RU2314324C1 - Polymer composition with elastomeric properties within wide temperature ranges and a method of preparing the same - Google Patents

Abstract

FIELD: polymer production.

SUBSTANCE: invention provides elastomeric polymer composition comprising at least polymers and copolymers obtained from substituted and unsubstituted vinylaromatic monomers and from diene monomers and including 15 to 85% copolymer containing (i) at least one block formed by 10 to 5000 mainly syndiotactic structural sequences of monomer units derived from at least one substituted or unsubstituted vinylaromatic monomer and (ii) at least one block formed by 10 to 4000 monomer units derived from at least one diene monomer with predominant 1,4-cis structure, wherein 15-85 wt % of polymer obtained from diene monomers has molecular weight between 6000 and 600000 with content of 1,4-cis monomer units constituting at least 90%, while up to 70% of polymer obtained from substituted and unsubstituted vinylaromatic monomers has molecular weight between 10000 and 500000 and degree of syndiotacticity (expressed through syndiotactic pentads) at least 95%, a part formed by monomer units derived from diene monomer is optionally partially or completely hydrogenised. Method of preparing such elastomeric composition is also described.

EFFECT: extended temperature range for elastomeric performance of composition.

42 cl, 5 tbl, 27 ex

Description

Field of Invention

The present invention relates to methods used in the preparation of the polymer composition, and more particularly, it relates to a polymer composition having elastomeric properties over a wide temperature range.

BACKGROUND OF THE INVENTION

There are a large number of applications of polymer compositions in which elements or parts of them require elastomeric properties, that is, manifestations of extensibility and elasticity, allowing them to restore their shape after significant stretching.

Based on the foregoing, over time, a wide variety of materials having elastomeric properties have been developed, with styrene-butadiene copolymers being among the most famous and widely used materials.

Although in the current state of affairs one can find a wide variety of elastomeric polymer compositions having various mechanical or physical properties, such as, inter alia, hardness, tensile strength, elastic modulus, the compositions known so far lose their elastomeric properties with a temperature that puts a limit on their optimum performance when they are to be used in high temperature applications.

With the development of more efficient polymerization catalysts, such as the catalyst described in patent application MX 9801717, it has become possible to adjust the structure of the polymers, thereby allowing regularity in the chains. So, in the case of styrene elastomers, syndiotactic polystyrene was used in order to achieve favorable results regarding the properties of the polymer composition from it.

For example, US Pat. No. 5,260,394 discloses a syndiotactic polystyrene copolymer with olefin and / or diene monomer inserts exhibiting the desired chemical and thermal resistance properties in addition to acceptable processability and good compatibility with other compositions. The copolymers described therein are intended to produce materials with good processability by injection molding due to their low glass transition temperature.

Similarly, U.S. Pat. No. 5,357,727 describes a rubber modified syndiotactic composition in order to give the composition better processing properties when it is recycled after it has been used once, while retaining its mechanical and thermal decomposition resistance after recycling.

In general, other documents, such as US patents 6046275, 6191197, 5352727, 5260395, 5543462 and 5777026, use different mixtures of syndiotactic polystyrene with other polymers or copolymers, which allows you to modify the mechanical and technological properties of such polymer compositions.

However, none of these documents represents a composition having elastomeric properties in wide temperature ranges, because due to the nature of the compatibility agents that are commonly used to obtain compositions of stereoregular polymers, such compositions cannot be used at low temperatures and therefore the use of such materials continues be limited to temperatures above 253.2K.

Based on the foregoing, the authors of the present invention set the goal of eliminating the disadvantages of known elastomeric compositions by producing polymer compositions that not only have elastomeric properties in wide temperature ranges, but can also be used at high temperatures and preserve their impact strength, chemical, mechanical and wear resistance at high temperatures in addition to maintaining their elastomeric properties at temperatures below 253.2K.

OBJECTS OF THE INVENTION

Based on the limitations of the compositions described in the foregoing sources, it is an object of the present invention to provide a polymer composition having elastomeric properties over a wide temperature range, which is homogeneous and compatible, obtained from stereoregular polymers and does not require the use of additional compatibilizing agents.

Another objective of the present invention is to provide a polymer composition having elastomeric properties over wide temperature ranges, which retains its chemical, mechanical and wear resistance properties, as well as its processability and impact strength properties.

Another objective of the present invention is to provide a polymer composition having elastomeric properties over wide temperature ranges, which is compatible with other polymeric materials when it is mixed with them.

Another objective of the present invention is to provide a polymer composition having elastomeric properties over wide temperature ranges, which can be suitably processed as a film, by thermoforming, injection molding or extrusion.

Brief Description of the Figures

New aspects, considered to be a feature of the present invention, will be presented in detail in the attached claims. However, the process, as well as its other objectives and advantages, will be better understood in light of the following detailed description of a specific embodiment of the invention, discussed respectively in the accompanying drawing, which shows a graph of the elastic modulus (G ') of some variants of the polymer composition of the present invention, which are shown in the examples.

DETAILED DESCRIPTION OF THE INVENTION

It has been found that a combination of diene vinyl aromatic polymers having an ordered structure can result in a polymer composition having elastomeric properties in the temperature range from -121 ° F (188.15 K) to 572 ° F (573.15 K).

More specifically, the polymer composition of the present invention, allowing to achieve elastomeric behavior in wide temperature ranges, includes from 15 to 85% wt. a copolymer having at least a block of 10 to 5000 structural sequences that are mainly syndiotactic in nature, monomer units derived from at least one substituted or unsubstituted vinyl aromatic monomer, and at least one block formed from 10 to 4000 monomer units derived from at least one diene monomer having mainly a 1,4-cis structure; from 15 to 85% wt. a polymer obtained from diene monomers having a molecular weight of from 1000 to 600000, wherein the content of 1,4-cis-type monomer units is at least 90%; and up to 70% of a polymer derived from substituted or unsubstituted vinyl aromatic monomers having a molecular weight of from 1000 to 500,000 and a degree of syndiotacticity described through syndiotactic pentads of at least 95%.

In a preferred embodiment of the present invention, vinyl aromatic monomers are selected from styrene and substituted styrene, with the substituents being preferably selected from alkyl, halide, alkoxyl and amine groups. In a specific embodiment, the vinyl aromatic monomers are selected from styrene, 4-methylstyrene, 4-tert-butylstyrene, 4-methoxystyrene, 4-trimethylsilyloxy styrene, 4-bromostyrene and 4- (N, N'-dimethylamine) styrene.

As for the diene monomer, in a preferred embodiment of the present invention, the diene monomer is selected from 1,3-butadiene and 2-methyl-1,3-butadiene.

In a further embodiment of the polymer composition of the present invention, the portion formed by the monomer units derived from the diene monomer may be partially or fully hydrogenated, i.e. monomer units —CH ₂ —CH = CH — CH ₂ —can be partially or completely converted to monomer units —CH ₂ —CH ₂ —CH ₂ —CH ₂ , whereas monomer units —CH ₂ —C (CH = CH ₂ ) H- can be converted into monomer units —CH ₂ —C (CH ₂ —CH ₂ ) H—, with 95% of the monomer units obtained from the diene monomer being preferably hydrogenated.

In an additional implementation of the present invention, the polymer composition contains from 0.01 to 4% wt. at least one organic or inorganic additive, depending on the final destination of the composition and, more preferably, less than 3.7%.

Preferably, the inorganic additives are selected from compounds containing aluminum, and, more preferably, from aluminum oxide or compounds of the general formula (-Al (X) O-) _n , where X represents a hydroxyl, alkoxide or alkyl group that is obtained by reacting the compounds, having the general formula (-Al (X) O-) _m with water or alcohols, where R represents an alkyl group, and n and m are natural numbers that may be residues from the catalyst system.

Similarly, it is preferred that the organic additives include at least one antioxidant, preferably selected from antioxidants used in compositions containing styrene and butadiene, and more preferably selected from antioxidants containing phenols, phosphates and amines.

The polymer composition of the present invention has

the first glass transition temperature (Tg1) in the temperature range from 173.2K to 183.2K; the second glass transition temperature (Tg2) in the temperature range from 368.2K to 393.2K; and also the melting temperature T _m in the temperature range from 493.2K to 573.2K. The elastomeric behavior of the composition of the present invention is manifested in the range from 188.2 K to the decomposition temperature of the diene polymer. Similarly, the elastic modulus of such a composition can vary from 10 to 1000 MPa in the temperature range from 188.2 K to 363.2 K and between 3 and 100 MPa in the temperature range from 393.2 K to the decomposition temperature of the diene polymer.

The polymer composition of the present invention can be obtained by a method comprising the first step of contact polymerization of at least one vinyl aromatic monomer, which is polymerized by a catalytic system comprising a precatalyst, consisting of one or more compounds belonging to the class of compounds such as titanium (IV) fluorenyl trialkoxide, and an activating compound selected from aluminum compounds obtained by hydrolysis of trialkylaluminum, and more preferably methylaluminoxane, such as described in patent application MX 9801717, in bulk or in the presence of a solvent selected from aromatic solvents and, more preferably, toluene, as well as from aliphatic solvents and, more preferably, 2,2,4-trimethylpentane, or from mixtures thereof, temperature from 273.2K to 363.2K for a period of time from 1 to 30 s; and this contact is followed by a second polymerization step by subsequently adding a diene monomer at a temperature of from 273.2 K to 343.2 K to form an unsaturated polymer composition.

The unsaturated polymer composition is polymerized for a period of time from 10 minutes to 6 hours and then mixed with an alcohol selected from aliphatic alcohols, where the aliphatic alcohol has from 1 to 4 carbon atoms, isopropanol being preferred, in order to complete the polymerization reaction in the preferred the implementation of the present invention.

After the reaction has come to an end, the composition is finally subjected to a catalytic residue removal step using a mixture of aliphatic alcohol and a solvent with at least one substituted or unsubstituted aromatic ring. In a preferred embodiment of the present invention, the aliphatic alcohol: aromatic solvent ratio is between 0.5: 1 and 5: 1, with a ratio of 1: 1 being preferred. The aliphatic alcohol from the catalytic residue removal step is preferably selected from alcohols having from 1 to 4 carbon atoms, preferably isopropanol, with toluene being the preferred aromatic solvent.

In a further embodiment of the present invention, it was unexpectedly found that at the end of the polymerization step of the diene monomer or after the diene monomer is at least 50% converted, the non-hydrogenated polymer composition can be subjected to an in situ hydrogenation step by direct contact with hydrogen at a partial pressure of hydrogen from 10 to 150 psig (g) at a temperature of 273.2 K to 363.2 K and, more preferably, at a partial pressure of 20 to 100 psig (g) and a temperature of 293.2 K to 343.2 K. Even more unexpectedly, the hydrogenation step of the non-hydrogenated polymer composition can be carried out without the need for additional hydrogenation catalysts, resulting in materials containing up to 95% hydrogenated polybutadiene.

The polymer composition of the present invention will be more clearly illustrated by the following examples, which are presented only for illustration and, thus, do not limit the invention.

Polymerization processes were carried out as described below.

Examples 1-9

A 600 ml glass reactor equipped with a stirring system, temperature and pressure control system, and a reagent supply system was charged with a mixture of 30 ml of toluene, 30 ml of vinyl aromatic monomer (see table II) and 3 g of dry methylaluminoxane. The reactor was heated to 323.2K and kept at this temperature for 10 minutes. Then a solution of (C ₉ H ₁₃ ) Ti (OS ₃ H ₇ ) ₃ in 5 ml of toluene was added. The vinylaromatic monomer / titanium compound molar ratio was 1000, while the Al / Ti ratio was 250. The reactor jacket was started to cool from the moment the initiator was added. 20 seconds after the start of polymerization, 200 ml of toluene was added to the reactor, which was previously cooled to 283.2K. At time t1 from the start of the polymerization (see Table II), 60 ml of butadiene was added. The reaction was allowed to proceed for 2 hours. The reaction mixture was mixed with 1 L of isopropanol.

In order to remove the remainder of the catalyst system, the product was extracted using a continuous extraction apparatus for 24 hours with 1: 1 toluene: isopropanol mixture, except for the case of Example 8, in which there was a higher content of component D, from which the catalyst residue separated.

In order to characterize the product, the resin was divided into one hexane soluble fraction and one hexane insoluble fraction. According to ¹ H and ¹³ C NMR analysis, the hexane soluble fraction consists of polybutadiene having from 91 to 95% 1,4-cis-monomer units, with the remainder being 1,2-monomer units. According to ¹ H NMR and ¹³ C and GPC NMR, the hexane insoluble fraction consists of a block copolymer of syndiotactic vinyl aromatic polymer and highly 1,4-cis polybutadiene, or a mixture of syndiotactic vinyl aromatic polymer, block copolymer syndiotactic vinyl aromatic polymer and highly 1,4-cis-polybutadiene.

The characteristics of each of the obtained polymer compositions are shown in table II, which uses the same abbreviations as in table I.

Table I A Generally refers to the properties of the (syndiotactic vinyl aromatic) - (1,4-cis-diene) copolymer B Generally related to the properties of 1,4-cis-diene polymer C Generally related to the properties of syndiotactic vinyl aromatic polymer D Organic and inorganic additives V Vinyl aromatic monomer St Styrene 4mest 4-methylstyrene 4BrSt 4-bromostyrene Meost 4-methoxystyrene 4NSt 4-dimethylaminostirol t1 The polymerization time of vinylaromatic monomer, minutes M _w A Weight average molecular weight A cA,% The content of 1,4-cis-monomer units in diene blocks A vA,% The content (wt.) Vinylaromatic blocks And PA,% The content (wt.) Of copolymer A in the composition M _p B Peak molecular weight B cB,% The content of 1,4-cis-monomer units PB,% The content (wt.) In the composition M _w C Weight average molecular weight C PC,% The content (wt.) C in the composition PD,% The content (wt.) D in the composition PV,% The total content (wt.) Vinylaromatic part in the composition SY,% The degree of syndiotacticity of the vinyl aromatic part T _g 1 The first glass transition temperature Tg2 Second glass transition temperature T _m Melting temperature ΔG ' Variation of the modulus of elasticity in the indicated temperature range

Table II The properties Example one 2 3 four 5 6 7 8 9 V St St St St St St St 4mest 4BrSt t1 thirty 25 twenty fifteen 10 5 2.5 twenty twenty Component (A) M _w A, x 10E-3 245 267 201 202 176 207 96 295 304 SA,% 92 93 93 93 92 93 91 95 93 VA,% 96 84 53.2 95.5 72.7 82.2 58.9 60.4 40.2 RA,% 30.2 33.2 36.8 22.6 19.3 19.5 17.5 46.5 15.3 Component (B) M _r B, x10E-3 246 231 256 385 485 450 284 233 297 cv,% 92.5 92.6 94.3 91.0 93 91 92.2 95 91.8 PB,% 66.2 64.8 55.0 76.5 78.9 80.0 79.5 39.4 67.6 Component (C) M _w C, x10E-3 - - 25.6 - - - - 50.7 62.3 RS,% 0 0 7.1 0 0 0 0 10.3 14.6 Component (D) PD,% 3.6 2 1.1 0.9 1.8 0.5 3 3.8 2.5 The properties Pv,% 29.0 27.9 26.7 22.0 15.6 16.0 10.3 38.4 20.8 SY,% 99.9 99.9 99.9 99.9 99.9 99.9 99.9 98 96.6 T _g1 , K 175.7 175.7 175.1 177.1 176.2 175.8 174.7 173.6 181 T _g2 , K 385.4 390.4 378.7 392.2 383.2 384.8 380,4 368.7 392.9 T _m , K 538.2 541.5 535.5 542.2 539.8 537.6 537.7 543.8 569.2 ΔG ', MPa from 213.2K to 363.2K - - - 208.4-59 194-140 194-95 86-68 - from 393.2K to 523.2K - - - 39.2-37.4 77-59 44.6-39.2 44.6-42.8 - -

Examples 10-18

A 600 ml glass reactor equipped with a stirring system, a temperature and pressure control system and a reagent supply system was charged with a prepared mixture of 30 ml of 2,2,4-trimethylpentane, 30 ml of vinyl aromatic monomer (see table II) and 3 g of dry methylaluminoxane. The reactor was heated to 323.2K and kept at this temperature for 10 minutes . Then a solution of (C ₉ H ₁₃ ) Ti (OS ₃ H ₇ ) ₃ in 5 ml of 2,2,4-trimethylpentane was added. The vinylaromatic monomer / titanium compound molar ratio was 1000, while the Al / Ti ratio was 250. The reactor jacket was started to cool from the moment the initiator was added. 20 seconds after the start of polymerization, 200 ml of 2,2,4-trimethylpentane maintained at 293.2K were added to the reactor. At time t1 from the start of the polymerization (see Table III), 60 ml of butadiene was added. The reaction was allowed to proceed for 2 hours. The reaction mixture was mixed with 1 L of isopropanol.

In order to remove the catalyst system residue, the product was extracted using a continuous extraction apparatus for 24 hours with a 1: 1 toluene: isopropanol mixture, except for the case of Example 10, in which there was a higher content of component D, of which the catalytic residue was part .

In order to characterize the product, the resin was divided into one hexane soluble fraction and one hexane insoluble fraction.

According to ¹ H and ¹³ C NMR analysis, the hexane-soluble fraction consists of polybutadiene having from 88 to 93% 1,4-cis-monomer units, with the remainder being 1,2-monomer units.

According to ¹ H NMR and ¹³ C and GPC NMR results, the hexane insoluble fraction consists of a mixture of syndiotactic vinyl aromatic polymer, a block copolymer of syndiotactic vinyl aromatic polymer and a high degree of 1,4-cis-polybutadiene.

The characteristics of each of the obtained polymer compositions are shown in table III, which uses the same abbreviations as in table I.

Table III The properties Example R 10 eleven 12 13 fourteen fifteen 16 17 eighteen V St St St St St St St St / MeOSt = 9/1 St / 4NSt = 9/1 t1 thirty 25 twenty fifteen 10 5 2.5 fifteen 5 Component (A) M _w A, x10E-3 248 201 220 195 151 175 499 193 333 SA,% 87.0 89.7 89.9 90.1 89.5 87.6 88.7 85 90.2 vA,% 76 71 58.5 59 53.5 43.5 40.5 10.5 21.5 RA,% 9.5 22.5 29.5 47.5 53.0 66.5 71.5 16.5 25.5 Component (B) M _p B, x10E-3 105 133 185 154 156 265 200 123 99 cB,% 88.7 90.6 91 89.2 90.3 89 88.1 93 91.8 PB,% 16.3 16.8 18.8 17.5 15.0 15.7 15.0 29.0 27.2 Component (C) M _w C, x10E-3 531 507 780 465 470 403 354 267 609 RS,% 70.2 57.2 51.1 32.0 31.0 14.2 10.5 51.1 44.8 Component (D) PD,% 4.0 3.5 2.8 3.0 1.0 3.6 3.0 3.4 2.5 The properties Pv,% 77.4 73.2 68.4 60.0 59.3 43.1 39.5 52.8 50.3 SY,% 99.9 99.9 99.9 99.9 99.9 99.9 99.9 98.2 97.1 T _g1 , K 182.2 180.7 182.9 182.7 182.1 180.8 183.1 179.5 181 T _g2 , K 388.2 389.3 390.2 386.3 388.7 387.7 393.2 366.7 393.7 T _m , K 549.8 551.2 549.2 553.2 555.2 547.2 542.2 528.2 563.2 ΔG, MPa from 213.2 K to 363.2 K - - - - - - 1832-1292 212-104 - 393.2 K to 523.2 K - - - - - - 400-300 104-212 -

The drawing compares the viscoelastic behavior of the polymer compositions of the present invention with the behavior of a conventional SBR elastomer. It is clearly seen that the elastic modulus (G ') of the polymer composition of the present invention is maintained in the range from 188.2K to 553.2K, the interval in which the material of the present invention does not undergo plastic deformation. In contrast, a conventional elastomer loses its viscoelastic properties before the T _g stage of polystyrene sets in, at about 343.2K.

Examples 19-23

The method was the same as in example 5. After 120 minutes of polymerization of butadiene, the reactor was filled with hydrogen at a partial pressure shown in table V, and kept at this pressure, as well as at the temperature shown in table V, for 24 hours. The reaction mixture was mixed with 1 L of isopropanol.

In order to remove the remainder of the catalytic system, the product was extracted in a continuous extraction apparatus for 24 hours with a toluene: isopropanol mixture in a 1: 1 ratio.

In order to characterize the product, the resin was separated into one hexane soluble fraction, one hot hexane soluble fraction and one fraction which was insoluble in such solvents.

According to ¹ H and ¹³ C NMR analysis, the hexane-soluble fraction consists of a high degree of 1,4-cis-polybutadiene.

According to ¹ H and ¹³ C NMR analysis, the soluble fraction in hot hexane consists of hydrogenated polybutadiene.

According to ¹ H NMR and ¹³ C and GPC NMR, the fraction that was insoluble in both solvents consists of a block copolymer of syndiotactic polystyrene and highly 1,4-cis-hydrogenated polybutadiene.

The characteristics of each of the obtained polymer compositions are shown in table V, which uses the same abbreviations as in table IV.

Examples 24-27

The method was the same as in example 14. After 120 minutes of polymerization of butadiene, the reactor was filled with hydrogen at a partial pressure shown in table V, and kept at this pressure, as well as at the temperature shown in table V, for 24 hours. The reaction mixture was mixed with 1 L of isopropanol.

In order to remove the remainder of the catalytic system, the product was extracted in a continuous extraction apparatus for 24 hours with a toluene: isopropanol mixture in a 1: 1 ratio.

In order to characterize the product, the resin was separated into one hexane soluble fraction, one hot hexane soluble fraction and one fraction which was insoluble in such solvents.

According to ¹ H and ¹³ C NMR analysis, the hexane-soluble fraction consists of a high degree of 1,4-cis-polybutadiene.

According to ¹ H and ¹³ C NMR analysis, the soluble fraction in hot hexane consists of hydrogenated polybutadiene.

According to ¹ H NMR and ¹³ C and GPC NMR, the fraction that was insoluble in both solvents consisted of a mixture of syndiotactic polystyrene, a block copolymer of syndiotactic polystyrene and highly 1,4-cis-hydrogenated polybutadiene.

The characteristics of each of the obtained polymer compositions are shown in table V, which uses the same abbreviations as in table IV.

Table IV A In general, it relates to the properties of (syndiotactic vinylaromatic) - (1,4-cis-diene hydrogenated) copolymer B Generally related to the properties of 1,4-cis-diene polymer Bh Generally refers to a 1,4-cis-diene hydrogenated polymer C Generally related to the properties of syndiotactic vinyl aromatic polymer D Organic and inorganic additives P Hydrogen Pressure in psi (g) T ^o C Hydrogenation temperature M _w A Weight average molecular weight A hA,% The proportion of hydrogenated monomer units in diene blocks A PA,% The content (wt.) Of copolymer A in the composition M _p B Peak molecular weight B PB,% The content (wt.) In the composition M _w BH Mass molecular weight VN hBH,% The proportion of hydrogenated monomer units PBH,% The content (wt.) VN in the composition M _w C Mass molecular weight C PC,% The content (wt.) C in the composition PD,% The content (wt.) D in the composition T _g 1 The first glass transition temperature T _g 2 Second glass transition temperature T _m Melting temperature ΔG ' Variation of the modulus of elasticity in the indicated temperature range

Table v The properties Example 19 twenty 21 22 23 24 25 26 27 P, psig 10 twenty 60 80 80 40 60 80 80 T, ° F 68 158 122 122 158 104 122 122 158 Component (A) M _w A, x10E-3 185 171 182 190 188 150 135 172 170 hA,% 0 27 68 86 95 5 44 71 89 RA,% 27 21 23 27 26 fourteen fourteen fifteen 12 Component (B) M _p B, x10E-3 263 151 128 101 360 133 105 71 287 PB,% 60 61 39 fourteen 2 fifty 38 21 5 Component (HV) M _w BH, x10E-3 fifteen 65,4 122.3 120: 3 99; 1.5 3 131; 2.5 125: 2 102; 1.5 hBH,% 55 62 85 93 98 75 83 95 99 RVN,% 10 16 36 57 70 26 39 54 75 Component (C) M _w C, x10E-3 - - - - - 465 482 290 472 RS,% 0 0 0 0 0 9 8 9 7 Component (D) PD,% 2 2 2 2 2 one one one one The properties ΔG, MPa from 213.2 K to 363.2 K - 176-95 - - - 44.6-33.4 - - - from 413.2 K
up to 523.2 K 64,4-60,8 - - - 33.2-33.8 - -

Based on what has been described above, it can be seen that the polymer composition with elastic properties over a wide temperature range of the present invention was developed in order to satisfy the requirements of elastic properties that are necessary for applications in the temperature range from 193.2K to 553 , 2K, and it should be clear to a person skilled in the art that the polymer composition options described above and illustrated in the preceding examples are for illustrative purposes only and do not limit the present invention. nly possible changes in the details without departing from the scope of the invention.

Although one specific embodiment of the invention has been shown and described, it should be emphasized that many of its modifications are possible, such as the use of several additives, substituents of a vinyl aromatic monomer or various conjugated diene monomers. Thus, the present invention should not be construed as limited except for the requirements of the prior art and compliance with the attached claims and their interpretation according to the detailed description.

Claims (42)

1. A polymer composition with elastomeric properties over a wide temperature range, comprising at least polymers and copolymers derived from substituted or unsubstituted vinyl aromatic monomers and from diene monomers, which comprises from 15 to 85 wt.% Copolymer containing at least one a block of from 10 to 5000 mainly syndiotactic structural sequences of monomer units derived from at least one substituted or unsubstituted vinyl aromatic monomer, and at least one block, formed by 10-4000 monomer units derived from at least one diene monomer having mainly a 1,4-cis structure, wherein from 15 to 85 wt.% of the polymer obtained from diene monomers has a molecular weight of from 6,000 to 600,000, where the content of 1,4-cis monomer units is at least 90%; and up to 70% of the polymer derived from substituted or unsubstituted vinyl aromatic monomers has a molecular weight of from 10,000 to 500,000 and a degree of syndiotacticity expressed through syndiotactic pentads of at least 95%, and optionally, a portion formed by monomer units derived from a diene monomer is partially or fully hydrogenated. 2. A polymer composition with elastomeric properties in wide temperature ranges according to claim 1, in which the vinyl aromatic monomers are selected from styrene and substituted styrenes. 3. A polymer composition with elastomeric properties over a wide temperature range according to claim 2, wherein the vinyl aromatic monomer is substituted styrene, whose substituents are selected from the alkyl, halide, alkoxyl and amine groups. 4. The polymer composition with elastomeric properties in a wide temperature range according to claim 2, in which the vinyl aromatic monomers are selected from styrene, 4-methylstyrene, 4-tert-butylstyrene, 4-methoxystyrene, 4-trimethylsilyloxystyrene, 4-bromostyrene and 4- (N, N '-dimethylamine) styrene. 5. The polymer composition with elastomeric properties in a wide temperature range according to claim 1, in which the diene monomer is selected from 1,3-butadiene and 2-methyl-1,3-butadiene. 6. The polymer composition with elastomeric properties in wide temperature ranges according to claim 1, in which the part formed by monomer units derived from diene monomer is 95% hydrogenated. 7. The polymer composition with elastomeric properties in a wide temperature range according to claim 1, further comprising from 0.01 to 4 wt.% At least one organic or inorganic additive. 8. The polymer composition with elastomeric properties in a wide temperature range according to claim 7, in which the inorganic additive is selected from compounds containing aluminum. 9. The polymer composition with elastomeric properties in a wide temperature range according to claim 8, in which the compounds containing aluminum are selected from aluminum oxide or compounds of the general formula (-Al (X) O-) _n , where X is selected from hydroxyl, alkoxide or alkyl groups, n represents a natural number. 10. A polymer composition with elastomeric properties in a wide temperature range according to claim 9, in which (-Al (X) O-) _{n is} obtained by reacting compounds of the general formula (-Al (X) O-) _m with water or alcohols, where R represents an alkyl group and m represents a natural number. 11. The polymer composition with elastomeric properties in a wide temperature range according to claim 7, in which the organic additive is at least an antioxidant. 12. The polymer composition with elastomeric properties in a wide temperature range according to claim 11, in which the antioxidant is selected from antioxidants containing phenols, phosphates and amines. 13. The polymer composition with elastomeric properties in a wide temperature range according to claim 1, additionally having a first glass transition temperature (T _g 1) in the temperature range from 173.2 to 183.2 K. 14. The polymer composition with elastomeric properties in a wide temperature range according to claim 1, additionally having a second glass transition temperature (T _g 2) in the temperature range from 368.2 to 393.2 K. 15. The polymer composition with elastomeric properties in wide temperature ranges according to claim 1, additionally having a melting point T _m in the temperature range from 493.2 to 573.2 K. 16. A polymer composition with elastomeric properties in a wide temperature range according to claim 1, where the elastomeric behavior of such a composition extends from 188.2 K to the decomposition temperature of the monomer units derived from the diene monomer. 17. A polymer composition with elastomeric properties in a wide temperature range according to claim 1, where the modulus of elasticity of such a composition lies in the range from 10 to 1000 MPa in the temperature range from 188.2 to 363.2 K. 18. The polymer composition with elastomeric properties in a wide temperature range according to claim 1, where the modulus of elasticity of such a composition lies in the range from 3 to 100 MPa in the temperature range from 393.2 K to the decomposition temperature of the diene monomer. 19. The method for producing the polymer composition according to claim 1, comprising the first step of contact polymerization of at least one vinyl aromatic monomer, which is polymerized by a catalytic system comprising a precatalyst, consisting of one or more compounds belonging to the class of compounds such as titanium fluorenyl trialkoxide and activating compounds selected from aluminum compounds obtained by hydrolysis of trialkylaluminum, followed by a second polymerization step by subsequent addition of dieno of the monomer, and finally, the third stage, which includes mixing the reaction mixture with alcohol to form a non-hydrogenated polymer composition, which then conducts the stage of removal of the catalytic residue using a mixture of aliphatic alcohol with a solvent having at least one substituted or unsubstituted aromatic ring. 20. The method of producing the polymer composition according to claim 19, in which the ratio of aliphatic alcohol: aromatic solvent is in the range from 0.5: 1 to 5: 1. 21. The method of producing the polymer composition according to claim 19, in which the ratio of aliphatic alcohol: aromatic solvent is 1: 1. 22. The method of producing the polymer composition according to claim 19, in which the aliphatic alcohol at the stage of removal of the catalytic residue is selected from alcohols having from 1 to 4 carbon atoms. 23. The method of producing the polymer composition according to claim 19, wherein the aliphatic alcohol in the step of removing the catalytic residue is isopropanol, while the aromatic solvent is toluene. 24. The method for producing the polymer composition according to claim 19, wherein the pre-catalyst is titanium fluorenyltriisopropoxide. 25. The method of producing the polymer composition according to claim 19, in which the activating component is methylaluminoxane. 26. The method of producing the polymer composition according to claim 19, in which the vinyl aromatic monomer is polymerized in bulk or in the presence of a solvent. 27. The method of producing the polymer composition according to p, in which the solvent is selected from aromatic solvents, aliphatic solvents or mixtures thereof. 28. The method of producing the polymer composition according to item 27, in which the aromatic solvent is toluene. 29. The method of producing the polymer composition according to item 27, in which the aliphatic solvent is 2,2,4-trimethylpentane. 30. The method for producing the polymer composition according to claim 19, wherein the contacting of the polymerizable vinyl aromatic monomer with the catalyst system is carried out at a temperature of from 273.2 to 363.2 K and for a period of time from 1 to 30 minutes. 31. The method for producing the polymer composition according to claim 19, wherein the contacting of the polymerizable vinyl aromatic monomer with the catalyst system is carried out at a temperature of from 293.2 to 323.2 K and for a period of time from 1 to 30 minutes. 32. The method of producing the polymer composition according to claim 19, in which the polymerization stage of the diene monomer is carried out at a temperature of from 273.2 to 343.2 K. 33. The method of producing the polymer composition according to claim 19, in which the first and second stages of polymerization are carried out over a period of time from 10 minutes to 6 hours 34. The method of producing the polymer composition according to claim 19, in which the alcohol is an aliphatic alcohol. 35. The method of producing the polymer composition according to clause 34, in which the alcohol is isopropanol. 36. The method for producing the polymer composition according to claim 19, wherein the polymerization step of the diene monomer is followed by a hydrogenation step by direct contact with hydrogen without the need for additional hydrogenation catalysts, and finally, a step that involves mixing the reaction mixture with alcohol to form a hydrogenated polymer composition . 37. The method of producing the polymer composition according to clause 36, in which the hydrogenation step is carried out at a partial pressure of hydrogen from 10 to 150 psig. 38. The method of producing the polymer composition according to clause 37, in which the hydrogenation step is carried out at a partial pressure of hydrogen from 20 to 100 psig. 39. The method of producing the polymer composition according to clause 36, in which the stage of hydrogenation is carried out at a temperature of from 273.2 to 363.2 K. 40. The method of producing the polymer composition according to § 39, in which the temperature is in the range from 293.2 to 343.2 K. 41. The method of producing the polymer composition according to clause 36, in which the diene monomer is converted at least 95%. 42. The method of producing the polymer composition according to clause 36, in which the resulting materials contain at least 95% hydrogenated polybutadiene.