significant impact on the cooling rate, although of course heavier samples cooled slower than light ones. For example, the highest cooling rates were achieved by placing the bowl without silicone oil on an ice cube, and the slowest cooling rates were achieved with a bowl covered with a soft coating of silicone oil placed on a piece of paper.

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Five polypropylene samples were prepared containing between 0% N, N-bis (2-hydroxyethyl) tallow fatty amine and 80% of said amine to study the influence of cooling rate on the forming structures. Approximately 5 rags of each sample to be tested were placed in a sealed dish on the DSC-2 at 40 ° C / min to a final temperature of 175 ° C for the 20% polypropylene sample, 23 ° C for the 40% sample. Polypropylene, 245 ° C for the sample with 60% polypropylene, 265 ° C for the sample with 80% polypropylene and 25O ° C for a sample consisting of 100% polypropylene.

Each of the samples was heated to the appropriate final temperature and held there for 5 minutes before being cooled. Bachdeia dl © samples were cooled at the desired cooling rate, the samples were subsequently analyzed after the extraction of N, N-bis (2-hydroxyäthy1) tallow fatty amine with the aid of methanol. The results of the study on the size of the cells in the obtained compounds in Micron (do) are summarized in Table 1. All measurements were determined from the associated scanning electron micrographs.

Table 1 20 ° C / min 40 ° C / min 80 ° C / min cooling 5 ° C / min none (D. none (D. none (1) composition 0.5 (2) none (3) none (3) 0% amine none (D. 2.0 (4) 2.0 (4) 0.7 (5) 20% amine 0.5 (2) 3.0 2.0 1.5 (6) 40% amine 2.5 (4) 4.0 3.0 3.0 (6) 601 amine 4.0 - M - 80% amine 0.5

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some irregular holes are present approximation of the largest cell size the porosity may be too small to be gesassson, su

some smaller gels measure 1/10 of the larger cells

in addition, © cells seig @ n zn small sum

(X) (2) (3)

(6) A © shape of a non-wedge-shaped structure

A further study of the influence of the Äbkühlgeschwindigkeit was carried out using samples with 20% polypropylene and 80% N, L? ~ Bis (2-hydroxyethyl) tallow fatty amine on the Kofier Bank. Five of these samples were cooled at different rates starting from a melted perir of 2 ° C. The results are summarized in Table 2; The dimensions of the cells are again given in microns and the same method was used to determine the data as for Table 1.

Table 2.

Cooling rate 200 ° C / min 87O ° C / min 1350 ⁰ C / rain

Eusammensetaung

Amin

0.5-1.5

1.5-2.5

no ropes

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It can be seen from Tables 1 and 2 that as the cooling rate increases, the size of the cells in the obtained material generally decreases. Further, it will be seen that with respect to the Polymsr / liquid system, which consists of 20% polypropylene and 80% N, N-bis (2-hydroxyethyl) tallow fatty amine, at a cooling rate between about 135O ° C / min and 1700 ° C / min in the final product, a transition from a clearly cellular to a non-cellular or no cell @ r * containing structure takes place. Such a transition in the resulting structure is consistent with the fact that the polymer substantially solidifies after the liquid-liquid phase separation has been initiated, but before the formation of a plurality of liquid droplets could take place, as explained in detail above.

Additional five samples of a 40% polypropylene and 60% N, N-bis (2 ~ hydroxyethyl) tallow fatty amine containing solution were prepared and at speeds of 69O ° C / min to about 7000 ⁰ C / min from a melt temperature of 2 35 C in accordance cooled with the procedure described above. It has been found that for such a ratio of polypropylene and said amine, the transition from the cellular structure to the non-cellular structure is at about 2000 ° C / min.

Finally, three further samples einar 20% polypropylene and 80% N, N-bis talgfettarain solution contained (2-hydröxySthyl) wurden- prepared and at speeds of 20 ° C, 1900 ⁰ C and cooled 65OO ° C / min to determine the effect of different cooling rates on the crystallinity of the resulting structures to investigate. From the. DSC-2 data for this

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Samples showed that the degree of crystallinity in the three samples was substantially the same. Changes in the cooling rate seem to have no appreciable influence on the degree of crystallinity of the resulting structures. It has been found, however, that upon substantial increase in the rate of cooling, the crystals formed would be formed as expected, incomplete.

En tfernung the liquid

After the homogenous solution of polymer and liquid has been cooled in corresponding whales © to produce a material suitable for processing, the microporous product can then be shaped, for example, the liquid by extracting with a suitable solvent for the liquid. however, should not be a solvent for the polymer used is removed. The relative miscibility or solubility of the liquid in the solvent used has an effect on the efficiency with respect to the time required for the extraction. To shorten the extraction time, if desired, the extraction or leaching process can also be carried out at elevated temperature but below the softening point of the polymer. Illustrative examples of useful solvents include isopropanol, Kothyläthy! Ketone, tetrahydrofuran, ethanol and heptane.

DI® each time required varies depending on ä @ x involved liquid, the temperature used and the required degree of extraction. That is, in some cases, it may be unnecessary to extract the liquid used in the system into IGOi, since smaller amounts are harmless

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the amount that can be tolerated depends on the intended use. The time required may accordingly be in a range of less than a few minutes to more than 24 hours, depending on many factors including the thickness of the respective material.

The removal of the liquid can also be done by other known techniques. Illustrative examples include evaporation, sublimation and displacement.

In addition, it should be noted, using conventional liquid extraction techniques, the cellular microporous polymer structures of the present invention can exhibit a liquid delivery behavior approaching zero, i.e., in the absence of solvent. the rate of liquid delivery may become practically constant after an initial phase at a high delivery rate. In other words, the rate of liquid delivery may be independent of the amount of liquid that has already been withdrawn; for example, the rate at which the liquid is withdrawn after 3/4 of the liquid has been removed from the structure may be approximately the same as if the structure were half-filled with liquid. An example of a system with a virtually constant rate of delivery is the extraction of N, N-bis (2-hydroxyethyl) tallow fatty amine from polypropylene with isopropanol as extractant. In some cases, a start-up period may possibly appear at the beginning before the delivery rate becomes identifiable. When the withdrawal of the liquid by evaporation takes place, the rate of delivery tends to be first order (tend to be first order).

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Characterization of the cell structure of the microparticulate polymers.

If the cooling of the polymer / liquid solution is such that the majority of the liquid droplets form on the inside, as shown above, and the liquid is removed from them, the resulting microporous product forms a relative homogeneous © cell structure containing in the microbial a series of essentially spherical, closed microcellons, which are distributed substantially uniformly throughout the structure. Adjacent cables are interconnected via smaller pores, or passage ©. This basic structure can be seen from the photomicrographs of FIGS. 4 and 5. It should be noted that the individual cells are indeed closed , but on the microphotographs they appear open to failure, which can not be avoided in sample preparation for the recording of microphotographs. In the macro range, at least as far as the crystalline polymers are concerned, the structure appears to have planes which are similar to the fracture planes along the corners of the crystal growth (Figure 2) and, as seen in Figure 3, has a coral-like appearance. The cell microstructure further has analogies to zeolite clay structures having defined "chamber" and "gate" regions. The cells correspond to the larger chamber areas of the zeolite structures, while the pores correspond to the gate regions.

In general, in cell structure, the average diameter of the cells may vary from about 1/2 to about 100 microns, with about 1/2 to about 50 microns being the preferred range, while the average diameter of the pores or connecting passageways is generally on the order of one order seems to be smaller. For example, if the sell through one eats

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microporous polymer structure according to the present invention is about 1 micron, the average diameter of the pores or interconnecting vias is about 0.1 micron. As already described above, the cell diameter and also the diameter of the pores or passages depends on the particularity of the respective polymer / liquid system, the cooling rate and the relative proportions of polymer and liquid. However, with respect to the cell to pore ratio, a wide range is possible, for example, of about 2; 1 to about 200: 1, preferably from about 5: 1 to about 40: 1.

As can be seen in the various figures, it may be anticipated that some of the exemplified microporous cellular polymer products do not have the uniform microcellular structure described herein. However, it must be kept in mind that this structure can sometimes be obscured by additional changes due to the use of a particular liquid or polymer or the particular weight ratios. This masstation effect may be local or anywhere, ranging from the formation of small polymer particles hanging on the walls of the cells to the formation of coarser platelet-like polymer structures that tend to completely obscure the framework on the microphotographs. As can be seen in Figures 21 and 25, small polymer beads are attached to the cell cavities of the structure. This extra education is understandable when one thinks of the manner of nucleation and growth described above. Thus, in systems with extremely high solvent or liquid content, the maximum void size is usually relatively large. This also means that the time, the

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is needed until the cavity or droplet reaches its maximum size, also increases. During this time, there is the possibility of additional nuclei forming in the vicinity. Two or more cores can then come into contact with each other before one of them has reached its maximum size. In such cases, the resulting cell structure has less integrity and somewhat less regularity than the basic structures described above. Moreover, even after the liquid droplets have reached their laaximum size, depending on the system of concern, the solvent or liquid phase © may still contain some of the residual polymer or vice versa. In such cases, as the system continues to cool, additional phase separation may subsequently occur. When the residual polymer simply separates from the solution, polymer spheres of a shape can be formed as shown in Figs. On the other hand, when the Reatpolyroer migrates to the polymer skin, the walls appear flaky and irregular, thus causing the leaf-like structure. This sheet-like structure may e.g. only partially mask the basic structure, as can be seen in Figures 28 and 29, but it can also completely mask the structure, as can be seen in FIG.

The leaf-like structure also occurs more frequently in certain polymers. Thus, the low density microporous polyethylene structures, possibly because of the solubility or the like of the polyethylene in the particular solvents used, generally cause this kind of structure. This can be observed in Figure 14. If the level of liquid used is extremely high, you can

C 1 U UU 8

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Furthermore, these structures occur in polymers such as polypropylene, which otherwise actually have the basic structure. This can be readily ascertained by comparing the leaflet type structure of the microporous product of Figure 6 with the basic structure of Figure 8 in which the polymer content is 40% by weight versus 10% polypropylene in the structure shown in Figure 6.

For most applications, a systome is preferably used in which the basic cell structure is formed. The relative homogeneity and regularity of this structure assures predictable results, as required, for example, in filtration applications. On the other hand, the leaflet type structure is more desirable where relatively large surface structures are required, e.g. in ion exchange or various absorption processes.

As can also be observed, some of the structures have narrow holes or openings in the walls of the cells. This phenomenon is understandable when you think about the nature of nucleation and growth. For example, e.g. in a region of the system in which already some spatially adjacent liquid droplets have reached their maximum size, each droplet is enclosed by a polynuclear-rich skin. However, in some cases, some of the solvent may be trapped between the enclosed droplets, and its migration to the larger droplets may not continue because of the penetrability of the skins. Accordingly, in such cases, a fluid germ may form and grow, resulting in a small cavity being embedded adjacent to the larger droplets

~ Ί

-5a- Α3ΑΜ13475 DT

lies. After extraction of the liquid, the smaller droplets appear as small holes or openings. This can be observed on the microporous structures shown in FIGS. 11-12 and 20.

Waiter © Interesting characteristic structure of the cell structure according to the present invention is improved by the extent of the surface of such structures. The theoretical surface area of the microporous sella structure, consisting of spherical cavities with a diameter of

2 is about 5 microns is about 2 to 4 ra / g. It has been found that microporous polymers made according to the present invention need not be limited to the theoretical size of the surface area of the surface. The determination of the surface area of the surface by the B.E.T. Mathode described by Brunauer, S., Emmett, P.K. and Teller, E. in "The Adsorption of Gases in Multilmolecular Layers" in J. Am. Chem. Soc., 60, 309-16 (1938), has given surface areas of surfaces far in excess of the theoretical model unrelated to voids, as shown in Table III for microporous polymers made of polypropylene and polypropylene N, N bis (2-hydroxyethyl) tallow fat amines are obtained.

Table III % empty space Specific surface area

89.7 96.2 m ² / g

72.7 95.5

60.1 98.0

50.5 99.8

28.9 88.5

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The surface can be reduced by careful annealing of the microporous polymers without attacking the basic structure. Microporous polypropylene prepared with 75% void volumes using N, N-bis (2-hydroxyethyl) t-alginate as the liquid component was extracted and dried at a temperature not exceeding room temperature, and then heated to the surface to change. The initial one

Surface was 96.9 m / g. After eleven 40 minute heating periods at 62 ° C, the surface dropped to 66 m / g. Further heating to 60 ° C for an additional 66 hours reduced the surface area to 51.4 m / g. Treatment of another sample at 9O ° C for 52 hours set the surface area at 96.9

2 "

33.7 m / g down. The microporous structure was hardly changed, as revealed by electron-scanning microscopy.

The results are summarized in Table IV.

table IV % Change treatment surface (m ² / g) None 96.9 32% eleven times 40 minutes 66.0 at 62 ° C more than 66 hours 47% at 60 ° C 51.4 65% 52 hours at 90 ° C 33.7

Obviously, the exceptional of the cell structures of the present invention is to be found in the presence of

A3AM13475 DT

both self-contained, substantially spherical, enclosed micro-lines uniformly distributed throughout the structure and self-contained pores interconnecting said cells, the pores having a smaller diameter than the cells. In addition, the cells and the connecting pores have substantially no spatial orientation and can thus be termed isotropic. Thus, there is no preferred direction, e.g. for the flow of a liquid through the structure. Thus, the invention contrasts in particular with materials of the prior art which do not possess such a cell structure. Many known systems possess an unclassifiable structure lacking any definable structural configuration. It is therefore particularly surprising that a microporous structure can be produced which has such a degree of uniformity, making it particularly suitable for many applications where a material of high uniformity is needed.

The cell structure can be defined by the ratio of the average diameter of the cells ("C") to the diameter of the pores ("P"). Thus, as discussed above, the ratio C / P may vary from about 2 to about 200, preferably from about 5 to about 100, more preferably from about 5 to about. Such C / P ratios distinguish the inch structures according to the present invention from all microporous polymeric products of the prior art. Since there are no known synthetic thermoplastic polymeric structures having self-contained cells and pores, it is believed that all of the prior art materials have a cell / pore ratio of one.

>. - par -

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Another means to characterize the cell structure of the invention is the so-called sharpness factor "S". The S-factor is determined by analysis of a quo-silver intrusion curve for the given structure. All mercury intrusion data discussed in this application was determined using a Micromeritics Mercury Penetration Porosimeter Model 910 series. The S value is defined as the ratio of the pressure at which 85% of the mercury has penetrated to the pressure at which 15% of the mercury has entered. This ratio is a direct measure of the variation in pore diameter over the 70% inner pores for any given coupon since the pore diameter is 176/8 divided by the pressure expressed in p.s.i.

The S value is then a ratio of the diameter of the pores, at which 15% of the mercury has penetrated, to the diameter of the pores, at which 85% of the mercury is intruded. The range of 1 to 15% and 85 to 100% of the mercury intrusion is neglected in the determination of the S-factor. The range of 0 to 15% is neglected because intrusion within this range can be attributed to cracks or fractures that have been introduced into the material due to fractures that may occur during freezing, prior to passing the mercury intrusion test was subjected. The range of 85 to 100 S is also neglected because the values obtained in such a range are due to the compression of the sample rather than the actual penetration of the mercury into the pores.

Characteristic for the narrow range of pore sizes, the structures have according to the present invention, S ~ Werta ^ ¹⁰ range from about 1 to about 30, preferably from

-5 * 6- 'A3AM13475 DT

from about 2 to about 20, more preferably from about 2 to about 1.0.

The mean size of the cells of the structure varies from about 0.5 to about 100 microns, preferably from about 1 to 30 microns, more preferably from about 1 to about 2 microns. As already mentioned, the cell size can vary depending on the particular plastic and compatible liquid used, the ratio of polymer to liquid, and the cooling rate used to form the particular microporous polymers. The same variables also affect the mean size of the pores in the resulting structure, generally between 0.05 to about 10 microns, preferably between about 0.1 to about 5 microns, but more preferably between about 0.1 to about 1 micron can vary. All information regarding the size of a cell and / or pore in the context of this invention refers to the average diameter of such a cell or pore, expressed in microns, unless stated otherwise.

By determining the mentioned factors, namely, cell size, pore size and S for the cellular microporous polymers of the present invention, the cellular microporous polymers according to the present invention can be accurately defined. A particularly useful means of defining the polymers is the logarithm of the cell to pore ratio (log C / P) and the logarithm of the ratio of the sharpening function S to the cell size (log S / C). Accordingly, the cellular microporous polymers of the present invention have a log C / P of about 0.2 to about 2.4 and a log S / C of about -1.4 to 1.0; Preferably, the polymers have a log C / P of about 0 _f 6 to about 2.2 and a log S / C of about -O, 6 to about 0.4.

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Noncellular structures

The noncellular structure according to the present invention, which results from cooling the homogeneous solution at a rate such that the polymer becomes substantially solid before most of the liquid droplets can form, may be particularly due to the narrow pore size distribution of the material in connection with the given pore size and the spatial uniformity of the structure.

In particular, the non-cellular microporous polymers can be characterized by a sizing function S described above with respect to the cell structure. The S-values exhibited by the non-cellular structures vary from about 1 to about 30, preferably from about to about 10, more preferably from about 6 to 9. However, if the pore size of the material is in the range of about 0.2 to 5 microns The S value varies from about 2 to about 10, preferably from about 5 to about 10. Such S values for olefinic polymers and oxidation polymers having a microporosity of such a size have heretofore been unknown except in cases highly oriented thin films made by drawing techniques. As already mentioned, the porous polymers of the invention are substantially isotropic. Therefore, a section of the polymers that can be laid through any plane of space shows essentially the same structural features.

The pore sizes of the noncellular structures according to the present invention are usually in the range of about 0.05 to 5 microns, preferably from about 0.1 to about 5 microns, more preferably from 0.2 to 1 micron.

Α3ΑΜ13475 DT

Obviously, it is a surprising effect of the present invention that it allows to make isotropic microporous structures of olefinic polymers and oxidation polymers, which structures have porosities in the range of 0.2 to 5 microns and a sharpness value of about 1 to about 10. It is particularly »surprising that these structures can be produced not only in the form of thin films but also in the form of blocks and more complicated FONA bodies.

General

For example, when casting a film or block onto a substrate e.g. On a metal plate, the surface of the microporous polymer structure of the present invention in contact with the plate has a surface skin which is not cellular. The other surface, however, is typically predominantly open. The thickness of the skin varies somewhat depending on the particular system employed as well as the particular process parameters that are employed. Most often, the thickness of the skin is approximately equal to the thickness of a single cell wall. Depending on the particular conditions, skins are possible which are completely impermeable to liquids up to those which have a certain degree of liquid permeability.

If only one cell structure is desired for subsequent use, the surface skin can be removed by any of several techniques. Thus, e.g. the skin is removed by one or more mechanical means, such as by abrasion, piercing the skin with needles or breaking the skin by passing it over

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of the film or other structure over rolls that move at different speeds. On the other hand, one can also remove the skin by means of a microtome.

The skin may also be removed by chemical means, e.g. by brief contact with a suitable solvent for the polymer.

If e.g. A solution of polypropylene in Ν, Ν-bis (2-hydroxyethyl, ethyl) tallow fat amine is continuously cast as a thin film on an endless stainless steel conveyor belt, causing a small amount of a dissolving liquid to be applied to the belt immediately before the zone where the solution is applied, removing the surface that has formed on the solution steel contact surface. Useful liquids include substances such as isoparaffinic hydrocarbons, decane, decalin, xylene, and mixtures such as xylene / isopropanol and decalin / isopropanol.

However, the presence of the skin for some end uses is not only no disadvantage but a necessary requirement. For example, in ultrafiltration and other applications where membranes are used, thin liquid-impermeable films are used. Accordingly, in such uses, the microporous portion of the structure according to the present invention has particular utility as a carrier for the surface skin which functions as a membrane in such applications. Structures which are completely cellular may also be prepared directly by various techniques, e.g. the polymer. Liquid system in Lvift or a liquid medium, ζ * B. Hexane, extruded.

The microporous polymer structures of the invention have such

-yf-

2 00 810

" ⁶⁰ *" Α3ΑΜ13475 DT

already discussed above, cell and pore diameters with an extremely narrow size distribution, which are an indication of the unique structure and its homogeneity. The narrow size distribution of the pore diameters, determined by means of Queeksilber intrusion data, can be seen from Figures 30 to 33. The same general distribution is obtained regardless of whether the structure is formed in the form of a film (Figs. 30 to 32) or a block (Fig. 33). The characteristic pore size distribution of the microporous structures of the invention are in marked contrast to the much broader pore size distributions of known microporous polymer products obtained by older processes, e.g. in US Pat. Nos. 3,310,550 and 3,378,507, which will be explained in detail in connection with the examples.

For any of the microporous polymers made in accordance with the present invention, the particular end use dictates the amount of voids and pore sizes required. Thus, for prefiltration purposes, the pore size is generally 0.5 microns, while in ultrafiltration the pore sizes should be less than 0.1 microns.

For purposes of use where the microporous structure serves as a reservoir for a valuable liquid, strength considerations dictate the amount of voids when controlled drainage of the collected fluid is required. Likewise, in such cases, the desired rate for draining the liquid prescribes the pore size? smaller pores generally cause smaller rates of deflation.

2 O 0 810

A3AM13475 DT

Where the microporous structures are used to form a liquid polymer additive, such as e.g. to convert a flame retardant to the solid state generally requires a certain minimum strength; also with this minimum strength it is also desired to be able to use as much liquid as possible since the polymer serves only as a receptacle or carrier.

A3AM13475

Functional Wirkflüssikkelten containing microporous polymers

The above makes it clear that it is within the scope of the present invention to produce microporous products which contain an effective liquid such as polymer additives (e.g., flame retardants) and behave as solids and can be processed as such. For this purpose, the resulting microporous polymer is mixed with the desired active liquid. This can be accomplished, for example, by known absorption techniques wherein the liquid volume taken up is substantially the same as the amount of liquid initially used to make the microporous polymer. Any useful organic liquid may be used, unless it is, of course, a solvent for the polymer or otherwise attacking or degrading the polymer at the processing temperature. The microporous products containing the appropriate active liquid may be prepared from or using microporous polymers having either the cellular or noncellular structure as a template into which the liquid is introduced.

Similarly, such microporous products can also be made, for example, by an exchange process. In this manufacturing process, the intermediate product for the microporous polymer is first prepared. The liquid is then displaced either by the desired efficacy or by a displacer intermediate fluid. In both cases, the liquid used to make the

Γ .. Π

Α3ΑΜ13475

microporous polymer intermediate was not removed by extraction but by conventional pressure or vacuum exchange or infusion techniques. Any active or displacer liquid which could also serve as the extraction liquid for the production of the microporous polymer can be used, that is to say, any of these. which, although not a solvent for the polymer, possesses a certain solvent odor mixing capacity with respect to the liquid to be displaced. It follows that small amounts of the displaced liquid or liquids can remain after the exchange process is carried out. The requirements for the final product, which arise from the intended use, determine the level of the required degree of exchange. Thus, residual Btengen of about 1 to 10 weight percent may be permissible in some cases. If desired, however, it is also possible to remove substantially all the liquid or all liquids completely by multi-stage replacement processes and / or by the use of liquids which can be removed completely by evaporation; In this way, a proportion of less than about 0.03 weight percent residual liquid can be achieved. From an economic point of view, it will generally be desirable to use a replacement liquid having a boiling point different from that of the. to be displaced liquid sufficiently far away to allow subsequent processing and reuse of the same. For this reason, it may be advantageous to use an exchange intermediate liquid.

As can also be seen from the above examples of suitable polymer-EJe23 fluid systems, one enables

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Another method for producing a polymer-functional active fluid The use of the microporous polymer intermediate without further processing, since numerous active fluids have been found, which are due to their compatibility with the respective polymer for the preparation of the solid microporous polymer intermediate suitable. In this way, intermediates that behave as solids can be prepared directly using liquids that can be used as lubricants, surfactants, lubricants, antiknock agents, pesticides, plasticizers, pharmaceuticals, fuel additives, polishes, stabilizers, insecticides, and so on Animal repellents, fragrance dispensers, flame retardants, anti-oxidants, odor control agents, anti-fogging agents, perfumes and the like suitable. For example, with a low density polyethylene, a useful intermediate containing a lubricant or a plasticizer may be prepared using either an aliphatic or aromatic ester having eight or more carbon atoms or a non-aromatic hydrocarbon having nine or more carbon atoms. Useful products containing a surfactant and / or wetting agent can be made from a low density polyethylene by using a polyethoxylated aliphatic amine having eight or more carbon atoms or a nonionic surfactant. From polypropylene, an intermediate containing an surfactant can be prepared by using ethoxylated aliphatic amines having eight or more carbon atoms. Polypropylene intermediates containing lubricants can be made using a phenylmethyl polysiloxane

- <oS-

A3AM13475

while low-density polyethylene lubricant intermediates can be prepared by the use of an aliphatic amine having from twelve to twenty-two carbon atoms. Low density polyethylene fuel additive intermediates may be prepared using an aliphatic amine having eight or more carbon atoms or an aliphatic dimethyl tertiary amine having twelve or more carbon atoms. The tertiary amine (s) may also be very useful intermediates for additions of methylpentene polyerenes; high and low density polyethylene intermediates containing a stabilizer may be prepared by the use of an alkylaryl phosphite.

Low density polyethylene intermediates with an anti-fogging agent can be prepared by using the glycerol nano or diester of a long chain fatty acid having at least 10 carbon atoms. Intermediates with flame retardants can be made from high and low density polyethylene, polypropylene and a mixture of polyphenylene oxide and polystyrene using a polyhalogenated aromatic hydrocarbon having at least four halogen atoms per molecule. The suitable materials should of course be liquid at the phase separation temperature, as already described. Other systems which have also been found suitable are described in more detail in connection with the examples given below.

Furthermore, certain ketone groups that are found to be particularly useful in polypropylene and high and low density polyethylene can be used in the present invention

Γ Π

Α3ΑΜ13475

have proven to be suitable as animal control products. Such ketones may include saturated aromatic ketones having from seven to nineteen carbon atoms, unsaturated aliphatic ketones having from seven to thirteen carbon atoms, 4-t-amyl cyclohexanone and 4-t-butylcyclohexanone.

The following examples are intended to further describe the present invention without, however, limiting it thereto. Unless otherwise specified, all subscriptions and extras are by weight.

VorbereJtungsverfahren

The porous polymer intermediates and the microporous polymers described in the Examples below were prepared by the following procedure:

A. Porous polymer intermediates :

The porous polymer intermediates were prepared by mixing together a polymer and a liquid precursive with it, heating the mixture to a temperature generally near or above the softening point of the plastic to form a homogeneous solution, and dissolving the solution was then cooled, without subjecting them to any mixing or other shear forces, to produce in this way a macroscopically solid homogeneous mass. When solid blocks of the intermediate were to be prepared, the homogeneous solution was poured into a suitable mold, generally made of metal or glass,

2008 10

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"" ⁶ * "Α3ΑΜ13475

and was then cooled at room temperature unless otherwise specified. Of course, the cooling rate at room temperature conditions depended on the sample thickness and composition, but was generally on the order of about 10 ° C to about 20 ° C / min. The mold was generally cylindrical with a diameter of 75 to about 2.5 inches (about 19 to about 63.5 mm) in diameter, and the solution was generally up to a height of about 0. 25 to about 2.0 inches (about 6.4 to about 50.8 mm) filled in the mold. To prepare intermediates in film form, the homogeneous solution was poured onto a suitable metal plate whose temperature was adjusted so that the solution could spread to a thin film. The metal plate was then placed in contact with a dry ice bath to cool the film rapidly below its melting point.

B. Porous polymers :

The microporous polymer was prepared by extracting the polymer compatible liquid used to prepare the porous polymer intermediate, generally by repeatedly washing the intermediate in a solvent such as isopropanol or methyl ethyl ketone, and then the solid microporous Mass was dried.

Examples

The following examples and tables describe some of the various combinations of polyisers and their compatible liquids useful for making porous extrusions.

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- £ 8 - Berlin, d, 27.9 «1978 IPC 08J / 200 810

Of all the combinations exemplified above, solid blocks and, if noted in the table, thin films of the intermediate were prepared using the method described above In the following tables, many of the intermediate compositions for making the microporous polymers of the present invention were used by using a suitable solvent to extract the polymer compatible liquid from the intermediate and then removing this solvent by evaporation.

Many of the compatible with the polymers liquids which are described in the following examples are as indicated in the tables, functional liquid active substances that are useful not only as to the polymers compatible liquids, but also as flame retardants, lubricants, etc. ₀ serve For this reason, the intermediate compositions prepared with such functional fluids are suitable both as solid polymer additives and the like, as well as intermediates for the preparation of the porous polymers. The functional actives listed in the following examples are as such characterized by one or more of the following symbols in the column "Type of active liquid": AF (anti-fogging agent); AO (antioxidant); AR (animal repellent); FA (fuel additive); FG (fragrance dispenser); FR (flame retardant); IR (insecticides);

20Ü81U

-63- Α3ΑΜ13475

L (lubricant); M (drug); MR (Moth Repellent); OM (Odor Improver)? P (plasticizer)? PA (polish); PE (pesticide); PF (Perfume)} S (Lubricant) f SP (Surfactant) and ST (Stabilizer).

Examples 1 to 27

Examples 1 through 27 in Table V, respectively, relate to the preparation of homogeneous porous polymer intermediate © in geetalt cylindrical cylindrical blocks having a radius of about 1.25 inches (about 31.8 mm) and a height of about 2 inches (about 50 inches) , 8 zsss) of high density polyethylene ( ^B HDPE ") and the compatible liquids which were found to be suitable using the standard manufacturing process The high density polyethylene was sold by Allied Chemical under the designation Plaskon AA 55-003 , and had a melt index of 0.3 g / 10 min and a density of 0.954 g / cm Many of the exemplified intermediates were treated by the extraction method to thereby yield porous polymers as shown in the Table specified.

The details of the preparation and the type of suitable functional active fluids listed are given in Table V:

- ßi -

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A3AM13475

Table V River. ⁰ C Type of functional fluid HDPE Beiep.Nr. Liquid type. % and liquid 75 230 Saturated aliphatic acids 1 Dean acid Primary saturated 75 220 PF alcohols 75 220 -. · '· · 2 ' decyl 3 1-dodecanol 75 220 , Secondary alcohols 75 23O 4 2-overkanol ⁺ 5 6-undecanol 75 , 230 Aromatic amines 6 N, N-diethylaniline ⁺ 70 220 diester 70 220 7 Dlbutylsebazat * 8th Dihexyl sebacate ⁺ 75 220 PF ether 70 220 PF 9 diphenyl ether 10 benzyl ether 70 250 FR Halogenated compounds 75 200 FR 11 hexabromobenzene 70 250 FR 12 Hexabromdiphenyl 70 200 FR 13 Hexabroracyclodekan 14 hexachlorocyclopentadiene

-. , ; · - · 2 0 0.8 1 0 -

~ J1- A3AM13475

Table V (continued) HDPE

Beiep.Nr. Flusslgk & itstyp% flow, ⁰ C Type of

and fluid functional

liquid

Octabroradiphenyl 70 280 FR

Cohesive hydrogens with a double bond "

1-hexadecene * 75 220

Di® liquid was extracted from the solid.

2 00810

Table V (continued) % River. A3AM1 3475 HDPK Liquid type and liquid Beisp.Nr. Aromatic coals 75 ° c Type of functional fluid hydrogens 70 DiphenyImethan 1.7 Naphthalene* 75 220 OM 18 Aromatic ketones 230 MR acetophenone 75 19 Aromatic esters 200 PF butylbenzoate 20 various 220 L, P

(2-hydroxyethyl) -tamine (1)

Sebum fatty amine (1) 70 250 22 dodecylamine 75 220 SF 23 24 24 N-hydrogenated tallow fat diethanolamine Firemaster BP-6 (2) 50 75 240 200 ST 25 Phosclere P 315C ⁺ (3) 75 220 M 26 quinoline 70 240 27 Dicocoamine (4) 75 220

The liquid was extracted from the solid

 (1) A stable antistatic agent having the following properties was used

Boiling point at 1 mm Hg. 215-220 ⁰ C; spes.Gewicht at 32.2 ° C (90 ⁰ F), 0.696; Viscosity, Saybolt universal seconds (SSU) at 32.2 ⁰ C (90 ⁰ F), 476th

u. i /

 , V .1. V '

2 0 0 810

-? 3- A3AM13475

(2) Trademarks of "Michigan Chemical Corp." for her hesabromodiphenyl; Flanunhemmendes agent was used with the following properties: softening point 72 ⁰ C; Tight at 25 ° C> 2.57 g / ml; Viscosity cps. 260-360 (Brookfield # 3 Spindle at 110 ° C).

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.2 OO 8 1 0

Α3ΑΜ13475 J

Table VI

LDPE

Beisp.Nr. Liquid type and liquid

% River

Type of

functional

liquid

Saturated allspatsch

acids 70 210 28 caprylic 70 190 29 Dean acid 70 190 30  f hexanoic acid 70 220 • 31 lauric acid 70 189 32 myristic 70 186 33 palmitic 70 222 34 stearic acid 70 203 35 undecanoic Unsaturated aliphatic see acids 70 219 36 Erucic acid (2) * 70 214 37 oleic acid • Aromatic acids

Phenylstearic acid Xylyl-benzeneserate

214 180

PA

The liquid was extracted from the solid.

(1) Union Carbide Company's "Bakelite" polyethylene having the following properties was used: Density 0.922 g / ciu. Melt index, 21 g / 10 min.

(2) This is an acid having a density of 0.8602 g / cm and a melting point of 33-34 ° C.

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A3AM13475

Beisp.Nr. Liquid type and liquid

Table VI {continued) LDPE

% River.

Type of

functional

liquid

Different acids

40 Acintol FA2 (tall oil acids) (1) 70 204 41 Olefinic acid L-6 70 206 42 Olefinic acid L-9 ⁺ 70 186 43 Olefinic acid L-11 ⁺ 70 203 44 Resin acid (rosin acid) 70 263 45 ToIy1Stearinsäure 70 183 Primary saturated alcohols 46 cetyl alcohol 70 176 47 decyl 70 220 48 1 ~ dodecanol 75 200 49 1-Heptadekanol 70 168 50 Nonylalkohöl 70 174 51 1-Octane1 70 178 52 Oleyl alcohol ⁺ 70 206 53 Tridecylaikohol 70 24o 54 1-undecanol 70 184 55 undecylenyl 70 199 Secondary alcohols

PF

PF

FA

Dinonylcarbiüol

70

201

PF

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Table VI (continued ) LDPE

Beiep.Nr. Liquid type and liquid

% River

Type of functional fluid

57 Diundecylcarbinol 70 226 58 2-octanol 70 174 - 59 2-undecanol 70 205

The liquid was extracted from the solid.

(1) Trademark of the Arizona Chemical Company for a mixture of fatty acids. The composition and physical properties are:

Fatty acid starting material 98.2% total amount; Linoleic acid, unconjugated 6%; oleic acid 47% saturated fat 3%; other fatty acids 8%; spec. Weight 25/25 ⁰ C, 0.898; Viscosity, Saybolt universal seconds (SSU) at 38 ⁰ C (100 ⁰ F) 94th

-yc-

- 7? - River. ⁰ C A3AM13475 I Table VI (continued) 70 164 Beisp.Nr. LDPE 70 196 Type of functional fluid_ Liquid type% and liquid 70 206 60 Aromatic alcohols 70 220 PF 61 1-phenylethanol ⁺ 62 1-phenyl-1-pentanol 70 19Ο .. - 63 Phenyl ~ stear ^: l-alcohol 70 206 SF, PE nonylphenol 64 Cyclic alcohols PE 65 4-t-butyl-cyclohexaEiol 70 1.80 PF Menthol* 70 268 Other OH-containing 70 -_- 66 links - 67 Neodol-25 (1) ⁺ 70 188 SF 68 Polyoxyethylene ether of oleyl alcohol (2) SF Polypropylene glycol 425+ (3) 69 aldehydes PF S & lizylaldehyd

The liquid was extracted from the solid.

(1) Trademark of Shell Chemical Company for its synthetic fatty alcohol containing 12-15 carbon atoms.

(2) Eg, Volpo 3, surfactant of Crod.a _r Ine, having the following properties was usedj acid value, max. 2.0, cloud point, 1% aqueous solution,

- 76 -

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'·, -IS.- A3AM13475

insoluble; HLB value, calculated, 6.6; Iodine Number, Wijs, 57-62; pH of a 3% aqueous solution, 6-7; Hydroxyl number, 135-150.

(3) Trademarks of Union Carbide Company for its Glycol with the following properties:

spez.Gewicht apparent, at 20 ⁰ C, 1.009; Hydroxyl number mg K0H / g 265; Acid number, mg KOH per g / sample, max. 0.2; , pH at 25 ⁰ C in 10x6 isopropanol / water solution 4.5-6.5.

Table VI -? 3 - 70 A3AM13475 | Type of functional fluid LDPE (Continuation) 70 Liquid type and liquid 70 PA Beisp.Nr. Primary amines % River. ° C FA FA 70 Dimethy1-dodecylamine 70 200 FA 71 Hexadecy laiain 207 72 octylamine 172 73. tetradecyl 186 Secondary amines

Bis (1-ethyl-3-methylpentyl) amine +

Tertiary amines

70

190

75 , Ν, Ν-Dimethylsoja-amine 70 198 FA 76 Ν, Ν-dimethyl tallow fatty amine + (2) 70 209 FA Ethoxylated amines 77 N-stearyl diäthanolarain 75 210 SF, AF Aromatic amines 78 diaminodiphenylmethane 70 236 79 aniline N-sec-butyl- 70 196 80 N, N-diethylaniline ⁺ 70 -_ 81 N, N-dimethylaniline ⁺ 70 169 82 Dlphenylainin 70 186 AO, PE 63 aniline Dodecy! 70 204 84 Phenylstearylamin 70 205 - ~ 85 N-ethyl-o-toluidine " ¹ " 70 182 86 P-toluidine ⁺ 70 184 -

2 00810

r .. -.- ^. : ..

-8O- Α3ΑΜ13475

The liquid was extracted from the solid.

(1) A tertiary amine having the following properties was used: *

Cloud point, ⁰ F, ASTM, »37.8 ⁰ C; Specific gravity at 25/4 ⁰ C, 0.813; Viscosity, Saybolt universal seconds (SSU) at 25 ⁰ C, 59,3i

(2) A tertiary amine having the following properties was used:

Schiaelzbereich, -2 to +5 ⁰ C (28 to 41 ⁰ F); Cloud point, 15.6 ^° C (60 ^° F); specific gravity, 25/4 ° C, 0.803; Viscosity, Saybolt universal seconds (SSU) at 25 ⁰ C,

Table VI (continued) \ River. A3AM13475 ° C Type of funktionellan liquid LDPE Flüssigkeitatyp \ and liquid 70 188 Beisp.Nr. diamines 70 220 1,8-diamino-p-menthane 87 N-erucyl-1,3-propanediamine + 70 242 68 Various amines 70 159 Branched tetramine L-PS (1) + 89 cyclododecylamine + 70 245 90 amides 70 262 IR Cocoamide ⁺ (2) 70 250 L, P 91 N, N-Diäthyltoluamid 70 250 L, P 92 Erucamide (3) 70 260 L, P 93 hydrogenated tallow fatty amide * 70. 255 L, P 94 Octadecylamide (4) 95 N-trimethylolpropane stearic acid amide 96 Aliphatic saturated 70 70 70 175 171 194 L ester 70 192 -A- ethyl laurate ethyl palmitate isobutyl stearate 70 285 • fe. ... y 97 98 99 Isopropylrayristat TOO Isopropvlpalmitat 101

200810

Table VI (Continuation) ⁰ C Type of functional fluid LDPE 182 195 Beisp.Nr. Liquid type and liquid % River. 202 L 102 103 Methyl caprylate methyl stearate * 70 70 104 tridecylstearate 70

The liquid was extracted from the solid.

(1) N-phenylstearo-1,5,9,13-azatridekan.

(2) An aliphatic amide having the following properties was used: appearance, dandruff; Flash point about 174 ⁰ C; Focal point about 185 ⁰ C; ·

(3) An amide having the following properties was used: specific gravity 0.88; Melting point 99-109 ⁰ C; Flash point 225 ⁰ C.

(4) An octadecylamide having the following properties was used: appearance, dandruff; Flash point about 225 ⁰ C focal point about 250 ⁰ C.

- es-

Table VI (continued ) LDPE

A3AM13475

Beisp.Nr. Liquid type and liquid% flow.

Type of

© functionally] *

liquid

110 111 112 113 1.14 115 116 117 118 119 120

Aliphatic

saturated esters 70 oleate * 70 Butylundecylen & t 70 stearyl Alkoxy ester 70 Butoxyethyl oleate ⁺ 70 Butoxyäthyl stearate Aromatic esters

benzyl

benzyl benzoate

Butyl benzoate ⁴ "

Ethyl benzoate ⁺ isobutyl phenyl stearate

methylbenzoate

methyl salicylate *

Phenyllaurate ⁺

Phenyl salicylate * tridecylphenyl stearate

Vinyl phenyl stearate diester

Dibutyl phthalate ⁺

196 L 205 2o5 200 _- 205 198 242 L, P 178 L, P 200 ^L ' ^P 178 L, P 170 L, P 200 L, P, PF 205 y , L.P. 211 L, P, M, F 215 L, P 225 L.P.

290

, P

2-00 81 o

Α3ΑΜ13475 J

Table VI Liquid type and liquid (Continuation) ⁰ C Type of functional fluid LDPE Dibutyl sebacate 238 L, P Beisp.Nr. Dicapryl adipate % River. 204 L, P 122 Dicapryl phthalate 70 204 123 Dicapryl sebacate 70 206 L, P 124 diethyl phthalate * 70 280 IR 125 Dihexyl sebacate * 70 226 ___ 126 70 127 VO

The liquid was extracted from the solid.

A3AM134

Beisp.Nr. Liquid type and liquid

Table VI ( Continuation) LDPS

% River.

Type of

functional

liquid

128

Diester (continued )

Dimethylphenylendistearat +

70

208

129 Dioctyliualeat 70 220 130 · Di-iso-octyl phthalate ~ 70 212 ' 131 Di-iso-octyl sebacate ~ 70 238 Ester poly & thylenglykol 132 PEG 400 diphenyistearate 70 326 Polyhydroxy1 ester 133 Castor oil 70 270 AF 134 Glycerol dioleate ⁺ (1) 70 230 AF 135 Glycerol distearate " ¹ " (2) 70 201 AF 136 Glycerol monooleate (3) 70 232 137 Glycerol iaonophenyl stearate 70 268 AF 138 Glycerol monostearate (4) 70 211 139 Trimethylolpropane mpnophenylstearat 70 260 y ether PF 140 Dibenzyl "** 70 189 --- 141 Diphenyl ether ⁺ 75 200

The liquid was extracted from the solid.

.2 00810

-j? * - A3AM13475 J

ι

(1) A glycerin ester having the following properties was used: flash point, COG 271 ⁰ C (520 ⁰ F) j solidification point: O ° C; Viscosity at 25 ^° C., 90 cp; specific gravity at 25/20 ⁰ C, 0.923-0.929.

(2) A solid substance having a melting point of 29.1 ⁰ C.

(3) A glycerin ester having the following properties was used: specific gravity 0.94-0.953; Flash point, COC, 230 ⁰ C (435 ⁰ F). Solidification point 20 ⁰ C; Viscosity at 25 ^° C., 204 cp.

(4) A glycerol ester having the following properties was used: mold at 25 ^° C., dandruff; Flash Point, COC, 210 ° C (410 ⁰ F); Melting point, 56.5-58.5 ⁰ C.

Α3ΑΜ1347 5

Table VI (continued) % River. ⁰ C Type of functional fluid Beisp.Nr. LDPE liquid type and liquid Halogenated ether 70 70 ⁺ 70 70 180 314 196 290 FR FR PR _# FR FR 142 143 144 145 4-bromodiphenyl ether FR 3OO BA (1) hexachlorocyclopentadiene Octabromodip.henvl

146

Hydrocarbon with terminal double bond

1-nonene

Hydrogen halide with non-terminal double bond

70

174

147 3-eicosene 70 204 148 2-heptadecene 70 222 149 2-nonadecene 70 214 150 .f. 9-nonadecene 70 199 151 2-nonene 70 144 152 2-undecene 70 196 Aromatic hydrocarbon matter 153 diphenylmethane 75 200 154 trans-stilbene ⁺ 70 218 155 Triphenv! Methane 70 225

PF

• Table VI • " " 70 20 0810 ⁰ C Type of functional fluid , LDPE JSS - A3AM13475 | Liquid type and liquid (Continuation) 206 Aliphatic ketones 238 Beisp.Nr. Dinonylketon % River. 205 AR '-: -. distearyl 183 156 2-Heptadekanon 70 152 157 8-Heptadekanon 70 225 158 2-heptanone 70 170 159 ' 70 160 70 161 Methylheptadecyl ketone 70 162 Methylnonyl ketone

The liquid was extracted from the solid. (1) Trademarks of Dow Chemical Corp. for their decabromodiphenyl oxide as a fire-drying agent. A preparation with the following properties was used:

81-83% bromine; Melting point, min. 285 ⁰ C; Decomposition temperature, DTA, 425 ° C.

-K-

i ' \ J

- SZ % River. A3AM13475 ° c Type of functional fluid Table VI (continued) * "70 210 AR Beisp.Nr. LDPE 70 205 Liquid type and liquid 70 214 163 Aliphatica ketones 70 194 _.- 164 Methylpentadecylketon 70 178 165 Me thy lunde cy lke ton 70 262 166 " 2-nonadecanone 70 168 167 10 Nonadecanan 70 205 168 8-pentadecanone 70 188 169 11-pentadecanone 170 2-Tridecanone ⁺ 70 190 PF 171 6-tridecanone 70 245 PF 6-undecanone 172 Aromatic ketones 70 220 PE 173 acetophenone 70 304. FR benzophenone 174 Various ketones 175 9-xanthone ⁺ Phosphorus compounds trixylenediophosphate various

176 N, N- _B is (2-hydroxyethyl) tallow fatty amine 5864 K 70 - 210 FG 177 Bath oil aroma no. Lertes 70 183 AO 178 EC-53 Stvrolia 70 191

Nony! Phenol (1)

-yf.

2 00810

Α3ΑΜ13475 |

Table VI (Continuation) ⁰ C Type of functional fluid LDPE 200 Beisp.Nr. Liquid type and liquid t river. 178 FG 179 mineral oil 50 200 180 Muget hyacinth 70 181 Phoseiere P 315C ⁺ 70

The liquid was extracted from the solid. (1) Trademark of Akzo Chemie NV, for its sterically hindered styrenated phenol.

, - 94 -

Table VI (continued ) LDPE A3AM13475

Beisp.Nr. Liquid type and liquid

River. ^W C 210 Type of functional fluid 70 173 AO 70 230 70 194 70 200 M, PF 75 204 FR 70 __-

182 183 184 185 186 187

Phosclere P 576 (1) ^T

quinaldine

Quinoline " ¹ "

Terpineol Prime No.

Firemaster BP-6

Benzyl alcohol / 1-heptadecanol (50/50)

Benzyl alcohol / 1-heptadecanol (75 / 25Γ

70 194

The liquid was extracted from the solid. (1) sterically hindered styrenated phenol from Akzo Chemie NV,

ι; ι! i>

I

2 00810

Photomicrographs of the porous polymers of Examples 38 and 122 are shown in Figs. 28 and 29, respectively. The photomicrographs at 2000X show the cellular structure with a pronounced amount of "tree growth" evenly distributed through the samples.

Examples 189 to 193

Examples 190-194 in Table VII illustrate the formation of homogeneous porous polymer intermediates by pouring the solution into a glass dish to form cylindrical blocks having a radius of about 4.4 cm and a height of about 0.6 cm.

were.

Except where indicated, the "Noryl" polymers and the compatible liquids found to be useful to which the standard manufacturing process was applied. In the examples given, the microporous polymer was also shown.

The details of the presentation and the type of functional useful liquid are given in Table VII.

-33-

Table VII

Bei3p.Nr. Liquid type and liquid

River

A3AM13475

Type of

functional fluid

Aromatic amides

189 diphenylamine 75 195 diester 190 dibutyl phthalate ' 75 210 Halogenated coals hydrogen 191 Hexabrorodiphenyl (2) 70 315 various 192 N, N-bis (2-hydroxyethyl) tallow fatty amine 75 250 193 N, N-bis (2-hydroxyethyl) tallow fatty amine 90 300

(1) "Noryl", a mixture of polyphenylene oxide condensate polyraerera with polystyrene having the following properties was used: Specific gravity at 22.8 ° C (73 ° F)>1.06; Tensile strength at 22.8 ⁰ C (73 ⁰ F) 674.8 kg / cm ² (9,600 psi); Elongation at break 22.8 ⁰ C (73 ⁰ F), 60%;

Modulus of elongation at 22.8 ⁰ C (73 ⁰ F) 28,116 kg / cm ² (psi 335,000); Rockwell hardness R 119..

(2) The "Horyl" microporous polymers prepared with hexabromobiphenyl and K, N-bia (2-hydroxyethyl) tallow fatty amine were poured to heights of 1.3 era.

Mikrophotogriphi

sine

192 is shown in Fig.

2500x

spherical

Examples 194 to homogeneous porous

2 oil

A3AM13475

"1

e of the microporous polymer of Example 25. The photomicrograph shows the microcellular structure on the walls of the cells.

enlargement Har deposits Examples 194 to 236

Figures 236 in Table VIII illustrate the formation of polymeric intermediates in the form of cylindrical blocks approximately 3.2 cm in radius and about 1.3 cm high in polypropylene ("PP") and the compatible fluids useful in the art Using the standard manufacturing process were found. In addition, in the examples given, blocks of about 15 cm

Height and / or five films produced. In addition, as stated, the microporous polymer was produced.

The details of the presentation and the type of functionally useful liquid are given in Table VIII:

:,) , .. · \ J i \?

Α3ΑΜ13475

199 Table VIII River. ° C Type dpr £ unktionel3.en liquid Beiap.Nr. 200 Liquid type% and liquid 70 260 M 201 Unsaturated acid 194 202 10 Undakansäure 70 260 203 alcohols 70 160 AO 195 204 2-Benzyl-1-amino-propanol 75 230th 136. 205 ionol CP ⁺ 70 185 PF 197 20S 3-Pheny1-1-propanol 196 207 Salizylal'dehyd 75 240 IR - 208 amides 209 Ν, Ν-diethyl-m-toluamide 70 230 amines 70 160 Diaminodiphenylmethane '*' 75 200 Benzylamine ⁺ 70 180 N-butylaniline 70 160 1,1'-diaminododecane "*" 75 200 1.8 diaminooctane 75 260 MW ·· dibenzylamine 75 250 N, N-Biäthsnolhöxylamln ⁺ 75 - 280 Ν, Ν-Diäthanoloctylami ^ 75 260 N, N'-bis-β-hydroxyethylcyclohexylamine N, N-bis- (2-hydroxyethyl) -hexyarain

2 00810

Α3ΑΜ13475

"1

Table VIII

Beisp.Nr. Liquid cube type and liquid

% River,

Type of

functional

liquid

210

N, N-bis- (2-hydroxyethyl-octylamine 75

260

The liquid was extracted from the solid. (1) "Marlex", polypropylene of Phillips Petroleum Company having the following properties was used:

* 3 density, 0.908 g / cm; Melt Flow, g / 10 min Melting point 171 ° C (340 ⁰ F); Tensile strength at manufacturing, 351.5 kg / cm ² (psi, 2 "/ min \ * 5000) Hardness to Shore D: 73

Table VIII (continued ) PP

A3AM13475

Beisp.Nr. Liquid type and liquid

% River.

Type of thinner functional film flow.

ester

211 benzyl 75 200 L _f P, PF 212 Benzyl benzoate ⁺ 75 235 L, P 213 butylbenzoate 75 190 L, P 214. Dibutyl phthalate ⁴ " 75 230 L, P, PF 215 methylbenzoate 70 190 L, P, PF 216 Methylsali-salicylate * 75 215 P 217 PhenyIsalicylat 70 240 ether PF 218 Dibenzylather 75 210 PF 219 Diphenyl ether ⁺ 75 200 Halocarboxylic acids FR 220 4-Bromodiphenyl ether +  70 200 FR 221 1, 1,2,2-tetrabromoethane + 70 180 FR 222 1,1,2,2-tetrabromoethane + 90 180 ketones 223 benzyl acetone 70 200 '-. "_ 224 Methylnonyl ketone 75 180

 - 226 Table VIII -9 * - 75 ° C z UU0ιy ' ¹ I Yes PP A3AM13475 j 22? Flüsaigkeitstyp 70 • and liquid (Continuation) Beisp.Nr. 200 Type of thinner various % Flüss. functionally film AO .--. N, N-bis (2-hydroxy- len river. ethyl) tallow fat amine 180 225 (1) Ä <2) N, N-bis (2-hydroxy- .75 160 ethyl) cocoamine <2) + Buty.liertes Hydroxytoluöl

Oil liquid was extracted from the solid.

(1) A block approximately 15 cm high was also made.

(2) A stable internal antistatic agent having the following physical properties was used: boiling point at 1 mm Hg, 170 ^° C; Viscosity, Saybolt universal seconds (SSU) at 32.3 ⁰ C (90 ° F), the 367th

\ f

A3AM13475

Beisp.Nr. Liquid type and liquid

Table VIII (continued ) PP

% River.

Type of thinner functional film len river.

Miscellaneous (continu-

Reduction). 50 75 260 S, L 228 D.C.550 Silicon Fluid (1) 70 75 190 S, L 229 DC 556 Silicon FIid ⁺ 75 70 210 230 EC-53 75 75 210 SF 231 N-hydrogenated rapeseed oil diethanolamine ⁺ N-hydrogenated tallow fat-75 diethanolamine 225 SF 232 Firemaster BP-6 2OO FR 233 NBC OIL 190 234 Chinaldin ⁴ " 2OO 235 Quinoline ⁺ 220 M 236

The liquid was extracted from the solid. (1) trade mark of Dow Corning v ^K "for their phenylmethyl polysiloxane was used, a preparation having the following properties:. Viscosity 115 € S and usable from -40 to +232 ⁰ C (-40 to + 450 ⁰ F) in open systems and up to 316 C (<§oo ⁰ F) in closed systems.

- yi -

2 0.081 o

-AOO Α3ΑΜ13475

Photomicrographs of the porous polymer of Example 225 are shown in Figures 2-5. The compripographies of Figures 2 and 3 at 55X and 550X, respectively, show the macrostructure of the microporous polymer. The photomicrographs of Figures 4 and 5 at 2200x and 5500x, respectively, show the microcellular structure of the polymer as well as the interconnecting pores.

Examples 237 to 243 .

Examples 237 to 243 in Table IX explain the formation of homogeneous porous polymer intermediates in the form of cylindrical blocks about 3.2 cm in radius and about 1.2 cm high in polyvinyl chloride ("PVC") and the appropriate liquids which have been found useful to use the standard manufacturing process. Many of the exemplified intermediates were extracted to form porous polymers as indicated in the table.

The details of the presentation and the type of functionally useful liquid are given in Table IX:

-ICM- River. A3AM13475 « Type of functional. liquid Tabella IX PVC 70 PF Beisp.Nr. Liquid type% and liquid ° C Aromatic alcohol © 237 4-methoxyfoenzyl alcohol + 70 150 Other OK-containing 70 PF links 70 238 1-3 _/ dichloro ~ 2-propanol + 170 239 Menthol * " 180 240 iO-undecene-1-ol 204-210

200810

Α3ΑΜ13475

~ Ί

Table IX (continued) % F1Ü88. ⁰ C Type of functional fluid PVC Beisp.Nr. (D Liquid type and liquid 70 165 FR halogenated 70 175 FR 241 Fireiaaster T 33P ⁺ (2) 242 Firemaster T 13p ⁺ (3) Aromatic carbon 70 190 - hydrogens 243 Trans-S tilben ⁺

The liquid was extracted from the solid.

(1) The polyvinyl chloride used was of dispersion grade grade, manufactured by American Hoechst, having an inherent viscosity of 1.20, a density of 1.40 and a bulk density of 0.3244 g / cm ³ (20.25 lbs./cu. ft)

(2) Trademarks of Michigan Chemical Corporation for its tris (1,3-dichloroisopropyl) phosphate flame retardant having the following properties:

Chlorine content, theoretically, t, 49.1; Phosphorus content, theoretical,%, 7.2; Boiling point, 4 mm Hg, abs. ⁰ C, 200 (decomposes at 2OO ⁰ C) refractive index, 1.509; Viscosity, Brookfield 22.8 ⁰ C (73 ⁰ F), Centlpoises, 2120th

structure

: f (ClCH ₂ ) ₂ CHO ₃ PO

ι · '· i; ί ) : π j ι

- -1O3, - A3AM1347 5

(3) Trademark of Michigan Chemical Corporation for its trishalogenated propyl phosphate flame retardant having the following properties:

Specific gravity at 25 ° C / 25 ⁰ C., 1.88; Viscosity, at 25 ⁰ C, centistokes, 1928; Refractive index, 1.540; pH, 6.4; Chlorine, % 18.9; Bromine,% 42.5; Phosphorus,% 5.5.

A photomicrograph of the porous polymer of Example 242 is shown in Figure 27. The photomicrograph, magnified 2,000 times, shows the extremely small cell size of this microporous polymer in contrast to the cell structure shown in Figures 7, 13, 18, 20, and 24. where the cells are larger and more noticeable at a comparable magnification. The photomicrograph also shows the presence of a large amount of resin that obscures the basic cell structure.

Examples 244 to 255

Examples 244 to 255, summarized in Table X, illustrate the formation of homogeneous porous polymer intermediates, in the form of cylindrical blocks having a radius of about 31.75-ram (1.25 inches) and a thickness of about 50.8 (2.0 inch) of methylpentene ("MPP") polymer and the compatible liquids therefor, which can be used according to the standard manufacturing procedures. Some of the listed intermediates were extracted to form porous polymers, such as

 ? I!

2 00810

j «. lei / - A3AM13475

indicated in the table. The details of the preparation and the type of the functionally active liquid are given in Table X:

- yefo -

Table X River. A3AM1 3475 I MPP Liquid type% liquid Beisp.Nr. (1) saturated aliphatic 75 ° C Type of functional fluid Acid Capric acid 75 244 Saturated alcohols 75 230 1-dodecanol * 75 245 2-hexanol ⁺ 230 -> _ 246 6-undecanol 75 230 247 amines 230 _- Laurylarain 75 246 ester 70 230 FA butylbenzoate 249 Dihexylsebazat 70 210 L, P, PF 250 ether 220 L, P Dibenzyl ether ⁺ 251 230 PF

The liquid was extracted from the solid. (1) Methylpentene polymer of Mitsui having the following properties was used:

Density, g / cm ³ 0.835; Melting point ⁰ C, 235;

Breaking strength, kg / cra, 23Or Elongation at break% _f 30, Rockwell Hardness, R; 85th

2 0 0 81

Table X (continued) % River. A3AM1 3475 1 MPP Liquid type and liquid 75 Beisp.Nr. hydrocarbons 70 ⁰ C Type of functional fluid 1-hexadecene 252 Naphthalene ⁴ " 75 220 253 various 75 240 MR EC-53 * 254 Phosclere P 315C ⁺ 230 AO 255 250

The liquid was extracted from the solid. A photomicrograph of the porous polymer of Example 253 is shown in Fig. 22. The photomicrograph at 2400 magnification shows the extremely flattened cell walls, comparable to the configuration seen in Fig. 14.

Examples 256-266

Examples 256-266, shown in Table XI, the formation of homogeneous porous polymer intermediates illustrate in the form of cylindrical blocks with a radius of about 31, 75 ram (1.25 inch) and a thickness of about 12.7 mm ( 0.5 inch) of polystyrene (" PS &quot;) and the compatible liquids usable therefor according to standard manufacturing methods. All of the intermediates listed were extracted to form porous polymers. The details of the preparation and the type of effective usable liquid are given in Table XI.

200

- ΊΟ? -

Α3ΑΜ13475

Table XI

Example (1) • No liquid type and liquid % River. ⁰ C Type of functional fluid 256 Firemaster T 13P 70 250 FR 257 Hexabromdiphenyl 70 260 FR 258 Phosclere P 315 C 70 270 259 Phosclere P 576 70 285 AO 260 Tribromoneopentyl alcohol 70 210 FR 261 FR 2249 (2) 70 240 FR 262 Fyrol CEF (3) 70 250 FR 263 Firemaster T 33P (4) 70 210 FR 264 Fyrol FR 2 (5) 70 240 FR 265 dichlorobenzene 80 160 MR, FR 266 1-dodecanol 75

(1) "Lustrex" polystyrene of Monsanto Chemical Comp, having the following physical properties was used: impact strength mkg / cm notch (injection molding) 0.021 (ft.lbs / in, notch (Inj.molded) 0.40)

Tear strength, kg / cm ² 527 (psi 7500); Elongation,% 2.5; Young's modulus kg / cm ² 0.315 (psi, XID ⁵ , 4.5)

2 '

Bending temp., Under load 18.48 kg / cm (264 psi) ° C 93.3 (° F 200);

Specific gravity, 1.05; Rockwell Hardness, M-75; Melt flow g / 10 min. 4.5 »

2ÖÖ81Ö

^ 4Ö ^ - X3AM13475 I

(2) Trademarks of Dow-Chemical Corp. for your F1 aroma chut agent of the following composition and properties:

Tribromoneopentyl alcohol, 60% χ

Voranol CP. 3000 polyol, 40%; Bromine, 43% i hydroxyl No. 130; Viscosity, cps, 25 ⁰ C (approximately) 1600J Density, g / cm, 1.45.

(3) Trademark of Stauffer Chemical Comp, for its tris-chloroethyl phosphate flame retardant having the following properties;

'Boiling point, at 0.5 mm Hg abs., ° C 145, at 760 mm Hg abs., C decomposition; Chlorine content, wt%, 36.7;

Phosphorus content, wt.% 10.8; Refractive index at 20 ⁰ C, 1.4745; Viscosity, cps at 22.8 ⁰ C (73 ⁰ F), 40th

(4) Trademarks of Michigan Chemical Corp. for your tris- (1,3-dichloroisopropyl phosphate) flame retardant, with the following properties:

Chlorine content, theoretical,%, 49.1; Phosphorus content theoretically,%, 7.2; Boiling point 4 ram Hg abs. ⁰ C, 200 (decomposes at 200 ° C); Refractive index, 1.5019;

Viscosity, Brookfield, 22.8 ⁰ C (73 ⁰ F), Centipolse, 2120. Composition: £ (ClCHp) ₂ CHO / ₃ PO

(5) Trademark of Stauffer-Cheraic & l Comp, for their tris (dichloropropyl) phosphate flame retardant additive with the following properties:

Melting point ° C, about 26.7 ( ⁰ F, 80) refractive index n _d at 25 ° C, 1.5019; Viscosity, Brookfield at 22.8 ⁰ C, cps, 2120th

- «o $ - A3AM13475

A micrograph of the microporous polymer of Example 260 is shown in Figure 26. Although the cells are small and narrow compared to those shown in Figures 4, 7, 13, 18 and 25, the basic microcellular structure is recognizable.

Example 267

This example describes the formation of a homogeneous porous polymer intermediate of 30% high impact polystyrene (V) and 70% hexabromodiphenyl, by the standard method of preparation, and heating the mixture to 280 ^° C. The polymer intermediate thus prepared had about 63.5 mm (2.5 inch)

Diameter and about 12.7 ram (0.5 inch) thickness. Hexabromodiphenyl is useful as a flame retardant and the porous intermediate is useful as a solid flame retardant additive.

Example 268

This example describes the preparation of a homogeneous porous polymer intermediate of 25% acrylonitrile-butadiene-styrene terpolymer (2) and 75% diphenylamine by the standard method of preparation and heating the mixture to 220 ° C. The polymer intermediate thus prepared had about 6 3.5 "(2.5 inch) diameter and about 50.8 mm (2 inch) thick. The microporous polymer was prepared by extracting the diphenylamine. The diphenylarain is useful as a pesticide and antioxidant, and the porous polymer intermediate has the same properties.

, .- 4'i®- A3AM13475

(1) "Bakelite" injection molded polystyrene of Union Carbide Comp, having the following properties was used: tear strength, kg / m ² , 352, (3.18 mm (1/8 "thick) psi, 5000); specific elongation ( 3.18 mm (thick)) (1/8 ^a ) 25;

Elongation modulus kg / cra ² 26.600, (3.18 mm thick (1/8 ^a ) (psi. 38O.OOO); Rockwell Hardness (6.35 χ 12.7 χ 127 am) (1/4 "x 1/2 * κ 5 ") 90; Specific gravity 1.04.

(2) Kralastic ABS Polyiaar from UniroyaX with the following properties' was used: Spes. Weight 1.07; Impact strength (1.18 mm (1/8 x *) sample rod); Izod impact strength of 22.8 ⁰ C (73 ⁰ F), mkg / cm ² notch © 0.071 to 0.103 (ft.lbs / in notch 1.3-1.9)

Tensile strength, kg / cm ² 618, (psi 8,800) and Rockwell hardness, R, 118.

Examples 269 and 270

The homogeneous porous polymer intermediates were prepared from 25% chlorinated polyethylene thermoplastic, supplied by Dow, having a melt viscosity of 15.Poise, 8% .crystallinity, containing 36% chlorine and 75% Ν, Ν-bis (2 -hydroxyäthyl) -Talgfettamin (Ex. 269) and 75% chlorinated polyethylene thermoplastic, and 25% of 1-dodecanol (Ex. 270), according to the standard manufacturing processes and by heating to 220 ⁰ C. The porous polymer intermediates had about 63 , 5 ram (2.5 inch) diameter and 50.8 mm (2 inch) thickness.

2 00810

-ΑΛΛ- Α3ΑΜ13475

Example 271

The homogeneous porous polymer intermediate was prepared according to the standard manufacturing processes and by heating to 210 ⁰ C, of 25% chlorinated polyethylene elastomer as used in Example 270, and 75% diphenyl ether. The porous polymer intermediate © was about 63.5 mm (2.5 inches) in diameter and about 50.8 mm (2 inches) thick. The diphenyl ether is useful as a perfume and the intermediate is also useful in perfumes.

Examples 272 to 275

Examples 272 to 275, summarized in Table XII, illustrate the formation of homogeneous porous polymer intermediates in the form of cylindrical blocks having a radius of about 31.75 mm (1.25 inches) and a thickness of about 12.7 mm (0, 5 inches) of styrene-butadiene ("SBR") rubber (1) and the compatible liquids usable therefor according to the standard manufacturing method. In addition to the indicated cylindrical blocks, thin films were also made. The details of the preparation and the type of effective usable liquid are given in Table XII.

(1) Kraton SBR polymer of Shell Chemical Comp, having the following properties was used:

Tear strength, kg / cm ² , 218-323, (psi, 3100- 46ÖO); Elongation at break, 880-1300; Rockwell hardness, Shore A, 35-70.

A3AM13475

Table XII SBR

Beisp.Nr. Liquid type% flow. ⁰ C type of thinner and liquid functional film

thin liquid,

272 N, N-bis (2-hydroxyethyl) tallow fat amine 80 195 PF I yes 273 decanol 70 190 PE, AO Yes 274 diphenylamine 70 200-210 PF Yes 275 · diphenyl ether 70 195 Yes

The liquid was extracted from the solid.

2 00810

- 443- '. A3AM13475 |

Examples 276 to 278

Examples 276 to 278, summarized in Table XIII, illustrate the formation of homogeneous porous polymer intermediates in the form of cylindrical blocks having a 31.75 ram (1.25 inch) radius and a thickness of about 12.7 mm (0.5 inch) of "Surlyn" (1) and dan compatible liquids, which can be used according to the standard manufacturing process. In addition to the indicated cylindrical blocks, thin films were also made. Two of the intermediates described were extracted to form porous polyesters as indicated in the table. The details of the preparation and the type of effective, useable liquid are given in Table XIII.

(1) "Surlyn" ionomer resin 1652, delivery number 115478, from E.I. du Pont de Nemours with the following properties was used: density, g / cm, 0.939;

Melt Flow Index Decigram / min. 4.4; Tear strength, kg / cm, 200, (psi, 2850); Yield strength, g / cm ² , 131.4, (psi, 1870); Elongation,%, 58O.

- ^ Mt, ... ⁰ C A3AM13475 I Thin film Table XIII 190 * 195 Yes Surlyn 200 Yes Beisp.Nr. (1) Liquid type and liquid % FIUSS. 195 Type of functio neilen Flussigk. Yes 276 N, ίί-bis (2-hydroxyethyl) tallow fat amine 70 277 diphenyl ether * 70 PF 278 dibutyl phthalate 70 L

The liquid was extracted from the solid.

Photomicrographs of the porous polymer of Example 277 are shown in Figures 23 and 24. Figure 23, at a magnification of 255, shows the microcellular structure of the polymer as slightly "leafy" and relatively thick cell walls, e.g. to Fig. 25.

- \ yl -

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Example 279

The homogeneous porous polymer intermediate was prepared according to the standard manufacturing processes and by heating to 200 ⁰ C, of equal parts of a high density polyethylene Polyäthylenchloriertes mixture and 75% 1-dodecanol. The porous polymer intermediate was poured into a film having a thickness of about 0.5-0.513 mm (20-25 mils). The HDPE and CPE were also used in previous examples.

Example 280

The homogeneous porous polymer intermediate was prepared according to the standard manufacturing processes and by heating to 200 ⁰ C, of equal parts of a high density polyethylene-polyvinyl chloride mixture and 75% 1-dodecanol. The intermediate thus prepared had about 50.8 mm (2 inches) of thickness and about 63.5 mm (2.5 inches) in diameter. The HDPE and PVC were also used in previous examples.

Example 281

The homogeneous porous polymer intermediate was prepared according to the standard manufacturing process and by heating at 200 ⁰ C of equal parts of a high density polyethylene / acrylonitrile-butadiene-styrene Terpolyraer mixture and 75% 1-dodecanol. The intermediate thus prepared was about 50.8 mm (2 inches) thick and about 63.5 mm (2.5 inches) in diameter. The HDPE and ABS were also used in previous examples.

A3AM13475

Examples 282 to 285

Examples 282 to 285, summarized in Table XIV. Illustrate the formation of homogeneous porous polymer intermediates in the form of 31.75 mm (1.25 inch) radius cylindrical blocks having a thickness of about 50.8 ram (2 inches). of equal parts of a low density polyethylene / chlorinated polyethylene blend and the compatible liquids usable therefor according to the standard manufacturing method. In Example 283, the above-mentioned method was used, but the intermediate was poured into a filin having a thickness of about 0.5-0.513 mm (20-25 mils). The LDPE and CPE were also used in previous examples.

The details of the preparation and the type of effective functional fluid are given in Table XIV.

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Table XIV % River. ° C Type of functional fluid Beisp.Nr. Liquid type and liquid 75 200 282 1-dodecanol 75 20O PF 283 diphenyl ether 50 200 PF 284 diphenyl ether 75 200 285 N, N-bis (2-hydroxyethyl) tallow fatty amine

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Examples 286 and 287

The homogeneous porous polymer intermediates were prepared from equal parts of a low density polyethylene / polypropylene gum and 75% N, HH3is (2-hydroxyethyl) tallow fatty amine (Ex. 286) and equal parts of a low density polyethylene / polypropylene blend and 50% Ν, Ν-bis (2-hydroxyethyl) -Talgfettarain (example 287) according to the standard manufacturing process and shower heating at 220 ⁰ C for example 286 and 27O ° C for example 287. Both poröeen intermediate polymer products had about 63, 5 inches (2.5 inches) in diameter and about 50.8 mm (2 inches) thick. The LPDE and PP were also used in previous examples.

Example 288 The homogeneous porous polymer intermediate was prepared by the standard method of preparation and by heating

ο 200 C of 50% Ν, Ν-bis (2-hydroxyethyl) tallow fat amine and 50% polypropylene / polystyrene mixture (% by weight polypropylene). The porous polymer intermediates were about 6 3.5 mm (2.5 inches) in diameter and about 50.8 mm (2 inches) thick. The PP and PS were also used in previous examples.

Example 289

The homogeneous porous polymer intermediate was prepared according to the standard manufacturing process and by heating at 200 ⁰ C of 75% 1-dodecanol and like parts of a polypropylene / chlorinated polyethylene mixture. The porous polymer was about 63.5 mm (2.5 inches) in diameter and about 12.7 sun

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(0.5 inch) thickness. The PP and CPE were also used in previous examples.

Examples 290 to 300

Examples 290 to 300 illustrate the range of concentrations of polymer-compatible liquid applicable to the preparation of a homogeneous porous polymer intermediate of high density polyethylene and Ν, Ν-bis (2-hydroxyfatty-tallow fatty amine 50.8 mm (2 inches) thick and about 63.5 mm (2.5 inches) in diameter The HDPE was also used in previous examples.

The details of the preparation and some physical properties are given in Table XV:

- AZO- A3AM13475

% River Table XV Beisp.Nr. 95 , ° C 290 90 275 291 80 292 75 250 293 70 220 294 65 250 295 60 220 296 55 250 297 50 220 298 40 240-260 299 30 260 300 200

Remarks

very soft; no firm condition; not processable

very greasy; leaching liquid} upper liquid limit was exceeded greasy greasy hard, firm

hard, tight

hard, tight

hard, tight

hard, tight

A photomicrograph of the porous polymer of Example 300 is shown in Fig. 19 at 2000X magnification. The cells are not clearly visible at this magnification. Fig. 19 can be compared with Fig. 17 at 2475 magnification, where the cell size is also very low with a comparable polymer concentration of 70%.

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Examples 301 to. 311 .

These examples illustrate the range of polymer-compatible liquid concentration useful for preparing a homogeneous porous polymer intermediate of low density polyethylene and Ν, Ν-bis (2-hydroxyethyl) fatty amine. In each example, the intermediate had about 12.7 (0/5 inch) thickness and about 63.5 inch (2.5 inch) diameter. The LDPE was also used in previous examples. The details of the preparation and some physical properties are given in Table XVI.

Α3ΑΜ13475

Table XVI Beisp.Nr. % River Remarks

301 302

303 304 305

 306 307 308 309 310 311

95 90

80 75 70 66 60 50 40 30 20

275 240

260 210 210 200 280

280-290 285 285

280-300

very soft? no firm condition; not processable

very greasy, leaching liquid, upper strength limit exceeded

hard, tight

hard, tight

hard, tight

hard, tight

hard, tight

hard, tight

hard, tight

hard, tight

hard / solid

Photomicrographs of the porous polymers of Examples 303, 307, and 310 can be seen in Figures 14-15 (at 250x and 2500x magnification, respectively), 16x (at 2500x magnification), and 17x (at 2475x magnification). , The figures show the decreasing cell size, from very large (Fig. 15, 20% polymer) to very narrow (Fig. 17, 70% polymer), with increasing polymer content. The relatively flattened cell walls of the 20% polymer, Example 303, are comparable to the methylpentene polymer (Fig. 22) and can be seen in Fig. 14. Fig. 15 is an enlarged section of the cell walls shown in Fig. 14. The microcellular structure of the porous polymer

- I / O -

Kf VO \ U

A3AM13475

can be observed in Fig. 16.

Examples 312 to 316

Examples 312 to 316 illustrate the range of polymer-compatible liquid concentration / s usable to prepare a homogeneous porous polymer intermediate of low density polyethylene and diphenyl ether. In each example, the intermediate had about 12.7 mm (0.5 inch) thickness and 63.5 mm (2.5 inch) diameter etv / a. The LDPE was also used in previous examples. The details of the preparation and some physical properties are given in Table XVII.

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Table XVII Belap.No. % Flow. C observations

312 90 185 very greasy? no fixed

Nature; not processed

' bar

313 80 185 very greasy; near the top

Flüasigkeitsgrenze but still to process

314 75 200 damp , firmly 315 70 190-200 light greasy 316 60 200 hard,. firmly

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Examples 317 to 321

Examples 317 to 321 illustrate the range of concentrations of polymer-compatible liquid useful for preparing a homogeneous porous polymer intermediate of low density polyethylene and 1-hexadecene. In each example, the intermediate product was about 2 inches thick and about 63.5 rna (2.5 inches) in diameter. The LDPE was also used in previous examples. ,

The details of the preparation and some physical properties are given in Table XVIII:

Table XVIII

Ex. No. »% Flow. ⁰ C Remarks

317 90 180 good strength.

318 80 180 low strength, workable

319 75 200 low strength, workable

320 70 177

321 50 180 good strength

A3AM13475

Examples 322 to 334

These examples illustrate the concentration range of polymer-compatible liquid useful for the preparation of a homogeneous porous intermediate of polypropylene and Ν, Ν-bis (2-hydroxyethyl) tallow fatty amine. In each example, the intermediate had 12.7 ram (0.5 inch) thickness and 63.5 mm (2.5 inch) diameter.

Additionally, as stated, films were made. The PP was also used in previous examples.

The details of the preparation and some physical properties are given in Table XIX.

% River table XIX Remarks Thin film Beisp.Nr. 90 , ⁰ C very wet Yes 322 85 200 323 80 200 firmly Yes 324 75 200 dry and hard Yes 325 70 180 Yes 326 65 200 , - 327 60 210 Yes 328 50 210 Yes 329 40 200 Yes 330 36.8 210 white crystalline 331 25 175 332 180

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% River table XIX (continued) thinner Movie Beisp.Nr. 20 15 , ° C Remarks Yes 333 334 180 180 •

Photomicrographs of Examples 322,326,328,330 and 333 are shown in Figures 6-10 (at 1325x, 1550x 1620x, 1450x and 1250x magnifications). The extreme foliarity of the 10% polymer-containing microporous polymer is shown in Fig. 6, but the microcellular structure is still preserved. These figures show the reduced cell size as the amount of polymer is increased. However, the microcellular structure is recognizable in each example, despite the small cell size.

Examples 335 to 337

The examples illustrate the concentration range of polymer-compatible liquid applicable to the preparation of a homogeneous porous polymer intermediate of polypropylene and diphenyl ether. In each example, the intermediate had about 12.7 mm (0.5 inch) thickness and about 63.5 m (2.5 inch) diameter. Additionally, as stated, thin films were also made. The PP was also used in previous examples. , ^;

- Ί3ί? - Α3ΑΜ13475

The details of the presentation and some physical characteristics are given in Table XX:

Table XX , Ex. No. % River. ⁰ C thin film

335 90 200 yes

336 80 200 yes

337 70 200 yes

microphotographs of the porous polymer of Examples 335,

and 337 are shown in Figures 11 (2000X magnification), (2059X magnification) and 13 (1950X magnification). These figures show that as the polymer concentration increases, the pore size decreases. Figure 11 shows the smooth cell walls, while Figures 12 and 13 illustrate the cells and connecting pores. In each of the figures, the microcellular structure is present.

Examples 338 to 346

These examples demonstrate the range of polymer compatible liquid concentration used to form a homogeneous porous polymer intermediate of styrene-butadiene rubber and Ν, Ν-bis (2-hydroxyethyl) tallow fatty amine. In each example, the intermediate has a depth of 12.7 mm. (0.5 inch) and a diameter of 63.5 mm (2.5 inches). As already mentioned, thin films are created. As in previous examples SBR was used. The details of the presentation and

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"Ί

some significant physicylic characteristics are recorded in Table XXI:

Table XXI

Beisp.Nr. % River , ⁰ C Remarks Thin film 338 90 200 soft, beyond the upper fluid limit Yes 339 80 195 rubbery Yes 340 75 195 rubbery Yes 341 70 195 • rubbery Yes 342 60 200 rubbery Yes 343 50 not referenced rubbery Yes 344 40 not referenced gumraiartig Yes 345 30 not referenced rubbery Yes 346 20 not referenced rubbery Y ^a

Photomicrographs of the styrene-butadiene rubber microporous polymers of Examples 339-340 are shown in Figures 20 (2550X magnification) and 21 (2575X magnification). The figures show the microcellular structure of the microporous polymers. Figure 21 shows the presence of spherical polymer deposits on the cell walls.

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Examples 347 to 352

Examples 347 to 352 show the range of polymer-compatible liquid concentration used to form a homogeneous porous polymer intermediate of styrene-butadiene rubber and decanol. In each example, the intermediate product has a depth of about 12.7 inches (0.5 inches) and a diameter of 63.5 inches (2.5 inches). As already mentioned, thin films are created. As in previous examples SBR was used. The details of the illustration and some physical characteristics are set out in Table XXII.

Table XXII

Beiep.Nr. % River. ⁰ C Comments Thin film

347 90 not beyond the top

Refers to fluid limit, not to be processed

348 80 190 rubbery There 349 7O 190 rubbery Yes 350 60 190 rubbery Yes 351 50 190 rubbery Yes 352 40 not referenced rubbery

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Examples 353-356

These examples demonstrate the range of polyracompatible plasmas concentration in the preparation of a homogeneous porous polymer intermediate of styrene-butadiene rubber and diphenylamine. In each example, the intermediate has a depth of approximately. 12.7 mm (0.5 inch) and a diameter of 63.5 mm (2.5 inches).

The details of the presentation and some physical characteristics are set forth in Table XXIII.

Table XXIII Belsp.Hr. % Liquid ⁰ C remarks

353 80 not

lecture

354 70 2ΟΟ-21Ο

355 60 215

356 50 200-210

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 '.' '· «" 13a-A3AM13475'

^r> Examples 357 to 361

Examples 357 to 361 show the range of polymer-compatible liquid concentration in the preparation of a homogeneous porous polymer intermediate from ^H Surlyn ^M resin used in the previous examples and N, N-bis (2-hydroxyethyld-tallow fatty amine For example, the intermediate has a depth of about 12.7 mm (0.5 inches) and a diameter of 63.5 nanometers (2.5 inches). As mentioned earlier, thin films are formed.

The details of the presentation and some physical characteristics are recorded in Table XXIV.

Table XXIV

Beisp.Nr. % River. ⁰ C Thin film 357 70 190-195 Yes 358 60 190 Yes 359 50 not referenced Yes 360 40 not referenced Yes 361 30 not referenced Yes

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Examples 362 to 370

These examples demonstrate the range of polyracompatible liquid concentration used to form a homogeneous porous polymer intermediate of ^M Surlyn ^H resin as used in the previous examples and diphenyl ether. In each example, the intermediate product has a depth of about 12.7 mm (0.5 inches) and a diameter of 63.5 mm (2.5 inches). As already mentioned, thin films are created. The details of the presentation and some physical characteristics are given in Table XXV.

% River, Table XXV Thin film Belsp.Nr. 90 , ° C Yes 362 80 207 Yes 363 70 190 Yes 364 60 200 Yes 365 50 185 Yes 366 40 not referenced 367 30 not referenced 368 20 not referenced 369 10 not referenced _- 370 not referenced

A3AM13475

Examples 371 to 379

Examples 371 to 379 show the range of polymer compatible liquid concentration used to form a homogeneous porous polymer intermediate from a "Surlyn" resin as used in the preceding Examples and dibutyl phthalate. In each example, the intermediate product has a depth of about 12.7 mm (0.5 inches) and a diameter of about 63.5 rams (2.5 inches).

The details of the presentation and some physical characteristics are recorded in Table XXVI.

% River Table XXVI Remarks Beisp.Nr. 90 , ° C 371 80 220 372 70 208 373 60 195 _-. 374 50 200 - 375 40 2O0 376 30 not referenced 377 20 not referenced 378 10 not referenced - 379 not referenced

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Examples 380 to 384 to the prior art . Examples 380 to 384 are reworks of various prior art compositions showing a different physical structure to those of the present invention.

Example 380

A porous polymer was made in accordance with the method of Example 1 of U.S. Patent 3,378,507 and also modified to provide a product with physical integrity

, and to use a soap as a water-soluble anionic surfactant instead of sodium bis (2-ethylhexyl) sulfosuccinate.

In an internally heated Brabender Plasti-Corder mixer 33 1/2 parts by weight of Exxon Chemical Corporation Type LD 6O6 ~ polyethylene and 66 2/3 parts by weight of Ivory soap flakes in a

• Machine temperature of about 175 ⁰ C (350 ⁰ F) mixed until a homogeneous mixture was achieved. The material was then compression molded with a rubber type die having a 63.5 mm (2.5 inch) and .127 mm (5.0 inch) cavity a depth of 0.5 mm (20 mils) at a temperature of about 175 ^° C. (350 ^° F.) and a pressure of 2500 kg / cm ² (36,000 psi). The samples obtained are washed for about 3 days in a slowly flowing tap water stream. The washing is then carried out by immersion in 8 baths with distilled water "in a perlode of about one hour each". They received samples

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still get some soap and show bad use properties.

Figures 47 and 48 are photomicrographs of the product of Example 380 at 195x and 2000x magnification, respectively. The product apparently has a relatively nonuniform polymer structure which has neither distinct cellular voids nor interconnecting pores.

Example 381

A porous polymer was prepared in accordance with the method of Example 2, Sample D, U.S. Patent 3,378,576, and so modified to obtain a product having a certain service life.

In a heated from the inside Brabender Plasti-Corder mixer 75 parts of Ivory soap flakes and 25 parts Exxon Chemical Corporation Type LD are mixed 66 polyethylene. · Is carried out at a machine temperature of about 175 ⁰ C (350 ⁰ F) and a Probenteraperatur of 165 ⁰ C (330 ⁰ F) until a homogeneous mixture is formed. The material is then injection molded in a 1 inch Watson Stilliaan injection molding machine having a 50 mm (2 inch) cavity diameter and a depth of 0.5 mils (20 mils). The obtained samples are continuously washed for about 3 days in a slowly flowing tap water stream. The washing is then carried out by dipping in an approximately one-hour period in 8 water baths with distilled water, The obtained samples still contain some soap.

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Figures 45 and 46 are photomicrographs of the product of Example 381 at 240X and 2400X, respectively. The product of this example does not have the typical cellular structure of the present invention, as can be seen from the microphotograph.

Example 382

In accordance with the procedure in Example 3, Sample A, U.S. Patent 3,378,507, a porous polymer is prepared.

In an internally heated Brabender Plasticorder mixer, 25 parts of Novaraont Corporation Type F 300 8N 19 polypropylene and 75 parts of Ivory Selflakes are mixed. It operates at a machine temperature of about 165 ^G C (330 ° F) until a homogeneous mixture is formed. The material is then molded with a rubber type die. It was found that the obtained sample has a very low strength. A portion of the obtained sample is continuously washed for about 3 days in a slowly flowing tap water stream. The washing is then carried out by dipping in about per one hour period in 8 water baths with distilled water. The washed product has extremely poor performance properties.

Figures 51 and 52 are photomicrographs of the product

- VKf-

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Α3ΑΜ1347 5

Example 382 at 206x and 2000x magnification, respectively. The photomicrographs show that the product does not have a cellular structure according to the present invention.

Example 383

The procedure of Example 3, Sample A, U.S. Patent 3,378,807, was modified to obtain a product with improved service lives.

In an open '2-roll rubber mill, manufactured by the Boiling Company, 25 parts of Novamont Corporation Type F are mixed 8 N 19 polypropylene and 75 parts of Ivory soap flakes for about 10 minutes at a temperature of about 176.67 ⁰ C to a homogeneous mixture is formed. The material is then injection molded with a 1-oz. Watson-Stillmann injection molded tube having a 50 mm cavity shape diameter and a depth of 0.5 ram (20 mils). The resulting sample is continuously washed for about 3 days in a flowing tap water stream. The washing is then carried out by immersion in 8 water baths with distilled water, per bath in an approximately one-hour period. The obtained sample still contains some soap. The product was found to be stronger than the product of Example 382.

Figures 49 and 50 are photomicrographs of the product

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Berlin, d, 27.9.1978 AP C O8J / 2OO 810

Example 383 at 195x and 2000x magnification respectively The irregular shapes in the photomicrograph are clearly distinguishable from the structure according to the present invention.

Example 384

A porous polymer was prepared according to Example II of US Pat. No. 3,310,505 and modified to obtain an improved homogeneous blend of the material

In a heated inside Brabender Plasti-Corder mixer 40 parts Exxoh Chemical Corporation Type LD 606-polyethylene and 60 parts Rohm and Haas Corporation polymethylmethacrylate about 10 minutes (at a machine temperature of about * 175 ° C 350 ⁰ F! ) until a homogeneous mixture is formed. The material is then rolled on a cold mill and subsequently press-formed in a heated 4-inch round press with a depth of 0.5 mm (20 mils) and 30 tons of pressure for about 10 minutes. The resulting mass is extracted with acetone for 48 hours in a large soxene extractor.

Figures 53 and make photomicrographs of the product of Example 384 in 205-fold or is ₀ · 2000-fold magnification. <

The unitary structure represented in the photomicrographs is easy to distinguish from the unitary structure according to the present invention *

Sm WV

-, Berlin, d *. 2? · 9 ♦ 1978 'IP C 08J / 200 810.

Physical labeling of Examples 225 and 358

In order to get a quantitative understanding of the homogeneous structure of the present invention, some samples of the microporous material and certain prior art samples were run on an amine co-mercury intrusion porosime. analyzed. Figures 30 and 31 are mercury intrusion curves of a 38.1 mm block (one-half inch) of Example 225 which was prepared with 25 % polypropylene and 75 % N, N bis (2-hydroxyethyl) tallow fat amine , Figure 32 is a 152.4 mm (6 inch) block mercury intrusion curve of the example; .225 · All mercury intrusion curves are shown on a half-log graph with the equivalent pore sizes, as shown on the log-shell abscissa. Figures 30 to 32 show the typical narrow pore size distribution in the material of the present invention. The 38.1 mm (one-half inch) sample of Example 225 was found to have an empty space of approximately 76 % and an average pore size of approximately 0.5 microns and the 152.4 mm block (6 inches). has an empty space of about 72% and an average pore size of about 0.6 microns.

Α3ΑΜ13475

Figure 33 is a mercury intrusion curve of the product of Example 358 made with 40% polypropylene and 60% N, N-bis (2-hydroxyethyl) tallow fatty amine. Figure 33 shows that the sample has the typical narrow pore size distribution. The sample was found to have an empty space of about 60% and an average pore size of about 0.15 microns.

It is in fact apparent that the compositions of this invention have such pore size distributions that at least 80% of the pores present in the material are within the abscissa of the mercury intrusion curve within no more than 1 decade. The pore size distribution of the compositions must therefore be described as "narrow".

Physical marking of the commercial

Materials of the prior art .

Example 385

The material of this example is the commercially available Celgard 3501 microporous polypropylene made by Celanese. Fig. 34 is a mercury intrusion curve of the sample showing a large number of pores in the range of 70 to 0.3 microns. The sample was found to have an empty space of about 35% and an average pore size of about 0.15 microns.

". 1

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^; - Ί · «- Α3ΑΜ13475

Example 386

The material of this example is the commercial A-20 microporous polyvinyl chloride made by Araerace. Fig. 35 is a mercury intrusion curve of a sample showing a very broad pore size distribution. The sample was found to have an empty space of about 75% and an average pore size of about 0.16 microns.

Example 387

The material of this example is the commercial A-30 microporous polyvinyl chloride manufactured by Araerace. Fig. 36 is a mercury intrusion curve of the sample showing a very wide pore size distribution. The sample was found to have an empty space of about 80% and an average pore size of about 0.2 microns.

Example 388

The material of this example is the commercial porex microporous polypropylene. Figure 37 is a mercury intrusion curve of the sample showing a very broad distribution of extremely small cells as well as a distribution of very large cells. The sample was found to have an empty space of about 12% and an average pore size of about 1 micron.

Α3ΑΜ13475

Example 389

The material of this example is the commercially available Millipore BDViP 29300 microporous polyvinyl chloride. Figure 38 is a © mercury intrusion curve of the sample showing a relatively narrow distribution in the range of 0.5 to 2 microns and a number of cells smaller than 0.5 microns. The sample was found to have an empty space of about 72% and an average pore size of about 1.5 microns.

Example 390

The material of this example is the commercial Metric TCM-200 microporous cellulose triacetate manufactured by Gelinan. Figure 39 is a mercury intrusion curve of the sample showing a broad pore size distribution up to about 0.1 micron. The sample was found to have an empty space of about 82% and an average pore size of about 0.2 microns.

Example 391

The material of this example is the commercial Acropor WA microporous acrylonitrile-polyvinyl chloride copolymer made by Gelman. Figure 40 is a mercury intrusion curve of the sample showing a broad pore size distribution. The sample was found to have an empty space of about 64% and an average pore size of about 1.5 microns.

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Physical identification of the prior art Examples 380 to 384

The prior art products, Examples 380-384, were also analyzed by mercury intrusion. Figures 41 to 43 are mercury intrusion curves showing the broad pore size distribution of the corresponding Examples 381, 380 and 383. Figure 44 is a mercury intrusion curve of the product of Example 384 showing a number of

Pores in the range of 45 to 80 microns and a number of extremely small pores. The products of Examples 380, 381, 383 and 384 were found to have an empty space of approximately 54, 46, 54 and 29% and an average pore size of approximately 0.8; 1.1; 0.56 and 70 microns.

Examples 392 to 399

These examples illustrate the concentration range of the polyracompatible liquid used to form the homogeneous porous polymer intermediate of polyraethyl methacrylate and 1,4-butanediol using the standard preparation method. In each example, the intermediate formed had a depth of about 12.7 mm (0.5 inches) and a diameter of 63.5 mm (2.5 inches). The polymethyl

methacrylate is supplied by Rohm and Haas under the name

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plexiglas Acryl-Plastic Melting Powder, Lot no. 386 491. The details of the preparation are shown in Table XXVII: \ j- "· _, ..

Table XXVII Example no. % River. ° C , '

215

225

225

210

229

230

229

225

392 90 393. 85 394 80 395 70 396 60 397 50 398 40 399 30

The 1,4-butanediol was removed from the product of Example 395 and the resulting structure was found to be the cell structure of the present invention. This can be seen in Fig. 61, which shows the microporous product at 5000x magnification. The same polymer-liquid system as used in Example 394 was also cooled at rates up to 4,000 ^° C per minute and still obtained the cellular structure of the present invention.

Berlin, d, 27.9.1978 AP C 08J / 200 810

Example 400

The porous polymer intermediate was prepared using the standard production process and by heating 30% of polymethylmethacrylate (as in the previous examples used) and 70% lauric acid to 175 ⁰ C 'and cooling, the porous polymer intermediate was formed The L _a urine acid was removed from the obtained intermediate to obtain the microporous cellular structure of the present invention;

Example 401

The porous polymer intermediate (prepared according to the standard manufacturing process) is prepared by heating 30% Nylon-11, supplied by Aldrich Chemical Comp ", and 70% ethylene carbonate to 218 ⁰ C and cooling the solution obtained to form the porous polymer Intermediate produced. The ethylene carbonate is removed from the intermediate and it has been found that the resulting microporous polymer has the cellular structure of the present invention.

Example 402

The porous polymer intermediate (prepared by the standard method of preparation) is prepared by heating 30 % nylon-H, as used in the previous example, and 70 % 1,2-propylene carbonate to a temperature of 215 ° ^C , followed by cooling resulting solution until the formation of the porous (porous) polymer intermediate product formed which is removed from the intermediate, the microporous polymer obtained shows the cellular structure der.vorliegenden invention ^*!

£. υ υ η ι υ

Berlin, d.27 ♦ 9 · 1978 AP C 08J / 200 810

Examples 403 to 422

Examples 403 "to 422 demonstrate the formation of the porous polymer intermediate from polymer / liquid systems containing varying amounts of nylon-11," such as tetramethylene sulfone, supplied by Shell under the name Sulfone-W. These contain approximately 2, 5 % water "The various concentrations are cooled at different rates and at different solution temperatures. It can be seen from Table XXVIII that, in general, decreasing cell sizes is achieved by increasing cooling rates and increasing concentration of the polymer."

9 7 Cu) in; ο

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Table XXVIII

Beisp.Nr. % River. T ⁰ C Cooling speed ° C / min. Cell size (microns) 403 90 195 20 10 404 80 198 5 15 405 80 198 20 14 406 80 198 40 9 407 80 198 80 5.5 408 70 200 5 11 409 70 200 20 5 410 70 200 40 6.5 411 70 200 80 6.5 412 60 205 5 5 413 60 205 20 4.5 414 60 205 40 4 415 6O 205 80 3.5 416 50 210 20 3 417 50 210 40 1.5 418 50 210 80. 2 419 60 212 20 420 70 215 20 421 80 217 20 - 422 90 220 20

The above Table XXVIII thus shows that at concentrations of 40% to 10% liquid no visible porosity occurs when the system has been cooled at 20 ° C (per minute). Such

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Results can be seen in advance from FIG. 62. This figure shows the Schraelz curve for the nylon 11 / tetramethylene sulfone concentration range, as well as the crystallization curves at different cooling rates. It can be seen from Fig. 62 that at 20 ^° C per minute cooling rate, the system containing 40% liquid does not fall in the substantially flat portion of the crystallization curve and is therefore unable to form the desired microporous structure. Fig. 63 is a microphotograph at 2000X magnification of Example 409, showing the typical cell structure of Examples 403-418.

Example 423

The porous polymer intermediate (prepared according to the standard manufacturing process) by heating 30% PoIycarbonat is (supplied by General Electric under the name Lexan) with 70% menthol to a temperature of 206 ⁰ C and created by cooling, wherein the porous Polymer intermediate forms. The menthol is extracted, thereby obtaining a microporous structure as shown in FIG. 64. Fig. 64 is a photomicrograph of the product of this example at 2000X magnification.

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Example 424

This example demonstrates the formation of a microporous cell structure according to the present invention of poly-2, 6-dimethy1-1,4-phenylene oxide (supplied by Scientific Polymer Products, generally known as polyphenylene oxide). The homogeneous microporous polymer intermediate is prepared from 30% of said polyphenylene oxide and 70% Ν, Ν-bis (2-hydroxyethyl) tallow fatty amine by heating to a solution temperature of 275 ° C. The intermediate was formed according to the standard procedure. The liquid is removed from the intermediate and the obtained cellular structure of the present invention is shown in Figure 65, which shows a photomicrograph of the product of this example at 2000X magnification.

Example 425

This example demonstrates the formation of a non-cellular product of this invention by cooling a homogeneous solution of 40% polypropylene (according to previous examples) and 60% dibutyl phthalate. This solution is extruded onto a cooling belt about 0.25 mm (10 mils) thick with the cooling rate greater than 2400 ° C / min. Before extruding the solution onto the belt, a quantum of dispersol is applied to the surface. The liquid is removed from the obtained film to obtain a non-cellular microporous product as shown in FIG. These

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Fig. 10 is a photomicrograph of the product of this example at 2000x magnification.

Example 426

This example demonstrates the formation of a non-cellular product of the invention by cooling a homogeneous solution of 25% propylene (according to previous examples) and 75% N, N-bis (2-hydroxyethyl) tallow fatty amine in the same manner as Example 425 Liquid is removed from the resulting film and a non-cellular product is formed. See Fig. 67 / which is a photomicrograph of the product of this example at 2000X magnification.

The products of Examples 425 and 426 were analyzed with a mercury intrusion porosimeter and their respective intrusion curves are shown in Figures 68 and 69. It is apparent that both products generally have narrow pore size distributions, but the product of Example 426 shows a narrower distribution than the product of Example 425. Thus, the product of Example 425 has a calculated S value of 24.4 throughout the product from Example 426 has a calculated S value of only 8.8.

The average pore size of Example 425 is very small, 0.096 microns, while the average pore size of the product of Example 426 is 0.589 microns. Ura the uniqueness of the cellular compositions according to the

- AST *. -

ZQU81

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In order to clarify the present invention, a number of such microporous products are prepared according to the standard method of preparation and the details of which are summarized in Examples 427 to 457 in Table XXIX. The products of these examples are analyzed by mercury intrusion porosity to determine their respective average pore diameter and S-value. The average cell size S is determined by a scanning electron microscope. The results of this analysis are listed in Table XXX.

Table XXIX .No. polymer Liquid% cavity Solution tercp. OC Ex polypropylene Ν, Ν-bis (2-hydroxyethyl) tallow fat 75 180 427 polypropylene N, N-bis (2-hydroxyethyl) tallow fat amine 60th 210 428 polypropylene diphenyl ether 9O 200 429 polypropylene diphenyl ether 80 200 430 polypropylene diphenyl ether 70 200 431 polypropylene 1 , 8-diaminooctane 70 180 432 polypropylene salicylate 70 240 433 1 polypropylene 4-Bromdiphenylather 70 200 434 polypropylene tetrabromoethane 90 180 435 polypropylene N-octyl diethanolamine 75 436

2 008 1 O

Table XXIX (continued) No. Polymer A3AM134 75 75 ' polypropylene 70 Eeisp. polypropylene Liquid% cavity 70 Solution temp. ° C 437 Polyethylene m. low density N-hexyl diethanolamine 70 260 438 Polyethylene m. low density salicylaldehyde 70 185 439 Low density polyethylene ra hexanoic 70 190 440 Polyäthylen.ra. low density 1-0ktanol 70 178 441 Low density polyethylene ra dibutyl 70 238 442 Polyethylene m. low density Phosclere EC-53 70 191 443 Polyethylene m. low density dicapryl 80 204 444 Polyethylene m. high density diisooctyl 75 204 445 polystyrene dibutyl phthalate 70 290 446 polystyrene N, N-bis (2-hydroxyethyl) tallow fat amine 70 250 447 polystyrene 1-dodecanol 75 220 448 polystyrene 1,3-bis (4-piperidine) propane 70 186 449 polystyrene diphenylamine 70 235 450 Po Iy me thy lraethacryla'd N-hexyl diethanolamine 260 451 Phosclere P315C 2.70 452 1,4-butanediol

\ Table XXIX (Continued 2 0081 0 1 diphenyl ether 85 185-207 A3AJM13475 · dibutyl phthalate 70 195 .No. polymer N, N-bis (2-hydroxyethyl) tallow fat amine 70 250 Ex Liquid% Cavity Solution temp. ° C Xthylencarbonat 75 453 Polymethylmeth- 1 _# 4-butanediol aerylate 70 454 Surlyn 455 Surlyn 456 Noryl 457 Nylon 11

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C table P XXX S loq C / P loq S / C Beisp.Nr. 5.0 0,520 G / P 2.86 0.982 -0.243 427 3.18 0.112 9.6 5.0 1.45 0.197 428 22.5 11.6 28.4 4.52 0,288 -0.697 429 6.49 0.285 1.94 27.1 1.36 0,621 430 6.72 0,136 22.8 7.01 1.69 0.0183 431 13.0 0.498 49.4 2.36 1.42 -0.741 432 13.8 0.272 26.1 4.29 1.71 -0.507 433 3.35 0,137 50.7 5.25 1.39 0.195 434 15.4 0.804 24.5 5.13 1.28 -0.477 435 16.6 0,850 19.2 2.52 1.29 -0.819 436 20.0 0.631 19.5 2.51 1.50 -0.901 437 7.9 0.105 31.7 3.22 1.88 -0.390 438 7.5 1.16 75.2 8.62 0.811 .0604 439 6.8 1.00 6.47 3.53 0,833 0.285 440 5.85 0.636 6.8 6.07 0.964 0.0160 441 3.40 0.512 9.20 5.30 0.822 0,193 442 5.0 0.871 6.64 8.21 0.759 0.215 443 4.75 0.631 5.74 3.54 0.877 -0.128 444 7.8 1.18 7.53 3.82 0,820 -0.310 445 34.5 0.696 6.61 4.34 1.70 -0.900 446 28.2 1.88 49.6 3.40 1.18 -0 * 919 447 1.08 .0737 15.0 2.87 1.17 0.424 448 6.65 0.631 14.7 63.5 1.02 0.980 44S 7.4 0.164 10.5 3.74 , 1.65 -0.296 450 45.1

'. 200 81 0

- · ί5Γ6- Α3ΑΜ13475

Table XXX (continued)

Beisp.Nr. C P C / P S log C / P loq S / C 451 ¹ ' ⁴ 0,151 9.27 2.26 0.967 0.208 452 9.2 0.201 45.8 3.68 1.66 -0.398 453 114 10.3  11.1 5.19 1.05 -1.34 454 6.8 0.631 10.8 2.13 1.03 -0.504 455 5.6 0.769 7.28 2.09 P 862 -0.428 456 19.0 0,179 106 2.74 2.03 -0.841 457 5.8 0,372 15.6 7.56 1.19 0.112

- IS * -

A3AM13475

Table XXXI Polymer Type Beisp.Nr. State of the art description polypropylene 458 Celgard 3501 polyvinylchloride 459 Amerace A-30 polypropylene 460 Porex cellulosic 461 Milipore EC cellulosic 462 Mitricel GA-8 polyvinylchloride 463 Sartorius SM 12807 cellulosic 464 Millipore HAWP cellulosic 465 Millipore G5WP 04700 cellulosic 466. Millipore VMWP 04700 cellulosic 467 Araicon 5UMO5 polypropylene 468 Celgard 2400 polyvinylchloride 469 Millipore SMWP 04700 polypropylene 470 Gelgard 2400 polyethylene 471 Product of Ex. 381 polyethylene 472 Product of Ex. 380 polypropylene 473 Product of Ex. 383 polyethylene 474 Product of Ex. 384

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γ- * -

Table XXXII

Beisp.Nr. C S log S / C 458 0.04 ⁺ 2.32 1.76 549 0.3 138 2.66 460 186 2.41 -1.89 461 0.2 ⁺ 26.3 1.85 462 0.2 * 9.14 1.66 463 0,2+ 31.5 2.2 464 0.8 ⁺ 2.94 0,565 465 O, 22 ⁺ 1.64 0.872 466 0,05+ 5.37 2.03 467 2.10 ⁺⁺ 61.8 1.79 468 0.02 ⁺ 5.08 2.40 469 5 ⁺ 1.55 -0.509 470 0.04 ⁺ 5.64 2.15 471 1.1 ⁺⁺ 11.5 1,019 472 0, 8 ⁺⁺ 17.5 1.34 473 0.56 16.8 1,477 474 70 1.34 -1.718

+) from Company Product Information ++) from Mercury Intrusion

The data listed in Tables XXIX to XXXII are summarized in Figure 70, which is a representation of the log S / C

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against the log C / P. From Figure 70, it can be seen that the cellular structure of the present invention can be defined as having a log C / P of about 0.2 to about 2.4 and a log S / C of about -1.4 to about 1.0 , The typical polymer will have a log C / P of about 0.6 to about 2.2 and a log S / C of about -0.6 to about 0.4

Thus, it will be appreciated that the present invention provides a simple process for producing microporous polymers from any synthetic thermoplastic polymer in widely varying thicknesses and shapes. The microporous polymers are believed to have a unique microcellular configuration and are in any case characterized by relatively narrow size pore diameters. These structures are firstly formed by the choice of a liquid that is compatible with the polymer - i. forms a homogeneous solution with the polymer - and can be removed from the polymer after cooling. Furthermore, by selecting the amount of liquid and performing the cooling of the solution in a manner that ensures that the desired microporous polymer configuration is achieved.

It will thus be appreciated that the present invention also provides microporous polymer products having a relatively large

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have functionally useful liquids, such as Polymerzusatzraittel and behave like solid state. These products can be used to advantage in various fields of application, e.g. in basic mixtures.

Claims (90)

AP C 08 J / 200 810 51 835 11 Claim for invention · An isotropic microporous polymer structure, characterized in that it consists of a synthetic thermoplastic polymer selected from the group of olefinic polymers, the oxidation polymers and mixtures thereof, and an average pore diameter of about 0.1 to about 5 microns and a S Value of about 1 to about 10. 2 00810 AP C 08 J / 200 810 51 835 11 said polymer being a synthetic thermoplastic polymer selected from the group of olefinic polymers, oxidation polymers and mixtures thereof, said cells and pores being at least partially filled with a liquid anti-fogging agent. 2 00810 AP C 08 J / 200 810 51 835 11 the average pore diameter is about 2: 1 to about 200: 1, said polymer being a synthetic thermoplastic polymer selected from the group of olefinic polymers, oxidation polymers and mixtures thereof, and said cells and pores at least in part with a liquid moth control agent are filled. 2 0 0 81 AP C 08 J / 200 810 51 835 11 2 0 0 810 - -lfcff- AP C 08 J / 200 810 51 835 11 , is allowed to cool said solution in said desired shape at a rate to a temperature sufficient to initiate liquid-liquid phase separation under the thermodynamic equilibrium conditions, to continue cooling thereon until formation of a solid, and at least removed a substantial portion of the liquid from the resulting solid to form the microporous polymer structure. , 2. A polymer structure according to item 1, characterized in that it consists of a plurality of substantially spherical cells of an average diameter of about 0.5 to about 100 microns, which are distributed substantially uniformly throughout the structure, wherein the adjacent cells with each other are connected by pores having a smaller diameter than said microcells, the ratio of the average cell diameter to the average pore diameter is about 2: 1 to about 200: 1, said pores and cells are empty, and said polymer is a synthetic thermoplastic polymer which is selected from the group of olefinic polymers, oxidation polymers and mixtures thereof. 3 ·. Polymer structure according to item 1, characterized in that the polymer is an olefinic polymer « &. ν w V / ι w - 463 - AP C 08 J / 200 810
V. 51 835 11 4. The polymer structure according to item 2, characterized in that the ratio of the average cell diameter to the average pore diameter is about 5 J 1 to about
40: 1. " The polymer structure according to item 4, characterized in that the average cell diameter is about 1 to about 20 microns and the average pore diameter is about 0.05 to about 10 microns. 6. Polymer structure according to item 5 »characterized in that the average pore size is about 0.1 to about 1.0 micrometer. 7 · Polymer structure according to item 6, characterized in that the polymer is a non-acrylic polyolefin. 8. Polymer structure according to item 7 », characterized in that the polymer is selected from the group of low density polyethylenes, high density polyethylenes, polypropylene, polystyrene, polyvinyl chloride, acrylonitrile-butadiene-styrene terpolymers, styrene-acrylonitrile copolymers , the styrene-butadiene copolymer, the poly (4-methyl-pentene-1), the polybutylene, the
Polyvinylidene chloride, polyvinyl butyral, chlorinated polyethylene, ethylene-vinyl acetate copolymers, polyvinyl acetate and polyvinyl alcohols. 9. Polymer structure according to item 6, characterized in that the polymer is an acrylic polyolefin. £ -UUO "I AP C 08 J / 200 810 51 835 11 10. The polymer structure according to item 9, characterized in that the polymer is selected from the group consisting of polymethyl methacrylate, polymethyl acrylate, ethylene-acrylic acid copolymers and ethylene-acrylic acid metal salts copolymers. 11. Polymer structure according to item 1, characterized in that the polymer is an oxidation polymer. 12. Polymer structure according to item 11, characterized in that the ratio of the average cell diameter to the mean pore diameter is about 5: 1 to about 40: 1. · The polymer structure according to item 12, characterized in that the average cell diameter is about 1 to about 20 microns and the average pore diameter is about 0.05 to about 10 microns. 14 · Polymer structure according to item 13 »characterized in that the mean pore diameter is about 0.1 to about 1 ', Ό microns. 15 · Polymer structure according to item 14, characterized in that the polymer is polyphenylene oxide. 16. Polymer structure according to item 2, characterized in that the polymer is a non-acrylic polyolefin. 17. A polymer structure according to item 2, characterized in that the polymer is selected from the group of low density polyethylenes, high density polyethylenes, polypropylene, polystyrene; Polyvinyl chloride, the acrylonitrile-butadiene-styrene terpolymers, the styrene 'Acrylonitrile' copolymers, styrene-butadiene copolymers, poly (4-methylpentene-1), polybutylene, Z Ü.Ü81 O AP C 08 J / 200 810
51 835 11 Polyvinylidene chloride, polyvinyl butyral, chlorinated polyethylene, ethylene-vinyl acetate copolymers, polyvinyl acetate and polyvinyl alcohols. ^; 18. Polymer structure according to item 2, characterized in that the polymer is an acrylic polyolefin. 19. The polymer structure according to item 2, characterized in that the polymer is selected from the group consisting of polymethyl methacrylate, polymethyl acrylate, ethylene-acrylic acid copolymers and ethylene-acrylic acid-metal salt copolymers. 20. Polymer structure according to item 2, characterized in that the polymer is polyphenylene oxide. 21. Polymer structure according to item 2, characterized in that the polymer is selected from the group of polyethylene terephthalate, polybutylene terephthalate, polycaprolactam, polyaminoundecanoic acid, polyaminotridecanoic acid, polyhexamethylene adipamide, polycarbonates and polysulfones. · ' 22. Polymer structure according to item 2, characterized in that said structure is in the form of a block
has a thickness of up to about 63.5 mm. The polymer structure according to item 2, characterized in that said structure has a substantially non-cellular skin. 24. The polymer structure according to item 23, characterized in that said skin is relatively impermeable to the passage of a liquid. AP G 08 J / 200 810 51 835 11 25 · Polymer structure according to item 2, characterized in that said structure has the form of a film. 26. A polymer structure according to item 1, characterized in that it consists of a synthetic thermoplastic polymer selected from the group of olefinic polymers, the oxidation polymers, and mixtures thereof, characterized by a G / P ratio of about 2 to about 200 , an S-value of about 1 to about 30 and an average cell size of about 0.5 to about 100 microns. 27. A polymer structure according to item 26, characterized in that the polymer is selected from the group of low-density polyethylenes, high-density polyethylenes, poly-type ropy lens, polystyrene, polyvinyl chloride, acrylonitrile-butadiene-styrene terpolymers, Styrene-acrylonitrile copolymers, styrene-butadiene copolymers, poly (4-methyl-pentene-1), polybutylene, polyvinylidene chloride, polyvinyl butyral, chlorinated polyethylene, ethylene-vinyl acetate copolymers, polyvinyl acetate and polyvinyl alcohol is selected. 28. The polymer structure according to item 27, characterized in that the polymer is selected from the group consisting of polymethyl methacrylate, polymethyl acrylate, ethylene-acrylic acid copolymer and ethylene-acrylic acid-metal salt copolymer. 29 * Polymer structure according to item 27, characterized in that the polymer is polyphenylene oxide. ;. , - Fig - AP C 08 "J / 200 810! 51 835 11 The polymer structure of item 26, characterized in that the C / P ratio is about 5 "to about 40, the S value is about 2 to about 10, and the average cell size is about 1 to about 20 microns. A polymer structure according to item 1, characterized in that it consists of a synthetic thermoplastic polymer selected from the group of olefinic polymers, oxidation polymers and mixtures thereof, characterized by a log C / P value of about -0.2 to about 2.4 and a log S / C of about 1.4 to about 1.0. 32. Polymer structure according to item 31, characterized in that the polymer is selected from the group of low-density polyethylenes, polypropylene, polystyrene, polyvinyl chloride, acrylonitrile-butadiene-styrene terpolymers, styrene-acrylonitrile copolymers, styrene-butadiene copolymers. Copolymers of poly (4-methyl-pentene-1), polybutylene, polyvinylidene chloride, polyvinyl butyral, chlorinated polyethylene, ethylene-vinyl acetate copolymers, polyvinyl acetate and polyvinyl alcohols. The polymer structure according to item 31, characterized in that the polymer is selected from the group consisting of polymethyl methacrylate, polymethyl acrylate, ethylene-acrylic acid copolymers and ethylene-acrylic acid-metal salt copolymers. 34. Polymer structure according to item 31, characterized in that the polymer is polyphenylene oxide. The polymer structure of item 31, characterized in that the log C / P value is about 0.6 to about 2.2 and the log S / C value is about -0.6 to about 0.4. AP C 08 J / 200 810 51 835 11 36. Polymer structure according to item 1, characterized in that the polymer is selected from the group of low-density polyethylenes, high-density polyethylenes, polypropylene, polystyrene, polyvinyl chloride, acrylonitrile-butadiene-styrene terpolymers, styrene-acrylonitrile Copolymers selected from styrene-butadiene copolymers, poly (4-methyl-pentene-1), polybutylene, polyvinylidene chloride, polyvinyl butyral, chlorinated polyethylene, ethylene-vinyl acetate copolymers, polyvinyl acetate and polyvinyl alcohols. 37 · polymer structure according to item!, Characterized in that the polymer is selected from the group of polymethyl methacrylate, polymethyl acrylate, ethylene-acrylic acid, copolymers and the ethylene-acrylic acid-metal salt copolymers. 38. Polymer structure according to item 1, characterized in that the polymer is polyphenylene oxide. The polymer structure according to item 1, characterized in that the average pore diameter is about 0.2 to about 1 micrometer and the S value is about 5 to about 10. 40. A process for producing a relatively homogeneous, isotropic, three-dimensional, microporous polymer structure according to item 1, characterized in that a mixture of a synthetic thermoplastic. Polymer selected from the group of olefinic polymers, the Oxydationspolymeren and mixtures thereof, and a compatible liquid to form a homogeneous solution at a sufficient temperature and for a sufficient time to heat the said solution to a desired shape 41. Method according to item 40, characterized in that substantially all of the liquid is removed. 42. Method according to item 40, characterized in that. said mixture containing about 10 to about 90% by weight of liquid » 43. Method according to item 40, characterized in that the homogeneous solution is poured into a film during cooling. 44. The method according to item 40, characterized in that 'the homogeneous solution during the. Cooling is poured in the form of a block. 45. The method of item 44, characterized in that the block has a thickness of up to about 63.5 mm. 46. The method of item 40, characterized in that the homogenous liquid is poured during cooling on a substrate which forms a substantially non-cellular skin on the surface of the microporous polymers in contact with the said substrate. 47. Method according to item 46, characterized in that the imaged skin is relatively impermeable to liquids. 48. The method of item 40, characterized in that the polymer is a non-acrylic polyolefin. Method according to item 40, characterized in that the polymer is selected from the group consisting of low density polyethylenes, high density polyethylenes, polypropylene, polystyrene, polyvinylchloride, acrylonitrile-butadiene-styrene-terplymeres, styrene-acrylonitrile copolymers which is selected from styrene-butadiene copolymers, poly (4-methyl-pentene-1), polybutylene, polyvinylidene chloride, polyvinyl butyral, chlorinated polyethylene, ethylene-vinyl acetate copolymers, polyvinyl acetate and polyvinyl alcohols. 50. The method according to item 40, characterized in that the polymer is an acrylic polyolefin. 51. The method according to item 40, characterized in that the polymer is selected from the group of polymethyl methacrylate, polymethyl acrylate, ethylene-acrylic acid copolymers and ethylene-acrylic acid-metal salt copolymers. 52. The method according to item 40, characterized in that the polymer is an oxidation polymer. Method according to item 40, characterized in that the polymer is polyphenylene oxide. .ν ι AP C 08 J / 200 810 51 835 11 A process for producing a relatively homogeneous, isotropic, three-dimensional, microporous polymer structure according to item 2, characterized in that a mixture of a polymer selected from the group of olefinic polymers, the oxidation polymers and mixtures thereof, and a compatible liquid to form a homogeneous solution at a sufficient temperature and for a sufficient time, substantially simultaneously forming a plurality of liquid droplets of substantially equal size in a continuous liquid polymer phase by cooling the solution, continuing said cooling until the polymer solidifies and removing at least a substantial portion of the liquid from the resulting solid to form the cellular polymer structure. 55. Method according to item 54, characterized in that substantially all of the liquid is removed. 56. The method of item 54, characterized in that said mixture contains about 10 to 90 weight percent liquid. , 57. The method according to item 54, characterized in that the homogeneous solution is poured into a film during cooling. , , 58. The method according to item 54, characterized in that the homogeneous solution is poured during cooling in the form of a block. Method according to item 58, characterized in that the block has a thickness of up to about 63.5 mm. AP C 08. J / 200 810 51 835 11 60. The method of item 58, characterized in that the homogeneous liquid is poured during cooling on a substrate which forms a substantially non-cellular skin on the surface of the microporous polymers in contact with the said substrate. 61. The method of item 58. characterized in that the skin formed is relatively impermeable to liquids. 62. The method according to item 54, characterized in that the polymer is a. nifcht acrylic polyolefin is. Method according to item 54, characterized in that the polymer is selected from the group of low density polyethylenes, high density polyethylenes, polypropylene, polystyrene, polyvinyl chloride, acrylonitrile-butadiene-styrene terpolymers, styrene-acrylonitrile Copolymers selected from styrene-butadiene copolymers, poly (4-methyl-pentene-1), polybutylene, polyvinylidene chloride, polyvinyl butyral, chlorinated polyethylene, ethylene-vinyl acetate copolymers, polyvinyl acetate and polyvinyl alcohol. ^: 64. The method of item 54, characterized in that the polymer is an acrylic polyolefin. Method according to item 54, characterized in that the polymer is selected from the group consisting of polymethyl methacrylate, polymethyl acrylate, ethylene-acrylic acid copolymers and ethylene-acrylic acid metal salt copolymers ο ZUUÖ1U - AP C 08 J / 200 810 I 51 835 11 66. The method according to item 54, characterized in that the polymer is an oxidation polymer. 67. Method according to item 54 », characterized in that the polymer is polyphenylene oxide. 68. A relatively homogeneous, three-dimensional, microporous cellular polymer structure according to item 2, characterized in that it consists of a plurality of substantially spherical cells of an average diameter of about 0.5 to about 100 microns, which distributes substantially uniformly throughout the structure wherein the adjacent cells are interconnected by pores having a smaller diameter than said microcells, the ratio of average cell diameter to average pore diameter being from about 2: 1 to about 200: 1, said polymer being a synthetic thermoplastic polymer, which is selected from the group of olefinic polymers, oxidation polymers and mixtures thereof, and said cells and pores are at least partially filled with a liquid lubricant. 69. Relatively homogeneous, three-dimensional, microporous cellular polymer structure according to item 2, characterized in that it consists of a plurality of substantially spherical cells of an average diameter of about 0.5 to about 100 microns, which distributes substantially uniformly throughout the structure where the adjacent cells are interconnected by pores having a smaller diameter than said microcells, the ratio of the average line diameter to the average pore diameter being from about 2 * 1 to about 200: 1, said polymer AP C 08 J / 200 810 51 835 11 represents a synthetic thermoplastic polymer selected from the group of olefinic polymers, oxidation polymers and mixtures thereof, and said cells and pores are at least partially filled with a liquid surfactant. 70. A relatively homogeneous, three-dimensional, microporous cellular polymer structure according to item 2, characterized in that it consists of a plurality of substantially spherical cells of an average diameter of about 0.5 to about 100 microns, which are substantially uniform are distributed throughout the structure with adjacent cells interconnected by pores having a smaller diameter than said microcells, the ratio of average cell diameter to average pore diameter being from about 2: 1 to about 200: 1, said polymer synthetic thermoplastic polymer selected from the group of olefinic polymers, oxidation polymers and mixtures thereof, and said cells and pores are at least partially filled with a liquid lubricant. Relatively homogeneous, three-dimensional, microporous, columnar polymer structure according to item 2, characterized in that it consists of a plurality of substantially spherical cells of an average diameter of about 0.5 to about 100 microns which are substantially uniform throughout Structure are distributed, wherein the adjacent cells are interconnected by pores having a smaller diameter than said microcells, the ratio of the average cell through 72. Relatively homogeneous, three-dimensional, microporous cellular. A polymer structure according to item 2, characterized in that it consists of a plurality of substantially spherical cells of an average diameter of about 0.5 to about 100 microns, which are distributed substantially uniformly throughout the structure, with the adjacent cells interconnected by pores The ratio of the average cell diameter to the average pore diameter is about 2: 1 to about 200: 1, said polymer being a synthetic thermoplastic polymer selected from the group of olefinic polymers, oxidation polymers and mixtures thereof, and said cells and pores are at least partially filled with a liquid pesticide. Relatively homogenous three-dimensional microporous cellular polymer structure according to item 2, characterized in that it consists of a plurality of substantially spherical cells of mean diameter of about 0.5 to about 100 microns, which distributes substantially uniformly throughout the structure , are, wherein the adjacent cells are interconnected by pores having a smaller diameter than said microcells, '- its- AP C 08 J / 200 810,' 51 835 11 the ratio of the average cell diameter to the average pore diameter is about 2: 1 to about 200: 1, said polymer being a synthetic thermoplastic polymer selected from the group of olefinic polymers, oxidation polymers and mixtures thereof, and said cells and Pores are at least partially filled with a liquid plasticizer. Relatively homogeneous, three-dimensional, microporous cellular polymer structure according to item 2, characterized in that it consists of a plurality of substantially spherical cells of a mean diameter of about 0.5 to about 100 microns, substantially uniform throughout the structure wherein the adjacent cells are interconnected by pores having a smaller diameter than said microcells, the average cell diameter to average pore diameter ratio is from about 2: 1 to about 200: 1, said polymer being a synthetic thermoplastic polymer which is selected from the group of olefinic polymers, oxidation polymers and mixtures thereof, and said cells and pores are at least partially filled with a liquid drug. Relatively homogeneous, three-dimensional, microporous cellular polymer structure according to item 2, characterized in that it consists of a plurality of substantially spherical cells of a mean diameter of about 0.5 to about 100 microns, substantially uniform throughout Structure are distributed, wherein the adjacent cells are interconnected by pores having a smaller diameter than said microcells, AP C 08 J / 200 810 51 835 11 the ratio of the average cell diameter to the average pore diameter is from about 2: 1 to about 200: 1, said polymer being a synthetic thermoplastic polymer selected from the group of olefinic polymers, oxidation polymers and mixtures thereof, and said cells and pores at least partially filled with a liquid fuel additive · Relatively homogeneous, three-dimensional, microporous cellular polymer structure according to item 2, characterized in that it consists of a plurality of substantially spherical cells of an average diameter of about 0.5 to about 100 microns, substantially uniform throughout Structure are distributed, wherein the adjacent cells are interconnected by pores having a smaller diameter than said microcells, the ratio of the average cell diameter to the average pore diameter from about 2: 1 to about 200: 1, said polymer is a synthetic thermoplastic polymer which is selected from the group of olefinic polymers, oxidation polymers and mixtures thereof, and said cells and pores are at least partially filled with a liquid polishing agent. Relatively homogeneous, three-dimensional, microporous cellular polymer structure according to item 2, characterized in that it consists of a plurality of substantially spherical cells of a mean diameter of about 0.5 to about 100 microns, substantially uniform throughout the structure are distributed, wherein the adjacent cells are interconnected by pores having a smaller diameter than the said microcells, the ratio of the average cellulosic percussion to durchdurch- AP C 08 J / 200 810 51 835 11 average particle diameter is about 2: 1 to about 200: 1, said polymer is a synthetic thermoplastic polymer selected from the group of olefinic polymers, oxidation polymers and mixtures thereof, and said cells and pores are at least partially filled with a liquid insect repellent are. 78. A relatively homogeneous, three-dimensional, microporous cellular polymer structure according to item 2, characterized in that it consists of a plurality of substantially spherical cells of an average diameter of about 0.5 to about 100 microns, which distributes substantially uniformly throughout the structure wherein the adjacent cells are interconnected by pores having a smaller diameter than said microcells, the ratio of the average cell diameter to the average pore diameter being from about 2: 1 to about 200: 1, said polymer being a synthetic thermoplastic polymer, which is selected from the group of olefinic polymers, oxidation polymers and mixtures thereof, and said cells and pores are at least partially filled with a liquid animal repellent. Relatively homogeneous, three-dimensional, microporous cell-shaped polymer structure according to item 2, characterized in that it consists of a plurality of substantially spherical cells of an average diameter of about 0.5 to about 100 microns, which distributes substantially uniformly throughout the structure are, wherein the adjacent cells are interconnected by pores having aii smaller diameter than said microcells, the ratio of AP C 08 J / 200 810 ^! 51 835 11 average cell diameter to average pore diameter is about 2: 1 to about 200: 1, said polymer is a synthetic thermoplastic polymer selected from the group of olefinic polymers, oxidation polymers and mixtures thereof, and said cells and pores at least partially with a liquid fragrance are filled. 80. A relatively homogeneous, three-dimensional, microporous cell-shaped polymer structure according to item 2, characterized in that it consists of a plurality of substantially spherical cells of an average diameter of about 0.5 to about 100 microns, substantially uniform in the the adjacent cells are interconnected by pores having a smaller diameter than the said microcells, the ratio of the average cell diameter to the average pore diameter is about 2: 1 to about 200: 1, said polymer is a synthetic thermoplastic Polymer selected from the group of olefinic polymers, oxidation polymers and mixtures thereof, and said cells and pores are at least partially filled with a liquid flame retardant. 81. Relatively homogeneous, three-dimensional, microporous cellular polymer structure according to item 2, characterized in that it consists of a plurality of substantially spherical cells of an average diameter of about 0.5 to about 100 microns are distributed substantially uniformly throughout the structure, the adjacent cells being interconnected by pores having a smaller diameter than the said microcells, the ratio of the average cell diameter to the average pore diameter. - · »- · AP C 08 J / 200 810 '* 51 835 11 is about 2: 1 to about 200: 1, 'said polymer is a synthetic thermoplastic polymer selected from the group of olefinic polymers, oxidation polymers and mixtures thereof, and said cells and pores are at least partially liquid Oxidation inhibitor are filled. 82. Relatively homogeneous, three-dimensional, microporous cellular polymer structure according to item 2, characterized in that it consists of a plurality of substantially spherical cells of an average diameter of about 0.5 to about 100 microns, substantially uniformly throughout Structure, wherein the adjacent cells are interconnected by pores having a smaller diameter than the said micro-lines, the ratio of the average cell diameter to the average pore diameter is about 2: T to about 200: 1, said polymer is a synthetic thermoplastic polymer which is selected from the group of olefinic polymers, oxidation polymers and mixtures thereof, and said cells and pores are at least partially filled with a liquid odor enhancer. Relatively homogeneous, three-dimensional, microporous cellular polymer structure according to item 2, characterized in that it consists of a plurality of substantially spherical cells of an average diameter of about 0.5 to about 100 microns, which distributes substantially uniformly throughout the structure where the adjacent cells are interconnected by pores having a smaller diameter than the said microcells, the ratio of the average cell diameter to the average pore diameter is about 2: 1 to about 200: 1. Relatively homogeneous, three-dimensional, microporous cellular polymer structure according to item 2, characterized in that it consists of a plurality of substantially spherical cells of an average diameter of about 0.5 to about 100 microns, substantially uniform throughout the structure wherein the adjacent cells are interconnected by pores having a smaller diameter than said microcells, the ratio of average cell diameter to average pore diameter being 2: 1 to about 200: 1, said polymer being a synthetic thermoplastic polymer which is selected from the group of olefinic polymers, oxidation polymers and mixtures thereof, and said cells and pores are at least partially filled with a liquid perfume. A process for producing a relatively homogeneous, isotropic, three-dimensional, microporous polymer structure according to item 2, characterized in that a mixture of a polymer selected from the group of olefinic polymers, the oxidation polymers and mixtures thereof, and a compatible liquid heated to a sufficient temperature and for a sufficient time, substantially simultaneously forming a plurality of liquid droplets of substantially equal size in a continuous liquid polymer phase by cooling the solution, said cooling until the pest of the poly AP C 08 J / 200 810 51 835 11 at least partially the compatible one-body fluid selected from the group of a displacer intermediate fluid, or a liquid functional agent selected from the group consisting of lubricants, surfactants, lubricants, moth control agents, pesticides, plasticizers, drugs, fuel additives, Polishing agents, stabilizers, insect repellents, fragrances, flame retardants, antioxidants, odorizers, anti-fogging agents and perfumes, with the proviso that when using a displacer intermediate liquid, it is then at least partially displaced by a liquid functional agent. 86. The method of item 85, characterized in that said compatible liquid is substantially completely displaced. Process according to item 86, characterized in that said compatible liquid is displaced by a liquid displacing intermediate. 88. The method of item 87, characterized in that the fluid displacing intermediate is substantially completely displaced by said liquid functional agent. 89 »Method according to item 85, characterized in that the polymer is an olefinic polymer. · 90. Method according to item 85, characterized in that the polymer is an oxidation polymer. lierau i & pages Zeichnunaen