High styrene and high vinyl styrene-butadiene rubber and methods for preparation thereof

Rubber with a high percentage of styrene and a high percentage of vinylstyrene-butadiene and methods for preparing it

And ways to prepare it

High Styrene and High Vinyl Styrene-Butadiene Rubber and Methods for Preparation Thereof

Full description

Background of the invention

The following instructions relate generally to high-vinyl, high-styrene-butadiene solution-based styrene-butadiene rubber (SSBR) and specifically to high-styrene-high-vinyl SSB with a specific styrene modification - and methods for their preparation.

SSBR rubber with a high percentage of styrene and a high percentage of vinyl is difficult to produce due to copolymerization kinetics. Typically, polar agents known as randomizers are added to the polymerization system to achieve random styrene modification. The use of certain randomizers can result in an SSBR with a high vinyl content but a low mass styrene content (<6 styrene units consecutively) of less than 10%, and it has been reported that long mass styrene can increase retardation, e.g. By S. Futamura and G. Day who observed a retardation of about 18% in delta tan tests at 60 C when the mass styrene content was increased from 2 to about 7% (Kautschuk Gummi Kunststoffe, 1987,40, No. 1, 39-43) in a composite filled with carbon black. . On the contrary, modification of small blocks of styrene can produce better corrosion resistance and better tensile strength, especially in silica compounds, according to I. Hattori et al. in:

(143rd Meeting of the Rubber Division of the ACS, Spring 1993, paper 22). The compound Potassium 3,7-dimethyl-3-octylate is described in US Patent No. 6,521,712 for the preparation of low-vinyl random soft blocks in block copolymers. Likewise, US Patent No. 6,197,889 describes the use of potassium 3,7-dimethyl-3-octylate as randomizer as a randomizer. In both patents, the molecular weight of the resulting polymer is very low (range 3,000-200,000 g/mol).

In US Patent No. 3,294,768, the use of sodium and potassium alcoholates as a trigger for randomization in low vinyl SSBR is described.

Tetramethylethylenediamine (TMEDA) is a stimulant compound. However, TMEDA results in a significantly broad molecular weight distribution compared to what is typically observed in anionic polymerizations when used to polymerize high-styrene SSBR (styre < 40%), especially in the polymerization of high-molecular-weight rubber.

The wide distribution of molecular weight in batch anionic polymerization can result from chain transfer, metal introduction, and/or slow initiation reactions. These reactions reduce the amount of polymer chains that remain alive at the conclusion of the polymerization reaction. Nowadays, high-performance SSBRs typically have a modified chain end. Although this chain-end modification can greatly improve the overall performance of the compound, it requires that the amount of live chain ends be as high as possible at the conclusion of the polymerization reaction. Moreover, the reaction rate is low and often requires more than 5 or 6 hours to finish polymerization in commercially relevant monomer conversions.

In summary, a method for the synthesis of SSBR that has a high percentage of styrene and a high percentage of vinyl with a narrow molecular weight distribution, a monomer conversion of more than 99%, a shorter polymerization time, and a large amount of living chain ends for polymerization is highly desired.

General description of the invention

Invention No. 1

By way of introduction, a polymer that exemplifies the properties of the current guidelines will have at least the following properties: (a) a bulk styrene content containing between 4 and 6 styrene units that is between about 27 and about 50 wt% of the total styrene content in the polymer; (b) The vinyl content is between about 30 and about 80 weight percent of the total amount of polymerized 1,3-butadiene; (c) a styrene content of between about 40 and about 70 weight percent of the total weight of the polymer,

A process for polymerizing a polymer comprising monomeric units derived from styrene monomer and 1,3-butadiene monomer that embodies the properties of the present guidelines includes polymerizing the monomeric units in the presence of an initiator and a polar agent having the formula I;

<img file="SA4014B1_D0001.tif" />

Where R1 and R2 each are an alkyl group; where R3, H4, R5, R6, R7 and R8 are each selected separately from the group consisting of an alkyl group and a hydrogen group; Where the molar ratio between the polar agent and the active initiator is greater than about 0.5; Where the styrene content in the monomer mixture added in polymerization is greater than about 40 percent by weight of the total weight of the monomers added; Where polymerization is carried out at a temperature less than about 80°C.

Invention No. 2

By way of example, a process for polymerization of a polymer comprising monomeric units derived from styrene monomer and 1,3-butadiene monomer that embodies the properties of the present guidelines includes polymerizing the monomeric units in the presence of an initiator, a first polar agent, and a polar agent polar agent second. The first polar agent has the formula (II):

R1'R2'NQ-NR3'R4' (II)

The second polar agent has the formula (I):

<img file="SA4014B1_D0002.tif" />

where R1', R2', R3', and R4' are each selected individually from the group consisting of an alkyl group and a hydrogen group;

Q contains an alkyl group, R1 and R2 each individually being an alkyl group; R3, R4, R5, R6, R7 and R8 are each selected separately from the group consisting of an alkyl group and a hydrogen group.

A polymer that exemplifies the properties of the current guidelines has at least the following properties: (a) a styrene content of between about 40 and about 70 weight percent of the total weight of the polymer; (b) The vinyl content is between about 30 and about 80 weight percent, preferably between about 40 and about 70 weight percent, of the total amount of polymerized 1,3-butadiene; and (c) a molecular weight distribution between about 1.05 and about 1.8.

Invention No. 3

By way of introduction, a polymer that meets the properties of the current guidelines shall have at least the following properties; (a) A bulk styrene content containing more than 4 successive styrene units is between about 40 and about 70 weight percent of the total styrene content in the polymer; (b) The vinyl content is between about 25 and about 80 weight percent of the total amount of polymerized 1,3-butadiene; (c) styrene content ranging from about 20 to about 75 weight percent of the total weight of the polymer;

and (d) a molecular weight distribution D (Mw/Mn) of 1.5 or less. The process of polymerizing a polymer containing monomer units derived from styrene monomer and 1,3-butadiene monomer that meets the properties of the current guidelines involves polymerizing the monomeric units in the presence of an initiator, potassium alcoholate, and a polar agent. The polar agent has the formula I:

<img file="SA4014B1_D0003.tif" />

Where R1 and R2 each are an alkyl group; Where R3, R4, R5, R6, R7 and R8 are each selected separately from the group consisting of an alkyl group and a hydrogen group.

Invention No. 4

By way of introduction, a polymer that embodies the properties of the current guidelines shall have at least the following properties: (a) a mass styrene content containing more than 6 successive styrene units between about 15 and about 35 weight percent of the total styrene content in the polymer; (b) The vinyl content is between about 25 and about 80 weight percent of the total amount of polymerized 1,3-butadiene; (c) styrene content of between about 35 and about 75 weight percent of the total weight of the polymer; and (d) a molecular weight distribution D (Mw/Mn) of 1.5 or less. The process of polymerizing a polymer comprising monomeric units derived from styrene monomer and 1,3-butadiene monomer that meet the properties of current guidelines includes polymerizing the monomeric units in the presence of an initiator, potassium alcoholate and an organic ether compound selected from dialkylether compounds having the formula R1-O -CH2-CH(R3)-O-R2, where R1 and R2 each represent an alkyl group with between 1 and 10 carbon atoms, and R3 represents hydrogen, methyl or ethyl. Whereas the molar ratio between potassium alcoholates and the active initiator is 0.4 mol/mol or less. In some embodiments, R1 is a methyl or ethyl and R2 is a branched alkyl group which, in some embodiments, is a t-butyl.

Brief explanation of the drawings

Figure No. 1a: shows the effect of adding ditetrahydrofurylpropane (DOP) to:

Tetramethylethylenediamine (TMEOA) as a polar agent on the dispersion (Mw/Mn) for molecular weight distribution.

Figure 1b: shows the effect of adding DOP to TMEDA (1.7 mol/mol) as a polar agent on the dispersion (Mw/Mn) of the molecular weight distribution.

Figure 1c: shows the effect of adding TMEDA to DOP (1 mol/mol) as a polar agent on the dispersion (Mw/Mn) of the molecular weight distribution.

Figure 2: Shows the effect of adding DOP to TMEDA as a polar agent on the ability of the chain ends to survive.

Figure 3: Shows the effect of adding TMEDA to DOP as a polar agent on the ability of the chain ends to survive.

Figure 4: Shows the effect of the molar ratio between DOP/TMEDA on the ability of the chain ends to survive.

Detailed description

Invention No. 1

Surprisingly and unexpectedly, the present inventors have discovered that SSBR has a high percentage of styrene and vinyl with a narrow molecular weight distribution, modifying styrene that is in the form of blocks of 4-6 units so that its percentage ranges from about 27 to about 50%, and block styrene of more than 6 units sequentially so that its percentage is not less than about 20%. Furthermore, the present inventors have also discovered - surprisingly and unexpectedly - that it is possible to prepare the previously described SSBR high in styrene and high in vinyl using an initiator (such as butyl lithium) and a randomizer (such as ditetrahydrofurylpropane, also known as 2 ,2-di(2-oxolanyl)propane or DOP) under the following conditions:, styrene content ≤40 wt%, molar ratio of DOP/active initiator ≤ 0.5; The polymerization temperature is ≥80°C.

In the context of the present invention, the following definitions must be considered:

In its broadest sense, the expression "polymer" refers to a substance prepared by polymerizing monomeric units. As used herein, the expression "polymer" includes the expressions "homopolymer" (a polymeric material prepared from one type of monomers), "copolymer" (a polymeric material prepared from two different types of monomers), and "interpolymer". (a polymeric material prepared from more than two different types of monomers).

The term "alkyl group" refers to a hydrocarbon chain that is straight, branched, or cyclic, with or without substitution, preferably containing between 1 and 20 carbon atoms. Distinctive examples of alkyl groups for which there is no substitution for use according to current guidelines include but are not limited to the following:

methyl, ethyl. propyl, iso-propyl. cyclopropyl, butyl, iso-butyl, tert-butyl, secbutyl,

cyclobutyl, and the like.

The term "process" when used to refer to polymerization reactions includes discontinuous, semi-continuous, and/or continuous processes.

The expression "discontinuous" or "semi-continuous" when used to refer to a polymerization process refers to a polymerization process in which more than 60% of the solvent is charged in the reactor along with additional polymerization components before the polymerization begins with an initiator charge.

The monomer can be charged immediately before adding the initiator, partially before adding the initiator, partially after adding the initiator, or directly immediately after adding the initiator over a specified period of time.

“Continuous polymerization” refers to a polymerization process in which the solvent, monomers, and any additional polymerization components are fed continuously into a reactor in specified volumetric proportions. In some embodiments, two or more polymerization reactors connected in series are used. In some embodiments, the reactor is driven into only one reactor.

The expression "vinyl content" refers to the percentage by mass (or weight) of butadiene located at positions 1, 2 in the polymer chain, based on the butadiene fraction (the total amount of polymerized butadiene) in the polymer.

The expression "styrene content" refers to the percentage by mass (or weight) of styrene in the polymer, based on the total weight of the polymer.

The expression “mass styrene content” refers to the weight percentage of styrene present as successive sequences of styrene units based on the total amount of styrene polymerized in the polymer.

The term “composition” refers to a mixture of substances including a polymer matrix and, optionally, reaction products and/or degradation products comprising the polymer matrix.

The expression "active initiator" (nBL,pm) refers to the amount of initiator (such as organolithium) involved in the polymerization reaction that has not been quenched by impurities in the reaction medium. The expression “excess initiator” (nBL,exc) refers to the amount of initiator charged to quench impurities in the system.

The expression "total amount of monomer feed stream" refers to the total amount of styrene and butadiene, in grams/min, driven into the continuous polymerization reactor, typically in the first continuous polymerization reactor.

The term "total polymer conversion" refers to the final conversion of the polymer (such as the final total conversion of styrene and butadiene) which is determined for the last polymerization reactor.

As a general introduction, a polymer that meets the properties of the current guidelines will have at least the following properties; (a) The content of bulk styrene containing between 4 and 6 styrene units is between about 27 and about 50 wt% of the total styrene content in the polymer; (b) The vinyl content is between about 30 and about 80 weight percent of the total amount of polymerized 1,3-butadiene; and (c) a styrene content of between about 40 and about 70 weight percent of the total weight of the polymer.

In some embodiments, the polymer having the properties of the present guidelines has a mass styrene content of more than 6 successive styrene units having at least about 10 weight percent of the total styrene content in the polymer. In some embodiments, the polymer having the properties of the present guidance has a mass styrene content of more than 6 successive styrene units having at least about 25 weight percent of the total styrene content in the polymer.

In some embodiments, the polymer having the properties of the present guidelines has an amount of styrene in which less than 4 successive styrene units are present between about 30 and about 73 weight percent of the total weight of the styrene being modified. In some embodiments, the amount of styrene present is less than 4 successive styrene units ranging from about 35 to about 70% by weight of the total weight of the styrene being modified.

In some embodiments, the polymer produced in batches according to current guidelines has a molecular weight distribution (Mw/Mn) between about 1.05 and about 2. In some embodiments, the molecular weight distribution is between about 1.1 and about 1.8. In some embodiments, the molecular weight distribution is between about 1.2 and about 1.6.

In some embodiments, the polymer produced continuously according to current guidelines has a molecular weight distribution (Mw/Mn) between about 1.5 and about 2.5. In some embodiments, the molecular weight distribution is between about 1.6 and about 2.4. In some embodiments, the molecular weight distribution is between about 1.8 and about 2.2.

In some embodiments, the polymer embodying the properties of the present guidelines has an average molecular weight greater than or equal to approximately 80,000 g/mol. In some embodiments, the number-average molecular weight is greater than or equal to and about 150,000 g/mol. In some embodiments, the number average molecular weight is greater than or equal to and about 300,000 g/mol,

In some embodiments, the polymer embodying the properties of the present guidelines has an average molecular weight by weight greater than or equal to and about 84,000 g/mol. In some embodiments, the average molecular weight by weight is greater than or equal to and about 155,000 g/mol. In some embodiments, the average molecular weight by weight is greater than or equal to and about 310,000 g/mol.

In some embodiments, the polymer embodying the characteristics of the current guidelines has a Mooney viscosity (ML 1+4 at 100 C) between about 20 and about 150. In some embodiments, the polymer embodying the characteristics of the current guidelines has a Mooney viscosity (ML 1 +4 at 100 C) between about 30 and about 120. In some embodiments, a polymer that embodies the properties of the current guidelines has a Mooney viscosity (ML 1+4 at 100 C) between about 30 and about 90.

Also by way of general introduction, a process for polymerization of a polymer comprising monomeric units derived from styrene monomer and 1,3-butadiene monomer in accordance with current guidelines comprises polymerizing the monomeric units in the presence of an initiator and a polar agent, wherein the agent is polar agent formula I:

<img file="SA4014B1_D0004.tif" />

In some embodiments, R1 and R2 each individually form an alkyl group. In some embodiments, R1 and R2 each individually form a C1-C4 alkyl group. In some embodiments, R1 and R2 are each a methyl.

In some embodiments, R3, R4, R6, R6, R7 and R8 are each individually selected from the group consisting of an alkyl group and a hydrogen group. In some embodiments, R3, R4, R5, R6, R7 and R8 are each individually selected from the group consisting of a hydrogen and an alkyl group C1-C4. In some embodiments, R3, R4, R6, R5, R7 and R8 are each individually selected from the group consisting of a hydrogen and a methyl - in some embodiments, R3, R4, R5t R6, R7 and R8 are each a hydrogen.

In some embodiments, the molar ratio between the polar agent and the active initiator is greater than about 0.5. In some embodiments, the molar ratio between the polar agent and the active initiator ranges from about 0.5 to about 10.

In some embodiments, the styrene content in the monomer mixture added in the polymerization is greater than about 40 weight percent of the total weight of the monomers added. In some embodiments, the polymerization process is performed in accordance with current guidelines at a temperature below about 80°C. In some embodiments, the polymerization process is performed in accordance with current guidelines at a temperature between about 10°C and about 80°C.

The currently preferred primers for use according to current guidelines include those suitable for anionic polymerizations. In some embodiments, the initiator used according to current guidelines is an organolithium compound (eg, alkyl mhium).

Representative alkyl mhium agents for use in accordance with current guidelines include, but are not limited to, the following: n-butyllithium, see-butyl lithium, tert-butyllithium, n-butyl lithium, and the like, and combinations thereof. In some embodiments, the initiator includes n-butyllithium .

In some embodiments, the total polymer conversion is greater than about 96 weight percent of the total amount of the monomer feed stream. In some embodiments, the total polymer conversion is greater than about 98 weight percent. In some embodiments, the total conversion of the polymer is greater than about 99 weight percent.

In some embodiments, the polymer having the properties of the present guidelines has a vinyl content of between about 30 and about 80 weight percent of the total amount of polymerized 1,3-butadiene. In some embodiments, the vinyl content ranges from about 40 to about 70 weight percent.

In some embodiments, the polymer embodying the properties of the current guidelines has a bulk styrene content containing between 4 and 6 styrene units that is between about 27 and about 50 weight % of the total styrene content in the polymer.

In some embodiments, the polymer having the properties of the present guidelines has a mass styrene content of more than 6 successive styrene units having at least about 10 weight percent of the total styrene content in the polymer.

In some embodiments, the polymer having the properties of the present guidelines has a bulk styrene content of more than 6 successive styrene units having at least about 25 weight percent of the total styrene content in the polymer,

It is currently preferred that polymerization processes according to current guidelines occur in solvents, with hydrocarbon solvents currently being preferred. In some embodiments, the polymerization solvent includes an alkane. In some embodiments, the polymerization solvent includes a cyclohexane. In some embodiments, the polymerization solvent includes a mixture of cyclohexane with one or more additional alkane.

Also by way of general introduction, a polymer is formed in accordance with current guidelines by a process of the type described herein.

In some embodiments, a polymer according to current instructions is modified using a modifying agent (or modifier). Examples of modifying agents include, but are not limited to: amines, amides, thioglycols, silicon alkoxides, silane-sulfide modifyers, and the like, and combinations thereof.

In some embodiments, a living polymer can be chemically modified according to current guidelines using chain-end modification and/or coupling reactions. Appropriate chain tip modification materials and/or coupling agents can be selected according to the target use and filler. Examples of coupling agents include, but are not limited to: tetrachloride, silicon tetrachloride, divinylbenzene, alkoxysilanes, and the like, and combinations thereof,

Examples of modifying materials include, but are not limited to: sulfenyl halides as described in EC No. 1016674, benzophenone, isocyanate, hydroxyl mercaptans as described in EC No. 0464478, and acrylamide compounds as described in EC No. 0334042 Additional means of modification include, but are not limited to, the following: Amines compounds, amides compounds, amides compounds, and nitrites modifiers as described in EC No. 548799, EC No. 510410, EC No. 451604, and EC No. 180141, and in US Patent No. 4412041. In some embodiments, silanes compounds including, but not limited to, epoxy-containing silanes compounds are used to modify the end of the polymer chain for use in silica fillers as described, for example, in European Application Document No. A-299074, Application EC No. A-102045, EC No. 0447066, and EC No. 0692493. Examples of additional amending materials and/or patent references that refer to these materials are in IS No. 2009/134665.

Also by way of general introduction, a composition embodying the properties of the current guidance contains a polymer of the type described herein, and in some embodiments, a composition in accordance with the current guidance also contains an oil. In some embodiments, a composition according to the current guidance also contains oil in an amount between about 5 and about 40 weight percent of the total weight of the polymer. In some embodiments, the composition according to the current instructions does not contain oil.

In some embodiments, a composition in accordance with current guidance contains a polymer of the type described herein and at least one additive. In some embodiments, the polymer is combined and/or reacted with one or more fillers, a vulcanizing agent, and/or optionally one or more other additives including but not limited to the following: accelerators, coupling agents, and elastomeric polymers. Unmodified non-crosslinked polymers (such as conventional non-crosslinked elastomer polymers that have not reacted with a modified material, but have been prepared and finished), etc., and combinations thereof.

In some embodiments, a composition according to current guidelines contains one or more fillers, which act as strengthening agents.

Typical examples of suitable fillers include, but are not limited to: carbon black, silica, carbon-silica double-phase fillers, clay, calcium carbonate, magnesium carbonate, and the like, and combinations thereof. In some embodiments, a combination of carbon black and silica, carbon black and silica dual-phase fillers or a combination of carbon and silica double-phase fillers and carbon black and/or silica are used.

In some embodiments, carbon black is manufactured by the furnace method, and has a specific surface area for nitrogen adsorption between about 50 and about 200 m2/g, and DBP oil adsorption between about 80 and about 200 mL/100 g (e.g., FEF, HAF, ISAF or carbon black of the SAF category). In some embodiments, "highly agglomerated type" carbon black is used. In some embodiments, carbon black or silica is added in an amount between about 2 and about 100 parts by weight per 100 parts by weight of the total polymer. In some embodiments, carbon black or silica is added in an amount between about 5 and about 100 parts by weight. In some embodiments, carbon black or silica is added in an amount between about 10 and about 100 parts by weight. In some embodiments, carbon black or silica is added in an amount between about 10 and 95 parts by weight.

Finally, also by way of general introduction, a product embodying the characteristics of the current guidelines includes at least one component of such composition, in some embodiments, the product being a tire. In some embodiments, the product is a component in the shoe.

The following examples and representative procedures illustrate properties according to current guidelines and are provided for illustration only. These examples are not intended to limit the scope of the attached or equivalent protections.

Examples

Monomer conversion was determined by measuring the solid content in the polymer solution at the completion of polymerization. The maximum solids concentration at 100 wt% conversion of charged butadiene (mBd) and styrene (mSt) to the final polymer is given by:

TSC max= (mBd+ mSt)/(mBd + mSt + mpolar agent + mBL+ mcyclohexane)*100%

A sample of the polymer solution ranging from about 1 g to about 10 g, depending on the expected conversion of the monomer, was drawn from the reactor directly into a 200 mL Erlenmeyer flask filled with ethanol (50 mL). The weight of the filled Erlenmeyer flask was determined before sampling (“A”) and after sampling (“B”). The precipitated polymer was removed from the ethanol by filtration on a weighted filter paper (Micro-glass fiber paper, 90 mm diameter, MUNKTELL, weight “C "), and dried at 140°C, using an HR73 moisture analyzer (Mettier-Toledo) until a constant weight was reached. Standard 5 was used. Finally, a second drying period was performed using closing standards 4 to obtain the final “D” mass of the dried sample on the filter paper. The polymer content in the sample was calculated as follows

TSC= (DC)/(BA)*100%

The final conversion of the polymer was calculated as TSC/TSC max*100%

Both the molecular weight and molecular weight distribution of the polymer were measured using size exclusion chromatography (SEC) at 40 mM based on polystyrene standard levels. Each polymer sample (9–11 mg) was dissolved in tetrahydrofuran (10 mL) to make a solution. The solution was filtered using a 0.45 μm filter. A 100 μL sample was fed to a GPC column (Hewlett Packard 1100 system with 3 PLgel 10 μM, MIXED-B columns). The refractive index trend was used as the detector for molecular weight analysis. The molecular weight was calculated as polystyrene based on titration with standard levels:

polystyrene EasiCaf PS1 (Easy A and B) from Polymer Laboratories. Average molecular weight numbers by number (Mn) and average molecular weight numbers by weight (Mw) are given based on polystyrene standard levels. The molecular weight distribution was expressed as the degree of dispersion D= Mw/Mn.

The vinyl content and total styrene content were measured using 1H-NMR, using the following method:

ISO 21561-2005. Using a BRUKER Avance NMR spectrometer, 400 MHz), and a 5 mm dual probe. CDCl3/TMS was used as solvent with a weight ratio of 0.05%:99.95%. The mass styrene content consisting of more than 6 consecutive styrene units was determined according to the method mentioned by:

Y. Tanaka et al, in Rubber Chemistry and Technology, 1981, 54, No. 4, 685-691 using the relative intensities of orthoph-proton signals that resonate at above 6.7 ppm.

The mass styrene content consisting of 4 consecutive styrene units or more was determined according to the method described in German Patent Document No. 69712962 using the relative intensity of the orthoph-proton signals that give a resonance ranging between 6.94 and 6 per million.

The mass styrene content, which consists of between 4 and 6 successive units, was calculated from the difference between each of the previously explained mass styrene contents.

Viscosity according to Mooney ML 1+4 (100 m)

Mooney viscosity was measured for polymer (no filler and no oil) according to ASTM D 1646 (2004), with a preheat time of 1 min, and a rotor actuation time of 4 min, at a temperature of 100 C [ML 1+4 (100 m)] on an MV2000 E from Alpha-Technologies.

Comparative example No. 1 (using DOP, 1 mol/mol, styrene percentage in monomer 21% 65 M)

Dried cyclohexane (255 g) was added to a 2 L air-free stainless steel reactor washed with nitrogen. 1,3-Butadiene (35.55 g), styrene (9.45 g), and DOP (0.2727 mmol, 25 wt% solution in cyclohexane) were fed to the reactor (DOP/active butyl lithium mol/mol = 1). The reaction was initiated by adding the following amounts of n-butyl lithium as 0.6278 mol/kg solution in cyclohexane: nBL,exc = 0.135 mmol to convert the impurity and nBL,pm = 0.2727 mmol to the reaction. The mixture was heated to 65°C while stirring. The reaction was terminated after 30 minutes by adding methanol as a termination agent. Bis(octyhiomethyl)-o-cresol 4,6, sold under the brand name IRGANOX 1520 (Ciba), has been introduced as an antioxidant.

A sample was drawn using a sampling tube equipped with a stopcock and a needle to determine the solid content. A conversion rate of 100% was measured.

The resulting polymer was analyzed using GPC: Mn= 215586, Mw= 236158, D= 1.095.

The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained: styrene = 21.2%, vinyl (1,2-polybutadiene, calculated based on butadiene percentage) = 62.2%, bulk styrene (&gt;6 styrene units): 2%, bulk styrene comprising 4-6 styrene units: 12%.

Although the DOP/nBL,pm ratio and temperature were in the innovative range, the styrene content of 21% was low enough to achieve an innovative mass styrene content of 4-6 styrene units.

Comparative Example No. 2:

(Use DOP, 0.4 mol/mol, styrene percentage in monomer 40%, 60 M)

Dried cyclohexane (255 g) was charged into a 2 L nitrogen-purged air-free stainless steel reactor. 1,3-butadiene (27 g), styrene (18 g), and DOP (0.1052 mmol, 23.38% solution in cyclohexane) were fed to the reactor (DOP/active butyl lithium mol/mol = 0.3974). The reaction was initiated by adding the following amounts of n-butyl lithium as 0.4451 mol/kg solution in cyclohexane: nBL,exc = 0.32 mmol to convert the impurity and nBL,pm = 0.2647 mmol to the reaction. The mixture was heated to 60°C while stirring. The coupled polymer was coupled after 120 minutes by adding TMS (0.075 mol/mol), and the remaining unconjugated polymer was terminated after 30 minutes by adding methanol as a termination agent. IRGANOX 1520 is introduced as an antioxidant.

A sample was drawn using a sampling tube equipped with a stopcock and a needle to determine the solid content. A conversion rate of 97.24% was measured.

The resulting conjugated polymer was analyzed using GPC: Mn=222029, Mw=381586, D=1.719 at 23% coupled polymer.

The fine composition and mass styrene content were measured using 1HNMR. The following results were obtained: styrene - 41.4%, vinyl (1,2-polybutadiene, calculated based on butadiene percentage) = 47%, bulk styrene (&gt;6 styrene units): 3%, bulk styrene including 4-6 units styrene: 24%.

Although the styrene content and temperature were in the innovative range, the DOP/Nbl,pm ratio of 0.3974 was too low to achieve an innovative mass styrene content of 4-6 styrene units.

Comparative example No. 3 (using DOP 0.4 mol/mol, styrene percentage in monomer 40% 85 M)

Dried cyclohexane (255 g) was added to an airless, nitrogen-purged 2 L stainless steel reactor. 1,3-butadiene (27 g), styrene (18 g), and DOP (0.1052 mmol, 23.38% solution in cyclohexane) were fed to the reactor (DOP/active butyl lithium mol/mol = 0.3974). The reaction was started by adding The following amounts of n-butyl lithium as 0.4451 mol/kg solution in cyclohexane: nBL,exc = 0.32 mmol for the impurity conversion and nBL,pm = 0.2647 mmol for the reaction. The mixture was heated to 85°C while stirring. The polymer was coupled after 30 minutes by adding TMS (0.075 mol/mol). The remaining unconjugated polymer was terminated after 30 min by adding methanol as a termination agent. IRGANOX 1520 was introduced as an antioxidant

A sample was drawn using a sampling tube equipped with a stopcock and a needle to determine the solid content. A conversion rate of 95.62% was measured.

The resulting conjugated polymer was analyzed with GPC: Mn=210590, Mw=378049, D=1.795 at 22.3% coupled polymer.

The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained: styrene = 42.1%, vinyl (1,2-polybutadiene, calculated based on butadiene ratio) = 33.4%, bulk styrene (&gt;6 styrene units): 14%, bulk styrene comprising 4-6 styrene units styrene: 20%.

Although the styrene content was in the inventive range, the DOP/butyl lithium ratio of 0.4 was too low and the exposure temperature of 85°C was too high to achieve an inventive mass styrene content of 4-6 styrene units.

Example 1 (using DOP, 1 mol/mol)

Dried cyclohexane (5208.11 g) was added to an air-free, nitrogen-purged 10-L stainless steel reactor, and fed with 1,3-butadiene (317.28 g), styrene (393.11 g), and DOP. (1.1866 mmol) to the reactor (active DOP/butyl lithium = 0.9808).

The mixture was heated to 50°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. When the end point was verified, polymerization was initiated by adding an amount of active butyl lithium nBL,pm of 1.2098 mmol (0.2585 mol/kg solution in cyclohexane) using a pump within 1 minute and 22 seconds. Then, the polymerization process began. The temperature in the reactor rose to 65°C within 30 minutes. The reaction was stopped after 200 minutes by adding methanol as a termination agent. IRGANOX 1520 was introduced as an antioxidant.

A sample was drawn using a sampling tube equipped with a stopcock and a needle to determine the solid content. A conversion rate of 99.26% was measured.

The resulting polymer was analyzed using GPC: Mn= 587535, Mw= 755240, D= 1.285. The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained: styrene = 55.9%, vinyl (1,2-polybutadiene, calculated based on butadiene ratio) = 49%, bulk styrene (&gt;6 styrene units): 8%, bulk styrene comprising 4-6 styrene units styrene: 37%.

Example 2 (using DOP, 1 mol/mol)

Dried cyclohexane (21236.38 g) was added to an airless, nitrogen-purged, 40 L stainless steel reactor. 1,3-butadiene (838.13 g), styrene (1018.1 g), and DOP (4.1567 mmol) were fed to the reactor (DOP/active butyl lithium mol/mol = 1.0924).

The mixture was heated to 50°C while stirring. The impurities in the system were calibrated step by step with butyl lithium. When the end point was verified, polymerization was initiated by adding 3.8051 mmol of n-butyllithium (0.2585 mol/kg solution in cyclohexane) using a pump over about 2 minutes. Then, the polymerization process began. The temperature in the reactor rose to 65°C within 30 minutes. The transformation was completed after 90 minutes. A sample was taken and the resulting polymer was analyzed using GPC: Mn= 528631, Mw= 638245, D= 1.207, the fine composition and mass styrene content were measured using 1H-NMR.

The reaction was stopped by adding a coupling agent and the remaining unconjugated chains were finally stopped after another 30 min by adding methanol as a termination agent. IRGANOX 1520 was introduced as an antioxidant.

The following results were obtained: styrene = 53.8%, vinyl (1,2-polybutadiene, calculated based on butadiene ratio) = 47.6%, bulk styrene (&gt;6 styrene units): 8%, bulk styrene comprising 4-6 units styrene: 37%.

Example 3 (using DOP, 41% styrene)

Dried cyclohexane (21194.98 g) was added to an airless, nitrogen-purged 40 L stainless steel reactor. 1,3-butadiene (1008.13 g), styrene (831.75 g), and DOP (2.3106 mmol) were fed to the reactor (DOP/active butyl lithium mol/mol = 0.9822).

The mixture was heated to 50°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. When the end point was verified, polymerization was initiated by adding 2.3524 mmol of n-butyllithium (0.2585 mol/kg solution in cyclohexane) using a pump within about 1 minute. The polymerization process then began. The temperature in the reactor rose to 65°C within 30 minutes. The reaction was stopped after 210 min by adding methanol as a termination agent. IRGANOX 1520 was introduced as an antioxidant.

A sample was drawn using a sampling tube equipped with a stopcock and a needle to determine the solid content. A conversion rate of 96.34% was measured.

The resulting polymer was analyzed using GPC: Mn= 1652619, Mw= 2578087, D= 1.56. The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained: styrene = 41%, vinyl (1,2-polybutadiene, calculated based on butadiene percentage) = 46.5%, bulk styrene (&gt;6 styrene units), 3%, bulk styrene comprising 4-6 units styrene, 29%.

Example 4 (using DOP, 46.5% styrene)

Dried cyclohexane (21,215.19 g) was charged into an airless, nitrogen-purged, 40 L stainless steel reactor. 1,3-butadiene (974 g), styrene (888.15 g), and DOP (2.16129 mmol) were fed to the reactor (DOP/active butyl lithium mol/mol = 0.9244).

The mixture was heated to 50°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. When the end point was verified, polymerization was initiated by adding 2.236 mmol of n-butyllithium (0.2585 mol/kg solution in cyclohexane) using a pump within approximately 1 minute. The polymerization process then began. The temperature in the reactor rose to 65°C within 30 minutes. A sample was withdrawn after 120 minutes using a sampling tube equipped with a stopcock and a needle to determine the solid content. A conversion rate of 99.17% was measured.

The polymer analyzed using GPC: Mn= 868986, Mw= 1117669, D= 1.286. The polymer was coupled after 30 min by adding TMS (0.078 mol/mol). The reaction was stopped after 240 minutes by adding methanol as a termination agent. IRGANOX 1520 was introduced as an antioxidant.

The polymer analyzed using GPC: Mn=980410, Mw=1562027, D=1.59 at 17% conjugation. The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained: styrene = 46.5%, vinyl (1,2-polybutadiene, calculated based on butadiene ratio) = 40.3%, bulk styrene (&gt;6 styrene units): 9%, bulk styrene comprising 4-6 units styrene: 42%.

Comparative Example No. 4 Continuous polymerization T= 85 m, DOP/active initiator = 2

The reaction was carried out in two CSTR reactors connected in series. The volume of the first reactor is 6.3 liters and the second is 12.6 liters.

The reactors are equipped with a screw stirrer suitable for mixing high viscosity solutions. The reactors were operated and fully filled. Using external circulation of water in the walls of the reactor, the required temperature was regulated. The components (styrene, butadiene, cyclohexane, DOP, 1,2-butadiene (1,2-Bde) and n-butyllithium) were fed to the first reactor head equipped with mass flow meters (Micromotion) that allow regulation of the required feed current and ensure a constant flow. The purification was carried out cyclohexane by passing it through an alumina column. The initiator (n-butyllithium in cyclohexane) was pushed at the inlet of the first reactor. DOP and 1,2-butadiene were diluted in cyclohexane until the exact amounts of the reaction could be delivered. Chemical dilution amounts are reported in the examples along with the solvent such as the cyclohexane feed stream.

A proportion of monomers in the total feed stream of 12% was used. The following conditions were used in this experiment: styrene: butadiene = 44 wt%: 56 wt%, DOP/nBL,pm (mol/mol) = 2.18. The temperatures of both reactors were maintained at 85°C. The flow of the total amount of components and solvent was regulated to achieve a residence time of 45 minutes in the first reactor and 90 minutes in the second reactor. The following amounts were fed to the first polymerization reactor: Sty = 5.31 g/min, Bde = 7.04 g/min, cyclohexane = 90.57 g/min, nBL,pm = 0.0692 mmol/min, nBL,exc = 0.0064 mmol/min , DOP = 0.151 mmol/min, 1,2-Bde = 0.121 mmol/min.

Methanol as a finishing agent and IRGANOX 1520 (0.15 phr) as an antioxidant were added to the polymeric solution outside the second reactor. A total conversion of 95% was obtained outside the first reactor, and a complete conversion was obtained outside the second reactor.

The polymer leaving the second reactor was analyzed using GPC with a titration with polystyrene, Mn = 254704 g/mol, Mw = 507879 g/mol, MWD = 1.994. The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained: styrene = 44.5%, vinyl (1,2-polybutadiene, calculated based on butadiene ratio) = 55%, bulk styrene (&gt;6 styrene units): 3%, bulk styrene comprising 4-6 styrene units styrene: 25%.

The Mooney ML 1+4 viscosity of the products was 69.1.

The DOP/nBL,pm ratio and styrene content were in the innovative range, but the reaction temperature was very high, so that an SSBR with 25% styrene by mass containing 4-6 styrene units was obtained.

Example 5 (continuous polymerization, T = 40 m, DOP/active initiator = 2)

The copolymerization of styrene - butadiene was carried out using the conditions described above. A ratio of monomers/total feed stream of 12% was used. The following conditions were used in this experiment:

styrene: butadiene = 44 wt%: 56 wt%, active DOP/lithium (mol/mol) = 2.44. The temperatures of both reactors were maintained at 40°C. Total flow of components and solvent The total flow of components and solvent is regulated to achieve a residence time of 70 minutes in the first reactor and 140 minutes in the second reactor. The following amounts were fed to the first polymerization reactor: Sty = 3.41 g/min, Bde = 4.53 g/min, cyclohexane = 58.22 g/min, nBL,pm = 0.0574 mmol/min, nBL,exc = 0.00739 mmol/min , DOP= 0.14 mmol/min, 1,2-Bde= 0.01037 mmol/min.

Methanol as a finishing agent and IRGANOX 1520 (0.15 phr) as an antioxidant were added to the polymeric solution outside the second reactor. A total conversion of 88.97% was obtained outside the first reactor, and a complete conversion was obtained outside the second reactor.

The polymer leaving the second reactor was analyzed using GPC with a titration with polystyrene: Mn = 206700, Mw = 375573, MWD = 1.817. The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained: styrene = 46%, vinyl (1,2-polybutadiene, calculated based on butadiene ratio) = 71.5%, bulk styrene (&gt; 6 styrene units): 9%, bulk styrene comprising 4-6 styrene units styrene: 42%.

The Mooney ML1+4 viscosity of the products was 54.7.

The DOP/active initiator ratio, styrene content, and temperature were in the innovative range. The resulting SSBR was obtained with more than 20% styrene by mass comprising 4-6 styrene units.

Invention No. 2

The present inventors have discovered, surprisingly and unexpectedly, a polymerization process for preparing an SSBR having a high percentage of styrene and a high percentage of vinyl with a very narrow molecular weight distribution, a high conversion rate (in some embodiments, greater than 99%), and a short reaction time (in some embodiments). models, less than 3 hours). As will be explained later, the process of the invention uses a combination of a first and second polar agent. In some embodiments, the first and second polar agents correspond to TMEDA and DOP, respectively.

Furthermore, the present inventors have also surprisingly and unexpectedly discovered that the use of certain combinations of polar agents I and II (such as DOP and TMEDA) results in not only a narrow distribution of the molecular weight of the polymer at the completion of the polymerization process, as shown in Figure 1a, but also a significant increase in the viability of the polymer chains at the end of the polymerization process compared to using only TMEDA, as shown in Figure 2, or using only DOP, as shown in Figure 3. The present inventors have also discovered that particularly good results have been achieved at a DOP/TMEDA ratio between about 0.5 and about 1 mol/mol, as shown in Figure 4. In summary, as will be explained in more detail later, the present inventors have achieved - in an exciting way - Surprisingly and unexpectedly, there was an improvement in the molecular weight distribution using a combination of polar agents compared to using only TMEDA, and an improvement in the ability of the chain ends to survive compared to using only DOP.

In the context of the present invention, the following definitions must be considered:

In its broadest sense, the expression "polymer" refers to a substance prepared by polymerizing monomeric units. As used herein, the expression "polymer" includes the expressions "homopolymer" (a polymeric material prepared from one type of monomers), "copolymer" (a polymeric material prepared from two different types of monomers), and "interpolymer". (A polymeric material that is prepared from more than two different types of monomers).

The term “alkyl group” refers to a straight, branched, or cyclic hydrocarbon chain, with or without substitution, preferably containing between 1 and 20 carbon atoms. Distinctive examples of alkyl groups for which there is no substitution for use according to current guidelines include but are not limited to the following:

methyl, ethyl, propyl, iso-propyl, cyclopropyl, butyl, iso-butyl, tert-butyl, secbutyl, cyclobutyl, and the like.

The expression "process" when used to refer to polymerization reactions contains discontinuous, semi-continuous, and/or continuous processes.

The expression vinyl.conten refers to the percentage by mass (or weight) of butadiene located at positions 1, 2 in the polymer chain, based on the butadiene fraction (the total amount of butadiene polymerized) in the polymer.

The expression "styrene content" refers to the percentage by mass (or by weight) of styrene in the polymer, based on the total weight of the polymer.

The term “composition” refers to a mixture of substances including a polymer matrix and, optionally, reaction products and/or degradation products comprising the polymer matrix.

The expression "active initiator" (nBL, pm) refers to the amount of initiator (such as a lithium-containing organic substance) involved in the polymerization reaction that has not been quenched by impurities in the reaction medium.

By way of general introduction, a process for polymerization of a polymer comprising monomeric units derived from styrene monomer and 1,3-butadiene monomer in accordance with current guidelines comprises polymerizing the monomeric units in the presence of an initiator, a first polar agent, and a polar agent. polar agent second. In some embodiments, the first polar agent has the form (II):

R1'R2'NQ-NR3'R4' (II)

In some embodiments, the second polar agent has the form I:

<img file="SA4014B1_D0005.tif" />

In some embodiments, R1', R2', R3', and R4' are each individually selected from the group consisting of an alkyl and a hydrogen group; in some embodiments, R1, R2', R3', and R4 are each individually selected from The group consisting of a hydrogen and a Ci-C alkyl group. In some embodiments, R1, R2, R3', and R4' are each individually selected from the group consisting of a hydrogen and a methyl. In some embodiments, R1, R2-, R3, and R4' are each a hydrogen.

In some embodiments, Q represents an alkylene group. In some embodiments, the alkylene group has the formula -(CH2)n-, where n is an integer equal to or greater than 2, in some embodiments, n is 2 (i.e., Q is ethylene), in some embodiments, n is 3 ( That is, Q is propylene.

In some embodiments, R1 and R2 each individually represent an alkyl group, in some embodiments, R1 and R2 each individually represent an alkyl group C1-C4. In some embodiments, R1 and R2 are each methyl.

In some embodiments, R3, R4, R5, R6, R7 and R8 are each individually selected from the group consisting of an alkyl and a hydrogen group; in some embodiments, R3, R4, R5, R6, R7 and R8 are each selected separately. From the group consisting of a hydrogen and an alkyl group C1-C4. In some embodiments, R3, R4, R5, R6, R7 and R8 are each individually selected from the group consisting of hydrogen and methyl. In some embodiments, R3, R4, R5, R6, R7 and R8 are each hydrogen.

In some embodiments, the first polar agent according to current guidelines is tetramethylethylenediamine (TMEDA). In some embodiments, TMEDA is used in an amount greater than 0.3 mol/mol. In some embodiments, TMEDA is used in an amount greater than 0.4 mol/mol. In some embodiments, TMEDA is used in an amount greater than 0.5 mol/mol.

In some embodiments, the second polar agent according to current guidance is ditetrahydrofurylpropane (also known as 2,2-di(2-oxolanyl)propane or DOP). In some embodiments, DOP is used in an amount greater than 0.2 mol/mol. In some embodiments, DOP is used in an amount greater than 0.3 mol/mol. In some embodiments, DOP is used in an amount greater than 0.5 mol/mol.

In some embodiments, the molar ratio between the second polar agent and the first polar agent (such as DOP/TMEDA) is between about 0.01 and about 10. In some embodiments, the molar ratio is between about 0.1 and about 3.

In some embodiments, the molar ratio ranges from about 0.3 to about 1.

In some embodiments, the styrene content in a polymer according to current guidelines ranges from about 20 to about 80 weight percent of the total weight of the polymer. In some embodiments, the styrene content ranges from about 40 to about 70 weight percent of the total weight of the polymer.

In some embodiments, the vinyl content of a polymer according to current guidelines ranges from about 30 to about 80 weight percent of the total amount of 1,3-butadiene polymerized. In some embodiments, the vinyl content of a polymer according to current guidelines ranges from about 40 to about 70 weight percent of the total amount of polymerized 1,3-butadiene.

In some embodiments, the polymer embodying the properties of the present guidelines has a molecular weight distribution between about 1.05 and about 1.8.

In some embodiments, the molecular weight distribution is between about 1.1 and about 1.7. In some embodiments, the molecular weight distribution is between about 1.2 and about 1.6.

In some embodiments, the polymer embodying the properties of the present guidelines has an average molecular weight greater than or equal to approximately 100,000 g/mol. In some embodiments, the number-average molecular weight is greater than or equal to and about 150,000 g/mol. In some embodiments, the number-average molecular weight is greater than or equal to and about 300,000 g/mol.

In some embodiments, the polymer embodying the properties of the present guidelines has an average molecular weight by weight greater than or equal to and about 180,000 g/mol. In some embodiments, the average molecular weight by weight is greater than or equal to and about 200,000 g/mol. In some embodiments, the average molecular weight by weight is greater than or equal to and about 360,000 g/mol. In some embodiments, a polymer according to the present guidelines has only one glass transition temperature (Tg). In some embodiments, Tg ranges from about -50 m to about 20 m. In some embodiments, Tg ranges between about -30 m and about 10 m.

In some embodiments, the molar ratio between the polar agent and the active initiator is greater than about 0.3. In some embodiments, the molar ratio is greater than about 0.4. In some embodiments, the molar ratio is greater than about 0.5.

In some embodiments, the molar ratio between the second polar agent and the active initiator is greater than about 0.2. In some embodiments, the molar ratio is greater than about 0.3. In some embodiments, the molar ratio is greater than about 0.5.

The currently preferred primers for use according to current guidelines include those suitable for anionic polymerizations. In some embodiments, the initiator used according to current guidelines is an organolithium compound (eg, alkyl mhium). Representative alkyl mhium agents for use in accordance with current guidelines include, but are not limited to, the following: n-butyllithium, see-butyl lithium, tert-butyllithium, n-butyl lithium, and the like, and combinations thereof, in some embodiments, the initiator comprising n- butyllithium.

It is currently preferred that polymerization processes according to current guidelines occur in solvents, with hydrocarbon solvents currently being preferred. In some embodiments, the polymerization solvent includes an alkane. In some embodiments, the polymerization solvent includes cyclohexane. In some embodiments, the polymerization solvent includes a mixture of cyclohexane with one or more additional alkane.

Also by way of general introduction, a polymer is formed in accordance with current guidelines by a process of the type described herein. In some embodiments, a polymer embodying the properties of the present guidance has at least the following properties: (a) a styrene content of between about 40 and about 70 weight percent of the total weight of the polymer; (b) The vinyl content is between about 30 and about 80 weight percent of the total amount of polymerized 1,3-butadiene; and (c) a molecular weight distribution between about 1.05 and about 1.8.

In some embodiments, a polymer is modified according to current guidelines using a modifying agent (or modifying agent).

Examples of modifying agents include, but are not limited to: amines, amides, thioglycols, silicon alkoxides, silane-sulfide modifyers, and the like, and combinations thereof.

In some embodiments, a living polymer can be chemically modified according to current guidelines using chain-end modification and/or coupling reactions. Appropriate chain tip modification materials and/or coupling agents can be selected according to the target use and filler.

Examples of coupling agents include, but are not limited to: tetrachloride, silicon tetrachloride, divinylbenzene, alkoxysilanes, and the like, and combinations thereof.

Examples of modifying materials include, but are not limited to, the following: sulfenyl halides as described in European Application Document No. 1016674, benzophenone, isocyanate, hydroxymercaptan compounds as described in European Application Document No. 0464478, and acrylamide compounds as described in European Application Document No. 0334042. Additional means of modification include, but are not limited to, the following: amines, amides, amides, and nitrite modifiers as described in EC No. 548799, EC No. 510410, EC No. 451604, and EC No. 180141, and in the patent. American No. 4412041. In some embodiments, silanes compounds including, but not limited to, epoxy-containing silanes compounds are used to modify the end of the polymer chain for use in silica fillers as described, for example, in European Application Document No. A-299074, Application EC No. A-102045, EC No. 0447066, and EC No. 0692493. Additional examples of amending articles and/or patent references that refer to these articles are found in IS No. 2009/134665.

Also by way of general introduction, a composition that embodies the properties of the current guidelines contains a polymer of the type described herein. In some embodiments, the composition according to the current instructions also contains oil. In some embodiments, the composition according to the current instructions does not contain oil.

In some embodiments, a composition in accordance with current guidance contains a polymer of the type described herein and at least one additive. In some embodiments, the polymer is combined and/or reacted with one or more fillers, a vulcanizing agent, and/or optionally one or more other additives including but not limited to the following: accelerators, coupling agents, non-stick elastomer polymers. Non-crosslinked modifiers (i.e. conventional non-crosslinked elastomeric polymers that have not reacted with a modifying substance, but have been primed and finished), the like, and combinations thereof.

In some embodiments, a composition in accordance with the present guidance contains one or more fillers, acting as reinforcing agents, characteristic examples of suitable fillers including but not limited to the following: carbon black, silica, dual-phase carbon-silica filler, clay , calcium carbonate, magnesium carbonate, and the like, and combinations thereof. In some embodiments, a combination of carbon black, silica, carbon black and silica double-phase fillers or a combination of carbon black, silica, carbon black and/or silica double-phase fillers is used.

In some embodiments, carbon black is manufactured by the fumace process, and has a specific surface area for nitrogen adsorption between about 50 and about 200 m2/g, and DBP oil adsorption between about 80 and about 200 mL/100 g (e.g., FEF, HAF, ISAF or SAF grade carbon black), in some embodiments, “highly agglomerated” carbon black is used. In some embodiments, carbon black or silica is added in an amount between about 2 and about 100 parts by weight per 100 parts by weight of the total polymer. In some embodiments, carbon black or silica is added in an amount between about 5 and about 100 parts by weight. In some embodiments, carbon black or silica is added in an amount between about 10 and about 100 parts by weight. In some embodiments, carbon black or silica is added in an amount between about 10 and 95 parts by weight.

Finally, also by way of general introduction, a product that embodies the properties of the current guidelines contains at least one component of this formulation. In some embodiments , the product is a tire. In some embodiments, the product is a component in the shoe.

The following representative examples and procedures illustrate features in accordance with current guidelines and are provided for illustration only. They are not intended to limit the scope of attached or equivalent protections.

Examples

Monomer conversion was determined by measuring the solid content of the polymer solution at the completion of polymerization. The maximum solids concentration at 100 wt% conversion of charged butadiene (mBd) and styrene (mSt) to the final polymer is given by:

TSC max= (mBd+ mSt)/(mBd + mSt + mpolar agent + mBL+ mcyclohexane)*100%

A sample of the polymer solution ranging from about 1 g to about 10 g, depending on the expected conversion of the monomer, was drawn from the reactor directly into a 200 mL Erlenmeyer flask filled with ethanol (50 mL). The weight of the filled Erlenmeyer flask was determined before sampling (“A”) and after sampling (“B”). The precipitated polymer was removed from the ethanol by filtration on a weighted filter paper (Micro-glass fiber paper, 90 mm, MUNKTELL, weight “C”). They were dried at 140°C using an HR73 moisture analyzer (Mettler-Toledo) until a constant weight was reached. Standard 5 was used. Finally, a second drying period was performed using 4 closure parameters to obtain the final “D” mass of the dried sample on the filter paper. The polymer content in the sample was calculated as follows:

TSC= (DC)/(BA)*100%

The final conversion of the polymer was calculated as TSC/TSC max*100%

The glass transition temperature, Tg, was measured and calculated according to ISO 11357-2 (1999) using a heating rate of 20 K/min with the following settings:

Sample weight: about 11 mg

Sample container: Standard aluminum pans (closed and sealed against vapor leakage)

Temperature range: -150 to 100 C

Heating rate: 20 K/min

Cooling rate: free cooling (10 to 20 K/min)

Purge gas: 20 ml He/min

Cooling agent: liquid nitrogen

Evaluation method: inflection point

Device: DSC Q2000 from TA Instruments

Two heating cycles without stopping between heating and cooling, Tg was determined using data from the second heating cycle.

Both the molecular weight and molecular weight distribution of the polymer were measured using size exclusion chromatography (SEC) at 40 mM based on polystyrene standard levels. Each polymer sample (9–11 mg) was dissolved in tetrahydrofuran (10 mL) to make a solution. The solution was filtered using a 0.45 μm filter. A 100 μL sample was fed to a GPC column (Hewlett Packard system 1100 with 3 PLgel 10μM MIXED-B columns). The refractive index trend was used as the detector for molecular weight analysis. Molecular weight was calculated as polystyrene based on titration with EasiCal PS1 (Easy A and B) polystyrene standard levels from Polymer Laboratories.

Average molecular weight values by number (Mn) and average molecular weight values by weight (Mw) are given based on polystyrene standard levels. The molecular weight distribution was expressed as the degree of dispersion D= Mw/Mn.

The vinyl content and total styrene content were measured using 1H-NMR, according to the ISO 21561-2005 method. Using a BRUKER Avance 400 MHz NMR spectrometer and a 5 mm dual probe. CDCl3/TMS was used as solvent with a weight ratio of 0.05%:99.95%. The mass styrene content consisting of more than 6 consecutive styrene units was determined according to the method reported by Y. Tanaka et al, in Rubber Chemistry and Technology, 1981, 54, No. 4, 685-691 using the relative intensities of the orthoph-proton signals that give resonances higher than 6.7 per million.

Procedures for Determining Livingness of Chain Ends:

As previously explained, using a combination of TMEDA and DOP results in higher survival of the chain ends at the end of the polymerization process. The proportion of viable chain ends at the end of the polymerization process is desirable because as the amount of chains included in the polymer increases, the interaction between the filler and rubber will improve and the rolling resistance of the resulting vulcanized compound will decrease.

The polymers were treated with an excess amount of N-methylpyrrolidone NMP after achieving a monomer conversion above 99% to evaluate the viability of the resulting polymer chains. The modification rate of the resulting polymer chains was analyzed using two different methods: Method 1 is based on comparing size exclusion chromatography (SEC) ratios of ultraviolet absorption intensity (UV) to the refractive index (RI) as described in U.S. Pat. No. 7700, 693b2 by Karato et al. ; Method 2 involves adsorption onto a silica gel column as described in US Patent Applications Nos. 2009/0163668A1 and 2009/0203843A1. It turns out that the absolute values obtained using Method 1 and Method 2 are different but have the same trends. Comparative Example 6 was set to be 100 in each method and all obtained data were calculated according to this reference (MR in %) form.

Comparative Example 5: Using TMEDA only

Dried cyclohexane (5371.18 g) was added to an airless, nitrogen-purged 10 L stainless steel reactor. 1,3-butadiene (326.657 g), styrene (404.13 g), and TMEDA (2.1205 mmol) were fed to the reactor (TMEDA/active butyl lithium mol/mol = 1.742).

The mixture was heated to 50°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. When the end point was verified, polymerization was initiated by adding an nBUpm amount of 1.2175 mmol n-butyllithium (15% solution in cyclohexane) using a pump over 2 min 16 s. Then the polymerization process began. The temperature in the reactor rose to 65°C within 30 minutes. The completion of the reaction was confirmed after 300 minutes by taking samples and determining that the monomer conversion was 100%. The resulting polymer was analyzed using GPC: Mn= 315898, Mw= 639432, D= 2.02. Butadiene (3.3 g) was added followed by NMP (1.32 mmol). After 15 minutes, the reaction was completed by adding methanol as a finishing agent. 4,6-bis(octylthiomethyl)-o-cresol sold under the brand name IRGANOX 1520 from Ciba has been introduced as an antioxidant.

The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained: styrene = 52.5%, vinyl (1,2-polybutadiene, calculated based on butadiene ratio) = 39.1%, bulk styrene = 15%.

Measurement of the glass transition temperature showed that there was a single glass transition temperature at -14.7 C. The modification rate analysis resulted in 49% (Method 1) and 48% (Method 2) versus Comparative Example 6 (100%).

Comparative Example 6: Using TMEDA only

Dried cyclohexane (5429.3 g) was added to an airless, nitrogen-purged 10 L stainless steel reactor. 1,3-butadiene (326.4 g), styrene (402.5 g), and TMEDA (3.759 mmol) were fed to the reactor (TMEDA/active butyl lithium mol/mol = 3.055).

The mixture was heated to 50°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. When the end point was verified, polymerization was initiated by adding an amount of nBL,pm of 1.2305 mmol n-butyllithium (15% solution in cyclohexane) using a pump during 2 min 16 s. Then the polymerization process began.

The temperature in the reactor rose to 65°C within 30 minutes. The reaction was completed after 260 minutes by taking samples and determining that the monomer conversion was 99.7%. The resulting polymer was analyzed using GPC: Mn = 319626, Mw = 584252, D = 1.892. Butadiene (3.3 g) was added followed by NMP (1.2286 mmol). After 15 minutes, the reaction was completed by adding methanol as a finishing agent. IRGANOX 1520 was introduced as an antioxidant.

The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained: styrene = 53%. Vinyl (1,2-polybutadiene, calculated based on butadiene percentage) = 42.1%, styrene bulk = 12%.

Measurement of the glass transition temperature showed that there was a single glass transition temperature at -9.8°C. The results of the modification rate analysis were used as a reference for all other experiments and were considered as 100 (method 1) and 100 (method 2).

Comparative Example 7: Use DOP only

Dried cyclohexane (5208.11 g) was added to an airless, nitrogen-purged 10 L stainless steel reactor. 1,3-butadiene (317.28 g), styrene (393.11 g), and DOP (1.1866 mmol) were fed to the reactor (DOP/active butyl lithium = 0.981).

The mixture was heated to 50°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. When the endpoint was verified, polymerization was initiated by adding an amount of nBL,pm of 1.21 mmol n-butyllithium (15% solution in cyclohexane) using a pump within about 1 minute. The polymerization process then began. The temperature in the reactor rose to 65°C within 30 minutes. The completion of the reaction was confirmed after 120 minutes by taking samples and determining that the monomer conversion had reached 99.49%. The polymer analyzed using GPC: Mn= 587535, Mw= 755240, D= 1.285. Butadiene (3.34 g) was added followed by NMP (1.257 mmol). After 15 minutes, the reaction was completed by adding methanol as a finishing agent. IRGANOX 1520 was introduced as an antioxidant.

The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained: styrene = 55.9, vinyl (1,2-polybutadiene, calculated based on butadiene ratio) = 49%, block styrene = 8%.

Measurement of the glass transition temperature showed that there was a single glass transition temperature at -7.1 C. The modification rate analysis resulted in 190% (Method 1) and 168% (Method 2) versus Comparative Example 6 (100%).

Comparative Example 8: Use DOP only

Dried cyclohexane (20,717.6 g) was added to an airless, nitrogen-purged, 40 L stainless steel reactor, fed with 1,3-butadiene (1,336.66 g), styrene (1,625.04 g), and DOP. (5.11 mmol) to the reactor (DOP/active butyl lithium = 1.025).

The mixture was heated to 50°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. When the endpoint was verified, polymerization was initiated by adding nBL,pm an amount of 4.8882 mmol of n-butyllithium (15% solution in cyclohexane) using a pump within about 1 minute, then the polymerization process was initiated. The temperature in the reactor rose to 65°C within 30 minutes. The reaction was stopped after 230 minutes by adding methanol as a termination agent. IRGANOX 1520 was introduced as an antioxidant.

A sample was drawn using a sampling tube equipped with a stopcock and a needle to determine the solid content. A conversion rate of 99.27% was measured.

The resulting polymer was analyzed using GPC: Mn= 640960, Mw= 837114, D= 1.306. The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained:

styrene = 54.9%, vinyl (1,2-polybutadiene, calculated based on butadiene ratio) = 50.1%, bulk styrene = 7%.

Measurement of the glass transition temperature showed that there was a single glass transition temperature at -2.7 C.

Comparative Example 9: Use DOP only

Cyclohexane (5213.13 g) was dried to an airless, nitrogen-purged, 10 L stainless steel reactor. 1,3-butadiene (317.28 g), styrene (393.01 g), and DOP (1.1825 mmol) were fed to the reactor (DOP/active butyl lithium = 0.971).

The mixture was heated to 50°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. When the end point was verified, polymerization was initiated by adding an amount of nBL,pm of 1.2175 mmol of n-butyllithium (15% solution in cyclohexane) using a pump within about 1 minute. Then, the polymerization process began. The temperature in the reactor rose to 65°C within 30 minutes. The completion of the reaction was confirmed after 90 minutes by taking samples and determining that the monomer conversion was 100%. The resulting polymer was analyzed with GPC: Mn=554765, Mw=690883, P=1.245. Butadiene (3.34 g) was added followed by NMP (1.2244 mmol). After 15 minutes, the reaction was completed by adding methanol as a finishing agent. IRGANOX 1520 was introduced as an antioxidant. The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained: styrene = 55.2%, vinyl (1,2-polybutadiene, calculated based on butadiene ratio) = 44.8%, bulk styrene - 13%.

Measurement of the glass transition temperature showed that there was a single glass transition temperature at -3.4 C.

The modification rate analysis resulted in 158% (Method 1) and 118% (Method 2) versus Comparative Example 6 (100%).

Example 6 Use of TMEDA/DOP

Dried cyclohexane (5198.72 g) was added to an airless, nitrogen-purged 10 L stainless steel reactor.

1,3-butadiene (318.38 g), styrene (390.99 g), TMEDA (2.1514 mmol), and DOP (1.1782 mmol) were fed to the reactor (TMEDA/active butyl lithium mol/mol = 1.778; DOP/butyl lithium Active = 0.974).

The mixture was heated to 50°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. When the endpoint was verified, polymerization was initiated by adding nBL,pm an amount of 1.2098 mmol of n-butyllithium (15% solution in cyclohexane) using a pump within about 1 minute, then the polymerization process was initiated. The temperature in the reactor rose to 65°C within 30 minutes. The completion of the reaction was confirmed after 140 minutes by taking samples and determining that the monomer conversion was 100%.

The resulting polymer was analyzed using GPC: Mn= 570040, Mw= 725648, D= 1.273. Butadiene (3.3 g) was added followed by NMP (1,260 mmol). After 15 minutes, the reaction was completed by adding methanol as a finishing agent. IRGANOX 1520 was introduced as an antioxidant.

The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained: styrene = 55.8%, vinyl (1,2-polybutadiene, calculated based on butadiene ratio) = 52.6%, bulk styrene = 7%.

Measurement of the glass transition temperature showed that there was a single glass transition temperature at 5.5°C.

The modification rate analysis resulted in 238% (Method 1) and 201% (Method 2) versus Comparative Example 6 (100%).

Example 7: Using TMEDA/DOP

Dried cyclohexane (21,303.39 g) was added to an airless, nitrogen-purged, 40 L stainless steel reactor. 1,3-butadiene (837.86 g), styrene (1018 g), TMEDA (0.9522 mmol), and DOP (1.3811 mol) were fed to the reactor (TMEDA/active butyl lithium mol/mol 0.421; DOP/active butyl lithium = 0.611).

The mixture was heated to 50°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. When the endpoint was verified, the polymerization was initiated by adding an amount of Nbl,prn amounting to 2.2593 mmol of n-butyllithium (15% solution in cyclohexane) using a pump within about 1 minute, then the polymerization process was initiated. The temperature in the reactor rose to 65°C within 30 minutes. The reaction was terminated after 150 minutes by adding methanol as a termination agent. IRGANOX 1520 was introduced as an antioxidant.

A sample was drawn using a sampling tube equipped with a stopcock and needle to determine the solid content. A conversion rate of 99.14% was measured.

The resulting polymer was analyzed using GPC: Mn= 716266, Mw= 924048, D= 1.29. The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained: styrene = 55.5%, vinyl (1,2-polybutadiene, calculated based on butadiene percentage) = 38.7%, bulk styrene = 17%.

Measurement of the glass transition temperature showed that there was a single glass transition temperature at -12 °C.

Example 8: Using TMEDA/DOP

Dried cyclohexane (5124.2 g) was added to an airless, nitrogen-purged 10 L stainless steel reactor.

1 3-butadiene (315.9 g), styrene (389.5 g), TMEDA (2.0387 mmol), and DOP (1.1787 mmol) were fed to the reactor (TMEDA/active butyl lithium mol/mol = 1.696; DOP/active butyl lithium = 0.981).

The mixture was heated to 50°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. When the endpoint was verified, polymerization was initiated by adding an amount of nBL,pm of 1.202 mmol of n-butyllithium (15% solution in cyclohexane) using a pump within about 1 minute, then the polymerization process was initiated. The temperature in the reactor rose to 65°C within 30 minutes. The reaction was completed after 150 minutes by taking samples and determining that the monomer conversion was 99.27%. The resulting polymer was analyzed using GPC: Mn= 579450, Mw= 802548, D= 1.385. Butadiene (3.34 g) was added followed by NMP (1.159 mmol). After 15 minutes, the reaction was completed by adding methanol as a finishing agent. IRGANOX 1520 was introduced as an antioxidant.

The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained: styrene - 56.2, vinyl (1,2-polybutadiene, calculated based on the percentage of butadiene) = 52.4%, styrene mass - 7%.

Measurement of the glass transition temperature showed that there was a single glass transition temperature at 6.1 C.

The modification rate analysis resulted in 235% (Method 1) and 188% (Method 2) versus the comparative example (100%).

Example 9: Using TM EDA/DOP

Dried cyclohexane (20951.95 g) was added to an airless, nitrogen-purged 40 L stainless steel reactor. 1,3-butadiene (1282 g), styrene (1573.83 g), TMEDA (8.3477 mmol), and DOP (4.8388 mmol) were fed to the reactor (TMEDA/active butyl lithium mol/mol = 1.793; DOP/butyl lithium Active = 1.039).

The mixture was heated to 50°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. Upon verification of the end point, polymerization was initiated by adding nBL,pm an amount of 4.6556 mmol of n-butyllithium (15% solution in cyclohexane) using a pump within about 1 minute, then the polymerization process was initiated. The temperature in the reactor rose to 65°C within 30 minutes.

The completion of the reaction was confirmed after 140 minutes by taking samples and determining that the monomer conversion was 99.69%. The resulting polymer was analyzed using GPC: Mn=621431, Mw=791497, D=1.274. Butadiene (3.34 g) was added followed by NMP (1.159 mmol). After 15 minutes, the reaction was completed by adding methanol as a finishing agent. IRGANOX 1520 was introduced as an antioxidant.

The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained: styrene = 55.2%, vinyl (1,2-polybutadiene, calculated based on butadiene ratio) = 53.2%, bulk styrene = 7%.

Measurement of the glass transition temperature showed that there was a single glass transition temperature at -5.8 C.

The modification rate analysis resulted in 229% (Method 1) and 215% (Method 2) versus Comparative Example 6 (100%).

Example 10: Using DOP/TMEDA (ratio 0.33)

Dried cyclohexane (5200.58 g) was added to an airless, nitrogen-purged 10 L stainless steel reactor. 1,3-butadiene (316.18 g), styrene (390.89 g), TMEDA (3.57 mmol), and DOP (1.1773 mmol) were fed to the reactor (TMEDA/active butyl lithium mol/mol = 2.967; DOP/butyl lithium Active = 0.977).

The mixture was heated to 50°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches.

When the endpoint was verified, polymerization was initiated by adding an amount of nBL,pm of 1.2046 mmol of n-butyllithium (15% solution in cyclohexane) using a pump within about 1 minute. Then, the polymerization process began. The temperature in the reactor rose to 65°C within 30 minutes.

The reaction was terminated after 300 minutes by adding methanol as a termination agent. IRGANOX 1520 was introduced as an antioxidant.

A sample was drawn using a sampling tube equipped with a stopcock and a needle to determine the solid content. A conversion rate of 98.06% was measured.

The resulting polymer was analyzed using GPC: Mn= 522906, Mw= 706231, D= 1.35. The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained: styrene = 55.8, vinyl (1,2-polybutadiene, calculated based on butadiene percentage) = 51.4%, bulk styrene = 6%,

Measurement of the glass transition temperature showed that there was a single glass transition temperature at -9.9°C.

Example 11: Using DOP/TMEDA (ratio 3.33)

Dried cyclohexane (5194.45 g) was added to an airless, nitrogen-purged 10 L stainless steel reactor. 1,3-butadiene (316.08 g), styrene (392.11 g), TMEDA (0.3647 mmol), and DOP (1.1776 mmol) were fed to the reactor (TMEDA/active butyl lithium mol/mol - 0.302; DOP/butyl lithium Active = 0.975).

The mixture was heated to 50°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. When the end point was verified, polymerization was initiated by adding an amount of nBL,pm of 1.2075 mmol of n-butyllithium (15% solution in cyclohexane) using a pump within about 1 minute. Then, the polymerization process began. The temperature in the reactor rose to 65°C within 30 minutes. The completion of the reaction was confirmed after 120 minutes by taking samples and determining that the monomer conversion was 99.37%. Butadiene (4.04 g) was added followed by NMP (1.21 mmol).

After 15 minutes, the reaction was completed by adding methanol as a finishing agent. IRGANOX 1520 was introduced as an antioxidant.

The resulting polymer was analyzed using GPC: Mn=594011, Mw=731376, D=1.231. The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained: styrene -55.9, vinyl (1,2-polybutadiene, calculated based on butadiene percentage) = 49.9%, bulk styrene = 7%.

Measurement of the glass transition temperature showed that there was a single glass transition temperature at -0.8 C.

Analysis resulted in a modification rate of 207% (Method #1) versus Comparative Example 6 (100%).

Example 12: Using DOP/TMEDA (ratio 1.67)

Dried cyclohexane (5187.95 g) was added to an airless, nitrogen-purged 10 L stainless steel reactor.

1,3-butadiene (316.08 g), styrene (39 1.7 g), TMEDA (0.7125 mmol), and DOP (1.1776 mmol) were fed to the reactor (TMEDA/active butyl lithium mol/mol = 0.601; DOP/ active butyl lithium 0.993).

The mixture was heated to 50°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. When the endpoint was verified, polymerization was initiated by adding an amount of nBL,pm of 1.1861 mmol of n-butyllithium (15% solution in cyclohexane) using a pump within about 1 minute. The polymerization process then began. The temperature in the reactor rose to 65°C within 30 minutes. The completion of the reaction was confirmed after 120 minutes by taking samples and determining that the monomer conversion was 100%.

The resulting polymer was analyzed using GPC: Mn= 639375, Mw= 794175, D= 1.242. Butadiene (3.24 g) was added followed by NMP (1.22 mmol). After 15 minutes, the reaction was completed by adding methanol as a finishing agent. IRGANOX 1520 was introduced as an antioxidant.

The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained: styrene = 54.5, vinyl (1,2-polybutadiene, calculated based on butadiene percentage) = 52.8%, bulk styrene = 7%. Measurement of the glass transition temperature showed that there was a single glass transition temperature at 2.8 C. Analysis resulted in a modification rate of 189% (Method 1) versus Comparative Example 6 (100%).

Example 13: Using DOP/TMEDA (ratio 0.18)

Dried cyclohexane (5220.87 g) was added to an airless, nitrogen-purged 10 L stainless steel reactor. 1,3-butadiene (323.08 g), styrene (400.33 g), TMEDA (2.0638 mmol), and DOP (0.3614 mmol) were fed to the reactor (TMEDA/butyl lithium active mol/mol = 1.7 02; DOP/butyl active lithium 0.298).

The mixture was heated to 50°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. When the endpoint was verified, polymerization was initiated by adding an amount of nBL,pm of 1.2124 mmol n-butyllithium (15% solution in cyclohexane) using a pump within about 1 minute. The polymerization process then began. The temperature in the reactor rose to 65°C within 30 minutes. The reaction was completed after 180 minutes by taking samples and determining that the monomer conversion was 99.9%. The polymer analyzed using GPC: Mn = 526290, Mw = 779925, D = 1.482. Butadiene (3.34 g) was added followed by NMP (1.8 37 mmol). After 15 minutes, the reaction was completed by adding methanol as a finishing agent. IRGANOX 1520 was introduced as an antioxidant.

The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained: styrene = 55.1, vinyl (1,2-polybutadiene, calculated based on butadiene percentage) = 45.4%, bulk styrene = 9%.

Measurement of the glass transition temperature showed that there was a single glass transition temperature at -1.2 C. Analysis resulted in a modification rate of 191% (Method 1) versus Comparative Example 6 (100%).

Example 14: Using DOP/TMEDA (ratio 0.35)

Dried cyclohexane (5257.45 g) was added to an airless, nitrogen-purged 10 L stainless steel reactor. 1,3-butadiene (319.98 g), styrene (396.32 g), TMEDA (2.042 mmol), and DOP (0.7172 mmol) were fed to the reactor (TMEDA/active butyl lithium mol/mol = 1.681, DOP/butyl lithium Active = 0.590).

The mixture was heated to 50°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. When the endpoint was verified, polymerization was initiated by adding an amount of nBL,pm of 1.2147 mmol of n-butyllithium (15% solution in cyclohexane) using a pump within about 1 minute. The polymerization process then began. The temperature in the reactor rose to 65°C within 30 minutes. The reaction was completed after 150 minutes by taking samples and determining that the monomer conversion was 98.97%.

The resulting polymer was analyzed using GPC: Mn=580671, Mw=811981, D=1.4. Butadiene (3.24 g) was added followed by NMP (1.2526 mmol). After 15 minutes, the reaction was completed by adding methanol as a finishing agent. IRGANOX 1520 was introduced as an antioxidant.

The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained: styrene = 56.2, vinyl (1,2-polybutadiene, calculated based on butadiene percentage) = 52.4%, bulk styrene = 7%.

Measurement of the glass transition temperature showed that there was a single glass transition temperature at 3.2 C.

Analysis resulted in a modification rate of 212% (Method 1) versus Comparative Example 6 (100%).

Invention No. 3

The present inventors have surprisingly and unexpectedly discovered an SSBR with a high percentage of styrene, a high percentage of vinyl with a narrow molecular weight distribution, inclusion of styrene in successive blocks of more than 4 styrene units ranging from about 40 to about 70%, and other properties as described. Later.

Furthermore, the present inventors have also discovered - surprisingly and unexpectedly - that it is possible to prepare the previously described SSBR high in styrene and high in vinyl using an initiator (such as butyl lithium) and a randomizer (such as ditetrahydrofurylpropane, also known as 2 ,2-di(2-oxolanyl)propane or DOP in combination with potassium alcoholate. In some embodiments, under the following conditions: styrene content ≤ 20 wt%, potassium alcoholates/active initiator molar ratio ≤0.05; and polymerization temperature ≤80°C.

In the context of the present invention, the following definitions will be used:

In its broadest sense, the expression "polymer" refers to a substance prepared by polymerizing monomeric units. As used herein, the expression "polymer" includes the expressions "homopolymer" (a polymeric material prepared from one type of monomers), "copolymer" (a polymeric material prepared from two different types of monomers), and "interpolymer". (A polymeric material that is prepared from more than two different types of monomers).

The term "alkyl group" refers to a straight, branched, or cyclic hydrocarbon chain, with or without substitution, preferably containing between 1 and 20 carbon atoms. Distinctive examples of alkyl groups for which there is no substitution for use according to current guidelines include but are not limited to the following:

methyl, ethyl, propyl, iso-propyl, cyclopropyl, butyl, iso-butyl, terl-butyl, secbutyl

cyclobuty

And so on.

The expression "process" when used to refer to polymerization reactions contains discontinuous, semi-continuous, and/or continuous processes.

The expression "discontinuous" or "semi-continuous" when used to refer to a polymerization process refers to a polymerization process in which more than 60% of the solvent is charged in the reactor along with additional polymerization components before the polymerization begins with an initiator charge. The monomer can be charged immediately before adding the initiator, partially before adding the initiator, partially after adding the initiator, or directly immediately after adding the initiator over a specified period of time.

The term "continuous polymerization" refers to a polymerization process in which the solvent, monomer(s), and any additional polymerization components are continuously forced into a reactor in specified volumetric proportions. In some embodiments, two or more polymerization reactors connected in series are used. In some embodiments, the reactor is driven into only one reactor.

The expression "vinyl content" refers to the percentage by mass (or weight) of butadiene located at positions 1, 2 in the polymer chain, based on the butadiene fraction (the total amount of polymerized butadiene) in the polymer.

The expression "styrene content" refers to the percentage by mass (or weight) of styrene in the polymer, based on the total weight of the polymer.

The expression “mass styrene content” refers to the weight percentage of styrene present as successive sequences of styrene units based on the total amount of styrene polymerized in the polymer.

The term “composition” refers to a mixture of substances including a polymer matrix and, optionally, reaction products and/or degradation products comprising the polymer matrix.

The expression "active initiator" (Nbl,pm) refers to the molar amount of initiator (such as organolithium) that is involved in the polymerization reaction and that has not been quenched by impurities in the reaction medium.

The expression “excess initiator” (nBL,exc) refers to the molar amount of initiator that is charged to quench impurities in the system.

The expression "total amount of monomer feed stream" refers to the total amount of styrene and butadiene, in grams/min, driven into the continuous polymerization reactor, typically in the first continuous polymerization reactor.

The term "total polymer conversion" refers to the final conversion of the polymer (such as the final total conversion of styrene and butadiene) which is determined for the last polymerization reactor and/or at the completion of the polymerization reaction.

As a general introduction, a polymer that embodies the properties of the current guidelines will have at least the following properties: (a) a bulk styrene content containing more than 4 successive styrene units between about 40 and about 70 weight percent of the total styrene content in the polymer; (b) The vinyl content is between about 25 and about 80 weight percent of the total amount of polymerized 1,3-butadiene; (c) styrene content ranging from about 20 to about 75 weight percent of the total weight of the polymer; and (d) a molecular weight distribution of 1.5 or less. In some embodiments, the polymer having the properties of the present guidance has a mass styrene content of more than 6 successive styrene units having between about 5 and about 30 weight percent of the total styrene content in the polymer.

In some embodiments, the polymer embodying the properties of the present guidelines has a total styrene level of between about 25 and about 85 weight percent, and in some embodiments between about 50 and 60 weight percent.

In some embodiments, the polymer is produced in batches, and in some embodiments, it is produced continuously. Currently, however, batch production is preferred. The polymer according to current guidelines has a molecular weight distribution (Mw/Mn) of 1.5 or less, such as between about 1.05 and about 1.4, and in some embodiments, the molecular weight distribution is between about 1.1 and about 1.4. In some embodiments, the molecular weight distribution is between about 1.2 and about 1.35.

In some embodiments, the polymer embodying the properties of the present guidelines has an average molecular weight greater than or equal to approximately 200,000 g/mol. In some embodiments, the number-average molecular weight is greater than or equal to and about 40,000 g/mol. In some embodiments, the number-average molecular weight is greater than or equal to and about 550,000 g/mol.

In some embodiments, the polymer embodying the properties of the present guidelines has an average molecular weight by weight greater than or equal to and about 250,000 g/mol. In some embodiments, the average molecular weight by weight is greater than or equal to and about 500,000 g/mol. In some embodiments, the average molecular weight by weight is greater than or equal to and about 600,000 g/mol.

It must be realized that all of the previously described models in any combination, including the currently preferred model combinations,

Also by way of general introduction, a process is provided for the polymerization of a polymer comprising monomeric units derived from styrene monomer and 1,3-butadiene monomer in accordance with current guidelines containing polymerizing the monomeric units in the presence of an initiator, potassium alcoholate and a polar agent. agent, where the polar agent has the form I:

<img file="SA4014B1_D0006.tif" />

In some embodiments, R1 and R2 each individually are an alkyl group, in some embodiments, R1 and R2 individually are a C1-C4 alkyl group. In some embodiments, R1 and R2 are each a methyl.

In some embodiments, R3, R4, R5, R6, R7, and R8 are each individually selected from the group consisting of an alkyl group and a hydrogen group. In some embodiments, R3, R4, R5, R6, R7 and R8 are each individually selected from the group consisting of a hydrogen and an alkyl group C1-C4. In some embodiments, R3, R4, R5, R6, R7 and R8 are each individually selected from the group consisting of a hydrogen and a methyl, in some embodiments, R3, R4, R5, R5, R7 and R8 are each a hydrogen.

In some embodiments, the molar ratio between the polar agent and the active initiator is greater than about 0.1. In some embodiments, the molar ratio between the polar agent and the active initiator ranges from about 0.2 to about 3.

In some embodiments, the styrene content in the monomer mixture added in the polymerization is greater than about 40 weight percent of the total weight of the monomers added.

In some embodiments, the polymerization process is performed in accordance with current guidelines at a temperature below about 80°C. In some embodiments, the polymerization process is performed in accordance with current guidelines at a temperature between about 10°C and about 80°C.

The currently preferred primers for use according to current guidelines include those suitable for anionic polymerizations. In some embodiments, the initiator used according to current guidelines is an organolithium compound (eg, alkyl mhium). Representative alkyl mhium agents for use in accordance with current guidelines include, but are not limited to, the following: n-butyllithium, see-butyl lithium, tert-butyllithium, n-butyl lithium, and the like, and combinations thereof, in some embodiments, the initiator comprising n- butyllithium.

In some embodiments, the total polymer conversion is greater than about 96 weight percent of the total amount of the monomer feed stream. In some embodiments, the total polymer conversion is greater than about 98 weight percent. In some embodiments, the total polymer conversion is greater than about 99 percent by weight.

In some embodiments, the polymer having the properties of the present guidelines has a vinyl content of between about 25 and about 80 weight percent of the total amount of polymerized 1,3-butadiene. In some embodiments, the vinyl content ranges from about 40 to about 75 weight percent.

In some embodiments of the process according to current guidelines, the potassium alcoholates include potassium-3,7-dimethyl-3-octylate.

In some embodiments of the process according to current guidelines, the molar ratio between the polar agent and potassium alcoholates is between about 30:1 and about 1:5.

Thanks to the process according to current guidelines the polymer can be prepared as described here.

It is currently preferred that polymerization processes according to current guidelines occur in solvents, with hydrocarbon solvents currently being preferred. In some embodiments, the polymerization solvent includes an alkane. In some embodiments, the polymerization solvent includes a cyclohexane. In some embodiments, the polymerization solvent includes a mixture of cyclohexane with one or more additional alkane.

Also by way of general introduction, a polymer is formed in accordance with current guidelines by a process of the type described herein.

In some embodiments, a living polymer can be chemically modified according to current guidelines using chain-end modification and/or coupling reactions. Appropriate chain end modification materials and/or coupling agents may be selected according to the intended use and filler. Examples of coupling agents include but are not limited to: tetrachloride, silicon tetrachloride, divinylbenzene, alkoxysilanes, the like, and combinations thereof.

Examples of modifying agents include but are not limited to: amine compounds, amides compounds, thioglycols compounds, silicon alkoxides, silane-sulfide modifying agents, sulfenyl halides as described in European Application Document No. 1016674, benzophenone isocyanate compounds, hydroxyl mercaptans compounds as It is described in European Application No. 0464478, acrylamide compounds as described in European Application No. 0334042, and the like, and combinations thereof. Additional means of modification include, but are not limited to, the following: amines, amides, amides, and nitrites modifiers as described in EC No. 548799, EC No. 510410, EC No. 451604, and EC No. 180141, and in the patent. American No. 4412041. In some embodiments, silanes compounds including, but not limited to, epoxy-containing silanes compounds are used to modify the end of the polymer chain for use in silica fillers as described, for example, in European Application Document No. A-299074, Application EC No. A-102045, EC No. 0447066, and EC No. 0692493. Additional examples of amending articles and/or patent references that refer to these articles are found in IS No. 2009/134665.

Also by general submission, a composition that embodies the properties of the current guidelines contains a polymer of the type described herein. In some embodiments, the composition according to the current guidelines also contains additives, such as oil. In some embodiments, a composition according to the current guidance also contains oil in an amount between about 5 and about 40 weight percent of the total weight of the polymer. In some embodiments, the composition according to the current instructions does not contain oil.

In some embodiments, a composition in accordance with current guidance contains a polymer of the type described herein and at least one additive.

In some embodiments, the polymer is combined and/or reacted with one or more fillers, a vulcanizing agent, and/or optionally one or more other additives including but not limited to the following: accelerators, coupling agents, and elastomeric polymers. Unmodified crosslinked polymers (i.e. conventional non-crosslinked elastomer polymers that have not reacted with a modified material, but have been prepared and finished), etc., and combinations thereof.

In some embodiments, a composition according to current guidelines contains one or more fillers, which act as strengthening agents. Typical examples of suitable fillers include but are not limited to: carbon black, carbon black and silica, double-phase fillers of carbon and silica, clay, calcium carbonate, magnesium carbonate, and the like, and combinations thereof. In some embodiments, a combination of carbon black, silica, carbon black and silica double-phase fillers or a combination of carbon black, silica, carbon black and/or silica double-phase fillers is used.

In some embodiments, carbon black is manufactured by the furnace method, and has a specific surface area for nitrogen adsorption between about 50 and about 200 m2/g, and DBP oil adsorption between about 80 and about 200 mL/100 g (e.g. FEF, HAF, ISAF or SAF grade carbon black). In some embodiments, "highly agglomerated type" carbon black is used. In some embodiments, carbon black or silica is added in an amount of between about 2 and about 100 parts by weight per 100 parts by weight of the total polymer. In some embodiments, carbon black or silica is added in an amount of between about 5 and about 100 parts by weight, in In some embodiments, carbon black or silica is added in an amount between about 10 and about 100 parts by weight. In some embodiments, carbon black or silica is added in an amount ranging from about 10 to 95 parts by weight.

Finally, also by way of general introduction, a product embodying the characteristics of the current guidelines includes at least one component of such composition, in some embodiments, the product being a tire. In some embodiments, the product is a component in the shoe.

The following examples and representative procedures illustrate properties according to current guidelines and are provided for illustration only. These examples are not intended to limit the scope of the attached or equivalent protections.

Examples

Monomer conversion was determined by measuring the solid content of the polymer solution at the completion of polymerization. The maximum solids concentration is obtained at 100 wt% conversion of charged butadiene (mBd) and styrene (mSt) into the final polymer according to the equation:

TSC max= (mBd+ mSt)/(mBd+ mSt + mpolar agent + mBL+ mcyclohexane)*100% A sample of polymer solution ranging from about 1 g to about 10 g, according to the expected monomer conversion, was drawn from the reactor directly into a 200 mL Erlenmeyer flask. Filled with ethanol (50 ml). The weight of the filled Erlenmeyer flask was determined before sampling (“A”) and after sampling (“B”). The precipitated polymer was removed from ethanol by filtration onto a weighted filter paper (glass microfiber paper, 90 mm diameter, MUNKTELL, weight “C”), dried at 140°C, using an HR73 moisture analyzer (Mettler-Toledo) until a weight of Fixed. Standard 5 was used. Finally, a second drying period was performed using closing standards 4 to obtain the final “D” mass of the dried sample on the filter paper. The polymer content in the sample was calculated as follows:

TSC= (DC)/(BA)*100%

The final conversion of the polymer was calculated as TSC/TSC max*100%

Both the molecular weight and molecular weight distribution of the polymer were measured using size exclusion chromatography (SEC) based on polystyrene standard levels. Each polymer sample (9–11 mg) was dissolved in tetrahydrofuran (10 mL) to make a solution. The solution was filtered using a 0.45 μm filter. A 100 μL sample was fed to a GPC column (Hewlett Packard system 1100 with 3 PLgel 10 μM MiXED-B columns at 40 m). The refractive index trend was used as the detector for molecular weight analysis. Molecular weight was calculated as polystyrene based on titration with EasiCal PS1 (Easy A and B) polystyrene standard levels from Polymer Laboratories. Average molecular weight values (Mn) and average molecular weight values (Mw) are given based on polystyrene standard levels. The molecular weight distribution was expressed as the degree of dispersion D= Mw/Mn.

The vinyl content and total styrene content were measured using 1H-NMR,

Following ISO 21561-2005, using a BRUKER Avance 400 MHz NMR spectrometer), and a 5 mm dual probe. CDCl3/TMS was used as solvent with a weight ratio of 0.05%:99.95%. The mass styrene content with more than 6 consecutive styrene units was determined according to the method reported by Y. Tanaka et al, in Rubber Chemistry and Technology, 1981, 54, No. 4, 685-691 Using the relative intensities of the orthoph-proton signals that give resonances above 6.7 ppm, the mass content of styrene having 4 or more consecutive styrene units was determined according to the method described in German Patent No. 69712962 using the relative intensities of the orthoph-proton signals. proton, which gives a resonance ranging between 6.94 and 6 per million. The mass content of styrene, which has between 4 and 6 sequential units, was calculated from the difference between each of the mass styrene contents described above.

Comparative Example No. 10: (use K-3,7-dimethyl-3-octylate or K hereafter) 50% in hexanes

5376.55 g of dried cyclohexane were added to an airless, nitrogen-purged, 10 L stainless steel reactor. 326.17 g of 1,3-butadiene, 403.73 g of styrene, and 0.083 mmol of K-3,7-dimethyl-3-octylate (50% in heptane) were fed to the reactor (active K/butyl lithium mol/ mol = 0.076). The mixture was heated to 50°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. Upon verification of the end point, polymerization was initiated by adding a total amount of 1.466 mmol of n-butyllithium (15% solution in cyclohexane) using a pump during 1 minute 19 seconds. Then the polymerization process began. The temperature in the reactor rose 65°C within 30 minutes. The reaction was terminated after 200 minutes by adding methanol as a stopping agent, and IRGANOX 1520 was introduced as an antioxidant.

A sample was taken using a sampling tube equipped with a stopcock and a needle to determine the solid content. A conversion rate of 99.57% was measured. The resulting polymer was analyzed using GPC: Mn= 533636, Mw= 674699, D= 1.264. The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained: styrene = 55.2%, vinyl (1,2-polybutadiene, calculated based on butadiene percentage) 12.3%, bulk styrene with more than 4 styrene units = 82%, and bulk styrene with more than 6 styrene units = 39 %.

Comparative Example No. 11: (Use of K-3,7-dimethyl-3-octylate (50% in hexanes))

5309.09 g of dried cyclohexane was added to an airless, nitrogen-purged, 10 L stainless steel reactor. 325.38 g of 1,3-butadiene, 398.27 g of styrene, and 0.5011 mmol of K-3,7-dimethyl-3-octylate (50% in heptane) were fed to the reactor (active K/butyl lithium mol/ mol = 0.38).

The mixture was heated to 50°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. When the end point was verified, polymerization was initiated by adding a total amount of 1.236 mmol of n-butyllithium (15% solution in cyclohexane) using a pump during 1 minute 50 seconds. Then the polymerization process began. The temperature in the reactor rose 65°C within 30 minutes. The reaction was terminated after 144 minutes by adding methanol as a stopping agent, and IRGANOX 1520 was introduced as an antioxidant.

A sample was taken using a sampling tube equipped with a stopcock and a needle to determine the solid content. A conversion rate of 99.18% was measured,

The resulting polymer was analyzed using GPC: Mn=510436, Mw=830705, D=1.627. The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained: styrene = 50.3%, vinyl (1,2-polybutadiene, calculated based on butadiene ratio) = 24.3%, bulk styrene with more than 4 units styrene = 64%, and bulk styrene with more than 6 units styrene = 20%.

Example 15: (Use of K-3,7-dimethyl-3-octylate (50%) (in hexanes/DOP)

5302.55 g of cyclohexane were charged, dried in an airless, nitrogen-purged 10 L stainless steel reactor, and fed with 324.98 g of 1,3-butadiene, 400.62 g of styrene, 0.5051 mmol. of K-3,7-dimethyl-3-octylate 50% in heptane), 0.4807 mmol DOP to the reactor (K/active butyl lithium mol/mol = 0.359, DOP/active butyl lithium 0.341). The mixture was heated to 50°C with stirring, and the impurities in the system were titrated by adding butyl lithium in batches. When the end point was verified, polymerization was initiated by adding a total amount of 1.4086 mmol of n-butyllithium (15% solution in cyclohexane) using a pump during 1 minute 33 seconds. Then the polymerization process began. The temperature in the reactor rose 65°C within 30 minutes. The reaction was terminated after 200 minutes by adding methanol as a stopping agent. IRGANOX 1520 was introduced as an antioxidant. A sample was taken using a sampling tube equipped with a stopcock and a needle to determine the solid content.

A conversion rate of 99.11% was measured. The resulting polymer was analyzed using GPC: Mn=502096, Mw=742517, D=1.479.

The fine composition and mass styrene content were measured by 1H-NMR. The following results were obtained: styrene = 55.5%, vinyl (1,2-polybutadiene, calculated based on the percentage of butadiene) = 40%, bulk styrene with more than 4 units styrene = 70%, and bulk styrene with more than 6 units styrene = 24%.

Example 16: (Use of K-3,7-dimethyl-3-octylate 50% (in hexanes/DOP)

5309.09 g of dried cyclohexane was added to an airless, nitrogen-purged, 10 L stainless steel reactor. 325.38 g of 1,3-butadiene, 398.27 g of styrene, 0.1265 mmol of K-3,7-dimethyl-3-octylate 50% in heptane), and 0.4807 mmol DOP were fed to the reactor (K/butyl Active lithium mol/mol = 0.1, DOP/active butyl lithium mol/mol = 0.398). The mixture was heated to 50°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. When the end point was verified, polymerization was initiated by adding a total amount of 1.2366 mmol of n-butyllithium (15% solution in cyclohexane) using a pump during 1 minute 50 seconds. Then the polymerization process began. The temperature in the reactor rose to 65°C within 30 minutes. The reaction was terminated after 120 minutes by adding methanol as a stopping agent. IRGANOX 1520 was introduced as an antioxidant. A sample was taken using a sampling tube equipped with a stopcock and a needle to determine the solid content. A conversion rate of 99.18% was measured. The resulting polymer was analyzed using GPC: Mn=606718, Mw=810367, D=1.336. The fine composition and mass styrene content were measured using 1H-NMR.

The following results were obtained: styrene = 54.4%, vinyl (1,2-polybutadiene, calculated based on butadiene percentage) = 37.6%, bulk styrene with more than 4 units styrene = 70%, and bulk styrene with more than 6 units styrene = 24%.

Example No. 17: (Use of K-3,7-dimethyl-3-octylate 50% (in hexanes)/DOP

524 1.7 g of dried cyclohexane was added to a 10 L nitrogen-purged, airless stainless steel reactor. 32148 g of 1,3-butadiene, 398.25 g of styrene, 0.1198 mmol of K-3,7-dimethyl-3-octylate 50% in heptane), and 1.1846 mmol DOP were fed to the reactor (active K/butyl lithium mol/mol = 0.087, active DOP/butyl lithium mol/mol = 0.894). The mixture was heated to 50°C while stirring. The impurities in the system were titrated by adding butyl lithium in batches. When the endpoint was verified, polymerization was initiated by adding a total amount of 1.3816 mmol of n-butyllithium (15% solution in cyclohexane) using a pump during 1 minute 50 seconds. Then the polymerization process began. The temperature in the reactor rose to 65°C within 30 minutes. The reaction was terminated after 120 minutes by adding methanol as a stopping agent. IRGANOX 1520 was introduced as an antioxidant. A sample was taken using a sampling tube equipped with a stopcock and a needle to determine the solid content. A conversion rate of 99.58% was measured. The resulting polymer was analyzed using GPC: Mn=557928, Mw=722762, D=1.246. The fine composition and mass styrene content were measured by 1H-NMR. The following results were obtained: styrene = 54.5%, vinyl (1,2-polybutadiene, calculated based on the percentage of butadiene) = 52%, bulk styrene with more than 4 styrene units = 86%, and bulk styrene with more than 6 styrene units = 20%.

Example No. 18: (Use of K-3,7-dimethyl-3-octylate 50% (in hexanes/DOP)

5344.73 g of dried cyclohexane were added to a 10 L airless, nitrogen-purged stainless steel reactor. 327.57 g of 1,3-butadiene, 401, 18 g of styrene, 0.1222 mmol of K-3,7-dimethyl-3-octylate (50% in heptane), and 3.531 mmol DOP were fed to the reactor (K/ Active butyl lithium mol/mol=0.102, DOP/active butyl lithium mol/mol-2.948). The mixture was heated to 50°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. When the end point was verified, polymerization was initiated by adding the total amount of 1.1978 mmol of n-butyllithium (15% solution in cyclohexane) using a pump within 1 minute 46 seconds, then the polymerization process began. The temperature in the reactor rose 65 CC within 30 minutes. The reaction was terminated after 200 minutes by adding methanol as a stopping agent.

IRGANOX 1520 was introduced as an antioxidant. A sample was taken with a sampling tube fitted with a stopcock and needle to determine solid content. A conversion rate of 99.13% was measured. The resulting polymer was analyzed using GPC: Mn=659095, Mw=859095, D=1.274. The fine composition and mass styrene content were measured using 1H-NMR.

The following results were obtained: styrene = 55.1%, vinyl (1,2-polybutadiene, calculated based on the percentage of butadiene) = 63.9%, bulk styrene with more than 4 styrene units = 66%, and bulk styrene with more than 6 styrene units = 19%.

Example 19: (Use of K-3,7-dimethyl-3-octylate 50% (in hexanes/DOP)

5417 g of dried cyclohexane was added to a 10 L nitrogen-purged, airless, stainless steel reactor. 302.28 g of 1,3-butadiene, 371 g of styrene, 0.112 mmol of K-3,7-dimethyl-3-octylate 50% in heptane), and 1.14 mmol DOP were fed to the reactor (K/butyl Active lithium mol/mol=0.105, DOP/active butyl lithium mol/mol-1.067). The mixture was heated to 70°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. When the end point was verified, polymerization was initiated by adding a total amount of 1.07 mmol of n-butyllithium (15% solution in cyclohexane) using a pump within 30 seconds. Then the polymerization process began. The temperature in the reactor was kept constant at 70°C. The reaction was terminated after 120 minutes by adding methanol as a stopping agent. IRGANOX 1520 was introduced as an antioxidant. A sample was taken using a sampling tube equipped with a stopcock and a needle to determine the solid content. A conversion rate of 98.88% was measured. The resulting polymer was analyzed with GPC: Mn-673082, Mw=880826, D=1.308. The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained: styrene = 55.6%, vinyl (1,2-polybutadiene, calculated based on the percentage of butadiene) = 42.6%, bulk styrene with more than 4 styrene units = 53%, and bulk styrene with more than 6 styrene units = 10%.

Example 20: (Use K-3,7-dimethyl-3-octylate 50% (in hexanes/DOP)

5387 g of dried cyclohexane was added to a 10 L nitrogen-purged, airless, stainless steel reactor. 400.52 g of 1,3-butadiene, 268 g of styrene, 0.111 mmol of K-3,7-dimethyl-3-octylate 50% in heptane), and 1.117 mmol DOP were fed to the reactor (K/butyl Active lithium mol/mol = 0.089, active DOP/butyl lithium mol/mol = 0.889). The mixture was heated to 70°C with stirring, and the impurities in the system were titrated by adding butyl lithium in batches. When the end point was verified, polymerization was initiated by adding a total amount of 1.26 mmol of n-butyllithium (15% solution in cyclohexane) using a pump over about 30 seconds. Then the polymerization process began. The temperature in the reactor was kept constant at 70°C. The reaction was terminated after 90 minutes by adding methanol as a stopping agent. IRGANOX 1520 was introduced as an antioxidant. A sample was taken using a sampling tube equipped with a stopcock and a needle to determine the solid content.

A conversion rate of 99.95% was measured. The resulting polymer was analyzed using GPC: Mn=606718, Mw=761935, D=1.256. The fine composition and mass styrene content were measured using 1H-NMR.

The following results were obtained: styrene = 40.7%, vinyl (1,2-polybutadiene, calculated based on butadiene ratio) = 40%, bulk styrene with more than 4 units styrene = 43%, and bulk styrene with more than 6 units styrene = 7%.

Example 21: (Use of K-3,7-dimethyl-3-octylate 50% (in hexanes/DOP)

18,787 g of cyclohexane were charged and dried in a 40 L airless, nitrogen-purged stainless steel reactor. 2343 g of 1,3-butadiene, 929.56 g of styrene, 1.693 mmol of K-3,7-dimethyl-3-octylate 50% in heptane), and 3.394 mmol DOP were fed to the reactor (K /butyl lithium active mol/mol=0.096, DOP/butyl lithium active mol/mol=0.192). The mixture was heated to 85°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. When the end point was verified, polymerization was initiated by adding a total amount of 17.6 mmol of n-butyllithium (15% solution in cyclohexane) by nitrogen pressure within 5 seconds. Then the polymerization process began. The temperature in the reactor was kept constant at 65°C. The reaction was terminated after 60 minutes by adding methanol as a stopping agent, and IRGANOX 1520 was introduced as an antioxidant. A sample was taken with a sampling tube equipped with a stopcock and needle to determine the solid content. A conversion rate of 99.67% was measured. The resulting polymer was analyzed using GPC; Mn=252670, Mw=275487, D=1.09.

The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained, styrene = 28%, vinyl (1,2-polybutadiene, calculated based on butadiene percentage) = 28.9%, bulk styrene with more than 4 styrene units = 45%, and bulk styrene with more than 6 styrene units = 10%.

Examples and comparative examples show that current guidance provides for a styrene-butadiene copolymer with a specific target styrene content that has more than 4 consecutive styrene units, in combination with a high total styrene content, the desired vinyl content and a narrow molecular weight distribution. Using a process in accordance with current guidelines, the new and innovative polymers mentioned in the protective elements can be polymerized using standard polymerization techniques with high yields. All properties of the polymers as disclosed herein are properties that precede any prior modifications, such as tip capping, conjugation, etc., as previously described. As a result of meeting current guidelines for providing polymers with a narrow molecular weight distribution, a large amount of live chain ends can be obtained at the completion of the polymerization, such that uniform modification of the chain end can be achieved.

Invention No. 4

The present inventors have surprisingly and unexpectedly discovered an SSBR containing a high percentage of styrene and a high percentage of vinyl with a narrow molecular weight distribution, incorporating the styrene in blocks of more than 6 successive styrene units ranging from about 15 to about 35%, which has other advantages as described. Below. In some embodiments, the SSBR having a high percentage of styrene and a high percentage of vinyl also includes styrene in successive blocks having more than 4 styrene units ranging from about 60 to about 80 weight percent.

Furthermore, the present inventors have also discovered - surprisingly and unexpectedly - that it is possible to prepare the previously described SSBR high in styrene and high in vinyl using an initiator (such as butyl lithium) and a dialkylether such as 2-(2-ethoxyethoxy)-2- methylpropane in combination with potassium alcoholate, in some embodiments under the following conditions: styrene content ≤ 35 wt%, molar ratio of potassium alcoholates/active initiator ≥ 0.4; The polymerization temperature is ≥90°C.

In the context of the present invention, the following definitions must be considered:

In its broadest sense, the expression "polymer" refers to a substance prepared by polymerizing monomeric units. As used herein, the expression "polymer" includes the expressions "homopolymer" (a polymeric material prepared from one type of monomers), "copolymer" (a polymeric material prepared from two different types of monomers), and "interpolymer". (A polymeric material that is prepared from more than two different types of monomers).

The term "alkyl group" refers to a straight, branched, or cyclic hydrocarbon chain, with or without substitution, preferably containing between 1 and 20 carbon atoms. Distinctive examples of alkyl groups for which there is no substitution for use according to current guidelines include but are not limited to the following:

methyl, ethyl, propyl, iso-propyl, cyclopropyl, butyl, isO-butyl, tert-butyl, secbutyl

cyclobutyl

And so on.

The expression "process" when used to refer to polymerization reactions contains discontinuous, semi-continuous, and/or continuous processes. The expression "discontinuous" or "semi-continuous" when used to refer to a polymerization process refers to a polymerization process in which more than 60% of the solvent is charged in the reactor along with additional polymerization components before the polymerization begins with an initiator charge. The monomer can be charged immediately before adding the initiator, partially before adding the initiator, partially after adding the initiator, or directly immediately after adding the initiator over a specified period of time.

The expression “continuous polymerization” refers to a polymerization process in which the solvent, monomers, and any additional polymerization components are continuously forced into a reactor in specified volumetric proportions. In some embodiments, two or more polymerization reactors connected in series are used. In some embodiments, two or more polymerization reactors connected in series are used. Pushing the reactor to just one reactor,

The expression "vinyl content" refers to the percentage by mass (or weight) of butadiene located at positions 1, 2 in the polymer chain, based on the butadiene fraction (the total amount of polymerized butadiene) in the polymer.

The expression "styrene content" refers to the percentage by mass (or weight) of styrene in the polymer, based on the total weight of the polymer.

The expression “mass styrene content” refers to the weight percentage of styrene present as successive sequences of styrene units based on the total amount of styrene polymerized in the polymer.

The term “composition” refers to a mixture of substances including a polymer matrix and, optionally, reaction products and/or degradation products comprising the polymer matrix.

The expression "active initiator" (nBL,pm) refers to the molar amount of initiator (such as organolithium) that is involved in the polymerization reaction and that has not been quenched by impurities in the reaction medium. The expression “excess initiator” (nBL,exc) refers to the molar amount of initiator charged to quench impurities in the system, the expression “total amount of monomer feed stream” refers to the total amount of styrene and butadiene, in g/min, driven into the polymerization reactor Continuous, typically in the first continuous polymerization reactor,

The term "total polymer conversion" refers to the final conversion of the polymer (such as the final total conversion of styrene and butadiene) which is determined for the last polymerization reactor and/or at the completion of the polymerization reaction.

As a general introduction, a polymer that meets the properties of the current guidelines will have at least the following properties; (a) A bulk styrene content containing more than 6 successive styrene units is between about 15 and about 35 weight percent of the total styrene content in the polymer; (b) The vinyl content is between about 25 and about 80 weight percent of the total amount of polymerized 1,3-butadiene; (c) styrene content of between about 35 and about 75 weight percent of the total weight of the polymer; and (d) a molecular weight distribution of 1.5 or less, in some cases Embodiments, a polymer under the present guidance also has at least the following additional properties: (e) a mass styrene content containing more than 4 successive styrene units between about 80 and about 80 weight percent of the total styrene content in the polymer.

In some embodiments, the polymer having the properties of the present guidelines has a mass styrene content of more than 6 successive styrene units having between about 20 and about 30 weight percent of the total styrene content in the polymer.

In some embodiments, the polymer embodying the properties of the present guidelines has a total styrene level of between about 40 and about 65 weight percent, in some embodiments between about 50 and about 60 weight percent.

In some embodiments, the polymer is produced in batches, and in some embodiments, production is continuous. Currently preferred, however, for batch production, the polymer according to current guidelines has a molecular weight distribution (Mw/Mn) of 1.5 or less, such as between about 1.05 and about 1.45. In some embodiments, the molecular weight distribution is between about 1.1 and about 1.4. In some embodiments, the molecular weight distribution is between about 1.2 and about 1.35.

In some embodiments, the polymer is produced by a continuous process in accordance with current guidelines.

In some embodiments, the polymer embodying the properties of the present guidelines has an average molecular weight greater than or equal to approximately 200,000 g/mol. In some embodiments, the number-average molecular weight is greater than or equal to and about 300,000 g/mol. In some embodiments, the number-average molecular weight is greater than or equal to and about 500,000 g/mol.

In some embodiments, the polymer embodying the properties of the present guidelines has an average molecular weight by weight greater than or equal to and about 300,000 g/mol. In some embodiments, the average molecular weight by weight is greater than or equal to and about 400,000 g/mol. In some embodiments, the average molecular weight by weight is greater than or equal to and about 600,000 g/mol.

All models described above should be understood in accordance with what has been disclosed in any combination, including combinations of currently preferred models.

Also by way of general introduction, a process for polymerization of a polymer comprising monomeric units derived from styrene monomer and 1,3-butadiene monomer in accordance with current guidelines comprises polymerizing the monomeric units in the presence of an initiator, potassium alcoholate and dialkylether.

In some embodiments, the molar ratio between dialkylether and the active initiator is greater than about 0.5. In some embodiments, the molar ratio between dialkylether and the active initiator ranges from about 0.5 to about 10.

In some embodiments, the styrene content in the monomer mixture added in the polymerization is greater than about 35 weight percent of the total weight of the monomers added.

In some embodiments, the polymerization process is performed in accordance with current guidelines at a temperature below about 90°C. In some embodiments, the polymerization process is performed in accordance with current guidelines at a temperature between about 10°C and about 80°C,

The currently preferred initiators for use under current guidelines include those suitable for anionic polymerizations; in some embodiments, the initiator used under current guidelines is an organolithium compound (e.g., alkyl mhium).

Representative alkyl mhium agents for use in accordance with current guidelines include, but are not limited to, the following: n-butyllithium, see-butyl lithium, tert-butyllithium, n-butyl lithium, and the like, and combinations thereof, in some embodiments, the initiator including n-butyllithium .

In some embodiments, the total polymer conversion is greater than about 96 weight percent of the total amount of monomer feed stream In some embodiments, the total polymer conversion is greater than about 98 weight percent In some embodiments, the total polymer conversion is greater than about 99 percent by weight.

In some embodiments, the polymer having the properties of the present guidelines has a vinyl content of between about 25 and about 80 weight percent of the total amount of polymerized 1,3-butadiene. In some embodiments, the vinyl content ranges from about 30 to about 75 weight percent.

In some embodiments of the process according to current guidance, the potassium alcoholates include potassium-3,7-dimetnyi-3-octylate.

In some embodiments of the process according to current guidelines, the molar ratio between dialkylether and potassium alcoholates is between about 40:1 and about 5:1.

Thanks to the process according to current guidelines the polymer can be prepared as described here,

It is currently preferred that polymerization processes according to current guidelines occur in solvents, with hydrocarbon solvents now being preferred. In some embodiments, the polymerization solvent includes an alkane. In some embodiments, the polymerization solvent includes cyclohexane. In some embodiments, the polymerization solvent includes a mixture of cyclohexane with one or more additional alkane.

Also by way of general introduction, a polymer is formed in accordance with current guidelines by a process of the type described herein.

In some embodiments, a living polymer can be chemically modified according to current guidelines using chain-end modification and/or coupling reactions. Appropriate chain tip modification materials and/or coupling agents can be selected according to the target use and filler. Examples of coupling agents include, but are not limited to: tetrachloride, silicon tetrachloride, divinylbenzene, alkoxysilanes, and the like, and combinations thereof.

Examples of modifying substances include, but are not limited to: amines, amides, thioglycols, silicon alkoxides, silane-sulfide modifying substances, sulfenyl halides as described in European Application Document No. 1016674, benzophenone, isocyanate, hydroxyl mercaptans as As described in European Application Document No. 0464478, acrylamide compounds as described in European Application Document No. 0334042, and the like, and combinations thereof. Additional means of modification include, but are not limited to, the following: amines, amides, amides, and nitrites modifiers as described in EC No. 548799, EC No. 510410, EC No. 451604, and EC No. 180141, and in the patent. American No. 4412041. In some embodiments, silanes compounds including but not limited to the following: epoxy-containing silanes compounds are used to modify the end of the polymer chain for use in silica fillers as described, for example, in European Application Document No. A-299074 , European Application No. A-102045, European Application No. 0447066, and European Application No. 0692493. Additional examples of amending articles and/or patent references that refer to these articles are found in ISBN 2009/134665.

Also by way of general introduction, a composition that embodies the properties of the current guidelines contains a polymer of the type described herein. In some embodiments, the composition according to the current guidance also contains additives, such as oil. In some embodiments, the composition according to the current guidance also contains oil in an amount between about 5 and about 40 weight percent of the total weight of the polymer. In some embodiments, the composition according to the current instructions does not contain oil.

In some embodiments, a composition in accordance with current guidance contains a polymer of the type described herein and at least one additive. In some embodiments, the polymer is combined and/or reacted with one or more fillers, a vulcanizing agent, and/or optionally one or more other additives including but not limited to the following: accelerators, coupling agents, and elastomeric polymers. Unmodified crosslinked polymers (i.e. conventional non-crosslinked elastomer polymers that have not reacted with a modified material, but have been prepared and finished), etc., and combinations thereof.

In some embodiments, a composition according to current guidelines contains one or more fillers, which act as strengthening agents. Typical examples of suitable fillers include, but are not limited to: carbon black, silica, carbon-silica double-phase fillers, clay, calcium carbonate, magnesium carbonate, and the like, and combinations thereof. In some embodiments, a combination of carbon black and silica, carbon black and silica dual-phase fillers or a combination of carbon and silica double-phase fillers and carbon black and/or silica are used.

In some embodiments, carbon black is manufactured by the furnace method, and has a specific surface area for nitrogen adsorption between about 50 and about 200 m2/g, and DBP oil adsorption between about 80 and about 200 mL/100 g (e.g. FEF, HAF, ISAF Or carbon black of the SAF category). In some embodiments, "highly agglomerated" carbon black is used, and in some embodiments, carbon black or silica is added in an amount of between about 2 and about 100 parts by weight per 100 parts by weight of the total polymer. In some embodiments, carbon black or silica is added in an amount between about 5 and about 100 parts by weight. In some embodiments, carbon black or silica is added in an amount from about 10 to about 100 parts by weight. In some embodiments, carbon black or silica is added in an amount from about 10 to about 95 parts by weight.

Finally, also by way of general introduction, a product embodying the properties of the current guidelines includes at least one component of such a composition, in some embodiments, the product being a vehicle tire. In some embodiments, the product is a component in the shoe.

The following examples and representative procedures illustrate properties according to current guidelines and are provided for illustration only. These examples are not intended to limit the scope of the attached or equivalent protections.

Examples

The monomer conversion was determined by measuring the solid content of the polymer solution. At the completion of polymerization, the maximum solids concentration is obtained at 100 wt% conversion of charged butadiene (mBd) and styrene (mSt) into the final polymer by the following relationship:

TSC max- (mBd+ mSt)/(mBd + mSt + mpolar agent + mSL+ mcyclohexane)*100% A sample of the polymer solution ranging from about 1 g to about 10 g, according to the expected monomer conversion, was drawn from the reactor directly into a 200 Erlenmeyer flask. ml filled with ethanol (50 ml). The weight of the filled Erlenmeyer flask was determined before sampling (“A”) and after sampling (“B”). The precipitated polymer was removed from ethanol by filtration on a weighted filter paper (Micro-glass fiber paper, 90 mm diameter, MUNKTELL, weight “C”), dried at 140°C, using an HR73 moisture analyzer (Mettier-Toledo) until reaching a Fixed. Criterion 5 was used.

Finally, a second drying period was performed using 4 closure parameters to obtain the final “D” mass of the dried sample on the filter paper. The polymer content in the sample was calculated as follows:

TSC= (DC)/(BA)*100%

The final conversion of the polymer was calculated as TSC/TSC max*100%

Both the molecular weight and molecular weight distribution of the polymer were measured using size exclusion chromatography (SEC) based on polystyrene standard levels. Each polymer sample (9–11 mg) was dissolved in tetrahydrofuran (10 mL) to make a solution. The solution was filtered using a 0.45 μm filter. A 100 μL sample was fed to a GPC column (Hewlett Packard system 1100 with 3 PLgel 10 μM MiXED-B columns at 40 m). The refractive index trend was used as the detector for molecular weight analysis. Molecular weight was calculated as polystyrene based on titration with EasiCal PS1 (Easy A and B) polystyrene standard levels from Polymer Laboratories. Average molecular weight values (Mn) and average molecular weight values (Mw) are given based on polystyrene standard levels. The molecular weight distribution was expressed as the degree of dispersion D= Mw/Mn.

The vinyl content and total styrene content were measured using 1H-NMR, according to the ISO 21561-2005 method. Using a BRUKER Avance 400 MHz NMR spectrometer and a 5 mm dual probe. CDCl3/TMS was used as the solvent with a weight ratio of 0.05%: 99.95%. The mass styrene content consisting of more than 6 successive styrene units was determined according to the method reported by Y. Tanaka et al, in:

Rubber Chemistry and Technology, 1981, 54, No. 4, 685-691 using the relative intensities of orthoph-proton signals that resonate at above 6.7 ppm. The mass styrene content consisting of 4 consecutive styrene units or more was determined according to the method described in German Patent Document No. 69712962 using the relative intensity of the orthoph-proton signals that give a resonance ranging between 6.94 and 6 per million. The mass styrene content, which consists of between 4 and 6 successive units, was calculated from the difference between each of the previously explained mass styrene contents.

Comparative Example No. 12: (Use K-3,7-dimethyl-3-octylate KDMO (or K hereafter) (50% in hexanes)).

5376.55 g of dried cyclohexane were added to an airless, nitrogen-purged 10 L stainless steel reactor. 326.17 g of 1,3-butadiene, 403.73 g of styrene, and 0.083 mmol of K-3,7-dimethyl-3-octylate 50% in heptane (active K/butyl lithium) were fed to the reactor mol/mol = 0.076).

The mixture was heated to 50°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. Upon verification of the end point, polymerization was initiated by adding a total amount of 1466 mmol of n-butyllithium (15% solution in cyclohexane) using a pump during 1 minute 19 seconds.

Then the polymerization process began. The temperature in the reactor rose 65°C within 30 minutes. The reaction was terminated after 200 minutes by adding methanol as a stopping agent. IRGANOX 1520 was introduced as an antioxidant.

A sample was taken using a sampling tube equipped with a stopcock and a needle to determine the solid content. A conversion rate of 99.57% was measured.

The resulting polymer was analyzed using GPC; Mn= 533636, Mw= 674699, D= 1.264. The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained: styrene = 55.2%, vinyl (1,2-polybutadiene, calculated based on butadiene ratio) = 12.3%, bulk styrene (&lt; 6 sequential units) = 43%, and bulk styrene (&lt; 4 sequential units) = 86% -

Comparative Example 13: Use of 2-(ethoxyethoxy)-2-methyl propane (CMX)

5366.99 g of dried cyclohexane were added to an airless, nitrogen-purged 10 L stainless steel reactor. 325.97 g of 1,3-butadiene, 403.32 g of styrene, and 3.6712 mmol of CMX were fed to the reactor (CMX/active butyl lithium mol/mol=2.57).

The mixture was heated to 50°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. When the end point was verified, polymerization was initiated by adding a total amount of 1.429 mmol of n-butyllithium (15% solution in cyclohexane) using a pump during 1 minute 47 seconds. Then the polymerization process began.

The temperature in the reactor rose 65°C within 30 minutes. The reaction was terminated after 200 minutes by adding methanol as a stopping agent. IRGANOX 1520 was introduced as an antioxidant.

A sample was taken with a sampling tube equipped with a stopcock and needle to determine the solid content, and a conversion rate of 98.25% was measured.

The resulting polymer was analyzed using GPC: Mn= 587397, Mw= 721914, D= 1.229.

The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained: styrene = 55.2%, vinyl (1,2-polybutadiene, calculated based on butadiene ratio) = 42.2%, bulk styrene (&lt; 6 sequential units) = 56%, and bulk styrene (&lt; 4 sequential units) = 71%.

Example No. 22: (Use of K-3,7-dimethyl-3-octylate 50% (in hexanes/CMX)

5342 g of dried cyclohexane were added to an airless, nitrogen-purged 10 L stainless steel reactor. 324.48 g of 1,3-butadiene, 401.02 g of styrene, 0.1208 mmol of K-3,7-dimethyl-3-octylate (50% in heptane), and 3.5544 mmol of CMX were fed to the reactor (K/ active butyl lithium mol/mol = 0.091, CMX/active butyl lithium 2.8). The mixture was heated to 50°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. When the end point was verified, polymerization was initiated by adding a total amount of 1.3217 mmol of n-butyllithium (15% solution in cyclohexane) using a pump during 1 minute 40 seconds. Then the polymerization process began. The temperature in the reactor rose to 65°C within 30 minutes. The reaction was terminated after 150 minutes by adding methanol as a stopping agent. IRGANOX 1520 was introduced as an antioxidant. A sample was taken using a sampling tube equipped with a stopcock and a needle to determine the solid content. A conversion rate of 99.63% was measured. The resulting polymer was analyzed using GPC: Mn=601903, Mw=782317, D=1.3. The fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained:

styrene = 55%, vinyl (1,2-polybutadiene, calculated based on butadiene percentage) = 43.3%, bulk styrene (&lt; 6 sequential units) = 28%, and bulk styrene (&lt; 4 sequential units) = 75%.

Example 23: (Use of K-3,7-dimethyl-3-octylate 50% (in hexanes/CMX)

5606.74 g of dried cyclohexane were added to an airless, nitrogen-purged 10 L stainless steel reactor. 217.6 g of 1,3-butadiene, 267.8 g of styrene, 0.116 mmol of K-3,7-dimethyl-3-octylate 50% in heptane), and 3.467 mmol of CMX were fed to the reactor (K/butyl Active lithium mol/mol = 0.0807, CMX/active butyl lithium 3.467). The mixture was heated to 50°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. When the end point was verified, polymerization was initiated by adding a total amount of 0.7 mmol of n-butyllithium (15% solution in cyclohexane) using a pump within 50 seconds. Then the polymerization process began. The temperature in the reactor rose to 65°C within 30 minutes.

The reaction was terminated after 120 minutes by adding methanol as a stopping agent. IRGANOX 1520 was introduced as an antioxidant. A sample was taken using a sampling tube equipped with a stopcock and a needle to determine the solid content. A conversion rate of 99.47% was measured.

The resulting polymer was analyzed using GPC: Mn = 606994, Mw = 893869, D = 1.47, the fine composition and mass styrene content were measured using 1H-NMR. The following results were obtained: styrene = 53.9%, vinyl (1,2-polybutadiene, calculated based on butadiene percentage) = 35.5%, bulk styrene (&lt; 6 sequential units) = 29%, and bulk styrene (&lt; 4 sequential units) = 74%.

Example 24: (Use of K-3,7-dimethyl-3-octylate 50% (in hexanes/CMX)

3568.29 g of dried cyclohexane were added to an airless, nitrogen-purged 10 L stainless steel reactor. 394.3 g of 1,3-butadiene, 265.56 g of styrene, 0.1103 mmol of K-3,7-dimethyl-3-octylate 50% in heptane), and 3.3014 mmol of CMX were fed to the reactor (K/butyl Active lithium mol/mol = 0.097, CMX/active butyl lithium 2.917). The mixture was heated to 70°C while stirring. Impurities in the system were titrated by adding butyl lithium in batches. Upon verification of the end point, polymerization was initiated by adding a total amount of 1.1316 mmol of n-butyllithium 15% solution in cyclohexane using a pump during 1 minute 50 seconds. Then the polymerization process began. The temperature in the reactor was kept constant at 70°C during the reaction. The reaction was terminated after 140 minutes by adding methanol as a stopping agent, and IRGANOX 1520 was introduced as an antioxidant. A sample was taken with a sampling tube equipped with a stopcock and needle to determine the solid content. A conversion rate of 99.71% was measured. The resulting polymer was analyzed using GPC: Mn=632055, Mw=913472, D=1.445, the fine composition and mass styrene content were measured using 1H-NMR.

The following results were obtained: styrene = 39.6%. Vinyl (1,2-polybutadiene, calculated based on butadiene ratio) = 30.4%, styrene by mass (&lt;6 sequential units) = 20%, and styrene by mass (&lt;4 sequential units) = 64%.

Example 25: (Use of K-3,7-dimethyl-3-octylate 50% (in hexanes/CMX)

5874.43 g of dried cyclohexane were added to an airless, nitrogen-purged 10 L stainless steel reactor. 394.4 g of 1,3-butadiene, 267.72 g of styrene, 0.1091 mmol of K-3,7-dimethyl-3-octylate (50% in heptane), and 3.3336 mmol of CMX were fed to the reactor (K/ Active butyl lithium mol/mol = 0.082, CMX/active butyl lithium 2.516). The mixture was heated to 50°C with stirring. The impurities in the system were titrated by adding butyl lithium in batches. When the end point was verified, polymerization was started by adding the total amount of 1.325 mmol of n-butyllithium (15% solution in cyclohexane) using a pump within 1 hour. 1 minute 10 seconds. Then the polymerization process began. The temperature in the reactor was kept constant at 50 C during the reaction. The reaction was terminated after 210 minutes by adding methanol as a stopping agent. IRGANOX 1520 was introduced as an antioxidant. A sample was taken using a sampling tube equipped with a stopcock and a needle to determine the solid content. A conversion rate of 98.24% was measured. The resulting polymer was analyzed using GPC: Mn=561807, Mw=676793, D=1.2055. The exact composition and mass content of styrene were measured using 1H-NMR, and the following results were obtained: styrene = 39.9%, vinyl (1,2-polybutadiene, calculated based on butadiene ratio) = 44%, styrene mass (&lt;6 sequential units) = 21%, and styrene mass (&lt;4 sequential units) = 65%.

Examples and comparative examples show that current guidance provides a styrene-diene copolymer with a specific target styrene content of more than 4 successive styrene units, in combination with a high total styrene content, the desired vinyl content and a narrow molecular weight distribution. Using a process in accordance with current guidelines, the new and innovative polymers mentioned in the protective elements can be polymerized using standard polymerization techniques with high yields. All properties of the polymers as disclosed herein are properties that precede any prior modifications, such as tip capping, conjugation, etc., as previously described. As a result of current guidelines providing polymers with a narrow molecular weight distribution, a large amount of live chain ends can be obtained at the completion of polymerization, such that uniform modification of the chain end can be achieved.

The entire contents of each of the above inventions and patent documents are incorporated by reference, except that in the event of any matter or definition inconsistent with the present specification, the present disclosure or definition shall be deemed to prevail.

The above detailed description is provided for explanation and clarification, and is not intended to limit the scope of the attached protections. Many of the changes to the currently preferred embodiments described herein would be within the reach of an individual of ordinary skill in the art, and would remain within the scope of the attached and equivalent safeguards.