WO2005111093A1 - Method for the synthesis of chemical materials, comprising the controlled interaction of gases or vapours in a mass of polymer material - Google Patents

Abstract

The invention relates to a method for the synthesis of chemical materials, comprising the controlled interaction of reactive gases or vapours in a mass of polymer material which is heated to between 180 °C and 750 °C, in which the gases or vapours, which can be solid or liquid at ambient temperature, serve as reaction inhibitors, catalysts and co-reagents, with or without the presence of external catalysts and inhibitors. Moreover, the reaction pressure is a control variable and may be equal to or different from atmospheric pressure.

Description

A PROCEDURE FOR THE SYNTHESIS OF CHEMICAL MATERIALS, BY THE CONTROLLED INTERACTION OF GASES OR REACTIVE VAPORS WITHIN A MASS OF POLYMER MATERIAL

TECHNICAL FIELD OF THE INVENTION

The present invention relates to a process for the synthesis of chemical materials from the controlled interaction of gases or vapors that are injected into and on a mass of polymeric material heated between 180 ° C and 750 ° C, acting as levers, catalysts and reaction inhibitors, together or without the presence of catalysts and external inhibitors and where the Reaction Pressure is also a control variable

STATE OF THE TECHNIQUE AND PROBLEMS TO BE SOLVED

The transformation of polymers or macromolecules into smaller molecules has been known and exploited for a long time.

Natural materials such as starch glucose polymers have been degraded and transformed into alcohol since ancient times, cellulose has also been depolymerized by distillation of wood and is currently transformed into sugars enzymatically, from residues derived from agricultural activity such as corn marlo, or bagasse, from which Xylitol can be produced, as well as Furfural It is known that synthetic polymers such as polyvinyl alcohol and polyvinyl acetate, or even Slightly transformed, such as cellulose acetate, are biodegradable, so are Polyhydroxyalkanoates, which are polyesters that accumulate as an energy reserve within the cells of many bacteria under conditions of limited growth (polymers synthesized and degraded by bacteria) [Major JM, Kaplan, DL "Biodegradabie materials: Balancing Degradability and performance" Advanced Materials, 12 (7), 227 - 234 (1994)]. The process of subjecting plastic waste to a thermal or catalytic process to recover the monomer or to produce a liquid fuel is also known. The first studies in this regard were published as early as 1948 with a study on Mass Spectrum Analysis for Thermal Decomposition of Polymers, (National Bureau Standards (US) .41.315-322)

In 1949, W.G. Oakes, R.B. Richards, published in J. Chem. Soc. (1949) pag 2929-35 works in this regard, also published a paper on the Pyrolysis of Hydrocarbon Polymers, in Science 111, page 360-361 in 1950

There are other similar published background such as:

[H. Staudinger, A. Steinhofer, Ann. Chem. 571 (1935) 35. [R. Simha, LA. Wall, J. Phys. Chem. 56 (1952) 707. [S.L. Madorsky, S. Straus, J. Res. Nati. Bur Stand 53 (1954) 361.

GIVES. Anderson, E.S. Freeman, J. Polym. Sci. 54 (1961) 253. -

[J.V. Schooten, P.W.O. Wijgo, Thermal Degradation of Polymers, Monograph no. I

13, Society of Chemical Industry, London, 1961, p. 432. [T.E. Davis, R.L Tobias, E.B. Peterli, J. Polym. Sci. 56 (1962) 485. R.M. Fuoss, O. Salyer, H.S. Wilson, J. Polym. Sci. A 2 (1964) 3147.

[Y. Tsuchiya, K. Sumi, J. Polym. Sci. A 7 (1969) 813.

[S.L. Malhotra, L Hesse, L.P. Blanchard, Polymer 16 (1975) 81.

E. Kiran, J.K. Gillham, J. Appl. Polym Sci. 20 (1976) 2045.

H. Nishizaki, K. Yoshida, JH Wang, J. Appl. Polym Sci. 25 (1980) 2869. The conversion of a polymer into the monomers that constitute it, so that they can be re-polymerized to generate the virgin polymer is well known since at least the fifties. This method can also be applied to macromolecules obtained by polycondensation, such as polyethylene terephthalate (PET) and polyamides and some polymers such as polyurethanes

PET recycling by hydrolysis to generate dicarboxylic acids and diols is known. However, the hydrolysis reaction takes place under very severe conditions and requires long reaction times, so it is not industrially viable. The recyclers prefer, in this case, the alcohololysis (methanolysis) to regenerate, after the corresponding separation and purification, the monomers used in the polymerization (dimethyl terephthalate and ethylene glycol). The process consists in mixing the granules of recovered PET with methanol in the presence of a catalyst. The mixture is heated under pressure to force depolymerization of PET into its base components. Finally, the products of methanolysis are cooled to crystallize dimethyl terephthalate (DMT), which is separated quite pure by filtration, followed by washing with methanol and distillation. Ethylene glycol is separated from the filtrate by distillation [Bauer, G. "Alcoholysis - a process for chemically recycling pur and mixed plastics waste" Kunstoffe Germán Plastics 91: 41991]. It is also possible to depolymerize PET by glycolysis by heating PET granules with ethylene glycol in an autoclave at 240 C [Derry, R. "Plastics recycling in North America" Department of Trade an Technology of UK (1991).].

The French Institute of Petroleum (IFP) and Technochim Enginecring, has developed a process for the recycling of bottles and PET by saponification of the polymer and subsequent hydrolysis of the salt obtained

As in the case of PET, polyurethane residues (PUR) can be depolymerized by wet means by hydrolysis, alcoholysis and glycolysis. By hydrolysis, the polyurethanes (PUR) give rise to the corresponding polyol, carbon dioxide and the amine corresponding to the starting isocyanate. Alcohololysis involves the attack of the long molecular chain of polyurethanes for a short chain alcohol. The reaction is carried out for two hours. The process is based on a series of reactions between a glycol and the urethane groups of the polymer that take place in a reactor at 200 ^e C. Under a nitrogen atmosphere and using a metal organ catalyst. Finally, a liquid product is obtained which, mixed with polyols, serves as the basis for the production of new polyurethane foams. "Method of depolymerizing polyethylene terephthalate and process for producing polyester resin", N ^s patent: WO03064510.

It is known the complete depolymerization by Ammonolysis that transforms the nylon into a block structure or monomers that can then be repolymerized to manufacture nylon in all its forms and for all markets.

There are also high-performance thermal processes to depolymerize Polymethylmethacrylate, used by Parachemic (Germany) and Ato-Haas (France). E.I. Dupont de Nemours also commercially uses thermal depolymerization of polyacetal to generate formaldehyde.

It has also been published that thermal decomposition at temperatures between 500 ^S C and 1,000 ^S C and in the absence of oxygen, of large organic molecules produces three fractions (gaseous, liquid and solid). (Chem.Abs. 47 3609, Heimrich Hopff, Kunstsoffe 42 .pag. 423-426 1952)

Under these conditions, the plastic does not burn, but smaller molecules break down, giving rise to various reusable commodities by the petrochemical industry (gas mixtures - ethylene, propylene and butadiene - and mixtures. Of light gasoline and tar) and a gas natural for domestic use.)

It is also known the partial oxidation of the polymer chains that constitute the plastic waste to produce synthesis gas (mixture CO + H), which can be used as raw material for the manufacture of methane, ammonia or OXO alcohols, as fuel for electricity generation , or even, as a reducing agent for the production of steel in blast furnaces. There are several patents granted on the gasification of plastic waste, the synthesis gas obtained, once cleaned, is burned in a gas turbine to produce electricity.

Also by treatment with hydrogen at elevated temperatures and pressures, plastic waste is converted into various hydrocarbons, leaving between 5 - 10% of non-hydrogenatable waste that occupies little space in landfills In US5369215 patent granted to PLATZ GERALD M (US) the 1994-11-29 "Depolymerization method for resource recovery from polymeric wastes", describes a process to recover monomers of vulcanized addition polymers, comprising the steps of: washing the polymer to remove the additives from the surface; (b) exposing the washed material to the gaseous ozone under sufficient conditions to break chemical bonds that formed during the polymer vulcanization process (c) heating the entire mixture formed in the previous step in the presence of a catalyst at a temperature and for a sufficient time to depolymerize the polymer and form the monomer; and (d) extract the monomer that continues to form in the mixture. Another more modern background is the patent: US6271427 / 2001-08-07 of ERSHAG BENGT-STURE (SE) "Method for recovery of carbon and combinations of hydrocarbons from polymers, preferably in the form of disposed tires, by pyrolysis in a pyrolysis reactor "is a method for the recovery of carbon and hydrocarbons from used covers or similar polymeric material, using a reactor in which the material is fragmented and heated to the temperature of the pyrolysis aided by the recirculation of the gas from the same pyrolysis

OBJECT OF THE INVENTION

Some of the processes mentioned above are complex and / or not designed so that the products obtained are different from the original monomers or that allow them to be characterized as sources of new raw materials of specific composition and in general its use is intended to recover monomers and / or produce hydrocarbon fuels of variable or indefinite composition

On a global scale, currently 70% of the plastic material that is available to be used for recycling, is formed by Polyethylenes or Polypropylenes Polyethylenes are usually differentiated by their density but from a scientific point of view the best distinction is the degree of branching of chains. The first polyethylene, later called PEBD, was and still is manufactured by a high pressure process that uses a free radical initiator / catalyst and is a polymer with a high degree of branching of the chains. Subsequently, low pressure processes were developed using related catalysts or Ziegler-Natta that allow to obtain a much more linear molecule.

These are high density polyethylenes (PE-HD); This technology is used today to manufacture a family of (chemically) related polyethylenes and all are linear - ULDPE (ultra high density PE), LLDPE (linear low density PE), MDPE (medium density PE), HMWPE (PE high molecular weight) and UHMWPE (ultra high molecular weight PE).

Polypropylene is a linear polyolefin that can be compared in several ways with high density and similarly manufactured polyethylene. The catalysts used control stereoregularity in such a way that commercial polypropylenes are usually predominantly isotactic. The number of products obtainable from the treatment by the method of this invention to these two polymers and their mixtures or derivatives, is very large and can be used with great advantage, because even when treated under similar conditions, they differ greatly, due to the degree of Branching of its chains One of the purposes of the present invention is the obtaining of economically accessible chemical materials, similar to that made from petroleum or "Petrochemicals", coal or "Carbochemicals" These and other purposes are achieved with the technique of the present invention, which consists in depolymerizing and recombining the macromolecules that make up the plastic substances with each other and with reactive coagents, to obtain new substances not present in the original polymer and other than its monomers. it is possible because, for example, in the case of polyolefins the reaction can be reversible and then depolymerization occurs. This requires considerable energy consumption, because 6.25 x 10-19 joules are necessary to break a CC type link. This value may seem small, but if we compare it with the 3.1 x 10-22 joules necessary to increase the temperature of a polyethylene from 5 ⁹ to 35 ^Q C, we see that 2000 times more energy is required to break the union ^' average CC of a polymer that to raise the temperature of those atoms by 30 ⁹ C.

The reason is that in polyolefins there is the following thermal degradation mechanism:

Where it is agreed that Polymer = Monomer for (n) times = M (n) Random Initiation (Random): 1) M (n) <-> M (j) «+ M (nj)» where (j) is the size of the new free radical generated Chain End Initiation: 2) M (n) <-> M (n-1) «+ M« Propagation 3) M (i) «<-> M + M (i-1) «Transfer

4) M (i) «+ M (n) <-> M (¡) + M (n)« Excision

5) M (n) «<-> M (k) + M (n-k)« Termination

6) M (k) «+ M (ji -> M (k + j) or also M (k). + M (j)« <-> M (k) + M (j) Thermal degradation of polymers consists of two kinds of cleavages or cuts, which occur simultaneously in the reactor. One is a split of chance and the other is a split at the end of the polymer chain. Random cleavage of DC links is the main cause of the reduction of the average molecular weight of the crude polymer in the reactor. The end cleavage of the CC link chain causes the main generation of products with low Molecular Weight, volatile at the reaction temperature.

The proportion of random cleavage is proportional to the number of CC links and the proportion of cleavage at the chain end is proportional to the number of molecules. It has been determined experimentally that the Reaction Pressure has an effect on the cleavage of the chain end, since it takes place on the Gas-Liquid interface which is the one that generates volatile products at the reaction temperature. On the other hand, the excision of chance does not exhibit any effect appreciable by pressure, since it takes place in the liquid phase. Consequently, the characteristic synthesis process of this invention controls the formation of low molecular weight and volatile products during thermal degradation of polymers, because this occurs in a heterogeneous reaction in which the reactant is in a liquid phase and The product is in a gas phase. On the contrary, when what is desired is to obtain non-volatile molecules of intermediate molecular weight, such as, for example, Polyethylene or Polypropylene Waxes, the method of this invention generates a uniform material with good performance because it reduces the formation of volatile products. . DETAILED DESCRIPTION OF THE INVENTION The invention presented here takes advantage of the aforementioned depolymerization mechanisms and other complementary ones called: Interference, Strapping, New Excision and New Termination, which occur in different polymers, presenting a potential usable alternative to control the creation and distribution of products. in a process to convert plastics during thermal degradation.

As an example we transcribe the proposed new equations to describe the stages mentioned:

Interference

8) M (¡) «+ A <-> A * + M (i) Belt

9) M (i). + A <-> AM (i). New Excision

10) AM (n). <-> AM (k) + M (nk) «New Completion 11) AM (k + AM (j). <- AM (k + j) or also AM (k + AM (j)» <-> AM ( k) + AM (j)

In order to better understand the idea of this invention, it is useful to assume that in the previous example in the Strapping stage, the substance injected and foreign to the polymer, called A, actually refers to a simple compound, of the type A = B (q) C (w), such as Carbonic Anhydride, C02, Water, H20 or also more complex of type A = B (q) C (w) D (x) such as Ethanol,

C2H60

In these circumstances the stages of New Excision and New Termination are more complex and are of the type: Examples of New Excisions

12) B (q) C (w) D (x) M (n) »-> B (q) C (w) D (x) M (k) + M (nk 13) B (q) C (w) D (x) M (n) «<-> D (x) M (k) + M (nk) + B (q) C (w)« 14) B (q ) C (w) D (x) M (n) «<-> C (w) D (x) M (k) + M (nk) + B (q

15) B (q) C (w) D (x) M (n ^ → B (q-y) C (w) D (x) M (k) + M (n-k) + B (y) «Examples of New Terminations

16) B (q) C (w) D (x) M (k) «+ B (t) C (u) D (g) M (j <-> B (q + t) C (w + u) D (x + g) M (k + j)

17) B (q) C (w) D (x) M (k) «+ B (q) C (w) D (x) M (j). -> B (q) C (w) D (x) M (k) + B (q) C (w) D (x) M (j)

These new equations are those used in the chemical transformation processes of this invention, because: A) There is the possibility of greatly modifying the products resulting from depolymerization, B) There are many reaction pathways leading to a multiplicity of final products , C) NOT all of these processes are going to be thermodynamically similar and even less so in the presence of catalysts or inhibitors or by modifying the Reaction Pressure which allows the reaction to be oriented in the desired direction. The above is just an example, the consequences of which are evident for those skilled in the art, not being exhaustive or limiting, since the concept of Interference and Strapping stages, with the appropriate qualifications, can also be applied to polymeric degradations that do not involve a Free Radical Mechanism and that refer to other reactions Chemicals such as Hydrolysis, Ammonolysis, Oxidation, etc. The breaking of the polymer chains can be carried out in the presence of a catalyst. Basically, the catalyst performs two functions: it accelerates the cracking reactions of the polymer, which allows working at lower temperatures with respect to purely thermal processes and also makes it practical to orient the reaction towards the formation of certain compounds. In this way, it is possible to control and increase the commercial value of the products resulting from the degradation of plastics.

One of the limiting factors in the use of solid catalysts in the conversion of certain plastics such as Polypropylene or Polystyrene, is the presence of lateral substituents in the polymer chains that prevents or restricts their access to the micropores inside the solid particles of the catalyst, so that the procedure of this invention solves this problem, by the creation of gas / liquid interface areas by means of the injection of gases or vapors directly into the polymer mass Another of the purposes of the present invention is to obtain chemical materials by synthesis, in reactors for continuous process, which can be constructed of small size, due to the high reaction rate which is achieved by the process proposed by this invention for the transformation of polymeric materials. Another purpose is the use of plastic waste, such as polyethylene, polypropylene, polystyrene, polyethylene terephthalate (PET) containers, etc. in the manufacture of said products. Another of the purposes of the present invention is to obtain cheap chemical materials, generating a source of new raw materials, by creating base molecules suitable for successive chemical transformations in a similar way to that made from petroleum or "petrochemical", These and other purposes are achieved with the technique of the present invention, which consists in depolymerizing and recombining the macromolecules that make up the plastic substances with each other and with reactive agents to obtain new molecules not present in the original polymer and other than their monomers. Basically the The technique of the present invention consists in interacting with the normal depolymerization mechanisms of macromolecules, adding gaseous belts or vapors at the reaction temperature and where the reaction pressure is also used as a control variable and can be equal to or different from the atmospheric pressure. all of which r it is carried out in the presence of inhibitors and catalysts or acting themselves as inhibitors and catalysts, in order to obtain certain chemical substances, other than the original monomer As will be seen in the following examples, the synthesis processes presented in this invention can be carried out in an industrial way, both in a batch process, and in a continuous way, through the continuous injection and extraction of the polymers, the reactive gases, catalysts and inhibitors.

Example 1: Material Parts by Weight Polypropylene 3,000 Gr.

1Gr copper stearate.

Procedure: Description of the equipment according to drawing N ° 1: (1) Borosilicate glass ball, Pyrex brand or similar, with 5 Its .. capacity and 3 frosted mouths, (2) Refrigerant, (3) Injector Tube surface gas, (4) Injector tube of gases or vapors in the melt, (5) Agitator, (6) and (7) Thermocouples, attached to digital thermometers, (8) Heating blanket, (9) Fraction collector Description of the technique:

The balloon (1) is loaded with 3 kg. of Cuyolen polypropylene pellets, manufactured by: Petrochemical Cuyo, The gas injector tube (4) is inserted according to the attached drawing and a thermocouple (6) connected to a digital thermometer with measuring capacity between 0 - 600 ° C, to the bottom of the container taking care that they are 5 and 10 mm from the bottom respectively. An inert atmosphere is generated by the injection of nitrogen at a rate of 10 ml. / minute, by entry No. 3 (according to the drawing). Once the inert atmosphere is established, it is gently heated to 180 ° C by means of the heating blanket (δ), so that the melt allows gentle agitation, at a rate of 6 turns per minute and also the injection of the reactive gas, in this case, water saturated with water vapor at 40 degrees, at a rate of 4 mi. / minute The condensed material begins to be received in the refrigerant (2), in the fraction collector. He continues to raise the temperature of the reaction at a rate of 2 ° C / minute until it reaches a temperature of 430 ° C, continuing the collection of condensate, until the melt inside the reactor is reduced to 10 millimeters in height, in order to always maintain covered the gas injection tube (4), mainly obtaining the following products:

Name CAS Number

2,4-DiMetil-1-Heptene 019549-87-2

7-Methyl-2-Decene 074630-23-2

1, 3,5 -TriMetil Cyclohexane 001795-26-2

3 - Dodecene 007239-23-8

4-Methyl- Decane 002847-72-5

2,5-DiMetiM, 6-Octadiene 068702-25-0

2,3-Dimethyl-Hex 000584-94-1

3-Methyl-2-Pentene 000922-62-3

1, 1, 3,4-TetraMetil - Cyclopentane 020309-77-7

Example 2: Material Parts by Weight

Polyethylene 3,000 Gr.

Iron Stearate 1 Gr.

Process:

Equipment description: idem Example No. 1

Description of the technique used:

The balloon (1) is loaded with 3 kg. of Alkathene Polyethylene pellets, low density grade, manufactured by: ICI Argentina, and 1 Gram of Iron Stearate. the rest of the conditions being equal to the previous example The gas injector tube (4) is inserted according to the attached drawing and a thermocouple (6) connected to a digital thermometer with measuring capacity between 0 - 600 ° C, to the bottom of the container taking care that they are 5 and 10 mm from the background respectively. An inert atmosphere is generated by the injection of Nitrogen at a rate of 10 ml / minute, through the entry No. 3 (according to the drawing) Once the inert atmosphere is established, it is gently heated to 180 ° C by means of the heating blanket (8 ), so that the melt allows for gentle agitation, at a rate of 6 revolutions per minute and also the injection of the reactive gas, in this case, water saturated with steam at 40 degrees, at a rate of 4 ml / minute

The condensed material begins to be received in the refrigerant (2), in the fraction collector. The temperature of the reaction is continued to rise at a rate of 2 ° C / minute until a temperature of 430 ° C is reached, continuing the collection of condensate, until the melt inside the reactor is reduced to 10 millimeters high in order to always maintain covered the gas injection tube (4),

Example 3

Material Parts by Weight

Polypropylene 3000 Gr.

Procedure: Description of the device: idem Example No. 1

Description of the technique used:

The balloon (1) is loaded with 3 kg. of Cuyolen polypropylene pellets, manufactured by: Petrochemical Cuyo, The gas injector tube (4) is inserted according to the attached drawing and a thermocouple (δ) connected to a digital thermometer with measuring capacity between 0 - 600 ° C, up to the bottom of the container taking care that they are 5 and 10 mm from the bottom respectively. An inert atmosphere is generated by the injection of Nitrogen at a rate of 10 ml / minute, through entry No. 3 (according to the drawing). Once the inert atmosphere is established, it is gently heated to 180 ° C by means of the heating blanket (8), so that the melt allows gentle agitation, at a rate of 6 turns per minute and also the injection of the reactive vapor, in this case Ethanol, carried by a stream of Nitrogen at a rate of 1 ml / minute. The condensed material begins to receive in the refrigerant (2), in the fraction collector. The temperature of the reaction is continued to rise at a rate of 2 ° C / minute until a temperature of 450 ° C is reached, continuing the collection of condensate, until the melt inside the reactor is reduced up to 10 millimeters in height in order to always maintain covered the gas injection tube (4),

Example 4: Material Parts by Weight

Polyethylene 3,000 Gr. Procedure:

Equipment description: idem Example No. 1

The balloon (1) is loaded with 3 kg. of Petropol pellets, High density, manufactured by

Petrosul SA. Argentina. The gas injector tube (4) is inserted according to the attached drawing and a thermocouple (6) connected to a digital thermometer with measuring capacity between 0 - 600 ° C, to the bottom of the container taking care that they are 5 and 10 mm from the background respectively. An inert atmosphere is generated by the injection of Nitrogen at a rate of 10 ml / minute, through the entry No. 3 (according to the drawing). Once the inert atmosphere is established, it is gently heated to 180 ° C by means of the heating blanket ( δ), so that the melt allows gentle agitation, at a rate of 6 turns per minute and also the injection of the reactive gas, in this case, in this case C02 reactive gas at a rate of 6ml / minute

The condensed material begins to be received in the refrigerant (2), in the fraction collector. The temperature of the reaction is continued to rise at a rate of 2 ° C / minute until a temperature of 450 ° C is reached, continuing the collection of condensate, until the melt inside the reactor is reduced up to 10 millimeters in height in order to always maintain covered the gas injection tube (4),

Example 5:

Material Parts by Weight Polyethylene 4,000 Gr.

Procedure: Description of the equipment: idem Example No. 1 Description of the technique used: The balloon is loaded, with 4 kg. of Alkathene Polyethylene pellets, low density grade. The gas injector tube (4) is inserted according to the attached drawing and a thermocouple (6) connected to a digital thermometer with measuring capacity between 0 - 600 ° C, to the bottom of the container taking care that they are 5 and 10 mm from the background respectively. An inert atmosphere is generated by the injection of Nitrogen at a rate of 10 ml / minute, through entry No. 3 (according to the drawing). Once the inert atmosphere is established, it is gently heated to 180 ° C by means of the heating blanket (δ), so that the melt allows gentle agitation, at a rate of 6 turns per minute and a nitrogen flow at a rate of 1 ml / minute Heating is continued with gentle agitation until it reaches 400 ° C and is maintained for 1 hour, the heating is cut off and allowed to cool to 180 ° C and the contents are removed to the liquid state that remains in the Balloon. When cooling, a polyethylene wax is observed, which is measured with a Hardness Meter ASTM SHORE D (Teclock Corp, Japan) which on a scale of 0 to 100 marks 43-45 and a Ring and Ball softening point measured according to ASTM E28-58 T Standard indicating 122 ^e C - 123 ^e C

Example 6:

Material Parts by Weight Polypropylene 4,000 Gr.

Procedure: Description of the equipment: previous idem. Installed according to drawing No. 1 Description of the technique used: The balloon is loaded, with 4 kg. of polypropylene pellets manufactured by

Petroquímica Cuyo, brand: Cuyolen, The gas injector tube (4) is introduced - according to the attached drawing and a thermocouple (6) connected to a digital thermometer with measuring capacity between 0 - 600 ° C, to the bottom of the container taking care that are 5 and 10 mm from the bottom respectively. An inert atmosphere is generated by the injection of Nitrogen at a rate of 10 ml / minute, through entry No. 3 (according to the drawing). Once the inert atmosphere is established, it is gently heated to 180 ° C by means of the heating blanket (δ), so that the melt allows gentle agitation, at a rate of 6 turns per minute and the injection of a stream of Nitrogen at a rate 1 ml / minute. Heating is continued with gentle stirring until it reaches 450 ° C, the heating is cut off and allowed to cool to 180 ° C and the contents are removed to the liquid state that remains in the Balloon. When cooling, a polypropylene wax is measured which measures with an ASTM SHORE D Hardness Meter (Teclock Corp, Japan), which on a scale of 0 to 100 marks 53-55 and a ring and ball softening point measured according to to ASTM E28-5δ T Standard indicating 146 ^Q C - 147 ⁹ C Example 7: Material Parts by Weight

Pieces of Polypropylene and Polyethylene from toys and plastic bottles 4,000 Gr.

Process:

Equipment description: previous idem. Installed according to drawing No. 1

Description of the technique used: same as previous example

Resulting a wax type material, which is measured with a Hardness Meter

ASTM SHORE D (Teclock Corp, Japan) which on a scale of 0 to 100 marks 47-4δ and a Ring and Ball softening point measured according to the

ASTM E2δ-5δ T standard indicating 139 ^S C - 140 ^Q C

Example 8: Material Parts by Weight Polyethylene / Polypropylene (50/50) 25 Kilos

Procedure: Description of the equipment:

Elements installed according to drawing No. 2 and numbered as follows: (1) 6 Its stainless steel reactor with 4 nozzles capacity, (2) Refrigerant, (3) Surface gas supply tube, (4) Tube gas bubbling, (5) Stirrer, (6 and 7) Two thermocouples connected with digital thermometers, with measuring capacity between 0 - 600 ° C, (δ) Heating blanket, (9) power extruder, (10) output of reactor material, (11) tube for reaction gas pressure control, (12) Condensate collector Description of the technique used:

An inert atmosphere is generated in the reactor (1), by injecting Nitrogen through the inlet (3) (according to the drawing) and then maintaining a continuous gas stream at a rate of 6 ml / minute. Once the inert atmosphere is established, the reactor is charged by the Extruder (9), with 4.5 kg. of a molten mixture at a temperature of 1δ0 ° C and in equal parts of brand Polyethylene, Alkathene, low density grade and Cuyolen Polypropylene manufactured by Petroquímica Cuyo. For the gas injector tube (4), according to the attached drawing. A stream of air and C02 is introduced into the melt at a rate of 6ml / minute. Using the heating blanket, heat gently until a constant temperature of 400 ⁹ C is maintained. Liquid condensed by the refrigerant (2) is received in the manifold (12). The material extracted from the reactor is replaced by new material that is made to enter molten by the Extruder, in order to replace the distilled material, maintaining a continuous process, without finishing the extruder loading material, being very important that at no time does it penetrate freely air through it

Other examples

It is also stated that the invention described herein or its most obvious variants, comprises the injection of reactive gases from the group of: Hydrocyanic Acid

CNH, Chlorine CI2, Fluorine F2, Acetylene HC2H, Ammonia NH3, Phosgene CI2CO, Carbon monoxide CO, Formaldehyde (methylene oxide) CH20, Ammonia NH3, Arsine AsH3, Phosphamine PH3, Hydrofluoric acid FH, Hydrogen sulfide SH2 , S03 Sulfuric Anhydride, Nitrogen Oxide, NO, N02, N204 and also liquid or solid substances capable of gasification or sublimation at the reaction temperature and / or being carried by a carrier gas stream, acting as reagents, catalysts or inhibitors, such as: Methanol CH30H, Ethanol CH50H, Iodine 12, Bromide and Methyl Chloride, Chloroacetaldehyde, Acetaldehyde and unsaturated aldehydes such as acrolein CH2 = CHCHO, aromatic compounds such as Benzene, Toluene or Naphthalene Being that the above list is only an example for application in the Invention presented here of said substances, their derivatives or mixtures, not being exhaustive or limiting.

We declare that the invention described herein can also be applied to initial polymeric materials of the group comprising: Polyacrylamide / acrylate. Polyacrylonitrile-Butadiene-Styrene ABS, Polyamide - Nylon 4.6 PA 4.6. Nylon 6, 6. Polyamide - Nylon 11 PA 11, Polyamide - Nylon 12 PA 12, Polyamide / imide PAI, Polyaramide - Poliparaphenylene terephthalamide, Polyaramide, Polymetaphenylene isophthamide, Polyaramide / Polysulfide Polypheramide, Polybamide, PBI, Polyamide, PBI PC, PCTFE polychlorotrifluoroethylene, PVDC Vinylidene Polychloride UPVC Polyvinylchloride, PS Polystyrene, Polystyrene - Polystyrene - Crosslinked PS - X - Linked. Polyethylene - High Density HDPE Polyethylene - Low Density LDPE, Polyethylene - UHMW UHMW PE. Polyethylene / Polyethylene Composite Fiber PE - Matrix PE, Vinylidene Polyfluoride PVDF, Vinyl Polyfluoride PVF, Polyhydroxybutyrate - Biopolymer PHB, Polyhydroxybutyrate / Polyhydroxy ... PHB92 / PHV δ, Polymethyl methacrylate

PMMA, Ethyl Polymethacrylate, Acrylic, TPX® Polymethyl Pentene, PEN Ethylene Polinaphthalate, PP Polypropylene, PPS Phenylene Polysulphide, PBT Butylene Polyethylene terephthalate, PETP, PETP, Polyethylene terethylether, PTFE PEEK, Poly Polyimide, Phenylene Polyoxide PPO

(modified), PPE (modified), Methylene Polyoxide - Acetal Copolymer - POMC Copolymer, Methylene Polyoxide - Acetal Homopolymer - POMH Homopolymer, PAN Polyacrylonitrile, Polyphenylsulfone. Since the above list is only an example for the application of the Invention here, presented thereon, its derivatives or mixtures, not being exhaustive or limiting. Changes in Reaction Pressure According to what is expressed on pages δ, 9 and following, the pressure must also be taken as a reaction variable, so that the previous examples of 1 to 4 inclusive, can be divided into at least 2 parts : the explicit ones and others similar, but developed at a lower atmospheric pressure, preferably a vacuum compatible with the glass material used, such as 30 or 50% lower. In stainless steel reactors such as those in the δ example, a split in 3 almost identical examples can be considered only by varying the pressure, A) as is explicit in the example equal to atmospheric pressure and two more examples, B) in the middle of that pressure or C) at twice the same. In all the examples the results will be altered in the proportions of the products obtained, under the following common denominator: Low Pressures increase the production of volatile products at the reaction temperature and High Pressures decrease them. So these cases now mentioned and their use within what is declared and protected by this invention are clear examples for those skilled in the art

DESCRIPTION OF THE FIGURES Figure 1:

(1) Borosilicate glass ball, Pyrex brand or similar, of 5 Its. capacity and 3 frosted mouths, (2) Refrigerant, (3) Surface gas injector tube, (4) Gas or vapor injection tube in the melt, (5) Agitator, (6) Thermocouple, for measuring fluid mass temperature, (7) Thermocouple for measuring condensation temperature, both attached to digital thermometers, with measuring capacity between 0 - 600 ° C, (δ) Heating blanket, (9) Material inside the Balloon, ( 10) Fraction collector Figure 2: 6 Its stainless steel reactor. Capacity with 4 nozzles, (2) Refrigerant, (3) Surface gas supply tube, (4) Gas bubble tube, (5) Agitator, (6 ) Thermocouple, for measuring fluid mass temperature, (7) Thermocouple for measuring condensation temperature, both attached to digital thermometers, with measuring capacity between 0 - 600 ° C, (δ) Heating blanket, (9) feed extruder, (10) reactor material outlet, (11) reaction gas pressure control tube, (12) Condensate collector

Claims

CLAIMS Having described and determined the nature and scope of the present invention and the manner in which it is to be carried out, it is stated that what is claimed as exclusive right and property is: 1. A procedure for the synthesis of chemical materials, characterized by the controlled interaction of reactive gases or vapors within and on a mass of polymeric material, in the presence of catalysts and reaction inhibitors and where the reaction pressure is a control variable, being equal to or different from atmospheric pressure 2. A method according to claim 1, characterized in that the reaction temperature is between 10 ° C and 650 ° C 3. A method according to claim 1, characterized in that the reaction catalyst is a gas or vapor at the reaction temperature 4. A method according to claim 1, characterized in that the active gas or vapor used contains C02, oxygen combined with other elements, oxygen in elemental form, ozone or mixtures thereof. 5. A method according to claim 1, characterized in that the active gas or vapor used contains unsaturations in the form of double or triple bonds. 6. A method according to claim 1, characterized in that the active gas or vapor used contains chlorine and / or elements belonging to group 7 of the periodic table. 7. A method according to claim 1, characterized in that the reaction catalyst is a liquid material that is gasified or vaporized at the reaction temperature 8. A method according to claim 1, characterized in that the reaction inhibitor is gas or vapor inert at the reaction temperature. 9. A method according to claim 1, characterized in that the reaction pressure is also a control variable being equal to or different from the atmospheric pressure. 10. A method according to claim 1, characterized in that the material resulting from the process is a substance such as polyethylene waxes, propylene waxes or mixtures of both, with a softening point between 70 and 160 degrees Celsius 11. A method according to claim 1, characterized in that the initial polymeric material comprises one or more materials selected from the group consisting of Polyethylene, Polypropylene, Polyethylene Teresphthalate, Polystyrene, derivatives thereof or mixtures containing them. 12. A method according to claim 1, wherein the initial polymeric material comprises one or more materials selected from the group of materials of biological origin. 13. A method according to claim 1, characterized in that at least one of the initial materials is a finely divided solid at the reaction temperature. 14. A method according to claim 1, characterized in that the final polymeric material comprises a chemically recycled material and different from the original material. 15. A method according to claim 1, characterized in that the material resulting from the process is formed by saturated and unsaturated hydrocarbons other than the original monomer. LIC. HÉCTOR LUIS GALANO