PROCESS FOR THE PRODUCTION IN WATERY EMULSION OF BLENDS OF POLYVINYLIC ALCOHOLS AND RESPECTIVE PRODUCTS OBTAINED

Abstract: Process for the preparation of watery emulsion of two or more polyvinylic alcohols (PVa) for the production of polyvinylchloride (PVC-S) in watery suspension in which at least a first polyvinylacetate (PVAc) with molecular weight measured in K value comprised between 30 and 110, preferably 50 is utilized and, with technique of alcoholysis acid or basic, to carry out the transesterification of the PVAc up to values of saponification number (NS) comprised between 598 and 135 preferably between 598 and 312, optimally 511; loading from 0.1 to 5 times preferably 0.7 times in weight respect to the first PVAc, of at least a second PVAc in solution of ethylic alcohol or methylic alcohol having molecular weight measured in K value comprised between 10 and 110, preferably 10 and 50, optimally 27; stopping the alcoholysis in order that, in the final alcoholic solution, the respective PVAc result is perfectly mixed in order to obtain: a) at least a first PVA, with saponification number, comprised between 230 and 95, preferably 230 soluble in water; b) at least a second PVA, with NS comprised between 598 and 312, preferably 480, insoluble in water; distilling during the stop of the alcoholysis or to termination, the residual solvents, adjoining water after the stopping of the alcoholysis with the scope of obtaining the coagulation in water of the second PVA in form of microparticles with granulometric distribution comprised between 0.01 micron and 10 microns.

Description: 1 Process for the production in watery emulsion of blends of polyvinylic alcohols and 2 respective products obtained. 3 4 5 The object of this invention is the process for the production of watery emulsion of 6 polyvinylic alcohols (PVa) with different saponification number. This invention, 7 more particularly, refers to the technology of preparation of polyvinylic alcohol 8 (PVa) to be utilized in the polymerization for the industrial production of the 9 polyvinylchlorure in watery suspension (PVC-S). 1 0 1 1 In the exposure of the following patent, -the following parameters of evaluation and 11 22 numeration of the characteristic of the products utilized and obtained are adopted: 1 3 - saponification number (NS) that represents the milligrams of potassium 1 4 hydrate necessary for saponifying 1 gr. of the sample. By example, operating in the 1 5 following order: 1 gr. of sample is weighted, then the product is melted in 50 cc of 1 6 water and 50 cc of methylic alcohol; 1 cc of alcoholic solution of phenolphtaleiπ is 7 adjoined; 100 cc of solution of KOH N/10 are adjoined and the product is hooted to 8 ebb for 1 hour. The product is titulated with HCI N/10 and after that stechiometric 9 calculations of the milligrams of KOH utilized for saponifying the product are made. 0 - Molecular weight of the polyvinylacetate (PVAc) expressed in K value of a 1 PVAc that is determined by means of measuring the viscosity relative of a solution 2 in acetone of the PVAc. The value of relative viscosity, by means of the table that 3 reports the previously determined values, is transformed in K value. The method is 4 the following: A gramme of sample perfectly desiccated is weighted, then it is 5 melted in 100 cc of acetone and with Viscosimeter Ostwald series 50, to 25°C , the 6 time of fall of the solution is measured. The ratio of the fall times of the solution and 7 of the pure acetone, furnishes the value of relative viscosity. It is known that for 8 producing PVC-S with optimum morphologic characteristics, in the formulations of 9 polymerization of the vinyl chloride monomer (VCM), in watery suspension, a system of suspending with basis of polyvinylic alcohols having distinguished characteristic of solubility and insolubility in water is utilized. The PVA with saponification number lower than 280 are soluble in water and are commonly called "primary suspensors". The PVA with saponification number over 280 are partly insoluble in water and are empirically called "secondary suspensors". In the production of the PVC-S, is of great importance to utilize secondary suspensors type PVA which are free from residues of methylic alcohol, methyl-acetate, ethylic alcohol, ethyl-acetate and preparations under the form of watery emulsion with microparticles of diameter lower than 10 microns, with NS over 280, preferably around to 480. Thanks to a perfect distribution, just from the first instants of polymerization, of the microparticles of the secondary suspensor in the bulk reaction, the main characteristic of the PVC-S: distribution of the internal porosity in the granules of PVC-S, the appearing density, the quantity of granules totally or partly gelled commonly called "fish-eyes", the granulometric distribution, the thermic stability, the resistivity of volume, are notably improved. EP-0123364 (STAMICARBON) discloses a method of production of the PVC-S that uses as suspending system a watery dispersion of polyvinylic alcohols; but this patent does not describe the technology of preparation of this watery dispersion. In the patent IT-83315-A-86, a technology of hydrolysis of microparticles of PVAc previously produced in watery emulsion is claimed. The method indicated utilizes a watery solution of sodium hydrate as basic catalyzer of hydrolysis and the simultaneous removal of the salts, coming from the hydrolysis, by means the process of ultrafiltration. But this method, allows only the utilizing of the technology of the direct saponification of the PVAc; the consequence is the obtainment of PVAc without alternated distributions of the hydroxylic groups called in literature "RANDOM", obtainable only with alcoholisis acid in presence of methylic alcohol or ethylic alcohol. Furthermore during the process of ultrafiltration, made for eliminating a great quantitative of sodium acetate coming from the process of hydrolysis basic, through the membranes waters containing fractions of polyvinylic alcohol at low molecular weight, soluble in water and verifiable by measuring the viscosity of theirs solutions to the 4% in water to the temperature of 20°C. with Viscosimeter Hoeppler, with values of viscosity comprised between 0,5 and 3,5 centipoises are discharged. This leakage of polyvinylic alcohol in the waters of discharge, nrgatively affects the costs of production and of biologic treatment of the waters of discharge. The main scope of the invention is to aport a sensible improvement to the technique of preparation of watery emulsion of polyvinylic alcohols to different saponification number obtained both with alcoholisis acid and with alcoholisis basic and to supply a cheap and reproducible technology of preparation of the same. In accord to what is claimed in the present invention, this scope is reached by means of a method for the preparation of a blend of PVA in watery emulsion for the use in the polymerization of the PVC-S, characterized by: - utilizing at least a first PVAc (polyvinylacetate) with molecular weight measured in K value comprised between 30 and 110, preferably 50 and, with catalyzer acid or basic in presence of ethylic alcohol or methylic alcohol, to carryout the alcoholisis of the PVAc up to values of saponification number comprised between 598 and 135, preferably between 598 and 312, optimally 51 1 ; - loading from 0,1 to 5 times, preferably 0,7 times, parts in weigh of at least a second PVAc having molecular weight measured in K value comprised between 10 and 90, preferably 10 and 50, optimally 25; - stopping the alcoholisis in order that, in the final alcoholic solution, the respective polyvinylic alcohols result perfectly mixed in order to obtain: a) at least a first polyvinylic alcohol, with saponification number, comprised between 280 and 95, preferably 230 soluble in water; b) at least a second polyvinylic alcohol, with saponification number comprised between 598 and 312, preferably 480, insoluble in water; - having the knowingness to distill during the alcoholisis, or at his termination, the residual solvents adjoining water after the stopping of the alcoholisis, with the scope of obtaining the coagulation in water of the second PVA in form of microparticles with granulometric distribution comprised between 0,01 microns and 10 microns, that result in watery emulsion with the first. This method furnishes hence a new technique of preparation of watery emulsion of PVA to different NS (numbers of saponification) based on a new process of simultaneous alcoholisis of two or more PVAc. The method permits further to maintain the fundamental characteristic applicative of primary suspensor and of the secondary suspensor of the PVA constituting the emulsion. The result IS the obtainment of a new product that can be utilized in the initial charge of the polymerization in watery suspension of the vinyl chloride monomer with advantageous effects in the morphologic characteristic of the finished PVC-S. This is confirmed from the detailed researches made from the inventor that has studied and applied the product object of the present invention with different technologies of polymerization of the PVC-S having confronted it with the primary and secondary suspensor known for producing the PVC-S obtaining the following surprising discoveries: the product is obtainable both with the technique of alcoholisis basic (BLOCKY) and acid (RANDOM), or with different combinations of the same; - the product has the double function of primary suspensor and secondary suspensor and can produce all the types of known PVC-S and with a great qualitative level; - the product has a powerful action of anti-blistering or anti-foam of the bulk in polymerization and allows of obtaining a time of reaction very short without harmful clogging of the upper portions of the autoclave and of the condenser of ebb; if a great quantitative of the product in formulation with the objective of improving the thermic stability of the finished PVC-S are loaded, we do not observe dangerous augmentations of the viscosity of the bulk in polymerization and the thermic exchange of the autoclave is notably improved; The product is perfectly compatible and miscible with the watery solution of all the primary suspensors employed for producing the PVC-S and, together with them, it can be utilized with different combinations of formulation for improving both the qualitative characteristic of the PVC-S and the technology of obtainment of the PVC- S itself; the product is perfectly stable in the time within intervals of temperature comprised between +60°C and -30°C. The freezing and the defreezing of the product do not fetch to the breakage of the emulsion with consequent precipitation of the fraction insoluble in water; the product permits of obtaining stable watery emulsion even to temperature lower to 0°C of the peroxidic catalyzers of the type solid or liquid emploied for the production of the PVC-S; if we load the product directly in the lines of charge to the autoclave of the hotting water of polymerization to the temperature of 65-70°C , sticky deposits are not observed in the pipages and the quality the of the PVC-S does not resent of the technique of charging the autoclave with high initial temperature. The advantages that are obtained in the production of the PVC-S are the following: minimum presence of residue salts and complete absence of residues of methylic alcohol or ethylic alcohol and thus obtainment of PVC-S adapt for sophisticated applications with high characteristic of resistivity of volume; it is possible to control all the characteristic of the PVC-S , which for example: internal porosity, appearing density, granulometric distribution, thermic stability etc., by means of different combinations of the type and of the grade of alcoholisis of the PVA constituting the emulsion itself; Thanks to the use of stable emulsions containing primary and secondary suspensors and peroxidic catalyzers, utilized for producing the PVC-S , the technology of automatic charge of the reactor of polymerization is notably simplified and definitively perfected in the technique of charge to container closed, in fact the emulsions are easily pumpable in the lines of autoclave charge and do not generate dangerous deposits in the same; In the plants of PVC-S , with the use of the product object of the present invention, a consisting improvement of the productive capacity, accompanied from a meaningful improvement of the ambient of work and of the ecologic habitat where is possible to find the plants itself is sensed; This advantages can be resumed in: - technology of charge of the autoclave with container closed; - diminution of issuing of VCM gas caused from the frequent openings of the container; - reduction of the quantity of air in the recovers of VCM with consequent leak in the atmosphere of uπdesired quantity of VCM gas universally individuated as powerful agent carcinogenic; - security in the handling and stocking of the catalyzers. EXAMPLES OF PREPARATION OF THE WATERY EMULSION OF POLYVINYLIC ALCOHOLS WITH DIFFERENT SAPONIFICATION NUMBERS AS CLAIMED WITH THE PRESENT INVENTION. For the execution of the following described tests, a reactor of the capacity of 580 liters with internal surface vitrified, .with ringleader with anchor (turns 10- 100), and liner of cooling has been utilized. On the upper part, through selvage of 3" a condenser to ebb vitrified with surface of exchange of about 1 mq, endowed of valves to three-orders for allowing the continuous taking of the condensed material was linked. The emulsions of PVA have been analyzed as the following methods of analysis: Determination of % of the active substance: it is determined with the simple method of evaporation of 5 gr. of sample put in capsule of aluminium and for 3 hours at. 1 10°C in ventilation stews. Viscosity to 20°C in centipoises of the watery solution of PVA: A watery solution containing 4% of activated substances of the sample to be analyzed is prepared, and at 20°C, with Viscosimeter Hoeppler, the time of fall is measured. By means of table of taring, furnished from the constructor of the Viscosimeter, it is possible go back to the value of viscosity of the solution. Determination of the type of alcoholisis - BLOCKY - RANDOM. The type of distribution of the ydroxylic groups OH, in the chain of the PVA, has been determined by means of use of the apparatus NMR (Nuclear Magnetico Resonance Spectroscopic). Diameter of partly hydrolyzed microparticles PVAc: The determination of the granulometric distribution of the microparticles of the PVAc insoluble in water has been effected with the apparatus commonly called COLTER-COUNTER. Example No .1 In the reactor are loaded: 250 Kg. of a watery solution containing 13 Kg. of polyvinyl-alcohol with NS equal to 137 and with viscosity of the solution, of 4% in water of 45, cps. 25 Kg. of Vinyl-Acetate-Monomer (VAM) 0,030 Kg. of ammonium persulphate. The product is polymerized to the temperature of 63°C for 90 minutes. For furthers 3 hours, further 125 Kg. of VAM are alimented. When the charge is accomplished, the temperature is augmented until to 95°C in a lapse of 2 hours, for completing (99,6%) the conversion of the VAM in polyvinylacetate PVAc in watery emulsion. His molecular weight or K value to the analysis results to be102. The emulsion is discharged and in the reactor 120 Kg. of the product are leaved; to the temperature of 40°C in 20 minutes is adjoin in the order 250 Kg. of methylic alcohol and 2.5 Kg. of H2S04 concentrated (d. 1.83). Finally the bulk is brought to the temperature of ebb and after that the alcoholisis acid is processed for 9 hours. In 10 minutes a methanolic solution containing the 50% of polyvinylacetate ( PVAc ) with K value equal to 25 is adjoined (this product can be obtained both with techniques of polymerization in solution and in break). Always to ebb, the distilled material constituted by the azeotrope methilacetate-methylicalcohol that is formed during the alcoholisis is taken, the operation requires furthers 9 hours with a total asportation of 170 Kg. of solvents. The alcoholisis is stopped with 2 Kg. of NaOH liquefied in 20 Kg. of H20. The methylic alcohol residue is tripped substituting it gradually with equal quantitative of water. The product is diluted with water until a percent of final solids of the 23%. During the final strippage the fraction of PVA, equal to the 30% respect the total of polyvinylic alcohols, having NS equal to 480, precipitates in form of microparticles with diameter comprised between 0,01 microns and 10 microns emulsified in the watery means containing a great quantity of polyvinylic alcohol with NS equal to 230. The final emulsion, subdued to the chromatographic analysis, results deprived of residual solvents, it is of blank color, stable at a temperature comprised between -25°C and +60°C. The test of dispersion in pure water or in the watery solution of other suspending of cellulosic type, acrylic, polyvinylic alcohols confirm its perfect dispersion and the absence of phenomenons of deposit in the found of sticky bulks. For the successive tests of polymerization of the PVC-S to this emulsion the code PVA - Al is given. The technology of alcoholisis utilized for obtaining the PVA-AI that emploies a blend of methylicalcohol-water-sulphuricacid furnishes a distribution of the hydroxylic groups in the chain of the PVA called in literature as "COMPLETELY RANDOM", and this results even from the publication: "Polyvinyl Alcohol Properties and Applications" written by C. A. FINCH, Crode POLIMERS LIMITED London , Chapter 4, pag. 93. Example No. 2 In the reactor are loaded in the order: 160 Kg. of VAM; 35 Kg. of methylic alcohol; 5 Kg. of Benzoil peroxide. The polymerization is made for 7 hours to the temperature of ebb for obtaining a final conversion in polyvinylacetate up to the 99%. I K value or index of his molecular weight, results equal to 49. The bulk is diluted with other 250 Kg. of methylic alcohol and the discharge is provided leaving in the reactor 200 Kg. Kg. 0,26 of H2S04 d. 1.83 are adjoined. The product is brought to ebb and maintained for 8 hours. Kg. 40 of methanolic solution of polyvinylacetate K 25 of the same type utilized in the example I is loaded. The azeotrope methyl-acetate-methylicalcohol is extracted for 15 hours until total extraction of 100 Kg. The process is stopped with 0,2 Kg. of NaOH liquefied in 50 It. of water. As in the example 1 the methylic alcohol residue is stripped and the product is diluted with water until a % solids of 30. As for the previous example to this new emulsion is given the code PVA-A2, the same results to be " constituted by 70 pp of PVA soluble in H20 with NS 230 and 30 pp of PVA insoluble in water with NS equal to 480. The technology of alcoholisis that emploies methylic anydrous alcohol and sulfuric acid has furnished a distribution of the groups OH classifiable in literature with the denomination "RANDOM". Example No. 3 In the reactor are loaded in the order: - 200 Kg. of methanolic solution with 26% of PVAc K50 of the same type described in the example 2; - Kg. 30 of solution of NaOH having the following composition: methylic alcohol Kg. 27, H20 Kg. 2,5, NaOH Kg. 0,3. The bulk is maintained to the temperature of ebb until observing a drop of temperature of 0.7°C. After that Kg. 50 of solution in methylic alcohol of PVAc K25 of the same type illustrated in the examples 1 and 2, are loaded. And the azeotrope methyl-acetate-methylicalcohol is taken for 8 hours until to a total taking of 100 Kg. The process is stopped with 0,6 Kg. of acetic acid (title 99%) fetching the pH to the value of 6.5. As for the examples 1 and 2, the process is prosecuted with the distillation of the methylic alcohol and adjoining water until a final % of solids equal to 30%. The aspect and the established of the emulsion, code PVC-A3, is equal to that referred to the preceding examples, its composition results the following: 65 p. p. of PVA with NS 230 and 10 cps (4% in H20) and 35 p. p. of PVA with 480 NS emulsified under the form of microparticles with diameter comprised between 0,01 microns and 10 microns. The technology of alcoholisis emploied for producing the emulsion PVA-A3 has been of the type comprising methylic alcohol + sodium hydrate + water and thus, as per literature, assume the denomination of "BLOCKY". This particular type of distribution of the hydroxylic groups easily verifiable by means of analysis with Nuclear Magnetic Resonance Spectroscopic (NMR), furnishes to the PVA distinct endowments of suspending agent and emulsifying agent and finds for this, particular use in the reactors for producing PVC-suspension of large dimensions, (100-150 mc) for which the problems of control of the granulometric distribution of the finished PVC-S are well known. Example No.4 With this test the inventor wants to demonstrate the importance that holds the technology of preparation and of pre-hogging, object of the present invention, of the polyvinylic alcohols to different NS, before the strippage of the solvents present in the same. The perfect hot jumble of pseudo-solutions of methylic alcohol-water of polyvinylic alcohols of different NS, allows in fact the creation of the habitat for the successive distillation of the methylic alcohol and the coagulation, in form of regulars microparticles with diameter comprised between 0.O1 microns and 10 microns of the polyvinylic alcohol totally insoluble in water. For carrying out this demonstration the inventor decided to carry out two separate alcoholisis and then to unite the bulks for the successive phases of strippage and dilution as claimed in the present invention. First phase of the example 4 In the reactor the inventor loaded Kg. 200 of methanolic solution with the 50% of PVAc-K25 equal to that emploied for the examples 1 -2-3, after that the inventor stabilized the product to the temperature of 37°C and in a time of 60 minutes, loaded Kg. 30 of a solution with 5% of sodium-methylate in methylic alcohol. After certain time the process is stopped with acetic acid until obtaining pH 6.5. IT is diluted with 30 Kg. of H20 demi. The solution containing polyvinylic alcohol with 480 NS is stocked separately for the successive adjoining to the solution coming from the second alcoholisis as described in the following. Second phase of the example 4 In the reactor 200 Kg. of methanolic solution with 50% of PVAc-K25 of the same type illustrated in the examples 2-3 are loaded. The temperature is increased to ebb and Kg. I of H2S04 d.1.83 is further loaded. The ebbing is prosecuted until dropping the temperature of the bulk in ebullition of 2°C. The process is arrested with Kg. 0.8 of NaOH liquefied in 50 Kg. of H20. The pH is controlled in order to be of 6.5 and the NS of the polyvinylalcohol be equal to 230. To the bulk hotting again and in agitation, is adjoined the methanolic solution produced with the first alcoholisis and homogenization is provided for at least 60 minutes. The process prosecutes with the successive operations of strippage and dilution as foreseen for the examples 1-2-3. The aspect of the emulsion, code PVA-A4, and the analytic result of the same, confirm the identity with the emulsions produced with the tests 1 -2-3. The polyvinylic alcohols present in the PVA-A4 came from two different technologies of alcoholisis and more exactly: RANDOM for the PVA soluble in water and BLOCKY for the PVA constituted from microparticles insoluble in water. Logically in the final emulsion the percentage of salts coming from the two separate hydrolysis, has a great level of % residual cinders, this % being 6 times more important then the % of the example No. 2 and more exactly from 0,05 to 0,33%. This augment of salts has a negative effect to the electrical properties of the PVC-S. Example No. 5 The good results obtained on the quality of the PVC suspension by means of the use of watery emulsion of polyvinylic alcohols (PVa), object of the present invention, with blends of PVA with technology of mixed alcoholisis RANDOM-BLOCKY, have fetched to the following new example: In the reactor 200 Kg. of methanolic solution of PVAc-K50 like to the examples 2- 3-4 is loaded. The temperature is stabilized to 35°C and in 4 hours, 10 Kg. of methanolic solution with the 5% of sodium methylate is loaded. After this time, 200 Kg. of solution of PVAc-K25 like to the examples 2-3-4 and Kg. 1.5 of H2S04 d.1.83 are further loaded. The product is brought to ebb and for further 6 hours the azeotrope methyl- acetate-methanol as already described with the preceding examples, is extracted. The total distilled is Kg. 120. The process is stopped with solution of NaOH in water until to pH 6.5. The process is prosecuted for the phases solvents strippage and dilution as for the preceding examples 1 -2-1 -2-3-4. The watery emulsion defined with code PVA-A5 is like to the preceding. The fraction of PVA soluble in water with distribution of the hydroxylic groups type BLOCKY-RANDOM, and the fraction of polyvinylic alcohol insoluble in water with distribution type random. In the enclosed table 1 all the data resumptive of the examples 1 -2-3-4-5 are reported. From the examination of the table I resumptive of the test of alcoholisis, it can be noted that the watery emulsion of different types of polyvinylic alcohols having different NS, can be obtained: - employing polyvinylacetate coming from polymerizations in watery emulsion, in watery suspension, in alcoholic solution and in break having thus different distributions of theirs molecular weights and with grade of polymerization as per the enclosed methods of analysis, indicated as K value variable from 10 to 1 10. - applying all the techniques of alcoholisis as known and reported in literature with the denominations " RANDOM-.BLOCKY" and with all theirs possible combinations. The process, object of the present invention, is highly reproducible and industrially applicable in economic and ecologic way for production of new suspending agent suitable to solve many problems of the polymerization of the vinyl chloride in suspension. Description of the examples of polymerization PVC-S reported in tables 2A and 2B. The tests of polymerization of the vinyl chloride monomer with types of PVA-AI- A2-A3-A4-A5, have been carried out with autoclave if 500 It. with internal walls in inox steel (AISI 316 LC), with ringleader type "impeller" and with two lames break wave mounted on the walls of the reactor in opposed position of 180°. The autoclave was provided by automatic system of charge with container closed, of the device of sputter of the solution anti-crust and of valve of internal washing with H20 Demi to 15 ATA. On the head of the reactor it was possible to insert a condenser to ebb of the surface of 2.5 mq. The polymerizations have been considered accomplished at the drop of the pressure of reaction to 3.5 bar and for each load the final conversion has been measured by means of degasage and recover of the not reacted VCM. The suspension has been stripped by means of injection directed of steam 4 ATA until to the temp, of 75°C. After the strippage, the suspension has been centrifugated and the PVC-S with the 23% of H20, after that is started the drying on fluid bed. After these treatments, equal for all the cited examples, the PVC-S has been analyzed as per the following methods of analysis: Appearing density: second DIN 53 - 468 - expressed in Kg/It. Plasticizing efficiency: second DIN 53 - 417 expressed in %; Granulometric distribution: second DIN 53 - 734; Resistivity of volume: second ASTM D257 - 66; Internal porosity of the medium diameter of the pores expressed in microns; medium volume of the pores expressed in cc/gr. Values sensed with mercury porosimeter of Carlo Erba series 200. .VCM residue after desiccation of the PVC-S, values expressed in p.p.m. sensed with gas-chromatographic method. Gelified particles - Fish-eyes: The following method has been utilized: For 5 minutes are mixed: 160 gr. of PVC-S, 80 gr. of phtalate of dioctyl , 0,8 gr. of stearate of zinky and 2,4 gr. of a premix made with PVC-S - carbon black and stearate of zinky. For calendering to 140°C a film of the thickness of 0,1 mm is prepared and after 5 minutes a board of 100 cm is taken and in transparence it is possible to count in the product obtained, the not pigmented particles (Fish-eyes) present in the sample of film. Thermic stability : This test is carried out on the samples of previously plasticized PVC-S, stabilized and lubricated as per standard proceedings and in comparison with samples of PVC- S. From the jumbles prepared after working for 10 minutes in calenders at 140°C, samples of the thickness of 1 mm, that are successively put in stews at 165°C are taken. After that the time expressed in minutes of variation of heat of the test in comparison with samples previously prepared is valued. More high is the time expressed in minutes and more the PVC-S will have a good thermic stability to the working. Examples 6-7-8-9-1 0 With this first series of tests it is demonstrated that the types of PVA-AI-A2A3- A4-A5, if empioied in formulation without the bearing of others primary suspensor or secondary suspensor can produce all the types of industrially known PVC-S. Thanks to the different compositions of the PVA-AI-A2-A3-A4-A5, it has been possibly to employ a constant quantitative of formulation for all the types of PVC-S with notable advantages, as well known to the skilled in art of the sector, in the successive phases of transformation and in the synergism with nontoxic stabilizing agents, etc . . In the test No. 6, a perfect compatibility of the PVA-A2 with the mercaptoethanol normally used as chain transfer for producing the PVC-S at low molecular weight has been observed. The inventor has verified that it is possible to utilize even other types of chain transfers Eg. trichloroethylene, dichloroethylene and, if necessary, a cross-linking type diallyl-maleate. Example 11 The use of the PVA-A2 with tests that provided the insertion of the condenser of ebb in the autoclave of polymerization, allowed to establish that the quality of the finished PVC-S does not undergo harmful worsening respect the others test swithout the condenser. After 20 loads carried out with PVA-A2 the condenser of ebb resulted perfectly cleaned to confirm the antifoam effect and anti-emulsion effect that the PVA-A2 furnishes just from the first moment of polymerization. The augmentation of productivity of the reactor has been of about 20%. Example 12 This test, carried out with initial load of H20 Demi at the temperature of 65-70°C, affronts and solves one of the main problems of the charging in autoclave and namely the possibility of reducing of at least 30 minutes the starting time of heating with liner expounds to the reactor. This important technique of charge, not only allows a notable reduction of the recycle of production, but also avoids the carrying out of prolonged overheating in liner of the reactor to all detriment of the efficacy of anti-crust effect by the special agents applied with various techniques to the intern of the reactor before the charge. The advantage of obtaining a homogeneous and instantaneous dispersion of all the microparticles of PVA insoluble in water just from the first instant of reaction starting, demonstrates in this case the extreme industrial interest; in fact, it is possibly to realize increments of production without undergoing the well known negative effects on the quality of the in the finished PVC-S. Example 13 The previously analyzed tests 6 to 12 have been carried out with value of pH of polymerization starting equal to 7 by means of use of 300 ppm of NaHC03 as tampon. The inventor relieved that it is further possible to control the value of pH even with other types of tampon, as for example: ammonium hydrate, sodium hydrate, sodium carbonate, magnesium hydrate, sodium phosphate. The test 13 demonstrates that in absence of tampon, and with some ppm of air residual (02) to the starting of charge in autoclave and hence with values of pH prox to 3, the quality the of the PVC-S is maintained to high values. The technique of the control of the residues (vacuum) in the reactor, finalized to control the granulometric distribution of the PVC-S, is perfectly applicable on formulations that employ the types of PVA object of the present invention. Example 14 With the test No. 14 in comparison with the test 6, the efficacy of the PVA type A2 in the case of charge of the same in two different moments of polymerization and exactly 1200 pp of initial charge and 600 ppm in 30' after the first hour of polymerization is demonstrated. The apparent density and the thermic stability of the PVC-S have had the foreseen improvement, the granulometric distribution is resulted of optimum level and the same for all the other characteristics. Examples 15 and 16 By means of the use of techniques of dispersion with rolling soakers and/or techniques that utilize the evaporation of the solvents (methyl-acetate, ethyl- acetate, etc.) with a great values of vacuum (-680 mm Hg) (point of ebullition 6°- 8°C), thhe inventor prepared with the PVA type A2 watery emulsion of the following catalyzers % % % % % total catal. PVA-A2 water ethilic solids alcohol a - laurilperoxide 3 0 1 5 1 5 70 - b - miristilipercarbonate 3300 1 5 1 5 70 - c - etil-esil-percarbonate 2244 1 2 1 2 6 0 1 6 d - culmil-perneodecaonate 2244 1 2 1 2 6 0 1 6 With the so prepared emulsions of the catalyzers for PVC-S, the inventor has carried out the tests of polymerization No. 15 and 16. From the kinetic behavior of the polymerization and from the analytic result of the finished PVC-S, the inventor verified that the PVA is a product particularly adapt to produce watery emulsion of catalyzers without the necessity of contemporary use of other types of suspending or emulsifying agents harmful for certain property of the PVC-S, as for example the resistivity of volume, the appearing density and the granulometric distribution. The optimum stability of the watery emulsion of the catalyzers type a-b-c-d and their efficacy in the final quality of the PVC-S is caused by the fact that the microparticles of catalyzer, obtained with the previously described techniques, with diameter comprised between 1 and 8 microns, is brought to touch other stable microparticles of equal diameter of polyvinylalcohol insoluble in water and together they are emulsified in water thanks to the great fraction of polyvinylic alcohol soluble in water present in the PVA. In the tests c and d the ethylic alcohol has the function of lowering the point of freezing of the emulsions around -20°C. The presence of the ethylic alcohol in the watery emulsion is intrinsic in the process of preparation and distillation of the PVA, object of the present invention, in fact, even if all the examples cited in the preparation of the PVA-AI-A2-A3-A4- A5 have been utilized the methylic alcohol , it is possible, and for the skilled man it is known, to carry out all the hydrolysis in ethylic alcohol and to the end to leave residues of ethylic alcohol second the necessity of the dots of freezing required to the emulsions itself. In all the cases the characteristics of the finished PVC-S are resulted of a great qualitative level. The pejorative phenomenons already observed in past by the skilled man and ought principally to the not good dispersion of the particles of catalyzer just from starting of polymerization have not been revealed. Examples 1 7- 18- 1 9-20-21 -22-23 This last group of tests has been carried out for illustrating to experts of this field certain important applications of the product object of the present invention. The limited number of examples reported should not however be considered as a limit to the multiplicity possible applications. By the examination of this group of tests the expert can be verify that the PVA-A2 is perfectly compatible with all the technologies and with all the known suspending agents emploied in the polymerization of the PVC-S. The morphologic characteristics of the finished PVC-S is confirmed in the levels of optimum qualification, overall for the values of granulometric distribution, of thermic stability, of internal porosity and of VCM residue after the desiccation of the PVC-S. During the tests it has been possible to disperse the PVA cold in the solutions of the various primary suspensors and with them conveied to the automatic lines of charging of the water to the reactor itself. The microparticles of PVA resulted stable and have not sensed phenomenons of adhesion or coagulation by contact both with the solutions of suspending agent, that by contact with the water non completely warmed before the charging of the autoclave. Example of cleaning of the autoclave With the formulation reported in the example No.ll the inventor has carried out cycles of 20 polymerizations by means of, after each polymerization, application of different types of anti-crust agents . The result is that in all the cases the optimum compatibility of the product object of the present invention with different anti-crust products has been confirmed. After 20 polymerizations carried out with each type of anti-crust agent, both the internal parts of the reactor and the condenser of ebb, resulted perfectly clean and exempt from residues that alternatively require the suspension of the cycle of test. Advantageously for a good result of the process the inventor suggests to utilize a catalyzer that comprises sulfuric acid, and/or sodium methilate, and/or sodium hydrate, respectively in the proportions parts in weigh respect to the PVAc present, comprised between 0,05 and 8 for each of the elements mentioned and independently one from the other. Preferably from the industrial necessity and looking at the costs, the alcohol utilized in the alcoholisis is methylic alcohol in the proportion in parts of weigh respect to the PVAc present, comprised between 0,2 and 20, preferably 3. Obviously the methylic alcohol in the same proportions can be advantageously substituted in all or in part with ethylic alcohol for toxical aspects or alternative use. table No.1 ABSTRACT OF THE EXAMPLES 1-2-3- 4 - 5 Example No. 1 2 3 4 5 a - code of the product PVA •A1 A2 A3 A4 A5 b - % active substance 30 30 30 30 30 c - % PVA soluble in water present 70 70 65 46 46 in the active solution d - number of saponification of the 230 230 230 230 230 fraction reported in (c) e - % PVAc insoluble in water present 30 30 35 54 54 in the active substance under the form of microparticles f - number of saponification of the 480 480 480 480 480 fraction reported in (e) g - viscosity at 20°C in cps of the .45 8 8 8 8 watery solution with 4% of the fraction indicated in (c) and (d) g - K value of the PVAc utilized for producing 102 49 49 49 4 the fraction indicated in (e) and (d) i - K value of the PVAc utilized for producing 25 25 25 25 2 the fraction indicated in (e) and (d) _ o Q >- 2 -: < ϋ I - type of alcoholisis as the definition DC _≥ O > _ι LU o - co Q reported in literature ϋ tΞ 1 < o _1 _ Q. ~z CO o O Έ o z < ϋ cc TABLE 2A example No 10 12 13 14 21 IDROXY-PROPIL-METHIL CELLULOSE or METHYL-CELLULOSE c pp 22 IDROXY-ETHIL-CELLULOSE or IDROXI-PROPIL-CELLULOSE PP - - - 23 PVA 137NSand43cps p.p. - 24 PVA 230 NS and 37 cps PP - - 25 PVA 290 NS and 5 cps pp. - - - " 26 SORBITOLE MONOUURATE orSORBITOLE MONOSTEREATE pp. - 27 MERCAPTO-ETHANOLE PP 200 - 28 time of reaction h m' 5 30 6 6 6 6 4 30 6 6 5 40 29 final conversion % 88 91 92 92 92 92 92 92 88 30 VCM residue after slripping ppm 28 23 18 20 20 20 20 22 25 31 Apparent density Kg/It 0,535 0,515 0,500 0,505 0,505 0,505 0,500 0,480 0,550 b 32 Internal porosity • volume of the respective pores cc/gr 0,23 0.33 0,39 0,35 0,36 0,37 0,39 0,40 0,22 33 Internal porosity - ponderated diameter of the pores micron 0,45 0,67 0,95 0,70 0,75 0,70 0,90 0,90 0,45 34 Absoption of the plastificant % 26 35 40 36 37 36 36 38 25 35 Gels or Fish - eyes No. <5 <5 <5 <5 <5 <5 <5 <5 <5 36 Resistivity of the volume 10 " • - 10 10 6 7 9.8 9.7 9,8 - 37 Thermal stability m' 120 120 115 100 105 110 115 95 120 38 Residual VCM after dessication PPm 1 1 <1 <1 <1 <1 <1 <1 <1 39 ( RESIDUAL PVC-S on 60 microns % 0 0 0 0 0 0 0 0 0 40 ( " 80 % 1 2 0 2 3 1 4 3 2 41 GRANULOMETRIC ( " 100 % 10 10 1 18 22 8 6 11 13 42 DISTRIBUTION ( " 140 % 68 75 65 65 62 77 75 73 62 43 ( " " 200 % 18 12 29 12 10 13 14 12 20 44 " BOTTOM % 3 1 5 3 3 1 1 1 3 TABLE 2A Example No. 6 7 8 9 10 11 12 13 14 1 type of PVC - S K Value 57 67 70 70 70 70 70 70 57 2 reactor with condenser of ebb ro to ND ND ND SI ND ND ND 3 TEMPERATURE of polymerization "C 64 57 54 54 54 54 54 54 64 4 TEMPERATURE of charge H 2 0 DEMI °C 30 30 30 30 30 30 65 30 30 5 H 2 0 DEMI PP 150 130 120 120 120 120 120 120 120 6 vinylchloride monomer (VCM) PP 100 100 100 100 100 100 100 100 100 7 NaHC0 3 - tampon PP 300 300 300 300 300 300 300 0 300 8 PVA - A1 PP - 1800 - - 9 PVA - A2 PP 1800 - - 1800 1800 1800 10 PVA - A3 PP - - 1800 - - - - 1200 3 11 PVA - A4 PP - - - 1800 - - - - - Cxi 12 PVA - A5 PP - - - - 1800 - - - 13 PVA - A3 second charge after 1 hour pp. - - - - - - - - 600 14 first empty of the VCM charge mm/Hg MAX MAX MAX MAX MAX MAX MAX 500 MAX 15 initial pH of polymerization ph 7 7 7 7 7 7 7 3,1 7 16 UNCHANGED LAUROIL-PEROXIDE PP 700 300 100 100 100 100 100 100 700 17 LAUROIL-PEROXIDE in watery emulsion with PVA - A2 PP - - - - - - - - 18 UNCHANGED MIRISTIL-PERCARBONATE PP 200 400 500 500 500 500 500 500 200 19 MIRISTIL-PERCARBONATE in watery emulsion with PVA -A2 pp. - - - - - - - - 20 2-ETIL-ESIL-PERCARBONATE + CUMIL - PERNEODECANOATE in emulsion water - ethanol with PVA - A2 PP TABLE 2B Example No. 15 16 17 18 1 s 20 21 22 23 21 IDROXI-PROPIL-METHIL CELLULOSE or methyl - cellulose p.p. - 0,03 0,03 0,03 22 IDROXI-ETHIL-CELLULOSE or IDROXI-PROPIL-CELLULOSE pp, - - 0,04 23 PVA 137 NS and 43 cps p.p. - - 0,06 0,05 0,04 24 PVA 230 NS and 37 cps p.p. - 0,03 - 25 PVA 290 NS and 5 cps PP - 0.03 0,06 26 SORBITOL MONOLAURATE or SORBITOL MONOSTEREATE PP 0,05 27 MERCAPTO-ETHANOL p.p. - - - 28 time of reaction h m' 6 5 6 6 6 6 6 6 6 29 final conversion % 92 92 92 92 92 92 92 92 92 30 residual VCM after stripping ppm 23 23 23 25 25 25 23 23 25 31 APPARENT DENSITY ' Kg/It 0.500 0, 500 0,502 0,498 0,500 0,538 0,500 0.50C 0,500 32 INTERNAL POROSITY -VOLUME OF PORES cc/gr 0,38 0, 37 0,37 0,37 0.33 0.28 0,36 0,37 0,37 33 INTERNAL POROSITY - AVERAGE DIAMETER OF PORES micron 0,85 0, 85 0,85 0,90 0 70 0,42 0,80 0,90 0,90 34 PLASTICIZING ABSORBTION % 36 38 38 35 32 31 36 36 36 35 FREEZES OR FISH -EYES No. <5 <5 <5 <5 <10 <25 <5 <5 <5 36 VOLUME RESISTIVITY 10 " 13 -_-vcm 10 10 9,9 9 6 8 8,5 9,2 7 37 THERMIC STABILITY m' 115 115 118 115 120 102 115 115 115 38 VCM RESIDUE AFTER DRYING ppm <1 <1 <1 <1 <1 <1 <1 <1 <1 39 ( RESIDUAL PVC-S on 60 microns % 0 0 0 0 0 0 0 0 0 40 ( " " " 80 % 3 4 0 4 3 4 4 4 4 41 GRANULOMETRIC ( " 100 % 21 18 16 19 23 25 11 11 20 42 DISTRIBUTION ( M 140 % 78 68 70 67 69 49 71 81 72 43 ( " " " 200 % 7 8 11 9 4 18 13 3 3 44 ( BOTTOM % 1 2 3 1 1 4 1 1 1 TABLE 2B Example No 15 16 17 18 19 20 21 22 23 1 type of PVC - S K Value 70 70 70 70 70 70 70 70 70 2 reactor with condenser of ebb ND MD ND ND ND ND 1*0 ND ND 3 themperature of polymerization C 54 54 54 54 54 54 54 54 54 4 themperature of charge H 2 0 DEMI C° 30 30 30 30 3C 30 30 30 30 5 H 2 ODEMI PP 120 120 120 120 120 120 120 120 120 6 chloride of vinyl monomer (VCM) pp. 100 100 100 100 100 100 100 100 100 7 NaHC0 3 - tampon pp. 300 300 300 300 300 300 300 300 300 8 PVA - A1 PP* 9 PVA - A2 PP 1200 1300 1200 1200 1200 1000 1300 1 200 1 200 12 PVA - A5 PP 13 PVA - E66-A3 second charge after 1 hour PP 14 empty first of the charge VCM mm/Hg MAX MAX MAX MAX MAX MAX MAX MAX MAX 15 pH initial of polymerization PH 7 7 7 7 7 7 7 7 7 16 Unchanged LAUROIL-PEROXIDE PP 100 100 100 100 100 1 00 1 00 (100) (200)' 17 LAUROIL-PEROSSIDO IN watery emulsion whith PVA - A2 PP 200 400 18 Unchanged MIRISTIL-PERCARBONATE PP 500 500 500 500 500 500 500 (500) * 19 MIRISTIL-PERCARBONATE in watery emulsion with PVA - A2 pp. 1000 20 2-ETIL-EXIL-PERCARBONATE + CUMIL-PERNEODECANOATE (330) * in emulsion water-ethanol with PVA - A2 PP 700 the values within ( * ) indicate the p p of effective catalyzer

Claims: 1 CLAIMS 2 1 - A process for the preparation of watery emulsion of two or more polyvinylic 3 alcohols (PVa) with different saponification number (NS) for the production of 4 polyvinylchloride (PVC-S) in watery suspension characterized from the following 5 steps: 6 - to utilize at least a first polyvinylacetate (PVAc) with molecular weight measured 7 in K value comprised between 30 and 110, preferably 50 and to carry out the 8 alcoholisis of the PVAc until the values of NS comprised between 598 and 135 9 preferably between 598 and 312, optimally 511 , in presence of ethylic alcohol or I 0 methylic alcohol with catalyzer acid or basic; I I - to load from 0,1 to 5 times preferably 0,7 times, parts in weigh respect to the 1 2 first PVAc, of at least a second PVAc having molecular weight measured in K value 1 3 comprised between 10 and 90, preferably between 10 and 50, optimally 25; 1 4 - to stop the alcoholisis in order that, in the final alcoholic solution, the respective 1 5 PVA result perfectly mixed in order to obtain: 1 6 a) at least a first PVA, with NS comprised between 280 and 95, preferably 230, 1 7 soluble in water; 1 8 b) at least a second PVA, with NS comprised between 598 and 312, preferably 1 9 480, insoluble in water; 20 - having the knowingness of distilling during the alcoholisis or at his termination, 2 1 the residual solvents adjoining after the alcoholisis, water with the scope of 22 obtaining the coagulation in water of the second PVA under the form of 2 3 microparticles with granulometric distribution comprised between 0,01 microns 24 and 10 microns. 25 2 6 2 - A process for the preparation of watery emulsion of two or more polyvinylic 27 alcohols (PVa) with different saponification number (NS) for the production of 2 8 polyvinylchloride (PVC-S) in watery suspension as claimed in claim 1 , 29 characterized in that said catalyzer is or sulfuric acid, and/or sodium methilate, 1 and/or sodium hydrate, respectively in the proportion parts in weigh respect to the 2 PVAc present, comprised between 0,05 and 8 for each of said elements and 3 independently one from the other. 4 5 3 - A process for the preparation of watery emulsion of two or more polyvinylic 6 alcohols (PVa) with different saponification number (NS) for the production of 7 polyvinylchloride (PVC-S) in watery suspension as claimed in claim 1 , 8 characterized in that the alcohol utilized in the alcoholisis is methylic alcohol in the 9 proportion in parts of weigh respect to the PVAc present, comprised between 0,2 0 and 20, times, preferably 3 times. 1 2 4 - A process for the preparation of watery emulsion of two or more polyvinylic 3 alcohols (PVa) with different saponification number (NS) for the production of 4 polyvinylchloride (PVC-S) in watery suspension as claimed in claim 1 , 5 characterized in that the alcohol utilized in the alcoholisis is ethylic alcohol in the 6 proportion in parts of weigh respect to the PVAc present, comprised between 0,2 and 20 times, preferably 3 times. 8 5 - A watery emulsion of two or more PVA with different NS as claimed in claim 1. 1 6 - The use of blends of watery emulsion of two or more PVA to different NS, realized according to the characteristics in claim 1 in the polymerization of the vinyl chloride in watery suspension (PVC-S).

Inventors: CARLIN FRANCESCO, CARLIN, FRANCESCO
Applicants: CARLIN FRANCESCO, CARLIN, FRANCESCO
Application year: 1990
Main classification: C08F8
IPC codes: C08F2, C08F8