DK171108B1 - Microporous polymer body and its preparation and use - Google Patents

Description

in DK 171108 B1

The invention relates to a three-dimensional, microporous, isotropic and substantially homogeneous polymer body having a relatively narrow pore size distribution, produced by heating a mixture of one or more synthetic thermoplastic polymers in admixture with a compatible liquid to a temperature and for a period of time. sufficient to form a homogeneous solution which has been allowed to assume a desired shape and that the solution in this form has been cooled and at least a substantial portion of the compatible liquid has been removed, said polymers being selected from olefinic polymers, condensation polymers and oxidation polymers. The invention further relates to a process for producing a three-dimensional, microporous, isotropic and substantially homogeneous polymer body with relatively narrow pore size distribution, wherein a process of mixing a mixture of one or more synthetic thermoplastic polymers in admixture with a compatible liquid is heated to a temperature. for a period of time sufficient to form a homogeneous solution which is made to assume a desired shape and that the solution in that shape is cooled and at least a substantial portion of the compatible liquid is removed, said polymers being selected from olefinic polymers, condensation polymers and oxidation polymers. The invention relates finally to the use of such a microporous body for the uptake and deviation of functional fluids.

Many different forms of technique have been developed in the past for the preparation of microporous polymer bodies. Such types of technique range from what is known in the art as classical phase rearrangement, to nuclear bombardment or incorporation of microporous solid particles into a carrier, which particles then exclude, or the synthesis of microporous particles in some form. Previous efforts in the field have resulted in yet other forms of technique as well as countless variations of what might be considered the classical technique or basic technique.

Interest in microporous polymer products is fueled by the myriad potential uses for materials of this type. These potential uses are well known and range from ink pads or the like to leather-like breathable sheets and filtration media. Notwithstanding all the potential uses, commercial exploitation has been relatively modest. Furthermore, the types of commercially exploited techniques have various limitations that impede the agility required to extend the applications to the entire potential market for microporous products.

As mentioned, certain commercially available microporous polymer products are produced by a nuclear bombardment technique. Such a technique is capable of producing a rather narrow pore size distribution. However, the pore volume must be relatively low (i.e. less than about 107. void volume) to ensure that the polymer will not degrade during manufacture. Many polymers cannot be used for such a technique due to the inability of the polymer to be attacked. Furthermore, the technique requires the use of a relatively thin plate or film of the polymer, and considerable expertise must be used in the practice of the method to avoid "double tracking" that results in the formation of oversized pores.

Classic phase rearrangement has also been used commercially to prepare microporous polymers from cellulose acetate and certain other polymers. Classical phase rearrangement is studied in detail by R.E. Kesting in Synthetic Polymeric Membranes, McGraw-Hill, 1971. In particular, on page 117 of this publication, it is clearly stated that classical phase rearrangement involves the use of at least three components, namely a polymer, a solvent for said polymer, and a non-solvent. for said polymer.

Reference is also made to U.S. Patent No. 3,945,926, which discloses the preparation of polycarbonate resin membranes from a casting solution containing the resin, a solvent and a swelling agent and / or a non-solvent. It is stated in lines 42-47, column 15 of said patent, that in complete absence of a swelling agent, phase rearrangement usually does not occur and that at low concentrations of swelling agents there are structures with closed cells.

From the foregoing, it is apparent that classical phase rearrangement requires the use of a solvent for the system at room temperature, which is why many other excellent polymers cannot be used in place of the listed polymers, such as cellulose acetate. From a process point of view, the classical phase rearrangement process will generally be limited to the formation of films, due to the large amount of solvent used in the preparation of the solution, which must later be extracted. It is also apparent that the classical phase rearrangement requires a relatively high degree of process control to obtain bodies of desired configuration. Thus, the relative concentrations of solvent, non-solvent and swelling agent must be controlled critically, as discussed in columns 14-16 of U.S. Pat.

On the other hand, in order to change the pore number and size and homogeneity of the resultant body, the above parameters must be changed experimentally.

Other commercially available microporous polymers are prepared by sintering microporous particles of polymers ranging from high weight polyethylene to polyvinylidene fluoride. However, such a technique is difficult to obtain for a product with the narrow pore size distribution required for many applications.

Yet another general technique which has been the subject of considerable interest involves heating a polymer with various liquids to form a dispersion or solution and then cooling, followed by removal of the liquid with a solvent or the like. This type of process is disclosed in the following U.S. Patents, which are merely representative and not exhaustive: No. 3,607,793, No. 3,378,507, No. 3,310,505, No. 3,748,287, No. 3,536,796, No. Nos. 3 308 073 and 3 812 224. It is not believed that the foregoing technique has been used commercially to any significant degree, if at all, presumably due to the lack of financial feasibility of the particular methods previously developed. The prior methods also do not allow the preparation of microporous polymers combining relatively homogeneous microcellular structures with the pore size and pore size distributions typically desired.

As to the microporous polymers obtained by the prior art, no previously known method has been able to provide isotropic olefinic polymers or oxidation polymers having most of the pore sizes in the range of from 0.1 to approx. 5 microns, while having a relatively narrow pore size distribution, so that in a sample thereof they exhibit a high degree of uniformity in pore size throughout the sample. Some known olefinic polymers or oxidation polymers have had pore sizes within the above range, but without a relatively narrow pore size distribution, so such materials have been of no significant value in such applications as filtration requiring a high degree of selectivity. Furthermore, prior microporous olefinic polymers or oxidation polymers, which may be considered to have relatively narrow pore size distributions, have had absolute pore sizes that are outside the above range, usually with significantly smaller pore sizes for use in such areas as ultrafiltration. Finally, some previously known olefinic polymers have had pore sizes within the above range and have what may be considered relatively narrow pore size distributions. However, such materials have been made by such techniques as stretching which result in a high degree of orientation of the resulting anisotropic material, making the material undesirable in many applications. Thus, there has been a need for microporous olefinic polymers and oxidation polymers having a pore size within a range of from ca.

0.1 to approx. 5 microns and characteristic of a relatively narrow isotropic pore size distribution.

Furthermore, a major disadvantage of many previously known microporous polymers has been the low flow rate of such polymers when used in such structures as microfiltration membranes. One of the major causes of such low flow rates is typically low void volume of many such polymers. Thus, perhaps 20% of the polymer structure or less may be "cavity" volume through which a filtrate can flow, while the remaining 80 percent of the structure is constituted by the polymer resin forming the microporous structure. thus, there has also been a need for microporous polymers with a high void volume, especially with respect to olefinic polymers.

It has now surprisingly been found that the above-mentioned disadvantages can be largely avoided and, by an easily practicable method, obtain a three-dimensional, microporous, isotropic and substantially homogeneous polymer body as defined above, from synthetic olefinic, condensation and oxidation polymers, the polymer body has a relatively narrow pore size distribution.

Accordingly, the microporous polymer body according to the invention is characterized in that the polymer body has a void volume of 10 -90% and a sharpness factor S of 1 - 30, the sharpness factor S being determined by analysis of a mercury penetration curve and defined as the ratio of the pressure. , at which 85% of the mercury has penetrated and the pressure at which 15% of the mercury has penetrated, and the body being prepared by the solution having been cooled for so long and so rapidly that a liquid liquid phase separation under thermodynamic non-equilibrium conditions is initiated and the cooling, while avoiding mixing or other shear forces, continues to form a solid body before removing at least a substantial portion of the compatible liquid in a manner known per se. of the microporous body.

The process of the invention for preparing such a microporous polymeric body is characterized in that the solution in said form is cooled so long and so rapidly that a liquid-liquid phase breakdown under thermodynamic equilibrium conditions is initiated and that the cooling is avoided by mixing or other shear forces. continued to form a solid body before removing at least a substantial portion of the compatible liquid in a manner known per se to obtain the microporous body.

Finally, the subject use is such a microporous polymeric body for the uptake and delivery of functional fluids.

The invention will now be described in more detail with reference to the drawings, in which Figure 1 is a diagram of temperature versus concentration for a hypothetical polymer-liquid system showing the binodial and spinodal curves and illustrating the concentration needed to obtain the microporous polymers and to practice the process of the present invention; 1A is a diagram of temperature versus concentration similar to that of FIG. 1, but also including freezing point depression phase line; FIG. 2 is a photomicrograph at 55X magnification showing the macrostructure of a microporous polypropylene polyor of the present invention having a void volume of about 5%. 75 percent; FIG. 3-5 are photomicrographs of the microporous polypropylene structure of FIG. 2 at 550X, 2200X and 5500X magnifications, respectively, showing a homogeneous cell structure; 6-10 are photomicrographs at 1325X, 1550X, 1620X, 1450X and 1250X magnifications of additional microporous polypropylene structures, respectively, showing the modifications in the structure as the void volume is reduced from 90% to 70%, 60%, 40% and 20%, respectively. 11-13 are photomicrographs at 2000X, 2050X and 1950X, respectively, magnification of still other microporous polypropylene structures of the present invention and illustrate the decreasing cell size as the polypropylene content rises from the 10% by weight level of FIG. 11 to 207. and 30% in FIG. 12 and 13, FIG. 14-17 are photomicrographs at 250X, 2500X, 2500X and 2475X magnification of microporous structures of ridiculous polyethylene according to the present invention; 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 407 and 707 polyethylene, respectively. 18-19 are photomicrographs at 2100X and 2000X magnification of high-density polyethylene microporous structures of the present invention, respectively, showing the structures at 30 and 70% by weight polyethylene, respectively. 20 and 21 are photomicrographs at 2550X and 2575X magnification of microporous SBR polymers of the present invention, respectively, and show a homogeneous cell structure; Fig. 22 is a photomicrograph at 2400X magnification of a microporous methyl pentene polymer; 23 and 24 are photomicrographs at 255X and 2550X magnification of a microporous ethylene-acrylic acid copolymer, respectively. Figure 25 is a photomicrograph at 2500X magnification of a microporous polymer made from a polyphenylene oxide-polystyrene blend; 26 is a photomicrograph at 2050X magnification and shows a microporous polystyrene polymer. 27 is a photomicrograph at 2000X magnification and shows a microporous polyvinyl chloride polymer; 28 and 29 are photomicrographs at 2000X magnification of light-weight polyethylene microporous polymers, showing the partial masking of the basic structure through the "leaf" type structure. 30 to 33 are mercury penetration curves for microporous polypropylene structures according to the present invention and show the narrow pore diameter distribution, for example.

ISLAND

Fig. 1 shows a characteristic characteristic of the polymers of the present invention. 34 to 40 are mercury penetration curves for commercial microporous products comprising "Celgard" polypropylene (Fig. 34), "Amerace A20" and "Amerace A30" polyvinyl chloride (Figs. 35 and 36, respectively), Porej® 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). 41 to 43 are mercury intrusion curves for microporous structures made according to U.S. Patent No. 3,378,507, using polyethylene (Figs. 41 and 42) and polypropylene (Fig. 43); 44 is a mercury intrusion curve for a microporous polyethylene material made in accordance with U.S. Patent No. 3,310,505; 45 and 46 are photomicrographs of a porous polyethylene product prepared by repeating Example 2 of U.S. Patent No. 3,378,507 using an injection molding technique; 45 (240X magnification) shows the macrostructure, and FIG. 46 (2400X magnification) shows the microstructure, FIG. 47 and 48 are photomicrographs of a porous polyethylene product prepared by repeating Example 2 of U.S. Patent No. 3,378,507 using a compression molding technique; 47 (195X magnification) shows the macro structure, and FIG. 48 (2000X magnification) shows the microstructure, FIG. 49 and 50 are photomicrographs of a porous polypropylene product prepared by repeating Example 2 of U.S. Patent No. 3,378,507 using an injection molding technique, 49 (195X magnification) shows the macrostructure, and FIG. 50 (2000X magnification) shows the microstructure, FIG. 51 and 52 are photomicrographs of a porous polypropylene product prepared by repeating Example 2 of U.S. Patent No. 3,378,507 using a compression molding technique; 51 (206X magnification) shows the macro structure, and FIG. 52 (2000X magnification) shows the microstructure, FIG. 53 and 54 are photomicrographs of a porous polyethylene product prepared by repeating Example 2 of U.S. Patent No. 3,310,505, with figs. 53 (205X magnification) shows the macro structure, and FIG. 54 (2Q00X magnification) shows the microstructure, fig. 55 shows a melting curve and a crystallization curve for a (polypropylene and quinoline) polymer / liquid system; 56 shows a melting curve and several crystallization curves for a (polypropylene and N, N-bis (2-hydroxyethyl) -talgamine) polymer / liquid system; 57 shows a melting curve and a crystallisation curve for a (polypropylene and dioctyl phthalate) polymer / liquid system, showing a system which does not fall within the scope of the invention; 58 shows the phase diagram of a (low molecular weight polyethylene and diphenyl polymer / liquid system) determined at cooling and heating speeds of 1 ° C / minute; 59 shows several melting and crystallization curves for a (low molecular weight polyethylene and diphenyl ether) polymer / liquid system; 60 shows a glass conversion curve for a (low molecular weight polystyrene and 1-dodecanol) polymer / liquid system; 61 is a photomicrograph at 5000X magnification of a microporous cell structure with 70% void volume of the present invention, prepared from polymethyl methacrylate; 62 shows melting and crystallization curves for a (Nylon 11 and tetramethylene sulfone) polymer / liquid system; Fig. 63 is a photomicrograph at 2000X magnification of a microporous cell structure with 707 cavity volumes of the present invention, manufactured from Nylon 11; 64 is a photomicrograph at 2000X magnification of a microporous cell structure with 707th void volume of the present invention made from polycarbonate; 65 is a photomicrograph at 2000X magnification of a microporous cell structure with the 70% cavity volian of the present invention made from polyphenylene oxide; 66 and 67 are photomicrographs at 2000X magnification of a microporous non-cellular structure of 607 and 757, respectively, voids lumen of the present invention, made from polypropylene; 68 and 69 are mercury penetration curves for a non-cellular microporous polypropylene structure having 607 and 757 cubic volumes, respectively, which fall within the scope of the invention; 70 is a graphical representation of the peculiar microporous cell structure of the present invention as compared to certain prior art compositions.

Certain novel microporous olefinic polymers and oxidation polymers of the present invention are characterized by a narrow pore size distribution determined by mercury penetration porosimetry. The narrow pore size distribution can be expressed analytically by a sharpness function "S" which is explained in more detail below. The "S" values of the olefinic polymer or the oxidation polymer of the present invention are from about 1 to about 10. The polymer of the invention is also characteristic of average pore sizes ranging from about 0.10 to about 5 microns, with from about 0.2 to about 1 micron being preferred, moreover, such microporous products are substantially isotropic and thus have 1 it essentially the same cross-sectional configuration analyzed along any spatial plane.

According to another aspect of the present invention, the process for preparing microporous polymers is practiced such that a blend comprising a synthetic thermoplastic polymer, in particular a polyolefin, an ethylene-acrylic acid copolymer, a polyphenylene oxide-polystyrene blend, or a blend of one or more of the foregoing polymers, and a compatible liquid is heated to a temperature and for a time sufficient to form a homogeneous solution. The solution is then cooled, forming essentially simultaneously many liquid droplets of substantially the same size. The cooling is then continued to solidify the polymer and at least a substantial portion of the liquid is removed from the resulting solid product to form the desired cellular polymer structure.

The foregoing method will result in microporous polymer products which are characteristic of a cellular, three-dimensional cavity microstructure, i.e. a variety of confined cells with substantially spherical shapes and pores or passage pathways connecting neighboring cells to each other. The basic structure is relatively homogeneous with the cells uniformly distributed over the three dimensions, and the interconnecting pores have diameters of relatively narrow size distribution as measured by mercury penetration. For simplicity, microporous polymers with such a structure will be referred to as '' cellular ''.

The microporous polymeric products obtained by the use of the invention behave as solids and contain relatively large amounts of functionally useful liquids such as polymer additives comprising flame retardants and the like. In this way, useful liquids can achieve the reprocessing benefits of a solid material that can be used directly, for example in a building batch. Such products can be prepared directly by using a functional liquid as the compatible liquid and failing to effect the removal of the compatible liquid, or indirectly by either providing the microporous polymer after the removal of the compatible liquid or by displacing the compatible liquid prior to removal. with a view to incorporating the functional fluid.

Broadly speaking, the practice of the process of the invention involves heating the desired polymer together with a suitable, thus compatible liquid to form a homogeneous solution, cooling said solution appropriately to form a solid, and subsequently extracting the liquid to form a solid. microporous material. The considerations which form part of the practice of the present invention will be described in detail below.

9 DK 171108 B1

Choice of polymer.

As mentioned, the present invention surprisingly provides a technique for making a synthetic polymer as defined above microporous. Thus, the process of the present invention is applicable to olefinic polymers, condensation polymers and oxidation polymers.

Examples of the useful non-acrylic polyolefins are lightweight polyethylene, high weight polyethylene, polypropylene, polystyrene, polyvinyl chloride, acrylonitrile-butadiene-styrene terpolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, poly (4). l), polybutylene, polyvinylidene chloride, polyvinylbutyral, chlorinated polyethylene, ethylene-vinyl acetate copolymers, polyvinyl acetate and polyvinyl alcohol.

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

Polyphenylene oxide is representative of the oxidation polymers that can be used. The condensation polymers useful include polyethylene terephthalate, polybutylene terephthalate, Nylon 6, Nylon 11, Nylon 13, Nylon 66, polycarbonates and polysulfone.

Choice of the compatible fluid.

Thus, in order to practice the present invention, only the choice of the synthetic thermoplastic polymer to be rendered microporous is required. Once the polymer is selected, the next step consists in selecting the suitable compatible liquid and the relative amounts of polymer and liquid to be used. Of course, in practicing the present invention, mixtures of one or more polymers may be used. In the practice, the polymer and liquid are heated with stirring up to the temperature required to form a clear, homogeneous solution. If a solution cannot be provided at any liquid concentration, the liquid is unsuitable and cannot be used with the polymer in question.

Due to the selectivity, it is not possible to provide absolute information regarding the utility of a particular liquid with a particular polymer. However, some useful guidelines can be provided. Thus, when the polymer in question is non-polar, non-polar liquids having similar solubility parameters at the solution temperature are most likely to be useful.

When such parameters are not available, the readily available solubility parameters at room temperature can be used as a general guide. Similarly, in polar polymers, polar organic liquids with similar solubility parameters must first be investigated. Furthermore, the relative polarity or non-polarity of the liquid must be adjusted to the relative polarity or non-polarity of the polymer. Further, with hydrophobic polymeric fluids typically typically have little or no solubility in water. On the other hand, polymers which tend to be hydrophilic will generally require a liquid with some solubility in water.

With regard to suitable liquids, particular species of various types of organic compounds have been found useful, including 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 heterocyclic compounds. However, it should be noted that there is selectivity. Thus, for example, not all saturated aliphatic acids will be useful, and not all fluids useful for high weight polyethylene will necessarily be useful for, for example, polystyrene.

The useful amounts of polymer and liquid for a particular system can easily be determined from an assessment of the parameters that will be discussed in more detail below.

When using mixtures of one or more polymers, usable liquids should typically be utilized with all the polymers included. However, it is possible for the polymer blend to have such characteristics that the liquid need not be able to function with all the polymers used. As an example, when one or more polymeric constituents are present in such relatively small quantities that there is no significant effect on the properties of the mixture, the liquid used need only be able to function with the essential polymer (s).

Although most useful materials are liquids at room temperature, materials that are solid at room temperature can be used if solutions can be formed with the polymer at elevated temperatures and the material does not interfere with the formation of the microporous structure. More specifically, it can be stated that a solid material can be used if the phase separation occurs by liquid-liquid separation rather than by liquid-solid separation during the cooling step, which will be discussed further below. The amount of liquid used can generally range from 10 to 90¾.

As mentioned above, any synthetic thermoplastic polymer can be used if the liquid selected forms a solution with the polymer and the concentration gives a continuous polymer phase by subdivision during cooling, as discussed further below. To give an impression of the range of usable (polymer and liquid) systems, some such systems need to be briefly mentioned.

11 DK 171108 B1

In preparing microporous polymers from polypropylene, the following liquids have been found 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-coco-diethanolamine, benzylamine, N, N-bis-β-hydroxyethyl-cyclohexylamine, diphenylamine and 1,12-diamino dodecane, esters such as methyl benzoate , benzyl benzoate, phenyl salicylate, methyl salicylate and dibutyl phthalate, and ethers such as diphenyl ether, 4-bromo diphenyl ether and dibenzyl ether. Furthermore, halocarbon hydrocarbons such as 1,1,2,2-tetrabromoethane and hydrocarbons such as trans-stilbene and other alkyl / aryl phosphites are also useful, as is the case with ketones such as methylnonyl ketone.

In preparing microporous polymers from high weight polyethylene, the following liquids have been found useful: a saturated aliphatic acid such as decanoic acid, primary saturated alcohols such as decyl alcohol and 1-dodecanol, secondary alcohols such as 2-undecanol and 6-undecanol, ethoxylated amines such as N-lauryl diethanolamine, aromatic amines such as Ν, Ν-diethylaniline, diesters such as dibutyl sebacate and dihexyl sebacate, 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, diphenylmethane and naphthalene, aromatic compounds such as acetophenone, and other organic compounds such as alkyl / aryl phosphites, and quinoline, and quinoline. such as methylnonyl ketone.

For the formation of microporous polymers from lightweight polyethylene, the following liquids have been found useful: saturated aliphatic acids including hexane acid, caprylic acid, decanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid and stearic acid, unsaturated aliphatic acids comprising oleic acid and eruclic acid, , phenyl stearic acid, polystearic acid and xylyl behenic acid, and other acids comprising branched carboxylic acids having average chain lengths of 6, 9 and 11 carbon atoms, tall oleic and resin acids, primary saturated alcohols comprising 1-octanol, nonyl alcohol, decyl alcohol, 1-decanol, 1-decanol tridecyl alcohol, cetyl alcohol and 1-heptadecanol, primary unsaturated alcohols comprising undecylenyl alcohol and oleyl alcohol, secondary alcohols comprising 2-octanol, 2-undecanol, dinonylcarbinol and diundecylcarbinol, and aromatic alcohols comprising 1-phenyl-ethanol, 1-phenyl-ethanol, , phenyl-stearyl alcohol and 1-naphthol . Other useful hydroxyl-containing compounds include oleyl alcohol polyoxyethylene ethers and a polypropylene glycol having an average molecular weight of approx. 400. Still other useful liquids include cyclic alcohols such as 4-t.butyl-cyclohexanol and menthol, aldehydes comprising salicylaldehyde, primary amines such as octylamine, tetradecylamine and hexadecylamine, secondary amines such as bis ( 1-ethyl-3-methyl-pentyl) -amine, and ethoxylated amines comprising N-lauryl-diethanolamine, N-tallow-diethanolamine, N-stearyl-diethanolamine, and N-coco-diethanolamine.

Further useful liquids include aromatic amines comprising N-sec-butylaniline, dodecylaniline, N, N-dimethylaniline, Ν, Ν-diethylaniline, p-toluidine, N-ethyl-o-toluidine, diphenylamine and aminodiphenylmethane, diamines comprising N cyl-1,3-propanediamine and 1,8-diamino-p-menthan, other amines comprising branched tetramines and cyclododecylamine, amides comprising cocoamide, hydrogenated tallow amide, octadecylamide, eruciamide, Ν, Ν-diethyltoluamide and N-triraethylolpropane stearamide, saturated aliphatic ester comprising, including methyl caprylate, ethyl laurate, isopropyl ray state, ethyl palmitate, isopropyl palmitate, methyl stearate, isobutyl stearate and tri-decyl stearate, unsaturated esters comprising stearyl acrylate, butylundecyl ethyl acetate, and , ethyl benzoate, butyl benzoate, benzyl benzoate, phenyl laurate, phenyl salicylate, methyl salicylic acid lat and benzyl acetate, and diesters comprising dimethylphenylenedistearate, diethyl phthalate, dibutyl phthalate, diisooctyl phthalate, dicapryl adipate, dibutyl sebacate, dihexylsebacate, diisooctylsebacate, dicaprylsebacate and dicaprylsebacate. Still other useful liquids are polyethylene glycol esters comprising polyethylene glycol (with an average molecular weight of about 400), diphenyl stearate, polyhydroxy esters comprising castor oil (triglyceride), glycerol monostearate, glycerol monooleate, glycerol distearate ether, glycerol diol etherate, glycerol dioleate and trimethylol propylate and trimethylol propylate comprising hexachlorocyclopentadiene, octabromobiphenyl, decabromodiphenyl oxide and 4-bromodiphenyl ether, hydrocarbons comprising 1-nonen, 2-nonen, 2-undecene, 2-neptadecene, 2-nonadecene, 3-eicose, 9-nonadecene, diphenylmethane, triphenylmethane, triphenylmethane ketones comprising 2-heptanone, methylnonyl ketone, 6-undecanone, methylundecyl ketone, 6-tridecanone, 8-pentadecanone, 11-pentadecanone, 2-heptadecanone, 8-heptadecanone, methylheptadecyl ketone, dinonyl ketone and distearyl ketone, aromatic ketones and acetone ketones other ketones comprising xanthone. Still other useful fluids include phosphorus compounds such as trixylenyl phosphate, polysiloxanes, Muget hyacinth (An Merigenaebler, Inc.) Terpineol Prime No. 1 (Givaudan-Delawanna, Inc.) Bath Oil Fragrance No. 5864 K (International Flavor & Flagrance, Inc.), Phosclere P315C (organophosphate), Phosclere P576 (organophosphate), styrenated nonylphenol, quinoline and quinalidine.

To form microporous polymer products with polystyrene, usable liquids include trihalogenated propyl phosphate, aryl / alkyl phosphites, 1,1,2,2-tetrabromoethane, tribramoneopentyl alcohol, 40% Voranol 3 P. 3000 polyol and tri-bromoneopentyl alcohol 607., tris-p-chloroethyl phosphate, tris- (1,3-dichloroisopropyl) phosphate, tri- (dichloropropyl) phosphate, dichlorobenzene and 1-dodecanol.

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

Furthermore, according to the present invention, microporous products have been prepared from other polymers and copolymers and mixtures. Thus, to form microporous products from styrene-butadiene copolymers, useful liquids include decyl alcohol, N-tallow-diethanolamine, N-coco-diethanolamine, and diphenylamine. Useful liquids for preparing microporous polymers from ethylene-acrylic acid copolymer salts include N-tallow diethanolamine, N-coco-diethanolamine, dibutyl phthalate and diphenyl ether. Microporous polymer products using highly compressed polystyrene can be prepared using liquids of hexabromobiphenyl and alkyl / aryl phosphites. With "Noryln polyphenylene oxide polystyrene blends (General Electric Company), microporous polymers can be prepared using N-coco diethanolamine, N-tallow diethanolamine, diphenylamine, dibutylphthalate and hexabromophenol. Microporous polymers from mixtures of lightweight 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, high weight polyethylene chloride. polyethylene, high weight polyethylene polyvinyl chloride and high weight polyethylene and acrylonitrile-butadiene-styrene (ABS) terpolymers For the production of microporous products from polymethyl methacrylate, 1,4-butanediol and lauric acid have been found to be useful using microporous Nylon 11 ethylene carbonate, 1,2-propylene carbonate or tetramethylene sulfone Menthol can also used for the preparation of microporous products from polycarbonate.

Selection of the concentrations of polymer and liquid.

The determination of the amount of liquid used is obtained by reference to the binodial and spinodal curves of the system, illustrative curves being shown in FIG. 1. As shown therein, the maximum temperature of the binodial curve (i.e., the maximum temperature of the system at which blnodial decomposition will occur) represents Tucg represents the upper critical solution temperature 14 (i.e., the maximum temperature at which spinodal decomposition will take place) indicates the polymer concentration at Tffl, indicates the critical concentration, and 0 den indicates the polymer concentration for the system required to obtain the particular microporous polymeric structures of the present invention. Theoretically, O 2 and E 0 should be identical, but as is known, due to molecular weight distributions of commercial polymer O 5% by weight or similar greater than the value of 0. To produce the particular microporous polymers of the present invention, the polymer concentration 0χ used for a given system must be greater than 0 ^. If the polymer concentration is less than / 2 ^, the phase breakdown that will occur as the system cools constitutes a continuous liquid phase with a discontinuous polymer phase. On the other hand, use of the proper polymer concentration will ensure that the continuous phase which will be formed upon cooling to phase partition temperature will be the polymer phase as required to obtain the distinctive microcellular structures of the present invention. Furthermore, it appears that the formation of a continuous polymer phase upon phase separation requires that a solution be initially formed. When the process of the invention is not followed and initially a dispersion is formed, the resulting microporous product is similar to that obtained by sintering polymer particles.

Accordingly, the applicable polymer concentration or the amount of liquid to be used will vary with each system. Suitable phase diagram curves for several systems have already been developed. However, if a suitable curve is not available, it can be readily obtained by prior art. A suitable technique is described, for example, in Smolders, van Aartsen and Steenbergen, Kolloid-Z.u.Z. Polymers, 243, 14 (1971).

A more general diagram of temperature versus concentration for a hypothetical polymer-liquid system is shown in FIG. 1A. The part of the curve that goes from Y to a represents thermodynamic equilibrium phase separation in liquid-liquid. The curve portion from α to β represents equilibrium phase distribution in liquid-solid, which can be considered the normal freezing-point depression curve for a hypothetical liquid-polymer system. The upper shaded area represents an upper liquid / liquid immiscibility which may be present in some systems. The dashed line represents the lowering of the crystallization temperature due to cooling at a rate sufficient to achieve thermodynamic non-weight-weight phase separation in liquid-liquid. The flat portion of crystallization versus composition curve defines a useful composition range that is a function of the cooling rate used, as discussed further below.

15 DK 171108 B1

Thus, for a given cooling rate, the crystallization temperature versus percent resin or compatible liquid can be recorded, and in this way the liquid / polymer concentration ranges which will give the desirable microporous structures at the given cooling rate can be determined. * For crystalline polymers, the concentration range via recording of the above crystallization curve a useful alternative for determining a phase diagram, as shown in FIG. 1. As an example of the foregoing, reference is made to FIG. 55, there is a record of temperature versus polymer / liquid concentration showing the melting curve at a heating rate of 16 ° C per minute. and the crystallization curve of polypropylene and quinoline over a wide concentration range. As can be seen from the reference to the crystallization curve, at a cooling rate of 16 ° C per minute. the appropriate concentration range from approx. 20% polypropylene to approx. 70% polypropylene.

FIG. 56 is a diagram of temperature versus polymer / liquid composition for polypropylene and N, N-bis (2-hydroxyethyl) -talgamine. The upper curve is a record of the melting curve at a heating rate of 16 ° C per minute. minute. The lower curves,! in descending order, records of the crystallization curves at cooling rates of 8 ° C, 16 ° C, 32 ° C and 64 ° C per annum. minute. The curves show two simultaneous phenomena that occur when the cooling rate is raised. First, the flat portion of the curve showing a relatively stable crystallization temperature over a wide concentration range is lowered with increasing cooling rate, which shows that the faster the cooling rate, the lower the actual crystallization temperature.

The other noticeable phenomenon is the change in the slope of the crystallization curve that occurs with a change in the cooling rate. Thus, it appears that the flat area of the crystallization curve is extended as the cooling rate is raised. Therefore, it can be assumed that by raising the cooling rate it is possible to extend the applicable concentration range for the preparation of the microporous structures of the present invention and for practicing the methods of the invention. It is apparent from the foregoing that in order to determine the usable concentration ranges for a given system, one need only prepare a few representative polymer / liquid concentrations and cool them at some desired rate. After the crystallization temperatures are recorded, the usable range of concentrations will become clear.

FIG. 57 is a diagram of temperature versus polymer / liquid concentration for polypropylene and dioctyl phthalate. The upper curve represents the melting curve of the system over a range of concentrations, and the lower curve represents the crystallization curve over the same concentration range. Since the crystallization curve shows no flat area over which the crystallization temperature remains substantially constant for a range of concentrations, one would not expect the polypropylene / dioctyl phthalate system to be capable of forming microporous structures , and neither does it.

In order to assess the excellent relationship between the phase diagram method for determining usable concentration ranges of polymer and liquid and the crystallization method for making such a decision, reference is made to Figs. 58 and 59. 58 is a phase diagram of a (low molecular weight polyethylene and diphenyl ether) polymer / liquid system as determined by a conventional light scattering technique using a thermally controlled container. From the phase diagram of FIG. 58 shows that lies at approx. 135 C and tenderness is at approx. 7 percent polymer. Furthermore, it appears that at approx. 45 percent polymer concentration intersects the cloud point curve freezing-point depression curve, indicating a useful concentration range from ca. 7 percent polymer to approx. 45 percent polymer.

The usable area determined from FIG. 58 can be compared with the range which can be determined from FIG. 59, showing melting curves for the same system at heating rates of 8 ° C and 16 ° C per second. per minute and crystallization curves for said system at cooling rates of 8 ° C and 16 ° C per minute. minute. From the crystallization curves, it appears that the substantially flat portion thereof ranges from slightly below 10 percent polymer concentration to about 42-45 percent polymer, depending on the rate of cooling. Thus, the results obtained from the crystallization curves agree surprisingly well with the results obtained from the blur point phase diagram.

For non-crystalline polymers, it is assumed that reference can be made to a temperature versus concentration record of the glass conversion ester operation as an alternative to reference to a phase diagram such as that of FIG. 1. FIG. 58 is thus a diagram of temperature versus concentration for the low-molecular-weight polystyrene glass transition temperature, provided by the Pennsylvania Industrial Chemical Corporation under the designation Piccolastic D-125, and 1-dodecanol, at various concentration levels.

In FIG. 58 shows that from approx. 8 percent polymer to approx. 50 percent polymer, the glass conversion temperature of polystyrene / l-dodecanol is substantially constant. It has therefore been suggested that the concentrations along the substantially flat portion of the glass conversion curve would be useful in practicing the present invention, analogous to the flat portion of the crystallization curves discussed above. Thus, it appears that a useful alternative for determining the phase diagram of systems with non-crystalline polymer is to determine the glass transformation curve and to operate within the substantially flat region of such a curve.

In all of the preceding figures, crystallization temperatures are determined with a DSC-2, scanning differential calorimeter manufactured by Perkin-Elmer, or similar apparatus. Further effects of cooling rates on practice 17 of the present invention will be discussed below.

After selecting the desired synthetic thermoplastic polymer, the compatible liquid and the potentially applicable concentration range, selection of, for example, the actual concentration of polymer and liquid to be used is required. In addition to considering, for example, the theoretically possible concentration range, other functional considerations must be taken into account when determining the amounts used for a particular system. Thus, with regard to the maximum amount of liquid to be used, the resulting strength properties must be taken into account. More specifically, the amount of liquid used should allow the resulting microporous structure to have sufficient minimal "handling strength" to avoid coincidence of the microporous or cellular structure. On the other hand, in selecting the maximum amount of resin viscosity limitations for the apparatus used, In addition, the amount of polymer used must not be so large as to result in confining the cells or other areas of microporosity.

The relative amount of liquid used will also depend to some extent on the desired effective size of the body corrosion, such as, for example, the specific cell and pore size requirements of the final application in question. Thus, for example, the average cell and pore size tends to increase somewhat with increasing fluid content.

In any case, the usefulness of a liquid and the concentration applicable to the liquid, in conjunction with a particular polymer, can be readily determined by using the liquid experimentally as described above.

Of course, the parameters discussed above must be followed. Of course, mixtures of two or more liquids can be used and the utility of a particular mixture can be determined as described herein. While a particular mixture may be applicable, one or more of the liquids individually may well be unsuitable.

The particular amount used will also often be dictated by the particular end use in question. As Illustrative Examples of Specific Examples Using High Weight Polyethylene and N, N-Bls (2-Hydroxyethyl) -talgamine, useful microporous products can be prepared using, by weight, of from about 30 to approx. 90% amine, with from 30 to 70% being preferred. With lightweight polyethylene and the same amine, the amount of liquid can be varied within the range of approx. 20 to approx. 90%, with 20 to 80% being preferred. When used as a liquid diphenyl ether, on the other hand, systems with low-density polyethylene contain no more than approx. 80% liquid, with a maximum of approx. 60%. When 1-hexadecene is used in combination with lightweight polyethylene, amounts of up to approx. 90% or more. When polypropylene is used in conjunction with the tallow amine described above, the amine can conveniently be used in amounts of from about 10 to approx. 90%, with a maximum amount of no more than approx. 857 .. With poly-1β DK 171108 B1 styrene and 1-dodecanol the concentration of the alcohol can vary from approx. 20 to approx. 90%, with a preference of approx. 30 to approx. 70%. When styrene-butadiene copolymers are used, the amine content may range from approx. 20 to approx. 90%. When a system of decanol and styrene-butadiene copolymer (i.e., SBR) is used, the liquid content may suitably vary from ca. 40 to approx. 90%, and with diphenylamine, the liquid content is suitably within the range of approx. 50 to approx. 80%. When microporous polymers are prepared from the amine and an ethylene-acrylic acid copolymer, the liquid content can range within the range of from approx. 30 to approx. 70%, and with diphenyl ether the liquid content can vary from approx. 10 to approx. 90%, as is the case when dibutyl phthalate is used as the solvent.

Formation of the homogeneous liquid.

After preparing the solution, it can then be worked up to provide any desired shape or configuration. In general, and depending on the system in each case, the thickness of the article may vary from a thin film of approx. 1 mile or less up to a relatively thick block with a thickness of approx. 2 1/2 inches or even more. Thus, the ability to form blocks allows the microporous material to be worked up into any desired complicated shape, such as using conventional extrusion, injection molding or other related technique. The practical considerations included in determining the thickness range that can be provided from a particular system include the degree of viscosity buildup that the system undergoes as it cools. In general, the higher the viscosity, the thicker the structure may be. Accordingly, the structure can have any thickness as long as a strong phase separation does not occur, ie. that two distinguishable layers become visible.

If liquid-liquid phase separation is allowed to take place under conditions of thermodynamic equilibrium, the result will be a complete breakdown into two separate layers, one layer consisting of molten polymer containing the soluble amount of liquid and a liquid layer containing the soluble amount of liquid. polymer in the liquid. This condition is represented by the blnodial line in the phase diagram of FIG. 1 and 1A. It will be seen that a limitation on the size of the article which can be manufactured is dictated by the heat transfer properties of the composition, because if the article is thick enough and the heat transfer is low enough, the cooling rate in the center of the article may be slow enough to reach conditions for thermodynamic equilibrium and result in a phase breakdown into separate layers, as described above.

Larger thicknesses can also be obtained by adding smaller amounts of thixo-tropic materials. For example, the addition of the commercial carbon dioxide silicon dioxide prior to cooling will significantly increase the usable thicknesses without any adverse effect on the characteristic microporous structure. The quantities of 19 DK 171108 B1 to be used can easily be determined '

Cooling of the homogeneous solution '

As can be seen from the above discussion, regardless of the nature of the work-up (eg casting for a film or the like), the solution must be cooled to form what behaves as, and appears as, a solid. The resulting material must have sufficient integrity that it will not crumble upon handling, e.g. with the hand. A further test to determine whether the necessary system has the desired structure is to use a solvent for the liquid used, but not for the polymer. If the material disintegrates, the system used does not meet the necessary criteria.

The rate of cooling of the solution may vary within wide limits. In the ordinary case, no exterior cooling need be used, and it is satisfactory merely, for example, to cast a film by pouring the hot liquid system onto a metal surface heated to a temperature which permits the film to be drawn, or alternatively to produce a block by pouring on a carrier at room conditions.

The cooling rate, as discussed above, must be sufficiently fast that the liquid-phase phase separation does not occur under conditions of thermodynamic equilibrium. Furthermore, the cooling rate can have a significant impact on the resulting microporous structure. For many polymer / liquid systems, if the cooling rate is sufficiently slow, but still meets the above criteria, the liquid-phase phase separation at substantially the same time will result in the formation of many liquid droplets of substantially the same size. If the rate of cooling is such that the many liquid droplets are not formed, if all other conditions discussed herein are met, the resulting microporous polymer will have the cellular microstructure as defined above.

It is generally believed that the peculiar structures of the microporous polymers of the present invention are obtained by cooling the liquid system to a temperature below the binodial curve, as shown in FIG. 1, so that liquid-phase phase separation is initiated. At this stage, germs will begin to form, consisting mainly of pure solvent. When the rate of cooling is such that the cellular microstructure emerges, it is also believed that as each such germ continues to grow, it is surrounded by a polymer-rich region which increases in thickness as it is depleted of liquid. Finally, this polymer-rich region resembles a skin or film that covers the growing drop of solvent. As the polymer-rich region continues to thicken, the diffusion of additional solvent decreases through the skin and the growth of the liquid droplet decreases accordingly until it completely stops, at which point the liquid droplet has reached its maximum size. At this point, the emergence of a new germ is more likely than continued growth of the large solution droplet droplet droplet. However, to achieve this type of growth it is necessary that nucleation be initiated by spinodal decomposition rather than by binodinal decomposition.

The cooling is carried out in such a way that at substantially the same time many liquid droplets of substantially the same size are formed in a continuous polymer phase. If this method of decomposition is not available, the cellular structure will not appear. The proper mode of decomposition is generally obtained by applying conditions which ensure that the system does not reach thermodynamic equilibrium until at least nucleation or droplet growth has been initiated. Process-wise, this can be achieved by simply allowing the system to cool without subjecting it to mixing or other shear forces. The time parameter may also be important where relatively thick blocks are formed which make faster cooling desirable in some cases.

Within the range over which cooling results in the formation of many liquid droplets, there are common indications that the rate of cooling may affect the size of the resulting cells, with increasing cooling rates resulting in smaller cells. In this context, it has been observed that an increase in the cooling rate from ca. Apparently, 8 ° C / minute will result in the cell size being reduced in half by a microporous polypropylene polymer. Accordingly, exterior cooling can, if desired, be used to control the final cell and pore size, as discussed in more detail below.

The manner in which the interconnecting pathways or pores are formed in the cellular structure is not fully elucidated. Without attaching themselves to any particular theory, however, there are various possible mechanisms that serve to explain this phenomenon, each of which is consistent with the principle described herein. Thus, the formation of the pores may be due to thermal creep of the polymer phase upon cooling, with the liquid solvent droplets behaving as non-compressible spheres when the solvent has a smaller coefficient of expansion than the polymer. Alternatively, and as stated above, even after the solvent droplets have reached their maximum size, the polymer-rich phase will still contain some residual solvent and vice versa. Consequently, as the system continues to cool, further phase separation may occur. Therefore, the residual solvent in the polymer-rich skin can diffuse to the solvent droplet, which reduces the volume of the polymer-rich skin and increases the volume of the solvent droplet. This may weaken the polymer skin, and the volume increase of the solvent or liquid phase may result in internal pressures capable of penetrating the polymer skin to provide connection between adjacent solvent droplets. Related to the latter mechanism, the polymer can redistribute itself to a more compact state as the residual liquid migrates out of the polymer skin, as in crystallization, when such type of polymer is used. In such a situation, the resulting polymeric skin is likely to shrink and exhibit imperfections or openings, probably located in the areas of particular weakness. The weakest areas are expected to be located between adjacent liquid droplets, and in such a situation, the openings will appear between neighboring liquid droplets and result in interconnection of the solvent droplets. In any case, and regardless of the mechanism, the interconnecting pores or pathways emerge as the process is carried out, as described herein.

An alternative explanation for the mechanism by which pores are formed is based on the "Marangoni effect" discussed in C. Marangonl, Nuovo Cimento [2] 5-6,239 (1871), [3], 3,97,193 (1878 ) and C. Harangoni, Ann.Phys.Lpz. (1971), 143, 337. The Marangoni effect has been used to explain the phenomenon that occurs when alcoholic beverages spontaneously reflux down the sides of drinking glasses, in particular the mechanism, which occurs when a condensed droplet flows back into the liquid mass. The liquid's liquid first penetrates through the liquid into the liquid mass followed by the rapid withdrawal of part of the liquid into the droplet. It has been hypothesized that a similar physical phenomenon exists with the liquid droplets, one drop can meet another drop, and the liquid from one can penetrate the liquid from the other followed by rapid separation of the two drops, leaving perhaps one part of the fluid which provides a connection between the two drops and forms the basis of the interconnecting pores in the cell structure. For a more recent discussion of the Marangoni effect, see Charles & Manson, J. Colloid.Sc., 15, 236-267 (1960).

If the homogeneous solution is cooled at a sufficiently high rate, the liquid-phase phase separation can take place under conditions of thermodynamic non-equilibrium, but significant solidification of the polymer can occur so rapidly that virtually no nucleation can occur and subsequent growth. In that case, many liquid droplets will not form, and the resulting microporous polymer will not have the particular cellular structure.

Thus, in some circumstances, it is possible to gain different microporous structures by using particularly high cooling rates. For example, when a solution of 75 parts of N, N-bis (2-hydroxyethyl) -talgamine and 25 parts of polypropylene is cooled at rates varying from approx. 5 ° C to approx. 1350¾ Per * minute, the cellular structure appears. The major effect of different cooling rates within the above range on the composition is the change in absolute cell size. When cooling speeds of approx. For example, at 2000 ° C / minute, the microstructures assume a fine, lace-like, non-cellular appearance. When a solution of 60 parts of N, N-bis (2-hydroxyethyl) -talgamine and 40 parts of polypropylene is treated in the same way, cooling rates of more than 22 parts must be reached. per minute, before the lace-like non-cellular structure is obtained.

To investigate the effect of the cooling rate of the system on the cell size of the cell structure and to investigate the rate of cooling required for transition from preparation of the cell structure to producing a structure without distinct cells, different concentrations of polypropylene and N, N-bis ( 2-hydroxyethyl) -talgamine prepared as homogeneous solutions. To conduct such a study, the DSC-2 mentioned above was used in conjunction with standard X-ray equipment and a scanning electric microscope. As the DSC-2 is capable of a maximum cooling rate of approx. 80 ° C / minute, a thermogradient bar was also used. The thermogradient bar was a brass bar capable of having a temperature differential of more than 2000 ° C over its length of 1 meter on which samples could be placed.

An infrared camera was used to determine the temperatures of the samples by first focusing the camera on a dish placed in the closest of the ten rod positions to a temperature of 110 ° C, measured with a thermocouple. The camera uncertainty control was then set until the camera temperature reading matched the thermocouple reading.

At each trial, the camera was focused on a position at which a given bowl containing the sample solution should cool. The dish with the sample was then placed on the thermogradient rod for two minutes. When the bowl was removed from the rod to be placed in the camera field, a stopwatch was started. As soon as the camera indicated that the bowl had a temperature of 110 ° C, the stopwatch was stopped and the time was recorded. Thus, the determined cooling rates were based on the time required for the sample to cool over a temperature range of approx. 100 ° C.

It turned out that the determining limitation on the cooling rate was not the amount of material that was cooled. It was observed that although heavier specimens were cooled more slowly than lighter specimens, the silicone oil used on the bottom of the bowl for thermal conduction between the bowl and rod had a significant influence on the cooling rate. Thus, the highest cooling rates were achieved by placing a bowl without any silicone oil on an ice cube, and the slowest cooling rates were obtained with a heavy silicone oil coating plate and placed on a piece of paper.

Five samples of polypropylene were prepared containing from 0% N, N-bis (2-hydroxyethyl) -talgamine to 80% of this amine, for use in investigating the effect of the cooling rate on the resulting structures. Approximately 5 milligrams of each of said samples were heated on DSC-2 inside closed bowls at 40 ° C per minute. per minute to a maintained temperature of 175 ° C for the sample containing 20% polypropylene, 230 ° C for the sample containing 40% polypropylene, 245 ° C for the sample containing 60% polypropylene, 265 ° C for the sample containing 80% polypropylene and 250 ° C for 100% polypropylene.

23 DK 171108 B1

Each preheat was heated to and bubbled at that temperature for 5 minutes prior to cooling. After the samples were cooled at the desired cooling rate, N, N-bis (2-hydroxyethyl) -talgamine was extracted from the sample with methanol and the sample analyzed. The results of the study are listed in Table I, showing the sizes of the cells in microns in the resulting compositions. All cell sizes were determined by taking measurements from the respective micrographs taken with the scanning electron microscope.

Table I

Cooling rate 5 ° C / min. 20 ° C / min. 40 ° C / min. 80 ° C / min.

Composition 0% Amine None ^ None ^ None ^ None ^^ 20% Amine 0.5 ^^ 0.5 ^^ None ^^ None ^ 40% Amine 2.5 ^ 2.0 ^ 2.0 ^ 0.7 ^ 60% Amine 4.0 3.0 2.0 1.5 ^ 80% Amine 0.5 4.0 3.0 3.0 (6 ^ (1) Some irregular holes existed (2) Approximately largest cell size (3 ) Porosity presumably too small to measure (4) Some small cells were available at 1/10 size of larger cells (5) Additional cells were too small to measure (6) Some formation of non-cellular structure

A further cooling rate study was performed using samples of 20% polypropylene and 807. N, N-bis (2-hydroxyethyl) -talgamine on the thermogradient rod. Five such samples were cooled at different rates from a melting temperature of 210 ° C, and the results are summarized in Table II, showing the sizes of the cells in microns, using the same method as in providing Table I data.

Table II

Cooling rate 200 ° C / min. 870 ° C / min. 1350 ° C / min. 1700 ° C / min.

Composition 80% Amine 0.5-3 0.5-1.5 1.5-2.5 non-cellular

Tables I and II show that with increasing cooling rates, the size of the cells in the resulting compositions generally decreases. In addition, with respect to the polymer / liquid system comprising 20% polypropylene and 80% N, N-bis (2-hydroxyethyl) -talgamine, it is apparent that at a cooling rate between ca. 1350 ° C per day per minute and 1700 ° C per minute. per minute, a transformation in the nature of the resulting polymer is accomplished from being essentially cellular to non-cellular. Such a transformation in the resulting structure corresponds to the fact that the polymer becomes substantially solidified after initiation of the liquid phase phase separation, but prior to the formation of many liquid droplets, as discussed above.

In addition, five samples of 40% polypropylene and 60% N, N-bis (2-hydroxyethyl) -talgamine were prepared which were cooled at rates of 690 ° C. to over 7000 ° C per minute. per minute, from melting temperatures of 235 ° C, by the method mentioned above. It was determined that for such a concentration of polypropylene and said amine, the conversion from cellular to non-cellular structure occurs at ca. 2000 ° C per day minute.

Finally, to investigate the crystallinity of structures prepared over a range of cooling rates, three samples of 20% polypropylene and 80% N, N-bis (2-hydroxyethyl) -talgamine, which were cooled at 20 ° C, were prepared. 1900 ° C and 6500 ° C per day. minute. From the DSC-2 data for such samples, it was determined that the degree of crystallinity of the three samples was essentially equivalent. Thus, it appears that variations in the cooling rate have no significant effect on the degree of crystallinity of the resulting structures. However, it was shown that when the cooling rate was significantly increased, the crystals that formed became less perfect as expected.

Removing the liquid.

After the homogeneous solution of polymer and liquid is formed and the solution is cooled appropriately to form a material of appropriate handling strength, the microporous product can then be prepared by removing the liquid by e.g. extraction with any suitable solvent for the liquid, but which is of course a non-solvent for the polymer in the system. The relative miscibility or solubility of the liquid in the solvent used will partially determine the efficiency in terms of the time required for extraction. The extraction or leaching operation can also, if desired, be carried out at an elevated temperature below the softening point of the polymer to lower the time requirements. Illustrative examples of useful solvents include 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, it may be unnecessary to extract 100% of the liquid used in the system and smaller quantities can be tolerated, the amount tolerable depending on the requirements of the intended end use. Accordingly, the time required may vary within the range of a few minutes or perhaps less to more than 24 hours or even more, depending on many factors including the thickness of the sample.

Removal of the liquid may also be accomplished by other prior art techniques. Illustrative examples of other useful forms of removal technique include evaporation, sublimation, and shear.

DK 171108 B1

It is further noted that the cellular microporous polymeric structures of the present invention, using conventional forms of liquid extraction technique, may exhibit release of a liquid contained in the structure in a manner approaching zero order, i.e. the release rate may be substantially cash after, perhaps, an initial period of high release rate. In other words, the release rate may be independent of the amount of liquid released. Thus, the rate at which the liquid is extracted after, for example, three-quarters of the liquid has been removed from the structure is approximately the same as when the structure was half filled with liquid. An example of such a system which exhibits a substantially constant release rate is the extraction of N, N-bis (2-hydroxyethyl) -talgamine from polypropylene with isopropanol as extractant. In any situation, there is also likely to be an initial induction 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 of the first order.

Characterization of the microporous polymers.

Cell structure.

When the polymer / liquid solution is cooled to form the plurality of liquid droplets, as discussed above, and the liquid is removed therefrom, the resulting microporous product forms a relatively homogeneous cell structure comprising, at microscale, a series of substantially spherical, enclosed microcells. essentially uniform throughout the structure. Neighboring cells are interconnected by smaller pores or passageways. This basic structure can be seen in the photomicrographs of FIG. 4 and 5. It is noted that the individual cells are in fact confined but appear open on the photomicrographs due to the breakage that is included in the sample preparation for recording the photomicrographs. On a macro scale, the structure appears, at least for the crystalline polymers, to have planes corresponding to the fracture planes along the edges of crystal growth (see Fig. 2) and are, as shown in Figs. 3, coral-like in appearance. The cellular microstructure can be further analogized with zeolite structures containing distinct "chamber" and "portal" regions. The cells correspond to the larger chamber areas of zeolite structures, while the pores correspond to the portal regions.

In the cell structure, in general, the average diameter of the cells will vary from ca. 1/2 micron to approx. 100 microns, with the range from about 1/2 to approx. 50 microns is the most typical, while the average diameter of the pores or interconnecting passageways typically appears to be about an order of magnitude smaller. Thus, for example, if the cell diameter of a microporous polymer structure of the present invention is about 1 micron, the average diameter of the pore or interconnecting pathway will be va. 0.1 micron. As pointed out above, the cell diameter and also the diameter of the pore or passage path will depend on the polymer-liquid system in each case, the rate of cooling, and the relative amounts of polymer and liquid used. However, a wide range of cell-to-pore ratios is possible, such as from ca.

2: 1 to approx. 200: 1, typically from approx. 5: 1 to approx. 40: 1.

As can be seen from several figures, it may appear that some of the cellular microporous polymer products shown as examples do not exhibit the distinctive microcellular structure described herein. However, it should be borne in mind that in some cases this structure may be masked by further modifications arising from the particular liquid or polymer involved or the relative amounts used. This masking may be complete or partial, ranging from small polymer particles bonded to the walls of the cells, to coarse "leaf type" polymer structures that tend to completely mask the basic structure in the photomicrographs. Thus, for example, as seen in FIG. 21 and 25, small polymer balls attached to the cell cavities of the structures. This additional occurrence can be understood by reference to the nucleation and growth principle described above. Thus, in systems with very high solvent or liquid content, the maximum cavity size will typically be relatively large. This means that the time required for the cavity or drop to reach its maximum size will be correspondingly increased. During this time, additional germs may be formed in the vicinity. Two or more germs can then come into contact with each other before each reaches its maximum size. In such cases, the resulting cell structure has less integrity and somewhat less regularity than the basic structure described above. Furthermore, even after the liquid droplets have reached their maximum size, depending on the present system, the solvent or liquid phase may still contain a certain amount of residual polymer or vice versa. In such situations, as the system continues to cool, some additional residual phase separation may occur. When the residual polymer is simply separated from the solution, spheres of polymer can be formed, as shown in FIG. 21 and 25. On the other hand, if the residual polymer diffuses to the polymer skin, the walls will appear blurry and irregular, thus forming the "leaf type" structure. This "blade type" structure can mask the basic structure only partially, as shown in FIG. 28 and 29, or it can completely mask the structure, as shown in FIG. 6th

The "leaf type" structure is also more likely to occur with certain polymers. Thus, the microporous structures of lightweight polyethylene, perhaps due to the solubility or similar of the polyethylene in the liquids used, typically produce this type of structure. This can be seen in FIG. 14. Furthermore, when the liquid levels used are very high, this would also happen with such polymers as polypropylene, which otherwise exhibit the basic structure. This can be easily observed by comparing the "leaf type" structure of the microporous product of FIG. 6 with the basic structure shown in FIG. 8, where the polymer content is 40% by weight compared to the 10% polypropylene in the structure shown in FIG. 6th

For most applications, it is preferred to use a system that results in the formation of the cellular basic structure. The relative homogeneity and irregularity of this structure yields predictable results as required for filtration purposes. However, the leaf type structure may be more desirable where relatively high surface area structures are desired, such as by ion exchange or various adsorption processes.

As can also be observed, some of the structures have small holes or openings in the walls of the cells. This phenomenon can also be understood by reference to the nucleation and growth principle. Thus, in a section of the system in which a few spatially connected liquid droplets have reached their maximum size, each droplet will be enclosed by a polymer-rich skin. However, in some cases, some solvent may be trapped between the droplets, but cannot continue its migration to the larger droplets due to the skin's impermeability.

Accordingly, in such cases, a germ of fluid can be formed and grow, resulting in a small cavity embedded adjacent to the larger droplets. After extraction of the liquid, the smaller droplets will appear as a small hole or small opening. This can be observed in the microporous structures shown in FIG. 11-12 and 20.

Another interesting feature of the cell structures of the present invention relates to the surface area of such structures.

The theoretical surface area of the microporous cell structure consisting of 2 interconnected spherical cavities of ca. 5 microns in diameter is about 2-4 m / g.

It has been found that microporous polymers made according to the present invention need not be limited to the theoretical boundary of the surface area. Determination of the surface area by the B.E.T. method described by S. Brunauer, P.H. Emmett and E. Teller, MThe Adsorption of Gases in Multimolecular Layers ", J. Am. Chem. Soc., 60, 309-316 (1938) have shown surface areas far above the theoretical model and which do not relate to the void volume, as shown in Table III, for microporous polymers made from polypropylene and N, N-bis (2-hydroxyethyl) -talgamine.

Table III

% Cavity Specific surface area 89.7 96.2 m2 / g 72.7 95.5 60.1 98.0 50.5 99.8 28.9 88.5

The surface area can be reduced by careful annealing of the microporous polymer without affecting the basic structure. Microporous polypropylene made with cavity volume using N, N-bis (2-hydroxyethyl) -talgamine as the liquid component was extracted and dried at temperatures not exceeding room temperature and then heated to affect the surface area. The initial surface area was 96.9 m / g. After eleven heating periods of every 40 minutes at 62 ° C, the surface area dropped to 66 m 2 / g. Further heating at 60 ° C for an additional 66 hours lowered the surface area to 51.4 m / g. Treatment of another sample at 90 ° C for 52 minutes lowered the surface area from 96.9 to 33.7 m / g. The micro-porous structures were not significantly altered according to study by scanning electron microscopy.

These results are summarized in Table IV.

Table IV

2

Treatment Surface area (m / g) 7. Change none 96.9 eleven, 40 min.

treatments at 62 ° C 66.0 327 «for more than 66 hours at 60 ° C 51.4 477.

53 hours at 90 ° C 33.7 657.

It will be appreciated that one of the peculiar features of the cell structures of the present invention relates to the presence of both spaced, substantially spherical, enclosed microcells that are uniformly distributed throughout the structure, and spaced pores interconnecting said cells, which are pores of a smaller diameter than said cells. Furthermore, said cells and interconnecting pores have essentially no spatial orientation and can be classified as isotropic. Thus, there is no preferred direction, such as for the flow of a liquid through the structure. This is in stark contrast to prior art materials which do not exhibit such cell structure. Many prior art systems have an indeterminate structure that lacks any structural configuration suitable for definition. It is therefore surprising that a microporous structure with such a degree of uniformity can be produced and which would be highly desirable for many applications requiring very uniform materials.

The cell structure can be defined by the ratio of the average diameter of the cells ("C") to the diameter of the pores ("P"). The ratio of C / P can thus, as mentioned above, vary from approx. 2 to approx. 200, the range from ca. 5 to approx. 100 is typical, and the range from ca. 5 to approx. 40 even more typical. Such a C / P ratio separates the cell structure of the present invention from any previously known microporous polymer product. Since there is no known synthetic thermoplastic polymer structure with separated cells and pores, all such known materials can be considered as having a cell-to-pore ratio of 1.

Another means of characterizing the cellular structures of the present invention is a sharpness factor, "S". The S-Factor is determined by analyzing a mercury intrusion curve for the given structure. All mercury penetration data discussed herein is determined using a Micromeritics Mercury Penetration Porosimeter, Model 910. The S value is defined as the ratio between the pressure at which 85 percent of the mercury penetrated and the pressure at which 15 percent of the mercury penetrated. This ratio is a direct measure of the variation in pore diameter across the central 70% of the pores in any given sample, as pore diameter equals 176.8 divided by the pressure in p.s.i.

Thus, the S-value is a ratio between the diameter of the pores at which 15 percent of the mercury has penetrated and the diameter of the pores at which 85 percent of the mercury has penetrated. The range of 1 to 15 percent and 85 to 100 percent mercury penetration is left out of consideration when determining the S factor. The range from 0 to 15 percent is omitted because penetration within this range may be due to cracks introduced into the material due to freeze-breaking which the material has been subjected to prior to the mercury penetration investigation. Also, the range of 85 to 100 percent is omitted, as data within such a range may be due to compression of the sample rather than actual penetration of the mercury into the pores.

Characteristic of the narrow range of pore sizes exhibited by the composition of the present invention, the usual S-value for such structures is within the range of approx. 1 to approx. 30, from approx. 2 to approx.

20 is typical and from ca. 2 to approx. 10 even more typical.

The average size of the cells in the structure ranges from approx. 0.5 to approx. 100 microns, starting from approx. 1 to approx. 30 microns are typical and from ca. 1 to approx. 20 microns even more typical. As noted, the cell size may vary depending on the particular resin and particular compatible liquid used, the polymer-liquid ratio, and the rate of cooling used to form the particular microporous polymer. The same variable will also have an effect on the average size of the pores in the resulting structure, which size usually varies from approx. 0.05 to approx. 10 microns, starting from approx. 0.1 to approx. 5 microns are typical and from ca. 0.1 to approx. 1.0 microns even more typical. All references to a cell and / or pore size herein refer to the average diameter of such cell or pore 1 micron, unless otherwise indicated.

By determining the aforementioned factors, cell size, pore size and S, for the cellular microporous polymers of the present invention, the cellular microporous polymers of the invention can be precisely defined. A particularly useful means of defining the polymers thus is through the log of cell-to-pore ratio ("log C / P") and log of the ratio of the sharpness function S to the cell size ("log S / C"). Thus, the cellular microporous polymers of the present invention have a log C / P of about 0.2 to approx. 2.4 and a log S / C from approx. -1.4 to approx. 1.0, and usually said polymer has a log C / P of from ca.

0.6 to approx. 2.2 and a log S / C from approx. -0.6 to approx. 0.4.

Non-cellular structure.

The non-cellular structure of the present invention, obtained by cooling the homogeneous solution at such a rate that the polymer solidifies substantially prior to the formation of the many liquid droplets, can be characterized primarily by the narrow pore size distribution of the material associated with the the true pore size and the spatial uniformity of the structure.

In particular, the non-cellular microporous polymers can be characterized by a sharpness function, S, as described above in connection with the cellular structures. The S values exhibited by the non-cellular structure range from ca. 1 to approx. 30, from approx. 1 to approx. 10 is preferred and from ca. 6 to approx. 9 is particularly preferred. However, when the pore size of the material is from approx. 0.2 to approx. 5 microns, the S value will range from approx. 5 to approx. 10 and will typically range from approx. 5 to approx. 10. Such S values for olefinic polymers and oxidation polymers of such magnitude have not been previously known, except in the case of highly oriented thin films made by a stretching technique. As noted above, the porous polymers of the present invention are substantially isotropic. Thus, a cross section of the polymers taken along any spatial plane will show essentially the same structural features.

The pore sizes of the non-cellular structures of the present invention are usually in the range of from about. 0.05 to approx. 5 microns, the range from about 0.1 to approx. 5 microns are typical and from ca. 0.2 to 1.0 microns even more typical.

It will be appreciated that a surprising feature of the present invention is the ability to produce isotropic microporous structures from olefinic polymers and oxidation polymers, the structures having a porosity in the range of from

0.2 to approx. 5 microns and a sharpness value of approx. 1 to approx. 10. It is especially surprising that such structures can be made not only in the form of thin films, but also in the form of blocks and complicated shapes.

When a film or block is prepared by pouring onto a support, such as a metal plate, the surface of the microporous polymer structure of the invention in contact with the plate will comprise a non-cellular surface skin.

The second surface, on the other hand, is typically predominantly open. The thickness of the skin will vary somewhat depending on the system in question as well as the process parameters used. However, the thickness of the skin will typically be approximately equal to the thickness of a single cell wall. Depending on the conditions in question, the skin may vary from a skin that is completely impervious to fluid passage to a skin that exhibits some degree of fluid porosity.

3i DK 171108 B1

If, for the final application, a purely cellular structure is desired, the surface skin can be removed using several different techniques. As illustrative examples, it can be stated that the skin can be removed by using any of a variety of mechanical means, such as scraping, puncturing the skin with needles, or tearing the skin by passing the film or other structure between rollers at different speeds. Alternatively, the skin can be removed by microtomation. The skin can also be removed by chemical means, ie. by short-term contact with a suitable solvent for the polymer.

For example, when a solution of polypropylene in N, N-bis (2-hydroxyethyl) -talgamine is continuously extruded as a thin film on an endless stainless steel conveyor belt, application of a small amount of liquid solvent to the conveyor belt immediately prior to the zone will be applied. where the solution is applied, effectively remove it at the interface between the solution and the steel formed surface. Suitable liquids are such materials as isoparaffinic hydrocarbons, decane, decalin, xylene and mixtures such as xylene-isopropanol and decalin-isopropanol.

However, for some applications, the presence of the skin will not only be a nuisance, but will be a necessary component. As is well known, e.g. ultrafiltration or other membrane type applications a thin, liquid-impervious film. Accordingly, in such applications, the microporous portion of the structure of the present invention will have particular utility as a carrier for the surface skin which will be a working membrane in such applications. Only cellular structures can also be made directly by various techniques. Thus, for example, the polymer-liquid system can be extruded into atmospheric air or a liquid medium such as hexane.

The microporous polymeric structures of the present invention have, as discussed above, cell and pore diameters with very narrow size distributions, indicative of the distinctive structures and their relative homogeneity. The narrow size distribution of the pore diameters is evidenced by mercury penetration data, as shown in FIG. 30-33. The same general distribution is obtained regardless of whether the structure is in the form of a film (Figs. 30-32) or as a block (Fig. 33). The characteristic pore size distribution of the microporous structure of the present invention is in marked contrast to the much wider pore size distribution of prior art microporous polymer products obtained by the known methods, such as those disclosed in U.S. Patent Nos. 3,310,505 and 3 378 507, as will be discussed in more detail in the examples below.

For any of the microporous polymers made in accordance with the present invention, the intended end use will typically determine the cavity volume and pore size requirements. For example, for use in pre-filtration, the pore size will typically be above 0.5 microns, while for ultrafiltration the pore sizes will be less than about 0.5 microns. 0.1 micron.

In applications where the microporous structure is in fact serving as a container for a functionally useful liquid, the strength requirements dictate the degree of void volume in which controlled release of the contained functional fluid is. In such cases, the corresponding pore size will be dictated by the desired release rate, with smaller pore sizes tending to cause slower release rates.

When the microporous structure is to be used to transform a liquid polymer additive, such as a flame retardant, into a solid, a certain amount of strength is generally required, but together with this minimum it will typically be desired to use as much liquid as possible because the polymer merely serves as a container or carrier.

Microporous polymers containing functional fluids.

From the above it will be seen that in the use of the invention, microporous products containing a functionally useful liquid, such as polymer additives (eg flame retardants), can be produced which behave as and can be processed as a solid. For this purpose, the resulting microporous polymer may be re-loaded with the desired functional fluid. This can be done by conventional absorption techniques and the amount of liquid absorbed will be substantially the same as the amount of liquid initially used in the preparation of the microporous polymer. Any useful organic liquid can be used inasmuch as the liquid is not a solvent for the polymer or otherwise attacks or degrades the polymer at the operating temperature. The microporous products containing the functionally useful liquid can be prepared from or using microporous polymers having either the cellular or non-cellular structure as the matrix into which the liquid is incorporated.

Similarly, such microporous products can be prepared by a displacement technique. According to this embodiment, the microporous polymer intermediate is first prepared, after which the liquid is displaced, either with the desired functionally useful liquid or with an intermediate used displacement fluid. In either case, instead of extracting the liquid used in preparing the microporous polymer intermediate, the displacement is carried out by conventional pressure or vacuum displacement or by infusion technique. Any functional or intermediate displacement fluid can be used which could be used as an extracting liquid to form the microporous polymer, i.e., which is a non-solvent for the polymer but has some solubility to or miscibility with the liquid. that must be displaced. As can be seen, smaller amounts of the liquid (s) displaced may remain after the displacement. The requirements imposed in connection with the end use will typically dictate the desired degree of displacement. Thus, quantities of from approx. 1 to approx. 10% by weight is tolerated in some applications. If necessary, by multiple displacements and / or using liquids which can be easily removed by evaporation, it is possible to obtain the removal of substantially all liquids or liquids displaced, i.e. less than approx. 0.03% by weight or similar of residual liquid. From an economic point of view, it will generally be desirable to use a displacement fluid having a boiling point sufficiently different from the boiling point of the displaced liquid to allow recovery and recycling. For this reason, it may be desirable to use an intermediate displacement fluid.

As will also be apparent from the above examples of useful polymer-liquid systems, a further process for preparing a polymer (functionally useful liquid) material involves the use of the microporous polymer intermediate without further processing, since many functionally useful liquids have been found to function as the compatible liquid with special polymers to form the solid microporous polymer intermediate. Thus, intermediates that behave as solids can be produced directly red liquids useful as lubricants, surfactants, abrasives, surfactants, pesticides, plasticizers, medical agents, fuel additives, polishes, stabilizers, insecticides and animal repellents, fragrances, flame retardants, antioxidants, odor masking agents, anti-fog agents, perfumes and the like. For example, in combination with non-odorous polyethylene, useful intermediates containing a lubricant or plasticizer may be provided by using either an aliphatic or aromatic ester having 8 or more carbon atoms or a non-aromatic hydrocarbon having 9 or more carbon atoms. Applicable products containing a surfactant and / or wetting agent may be prepared together with non-abrasive polyethylene using a polyethoxylated aliphatic amine having 8 or more carbon atoms or a nonionic surfactant. Together with polypropylene, intermediates containing surfactant can be prepared using diethoxylated aliphatic amines with 8 or more carbon atoms. Polypropylene intermediates containing abrasives can be prepared using a phenylmethylpolysiloxane, while (non-abrasive polyethylene) abrasive intermediates are prepared using an aliphatic amide of 12 to 22 carbon atoms. (Lawful polyethylene) fuel additive intermediates can be prepared using an aliphatic amine of 8 or more carbon atoms or an aliphatic dimethyl tertamine of 12 or more carbon atoms. The tertiary amines can also form useful additive intermediates with methylpenten polymers. (High and low weight polyethylene) intermediates containing a stabilizer can be prepared using an alkylaryl phosphite.

DK 171108 B1 34

Medium-weight polyethylene intermediates containing an anti-fog agent may be provided by using glycerol mono- or diester of a long chain fatty acid having at least 10 carbon atoms. Intermediates with flame retardants incorporated therein can be prepared together with high and light weight polyethylene, polypropylene and a polyphenylene oxide-polystyrene blend using a polyhalogenated aromatic hydrocarbon having at least 4 halogen atoms per minute. molecule. Applicable materials must, of course, be liquid at the phase separation temperature, as described herein. Other systems found useful will be discussed in connection with the examples below.

In addition, for polypropylene, high weight polyethylene and low weight polyethylene, certain classes of ketones which have proved particularly useful as animal propellants can be widely used in the practice of the present invention. Such ketones may include saturated aliphatic ketones having from 7 to 19 carbon atoms, unsaturated aliphatic ketones having from 7 to 13 carbon atoms, 4-t.amyl-cyclohexanone and 4-t.butylcyclohexanone.

The invention will be described in more detail by the following examples. In the examples, all parts and percentages are by weight unless otherwise indicated.

Method of production.

The porous polymer intermediates and the microporous polymers described in the examples below were prepared by the following method: A. Porous polymer intermediates:

The porous polymer intermediates were prepared by mixing a polymer and a compatible liquid, heating the mixture to a temperature usually near or above the resin softening temperature to form a homogeneous solution, and then cooling the solution without exposing it to mixture or other shear forces, to form a macroscopically solid homogeneous mass. When solid blocks are to be prepared from the intermediates, the homogeneous solution is allowed to take a desired shape by pouring the solution into a suitable container usually made of metal or glass, and the solution is allowed to cool under ambient conditions. , unless otherwise stated. The cooling rate at room temperature conditions will vary according to such factors as sample thickness and composition, but will usually be within the range of from 10 ° to approx. 20 ° C per day. minute. The container is typically cylindrical in shape with a diameter of from approx. 1.9 to approx. 6.5 cm> and the solution is typically poured to a depth of approx. 0.65 to approx. 5 cm. When making films of the intermediates, the homogeneous solution is poured onto a metal plate heated to a temperature sufficient to allow drawing of the solution into a thin film. The metal plate is then placed in contact with a dry ice bath to cool the film rapidly below its solidification temperature.

B. DK 171108 B1 B. Porous polymer:

The microporous polymer is prepared by extracting the compatible liquid used to form the porous polymer intermediate, typically by repeatedly washing 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 polymer / (compatible liquid) combinations that can be used in the preparation of porous polymer intermediates as mentioned above, and various previously known or commercially available microporous products. Solid blocks of the intermediates were prepared for all the exemplified combinations, and where indicated in a table, thin films of the intermediate were also prepared using the method described above. As set forth in the tables below, many of the intermediate compositions were used to form the microporous polymers of the invention by using a suitable solvent to extract the compatible liquid from the intermediate composition and then remove said solvent, e.g. by evaporation.

Many of the compatible liquids illustrated in the following examples are, as indicated in the tables, functional liquids which are not only useful as compatible liquids but also as flame retardants, release agents and the like. Thus, the intermediate compositions prepared with such functional fluids are useful as solid polymer additives and the like and also as intermediates in the preparation of porous polymers. The functional fluids found in the following examples are stated to be such by one or more of the following symbols under the column "Functional fluid type": AF (anti-fog agent), AO (antioxidant), AR (animal exfoliator) , FA (fuel additive), FG (fragrance), FR (flame retardant), IR (insect repellent), L (lubricant), M (medical product), MRI (moth propellant), OM (odor masking agent), P (plasticizer) , PA (polish), PE (pesticide), PF (perfume), S (abrasive), SF (surfactant) and ST (stabilizer).

Examples 1-27

Examples 1 to 27 of Table V illustrate the formation of homogeneous porous polymeric intermediates in the form of cylindrical blocks having a radius of approx. 3.2 cm and a height of approx. 5 cm, based on high weight polyethylene ("HDPE") and the compatible liquids found useful, using the standard manufacturing method. The high weight polyethylene was supplied by Allied Chemical 36 DK 171108 B1 under the designation Falskon AA 55-003 with a melt index of 0.3 g / 10 minutes and a density of 0.954 g / cm. Many of the exemplified intermediates were extracted to form porous polymers, as listed in the table.

Details of preparation and type of functionally applicable liquid are given in Table V.

Table V HDPE

Ex. no. Liquid type and liquid 7. Wash ° C Type of functional liquid Saturated aliphatic acids 1 decanoic acid * 75 230 - - -

Primary saturated alcohols

2 decyl alcohol * 75 220 PF

3 l-dodecanol * 75 220 -----

Secondary alcohols 4 2-undecanol K 75 220 ----- 5 6-undecanol * 75 230 -----

Aromatic amines 6 Ν, Ν-diethylaniline * 75 230

diesters

7 dibutylsebacate * 70 220 L, P

8 dihexylsebacatK 70 220 L, P

ethers

9 diphenyl ether 75 220 PF

10 benzyl ether * 70 220 PF

halogenated

11 hexabromobenzene 70 250 FR

12 hexabromobiphenyl 75 200 FR

13 hexabromocyclodecane 70 250 FR

14 hexachlorocyclopentene

tadien 70 200 FR

15 octabromobiphenyl 70 280 FR

Hydrocarbons with End-linked Double Bond 16 1-Hexadecene H 75 220 ----- K The liquid was extracted from the solid product.

(continued) 37 DK 171108 B1

Aromatic hydrocarbons

17 diphenylmethane * 75 220 OM

18 naphthalene * 70 230 MR

Aromatic ketones

19 acetophenone 75 200 PF

Aromatic esters

Butyl benzoate * 75 220 L, P

Mixed 21 N, N-bis (2-hydroxyethyl) -talgamine (1) K 70 250 ----- 22 dodecylamine * 75 220 ----- 23 N-hydrogenated tallow

diethanolamine 50 240 SF

24 Firemaster BP-6 (2) 75 200 -----

25 Phosclere P315CK (3) 75 220 ST

26 quinoline 70 240 M

27 dicocoamine (4) 75 220 ----- x The liquid was extracted from the solid product.

(1) A permanent internal antistatic agent having the following properties was used: Boiling point 1 mm Hg, ° C: 215-220, specific gravity 32 ° C: 0.896, viscosity, SSU, 32 ° C: 476.

(2) Michigan Chemical Corporation's trade name for their hexabromobiphenyl; a flame retardant having the following properties was used: Soften point, ° C: 72, density, 25 ° C, g / ml: 2.57, viscosity, cps: 260-360 (Brookfield No. 3 spindle at 110 ° C) .

38 DK 171108 Bl

Table VI LDPE

Ex. No. (1) Liquid type and wash% Liquid ° C Type of functional liquid Aliphatic matted acid 28 caprylic acid * 70 210 ----- 29 decanoic acid * 70 190 ----- 30 hexanoic acid * 70 190 ----- 31 lauric acid * 70 220 ----- χ 32 myristic acid 70 189 ----- 33 palmitic acid * 70 186 ----- 34 stearic acid * 70 222 ----- 35 undecanoic acid 70 203 -----

Unsaturated aliphatic acids 36 erucic acid (2) * 70 219 -----

37 oleic acid * 70 214 PA

Aromatic acids 38 phenyl stearic acid11 70 214 ----- 39 xylyl behenoic acid * 70 180 ----- K The liquid was extracted from the solid product.

(1) Union Carbide Company's Bakelite® polyethylene having the following properties 3 was used: density, g / cm: 0.922, melt index, g / 10min: 21.

(2) This is an acid having a density of 0.8602 g / cin and a m.p. at 33-34 ° C.

(continued) 39 DK 171108 B1

Mixed acids 40 Acintol FA2 (tall oleic acids) (1) X 70 204 ----- 41 oleic acid L-6K 70 206 ----- 42 oleic acid L-9K 70 186 ----- 43 oleic acid L-11X 70 203 ----- 44 resin acid * 1 70 262 ----- 45 tolylstearic acid 70 183 -----

Primary Saturated Alcohols 46 Cetyl Alcohol * 1 70 176 -----

47 decyl alcohol * 1 70 220 PF

48 l-dodecanolx 75 200 _____ 49 l-heptadecanolX 70 168 -----

50 nonyl alcohol ** 70 174 PF

51 1-octanol ** 70 178 -----

52 oleyl alcohol * 1 70 206 FA

53 tridecyl alcohol 70 240 ----- 54 l-undecanolX 70 184 _____ χ 55 undecylenyl alcohol 70 199 -----

Secondary alcohols χ

56 dinonylcarbonol 70 201 PF

57 diundecylcarbinol 70 226 _____ 58 2-octanol 70 174 _____ 59 2-undecanolX 70 205 _____ The liquid was extracted from the solid product.

(1) Arizona Chemical Company1's trade name for a mixture of fatty acids.

The composition and physical properties are: fatty acid composition (98.27. Of total): linoleic acid, non-conjugated, 7 .: 6, oleic acid, 7.: 47, saturated, 7.: 3, other fatty acids, 7.: 8 ; specific gravity, 25/25 ° C: 0.898, viscosity, SSU, 389c: 94.

(continued) 40 DK 171108 B1

Aromatic alcohols

60 1-phenylethanol * 70 184 PF

61 1-phenyl-l-pentanol 70 196 ----- 62 phenylstearyl alcohol 70 206 _____

63 nonylphenol11 70 220 SF, PE

Cyclic Alcohols 64 4-t-Butyl-Cyclohexane

nolK 70 190 PE

65 menthol * 70 206 PF

Other -OH-containing compounds_ 66 Neodol-25 (1) * 70 180 ....

67 polyoxyethylene ether

of oleyl alcohol (2) 70 268 SF

68 Polypropylene Glycol

425 * (3) 70 --- SF

aldehydes

69 salicylic aldehyde * 70 188 PF

[The liquid was extracted from the solid product.

(1) Shell Chemical Company's trade name for their synthetic fatty alcohol of 12-15 carbon atoms.

(2) Croda, Inc.'s Volpo 3 surfactant having the following properties was used: Acid number, max .: 2.0, dispunct, 1% aqueous solution, insoluble; HLB value, calculated: 6.6, vertical, Wijs: 57-62, pH of 37. aqueous solution: 6-7, hydroxyl number: 135-150.

(3) Union Carbide Company's trade name for its glycol having the following characteristics: Apparent specific gravity, 20/20 ° C: 1,009, average hydroxyl number, mg KOH / g: 265, acid number, mg KOH / g sample, max .: 0.2 , pH at 25 ° C in 10: 6 iso-propanol: water solution: 4.5-6.5.

(continued) „DK 171108 B1

Primary officials

70 dimethyldodecylamine 70 200 FA

71 hexadecylamine 70 207 FA

72 octylamine * 70 172 FA

73 tetradecylamine H 70 186 FA

Secondary amines 74 bis (1-ethyl-3-methyl-pentyl) -amine 70 190 -----

Tertiary amines 75 N, N-dimethylsoya

amine * (1) 70 198 FA

76 N, N-dimethyl tallow

amine * (2) 70 209 FA

Ethoxylated amines

77 N-stearyl diethanolamine 75 210 SF, AF

Aromatic amines 78 aminodiphenylmethane 70 236 ----- 79 N-sec-butylaniline 70 196 ----- 80 N, Ν-diethylaniline11 70 --- .....

81 N, N-dimethylaniline 70 169 .....

82 diphenylamine 70 186 A0, PE

83 dodecylaniline * 70 204 84 phenylstearylamine * 70 205 ----- 85 N-ethyl-o-toluidine * 70 182 .....

86 p-toluidine * 70 184 -----

X

The liquid was extracted from the solid product.

(1) A tertiary amine having the following properties was used: cloud point,, ASTM: 38, specific gravity, 25/4 ° C: 0.813, viscosity, SSU, at 25 ° C: 59.3.

(2) A tertiary amine having the following properties was used: Melting range, t: -2 to 5, cloud point, 9C: 16, specific gravity, 25/4 ° C: 0.803, viscosity, SSU, 25 ° C: 47.

(continued) 42 DK 171108 B1

Diamines 87 1,8-Diamino-p-menthane 70 188 ----- 88 N-erucyl-1,3-propanediamine * 70 220 _____

Mixed amines 89 branched tetramine L-PS (1) "70 242 ....

J | 90 cyclododecylamine 70 159 _____

Amider 91 cocoamid11 (2) 70 245 -----

92 N, N-diethyltoluamide 70 262 IR

93 erucamide * (3) 70 250 L, P

j |

94 hydrogenated tallow amide 70 250 L, P

95 octadecylamide (4) 70 260 L, P

96 N-trimethylolpropane

stearamide 70 255 L, P

Aliphatic matted esters 97 ethyl laurate * 70 175 ----- 98 ethyl palmitate * 70 171 -----

99 isobutyl stearate * 70 194 L

100 isopropyl myristate * 70 192 ----- 101 isopropyl palmitate * 70 285 ----- 102 methylcaprylate 70 182 ----- 103 methyl stearate * 70 195 -----

104 tridecyl stearate 70 202 L

j | The liquid was extracted from the solid product.

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

(2) An aliphatic amide having the following properties was used: Appearance: Flakes, ignition point, ° C: approx. 174, mp, ° C: ca. 185th

(3) An amide having the following properties was used: Specific gravity: 0.88, mp, ° C: 99-109, ignition point, ° C: 225.

(4) Octadecylamide having the following properties was used: Appearance: Flakes, ignition point, ° C: approx. 225, focal point, ° C: ca. 250th

(continued) 43 DK 171108 B1

Aliphatic unsaturated esters

105 butyl oleate * 70 196 L

106 butylundecylenate11 70 205 ----- 107 stearyl acrylate * 70 205 -----

Alkoxy esters 108 butoxyethyl oleate * 70 200 ----- 109 butoxyethyl stearate * 70 205 -----

Aromatic esters 110 benzyl acetate 70 198 -----

111 benzyl benzoate * 70 242 L, P

112 butyl benzoate * 70 178 L, P

113 ethyl benzoate * 70 200 L, P

114 isobutylphenyl-

stearate * 70 178 L, P

115 methyl benzoate * 70 170 L, P

116 methyl salicylate * 70 200 L, P, PF

117 phenyl laurate * 70 205 L, P

118 phenyl salicylate 70 211 L, P, M, F

119 tridecylphenyl-

stearate * 70 215 L, P

120 vinyl phenyl stearate * 70 225 L, P

diesters

121 dibutyl phthalateK 70 290 L, P

122 dibutylsebacateH 70 238 L, P

123 dicapryladipate 70 204 L, P

124 dicapryl phthalate 70 204 -----

125 dicaprylsebacat 70 206 L, P

126 diethyl phthalate * 70 280 IR

127 dihexylsebacate 70 226 ----- χ The liquid was extracted from the solid product.

(continued) 44 DK 171108 B1

Diesters (continued) 128 dimethylphenylene distearate * 70 208 ----- 129 dioctyl maleate 70 220 ----- 130 di-iso-octyl phthalate 70 212 131 di-iso-octyl sebacate 70 238 -----

Estere-Polyethylene Glycol 132 PEG 400 Diphenyl Stearate 70 326 -----

Polyhydroxylic Esters 133 Castor Oil 70 270 -----

134 glycerol dioleate * (1) 70 230 AF

135 glycerol distearate (2) 70 201 AF

136 glycerol monooleate (3) 70 232 AF

137 glycerol monophenyl stearate 70 268 -----] | 138 glycerol monostearate

(4) 70 211 AF

139 trimethylol propane monophenyl stearate 70 260 -----

ethers

140 dibenzyl ether * 70 189 PF

141 diphenyl ether * 75 200

X

The liquid was extracted from the solid product.

(1) A glycerol ester having the following properties was used: Ignition point, COC, ° C: 271, freezing point, ° C: 0, viscosity at 25 ° C, cp: 90, specific gravity 25/20 ° C: 0.923-0.929.

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

(3) A glycerol ester having the following properties was used: Specific gravity: 0.94-0.953, ignition point, COC, ° C: 224, freezing point, ° C: 20, viscosity at 25 ° C, cp: 204.

(4) A glycerol ester having the following properties was used: Form at 25 ° C: Flakes, ignition point, COC, ° C: 210, mp, ° C: 56.5-58.5.

(continued) 45 DK 171108 B1

Halogenated ethers

142 4-Bromodiphenyl Ether1 70 180 FR

143 FR 300 BA (1) 70 314 FR

144 hexachlorocyclopentene

serve1 70 196 PE, FR

145 octabromobiphenyl * 2 70 290 FR

Hydrocarbons with end-linked double bond

146 l-nun * 70 174 l

Hydrocarbons with internal double bond_ 147 3-eicose1 70 204 ----- 148 2-heptadecene1 70 222 ----- 149 2-nonadecene1 70 214 ----- 150 9-nonadecene1 70 199 -----

151 2-nuns1 70 144 L

152 2-undecen 70 196 -----

Aromatic hydrocarbons

153 diphenylmethane 75 200 PF

154 trans-stilben1 70 218 ----- 155 triphenylmethane 70 225

Aliphatic ketones 156 dinonyl ketone * 70 206 ----- 157 distearyl ketone * 2 70 238 ----- 158 2-heptadecanone 70 205 ----- 159 8-heptadecanone 70 183 ----- 160 2-heptanone * 70 152 ----- 161 methylheptadecyl ketone 70 225 -----

162 methylnonyl ketone * 70 170 AR

(continued) The liquid was extracted from the solid product.

(1) Dow Chemical Company's trade name for their decabromodiphenyloxide herbicide having the following properties: bromine, 7 ': 81-83, m.p., min. 285 ° C, decomposition temperature, DTA; 425 ° C.

2 46 DK 171108 B1

Aliphatic Ketones (continued) 163 methylpentadecyl

ketone 70 210 AR

164 methylundecylketone 70 205 ----- 165 2-nonadecanone 70 214 ----- 166 10-nonadecanone 70 194 ----- 167 8-pentadecanone K 70 178 ----- 168 ll-pentadecanone 70 70 - --- 169 2-tridecanonK 70 168 ----- 170 6-tridecanonX 70 205 ----- 171 6-undecanon * 70 188 -----

Aromatic ketones

172 acetophenone * 70 190 PF

173 benzophenone 70 245 PF

Mixed ketones

174 9-xanthonK 70 220 PE

PhosphorforbindeIser

175 trixylenyl phosphate * 70 304 FR

Mixed 176 N, N-bis (2-hydroxyethyl) -talgamine * 70 210 ----- 177 bath oil fragrance

No. 5864K 70 183 FG

178 EC-53 Styreneated nonyl-

phenol (1) K 70 191 AO

179 Mineral oil 50 200 L

180 Muget hyacinth 70 178 FG

181 Phosclere P315C * 70 200 .....

|| The liquid was extracted from the solid product. 1 (continued)

Akzo Chemie NV.'s trade name for their styrenated hindered phenol.

47 DK 171108 B1

Mixed (continued)

182 Phosclere P576 (1) * 70 210 AO

183 Quinalidin 70 173 .....

184 Quinoline * 70 230 .....

185 Terpineol Prime no. 1 70 194 M, PF

186 Firemaster · BP-6 75 200 FR

187 benzyl alcohol / 1-heptadecanol (50/50) X 70 204 ----- 188 benzyl alcohol / 1-heptadecanol (75/25) ** 70 194 The liquid was extracted from the solid product.

(1) Akzo Chemie NV's styrenated hindered phenol.

Microphotographs of the porous polymers of Examples 38 and 122 are shown in Figs. 28 and 29. The photomicrographs, at 2000X magnification, show the cell structure with a significant amount of "leaf formation" uniformly present throughout the entire sample.

Examples 189-193

Examples 189 to 193 of Table VII illustrate the formation of homogeneous porous polymeric intermediates by pouring the solution into a glass dish to form cylindrical blocks having a radius of approx. 4.5 cm and a height of approx.

0.65 cm, except where indicated, from NoryiB ^ polymer (1) and the compatible liquids found to be usable, using the standard preparation method. In the cases indicated, the microporous polymer was also prepared.

Details of the preparation and type of functionally applicable liquid are given in Table VII.

Table VII o

Ex. no (1) Liquid type and liquid% Liquid C Type of functional liquid Aromatic amine

189 diphenylamine 75 195 PE, AO

diester

190 dibutyl phthalate 75 210 L

Halogenated hydrocarbon 191 hexabromobiphenyl

(2) 70 315 FR

(continued) 48 DK 171108 B1

Mixed 192 N, N-bis (2-hydroxyethyl) - talgamine * 75 250 ----- 193 N, N-bis (2-hydroxyethyl) - talgamine 90 300 ----- (r) (1) General Electric Company's Noryr®, a blend of polyphenylene oxide condensation polymer with polystyrene, having the following properties was used: Specific gravity, 23 ° C: 1.06, tensile strength, at 23 ° C: 66, elongation at break, 7. at 23 ° C: 60, Tensile modulus, MPa at 23 ° C: 2450, and Rockwe11 hardness, R: 119.

Æ) (2) The microporous Noryl polymers prepared with hexabromobiphenyl and N, N-bis (2-hydroxyethyl) -talgamine were poured to a depth of 0.65 cm.

A photomicrograph of the microporous polymer of Example 192 is shown in FIG. 25. The photomicrograph shows, at 2500X magnification, the microcellular structure with spherical resin deposits on the walls of the cells.

Example 194-236

Examples 194 to 236 of Table VIII illustrate the formation of homogeneous porous polymeric intermediates in the form of cylindrical blocks having a radius of approx.

3.2 cm and a height of approx. 0.65 cm, from polypropylene ("PP") and the compatible liquids found useful, using the standard method of preparation. In the examples given, blocks having a height of approx. 15 cm and / or thin films. Furthermore, as indicated, the microporous polymer was prepared.

Details of preparation and type of functionally applicable liquid are given in Table VIII.

49 DK 171108 B1

Table VIII PP

Type of functional

Ex. No. (1) Liquid type and liquid% Wash ° C liquid_

Unsaturated acid

194 10-undecenoic acid K 70 260 M

Alcohols 195 2-benzylamino-1- 70 260 ----- propanol

196 lonol CP * 70 160 AO

197 3-phenyl-1-propanol 75 230 -----

198 salicylic aldehyde 70 185 PF

amides

199 N, N-diethyl-m-toluamide 75 240 IR

Amines and 200 aminodiphenylmethane 70 230 ----- 201 benzylamine11 70 160 ----- 202 N-butylaniline 75 200 ----- 203 1,12-diaminododecane 70 180 ---- 204 1,8-diaminooctane 70 180 ----- 205 dibenzylamine * 75 200 ----- 206 Ν, Ν-diethanolhexylamine11 75 260 ----- 207 N, N-diethanoloctylamine K 75 250 ----- 208 N, N-bis- P-hydroxyethyl-75 280 ----- cyclohexylamine 209 N, N-bis- (2-hydroxyethyl) -75 260 -----hexylamine 210 N, N-bis- (2-hydroxyethyl) -75 260 --- octylamine

X

The liquid was extracted from the solid product.

(1) Philips Petroleum Company's "Marlex" polypropylene having the following properties was used: Density, g / cin: 0.908, melt flow, g / min. Mp, C: 171, yield strength at yield, MPa, 2 "/ min: 34.5, hardness Shore D: 73.

50 DK 171108 B1

Table VIII (continued)

PP

Type of functional Thin

Ex. No. Liquid type and liquid% Liquid ° C liquid_ film

Esther 211 benzyl acetate * 75 200 ----- --- 212 benzyl benzoate * 75 235 L, P, PF --- 213 butyl benzoate 75 190 L, P - 214 dibutyl phthalate * 75 230 L, P yes 215 methyl benzoate 70 190 L, P, PF ---

216 methyl salicylate * 75 215 L, P, PF

217 phenyl salicylate K 70 240 P ---

Ethere 218 dibenzyl ether 75 210 PF --- 219 diphenyl ether * 1 75 200 PF yes

Carbon halides 220 4-bromodiphenyl ether * 70 200 FR --- 221 1,1,2,2-tetrabromoethane * 70 180 FR --- 222 1,1,2,2-tetrabromoethaneK 90 180 FR ---

Ketones 223 benzylacetone 70 200 ----- --- 224 methylnonyl ketone 75 180 ----- ---

Mixed 225 N, N-bis (2-hydroxyethyl)-talgamine * (1) & (2) 75 200 ----- yes 226 N, N-bis (2-hydroxyethyl) - cocoamine (2) 75 180 - --- --- 227 butylated hydroxytoluene 70 160 AO --- χ The liquid was extracted from the solid.

(1) A block with a height of approx. 15 cm was also produced.

(2) A permanent Internal Antistatic agent having the following physical properties was used: bp, 1 mm Hg, ° C: 170, viscosity, SSU, 32 ° C: 367.

are DK 171108 B1

Table VIII (continued)

Type of functional Thin

Ex. No. Liquid type and wash% Liquid ° C wash_ film

Mixed (continued) 228 D.C. 550 Silicone fluid (1) 50 260 S, L --- 229 D.C. 556 Silicone fluid * 70 190 S, L --- 230 EC-53 75 210 ....

231 N-hydrogenated rapeseed diethanolamine * 75 210 SF --- 232 N-hydrogenated tallow diethanolamine 75 225 SF --- 233 Firemaster BP-6 75 200 FR --- 234 NBC oil 75 190 .....

235 quinaldine * 70 200 ----- -

236 quinoline * 75 220 M

χ The liquid was extracted from the solid product.

(1) Dow Coming's trade name for their phenylmethylpolysiloxane having the following properties: viscosity 115CS and serviceable from -40 to 232 ° C in open systems and to 315 C in closed systems.

Microphotographs of the porous polymer of Example 225 are shown in Figs. 2 to 5. The microphotographs of Figs. 2 and 3 show, at 55X and 550X magnification, the macrostructure of the microporous polymer. The photomicrographs of Figures 4 and 5 show, at 2,200X and 5,500X magnification, the microcellular structure of the polymer as well as the interconnecting pores.

Examples 237-243

Examples 237 to 243 of Table IX illustrate the preparation of homogeneous porous polymer intermediates in the form of cylindrical blocks having a radius of approx.

3.2 cm and a height of approx. 0.65 cm, based on polyvinyl chloride ("PVC") and the compatible liquids found useful, using the standard method of preparation. Many of the exemplified intermediates were extracted to form porous polymers, as listed in the table.

Details of preparation and type of functionally applicable liquid are given in Table IX.

52 DK 171108 B1

Table IX PVC

Ex. No. (1) Wash type and wash 7 «Wash ° C Type of functional wash

Aromatic Alcohols 237 4-Methoxybenzyl

alcoholK 70 150 PF

Other - (OH) -containing compounds 238 1,3-dichloro-2-propanol K 70 7

239 menthol * 1 70 180 PF

240 10-undecen-1-olH 70 204-210

halogenated

241 Firemaster T33P * (2) 70 165 FR

242 Firemaster T13P * (3) 70 175 FR

Aromatic Hydrocarbons 243 Trans-Style Bench 70 190 ----- χ The liquid was extracted from the solid product.

(1) The polyvinyl chloride used was of dispersion grade manufactured by American Hoechst, with an inherent viscosity of 1.20, a density of 1.40 and a mass density of '0.328 q / cw', (2) the Michigan Chemical Corporation trademark for their tris. (1,3-dichloroisopropyl) phosphate fire retardant having the following properties: chlorine content, theoretical, 7.: 49.1, phosphorus content, theoretical, 7.: 7.2, bp, 4 mm Hg, abs., ° C: 200 (dec. At 200 ° C), refractive index, 1.50.9, viscosity, Brookfield, 23 ° C, cp: 2120.

Structure: [(CICH ^ CHO ^ P-O

(3) Michigan Chemical Corporation's trademark for their trls-halogenated propyl phosphate flame retardant having the following properties: Specific density, at 25 ° C / 25 ° C: 1.88, viscosity, at 25 ° C, centistoke: 1928, refractive index : 1.540, pH: 6.4, chlorine,%: 18.9, bromine,%: 42.5, phosphorus, 7.: 5.5.

A photomicrograph of the porous polymer of Example 242 is shown in FIG. 27. The photomicrograph shows, at 2000X magnification, the very small cell size of this microporous polymer as opposed to the cell structure exemplified in FIG. 7, 13, 18, 20 and 24, where the cell size is larger and more readily observable at a similar magnification. The photomicrograph also shows the presence of a large amount of resin masking the base cell structure.

53 DK 171108 B1

Examples 244-255

Examples 244 to 255 of Table X illustrate the preparation of homogeneous porous polymer intermediates in the form of cylindrical blocks having a radius of approx. .3,2. cm and a height of approx. 5 cm from methyl pentane ("MPP'O polymer and the compatible liquids found useful using the standard preparation method. Many of the exemplified intermediates were extracted to form porous polymers, as listed in the table.

The details of preparation and type of functionally applicable liquid are given in Table X.

Table X MPP

ISLAND

Ex. No. (1) Liquid type and wash 7. Liquid C Type of functional wash Saturated aliphatic acid 244 decanoic acid * 75 230 ----- Saturated alcohols 245 l-dodecanolK 75 230 ----- 246 2-undecanolK 75 230 - --- 247 6-undecanol * 75 230 -----

Amin

248 dodecylamine 75 230 FA

esters

249 butyl benzoate * 75 210 L, P, PF

250 dihexylsebacatK 70 220 L, P

ethers

251 dibenzyl ether ** 70 230 PF

Hydrocarbons 252 l-hexadecene K 75 220 -----

253 naphthalene11 70 240 MR

mixed

254 EC-531 * 75 230 AO

255 Phosclere P315CK 75 250 .....

χ The liquid was extracted from the solid product.

(1) Mitsui's methylpentane polymer having the following properties was used: density, 3 o 2 g / cm: 0.835, m.p. C: 235, tensile breakage, kg / cm: 230, breakage 7: 2 2

Rockwell hardness, R: 85.

54 DK 171108 B1

A photographer! of the porous polymer of Example 253 is shown in FIG.

22. The photomicrograph shows, at 2400X magnification, the very flat cell walls compared to the one in FIG. 14.

Examples 256 to 266

Examples 256 to 266 of Table XI illustrate the formation of homogeneous porous polymeric intermediates in the form of cylindrical blocks having a radius of approx. 3.2 cm and a height of approx. 1.3 cm, based on polystyrene ("PS") and the compatible liquids found useful, using the standard manufacturing method. All the exemplified intermediates were extracted to form porous polymers.

The details of preparation and type of functionally applicable liquid are given in Table XI.

Table XI

Ex. No. (1) Liquid type and liquid 7. Liquid ° C Type of functional fluid

256 Firemaster T-13P 70 250 FR

257 hexabromobiphenyl 70 260 FR

258 Phosclere P315C 70 270 .....

259 Phosclere P576 70 285 AO

260 tribromoneopentyl alcohol 70 210 FR

261 FR 2249 (2) 70 240 FR

©

262 Former CEF (3) 70 250 FR

263 Firemaster T33P (4) 70 210 FR

264 FyroP FR (5) '70 240 FR

265 dichlorobenzene 80 160 MR, FR

266 1-dodecanol 75 --- ----- 1

Monsanto Chemical Company's Lustrei® polystyrene having the following physical properties was used: impact strength, Nm / in groove (injection molded): 0.55 tensile strength, MPa: 52, elongation,%: 2.5, modulus of elasticity, MPa, XID: 0.031 , bending temperature, under load 1.82 MPa, cC: 93 ^ specific gravity: 1.05, Rockwell hardness, M-75, melt flow, g / 10min: 4.5.

(2) Dow Chemical Corporation's trade name for their fire retardant having the following composition and properties: Tribromoneopentyl alcohol: 60%, Voranol CP.3000 polyol: 407., bromine, 7.: 43, hydroxyl number: 130, viscosity, cps, 25 ° C: 3 approx. 1600, density, g / cm: 1.45.

(3) Stauffer Chemical Company's trademark for their tris-chloroethyl phosphate fire retardant having the following properties: bp, at 0.5 mm Hg abs., ° C: 145, at 760 mm Hg abs., ° C: decomposes, chlorine content , weight%: 36.7, 55 DK 171108 B1 phosphorus content, weight%: 10.8, refractive index at 20 ° C: 1.4745, viscosity, cps at 22, Λ: 40..

(4) Michigan Chemical Corporation's trade name for their tris (1,3-dichloroisopropylphosphate) fire retardant having the following properties: Chlorine content, theoretical,%: 49.1, phosphorus content, theoretical,%: 7.2, b.p. 4 mm Hg abs., ° C: 200 (decomposes at 200 ° C), refractive index: 1.5019, viscosity, Brookfield, 22.8 ° C, cps .: 2120.

Structure: [(ClCH2) 2CH0] 3P-0 (5) Stauffer Chemical Company's trademark for their tris (dichloropropyl) phosphate and flame retardant additive having the following properties: mp, f: ca. 80, refractive index n 2 at 25 ° C: 1.5019, viscosity, Brookfield at 22.8 ° C, cps .: 2120.

A photographer! of the microporous polymer of Example 260 is shown in FIG. 26. Although the cells are small compared to the cells shown in FIG. 4, 7, 13, 18 and 25, the basic microcellular structure is present.

Example 267

This example illustrates the formation of a homogeneous porous polymer intermediate from 30% highly compressed polystyrene (1) and 70% hexabromobiphenyl using the standard preparation method and heating the mixture at 280 ° C.

The polymer intermediate thus produced had a diameter of approx. 6 cm and a height of approx. 1.3 cm. Hexabromobiphenyl is useful as a flame retardant and the porous intermediate is useful as a solid flame retardant additive.

(1) Union Carbide Company's "Bakelite" polystyrene for injection molding, having the following properties, was used: Tensile strength, MPa (3.2 mm thick): 34.5, final extension (3.2 mm thick): 25, tensile modulus, MPa, ( 3.2 mm thick): 2620, Rockwell hardness (0.63 x T, 27 x 12.7cm) in 90, specific gravity, natural: 1.04.

Example 268

This example illustrates the formation of a homogeneous porous polymer intermediate from 25% acrylonitrile-butadiene-styrene terpolymer (2) and 75% diphenylarain using the standard preparation method and heating the mixture to 220 ° C. The polymer intermediate thus produced had a diameter of approx. 6 cm and a height of about 5 cm. The microporous polymer was prepared by extracting the diphenylamine. Diphenylamine is useful as a pesticide and antioxidant, and the porous polymer intermediate has the same utility, (2) Uniroyal's Kralastic ABS polymer having the following properties was used: Specific gravity: 1.07, impact strength (3.2 mm Rod Sample), Izod slotted, 23 ° C (Nm / in.- 56 DK 171108 Bl notch: 1.75 - 2.55, tensile strength, MPa: 61, and Rockwell hardness, R: 118.

Examples 269 and 270

The homogeneous porous polymer intermediates were prepared from Dow's 257 "thermoplastic chlorinated polyethylene resin, having a melt viscosity of 15 poise, 8 percent crystallinity and containing 36 percent chlorine, and 75% N, N-bis (2-hydroxyethyl) -talgamine ( Example 269) and 75% thermoplastic chlorinated polyethylene resin and 257. 1-dodecanol (Example 270), using the standard preparation method and heating to 220 ° C. The porous polymer intermediates had a diameter of approx. 2.5 inches and a height of approx. 2 inches.

Example 271

The homogeneous porous polymer intermediate was formed using the standard preparation method and heating to 210 ° C from 257. chlorinated polyethylene elastomer, as used in Example 270, and 757. diphenyl ether. The porous polymer intermediates were approx. 6 cm in diameter and approx. 5 cm high. Diphenyl ether is useful as a perfume and the intermediate is also useful in perfumes.

Examples 272-275

Examples 272 to 275 of Table XII illustrated the formation of homogeneous porous polymer intermediates in the form of cylindrical blocks having a radius of approx.

3.2 cm and a height of approx. 1.3 cm from styrene-butadiene (HSBR ") - rubber (1) and the compatible fluids found usable using the standard manufacturing method. In addition to the cylindrical blocks, thin films were also made as indicated.

The details of preparation and type of functionally applicable liquid are given in Table XII.

® (1) Shell Chemical Company's Kraton SBR polymer having the following properties was used:

Tensile strength, MPa: 21.5-32, fracture elongation: 880-1300, and Rockwell hardness, Shore A: 35-70.

Table XII

SBR „r _, - Type of function

Ex. No. Liquid Type and Liquid 7. Liquid C Tional Liquid Thin Film 272 N, N-bis (2-hydroxyethyl) - 80 195 ----- yes tallow old 273 decanol * 70 190 PF yes 274 diphenylamine 70 200-210 PE, A0 yes 275 diphenyl ether 70 195 PF yes 57 DK 171108 B1 M The liquid was extracted from the solid product.

Examples 276-278

Examples 276 to 278 in Table XIII illustrate the formation of homogeneous porous polymeric intermediates in the form of cylindrical blocks having a radius of approx. 3.2 cm and a height of approx. 1.3 cm from Surlyrn (1) and the compatible liquids found usable using the standard method of preparation. In addition to the cylindrical blocks, as indicated, thin films were also prepared. Two of the exemplified intermediates were extracted to form porous polymers as indicated in the table.

The details of preparation and type of functionally applicable liquid are given in Table XIII.

(1) E.I. du Pont de Nemour's Surlyrr Ionomer Resin 1652, lot number 115478, 3 having the following characteristics were used: Density g / cm: 0.939, melt flow index, decigram / min: 4.4, tensile strength, MPa: 1950, tensile limit, MPa : 1290, extension,%: 580.

Table XIII SURLYN

Type of Functional

Ex., No. (1) Liquid type and liquid 7. Liquid ° C Tional liquid Thin film 276 N, N-bis (2-hydroxy- 70 190- ----- yes ethyl) -talgamine 195 277 diphenyl ether * 70 200 PF yes 278 dibutyl phthalate 70 195 L yes χ The liquid was extracted from the solid product.

Microphotographs of the porous polymer of Example 277 are shown in FIG.

23 and 24. FIG. 23 shows, at 255X magnification, the macrostructure of the polymer. FIG. 24 shows, at 2550X magnification, the microcellular structure of the light "polymer formation" polymer and relatively thick cell walls compared to, for example, FIG. 25th

Example 279

The homogeneous porous polymer intermediate was prepared using the standard preparation method and heated to 200 ° C, from a mixture of equal parts high weight polyethylene (HDPE) and chlorinated polyethylene (CPE) and 757. 1-dodecanol. The porous polymer intermediate was molded into a film having a thickness of approx. 20-25 mils. Said HDPE and CPE were as used in previous examples.

Example 280

The homogeneous porous polymer intermediate was prepared using the standard preparation method and heated to 200 ° C, from a mixture of equal parts high weight polyethylene and polyvinyl chloride (PVC) and 75% 1-dodecanol. The intermediate product thus obtained had a height of approx. 5 cm and a diameter of approx. 6 cm. Said HDPE and PVC were as used in the preceding examples.

Example 281

The homogeneous porous polymer intermediate was prepared, using the standard preparation method and heating to 200 ° C, from a mixture of equal parts high weight polyethylene and acrylonitrile-butadiene styrene terpolymer (ABS) and 75% 1-dodecanol. The intermediate product thus obtained had a height of approx.

5 cm and a diameter of approx. $ cm. Said HDPE and ABS were as used in previous examples.

Examples 282-285

Examples 282 to 285 of Table XIV illustrate the preparation of homogeneous porous polymer intermediates, in the form of cylindrical blocks having a radius of approx.

3.2 cm and a height of approx. 5 cm, from a mixture of equal parts by weight polyethylene (LDPE) and chlorinated polyethylene and the compatible liquids found usable, using the standard preparation method. In Example 283, the method described previously was used, but the intermediate was molded into a film having a thickness of approx. 20-25 mils. Said LDPE and CPE were as used in previous examples.

Details of preparation and type of functionally applicable liquid are given in Table XIV.

Table XIV

Ex. No. Liquid type and liquid% Liquid ° C Functional liquid type 282 1-dodecanol 75 200 -----

283 diphenyl ether 75 200 PF

284 diphenyl ether 50 200 PF

285 N, N-bis (2-hydroxyethyl) - 75 200 ----- talgamine 59 DK 171108 B1

Examples 286 * 287

The homogeneous porous polymer intermediates were prepared from a mixture of equal parts of light weight polyethylene and polypropylene and 75¾ N, N-bis (2-hydroxyethyl) -talgamine (Example 286) and from a mixture of equal parts of lightweight polyethylene and polypropylene and 507 ° N, N-bis (2-hydroxyethyl) -talgamine (Example 287) using the standard preparation method and heating to 220 ° C for example 286 and to 270 ° C for example 287. Both porous polymeric intermediates had a diameter of ca. 6 cm and a height of approx. 5 cm. Said LDPE oak PP was as used in the preceding examples.

Example 288

The homogeneous porous polymer intermediate was prepared using the standard preparation method and heated to 200 ° C from 507. N, N-bis (2-hydroxyethyl) -talgamine and 507. polypropylene / polystyrene mixture (25 parts polypropylene). The porous polymer intermediates had a diameter of approx. 6 cm and a height of approx. 5 cm. The PP and PS mentioned were as used in the previous examples.

Example 289

The homogeneous porous polymer intermediate was prepared using the standard preparation method and heated to 200 ° C from 757. 1-dodecanol and a mixture of equal parts polypropylene and chlorinated polyethylene. The porous polymer intermediate had a diameter of approx. 6 cm and a height of approx. 1.3 cm. The PP and CPE mentioned were as used in the previous examples.

Examples 290-300

Examples 290 to 300 illustrate the polymer (compatible liquid) concentration range which can be used in the preparation of a homogeneous porous polymer intermediate from high weight polyethylene and N, N-bis (2-hydroxyethyl) -talgamine. In each example, the intermediates had a height of approx. 5 cm and a diameter of 6 cm. Said HDPE was as used in previous examples.

Details of manufacture and physical properties investigated are given in Table XV.

Table XV

Ex. No. ¾ Wash ° C Remarks 290 95 275 very weak, no solids integrity, not applicable 291 90 --- very greasy, liquid leaked out, upper liquid limit exceeded 292 80 250 greasy (continued) 60 DK 171108 B1

Ex. No.% Liquid ° C Remarks 293 75 220 greasy 294 70 250 hard solid product 295 65 220 ....

296 60 250 hard solid product 297 55 220 .....

298 50 240-260 hard solid product 299 40 260 hard solid product 300 30 200 hard solid product

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

Examples 301-311

These examples illustrate the polymer (compatible liquid) concentration range that can be used in the preparation of a homogeneous porous polymer intermediate from scavenging polyethylene and N, N-bis (2-hydroxyethyl) -talgamine. In each example, the intermediate had a height of approx. 1.3 cm and a diameter of approx. 6 cm. Said 1DPE was as used in previous examples.

The details of manufacture and physical properties investigated are given in Table XVI.

Table XVI o

Ex. No.% Liquid C Remarks 301 95 275 very weak, no solids integrity, not applicable 302 90 240 very greasy, liquid leaked, upper liquid limit exceeded 303 80 260 hard solid product 304 75 210 hard solid product 305 70 210 hard solid product 306 66 200 hard solid product 307 60 280 hard solid product 308 50 280-290 hard solid product 309 40 285 hard solid product 310 30 285 hard solid product 311 20 280-300 hard solid product 61 DK 171108 B1

Microphotographs of the porous polymers of Examples 303, 307 and 310 are shown in Figs. 14-15 (at 250X and 2500X magnification, respectively); 16 (at 2500X magnification) and FIG. 17 (at 2475X magnification). The figures show the decreasing cell size, from very large (Fig. 15, 20¾ polymer) to very small (Fig. 17, 70% polymer), with increasing polymer content. The relatively flat cell walls of the 20% polymer product, Example 303, correspond to the methyl pentene polymer (Fig. 22) and can be seen in Figs. 14. FIG. 15 is an enlargement showing a portion of a cell wall shown in FIG. 14. The microcellular structure of the porous polymer can be seen in FIG. 16th

Examples 312-316

Examples 312-316 illustrate the polymer (compatible liquid) concentration range that can be used in the preparation of a homogeneous porous polymer intermediate from non-volatile polyethylene and diphenyl ether. In each example, the intermediate had a height of approx. 1.3 cm and a diameter of approx. 6 cm. Said LDPE was as used in previous examples.

Details of manufacture and physical characteristics investigated are given in Table XVII.

Table XVII

Ex. No.% Liquid ° C Remarks 312 90 185 very greasy, no solid integrity, not applicable 313 80 185 very greasy, near upper liquid limit, but still applicable 314 75 200 wet, strong 315 70 190-200 slightly greasy 316 60 200 hard solid product

Examples 317-322

Examples 317-322 illustrate the polymer (compatible liquid) concentration range that can be used in the preparation of a homogeneous porous polymer intermediate from non-volatile polyethylene and 1-hexadecene. In each example, the intermediate had a height of approx. 5 cm and a diameter of approx. 6 cm. Said LDPE was as used in previous examples.

The details of manufacture and physical characteristics examined are given in Table XVIII.

62 DK 171108 B1

Table XVIII

Ex. No. 7. Wash ° C Remarks 317 90 180 good strength 318 80 180 small strength, useful 319 75 200 small strength, useful 320 70 177 .....

321 50 180 good strength

Examples 322-334

These examples illustrate the polymer (compatible liquid) concentration range that can be used in the preparation of a homogeneous porous polymer intermediate from polypropylene and N, N-bis (2-hydroxyethyl) -talgamine. In each example, the intermediate had a height of approx. 1.3 cm and a diameter of approx. $ cm. Furthermore, as indicated, films were made. Said PP was as used in previous examples.

Details of manufacture and physical characteristics investigated are given in Table XIX.

Table XIX

Ex. No. 7. Liquid ° C Notes Thin film 322 90 200 fairly wet yes 323 85 200 .....

324 80 200 strong yes 325 75 180 dry and hard yes 326 70 200 yes 327 65 210 .....

328 60 210 yes 329 50 200 yes 330 40 210 yes 331 36.8 175 white-crystalline --- 332 25 180 .....

333 20 180 yes 334 15 180 ....

Microphotographs of Examples 322, 326, 328, 330 and 333 are shown in FIG. 6 to 10 (at 1325X, 1550X, 1620X, 1450X and 1250X magnification, respectively). The very strong leaf formation of the microporous polymer with 107 polymer is shown in FIG. 6, but the microcellular structure is still preserved. These figures illustrate the decreasing cell size as the amount of polymer increases. However, regardless of the small cell size, the microcellular structure present in each example is present.

Examples 335-337

The Examples Illustrate the polymer (compatible liquid) concentration range that can be used in the preparation of a homogeneous porous polymer intermediate from polypropylene and diphenyl ether. In each example, the intermediate had a height of approx. 1.3 cm and a diameter of approx. 6 cm. Furthermore, as indicated, thin films were also made. Said PP was as used in previous examples.

The details of manufacture and physical characteristics investigated are given in Table XX.

Table XX

Ex. No. 7. Liquid ° C Thin film 335 90 200 yes 336 80 200 yes 337 70 200 yes

Microphotographs of the porous polymer of Examples 335, 336 and 337 are shown in Figs. 11 (2000X magnification), fig. 12 (2059X magnification) and FIG. 13 (1950X magnification). The figures show that as the polymer concentration increases, the pore size decreases, and fig. 11 shows the smooth cell walls, while FIG. 12 and 13 show the cells and the connecting pores. In each of the figures, the microcellular structure is present.

Examples 338-346

These examples illustrate the polymer (compatible liquid) concentration range that can be used in the preparation of a homogeneous porous polymer intermediate from styrene-butadiene rubber (SBR) and N, N-bis (2-hydroxyethyl) -talgamine. In each example, the intermediate had a height of approx. 1/3 cm and a diameter of approx. 6 cm. Furthermore, as indicated, thin films were made. Said SBR was as used in previous examples.

The details of the manufacture and physical characteristics investigated are given in Table XXI.

Table XXI

Ex. No. 7 «Liquid ° C Remarks Thin film 338 90 200 weak, beyond the yes upper liquid limit 339 80 195 rubbery yes 340 75 195 rubbery yes 341 70 195 rubbery yes 64 DK 171108 B1

Table XXI (continued)

Ex. No.% Wash ° C Remarks Thin film 342 60 200 rubbery yes 343 50 not rubbery yes 344 40 not rubbery yes 345 30 not rubbery yes 346 20 not rubbery yes

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

Examples 347-352

Examples 347-352 illustrate the polymer (compatible liquid) concentration range that can be used in the preparation of a homogeneous porous polymer intermediate from styrene-butadiene rubber and decanol. In each example, the intermediate had a height of approx. 1.3 cm and a diameter of approx. 6 cm. Furthermore, as indicated, thin films were made. Said SBR was as used in previous examples.

The details of manufacture and physical characteristics investigated are given in Table XXII.

Table XXII

Ex. No. 7. Liquid Temp., ° C Remarks Thin film 347 90 not specified beyond upper liquid limit, not applicable 348 80 190 rubbery yes 349 70 190 rubbery yes 350 60 190 rubbery yes 351 50 190 rubbery yes 352 40 not stated rubbery - ·

Examples 353-356

Examples 353-356 relate to styrene-butadiene rubber and diphenylamine. The data are listed in Table XXIII.

65 DK 171108 B1

Table XXIII

Ex. No.% Liquid ° C Remarks 353 80 not specified ----- 354 70 200-210 .....

355 60 215 .....

356 50 200-210 .....

Examples 357-361

Examples 357-361 illustrate the polymer (compatible liquid) concentration range that can be used in the preparation of a homogeneous porous polymer intermediate from a Surlyrr resin, as used in the previous examples, and N, N-bis (hydroxyethyl) ) tallowamine. In each example, the intermediate had a height of approx. 1.3 cm. and a diameter of approx. 6 cm. Furthermore, as indicated, thin films were made.

The details of manufacture and physical characteristics examined are given in Table XXIV.

Table XXIV

Ex. % Liquid ° C Thin film 357 70 190-195 yes 358 60 190 yes 359 50 not stated yes 360 40 not stated yes 361 30 not stated yes

Examples 362-370

These examples illustrate the polymer (compatible liquid) concentration range that can be used in the preparation of a homogeneous porous polymer intermediate from a Surlyf® resin, as used in the previous examples, and diphenyl ether. In each example, the intermediate had a height of approx. 1.3 cm and a diameter of approx. 6 cm. Furthermore, as stated, thin films were made.

The details of manufacture and physical characteristics investigated are given in Table XXV.

Table XXV

Ex. no aL Wash ° C Thin film 362 90 207 yes 363 80 190 yes 364 70 200 yes 365 60 185 yes 66 DK 171108 B1

Table XXV (continued)

Ex. No. 7. Wash ° C Thin films 366 50 not stated yes 367 40 not specified --- 368 30 not specified - 369 20 not specified --- 370 10 not specified ---

Examples 371-379

Examples 371-379 illustrate the polymer (compatible liquid) concentration range that can be used in the preparation of a homogeneous porous polymer intermediate from a Surlyn resin, as used in the previous examples, and dibutyl phthalate. In each example, the intermediate had a height of approx. 1.3 cm and a diameter of approx. 6 cm.

The details of manufacture and physical characteristics investigated are given in Table XXVI.

Table XXVI

Ex. No.% Liquid ° C Remarks 371 90 220 .....

372 80 208 .....

373 70 195 .....

374 60 200 .....

375 50 200 ....

376 40 not specified ----- 377 30 not specified ----- 378 20 not specified ----- 379 10 not specified -----

Examples 380-384 (Prior Art)

Examples 380-384 are reproductions of various known compositions which have been found to have a physical structure different from the structure of the present invention.

Example 380

A porous polymer was prepared by the method of Example 1 of U.S. Patent No. 3,378,507, modified to obtain a product of some physical integrity and to use a soap as the water-soluble anionic surfactant instead of sodium bis (2-ethylhexyl) -sulfosucclnat.

In an internally heated Brabender-Plastic-Corder mixer, 33 1/2 wt. 67 DK 171108 B1 parts of Exxon Chemical Corporation polyethylene type LD 606 and 66 2/3 parts of Ivory Soap shavings mixed bed a machine temperature of approx. 177 ° C until a homogeneous mixture was formed. The material was then compression molded in the form of a chewing gum type having a cavity of 6.4 cm x 12.7 cm and a depth of 20 mils, at a temperature of about 177 ° C and a pressure of 248 MPa. The resulting sample was washed continuously for approx. 3 days in a slow stream of hydroelectric water and then in succession washed by immersion in eight baths of distilled water, each time for a period of approx. 1 hour. The resulting sample still contained some soap and had poor handling properties.

FIG. 47 and 48 are photomicrographs of the product of Example 380, at 195X and 2000X magnification, respectively. It appears that the product has a relatively non-uniform polymeric structure with neither clear cell voids nor interconnecting pores.

Example 381

A porous polymer was prepared by the method of Example 2, Sample D, in U.S. Patent No. 3,378,507, modified to obtain a sample having some handling strength.

In an internally heated Brabender-Plastic-Corder mixer, 75 parts of Ivory Soap ^ nails and 25 parts of Exxon Chemical Corporation polyethylene type LD 606 were mixed at a machine temperature of approx. 177 ° C and a sample temperature of approx. 166 ° C until a homogeneous mixture was formed. The material was then injection molded into a 1-ounce Watson-Stillman injection molding machine with a mold cavity diameter of 5 cm and a depth of 20 mils. The resulting sample was washed continuously for approx. three days in a slow stream of waterworks water and then successively washed by immersion in eight baths of distilled water, each time for a period of approx. 1 hour. The resulting sample still contained some soap.

FIG. 45 and 46 are photomicrographs of the product of Example 381 at 240X and 2400X magnification, respectively. The product of this example did not have the typical cellular structure of the present invention as shown in the photomicrographs.

Example 382

In the method of Example 3, sample A, in U.S. Pat.

3,378,507 a porous polymer was prepared.

In an internally heated Brabender-Plastic-Corder mixer, 25 parts of Novamont Corporation polypropylene type F300 8N19 and 75 parts of Ivory Soaf ^ nails were mixed at a machine temperature of approx. 166 ° C until a homogeneous mixture was formed. The material was then compressed with a rubber-type form.

The resulting sample was found to have very little strength. Part of the resulting sample was washed continuously for approx. 3 days in a slow stream of waterworks water and then successively washed by immersion in eight baths of distilled water, each time for a period of approx. 1 hour. The washed product was found to have very poor handling properties.

FIG. 51 and 52 are photomicrographs of the product of Example 382 at 206X and 2000X magnification, respectively. The photomicrographs show that the product does not have the cellular structure of the present invention.

Example 383

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

On an open two-roll rubber mill, manufactured by Bolling Company, 25 parts of Novamon ^ Corporation polypropylene type F300 8N19 and 75 parts of Ivory Soa ^ mugs were mixed for approx. 10 minutes at a temperature of approx. 177¾ until a homogeneous mixture was formed. The material was then injection molded with a 1-ounce Watson-Stillman injection molding machine with a mold cavity diameter of 5 cm and a depth of 20 mils. The resulting sample was washed continuously for approx. 3 days in a slow stream of waterworks water and then successively washed by immersion in eight baths of distilled water, each time for a period of approx. 1 hour. The resulting sample still contained some soap. The resulting product was found to be stronger than the product of Example 382.

FIG. 49 and 50 are photomicrographs of the product of Example 383 at 195X and 2000X magnification, respectively. The irregular shapes shown in the photomicrographs are easily distinguishable from the structure of the present invention.

Example 384

A porous polymer was prepared according to Example II of U.S. Pat.

3 310 505, modified to obtain a more homogeneous mixture of the materials.

In an internally heated Brabender-Plastic-Corder mixer, 40 parts of Exxon Chemical Corporation polyethylene type LD 606 and 60 parts of Rohm and Haas Corporation polymethylmethacrylate were mixed in approx. 10 minutes at a machine temperature of approx. 177 ° C until a homogeneous mixture was formed. The material was then plated on a cold mill and then compressed using a heated circular mold of 10 cm with a depth of 20 mils and at 30 tons pressure for approx. 10 minutes. The resulting composition was extracted for 48 hours with acetone in a large Soxlet extractor.

FIG. 53 and 54 are photomicrographs of the product of Example 384 at 205X and 2000X magnification, respectively. The non-uniform structure shown in the photomicrographs is easily distinguishable from the uniform structure of the present invention.

69 DK 171108 B1

Physical characterization of Examples 225-358

In order to gain a quantitative understanding of the homogeneous structure of the present invention, certain samples of the microporous material and certain prior art samples were analyzed on an Aminexquickwind penetration parameter. FIG. 30 and 31 show mercury penetration curves for the 1.3 cm block of Example 225 prepared with 25 percent polypropylene and 75 percent N, N-bis (2-hydroxyethyl) -talgamine, and Figs. 32 shows a mercury penetration curve for the 15 cm block. according to Example 225. All mercury intrusion curves are shown in a semi-log diagram with the equivalent pore sizes shown on the log-scale abscissa. FIG. 30 to 32 show the typical narrow distribution of pore sizes of the composition of the present invention. It was shown that the sample of 1.3 cm according to Example 225 had a void volume of approx. 76 percent and an average pore size of approx. 0.5 microns and that the 15 cm block had a void volume of approx. 72 percent and an average pore size of approx. 0.6 microns.

FIG. 33 shows a mercury penetration curve for the product of Example 358 prepared with 40 percent polypropylene and 60 percent N, N-bis (2-hydroxyethyl) -talgamine. FIG. 33 shows that the sample had the typical narrow pore size distribution. It was shown that the sample had a void volume of approx. 60 percent and an average pore size of approx. 0.15 microns.

It is seen that the compositions of the present invention have such pore size distributions that at least 80 percent of the pores present in the composition fall within no more than one decade on the mercury intrusion curve abscissa. Thus, the pore size distribution of the composition can be characterized as "narrow".

Physical characterization of commercial compositions of the prior art.

Example 385

The composition of this example is commercially available microporous polypropylene Celgard 3501, made by Celanese. FIG. 34 shows a mercury intrusion curve for the sample and shows a large amount of pores in the range of 70 to 0.3 microns. The sample was shown to have a void volume of approx. 35 percent and an average pore size of approx. 0.15 microns.

Example 386

The composition of this example was commercially available microporous polyvinyl chloride A-20 made by Amerace. FIG. 35 shows a mercury penetration curve for the sample and shows a very wide pore size distribution. The sample was shown to have a void volume of approx. 75 per cent and an average pore size of about 70 per cent. 0.16 tnikron.

Example 387

The composition of this example was commercially available microporous polyvinyl chloride A-30, manufactured by Amerace. FIG. 36 shows a mercury intrusion curve for the sample and shows a very wide pore size distribution. The sample was shown to have a void volume of approx. 80 percent and an average pore size of approx. 0.2 microns.

Example 388

The composition of this example was commercially available microporous polypropylene Porex. FIG. 37 shows a mercury entrapment curve for the sample and shows a very wide distribution of very small cells as well as a distribution of very large cells. The sample was shown to have a void volume of approx. 12 percent and an average pore size of approx. 1 micron.

Example 389

The composition of this example was commercially available microporous polyvinyl chloride Millipore BDWP 29300. Figure 38 shows a mercury intrusion curve for the sample and shows a relatively narrow distribution within the range of 0.5 to 2 microns as well as a number of cells less than ca. 0.5 microns. The sample was shown to have a void volume of approx. 72 percent and an average pore size of approx. 1.5 microns.

Examples 390-391 (Prior Art)

Example 390

The composition of this example was commercially available microporous cellulose triacetate Metricel TCM-200, from Gelman. FIG. 39 is a mercury penetration curve for the sample and shows a wide pore size distribution up to approx. 0.1 micron. The sample was shown to have a void volume of approx. 82 percent and an average pore size of approx. 0.2 microns.

Example 391

The composition of this example was commercially available mlcroporous acrylonitrile-polyvinyl chloride copolymer Acropor WA from Gelman. FIG. 40 shows a mercury intrusion curve for the sample and shows a wide pore size distribution. The sample was shown to have a void volume of approx. 64 percent and an average pore size of approx. 1.5 microns.

7i DK 171108 B1

Physical characterization of Examples 380-384 of the prior art.

The products of Examples 380-384 illustrating prior art were also analyzed by mercury penetration. FIG. Figures 41-43 show mercury penetration curves showing the wide pore size distribution of the products of Examples 381, 380 and 383, respectively. 44 shows a mercury penetration curve for the product of Example 384 and shows a collection of pores in the range of 45 to 80 microns as well as a number of very small pores. The products of Examples 380, 381, 383, and 384 were found to have a void volume of 54, 46, 54, and 29 percent, respectively, and an average pore size of ca. 0.8, 1.1, 0.56 and 70 microns.

Examples 392-399

These examples illustrate the polymer / (compatible liquid) concentration range that can be used in the preparation of homogeneous porous polymer intermediates from polymethyl methacrylate and 1,4-butanediol using the standard preparation method. In each example, the manufactured intermediate had a height of approx. 1.3 cm and a diameter of approx. 6 cm. The polymethyl methacrylate (s) was supplied by Rohm and Haas under the designation Plexiglas ^ Acrylic Plastic Molding Powder, lot number 386491. The details of manufacture are given in Table XXVII.

Table XXVII

Ex. No.% Liquid Temp ,, ° 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 The present invention, as shown in FIG. 61, showing the microporous product at 5000X magnification. The same polymer / liquid system as that of Example 394 was also cooled at rates up to 4000 ° C per minute. per minute and still produced the cellular structure of the invention.

72 DK 171108 B1

Example 400

The porous polymeric nickel product was prepared using the standard preparation method and by heating 30 percent polymethyl methacrylate, as used in the previous examples, and 70 percent lauric acid to 175 ° C and cooling to form the porous polymer intermediate. The lauric acid was removed from the resulting intermediate to form the microporous cell structure of the present invention.

Example 401

The porous polymer intermediate was prepared using the standard preparation method and heating 30 percent Nylon 11, from Aldrich Chemical Company, and 70 percent ethylene carbonate to a temperature of 218 ° C and then cooling the resulting solution to form the porous polymer intermediate. The ethylene carbonate was removed from the intermediate and the resulting microporous polymer was shown to have the cell structure of the present invention.

Example 402

The porous polymer intermediate was prepared using the standard preparation method and heating 30 percent Nylon 11, as used in the previous example, and 70 percent 1,2-propylene carbonate to a temperature of 215 ° C and then cooling the resulting solution to form of the porous polymer intermediate. The propylene carbonate was removed from the intermediate and the resulting microporous polymer was shown to have the cell structure of the present invention.

Examples 403-422

Examples 403-422 show the preparation of the porous polymer intermediates from polymer / liquid systems containing various amounts of Nylon 11, as used in the preceding Examples, and tetramethylene sulfone, from Shell under the designation Sulfone W, and containing ca. 2.5 percent water. The different concentrations were cooled at different rates and from different solution temperatures, as listed in Table XXVIII, which also shows that increasing cooling rates and increasing concentration of the polymer generally cause the resulting cell sizes to decrease.

73 DK 171108 B1

Table XXVIII

Cooling rate Cell size

Ex. No.% Liquid T ° C ° C / min (micron) 403 90 195 20 10 404 80 198 5 15 405 80 198 20 14 406 80 198 40 9 407 80 198 80 5.5 408 70 200 5 11 409 70 200 20 5 410 70 200 40 6,5 411 70 200 80 6,5 412 60 205 5 5 413 60 205 20 4,5 414 60 205 40 4 415 60 205 80 3,5 416 50 210 20 3 417 50 210 40 1.5 418 50 210 80 2 419 40 212 20 420 30 215 20 421 20 217 20 422 10 220 20

The preceding Table XXV111 also shows that at concentrations from 40 percent to 10 percent washes, no visible porosity of the system is cooled at 20 ° C per day. minute. Such results were expected, as can be seen in FIG. 62, showing the melting curve of the Nylon 11 / tetramethylene sulfone concentration range as well as the crystallization curves at the different cooling rates. It can be seen from FIG. 62, that at the cooling rate of 20 ° C / minute, the system containing 40% liquid does not fall within the substantially flat portion of the crystallization curve and thus would not be expected to form the desired microporous structure. FIG. 63 is a photomicrograph at 2000X magnification of the product of Example 409 and shows the typical cellular structure of Examples 403-418.

Example 423

The porous polymer intermediate was prepared using the standard preparation method and heating 30 percent polycarbonate, from General Electric under the designation Lexai®, and 70 percent menthol to a temperature of 206 ° C.

74 DK 171108 B1 and cooling to form the porous polymer intermediate. The menthol was extracted and a microporous cell structure emerged, as shown in FIG. 64, there is a photomicrograph of the product of this example at 2000X magnification.

Example 424

This example demonstrates the preparation of the microporous cell structure of the present invention from poly-2,6-dimethyl-1,4-phenylene oxide, from Scientic Polymer Products and commonly referred to as polyphenylene oxide. The homogeneous microporous polymer intermediate was prepared from 30 percent of said polyphenylene oxide and 70 percent N, N-bis (2-hydroxyethyl) talgamine heated to a solution temperature of 275 ° C and the intermediate was prepared using the standard preparation method. . The liquid was removed from the intermediate and the cell structure of the invention emerged, as shown in FIG. 65, there is a photographer! of the product of this example at 2000X magnification.

Example 425

This example demonstrates the preparation of the non-cellular product of the invention by cooling a homogeneous solution of 40 percent polypropylene, as used in the previous examples, and 60 percent dibutyl phthalate. The solution was extruded on a cooled conveyor belt to a thickness of about 10 mm. 10 mils and the cooling rate was above 2,400 ° C. A certain amount of dispersal was applied to the conveyor surface at a location prior to the solution extruded on the belt. The liquid was removed from the resulting film and a non-cellular microporous product was obtained, as shown in FIG. 65, which is a photomicrograph of the product of this example at 2000X magnification.

Example 426

This example demonstrates the preparation of the non-cellular product of the invention by cooling a homogeneous solution of 25 percent polypropylene, as used in the preceding Examples, and 75 percent N, N-bis (2-hydroxyethyl) -talgamine in the same manner as in Example 1. 425. The liquid was removed from the resulting film and a non-cellular microporous product was obtained, as shown in FIG. 67, there is a photomicrograph of the product of this example at 2000X magnification.

The products of Examples 425 and 426 were analyzed by mercury penetration porosimetry and their respective penetration curves are shown in Figs. 68 and 69. It can be seen that both products generally had narrower pore size distributions, but the product of Example 426 showed a much narrower distribution than the product of Example 425. Thus, the product of Example 425 had a calculated S value of only 24.4, while the product According to Example 426, a calculated S value of only 8.8. However, the average pore size for example 425 was very small, 0.096 microns, while the average pore size for the product of example 426 was 0.589.

To quantitatively demonstrate the peculiarity of the cellular compositions of the present invention, a number of such microporous products were prepared by the standard preparation method, and the details of this preparation are set forth in Examples 427-457 of Table XXIX. The products of said examples were analyzed by mercury intrusion porosimetry to determine their respective average pore diameter and S values, and by scanning electron microscopy to determine their average cell size, S. The results of such analysis are given in Table XXX.

Table XXIX

Ex. No. Polymer Liquid 7. Cavity Solution temperature ° C

427 polypropylene N, N-bis (2-hydroxy-70-ethyl) -talgamine 180 428 polypropylene N, N-bis (2-hydroxy-60-210-ethyl) -talgamine 429 polypropylene diphenyl ether 90 200 430 polypropylene diphenyl ether 80 200 431 polypropylene diphenyl ether 200 432 polypropylene 1,8-diaminooctane 70 180 433 polypropylene phenyl salicylate 70 240 434 polypropylene 4-bromodiphenyl 70 200 ether 435 polypropylene tetrabromoethane 90 180 436 polypropylene N-octyldiethanol-75 --- amine 437 polypropylene N-hexyldiethanol polypropylene salicylic aldehyde 70 185 439 low weight hexanoic acid 70 190 polyethylene 440 low density 1-octanol 70 178 polyethylene 441 low density dibutylsebacate 70 238 polyethylene 442 low density Phosclere EC-53 70 191 polyethylene 443 high density dicaprylic dipole 70 20 70 290 polyethylene (continued) 76 DK 171108 B1 446 high weight N, N-bis (2-hydroxy-80 250 polyethylene ethyl) -talgamine 4 47 polystyrene 1-dodecanol 75 220 448 polystyrene 1,3-bis (4-piperidine) - 70 186 propane 449 polystyrene diphenylarain 70 235 450 polystyrene N-hexyldiethanolamine 75 260 451 polystyrene Phosclere P315C 70 270 452 polymethyl 1,4-butanediol 70 --- methacrylate 453 polymethyl 1,4-butanediol 85 --- methacrylate 454 Surlyn diphenyl ether 70 185-207 455 Surlyr dibutyl phthalate 70 195 456 Noryi® N, N-bis (2-hydroxy-75 250 ethyl) -talgamine 457 Nylon 11 Ethylene Carbonate 70 ---

Table XXX

Ex. No. C P C / P S log C / P log S / C

427 5.0 0.520 9.6 2.86 0.982 -0.243 428 3.18 0.112 28.4 5.0 1.45 0.197 429 22.5 11.6 1.94 4.52 0.288 -0.697 430 6.49 0.285 22.8 27.1 1.36 0.621 431 6.72 0.136 49.4 7.01 1.69 0.0183 432 13.0 0.498 26.1 2.36 1.42 -0.741 433 13.8 0.272 50, 7 4.29 1.71 -0.507 434 3.35 0.137 24.5 5.25 1.39 0.195 435 15.4 0.804 19.2 5.13 1.28 -0.477 436 16.6 0.850 19.5 2, 52 1.29 -0.819 437 20.0 0.631 31.7 2.51 1.50 -0.901 438 7.9 0.105 75.2 3.22 1.88 -0.390 439 7.5 1.16 6.47 8, 62 0.811 0.0604 440 6.8 1.00 6.8 3.53 0.833 0.285 441 5.85 0.636 9.20 6.07 0.964 0.0160 442 3.40 0.512 6.64 5.30 0.822 0.193 443 5 0,871 5.74 8.21 0.759 0.215 444 4.75 0.631 7.53 3.54 0.877 -0.128 445 7.8 1.18 6.61 3.82 0.820 -0.310 446 34.5 0.696 49.6 4 , 34 1.70 -0.900 447 28.2 1.88 15.0 3.40 1.18 -0.919 (continued) 77 DK 171108 B1 448 1.08 0.0737 14.7 2.87 1.17 0.424 449 6.65 0.631 10.5 63.5 1.02 0.980 450 7.4 0.164 45.1 3.74 1.65 -0.296 451 1.4 0.151 9.27 2.26 0.967 0.208 452 9.2 0.201 45, 8 3.68 1.66 -0.398 453 114 10.3 11.1 5.19 1.05 -1.34 454 6.8 0.631 10.8 2.13 1.03 -0.504 455 5.6 0.769 7.28 2.09 0.862 -0.428 456 19.0 0.179 106 2.74 2.03 - 0.841 457 5.8 0.372 15.6 7.56 1.19 0.112

Table XXXI

Ex. No. Description of the Prior Art Polymer Type 458 Celgard 3501 Polypropylene 459 Ameracide A-30 Polyvinyl Chloride 460 Porex Polypropylene 461 Millipore EG Cellulose Type 462 Metricel GA-8 Cellulose Type 463 Sartorius SM 12807 Polyvinyl Chloride 464 Millipore HAWP Cell Millipore G5WP 04700 Cellulose Type 466 Millipore VMWP 04700 Cellulose Type 467 Amicon 5UM05 Cellulose Type 468 Celgard 2400 Polypropylene 469 Millipore SMWP 04700 Polyvinyl Chloride 470 Celgard 2400 Polypropylene 471 Product by Example 381 Polyethylene 472 Product by Example 381 Polyethylene 472 Product by Example 474 Product of Example 384 polyethylene

Table XXXII

Ex. No. C £ log S / C

458 0.04 * 2.32 1.76 459 0.3 138 2.66 460 186 2.41 -1.89 461 0.2K 26.3 1.85 462 0.2K 9.14 1.66 463 0 , 2K 31.5 2.2 464 0.8 * 2.94 0.565 (continued) 78 DK 171108 B1 465 0.22 * 1.64 0.872 466 0.05 * 5.37 2.03 467 2.10 ** 61.8 1.79 468 0.02 * 5.08 2.40 469 5 * 1.55 -0.509 470 0.04 * 5.64 2.15 471 1.1 ** 11.5 1.019 472 0.8 ** 17.5 1.34 473 0.56 16.8 1.477 474 70 1.34 -1.718

X

According to company product information

XX

According to mercury intrusion

The data contained in Tables XXIX to XXXII are summarized in FIG. 70, there is a record of log S / C versus log C / P. In FIG. 70, it can be seen that the cell structure according to the present invention can be defined by having a log C / P of from ca. 0.2 to approx. 2.4 and a log S / C of approx. -1.4 to approx. 1.0, and usually said polymer will have a log C / P of from ca. 0.6 to approx. 2.2 and a log S / C of approx. -0.6 to approx. 0.4.

Thus, the present invention provides an easy method for preparing microporous polymers from any thermoplastic polymer of widely varying thicknesses and shapes. The microporous polymers may have a distinctive microcellular configuration and are in any case characterized by pore diameters of relatively narrow size distribution. These structures are produced by first selecting a liquid which is compatible with a polymer, i.e. form a homogeneous solution with the polymer and can be removed from the polymer after cooling, and then select the amount of the liquid and cool the solution in a manner which ensures that the desired microporous polymer configuration will appear.

As will also be apparent, the use of the present invention also provides microporous polymer products which contain relatively large amounts of functionally usable fluids, such as a polymer additive, and behave as a solid. These products can advantageously be used in a variety of applications, such as for blends in the building industry.

Claims (11)

A three-dimensional, microporous, isotropic and substantially homogeneous polymer body having a relatively narrow pore size distribution, prepared by heating a mixture of one or more synthetic thermoplastic polymers in admixture with a compatible liquid to a temperature and for a period of time. are sufficient to form a homogeneous solution which has been allowed to assume a desired shape and that the solution in this form has been cooled and at least a substantial portion of the compatible liquid has been removed, said polymers being selected among olefinic polymers, condensation polymers and oxidation polymers, characterized in that the polymer body has a hollow space volume of 10 - 90% and a sharpness factor S of 1 - 30, the sharpness factor S being determined by analysis of a mercury intrusion curve and defined as the ratio of that pressure at which 85% of the mercury is penetrated and the pressure at which 15% of the mercury is penetrated, and the body being prepared by the solution having cooled in said form for so long and so rapidly that a liquid-liquid phase separation is initiated under thermodynamic non-equilibrium conditions, and that cooling, avoiding mixing or other shear forces, continues to form a solid body before removing at least a substantial portion of the compatible liquid in a manner known per se to obtain the microporous body. Microporous body according to claim 1, characterized in that it contains a large amount of substantially spherical cells with a mean diameter C of 0.5 - 100 μπι, which is substantially distributed over the whole structure, the adjacent cells being connected. with each other via pores having a smaller diameter P than the cells, and that the ratio of the mean cell diameter to the mean pore diameter C / P is 2: 1 - 200: 1, log C / P is 0.2 - 2.4, and log S / C is -1.4 - +1. Microporous body according to claim 2, characterized in that it has a mean cell diameter C of 1-20 μπι and a mean pore diameter P of 0.05 -10 μπι. Microporous body according to claims 2-3, characterized in that it has a sharpness factor S of 2 - 20. Microporous body according to claims 1-3, characterized in that it has a sharpness factor S of 1 - 10. Microporous body according to claim 1, characterized in that the thermoplastic polymer is polypropylene and that the body has a sharpness factor S of 1 - 10 and pores with a mean diameter P of 0.2 - 20 μιη. DK 171108 B1 80 Process for preparing a three-dimensional, microporous, isotropic and substantially homogeneous polymer body according to claim 1, characterized in that the solution in said form is cooled so long and so rapidly that a liquid-liquid phase separation is initiated under thermodynamic equilibrium conditions, and that cooling, avoiding mixing or other shearing forces, is continued to form a solid body before removing at least a substantial portion of the compatible liquid in a manner known per se to obtain the microporous body. 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. Process according to claim 7 or 8, characterized in that the cooling is carried out at a rate so that, in the cooling in a continuous liquid polymer phase, a large amount of liquid droplets of substantially uniform size are formed. 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 body according to claims 1-6 for the uptake and delivery of functional fluids.