SE441928B - MICROPOROS, RELATIVE HOMOGENIC BODY OF A POLYMER, PROCEDURE FOR ITS PREPARATION AND ITS USE - Google Patents

Abstract

A three-dimensional, microporous polymer cell structure has a multiplicity of essentially spherical microcells. These have a mean diameter C of 0.5 - 100 microns and are essentially uniformly distributed over the structure. Adjacent cells are connected to one another by pores. The diameter of these pores is smaller than that of the microcells. The pore size distribution corresponds to a sharpness factor S in the range from 1 - 30. The decimal logarithm of the ratio between the mean cell diameter C and the mean pore diameter P has a value in the range from 0.2 - 2.4, and the decimal logarithm of the ratio between the sharpness factor S and the mean cell diameter C has a value in the range from -1.4 to 1.0. The pores and the cells are empty, and the polymer is a synthetic thermoplastic polymer from the class consisting of homopolymers and copolymers of ethylenically unsaturated monomers, condensation polymers and oxidation polymers, or a mixture of synthetic thermoplastic polymers belonging to this class. A further three-dimensional, microporous polymer cell structure corresponds to the above-described polymer cell structure, but at least some of the cells and pores therein are filled with a liquid active ingredient. The liquid active ingredient can be a lubricant, a surfactant, a glidant, a pesticide, a plasticiser, a medicament, a propellant additive, a polish, an insect-protection agent (insecticide), a flameproofing agent, an antioxidant, an antifogging agent or a fragrance.

Description

In addition, the methods used have various limitations which do not leave room for the adaptability required for them to enter the potential market for microporous products.

Some commercially available microporous polymer products are prepared as mentioned by particle coating techniques. Such a technology creates the possibility of achieving a rather narrow pore size distribution.

However, the pore volume must be relatively small (ie a porosity of less than about 10%) to ensure that the polymer will not degrade during production. Many polymers cannot be used in such technology due to the inability of the polymer to etch. The technology also requires that a relatively thin sheet or film of the polymer be used, and that great expertise must be used in the procedure to avoid "double tracking", which results in the formation of oversized pores.

The classical phase inversion has also been used to prepare microporous polymers of cellulose acetate and certain other polymers.

The classic phase inversion has been the subject of an in-depth discussion of R.3. Kesting in "Synthetic Polymeric Membranes", Hcüraw-Hill, 1971. In particular on page 117 of the book it is explicitly stated that the classical phase inversion requires the use of at least three components, a polymer, a solvent for the polymer and a non-solvent for the polymer. .

Reference may also be made to U.S. Patent No. 3,945,926, which discloses the preparation of carbonate plastic membranes from a casting solution containing the plastic, a solvent, and a swelling agent and / or a non-solvent. I sp. 15, pp. 42-47 of the patent specification state that phase inversion in the complete absence of a swelling agent usually does not occur, and that at low concentrations of swelling agent structures with closed cells are obtained.

From the foregoing discussion, it is apparent that the classical phase inversion requires the use of a solvent for the system at room temperature, so that many other polymers useful per se cannot be substituted for such polymers as cellulose acetate. Also from a process point of view, the classical phase inversion process will usually be limited to the formation of films due to the large amount of solvent used in the preparation of the solutions which must be extracted later. It is also obvious that the classical phase inversion requires a relatively high degree of process control in order to obtain structures with the desired configuration. The relative concentrations of solvents, non-solvents and swelling agents must therefore be carefully controlled, as stated in sp. 14-16 1 U.S. Patent No. I ... ia, h _, 3,7708655-6 3,045,926. In order to change the number, size and homogeneity of the resulting structure, on the other hand, one must modify the above parameters by trial and error.

Other commercially available microporous polymers are prepared by sintering microporous particles of polymers ranging from HD polyethylene to polyvinylidene fluoride. With such a technology, however, it is difficult to obtain a product with the narrow pore size distribution required for many applications.

Another general technique which has been the subject of considerable effort involves heating a polymer with various liquids to form a dispersion or solution and then cooling, accompanied by the removal of the liquid with a solvent or the like. This type of process is described in U.S. Patent Nos. 3,607,793, 3,378 SO7, 3,310,505, 3,74,28.7, 3,536,796, 3,308,073 and 3,812,224. It is believed that the prior art has not been used commercially in any to a significant extent, if at all, probably because the previously developed special processes have not been economically feasible ~ The previous processes also do not allow the production of microporous polymers that combine relatively homogeneous microcell structures with the typically desired pore sizes and pore size distributions.

Regarding the microporous polymers prepared according to previous processes, there is no previously known process by means of which it has been possible to prepare isotropic olefin or oxidation polymers with the predominant part of the pore sizes in the range about 9.1 - 5 μm at the same time with a relatively narrow pore size distribution, whereby the polymers shows a high degree of uniformity in pore size. Some prior olefin or oxidation polymers have had pore sizes in the above range, although without a relatively narrow pore size distribution fi, thus rendering such materials unsuitable for applications such as filtration, which require a high degree of selectivity. Previously, microporous olefin or oxidation polymers, which have been considered to have relatively narrow pore size distributions, have had absolute pore sizes outside the above range, usually with significantly smaller pore sizes, for use in such areas as ultrafiltration. Finally, some previous olefin polymers have had pore sizes in the above range and what could be considered to be relatively narrow pore size distributions. However, such materials have been prepared by applying such techniques as stretching, which imparts a high degree of orientation to the resulting anisotropic material and therefore makes it unsuitable for many applications. Thus, there has been a need for microporous olefin and oxidation polymers having a pore size in the range of about 0.1 to 5 microns and which are characterized by a relatively narrow, isotropic, pore size distribution.

In addition, a significant disadvantage of many previously available microporous polymers has been the low volume flow of such polymers when used in such structures as microfiltration membranes.

One of the major reasons for such small volume flows is the typically low pore volume of many such polymers. Thus, possibly ZQ 3 of the polymer structure or less may constitute "pore volume", through which a filtrate may flow, while the remaining 80% of the structure is the polymeric material forming the microporous structure. Thus, there has also been a need for high porosity microporous polymers. especially in the case of olefin polymers.

Accordingly, an object of the invention is to provide microporous polymer products which are characterized by relatively high homogeneity and narrow pore size distributions.

Another object is to provide a simple process which enables an economical production of microporous polymers.

Another object is to provide for the production of microporous polymeric products a process which can be applied to a wide range of useful thermoplastic polymers. A Related and More Specific Purpose is to provide such a process which makes it possible to readily prepare microporous polymers from any synthetic thermoplastic polymers, including polvolefins, condensation polymers and oxidation polymers.

A further object of the invention is to provide microporous polymers in structures ranging from thin films to relatively thick blocks. A related purpose is to create the opportunity to produce microporous polymers in complicated forms.

A further object is to effect the conversion of Functional liquids into materials which exhibit the properties of a solid.

The invention appears from the appended claims.

Other objects and advantages of the invention will become apparent from the following description and from the figures, in which: Figs. 1 is a graph showing the temperature as a function of the concentration of a hypothetical polymer-liquid system, indicating the binodial and spinodal curves, showing the concentration required to achieve the microporosity of the polymers and to apply the process of the invention; Pig. 1A is a graph similar to the temperature shown in Fig. 1 as a function of concentration, but also shows the phase line of the freezing point reduction; Pig. 2 is a photomicrograph at about 45 times magnification, showing the macrostructure of a microporous polypropylene polymer according to the invention with about 75% porosity; Pig. 3 - S are photomicrographs of a porous polypropylene structure according to Fig. 2 at 470, 1570 resp. 4675 times magnification, showing a homogeneous cell structure; Figs. 6 - 10 are photomicrographs at 1125, 1320, 1380, 1230 resp. 1060 times magnification of additional microporous polypropylene structures and shows the structural changes as the porosity is reduced from 90% to 70%, to 60%, to 40% resp. to 20%; Pig. 11 - 13 are microphotos at 1700, 1740 resp. 1660 times magnification of additional microporous polymer structures according to the invention, and shows the decreasing cell size as the polypropylene content is increased from 10% by weight in Fig. 11, to 20% and to 30%, in Figs. 13; Pig. 14 - 17 are microphotos at 210, 2125, 2125 resp. 2105 times magnification of microporous LD polyethylene structures according to the invention, wherein Figs. 14 and 15 show the macro and microstructure of a microporous polymer containing 20% by weight of polyethylene, and Figs. 16 and 17 show the microstructure with 40 and 70% polyethylene; Figs. 18 and 19 are photomicrographs at 1785 and 1785, respectively. 1700 times magnification of microporous HD polyethylene structures according to the invention, and shows the structures at 30 resp. 70% by weight of polyethylene; Figs. 20 and 21 are photomicrographs at 2170 and 2170, respectively. 2190 times magnification of microporous SBR polymers according to the invention and shows a homogeneous cell structure; Fig. 22 is a photomicrograph at 2040x magnification of a microporous methylpentene polymer; Figs. 23 and 24 are photomicrographs at 215 and 215, respectively. 2170 times magnification of a microporous ethylene-acrylic acid copolymer; Pig. Is a photomicrograph at 2125x magnification of a microporous polymer made from a polyphenylene oxide-polystyrene blend; Pig. 26 is a photomicrograph at 1745 magnification showing a microporous styrene polymer; Fig. 27 is a photomicrograph at 1700 times magnification showing a microporous vinyl chloride polymer; Figures 28 and 29 are photomicrographs at 1700 times magnification of microporous LD polyethylene polymers and show the partial deworming of the base structure by a "foiled" structure; 7708653-6 6 Pig. 30-33 are mercury penetration curves for microporous polypropylene structures according to the invention and show the narrow distribution of the pore diameter characteristic of the polymers according to the invention; Fig. 34 - 40 are mercury penetration curves for commercial microporous products including "Celgard" polypropylene (Fig. 34), "Amerace A20" and "% merace A30" polyvinyl chloride (Figs. 35 and 36, respectively), "Forex" 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, respectively); Figs. 41-43 are mercury penetration curves. prepared according to U.S. Patent No. 3,37? SO7 using polyethylene (Figs. 41 and 42) and polypropylene (Fig. 43); Fig. 44 is a mercury penetration curve for a microporous polyethylene material prepared according to U.S. Patent No. 3,310,500; Figs. 45 and 46 are photomicrographs of a porous polyethylene product prepared by duplicating Example 2 of U.S. Patent 3,376,507 using an injection molding technique; Fig. 45 (205x magnification) showing the macrostructure and Fig. 46 (2040 times magnification) showing the microstructure; Fig. 47 o ch 48 are photomicrographs of a porous polyethylene product prepared by duplicating Example 2 of U.S. Patent 3,37% 507 using a compression molding technique, FIG. 47 (195 times magnification) showing the macrostructure and Fig. 48 (1700 times magnification) showing the microstructure; Figs. 49 and 50 are photomicrographs of a porous polypropylene product prepared by duplicating Example 2 of U.S. Patent 3,37b SO7 using an injection molding technique; Figs. 49 (165x magnification) showing the macrostructure and Figs. S0 (1700 times magnification) visaude microstructure; Figs. S1 and 52 are photomicrographs of a porous polypropylene product prepared by duplicating Example 2 of U.S. Patent 3,376 SO7 using a compression molding technique; Figs. 51 (175x magnification) showing the microbrewery and Figs. S2 (1700 times magnification) showing the microstructure, and Figs. 53 and 54 are photomicrographs of a porous polyethylene product prepared by duplicating Example 2 of U.S. Patent 3,310,505, Sig. 53 (175 times magnification) showed the macrostructure and fig. 54 (1700 times magnification) showing the microstructure.

Fig. 55 shows a melting curve and a crystallization curve for a polymer / liquid system of polypropylene and quinoline. 7 Ä 7708653-6 “ig. S6 shows a melting curve and several crystallization curves for a polymer / liquid system of polypropylene and N, N-bis (2-hydroxyethyl) tallow fatty amine.

Pig. S7 shows a melting curve and a crystallization curve for a polymer / liquid system of polypropylene and dioctylphthalate, and demonstrates a system which is not within the scope of the invention.

Pig. 58 shows the phase diagram of a polymer / liquid system of LD polyethylene and diphenyl ether, determined at cooling and heating rates of 1 K / min.

Pig. S9 shows several melting and crystallization curves for a polymer liquid system of LD polyethylene and diphenyl ether.

Pig. 60 shows a glass conversion curve for a polymer / liquid system of LD polystyrene and 1-dodecanol.

Pig. 61 is a photomicrograph at 4250 times magnification of a microporous cell structure produced from polymethylmeuacrylab according to the invention with 70% porosity.

Fig. 62 shows melting and crystallization curves for a polymer / liquid system of nylon 11 and tetramethylene sulfone.

Pig. 63 is a photomicrograph at 1700 times magnification of a microporous cell structure made of nylon 11 according to the invention with 70% porosity.

Fig. 64 is a photomicrograph at 1700 times magnification of a microporous cell structure made of polycarbonate according to the invention with 70% porosity.

Pig. 65 is a photomicrograph at 1700 times magnification of a microporous cell structure produced from polyphenylene oxide according to the invention with 70 ß porosity.

Figs. 66 and 67 are photomicrographs at 1700 times magnification of a microporous non-cellular use produced from polypropylene according to the invention by 60% and 75% porosity.

Figs. 68 and 69 show mercury penetration curves for a non-metallic microporous polypropylene structure according to the invention with 60% and 75% porosity.

Fig. 70 is a graphical representation of the unique microporous structures of the invention compared to certain prior art compositions.

While the invention is susceptible to various modifications and alternative forms, the preferred embodiments will be described in detail herein. It should be noted, however, that the intention is not to limit the invention to the specifically described embodiments, but rather to include those modifications and alternative embodiments which fall within the scope of the invention since they are defined in the claims.

Summary of the Invention According to the invention, it has now been found that any synthetic thermoplastic can be made microporous by first heating the polymer and a compatible liquid, as explained below, to a temperature and for a time sufficient to form a homogeneous solution. The solution thus formed is then allowed to assume a desired shape and is then cooled in this shape at a rate and to a temperature sufficient to initiate a thermodynamic imbalance separation of the liquid phases. While the solution cools in the desired shape, no shear or other shear force is applied while the solution cools. The cooling continues so that a solid body is formed. This only needs to assume sufficient mechanical integrity to be able to be handled without breaking. Finally, at least a substantial amount of the combinable liquid is removed from the resulting solid to form the desired microporous polymer.

Certain new microporous olefin and oxidation polymers according to the invention are characterized by a narrow pore size distribution, which is determined by mercury penetration testing. The narrow pore size distribution can be analyzed analytically in terms of a sharpness function "5", which will be explained in detail below. The S-values of the olefin and oxidation polymers of the invention range from about 1 to about 10. These polymers of the invention are also characterized by average pore sizes ranging from about 0.10 to about 5 microns, preferably from about 0.2 to about 5 microns. 1 pm.

Furthermore, such microporous products are practically isotropic and thus have essentially the same cross-sectional shape when analyzed along an arbitrary space plane.

In another aspect of the invention, the process for the preparation of microporous polymers is carried out in such a way that 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 the foregoing polymers, and a combinable liquid is heated to a temperature and for a time sufficient to form a homogeneous solution. The solution is then cooled, whereby a plurality of liquid droplets of substantially the same size are formed almost simultaneously. The cooling is then continued to solidify the polymer, and at least a substantial amount of the liquid is removed from the resulting solid to form the desired cellular polymer structure. The above process will result in microporous polymer products characterized by a cellular, three-dimensional micropore structure, i.e. a series of closed cells with mainly spherical shapes and pores or channels connecting the neighboring cells. The basic structure is relatively homogeneous with the cells evenly distributed in all three dimensions, and the connecting pores have diameters with a relatively narrow size distribution, measured by mercury penetration. Microporous polymers with such a structure are simply called "cellular".

According to the invention, new microporous polymer products are also provided, which behave as solid bodies and contain relatively large amounts of functionally useful liquids, e.g. polymer additives including fire retardants and the like. In this way, usable liquids can obtain the process-technical advantages of a solid material that can be used directly, e.g. in a premix. Such products can be formed either directly by using a functional liquid as the combinable liquid without removing it, or indirectly by either filling the microporous polymer after the removal of the combinable liquid or displacing the combinable liquid for mixing of the functional fluid.

Detailed description of the invention The application of the process according to the invention consists essentially in that the desired polymer is heated with a suitable combinable liquid to form a homogeneous solution. This is cooled in a suitable manner to form a solid material, from which the liquid is then extracted to form a microporous material. The views which must be taken into account in the application of the invention will be described in more detail in the following.

The present invention surprisingly offers, as mentioned, a technique for making an arbitrary synthetic thermoplastic polymer microporous. The process according to the invention thus applies to olefin polymers, condensation polymers and oxidation polymers.

Examples of useful non-acrylic polyolefins are LD polyethylene, HD polyethylene, polypropylene, polystyrene, polyvinyl chloride, acrylonitrile-butadiene-styrene terpolymers, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, poly (4-methyl- 1-pentene), polybutene, polyvinylidene chloride, polyvinyl butyral, chlorinated polyethylene, ethylene-vinyl acetate copolymers, polyvinyl acetate and polyvinyl alcohol.

Useful acrylic acid-based polyolefins include polymethyl methacrylate, polymethyl acrylate, ethylene-acrylic acid copolymers and ethylene-fluoroacetic acid acrylic metal salt copolymers.

Polyphenylene oxide is representative of useful oxidation polymer numbers. The useful condensation polymers include polyethylene torvitalate, polybutylene terephthalate, nylon 6, nylon 11, nylon 13, nylon 66, polycarbonate and polysulfone.

Choice of compatible liquid For the practice of the invention, one only needs to first select the synthetic thermoplastic polymer to be made microporous.

Next, it is important to select the appropriate combinable liquid and the relative amounts of polymer and liquid to be used. Of course, according to the invention, mixtures of one or more polymers can be used. The polymer and liquid are heated with stirring to the temperature required to form a clear, homogeneous solution. If a solution cannot be formed at any concentration of the liquid, it is unsuitable and cannot be used with the polymer in question.

Due to the selectivity, it is not possible to determine with certainty the compatibility of a particular liquid with a particular polymer. However, some general guidelines can be stated. Thus, when the polymer in question is non-polar, it is more likely that non-polar liquids with similar solubility parameters at the solution temperature will be useful. If such parameters are not available, reference can be made as a general guide to the more readily available solubility parameters at room temperature. Similarly, with respect to polar polymers, one can start by examining polar organic liquids with similar solubility parameters. The relative polarity or non-polarity of the liquid must also be adapted to the relative polarity or non-polarity of the polymer. In addition, in the case of hydrophobic polymers, useful liquids will typically have little or no water solubility. Polymers with a tendency to be hydrophilic, on the other hand, will usually require a liquid with some water solubility.

Regarding suitable liquids, as special examples of various types of organic compounds, which are particularly useful, mention may be made of aliphatic and aromatic acids, aliphatic, aromatic and cyclic alcohols, aldehydes, primary and secondary amines, aromatic and ethoxylated amines, diamines, amides, esters and diesters, ethers, ketones and various hydrocarbons and heterocycles. It should be emphasized, however, that the concept is completely selective. Thus, for example, not all saturated aliphatic acids will be useful. Furthermore, not all the liquids useful for HD polyethylene need necessarily be useful for, for example, polystyrene.

As will be appreciated, the useful proportions of polymer and liquid may be. _-_......_....___-..... ___-___... 11 vvoeßssw for a particular system is easily determined by evaluating the parameters to be discussed in the following.

If mixtures of one or more polymers are used, usable liquids must of course be capable of working with all polymers. However, the polymer blend may have such properties that the liquid need not be workable with all of the polymers used. For example, when one or more polymer components are present in such relatively small amounts that they do not significantly impair the properties of the mixture, the liquid used need only be operable together with the main polymer or polymers.

In addition, although the most useful materials are liquids at ambient temperatures, materials that are solid at room temperature can be used as long as solutions can be formed with the polymer at elevated temperatures and the material does not interfere with the formation of the microbial structure. Thus, a solid material can be used as long as phase separation during the cooling step occurs by liquid-liquid separation instead of liquid-solid separation, as will be discussed below. The amount of liquid used can generally vary from about 10% to about 90%.

As mentioned, any synthetic thermoplastic polymer can be used as long as the selected liquid forms a solution with the polymer and the concentration gives a continuous polymer phase upon separation under cooling, as will be discussed in more detail below. In order to get an idea of the range of viable polymer and hydrogen systems, a brief summary of some systems may be useful.

In the preparation of microporous polymers from polypropylene, for example, the following combinable liquids have proved useful: alcohols such as 2-benzylamino-1-propanol and 3-phenyl-1-propanol; aldehydes such as salicylaldehyde; amides such as N, N-diethyl-m-toluamide; amines such as N-hexyl-diethanolamine, N-behenyl-diethanolamine, N-coconut-diethanolamine, benzylamine, N, N-bis-β-hydroxyethyl-cyclohexylamine, diphenylamine and 1,12-diamino-dodecane; esters such as methyl benzoate, benzyl benzoate, phenyl silicone, methyl salicylate and dibutyl phthalate; and ethers such as diphenylethene no. 4-bromo-diphenyl ether and dibenzyl ether. In addition, halogenerado hydrocarbons such as 1,1,2,2-tetrabromoethane and hydrocarbons such as trans-stilhan, and alkyl / aryl phosphite, as well as ketones such as methylnonyl ketone are useful.

In the preparation of microporous polymers from UD polyethylene, the following compatible liquids have proved suitable: saturated aliphatic acids such as capric acid, primary saturated alcohols such as decyl alcohol and 1-dodecanol, secondary alcohols such as 2-undecanol and 6-undecanol. Ethoxylated amines such as Naauryldiethanolamine, aromatic amines such as N, N-diethylaniline, diesters such as dibutyl sebacate and dihexyl sebaoate and ethers such as diphenyl ether and benzyl ether. Other useful liquids include halogenated compounds such as octabromodiphenyl, hexabromobenzene and hexabromocyclodecane, hydrocarbons such as 1-hexadecane, diphenylmertan and naphthalene, aromatic compounds such as necetophonone and other organic compounds such as alkyl / arylphosphite, and quinoline and ketonyl methonetonetonetonetone

For the preparation of microporous polymers from LD polyethylene, the following liquids have proved useful: saturated aliphatic acids including caproic acid, caprylic acid, capric acid, undecylic acid, lauric acid, myristic acid, palmitic acid and stearic acid, including unsaturated aliphatic acid aromatic acids and tyros including benzoic acid, phenylstearic acid, polystearic acid and xylylbenzic acid and other acids including branched carboxylic acids having average chain lengths of 6, 9 and 11 C atoms, tall oil acids (pine fatty acid, tall resin resin acid) and resin acid (rosin-containing alcohols); 1-octanol, nonyl alcohol, decyl alcohol, 1-decanol, 1-dodecanol, lridecyl alcohol, cetyl alcohol and 1-heptadecanol, primary unsaturated alcohols including undecylenyl alcohol and oleyl alcohol, secondary alcohols including 2-octanoi, 2-undecarbinecanol and dinon 1 ~ phenylethanine. 1-phenyl-1-pentanol, nonylphenol, phenylstearyl alcohol and 1-naphthol. Other useful hydroxyl group-containing compounds include polyoxyethylene ethers of oleyl alcohol and polypropylene glycol having an average molecular weight of about 400. Other useful liquids include cyclic alcohols such as 4- (t-butyl) cyclohexanol and menthol, aldehydes including salicylaldehydes octylamine, tetradecylamine and hexadecylamine, secondary amines such as bis (1-ethyl-3-methylpentyl) amine and ethoxylated amines including N-lauryl-diethanolamine, N-tallow fatty-diethanolamine, N-stearyl-diethanolamine and N-coconut-diethanolamine.

Additional useful liquids include aromatic amines including N-sec-butylaniline, dodecylaniline, N, N-dimethylaniline, N, N-diethylaniline, p-toluidine, N-ethyl-O-toluidine, diphenylamine and aminodiphenylmethane, diamines including N-erucyl-1,3-propanediamine and 1,8-diamino-p-mintan, other amines including branched tetraamines and cyclododoylamine, amides including coconut fatty amide, hydrogenating tallow fatty acid octadecylamide, erucamide, N, N-diethyltdluamide and N-trimethylpolamide stearamide, saturated aliphatic esters including methyl caprylate, ethyl nurate, isopropyl myristate, ethyl palmitate, isopropyl palmitate, methyl zinc- ... v www-: wv - a ...., -....., 7 .., _. _. 13 7708653-6 stearate, isobutyl stearate and tridecyl stearate, unsaturated esters including stearyl acrylate, butylundecylenat and butyl oleate, alkoxy esters including butoxyethylstearate and butoxíetyloleat, aromatic fi c esters including vinylfenylstearat, isobutylfenylstearat, tridecylfenylstearat, methyl benzoate, ethyl benzoate, butyl benzoate, benzyl benzoate, phenyl laurate, phenyl salicylate, methyl salicylate and benzyl acetate; diesters including dimethylphenylene distearate, diethyl phthalate, dibutyl phthalate, diisooctyl phthalate, dicapryladipate, dibutyl sebacate, dihexyl sebacate, diisooctyl sebacate, dicapryl sebacate and dioctyl maleate. Additional useful liquids include polyethylene glycol esters including polyethylene glycol (having an average molecular weight of about 400), diphenyl stearate, polyhydroxy esters including castor oil (triglyceride), glycerol monostearate, glycerol monooleate, glycerol dietooletylpolate, glycerol diolithofilstearate Generated compounds including hexachlorocyclopentadiene, octabromobiphenyl, decabromodiphenyloxide and 4-bromodiphenyl ether, hydrocarbons including 1-nonene, 2-nonene, 3-undecene, 2-heptadecene, 2-nonadecene, 3-eicosene, triphenylmethadecane, 9-nonmethane methane and trans-stilbene, aliphatic ketones including 2-heptanone, methylnonyl ketone, 6-undecanone, methyl undecyl ketone, 6-tridecanone, 8-pentadecanone, 11-pentadecanone, 2-heptadecanone, 8-heptadecanone, methylheptone quetone ketone ryl ketone, aromatic ketones including acetophenone and benzophenone and other ketones including xanthone. Additional useful liquids include phosphorus compounds, including trixylenyl phosphate, polysiloxanes, Muget hyacinth (An Medgenaebler, Tnc), Terpineol prime No. 1 (Givaudan-Delawanna, Inc.), Bath Oil Fragrance 5864 K (International Flavor & Fragrance, Inc.), Phosclere P31SC (organophosphite), Phosclere PS76 (organophosphite), styrenated nonylphenol, quinoline and quinaldine.

For the formation of microporous polymer products with polystyrene, useful liquids include tris-halogenated propyl phosphate, aryl / alkylphosphite, 1,1,2,2-tetrabromoethane, tribromoneopentyl alcohol, 40 Z Voranol C.P. 3600 polyol and tribromoneopentyl alcohol 60%; tris-β-chloroethyl phosphate, tris (1,3-dichloroisopropyl) phosphate, tris (dichloropropyl) phosphate, dichlorobenzene and iododecanol.

In the preparation of microporous polymers using polyvinyl chloride, useful liquids include aromatic alcohols including methoxybenzyl alcohol, 2-benzylamino-1-propanol and other hydroxyl group-containing liquids including 1,3-dichloro-2-propanol. Additional useful liquids include halogenated compounds including Pure Master T33P (tetrabromophthalic acid diester) and aromatic hydrocarbons containing trans stilbene.

In addition to this, microporous products have been prepared according to the invention from other polymers and copolymers and mixtures. Thus, for the preparation of microporous products of styrene «butadiene copolymers, useful liquids include decyl alcohol, N-tallow fat-diethanolamine, N-coconut fat-diethanolamine and diphenylamine. Useful liquids for preparing microporous polymers from ethylene-acrylic acid copolymer salts include N-tallow-but-diethanolamine, N-coco-fatty-diethanolamine, di-butyl phthalate and diphenyl ether. Microporous polymeric products using impact resistant polystyrene can be prepared by using liquids such as hexabromobiphenyl and alkyl / aryl phosphite. Hot "Noryl" polyphenylene oxide-polystyrene blends (General Electric Company) microporous polymers can be prepared using N-coconut-diethanolamine, N-tallow-diethanolamine, diphenylamine, dibutyl phthalate and hexabromophenol. Microporous polymers from blends of LD polyethylene and chlorinated polyethylene can be prepared using 1-dodecanol, diphenyl ether and N-tallow-diethanolamine. Using 1-dodecanol as a liquid, microporous polymer products can be prepared from the following mixtures: polypropylene-chlorinated polyethylene, HD-polyethylene-chlorobab polyctene, HD-polyethylene-polyvinyl chloride and HD-polyethylene and acrylonitrile-butadiene »styrene terpolymers (ABS) . For the preparation of microporous products from polymethyl methacrylate, 1,4-butanediol and lauric acid have proved useful. Microporous nylon 11 can be prepared using nanocarbonate, 1,2-propylene carbonate or tetramethylusulfone. Hentol can also be used to make microporous products from polycarbonate.

Selection of the concentrations of polymer and liquid The amount of liquid used is determined by reference to the binodial and spinodal curves of the system, Fig. 1 showing illustrative curves. As shown therein, Tm represents the maximum temperature of the binodial curve (ie the maximum temperature of the system at which binodial decomposition will take place), Tucs represents the upper critical solution temperature (ie the maximum temperature at which spinodal decomposition will take place), øm represents the polymer concentration at the temperature Tm, øc indicates the critical concentration and øx represents the polymer concentration required in the system in order to obtain the unique microporous polymer structures according to the invention. Theoretically, øm and øc should be practically idvn- tical. However, as is known, due to the molecular weight distributions of commercially available polymers, øc can be about 5% by weight greater than the value fi of øm. For the preparation of the unique microporous polymers according to the invention, the polymer concentration øx used for a particular system must be greater than øc. If the polymer concentration is lower than øc, the phase separation occurring during cooling of the system will result in a continuous liquid phase with a discontinuous polynphase. By using the correct polymer concentration, on the other hand, it is ensured that the continuous phase which will be formed during the cooling of the system to the phase separation temperature will be the polymeric phase, as required to obtain the unique microcellular structures according to the invention. . As will be appreciated, the formation of a continuous polymer phase at the phase separation likewise requires that a solution be formed initially. If the process of the invention is not followed and a dispersion is initially formed, the resulting microporous product will be similar to that obtained by sintering polymer particles.

It will thus be appreciated that the useful polymer concentration and amount of liquid that may be used will vary with each system. Suitable phase diagrams for several systems have already been developed.

However, if a suitable curve is not available, such a curve can be easily prepared in a known manner. A suitable technique is stated, for example, in Smolders, van Aartsen and Steenbergen, Colloid - Z. u. Z. Polymere, ÃÅÃ »14 (1971) - A more general graph of temperature as a function of concentration for a hypothetical polymer-liquid system shown in Fig. 1A. The curve part from Y to a represents thermodynamic equilibrium for separation between the liquid phases. The curve part from a to ß represents equilibrium for separation between liquid phase and solid phase, which is expressed in the normal freezing point reduction curve for a hypothetical liquid-polymer system. The upper shaded area represents an upper immiscibility between the liquid phases that may occur in some systems. The dashed line represents the decrease of the crystallization temperature as a result of cooling at a rate sufficient to achieve a liquid-liquid-phase separation under thermodynamic equilibrium conditions. The flat part of the crystallization composition curve indicates a useful composition range which is a function of the rate of cooling used, as will be discussed in more detail.

Thus, for a given rate of cooling, the crystalline temperature can be plotted against the percentage of plastic or combustible liquid, thereby determining the concentration ranges of the liquid and polymer which at the given rate of cooling will give the desired microporous structures. For crystalline polymers, the determination of ...___ ...__. ~ _- | 7708655-6 M the useful concentration range by the crystallization curve of dotting is a viable alternative to the determination of an Easdian frame, as shown in fig. As an example of the former alternative, reference may be made to Fig. 55, which is a graph showing the temperature as a function of polymer / liquid / concentration, showing the melting curve at a heating rate of 16 K / min, and the crystallization curve for polypropylene and quinoline. over a wide range of concentrations. As can be seen from the crystallization curve, the appropriate concentration range extends at a cooling rate of 16 K / min from about 20 Å of polypropylene to about 70 Å of polypropylene.

Pig. 56 is a graph showing the temperature as a function of the polymer / liquid concentration of polypropylene and N, N-bis (2-hydroxyethyl) tallow fatty amine. The upper curve shows the melting curve at a heating rate of 16 K / min. The lower curves are in descending order of magnification of the crystallization curves at cooling rates of 8 K / min, 10 K / min, 32 Kfmín and 64 K / min. The curves provide evidence for About simultaneous phenomena that occur when the cooling rate is increased. First, the flat part of the interior shows a relatively stable crystallization temperature over a wide concentration range, after which the curve is deflected with increasing cooling rate, from which it appears that the actual crystallization temperature becomes lower the greater the cooling rate.

The second observable phenomenon is the change in the inclination of the crystallisation nucleus which occurs with changes in the cooling rate unit.

It can thus be seen that the flat area of the crystallization curve widens as the cooling rate increases. It can therefore be taken for granted that by increasing the cooling rate in a corresponding manner one can increase the viable concentration range for the formation of the microporous structures according to the invention and for the application of the processes according to the invention. From the foregoing it appears that in order to determine the workable concentration ranges for a given system, only a few polymer / liquid mixtures with representative concentrations need be prepared and cooled at a certain desired speed. After the dot of the crystallization temperatures, one easily finds the workable range of concentrations.

Pig. 57 is a graph showing the temperature as a function of the polymer / liquid concentration of polypropylene and dioctyl phthalate. The upper curve represents the melting curve of the system over a concentration range and the lower curve represents the crystallization curve over the same concentration range. Since the crystallization curve does not show any flat area over which the crystallization temperature remains substantially constant for a range of concentrations, it would be expected that the polypropylene / dioctyl phthalate system could not form microporous structures, and this is certainly the case.

To show the excellent correlation between the phasing diagram method for the determination of the viable concentration ranges for polymer and liquid and the crystallization method for making such a determination, reference may be made to Big. 58 and 59. Fig. S8 is a phase diagram of a polymer / liquid system of LD polyethylene and diphenyl ether determined by a conventional light scattering technique using a thermostatically controlled vessel. From the phase diagram in Fig. S5 it appears that Tm is at about 13,500 and øm at about 7% polymer. Furthermore, it appears that the curve for the crumb point at about 45% polymer concentration intersects the curve for the freezing point reduction, which thus indicates a workable concentration range of about 7 - 45% polymer.

One can compare the workable area determined from Big. So with the range that can be determined from Fig. S9, which shows melting curves for the same system at heating rates of 8 R / min and 16 K / min and crystallization curves for the same system at cooling rates of 5 K / min and 16 K / min. From the crystallization curves it appears that the substantially flat part of these extends from slightly below 10 Å polymer concentration to about 42-45 Å polymer, depending on the rate of cooling. The results obtained from the crystallization curves thus correspond surprisingly well with the results obtained from the phase diagram for the cloud point.

For non-crystalline polymers, it is believed that, instead of referring to a phase diagram as shown in Fig. 1, one can refer to a graph showing the temperature as a function of the concentration of the glass transition point. Fig. 58 is thus a graph showing the temperature as a function of the concentration of the glass transition point of loan »molecular polystyrene marketed by Pennsylvania Industrial Chemï (; I Lovporation under the name Píccolastic D-125) and 1-dodecanol at different concentrations.

By Elk. It can be seen that the glass transition temperature of the polystyrene / 1-dodecanol system is substantially constant from about P% polymer to SO 4 polymer. It has therefore been assumed that the concentrations along the substantially flat portion of the glass conversion curve, by analogy with the flat q fi jpn of the previously discussed crystallization curves, should be workable in the practice of the invention. A viable alternative to determining the phase diagram of non-crystalline polymer systems therefore appears to be to determine the glass conversion curve and operate in the substantially flat area of the Lur-., 'Iiwsas-a fl' "7708653-6 18".

In all the foregoing figures, the crystallization temperatures were determined with a DSC-2 differential scanning calorimeter, manufactured by Perkin-Elmer, or a comparable apparatus. Additional effects of cooling rates as well as the practical implementation of the invention will be discussed below.

When selecting the desired synthetic thermoplastic polymer), the compatible liquid and the potentially useful concentration range, one must, for example, select the actual concentration of polymer and liquid to be used. In addition to, for example, taking into account the theoretically possible concentration range, other functional considerations must be taken into account when determining the proportions used for a particular system. Thus, the resulting pour strength properties must be taken into account when determining the maximum amount of liquid that may be used. Consequently, the amount of liquid used must enable the resulting microporous structure to assume a sufficiently minimal "handling strength" that the microporous cell structure will not collapse. On the other hand, due to limitations with respect to viscosity, the particular equipment used may dictate the choice of the tolerable maximum polymer or plastic content. In addition, the amount of polymer used must not be so large that it results in the closure of the cells or other areas of the microporosity.

The relative amount of liquid used will also depend to some extent on the desired effective size of the microporosity, e.g. the special cell and pore size requirements for the end use. Thus, for example, the average sizes of cells and pores may tend to increase slightly with increasing fluid content.

In any case, the utility of a liquid and its workable concentration for a particular polymer can be readily determined experimentally using the liquid described.

The previously discussed parameters must of course be followed. However, landings of two or more liquids can of course be used, and the usefulness of a particular mixture can be examined as described herein. However, it may also be the case that a particular mixture may be useful, although one or more of the liquids individually may be unsuitable.

The special amount of a used liquid will of course also often be dictated by the end use. As illustrative examples, useful microporous products can be prepared from HD polyethylene and N, N-bis (2-hydroxyethyl) tallow fatty amine using about 30-90 liters, preferably 30-70% amine. With LD polyethylene and the same amine, the useful amount of the liquid can be about 29 ~ 90 Å, preferably 20 ~ 50%. When using diphenyl ether as a liquid, on the other hand, usable LD polyethylene systems do not contain more than Ca BO É of the liquid, with a maximum of about 60 É being preferred. With the use of 1-hexadecane together with Lh-polyethylene, it is possible to easily use up to about 90 Å or more of vinegar. When using polypropylene together with the previously mentioned tallow fatty amine, the amine can suitably be used in amounts of about 10 - 90 Å, preferably at most 55%. With polystyrene and 1-dodecanol, the concentration of alcohol can be about 20-90%, preferably about 39-70%. When using styrene-butadiene copolymers, the amine content can be about 20-90%. When using a system of decanol and a styrene-butadiene copolymer (SMR), the liquid content may suitably be about 40-90 3; with diphenylamine, the liquid content may suitably be in the range of about 50 - b0 å.

In the preparation of microporous polymers of the amine and an ethylene-acrylic acid copolymer, the liquid content may be in the range of about 30-70%; with diphenyl ether, the liquid content can be in the range of about 10 - 90 3, as is also the case when using dibutyl phthalate as solvent.

Forming the Homogeneous Liquid After forming the solution, it can then be processed into any desired shape or configuration. Depending on the special system used, the thickness of the object can generally vary from an approximately 25 .mu.m thin film or less up to a relatively thick block with a thickness of about 65 mm or even larger. The possibility of forming blocks thus opens the way for the microporous processing of the material into any desired complicated shape, e.g. using ordinary extrusion, injection molding or other related technology. The practical considerations in determining the range of thicknesses that can be obtained with a particular system include the rate at which the viscosity of the system increases upon cooling. The higher the viscosity, the thicker the structure L can generally be. Consequently, the structure can have any thickness as long as a strong phase separation does not occur, ie two discernible layers become visible.

It should be emphasized that a phase separation between the liquids, if allowed to take place under thermudynamic equilibrium conditions, will result in a complete separation into two separate layers. One layer consists of molten polymer, which contains the soluble amount of the liquid, and a liquid layer, which contains the soluble amount of the polymer in the liquid. This condition is represented by the pinodial curve in the phase diagrams of Figs. 1 and 1A. It is obvious that a limitation on the size of an article that can be produced is determined by the heat transfer properties of the mixture, since the cooling rate in the center of the article, if the article is thick enough and the heat transfer poor enough, may be slow enough for the system to approach thermodynamic equilibrium conditions and result in a phase separation in distinct layers as previously described. Increased thicknesses can also be achieved by adding small amounts of thixotropic materials. By adding colloidal silica before cooling, for example, the usable thicknesses are significantly increased, even though the addition does not adversely affect the characteristic microporous structure. The amounts required in each particular case can be easily determined.

Cooling_§ of the homogeneous solution The above discussion shows that the solution, regardless of the type of processing (eg casting into a film or the like), must be cooled to form something that behaves and looks like a solid body. The resulting material must have sufficient integrity to not break during handling, e.g. when grasping it with your hand.

Another test to determine if the required system has the desired structure is to use a liquid which is a solvent for the liquid present in the system but not for the polymer. If the material breaks, the system did not meet the necessary criteria.

The cooling rate of the solution can be varied within wide limits. In the ordinary case, although no external cooling needs to be resorted to, it is sufficient, for example, to cast a film by pouring the hot liquid system onto a metal surface heated to a temperature which enables the film to be drawn off or, alternatively, to form a block by casting on a substrate under ambient conditions.

As mentioned earlier, the cooling must take place fast enough so that the separation between the liquid phases does not take place under thermodynamic equilibrium conditions. The cooling rate can also have a significant influence on the resulting microporous structure. For many polymer / liquid systems, the phase separation between the two liquids, if the cooling rate is low enough but still meets the above criteria, may result in almost simultaneous formation of a plurality of equal droplets of liquid. If the cooling takes place at such a rate that the plurality of liquid droplets are formed, the resulting microporous polymer, as long as all the other conditions discussed here are met, will have the previously described essence in the microcellular structure. .

It is generally believed that the unique structures of the microporous polymers of the invention are achieved by cooling the liquid system to a temperature below the binodial curve shown in Fig. 1, thereby initiating liquid-liquid phase separation. In this state, sprouts of mainly pure solvent will begin to form. When the cooling rate is such that the cellular microstructure is formed. it is also believed that each such germ, as it continues to grow, is surrounded by a polymer-rich area which increases in thickness while being depleted of liquid. This polymer-rich area eventually resembles a film or film covering the growing drop of solvent. As the polymer-rich area continues to thicken, the diffusion of additional solvents through the membrane decreases. The growth of the liquid droplet decreases correspondingly until it ceases, when the liquid droplet reaches its maximum size. At this stage, the probability of forming a new germ is greater than that the large liquid drop will continue to grow. However, in order for this growth behavior to be achieved, germination must be initiated by spinodal rather than by binodial decomposition. The cooling is carried out in such a way that a variety of practically equal-sized liquid droplets are formed in a continuous polymer phase almost simultaneously. If the decomposition does not take place in this way, the cell structure will not be formed either. The appropriate disintegration method is generally achieved under conditions which ensure that the system does not reach thermodynamic equilibrium until at least the germination or droplet growth has been initiated. In terms of process technology, this can be achieved by simply letting the system cool down without exposing it to mixing or other shear forces. The time parameter can also be important in the production of relatively thick blocks, which in such cases makes a faster cooling desirable.

Within the range over which cooling results in the formation of a plurality of liquid droplets, there is a general indication that the rate of cooling may affect the size of the resulting cells, with increasing cooling rates resulting in smaller cells. In this connection, it has been observed that an increase in the cooling rate from about 8 K / min apparently results in a decrease in the cell size to half for a microporous propylene polymer. External cooling can thus, if desired, be used to control the final cell and pore size, as will be discussed in more detail. : It is not entirely clear in what way the connecting channels or pores are formed in the cell structure. Although we do not want to commit to any particular theory, there are various possible mechanisms for explaining this phenomenon. The formation of the pores may consequently be due to heat shrinkage of the polymeric phase on cooling, the solvent droplets behaving as uncompressible spheres when the solvent has a smaller coefficient of heat evolution than the polymer. Alternatively, and as already pointed out, the polymer-rich phase, even after the solvent droplets have reached their maximum strength, will still contain some residual solvent and vice versa. In the event of further cooling of the system, further phase separation can thus take place. The remaining solvent in the polymer-rich film can therefore diffuse to the solvent droplet, whereby the volume of the polymer-rich film decreases and the volume of the solvent droplet increases.

This can result in the polymeric membrane weakening and the increase in volume of the solvent phase can result in an internal pressure which spreads through the polymeric membrane and connects neighboring droplets to each other. In connection with the latter mechanism, the polymer itself may redistribute to a more compact state as the remaining liquid migrates out of the polymeric membrane, e.g. by crystallization when this type of polymer is used. In such a situation, the resulting polymeric membrane would probably shrink and show defects or holes, probably wholly in the particularly weak areas. The weakest areas could be expected to be located between adjacent drops. In this case, the holes would form between the neighboring droplets and result in them being forced to communicate with each other. In any case, and apart from the mechanism, the connecting pores or channels are formed when the process is carried out as described above.

Another explanation for the mechanism by which the pores are formed has been based on the "lmrangoni effect", discussed L Harangoní, C, ïyovo Cimento / 2 / 5-6.239 (lë7l); 3,97,193 (lb7b) and Harangonl, C, ¿nn.Phys.Lp '. (l71), 143,337. The ßhrangoni effect has been used to clarify the phenomenon which occurs when sprayed beverages spontaneously drain from the sides of drinking glasses, in particular the mechanism which npp «occurs when a condensed droplet flows back into the mass of the liquid. The liquid in the droplet first penetrates the liquid mass, followed by a rapid backflow of a part of the liquid into the droplet. he has established the theory that a similar physical phenomenon occurs with the small droplets of liquid formed as a result of the liquid-liquid-Easseparatinnan.

Thus, one droplet may meet another and the liquid from one may penetrate into the other, accompanied by a rapid separation of the two droplets- * Uk .ww- X CA! 23 77086 "-6 pairs, possibly then leaving some of the liquid which connected the two droplets and forms the starting point for the connecting pores in the structure. A later discussion of the Maranuuni effect can be found in Charles ä Mason, J. Colloid ”§Gi¿, li, 236-277 (1960).

If the cooling of the homogeneous solution takes place fast enough, the liquid-liquid separation can take place under clay-equilibrium conditions, but a significant solidification of the polymer can take place so fast that no significant germination with concomitant growth can take place. In such a case, a plurality of small droplets of liquid will not be formed, and the resulting microporous polymer will not have the determined cell structure.

Thus, under certain circumstances, it is possible to obtain different microporous structures by using exceptionally high cooling rates. For example, if a solution of 75 parts of N, N-bis (2-hydroxyethyl) -alga fatamine and 25 parts of polypropylene is cooled at rates ranging from 5 K / min to about 1350 K / min, the cellular microstructure is formed. The main effect of the different cooling rates in the uninhabited area on the composition is the change in the absolute cell size. tissue cooling rates of about 2000 K / min are achieved, the microstructure assumes, for example, a fine tip-like, non-cellular appearance. When a solution of 60 parts of N, N-bis (2-hydroxyethyl) tallow fatty amine and 40 parts of polypropylene is treated in the same way, cooling rates greater than 2900 K / min must be achieved before the tip-like non-cellular struh turu is formed.

To investigate the influence of the cooling rate on the cell size of the cell structure, and to examine the rate of cooling required for a conversion from the formation of the cellular structure to the formation of a structure without definite cells, Prepare homogeneous solutions with varying concentrations of pullyrup and N, N-bis (2-hydroxyethyl) tallow amine. In this examination, the previously mentioned differential scanning calorimeter of type DSC-2 Lillmmmmans with a standard X-ray equipment and a scanning electron microscope was used.

Since the DSC-2 is capable of a maximum cooling rate of about 83 K / min, a temperature gradient rod was also used. The temperature grad1cnL ~ rod was a brass rod that gave a temperature difference of more than 2090 K over its one meter long length, on which samples could be placed.

An infrared camera was used to determine the temperatures of the samples by first focusing the cameras on a beaker, which was placed in ... O 1 - the nearest of the ten rod layers to a temperature of 110 L, matt with a thermocouple. _. __-....._..._.._........_.._.......... I 7708653-6 24 Camera emlsslvíLeLsLouLroll lusfälldos dävoíler ljlls ka: rund lvmperaturavlüsuing dverensstämde med tevmoelemencels.

For each run, the fight was focused on QLL place where vu givvw cups with the sample solution would cool. Háqarøn with the sample is then placed on the temperature gradient rod for two minutes. Xdr hugager was removed from the bar to be placed in LamerafälLnt, ssnrrados oil stopwatch. As soon as the camera showed that the beaker had cooled to 11006, the clock was stopped and the time was recorded. The determined cooling conditions were thus based on the time it took for the sample to cool over a temperature difference of about 100 K.

It was found that the limiting factor on the cooling rate was not the amount of material to be cooled. Although part 513 showed that heavier samples cooled more slowly than lighter ones, it was noted that the silicone oil used on the bottom of the beaker for the thermal conductivity between the beaker and the stand had a significant influence on the cooling rate. The highest cooling rates were thus obtained by placing a beaker without any silicone oil on a block, and the read cooling rates were achieved with a beaker which was filled with a thick layer of silicone oil and placed on a paper.

Five samples of polypropylene were prepared, containing from 0 to WW W W, N - bls (2-hydroxylethyl) tallow fatty amines, for use in examining the effect of the rate of cooling on the resulting structures.

Approx. 5 mg of each of the samples was heated on BbC ~ 2 l of closed beakers with a heating rate of 40 K / min to a holding temperature of 175% for the sample with 20 fi of polypropylene, 230 ° C for samples, propylene, 245OC for the sample with 60% polypropylene, ZUSOC for the sample with SO% polypropylene and ZSOOC for the sample of 100 S polypropylene.

Each of the samples was heated to and maintained for X min at the current holding temperature before cooling. When the samples were cooled to the desired rate of cooling, the N, W-bis (2-hydroxy-Lyl} tallow fatty amine was extracted from the sample with methanol and the sample was analyzed. The results are summarized in Table T, which shows the sorrel numbers of the cells, in μm, in the All oil sizes were determined by measurements from the residual sulfur micron microns. 7 7708653-6 Table I Cooling rate 5 K / min 20 K / min 40 K / min 80 K / min Composition O% amine None (1) None (1) None ( l) Tngen (1) 20% amine 0,5 (2) 0, S (2) Ingen (3) Ingen 3 40 få amin 2,504) 2,09) Lou) o, 7 (5) 60% amin 4,0 3.0 2.0 1, S (6) 80 f? amine 0.5 4.0 3.0 3, o (6) (1) Some irregular holes present (2) Approximation of the largest cell size (3) Porosity probably too small to be measured (4) Some small cells present in about 1/10 size of larger cells (S) Other small cells that are too small to be measured (6) Some formation of non-cellular structure A further study of the influence of the cooling rate was performed using samples containing 20% polypropylene and 80% N, N-bis (2-hydroxyethyl) tallow fatty amine on the temperature gradient rod. Five such samples were cooled at different rates from a melting temperature of 21,000, with the results summarized in Table II, showing the sizes of the ore in μm, using the same procedure as in obtaining the data for Table I.

Table II Cooling rate ZOO K / min S70 K / min 1350 K / min 1700 K / min Composition 50% amine 0.5-3 0.5-1.5 1.5-2.5 non-cellular From Tables I and II It can be seen that the cell sizes in the resulting compositions generally decrease with increasing cooling rates.

In view of the polymer / liquid system of 20% polypropylene and 50% N, N-bis (2-hydroxyethyl) tallow fatty amine, it is further found that a conversion in nature nv the resulting polymer from a substantially cellular structure to a non-cellular -cellular structure occurs at a cooling rate between about 1350 K / min and 1700 K / min. Such a transformation in the resulting structure corresponds to the fact that the polymer becomes substantially solidified after the initiation of the liquid-liquid phase separation but before the formation of a plurality of liquid droplets, as discussed earlier.

Five more samples of 40 l of polypropylene Oßh 60 3 N, N-bis (ï-hydf fl xt. .___ _: v-ffm ': ~ _ fl _..- 7708653-6 u * ethyl) ta1gfetamine were prepared and cooled at rates from 690 K / min to over 7000 K / min, from melting temperatures of QJSUC, in accordance with the procedure discussed above. For such a concentration of the polypropylene and the amine, it was found that the conversion from cellular to non-cellular structure takes place at a cooling rate of about 2000 K / min.

To test the crystallinity of the structures prepared over a range of cooling rates, the final line was presented with three samples of 20 Å polypropylene and 50 Å N, ¥ bis (2-hydroxyethyl) tallow fatty amine and cooled at speeds of 20 K / min, 1900 K / min. min and 6500 K / min. From the DSC-2 data for such samples, it was found that the degree of crystallinity in the three samples was almost equal. It can thus be seen that variations in the rate of cooling have no significant influence on the crystallinity of the resulting structures. However, it was found, as expected, that the crystals formed became less perfect as the rate of cooling increased significantly.

Removal of the liquid When the homogeneous solution of polymer and liquid is formed and the solution is then suitably cooled to form a material of suitable handling strength, the microporous product can then be formed by the removal of the liquid, e.g. by extraction with a suitable solvent for the liquid, which of course must at the same time be a non-solvent for the polymer in the system. The relative miscibility or solubility of the liquid in the solvent used will to some extent determine the efficiency of the extraction time required for the extraction. The extraction or leaching can, if desired, also be carried out at an elevated temperature, which is below the softening point of the polymer, in order to shorten the extraction time thereby. Illustrative examples of useful solvents are isopropanol, methyl ethyl ketone, tetrahydrofuran, ethanol and heptane.

The time required will vary depending on the liquid used, the temperature used and the degree of extraction required. In some cases, for example, it may be unnecessary to extract 100 Å of the liquid used in the system and smaller amounts can be tolerated, the tolerable amount depending on the requirements set for the intended use. Thus, the time required may vary anywhere in the range from several minutes or perhaps less to more than 24 hours or more, depending on many factors, including the thickness of the sample.

The liquid can also be removed in another known manner. As illustrative examples in other ways for the removal of the liquid may be mentioned vapor deposition, sub «limntlon and constriction.

It should also be noted that the cellular microporous polymer structures of the invention, using conventional liquid extraction methods, can release a liquid present in the structure in a manner approaching zero, i.e. the release rate can be substantially constant after, perhaps, an initial period of high release rate. In other words, the release rate can be independent of the amount of liquid released. The rate at which liquid is extracted since, for example, 3/4 of the liquid is removed from the structure is thus approximately the same as when the structural iron was half filled with liquid. An example of such a system which shows a substantially constant release rate is the extraction of ¶, N-bis (2-hydroxyethyl) tallow ethamine from polypropylene with isopropanol as extractant. In any other situation, there will probably also be an initial initiation period before the release rate becomes identifiable. When the release of a liquid is allowed to proceed by evaporation, the release rate tends to be first class.

Characterization of the microporous polymers Cell structure When the polymer / liquid solution is cooled in such a way that a plurality of liquid droplets are formed in the manner previously described, and the liquid is removed, the resulting microporous product forms a relatively homogeneous cell structure which, seen in microscope, consists nv a series of mainly spherical, closed microcells that are essentially evenly distributed in the structure. Neighboring cells are connected to each other by smaller pores or channels. You can see this basic structure on the microphotos in fia. 4 and S. It should be noted that the individual cells are in fact closed, although on the photomicrographs they appear to be open due to the breaks that have occurred during the sample preparation for photography. On a micro scale, the structure, at least for the crystalline polymers, appears to have planes similar to the cleavage planes along the edges of crystal growth (see Fig. 12, and has a coral-like appearance (see Fig. 3). The cellular microstructure can be further likened to zeolite structures, which contain specific areas of “chambers” and “channels.” The cells correspond to the larger chambers of the zeolite structure, while the pores correspond to the channels.

In the cell structure, the average diameter of the cells 1 will generally vary from about 0.5 microns to about 100 microns, with about 10 microns 50 microns being more typical, while the average diameter of the pores or connecting channels typically appears to be about an order of magnitude smaller. Thus, if the cell diameter of a microporous polymer structure according to the invention is, for example, about 1 Pm, the average diameter of the pore or connecting channel will be about 0.1 Pm. As previously pointed out, the cell diameter as well as the diameter of the pore or channel will depend on the actual polymer-liquid system, the rate of cooling and the relative amounts of polymer and liquid used. However, a different area of the cell / pore ratio is possible, e.g. from about 2: 1 to about 200: 1, and typically from about 5: 1 to about 40: 1.

As can be seen from the many figures, it may appear that some of the cellular microporous polymeric products shown by way of example do not have the unique microcellular structure described herein. It is emphasized here, however, that in some cases this structure may be covered by further modifications resulting from the particular liquid or polymer or the relative amounts used. This coating can be complete or partial, ranging from small, polymer-adherent polymer particles to large "film-type" polymer aggregates, which on the microphotons tend to completely obscure the basic structure. As stated in Eig. 21 and 25, for example, adhere small polymer beads to the cell cavities of the structures. These additional formations can be understood by reference to the previously described germination and growth process. Thus, in systems with extremely high levels of solvent or liquid, the cavity will typically have a maximum BH Jåmföfêlseviß St0P size. This also means that the time required for the cavity or droplet to reach its maximum size also comes nt! extended. During this time it is possible an additional sprouts car dns close to each other._Two or more sprouts can then come into contact with each other before they reach their maximum size. In such cases, the resulting cell structure has less integrity and somewhat less regularity than the previously described seed structure. In addition, even after the liquid droplet has reached its maximum size, depending on the system in question, the solvent or liquid phase will still contain a certain amount of residual polymer or vice versa. In such situations, some additional residual phase separation may occur as the system continues to cool. If the remaining polymer is readily separated from the solution, spheres of the polymer can be formed, as shown in Big. 21 and 25. If the remaining polymer on the other hand diffuses to the polymeric membrane, the walls will appear blurred and irregular, thus giving the structure a "foiled type". Henna structure of "Oiled type" can only partially cover the oak structure. 7708653-6 fig. 2% and 29, or may cover the structure Completely,. . . N as shown in 1 lig. 6.

Some polymers also have a greater tendency to adopt a structure as seen in the "foiled type". thus, the microporous structures of LU polyethylene typically provide this kind of structure, probably due to the solubility of the polyecene in the particular liquids used. heat can be observed 1 fine. 14. Furthermore, this structure can also occur in such polymers as polypropylene, which otherwise have the basic structure, if the concentrations of the liquid used are extremely high. This can be easily unnerved by the contrast between the microporous product according to the figure. Û with its "foiled" structure and the basic structure according to Fig. B, where the polymer content is 40% by weight compared with 10 Å of structural polypropylene in pure according to FIG. 6.

For most uses, it is preferred to use a system that results in the formation of the cellular base structure. The relative homogeneity and regularity of this structure gives indeterminate results, as required for filtration. However, the foiled type of structure may be more desirable in cases where structures with a relatively large specific area are desired, e.g. in ion exchange processes and various adsorption processes.

As can also be observed, some of the structures have small holes or openings in the cell walls. This phenomenon can also be understood by reference to the concept of germination and growth. Thus, in a section of the system in which a few in-room associated liquid droplets have already reached their maximum size, each droplet may be enclosed by a polymer-rich membrane. In some cases, however, some solvents may be trapped between the entrapped the droplets but cannot continue their migration to the larger droplets due to the impermeability of the membranes. In such cases, therefore, a germ of the liquid may form and grow, resulting in a small cavity being embedded adjacent to the larger droplets. After extraction of the liquid, the smaller droplets will leave small holes or openings. This can be observed in 11, Another similar to the structures shown in Figs. 1B and 20. property of the cell structures according to the invention applies to the specific area of the structures.

The theoretical specific area of the cellular microporous structure of interconnected spherical cavities with about 5 μm diameter 4 mz / g. It has been found that the microporous polymers prepared according to the present invention need not be limited to the theoretical limit value for the specific area according to the & E.T. method described in the specific area. Bestäm- irunauer, S, Emmett, PH och Teller, 3, "fhe Adsorptíon of Gases in Multimolecular Layers", J.Am.Chem.Soc., 60, 339-316 (l fl ßå), has shown areas far larger than the theoretical model not relating to the pore volume, as shown in Table III, for microporous polymers [prepared from polypropylene and N, N-bis (2-hydroxyethyl) tallow phthalamine.

Table III Porosity Specific area% m / s ë9.7 96.2 72.7 95.5 00.1 95.0 50.5 90, & 2 & .9 86.5 By careful heat treatment of the microporous polymer, the specific area can reduced without affecting the basic use. Micropurous polypropylene, prepared with the 75 K porosity using N, N-bis (2-hydroxyethyl) tallow fatty amine as the liquid component, was extracted and dried at temperatures not exceeding room temperature and then heated to reduce the specific surface area. The original specific surface area was 96.9 m2 / g. After eleven 40 minutes of heating period at 62 ° C, the surface area decreased to 66 m2 / g. An additional 66 hours of heating at 6000 reduced the specific surface area to 51.4 m2 / g. At S2 h heating of another sample at QOOC, the surface area decreased from 96.9 to 33.7 mg / g. When examined with a scanning electron microscope, the microporous structures showed no significant change. These results are summarized in Table IV.

Table IV I) a '4 Treatment Speciflk area, m' / g \ ndr | ng, n no 96.9 ~ eleven 40 min treatments at 62% 66.0 3: ymfvrligafe 66 h at 6o ° c 51.4 47 sz It is quite clear that one of the unique features of the cellular structures of the invention is the presence of both distinct, substantially spherical, entrapped microwaves, which are uniform. __... 4 _. \ ...., .f 3 7708653-6 distributed in the structure, and distinct pores, which connect the cells to each other and have a smaller diameter than the cells. Furthermore, these cells and the connecting pores have virtually no orientation in space, and can be classified as isotropic. There is thus no pro ~ directional direction, e.g. for the flow of a liquid through the structure.

This is in stark contrast to previous material that does not show such a cell structure. Many previous systems lack a definable structural configuration. It is therefore quite surprising that a microporous structure can be produced with such a degree of uniformity, which can be particularly desirable for many applications that require extremely smooth materials.

The cell structure can be defined by the ratio of the average diameters of the cells (C) to the pores (P). Thus, as mentioned, the C / P ratio should vary from about 2 to about 200 microns, with the range of about 5-100 microns being typical and about 5 to 40 microns being even more typical. Such a C / P ratio distinguishes the cell structure according to the invention from any previously known microporous polymer product. Since there is previously no known synthetic thermoplastic polymer structure with distinct cells and pores, all such prior art materials must be considered to have an L / P ratio p 1.

Another means of characterizing the cell structures according to the invention is through the so-called sharpness factor S. The S-factor is determined by analyzing a mercury penetration curve for the given structure.

All of the mercury penetration data discussed in this specification were determined using a Micromeritics Mercury Penetration Porosimeter, Model 910 series. The S-value is defined as the ratio between the pressure at which 85% of the mercury penetrated and the pressure at which 15 ß of the mercury penetrated. This ratio is a direct indication of the variation in pore diameter over the central 70% amount of the pores in a given sample, when the pore diameter is equal to 176, t divided by the pressure expressed in psi.

The S-value is then the ratio between the diameter of the pores at which 15 É of the mercury penetrated, and the diameter of the pores at which So Z of the mercury penetrated. In determining the 5-factor, the range of 0 - 15% and 85 - 100 ß penetration of mercury is disregarded.

The range from 0 to 15% is not taken into account, as the penetration in this range may be due to cracks introduced into the material as a result of the freeze cracking to which the material was subjected before the performance of the mercury penetration test. \ mn also disregards the ES - 100 1 range, as the data in this range may be retrieved from the sample compression instead of a sample compression instead of a sample of 7708653-6. actual intrusion of the mercury into the pores.

As is characteristic of the narrow pore size range of the products of the invention, the usual 5-value for such structures is in the range of from about 1 to about 30 microns, with 2 to 10 microns being typical and about 2 to 10 microns being more typical.

The average size of the cells in the structure varies from about 0.5 to about 100 microns, with about 1 to 30 microns being typical and about 1 to 20 microns more typically.

As mentioned, the cell size can vary depending on the special plastic and combinable liquid used, the polymer: liquid ratio, and the cooling rate used in the formation of the special microporous polymer. The same variable will also have an effect on the average size of the pores in the resulting structure, which usually varies from about 0.05 to about 10 μm, with about 0.1 - 5 μm being typical and about 0.1 - 1.0 Pm is more typical. All references to a cell and / or pore size in this specification, unless otherwise indicated, refer to the average diameter of such a cell or pore, expressed in Pm.

By determining the foregoing factors, cell size, pore size and S, for the cellular microporous polymers according to the invention, one can concisely define the cellular microporous polymers according to the invention. A particularly useful way of defining polymer number is through the logarithm of the relationship between the mean cell diameter L and the mean pore diameter P, i.e. log C / P, and the logarithm of the relationship between the sharpness function S and the mean cell diameter C, i.e. log 5 / C. Accordingly, the cellular microporous polymers of the invention have an Ion C / P value of from about 0.2 to about 2.4 and a 10 g b / C value of from -1.4 to about * 1.0. More commonly, the polymer has a log Lfr value of from about 0.6 to about 2.2 and a log b / C value of from about -0 "to about 0.4. The cellular structure of the invention, which results from the homogeneous solution cooling at the rate at which the polymer solidifies substantially prior to the formation of the plurality of liquid droplets, can be primarily characterized with respect to the narrow pore size distribution in the material along with the actual pore size and structure. uniformity in the room.

In particular, the non-cellular microporous polymers can be characterized by a sharpness function S, as described previously in connection with the cellular structures. The non-cellular structure shows b) to \ Q 1 CD CO Ck in (N 1. "'\ 5 values of from about 1 to about 30, with about 1 ~ 10 being preferred and about Ö ~ 0 being a more preferred range. However, when the pore size of the material ranges from about 0.2 to about 5 microns, the S value will vary from about 5 to about 10 and typically from about 5 to about 10. Such 5 values for olefin and oxidation polymers having a microporosity of such size has been unknown in the past, except in the case of highly oriented thin films made by stretching.As mentioned earlier, the porous polymers of the invention are practically isotropic.A cross-section between the polymers taken in an arbitrary plane in the rooms will thus to reveal practically the same structural shield.

The pore sizes of the non-cellular structures of the invention usually range from about 0.05 to about 5 μm, with the range of about 3.1 to 5 μm being typical and the range of about Ü, Z - 1.0 μm being typical.

It is obvious that a surprising feature of the invention is the possibility of producing isotropic microporous structures of olefin and oxidation polymers, with the structures having Phr sizes in the range from about 0.2 to about É pm and a sharpness value of from about 1 to about KO. It is particularly surprising that such structures can be produced in the form not only of thin films, but also in the form of blocks and intricately shaped shaped bodies. '.fë-Lli fi ší fl ä When forming a film or block by casting on a substrate, e.g. a metal plate, the surface of the microporous polymeric structure of the invention which is in contact with the plate will consist of a surface membrane which is non-cellular. In contrast, the second surface is typically predominantly open. The thickness of the membrane will vary slightly depending on the particular system as well as the special process parameters used. However, the thickness of the membrane is typically about the same as the thickness of a single cell wall. Depending on the particular conditions, the membrane may vary from one which is completely impermeable to the passage of liquids to one which shows a certain degree of permeability.

If, for the end use, a cell structure is desired throughout, the surface membrane can be removed in a number of different ways. As an illustrative example, the film could be removed using any of a variety of mechanical means such as grinding, puncturing the film with needles or grinding the film by feeding the film or other structure between rollers driven at different speeds. Alternatively, the membrane could be removed using a microtome. The film can also be removed by chemical means, ie by short-term contact with a suitable solvent for the polymer.

For example, if a solution of polypropylene in E, N-bis (2-hydroxyethyl) «tallow fatty amine is continuously sprayed as a thin film on an endless steel hand conveyor, the surface formed at the interface between the non-release and the steel strip will be effectively removed by applying a small amount of liquid solvent on the steel strip immediately before the place where the casting solution is applied. Useful liquids are materials such as isoparaffinic hydrocarbons, decane, decalin, xylene and mixtures such as xylene-isopropanol and decalin-isopropanol.

For some end uses, however, the membrane will not only be a non-harmful, but also a necessary component. As is known, for example in ultrafiltration or other operations where different types of membranes are used, a thin, liquid-impermeable film is used. Accordingly, in such applications, the microporous portion of the structure of the invention would have particular utility in supporting the surface membrane, which in such applications would have the function of a membrane. Completely cellular structures can also be produced directly by various techniques. Thus, for example, the polymer-liquid system could be extruded into air or a liquid medium, e.g. hexane.

The microporous polymer structures of the invention have, as previously described, cell and pore diameters with extremely narrow size distributions, which testify to the unique structures and their relative homogeneity. The narrow size distribution of the pore diameters is apparent from mercury penetration data, as can be seen from Pig. 30-33. The same general distribution is obtained regardless of whether the structure has the shape of a film (Figs. 30-32) or a block (Fig. 33). The characteristic pore size distribution of the microporous structure according to the invention is in stark contrast to the significantly wider pore size distribution features of previous microporous polymer products obtained by prior processes, e.g. those disclosed in U.S. Patent Nos. 310 SOS and 3,378 SO7, as will be discussed in more detail in connection with the examples.

For any of the microporous polymers prepared according to the invention, the particular end use will typically be decisive for the pore volume and pore size requirements. When used as a pre-filter, for example, the pore size will typically not be higher than 0.5 μm, while the pore sizes in ultrafiltration must be less than about 0.1 μm.

In such cases where the microporous structure is to function as a storage space for a functionally useful liquid, solidity considerations dictate the amount of pore volume in which controlled release of the entrapped functional liquid is involved. In such cases, the purge size will also be dictated by the desired release rate, with smaller pore sizes tending to see slower release rates.

When the microporous structure is to be used to convert a liquid polymer additive, e.g. a fire retardant, to a solid, usually requires minimal strength. However, in accordance with this minimum, it will typically be desirable to use as much liquid as possible, since the polymer only serves as a storage space or a carrier.

Microporous Polymers Containing Functional Liquids From the foregoing discussions, it should be understood that microporous products which, according to one aspect of the present invention, contain a functionally useful liquid such as polymer additives (eg, fire retardants) may be prepared which behave and can be processed as a solid body. For this purpose, the resulting microporous polymer can be filled with the desired functional liquid. This can be accomplished by conventional absorption techniques, and the amount of liquid absorbed will be substantially equal to the amount of liquid used in the first case in the formation of the microporous polymer. Any useful organic liquid can be used, of course, provided that the liquid is not a solvent for the polymer or otherwise attacks or degrades the polymer at the processing temperature. The microporous products containing the functionally useful liquid can be formed by or using microporous polymers having either cellular or non-cellular structure, such as the matrix or matrix in which the liquid is incorporated.

Likewise, such microporous products can be produced by a narrowing technique. According to this embodiment, the microporous polymer is first prepared as an intermediate. Thereafter, the liquid is displaced, either with the desired functionally useful liquid or with an intermediate displacement liquid. Instead of extracting it at. the liquid used in the preparation of the microporous polymeric intermediate, according to this embodiment the liquid is thus displaced in either case by customary pressure or vacuum displacement or by infusion. Any functional or intermediate displacement liquid can be used which could be used as the extraction liquid to form the microporous polymer, i.e. a non-solvent for the polymer but which nevertheless has some solubility or _. i. ....-.-.-., -._-_ ~ g (s) O ~ 7708653-6 miscibility with the liquid to be displaced. It is obvious that smaller amounts of the constriction liquid or liquids may remain after the constriction. The receivables for the final use determine the required efficiency of the narrowing.

Thus, in some cases, amounts of about 1% by weight may be tolerated.

If required, it is possible to remove practically the entire amount of the liquid or liquids to be displaced by repeated constrictions and / or by using liquids which can be easily removed by evaporation, ie a residual amount of liquid of less than From an economic point of view it is desirable to use a displacement liquid whose boiling point deviates slightly from the boiling point of the liquid to be displaced, in order for a recovery and re-use to be possible. For this reason, it is desirable to use an intermediate penetration fluid.

As is also apparent from the foregoing examples of useful polymer-liquid systems, a further method of making a polymer-functionally useful liquid material consists in refining the microporous polymeric intermediate without further processing, since numerous functionally useful liquids have been shown to be useful as a compatible liquid with special polymers for the formation of a solid, microporous polymer intermediate. Solid products which behave as solids can thus be worked up directly with liquids useful as lubricants, surfactants, lubricants, mosquito repellents, pesticides, polishes, stabilizers, plasticizers, drugs, fuel additives, fragrances, fire retardants, antioxidants or odor masking agents. , perfumes and the like. Hed LU polyethone can be provided with secticides, ring agents, for example useful intermediates containing lubricants or a plasticizer using the antenna of an aliphatic or aromatic ester having 8 or more carbon atoms or a non-aromatic hydrocarbon having 9 or more carbon atoms. Useful products containing a surfactant and / or a wetting agent can be prepared with LD-polyethylene using a polyethoxylated aliphatic amine having 8 or more carbon atoms or a nonionic surfactant. Hot polypropylene intermediates may be provided by the use of diethoxylated aliphatic amines having 8 or more carbon atoms. Polypropylene lubricants containing lubricants can be prepared using a phenylmethylpolysiloxane, while LD polyethylene intermediates containing sliding lubricants can be prepared using an aliphatic anion. with 12 - 22 carbon atoms. LD-polyethylene fuel additive intermediates can be prepared using an aliphatic amine having 8 or more carbon atoms or an aliphatic tertiary dimethylamine down to 12 or more. several hollow atoms. The tertiary amines can also form useful additive intermediates with methylpentene polymers. UD and LD polyethylene intermediates containing a stabilizer can be prepared using an alkylaryl phosphite.

Intermediates of LD polyethylene containing a fumigant can be provided using the glycerol mono- or diester of a long chain fatty acid having at least 10 carbon atoms. Alkylan products with fire retardants incorporated therein can be prepared with HH and LO polyethylene, polypropylene and a polyphenol oxide-polystyrene mixture using a polyhalogenated aromatic hydrocarbon having at least 4 halogen atoms per molecule. As mentioned earlier, useful materials must, of course, be liquid at the phase separation temperature. Other systems that have been found useful will be identified in connection with the examples.

For polypropylene, HD polyethylene and LD polyethylene, certain classes of ketones can also be used, which have proven to be particularly useful as animal repellents. be used generally in the practice of the invention. Such ketones may include saturated aliphatic ketones having 7 to 19 carbon atoms, unsaturated aliphatic ketones having 7 to 13 carbon atoms, 4-t-amylcyclohexanone and 4-methylcyclohexanone.

The invention will be described in more detail below with the embodiment. example. However, these are merely illustrative of the invention and are not intended to limit its scope. All parts and percentages are by weight unless otherwise indicated.

Preparation Procedure The porous polymeric intermediate grooves and microporous polymers described in the examples were prepared according to the following procedure: A. Porous polymeric intermediates The porous polymeric intermediates are prepared by mixing a polymer and a combinable liquid, heating the mixture to a temperature usually close to or above the plastic. softening temperature so that a homogeneous solution is formed, and then cooling of the solution, without exposing it to mixing or other shear forces, to form a macroscopically solid, homogeneous mass. When solid blocks of the intermediates are to be formed, the homogeneous solution is allowed to assume a desired shape by casting in a suitable container, usually made of metal or glass, and lüsninßew is allowed to cool under ambient room conditions, unless otherwise noted. The rate of cooling under room temperature conditions will vary depending on such factors as the thickness and composition of the sample, but will usually be in the range of about 10 to 20 K / min. The container typically has a cylindrical shape with about 20 - 65 m, in% ß the tube is typically filled to a depth of about 6 - 50 mm. In the production of films of the intermediates, the homogeneous solution is cast on a meta-plate heated to a temperature high enough for the solution to be drawn out into a thin film. The metal plate is then placed in contact with a dry ice bath to allow the film to cool rapidly below its solidification temperature.

B. Porous Polymers The microporous polymer is prepared by extracting the combinable liquid used in the preparation of the porous polymeric intermediate, typically by repeated washes of the intermediates in a solvent such as isopropanol or methyl ethyl ketone, and then drying the solid microporous mass. Examples The following examples and tables illustrate some of the various combinations of polymer and compatible liquid which may be used in the preparation of the porous polymeric intermediates of the invention and various prior art or commercially available microporous products. Solid blocks of the intermediates were prepared for all the Ge exemplified combinations, and in addition, films of the intermediates were also prepared using the procedure described above, as noted in the table. As indicated in the following tables, many of the intermediates for the preparation of microporous polymers according to the invention were used using a suitable solvent to extract the combinable liquid from the intermediate, and subsequent removal of the solvent, e.g. by evaporation.

Many of the combinable liquids illustrated in the following examples are, as noted in the tables, functional liquids with utility not only as combinable liquids but also as fire retardants, lubricants and the like. The intermediates prepared with such functional liquids are therefore useful as solid polymer additives and the like, and also as intermediates in the preparation of porous polymers. The functional fluids mentioned in the following examples are indicated as such by noting one or more of the following symbols under the column "Type of functional fluid": AF (anti-fog agent1); A0 (antioxidant); AR (animal repellent); FA (fuel additive); FG (fragrance); FR (fire retardant); IR (insecticide); L (lubricant 30 7708653-6 M (Drug); MR (mosquito repellent); OM (1uk masking agent); P (emollient); PA (polish); PE (pesticide); PF (perfume); 5 (lubricant); SF (surfactant) ) and ST (stabilizer).

Examples 1 - 27 Examples 1 - 27 in Table V illustrate the preparation of homogeneously porous polymeric intermediates in the form of cylindrical blocks with a radius of about 30 mm and a depth of about 50 mm, of HD polyatcu (UUPJ) and the combinable liquids which have been found to be useful, using the standard manufacturing procedure. The HJ polyethylene had been supplied by Allied Chemical under the name Plnskon AA SS-303, with a melt index of 0.2 g / 10 min and a density of 0.954 g / omg. Many of the exemplary intermediates were extracted to form porous polymers, as noted in the table. The details of the preparation and the type of functionally useful liquid are given in Table V: 7708653-6 4 ° Table V HDPE Ex. No. Liquid type and liquid É Liquid: Q Type of functional liquid Aliphatic saturated acids 1 capric acid * 75 230 --- Qgigära a1kaqg ; gg 2 decanolx 75 220 PP 3 1_ <10a @ kan01 * 75 220 -__ Secondary alkanols 2-undecanclx 75 220 --- 6-undecanolx 75 230 --- Aromatic amines 6 N, N-diethylaniline * 75 230 ___ Diesters 7 díbutyl sebacatx 70 220 L, P 8 dihexyl sebacat * 70 220 L, P _3221: 9 diphenyl ether 75 220 PF 10 benzylecev * 70 220 mf 11 hexnhromobenzene 70 250 Fk 2 hexabromobiphenyl 7§ 200 Fk 13 hexabromucyclodecan / O 250 FR 14 hexachlorocyclopene octabromubiphenyl 70 260 FK Hydrocarbons with terminal double bond gr 15 1-hexadecene * 75 220 --- K The liquid extracted from the solid material. i w-. fl x - - ¿_ _ _ M 7708653-6 §3§g; ¿_! (continued) ÉQÉÃ g¿¿g¿ yätskug and liquid ß liquid 29 Type of functional Xägska _____ Aromatic hydrocarbons 17 diphenylmethanex 75 220 UH 18 naphthalene * 70 zßø vw Aromatic ketones 19 acetophenone 75 ZOO PF Aromatic esters 20 bucylbenzoac ”75 Miscellaneous 21 N, N-bis (2-hydroxyethyl) -lattegatamine (1) * 70 250 --- 22 dodecylaminex 75 220 --- 23 N-hydrogenated tallow-diethanolamine SO 240 SP 24 Firemaster BP-6 (2) 75 200 --- zs Phosclere P31sc * (3) 75 220 sr 26 quinoline 70 240 M 27 dicocose febtamine (4) 75 zzo --- 5 The liquid extracted from the solid material. (1) (2) ._ .__-__. L.

A permanent internal antistatic agent with the following properties was used: K0kpunk fi = 215-2zo ° c / 1 drill; density (3200): 0.896 g / cm3 viscosity (32 ° c) = 476 ssu; Michigan Chemical Corporation's trademark for hexabrumo-bienyl, a fire retardant having the following properties: Softening point 72 ° C; density (2500): 2.57 g / cma; viscosity (110 c) = zoo-360 CP (ßrøokfield, spindle no. 3). * - ---- ~ - _. ...._ .., _..... ..__-__. fl._. _ ___ 7708653-6 42 Table VT LDPE g_¿g; _L¿) yätskec and liquid% liquid fi g Type of funkLi0_ fl sll; ¿EüæäsL ___ Aliphatic saturated acids 28 capylic acid * 70 210 --- 29 capric acid 70 190 --- 30 capr 190 --- 31 'lauric acid 70 220 --- 32 myristic acid * 70 189 --- 33 palmitic acid 70 156 --- 34 stearic acid 70 222 --- V 35 undecylic acid fi 70 203 --- g unsaturated aligetic acids É 36 erucic acid ( 2) * 70 219 - ~ - å 37 oleic acid * 70 214 PA * gggmatic acids 38 phenylstearic acid 70 214 --- 39 xylylbenzic acid 70 1bO --- K The liquid extracted from the solid material. (1) Union Carbide Company "Bakelite" polyethylene having the following properties: Density: 0.922 g / cm3; melt index 21 g / 10 min. (2) Cis-13-docosenoic acid; denstiet O, ê602 g / cmg; m.p. 33-34UC 43 Table VI (continued) 77Û8653 ~ 6 LQZE Ex.nr Liquid type and liquid% liquid 22 Type of functional Liquid Other Ggror 40 Acintol FA2 (pine fatty acids) (1) * 70 204 --- 41 olefinic acid L-6 * 70 206 --- 42 olefinic acid L-9 * 70 1: 0 _-_ 43 olefinic acid L-11 * 70 203 --- 44 rosin * 70 262 --- 45 tolylstearic acid 70 103 --- primary saturated acids 46 ce0y1a1k0h ° 1 * 70 170 --- 47 decyl alcoholx 70 220 PP 48 1-dodecanol * 7 200 --- 40 1-hepcadekan fl l ”70 168 --- 50 nonyl alcohol * 70 174 rv 51 1-0ktan01 * 70 178 --- 52 oleylaluohul * 70 206 FA S3 tridecylalkohnl 70 240 --- 54 1-undecanol * 70 1 $ 4 --- ss undecylenyl alcohol * 70 190 --- Secondary acids 50 dinonylcarbinol * 70 201 PF S7 diundecylcarbinol 70 226 --- 58 2-octanol 70 174 --- 50 2-undecane beer * 70 205 --- X (1) Arizona Chemical Company having the following composition and properties: total: 98.2% of total weight; linoleic acid, non-acidic: 47%; measured 0 898 g / cm Fatty acids, conjugated: 6%; oil 8%; density (25/25 C): the liquid extracted from the solid material. 's brand of a fatty acid mixture Bath: 3%; other fatty acids:; viscosity (30 C) = 94 SSU. 7708653-6 44 Table VI (Continued) EQÉÉ Ex. No. Liquid type and liquid ß liquid gg Type of functional liquid ”___ Aromatic alcohols 60 1-phenylethanolx 70 164 PF 61 1-phenyl-1-pentanol 70 196 - ~ - 62 phenylstearyl alcoholx 70 206 --- 63 nonylphenol * 70 220 sF, Ps Cyclic alcohols 6.4 44; -bu, cyclcy | <1011exano1. * 70 190 P3 65 nlentol * 70 206 m 'Other -OH-containing compound 66 Neodol-zs (1) * 70 mo --- 67 polyoxyethylene ethers of oleyl alcohol (2) 70 268 SF 6% polypropylene glycol-425 * (3) 70 --- SF Aldehydes 69 salicylaldehyde * 7o 188 wx the liquid extracted from the solid material. (1) Shell Chemical Company's trademark for their synthetic fat alcohol with 12-15 C atoms. (2) Croda, Inc.'s Volpo 3 surfactant with the following properties was used: Acid number: max. 2.0; cloud point, 1% water soluble, insoluble; HLB value, calculated: 6.6; iodine, Wijs: 57-62; pH of 3% aqueous: 6-7; hydroxyltalz 135-150. (3) Union Carbide Company's trademark for a glycol having the following properties: Apparent density (20/2000): .009 g / cm; hydroxyl number, average: 265; acid number: max. 0.2; pH at 25 DEG C. in 10: 6 isopropanol / aqueous solution: 4.5 ~ 6.5.

Wi * - «- -ßw 45 7708653-6 Table VI (continued) LQÉÉ ßx.nf liquid type and liquid% liquid 29 Type of funk fi i0ne1L liquid Primary amines 70 dimethyldodecylamine 70 200 FA 71 hexadecylamine * 70 207 FA 72 octylamine * 70 172 FA 73 tetradocylamine 70 186 FA Secondary amine 74 b1s (1-euyl-3-methylpenzyl) amine * 70 190 --_ Tertiary amines 75 N, N-dimethylsoleaphetuamine * (1) 70 198 FA 76 N, N-dimeuyl tallow feecamine * ( 2) 70 209 FA Ethoxylated amines 77 N-stearyl diethanolamine 75 210 SF, AF Aromatic amines 7 aminodiphenylmethane 70 236 --- 70 N-sec.butylaniline 70 196 --- 80 N, N-ethylaniline * 70 __- --- fi x N, N-aimecylaniline * 70 109 --- ë¿ diphenylamine 70 156 A0, P5 ag doaecylaniline * 70 204 -__ 54 phenylstearylaminex 70 205 --- 83 N-ethyl-0-toluidine * 70 182 --- ha p_t @ 1uidine * 70 104 --- x The liquid extracted from the solid material. (1) Than tertiary amine with the following properties was used: 3 Grumllngpunkt (ASTM): 38 C; density (25/4 C): 0.813 g / cm viscosity (25 ° C) = 59.3 SSU- (2) A tertiary amine with the following properties was used Melting point: -Zotill +5 C; gruglingspunktz 16 Cö density (25/4 C): 0.803 g / cm; viscosity (25 47 SSU.

C): rhäwt. 7708653-6 46 Table vr (continued LDPÉ Bx.nr Liquid type and liquid §_1§g§g¿: Q Type of functional fluid É7 1,8-diamino-p-menthane 70 lhä --- 88 N-erucyl-1, 3-propanediamine * 70 220 --- An§s fi_ am¿2ss 89 branched tetraamine L-PS (1) * 70 242 --- 00 cyclododecylamine * 70 159 --- Amides 91 k0k0sfettam1a * (z) 70 245 --- 92 N, N-diethyltoluamide 70 262 IR 93 erucaamidex (3) 70 250 L, P 04 hydrogenated tallow fatty amidex 70 250 L, P 95 bctadecylamide (4) »70 260 L, P 96 N-trimethylolpropane stearamide 70 255 L, P Aliphatic saturated estgâg 07 etynäufat * 70 175 --- vr ptylpalmitat * 70 171 --_ qo isobutylstearatx 70 194 L 100 isopropylmyristat * 70 192 --- IOI isopropylpylmitat * 70 255 --- 102 methylkaprylat 70 182 --- 1o3 methylstearate * 7o 105 --- 104 tridecyl stearate 70 202 L x The liquid extracted from the solid material 1) ¶ ~ phenylstearo-1,5,9,13-azatridecane. (2 An aliphatic_amine_with The following properties were used: U Appearance: fgäll; flash point: about 174 ° C; brinnpunkbz about lüí C. (3) An amide with the following properties was used: Density: 0.88 g / cm 2; melting point: 99-10900; flash point : ZZS C.

Jktadecylamide with the following properties was used: U Appearance: scales; flash point about 225 ° C; briunpunkt: cn 250 C Wiäpum fi m-.wß-f. ~ ~ - _. 1- 47 7708653-6 Table_! 1 (continued) LQÉÉ 3x.nr Liquid type and liquids Å_Liquid: Q Type nv functional Xëëpka Aliphatic unsaturated fl de esters 105 buty1 ° 1eat * 70 106 L 100 bucylunapcylenate * 70 205 _-- É 107 stearyl acrylate * 205 --- É Alkoxieqggëg 1 108 bucoxioleate * 70 zoo -__ l09 butoxyethyl stearate * 70 205 --- Aromatic esters 110 benzyl acetate 70 198 - ~ 111 benzylbenzoabx 70 242 L, P 112 butyl benzoatex 70 173 L, 113 ecyl benzoate * 70 200 1 , v 114 isobutylphenyl stearatex 70 178 L, P 115 mecyl benzoate * 70 170 L, P 116 mecylsalicyla fi * 70 200 L, v, PF 117 phenyl leaf-at * 70 205 L, P 115 phenylsalicylate - 70 211 L, F, M, F ' 110 tridecylphenyl stearatex 70 215 L, P 120 vinylphenyl stearatex 70 225 L, P Qiestrar 121 aibutylfualan * 70 290 1, v 122 dibutyl sebacatx 70 238 L, P 123 dicapryl adipate 70 204 L, P 124 dicapryl phthalate 70 204 --- 12 dicapryl 6 P 120 dienylphcalan * 70 zßo IR 127 dihexyl sebacate 70 226 --- x The tissue extracted from the solid material.

P- ~ 7708653-6 45 Table VT (continued) Llllå Ex. No. Liquid type and liquid Å liquid EQ Type of functional liquid Diesters cont. 12 & dimethylphenylene-aiscearac * 7u 208 --- 129 dioctyl maleate 70 220 --- l30 diisooctyl phthalate 70 E12 --- 131 diisooctyl sebacate 70 238 --- Esters of polyethylene glycol (PSG) 132 PEG 400-diphenyl stearate 70 326 --- folic hydroxide 70 270 --- 134 glycerol oleate * (1) 7 230 AF 13§ glycefol distearate * (2) 7o 201 AF 136 glycerol monooleatex (3) 70 232 AF 137 glycerol monophenyl stearate 70 Zoa --- 138 glycerol monostearate (4) x 70 211 AF 139 trimethylolpropane monoEenyl stearab 70 260 --- šäsaz 14ø dibenzylecer * 70 159 PF 141 diphenyl ether * 75 zøo --- X The liquid extracted from the solid material. (1) A glycerol ester having the following properties: flash point: 271 freezing point: 0 C; viakosltet (25 0): 90 cP; density (25 / zo L) = 0.923-0.929 g / cm. (2) A solid with m.p. 29,100. (3) A glycerol ester having the following characteristics: 0.940-0.953 cm; flash point 224 C; pressure point 20 ° C; liquid content (25 ° C): 204 cP. (4) A glycerol star with the following properties was used: Mold at 25 ° C: scales; flash point: ZIOOC; m.p .: 56.5-SE, SO3. 49 7708653-6 Table VI (continued) EEE Ex. No. Liquid type and liquid% hydrogen: Q Type of functional liquid Halogenated ethers 142 4-bfomoaiphenylecer * 70 100 vu 143 FR 300 BA (1) 70 314 Fu 144 hexachlorocyclopene cadiene * 70 196 P0 , ra 145 occabrumobiphenyl * 70 290 Fu Hydrocarbon with terminal double-bond 140 1-nunen * 70 174 L Hydrocarbon with internal double-bond 147 3-eikosen * 70 204 --- 148 2-nepcadeuen * 70 222 --- 149 2-nonadeken * 70 214 --- 150 9-nønaaeken * 70 199 --- 151 2-nonenx 70 144 L 152 2-undeken 70 196 --- Aromatic hydrocarbons 153 diphenylmethane 75 200 PF 154 -väns-suilben * 70 218 --- 155 triphenylmethane 70 225 --- Aliphatic ketones ISÖ dinonyl ketone * 70 206 --- IS7 distearyl ketone * 70 Zßê --- 158 2-heptadekanon 70 ZOS --- 150 0-heptaaekanon * 70 1 & 3 --- IÖÜ 2-heptanone * 70 152 - - ïhl methyl ptadecyl ketone * 70 225 --- 162 methyl nnyl ketone x 70 170 AR (1) The liquid extracted from the solid material.

Dow Chemical Company's trademark for the fire retardant decabromodiphenyloxide with the following own capers was used: O Bromine: beer-03%; m.p .: min. 205 C; decomposition temperature 425 C. 7708653-6 sa Table VI (continued) LQKE sLnv liquid type and liquid g liquid fg 'ryp of functional liquid Aliphatic ketones (cont.) 163 methyl pentadecyl ketone * 70 210 AR 164 methylundecyl ketone 70 20 20 214 --- 166 10-nonadekanon 70 194 --- 167 ës-peflcaaekanon * 70 178 --- 168 11-pentadekanonx 70 262 --- IOQ 2-trideknnon * 70 168 --- 170 6-tridekanonx 70 205 - - 171 6-undecanone * 70 188 --- Aromatic ketones 172 acetophenonex 70 190 PF 173 benzophenone 70 245 PF 174 9-xanwn * 70 220 vs Phosphorus compounds 175 trixylenyl phosphate * 70 394 FK Other 176 N, N-bis (š-hydroxyethyl) tallow oils 70 210 --- 177 bath oil perfume 5E64K 70 1b3 FG 178 EC-S3 styrenated nonylphenol (1) x 70 191 Ad 179 mineral oil SO 200 L lëü Muget hyacinth 70 178 FG 1271 Phøsclere P315c * 70 zoo --- Y: The liquid extracted from the solid material. (1) Akzo Chemie NV.'s trademark for their styrenic blocked Eenol. Ü 77Ü8653 ~ 6 Table VI (continued) Ex. No. Liquid type and liquid% liquidq: Q Type of functional liquid _ Övrí a fortsäbtnín 152 Phoscler. P576. (1) * 70 z1o .m IFS kinaldín 70 173 --- 1æ4 mnolin * 70 23 :) ___ 155 Terpineol Prime No. 1 70 194 M, PF 156 Firemaster BP-Ö 75 200 FR lä? benzyl alcohol / 1-heptadecanol (so / 50) * 70 204 --- 1% 8 benzyl alcohol / 1-heptadecanol (rs / 25) * 7u 194 --- * The liquid extracted from the solid material. (1) Akzo Chemie NV.'s trademark for their styrenated blocked phenol.

Microphotos of the porous polymers from Example Bë and 122 show »in Big. 28 and 29. The microphotos taken at 1700 times magnification show the cell structure with a significant amount of "foil" evenly distributed in the samples.

Examples gel 189 ~ 193 Examples 189 - 193 in Table VII illustrate the preparation of nomogenic porous polymeric intermediates by casting the solution in a glass bowl to form cylindrical blocks of about 45 mm radius and about 6 mm depth, except where noted, by "Noryl" polymer and the compatible liquids which have been found to be useful, using the standard procedure of preparation. In the cases indicated, the microporous polymer was also prepared.

Details on the preparation and the type of functionally useful liquid are given in Table VII: 7708655-6 52 Table VII Ex. No. (1) Liquid type and liquid% liquid _ & Type of functional liquid ____ _____ Agggatic amiu 159 diphenylamine 75 195 P3, AO Diester IQÛ dibutyl phthalate 7; 210 L Halogenated hydrocarbon 191 hexabromobiphenyl (2) 70 315 FR Other 192 N, N-bis (2-hydroxyethyl) tallow fattyamine * 7 5 2 50 ___ 193 N, N-bis (2-hydroxyethyl) tallow fatty amine 90 300 - - (1) General Electric Lumpany's "Noryl", a mixture of phenylene oxide condensation polymer with polystyrene, having the following properties is used: Density (23 C): 1¿O6 g / cm; traction break grägs (23): 66 MP3; elongation at break (23 ° C): 60%; drag module (23 C): 2450 Äwa; nad Rockwell hardness: R119. (2) The microporous polymers of the "Noryl" type produced with hexabromobiphenyl and N, N-bis (2-hydroxyethyl) tallow ethamine were cast to a depth of 13 mm.

A photomicrograph of the microporous polymer of Example 192 is shown in FIG. 25. The microfotule taken at 2125 times magnification shows the microcellular structure with spherical plastic deposits on the cell walls.

Example IQQ - 236 Examples 194 - 236 in Table VIII illustrate the preparation of homogeneous porous polymeric intermediates in the form of cylindrical blocks of about 30 mm radius and about 13 mm depth, of polypropylene (PP) and the compatible liquids which have proved useful, applying the standard procedure for production. In the marked examples, blocks with a depth of about 150 mm and / or thin films were also produced. Also, the microporous polymer was prepared as indicated.

Details on the preparation and type of nngívvn EunkLionelLL hnandable liquid are found in Table VIII: Ex. nrQ) 194 195 196 197 108 200 201 202 203 204 205 206 207 208 209 210 x The liquid extracted from the solid matter (1) Phillips Petroleum Company's "Marlex" Table VIII EX Liquid type and liquid Unsaturated heavy 10-undecenylic acid * Alcohols 2-benzylamino -1-propanol Ionol CP * 3-Ethyl-1-propanol salicylaldehyde Amides 53 N, N-diethyl-m-toluamide Amines aminodiphenylmethane * benzylamine N-butylaniline 1,12-aminomethane * 1,8-diaminoctane dibenzylamine N, N-dimethylamine N, N-diethanuloctylamine N, N-bis (β-hydroxyethyl) cyclohexylamine N, N-bis (2-hydroxyethyl) -hexylamine 0, N-bis (2-hydroxyethyl) -octyl] amine P 6 W liquid SQ 70 260 70 260 70 160 75 230 70 185 75 240 70 230 70 100 75 200 70 180 70 180 75 200 75 260 75 250 75 280 75 260 260 Type of functional gëgskn P-.O PF Th properties were used: 3 Density: nlet. polypropylene having the following 0.908 g / cm; melting point: 17006; yield strength, SO mm / min, 35 MPa; hardness, Shore D: 73. 7708653-6 54 Table VIIT (continued) EE Ex. no. Liquid TV and liquid É liquid: Q Type of function- Thin liquid šily åâšëâå 211 benzyl acetate * 75 200 --- --- 2l2 benzyl benzoatex 75 235 L, P, PF --- 213 butyl benzoate 75 190 L, P ---. 214 qibutylphcalate * 75 230 L, P and 213 methyl benzoate 70 190 L, P, PF --- 21U methyl salicylatex 75 215 L, P. PF --- 217 fi phenyl salicylate * 70 24- »v ___ § &! ÅE 218 dibenzyl ether 75 210 PF --- 210 diphenyletherx 75 200 PF and Halogenated hydrocarbons 220 4-bromodiphenyletherx 70 200 FR --- 221 1,1, z, z-ureabroloethane * 70 180 m --- 222 1,1,2,2 z-cetrabromoethane * 90 180 FK __- Ketones 223 benzyl acetone 70 ZOO '--- --- 224 methylnonyl ketone 75 180 --- --- Other 225 N, N-bis (2-hygroxyethyl) - ßalgfettalnin (1) and (z) 75 zoø ___ ja 226 N, x ~ rL> is (2-hydroxyethyl) - coconut fatty amine (2) 75 180 --- --- 227 butylated hydroxytoluene 70 160 AU --- * The liquid is extracted from the solid material.

(I) One block with a depth of about 150 mm was also prepared. (2) One permanent internal antistatic agent having the following properties was used: U O bp: 170 C / 1 torr; viscosity (32 C): 367 SSU. : fmfcsa- ss - 7709653-6 Table VIII (continued) Zl Ex. no. Liquid fabric and liquid Å liquid SQ Type of function- Thin __ _ ggll_yätska Éilm Other (Eorts.) 228 n.c. 550 Silicone nuidü) 50 260 s, L __- 229 n.c. 556 siliwne Fluid * 70 '190 s, L __- 23O EC-53 75 210 - ~ --- 231 N-hydrogenated rapeseed oil- diethanolamine, 75 210 SF --- 232 N-hydrogenated tallow fat- diethanolamine 75 225 SF - - 233 Firemaster BP-6 75 200 FR --- 234 Nßc oil 75 190 --- --- 235 xinaldine * 7o zoo --- --- 236 xcinolin * 75 220 M --- * The liquid extracted from the solid material . (1) Dow Corning's trademark for phenylmethylpolysiloxane with the following properties was used: O Viscosity: ISO cSt and operable from -40 to 232 ° C in open systems and to 31S ° C in closed systems.

Microphotos of the porous polymer from Example 225 are shown in Big. 2 - 5. The microphotons according to Figs. 2 and 3, one at 47 and the other at 470 times magnification, show the macrostructure of the microporous polymer. The photomicrographs of Figures 4 and 5, one at 1870 and the other at 4675 times magnification, show the microcellular structure of the polymer and the connecting pores.

Examples 2 - 2 Examples 237 - 243 in Table IX illustrate the preparation of homogeneous porous polymeric intermediates in the form of cylindrical blocks of about 30 mm radius and about 13 mm deep, of polyvinyl chloride (PVC) and the combinable liquids which have proved useful, with use of the standard procedure for production. Many of the exemplified intermediates were extracted to form porous polymers, as shown in the table.

Details on the preparation and the type of functionally useful liquid are given in Table IX: 56 Table IX EXE Ex. No. Liquid fabric and liquid Å liquid OC Type of functional liquid ___ Aromatic alcohols 237 4-methoxybenzyl alcohol * 7u 150 PF Second -OH group-containing compound 238 1- 3, -dichloro-2-propanol * 70 170 --- 239 mental * 70 180 PF 240 10-undeken-1-01 * 70 204- 210 --- Halogenergg 241 Piremaster T33P * (2) 70 165 Fu 242 Firemaster TIBP * (3) 70 175 FR Aromatic hydrocarbons 243 trans-sail legs * 70 190 --_ * The liquid extracted from the solid material. (1) The polyvinyl chloride used was of dispersion grade, manufactured by American Hoech t, and having an intrinsic viscosity of 1 20, a density of 1.40 g / cm 3 and a bulk density of 325 kg / m 2. (2) the trademark of the Michigan Chemical Corporation for the flame retardant tris (1,3-dichloroisopropyl) barrel having the following properties: Cl, 49.1%; P, 7.2%; Kp. 200 DEG C./4 torr (division); refractive index, 1,509; viscosity, Brookfield (23 C), 2120 cP. structure = / (c1cn2) 2cno / 3? -o (3) Michigan Chemical Corporation's trademark for their flame retardant tris-halo enerated propy phosphate having the following properties: density, 25/25 c, 1.88 g / cm; viscosity (z5 ”c), 192: est; refractive index, 1,540; pH, 6.4; Cl, 18.9 Å; Br, l2, S $; P, 5, SÃ.

A photomicrograph of the porous polymer of Example 242 is shown in Fig. 27. The photomicrograph taken at 1700 times magnification shows the extremely small cell size of this porous polymer in contrast to those with the photomicrographs of Figs. 7, _l3, 18, 20 and Z4 exemplified the cell structures, where cell structure is lower and lighter observed at a comparable magnification. The microphot also shows the presence of a large amount of plastic that obscures the basic cellular structure.

Examples> e1 2 ~ 2 Examples 244 - 255 in Table X illustrate the preparation of homogeneous porous polymeric intermediates in the form of cylindrical blocks with a radius of about 30 mm and about 50 mm deep, of methylpentene polymer (MFP) and the - - -ww W 770865Z ~ 6 compatible liquids which proved to be suitable, using the standard manufacturing procedure. Many of the exemplified intermediates were extracted to form porous polymers, as shown in the table.

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

Table X ÉLPIÄ Ex.nr (; l Liquid type and liquid 1 liquid Bg Type of functional ïšgska Saturated aliphatic szra 244 capric acid * 75 230 --- Saturated alcohols 245 1-dodecane * 75 z3o --- z46 z-unaecanol * 75 230 - - 247 6-undecanol 75 230 --- Amine 248 dodecylamine 75 230 FA Estrar 249 butyl benzoate * 75 210 L, P, PF 250 dihexyl sebacate * 70 220 L, P 13133233 251 dibenzyl ether 70 230 PF Hydrocarbons 2 2 1-hexaacene * 75 220 --- 253 naphthalene * 70 240 now Other 254 ßc-Sß * 75 230 Au 255 Phosclere Pgxsc * 75 250 --- x The liquid extracted from the solid material.

(I) Mitsui's methylpentene polymer with the following properties was used: Density, 0.835 g / cm; melting point: 235 ° C; tensile strength: 22.5 MPa; elongation at break: 30%; Rockwell hardness: b5 R. 58 77086 53 ~ 6 A photomicrograph of the porous polymer of Example 253 is shown in FIG. 22. The photomicrograph taken at 2040 times magnification shows the extremely unflattened cell walls, in contrast to the one in fia. 14 showed the configuration.

Examples 256 - 266 Examples 256 - 206 in Table XI illustrate the formation of homogeneous porous polymeric intermediates in the form of cylindrical blocks of about 30 mm radius and about 13 mm depth, of polystyrene (PS) and the compatible liquids which proved useful, using of standard procedure for the production. All of the exemplified intermediates were extracted to form porous polymers.

The details of the preparation and the type of functionally useful liquid indicated are given in Table XI. Ü fl¿ wh ~ S9 7708653-6 Table XI Ex.nr (ll Liquid type and liquid% liquid: Q Type of functional liquid ___ 256 Firemaster T-13P 70 250 Fn 257 hexabromobiphenyl 70 260 Fk 258 Phosclere PSISC 70 270 »- 2S0 Phosclere P576 T 285 A0 260 tribromoneopentyl alcohol 70 210, Fk 261: fu 2249 (2) 70 240 Hz. 262 Fyrol CEF (3) 70 250 in 263 Firemaster T33P (4) 70 210 Fk 204 Fyrol FK 2 (S) 70 240 Fk 203 dlklurubenzene 80 100 Nä, Fä 200 1-dodecanol 75 --- --- (1) (2) (3) (4) Monsanto Chemical Company's "Lustrex" polystyrene with the following physical properties was used: Skårslagsæghetz 20 Nm / m (sprayed) ; tensile strength: 52 MPa; modulus of elasticity, psi, oxide, 4.5; deflection temperature below 1820 kPa load: 93 C; density: 1.05 U / Om; Rockwell hardness: bh75; melt index: 4.5 g / 10 min.

Dow Chemical Corporation's trademark for a fire retardant having the following composition and properties: Tribromoneopentyl alcohol, 60%; Voranol CP 000 polyol, 40%; bromine, 43%; hydroxyl a1: 130; viscosity (25 ° C): about 1600 cP; density: 1.45 g / cm.

Stauffer Chemical Company's trademark for the fire retardant tris (chloroethyl) Eosphate having the following properties: bp 145 ° C / 0.5 dry decomposition); Cl, 36.7%; P 10, h $; refractive index (20 C): 1.4745; viscosity (22, & C): 40.

Michigan Chemical Corporation's trademark for the fire retardant tris (1,3-dichloroisopropyl) phosphate having the following properties: Cl, 49.1%; P, 7.2%: bp: 200 C / 4 torr (decomposition); refractive index: 1, S019; viscosity, smokfield (22.8 C): 2120 cP. structure: / (c1c1-12) 2cfxo / 3P-0 Stauffer Chemical Company's trademark for a tris (dichloropropyl) phosphate intended as a fire retardant additive with the following properties: mpb about 27 ° C; refractive index nd, 1.5019; viscosity, Brookfield (23 C), 2120 CP. 7708653-6 60 A photomicrograph of the microporous polymer of Example 260 is shown in FIG. 26. Although the cells are small compared to those in fig. 4, 7, 13, 13 and 25, the microcellular structure is present. Example 261 This example illustrates the preparation of a homogeneous porous polymeric intermediate from 30% high impact polystyrene II) and 70% hexabromobiphenyl using the standard procedure. For the preparation and heating of the mixture to 28006. The polymeric intermediate formed was about 65 mm in diameter and about 13 mm deep. Hexabromobiphenyl is useful as a flame retardant, and the porous intermediate is useful as a solid flame retardant additive.

Example Gel 268 This example illustrates the preparation of a homogeneous porous polymeric intermediate from 25% acrylonitrile-butadiene-styrene terpolymer (2) and 75% diphenylamine using the standard procedure for the preparation and heating of the mixture to 220 ° C. The polymeric intermediate formed had a diameter of about 65 mm and a depth of about 50 mm. The microporous polymer was formed by extraction of the diphenylamine. The dieneylamine is useful as a pesticide and antioxidant, and the porous polymeric intermediate has the same utility. (1) Union Carbide Company's "Bakelite" polystyrene for injection molding, with the following properties used: Tensile strength (3 mm thickness): 34.5 MPa; elongation: (3 mm thickness): 25%; fracture modulus (3 mm thick): 2620 MPa; Rockwell hardness (6.35 x 12.7U x 127 mm): 90; density: 1.04 g / cm3. (2) Uniroya1's Kralastic ABS polymer with the following properties and density: 1.07 g / cm3; impact strength (3 mm test rod, 23 C, [zod with notch): 69.4 - 101.4 N.m / m; tensile strength: 60.6 MPa; Rockwell Hardness: 188 R. q. .Ma ».- o1 77Û8653 ~ 6 š šgmgel 269 and 270 The homogeneous porous polymeric intermediates were prepared from 25% chlorinated ethylene plastic from Dow Chemical Company, with a melt viscosity of IS pois, 8% crystallinity, and containing 36% chlorine and 75 Å N, N-bis (2-hydroxyethyl) tallow ethamine (Example 269) and 75 Å chlorinated ethylene plastic and 25% 1-dodecanol (Example 270), using the standard procedure for preparation and heating to 22006. The porous polymeric intermediates were about 65 mm in diameter and about 50 mm deep.

Example 221 The homogeneous porous polymeric intermediate was prepared from 25% chlorinated ethylene plastic using the standard procedure of preparation and 75 2 diphenyl ether, and heated to 210 ° C. The porous polymeric intermediates were about 65 mm in diameter and about 50 mm deep. The diphenyl ether is useful as a perfume and the intermediate is also useful in perfumes.

Examples 222 - 275 Examples 272 - 275 in Table XII illustrate the preparation of homogeneous porous polymeric intermediates in the form of cylindrical blocks with a radius of about 30 mm and a depth of about 13 mm of styrene-butadiene rubber (SBK) (lä and the compatible liquids shown In addition to the cylindrical blocks, thin films were also produced where noted.

Details of the preparation and type of the functionally useful liquid indicated are given in Table XII (1). Shell Chemical Company's SBR polymer marketed under the brand name Kraton with the following properties were used: Tensile strength, 21.4 - 31.7 MPa; yield strength, 6.1 - 9.0 MPa; Rockwell Hardness, Shore A, 35-70.

Table XIT SBR Sx.nr Liquid type and liquid Z liquid gg Type of function- Thin onell_liquid_ film 272 N, N-bis (2-hydroxyethyl) - tallow fatty amine BO 195 --- yes 273 aecanol * 70 190 PF yes 274 diphenylamine 70 200- PB, AO yes 210 275 diphenyl ether 70 195 PF yes * the liquid extracted from the solid material. Examples 226 - 278 Examples 276 - 27% in Table XIIT illustrate the preparation of homogeneous porous polymeric intermediates in the form of cylindrical blocks of about 30 mm radius and about 13 mm depth, of "Surlyn" (1) and the combined only liquids which have proved useful, using the standard manufacturing procedure. In addition to the cylindrical blocks, thin films were also produced where noted. Two of the exemplified intermediates were extracted to form porous polymers, as noted in the table.

The details of the preparation and the type of indicated functionally useful liquid are given in Table XIII: Table XIII SURLYN Gx.nr Liquid type and liquid 2 liquid: Q Type of functional- Thin liquid film 276 N, N-bis (2-hydroxyethyl) - tallow fatty amine 70 190 ~ - ~ yes 195 177 diphenyl ether * 7o zoo PF _13 276 dibutyl phthalate 70 195 L yes * the liquid extracted from the solid material.

Microphotos of the porous polymer from Example 277 are illustrated in FIG. 23 and 24. Fig. 23 shows the macrostructure of the polymer at 217 times magnification. Fig. 24 shows the microcellular structure of the polymer at 2179 times magnification with small "Eoliation" and relatively thick cell walls, compared with, for example, Fig. 25.

Example 222 The homogeneous porous polymeric intermediate was prepared using the standard procedure and heating to 100 ° C, of 25 Å of a mixture of equal parts HD polyethylene (HDP3) and chlorinated polyethylene (GPS), and 75% I-dodecanol. The porous polymeric intermediate is cast into a film having a thickness of about 0.50 - 0.65 mm. UDP5 and LPE were the same as used in previous examples. fl) E.I. du "ont de Nemouris" Surlyn "ionomer plasf 1552, with The following properties were used: Density: 0.939 g / cm3; melt index: 4.4 de / min; dšagårottgränsz 19.5 MPa; yield strength: 12.9 MPa; Förlänsningz 5 0.

: WWW '63 7708655-6 Exemgel 280 The homogeneous porous polymeric intermediate was prepared using the standard procedure and heating to ZCOUC, of 25 ä of a mixture of equal parts of HD polyethylene and polyvinyl chloride, and 75 É of 1-dodecanol. The intermediate produced was about 50 mm deep and about 65 mm in diameter. HDPE and PVC were the same as used in the previous examples.

Example 281 The homogeneous porous polymeric intermediate was prepared using the standard procedure and heating to ZOOOL, by ZS Z of a mixture of equal parts of HD polyethylene and acryloniboxyl-huLadien styrene terpolymer, and obtaining Å 1-dodecanol. The intermediate product produced had a depth of about 50 mm and a diameter of about 65 mm. UDP? and ABS was the same as used in previous examples.

Examples 282 - 285 in Table XIV illustrate the preparation of homogeneous porous polymeric intermediates in the form of cylindrical blocks with a radius of about 30 mm and about 50 mm depth, of a mixture of equal parts of LD-polyethylene and chlorinated polyethylene, and the compatible liquids which useful, using the standard procedure for production. Example 283 The above procedure was used, but the intermediate was cast into a film having a thickness of about 0.50 - 0.65 mm. LDP3 and CPB were the same as used in previous examples.

The details of the preparation and the type of specified functionally useful liquid can be found in Table XIV: Table XTV 3x.nr Liquid type and liquid Ä liquid gg Type of functional Xëlâk fl _ * 82 1-ducedanol 75 200 --- 283 diphenyl ether 75 200 PF 50 200 PF 284 diphenyl ether 2bS N, N-bis (2-hydruxyethyl) -talgiettamine 7 § 290 - ~ Example 286 - 282 The homogeneous porous polymeric intermediates were prepared from 25% of a mixture of equal parts of LD-polyethylene and polypropylene, and 75% N, N-bis (2-hydroxyethyl) tallow fatty amine (Example 286), and SO ß of a mixture of equal parts LD-polyethylene and polypropylene, and 50 Å N, N-bis-tallow fatty amine (2-hydroxyethyl) tallow fatty amine ( Example 28f), using the standard procedure and heating to 220 ° C for Example 286 and to 27 ° C for Example 287. Both porous polymeric intermediates had about 6? mm diameter and about 53 mm depth. LUPE and PP were the same as used in previous examples.

Example 288 The homogeneous porous polymeric intermediate was prepared using the standard procedure and heating to ZOOOC, of SO%, β-bis (2-hydroxyethyl) tallow fatty amine and 50X polypropylene / polystyrene blend (25 parts polypropylene). The porous polymeric intermediate product was about 65 mm in diameter and about 50 mm deep. PP and PS were the same as used in previous examples.

Example 289 The homogeneous porous polymeric intermediate was prepared using the standard procedure and heating to ZOJUC, with 1 Dodecanol and 25% of a mixture of equal parts polypropylene and chlorinated polyethylene. The porous polymeric intermediate had a diameter of about 65 mm and a depth of about 13 mm. PP and CPE were the same as used L previous examples. Axis Gel 290 - 100 Examples 290 - 300 illustrate the useful concentration range of polymer and compatible liquid for the preparation of a homogeneous porous polymeric intermediate of HU-polyethylene and N, N-bis (2-hydroxybyl) tallow fatty amine. In all the examples, the intermediates had about 50 mm depth and about 65 mm diameter. HDPE was the same as used in previous examples.

The details of the preparation and noted physical properties are given in Table XV: Table XV; ¿¿¿¿ß liquid gg 535. 290 95 275 very weak; no fixed sammadüllniug; unmanageable 291 90 --- very greasy; ubsipping of liquid; upper limit for liquid retention exceeded 202 80 250 lubricating 293 75 220 lubricating 204 70 250 hard solids 295 OS 220 --- 296 60 250 hard solids 297 55 220 --- 208 SO 240-260 hard solids 200 40 260 hard solids 300 30 200 hard fdstämne A photomicrograph of the porous polymer from example 300 is shown in 19 in 1700 times magnification. The cells are not clearly visible at this 19 can be compared to Big. IJ, at 2100 times magnification, fig- magnification. Pig. where the cell sizes are also very small at the same polymer customer concentration of 70 1. §¿gmQe1 301 _ 311 These examples illustrate the useful concentration range of the polymer and the compatible liquid for the preparation of a homogeneous porous polymeric intermediate of LD-polyethylene and N, N- bis (2-hydroxyethyl) tallow fatty amine. In each example, the intermediate product was about 13 mm deep and about 65 mm in diameter. LDPE was the same as used in previous examples.

The details of the preparation and noted physical properties are given in Table XVT: 7708653-6 66 gânell lv; 3Û1 95 275 mkt svan; No fixed convergence; unhinderable 332 00 240 mkt smörjieq utsípprlnü of liquid; Upper grdnseu for liquid equilibrium exceeding 303 80 260 hard solids FOI 7§ 210 hard fnsLümnn QOS 70 210 hard solids fi 300 66 200 hard solids 307 60 280 hard solids 395 50 280-290 hard solids 309 40 285 hard solids 310 30 285 hard East substance RI 280-300 hard solids Microfuture of the porous polymers of Examples 303, 307 and 310 are shown in Figures 14-15 (210 and 2125 times first, respectively), fin. ln (2125 times magnification), and fig. 17 (2100 times magnification). The figure shows the decreasing cell size, from very large (fig. 15, 20 5 polymer) to very small (fig. 17, 70 Å polymer), which is the result of the aluminum polymer content increasing. The relatively flattened cell walls of the 20 Z polymer product (Example 303) are similar to the methylpentene polymer (Fig. 22) and can be observed in Fig. 14. Fig. 15 is an enlargement showing a portion of a cell wall illustrated in Fig. 14. The microcellular structure of the porous polymer can be seen in Fig. 16. Examples 11.2 - 31.6 Examples 312 - 316 illustrate the useful concentration range of polymer and combinable liquid for the preparation of a homogeneous porous polymeric intermediate of LD polyethylene and diphenyl ether. For each example, the intermediate product was about 13 mm deep and about 65 mm in diameter. Lu fi * was the same as used in previous examples.

The details of the petition and the listed Fyslhalíswa properties are given in Table XVIÛ åælus š_! Ë & §ka få 312 90 185 313 80 155 314 75 zoo 315 70 190-zoo 316 60 zoo Table XVIT Note. very greasy; very greasy; no solid cohesion; unmanageable near the upper limit of fluid treatment but still manageable wet; strong slightly lubricating hard East substance 07 o 77ose53 ~ 6 Qxemgel 317 - 321 Examples 317 - 321 illustrate the useful concentration range of polymer and combinable liquid for the preparation of a homogeneous porous polymer intermediate of LD-polyethylene and 1-hexene decane. In each example, the intermediate had about 50 mm depth and about 65 mm diameter. LUPE was the same as used in previous examples.

The details of the preparation and noted physical properties are shown in Table XVTTI: Table XVIII o §5¿g§ @ liquid _g Ag5¿ 317 90 180 god strength 315 80 180 small strength, manageable 319 75 200 small strength, manageable 320 7Û 177 --- BZI SO 180 Good Strength Exemgel 522 - 314 These examples illustrate the useful range of polymer and liquid conjugation for the preparation of a homogeneous porous polymeric intermediate of polypropylene and N, N-bis (2-hydroxyethyl) tallow febtamine. For each example, the intermediate product was about 13 mm deep and about 65 mm in diameter.

In addition, films were produced where noted. PP was the same as used in previous examples.

The details of the preparation and noted physical properties can be found in Table XIX: Table XIX §š¿E5% liquid 22 Agg¿ Thin film 322 90 200 very wet yes 322 55 zoo ___ __- 324 80 200 strong yes 325 75 180 dry and hard yes 320 70 200 ~~~ ja 327 65 210 --- --- 328 60 210 --- 329 SO 200 ~~ - ja 330 40 210 --- ja 331 30,8 175 vit, krístallin ~ - 332 25 180 - - --- 333 20 180 --- ja 334 15 180 - ~ - * “'......_.. - ..__.___......... -_ _. . _... .__...__. - _ 7708653-6 ef.

Microphotos of the products of Examples 322, 32n, 328, 330 and 333 are shown in Figures 6 to 10 (in 1125, 1215, 1375, 1230 and 1060 EE? Magnification). The extreme foiling of the microporous polymer with 10 Å of polymer is shown in Fig. 6, although the microcellular structure is still maintained. These figures show the decreasing cell size as the amount of polymer increases. However, the microcellular structure still remains in each example despite the small cell size.

Examples Gel 135 - 337 The examples illustrate the concentration range of polymer and compatible liquid used for the preparation of a homogeneous porous polymeric intermediate of polypropylene and diphenyl ether. In each example, the intermediate product had a depth of about 13 mm and a diameter of about Ö mm. In addition, films were also made where so noted. PP was the same as used in L previous examples.

The details of the preparation and noted physical properties are given in Table XX: Table XX Ex. No. ß Liquid EQ Thin Film 335 9Ü 200 and 330 80 ZÛÛ and 337 7Û 200 and Microphotos of the porous polymer from Examples 335, 330 and 337 are shown in Figs. 11 (1700 times magnification), fig. 1: (175J times magnification) and fig. 13 (1660 times magnification). The figures show that the pore size decreases as the polymer concentration increases. Fíu. Fig. 11 shows the smooth cellular pathways, while Figs. 12 and 13 show the cells and trapped pores. In each of the figures, the microvullular structure is present. limee1 __._ 3 ____ §? This example illustrates the useful polymerization compound and combines liquid for the preparation of a homogeneous porous polymeric intermediate of styrene-butadiene rubber and γ, β-his (2-hydroxyethyl) tallow fatty amine. In each example, the intermediate product was about 13 mm deep and 65 mm in diameter. In addition, thin films were produced where noted.

SHR was the same as used in previous examples.

The details of the preparation and noted physical properties can be found in Table XXI: Leo.- 7708653-6 Table XXT Ex. No.% Liquid EQ Note. Tunn _¿im 335 90 200 svan; in addition to the yes upper Liquid limit 339 80 195 rubbery yes 340 75 195 rubbery _p1 341 G 195 rubbery Yes 342 60 ZOO rubbery yes 343 SO ej rappor- rubbery yes terat 344 40 ej rappo fl erxgummíartad Yes 345 30 ej rappor gummiartad rubbery iodinated The microfoot of the microporous SHR polymer of Examples 339 and 340 is illustrated in Fig. 20 (2170 times magnification) and fine. 21 (2190 eur magnification). The figures show the microstructure of the microporous polymers. Fig. 21 also shows spherical deposits of the polymer on the coll walls. Examples 347-352 Examples 347-352 illustrate the concentration range of polymer and compatible liquid used for the preparation of a homogeneous pure polymeric intermediate of SBR and decanol. In each example, the intermediate product was about 13 mm deep and 65 mm in diameter. In addition, films were produced where noted. SUR was the same as used L Previous example.

The details of the preparation and noted physical properties are given in Table XXTT: Table XXIT f; turned-ska. ïß; Am. 347 90 not reported above the upper fluid limit; unmanageable 34b 80 190 gnmmiartnd yes 340 70 190 rubbery yes 350 GO 1§0 rubbery yes 351 SO 190 rubbery yes 352 40 not reported rubbery - ~ 1708653-6 70 Example gel 35 - 56 Examples 353 - 356 are directed to Search and diphenylamine. The details of the preparation and noted physical properties are given in Table XXITT.

Table xx__r_Il 0 §š¿Er fi_ yätska _§ Anm¿ 353 80 not reported --- BS4 70 200-210 --- 355 60 _ 215 - ~ - 356 50 200-210 --- Exemgel 357 - 361 Exemplen 357 - 361 illustrates the useful concentration range of polymer and combinable liquid for the preparation of a homogeneous porous polymeric intermediate of "Surlyn" plastic, used in previous examples, and N, N-bis (hydroxyethyl) tallow fatty amine. In each example, the intermediate product was about 13 mm deep and about 65 mm in diameter. In addition, thin films were produced where noted.

The details of the preparation and noted physical properties are found in Table XXIV: Table XXIV ä_ ~ '_ä._t ____ sl 357 70 190-195 Yes 353 60 190 yes 359 50 not reported yes 360 40 not reported yes 361 30 not reported yes Exemgel 362 - 370 These example illustrates the possible concentration range of the polymer and the compatible liquid for the preparation of a homogeneous porous polymeric intermediate of "Surlyn" plastic, used in previous examples, and diphenyl ether. In each example, the intermediate product was about 13 mm deep and about 65 mm in diameter. In addition, thin films were produced where noted.

The details of the preparation and noted physical properties are given in Table XXV: man-who * - 'a än »: n 71 7708653-6 Table XXV §¿¿nr% liquid gg Thin films 302 90 207 yes 3n3 80 190 yes 364 70 200 yes 105 60 155 yes 366 50 not reported yes 367 40 not reported --- ßß fi 30 not reported --- 360 20 not reported --- 37J 10 not reported --- g ggmgel E71 - 379 Examples 371 - 379 illustrate the useful concentration range of the polymer and the combined liquid for the preparation of a polymeric intermediate of "Surlyn" plastic used in and dibutyl phthalate. about 13 mm deep and about 65 mm in diameter. homogeneous porous previous examples, In each example the intermediate details of the preparation and noted physical properties are found in Table XXVI: Table XXVI ..._.___.___..__ §¿¿n§ ß liquid gg Note 271 90 220 - - 372 80 208 --- 373 70 19% --- 374 60 200 --- 375 S0 200 --- 37Ö 40 not reported --- 377 30 not reported --- 378 20 not reported --- 370 10 not reported --- Comparative Example Examples 380 - are found to have a physical structure that differs from that of the present 384 reproductions of various compositions according to the present invention.

Example QBO A porous polymer was prepared in accordance with Example 1 according to U.S. Patent No. 3,378,507, which was modified to give a product of certain physical integrity and to use a doubt as a water-soluble anionic surfactant instead. for sodium bis (2-ethylhexyl) sulphosuccinate.

In an internally heated mixer-Plnsti-border mixer, 331 parts by weight of LU polyethylene (Exxon Chemical Corporation type LUITMU and 66 2/3 parts of marseille whale flakes were mixed at a machine temperature of 175 DEG C. until a homogeneous mixture was formed. rubber mold with a 63.5 x 127 mm mold cavity with a depth of about 0.5 mm, at a temperature of about IYSOC and a pressure of 24b MPa.

The resulting sample was washed continuously for about 3 days in slowly flowing tap water and washed successively by immersion in eight baths of distilled water, each time for about 1 hour. The resulting sample still contained some soap and had poor handling properties. creates.

Pig. 47 and 48 are photomicrographs of the product of Example 380, the first at 166 and the second at 1700 times magnification. It is obvious that the product has a relatively heterogeneous polymer structure and has neither delimited cells nor connecting pores.

Example 81 A porous polymeb was prepared according to the procedure of Example 2, Sample D, of U.S. Patent No. 3,378,507, which was modified to obtain a sample of the same handling strength.

In the same internally heated mixer as in Example 380, 73 parts of semicircular soap flakes and 25 parts of LD polyethylene of the same type as in the previous example were mixed at a machine temperature of about 175 DEG C. and a sample temperature of about 160 DEG C. until a homogeneous mixture was formed. The material was then compression molded in a 30 g Watson-Stillman injection molding machine having a mold cavity diameter of 50 .mu.m and a depth of 0.5 mm. The resulting sample was then washed continuously for about 3 days in lukewarm running tap water and then sequentially by H94 dipping in eight baths of distilled water, each time for a period of about 1 hour. The resulting sample still contained some soap.

Pig. 45 and 46 are photomicrographs of the product of Example 381, one at 204 and the other at 2040 times magnification. The product of the example does not have the typical cell structure of the invention, as shown by the photomicrographs.

Example 382 A porous polymer was prepared according to the procedure of Example 3, Sample A, in U.S. Patent 3,378 SO7.

In an internally heated mixer of type ßrabender-Plasti ~ Corder gprda-nßuuwy www ... in 73 7708653-6 25 parts of polypropylene (Novamont Corporation type F30O SKI9) and 75 parts of marseille soap flakes were mixed at a machine temperature of about 165 ° C until a homogeneous mixture was formed. The material was then molded with a rubber mold. The resulting sample was found to have very low rock strength. A portion of the resulting sample was washed continuously for about three days in slow flowing tap water and then sequentially by immersion in eight baths of distilled water, each time for about 1 hour. The washed product was found to have extremely poor handling properties.

Pig. 51 and 52 are photomicrographs of the product of Example 382 at 115 and 115, respectively. 1700 times magnification. The microphotos show that the product does not have the microcell structure according to the invention.

Example ÅSQ The procedure of Example 3, Sample A, of U.S. Patent No. 3,378,507 was modified to obtain a product with improved handling strength.

On a two-roll open rubber mixer manufactured by ßollíng Company, 25 parts of polypropylene (Novamont Corporation type F300 8N19) and 75 parts of marseille soap flakes were mixed for about 10 minutes at a temperature of about 175 ° C until a homogeneous mixture was formed. The material was then injection molded with a 30 g Watson-Stillmao injection molding machine having a mold cavity diameter of 50.7 mm and a depth of 0.5 mm. The resulting sample was washed continuously for about three dunes in slow flowing tap water and then in turn by immersion in eight baths of distilled water, each time for about 1 hour. The resulting sample still contained some soap. . The product was found to be stronger than the product of Example 382. In Figs. 49 and SO, photomicrographs of the product of Example 383 are shown in Figs. 1700 times magnification. The irregular shapes shown in the photomicrographs are easily distinguishable from the structure of the present invention. A porous polymer was prepared in accordance with Example IT of U.S. Patent No. 3,319 SOS, which was modified to give a more homogeneous mixture. [an internally heated Brabender-Plasti-Corder mixer blended 40 parts LD polyethylene (Exxon Chemical Corporation type 606) and 60 parts polymethyl methacrylate (Rohm and Haas Corp.) for about 10 minutes at a machine temperature of about 17S ° C until a homogeneous mixture is formed. On a cold rolling mill, a film was then formed which was then compression molded for about 10 minutes at a pressure of 30 ions using a circular press pad with a diameter of 0.5 mm and a depth of 0.5 mm. The resulting product was extracted for 48 hours with acetone in a large Soxlet extractor.

Figs. S3 and S4 show photomicrographs of the product of Example 384 in 174 and 174, respectively. 1700 times magnification. The non-uniform structure revealed by the photomotons can be easily distinguished from the smooth structure of the products according to the invention.

Physical characterization of Examples 225 and R fi b In order to obtain a quantitative view of the homogeneous structure according to the invention, certain samples of the microporous material and some previously known samples of a mercury penetration porosimeter from Aminco were analyzed. Fig. low and 31 are mercury penetration curves for the 13 mm block from Example 225, prepared with 25% polypropylene and 75 X N, N-bls (2-hydroxyethyl) tallow fatty amine, and Elg. 32 is a mercury penetration curve for the 159 mm block from Example 22 §. All mercury penetration curves are shown on a semilogarithmic graph with the equivalent pore sizes shown on the logarithmic scale abscissa. Pig. 30 - 32 show the typical narrow distribution of pore sizes in the composition according to the invention. it was determined that the 13 mm sample from Example 225 had a porosity of about 45 Å and an average pore size of about 0.5 μm, and that the ISO mm block had a pore volume of about 72 and an average pore size of about 0.6 hm.

Fig. 33 is a mercury penetration curve for the product of Example 38, prepared with 40 X polypropylene and ÖÛ Å N, Y-bis (2-hydroxyethyl) tallow fatty amine. Pig. 33 shows that the sample has a typical narrow pair size. It was determined that the sample had a porosity of about LO 3 and an average pore size of about 0.15 microns.

It is easy to see that the compositions of this invention have such pore size distributions that at least 10% of the pores present in the composition fall within a decade of the mercury penetration curve nb sketch. The pore size distribution of the composition can thus be characterized as "narrow".

Prior Art Exemgel 385 The composition of this example is a commercially available microporous polypropylene, Celgard 3501, made from Lelanose Corporutnnn Pig, 34 is a mercury penetration curve of the sample, showing a large population of pores in the region 70 - 0.3 Pm. The sample was determined to have a porosity of about 35 Å and an average pore size of about 0.15 μm. Example 386 The composition of this example is a commercially available microporous polyvinyl chloride, manufactured by Amerace and called A-20. Pig. Is a mercury penetration curve of the sample and shows a very wide pore size distribution. The sample was determined to have a porosity of about 75% and an average pore size of about 0.16 μm.

Example 382 The composition of this example is a commercially available microporous polyvinyl chloride, manufactured by Amerace and called A-30. Fig. 36 is a mercury penetration curve of the sample and shows a very wide pore size distribution. The sample was determined to have a porosity of about 80% and an average pore size of about 0.2 .mu.m.

Example 388 The composition of this example is a commercially available microporous polypropylene designated Porex. Pig. 37 is a mercury penetration curve of the sample and shows a very broad distribution of extremely small cells as well as a distribution of very large cells. The sample was determined to have a porosity of about 12% and an average pore size of about 1 μm.

Example 382 The composition of this example is a commercially available Millipore BDWP 29300 microporous polyvinyl chloride. Fig. 38 is a mercury penetration curve of the sample and shows a relatively narrow distribution in the range 0.5 - 2 μm as well as a plurality of cells smaller than about 0.5 μm. The sample was determined to have a porosity of about 72% and an average pore size of about 1.5 .mu.m.

Example 320 The composition of this example is a microporous cellulose triacetate commercially available under the name Metricel TCM-200 manufactured by Gelman. Fig. 39 is a mercury penetration curve of the sample and shows a wide distribution of pores with sizes of up to 0.1 μm. The sample was determined to have a porosity of about S2% and an average pore size of about 0.2 μm.

Example 321 The composition of this example is a commercially available Acropor WA microporous acrylonitrile-polyvinyl chloride copolymer made by Gelman. Fig. 40 is a mercury penetration curve of the sample and shows a wide pore size distribution. The sample was determined to have a porosity of about 64% and an average pore size of about 1.5 microns. The physical characterization of the reference examples 80-8. The products representative of the state of the art from Examples 350-354 were also analyzed by mercury penetration. . Figs. 41 - 43 are mercury penetration curves showing the wide pore size distribution of the products of examples 381, 380 and 380, respectively. 383. Pig. 44 is a mercury penetration curve for the product of Example 384 showing a population of pores in the range of 45-80 microns and a plurality of extremely small pores. The products of Examples 380, 381, 383 and 384 were determined to have porosities of about S4, 46, S4 and S4, respectively. 29 X with average pore sizes of about 0.8, 1.1, 0.56 resp. 70 pm.

Examples 2 - 9 These examples illustrate the concentration range of the combinable liquid in the polymer / combinable liquid system useful for the formation of homogeneous porous polymer intermediates of polymethyl methacrylate and 1,4-butanediol using the standard preparation procedure. . In each example, the intermediate produced was about 13 mm deep and about 65 mm in diameter. The polymethyl methacrylate had been supplied by Rohm and Haas under the designation Plexiglas Acrylic Plastic Molding Powder, lot no. 386491. The details and preparation can be found in Table XXVII: Table XXVIT §š¿nr E liquid Temg., ° C 392 90 215 393 85 225 394 80 225 395 70 210 396 60 229 397 50 230 398 40 229 399 30 225 The 1,4-butanediol was removed from the product of Example 395, and the resulting structure was found to be the cellular structure of the invention, as shown in Fig. 61, which shows the microporous product at 4250 times magnification. The same polymer / liquid system as in Example 394 was also cooled at speeds of up to 4000 K / min and still formed the cellular structure of the invention. usa-nuv-> »- v., V .. 17 7708653-6 Example 500 The porous polymeric intermediate was prepared using the standard procedure for the preparation and heating of a mixture of 30% polymethylemethacrylate, as used in the previous examples, and 70 X lauric acid to 17500 and cooling to give the porous polymeric intermediate. The lauric acid was removed from the resulting intermediate to form a microporous cellular structure of the invention.

Example 501 The porous polymeric intermediate was prepared using the standard procedure for the preparation and heating of a mixture of 30 l of nylon 11, supplied by Aldrich Chemical Company, and 70% of ethylene carbonate to 218 ° C and then cooling of the resulting solution to formation of the porous polymeric intermediate. The ethylene carbonate was removed from the intermediate and the resulting microporous polymer was found to have the cellular structure of the invention.

Example 02 The porous polymeric intermediate was prepared using the standard procedure for the preparation and heating of a mixture of 30% nylon 11, as used in the previous examples, and 70% 1,2-propylene carbonate to 21S ° C and then cooling of the resulting mixture to form the porous polymeric intermediate. The propylene carbonate was removed from the intermediate and the resulting microporous polymer was found to have the cellular structure of the invention.

Examples 503 - 422 Examples 403 - 422 illustrate the formation of the porous polymeric intermediates of polymer / liquid systems containing various amounts of nylon 11, as used in previous examples, and tetramethylene sulfone, supplied by Shell under the name Sulfone W, and containing about 2, 5% water. The polymer / liquid systems with the different concentrations were cooled at different rates and from different solution temperatures, as indicated in Table XXVIII, which also shows that increased cooling rate and increased concentration of the polymer generally result in reduced cell sizes. , _..__ - ... w ~ .._, ..,. a. V,, 7708653-6 ”Table XXVIII fi gggg% liquid: gg Cooling rate Cell size Kfmin Em 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 S 11 409 70 200 20 5 410 70 zoo 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 60 205 80 3.5 416 S0 210 20 3 417 50 210 40 1.5 418 50 210 80 2 419 60 212 20 _-- 420 70 215 20 --- 421 50 217 20 --- 422 90 220 20 --- It also appears from Table XXVIII that there was no discernible porosity in it. with K / min cooled system at liquid concentrations from 40 Å to 10%. Such results are fully in line with expectations, as can be seen in Eig. 62, which shows the melting curve for the concentration range of nylon 11 / tetramethylene sulfone, as well as the crystallization curves at the different cooling rates. From Fig. 62 it can be seen that the system, which contains 40% liquid, at the cooling rate 20 K / min does not fall within the substantially planar part of the crystallization curve and thus would not be expected to form the desired microponous structure. Pig. 63 is a photomicrograph at 1700x magnification of the product of Example 409 showing the typical cell structure of the samples prepared according to Examples 403-418.

Example 423 The porous polymeric intermediate was prepared using the standard procedure and heating a mixture of 30 l of polycarbonate supplied by General Electric under the name Lexan and waves-m. in 70% lentol, to a temperature of 206 ° C and cooling to form the porous polymeric intermediate. The menthol was extracted and the formed microporous cell structure is shown in Fig. 64, which is a photomicrograph of the product at 1700 times magnification.

Example 524 This example demonstrates the formation of the microporous cellular structure of the invention from poly-2,6-dimethyl-1,4-phenylene oxide supplied by Scientific Polymer Products, commonly referred to as polyphenylene oxide. The homogeneous microporous polymeric intermediate was prepared from 30% of said polyphenylene oxide and 70% of N, N-bis (2-hydroxyethyl) tallow fatty amine, which was heated to a solution temperature of 275 ° C, and the intermediate was prepared using the standard procedure. Liquid was removed from the intermediate and the cellular structure of the invention was obtained, as shown in Fig. 65, which is a photomicrograph of the product of this example at 1700 times magnification.

Example 525 This example demonstrates the preparation of the non-cellular product of the invention by cooling a homogeneous solution of 40% polypropylene, also used in the previous examples, and 60% dibutyl phthalate. The solution was extruded on a cooled strip to a thickness of about 0.25 mm, and the cooling rate was above 2400 K / min.

An amount of dispersol was applied to the surface of the belt at a place in front of the place where the solution was extruded onto the conveyor belt. The liquid was removed from the formed film, and a non-cellular microporous product was obtained, as shown in Fig. 65, which is a photomicrograph of the product at 1700 times magnification.

Example 526 This example demonstrates the formation of the non-cellular product of the invention by cooling a homogeneous solution of 25% polypropylene used in previous examples, and 75 N, N-bis (2-hydroxyethyl) tallow fatty amine in the same manner as described in Example 425- The liquid was removed from the formed film, and a non-cellular microporous product was obtained, as shown in Fig. 67, which shows a photomicrograph of the product at 1700 times magnification.

The products of Examples 425 and 426 were analyzed by mercury penetration porosimetry, and their respective penetration curves are shown in Figures 66 and 69. It can be seen that both products generally have narrow pore size distributions, but the product of Example 426 shows a much narrower distribution than the product of Example 425. The product from 7703655-6 8 ° Example 425 thus has a calculated S-value of 24.4, while the product from Example 426 has a calculated S-value of only 8.8. However, the average pore size of the product of Example 425 is very small, 0.096 μm, while the product of Example 426 has an average pore size of 0.559 μm.

In order to quantitatively demonstrate the outstanding cellular compositions of the invention, a number of such microporous products were prepared according to the standard procedure, and details thereof have been summarized in Examples 427 - 457 in Table XXIX. The products of these examples were analyzed by mercury penetration porosimetry to determine their mean pore diameter and S-value, and with scanning electron microscopes to determine their mean cell size S. The results of these analyzes are shown in Table XXX.

Table XXIX §¿¿gr Polymer Liquid Porosity Solution temp- C 427 polypropylene N, N-bis (2-hydroxyl-75 180 ethyl) tallow fatty amine 428 polypropylene N, N-bis (2-hydroxyl-ethyl) tallow fatty amine 60 210 429 polypropylene diphenyl ether 90 200 430 polypropylene diphenyl ether 80 200 431 polypropylene diphenyl ether 70 200 432 polypropylene 1,8-diaminooctane 70 180 433 polypropylene phenyl salicylate 70 240 434 polypropylene 4-bromodiphenyl ether 70 200 435 polypropylene tetrabromoethane 90 180 436 polypropylene N-octyldiethanolamine 75 N-hexyldietethanolamine 75 260 438 polypropylene salicylaldehyde 70 185 439 LD polyethylene capric acid 70 190 440 LD polyethylene 1-octanol 70 178 441 LD polyethylene dibutyl sebacate 70 238 442 LD polyethylene Phosclere EC-S3 70 191 443 LD polyethylene dicapryl adipate 70 204 444 LD-polyethylene diisooctyl phthalate 70 204 445 LD-polyethylene dibutyl phthalate 70 290 446 HD polyethylene N, N-bis (2-hydroxyl-ethyl) tallow fatty amine 80 250 447 polystyrene 1-dodecanol 75 220 448 polystyrene 1,3-bis ( 4-piperdin) - propane 70 186 link .wf, .______ w _ "« @ SX.nr 449 450 451 452 453 454 455 456 457 §š; 2E 427 428 429 430 431 432 433 434 435 436 437 438 439 440 441 442 443 444 445 446 447 Polzger polystyrene polystyrene polystyrene polymethyl methacrylate polymethyl methacrylate Surlyn Surlyn Noryl nyl nylon 3.18 22.5 6.49 6.72 13.0 13.8 a, ss 15.4 16.6 20.0 7.9 1.5 6.8 5.65 3.40 s, o 4, 75 1.8 34.5 28.2 11 I 0.520 0.112 11.6 0.285 0.136 01498 02272 0.137 0.804 0.550 0.631 6.105 1.16 1.00 0.636 0.512 0.671 0.631 1.18 0.696 1.88 81 Table XXIX (continued) ~ ___________ Liquid diphenylamine N-hexyldiethanolamine 7708653-6 Porosity 70 75 Phosclere P31SC 70 1,4-butanediol 1,4-butanediol diphenyl ether dibutyl phthalate 70 85 70 70 N, N-bis (2-hydroxy1-ethyl) ta1gfettamine XX ethylene carbonate SLE § 9.6 2.86 28.4 5.0 1.94 4.52 22.6 27.1 49.4 7.01 26.1 2.36 50.7 4.29 24.5 5.25 19.2 5.13 19.5 2.52 31.7 2.51 75.2 3.22 6.47 8.62 6.6 3.53 9.20 6.07 6.64 5.30 5.74 8 , 21 7.53 3.54 6.61 3.62 49.6 4.34 15.0 3.40 70 lo 'CP 0.982 1.45 0.288 1.36 1.69 1.42 1.71 1.39 1.28 1.29 1.50 1.8 8 0.811 0.533 01964 0.522 0.759 91577 0.820 1.70 1.18 Solution solution. C 235 260 270 1ê5-207 195 250 lo SC -0.243 0.197 -0.697 0.621 0.0153 -0.741 -0.507 0.195 -0.477 -0.619, -0.901 -o, 39o 0.0604 0.255 o, o16o 0.193 0.215 -0.125 -o, 31o -o, 9oo -o, 919 77086 53-6 82 šzlna Q 2 QAR 448 1.08 010737 14.7 449 6.65 0.631 10.5 450 7.4 01154 4511 451 1.4 0.151 9.27 452 9 .2 0.201 45.8 453 114 10.3 11.1 454 6.8 0.631 10.8 455 5.6 0.769 7.28 456 19.0 0.179 106 457 5.8 0.372 15.6 Table XXXI Ex. No. § 2åkrivning, ¿v known; produktgg 458 Celgard 3501 459 Amerace A-30 460 Porex 461 Milípore E 462 Metricel GA-8 463 Sartoríus SM 12507 464 Millipore HAWP 465 Millipore GSWP 04700 466 Millipore VMWP 04700 467 Amicon SUMOS 468 Celgard 2400 469 Millipore 47P Millipore SMP Example 381 472 Product of Example 380 473 Product of Example 383 474 Table XXX (continued) Product of Example 384 S 2.87 63.5 3.74 2.26 3.68 5.19 2.13 2.09 2.74 7.56 lo CP lo C 1.17 1 oz 1.65 0.96 1.66 1.05 1.03 0.862 2.03 1.19 0.424 0.980 -0.296 7 0.208 -0.398 -1.34 -0.504 -0.428 -0.641 0,112 Polggertgg polypropylene polyvinyl chloride polypropylene cellulose-based cellulose-based polyvinyl chloride cellulose-based cellulose-based cellulose-based cellulose-based polypropylene polyvinyl chloride polypropylene polyethylene polypropylene polyethylene ss 7708653-6 Table XXXII gssåg 45 gm 186 2.41 -1.89 461 0.2 * 26.3 1.85 462 0.2 * 9.14 1.66 403 0.2 * 31.5 2.2 404 0.8 * 2.04 0.565 465 0.22 * 1.64 0.672 466 0.05 * 5.37 2.03 467 2.1o ** 61.8 _ 1.79 468 0.02 * 5.08 2.40 460 5 * 1.55 - 0.500 470 0.04 * 5.64 2.15 471 1.1 * ”11.5 1.019 472 0, s ** 17.5 1.34 473 0.56 16.8 1.477 474 70 1.34 -1.718 I From the company's product information x * From the mercury penetration test The data collected in Tables XXIX to XXXII have been summarized in Fig. 70, which is a graph showing log S / C as a function of log C / P. From Fig. 70 it can be seen that the cellular structure according to the invention can be defined as having a log C / P value of from about 0.2 to about 2.4 and a log S / C value of from about -1.4 to about 1.0, and more commonly the polymer will have a log C / P value of from about 0.6 to about 2.2 and a log S / C value of from about -0.6 to about 0, 4.

As can be seen from the foregoing, the invention provides a simple process for the preparation of microporous polymers of any synthetic thermoplastic polymer in a wide variety of thicknesses and shapes. The microporous polymers can have a unique microcellular configuration and are in any case characterized by pore diameters with a relatively narrow size distribution. In the preparation of these structures, one first selects a liquid compatible with the polymer, i.e. which is capable of forming a homogeneous solution with the polymer, and can be removed from the polymer after cooling, after which the amount of liquid is selected and the solution is cooled in a manner SOM 7708653-6 84 ensures that the desired microporous polymer structure is obtained.

As is also apparent from the foregoing, the invention provides microporous polymer products which contain relatively large amounts of functionally useful liquids, e.g. as a polymer additive, and behaves as a solid. These products can be used to advantage in a variety of applications, e.g. in case of premixing.

Claims (11)

7708653-6 Patent claims Microporous, relatively homogeneous body of a polymer, characterized by a thermoplastic polymer, selected from the group of olefin polymers, condensation polymers, oxidation polymers or mixtures thereof, having a substantially isotropic structure and a sharpness factor S of 1 to 30 , the sharpness factor S being determined by analysis of a mercury penetration curve and defined as the ratio between the pressure at which 85% of the mercury penetrated and the pressure at which 15% of the mercury penetrated, the body preferably consisting of a plurality of substantially spherical cells with an average diameter C of 0.5 to 100 μm, which are distributed substantially evenly throughout the structure, the adjacent cells being connected to each other by means of pores, which have a smaller diameter P than the said cells, the ratio of the average the cell size and the average pore diameter C / P is 2: 1 to 200: 1, log C / P is 0.2 - 2.4 and log S / C -1.4 to +1. A microporous body according to claim 1, characterized by an average diameter C of 1 to 20 μm and an average pore diameter of 0.05 to 10 μm. Microporous body according to claims 1-2, characterized by a sharpness factor of 2 to 20. 4. A microporous body according to claims 1-3, characterized by a sharpness factor of 1 - 10. 5. A microporous body according to claims 1-4, characterized by polypropylene as a thermoplastic polymer. Microporous body according to claim 1, characterized by polypropylene as a thermoplastic polymer, a sharpness factor of 1 to 10 and by pores with an average diameter of 0.2 to 5 μm. Process for producing a substantially homogeneous microporous polymer structure, characterized in that a mixture of one or more thermoplastic polymers, selected from the group of olefin polymers, condensation polymers and oxidation polymers, in a mixture with a combinable liquid to form a homogeneous solution is heated to a sufficient temperature for a sufficient time, the homogeneous solution is formed and the shaped solution is cooled so far and so fast that thermodynamic non-equilibrium conditions are achieved and a liquid / liquid phase separator is obtained. ring is initiated and the cooling is continued, avoiding mixing or other shear forces, until a solid body is formed, and to form the microporous structure at least a substantial part of the combinable liquid is removed. Process according to Claim 7, characterized in that the mixture is heated to a temperature near or above the softening point of the thermoplastic polymer to form a solution. 9. A method according to claims 7-8, characterized in that cooling takes place at a rate so that during cooling a plurality of liquid droplets of substantially the same size are formed in a continuous liquid polymer phase. 10. A process according to claims 7-9, characterized in that a mixture of 90-10% polymer and 10-90% inert liquid is used. Use of the microporous polymer structures according to claims 1-10 for the uptake and release of active liquids.