NZ250249A - Preparation of porous material by freezing a polymer dispersion which contains a liquid crystallisable dispersion medium such that phase inversion occurs followed by thawing - Google Patents

Description

Specification Filed: CQS^S.; /£*...£&Sw:!.:. 93> ... ;■.<?.% cmv:Sa\<?<f? . :»cjtion Pais: 2.?..J.U.L!S?5 JJLJIILBS.

I33t±., NO ?SlSS NEW ZEALAND PATENTS ACT, 1953 No.: Date: COMPLETE SPECIFICATION POROUS POLYMER MATERIAL AND PROCESS FOR PRODUCTION THEREOF We, EFIM SEMENOVICH VAINERMAN, of Russian Federation, Moscow, proezd Karamzina, 9, kv. 337; and IRINA BORISOVNA PORTNAYA, of Russian Federation, Moskovskaya oblast, Odintsovo, poselokBakovskogo zavoda rezinovykh izdely, 3, kv. 9, both citizens of Russian Federation hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement- followed by page la) 250249 - la - Field of Art The present invention relates to a porous poly-5 mer material and a process for its production from polymer dispersions. N Background of the Invention Widely known in the prior art are the processes for the production of polymer materials invol-10 ving coagulation of polymer dispersions by ionic deposition, electrodeposition, drying and thermo-sensibilization. The indispensable prerequisites for implementation of these processes include constant properties of polymer dispersions, high con-15 centration of polymer dispersed phase from 40 to 60 wt.-%, strict control of temperature and time parameters, employment of coagulants.

These processes are good mainly for the production of polymer films. Control of structure and, 20 consequently, physicomechanical properties of such materials in the desired direction is hardly attainable due to the technological difficulties in maintaining said parameters within the necessary interval. .

Known in the prior art is a process for the production of a microporous polymer leather-like watertight sheet material (US, A, 3.376.158) which involves applying an aqueous polymer disper3ion-la-tex to a porous flexible fibrous substrate,, coagu-30 lating polymer latex by freezing at minus 100 to ^ minus 10°C, and drying the resulting product. r o\ / V -<A ' 10 FEB 199431 v o e , ^ 0 2 4 g The process envisages treatment of polymer latexes capable of coalescing within a temperature interval from 10 to 100°C and characterized by a secant module which is not under 22 Pa at a 5% tens-5 ion. Concentration of the polymer dispersed phase ranges from 10 to 75 wt.-56, when a layer of latex 0.07 to 2.3 nsm thick is deposited on the fibrous substrate. Before depositing, the latex is thickened to 10-40 P with caseinate and ammonium alginate, 10 methyl cellulose and sodium polyacrylate. The polymer latex is also treated with crosslinking agents, accelerators and crosslinking activators, thickeners and fibrous additives. All these ingredients, particularly in presence of an additional destabili-15 zing factor, in this case freezing, tend to create an orderly structure and speed up this process, thus forming a microporou3 polymer structure. It should be noted, that this structure is also largely defined by the structure of the porous fibrous 20 substrate to which latex ia applied.

In realizing the above process, freezing and resulting coagulation form a discrete polymer structure on the substrate. Owing to the effect of cross-linking agents and the coalescing capacity of the 25 used polymers said structure is transformed by drying into a thin polymer coating of irregular thickness. This structure is then improved by repeated deposition of latex on the resulting polymer coating, followed by freezing and drying. 30 The above-described process denies the possibi lity of directional control over the structure of the microporous polymer material since freezing combined with the use of above-mentioned additions exerts but a destabilizing effect, so that said structure de-,__ pends predominantly upon the structure of the I "4 to FEB 1994 m; \ i c2 4 j roufl aubatrate and the drying conditions. The irregularity of thickness of the material structure is apt to impair the physicomechanical properties..

There is another known process for the product-5 ion of a porous polymer material in the form of a silicone elastomer sponge with mostly closcd pores from an aqueous polymer dispersion-emulsion of polyorganosyloxane with pH » 9-11.5 and a molecular weight over 10.000 in the presence of calloidal 10 silica and an organic compound of tin (EP> 0097914).

This process involves freezing of the silicone emulsion to form a conjugate-dispersed polymer system in the form of an article, thawing said article to produce a wet elastic sponge article, and drying 15 the wet article until water is removed therefrom.

The silicone elastomer sponge is produced from a concentrated emulsion of polyorganosyloxane (30-60 wt.-%) which is frozen at minus 18°C for 24 h followed by thawing the frozen article at room 20 temperature for 6 h and drying it at 70°C. It should be noted that a mandatory prerequisite for sponge production is the use of emulsion containing a filler (colloidal silica) and an organic compound of tin.

The filler forms the structure of emulsion due to sorption of polyorganosyloxane which reacts with the organic tin compound, ensuring the formation of sponge polymer structure at freezing-thawing stages. To enhance uniform distribution in the emulsion, the 30 filler is introduced in the form of a stabilized aqueous dispersion of silica which later will ensure a more regular structure of silicone elastomer sponge. It is precisely the fillor and the organic tin compound which allow the sponge structure of the^-...^ 35 article to be fixed before drying. The closed-pore^5* o t! A <,V * 10 F E B1994 silicone elastomer sponge is produced only when drying a wet sponge article whose wet polymer walls of pores stick partly together. The sticking effect shows itself to a maximum when producing film-like 5 specimens whose porosity can be improved by forming the emulsion before freezing.

The process referred to above is simple from the viewpoint of technology and releases no toxic materials. However, said process fails to change 10 the structure of silicone sponge within broad limits to suit various applications. This is attributable to the fact that freezing is a destabilizing factor which favours coagulation of polymer dispersion so that the structure of sponge depends 15 on stability of emulsion, molecular weight of polymer, the quality and quantity of the filler and organic tin compound. The effect of these parameters denies the possibility of producing silicone 3ponge with a regular structure throughout its volume, and 20 with valuable physicomechanical properties.

Disclosure of the Invention The main object of the invention resides in providing a porous polymer material whose structure would endow it with the required properties for va-25 rious applications, and in developing a process for the production of porous polymer materials by changing the freezing and thawing conditions and using a polymer dispersion whose components would enable the structure and properties of the produced 30 material to be regulated within a broad range.

This object is achieved by providing a process for the production of a porous polymer material involving freezing a polymer dispersion to form a conjugate-dispersed polymer 3ystera followed by / * ■ / r EB1994 mj 2 5 (; •>, treating it to form a porous polymer material wherein, according to the invention, the polymer dispersion being frozen contains a liquid crystallizable dispersion mediun and a polymer dispersed phase 5 capable of autohesion at a temperature lower thaft the initial melting point of the crystals of the dispersion medium, wherein freezing is carried out at a temperature sufficient for obtaining a conjugate-dispersed polymer system with a volume ratio 10 of the polymer dispersed phase to the noncrystalli-zed dispersion medium varying from 3-11 to .1 and wherein the conjugate-dispersed polymer system is treated by holding it at a temperature below the initial melting point of crystals in the dispersion 15 medium v/ithin a time period sufficient for reversal of phases in which the polymer dispersed phase is transformed into a dispersion medium and the dispersion medium into a dispersed phase thus forming a reversed conjugate-dispersed polymer system which 20 is thawed at a temperature higher that the initial melting point of crystals in the dispersed phase until a porous polymer material is produced.

The disclosed process is characterized by technological simplicity, allows the porous polymer ma-25 terials to be produced from dispersions with a low concentration of polymer (down to 0,1 wt.-&) and from mixtures of dispersions of various polymers. In realizing the disclosed process the structure of porous polymer materials is regulated and their pro-3C perties (elasticity, hardness) are changed to suit the prospective application both by changing the parameters of treating the source polymer dispersions and by combining dispersed polymers having different characteristics with functional additions, The disclosed process provides for forming a po3?6ji& 'v FEB 1994 m J / 0 2 ^ polymer •/structure of the material without introduction of fillers, crosslinking, thickening and other additions into polymer dispersions. The process according to the invention is free of any harmful fumes 5 and toxic substances.

The mechanism for forming the polymer structure of the material, according to the invention, depends on changes in the aggregate state of the dispersion medium and on the envelopment of phase 10 contacts between polymer particles. The first of these factors influences the macroatructure of the material while the second one allows it to be formed and influences its microstructure. It should be noted that the properties of polymer do not 15 change irreversibly in the disclosed process. The material is structurized mainly while the polymer dispersion is being frozen to a conjugate-dispersed system and held at a temperature below the initial melting point of crystals in the dispersion 20 medium within the time period sufficient for phase reversal.

According to the invention, the polymer dispersion being frozen contains a liquid crystallizable dispersion medium and a polymer dispersed 25 phase which is capable of autohesion at a temperature below the melting point of crystals in the dispersion medium. The term "autohesion" shall be understood as development of interaction between the molecules in the surface layers of condensed 30 phases. The ends or middle portions of molecular chains of a polymer located on the surface of one polymer particle and taking part in heat motion penetrate into the surface layer of another polymer. particle. This interdiffusion may establish a su^-*"c 35 ficiently strong bond between particles thus e&i *10 FEB 1994 250249 tablishing a phase contact. A rise of temperature and a longer time of contact between polymer particles favours the formation of stronger autohesion contacts between polymer particles. The disclosed 5 process utilizes mostly the polymer dispersions wherein the polymer dispersed phase is formed by at least one polymer chosen from a group including polyisoprene, polybutadlenestyrene, polymethylsty-rene, polybutadieneacrylonitrile, polyacrylonitrile, or 10 by a collagen. The material according to the invention is produced mostly from a polymer dispersion with a concentration of polymer dispersed phase ranging from 0.1 to 65 wt.-S6.

Formation of the macrostructure of the material 15 acco.ding to invention is associated with the size and shape of crystals in the dispersion medium which depend on the freezing temperature of the polymer dispersion. Freezing is conducted at a temperature sufficient for producing a conjugate-dispersed sys-20 tem wherein a volume ratio of polymer dispersed phase to noncrystallized despersion medium is within a range of 3-11-1. The volume of noncrystallized dispersion medium is found from a difference between the volume of the dispersion medium in the 25 source polymer dispersion and the volume of the liquid contained in the pores of the material ob-' tained after thawing. The volume of said liquid is determined experimetally by the corresponding salient point on the curve representing the kinetics of 30 drying the material specimen at 70°C. Freezing of the polymer dispersion results at point in a general concentration of dispersion with respect to polymer phase due to partial freezing out of the dis peraed medium then, in the course of further freez 35 ing and crystallization in the volume of diapers £ i. » *>• in an additional local concentration of the dispersed phase. Thus, the polymer dispersion is frozen not to the point of complete freezing-out of the dispersed medium hut to a certain relation between 5 the polymer phase and noncrystallized dispersion medium . Crystallization of the dispersed medium in the volume of dispersion is marked by convergence of particles in the regions of noncrystallized dispersion medium between the growing crystals 10 concentration benefits the for mation of pin-point contacts between the particles of the polymer dispersed phase. The attainment in the noncrystallized liquid of the concentration of polymer particles corresponding to the 15 formation of chains of multiple pin-point contacts between the particles of the polymer dispersed phase is one of the prerequisites for the subsequent reversal of phases. If the relation of the polymer dispersed phase to the noncrystallized 20 dispersed medium is less than 3s1» the pin-point contacts between the particles will be either local or absent whatsoever. Thawing of such a system produces a polymer dispersion resembling the sourse dispersion wherein the particles of the dispersed 25 phase are not fixed to one another. If, however, the relation of the polymer dispersed phase to the noncrystallized dispersed medium is larger than 11:1, the'particles will be distorted by pressing into one another which eventually will result in 30 the formation of grainy coagulum. It should be pointed out that a certain optimum relation between the polymer dispersed phase and the noncrystallized dispersed medium has been experimentally established for each polymer dispersion depending on the part-35 icle size of the dispersed phase and the degree of FEB 1994 m, l ? v polydispersity of the system. The smaller the particles of the polymer dispersed phase and the higher the degree of polydispersity of the polymer dispersion, the greater this relation will be. It is de-5 sirable that the polymer dispersion be frozen within a -8 to -70°C temperature bracket. The upper limit (-8°C) is determined by the initial melting point of crystals of the dispersion medium in the system while the lower one (-70°C) depends on the 10 low mobility of the polymer dispersed phase in the course of freezing. It is expedient that the polymer dispersion to be frozen should contain mostly water and water-soluble additions or be constituted by an aqueous solution of an organic liquid capab-15 le of crystallizing, for example an aqueous solution of dimethylformamide. It follows from the above that changing the freezing temperature of polymer dispersion in the above-stated limits and varying the composition of the dispersion medium one can 20 regulate the macrostructure of the polymer porous material according to the invention. Pinal forming of the porous polymer structure occurs during development of phase contacts between polymer particles. This takes place at the seasoning stage of the conju-25 gate-dispersed polymer system at a temperature which is below the initial melting point of crystals of the dispersion medium within the time sufficient for phase reversal in which the polymer dispersed phase is transformed into the dispersion medium and 30 the dispersion medium, into the dispersed phase. The phase reversal occurs only when the pin-point contacts between polymer particles develop into phase contacts due to autohesion of polymer particles. It has been found from experiments that not all poly-^T 35 mer particles are capable of autohesion at free£L&g FEB 1994 > 250249 temperatures of the dispersed medium. Thus, when polystyrene latexes are frozen in the above-mentioned temperature interval, the absence of autohesion capacity due to a low mobility of the portions of 5 molecular chains prevents the development of phase contacts between the particles and there occurs no phase reversal. It should be noted that the mobility of macromolecules of a polymer distributed in the liquid phase in the form of particles of colloidal 10 size must not be identified with their mobility en masse since the freedom of rotation of chain segments disposed at the periphery of polymer particles is not retarded by intermolecular interaction undergone by the chain segments in the volume of 15 polymer particles. The depth of autohesion contact depends on the nature of the polymer dispersed phase and the conditions of seasoning the conjugate-dis-persed polymer system, i.e. temperature and time. It is desirable that the conjugate-dispersed system 20 should be seasoned at a temperature which is 5-60°C lower than the initial melting point of crystals of the dispersion medium. This is the temperature at which the particles are not yet fixed relative to one another and retain their autohesion capacity 25 which ensures tha reversal of phase. The autohesion contact can be intensified by using a polymer dispersion which contains a crosslinking agent, an inorganic or" organic filler in the amount of 1 to 250 pts wt per 100 pts wt of the polymer dispersed 30 phase. The inorganic filler may be calcium carbonate, kaolin, titanium dioxide while the organic filler may be represented by coloring pigments, lignin, cellulose fibera. The fillers can be introduced in the form of powders or suspensions. The depth of _ 35 autohesion contact infleunce3 to a certain extenxit,%< 250249 the structure of the poroua polymer material (nature and size of pores) and its strength. The use of crosslinking agents and fillers strengthens even shallow autohesion contacts between polymer 5 particles and expands the range of applications of the produced materials. The duration of seasoning the conjugate-dispersed system depends on the nature of polymer and may vary for each particular system depending on the depth of autohesion con-10 tact between polymer particles. The seasoning temperature of the conjugate-dispersed system before reversal of phases may be equal to, or higher than, the freezing temperature but it must not be higher than the initial melting temperature of crystals 15 in the dispersion medium. Seasoning of the conjugate-dispersed system at higher than the freezing temperature is expedient for intensifying inter-diffusion between particles and the chemical processes which may take place if the system has been 20 treated with crosslinking additions or fillers.

Such a treatment turns the conjugate-deispersed system into a reversed conjugate-dispersed system wherein the polymer dispersed phase is transformed into a dispersion medium while the dispersion me-25 dium, into a dispersed phase. Reversal of phases in the polymer dispersion in the course of its freezing and seasoning is the basic prerequisite for realizing the process according to the invention since the porous polymer material is formed just 30 at those stages.

After seasoning, the reversed conjugate-dispersed system is thawed at a temperature higher than the initial melting point of crystals in the dispersed phase. As a result, the pore space is freed 35 of liquid resulting from transformation of the L, dispersed phase. To intensify removal of liquid ftfom V FEB the pore space of the material it is desirable that the thawing stage should include heating of the reversed conjugate-dispersed system. If the porous polymer material is to be compacted by partial 5 changes of its macrostructure, it is practicable that thawing should be conducted at room temperature until the reversed conjugate-dispersed system turns into a wet porous material. Then the material should bo subjected to compulsory syneresis at a 10 surplus unit pressure of 0.01-2.0 Pa and seasoned while heating. Changes of macrostructure are still possible at this stage since the wet porous material is sufficiently plastic and retains a certain capacity of irreversible deformation. To broaden 15 the field of application of the porous polymer material it is desirable that the polymer dispersion should contain cells of microorganisms. The immobilised cells do not lose their productivity, i.e. fermenting activity. Such a material v/ill prove 2C its worth in food or medical industries.

The problem is also solved by disclosing a porous polymer material having interrelated micro-and anisodiametric macropores in which said macro-pores are located mainly on peripheral sections of 25 its thickness, the volume ratio of micro- and anisodiametric macropores being 1:3-7.

The disclosed material is produced by the process according to the invention and can have the form of a film or a three-dimensional article. Its 30 pores vary from 0.01 to 10 mm in size. The shape and size of pores can be regulated by the nature of the polymer dispersed phase, concentration of the polymer dispersion, composition of the dispersion medium and content of functional additions in / >s the dispersion. // * V; : 50FEB!994 -J C24 * The material according to the invention is no-tod for a high elasticity owing to the above-aientio-ned volume ratio and appropriate arrangement of micro- and anisodiametric macropores which ensure 5 differant dofonaation throughout the thickness of the material. This material is sufficiently strong and will be used to advantage in the manufacture of sports and orthpaedic footwear.

To expand the field of application, it is expe-10 dient that the porous polymer material according to the invention should contain a liquid} mostly water, enclosed in micro- and anisodiametric macropores.

This material will also prove useful in the manufacture of cosmetic prosthetic appliances# Brief Description of the Drawings for better understanding of the present invention, it will now be described by way of its concrete embodiments with reference to the accompanying drawings in which: 2o Figs 1-5a, b illustrate the scanning electro nic photomicrographs of the central and peripheral sections, respectively, of the porous polymer material for the specimens produced in keeping with examples 1-4, 5, 7, 25 according to the invention. 25 To show the scale, the small line in the lower right-hand part of the photomicrograph in Pigs 1at, corresponds to a length of 10. 0 um while in Figsr^f? 2-5a, b, to a length of 100.0 um.

FEB 1994!..

Best node of Carrying out the Invention ? Jj The porous polymer material is produced f rora* ? g, >j a polyme dispersion wherein the polym^r^dispersed phase is represented by polybutadienef containing 30# of styxene units. Concentration C of the polymer dispersed phase (C d.ph. ) is 20 wt.-#. The dispersion medium is, basically) water with a small amount (up to 0.05 wt.-$) of dissolved potassium paraffi-nate which is a surface-active stabilizer of poly-5 butadienestyrene aqueous dispersion. The initial melting point (Tm) of crystals in the dispersion medium found from a thermogram is minus 0.28°C. A 200-g amount of polymer dispersion is poured into a flat open glass container and placed into a cool-10 ing cabinet at minus 60°C where it is frozen for 0. 5 h until a conjugate-dispersed system is formed in v/hich the volume ratio of the polymer dispersed phase (V1) and noncrystallized dispersion medium (V2) is 5.9:1. The resulting conjugate-dispersed 15 polymer system is seasoned at minus 60°C for 3.5 h to the point of phase reversal which marks the formation of a specimen from the reversed conjugate-disperaed system. The weight of the produced specimen is determined by weighing it in a container 20 closed by a tightly ground stopper. To thaw a specimen, the container without stopper is placed into a controlled-heat cabinet at 70°C and weighed periodically at 15-min intervals. The obtained data are used for plotting a chart showing the loss of 25 specimen weight in time due to evaporation of liquid. AB all liquid has evaporated from the pore apace, there appears a salient point on the kinetic curve. The value of the ordinate corresponding to said salient point is 153 g (153 ml). The difference bet-30 v/een the volume of the dispersion medium in the source system (160 ml) and the volume of the liquid in the pores of the porous polymer material produced after thawing is 7 nil (V2). The volume of the polymer dispersed phase is about 41 nil (V1), the densi-35 ty of the polymer phase being 0.98 g/cn^. Hence tO FEB 1994 mi 2r C 1 4 & the volume ratio of the polymer diaperced phaae to the noncrystallized diaperaion medium is 5-9:1. The material produced after thawing has interrelated micro- and anisodiametric macropores* the former 5 being dispoaed mostly in the central aection and the latter ones, on the peripheral portiona of ita thickness (20 mm).

The volume ratio of micro- and macropores found experimentally by geometric measurements is 10 5 . The apparent density of the material ($ r) determined as the relation of weight of the porous specimen to its volume is 0.385 g/cm^.

The mechanical properties of the dried material are estimated by the parameter of instantaneous 15 deformation ( £ ^) measured on a laboratory penetration tester under a force of 5 N. This deformation of the resulting material is 3.5 mm.

Given hereinbelow in the Table are other examples of producing a porous polymer material 20 according to the invention, stating the characteristics of the polymer dispersion, technological parameters of the disclosed process and characteristics of the produced material. In the specimens of Examples 1-25 the volume ratio of the polymer dispersed 25 phase to the noncrystallized dispersion medium as v/ell as the paremeters of the material are determined as described above. The specimens are 20-mm thick except thosfe of Examples 3» 6 which are films 1-nra thick. ":10FEB5994«;j to U <. * s, Example No.

Table Characteristics of Polymeric Dispersion 6 Dispersed polymeric phase (composition) C of Dispersion Ini- Functio- dis- medium per- (composi-sed tion) phase tial nal addi-mel- tions ting Com- pts poi- po- wt nt sit- per °C ion 100 mol. pts of polymer 1 Polybutadi enes ty-rene with 30^ of styrene units 65 Mainly wa- -0.32 ter, traces of stabilizing surfactant 2 3 Q0 do Polyisoprene-polymer of natural latex-Quali-tex do do Mixture of equal parte of 30% poly-butadionestyrono with polynor of 0.1 45 -0.28 -0.25 -0. 50 0.1 10 do do Latex serum mainly water do -0.40 do -0.33 Natural -0.40 latex serum, traces of stabili- FEB 1994 - V- (•' '■ v Table (continued) 8 natural latex-Qualitex, 1:1 Carboxylated polybutadiene-styrene with # of styrene units and 3% of carboxyl groups 9 Carboxylated polybut adienesty-rene with 65# of styrene units and 1# of carboxyl groups 70# polybutadie-nestyrene 11 Polymethylsty-rene with 50# of styrene units 12 Carboxylated po-lybutadienenit-rile, 40# of nitrile unita an«$4# of carboxyl groups 13 Copolymer of ac-rylnitrile acid with vinylacetate 20 zing surfactant, mainly water Mainly wa- -0.35 ter, traces of stabilizing surfactant do -0.35 do do •0.30 •0.30 do -0. 50 do -0.60 ■•;Z 10 F E B1994 Sj a 4 Table (continued) 14 16 17 Mixture of equal parts of 30# po-lybutadienestyre-ne and copolymer of acrylonitrile acid with vinylacetate $S polybutadie-nestyrene do do 18 Collagen 19 Collagen Collagen 5 Mainly wa- -0,60 ter, traces of stabilizing surfactant Mainly water, traces of stabilizing surfactant gelatin do -0,28 gelatin 2.5 6t ■0,7 Mainly wa- -0.4 ter, traces of stabilizing surfactant Mainly wa- -0.1 ter do -0.1 5% aqueous solution of tertbutanol po- 0.25 tas-aium chloride VUl- 8.5 cani-zing group* 10PEB 1994'Sji $ 250 2 4 9 1 Table (continued) 21 Collagen 22 do 23 do 5% aqueous < solution of tertbutanol 5% aqueous ( solution of dimethyl-sulfoxide 20 do ( Epi- ch- loro- hyd- rin 24 Mixture of collagen with chromed collagen do 3.125 Mainly wa- 1 ter Epi- ch-loro- hyd- rin 3.125 do -0. 1 Glu-ta-ric dial-dehy-di ♦ The vulcanizing group comprises (pts wt): sulfur 1,88; diphenylguanidine, 1,0; zinc diethyl-dithiocarbomate, 0.75; zinc mercaptobenzothiazo-late, 0.75; zinc oxide, 3-75; leuconol, 0^37... (1= 8.5). • 25024 Table (continued) Ejta- Technological Charactoristica of Claimed , Proceaa No. freezing ' seasoning ' thawing T, °C HI I i F ' ' VV2 1 T, °C ' r, h' T, °C 1 8 9 11 12 13 1 -60 0.5 8.1:1 -60 3.5 70 2 -60 0.5 6.5:1 -60 3.5 50 3 -60 0.5 6.3:1 -60 3.5 4 -15 1.5 9:1 -5.5 .5 -60 0.5 8.5:1 -60 3.5 6 -15 1.5 8.2:1 -15 .5 7 -60 0.5 8.7:1 -60 3-5 70 8 -60 0.5 .1:1 -20 3.5 9 -60 0.5 11:1 -60 3-5 -60 0.5 .8:1 -60 3.5 11 -60 0.5 8. 5:1 -6o 3-5 70 12 -60 0.5 9.3:1 40 4.5 13 -50 0.5 7.1:1 -30 .5 14 - 8 3-5 7:1 - 8 3.5 -60 0.5 6.6:1 -40 3.5 16 -70 0.5 7.0:1 -60 2.5 17 -70 0.5 3.0:1 -50 3.5 18 -65 C. 5 4.0:1 -18 2.5 19 -60 0.5 3:1 -18 2.5 -40 0.5 4-8:1 -40 2.5 2.1 -40' 0.5 4.1:1 -40 2.5 22 -40 0.5 :1 0 1 2.5 23 -40 0.5 4.1:1 -40 2.5 24 -40 0.5 4.2:1 -18 3.5 -40 0.5 3.1:1 -18 3.5 V z V { to FEB 1994:31 V ^ 'V.

Tablo (continued) Exa- Characteristics of Claimed Porous Polymer ^ Material Ho. f r* g/cm3 Relation of micro ,mm pores and macropores 1 14 16 1 0.765 1130 1.8 2 0.360 1:5.5 3.7 3 0.358 1:5.5 4 0.651 1:3.8 2.4 0.401 1:5 3.7 6 0.400 7 0.275 1:7 3.7 8 0.520 1:4.5 3.0 9 0.531 1:4 3.0 0.528 1:3.5 11 0.515 1:4.2 3.0 12 0.542 1:3.8 2.8 13 0.605 1:3.5 4.2 14 0.430 1:4.5 4.1 0.382 1:6 2.5 16 0.365 1:6 3.1 17 0.342 1:7 2.0 18 0.242 1:3 .0 f 19 0.211 1 ;3 4.8 0.251 1:3 4.5 , v 21 0.223 1:3 4.3 22 0.248 1:3 4.8 f< 23 0.225 1:3 4.5 24 0.240 1:4 4.2 * 0.202 1:4.5 4.0 ^ *-fc; tOFEB!994i £! Ilicrophotographs in Piga 1-5a illustrate the structure of peripheral portions of materials in Examples 35 1i 4, 5, 7» 25 composed mostly of anisodiametric mac- • 250 2 4 9 ropores.

The scale for photomicrographs in Pigs 1-5a corresponds to that in Pigs 1-5b.

The photomicrographs in Figs 1-5b illustrate 5 the central portions of the same materials composed mostly of micropores# Example 26.

The porous polymer material is produced from a polymer dispersion wherein the polymer dispersed 10 phase is constituted by polybutadienestyrene containing 30% of styrene units# Concentration of the polymer dispersed phase is 20 wt.-$. Said polymer dispersion contains also 1 pts wt of the filler, i.e. blue phthalocyanine pigment per 100 pts wt of 15 polymer. The dispersion medium is mostly water with a small amount (up to 0.05 wt.-5S) of potassium pa-raffinate acting as a stabilizing surfactant of the polybutadienestyrene aqueous dispersion. The initial metling point (Tm) of crystals in the dispersion me-20 dium determined from a thermogram is minus 0»28°C. A 200-g quantity of polymer dispersion is poured into a flat open glass container and placed into a cooling cabinet at minus 60°C where it is frozen for 0.5 h to form a conjugate-dispersed system where-25 in the volume ratio of the polymer dispersed phase (V^) to the noncrystallized dispersion medium (V2) is 6.3:1. The resulting conjugate-dispersed system is seasoned at -50° C for 3*5 h to the point of phase reversal when a specimen is formed from the reversed conjugate-dispersed system. The specimen is thawedf* •< r o '< c at 70 C. The ratio of volumes equal to 6.3:,1 is determined by the above-described methods. The 7 o ^EB1994 7 difference between the volume of the dispersion medium in the polymeric dispersion (159 ml) and thd^ 25024S volume of the liquid filling the pores of the thawed porous polymeric material (152.5 ail) is 6.5 ml (V2). The volume of the polymer dispersed phase is about 41 ml (V2)i the density of the polymer phase being 0.98 g/cn?, The micropore-to-macropore volume ratio found experimentally by geometric measurement a is 1*5. The apparent density (^r) of the material is 0.38 g/cm3. The value of instantaneous deformation ( £ is 3.5 mm.

Example 27.

The porous polymer material is produced from polymer dispersion whose polymer dispersed phase is polybutadienestyrene containing 30% of styrene units. Concentration of the polymer dispersed phase is 20 wt.-%. Said polymer duspersion also contains 250 pts wt of a filler - precipitated calcium carbonate - per 100 pts wt of polymer. The dispersion medium is mainly water. The initial melting point (Ta) of crystals in the dispersion medium found from a thremogram Is minus 0.44°C. A 200-g portion of polymer dispersion is poured Into a flat open glass container and placed into a cooling cabinet at minus 70°C where it is frozen for 0.5 k to fonn a conjugate-dispersed system wherein the volume ratio of the polymer dispersed phase (V^) to noncrystallized dispersion medium (V2) is 4.1:1. The resultant conju-gate-dispersed polymer system is held at minus 40°C for 5.5 h to the point of phase reversal at which the specimen is formed from the reversed conjugate-dispersed system. The specimen is thawed at 70°C. The relation of volumes V\j:V2 a 4.1:1 is determined as described above. The difference between the volume of dispersion medium in the polymer dispersion (60 ml) and that of liquid in the pores of the thaWed 0 2 4 porous polymer material (50 ml) ia 10 ml (V2). The volume of the polymer dispersed phase is about 41 ml (V ), the density of the polymer phase being equal 2 3 to 0.98 g/cnr, Thus, the volume ratio of the polymer 5 dispersed phase to the noncrystallized dispersion medium is 4*1:1* The coloured porous polymer material produced after thawing contains interrelated micro- and anisodiametric pores, the former occupying mostly the central part while the latter ones 10 are distributed over peripheral portions 20 mm thick. The volume ratio of m'cro- and macropores found experimentally by geometric measurements is 1:3* The apparent density of the material (<f r) is 0.942 g/cm3. The instantaneous deformation (^>i) is 1.5 15 mm.

Example 28.

The porous polymer material with cells of microorganisms immobilized in its pores is produced from a polymer dispersion wherein the polymer dis-20 persed phase is constituted by polybutadienestyrene containing 30% of styrene units. Concentration of the polymer dispersed phase is 20 wt.-J$. Said polymer dispersion also contains cells of yeast Saccha-romyces cerevisae. Said cells are introduced into 25 the polymer dispersion in the form of a 5% aqueous suspension. The dispersion medium is mostly water with a small amount (up to 0.05 wt.-%) of dissolved potassium paraffinate which functions as a stabilizing surfactant of the polybutadienestyrene aqueous 30 dispersion. The initial melting point (5^) of the crystal of the dispersion medium found from a thermogram is minus 0.28°C. A quantity of 200 g of polymer dispersion is poured into a flat open glaas^>^ ^ ^ container and placed into a cooling cabinet at a ' " ^ fOrEB!994S,j ' y * * f 250?4^ temperature of -40° C where it is frozen for 1,0 h to form a conjugate-dispersed system wherein the volume ratio of the polymer dispersed phase (V^) to the noncrystallized dispersion medium (Vo) is 7-411• C ^ 3 The resultant conjugate-dispersed polymer system is held at minus 40°C for 3 h to the point of reversal of phases at which the specimen is formed from the reversed conjugate-dispersed system. Then tho specimen is thawed at 70°C. The ratio of volumes V1:V2 e<lual 7.411 is determined by the above-dos-cribed method* The difference between the volume of the dispersion medium in the polymer dispersion (150 ml) and that of the liquid contained in the pores of the thawed porous polymer material (153*5 ^ ml) is 5*5 ml (V2). The volume of the polymer dispersed phase i3 about 41 ml (V0)i the density of the polymer phase being 0.98 g/cnr. Thus, the volume ratio of the polymer dispersed phase to the noncrya-tallized dispersion medium is 7*4»1. The coloured porou3 polymer material produced after thawing has interrelated micro- and anisodiametric pores of which the former ones are located mostly in the central part while the latter ones, on tho peripheral sections 20 mm thick* 2^ The volume ratio of micro- and macropores found experimentally by geometric measurements is 1:5* The apparent density (j*r) of the material is 0.384 g/cnr and the instantaneous deformation ( £^) is 3*5 mm.

Part of pores of the porous polymer material 3° produced after thawing is filled with cells of said microorganisms. The relative productivity of immobilized cells is determined as the ratio of their total productivity in a flow-through reaction vessel for biosynthesis of yeast acidic phosphatase within 100 h of contin¥OU3 operation to the total productivity/ / ^' c A 1OFEB1994 £1 250249 the 3ame initial amount of blomass of said celle after 100 h of functioning in inoculation vessels. The relative productivity of the immobilized cells of sacc-haronyces cerevisial is 0.8# Example 29# The porous polymer material is produced from a polymer dispersion of polybutadienestyrene containing 30% of styrene units. Concentration of the polymer dispersed phase is 20 wt#-%.

The processes of freezing and thawing are con ducted as in Example 25# The specimen is thawed at 20°C for 3 h until reversed dispersed polymer system turns into a wet porous polymer material. Then the material specimen discharged from the container 15 and placed under a press for conducting compulsory syneresis under a surplus unit pressure of 0.01 Pa. The thickness of the specimen after compulsory syneresis is 18 mm# On peripheral sections the produced porous polymer material mostly has macropores whose 20 anisodiametric characteristic diminishes by 10$S from the macropores shown in photomicrograph in Pig. 1a. However, the shape and size of micropores in the central part stay unchanged# The volume ratio of micro- and macropores found 25 experimentally by geometric measurements is 1:4.7.

The apparent density of the material (P„) is 0,372 3 g/cnr and the instanl.an.:ous deformation (£_i) is 3.1 mm.

Industrial Applicability The porous polymer material according to the invention will be quite useful in medicine, biotechnology for making cosmetic prostheses and immobili- ; zing cells of microorganisms, in light industry for FEB 1994 Jj a 250 24® making footwear components, protection means for sportsmen, also in the capacity of heat-and-sound insulating materials utilized in various branches of engineering# The process according to the invention can be used in the branches of industry where polymer dispersions serve as the main raw material, namely in rubber industry, production of plastic and building materials; polymer dispersions are ob-10 tained as byproducts of the main process, e.g. in woodworking or hide-and-skin industry. eiM* v* — 28 —

Claims (12)

WHAT WE CLAIM IS:

1. A process for producing a porous polymer ma-terial involving freezing a polymer dispersion to form a conjugate-dispersed system with subsequent

5 treatment to produce porous polymer material characterized in that the polymer dispersion subjected to freezing contains a liquid crystall-zable dispersion medium and a polymer dispersed phase capable of autohesion at a temperature lower than 10 the initial melting point of crystals in the dispersed medium, in that freezing is carried out at a temperature sufficient for producing a conjugate-dispersed polymer system wherein the volume ratio of the polymer dispersed phase to the noncrystalli-15 zed dispersion medium is 3-11:1, in that the con-jugate-dispersed system is treated by seasoning it at a temperature lower than the initial melting point of crystals in the dispersion medium within a time period sufficient for the reversal of phases 20 at which the polymer dispersed phase turns into a dispersion medium while the dispersion medium turns into a dispersed phase and in that the formed reversed conjugate-dispersed polymer system is thawed at a temperature which exceeds the initial melting 25 point of crystals in the dispersed phase to produce a porous polymer material.

2. A process as claimed in Claim 1 characterized in that freezing is carried out within a temperature range from minus 8 to minus

30 70°C.

3. A process as claimed in Claim 1 characterized in that the conjugate-dispor-sed system is seasoned at a temperature v/hich is

5 -60°C lower than the initial melting point of 35 tals in the dispersion medium, /

\ r ^ \ '

250249

- 29 -

4* A process as claimed in any one of Claims 1-3 characterized in that the thawing stage includes heating of the reversed conjugate-dispersed polymer system.

5 5. A process as claimed in any one of Claims

1-3 characterized in that thawing is carried out at room temperature until the reversed conjugate-dispersed polymer system turns into a wet porous polymer material which is then sub-

10 jected to compulsory syneresis at a surplus unit pressure from 0.01 to 2.0 Pa and seasoned on being heated.

6, A process as claimed in any one of Claims 1-5 characterized in that the

15 polymer dispersion has a polymer dispersed phase formed by at least one polymer chosen form a group consisting of polyisoprent>, polybutadienestyrene, polymethylstyrene, polybutadieneacryionitriie, poiyacrylo-nitrile.

20

7. A process as claimed in any one of Claims

1-5 characterised in that the polymer dispersed phase in the polymer dispersion is formed by collagen.

8. A process as claimed in either one of Claims

25 6 and 7 characterized in that concentration of polymer dispersed phase in the freezing polymer dispersion ranges from 0.1 to 65 wt.-%.

9. A process as claimeCTany one of Claims 1-8 characterized in that in said freez-

30 ing polymer dispersion the dispersion medium contains mainly water and water-soluble additives.

10. A process as claimed in any one of claims 1-8 characterised in that the dispersion medium in said freezing polymer dispers-

35 on is formed by an aqueous crystallizable solut^rf^rv^x^ of an organic liquid.

250

- 30 -

11. A process as claimed In any one of claims 6-10 characterized in that said polymer dispersion contains a crosslinking agent.

5

12. A process as claimed in any one of claims

6-10 characterized in tliat said polymer dispersion contains an inorganic or organic filler taken in the amount of 1 to 250 pts wt of the polymer dispersed phase#

10 13* A process as claimed in Claim 1 characterized in that said polymer dispersion contains cells of microorganisms.

14. A porous polymer material containing interrelated micro- and anisodiametric macropores wherein

15 said macropores are disposed mainly on peripheral portions throughout its thickness, the volume ratio of micro- and anisodiaaetric macropores being 1:3.7*

15. A porous polymer material as claimed in Claim 14 characterized in that it

20 contains a liquid, mainly water, enclosed in micro-and anisodiametric macropores.

16. A process as claimed in Claim 1 and substantially as herein described with reference to any embodiment disclosed.

17. A porous polymer material when made by the process of any one of the preceding claims.

18. A porous polymer material as claimed in Claim 14 and substantially as herein described with reference to any embodiment disclosed.

S&ne.na\A(Jn Vctinci-mo-n