CH649565A5 - Polymer cell structure, and process for the production thereof - Google Patents

Description

The present invention relates to a three-dimensional, microporous polymer cell structure which is characterized in that it has a multiplicity of essentially spherical microcells which have an average diameter C of 0.5-100 micrometers and are distributed substantially uniformly over the structure , adjacent cells being connected to one another by pores whose diameter is smaller than that of the microcells, that the polymer cell structure has a pore size distribution which corresponds to a sharpness factor S from 1 to 30, the sharpness factor S being determined and defined by analyzing a mercury intrusion curve is, as the ratio of the pressure at which 85% of the mercury has penetrated to the pressure at which 15% of the mercury has penetrated, the decimal logarithm of the ratio of the mean cell diameter C to the mean pore diameter P has a value in the range of 0. 2-2.4 and the decadal Logarithm of the ratio of the sharpness factor S to the average cell diameter C has a value in the range from -1.4 to 1.0, that the pores and the cells are empty, and that the polymer is a synthetic thermoplastic polymer from the class consisting of the Homo - and copolymers of ethylenically unsaturated monomers, the condensation polymers and the oxidation polymers, or a mixture of synthetic thermoplastic polymers belonging to this class.

The process for producing this polymer cell structure is characterized in that a mixture of one or more than one synthetic thermoplastic polymer from the class consisting of the homo- and copolymers of ethylenically unsaturated monomers, the condensation polymers and the oxidation polymers, and a compatible liquid heated to a sufficient temperature for a sufficient time to form a homogeneous solution, forms the homogeneous solution, and cools the shaped solution so that liquid-liquid phase separation occurs, thereby at the same time a plurality of liquid droplets of substantially the same size is formed in the continuous liquid polymer phase, cooling continues to solidify the polymer, and substantially all of the liquid is removed from the solid body formed so as to form the polymer cell structure.

Furthermore, the invention relates to a three-dimensional microporous polymer cell structure, the cells and pores of which are at least partially filled with an active substance liquid which is characterized in that it has a multiplicity of essentially spherical microcells which have an average diameter C of 0.5- 100 microns and are distributed substantially uniformly over the structure, with neighboring cells being connected to one another by pores whose diameter is smaller than that of the microcells, that the polymer cell structure has a pore size distribution which corresponds to a sharpness factor S of 1 to 30, the Sharpness factor S is determined by analysis of a mercury intrusion curve and is defined as the ratio of the pressure at which 85% of the mercury has penetrated to the pressure at which 15% of the mercury has entered that the decimal logarithm of the ratio of the mean cell diameter C to the mean pore diameter P has a value in the range of 0.2-2.4 and the decimal logarithm of the ratio of the sharpness factor S to the mean cell diameter C has a value in the range of - 1.4 to 1.0 that the pores and cells are at least partially filled with an active ingredient liquid, and that the polymer is a synthetic thermoplastic polymer from the

Class consisting of the homo- and copolymers of ethylenically unsaturated monomers, the condensation polymers and the oxidation polymers, or a mixture of synthetic thermoplastic polymers belonging to this class.

Several different methods were previously developed for the production of microporous polymer cell structures. Such processes range from classic phase inversion to nuclear bombardment, in order to incorporate microporous, solid particles into a substrate, which are then leached out, or for sintering together microporous particles in any way. Previous efforts in this area have brought with it other processes, as well as countless variations of what can be considered classic or basic processes.

The interest in microporous polymer cell products has been caused by numerous possible applications for materials of this nature. These possible applications are well known and range from ink pads, etc. to leather-like breathing sheets or filter media. In addition, despite all possible uses, commercial use remained relatively modest. To this end, the commercially used methods have various limitations; they do not allow the kind of changeability that is required to expand applications to reach the potential market for microporous products.

As previously mentioned, some commercially available microporous polymer cell products are made by nuclear bombardment. With such a method it is possible to achieve a fairly narrow pore size distribution; however, the pore volume must be relatively low (i.e. less than about 10% empty space) so that one is certain that the polymer will not degrade during manufacture. Many polymers cannot be used in such a process because the polymer does not have the ability to etch, the process further requires that a relatively thin layer or film of the polymer be used and that significant investigations are made in carrying out the process in order to avoid a “double trace”, which leads to the formation of oversized pores.

Classic phase inversion has also been used commercially to produce microporous polymers from cellulosic tat and certain other polymers. The classic phase inversion was described in detail by R.E. Kesting in Synthetic, Polymeric Membranes, Mc-Graw-Hill, 1971. In particular, on page 117 of the cited publication, it is expressly stated that the classic phase inversion involves the use of at least three components, i.e. a polymer, a solvent for the said polymer and a non-solvent for the said polymer.

Attention is also drawn to U.S. Patent No. 3,945,926 which discloses the formation of polycarbonate resin membranes from a casting solution containing the resin, a solvent, a swelling agent and / or a non-solvent. It is stated in lines 42-47, column 15 of the cited patent that phase inversion usually does not take place in the complete absence of a swelling agent and that structures with closed cells are found at low concentrations of the swelling agent.

From the previous discussion, it is quite evident that the classic phase inversion requires the use of a solvent for the system at room temperature, so many other useful polymers

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cannot be replaced by polymers such as cellulose acetate. From the point of view of the process, the classical phase inversion process will usually also be limited to the formation of films, due to the large amount of solvents used in the preparation of solutions, which then have to be extracted. It can also be seen that the classical phase inversion requires a relatively high degree of monitoring of the method in order to obtain structures of the desired configuration. Thus, the relative concentrations of solvent, nonsolvent, and swelling agent must be critically controlled, as described in columns 14-16 of U.S. Patent No. 3,945,926. On the other hand, in order to change the number, size and homogeneity of the resulting structure, the parameters mentioned above have to be modified according to empirical determination methods.

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

Another general process, which has been the subject of significant previous efforts, 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, etc. This type of process is e.g. disclosed in the following U.S. patents; 3,607,793; 3,378,507; 3,310,505; 3,748,287; 3,536,796; 3,308,073; and 3 812 224. It is not believed that the methods mentioned will be used commercially to any significant extent; if at all, only because the previously feasible methods were not economically viable. The previous methods also do not allow the production of microporous polymers which combine relatively homogeneous, microcellular structures with the pore size and the pore size distributions, although these are particularly desired.

With regard to the microporous polymers obtained by known processes, no process is known to date, according to which isotropic olefinic or oxidation polymers can be produced, the pore sizes of which are to a considerable extent in the range from about 0.1 to about 5 micrometers and at the same time one have a relatively narrow pore size distribution and thus show a high degree of uniformity with regard to the pore size in a polymer sample. Some known olefinic or oxidation polymers had pore sizes in the range mentioned above, but without a relatively narrow pore size distribution, which resulted in materials being made without significant application value. An example of such an application is filtration, which requires a high degree of selectivity. In addition, previous microporous olefinic or oxidation polymers, which are believed to have relatively narrow pore size distributions, had absolute pore sizes outside the range mentioned above (usually with substantially smaller pore sizes) for use in applications such as ultra -Filtration, lay. Finally, some known olefinic polymers had pore sizes in the range given above, and it could be thought that they showed relatively narrow pore size distributions. However, such materials were made using such methods as stretch drawing, which gave the resulting anisotropic material a high degree of orientation, making it unsuitable for many applications. There was therefore a need for microporous, olefinic and oxidation polymers which have a pore size in a range from 0.1 to about 5 micrometers and are characterized by a relatively narrow, isotropic pore size distribution.

A major disadvantage of many of the mi-lo croporous polymers available to date has also been that the flow rate of such polymers is slow when used in structures such as microfiltration membranes. One of the main reasons for such low flow rates is the typically low pore volume of many such polymers; thus, maybe 20% or less of the polymer structure can be "empty" volume through which a filtrate can flow, with the remaining 80% of the structure being the polymer resin that forms the microporous structure. Thus there was also a Be-20 requirement for microporous polymers with a high degree of «empty» volume, in particular with regard to olefinic polymers.

It is accordingly an object of the present invention to provide microporous polymer cell products which are characterized by a relative homogeneity and narrow pore size distributions.

An additional aim is to provide a process for the production of microporous polymer cell structures in which a large number of useful ther-30 moplastic polymers can be used.

In this process, microporous polymers with a cell structure can easily be produced from a synthetic, thermoplastic polymer, namely polyolefins, condensation polymers and oxidation polymers or mixtures thereof.

The polymer cell structure according to the invention can be in the form of thin films up to relatively thick blocks, and polymer cell structures can also be provided in complicated shapes.

40 In the process for producing the polymer cell structure according to the invention, functional liquids are converted into materials which have the characteristics of a solid.

Fig. 1 is a graphical representation of temperature 45 plotted against concentration for a hypothetical polymer / liquid system, showing the binodial and spinodal curves and explaining the concentration used to achieve the microporous polymers and to exercise the Verso driving according to the invention required;

Figure 1A is a graph of temperature versus concentration; it is similar to that of Fig. 1 but also contains the freezing point depression curve;

55 FIG. 2 is a photomicrograph at a magnification of 55 times, which shows the macrostructure of a microporous polypropylene polymer according to the invention having a cell structure and having a pore volume of approximately 75%;

3 to 5 are microphotographs of the porous poly-6o propylene structure from FIG. 2, at a magnification of 550, 2200 and 5500 times, respectively, and explain the homogeneous cell structure;

6 to 10 are photomicrographs at 1325, 1550, 1620, 1450 and. 1250x magnification of additional 65 microporous polypropylene structures and they show the modifications in the structure when the pore volume is reduced from 90% to 70%, to 60%, to 40% or to 20%;

11 to 13 are microphotographs at a magnification of 2000, 2050 and 1950 times of still further microporous polypropylene cell structures according to the invention and they illustrate the decrease in cell size when the polypropylene content increases from 10% by weight in FIG. 11 to 20% or 30% is increased in Figures 12 and 13;

14 to 17 are microphotographs at a magnification of 250, 2500, 2500 and 2475 times of microporous cell structures of low density polyethylene according to the invention, with FIGS. 14 and 15 showing the macro and microstructure of a microporous polymer which is 20th % By weight of polyethylene, and FIGS. 16 and 17 show the microstructure with 40% and 70% polyethylene, respectively;

18 and 19 are photomicrographs at 2100 and 2000 times magnification of microporous cell structures according to the invention made of high-density polyethylene and they illustrate the structures at 30% by weight and 70% by weight of polyethylene, respectively;

20 and 21 are photomicrographs at 2550 and 2575 times magnification of microporous SBR polymers according to the invention with cell structure and they show a homogeneous cell structure;

22 is a photomicrograph at 2400x of a microporous methylpentene polymer;

23 and 24 are photomicrographs at 225 and 2550 magnifications, respectively, of a microporous ethylene-acrylic acid copolymer;

Fig. 25 is a photomicrograph at 2500X of a microporous polymer formed from a polyphenylene oxide / polystyrene mixture;

Fig. 26 is a photomicrograph at 2050 magnifications; it illustrates a microporous polystyrene polymer;

Fig. 27 is a microphotograph at 2,000 times and shows a microporous polyvinyl chloride polymer;

28 and 29 are microphotographs at 2,000 times magnification of microporous polymers made of low density polyethylene; they show a partial concealment of the basic structure by a structure in the manner of "foliage";

30 to 33 are mercury penetration curves of the microporous polypropylene structures according to the invention; they illustrate the narrow pore diameter distribution which is characteristic of the polymers of the present invention;

34 to 40 are mercury penetration curves of commercial microporous products such as "Celgard" polypropylene (Fig. 24), "Amerace A20" and "Amerace A30" polyvinyl chloride (Fig. 35 and 36), "Porex" - Polypropylene (Fig. 37), "Milliporen BDWP 29300" cellulose acetate (Fig. 38), "Gelman TCM-200" cellulose triacetate and "Gel-man Acropor WA" acrylonitrile-polyvinyl chloride copolymer (Fig. 39 or 40);

Figures 41 through 43 are mercury penetration curves of microporous structures made in accordance with U.S. Patent No. 3,378,507 using polyethylene (Figures 41 and 42) and polypropylene (Figure 43);

44 contains a mercury penetration curve of 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 made by repeating Example 2 of U.S. Patent No. 3,378,507 using an injection molding process; Fig. 45 (magnification 240 times) shows the macro structure and

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Fig. 46 (2400 times magnification) shows the microstructure;

47 and 48 are photomicrographs of a porous polyethylene product made by repeating Example 2 of U.S. Patent 3,378,507 using an injection molding process; Fig. 47 (195 times magnification) shows the macro structure and Fig. 48 (2000 times magnification) shows the microstructure;

Figures 49 and 50 are photomicrographs of a porous polypropylene product made by repeating Example 2 of U.S. Patent 3,378,507 using an injection molding process; Fig. 49 (195 times magnification) shows the macro structure and Fig. 50 (2000 times magnification) shows the microstructure;

51 and 52 are photomicrographs of a porous polypropylene product made by repeating Example 2 of U.S. Patent 3,378,507 using an injection molding process, Fig. 51 (206x magnification) the macrostructure and Fig. 52 (2000 times magnification) show the microstructure;

53 and 54 are photomicrographs of a porous polyethylene product made by repeating Example 2 of U.S. Patent 3,310,505, with Fig. 52 (205X magnification) the macrostructure and Fig. 54 (200X magnification) ) show the microstructure;

Fig. 55 shows a melting and a crystallization curve for a polypropylene and quinoline polymer / liquid system;

Figure 56 shows a melting curve and multiple crystallization curves for a polypropylene and N, N-bis (2-hydroxy-ethyl) tallow amine polymer / liquid system;

Fig. 57 shows a melting and crystallization curve for a polypropylene and dioctyl phthalate polymer / liquid system, demonstrating a system which does not fall under the present invention;

58 shows the phase diagram for a low molecular weight polyethylene and a diphenyl ether polymer / liquid system, the determination with cooling and heating rates of 1 ° C./min. took place;

59 shows several melting and crystallization curves for a low molecular weight polyethylene and a diphenyl ether polymer / liquid system;

60 shows a glass conversion curve for a low molecular polystyrene and a 1-dodecanol polymer / liquid system;

61 is a microphotograph at a magnification of 5,000 times of a microporous cell structure according to the invention with 70% pore volume, which was produced from polymethyl methacrylate;

Figure 62 shows melting and crystallization curves for a nylon 11 and a tetramethylene sulfone polymer / liquid system;

63 is a microphotograph at a magnification of 2,000 times of a microporous cell structure according to the invention with 70% empty pore volume, which was produced from nylon 11;

64 is a microphotograph at a magnification of 2,000 times of a microporous cell structure according to the invention with 70% empty pore volume, which was produced from polycarbonate;

65 is a microphotograph at a magnification of 2,000 times of a cell structure according to the invention with 70% empty pore volume, which was produced from polyphenylene oxide;

66 and 67 are microphotographs at a magnification of 2,000 times of a microporous non-cell structure

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with 60% or 75% empty pore volume, which was made from polypropylene;

68 and 69 are mercury penetration curves for a non-cellular, microporous polypropylene structure with 60% and 75% empty pore volume;

70 is a graphical representation of the unique microporous cell structures of the present invention compared to certain known compositions.

While the invention allows for various modifications and alternative forms, the preferred embodiments are to be described in detail here. However, it should be understood that the intention is not to limit the invention to the specific forms disclosed. All modifications and alternative forms are to be encompassed which fall within the scope of the invention, which is set out in the claims.

It has now been discovered that the three-dimensional, microporous polymer cell structure defined above can be obtained by using a mixture of one or more than one synthetic thermoplastic polymer from the class consisting of the homo- and copolymers of ethylenically unsaturated monomers, the condensation polymers and the oxidation polymers, and a compatible liquid to form a homogeneous solution is heated to a sufficient temperature for a sufficient time, forms the homogeneous solution, and cools the molded solution so that liquid-liquid phase separation occurs while doing a variety at substantially the same time is formed by liquid droplets of substantially equal size in the continuous liquid polymer phase, which continues to cool to solidify the polymer and removes substantially all of the liquid from the solid body formed so as to form the polymer cell structure.

If the solution cools in the desired form, it is not necessary to use a mixing process or other stress while cooling the solution. Cooling continues so that a solid is obtained. To achieve sufficient mechanical integrity, the solid merely requires that it can be processed in such a way that no physical deformation occurs.

Certain new microporous olefinic and oxidation polymers according to the invention with cell structure are characterized by a narrow pore size distribution, as determined by the mercury penetration capacity into the pores. The narrow pore size distribution is analytically expressed by the sharpness factor S, which is explained below. The “S” values of the polymer cell structure according to the invention range from 1 to 30. The mentioned polymers with cell structure according to the invention are also characterized by the average pore sizes, which in particular range from 0.10 to 5 micrometers, with 0.2 to 1 micrometer being preferred. Moreover, such microporous products with a cell structure are essentially isotropic; thus above all they have the same cross-sectional configuration if they are analyzed along any spatial plane.

In a preferred embodiment, the process for producing the microporous polymers with a cell structure is carried out such that a mixture comprising a synthetic thermoplastic polymer, in particular a polyolefin, an ethylene-acrylic acid copolymer, a polyphenylene oxide-polystyrene mixture or a Contains mixture of one or more of the above-mentioned polymers and a compatible liquid are heated to a temperature and for a time sufficient to form a homogeneous solution. The solution is then cooled, producing a multitude of liquid droplets of substantially the same size at substantially the same time. Cooling then continues so that the polymer solidifies; at least a substantial portion of the liquid is removed from the resulting solid to form the desired polymer cell structure.

The above process will result in microporous polymer products characterized by a cellular three-dimensional, pore-containing microstructure, i.e., a series of enclosed cells with essentially spherical shapes and pores or passageways that interconnect the neighboring cells. The basic structure is relatively homogeneous, 15 with the cells being uniformly distributed over the three dimensions and the interconnecting pores having diameters which are relatively narrow in relation to the size distribution, as was measured by the penetration of mercury. To simplify reference 20, the microporous polymers with such a structure are referred to below as "cellular".

In the three-dimensional polymer cell structure defined above, the cells and pores of which are at least partially filled with an active substance liquid, the active liquid is a lubricant, a surface-active agent, a lubricant, a pesticide, a plasticizer, a drug, a fuel additive, a polishing agent , an insect repellent, a flame retardant, an antioxidant, an anti-fogging agent or a fragrance is preferred. In this way, the active liquids can obtain the processing advantages of a solid. in a basic mixture, can be used. Such products can be created directly by using a functional liquid as the compatible liquid and failing to remove the compatible liquid, or indirectly by either reloading the microporous polymer after the compatible liquid is removed or the compatible one Fluid displaced prior to removal to incorporate the functional fluid.

In brief, the method according to the invention relates to the following steps: heating the desired polymer with a compatible liquid to form a homogeneous solution; Cooling said solution in a suitable manner to form a solid material and then extracting the liquid to form a microporous material.

As already stated, the present invention surprisingly enables a method in which such a synthetic thermoplastic polymer can be made microporous. The method according to the invention is thus used in olefinic polymers, condensation polymers and oxidation polymers or mixtures thereof.

55 Examples of useful non-acrylic polyolefins are low density polyethylene, high density polyethylene, polypropylene, polystyrene, polyvinyl chloride, acrylonitrile-butadiene-styrene terpolymers, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, poly (4-methylpentene-60 1), polybutylene, polyvinylidene chloride, polyvinyl butyral, chlorinated polyethylene, ethylene-vinyl acetate copolymers, polyvinyl acetate and polyvinyl alcohol.

Useful acrylic polyolefins are e.g. Polymethyl methacrylate, polymethyl acrylate, ethylene-acrylic acid copolymers and ethylene-acrylic acid metal salt copolymers.

Polyphenylene oxide is representative of the oxidation polymers that can be used. Useful condensation polymers are e.g. Polyethylene terephthalate, poly

butylene terephthalate, nylon 6, nylon 11, nylon 13, nylon 66, polycarbonates and polysulfones.

To practice this invention, it is therefore only necessary to first select the synthetic thermoplastic polymer that is to be made microporous. After the polymer is selected, the next step is to choose the compatible liquid and the amounts of polymer and the amounts of liquid to be used. Of course, mixtures of one or more polymers can be used in the practice of the process. The polymer and the liquid are expediently heated with stirring to the temperature required to form a clear, homogeneous solution.

If no solution can be formed at any liquid concentration, then the liquid is unsuitable and cannot be used with the polymer.

Due to the selectivity, an absolute predictability with respect to the prediction of the feasibility when using a specific liquid with a specific polymer is not possible. However, some useful general guidelines can be given. Thus, if the polymer contained is non-polar, non-polar liquids with similar solubility parameters are much more useful at the solution temperature. If such parameters are not available, one can refer to the much more readily available solubility parameters at room temperature for general guidance. Similarly, in the case of polar polymers, polar organic liquids with similar solubility parameters should first be examined. Likewise, the relative polarity or non-polarity of the liquid should correspond to the relative polarity or non-polarity of the polymer. Furthermore, with respect to hydrophobic polymers, it should be said that useful liquids will typically have little or no water solubility. On the other hand, polymers that have a hydrophilic tendency generally require a liquid that is somewhat soluble in water.

With regard to convenient liquids, it has been found that a particular type of different types of organic liquids are useful; Examples are aliphatic and aromatic acids, aliphatic, aromatic and cyclic alcohols, aldehydes, primary and secondary amines, aromatic and ethoxylated amines, diamines, amides, esters and diesters, ethers, ketones and various hydrocarbons and heterocycles. However, it should be noted that the view is quite selective. Thus e.g. not all saturated aliphatic acids are useful; furthermore, not all liquids useful for high density polyethylene are necessarily e.g. be useful for polystyrene.

It is assumed that the expedient ratios of polymer and liquid for any particular system can be conveniently developed from an evaluation of the parameters, which are subsequently explained.

It should be understood that where mixtures of one or more polymers are used, it must be possible to work with the useful liquids for all of the polymers mentioned. However, it can happen that the polymer mixture has such characteristics that working with the liquid does not have to work for all polymers used. An example is where one or more polymer components are present in relatively small amounts, which means that they do not significantly affect the properties of the mixture, so working with the liquid used only has to work with the main polymer or polymers.

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Furthermore, while most useful materials at ambient temperatures are liquids, materials that are solid at room temperature can be used as long as solutions can be formed with the polymer at elevated temperatures and the material does not interfere with the formation of the microporous structure. Preferably, a solid material can be used as long as phase separation by liquid / liquid separation occurs rather than liquid / solid separation during the cooling step, which will be explained below. The amount of liquid used can generally be varied from 10 to 90%.

As mentioned above, any synthetic thermoplastic polymer can be used as long as the selected liquid forms a solution with the polymer and the concentration results in a continuous polymeric phase upon separation during cooling, as will be described in more detail below. A brief summary of some of such systems can be useful to assess the range of operable polymer and liquid systems.

In the formation of microporous polymers from polypropylene, it was found that alcohols such as 2-benzylamino-l-propanol and 3-phenyl-l-propanol; Aldehydes, e.g. Salicylic aldehyde; Amides, e.g. B. N, N-Diethyl-m-toluamide; Amines such as N-hexyldiethanolamine, N-behenyldiethanolamine, N-coconut diethanolamine, benzylamine, N, N-bis-β-hydroxyethylcyclohexylamine, diphenylamine and 1,12-diaminodode-can; Esters such as methyl benzoate, benzyl benzoate, phenyl salicylate, methyl salicylate and dibutyl phthalate; as well as esters such as diphenyl ether, 4-bromodiphenyl ether and dibenzyl ether. In addition, halogenated hydrocarbons such as 1,1,2,2-tetrabromoethane and hydrocarbons such as trans-stilbene and other alkyl / aryl phosphites are also useful, as are ketones such as methyl nonyl ketone.

In the formation of high density polyethylene microporous polymers, it was found that 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-Lauryldiethanolamine, aromatic amines such as N, N-diethylaniline, diesters such as dibutyl sebacate and dihexyl sebacate and ethers such as diphenyl ether and benzyl ether are useful. Other useful liquids are e.g. B. halogenated compounds such as octabromodiphenyl, hexabromobenzene and hexabromocyclodecane, hydrocarbons such as 1-hexadecane, diphenylmethane and naphthalene, aromatic compounds such as acdtophenone, and other organic compounds such as alkyl / arylphosphites and quinolines, and ketones such as methylnonyl ketone.

The following liquids have been found useful in forming microporous polymers from low density polyethylene: saturated aliphatic acids such as hexanoic acid, caprylic acid, decanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid and stearic acid, unsaturated aliphatic acids such as oleic acid and erucic acid -re, aromatic acids, such as benzoic acid, phenylstearic acid, polystearic acid and xylylbehenic acid and other acids such as branched carboxylic acids with an average chain length of 6.9 and 11 carbon atoms, tall oil acid and resin acid, primary saturated alcohols, for example 1-octanol, nonyl alcohol , Decyl alcohol, 1-decanol, 1-do decanol, tridecyl alcohol, cetyl alcohol and 1-heptadecanol, primary unsaturated alcohols such as undecylenyl alcohol and oleyl alcohol, secondary alcohols such as 2-octanol, 2-undecanol, dinonyl carbinol and diundecyl alcohols and aromatic such as 1-phenylethanol, 1-phenyl-1-pentanol, nonylphenol, phenylstearyl alcohol l and 1-naphth

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toi. Other useful hydroxyl-containing compounds are e.g. Polyoxyethylene ether of oleyl alcohol and a polypropylene glycol with an average molecular weight of about 400. Other useful liquids are e.g. cyclic alcohols such as 4-t-butylcyclohexanol and menthol, aldehydes such as salicylaldehyde, primary amines such as actylamine, tetradecylamine and hexadecylamine, secondary amines such as bis- (l-ethyl-3-methylpentyl) amine and ethoxylated amines such as N-lauryl diethanolamine, N-tallow diethanol amine, N-stearyl diethanolamine and N-coconut diethanolamine.

Additional compatible liquids contain, in particular, aromatic amines, such as N-sec-butylaniline, dode-cylaniline, N, N-dimethylaniline, N, N-diethylaniline, p-tolui-din, N-ethyl-o-toluidine, diphenylamine and aminodiphenylmethane , Diamines, such as N-eerucyl-l, 3-propanediamine and 1,8-diamino-p-methane, other amines, such as branched tetramines and cyclododecylamines, amides, such as coconut amides, hydrogenated tallow amide, octadecyl amide, eruciamide, N, N-diethyl I- toluamide and N-trimethylolpropane stearamide, saturated aliphatic esters, such as methyl caprylate, ethyl laurate, isopropyl myristate, ethyl palmitate, isopropropyl palmitate, methyl stearate, isobutyl stearate and tridecyl stearate, unsaturated esters, such as stearyl acrylate, butyl ethoxylate, butyl acrylate, butyl acrylate, butyl acrylate, butyl acrylate, butyl acrylate, butyl acrylate, butyl acrylate, butyl acrylate and butyl acrylate, butyl acrylate, butyl acrylate, butyl acrylate, butyl acrylate, and butyl acrylate, butyl acrylate, butyl acrylate, such as butyl acrylate, and butyl acrylate, butyl acrylate, such as butyl acrylate, and butyl acrylate, butyl acrylate, butyl acrylate, butyl, and ethyl ester, butyl, and such as vinylphenyl stearate, isobutylphenyl stearate, tridecylphenyl stearate, methyl benzoate, ethyl benzoate, butyl benzoate, benzyl benzoate, phenyl laurate, phenyl salicylic acid, methyl salicylate and benzylaceta t, and diesters such as dimethylphenylene distearate, diethyl phthalate, dibutyl phthalate, di-iso-octyl phthalate, dicapryl adipate, dibutyl sebacate, dihexyl sebacate, di-isooctyl sebacate, dicapryl sebacate and dioctyl maleate. Other compatible liquids preferably contain polyethylene glycol esters, such as polyethylene glycol (with an average molecular weight of about 400), diphenyl stearate, polyhydroxyl esters, such as castor oil (triglyceride), glycerol monostearate, glycerol monooleate, glycerol distearate, glycerol dioleate and trimethylolpropane monophenyl stearyl ether, ether, benzyl stearate, ether, ether halogenated compounds such as hexachlorocyclopentadiene, octabromobiphenyl, decabromodiphenyl oxide and 4-bromodiphenyl ether, hydrocarbons such as 1-non, 2-non, 2-undecene, 2-heptadecene, 2-nonadecene, 3-eicosene, 9-nonadecene, diphenylmethane, triphen and trans-stilbene, aliphatic ketones such as 2-heptanone, methyl nonyl ketone, 6-undecanone, methyl undecyl ketone, 6-trideca-non, 8-pentadecanone, 11-pentadecanone, 3-heptadecanone, 8-heptadecanone, methylheptadecyl ketone, dinonyl ketone, aromatische and distearyl Ketones such as acetophenone and benzophenone and other ketones such as xanthone. Other useful liquids contain phosphorus compounds, such as trixylenyl phosphate, polysiloxanes, woodruff hyacinths (An Merigenaebler, Ind.), Terpineol Prime No. 1 (Gi-vaudan-Delawanna, Inc.) "Bath oil fragrance 5864 K" (International Flavor & Fragrance, Inc.), "Phosclere P315C" (organophosphite), Phosclere P576 "(organophosphite), styrene-based nonylphenol, quinoline and Quinalidine.

For the formation of microporous polymer products with polystyrene, compatible liquids contain above all tri-halogenated propyl phosphate, aryl / alkyl phosphite, 1,1,2,2-tetrabromethane, tribromoneopentyl alcohol, 40% Voranol C.P. 3000 polyol and tribromoneopentyl alcohol, 60% tris-ß-chloroethyl phosphate, tris (1,3-dichloroisopropyl) phosphate, tri- (dichloropropyl) phosphate, dichlorobenzene and 1-dodecanol.

If polyvinyl chloride has been used to form microporous polymers, the compatible liquids usually contain aromatic alcohols, such as methoxybenzyl alcohol, 2-benzylamino-l-propanol, and others

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hydroxyl-containing liquids, such as 1,3-dichloro-2-propanol. Additional useful liquids include halogenated compounds such as Firemaster T33P (diester of tetra-bromophthalic acid) and aromatic hydrocarbons, 5 such as trans-stilbene.

In addition, microporous products have been made from other polymers, copolymers, and blends in accordance with the present invention. Thus, e.g. for the formation of microporous products from io styrene-butadiene copolymers decyl alcohol, N-tallow diethanolamine, N-coconut diethanolamine and diphenylamine. Compatible liquids for forming microporous polymers from ethylene-acrylic acid copolymer salts usually contain N-tallow diethanolamine, N-coconut diethanolamine, dibutyl phthalate and diphenyl ether. Microporous polymer products using high impact polystyrene can be formed using hexa-bromobiphenyl and alkyl / aryl-phosphites as liquids. Microporous polymers can be produced using “Noryl” polyphenylene oxide / polystyrene mixtures (Ge-20 general electric company), using coconut diethanolamine, N-tallow diethanolamine, diphenylamine, dibutyl phthalate and hexa-bromophenol. Microporous polymers made from blends of low density polyethylene and chlorinated polyethylene can be made using 1-dodecanol, diphenyl ether and N-tallow diethanolamine. If 1-dodecanol is used as the liquid, microporous polymer products can be made from the following mixtures: polypropylene-chlorinated polyethylene, 30 high-density polyethylene, polyethylene-chlorinated polyethylene, high-density polyethylene, polyvinyl chloride and high-density polyethylene, and acrylonitrile-butadiene- Styrene (ABS) terpolymers. 1-4, butanediol and lauric acid were found to be useful in forming microporous products from polymethyl methacrylate. Microporous nylon 11 can be made using ethylene carbonate 1,2-propylene carbonate or tetramethylene sulfone. Menthol can also be used to form microporous products from polycarbonate. 40 The amount of liquid to be used is determined by referring to the binodial and spinodal curves for the system, with illustrative curves shown in FIG. 1. As shown there, Tm represents the maximum temperature of the binodial curve (ie the maximum system temperature at which the binodial separation will occur), Tucs represents the upper critical solution temperature (ie the maximum temperature at which the spinodal separation occurs )> 3> m represents the polymer concentration at Tm, €> c denotes the critical concentration and Ox represents the polymer concentration of the system, which is required to produce the unique, microporous polymer structures according to the invention. Theoretically, <DC should be essentially the same; however, it is known that ®c may be about 5% by weight 55 or greater than the value of <Dm due to the molecular weight distributions of the commercially available polymers. To form the microporous polymers according to the invention, the polymer concentration used for a special system ®x must be greater than 6o ser than ®c. If the polymer concentration is less than <tf, the phase separation that will occur when the system cools will form a continuous liquid phase with a discontinuous polymer phase. On the other hand, the use of the appropriate polymer concentration will ensure that the continuous phase, which is formed on cooling to the phase separation temperature, will be the polymer phase, as is required, in order to obtain the microcellular structures according to the invention

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receive. As can be seen, the formation of a continuous polymer phase in phase separation requires that a solution be formed initially. If the process according to the invention is not followed and a dispersion is formed initially, the resulting microporous product is similar to that which is obtained by sintering polymeric particles together.

Accordingly, it is recognized that 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, you can easily develop it using recognized procedures. For example, such a method is in Smolders, van Aartsen and Steenbergen, Kolloid-Z.u.Z. Polymer, 243, 14 (1971).

A more general graph of temperature versus concentration for a hypothetical polymer / liquid system is shown in Figure 1A. The part of the curve which extends from y to a represents the thermodynamic equilibrium liquid / liquid phase separation. The curve part from a to ß represents the equilibrium liquid / solid phase separation, which is the normal freezing point-lowering curve of a hypothetical liquid / polymer system is recognized. The upper hatched area represents an upper liquid / liquid immiscibility, which may be present in some systems. The hatched line shows the decrease in crystallization temperature as a result of cooling at a rate sufficient to achieve thermodynamic non-equilibrium liquid / liquid phase separation. The flat part of the crystallization curve against the composition defines a usable composition range, which is a function of the cooling rate used, as will be described in more detail below.

Thus, for any given rate of cooling, one can plot the crystallization temperature against the resin or compatible liquid in percent and thus determine the liquid / polymer concentration ranges which will give the desired microporous structures at a given rate of cooling . For crystalline polymers, determining the concentration range that can be used by plotting the crystallization curve mentioned above is a real alternative to determining a phase diagram, as shown in FIG. 1. As an example of the above, reference can be made to Fig. 55, in which the temperature is plotted against the polymer / liquid concentration, showing the melting curve at a heating rate of 16 ° C per minute, as well as the crystallization curve for Polypropylene and quinoline over a wide range of concentrations. As can be seen in relation to the crystallization curve, the appropriate concentration range at a cooling rate of 16 ° C per minute is from about 20% polypropylene to about 70% polypropylene.

Figure 56 is a graph of temperature versus polymer / liquid composition for polypropylene and N, N-bis (2-hydroxyethyl) tallow amine. The melting curve is plotted in the upper curve at a heating rate of 16 ° C. per minute. The lower curves show the course of the crystallization curves in descending order at cooling rates of 8 ° C, 16 ° C, 32 ° C and 64 ° C per minute. These curves impressively show two competing phenomena that occur when the cooling rate is increased. First the flat part of the curve,

which demonstrates a relatively stable crystallization temperature over a wide range of concentrations, decreases with increasing cooling rate, thereby showing that the faster cooling occurs, the lower the actual crystallization temperature.

The second observable phenomenon is the change in the dependency of the crystallization curve, which takes place with the changes in the cooling rate, so it seems that the flat part of the crystallization curve is expanded as the cooling rate is increased. Accordingly, it can be assumed that by increasing the cooling rate, the working concentration range for forming the microporous structures according to the invention and for carrying out the methods according to the invention can be increased accordingly. From the foregoing, it is clear that to determine the working concentration ranges for a given system, only a few representative polymer / liquid concentrations have to be prepared and the same cooled at any desired rate. After the crystallization temperatures are plotted, the working range of the concentrations will become very clear.

Figure 57 is a graph of temperature versus polymer / liquid concentration for polypropylene and dioctyl phthalate. The upper curve represents the melting curve for the system over a range of concentrations and the lower curve shows the crystallization curve over the same concentration range. Since the crystallization curve does not show a flat part over which the crystallization temperature remains essentially constant for a range of concentrations, one would not assume that the polypropylene / dioctylphtha-35 lat system is able to form microporous structures; in fact it cannot.

To recognize the excellent correlation between the phase diagram method for determining the working concentration ranges of the polymer and the liquid on the one hand and the crystallization method for creating such a determination on the other hand, one can refer to FIGS. 58 and 59. Fig. 58 is a phase diagram of the polymer / liquid system for low molecular weight polyethylene and diphenyl ether, as determined by a conventional light resolution method using a thermally controlled container. 58 shows that Tm is about 135 ° C and <Bm is about 7% polymer. Furthermore, it is obvious that at a polymer concentration of approximately 45% the crystallization curve intersects with the freezing point-lowering curve, whereby a working concentration range from approximately 7% polymer to approximately 45% polymer is indicated.

55 The working range determined from FIG. 58 can be compared with the range that can be determined from FIG. 59, these showing the melting curves of the same system at heating speeds of 8 ° C. and 16 ° C. per minute, and crystallization curves for the system mentioned at cooling-60 show speeds of 8 ° C and 16 ° C per minute. For the crystallization curves, it appears that the substantially flat portion thereof is expanded from a polymer concentration just below 10% to about 42 to 45%, depending on the rate of cooling. Thus, the results obtained from the crystallization curves agree surprisingly well with the results obtained from the start of crystallization phase diagram.

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For non-crystalline polymers it is believed that one can refer to the curve of the temperature versus the concentration of the glass transition temperature, this being an alternative with respect to a phase diagram, e.g. that of Fig. 1. Thus, Fig. 58 is a graph of temperature versus concentration for the glass transition temperature of low molecular weight polystyrene supplied by Pennsylvania Industriai Chemical Corporation under the designation "Piccolastic D-125" and 1-dodecanol at various concentration levels.

58 shows that from about 8% to about 50% polymer, the glass transition temperature for the polystyrene / 1-dodecanol system is substantially constant. It has therefore been suggested that the concentrations along the substantially flat portion of the glass conversion curve would be operable in the practice of the present invention, analogous to the flat portion of the crystallization curves previously discussed. It thus appears that a real alternative to determining the phase diagram for non-crystalline polymer systems is to determine the glass conversion curve and to work essentially in the flat part of such a curve.

In all of the previous figures, the crystallization temperatures were determined with a DSC-2, (Differential Scanning Calorimeter) manufactured by Perkin-Elmer, or a comparable equipment. Further effects of cooling rates in the practice of the present invention are discussed below.

After having selected the desired synthetic thermoplastic polymer, the compatible liquid and the concentration range which can be carried out, it is necessary to e.g. B. selects the actual polymer and liquid concentration to be used. If you e.g. Considering the theoretically possible concentration range, other functional considerations should also be made to determine the conditions to be used for a particular system. In so far as it concerns the maximum amount of liquid that should be used, the resulting strength indicators must be taken into account. In particular, the amount of liquid used should enable the resulting microporous structure to have a minimum of “processing resistance” to avoid collapse of the microporous or cellular structure. On the other hand, the selection of the maximum amount of resin, restrictions on viscosity in the particular equipment used can determine the maximum toleral polymer or resin content. In addition, the amount of polymer used should not be so large that the cells or other microporosity areas are sealed off.

The relative amount of liquid to be used will also depend to some extent on the desired effective size of the microporosity, for example the requirements regarding the particular cell and pore size for the final application in question. Thus, e.g. the average cell and pore size to become approximately larger with increasing fluid content.

In any event, the usability of a liquid and its concentration when carried out for a particular polymer can be easily determined by experimentally using the liquid as described above.

The parameters explained above should of course be observed. It is actually understandable that mixtures of two or more liquids can be used; the usability of a special Mi10

can be ensured as described above. While a particular mixture is useful, one or more liquids individually may not be suitable.

It is recognized that the particular amount of liquid used is often also determined by the end use application. As illustrative cases of specific examples in which high density polyethylene and N, N-bis (2-hydroxyethyl) tallow amine are used, microporous products can be obtained by using from about 30% to about 90% by weight amine, preferably 30 to 70% by weight of amine. With low density polyethylene and the same amine, the amount of liquid can conveniently be varied within the range of about 20 to 90%, preferably between 20 and 80%. Conversely, when the phenyl ether is used as a liquid, the useful low density polyethylene systems contain no more than about 80% of the liquid, with a maximum of about 60% being preferred. When 1-hexadecene is used with low density poly-20 ethylene, amounts up to about 90% or more can be conveniently used. If polypropylene is used with the tallow amine described above, the amine can be conveniently used in amounts of about 10 to about 90%, with a maximum amount of no more than about 85% being preferred. With polystyrene and 1-dodecanol, the concentration of the alcohol can be varied from about 20 to about 90%, preferably from about 30 to about 70%. If styrene-butadiene copolymers are used, the aminge-30 content can range from about 20% to about 90%. If a system of dodecanol and a styrene-butadiene copolymer (i.e. an -SBR system) is used, the liquid content can suitably be varied from about 40 to about 90%; with diphenylamine, a liquid content of 35 about 50 to about 80% is suitable. If microporous polymers are formed from the amine and an ethylene-acrylic acid copolymer, the liquid content can range from about 30 to about 70%; with diphenyl ether the liquid content can be varied from about 10 to about 90%; the same applies in the case where dibutyl phthalate is used as a solvent.

If one follows the formation of a solution, it can then be subjected to a process to create any desired shape or configuration. In general, the thickness of the article can range from a thin film of about 0.025 mm or less to a relatively thick block about 6.4 cm or even thicker, depending on the particular system in question. The ability to form blocks thus allows the microporous material to be subjected to a process of making any desired complex shape, such as by using conventional pressing, injection molding, or other related methods. The practical considerations included in determining the The range of thickness that can be made from a specific system includes the viscosity build-up rate that the system undergoes as it cools. In general, the higher the viscosity, the 60 thicker the structure can be. Accordingly, the structure can be of any thickness as long as the overall phase separation does not take place, i.e. two visible layers of the eye become visible.

It is recognized that if the liquid / liquid phase separation can take place under thermodynamic equilibrium conditions, a complete separation in two different layers will result. One layer consists of a molten polymer, which is the releasable

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Contains amount of liquid and there is a liquid layer which contains the releasable amount of the polymer in the liquid. This condition is represented by the binodial line in the phase diagram in FIGS. 1 and 1A. It is obvious that a limitation on the size of the article to be manufactured is determined by the characteristics of the composition of the heat transfer, since if the object is thick enough and the heat transfer is small enough, the speed of cooling in the center of the object will be slow enough can, in order to approximate the thermodynamic equilibrium conditions and to achieve a clear, distinct layer phase separation, as described above.

Increased thicknesses can also be achieved by adding small amounts of thioxotropic materials. For example, the addition of commercially available colloidal silica prior to cooling provides significant, useful thicknesses; nevertheless, it does not have a detrimental effect on the characteristic, microporous structure. The specific amounts to be used can be conveniently determined.

As can be seen from the above explanation, apart from the type of processing (for example, gluing into a film, etc.), the solution to form what appears to be a solid and must appear to be cooled. On the one hand, the resulting material should have sufficient integrity so that it does not crumble during processing. Another test to determine whether the required system has the desired structure is to use a solvent for the liquid used, but not for the polymer. If the material separates, the system used does not meet the required criteria.

The cooling rate of the solution can be varied within wide limits. In fact, it is normally not necessary to cool from the outside and, for example, it is satisfactory to cast only a film by pouring the hot liquid system onto a metallic surface which has been heated to a temperature at which a film can be drawn or, on the other hand, to form a block by pouring it onto a substrate at ambient temperatures.

As described above, the cooling rate must be sufficiently high so that the liquid / liquid phase separation does not take place under thermodynamic equilibrium conditions.

Furthermore, the cooling rate can have a significant effect on the resulting microporous structure. If the rate of cooling is sufficiently slow in many polymer / liquid systems but still meets the criteria mentioned above, then the liquid / liquid phase separation will result at substantially the same time that a plurality of liquid droplets of substantially of the same size. If the rate of cooling is such that a plurality of liquid droplets are formed as long as all other conditions discussed here are met, the resulting microporous polymer will have the cellular microstructure defined above.

It is generally believed that the microporous polymer structures of the present invention are obtained by cooling the liquid system to a temperature below the binodial curve, as shown in FIG. 1, so that liquid / liquid phase separation is initiated. In this state, cores begin to form, which mainly consist of pure solvent. If the rate of cooling is such that the cellular microstructure results, it is also believed that as each such core continues to grow, it will be surrounded by a polymer-rich zone which will increase in thickness as the liquid is freed . Ultimately, this polymer-rich region resembles a skin or film that covers the growing droplets of solvent. As the polymer-rich region continues to increase in thickness, the diffusion of additional solvent through the layer decreases; the growth of the liquid droplets decreases accordingly until it effectively stops, whereby the liquid droplets have reached their maximum size. At this point, the formation of a new nucleus is more likely than the continued growth of the large solvent droplets. However, in order to achieve this type of growth, it is necessary that the nucleation takes place by spinodal rather than binodial separation.

The cooling is thus preferably carried out in such a way that a plurality of liquid droplets of substantially the same size are formed in a continuous polymer phase at substantially the same time. If this separation mode does not take place, no cellular structure will result. This type of segregation is generally accomplished using conditions that ensure that the system does not reach thermodynamic equilibrium until at least nucleation or droplet growth has been initiated. In the process, this can be achieved by simply allowing the system to cool without subjecting it to a mixing process or other distribution forces. The time parameter can also be important when producing relatively thick blocks, which makes faster cooling desirable in some cases.

Within the range over which cooling leads to the formation of a large number of liquid droplets,

there is a general indication that the rate of cooling can affect the size of the resulting cells, because with increasing cooling rates, smaller cells result. In this connection it was observed that an increase in the cooling rate of about 8 ° C / min. obviously will result in a decrease in cell size in half for a microporous polypropylene polymer. Accordingly, external cooling may be used to control the final cell and pore size, as will be explained in more detail below.

The way in which the interconnecting passages or pores are formed in the cellular structure is not fully understood. However, while not wishing to be bound by any particular theory, there are various possible mechanisms that can be used to explain this phenomenon, each of which is compatible with the concept described above. The formation of the pores can accordingly be attributed to thermal shrinkage of the polymeric phase on cooling, the liquid solvent droplets behaving like non-compressible spheres if the solvent has a smaller coefficient of expansion than the polymer. On the other hand, even after the solvent droplets have reached their maximum size (and it has already been pointed out), the polymer-rich phase will still contain some residual solvent and vice versa. If the system cools further, a further phase separation can take place. The remaining solvent in the polymer-rich "skin" can therefore diffuse to the solvent droplet, reducing the volume of the polymer-rich layer and the volume of the solvent droplet

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increases. This can understandably make the polymer skin weaker; the increase in volume of the solvent or liquid phase can result in an internal pressure that is able to break through the polymer skin that connects the adjacent solvent droplets. Similar to this latter mechanism, the polymer can redistribute itself to a more compact state when the remaining liquid migrates out of the polymer skin, such as by crystallization,

if this type of polymer is used. In such a situation, the resulting polymer skin would also shrink and have imperfections or openings that are likely to be in areas of particular weakness. These weakest areas can be expected to be between adjacent liquid droplets; in such a case the openings between adjacent liquid droplets would form and lead to a connection of the liquid droplets. At any speed, and apart from the mechanism, adherent interconnecting pores or passageways result when the above described process is carried out.

An alternative interpretation of the mechanism by which the pores are formed is based on the "Marango-ni effect", which is described in Marangoni, C. Nuovo Cimento (2) 5-6.239 (1871; (3), 3,97,193 (1878 ) and Marangoni, C. Ann. Phys. Lpz. (1871), 143, 337. The "Marango-ni-Effect" was used to explain the phenomenon that occurs when alcoholic beverages spontaneously come from the side of a Flowing away drinking glasses, especially the mechanism when a condensed drop flows back into the bulk of the liquid. The flow of the droplet penetrates the main liquid first, followed by a rapid withdrawal of some of the liquid into the droplet. The hypothesis has been made that Similar physical phenomenon occurs in a liquid droplet that resulted from the liquid / liquid phase separation, so one droplet can meet another and the liquid from one can penetrate through the other followed by a rapid separation of the two droplets, perhaps leaving behind a portion of the liquid that connects the two droplets and forms the basis for the connecting pores of the cellular structure. For a more recent discussion of the “Marangoni effect”, Charles & Mason, J. Colloid Sc; 15, 236-267 (1960).

If the homogeneous solution is cooled at a sufficiently high rate, the liquid / liquid phase separation can take place under thermodynamic non-equilibrium conditions; however, the substantial solidification of the polymer can take place so quickly that essentially no nucleation and then no growth takes place. In such a case, there will be no large number of liquid droplets and the resulting microporous polymer will not have a visible cellular structure.

Thus, under certain circumstances, it is possible to obtain various microporous structures by using extremely high cooling rates. For example, when a solution of 75 parts N, N-bis (2-hydroxyethyl) tallow amine and 25 parts polypropylene is cooled at rates ranging from about 5 ° C to about 1350 ° C per minute, the cellular microstructure results. The main effect of the different cooling rates in the previous range for the composition is the change in the absolute cell size. Where cooling rates of around 2000 ° C / min. achieved, the microstructures take on a non-cellular appearance, for example. If e.g. B. a solution of 60 parts of N, N-bis (2-hydroxyethyl) tallow amine and 40 parts of polypropylene is treated in the same way, cooling rates must be above 2000 ° C / min. can be achieved before the non-cellular structure is obtained.

In order to investigate the effect of the speed of the cooling system on the cell size of the cellular structure and to clarify the speed required for the conversion from the production of the cellular structure to the production of a structure with recognizable cells, various concentrations of polypropylene and N, N-bis ( 2-Hydroxyethyl) tallow amine produced as homogeneous solutions. To carry out such an examination, the aforementioned DSC-2 was used together with standard X-ray equipment, as was a scanning electron microscope. Since the DSC-2 device with a maximum of about 80 ° C / min. was able to cool, a thermal gradient rod was used. The thermal gradient rod was a brass rod, which was able to have a temperature differential of more than 2000 ° C across one meter of its length to which the samples could be placed.

An infrared camera was used to determine the temperatures of the samples by first focusing the camera on a vessel which was brought to a temperature of 110 ° C on the next of the ten rack positions; the measurement was carried out with a thermocouple.

The control of the camera emissivity was then adjusted until the camera temperature at the end of the scale matched the reading of the thermocouple.

For any given experiment, the camera was focused on a location where a given rod should be cooled that contained the sample solution. The vessel with the sample was then placed on the thermal gradient rod for 2 minutes. When the vessel was removed from the wand to be brought into the field of the camera, a stopwatch was started. As soon as the camera indicated that the vessel was at a temperature of 110 ° C, the stopwatch was turned off and the time was recorded.

Thus, the specific cooling speeds were based on the time required to cool the sample over a temperature range of approximately 100 ° C.

It was found that the condition affecting the cooling rate was not the amount of material to be cooled. It was found that, although heavier samples cooled more slowly than light ones, the sihkon oil used at the bottom of the vessel for thermal conductivity between the vessel and the rod had a significant impact on the rate of cooling. Thus, the highest cooling rates were obtained by placing a vessel without silicone oil on an ice cube; the slowest cooling rates were obtained with a jar that had a thick coating of silicone oil placed on a piece of paper.

Five samples of polypropylene were prepared, which contained a content of N, N-bis (2-hydroxyethyl) tallow amine from zero to 80% of said amine; they were made for use in examining the rate of cooling for the resulting structures. Approximately 5 milligrams of each of the above samples were measured on the DSC-2 in closed vessels at 40 ° C

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per minute up to a constant temperature of 175 ° C

heated with 20% polypropylene for the sample,

230 ° C for the sample with 40% polypropylene,

245 ° C for the sample with 60% polypropylene,

265 ° C for the sample with 80% polypropylene, and

250 ��C for 100% polypropylene.

Each of the samples was heated and held at an appropriate constant temperature for 5 minutes before cooling. After the samples cooled at the desired cooling rate, the N, N-bis (2-hydroxyethyl) tallow amine was extracted from the sample with methanol and the sample analyzed. The results of the study are summarized in Table I, 5 where the sizes of the cells in the resulting compositions are given in micrometers. All cell sizes were determined by taking measurements from corresponding recordings with the scanning electron microscope.

Table I

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

dizziness

composition

0% amine none (1) none (1) none (1) none (1)

20% amine 0.5 (2) 0.5 (2) none (3) none (3)

40% amine 2.5 (4) 2.0 (4) 2.0 (4) 0.7 (5)

60% amine 4.0 3.0 2.0 1.5 (6)

80% amine 0.5 4.0 3.0 3.0 (6)

(1) There are some irregular holes

(2) approximation of the largest cell size,

(3) porosity, probably too small to measure,

(4) Some cells with Vio the size of the larger cells are present,

(5) Additional cells are available which are too small for the measurement,

(6) Some material with non-cellular structure was formed.

An additional cooling rate study was performed using 20% polypropylene and 80% N, N-bis (2-hydroxyethyl) tallowamine samples on the thermal gradient bar. Five of such samples were from different

Speeds cooled from the melting temperature of 210 ° C; the results are summarized in Table II with cell sizes in microns and the same procedure used to obtain the data for Ta-35 belle I.

Table II

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

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composition

80% amine 0.5-3 0.5-1.5 1.5-2.5 non-cell

lar

It can be seen from Tables I and II that as the cooling rates increase, the size of the cells in the resulting compositions generally decreases. Furthermore, with regard to the polymer / liquid system, which contains 20% polypropylene and 80% N, N-bis (2-hydroxyethyl) tallow amine, it can be seen that at a cooling rate between about 1350 ° C./min. and 1700 ° C / min. a transformation in the nature of the resulting polymer from essentially cellular to non-cellular is accomplished. Such a transformation in the resulting structure corresponds to the fact that the polymer substantially solidifies after the liquid / liquid phase separation is initiated, but before the formation of a plurality of liquid droplets, as previously explained.

In addition, five samples were made from 40% polypropylene and 60% N, N-bis (2-hydroxyethyl) tallow amine and at speeds of 690 ° C / min. up to 7000 ° C / min. cooled from the melting temperatures of 235 ° C in accordance with the previously discussed process. It was determined that for such a concentration of polypropylene and said amine, the conversion from cellular to non-cellular at about 2000 ° C / min. he follows.

Finally, three specimens were made from 20% polypropylene and 80% N, N-bis (2-hydroxyethyl) tallow amine to study the crystallinity of the structures produced over a range of cooling rates; cooling was carried out at speeds of 20 ° C, 1900 ° C and 6500 cC / min. from. From the DSC-2 data for such samples, it was determined that the degree of crystallinity in the three samples was essentially equivalent. Thus, it appears that the variations in cooling rate have no significant impact on the degree of crystallinity of the resulting structures. However, it was determined that when the cooling rate was significantly increased, the crystals produced became less perfect, as expected.

After the homogeneous polymer and liquid solution has been formed and the solution has been cooled in a convenient manner to produce a material of suitable processing strength, the microporous product can then be formed by removing the liquid, for example by extracting it with any suitable solvent this liquid, which is also quite obviously a non-solvent for the polymer system. The relative miscibility or solv55

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The liquidity in the solvent to be used will in part determine the effectiveness in relation to the time required for the extraction. Optionally, the extraction or leaching process can also be carried out at an elevated temperature, which is below the softening point of the polymer, in order to reduce the time requirements. Illustrative examples of useful solvents are isopropanol, methyl ethyl ketone, tetrahydrofuran, ethanol and heptane.

The time required will vary depending on the liquid used, the temperature used and the extent of the extraction required. In particular, it may not be necessary in some cases to extract 100% of the liquid used in the system; smaller amounts can be tolerated, the amount that can be tolerated depends on the requirements of the intended end use application. Accordingly, the time required can vary anywhere from a few minutes or maybe less to more than 24 hours or even more, depending on many factors, including sample thickness.

Removal of the liquid can also be accomplished by other known methods. Illustrative examples of other useful removal methods are evaporation, sublimation, and displacement.

In addition, it should also be noted that, if conventional liquid extraction methods are used, the cellular, microporous polymer structures according to the invention can show the release of a liquid contained in the structure in a manner which reaches the zero order, i.e. the rate of release may be substantially constant after an initial period of high delivery rate. In other words, the rate of release can be independent of the amount of liquid that has been dispensed; thus the rate at which the liquid was extracted after, for example, 3A of the liquid was removed from the structure is approximately the same as when the structure was half-filled with liquid. An example of such a system, which shows a substantially constant release rate, is the extraction of N, N-bis (2-hydroxyethyl) tallow amine from polypropylene with isopropanol as the extraction agent. There will also be an initial introductory period in any situation before the rate of delivery becomes identifiable. When a liquid is released through an evaporation process, the rate of release tends to be first order.

If the cooling of the polymer / liquid solution takes place in such a way that the plurality of liquid droplets, as mentioned above, are formed and the liquid is removed therefrom, the resulting microporous product forms a relatively homogeneous cellular structure, which in the micro range is a series of im essentially spherical, sealed microcells, which are distributed substantially uniformly over the structure. Adjacent cells are interconnected by small pores or passages. This basic structure can be seen from the microphotographs of FIGS. 4 and 5. It should be recognized that the individual cells are actually encased but appear open in the photomicrographs due to the breaking caused by the preparation of the samples for taking the photomicrographs. On a macroscale, the structure appears to have planes, at least for the crystalline polymer, similar to the fracture planes along the edges of the crystal growth (see Fig. 2); 3, the structure has a coral-like appearance. The cellular microstructure can also show a similarity to zeolitic clay structures, which contain defined «chamber» and «entrance» regions. 5 The cells correspond to the larger chamber areas of the zeolite structures, while the pores correspond to the entrance regions.

Generally, in the cellular structure, the average diameter of the cells will range from about 0.5 to about 100 microns, with about 0.5 to about 50 microns being more typical, while the average diameter of the pores or interconnecting passages will typically be about appears to be an order of magnitude smaller. Thus, if the cell diameter in a microporous polymer structure according to the invention is, for example, about 1 micrometer, the average diameter of the pore or connecting passage will be about 0.1 micrometer. As previously indicated, the cell diameter and, if the diameter of the pores or passageways, will depend on the particular polymer / liquid system in question, the rate of cooling and the relative amounts of polymer and liquid used. However, a wide range of cell to pore ratios is possible, for example from about 2: 1 to about 200: 1, preferably from about 5: 1 to about 40: 1.

As can be seen from the various figures, it can be believed that some of the exemplary cellular microporous polymer products do not have the microcellular structure described above. It should be noted, however, that in some cases this structure may be hidden by additional modifications due to the particular liquids or polymers 35 contained or the relative amounts used. This masking can be present in whole or in part in the photomicrographs, this ranges from small polymer particles which are attached to the walls of the cells to coarse polymer collections of the "foliage-40 type"; this tends to completely hide the basic structure. How e.g. 21 and 25, the small polymer balls adhere to the cell cavities of the structures. This additional formation can be understood on the basis of nucleation and the previously described growth concept. Thus, in systems with an extremely high solvent or liquid content, the maximum cavity size will typically be comparatively large. This also means that the time required for the cavity or droplet to reach the maximum size will be increased similarly. During this time, it is possible for additional germs to form nearby. Two or more germs can then come into contact with each other before each has reached its maximum size; in such cases the resultant cellular structure is less intact and less uniform than the basic structure mentioned above. Even after the liquid droplets have reached their maximum size, depending on the system in question, the solvent or liquid phase may still contain some remaining polymer or vice versa. If the system continues to cool down in such situations, an additional, remaining phase separation can take place. If the remaining polymer simply separates from the solution, polymer spheres can be formed as shown in FIGS. 21 and 25. On the other hand, if the rest of the polymer diffuses into the polymer layer, the walls will blur and appear irregular, resulting in er

15

649 565

creation of a structure of the "foliage type". This "foliage-type" structure can only partially obscure the basic structure, as shown in FIGS. 28 and 29, or may completely obscure the structure, as shown in FIG. 6.

The "foliage-type" structure also tends to occur with certain polymers. Thus, the microporous, low density polyethylene structures typically produce this type of structure, perhaps due to solubility or a similar factor of the polyethylene in the specific liquids used. This can be observed in Fig. 14. Furthermore, if the levels of the liquid used are extremely high, this will also happen with polymers such as polypropylene, which otherwise show the basic structure. This can be easily observed by contrasting the "leaf type" structure of the microporous product of Fig. 6 with the basic structure of Fig. 8 in which the polymer content is 40% by weight compared to 10% polypropylene in the structure which is illustrated in Fig. 6.

For most applications it is preferred to use a system which leads to the formation of the basic cellular structure. The relative homogeneity and uniformity of this structure gives predictable results as are required for filtration applications. On the other hand, the "leaf-type" structures may be desirable where structures with a relatively high surface area are desired, as is desired, for example, in ion exchange or various adsorption processes.

As can also be seen, some of the structures have small holes or openings in the walls of the cells. This phenomenon can also be understood if one refers to the nucleation and growth concept. Thus, in a section of the system in which a few spatially connected liquid droplets have already reached their maximum size, each droplet will be enclosed by a polymer-rich skin. In some cases, however, some solvent may be trapped between the trapped droplets. These cannot continue their migration to the larger droplets due to the impenetrability of the skins. Accordingly, in some cases, a seed of the liquid can form and grow, resulting in a small cavity which is enclosed in the adjacent larger droplets. After the liquid is extracted, the smaller droplets will appear as a small hole or opening. This can be seen in the microporous structures shown in Figs. 11-12 and 20.

Another interesting characteristic of the cellular structures according to the invention relates to the surface area of such structures.

The theoretical surface area of the cellular microporous structure, which consists of interconnected spherical cavities of approximately 5 micrometers in diameter, is approximately 2-4 m2 / g. It has been found that the microporous polymers made according to the present invention need not be limited to the theoretical limit of the surface area. The determination of the surface area according to the BET method, which is described in Brunauer, S., Emmett, P.H. and Teller, E. “The absorption of gases in multimolecular layers” J. Am. Chem. Soc., 60, 309, -16 (1938), has shown surface areas that are well in excess of the theoretical model, which is not related to empty space, as made in Table III for microporous polymers Polypropylene and N, N-bis (2-hydroxy-ethyl) tallow amine.

Table III

% Empty

Specific surface area

89.7 io 72.7 60.1 50.5 29.9

96.2 m2 / g 95.5 m2 / g 98.0 m2 / g 99.8 m2 / g 88.5 m2 / g

15 The surface area can be reduced by carefully tempering the microporous polymer without damaging the basic structure. Microporous polypropylene, produced at 75% empty volume using N, N-bis (2-hydroxyethyl) tallow amine as the liquid component, 20 was extracted and dried at temperatures which did not exceed room temperature and then heated to influence the surface area. The initial surface area was 96.9 m2 / g. After eleven heating times of 40 minutes at 62 ° C, the surface area was only 66 m2 / g. Further heating at 60 ° C for another 66 hours caused the surface area to drop to 51.4 m2 / g. Treatment of another sample at 90 ° C for 52 hours caused the surface area to drop from 96.9 to 33.7 m2 / g. The micropo-30 structures were not significantly changed when they were examined with the scanning electron microscope.

These results are summarized in Table IV.

35

Table IV

treatment

Surface% change range (m2 / g)

40 none 96.9 eleven, 40 min. Treatment at 62 ° C 66.0 as above + 66 hours at 60 ° C 51.4

45 52 hours at 99 ° C 33.7

32

47 65

It should be quite obvious that one of the special properties of the cellular structures according to the invention relates to the presence of both clear, essentially spherical, closed microcells, which are uniformly distributed over the structure, and clear pores, which are mentioned Connect cells to one another, the pores mentioned being smaller in diameter than the cells referred to. Furthermore, the 55 cells and connecting pores mentioned have essentially no spatial orientation and they can be classified as isotropic. Thus there is no preferred orientation, for example for the flow of a liquid through the structure. This is in marked contrast to the prior art materials which do not show such a cellular structure. Many known systems have a structure not described, lacking any structural configuration with which the system could be defined. It is therefore quite surprising that a microporous structure can be produced with such a degree of uniformity, which can be particularly desirable for many applications that require extremely uniform materials.

649 565

16

The cellular structure can be defined in terms of the ratio of the average diameter of the cells («C») to the diameter of the pores («P»). Thus, the above-mentioned C / P ratio can be varied from 2 to 200, with 5 to 100 being preferred and 5 to 40 being much more typical. Such a C / P ratio distinguishes the cell structure according to the invention from the microporous polymeric products according to the prior art. Since there is no synthetic, thermoplastic, polymeric structure with separate cells and pores according to the prior art, it must be assumed that all such materials have a cell to pore ratio of 1.

Another means of characterizing the cell structures according to the invention is the sharpness factor “S”. The “S” factor is determined by analyzing a mercury penetration curve for a given structure. All mercury penetration data discussed in this application were determined using a "Micromeritics" mercury penetration porosimeter, 910 series model. The S value is defined as the ratio of the pressure at which 85% of the mercury has entered to the pressure at which 15% of the mercury has entered. This ratio provides a direct indication of the variation in pore diameter through the central 70% of the pores in any given sample, since the pore diameter is 176.8 divided by the Newton pressure 1.47 cm2.

The S value is then a ratio of the diameter of the pores at which 15% of the mercury has penetrated to the diameter of the pores at which 85% of the mercury has gone. The 1-15% and 85-100% mercury penetration range is ignored when determining the S factor. The range of 0 to 15% is neglected because penetration in this region can be attributed to cracks that have been introduced into the material as a result of freeze-breaking, the material being subjected to this process prior to the mercury penetration test . The data in the range from 85% to 100% are also not recorded, which can be explained more by the compression of the sample than by the actual penetration of mercury into the pores.

Characteristic of the narrow range in relation to the pore sizes which the composition according to the invention shows is an S value for such structures in the range from 1 to 30, preferably from 2 to 20, in particular from 2 to 10.

The average size of the cells in the structure ranges from 0.5 to 100 microns, preferably from 1 to 30 microns, especially from 1 to 20 microns. As previously indicated, the cell size may depend on the particular resin and compatible liquid used, the ratio of polymer to liquid, and the rate of cooling used to form the specific microporous polymer. The same variable will also have an effect on the average size of the pores in the resulting structure, which usually range from 0.05 to 10 microns, with 0.1 to 5 microns being preferred and 0.1 to 1.0 microns being most typical . All indications of a cell and / or pore size relate here to the average diameter of such a cell or pore, these data, unless stated otherwise, are given in micrometers.

By determining the above factors, cell size, pore size and S factor for the cellular, microporous polymers according to the invention, the cellular, microporous polymers according to the invention can be precisely defined. A particularly useful means is to use the polymers in the form of the decimal logarithm of the ratio of the cell to the pore ("log C / P") and the decadic logarithm of the ratio of the sharpness function S to the cell size ("log S / C" ) define. Accordingly, the cellular, microporous polymers according to the invention have a log C / P of 0.2 to 2.4 and a log S / C of -1.4 to 1.0; in particular, the polymers mentioned have a log C / P of 0.6 to 2.2 and a log S / C of -0.6 to 0.4.

A non-cellular structure resulting from the cooling of the homogeneous solution at such a rate that the polymer solidifies substantially before the formation of the large number of liquid droplets can primarily due to the narrow pore size distribution of the material in Connection with the actual pore size and the spatial uniformity of the structure can be characterized.

The non-cellular, microporous polymers can also be characterized by a sharpness function S in the manner in which the cellular structures have been described. The S values that the non-cellular structures usually have range from 1 to 30, preferably from 1 to 10, especially from 6 to 9. However, when the pore size of the material ranges from 0.2 to 5 microns, the the S value ranges from 5 to 10, in particular from 5 to 10. Such S values for olefinic polymers and oxidation polymers with a microporosity of such a size have hitherto been unknown, except in the case of highly oriented thin films which have been produced by a stretching process. As mentioned above, the porous polymers according to the invention are essentially isotropic. Thus, a cross-section taken along any spatial plane will show essentially the same structural properties.

The pore sizes of the non-cellular structures are usually in the range from 0.05 to 5 micrometers, preferably between 0.1 and 5 micrometers, in particular from 0.2 to 1.0 micrometers.

It can be seen that a surprising property is the ability to produce isotropic, microporous structures from olefinic polymers and oxidation polymers, the structures having a preferred porosity in the range from 0.2 to 5 micrometers and a preferred sharpness value from 1 to 10 show. It is particularly surprising that such structures can be produced not only in the form of thin films, but also in the form of blocks and complex shapes.

If a film or block is cast onto a substrate, e.g. If a metal plate is formed, the surface of the microporous polymer structure that is in contact with the plate will contain a non-cellular surface skin. In contrast, the other surface will usually be mostly open. The thickness of the skin will vary somewhat in accordance with the particular system, as will the individual process parameters used. However, the thickness of the skin is characteristically about the same as the thickness of a single cell wall. Depending on the individual conditions, the skin can range from a surface that is completely impervious to the passage of liquids to a surface that exhibits a certain degree of liquid porosity.

If a purely cellular structure is desired for final use, the surface skin can be removed by any of several methods. As illustrative examples, the skin could be s

io

15

20th

25th

30th

35

40

45

50

55

60

65

any of several mechanical means, such as abrading, needling, or breaking the surface by letting the film or other structure pass through rollers at different speeds, are removed. On the other hand, the skin could be removed by micro-rolling. The skin can also be removed by chemical means, i.e. by brief contact with a solvent suitable for the polymer.

If e.g. B. a solution of polypropylene in N, N-bis (2-hydroxyethyl) tallow amine is continuously pressed as a thin film on an endless stainless steel belt, the application of a small amount of liquid solvent to the belt immediately before the application area of the Solution effectively remove the surface formed at the solution-steel interface. Useful liquids are substances such as isoparaffinic hydrocarbons, decane, decalin, xylene and mixtures such as xylene-isopropanol and decalin-isopropanol.

However, for some end use uses, the presence of the skin will not only be a disadvantage, but this skin will be a necessary component. It is Z. For example, it is known that a thin, liquid impermeable film is used in applications for ultrafiltration membranes or other types of membranes. Accordingly, in such applications the microporous portion of the structure according to the invention would have particular utility as a carrier for the surface skin, which would be a functioning membrane in such applications. Fully cellular structures can also be made directly by various methods. For example, the polymer-liquid system in air or a liquid medium, such as. B. hexane.

As already mentioned above, the microporous polymer structures according to the invention have cell and pore diameters with extremely narrow size distributions, which are evidence of the unique structures and their relative homogeneity. The narrow size distribution of the pore diameters can be seen from the mercury penetration data, as can be seen from FIGS. 30-33. The same general distribution is obtained regardless of whether the structure is in the form of a film (Fig. 30-32) or a block (Fig. 33). The characteristic pore size distribution of the microporous structure according to the invention stands in remarkable contrast to the significantly wider pore size distributions of earlier, microporous polymer products which were achieved by earlier processes; Examples of these are given in U.S. Patent Nos. 3,310,50 and 3,378,507; this will be explained in much greater detail in connection with the examples.

For all microporous polymers made in accordance with the present invention, the individual end use application will characteristically determine the amount of empty space and the pore size requirements. The pore size is e.g. for prefilter applications are typically above 0.5 microns, while in ultrafiltration the pore sizes should be less than about 0.1 microns.

In cases where the microporous structure actually serves as a container for a functionally useful liquid, strength considerations determine the amount of empty space where the controlled release of the contained functional liquid is included. Similarly, in such cases the pore size is determined by the rate of release desired, with smaller pore sizes tending to give slower delivery rates.

17 649 565

Where the microporous structure is to be used to convert a liquid polymer additive, such as a fire retardant, to a solid, minimal strength is generally desired; however, in accordance with this minimum, it is generally desirable to use as much liquid as possible since the polymer serves only as a container or carrier.

It should be apparent from the above discussions that, in accordance with one aspect of the present invention, microporous products containing a functionally useful liquid, such as a polymer additive (e.g., a fire retardant), can be made that behave like solids and can be edited as such bear-i5.

For this purpose, the resulting microporous polymer can be loaded with the desired functional liquid again. This can be achieved using conventional absorption methods; the amount of liquid increasing will be substantially the same as the amount of liquid used to form the microporous polymer in the first case. Any useful organic liquid can be used as long as the liquid is of course not a solvent for the polymer or attacks or decomposes the polymer at working temperatures. The microporous products containing the functionally useful liquid can be formed from or by using microporous polymers which, as the matrix in which the liquid is incorporated, have either the cellular or the non-cellular structure.

Similarly, such microporous products can be made by a displacement process. In accordance with this embodiment, the microporous polymer intermediate is usually first prepared; the liquid can then be shifted either with the desired functionally useful liquid or with a displacing intermediate liquid. In either case, displacement can be accomplished by conventional pressure or vacuum displacement or by infusion techniques rather than by extraction of the liquid used in the formation of the microporous polymer intermediate. Any functional or displacing intermediate liquid can be used which could be used as an extraction liquid to form the microporous polymer, i.e. the liquid is a non-solvent for the polymer and also has a certain solubility or miscibility with the liquid to be displaced. It is thus clear that small amounts of the displaced liquid or liquids may remain after the replacement. The end use requirement will typically determine the level of displacement desired; thus amounts of about 1 to 10% by weight can be tolerated in some applications. Where appropriate, multiple displacements and / or the use of liquids which can be easily removed by evaporation allow removal of substantially all of the liquid or liquids to be used, i.e. 60 less than about 0.03 remaining liquid can be achieved. From an economic point of view, it will generally be desirable to use a displacement liquid which has a boiling point which is sufficiently different from that of the liquid to be displaced; this allows recovery and use. For this reason it may be desirable to use a displacement fluid.

649 565

18th

As can be seen from the foregoing examples of the useful polymer / liquid systems, another method of making a polymer containing useful liquid material involves the use of the microporous polymer intermediate without further operations since numerous functionally useful liquids have been found to be compatible liquids can be used with the individual polymers to form the solid, microporous polymer intermediate. Intermediates which behave as solids can thus be directly e.g. are produced with the following useful liquids: lubricants, surface-active agents, lubricants, moth agents, pesticides, plasticizers, insect and animal repellants, medicines, polishing agents, stabilizers, antioxidants, fuel additives, odor masking agents, anti-fog agents, perfumes, Fragrances, fire retardants, etc. For example, low-density polyethylene can be used to create a convenient intermediate that contains a lubricant or plasticizer. This can be achieved by using either an aliphatic or an aromatic ester with 8 or more carbon atoms or a non-aromatic hydrocarbon with 9 or more carbon atoms. Useful products containing a surfactant and / or a wetting agent can be obtained with low density polyethylene by using a polyethoxylated aliphatic amine having 8 or more carbon atoms or a non-ionic surfactant. Polypropylene can be used to produce detergent-containing intermediates using diethoxylated aliphatic amines with 9 or more carbon atoms. Polypropylene intermediates with lubricants can be made by using a phenylmethylpolysiloxane, while intermediates of low density polyethylene and a lubricant are made by using an aliphatic amide having 12 to 22 carbon atoms. Intermediates of low density polyethylene and fuel additives can be made using an aliphatic amine having 8 or more carbon atoms or an aliphatic tertiary dimethylamine having 12 or more carbon atoms. The tertiary amines can also form useful additive intermediates with methyl pentene polymers. High and low density polyethylene intermediates containing a stabilizer can be made by employing an alkylaryl phosphite.

Intermediates of low density polyethylene containing an anti-fogging agent can be produced using the mono or diester of glycerol with a long chain fatty acid of at least 10 carbon atoms. Intermediates in which fire retardants are incorporated can be made with high and low density polyethylene, polypropylene and a blend of polyphenylene oxide polystyrene using a polyhalogenated aromatic hydrocarbon with at least 4 halogen atoms per molecule. Appropriate materials should of course be liquid at the phase separation temperature as described above. Other systems which are believed to be useful are disclosed in connection with the following examples.

Furthermore, for polypropylene, high density polyethylene, and low density polyethylene, certain classes of ketones which have been found to be particularly useful as animal repellants can preferably be used in the practice of the present invention.

Such ketones can be saturated aliphatic ketones with 7 to 19 carbon atoms, unsaturated aliphatic ketones with 7 to 13 carbon atoms, 4-t-amylcyclohexanone and 4-t-butylcyclohexanone.

s In the following examples, all parts and percentages are by weight unless otherwise specified.

Preparations io The porous polymer intermediates and the microporous polymers, which are described in the examples shown below, were produced according to the following method:

15 A. Porous polymeric intermediates:

The porous polymeric intermediates are made as follows:

Mixing a polymer with a compatible liquid,

20 - heating the mixture to a temperature which is usually close to or above the softening temperature of the resin, so that a homogeneous solution is obtained,

Cooling the solution without the system being subjected to a mixing process or other distributing forces.

25 is set to form a macroscopically solid, homogeneous mass.

If solid blocks of the intermediate products are to be formed, the homogeneous solution is allowed to take on a desired shape by pouring it into a suitable container 30, usually made of metal or glass; the solution is allowed to cool under room temperature conditions unless otherwise noted. The rate of cooling under room temperature conditions will vary, depending on the article, such as the sample thickness, and the composition; however, it will usually range from about 10 ° to about 20 ° C / min. to find oneself. The container is typically cylindrical in shape from about 1.9 to about 6.3 cm in diameter and the solution is typically cast to a height of about 0.63 to about 5.1 cm. When films of the intermediate products are formed, the homogeneous solution is placed on a metal plate which has been heated to a temperature sufficient to allow the solution to be drawn into a thin film. The metal plate is then brought into contact with a dry ice bath so that the film is rapidly cooled below the solidification temperature.

B. Porous polymers:

The microporous polymer is formed by extracting the compatible liquid used to form the porous polymer intermediate, which is usually done by repeatedly washing the intermediates in a solvent such as e.g. Isopropanol or 55 methyl ethyl ketone, and then drying the fused, microporous mass.

Examples

The following examples and tables illustrate some 60 of the various polymer / compatible liquid combinations which are expedient for the formation of the porous polymeric products according to the invention, as well as various products according to the prior art or commercially available microporous products. Solid blocks of the 65 intermediates were formed for all of the example combinations and, if so indicated in the table, films of the intermediate were also made using the procedure described above

19th

649 565

was applied. As indicated in the following tables, many of the intermediate compositions were used to form the microporous polymers of the present invention by using an appropriate solvent to extract the compatible liquid from the intermediate composition and then removing said solvent, for example by evaporation.

Many of the compatible fluids illustrated in the following examples are functional fluids that are useful not only as compatible fluids but also as fire retardants, lubricants, etc. These liquids are given in the tables. Thus, the intermediate compositions resulting from such functional liquids are useful as solid polymer additives, etc., as well as intermediate in the formation of porous polymers. The functional fluids that appear in the following examples are given to be in the form of one or more of the following symbols under the "Functional Fluid Type" column: AF (Antinebel agent); AO (antioxidant); AR (animal repellent); FA (fuel additive); FG (fragrance); FR (fire retardant agent); IR (insect repellent); L (lubricant); M (drug); MR (moth repellent); OM (odor masking agent); P (plasticizer); PA (polishing agent); PE (pesticide); 5 PF (perfumes); S (lubricant); SF (surfactant); and ST (stabilizer).

Examples 1 to 27 Examples 1 to 27 in Table V illustrate the formation of the homogeneous, porous, polymeric intermediate products in the form of cylindrical blocks with a radius of about 3.2 cm and a depth of about 5.1 cm, made of polyethylene high density ("HDPE") and compatible fluids found useful, using standard manufacturing techniques. The high density polyethylene was supplied by Allied Chemical under the name "Plaskon AA 55-003" with a melt index of 0.3 g / 10 minutes and a density of 0.954 g / cm3. Many of the exemplary intermediates were extracted to form the porous polymers, as shown in the table. The details of the preparation and the noted type of the functionally useful liquid are summarized in Table V:

Table V HDPE

Example No.

Liquid type and liquid

% Liquid

Functional liquid type

2nd

3rd

4th

5

6

7

9

10th

11

12

13

14

15

16

17th

18th

19th

Saturated aliphatic acids decanoic acid * 75

Primary saturated alcohols Decyl alcohol * 75

1-dodecanol * 75

Secondary alcohols

2-undekanol * 75 6-undecone * 75

Aromatic amines

N, N-diethylaniline * 75

Diester

Dibutyl sebacate * 70

Dihexalsebacate * 70

Ether

Diphenyl ether 75

Benzyl ether * 70

Halogenated hydrocarbons

Hexabromobenzene 70

Hexabromobiphenyl 75

Hexabromocyclodecane 70

Hexachlorocyclopentadiene 70

Octabromobiphenyl 70

Hydrocarbons with terminal double bonds

1-hexadecene * 75

Aromatic hydrocarbons diphenylmethane * 75

Naphthalene * 70

Aromatic ketones

Acetophenone 75

230

220 220

220 230

230

220 220

220 220

250 200 250 200 280

220

220 230

200

PF

L, P L, P

PF PF

FR FR FR FR FR

OM MR

PF

649 565 20

Table V (continued) HDPE

Example liquid type and liquid% liquid ° C type of function

No liquid

Aromatic esters

20th

Butyl benzoate *

75

220

L, P

Various

21st

N, N-bis (2-hydroxyethyl) tallow amine (1) *

70

250

-

22

Dodecylamine *

75

220

-

23

N-hydrogenated tallow diethanolamine

50

240

SF

24th

"Firemaster BP-6" (2)

75

200

_

25th

"Phosclere P315C" *

75

220

ST

26

Quinoline

70

240

M

27th

Dicocosamine (4)

75

220

-

* The liquid was extracted from the solid.

(1) A permanent internal antistatic agent with the following properties was used: Boiling point (1 133 Pa): 215-220 ° C; specific weight (at + 32 ° C): 0.896 g / cm3; Viscosity (at + 32 ° C): 476 10 ~ 3 Pas (SSU).

(2) trademark of Michigan Chemical Corporation for its hexabromobiphenyl; a fire retardant was used with the following properties: softening point, 72 ° C, density (at 25 ° C) 2.57 g / ml, viscosity 260-360 10 ~ 3 Pas (Brookfield # 3 axis at 110 ° C).

Table VI LDPE

Example liquid type and liquid% liquid ° C type of function

No liquid

Aliphatic saturated acids

28 caproic acid * 70 210 -

29 decanoic acid * 70 190 -

30 hexanoic acid * 70 190 -

31 lauric acid * 70 220

32 myristiric 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 phenylstearic acid * 70 214 -

39 xylyl behenic acid 70 180

* The liquid was extracted from the solid.

(1) Union Carbide Company's Bakelite polyethylene with the following properties was used. Density: 0.922 g / cm3; Melt index: 21 g / 10 min.

(2) This is an acid with a density of 0.8602 g / cm3 and a melting point of 33-34 ° C.

Table VI (continued) LDPE

Example liquid type and liquid% liquid ° C type of function

No liquid

Different acids

40 "Actintol FA2" (tall oil acids) (1) * 70 204

41 olefinic acid L-6 * 70 206

42 olefinic acid L-9 * 70 186

43 olefinic acid L-II * 70 203

44 resin acid * 70 262

45 tolylstearic acid 70 183

21st

Table VI (continued)

LDPE

Example No.

Liquid type and liquid

% Liquid

Functional liquid type

46

47

48

49

50

51

52

53

54

55

56

57

58

59

Primary saturated alcohols

Cetyl alcohol *

Decyl alcohol *

1-dodecanol *

Heptadecanol *

Honey alcohol *

1-octanol *

Oleyl alcohol *

Tridecyl alcohol

1-undekanol * undecylenyl alcohol *

Secondary alcohols

Dinonylcarbinol *

Diundecylcarbinol

2-octanol 2-undecanol *

70 70 75 70 70 70 70 70 70 70

70 70 70 70

176 220

200 168 174 178 206 240 184 199

201 226 174 205

PF

PF FA

PF

* The liquid was extracted from the solid.

(1) The composition and the physical properties are: fatty acid composition (98.2% of the total): linoleic acid, non-conjugated 6%, oleic acid 47%, saturated fatty acids 3%, other fatty acids 8%, specific weight (at 25/25 ° C: 0.898 g / cm3; viscosity (at 38 ° C): 94 10 "3 Pas.

Table VI (continued) LDPE

Example No.

Liquid type and liquid

% Liquid

Functional liquid type

60

61

62

63

64

65

66

67

68

69

Aromatic alcohols 1-phenylethanol *

1-phenyl-1-pentanol phenylstearyl alcohol * nonylphenol *

Cyclic alcohols

4-t-butylcyclohexanol *

Menthol*

other -OH-containing compounds «Neodol-25» (1) * polyoxyethylene ether of oleyl alcohol (2)

Polypropylene glycol 425 * (3)

Aldehydes salicylaldehyde *

70 70 70 70

70 70

70

70 70

70

184 196 206 220

190 206

180 268

188

PF

SF, PE

PE PF

SF SF

PF

* The liquid was extracted from the solid.

(1) Shell Chemical Company trademark for their synthetic fatty alcohol with 12-15 carbon atoms.

(2) Surfactant "Volpe 3" from Croda, Inc. with the following properties was used: Acid value: maximum 2.0; Fog point: 1% aqueous solution insoluble; calculated HLB value: 6.6; Iodine value 57-62; pH values in 3% aqueous solution: 6-7; Hydroxyl value: 135-150.

(3) Union Carbide Company trademark for their glycol with the following properties: Apparent Specific Weight (at 20/20 C): 1.00 g / cm3; average hydroxyl number: 265 mg KOH / g; Acid number: maximum 0.2 mg KOH per g sample; pH at 25 C in 10: 6 isopropanol / water solution: 4.5-6.5.

649565

22

Table VI (continued)

LDPE

Example No.

Liquid type and liquid

% Liquid

Functional liquid type

70

71

72

73

74

75

76

77

78

79

80

81

82

83

84

85

86

Primary amines

Dimethyldodecylamine 70

Hexadecylamine * 70

Octylamine * 70

Tetradecylamine * 70

Secondary amines bis (1-ethyl-3-methylpentyl) amine * 70 tertiary amines

N, N-Dimethylsoyaamine * (1) 70

N, N-Dimethyltalgamine * (2) 70

Ethoxylated amines

N-stearyldiethanolamine 75 Aromatic amines

Aminodiphenylmethane 70

N-sec-butylaniline 70

N, N-diethylaniline * 70

N, N-dimethylaniline * 70

Diphenylamine 70

Dodecylaniline * 70

Phenylstearylamine * 70

N-ethyl-o-toluidine * 70

p-toluidine * 70

200 207 172 186

190

198

209

210

236 196

169 186

204

205 182 184

FA FA FA FA

FA FA

SF, AF

AO, PE

* The liquid was extracted from the solid.

(1) A tertiary amine with the following properties was used: Start of crystallization: + 38 ° C ASTM; specific weight (at 25/4 ° C): 0.813 g / cm3; Viscosity (at 25 ° C): 59.3 10 ~ 3 Pas,

(2) a tertiary amine with the following properties was used: melting range: -2 ° -t-5 ° C: fog point + 16 ° C; specific gravity (at 25/4 ° C): 0.803 g / cm3; Viscosity (at 25 ° C): 47 lo-3 Pas.

Table VI (continued) LDPE

Example liquid type and liquid% liquid ° C type of function

No liquid

Diamines

87 1,8-diamino-p-methane 70 188 -

88 N-terucyl-l, 3-propanediamine * 70 220 -

Various amines branched tetramine L-PS 70 242 -

Cyclodocecylamine * 70 159 -

Amides

91 coconut amide * (2) 70 245 -

92 N, N-diethyltoluamide 70 262 IR

93 "Terucamide" * (3) 70 250 L, P.

94 hydrogenated tallow amide * 70 250 L, P

95 octadecylamide (4) 70 260 L, P

96 N-trimethylolpropane stearamide 70 255 L, P

Aliphatic saturated 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 methyl caprylate 70 182 -

23 649565

Table VI (continued)

■ LDPE

Example liquid type and liquid% liquid ° C 'type of function

No liquid

103 methyl stearate * 70 195 -

104 tridecyl stearate 70 202 L.

* The liquid was extracted from the solid.

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

(2) an aliphatic amide with the following properties was used: appearance: flake: flash point: about 174 ° C; Focus: about 185 ° C,

(3) an amide with the following properties was used: specific gravity: 0.88 g / cm 3; Melting point: 99-109 ° C; Flash point: 225 ° C.

(4) Octadecylamide with the following properties was used: Appearance: flakes; Flash point: about 225 ° C, focus: about 250 ° C

Table VI (continued) LDPE

Example liquid type and liquid% liquid ° C type of function

No liquid

Aliphatic unsaturated esters

105

"Butyl oleate" *

70

196

L

106

Butylundecylenate *

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

Vinylphenyl stearate *

70

225

L, P

Diester

121

Dibutyl phthalate *

70

290

L, P

122

Dibutyl sebacate *

70

238

L, P

123

Dicapryl adipate *

70

204

L, P

124

Dicapryl phthalate *

70

204

Diester

125

Dicapryl sebacate

70

206

L, P

126

Diethyl phthalate *

70

280

IR

127

Dihexyl sebacate

70

226

-

128

Dimethylphenylene distearate *

70

208

-

129

Dioctyl maleate

70

220

-

130

Di-iso-octyl phthalate

70

212

-

131

Di-iso-octyl sebacate

70

238

-

Ester polyethylene glycol

132

"PEG 400 diphenyl stearate"

70

326

-

Polyhydroxyl esters

133

castor oil

70

270

_

134

Glycerol dioleate * (1)

70

230

AF

135

Glycerin Distearate * (2)

70

201

AF

136

Glycerol Monooleate * (3)

70

232

AF

137

Glycerol monophenyl stearate

70

268

-

24th

Table VI (continued)

LDPE

Example liquid type and liquid% liquid ° C 'type of function

No liquid

138 glycerol monostearate * (4) 70 211 AF

139 trimethylolpropane monophenyl stearate 70 260 -

Esters

140 dibenzyl ether * 70 189 PF

141 diphenyl ether * 75 200 -

* The liquid was extracted from the solid.

(1) A glycerol ester with the following properties was used: Flash point: 271 ° C (COC); Freezing point: 0 ° C; Viscosity (at 25 ° C): 90 10 ~ 3 Pas; specific gravity (at 25/20 ° C): 0.923-0.929 g / cm3.

(2) a solid with a melting point of 29.1 ° C

(3) a glycerol ester having the following properties was used: specific gravity: 0.94-0.953 g / cm3, flash point: 224 ° C (COC); Freezing point: 20 ° C; Viscosity (at 25 ° Q: 204 10 ~ 3 Pas

(4) a glycerol ester with the following properties was used: mold at 25 ° C; Flakes: Flash point: 210 ° C (COC), melting point: 56.8-58.5 ° C.

Table VI (continued) LDPE

Example liquid type and liquid% liquid ° C type derfunction

No liquid

Halogenated ethers

142 4-bromodiphenyl ether * 70 180 FR

143 "FR 300 BA" (1) 70 314 FR

144 hexachlorocyclopentadiene * 70 196 PE, FR

145 octabromobiphenyl * 70 290 FR

Double bond hydrocarbons

146 1-nons * 70 174 L.

Hydrocarbons with double bonds inside

147 3-eicosen * 70 204

148 2-heptadecene * 70 222 -

149 2-nonadecene * 70 214 -

150 9-nonadecene * 70 199 -

151 2-nons * 70 144 L.

152 2-Undecen 70 196

Aromatic hydrocarbons

153 diphenylmethane 75 200 PF

154 trans stilbenes * 70 218 -

155 triphenylmethane 70 225 -

Aliphatic ketones

156 dinonyl ketone * 70 206 -

157 distearyl ketone * 70 238 -

158 2-heptadecanone 70 205 -

159 8-heptadecanone * 70 183 -

160 2-heptanone * 70 152 -

161 methylheptadecyl ketone * 70 225 -

162 methyl nonyl ketone * 70 170 AR

* The liquid was extracted from the solid.

(1) Dow Chemical Company's trade name for their decabromodiphenyl oxide. Fire retardant with the following properties was used: bromine 81-83%; Melting point: minimum 285 ° C; Decomposition temperature 425 ° C (DTA).

25th

649 565

Table VI (continued)

LDPE

Example No.

Liquid type and liquid

% Liquid ° C

Functional liquid type

163

164

165

166

167

168

169

170

171

172

173

174

175

176

177

178

179

180

181

Aliphatic Ketones (continued)

Methyl pentadecyl ketone * 70

Methylundecyl ketone 70

2-nonadecanone 70

10-nonadecanone 70

8-pentadecanone * 70

1-pentadecanone * 70

2-tridecanone * 70 6-tridecanone * 70 6-undecanone * 70

Aromatic ketones

Acetophenone * 70

Benzophenone 70

Different ketones

9-Xynthon * 70

Compounds containing phosphorus

Trixylenyl phosphate * 70

Various

N, N-bis (2-hydroxyethyl) tallow amine * 70

"Bath oil fragrance # 5864K" 70 "EC-53 styrenated nonylphenyl" (1) * 70

Mineral oil 50

"Lily of the Valley Hyacinths" 70

"Phosclere P315C" * 70

210 205 214 194 178 262 168 205 188

190 245

220

304

210 183

191 200 178 200

AR

PF PF

PE

FR

FG AO L

FG

* The liquid was extracted from the solid.

(1) Trademark of Akzo Chemie Nv. for their styrenized hindered phenol.

Table VI (continued) LDPE

Example liquid type and liquid% liquid ° C type of function

No liquid

Various (continued)

182

"Phosclere P576" (1) *

70

210

AO

183

Quinalidine

70

173

-

184

Quinoline *

70

230

-

185

"Terpineol No. 1"

70

194

M, PF

186

"Firemaster BP-6"

75

200

FR

187

Benzyl alcohol / 1-heptadecanol (50/50) *

70

204

-

188

Benzyl alcohol / 1-heptacecanol (75/25) *

70

194

-

* The liquid was extracted from the solid. (1) Styrenated hindered phenol from Akzo Chemie Nv.

The photomicrographs of the porous polymers of Examples 38 and 122 are illustrated in Figures 28 and 29, respectively. The microphotographs at a magnification of 2,000 show the cellular structure with a significant amount of "foliage", which is uniformly present in the samples.

Examples 189 to 193 Examples 190 to 194 in Table VII illustrate the formation of the homogeneous, porous polymer intermediates by pouring the solution into a glass dish.

to form cylindrical blocks with a radius of approximately 60 4.45 cm and a depth of 0.64 cm. Except where noted, these were made from the "Noryl" polymer and the compatible fluids found useful, using standard manufacturing methods. In the examples given, the 65 microporous structure was obtained in the same way.

The details of the preparation and the type of functionally useful liquid recorded are summarized in Table VII:

649 565

26

Table VII

Example No.

Liquid type and liquid

% Liquid ~ C

Functional liquid type

189

190

191

192

193

Aromatic amine

Diphenylamine 75

Diester

Dibutyl phthalate 75

Halogenated hydrocarbons hexabromobiphenyl (2) 70

Various

N, N-bis (2-hydroxyethyl) tallow amine * 75

N, N-bis (2-hydroxyethyl) tallow amine 90

195

210

315

250 300

PR, AO L

FR

(1) General Electric Company's "Noryl" polymer, a blend of polyphenylene oxide condensation polymer with polystyrene, having the following properties was used: specific gravity (at 23 ° C): 1.06 g / cm3; Tensile strength (at 23 ° C) 9,600 67.2,106Pa: elongation at break (at 23 ° C) 60%; Tensile modulus (at 23 ° C): 2345.106Pa; nad Rockwell hardness: R119.

(2) The "Noryl" microporous polymers formed with hexabromobiphenyl and N, N-bis (2-hydroxymethyl) tallow amine were cast to a depth of 1.27 cm.

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

Examples 194-236 Examples 194 to 236 in Table VIII illustrate the formation of the homogeneous porous polymer intermediates in the form of cylindrical blocks with a radius of approximately 3.17 cm and a depth of approximately 1.27 cm from polypropylene (“PP” ) and the acceptable compatible liquids, using standard manufacturing methods. In addition, blocks of about 15.24 cm in depth and / or thin films were made in the examples given. As indicated, the microporous polymer was also made.

The units of manufacture and the type of functionally useful liquids indicated are summarized in Table VIII:

30th

Table VIII PP

Example No.

Liquid type and liquid

% Liquid

° C

Functional liquid type

Unsaturated acid

194

10-undecenoic acid *

70

260

M

Alcohols

195

2-benzylamino-l-propanol

70

260

-

196

"Ionol CP" *

70

160

AO

197

3-phenyl-l-propanol

75

230

-

198

Salicylaldehyde

70

185

PF

Amides

199

N, N-diethyl-m-toluamide

75

240

IR

Amines

200

Aminodiphenylmethane *

70

230

-

201

Benzylamine *

70

160

-

202

N-butylaniline

75

200

-

203

1,12-diaminododecane *

70

180

-

204

1,8-diaminooctane

70

180

-

205

Dibenzylamine *

75

200

-

206

N, N-diethanolhexylamine *

75

260

-

207

N, N-diethanoloctylamine *

75

250

-

208

N, N-bis-ß-hydroxyethylcyclohexylamine

75

280

-

209

N, N-bis (2-hydroxyethyl) hexylamine

75

260

-

210

N, N-bis (2-hydroxyethyl) octylamine

75

260

-

* The liquid was extracted from the solid.

(1) "Marlex" polypropylene from Phillips Petroleum Company with the following properties was used: Density: 0.908 g / cm3 Melt flow: 9/10 min.

Melting point: 171 ° C

Breaking strength at 35.106Pa = approx. 5 cm / min.

Shore hardness: 73 D.

27th

649 565

Table YIII (continued)

PP

Example No.

Liquid type and liquid

% Liquid

Functional liquid type thin film

211

212

213

214

215

216

217

218

219

220

221

222

223

224

225

226

227

Esters

Benzyl acetate * 75

Bezyl benzoate * 75

Butyl benzoate 75

Dibutylphthalate 75

Methyl benzoate 70

Methyl salicylate * 75

Phenyl salicylate * 70

Ether

Dibenzyl ether 75

Diphenyl ether * 75

Halogenated hydrocarbons

4-bromodiphenyl ether * 70

1,1,2,2-tetrabromethane * 70

1,1,2,2-tetrabromethane * 90

Ketones

Benzylacetone 70

Methyl nonyl ketone 75

Various

N, N-bis (2-hydroxethyl) tallow amine * (1) + (2) 75

N, N-bis (2-hydroxyethyl) cocosamine (2) 75

butylated hydroxytoluene 70

200 235 190 230 190 215 240

210 200

200 180 180

200 180

200 180 160

L, P, PF

L, P

L, P

L, P, PF

L, P, PF

P

PF PF

FR FR FR

AO

Yes Yes Yes

* The liquid was extracted from the solid.

(1) A block about 15.2 cm deep was also made.

(2) A permanent internal antistatic agent with the following physical properties was used: Boiling point 133 Pa: 170 ° C, viscosity (at 32 ° C): 367 10 ~ 3 Pas

Table VIII (continued)

Example liquid type and liquid% liquid ° C type of function-thinner

No nellen liquid film

Various (continued)

228

«D.C. 550 silicone liquid »(1)

50

260

S, L

229

«D.C. 556 silicone liquid »*

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

Quinaldin *

70

200

236

Quinoline *

75

220

M

* The liquid was extracted from the solid.

(1) Dow Corning's trademark was used for its phenylmethylpolysiloxane with the following properties: viscosity 115.10 ~ 3 Pa and usable from -40 ° C to 232 ° C in open systems and up to 316 ° C in closed systems.

The photomicrographs of the porous polymer of Example 225 are illustrated in Figures 2-5. The microphotographs of FIGS. 2 and 3 at a magnification of 55 and 550 times show the macrostructure of the microporous polymer. The microphotographs of FIGS. 4 and 5 at 2200x and 5500x magnification show the microcellular structure of the polymer, as well as the connecting pores.

Examples 237 to 243 Examples 237 to 243 in Table IX illustrate the formation of the homogeneous, porous, polymeric intermediate products in the form of cylindrical masses with an Ra-65 dius of approximately 3.17 cm and a depth of approximately 1.27 cm from polyvinyl chloride («PVC») and the compatible liquids found to be useful, using standard manufacturing processes. Many of the exemplary intermediate

649 565 28

Products were used to form the porous polymers. The details of the production and the type of

extracted as indicated in the table. Functionally useful liquids are summarized in Table IX.

Table IX PVC

Example liquid type and liquid% liquid ° C type of function

No liquid

Aromatic alcohols

237 4-methoxybenzyl alcohol * 70 150 PF

Other - (OH) -containing compounds

238 l-3, -Dichlor-2-propanol * 70 170 -

239 menthol * 70 180 PF

240 10-Undecen-l-ol * 70 204-210

Halogenated

241 «Firemaster T33P» * (2) 70 165 FR

242 «Firemaster T13P» * (3) 70 175 FR

Aromatic hydrocarbons

243 trans-stilbenes * 70 190 -

* The liquid was extracted from the solid.

(1) The polyvinyl chloride used had the degree of dispersion, which was manufactured by American Hoechst, with an inherent viscosity of 1.20.10 ~ 3 Pa, a density of 1.40 and a bulk density of 0.3244 g / cm3.

(2) Trademark of Michigan Chemical Corporation for its fire retardant tris (1,3-dichloroisopropyl) phosphate with the following properties:

Chlorine content, theoretical: 49.1%

Phosphorus content, theoretical: 7.2%

Boiling point 532 Pa: 200 ° C (decomposes at 200 ° C)

Refractive index: 1.50.9 viscosity, Brookfield, 23 ° C): 2120 10 ~ 3 Pas structure: [(ClCH2) 2CHO] 3 P-O

(3) Trademark of Chemical Corporation for its fire retardant tris-halogenated propyl phosphate with the following properties:

Specific weight (at 25 ° C / 25 ° C: 1.88 g / cm3 viscosity (at 25 ° C): 1928 10 "3 Pas refractive index: 1.540 pH: 6.4

Chlorine content: 18.9%

Bromine content: 42.5%

Phosphorus content: 5.5%

Photomicrographs of the porous polymer of Example 242 are illustrated in Figure 27. The microphotograph at a magnification of 2,000 shows the extremely small cell size of this microporous polymer in contrast to the exemplary cell structure of FIGS. 7, 13, 18, 20 and 24, in which the dimensions of the cell are larger and are easier to observe at a comparable magnification. The photomicrograph also shows the presence of a large amount of resin covering the basic cell structure.

Examples 244 to 255 Examples 244 to 255 in Table X illustrate the formation of homogeneous, porous polymeric intermediates in the form of cylindrical blocks with a radius 45 of approximately 3.2 cm and a height of approximately 5.1 cm from methylpentene -Polymer («MPP») and the compatible liquids deemed useful, using the standard manufacturing process. Many of the exemplary intermediates were extracted to form the porous polymers as shown in the table. The details of the preparation and the nature of the functionally useful liquid noted are summarized in Table X:

Table X MPP

Example liquid type and liquid% liquid ° C type of function

No. (1) nelles liquid saturated aliphatic acid

244 ecanoic acid * 75 230

saturated alcohols

245 1-dodecanol * 75 230

29

649 565

Table X (continued)

MPP

Example No. (1)

Liquid type and liquid

% Liquid

Functional liquid type

246

247

248

249

250

251

2-undecanol * 6-undecanol *

Amines

Dodecylamine ester

Butyl benzoate * dihexyl sebacate *

Ether

Dibenzyl ether *

75 75

75

75 70

70

230 230

230

210 220

230

* The liquid was extracted from the solid.

(1) The methyl pentene polymer from Mitsui with the following properties was used: Density: 0.835 g / cm3 Melting point: 235 ° C Tear strength: 230.105 Pa Elongation at break: 30%

Rockwell hardness: R 85

Table X (continued) MPP

FA

L, P, PF L, P

PF

Example No.

Liquid type and liquid

% Liquid ° C

Functional liquid type

252

253

254

255

Hydrocarbons

1-hexadecene *

Naphthalene*

Various «EC-53» * «Phosclere P315» *

75 70

75 75

220 240

230 250

MR AO

* The liquid was extracted from the solid.

A photomicrograph of the porous polymer of Example 253 is illustrated in Figure 22. The photomicrograph at a magnification of 2400 shows the extremely flattened cell walls, as is comparable to the configuration observed in FIG. 14.

Examples 256 to 266 Examples 256 to 266 in Table XI illustrate the formation of the homogeneous, porous polymer intermediates in the form of cylindrical blocks with a radius 45 of approximately 3.2 cm and a height of approximately 1.3 cm from polystyrene ( “PS”) and the compatible fluids deemed useful, using standard manufacturing methods. All exemplary intermediates were extracted to form porous polymers. The details of the preparation and the type of the functionally useful liquid are summarized in Table XI.

Table XI

Example No. (1)

Liquid type and liquid

% Liquid

° C

Functional liquid type

256

"Firemaster T-13P"

70

250

FR

257

Hexabromobiphenyl

70

260

FR

258

"Phosclere P315C"

70

270

259

"Phosclere P576"

70

285

AO

260

Tribromo neopentyl alcohol

70

210

FR

261

"FR 2249" (2)

70

240

FR

262

"Fyrol CEF" (3)

70

250

FR

263

"Firemaster T33P" (4)

70

210

FR

264

"Fyrol FR 2" (5)

70

240

FR

649 565

30th

Table XI (continued)

Example liquid type and liquid% liquid ° C type of function

No. (1) bright liquid

265 dichlorobenzene 80 160 MR, FR

266 1-dodecanol 75. - -

(1) Monsanto Chemical Company's «Lustrex» polystyrene with the following physical properties was used:

Tensile strength: 525.10s Pa elongation: 2.5%

Modulus of elasticity (XID): 315.102 Pa deflection temperature (under stress): 93.3 ° C

2348.103 Pa Specific weight: 1.05 g / cm3 Rockwell hardness: M 75 Melt flow: 4.5 g / 10 min.

(2) Trademark of Dow Chemical Corporation for its fire retardant, which has the following composition: Tribromone neophenyl alcohol: 60%

Voranol CP 3000 polyol: 40%

Hydroxyl number: 130

Viscosity (25 ° C): about 1600.10 ~ 3 Pas density: 1.459 g / cm3

(3) Trademark of Stauffer Chemical Company for their tris-chloroethyl phosphate, fire retardant with the following properties:

Boiling point (at approx. 66.5 Pa): 145 ° C

(at approx. 100 Pa 102 decomposition): 146 ° C chlorine content: 36.7% by weight

Phosphorus content: 10.8% by weight

Refractive index (at 20 ° C): 1.4745 viscosity (22.8 ° C): 40 10 "3 Pas

(4) Trademark of Michigan Chemical Corporation for their tris (1,3-dichloroisopropyl phosphate fire retardant with the following properties:

Chlorine content, theoretical: 49.1%

Phosphorus content, theoretical: 7.2%

Boiling point (532 Pa): 200 ° C

(decomposes at 200 ° C)

Refractive index: 1.5019 viscosity (Brookfield, 22.8 ° C): 2120 10 ~ 3 Pas structure: [(ClCH2) 2CHO] 3 P-0

(5) Stauffer Chemical Company trademark for their tris (dichloropropyl) phosphate. Fire retardant with the following properties:

Melting point: about 27 ° C refractive index nd at 25 ° C: 1.5019 viscosity (Brookfield, 22.8 ° C): 2120 IO "3 Pa.s

A microphotograph of the microporous polymer of Example 260 is illustrated in FIG. 26. Although the cells are small compared to those in Figures 4, 7, 13, 18 and 25, the fundamental microcellular structure is present.

Example 267

This example illustrates the formation of a homogeneous, porous intermediate polymer from 30% high impact polystyrene (1) and 70% hexabromobiphenyl using the standard manufacturing process and heating the mixture to 280 ° C. The polymer intermediate thus formed was about 63.5 mm in diameter and about 12.7 mm in height. The hexabromobiphenyl is useful as a fire retardant and the porous intermediate is useful as a solid fire retardant additive.

Example 268

This example illustrates the formation of a homogeneous, porous intermediate polymer from 25% acrylonitrile-butadiene-styrene terpolymer (2) and 75% diphenylamine using the standard preparation procedure and heating the mixture to 220 ° C. The polymer intermediate thus formed was about 63.5 mm in

45 diameters and about 50.8 mm in height. The microporous polymer was formed by extracting the diphenylamine. The diphenylamine is useful as a pesticide and antioxidant and the porous polymeric intermediate has the same utility.

see (1) Union Carbide Company's Bakelite polystyrene for injection molding with the following properties was used:

Breaking strength (thickness: 3.2 mm): 5000 35 • 106 Pa final elongation (thickness: 3.2 mm: 175 • 103 Pa

55 modulus of elasticity (thickness: 3.2 mm: 2760 ■ 10® Pa

Rockwell hardness

(6.3 mm x 12.7 mm x 127 mm: 90

natural specific weight: 1.04 g / cm3

(2) Kralastic ABS polymer from Uniroyl with the following 6o properties was used:

Specific weight: 1.07 g / cm3

Tensile strength: 616 • 10s Pa

Rockwell hardness: R 118

65 Examples 269 and 270

The homogeneous, porous polymer intermediates were made from 25% chlorinated polyethylene thermoplastic supplied by Dow, a melt viscosity

31

649 565

of 15 IO-3 Pas and 8% crystallinity and contained 36% chlorine and 75% N, N-bis (2-hydroxyethyl) tallow amine (Example 270) or 75% chlorinated polyethylene thermoplastics and 25% 1-dodecanol (Example 271), using the standard manufacturing process and heating to 220 ° C. The porous polymer intermediates were about 6.35 cm in diameter and about 5.08 cm in height.

Example 271

The homogeneous, porous intermediate polymer was formed using the standard manufacturing process and heated to 210 ° C, and made from 25% chlorinated polyethylene elastomer as used in Example 271 and 75% diphenyl ether. The porous polymer intermediates were about 6.35 cm in diameter and about 5.08 cm in height. The diphenyl ether is useful as a perfume and the intermediate can also be used in perfumes.

Examples 272 to 275 Examples 272 to 275 in Table XII illustrate the formation of homogeneous, porous polymer intermediates in the form of cylindrical blocks with a 5 radius of about 31.75 mm and a height of about 12.7 mm from styrene -Butadiene («SBR») - rubber (1) and the compatible liquids found useful, using the standard manufacturing process. In addition to the cylindrical blocks 10 already specified, thin films were also formed.

The details of the preparation and the type of the functionally useful liquid listed are summarized in Table XII.

(1) Shell Chemical Com-i5 pany's Kraton SBR polymer with the following properties was used: Tensile strength: 3100-4600 psi 217 • 105 Pa-332 • 105 Pa Elongation at break: 880-1300

Rockwell hardness: Shore A, 35-70.

Table XII SBR

Example No.

Liquid type and liquid

% Liquid

Type of functional thin liquid film

272

273

274

275

N, N-bis (2-hydroxyethyl) tallow amine

Decanol *

Diphenylamine

Diphenyl ether

80 70 70 70

195 190

200-210 195

PF

PE, AO PF

yes yes yes yes

* The solid was extracted from the liquid.

Examples 276 to 278 Examples 277 to 279 in Table XIII illustrate the formation of the homogeneous, porous polymer intermediates in the form of cylindrical blocks with a radius of 31.75 mm and a height of 12.7 mm from "Surlyn" ( 1) and the compatible liquids considered appropriate, using the standard manufacturing process. In addition to the cylindrical blocks indicated, films were also made. Two of the exemplary intermediates were extracted to form porous polymers, as shown in the table.

35 The details of the preparation and the type of the functionally useful liquid indicated are summarized in Table XIII:

(1) "Surlyn" ionomeric resin 1652, delivery number 115478 from E.I. du Pont de Nemour with the following properties was used:

Density: 0.939 g / cm3

Melt flow index: 4.4 decigm / min.

Tensile strength: 1995 • 104 Pa

Yield strength: 1309 • 104 Pa

45 elongation: 580%

Table XIII Surlyn

Example liquid type and liquid% liquid ° C type of function-thinner

No nellen liquid film

276

N, N-bis (2-hydroxyethyl) tallow amine

70

190

_

Yes

195

277 *

Diphenyl ether *

70

200

PF

Yes

278

Dibutyl phthalate

70

195

L

Yes

* The solid was extracted from the liquid.

The photomicrographs of the porous polymer of Example 277 are illustrated in Figures 23 and 24. 23 shows the macrostructure of the polymer at a magnification of 255 times. FIG. 24 illustrates the microcellular structure of the polymer with a slight “foliage” at a magnification of 2550 times and, compared to, for example, FIG. 25, relatively thick cell walls.

Example 279

The homogeneous, porous polymer intermediate was made from a mixture containing equal proportions high density polyethylene 65 and chlorinated polyethylene and 75% 1-dodecanol using the standard manufacturing process and heating to 200 ° C. The porous polymer intermediate was

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32

cast a film with a thickness of about 0.51 to 0.64 mm. The HDPE and CPE were used in the previous examples.

Example 280

The homogeneous, porous, polymeric intermediate was made from a mixture containing equal proportions high density polyethylene and polyvinyl chloride and 75% 1-dodecanol using the standard manufacturing process and heating to 200 ° C. The intermediate product thus formed was about 5.1 cm in height and about 6.4 cm in diameter. The HDPE and PVC were used as in the previous examples.

Example 281

The homogeneous, porous polymer intermediate was made from a terpolymer blend containing equal proportions of high density polyethylene, acrylonitrile, butadiene and styrene, and 75% 1-dodecanol using the standard manufacturing process Heated up to 200 ° C. The intermediate product thus formed was about 5.1 cm in height and about 6.4 cm in diameter. The HDPE and ABS were used as in the previous example.

5

Examples 282 to 285 Examples 282 to 285 in Table XIV illustrate the formation of the homogeneous, porous polymer intermediates in the form of cylindrical blocks with a radius io of 31.75 mm and a height of about 50.8 mm from a mixture, which contained equal proportions of low density polyethylene and chlorinated polyethylene and the compatible fluids believed useful, using the standard manufacturing process. In example 283 the above-mentioned method was used, whereas the intermediate product was cast into a film with a thickness of approximately 0.51 to 0.64 mm. The LDPE and CPE were used in the previous examples. The details of the preparation and the type of the functionally useful liquid listed are summarized in Table XIV:

Table XIV

Example No.

Liquid type and liquid

% Liquid

Functional liquid type

282

283

284

285

1-dodecanol 75

Diphenyl ether 75

Diphenyl ether 50

N, N-bis (2-hydroxyethyl) tallow amine 75

200 200 200 200

PF PF

Examples 286 and 287 The homogeneous, porous polymer intermediates were prepared from a mixture which contained equal amounts of low-density polyethylene and polypropylene, and 75% N, N-bis (2-hydroxyethyl) tallow amine (Example 286) and a mixture, which contained equal amounts of low density polyethylene and polypropylene, and 50% N, N-bis (2-hydroxyethyl) tallow amine (Example 287), using the standard manufacturing process and using Example 286 at 220 ° C and Example 288 heated to 270 ° C. Both porous polymer intermediates were approximately 6.4 cm in diameter and 5.1 cm in height. The LDPE and PP were used as in the examples above.

Examples 290 to 300 35 Examples 290 to 300 illustrate the polymer / compatible liquid concentration range suitable for forming a homogeneous, porous polymer intermediate product from high-density polyethylene and N, N-bis (2-hydroxyethyl) tallow amine. In each example, the 40 intermediates were approximately 5.1 cm in height and approximately 6.35 cm in diameter. The HDPE were used as in the previous examples.

The details of the production and the physical properties are summarized in Table XV:

45

Example 288

The homogeneous, porous polymer intermediate was made from 50% N, N-bis (2-hydroxyethyl) tallow amine and 50% of a polypropylene / polystyrene blend (25 parts polypropylene) using the standard manufacturing process and at 200 ° C warmed. The porous polymer intermediates were about 6.35 cm in diameter and about 5.1 cm in height. The PP and PS were used in the examples above.

Table XV

50.

Example No.

% Liquid

Remarks

290 95 275 very weak, no firm

55 wholeness; not editable,

291 90 - very greasy; Leaching the

Liquid; upper liquid limit was exceeded,

Example 289

6o 292

80

250

greasy

The homogeneous, porous polymer intermediate was

293

75

220

greasy from 75% 1-dodecanol and a mixture that is too smooth

294

70

250

hard solids content of polypropylene and chlorinated polyethylene

295

65

220

-

held, manufactured using the standard manufacturing process

296

60

250

hard solid was used and heated to 200 ° C. The porous

65 297

55

220

-

Polymer intermediate was approximately 6.35 cm in diameter

298

50

240-260 hard solid water and about 1.27 cm in height. The PP and CPE were

299

40

260

hard solid as used in the examples above.

300

30th

200

hard solid

33

649565

A photomicrograph of the porous polymer of Example 300 is illustrated in Fig. 19 at 2000X magnification. At this enlargement, the cells are not clearly visible. FIG. 19 can be compared to FIG. 17 at a magnification of 2475, in which the cell sizes are also very small with a similar polymer concentration of 70%.

Examples 301 to 311 These examples illustrate the polymer / compatible liquid concentration range useful for forming a homogeneous, porous intermediate polymer from low density polyethylene and N, N-bis (2-hydroxyethyl) tallow amine. In each example, the intermediate was approximately 1.27 cm in height and approximately 6.35 cm in diameter. The LDPE was used as in the example above.

The details of manufacture and the physical properties are given in Table XVI:

Table XVI

Table XVII

example

% Liquid

° C

Remarks

No.

speed

301

95

275

very greasy; not quite firm; not editable,

302

90

240

very greasy; Leaching of the liquid; upper liquid limit exceeded,

303

80

260

hard solid

304

75

210

hard solid

305

70

210

hard solid

306

66

200

hard solid

307

60

280

hard solid

308

50

280-290

hard solid

309

40

285

hard solid

310

30th

285

hard solid

311

20th

280-300 hard solid

Example% liquid ° C no

Remarks

312

313

314

315

316

90 80

75 70 60

185

very greasy; not quite firm; not editable,

very greasy; close to the upper fluid limit, but still workable,

wet; strong 190-200 slightly greasy 200 hard solid

185

200

Examples 317 to 322 Examples 317 to 322 illustrate the polymer / compatible liquid concentration range suitable for producing a homogeneous, porous polymer intermediate product from low-density polyethylene and 1-hexadecene. In each example, the intermediate was approximately 5.1 cm in height and approximately 6.35 cm in diameter. The LDPE was used as in the previous examples.

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

Table XVIII

25th

30th

35

40

Example% liquid ° C

Remarks

No.

speed

317

90

180

good strength

318

80

180

low strength, processing

bar

319

75

200

low strength, processing

bar

320

70

177

-

321

50

180

good strength

The photomicrographs of the porous polymers of Examples 303, 307 and 310 are in Figures 14-15 (at 250x and 2500x magnification), 16 (at 2500x magnification) and 17 (at 2475x magnification) ) illustrated. The figures show the decreasing cell size with increasing polymer content, from very large (Fig. 15.20% polymer) to very small (Fig. 17, 70% polymer). The relatively flattened cell walls of 20% polymer, Example 303, are similar to those of the methylpentene polymer (Fig. 22); they can be seen in Fig. 14. Fig. 15 is an enlargement showing part of a wall illustrated in Fig. 14. The microcellular structure of the porous polymer can be seen in FIG. 16.

Examples 312 to 316 Examples 312 to 316 illustrate the polymer / compatible liquid concentration range useful for forming a homogeneous, porous intermediate polymer from low density polyethylene and diphenyl ether. In each example, the intermediate was approximately 1.27 cm in height and approximately 6.35 cm in diameter. The LDPE was used as in the examples above.

The details of the preparation and the physical properties are summarized in Table XVII:

Examples 322 to 334 These examples illustrate the polymer / liquid concentration range which is suitable for forming a homogeneous, porous, polymeric intermediate product from polypropylene and N, N-bis (2-hydroxyethyl) tallow amine. In each example, the intermediate was approximately 1.27 cm in height and 6.35 cm in diameter. In addition, films were made as indicated. The PP was used as in the examples above.

The details of manufacture and the physical properties are given in Table XIX:

Table XIX

example

% Liquid

° C

Comments thinner

55 no.

speed

Movie

322

90

200

all wet yes

323

85

200

-

-

324

80

200

strong yes

60 325

75

180

dry and hard yes

326

70

200

-

Yes

327

65

210

-

328

60

210

-

Yes

329

50

200

-

Yes

65 3 30

40

210

-

Yes

331

36.8

175

white-crystalline

332

25th

180

-

-

333

20th

180

-

Yes

649565

34

The microphotographs of Examples 322, 326, 328, 330 and 333 are illustrated in FIGS. 6 to 10 or at 1325-fold, 1550-fold, 16'20-fold, 1450-fold and 1250-fold magnification. The extreme foliage of the microporous polymer of 10% polymer is shown in Fig. 6, furthermore the microcellular structure is still preserved. These figures explain the decrease in cell size,

if the amount of polymer is increased. However, regardless of the small cell size, the microcellular structure is present in every example.

Examples 335 to 337 These examples illustrate the polymer / compatible liquid concentration range useful for forming a homogeneous, porous intermediate polymer product from polypropylene and diphenyl ether. In each example, the intermediate was approximately 1.27 cm in height and approximately 6.35 cm in diameter. In addition, as indicated, thin films were also made. The PP was used in the examples above.

The details of the manufacture and the physical properties are given in Table XX:

Table XX

Example No.% liquid

Thin film

335

336

337

90 80 70

200 200 200

Yes Yes Yes

Table XXI

Example No.

% Liquid

Remarks

338 90 200 weak, below the upper fluid limit yes

Example% liquid no. speed

° C

Remarks thin film s 343 50 not found to be rubbery

344 40 not found to be rubbery

345 30 not found to be rubbery

346 20 not found

10th

rubbery yes yes yes yes

The photomicrographs of the porous polymer of Examples 335, 336 and 337 are illustrated in Figures 11 (2000X magnification) 12 (2059X magnification) and 13 (1950X magnification). The figures impressively show that as the concentration of polymer increases, the pore size becomes smaller. Figure 11 illustrates the smooth cell walls, while Figures 12 and 13 show the cells and interconnecting pores. The microcellular structure is present in each of the figures.

Examples 338 to 346 These examples illustrate the polymer / compatible liquid concentration range suitable for forming a homogeneous, porous polymer intermediate product from styrene / butadiene rubber and N, N-bis (2-hydroxyethyl) tallow amine. In each example, the intermediate was approximately 1.27 cm in height and 6.35 cm in diameter. In addition, thin films were made as indicated. The SBR was used as in the previous examples.

The details of the manufacture and the physical properties are given in Table XXI:

The microphotographs of the microporous styrene / butadiene rubber polymer of Examples 339 and 340 are illustrated in Figures 20 (2550 magnifications) and 21 (2575 magnifications). The figures show the microcellular structure of the microporous polymer. 21 also shows the presence of spherical polymer deposits on the cell walls.

25th

Examples 347 to 352 Examples 347 to 352 illustrate the range of polymer / compatible liquid concentration which is expedient for the formation of a homogeneous, porous polymer intermediate product from styrene / butadiene rubber and decanol. In each example, the intermediate was approximately 1.27 cm in height and 6.35 cm in diameter. In addition, thin films were made as indicated. The SBR was used in the previous examples. 35 The details of manufacture and the physical characteristics are given in Table XXII:

Table XXII

Example% liquid no. speed

Remarks thin film

347

45

348

349 to 350

351

352

90

80 70 60 50 40

none below the above liquid limit; not editable rubbery yes rubbery yes rubbery yes rubbery yes rubbery yes

190

190

190

190

no

specification

55

Examples 353 to 356 Examples 353 to 356 relate to styrene / butadiene rubber and diphenylamine (see Table XXII).

thin film

60

Table XXIII

Example No.% liquid

Remarks

339

80

195

rubbery yes it 353

80

no information

340

75

195

rubbery yes

354

70

200-210

341

70

195

rubbery yes

355

60

215

342

60

200

rubbery yes

356

50

200-210

Examples 357 to 361 Examples 357 to 361 illustrate that useful for forming a homogeneous, porous polymer intermediate from a "Surlyn" resin (as used in the previous examples) and N, N-bis (2-hydroxyethyl) tallow amine Polymer / compatible liquid concentration range. In each example, the intermediate was approximately 1.27 cm in height and 6.35 cm in diameter. In addition, thin films were made as indicated.

The details of manufacture and the physical characteristics are summarized in Table XXIV:

Table XXIV

Example No.% liquid ° C Thin films

357 70 190-195 yes

358 60 190 yes

359 50 no answer yes

360 40 no answer yes

361 30 no answer yes

Examples 363 to 370 These examples illustrate the polymer / compatible liquid concentration range suitable for forming a homogeneous, porous intermediate polymer from a "Surlyn" resin (as used in the previous examples) and diphenyl ether. In each example, the height of the intermediate was approximately 1.27 cm and the diameter was approximately 6.35 cm. In addition, thin films were made as indicated.

The details of manufacture and the physical characteristics are summarized in Table XXV:

Table XXV

Example No.% liquid ° C Thin films

362 90 207 yes

363 80 190 yes

364 70 200 yes

365 60 185 yes

366 50 no answer yes

367 40 not specified -

368 30 not specified -

369 20 not specified -

370 10 not specified -

Examples 371 to 379 Examples 371 to 379 illustrate the polymer / compatible liquid concentration range suitable for forming a homogeneous, porous polymer intermediate from a "Surlyn" resin (as used in the previous examples) and dibutyl phthalate. In each example, the height of the intermediate was approximately 1.27 cm and the diameter was approximately 6.35 cm.

The details of the production and the physical characteristics are summarized in Table XXVI:

35 649 565

Table XXVI

Example No.% liquid ° C Remarks s 371 90 220

372 80 208

373 70 195

374 60 200

375 50 200

io 376 40 not specified -

377 30 not specified -

378 20 not specified -

379 10 not specified -

15 Comparative Examples According to the Prior Art 1-5 Examples 1 to 5 Examples 1 to 5 are reproductions of various compositions according to the prior art, in which the difference in the physical structure is shown in contrast to the structure according to the invention should.

Comparative Example 1 A porous polymer was prepared in accordance with the procedure of Example 1 of U.S. Patent No. 3,378,507, which was modified to provide a product with some physical integrity and soap instead of water-soluble anionic detergents Sodium bis (2-ethylhexyl) sulfosuccinate used. 30 In a "Brabender Plasti-Corder" internally heated mixer, 33.5 parts by weight of polyethylene from Exxon Chemical Corporation type LD 606 and 662/3 parts of ivory soap flakes were mixed at a machine temperature of about 177 ° C. until a homogeneous mixture was obtained . The material was then compression molded with a rubber type with a cavity of 6.35 cm x 12.7 cm and a height of 0.51 mm at a temperature of about 177 ° C and a pressure of 2520 kg / cm2 . The resulting sample was then continuously washed in a slow flowing stream of tap water for about 3 to 40 days and then washed by immersing in 8 baths of distilled water for about 1 hour each. The resulting sample still contained some soap and showed poor processing properties.

47 and 48 are microphotographs of the product from comparative example 1 at a magnification of 195 and 2000 times, respectively. It can be seen that the product is a relatively non-uniform polymeric structure, which has neither clear cellular voids nor connecting pores.

Comparative Example 2 A porous polymer was made in accordance with 55 the procedure of Example 2, Sample D of U.S. Patent No. 3,378,507, which was modified to provide a sample with some working strength.

In an internally heated “Brabender Plasti-Corder” mixer, 75 parts of ivory-white soap flakes and 60 25 parts of Exxon Chemical Corporation's type LD 606 polyethylene were mixed at a machine temperature of about 177 ° C. and a sample temperature of about 166 ° C., until a homogeneous mixture was formed. The material was then injection molded in an one ounce Watson-Stillman 65 injection molding machine with a die diameter of 5.1 cm and a depth of 0.51 mm. The resulting sample was then run continuously for about 3 days in a slow flowing stream of tubing

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36

washed water and then washed by immersing in 8 baths of distilled water for about an hour each. The resulting sample still returns some soap.

46 and 46 are microphotographs of the product of Comparative Example 2 at a magnification of 240 and 2400 times, respectively. The product of this example does not have the typical cellular structure according to the invention, as can be seen from the microphotographs.

Comparative Example 3 A porous polymer was made in accordance with the procedure of Example 3, Sample A of U.S. Patent No. 3,378,507.

In an internally heated “Brabender Plasti-Corder” mixer, 25 parts of Novamont Corporation's type F300 8N19 polypropylene and 75 parts of ivory soap flakes were mixed at a machine temperature of about 166 ° C. until a homogeneous mixture was formed. The material was then compression molded with a rubber type mold. The resulting sample was found to be of very low strength. A portion of the resulting sample was continuously washed in a slow flowing stream of tap water for about 3 days and then washed by immersing in 8 baths of distilled water for approximately one hour each. The washed product showed extremely low treatment characteristics.

FIGS. 51 and 52 are photomicrographs of the product from comparative example 3 at a magnification of 206 and 2000 times, respectively. The microphotographs show that the product has no cellular structure according to the invention.

Comparative Example 4 The procedure of Example 3, Sample A of U.S. Patent No. 3,378,507 was modified to produce a product with improved treatment strength.

On an open, two-roll rubber mill manufactured by Bölling Company, 25 parts of Novamont Corporation, type F300 8N19 polypropylene and 75 parts of ivory white soap flakes were mixed for about 10 minutes at a temperature of about 177 ° C until a homogeneous mixture was obtained . The material was then injection molded using an one ounce Watson-Stillman injection molding machine with a die diameter of approximately 5.1 cm and a height of approximately 0.51 mm. The resulting sample was continuously washed in a slow flowing stream of tap water for about 3 days and then washed by immersing in 8 baths of distilled water for about one hour each. The resulting sample still retained some soap. The resulting product was found to be stronger than the product of Example 382.

49 and 50 are microphotographs of the product of Comparative Example 4 at a magnification of 195 and 2000, respectively. The irregular shapes shown by the microphotographs can easily be distinguished from the structure according to the invention.

Comparative Example 5 A porous polymer was made in accordance with II of U.S. Patent No. 3,310,505, which was modified to provide more homogeneous mixing of the materials.

40 parts of Exxon Chemical's polyethylene were placed in an internally heated Brabender Plasti-Corder mixer

Corporation, type Ld 606 and 60 parts of polymethyl methacrylate from Rohm and Haas Corporation, were mixed for about 10 minutes at a machine temperature of about 177 ° C. until a homogeneous mixture was obtained. The material was then reduced to plates on a cold mill and then press molded using a heated 10.2 cm circular mold with a depth of 0.51 mm and 30 tons of pressure for about 10 minutes. The resulting composition was then extracted with acetone in a large Soxlet extractor for 48 hours.

FIGS. 53 and 54 are microphotographs of the product from comparative example 384 at a magnification of 205 and 2000 times, respectively. The 15 non-uniform structure shown by the microphotographs can easily be distinguished from the uniform structure according to the invention.

20 Physical Characterization of the Products of Examples 225 and 358 In order to obtain a quantitative understanding of the homogeneous structure according to the invention, certain samples of the microporous material and certain samples according to the prior art were analyzed on an “Aminco” mercury-penetrating porosimeter. Figures 30 and 31 are mercury penetration curves of the 1.27 cm block of Example 225 made from 25% polypropylene and 75% N, N-bis (2-hydroxyethyl) tallow amine; Fig. 32 30 is a mercury penetration curve of the 15.2 cm block of Example 225. All mercury penetration curves are shown on a semi-logarithmic plot, with the equivalent pore sizes shown on the abscissa of the logarithmic scale. 30 to 32 show the 35 typical narrow pore size distribution in the composition according to the invention. The 1.27 cm sample of Example 225 was determined to have a pore volume of about 76% and an average pore size of about 0.5 microns; the 15.2 cm block had a 40 pore volume of approximately 72% and an average pore size of approximately 0.6 microns.

Figure 33 is a mercury penetration curve of the product of Example 358 made from 40% polypropylene and 60% N, N-bis (2-hydroxyethyl) tallow amine. Fig. 33 45 shows that the sample has the typical narrow pore size distribution. A pore volume of approximately 60% and an average pore size of approximately 0.15 micrometers were determined for the sample.

It is easy to see that the compositions according to the invention have such pore size distributions that at least 80% of the pores present in the composition fall within no more than one group of ten on the abscissa of the mercury penetration curve. The pore size distribution of the composition can therefore be characterized as “narrow”.

Physical Characterization of Commercial Compositions According to the Prior Art 60 Comparative Example 6

The composition of this sample is commercially available microporous polypropylene, Celgard 3501, manufactured by Celanese. Figure 34 is a mercury penetration curve of the sample showing a wide population of pores in the 70 to 0.3 micron range. The sample was determined to have a pore volume of about 35% and an average pore size of about 0.51 microns.

Comparative Example 7 The composition of this example is commercially available microporous polyvinyl chloride A-20 manufactured by Amerace. Figure 35 is a mercury penetration curve of the sample and shows a very wide pore size distribution. An empty space of approximately 75% and an average pore size of approximately 0.16 micrometers were determined in this sample.

Comparative Example 8 The composition of this sample is commercially available microporous polyvinyl chloride A-30 manufactured by Amerace. Figure 36 is a mercury penetration curve from this sample; it shows a very wide pore size distribution. A pore volume of approximately 80% and an average pore size of approximately 0.2 micrometers were determined in this sample.

Comparative Example 9 The composition of this sample is commercially available, microporous polypropylene “Porex”. Fig. 37 is a mercury penetration curve of the sample, showing a very wide distribution of extremely small cells as well as a distribution of very large cells. A pore volume of approximately 12% and an average pore size of approximately 1 micrometer were determined in this sample.

Comparative Example 10 The composition of this sample is commercially available, microporous polyvinyl chloride “Millipore BDWP 29300”. Figure 38 is a mercury penetration curve of the sample, showing a relatively narrow distribution in the range of 0.5 to 2 microns, as well as a number of cells less than about 0.5 microns. A pore volume of approximately 72% and an average pore size of 1.5 micrometers were determined in this sample.

Comparative Example 11 The composition of this sample is a commercially available microporous cellulose triacetate “Metricel TCM-200” from Gelman. Figure 39 is a mercury penetration curve of the sample showing a wide pore size distribution up to about 0.1 micron. A pore volume of approximately 82% and an average pore size of approximately 0.2 micrometers were determined in this sample.

Comparative Example 12 The composition of this sample is a commercially available, microporous acrylonitrile-polyvinyl chloride copolymer “Acropor WA” from Gelman. Fig. 40 is a mercury penetration curve of the sample, which shows a wide pore size distribution. An empty volume of approximately 64% and an average pore size of approximately 1.5 micrometers were determined in this sample.

Physical characterization of comparative examples 1 to 5 according to the prior art The products of comparative examples 1 to 5 according to the prior art were also analyzed by the penetration of mercury. Figures 41-43 are mercury penetration curves showing the wide pore size distribution of the products from Comparative Examples 2,1 and 4, respectively. Figure 44 is a mercury penetration curve for the product of Comparative Example 5, showing a population of pores in the range of 45 to 80 microns as well as a number of extremely small pores. With the products

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of comparative examples 1, 2, 4 and 5, pore volumes of about 54.46, 54 and 29%, and average pore sizes of about 0.8, 1.1, 0.56 and 70 micrometers were determined.

Examples 381 to 388 These examples illustrate the polymer / compatible liquid concentration range suitable for forming the homogeneous, porous polymer intermediates from methyl methacrylate and 1,4-butanediol using the standard manufacturing process. In each example, the height of the intermediate formed was about 1.27 cm and the diameter was about 6.35 cm. The poly-methyl methacrylate was supplied by Rohm and Haas under the designation “Plexiglas-acrylic plastic press powder”, production number 386 491. The details of the preparation are given in Table XXVII:

Table XXVII

Example No.

% Liquid

Temperature ° C

381

90

215

382

85

225

383

80

225

384

70

210

385

60

229

386

50

230

387

40

229

388

30th

225

The 1,4-butanediol was removed from the product of Example 384 and the resulting structure was determined to be the cellular structure of the present invention as seen in Fig. 61 which shows the microporous product at 5000X magnification. The same polymer / liquid system as that of Example 383 was also run at speeds up to 4000 ° C / min. cooled and still produced the desired cell structure.

Example 389

The porous polymer intermediate was prepared using the standard manufacturing process and heating 30% polymethyl methacrylate as used in the previous examples and 70% 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 according to the invention.

Example 390

The porous polymer intermediate was prepared using the standard manufacturing process and heating 30% Nylon 11 supplied by Aldrich Chemical Company and 70% ethylene carbonate to a temperature of 218 ° C and then the resulting solution to form the porous polymer Intermediate cooled. The ethylene carbonate was removed from the intermediate and the resulting microporous polymer was determined to have the desired cell structure.

Example 391

The porous polymer intermediate was prepared using the standard manufacturing process and using 30% Nylon 11 as in the previous examples37

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

649 565

38

sets, and heated 70% 1,2-propylene carbonate to a temperature of 215 ° C and then cooled the resulting solution to form the porous polymer intermediate. The propylene carbonate was removed from the intermediate and the resulting microporous polymer was found to have the desired cell structure.

Example 392

Examples 391-411 demonstrate the formation of the polymer / liquid system porous polymer intermediates, which included various amounts of nylon 11 as used in the previous examples and tetramethylene sulfone supplied by Shell under the designation "Sulfon W" and approximately Contained 2.5% water. The various concentrations were cooled at different rates and from different solution temperatures, as indicated in Table XXVIII, which also demonstrates that increased cooling rates and increased polymer concentration generally result in a decrease in the resulting cell sizes.

Table XXVIII

example

% Liquid

T ° C

Cooling area

Cell size

No.

speed

speed ° C / min.

(Micrometer)

392

90

195

20th

10th

393

80

198

5

15

394

80

198

20th

14

395

80

198

40

9

396

80

198

80

5.5

397

70

200

5

11

398

70

200

20th

5

399

70

200

40

6.5

400

70

200

80

6.5

401

60

205

5

5.0

402

60

205

20th

4.5

403

60

205

40

4th

404

60

205

80

3.5

405

50

210

20th

3rd

406

50

210

40

1.5

407

50

210

80

2nd

408

60

212

20th

-

409

70

215

20th

-

410

80

217

20th

-

411

90

220

20th

-

The previous Table XXVIII also demonstrates that at concentrations of 40% to 10% liquid there is no visible porosity for the at 20 ° C / min. cooled system results. Such results are fully predicted, as can be seen with reference to Fig. 62, which shows the melting curve for the nylon 11 / tetramethylene sulfone concentration range, as well as the crystallization curves at various cooling rates. It can be seen from Fig. 62 that at a cooling rate of 20 ° C / min. the 40% liquid containing system does not fall within the substantially flat portion of the crystallization curve and the formation of the desired microporous structure cannot be expected. Fig. 63 is a 2000x photomicrograph of Example 398 showing the typical cell structure of Examples 392-407.

Example 412

The porous polymer intermediate was prepared using the standard manufacturing process and heating 30% polycarbonate, supplied by General Electric s under the name "Lexan", and 70% menthol to a temperature of 206 ° C to form the porous Intermediate polymer cooled. The menthol was extracted and resulted in a microporous cell structure, as shown in Fig. 64, which is a microphotograph of the product of this example at a magnification of 2000 times.

Example 413

This example demonstrates the formation of the microporous cell structure of the invention from poly-2,6-dimethyl-1,4-phenylene oxide supplied by Scientific Polymer Products, usually relating to polyphenylene. The homogeneous, microporous intermediate polymer was prepared from 30% of the polyphenylene oxide mentioned and 70% N, N-bis (2-hydro-20 xyethyl) tallow amine, which were heated to a solution temperature of 275 ° C .; the intermediate product was created using the standard manufacturing process. The liquid was removed from the intermediate product and the result was the cellular structure according to the invention, as can be seen from FIG. 65, which is a photomicrograph of the product of this example magnified 2000 times.

30 Example 414

This example demonstrates the formation of a non-cellular product by cooling a homogeneous solution of 40% polypropylene as used in the previous examples and 60% dibutyl phthalate was pressed onto a chilled cast tape at a thickness of about 3.54 mm; the cooling rate was over 2400 ° C / min. A portion of Di-spersol was placed on the surface of the tape at a time before the solution was pressed. The liquid was removed from the resulting film and 40 a non-cellular, microporous product was formed, as can be seen from Fig. 65, which is a microphotograph of the product of this example at 2000X magnification.

45 Example 415

This example demonstrates the formation of a non-cellular product by cooling a homogeneous solution of 25% polypropylene as used in the above examples and 75% N, N-bis (2-hydroxyethyl) tallow amine in the same manner as in example 425. The liquid was removed from the resulting film and a non-cellular, microporous product was formed, as can be seen in Fig. 67, which is a microphotograph of the product of this example at 2000X magnification.

The products of Examples 414 and 415 were analyzed by mercury penetration porosimetry and their corresponding penetration curves, as shown in FIGS. 68 and 69. It is obvious that both products 6o generally have narrow pore size distributions, whereas the product of example 415 shows a much narrower distribution than the product of example 414. Thus the product of example 414 has a calculated S-value of 24.4 while the product of Example 415 has a calculated S value of only 8.8. However, the average pore size of Example 414 is very small, 0.096 microns, while the average pore size of the product of Example 415 is 0.589.

39

649 565

To illustrate the uniqueness of the cellular compositions of the invention, a number of such microporous products have been obtained in accordance with the standard manufacturing process; the related details for Examples 416 through 446 are summarized in Table XXIX. The products of the examples mentioned were analyzed by the mercury penetration porosity in order to determine their particular average pore diameter and the S values and to determine the average cell size S by scanning electron microscopy. The result of such analyzes is shown in Table XXX.

Table XXIX

Example No.

polymer

liquid

% Pores

Solution temperature ° C

416

Polypropylene

N, N-bis (2-hydroxylethyl) tallow

75

180

417

Polypropylene amm

N, N-bis (2-hydroxylethyl) tallow

60

210

418

Polypropylene amm

Diphenyl ether

90

200

419

Polypropylene

Diphenyl ether

80

200

420

Polypropylene

Diphenyl ether

70

200

421

Polypropylene

1,8-diaminooctane

70

180

422

Polypropylene

Phenyl salicylate

70

240

423

Polypropylene

4-bromodiphenyl ether

70

200

424

Polypropylene

T etrabromethane

90

180

425

Polypropylene

N-octyldiethanolamine

75

-

426

Polypropylene

N-hexyldiethanolamine

75

260

427

Polypropylene

Salicylaldehyde

70

185

428

Lower polyethylene

Hexanoic acid

70

190

density

429

Lower polyethylene

1-octanol

70

178

density

430

Lower polyethylene

Dibutyl sebacate

70

238

density

431

Lower polyethylene

Phosclere EC-53

70

191

density

432

Lower polyethylene

Dicapryl adipate

70

204

density

433

Lower polyethylene

Diisooctyl phthalate

70

204

density

434

Lower polyethylene

Dibutyl phthalate

70

290

density

435

High density polyethylene

N, N-bis (2-hydroxyethyl) tallow

80

250

436

Polystyrene amine

1-dodecanol

75

220

437

Polystyrene

1,3-bis (4-piperdine) propane

70

186

438

Polystyrene

Diphenylamine

70

235

439

Polystyrene

N-hexyldiethanolamine

75

260

440

Polystyrene

Phosclere P315C

70

270

441

Polymethyl methacrylate

1,4-butanediol

70

-

442

Polymethyl methacrylate

1,4-butanediol

85

-

443

Surlyn

Diphenyl ether

70

185-207

444

Surlyn

Dibutyl phthalate

70

195

445

Noryl

N, N-bis (2-hydroxyethyl) tallow

75

250

446

Nylon 11

amm

Ethylene carbonate

70

_

Table XXX

Example No.

C.

P

C / P

S

log C / P

log S / C

416

5.0

0.520

9.6

2.86

0.982

-0.243

417

3.18

0.112

28.4

5.0

1.45

0.197

418

22.5

11.6

1.94

4.52

0.288

-0.697

419

6.49

0.285

22.8

27.1

1.36

0.621

420

6.72

0.136

49.4

7.01

1.69

0.0183

649 565 40

Table XXX (continued)

Example No.

C.

P

C / P

S

log C / P

log S / C

421

13.0

0.498

26.1

2.36

1.42

-0.741

422

13.8

0.272

50.7

4.29

1.71

-0.507

423

3.35

0.137

24.5

5.25

1.39

0.195

424

15.4

0.804

19.2

5.13

1.28

-0.477

425

16.6

0.850

19.5

2.52

1.29

-0.819

426

20.0

0.631

31.7

2.51

1.50

-0.901

427

7.9

0.105

75.2

3.22

1.88

-0.390

428

7.5

1.16

6.47

8.62

0.811

0.0604

429

6.8

1.00

6.8

3.53

0.833

0.285

430

5.85

0.636

9.20

6.07

0.964

0.0160

431

3.40

0.512

6.64

5.30

0.822

0.193

432

5.0

0.871

5.74

8.21

0.759

0.215

433

4.75

0.631

7.53

3.54

0.877

-0.128

434

7.8

1.18

6.61

3.82

0.820

-0.310

435

34.5

0.696

49.6

4.34

1.70

-0.900

436

28.2

1.88

15.0

3.40

1.18

-0.919

437

1.08

0.0737

14.7

2.87

1.17

0.424

438

6.65

0.631

10.5

63.5

1.02

0.980

439

7.4

0.164

45.1

3.74

1.65

-0.296

440

1.4

0.151

9.27

2.26

0.967

0.208

441

9.2

0.201

45.8

3.68

1.66

-0.398

442

114

10.3

11.1

5.19

1.05

-1.34

443

6.8

0.631

10.8

2.13

1.03

-0.504

444

5.6

0.769

7.28

2.09

0.862

-0.428

445

19.0

0.179

106

2.74

2.03

-0.841

446

5.8

0.372

15.6

7.56

1.19

0.112

Table XXXI Table XXXII

Comparative Example No.

State of the art

Type of polymer

35 Comparative Example No.

C.

S

log S / C

13

Celgard 3501

Polypropylene

17th

0.2 *

9.14

1.66

14

Amerace A-30

Polyvinyl chloride

18th

0.2 *

31.5

2.2

15

Porex

Polypropylene

40 19

0.8 *

2.94

0.565

16

Milipore EG

Cellulose derivatives

20th

0.22 *

1.64

0.872

17th

Metricel GA-8

Cellulose derivatives

21st

0.05 *

5.37

2.03

18th

Sartorius SM 12807

Polyvinyl chloride

22

2.10 **

61.8

1.79

19th

Millipore HAWP

Cellulose derivatives

23

0.02 *

5.08

2.40

20th

Millipore G5WP 04700

Cellulose derivatives

45 24

5 *

1.55

-0.509

21st

Millipore VMWP 04700

Cellulose derivatives

25th

0.04 *

5.64

2.15

22

Amicon 5UM05

Cellulose derivatives

26

1.1 **

11.5

1,019

23

Celgard 2400

Polypropylene

27th

0.8 **

17.5

1.34

24th

Millipore SMWP 04700

Polyvinyl chloride

28

0.56

16.8

1,477

25th

Celgard 2400

Polypropylene sun 29

70

1.34

-1.718

26

Product of comparison case

game 2

Polyethylene

* from the company's product information

27 Product of Comparative Example 1

28 Product of Comparative Example 4

29 Product of Comparative Example 5

Table XXXII

Polyethylene

Polypropylene

Polyethylene

Comparative example no.

log S / C

13

14

15

16

0.04 * 0.3 186 0.2 *

2.32 138 2.41 25.3

1.76 2.66 -1.89 1.85

** from the penetration of mercury

55

The data contained in Tables XXIX to XXXII are summarized in Fig. 70, in which log S / C is plotted against log C / P. It can be seen from FIG. 70 that the cellular structure according to the invention can be defined with log C / P values 60 from 0.2 to 2.4 and log S / C values from -1.4 to 1.0; very often the polymers mentioned will have log C / P values from 0.6 to 2.2 and log S / C values from -0.6 to 0.4.

As can be seen from the foregoing, the present invention provides a simple process for making microporous polymers of any synthetic thermoplastic polymer by widely varying the thicknesses and shapes. The microporous poly

41

649 565

mers can have a unique, microcellular configuration and are characterized in each case by the pore diameter with a relatively narrow size distribution. These structures are e.g. B. Made by first choosing a liquid that is compatible with a polymer, i.e. forms a homogeneous solution with the polymer and can be removed from the polymer after cooling, and then determines the amount of liquid and performs the cooling of the solution in a manner that ensures that the desired microporous polymer configuration will result.

It is also apparent that the present invention also produces microporous polymer products that contain relatively large amounts of functionally useful liquids, as well as a polymer additive, and behave like a solid. These products can advantageously be used in a variety of applications, for example in base mixtures.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

S

33 sheets of drawings

Claims (18)

649 565 2nd PATENT CLAIMS 1. Three-dimensional, microporous polymer cell structure, characterized in that it has a multiplicity of essentially spherical microcells which have an average diameter C of 0.5-100 micrometers and are distributed essentially uniformly over the structure, with neighboring cells being interconnected by pores whose diameter is smaller than that of the microcells, that the polymer cell structure has a pore size distribution which corresponds to a sharpness factor S of 1 to 30, the sharpness factor S being determined by analyzing a mercury intrusion curve and being defined as the ratio of the pressure, at which 85% of the mercury has penetrated, to the pressure at which 15% of the mercury has penetrated, that the decimal logarithm of the ratio of the mean cell diameter C to the mean pore diameter P has a value in the range of 0.2-2.4 and the decimal logarithm of the ratio of the sharpness factor S z has an average cell diameter C ranging from -1.4 to 1.0, that the pores and cells are empty, and that the polymer is a synthetic thermoplastic polymer of the class consisting of the homo- and copolymers of ethylenically unsaturated Monomers, the condensation polymers and the oxidation polymers, or a mixture of synthetic thermoplastic polymers belonging to this class. 2. Polymer cell structure according to claim 1, wherein the polymer is a low density polyethylene, a high density polyethylene, polypropylene, polystyrene, polyvinyl chloride, an acrylonitrile-butadiene-styrene terpolymer, a styrene-acrylonitrile copolymer, a styrene-butadiene copolymer, Po -ly (4-methyl-penten-l), polybutylene, polyvinylidene chloride, polyvinylbutyral, chlorinated polyethylene, an ethylene-vinyl acetate copolymer, polyvinyl acetate, polyvinyl alcohol, poly-methyl methacrylate, polymethylacrylate, an ethylene-acrylic acid copolymer or a Ethylene acrylic acid metal salt copolymer is. 3. The polymer cell structure of claim 1, wherein the polymer is a polyethylene terephthalate, polybutylene terephthalate, nylon 6, nylon 11, nylon 13, nylon 66, polycarbonate or polysulfone. 4. Polymer cell structure according to one of claims 1 to 3, wherein the ratio of C to P is 5: 1 to 40: 1. 5. Polymer cell structure according to one of claims 1 to 3, wherein C is in the range of 1 to 20 microns and P is in the range of 0.05 to 10 microns. 6. The polymer cell structure of claim 5, wherein P is in the range of 0.1 to 1.0 microns. 7. Polymer cell structure according to one of claims 1 to 6, wherein the S value is in the range from 2 to 20. 8. The polymer cell structure according to one of claims 1 to 3, wherein the decimal logarithm of the quotient C / P is in the range from 0.6 to 2.2 and the decimal logarithm of the quotient S / C is in the range from -0.6 to 0.4 . 9. Polymer cell structure according to one of claims 1 to 5, wherein P is in the range from 0.1 to 5 micrometers and S has a value in the range from 2 to 10. 10. Polymer cell structure according to one of claims 1 to 9, characterized in that it bears an essentially non-cellular skin. 11. Polymer cell structure according to claim 10, characterized in that the skin adjacent to it is essentially impermeable to the passage of liquids. 12. A method for producing a polymer cell structure according to claim 1, characterized in that one Mixture of one or more than one synthetic thermoplastic polymer from the class consisting of the homopolymers and copolymers of ethylenically unsaturated monomers, the condensation polymers and the oxidation polymers, and a compatible liquid for forming a homogeneous solution to a sufficient temperature above heated for a sufficient time, forming the homogeneous solution and cooling the shaped solution so that liquid-liquid phase separation occurs and essentially a large number of liquid droplets of essentially the same size in the continuous liquid polymer phase at the same time is formed, cooling continues to solidify the polymer, and substantially all of the liquid is removed from the solid body 15 formed so as to form the polymer cell structure. 13. The method of claim 12, wherein the mixture contains 10 to 90 percent by weight of the liquid. 14. The method of claim 12 or 13, wherein the homogeneous solution is poured onto a substrate on which 20 it takes the desired shape and is cooled, forming an essentially non-cellular skin on the surface in contact with the substrate. 15. The method of claim 14, wherein the skin that is formed is substantially impervious to fluid. 25th is. 16. The method according to claim 12 or 13, wherein the homogeneous solution is cast into a film and thereby cooled. 17. The method according to claim 12 or 13, wherein the ho-30 mogeneous solution is poured into a block and thereby cooled. 18. Three-dimensional, microporous polymer cell structure, the cells and pores of which are at least partially filled with an active substance liquid, characterized in that they 35 has a multiplicity of essentially spherical microcells which have an average diameter C of 0.5-100 micrometers and are distributed substantially uniformly over the structure, adjacent cells being connected to one another by pores whose diameter is smaller than 40 that of the microcells that the polymer cell structure has a pore size distribution which corresponds to a sharpness factor S of 1 to 30, the sharpness factor S being determined by analysis of a mercury intrusion curve and being defined as the ratio of the pressure 45 at which 85% of the mercury has penetrated, to the pressure at which 15% of the mercury has penetrated, the decimal logarithm of the ratio of the average cell diameter C to the average pore diameter P has a value in the range of 0.2-2.4 and the decadic logarithm of the ratio of the sharpness factor S for the mean cell diameter C a value in the range from -1.4 to 1.0 a Indicates that the pores and cells are at least partially filled with an active substance liquid, and that the polymer is a synthetic thermoplastic polymer from 55 of the class consisting of the homo- and copolymers of ethylenically unsaturated monomers, the condensation polymers and the oxidation polymers, or a mixture of synthetic thermoplastic polymers belonging to this class. 19. The polymer cell structure according to claim 18, characterized in that the active substance liquid is a lubricant, a surface-active agent, a lubricant, a pesticide, a plasticizer, a medicament, a fuel additive, a polishing agent, an insect repellent, a flame-65 protective agent, an antioxidant , an anti-fogging agent or a fragrance. 3rd 649 565