Untitled record

full description

hidden invention

This request is a partial request from Request No. 11323217, which was filed in the Kingdom of Saudi Arabia on 4/11/1422 AH corresponding to 2/4/3313 CE.

. The following instructions are in general for a basic, portable styrene-butadiene rubber

solution-based styrene-butadiene rubber and a high percentage of vinyl 5 high from

(SSBR) - especially with SSB with a high percentage of styrene and a high percentage of vinyl with modification of a certain percentage of styrene - and methods of preparation.

SSBR rubber with a high proportion of styrene and a high proportion of vinyl is difficult to produce due to the kinetics of the co-polymerization of a polymer. Typically, . is added

<p>13 Polar agents known as stochastic precipitators to a polymeric polymerization system to achieve a random styrene modification. The use of certain random agents can result in SSBR with a high percentage of vinyl but a low content of blocky styrene &lt;6 (a styrene block, a sequential styrene unit) less than:13. For example, by S. Futamura and G. Day who observed a dystonia of about 18: in</p>

<p>15th Delta was tested at 63°C when the styrene block content was increased from 3 to about 7.</p>

<p>: periodical titled 1987 AD, Frozen No. 1, pages No. 29 to 42. In a compound filled with carbon black . Conversely, modification of small lumps of styrene can result in better abrasion resistance and better tensile strength, especially in silica compounds according to inventor Hattori et al. in:</p>

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(143rd Meeting of the Rubber Division of the ACS, Spring 1993, paper

22). Potassium 3,7-dimethyl-3-octylate is annotated in US Pat. No. 6531713 for the preparation of low-vinyl random soft blocks in occlusive copolymers. Similarly, US Pat. No. 6197889 describes the use of potassium 3,7-dimethyl-3 -octylate

5 As randomizer as a randomizer, in both quantities, the molecular weight of the resulting polymer is very low (ranging between 2333-333333 g/mol).

In US Pat. No. 2394768, the use of sodium and potassium alcoholate as a randomizer in low vinyl SSBR was explained.

Tetramethylethylenediamine (TMEDA) is a randomizing compound. However, 13 TMEDA results in a significantly wider distribution of molecular weight compared to what is typically observed in anionic polymerization reactions when used to polymerize

<p>styrene &gt; 43 styrene with SSBR polymerization of a polymer</p>

Especially in the polymerization of rubber with high molecular weights

. molecular weights

<p>15th The wide distribution of molecular weight in batch anionic polymerization can result from simultaneous transfer, metal introduction, and/or slow initiation reactions. These reactions reduce the amount of polymer chains that still live at the end of a polymerization reaction. Nowadays, high-performance SSBR is typically a modified lug tip. Although this segregation at the end of the modification can significantly improve the overall performance</p>

<p>33 For the compound, it requires that the amount of live cell extremities be as high as possible at the conclusion of the polymerization reaction.</p>

Moreover, the reaction rate is low and often more than 5 or 6 hours are required to complete the polymerization in commercially relevant monomer conversion.

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In summary, a method for the synthesis of SSBR which has a high proportion of styrene and a high proportion 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 of a polymerization, is A very much needed thing.

5 Description of the invention

Invention No. 1

By way of introduction, a polymer that embodies the properties of the current guidelines will have at least the following properties: (a) A content of a styrene block containing between 4 and 6 styrene units ranging from about 2 7 to about 0.5 X by weight of the total styrene content in the 10 polymer; (b) The vinyl content varies between about 30 and about 80 percent by weight of the total amount of 1,3-diene, preferably 3-butadiene! ; and (c) a styrene content ranging from about 0.4 to about 0.7 percent by weight of the total weight of the polymer, involving a polymerization of a polymer comprising monomeric units derived from 3-butadiene monome^ styrene monomer,! which exemplify the properties of 1 5 current guidelines for the polymerization of monomeric units in the presence of a starter and a polar agent

have the form I;

1

"B A N A

where !R and R2 are separately an alkyl group; where R5, Η4, R3,

86, R7 and R8 are each selected individually from the group consisting of alkyl group 0 2 and hydrogen; Where the molar ratio between the polar agent and the active initiator is greater than about 5. 0; Where is the styrene content in the monomer mixture added in the polymerization

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polymerization of a polymer greater than about 0.4 by weight of the total weight of the monomers added; Whereas the polymerization is carried out at a temperature of less than about 80°C.

Invention No. 2

By way of introduction, 025312550 of a polymer includes a 0 comprising

1,3-butadiene monome^styrene monomer 5 units •1]000065 derived from

The current guidelines characterize the polymerization of monomeric units in the presence of an initiator, a first polar agent, and a second polar agent. The first polar factor has the formula (Aa):

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

The second polar agent has the form (a):

<img file="SA4434B1_D0001.tif" />

<a name="caption2"></a>

8؟

where 1, 52, 'R3, and ^R4 are individually selected from the group consisting of an akyl group and a hydrogen;

0) have a RI group, alkylene and R2 each separately being an alkyl group; 3, R7, 86, R5, R4 and R8 are each selected individually from the group that 1 5 consists of an alkyl group and a .hydrogen.

A polymer that embodies the properties of the present guidelines has at least the following properties: (a) a styrene content of between about 0.4 and about 0.7 by weight of the total weight of the polymer; (b) The content of 6A7 ranges from about 30 to about 80 percent by weight, preferably between about 40 and about 0.7 percent by weight, of the total amount of 1,3-butadiene; and (c) a molecular weight distribution between 20 about 1.05 and about 1.8.

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Invention No. 3

By way of introduction, a polymer that embodies the properties of the present guidelines will have at least the following properties; (a) A content of a styrene block containing more than 4 consecutive styrene units between about 0 4 and about 0 7 percent by weight of the total 5 styrene content in the polymer; (b) Vinyl content ranging from about 25 to about 0-8 percent by weight of the lot

Total of 3-butadiene, ! ; (c) A styrene content of about 0.2 to about 75 wt.% of the total weight of the polymer;

and (d) a molecular weight distribution (Mw/Mn) of H. 1 or less. Includes a polymerization process

styrene is derived from monomeric comprising polymerization units of a polymer

0 1 monomer and 3-butadiene monomer,! which exemplify the properties of the present guidelines for the polymerization of monomeric units in the presence of a starter, potassium alcoholatej and a polar agent. A polar agent has the form A:

<img file="SA4434B1_D0002.tif" />

where !R and R2 are separately an alkyl group; where R5, R4, R3, 5 1 86, R7 and R8 are each selected separately from the group consisting of the alkyl group

and hydrogen.

Invention No. 4

By way of introduction, a polymer that embodies the properties of the present instructions has the following properties

At least: (a) a styrene block containing more than 6 20 styrene units in succession between about 15 and about 35 percent by weight of the total styrene content

in polymer; (b) Vinyl content between about 25 and about 80 percent by weight of the quantity

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Quantity of 1,3-butadiene; (c) a styrene content ranging from about 25 to about 75 percent by weight of the total weight of the polymer; and (d) a molecular weight distribution (D (Mw/Mn) of 1.5 or less. A polymerization of a polymer comprising units

1,3-butadiene monomer and styrene monomer are derived from monomeric

5 The properties of the present instructions for the passage of monomeric units in the presence of a starter, potassium alcoholate and an organic ether compound are selected from the dialkylethers having the formula R1-O-CH2-CH(R3)-O-R2, where R1 and R2 separately represent its alkyl group. Between 1 and 13 R3, carbon atoms represent methyl, hydrogen or ethyl. The molar ratio between potassium alcoholate and the active initiator is 3.4 mol/mol or less. in a

13 Some embodiments, R1 is methyl or ethyl and R2 is a branched alkyl group which, in some embodiments, is t-butyl.

Brief explanation of drawings

Figure 1a: shows the effect of adding (ditetrahydrofurylpropane (DOP) to

polar agent dispersion blindness as a tetramethylethylenediamine (TMEDA) polar agent

15th (Mw/Mn) dispersity) for the molecular weight distribution.

Figure 1b: shows the effect of adding DOP to TMEDA

On the dispersion of a polar agent 1.7 mol/mol) as a polar agent (etramethylethylenediamine

(Mw/Mn) dispersity) for the molecular weight distribution.

Figure 1c: shows the effect of adding TMEDA to (1 mol/mol DOP) as a polar agent on 33 (Mw/Mn) dispersion of the molecular weight distribution.

Figure 3: shows the effect of adding DOP to TMEDA as a polar agent on the ability of the limbs to live.

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Figure 2: shows the effect of adding TMEDA to DOP as a polar agent on the ability of the periphery

Sesame uncle life.

Figure 4: shows the effect of the molar ratio between DOP/TMEDA on the ability of the limbs to live.

5 Description:

Invention No. 1

Surprisingly and unexpectedly, the current inventors discovered SSBR with a high percentage of styrene and vinyl with a narrow molecular weight distribution, and a modification of styrene in the form of blocks of 46 units so that its ratio ranges between about 37 and about 53:, and styrene block with 13 more of 6 consecutive units so that its ratio is not less than about 33:. Besides, find out

Surprisingly and unexpectedly, current inventors also show that SSBR that is high in styrene and high in vinyl can be prepared using a starter (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

<p>15th ≥43 : wt, molar ratio of DOP/active initiator ≥ 3.5; and temperature in the polymer corridor</p>

<p>83≥ polymerization of a polymer °C.</p>

In the context of the present invention, the following definitions must be taken into account:

The term "polymer" refers in a broad sense to a substance that is prepared by means of a crossover

polymerization of polymerization of monomeric units

33 monomeric units. As used herein, the term “polymer” includes the terms “homopolymer” (a polymeric material prepared from one type of monomer), and “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).

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The term “alkyl group” refers to a straight, branched, or cyclic hydrocarbon chain, with or without substitution, preferably containing between 1 and 33 carbon atoms. Characteristic examples of alkyl groups that have no substitute for use according to the instructions

methyl, ethyl, propyl, iso-propyl. The current includes the following, but is not limited to:

And what a shabu. 5, cyclopropyl, butyl, iso-butyl, tert-butyl, sec- butyl, cyclobutyl

The term “process” when used to refer to reactions in the polymerization of a polymer includes discontinuous, semi-continuous, and/or continuous processes.

The term “discontinuous” or “semi-continuous” when used to refer to a lane process refers to a lane process in which more than 63 lanes of solvent are charged in the reactor along with additional lane components before the polymerization of a polymer begins with the initiator charge. can charge

The monomer immediately before the addition of the initiator, or partly before the addition of the initiator, or partly after the addition of the initiator, or immediately after the addition of the initiator over a certain period of time.

“continuous polymerization” refers to a process in which a solvent, monomer(s), and any additional passive components are fed with a solvent.

15th In some embodiments, two or more polymerization of a polymer reactors connected in series are used. In some embodiments, the reactor is driven into only one reactor.

The term “vinyl content” denotes the percentage of muted (or weighted) butadiene present at position 1, 3 in the polymer, based on the butadiene fraction (the quantitative amount of polymerized 33 butadiene) in the polymer.

The term “styrene content” refers to a percentage of the muted (or weighted) styrene in the polymer, based on the quantitative weight of the polymer.

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The term “styrene block citrine content” refers to the weight ratio of styrene present in successive sequences of styrene units based on the quantitative amount of citrine transmogrified into the polymerized styrene in the polymer.

The term "composition" refers to a mixture of materials including a polymer and, optionally,

5 Reaction products and/or products bearing a component of the polymer material.

The expression “active initiator nBL,pm” refers to the amount of an initiator (such as an organ lithium compound) that participates in a reaction in a polymerization reaction that has not been damped by impurities in the reaction medium. The expression “excess initiator” deactivate the

. impurities in the system 13

The expression “total amount of monomer feed” refers to the quantitative amount of styrene and butadiene, in g/min, driven into a continuous bypass reactor and, typically, in the first continuous polymerization reactor.

The term “polymer quantitative transformation” refers to the final transformation of a polymer (such as

15th The final polymer, styrene and butadiene (which is determined for the last reactor bypass.

As a general introduction, a polymer that embodies the properties of the present guidelines will have at least the following properties; (a) Content of a styrene block that contains between

4 and 6 styrene units range from about 37 to about 53: by weight the quantitative content of styrene in the polymer; (b) The vinyl content varies between about 23 and about 83 percent by weight

33 from the quantitative amount of 1,3-butadiene; and (c) a styrene content ranging from about 43 to about

73 % by weight of the quantitative weight of a polymer.

In some embodiments, a polymer that embodies the properties of the present guidelines has a styrene block styrene content of more than 6 consecutive styrene units with at least about 13 percent by weight of the quantitative styrene content in the polymer. In some embodiments, it is in

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polymer that embodies the properties of the present guidelines has a styrene block content of more than 6 consecutive styrene units with at least about 35 percent by weight of the quantitative styrene content in the polymer.

. In some embodiments, the polymer that embodies the properties of the current instructions has an amount of

5 styrene There are fewer than 4 styrene units in a row between about 23 and about 72 in

Percent by weight of the quantitative weight of the styrene that is being permeated. In some embodiments, the amount of styrene present is less than 4 sequential styrene units ranging from about 25 to about 73 by weight of the quantitative weight of the styrene being modified.

In some embodiments, the polymer produced in batches according to current guidelines 13 has a molecular weight distribution (Mw/Mn) between about 1.35 and about 3. 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 1.3 and about 1.6.

In some embodiments, a continuously produced polymer according to current guidelines has a molecular weight distribution (Mw/Mn) between about 1.5 and about 3.5. In some embodiments, the molecular weight distribution 15 is between about 1.6 and about 3.4. In some embodiments, the molecular weight distribution is between about 1.8 and about 3.3.

In some embodiments, a polymer that embodies the properties of the present guidelines has an average molecular weight greater than or equal to and about 83333 g/mol. In some embodiments, the mean molecular weight according to the polymorph is greater than or equal to and is about 153,333 g/mol. In some embodiments, the average molecular weight of 33 is greater than or equal to and about 233,333 g/mol,

In some embodiments, a polymer that embodies the properties of the present guidelines has an average molecular weight of greater than or equal to and about 84,333 g/mol. In some embodiments, the mean molecular weight according to weight is greater than or equal to and about 155,333 g/mol. In some embodiments, the mean molecular weight according to weight is greater than or equal to and about 213333 g/mol.

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In some embodiments, the polymer that embodies the properties of the current guidelines for viscosity according to d (Ml 14 Mooney at 100 µm) is between about 20 and about 150, in some embodiments, it is in a polymer that embodies the properties of the current guidelines for viscosity according to Ml 14 Mooney at 0 1 5 0 C) between about 30 and about 120 C. In some embodiments, a polymer that wrings properties of current guidelines has a viscosity according to Ml 14 (Mooney at 100 C) between about 30 and about 90. Also by way of general introduction, a process of polymerization of a polymer

],3-butadiene and styrene monomer are derived from monomeric comprising units

monomer according to the current guidelines on the polymerization of monomeric units in the presence of an initiator and 1 0 polar agent, where the polar agent has the form A:

<img file="SA4434B1_D0003.tif" />

In some embodiments, RI and R2 are separately an alkyl group. In some embodiments, RI and R2 are separately C1-C4 alkyl group. In some embodiments, RI and 52 are both methyl.

5 1 In some embodiments, R4, 56a, R3, 56a, R7 and R8 are selected separately from the group consisting of an alkyl group and a hydrogen. In some embodiments, R3, R4, 5, 86, R7 and R8 are each selected separately from the group consisting of a hydrogen and a C1-C4 alkyl group. In some embodiments, R4, 56, 03, R7, R5 and R8 are each selected individually from the group consisting of hydrogen methyb—in some embodiments, R3, 0 2 R7, R5t R6, R4 and R8 are each hydrogen.

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In some embodiments, the molar ratio between the polar agent and the active initiator is greater than about 3.5. In some embodiments, the molar ratio between the polar agent and the active initiator ranges between about 3.5 and about 13.

In some embodiments, the content of styrene in the blend of monomer added is in the polymeric process

5 polymerization of a polymer is greater than about 43 percent by weight of the quantitative weight of monomerart added. In some embodiments, a polymerization of a polymer is carried out according to current guidelines at a temperature of less than about 83 °C. In some embodiments, a bypass process is performed according to current guidelines at a temperature between about 13°C and about 83°C.

13 Primers currently preferred for use according to current guidelines include those suitable for anionic polymerizations. In some embodiments, the initiator according to current guidelines is an organ lithium compound (eg alkyl lithium).

Examples of alkyl lithium agents for use according to current guidelines include the following:

Example: n-butyllithium, sec-butyl lithium, tert-butyllithium, n-

15th pentyllithium, shabu, and combinations thereof In some embodiments, the prefix includes -n

. butyllithium

In some embodiments, the quantitative shift of the polymer is greater than about 96 wt% of the quantitative amount from the monomer feed stream, in some embodiments the quantitative shift of the polymer is greater than about 98 wt%. In some embodiments, the quantitative shift of the polymer is greater than 33% of about 99 percent by weight.

In some embodiments, the polymer that embodies the properties of the present guidelines has a vinyl content of between about 23 and about 83 percent by weight of the quantitative amount of 1,3-butadiene. In some embodiments, the vinyl content varies between about 43 and about 73 percent by weight.

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In some embodiments, a polymer that embodies the properties of the present guidelines has a styrene block content that contains between 4 and 6 styrene units between about 37 and about 53: by weight of the total styrene content in the polymer.

In some embodiments, a polymer that embodies the properties of the present guidelines will have a 5-block styrene content of more than 6 consecutive styrene units with at least about 13 percent by weight of the quantitative styrene content in the polymer.

In some embodiments, a polymer that embodies the properties of the present guidelines has a styrene block styrene content of more than 6 consecutive styrene units with at least about 35 percent by weight of the quantitative styrene content in the polymer,

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

15th Also for general introduction, the polymer is formed according to the present guidelines with a process of the type described herein.

In some embodiments, the polymer according to current guidelines is modified using a modifying agent (or modifier). Examples of modifying agents include, but are not limited to: compounds, amines,

Modifiers, amides, thioglycols, silicon alkoxides, silane-sulfide modifiers

33 of silane-sulfide, ma-shabu, and minya combinations.

In some embodiments, chemical modification of a live polymer can be made according to current guidelines using sesamoid tip modification and/or coupling reactions. Appropriate adjusting agents for the separating tip and/or coupling agents can be selected according to the intended use and the filler. Examples of coupling agents include, but are not limited to: tin tetrachloride,

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divinylbenzene, silicon tetrachloride, alkoxysilanes, etc., and mina combinations,

Examples of modification materials include, but are not limited to, the following: sulfenyl halides as described in European Application Document No. 1316674, benzophenone isocyanate, compounds

5 hydroxyl mercaptans as described in EC Document No. 3464478, acrylamide compounds as described in EC No. 3224343, and additional modifiers include, but are not limited to: amines, amides, amides, and nitriles as described in EA Document No. 548799, EA No. 513413, EA No. 451634, EA No.

13 183,141, and in US Patent No. 4413341. In some embodiments, compounds . are used

silanes including, but not limited to, epoxy-containing silanes for modifying the polymer chain tip for use in silica fillers as described, for example, in EO No. A-399374, EO No.- A-133345, EC No. 3447366, EC No. 3693492.

15th Additional amendment articles and/or references to the opinions that refer to these articles are found in International Application Document No. 124665/3339.

Also for general presentation, a composition embodying the properties of the present instructions contains a polymer of the type described herein. In some embodiments, a composition according to the present instructions also contains an oil. In some embodiments, the composition according to the current guidelines also contains oil in an amount ranging

33 Between about 5 and about 43 percent by weight of the quantitative weight of a polymer. In some embodiments, the composition according to current instructions does not contain oil.

In some embodiments, a composition according to the present instructions contains a polymer of the type described herein and at least one additive. In some embodiments, the polymer is incorporated and/or reacted with one or more fillers, a vulcanization agent, and/or optionally another additive.

35 one or more including but not limited to the following: accelerators,

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coupling agents, uncrosslinked elastomeric polymers (such as conventional crosslinked elastomers that did not react with a modifier, but were prepared and annealed), etc., and combinations thereof.

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

13 black, silica, carbon and silica double-phase fillers, or a combination of dual-phase filler, carbon, silica, carbon black and/or silica.

In some embodiments, carbon black is manufactured by the furnace method, and if the surface area of ​​nitrogen adsorption is between about 53 and about 333 m 3 / g,

15th DBP oil absorption was between about 83 and about 333 ml/133 g (such as FEF, ISAF, HAF or SAF class carbon black). In some embodiments, “highly agglomerating” carbon black is used in In some embodiments, carbon black or silica is added in an amount ranging from about 3 to about 133 parts by weight for every 133 parts by weight of the quantitative polymer.In some embodiments, carbon black is added

33 carbon black or silica in an amount ranging from about 5 to about 133 parts by weight. In some embodiments, carbon black or silica is added in an amount ranging from about 13 to about 133 parts by weight. In some embodiments, carbon black or silica is added in an amount between about 13 and 95 parts by weight.

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Finally, also for general presentation, a product embodying the characteristics of the current guidelines contains at least one component of this formulation, in some embodiments, the product being a frame. In some embodiments, the product is an ingredient in the shoe.

5 The following examples and procedures illustrate the characteristics according to the current guidelines, and are provided only for the sake of illustration. This offense is not intended to limit the scope of the applicable elements of protection or their equivalent.

the sinners

The monomer shift was determined by measuring the concentration of solids in a polymer carrier at the end of the polymerization of a polymer lane. The maximum solids concentration is obtained at

polymer to styrene (mSt) and (mBd) charged butadiene 133: wt.

13 Ultimate relationship:

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

A sample of a polymer pellet ranging from about 1 g to about 13 g, according to the expected conversion of a monomer, was drawn from the reactor directly into a 333 mL Erlenmeyer flask filled with

15th ethanol (53 ml). The weight of the filled Erlenmeyer flask was determined before sampling (“A”) and after sampling

sample ("B"). Precipitated polymer was removed from ethanol by filtration on a weighted paper filter (Micro-glass, 93 mm diameter, MUNKTELL, weight “C”), and dried at 143 °C, using a moisture loader HR73 moisture analyzer (Mettier). -Toledo) until a constant weight is reached. Criterion 5 was used. Finally, a period

33 Second drying using closing criteria 4 to obtain the final mass “D” of the dry sample on the filter paper. The polymer content in the sample was calculated as follows

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

The final transformation of the polymer was calculated as 100*TSC/TSC max:

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The molecular weight and molecular weight distribution of the polymer were measured using the Arvia size-exclusion chromatogram (SEC) at 43°C based on standard levels of polystyrene. Each sample 9-11 (polymer) was dissolved in 13 ml (tetrahydrofuran) to make a carrier. The solution was filtered using a 3.45 µm filter. Sample 133 was fed.

5 μL to GPC column (1100 Hewlett Packard System Po2 13 PLgel μM, MIXED-B columns). Refraction Index-detection was used as the detector for analyzing the molecular weight. The molecular weight was calculated as polystyrene. Based on polystyrene EasiCaf PS1 (Easy A and B) titration from Polymer Laboratories. Figures

13 The mean molecular weight according to the modifier (Mn) and the mean molecular weight according to the modulator (Mw) numbers are given based on the standard levels of polystyrene. The molecular weight distribution was expressed as D = Mw/Mn dispersity.

The vinyl content and styrene content were quantified using 1H-NMR, by a method:

21561-2005 ISO. Using a BRUKER Avance NMR spectrophotometer,

<p>15th 433MHz), and a 5mm dual sensor. CDCl3/TMS was used as solvent with a weight ratio of 3.35.</p>

<p>:: 99.95:. The content of a styrene block consisting of more than 6 sequential styrene units was determined according to the mnemonic method:</p>

Rubber Chemistry and Technology, 1981, 54, No. 4, in Y. Tanaka et al,

685-691 using the relative intensities of the ortho Ph-proton signal that gives resonance at blind 33 of 6.7 ppm.

The content of a styrene block consisting of 4 or more consecutive styrene units was determined according to the method described in German patent No. 69713963 using the relative strength of the ortho Ph-proton signals that give a resonance ranging between 6.94 and 6 per million.

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The content of a styrene block consisting of between 4 and 6 successive units was calculated from the difference between each of the previous styrene block contents annotated.

Mixed according to Mooney ML (133 °C 4+1 °C)

Viscosity measured according to Mooney for polymer (without filler and no oil) according to ASTM D 5 (2004) 1646, with preheating time of 1 minute, rotor operating time of 4 minutes,

At a temperature of 133 °C [4+1 133 ML °C)] on the Alpha-MV2000 E device

.Technologies

Comparative Example #1 (use of 1 mol/mol DOP, styrene ratio in monomer: 31, 65

°m(

13 The dried cyclohexane (355 g) was added to a 3 L nitrogen-purged, nitrogen-purged stainless steel reactor fed with 1,3-Butadiene (25.55 g), and styrene (9.45 g). , and 3.3737 mmol DOP (35 mmol DOP): by weight carried in cyclohexane) to the reactor (active butyl lithium /DOP mol/mol = 1). The reaction was started by adding the following amounts of n-butyllithium as

15th 3.6378 mol/kg carried in 3.125 = nBL,exc:cyclohexane mmol to convert

Impurities and 3.3737 = nBL,pm mmol for the reactant. The mixture was heated to 65 °C with agitation. The reaction was terminated after 23 minutes by adding methanol as a denaturing agent. 4,6-bis . compound has been introduced

IRGANOX 1520 (Ciba) sold under the trade name (octy hiomethyl)-o-cresol

As an antioxidant.

33 A sample was withdrawn from a sampling tube fitted with a stopcock stopper and a needle to determine the solids content. The TPMG 133 shift ratio was measured:.

The resulting polymer was loaded with GPC 1.395: D=, Mw = 326158, 315586, Mn = 326158.

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The microstructure and styrene block content were measured using 1H-NMR. The following results were obtained: 1,2-polybutadiene (vinyl,: styrene = 31.3, calculated on the basis of the ratio of 63.3 = (butadiene): styrene block styrene block (&lt; of 6 units: 3: styrene): styrene block containing styrene block includes: 4-6 13: styrene units:.

5 Although the DOP/nBL,pm ratio and temperature were in the inventive range, the styrene content of 31:31 was low enough to achieve an inventive styrene block of 4-6 styrene units.

Comparative Example 3 (Using DOP, 3.4 mol/mol, styrene ratio in monomer 43:, 63

°m(

13 The cyclohexane was charged and dried (355 g) in a 3 L nitrogen-purged (37 g), styrene (37 g), styrene (18 g), and 3.1353) stainless steel reactor. DOP mmol, 32.28: carried in cyclohexane) was fed to the reactor (active butyl lithium /DOP mol/mol = 3.2974). The reaction was started by adding the following amounts of n-butyllithium as

15th 3.4451 mol/kg carried in cyclohexane: 3.23 mmol = nBL,exc to convert

Impurities and 3.3647 mmol = nBL,pm for the reactant. The mixture was heated to 63 °C with stirring. The conjugated polymer was coupled after 133 minutes by adding 3.375 TMS (3.375 mol/mol), the remaining unconjugated polymer was finalized after 23 minutes by adding methanol as a coating agent. IRGANOX 1520 was introduced as an antioxidant.

33 A sample was withdrawn from a sampling tube fitted with a stopcock stopper and a needle to determine the solids content. The TPMG shift ratio of 97.34 was measured:.

The resulting coupled polymer was loaded using D, Mw = 281586, GPC = 1.7: Mn = 333339 19 at 32: coupled polymer.

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The microstructure and styrene block content were measured using 1HNMR. The following results were obtained: 1,2-polybutadiene (vinyl,:41.4-styrene, computed on the basis of the ratio of 47 = (butadiene):, styrene block styrene block (&lt; of 6 units: 2 :) styrene block): styrene block comprising 4-6 34: styrene units:.

5 Although styrene content and temperature were in the inventive range, the DOP/Nbl,pm ratio of 3.2974 was low enough to achieve an inventive styrene block comprising 4-6 styrene units.

Comparative Example 2 (using 3.4 mol/mol DOP, styrene ratio in monomer 43:85)

°m(

13 The dried cyclohexane (355 g) was added to a 3-L nitrogen-purged stainless steel reactor of 1,3-Butadiene (37 g), styrene (18 g), and 3.1353). DOP mmol, 32.28: carried in cyclohexane (fed with active butyl lithium /DOP mol/mol = 3.2974). The reaction was started by adding the following amounts of n-butyllithium as

15th 3.4451 mol/kg carried in cyclohexane: 3.23 mmol = nBL,exc to convert

Impurities and 3.3647 = nBL,pm mmol for the reactant. The mixture was heated to 85 °C with stirring. The conjugated polymer was coupled after 23 minutes by adding 3.375 mol/mol TMS. The remaining unconjugated polymer was quenched after 23 minutes by adding methanol as a cooking agent. IRGANOX 1520 was introduced as an antioxidant.

33 A sample was withdrawn from a sampling tube fitted with a stopcock stopper and a needle to determine the solids content. The TPMG conversion ratio of 95.63: was measured.

The resulting conjugated polymer was loaded using GPC 1.7 95: D = 278349, Mw = 278349, 313593 at 33.2: conjugated polymer.

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The microstructure and styrene block content were measured using 1H-NMR. The following results were obtained: polybutadiene-2,1 (vinyl,: styrene = 43.1, calculated on the basis of the ratio of 22.4 = (butadiene): styrene block styrene block (&lt; of 6 units): 14 styrene: styrene block: styrene block includes: 4-6 33: styrene units 5:.

Although the styrene content was in the inventive range, the butyl lithium/DOP ratio of 3.4 was too low and the scalding temperature of 85 °C was too high for an innovative styrene block comprising 4-6 styrene content.

.units

13 Example 1 (using 1 DOP mol/mol)

cyclohexane was added (5338.11 g) dehydrated to a nitrogen-purged 13 L stainless steel reactor, and fed with 1,3-Butadiene (217.38 g), and styrene (292.11 g) , and DOP (1.1866 mmol) to the reactor (active butyl lithium / DOP = 3.9838).

15th The mixture was heated to 53°C with stirring. The impurities in the system were titrated by adding butyl lithium in batches. Upon verification of the end point, the polymerization of a polymer was started by adding an amount of active butyl lithium nBL,pm of 1.3398 mmol (3.3585 mol/kg carried in cyclohexane) using a pump over 1 min 33 sec. polymerization of a polymer . The temperature increased in

33 reactor to 65 °C in 23 minutes. The reaction was stopped after 333 minutes by adding methanol as a simmering agent. IRGANOX 1520 has been introduced as an antioxidant.

A sample was withdrawn from a sampling tube fitted with a stopcock stopper and a needle to determine the solids content. The TPMG shift ratio of 99.36: was measured.

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The resulting polymer was loaded with D, Mw = 755343, GPC = 1.385: 587525 Mn. The microstructure and styrene block content were measured using 1H-NMR. The following results were obtained: 1,2-polybutadiene (vinyl,: styrene = 55.9, calculated on the basis of the ratio of 49 = (butadiene): styrene block (&lt; out of 6).

5 8 :) styrene units:, styrene block includes 4-6 styrene units: 27:.

Example 3 (use 1 DOP mol/mol)

The cyclohexane (31326.28 g) was dried and added to a 43 L nitrogen-purged stainless steel reactor.

13 (828.12,3-Butadiene g), (1,318.1 g) styrene, and (4.1567) DOP mmol)

B was fed to the reactor (active butyl lithium /DOP mol/mol=1.3934).

The mixture was heated to 53°C with stirring. The impurities in the system were calibrated in addition step by step butyl lithium. When checking the end point, the polymerization of a polymer was started by adding an amount of active butyl lithium nBL,pm amounting to 2.8351 mmol of -n

15th . 3.3585 butyllithium mol/kg carried in cyclohexane) using a pump through

About two minutes. Then, a polymerization of a polymer process began. The temperature in the reactor increased to 65°C within 23 minutes. The transformation was completed after 93 minutes. A sample was taken and the resulting polymer loaded with D, Mw = 628345, GPC = 1.337 Mn = 538621, the microstructure and styrene block content were measured using 1H-NMR.

33 The reaction was stopped by the addition of coupling agent and the remaining unconjugated chains were finally stopped after another 23 minutes by adding methanol as a boiling agent. IRGANOX 1520 has been introduced as an antioxidant,

The following results were obtained: 1,2-polybutadiene (vinyl,: styrene = 52.8, calculated on the basis of the ratio of 47.6 = (butadiene): styrene block (&lt; out of 6).

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8 :) styrene units:, styrene block includes 4-6 styrene units: 27:.

Example #2 (Using styrene: DOP, 41)

The dried cyclohexane (31194.98 g) was added to a nitrogen-purged 43 liter nitrogen-purged 5 reactor of stainless steel.

(1,338.12 g),3-Butadiene, (821.75 g styrene), and 3.2136 mmol DOP were fed to the reactor (active butyl lithium /DOP mol/mol=3.9833).

The mixture was heated to 53°C with stirring. The impurities in the system were titrated by adding butyl lithium in batches. Upon verification of the end point, the polymerization of . is initiated

13 a polymer by adding 3.2534 mmol of active butyl lithium Nbl,pm of n-butyllithium (3.3585 mol/kg carried in cyclohexane) using a pump during about 1 minute, then, a polymerization process of a polymer was started. The temperature increased. In the reactor to 65 °C within 23 minutes The reaction was stopped after 313 minutes by adding methanol as a simmering agent IRGANOX 1520 was introduced as an antioxidant.

. antioxidant 15

A sample was withdrawn from a sampling tube fitted with a stopcock stopper and a needle to determine the solids content. A 96.24 TPMG shift ratio was measured:.

The resulting polymer was loaded with D, Mw = 3578387, GPC = 1.56: Mn = 1653619. The microstructure and styrene block content were measured using 1H-NMR.

33 The following results were obtained: 1,2-polybutadiene (vinyl,: 41 = styrene, calculated on the basis of a ratio of 46.5 = (butadiene): styrene block styrene block (&lt; of 6 units), styrene: blocky styrene, which includes 4-6 39,styrene units:.

Example No. 4) use of styrene: 46.5, DOP

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The cyclohexane was charged and dried (31315.19 g) in a 43 L nitrogen-purged, stainless steel reactor.

(974) 1,3-Butadiene g, (888.15 g styrene), and DOP (3.16139 mmol) were fed to the reactor (active butyl lithium /DOP mol/mol = 3.9344).

5 The mixture was heated to 53°C with stirring. The impurities in the system were titrated by adding butyl lithium in batches. Upon verification of the end point, the polymerization of a polymer was started by adding an amount of active butyl lithium nBL,pm of 3.326 mmol of n- 3.3585 butyllithium mol/kg carried in cyclohexane) using a pump during about 1 minute. polymerization of a polymer

13 The temperature in the reactor rose to 65°C within 23 minutes, a sample was drawn after 133 minutes with a sampling tube fitted with a stopcock and a needle to determine the solids content. The TPMG shift ratio of 99.17: was measured.

The polymer was loaded with GPC: D = 1.386, Mw = 1117669, and GPC: Mn = 868986. It was completed

paired polymer after 23 minutes by adding 3.378 TMS (3.378 mol/mol). The reaction was stopped after 343

15th minutes by adding methanol as a denaturing agent. IRGANOX 1520 has been introduced as an antioxidant

. antioxidant

The polymer was loaded with D = 1.59, Mw = 1563337, and GPC: Mn = 983413 at

17 : Aqarn. The microstructure and styrene block content were measured using -1H NMR. The following results were obtained: 1,2-polybutadiene (vinyl,: 46.5 = styrene

33 , computed based on the ratio of 43.2 = (butadiene:, styrene block) &lt; out of 6

9 :) styrene units:, styrene block includes 4-6 styrene units: 43:.

Comparative Example 4 (T Continuous Polymerization = 85 °C, DOP/Active Initiator = Approx. 3)

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The reaction was performed in two CSTR reactors connected respectively. The volume of the first reactor is 6.2 liters and the second is 13.6 liters.

The reactors are equipped with a helicoidal stirrer suitable for mixing of high viscosity solutions. The reactors have been operated fully filled.

<p>5 Using the external circulation of water in the reactor wall, the required temperature was regulated. The components (1,2-(1,2-(1,2-butadiene, DOP, cyclohexane, butadiene, styrene Bde) and n-butyllithium) and n-butyllithium were fed to the first reactor beds with micromotion meters allowing the required feed stream to be regulated and ensuring a steady flow. The initiator (n-butyllithium) was pushed through an alumina column.</p>

<p>13 cyclohexane) at the inlet of the first reactor. DOP and 1,2-butadiene were diluted in cyclohexane so that exact amounts of the reactant could be delivered. Dilution amounts of the chemicals in the sample were reported along with the solvent as the cyclohexane feed stream.</p>

In the quantitative feeding stream, a ratio of 13:3 to mmonumartrate was used. The following conditions were used in this experiment: styrene: butadiene = 44 wt: 56: wt, DOP/nBL,pm (mol/15 mol) = 3.18. The temperatures of both reactors were maintained at 85 °C. Quantitative amount of components and solvent to achieve a residence time of 45 minutes in the first reactor and 93 minutes in the second reactor. The following quantities were fed to the first polymerization reactor: first reactor Sty = 5.21 g/min, Bde = 7.34 g/min, cyclohexane = 93.57 g/min, nBL = 3.3693 mmol/min, nBL = 3.3364 mmol/min. /

<p>33 min, DOP = 3.151 mmol/min, 1.3-3.131 Bde = mmol/min.</p>

Methanol was added as a finishing agent and IRGANOX 1520 (phr3.15) as an antioxidant to the polymeric mobile outside the second reactor. A total transformation of 95 was obtained outside the first reactor, and a complete transformation was obtained outside the second reactor.

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The polymer coming out of the second reactor was loaded using GPC and titrated with polystyrene, Mn = 354734 g/mol, Mw = 537879 g/mol, MWD = 1.994. The microstructure and styrene block content were measured using 1H-NMR. The following results were obtained: 1,2-polybutadiene (vinyl,: 44.5 = styrene, calculated on the basis of the ratio of

5 55 = (butadiene:, styrene block) &lt; of 6 units 2 :) styrene:,

styrene block includes 4-6 35 styrene units:.

The admixture was according to 4+1 Mooney ML for products ie 69.1.

The ratio of DOP/nBL,pm and styrene content were in the innovative range, but the reaction temperature was very high, so that SSBR was obtained with 35: styrene block 13 comprising 4-6 styrene units.

Example 5 (with continuous lane T = 43, Continuous Polymerization °C, DOP/ Active Initiator = 3)

The copolymerization of Styrene-butadiene was carried out using the conditions described above. A ratio of aluminum ART/quantitative feed stream of 13: was used. Conditions have been used

15th following in this experiment:

44 = butadiene: styrene: wt: 56: wt, DOP/active lithium (mol/mol) = 3.44. The temperatures of both reactors were maintained at 43°C. Quantitative flow of quantitative effluent from components and solvent was regulated. To achieve a residence time of 73 minutes in the first reactor and 143 minutes in the second reactor, the following quantities were fed to the reactor

33 Polymerization reactor first: Sty = 2.41 g/min, Bde = 4.52 g/min, cyclohexane = 58.33 g/min, nBL = 3.3574 mmol/min,

nBL, exc = 3.33729 mmol/min, DOP = 3.14 mmol/min, 1, 3-Bde = 3.31327 mmol/min .

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

The polymer coming out of the second reactor was loaded with GPC and titrated with polystyrene:

5 Mw = 1.817, Mw = 275572, Mn = 336733. The exact composition and content of . were measured

styrene block using 1H-NMR. The following results were obtained: styrene = 46:, polybutadiene-2,1 (vinyl, calculated on the basis of the ratio of 71.5 = (butadiene):, styrene block styrene block (&lt; of 6 units 9): styrene:, styrene block includes styrene block that includes 4-6 43: styrene units:.

13 The combination according to 4+Mooney ML1's products was 54.7.

DOP/active initiator ratio, styrene content, and temperature were in the innovative range. The resulting SSBR was obtained with more than 33: styrene block comprising

.styrene units 6-4

Invention No. 3

15th Surprisingly and unexpectedly, current inventors have discovered a process of polymerization for the preparation of SSBR with a high percentage of styrene and a high percentage of vinyl.

With a very narrow molecular weight distribution, a high conversion ratio (in some embodiments, greater than :99), and a short reaction time (in some embodiments, less than 2 hours). As will be explained later, the process for the invention uses a combination of a polar agent first and second agent.In some models,

33 The first and second polar agents Warren correspond to TMEDA and DOP, respectively.

Moreover, current inventors have also surprisingly and unexpectedly discovered that the use of certain combinations of polar I and II agents (such as DOP and TMEDA) results in not only a narrow distribution of the molecular weight of the polymer at the end of the polymerization of

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a polymer, as shown in Figure 1a, but also a significant increase in the viability of polymer chains upon completion of the polymerization of a polymer compared to using only tetramethylethylenediamine (TMEDA), as shown in Figure 3, Or when using DOP only, as shown in Figure 2.

5 The current inventors also discovered that particularly good results were achieved at a TMEDA/DOP ratio between about 3.5 and about 1 mol/mol, as shown in Figure 4. In short, as will be explained in more detail later, the current inventors have achieved—excitingly Surprising and unexpected - an improvement in the molecular weight distribution using a combination of polar factors compared to using TMEDA only, and an improvement in the viability of the life-giving limbs compared to using TMEDA only.

13 DOP only.

In the context of the present invention, the following definitions must be taken into account:

The term "polymer" refers in a broad sense to a substance prepared by passing polymerization of monomeric units. As used herein, the term “polymer” includes the expressions “homopolymer” (a polymeric material 15 prepared from one type of monomer), “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 straight, branched, or cyclic hydrocarbon chain, with or without substitution, preferably containing between 1

33 and 33 carbon atoms. Characteristic examples of alkyl groups that have no substitution for use according to current guidelines include, but are not limited to:

methyl, ethyl, propyl, iso-propyl, cyclopropyl, butyl, iso-butyl, tort-butyl,

sec- butyl, cyclobutyl, etc.

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

The expression "vinyl content" indicates the percentage of mass (or weight) butadiene present at position 1, 2 in the polymer chain, based on the fraction of butadiene (the total amount of 5 polymerized butadiene) in the polymer.

The expression "styrene content" indicates a percentage of the mass (or weight)^styrene in the polymer, based on the total weight of the polymer.

The term "composition" refers to a mixture of materials including a polymer and, optionally, reaction products and/or degradation products made up of the polymer material.

0 1 The term “active initiator” (πΒΙ-, pm) refers to the amount of initiator (eg an organic material containing lithium) that is involved in the polymerization reaction and that is not damped by impurities in the reaction medium.

By way of general introduction, a process for the polymerization of a polymer comprising the noose monomeric units of styrene monomer and 3-butadiene monomer,! According

1 5 of the present instructions contain the polymerization of monomeric units in the presence of a starter, a first polar agent, and a second polar agent. In some embodiments, the first polar factor has the form (A):

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

In some embodiments, the second polar factor has the form (a):

<img file="SA4434B1_D0004.tif" />

٢٠

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In some embodiments, 'R3', R2', R1, and 'R4' are selected separately from the group consisting of an alkyl group and hydrogen, in some embodiments, R3', R2', R1, and R4 are each selected separately. From the group consisting of a hydrogen and a C-a Ci alkyl group. In some embodiments, R3', R2', R1, and R4' are selected separately from the group that makes up

5 of hydrogen and methyl. In some embodiments, R3, -R2, R1, and 'R4' are each

.hydrogen

In some embodiments, Q represents the alkylene group. In some embodiments, the alkylene group is of the formula -CH2)n), where n is an integer equal to or greater than 3, in some embodiments, n is 3 (i.e. Q is ethylene), in some embodiments, n is 2 ( i.e. Q13 is propylene (.

In some embodiments, R1 and R2 separately represent the alkyl group, in some embodiments, R1 and R2 separately are a C1-C4 alkyl group. In some embodiments, R1 and methyl R2 are each.

In some models, R7, R6, R5, R4, R3 and R8, each of them is selected separately from

15th The group consisting of an alkyl group and a hydrogen, in some embodiments, R5, R4, R3, R7, R6 and R8 are each selected separately from the group consisting of hydrogen and the alkyl group C1-C4. In some embodiments, R7, R6, R5, R4, R3, and R8 are each selected separately from the group consisting of hydrogen and methyl. In some embodiments, R3, R7, R6, R5, R4 and R8 are all hydrogen.

33 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 3.2 mol/mol. In some embodiments, TMEDA is used in an amount greater than 3.4 mol/mol. In some embodiments , TMEDA is used in an amount greater than 3.5 mol/mol.

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In some embodiments, the second polar factor according to current guidelines is

2,2-di(2-oxolanyl)propane which is also known as (ditetrahydrofurylpropane)

or DOP). In some embodiments, a DOP is used in an amount greater than 3.3 mol/mol. In some embodiments, a DOP is used in an amount greater than 3.2 mol/mol. In some embodiments, 5 DOP is used in an amount greater than 3.5 mol/mol.

In some embodiments, the molar ratio between F2 and F1 (such as DOP/TMEDA) ranges between about 3.31 and about 13. In some embodiments, the molar ratio ranges between about 3.1 and about 2.

In some embodiments, the molar ratio varies between about 3.2 and about 1.

13 In some embodiments, the styrene content in the polymer according to current guidelines ranges between about 33 and about 83 percent by weight of the bulk weight of the polymer. In some embodiments, the styrene content ranges from about 43 to about 73 wt.% of the bulk weight of the polymer.

In some embodiments, the vinyl content of the polymer according to current guidelines ranges between about 23 and about 83 percent by weight of the quantitative amount of 1,3-butadiene. In some embodiments, the vinyl content of the polymer 15 according to current guidelines ranges between about 43 and about 73 percent by weight of the quantitative amount of 1,3-butadiene.

In some embodiments, a polymer that embodies the properties of the current guidelines has a molecular weight distribution between about 1.35 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 1.3 and about 1.6.

33 In some embodiments, a polymer that embodies the properties of the present guidelines has an average molecular weight of greater than or equal to and about 133,333 g/mol. In some embodiments, the mean molecular weight according to the polymorph is greater than or equal to and is about 153,333 g/mol. In some embodiments, the mean molecular weight according to the polymorph is greater than or equal to and is about 233,333 g/mol.

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In some embodiments, a polymer that embodies the properties of the present guidelines has an average molecular weight of greater than or equal to and about 183,333 g/mol. In some embodiments, the mean molecular weight according to weight is greater than or equal to and about 333,333 g/mol. In some embodiments, the mean molecular weight according to weight is greater than or equal to and about 263,333 g/mol. in a

5 In some embodiments, polymer according to current guidelines has only one glass transition temperature (Tg). In some embodiments, Tg ranges from about -53 °C to about 33 °C. In some embodiments, Tg ranges between about -53 °C and about 33 °C. -23 °C and about 13 °C.

In some embodiments, the molar ratio between polar factor I and the active initiator is greater than about

3.2. In some embodiments, the molar ratio is greater than about 3.4. In some embodiments, the 13 molar ratio is greater than about 3.5.

In some embodiments, the molar ratio between polar factor II and the active initiator is greater than about 3.3. In some embodiments, the molar ratio is greater than about 3.2. In some embodiments, the molar ratio is greater than about 3.5.

Starters currently preferred for use according to current guidelines include those suitable for polymerization processes

15th anionic polymerizations. In some embodiments, the initiator for use according to current guidelines is an organ lithium compound (such as alkyl lithium). Examples of alkyl lithium agents for use according to current guidelines include, but are not limited to:

n-butyllithium n-butyllithium, sec-butyl lithium, tert-butyllithium, n-

pentyllithium, shabu, and combinations thereof, in some embodiments, the prefix has the -n

. butyllithium 33

It is currently preferred that processes take place with a polymerization of a polymer according to current guidelines in solvents, with hydrocarbon solvents currently being preferred. In some embodiments, the polymerization solvent includes an alkane. In some embodiments, . includes

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polymerization solvent blindness to cyclohexane. In some embodiments, the polymerization solvent comprises a mixture of cyclohexane with one or more additional alkane.

Also for general introduction, the polymer is formed according to the present guidelines with a process of the type described herein. In some embodiments, the polymer that embodies the properties of the current instructions is

5 At least the following properties: (a) styrene content ranging between about 43 and about 73 wt% of the bulk weight of the polymer; (b) vinyl content ranging between about 23 and about 83 wt% of the quantitative amount of 1,3-butadiene; and (c) a molecular weight distribution between about 1.35 and about 1.8.

In some embodiments, the polymer is modified according to current guidelines using a modifying agent (or modifying agent 13). Examples of modifying agents include, but are not limited to: amines,

amides, silicon alkoxides, thioglycols, modifiers of -silane sulfide, shabu, and mena combinations.

In some embodiments, chemical modification of a live polymer can be made according to the current guidelines using sesamoid tip modification and/or coupling reactions. Suitable modification materials can be selected for the sesame tip and/

15th or coupling agents according to the intended use and the filler.

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

Examples of modification materials include, but are not limited to, the following: sulfenyl halides as described in EO Document No. 1316674, benzophenone isocyanate, compounds

hydroxyl mercaptans as described in EOC No. 3464478, and acrylamides as described in EOC No. 3224343. Additional modifiers include, but are not limited to, the following: amines, amides, amides, and nitrites as annotated In European Request Document No.

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548799, EP No. 513413, EP No. 451634, EE 183141, and US Patent No. 4413341. In some embodiments, silanes including, but not limited to, epoxy-containing silanes are used to modify the polymer chain linkage. polymer chain for use in silica fillers

5 As annotated, for example, in EC-A-399374, EC-A-133345, EC 3447366, and EC 3693492. Additional examples of amendment articles and/or references to opinions referring to These materials are found in International Application Document No. 124665/3339.

Also for general presentation, the formulation embodying the properties of the present guidelines contains 13 polymers of the type described herein. In some embodiments, the composition according to current guidelines also contains

Uncle Zeit. In some embodiments, the composition according to current instructions does not contain oil.

In some embodiments, a composition according to the present instructions contains a polymer of the type described herein and at least one additive. In some embodiments, the polymer is incorporated and/or reacted with one or more fillers, a vulcanization agent, and/or optionally another additive.

15th one or more including, but not limited to: accelerators, coupling agents, uncrosslinked elastomeric polymers that do not have crosslinks (i.e. conventional crosslinked elastomers that do not react With an amendment material, but it has been prepared and intended), and what it is, and its combinations.

33 In some embodiments, a composition according to the current instructions contains one or more fillers that act as reinforcing agents. The distinctive examples of suitable fillers include, but are not limited to: carbon black, silica, and a dual-phase filler from Carbon and silica, blast magnesium carbonate, calcium carbonate, clay, etc., and minya combinations. In some embodiments, a combination of carbon black . is used

35 black and silica, double-phase fillers of carbon and silica or a combination of the filler

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Dual-phase filler of carbon, silica, carbon black and/or silica.

In some embodiments, carbon black is manufactured by fumace method, if the nitrogen adsorption surface area is between about 53 and about 333 m3/g, and oil adsorption is

5 DBP oil absorption between about 83 and about 333 mL/133 g (as HAF, FEF, ISAF or SAF class carbon black), in some embodiments “highly agglomerated type” carbon black is used. In some embodiments, carbon black is added or silica in an amount ranging from about 3 to about 133 parts by weight for every 133 parts by weight of the quantitative polymer In some embodiments, carbon black or silica is added in an amount between about 5 and about 133 parts by weight.

13 In embodiments, carbon black or silica is added in an amount ranging from about 13 to about 133 parts by weight. In some embodiments, carbon black or silica is added in an amount between about 13 and 95 parts by weight.

Finally, also for general presentation, 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 frame. in a

15th In some models, the product is a component of the shoe.

The following examples and procedures illustrate features in accordance with current guidelines, and are provided for the sake of clarity. It is not intended to limit the scope of the applied elements of protection or their equivalent.

the sinners

The monomer shift was determined by measuring the solids concentration of a polymer mobile at the end of a polymer lane

33 polymerization of a polymer . The maximum solids concentration is obtained at 133 by weight: charged butadiene (mBd) and styrene (mSt) are converted to the final polymer with the relationship:

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

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A sample of a polymer pellet ranging from about 1 g to about 13 g, according to the expected conversion of a monomer, was drawn from the reactor directly into a 333 mL Erlenmeyer flask filled with (53 mL) ethanol. The weight of the filled Erlenmeyer flask was determined prior to sampling (“A”). ") and after sampling ("B"). The precipitated polymer was removed from ethanol by filtration on a weighted filter paper

5 weighted paper filter (Micro-glass, 93 mm, MUNKTELL, weight “C”), dried at 143°C, using HR73 moisture analyzer (Mettler-Toledo) until constant weight, standard 5 was used Finally, a second drying period was carried out using closing criteria 4 to obtain the final mass “D” of the dry sample on the filter paper.

:TSC= (DC)/(BA)*100 13

The final transformation of the polymer was calculated as 100*TSC/TSC max:

The transition temperature of the frit, Tg, was measured mathematically according to ISO 11357-2 (1999) using a heating rate of 33 km/min with the following settings:

Sample weight: about 11 mg

15th Sample container: Standard aluminum containers (sealed and vapor-tight)

Temperature range: -153 to 133 ° C

Heating rate: 33 km/min

Cooling rate: free cooling (13 to 33 km/min)

33 Cleaning gas: 33 ml He/min

Cooling agent: liquid nitrogen

Evaluation method: Inflection point

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Device: DSC Q2000 from TA Instruments

Two non-stop heating cycles between heating and cooling, Tg was determined using data from the second heating cycle.

The molecular weight and molecular weight distribution of the polymer were measured using the Arvia size-exclusion chromatogram (SEC) 5 at 43°C based on standard levels of polystyrene. Each sample (9-11 mg) polymer was dissolved in 13 mL tetrahydrofuran (13 mL) for a portable make. The solution was filtered using a 3.45 µm filter. A 133 µL sample was fed to a Hewlett Packard system 1100 (GPC) column with 3 PLgel 13 µm columns. MIXED-B(. Refraction Index 13 detection was used as the detector for analyzing the

molecular weight. The molecular weight was calculated as HR polystyrene based on titration with

EasiCal PS1 (Easy A and B) Polystyrene Standard Levels of Polymer Laboratories.

The mean molecular weight values ​​according to the modifier (Mn) and the mean molecular weight values ​​according to the weight (Mw) 15 are given based on the standard levels of polystyrene. The molecular weight distribution was expressed in

Image of degree of dispersion D = Mw/Mn dispersity.

Vinyl and styrene content were quantified using 1H-NMR, ISO 2005-21561 method. Using a 433BRUKER Avance MHz NMR spectrophotometer and a 5 mm dual probe. CDCl3/TMS was used as solvent with a weight ratio of 3.35::99.95:. 33 The content of a styrene block consisting of more than 6 styrene units has been determined

Rubber Chemistry and In Y. Tanaka et al., sequenced according to the Ph-ortho memory method using the relative intensity of signals. Technology, 1981, 54, No. 4, 685-691

proton that gives a resonance at a blind of 6.7 in the mycelium.

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Procedures for Determining Livingness of Chain Ends: As previously explained, the use of a combination of TMEDA and DOP results in a blind survival capacity of the ends of the chain at the end of a polymerization of a polymerization process. The percentage of chain ends that are able to survive at the end of a process with a desired polymer passage because the higher the number of chains contained in the polymer,

5 The overlap between the filler and the rubber will improve and the rolling resistance of the resulting vulcanizer compound will decrease.

The polymers were treated with an excess of N-methylpyrrolidone NMP after achieving a monomer shift greater than 99: to assess the viability of the resulting polymer chains. The modification rate of the resulting polymer chains was loaded using two different methods: Method 1 is based on a comparison of size exclusion chromatography.

13 Refraction Index detection (SEC) for the intensity of ultraviolet radiation (SEC) as explained in US Pat. No. 7733, 692B3 to Karato et al.; Method 3 involves adsorption on a silica gel column as described in US Patent Applications Nos. 3339/3162668A1 and 3339/3332842A1. It turns out that the absolute values ​​obtained using Method 1 and Method 3

15th Different, but the same directions.

The comparative example 6 was set to be 133 in each method and all the data obtained were calculated according to this reference (MR in the form of:).

Comparative Example #5: Using TMEDA only

The dried cyclohexane (5271.18 g) was added to the airless and washed reactor.

33 Nitrogen-purged 13 liter capacity of stainless steel. (236.657 1,3-Butadiene g), (434.12 g) styrene, and (3.1335 mmol TMEDA) were fed to the reactor (active butyl lithium / TMEDA mol/mol = 1.743).

The mixture was heated to 53°C with stirring. The impurities in the system were titrated by adding butyl lithium in batches. Upon verification of the end point, the polymerization of . is initiated

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a polymer by adding an amount of nBUpm of 1.3175 mmol of (15 n-butyllithium: carried in cyclohexane) using a pump during 3 min 16 sec. The process was then started by polymerization of a polymer. The temperature in the reactor was raised to 65 °C during 23 minutes The completion of the reaction was confirmed after 233 minutes by taking samples and determining that the transformation

5 Monomer 133:. The resulting polymer was loaded with Mw, GPC= ., Mn = 215898

629423, D = 3.33. (2.2 g butadiene) was added and this was achieved (1.23 mmol NMP). After 15 minutes, the reaction was completed by adding methanol as a quenching agent. 4.6 bis was introduced

(Ciba) from IRGANOX 1520 sold under the trade name (octylthiomethyl)-o-cresol

As an antioxidant.

13 The microstructure and styrene block content were measured using 1H-NMR. The following results were obtained: 1,2-polybutadiene (vinyl),: 53.5 = styrene, calculated on the basis of styrene ratio,: 29.1 = (massive butadiene = 15:).

The measurement of the glass transition temperature showed that there is one transition temperature of the glass transition at -14.7 °C. Adjustment rate analysis resulted in 49: (Method No. 1) and 48: (Method No. 3) compared to the comparative example: 6 15 (133:).

Comparative Example #6: Using TMEDA only

The dried cyclohexane (5439.2 g) was added to a 13 L nitrogen-purged stainless steel washed reactor. It was fed with 1,3-Butadiene (23624 g), and styrene (433.5 g). , and 33 TMEDA (2.759 mmol) to the reactor (active butyl lithium / TMEDA mol/mol = 2.355).

The mixture was heated to 53°C with stirring. The impurities in the system were titrated by adding butyl lithium in batches. Upon verification of the end point, the polymerization of a polymer was started by adding an amount of nBL,pm of 1.3235 mmol of (15 n-butyllithium: carried in cyclohexane) using a pump over 3 min 16 sec.

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With a polymer pass. The temperature in the reactor increased to 65°C within 23 minutes. The completion of the reaction was confirmed after 363 minutes by sampling and determining that the monomer shift was 99.7:. The resulting polymer was loaded with GPC: D = 1.893, Mw = 584353, and Mn = 219636. (2.2 g butadiene) was added and this was achieved (1.3386 mmol NMP). After 15 minutes, the reaction was completed.

5 By adding methanol as a denaturing agent. IRGANOX 1520 has been introduced as an antioxidant

. antioxidant

The microstructure and styrene block content were measured using 1H-NMR. The following results were obtained: 1,2-polybutadiene (vinyl.: 52 = styrene, computed on the basis of styrene ratio,: 43.1 = quantitative butadiene = 13:.

13 Measurement of the glass transition temperature showed the presence of one transition temperature of the glass transition at -9.8 °C. Adjustment rate analysis results were used as a reference for all other experiments and considered as 133 (Method No. 1) and 133 (Method No. 3).

Comparative Example #7: Using DOP Only

The dried cyclohexane (5338.11 g) was added to a nitrogen-purged 13 L reactor washed with 15 L of stainless steel.

1,3-Butadiene (217.38 g), 292.11 g styrene), and DOP (1.1866 mmol) were fed to the reactor (butyl lithium /active DOP = 3.981).

The mixture was heated to 53°C with stirring. The impurities in the system were titrated by adding butyl lithium in batches. When the end point was verified, the polymerization of 33 a polymer lane was started by adding an amount of nBL,pm of 1.31 mmol: (15 n-butyllithium carried in cyclohexane) using a pump during about one minute, then, a polymer lane was started. The temperature in the reactor reached 65 °C within 23 minutes The completion of the reaction was confirmed after 133 minutes by sampling and determining that the monomer conversion amounted to 99.49: 99.49 was loaded.

polymer using D = 1.385, Mw = 755343, and GPC: Mn = 587525. . has been added

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(2.24 g butadiene) and this was achieved (1.357 mmol NMP). After 15 minutes, the reaction was completed by adding methanol as a simmering agent. IRGANOX 1520 was introduced as an antioxidant

. antioxidant

The microstructure and styrene block content were measured using 1H-NMR. The following results were obtained: 1,2-polybutadiene (vinyl, 55.9 = styrene, calculated on the basis of the ratio of 8 = styrene block,: 49 =) butadiene:.

The measurement of the glass transition temperature showed that there is one transition temperature of the glass transition at -7.1 °C. Adjustment rate analysis resulted in 193: (Method No. 1) and 168: (Method No. 3) against the comparative example 6 (133:).

13 Comparative Example #8: Using DOP Only

cyclohexane was dried (33717.6 g) was added to a 43 L nitrogen-purged nitrogen-washed reactor of stainless steel, fed with 1,3-Butadiene (1226.66 g), and styrene (1635.34 g) , and DOP (5.11 mmol) to the reactor (active butyl lithium /DOP = 1.335).

15th The mixture was heated to 53°C with stirring. The impurities in the system were titrated by adding butyl lithium in batches. When the end point was checked, the polymerization of a polymer was started by adding an amount of nBL,pm of 4.8883 mmol of (15 n-butyllithium: carried in cyclohexane) using a pump over about 1 minute, at which point, the polymerization process was started. The temperature in the reactor reached 65 °C within 23 minutes The reaction was stopped after

33 323 min by adding methanol as a boiling agent. IRGANOX 1520 has been introduced as an antioxidant

. antioxidant

A sample was withdrawn from a sampling tube fitted with a stopcock stopper and a needle to determine the solids content. The TPMG shift ratio of 99.37: was measured.

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The resulting polymer was loaded with D, 827114 = Mw, 643963 = Mn: GPC = 1.236. The microstructure and styrene block content were measured using 1H-NMR. The following results were obtained:

1,2-polybutadiene (vinyl,: 54.9 = styrene, calculated on the basis of the ratio of 5 styrene,: 53.1 =) butadiene quantum = 7:.

The measurement of the glass transition temperature showed that there is one transition temperature of the glass transition at -3.7 °C.

Comparative Example #9: Using DOP Only

The cyclohexane (5312.12 g) was dried into a 13 L nitrogen-purged nitrogen-washed reactor of stainless steel. 13 was fed with 1,3-Butadiene (1,3-Butadiene) 13 and 292. styrene (31 g), and DOP

(1.1835 mmol) to the reactor (active butyl lithium /DOP = 3.971).

The mixture was heated to 53°C with stirring. The impurities in the system were titrated by adding butyl lithium in batches. When the end point was verified, the polymerization of a polymer was started by adding an amount of nBL,pm of 1.3175 mmol of 15 n-butyllithium (15: n-butyllithium: carried in cyclohexane) using a pump over about 1 minute.

With a polymer pass. The temperature in the reactor increased to 65°C within 23 minutes. The completion of the reaction was confirmed after 93 minutes by sampling and determining that the monomer transformation was 133:. The resulting polymer was loaded with butadiene (P = 1.345, Mw = 693882, Mn = 554765 mmol) (2.24 g) NMP (1.3344 mmol) was added. After 15 minutes, reaction 33 was completed by adding methanol as a quenching agent. 1520 was introduced. IRGANOX as an antioxidant.The micro-composition and content of styrene block were measured using 1H-NMR. The following results were obtained: 1,2-(vinyl,: 55.3 = styrene polybutadiene, calculated on the basis of the proportion of styrene,: 44.8 =) lumpy butadiene - 12:. Measurement of the glass transition temperature showed the presence of one transition temperature of the glass transition at -2.4 °C.

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Adjustment rate analysis resulted in: 158 (Method No. 1) and 118: (Method No. 3) compared to the comparative example 6 (133:).

Example #6 Using TMEDA/DOP

The dried cyclohexane (5198.73 g) was added to the airless and washed reactor.

5 Nitrogen-purged 13 liter capacity of stainless steel. 1,3-butadiene (218.28 g), 293.99 g styrene), TMEDA (3.1514 mmol), and DOP (1.1783 mmol) were fed to the reactor (active butyl lithium/TMEDA mol/mol=1.778; butyl Active lithium /DOP = 3.974).

The mixture was heated to 53°C with stirring. The impurities in the system were titrated by adding butyl

13 lithium uncle batches. When the end point was verified, the polymerization of a polymer was started by adding an amount of nBL,pm of 1.3398 mmol of (15 n-butyllithium: carried in cyclohexane) using a pump over about 1 minute, then, a polymerization process was started. The temperature in the reactor reached 65 °C within 23 minutes The completion of the reaction was confirmed after 143 minutes by taking samples and determining that the monomer conversion: 133.

15th The resulting polymer was loaded with GPC: D = 1.372, Mw = 735648, and GPC: Mn = 573343. (2.2 g butadiene) was added and this was achieved (1.363 mmol NMP). After 15 minutes, the reaction was completed by adding methanol as a cooking agent. IRGANOX 1520 was introduced as an antioxidant.

The microstructure and styrene block content were measured using 1H-NMR. 33 The following results were obtained: polybutadiene-2,1 (vinyl,: 55.8 = styrene, calculated on the basis of the proportion of styrene,: quantitative: 53.6 =) butadiene butadiene = 7.

The measurement of the glass transition temperature showed the presence of one transition temperature of the glass transition at 5.5 °C.

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Adjustment rate analysis resulted in 328: (Method No. 1) and 331: (Method No. 3) against the comparative example 6 (133:).

Example 7: Using TMEDA/DOP

The dehydrated cyclohexane (31232.29 g) was added to a nitrogen-purged 43 L reactor washed 5 L of stainless steel.

1,3-butadiene (827.86 g), (1,318 g) styrene, TMEDA (3.9533 mmol), and (1.2811 mol DOP) were fed to the reactor (active butyl lithium /TMEDA 3.431 mol/mol; butyl lithium /DOP). Active = 3.611 (.

The mixture was heated to 53°C with stirring. The impurities in the system were titrated by adding butyl

13 lithium ion batches. When the end point was checked, the polymerization of a polymer was started by adding an amount of Nbl,prn of 3.3592 mmol of (15 n-butyllithium: carried in cyclohexane) using a pump during about 1 minute, then, the polymerization of a polymerization of a polymer was started. a polymer The temperature in the reactor was raised to 65 °C within 23 min The reaction was terminated after 153 min by adding methanol as a brine ing agent.

15th 1520 IRGANOX As an antioxidant.

A sample was withdrawn with a stopcock sampling tube and a needle to determine the solids content, a shift ratio of 99.14:9PM was measured.

The resulting polymer was loaded with GPC: D = 1.39, Mw = 934348, and GPC: Mn = 716366.

The microstructure and styrene block content were measured using 1H-NMR. It was completed

33 The following results were obtained: 1,2-polybutadiene (vinyl,: 55.5 = styrene, calculated on the basis of styrene ratio, : 28.7 = quantitative butadiene = 17:.

The measurement of the glass transition temperature showed the presence of one transition temperature of the glass transition at -13 °C.

Example 8: Using TMEDA/DOP

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The dried cyclohexane (5134.3 g) was added to a 13 L nitrogen-purged, stainless steel reactor.

1,3-butadiene (215.9 g), styrene (289.5 g), 3.3287 TMEDA mmol),

and DOP (1.1787 mmol) were fed to the reactor (active butyl lithium / TMEDA 5 mol/mol = 1.696; active butyl lithium / DOP = 3.981).

The mixture was heated to 53°C with stirring. The impurities in the system were titrated by adding butyl lithium in batches. When the end point was verified, the polymerization of a polymer lane was started by adding an amount of nBL,pm of 1.333 mmol of: (15 n-butyllithium carried in cyclohexane) using a pump over about 1 minute, then, the polymerization lane was started of a polymer The temperature in the reactor increased to 65 °C during

23 Accurate. The completion of the reaction was confirmed after 153 minutes by sampling and determining that the monomer shift was 99.37:. The resulting polymer was loaded with Mw = 833548, GPC: Mn = 579453, D = 1.285. 2.24 g butadiene was added and this was achieved (1.159 mmol NMP). After 15 minutes, the reaction was completed by adding methanol as a cooking agent. 1520 IRGANOX 15 was introduced as an antioxidant.

The microstructure and styrene block content were measured using 1H-NMR. The following results were obtained: 1,2-polybutadiene (vinyl, 56.3 - styrene, calculated on the basis of styrene ratio, -7:53.4 =) lump butadiene.

The measurement of the glass transition temperature showed the presence of one transition temperature of the glass transition at 6.1 °C.

33 Adjustment rate analysis resulted in 325: (Method No. 1) and 188: (Method No. 3) versus the comparative example (133:).

Example 9: Using TM EDA/DOP

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The dried cyclohexane (33951.95 g) was added to a 43 L nitrogen-purged stainless steel washed reactor. It was fed with 1,3-butadiene (1,383) and styrene (1572.82) g. TMEDA (8.2477 mmol), and DOP (4.8288 mmol) to the reactor (active butyl lithium / TMEDA 5 mol/mol = 1.792; butyl lithium / active DOP = 1.329).

The mixture was heated to 53°C with stirring. The impurities in the system were titrated by adding butyl lithium in batches. When the end point was checked, the polymerization of a polymer was started by adding an amount of nBL,pm of 4.6556 mmol of (15 n-butyllithium: carried in cyclohexane) using a pump during about 1 minute, then, the polymerization process was started 13 of a polymer The temperature in the reactor was raised to 65°C within 23 minutes. The completion of the reaction was confirmed after 143 minutes by sampling and determining that the monomer shift was 99.69:. The resulting polymer was loaded with GPC = 791497: Mn = 631421, Mw = 1.374. 2.24 (butadiene g) was added and 1.159 NMP (1.159 mmol). After 15 minutes, the reaction was completed by adding methanol as a quenching agent. 15 1520 was introduced. IRGANOX as an antioxidant.

The microstructure and styrene block content were measured using 1H-NMR. The following results were obtained: 1,2-polybutadiene (vinyl),: 55.3 = styrene, calculated on the basis of styrene ratio,: 52.3 = (butadiene quantum = 7:).

The measurement of the glass transition temperature showed that there is one transition temperature of the glass transition at -5.8 °C.

33 Adjustment rate analysis resulted in 339: (Method No. 1) and 315: (Method No. 3) against the comparative example 6 (133:).

Example 13: Using DOP/TMEDA (ratio 3.22)

The dried cyclohexane (5333.58 g) was added to a 13 L nitrogen-purged, stainless steel reactor.

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1,3-butadiene (216.18 g), 293.89 styrene g), TMEDA (2.57 mmol), and (1.1772 mmol DOP) were fed to the reactor (active butyl lithium /TMEDA mol/mol = 3.967; active butyl lithium /DOP= 3.977(.

The mixture was heated to 53°C with stirring. The impurities in the system were titrated by adding butyl 5 lithium in batches. When the end point was checked, the polymerization of a polymer was started by adding an amount of nBL,pm of 1.3346 mmol of (15 n-butyllithium: carried in cyclohexane) using a pump over about 1 minute, then, the polymerization of a polymerization of a polymer was started. a polymer The temperature in the reactor was raised to 65°C within 23 minutes The reaction was terminated after 233 minutes by adding methanol as a brine. 13 1520 IRGANOX has been introduced as an antioxidant.

A sample was withdrawn from a sampling tube fitted with a stopcock stopper and a needle to determine the solids content. The TPMG conversion ratio of 98.36: was measured.

The resulting polymer was loaded with GPC: D = 25.1, Mw = 736321, and GPC: Mn = 533936.

The microstructure and styrene block content were measured using 1H-NMR. 15 The following results were obtained: 1,2-polybutadiene (vinyl = 55.8 styrene, calculated on the basis of styrene ratio, quantitative = 51.4) butadiene = 6:,

The measurement of the glass transition temperature showed the presence of one transition temperature of the glass transition at -9.9 °C.

Example 11: Using DOP/TMEDA (ratio 2.22)

33 cyclohexane (5194.45 g) was dehydrated and added to a 13 L nitrogen-purged reactor of stainless steel fed with 1,3-butadiene (216.38 g), and 293.11 g styrene. ), TMEDA (3.2647 mmol), and DOP (1.1776 mmol) to the reactor (active butyl lithium / TMEDA mol/mol - 3.233; butyl lithium / active DOP = 3.975).

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The mixture was heated to 53°C with stirring. The impurities in the system were titrated by adding butyl lithium in batches. When the end point was verified, the polymerization of a polymer was started by adding 1.3375 mmol of nBL,pm of n-butyllithium (15: carried in cyclohexane) using a pump over about 1 minute.

5 polymerization of a polymer . The temperature in the reactor increased to 65°C within 23 minutes. The completion of the reaction was confirmed after 133 minutes by sampling and determining that the monomer shift was 99.27:. (4.34 g butadiene) was added and this was achieved (1.31 mmol NMP). After 15 minutes, the reaction was completed by adding methanol as a cooking agent. IRGANOX 1520 was introduced as an antioxidant.

13 The resulting polymer was loaded with D, Mw = 721276, GPC = 1.321: Mn = 594311. The microstructure and styrene block content were measured using 1H-NMR. The following results were obtained: 1,2-polybutadiene (vinyl, 55.9 - styrene, calculated on the basis of styrene ratio, quantitative: 49.9 =) butadiene butadiene = 7.

The measurement of the glass transition temperature showed that there is one transition temperature of the glass transition at -3.8 °C.

15th Adjustment rate analysis resulted in 337: (Method No. 1) versus Comparative Example 6 (133:).

Example 13: Using DOP/TMEDA (ratio 1.67)

The dried cyclohexane (5187.95 g) was added to a 13 L nitrogen-purged, stainless steel reactor.

fed with 1,3-butadiene (216.38 g), and 1 1.7 (29 g) TMEDA 1.7

33 (3.7135 mmol), and (1.1776 mmol DOP) to the reactor (butyl lithium / TMEDA).

active mol/mol = 3.631; Active butyl lithium /DOP 3.992).

The mixture was heated to 53°C with stirring. The impurities in the system were titrated by adding butyl lithium in batches. When checking the end point, the polymerization of a polymer was started by adding an amount of nBL,pm of 1.1861 mmol of 15 (n-butyllithium).

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: carried in cyclohexane) using a pump within about one minute, then, a polymerization of a polymer process began. The temperature in the reactor was raised to 65 °C within 23 minutes. The completion of the reaction was confirmed after 133 minutes by sampling and determining that the conversion Monomer 133:.

5 The resulting polymer was loaded with D, Mw = 794175, GPC = 1.343: Mn = 629275. (2.34 g butadiene) was added and this was achieved (1.33 mmol NMP). After 15 minutes, the reaction was completed by adding methanol as a cooking agent. IRGANOX 1520 was introduced as an antioxidant.

The microstructure and styrene block content were measured using 1H-NMR. 13 The following results were obtained: 1,2-polybutadiene (vinyl, 54.5 = styrene, calculated on the basis of styrene ratio: 53.8 =) quantitative butadiene = 7:. The measurement of the glass transition temperature showed the presence of one transition temperature of the glass transition at 3.8 °C. Adjustment rate analysis resulted in 189: (Method No. 1) compared to the comparative example 6 (133:).

Example 12: Using DOP/TMEDA (ratio 3.18)

15th cyclohexane (5333.87 g) was dried and added to a 13 L nitrogen-purged stainless steel washed reactor. It was fed with 1,3-butadiene (232.38 g), and styrene (433.22 g) TMEDA, (3.3628 mmol), and DOP (3.2614 mmol) to the reactor (active butyl lithium /TMEDA /mol = 1.7 33; active butyl lithium /DOP 3.398).

33 The mixture was heated to 53°C with stirring. The impurities in the system were titrated by adding butyl lithium in batches. When the end point was verified, the polymerization of a polymer was started by adding an amount of nBL,pm of 1.3134 mmol of (15 n-butyllithium: carried in cyclohexane) using a pump during about 1 minute, then, the polymerization of a polymerization of a polymer was started. a polymer The temperature in the reactor increased to 65 °C

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Within 23 minutes. The completion of the reaction was confirmed after 183 minutes by sampling and determining that the monomer shift was 99.9:. The polymer was loaded with Mw, 536393 = Mn: GPC =

779935, D = 1.483. 2.24 (butadiene g) was added and this was achieved (27 1.8 mmol NMP). After 15 minutes, the reaction was completed by adding methanol as a cooking agent. 5 1520 IRGANOX was introduced as an antioxidant.

The microstructure and styrene block content were measured using 1H-NMR. The following results were obtained: 1,2-polybutadiene (vinyl = 55.1 styrene, calculated on the basis of styrene ratio, quantitative = 45.4) butadiene = 9:.

The measurement of the glass transition temperature showed that there is one transition temperature of the glass transition at -1.3 °C. Resulting in 13 analysis of the modification rate: 191 (Method No. 1) compared to the comparative example 6 (133:).

Example 14: Using DOP/TMEDA (ratio 3.25)

The dried cyclohexane (5,357.45 g) was added to a 13 L nitrogen-purged stainless steel-washed reactor. It was fed with 1,3-butadiene (219.98 g), and styrene (296.23 g). TMEDA, 15 (3.343 mmol), and DOP (3.7173 mmol) to the reactor (butyl lithium / TMEDA).

active mol/mol = 1.681, active butyl lithium /DOP = 3.593).

The mixture was heated to 53°C with stirring. The impurities in the system were titrated by adding butyl lithium in batches. Upon verification of the end point, the polymerization of a polymer was started by adding an amount of nBL,pm of 1.3147 mmol of butyl lithium - n 33 (15: carried in cyclohexane) using a pump over about 1 minute.

polymerization of a polymer . The temperature in the reactor rose to 65°C within 23 minutes. The completion of the reaction was confirmed after 153 minutes by sampling and determining that the monomer shift was 98.97:.

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The resulting polymer was loaded with D = 1.4, Mw = 811981, and GPC: Mn = 583671. 2.34 g butadiene was added and this was achieved (1.3536 mmol NMP). After 15 minutes, the reaction was completed by adding methanol as a cooking agent. IRGANOX 1520 was introduced as an antioxidant.

5 The microstructure and styrene block content were measured using 1H-NMR. The following results were obtained: polybutadiene-2,1 (vinyl, 56.3 = styrene, calculated on the basis of the proportion of styrene: 53.4 =) butadiene quantum = 7:.

The measurement of the glass transition temperature showed that there was one transition temperature of the glass transition at 2.3 °C, which resulted from the analysis of the modification rate: 313 (method No. 1) versus the comparative example 6 (133:).

13 Invention No. 2

The present inventors surprisingly and unexpectedly discovered SSBR with a high percentage of styrene, and a high percentage of vinyl with a narrow molecular weight distribution, incorporation of styrene in the form of successive blocks with more than 4 styrene units ranging between about 43 and about 73:, and other properties as it is Explained later.

15th Moreover, the present inventors have also surprisingly and unexpectedly discovered that the previously described SSBR with a high percentage of styrene and a high percentage of vinyl can be prepared using a starter (such as butyl lithium) and a randomizer (such as

ditetrahydrofurylpropane, which is also known as 2,2-di(2-oxolanyl)propane or DOP in combination with potassium alcoholate. In some embodiments, in the following circumstances:

33 Content of ≥ 33styrene: by weight, molar ratio of potassium alcoholate/active initiator ≥3.35; And a pass-through temperature of ≥83°C.

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

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The term "polymer" refers in a broad sense to a substance prepared by passing polymerization of monomeric units. As used herein, the term “polymer” includes the terms “homopolymer” (a polymeric material prepared from one type of monomer), “copolymer” (a polymeric material prepared from two different types of monomers), and “interpolymer” (a polymeric material prepared from more than

Two different types of monomer (.

The term “alkyl group” refers to a straight, branched, or cyclic hydrocarbon chain, with or without substitution, preferably containing between 1 and 33 carbon atoms. Distinctive examples of non-substituted alkyl groups for use according to current guidelines

13: methyl, ethyl, propyl, iso-propyl, including, but not limited to, the following and the like. , cyclopropyl, butyl, iso-butyl, terl-butyl, sec- butyl, cyclobutyl

The term "process" when used to refer to reactions in the polymerization of a polymer that include discontinuous, semi-continuous, and/or continuous processes.

The term “discontinuous” or “semi-continuous” when used to refer to a bypass process refers to a 15 bypass process in which more than 63 of the solvent is charged in the reactor along with the pass-through components

The polymerization of a polymer with the initiator charge begins. The monomer may be charged immediately before initiator addition, partly before initiator addition, partly after initiator addition or continuously immediately after initiator addition over a period of time.

33 “continuous polymerization” refers to the pass-through process in which the solvent, monomer (monomer) and any additional pass-through components are continually pushed into a reactor in proportions

specific volume. In some embodiments, two or more polymerization reactors connected in series are used. In some embodiments, the reactor is driven

to only one reactor.

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The term “vinyl content” denotes the percentage of mum (or weighted) butadiene present in the position

<p>1, 3 per polymer, based on the butadiene fraction (the quantitative amount of polymerised butadiene</p>

.) butadiene polymerization

The term “styrene content” refers to a percentage of the mass (or weight) of styrene in the polymer,

<p>5 Based on the quantitative weight of the polymer.</p>

The term "blocking styrene content" refers to the weight percentage of styrene present in successive sequences of styrene units based on the quantitative amount of styrene adsorbed in the polymer

. polymerized styrene in the polymer

The term "composition" refers to a mixture of substances including a polymer and, optionally, reaction products and/or

13 Products bearing a polymer component.

The term “active initiator” (Nbl,pm) refers to the molar amount of an initiator (such as an organ lithium) that participates in a polymerization reaction that has not been quenched by impurities in the reaction medium.

The term "initiator plus" (nBL,exc) refers to the molar amount of the initiator that is charged to dampen

15th Deactivate the impurities in the system.

The term “quantitative amount from the monomer feed stream” refers to the quantitative amount of styrene and butadiene, in g/min, driven into a continuous-pass reactor and, typically, in a first-pass polymerization of a polymer reactor.

The term “polymer quantitative transformation” refers to the final transformation of a polymer (such as

33 The final polymer, styrene and butadiene (which is determined for the last reactor in a passage and/or at the end of a reaction in a polymerization reaction.

As a general introduction, a polymer that embodies the properties of the present instructions will have at least the following properties: (a) a styrene block content containing more than 4 units

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sequential styrene between about 43 and about 73 wt.% of the quantitative content of styrene in the polymer; (b) a vinyl content ranging from about 35 to about 83 wt% of the quantitative weight of 1,3-butadiene; (c) a styrene content ranging from about 33 to about 75 wt% of the quantitative weight of the polymer; and (d) the distribution of A molecular weight of 1.5 or less.In some embodiments,

5 A polymer that embodies the properties of the present guidelines shall have a styrene block styrene content of more than 6 styrene units in series between about 5 and about 23 percent by weight of the quantitative styrene content in the polymer.

In some embodiments, the polymer that embodies the properties of the present guidelines has a quantitative level of styrene between about 35 and about 85 percent by weight, and in some embodiments between about 53

13 and 63 percent by weight.

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

15th The molecular weight distribution is between about 1.3 and about 1.25.

In some embodiments, a polymer that embodies the properties of the present guidelines has an average molecular weight of greater than or equal to and about 333,333 g/mol. In some embodiments, the mean molecular weight according to the polymorph is greater than or equal to and about 43,333 g/mol. In some embodiments, the mean molecular weight according to the polymorph is greater than or equal to and about 553,333 g/mol.

33 In some embodiments, a polymer that embodies the properties of the present guidelines has an average molecular weight greater than or equal to and about 353333 g/mol. In some embodiments, the mean molecular weight according to weight is greater than or equal to and about 533,333 g/mol. In some embodiments, the mean molecular weight according to weight is greater than or equal to and about 633,333 g/mol.

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It should be recognized that all models previously described in any combination, including combinations of the currently preferred models,

Also by way of general introduction, a process for the polymerization of a polymer . is presented

],3-butadiene and styrene monomer are derived from monomeric comprising units

5 monomer according to the current guidelines contains the polymerization of monomeric units in the presence of a starter, 45H0060A365A5E04 and a polar agent, where the polar agent has the form A:

Is it fun?

In some embodiments, R2 j RI separately is an alkyl group, in some embodiments, and R2 is separately an alkyl Cl group^-C4. In some 1 0 forms, RI and 52 are both methyl.

In some embodiments, 56, 5, R4, R3, and R7 are selected separately from the group consisting of an alkyl group and a hydrogen group. In some embodiments, R3, R4, 5, 86, R7 and R8 are each selected separately from the group consisting of a hydrogen and a C1-C4 alkyl group. In some embodiments, 03, 56, R5, R4, R7 and R8 each 1 5 are selected separately from the group consisting of methyb hydrogen, in some embodiments,

R7, R5, R5, R4 and R8 are each 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 between about 00 and about 3.

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In some embodiments, the styrene content in the monomer mixture added in the polymerization of a polymer is greater than about 43% by weight of the quantitative weight of the added monomer.

In some embodiments, a bypass process is performed according to current guidelines at a temperature of less than about 5 83 °C. In some embodiments, a corridor process is performed according to current guidelines at a temperature ranging from

Between about 13 °C and about 83 °C.

Primers currently preferred for use according to current guidelines include those suitable for anionic polymerizations. In some embodiments, the initiator for use according to current guidelines is an organ lithium compound (such as alkyl lithium). Examples of alkyl 13 lithium agents for use under current guidelines include, but are not limited to: n-pentyl lithium, butyl lithium -t, butyl lithium-s, n-butyllithium, and shabu, and combinations thereof, in some embodiments, the initiator includes n-butyllithium.

In some embodiments, the quantitative shift of the polymer is greater than about 96 wt% of the quantum amount of the monomer feed stream, in some embodiments, the quantitative shift of the polymer 15 is greater than about 98 wt%, in some embodiments, the quantitative shift of polymer is greater than about 99 percent by weight.

In some embodiments, the polymer that embodies the properties of the present guidelines has a vinyl content of between about 35 and about 83 percent by weight of the quantitative amount of 1,3-butadiene. In some embodiments, the vinyl content ranges from about 43 to about 75 percent by weight.

33 In some process embodiments according to current guidelines, potassium alcoholate includes

. potassium-3,7- dimethyl 3-octylate

In some process models, according to the current guidelines, the molar ratio between the polar agent and potassium alcoholate ranges between about 23:1 and about 1:5.

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

It is currently preferred that processes take place with a polymerization of a polymer according to current guidelines in solvents, with hydrocarbon solvents currently being preferred. In some embodiments, the polymerization solvent includes an alkane. In some embodiments, . includes

5 The polymerization solvent based on cyclohexane, in some embodiments, includes

Additional alkane with cyclohexane blinding mixture of polymerization solvent

one or more.

Also for general introduction, the polymer is formed according to the present guidelines with a process of the type described herein.

13 In some embodiments, chemical modification of a live polymer can be made according to the current guidelines using sesamoid tip modification and/or coupling reactions. The appropriate adjusting agents for the separator tip and/or coupling agents can be selected according to the intended use and the filler. Examples of coupling agents include, but are not limited to, the following: tin tetrachloride, divinylbenzene, silicon tetrachloride, alkoxysilanes, and the like, and combinations

15th Minya.

Examples of modifying agents include, but are not limited to, the following: amines, amides, silicon alkoxides, thioglycols, silane-sulfide modifiers, sulfenyl halides as described in EO 1316674, isocyanate, benzophenone, hydroxyl cap As described in 33 EC 3464478, acrylamide compounds as described in EC 3224343, etc., and combinations thereof. Additional modifiers include, but are not limited to, the following: amines, amides, amides, and nitriles as described in Document EC 548799, EC 513413, EC 451634, and EC 183141, and in see

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American No. 4413341. In some embodiments, silanes including, but not limited to, epoxy-containing silanes are used to modify the polymer chain tip for use in silica fillers as described, for example, in the order document European Application No. A-399374, European Application No. A-133345, Application

5 European Application No. 3447366, and European Application No. 3693492. Additional examples of Articles of the Amendment and/or references to opinions referring to these Articles are in International Application Document No.

124665/3339.

By way of general introduction also, the composition embodying the properties of the present instructions contains a polymer of the type described herein. In some embodiments, the composition according to current guidelines also contains

13 Blinding additives, such as oil. In some embodiments, the composition according to the current guidelines also contains oil in an amount between about 5 and about 43 percent by weight of the total weight of the polymer. In some embodiments, the composition according to current guidelines does not contain oil.

In some embodiments, a composition according to the present instructions contains a polymer of the type described herein and at least one additive. In some embodiments, the polymer is incorporated and/or reacted with a material

15th One or more fillers, a vulcanization agent, and/or optionally one or more other additives including, but not limited to: accelerators, coupling agents, uncrosslinked elastomeric polymers that are not with crosslinks (i.e., conventional elastomer polymers that do not have crosslinks and that have not reacted with a modified material, but have been prepared and finished), etc.

33 Shabu, and Minya combinations.

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

35 and magnesium carbonate, and shabu, and minya combinations. In some embodiments, a combination of black

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Carbon black and silica, and dual-phase fillers of carbon and silica or a combination of a dual-phase filler of carbon, silica, carbon black and/or silica are used.

In some models, carbon black is manufactured by the oven method, and it has space

5 The surface quality of nitrogen adsorption ranged between about 53 and about 333 m 3 / g, and DBP oil absorption was between about 83 and about 333 ml / 133 g (such as FEF, ISAF, HAF or carbon black of the SAF class). embodiments, “highly agglomerated type” carbon black is used. In some embodiments, carbon black or silica is added in an amount ranging from about 3 to about 133 parts by weight for every 133 parts by weight of

13 For quantitative polymer, in some embodiments, carbon black or silica is added in an amount between about 5 and about 133 parts by weight, in some embodiments, carbon black or silica is added in an amount between about 13 and about 133 parts by weight. In some embodiments, carbon black or silica is added in an amount ranging from about 13 to 95 parts by weight.

Finally, also for general presentation, a product embodying the properties of the current guidelines contains at least one 15 component of this formulation, in some embodiments, the product being a frame. in a

In some models, the product is a component of the shoe.

The following examples and procedures illustrate the characteristics according to the current guidelines, and are provided only for the sake of illustration. This offense is not intended to limit the scope of the applicable elements of protection or their equivalent.

the sinners

33 The monomer shift was determined by measuring the solids concentration of a polymer carrier at the end of the polymerization of a polymer lane. The maximum solids concentration is obtained at 133 wt. Convert charged butadiene (mBd) and styrene (mSt) to the final polymer according to the equation:

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TSC max= (mBd+ mSt)/(mBd+ mSt + mpolar agent + mBL+

(mcyclohexane*100: A sample of a polymer cell ranging from about 1 g to about 13 g, according to the expected conversion of a monomer, was drawn from the reactor directly into a 333 mL Erlenmeyer flask filled with 53 mL ethanol). The weight of the filled Erlenmeyer flask was determined before 5 Sampling (“A”) and after sampling (“B”). The precipitated polymer from ethanol was removed by filtration on a weighted paper filter (a sheet of fine fiberglass, 93 mm diameter, MUNKTELL, weight “C”). , and dried at 143 °C, using a moisture loading device

Mettler-Toledo (HR73 moisture analyzer) until a constant weight is reached. Criterion 5 was used. Finally, a second drying period was carried out using closing criteria 4 to obtain the final 13 mass “D” of the dry sample on the filter paper. The polymer content was calculated in The sample is as follows:

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

The final transformation of the polymer was calculated as 100*TSC/TSC max:

Both the molecular weight and molecular weight distribution of the polymer were measured using the Arvia size-exclusion chromatogram (SEC) based on standard levels of polystyrene. Each polymer sample 15 (9-11 mg) was dissolved in 13 ml tetrahydrofuran) to make a portable. The cell was filtered

solution was filtered using a 3.45 µm filter. A 133 µl sample was fed to a Hewlett Packard system 1100 GPC column with 13 3 µm PLgel columns MiXED-B at 43 °C). The Refraction Index direction was used.

detection as the detector for analyzing the 33 molecular weight. The molecular weight was calculated as HR polystyrene based on titration with

Polymer of polystyrene EasiCal PS1 Standard Levels (Easy A and B)

Laboratories. The values ​​of the mean molecular weight according to the polystyrene (Mn) and the values ​​of the mean molecular weight according to the weight (Mw) are given based on the standard levels of polystyrene. The molecular weight distribution is expressed as the degree of dispersion D = Mw/Mn dispersity.

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Vinyl content and styrene content were quantified using 1H-NMR,

Following ISO 2005-21561, using a BRUKER Avance 433MHz NMR spectrophotometer, 5 mm duplex probe. CDCl3/TMS was used as a solvent by weight of 3.35:: 99.95:. The styrene content of more than 6 was determined. units

Rubber Chemistry in Y. Tanaka et al, Sequential according to the method that memory styrene 5 ortho using relative strength signals and Technology, 1981, 54, No. 4, 685-691

Ph-proton giving a resonance at a blinding value of 6.7 per million, the content of a styrene block of 4 or more consecutive styrene units was determined according to the method explained in German patent document No. 69713963 using the relative strength of the ortho Ph-proton signs that

13 Raneena gives a range between 6.94 and 6 per cent. The content of a styrene block that ranged between 4 and 6 successive units of difference between each of the previous styrene block contents was annotated.

Comparative Example 13: (KDMO use) K-3,7-dimethyl-3-octylate or K below)

(hexanes 53: in)

15th 5276.55 g of dried cyclohexane was added to a 13 L nitrogen-purged, stainless steel reactor. 236.17 g of 432.72, 1,3-butadiene g of styrene, and 3.382 mmol of (53,7-dimethyl-3-octylate: K-3,7-dimethyl-3-octylate: in heptane) were fed to the reactor (active K/butyl lithium mol/ mol = 3.376). The mixture was heated to 53°C with agitation. Done

33 Calibrate the impurities in the system by adding butyl lithium in batches. When the end point was checked, the polymerization of a polymer was started by adding the quantitative amount of 1.466 mmol of (15 n-butyllithium: carried in cyclohexane) using a pump during 1 min 19 sec. The process was then started by the polymerization of a polymer. The temperature in the reactor was increased by 65°C during 23 minutes The reaction was terminated after 333 minutes by adding methanol

35 As a stopping agent, IRGANOX 1520 was introduced as an antioxidant.

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A sample was taken with a sampling tube fitted with a stopcock stopper and a needle to determine the solids content. The shift ratio of TPMG was measured as 99.57:. The resulting polymer was loaded with D = 1.364, Mw = 674699, and GPC: Mn = 522626. The microstructure and styrene block content were measured using 1H-NMR. The following results were obtained: styrene

5 = 55.3:, 1,2-polybutadiene (vinyl), calculated on the basis of the ratio of 13.2 (butadiene)

:, opaque citrine styrene block bu more than 4 units = 83 styrene:, and opaque citrine styrene block bu more than 6 units = 29 styrene:.

Comparative Example No. 11: (Use: 53) K-3,7-dimethyl-3-octylate in (hexanes)

5239.39 g of cyclohexane was added dried to a clean-air reactor and washed 13 L with nitrogen-purged, from a stainless steel.

fed with 235.28 g of 298.37, 1,3-butadiene g of styrene, and 3.5311

mmol of (53,7-dimethyl-3-octylate: K-3,7-dimethyl-3-octylate in heptane) to the reactor (active K/ butyl lithium mol/mol = 3.28).

The mixture was heated to 53°C with stirring. The impurities in the system were titrated by adding butyl

15th lithium uncle batches. Upon verification of the end point, the polymerization of . is initiated

a polymer by adding the quantitative amount of 1.326 mmol of 15 (n-butyllithium: portable

in cyclohexane) using a pump during 1 min 53 sec. The polymerization of a polymer was then started. The temperature in the reactor was raised 65°C during 23 min.

The reaction was terminated after 144 min by adding methanol as a stopping agent, IRGANOX . was introduced

33 1520 as an antioxidant.

A sample was taken with a sampling tube fitted with a stopcock stopper and a needle to determine the solids content. The TPMG shift ratio of 99.18:, was measured.

The resulting polymer was loaded with D = 1.637, Mw = 823735, and GPC: 513426 = Mn.

The microstructure and styrene block content were measured using 1H-NMR. It was completed

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The following results were obtained: polybutadiene-2,1 (vinyl,: styrene = 53.2, calculated on the basis of the ratio of 34.2 =) butadiene: styrene block, which has more than 4 units styrene = 64, and styrene block which has more than 4 units from 6 units

.: 33 = styrene

5 Example 15: (Using 53 K-3,7-dimethyl-3-octylate: (in DOP/hexanes)

5233.55 g of cyclohexane were drained into a nitrogen-purged 13 L nitrogen-purged reactor and fed to 234.98 g of 433.63 g of styrene, 3.5351 mmol. of 53 (k-3,7-dimethyl-3-octylate: at 3.4837), heptane

13 mmol DOP to the reactor (K/ active butyl lithium mol/mol = 3.259, butyl /DOP lithium active 3.241). The mixture was heated to 53 °C with stirring, the impurities in the system were calibrated by adding butyl lithium in batches. When checking point The end polymerization of a polymer was initiated by adding a quantitative amount of 1.4386 mmol of n-15 (butyllithium: carried in cyclohexane) using a pump during 1 min 22 sec.

15th Then a process of polymerization of a polymer began. The temperature in the reactor rose to 65°C within 23 minutes. The reaction was terminated after 333 minutes by adding methanol as a stopping agent. IRGANOX 1520 has been introduced as an antioxidant. A sample was taken with a sampling tube fitted with a stopcock stopper and a needle to determine the solids content. The TPMG shift ratio of 99.11: was measured. The resulting polymer was loaded using 533396=Mn :GPC,

33 D = 1.479, Mw = 743517. Microstructure and styrene content were measured

block by 1H-NMR. The following results were obtained: vinyl,: 55.5 styrene = 1,2-polybutadiene, calculated on the basis of the ratio of (butadiene = 43), styrene block, which has more than 4 units, styrene = 73:, and styrene block that contains More than 6 units.: 34 = styrene

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Example 16: (use 53) K-3,7-DIMETHYL-3-OCTYLATE: (in hexanes/

(DOP .)

5239.39 g of cyclohexane was dried and dried to a 13 L nitrogen-purged, stainless steel reactor was added.

5 235.28 g of 298.37, 1,3-butadiene g of 3.1365, styrene (53 mmol of K-3,7-DIMETHYL-3-OCTYLATE: in heptane), and 3.4837 mmol of DOP were fed to the reactor (butyl lithium). /K active mol/mol=3.1, /butyl DOP

Active lithium mol/mol = 3.298). The mixture was heated to 53 °C with stirring. The impurities were titrated in the system by adding butyl lithium in batches. When the end point was checked, the polymerization of a polymer was started by adding the quantitative amount of 1.3266 mM. mole of (15 n-butyllithium: carried in cyclohexane) using a pump during 1 min 53 sec. The polymerization of a polymer was then started. The temperature in the reactor was raised 65 °C during 23 minutes, the reaction was terminated after 133 minutes by adding methanol as a stopping agent, IRGANOX 1520 was introduced as an antioxidant, and sample 15 was taken with a sampling tube fitted with a stopcock stopper and a needle to determine the content of substances

bulge. The TPMG shift ratio of 99.18: was measured. The resulting polymer was loaded with GPC: D = 1.226, Mw = 813267, and 636718 = Mn. The microstructure and styrene block content were measured using 1H-NMR. The following results were obtained: 54.4 = 1,2-polybutadiene (vinyl) styrene, computed on the basis of the ratio of 27.6 =)butadiene:, citrine 33 blocky styrene block which has more than 4 units 73 = styrene block, and styrene block which bu more than 6 units = 34 styrene:.

Example 17: (use 53) k-3,7-dimethyl-3-octylate: (in DOP/)hexanes

1 534 1.7 g of cyclohexane dehydrated was added to an air-free reactor

Nitrogen-purged 13 liter capacity, stainless 35 23148 ​​stainless steel. steel g of 298.35, 1,3-butadiene g of 3.1198, styrene mm

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mol of (53 k-3,7-dimethyl-3-octylate: in heptane), 1.1846 mmol DOP was fed to the reactor (active butyl lithium /K mol/mol=3.387, active butyl /DOP lithium mol/mol= 3.894). The mixture was heated to 53°C with stirring. The impurities in the system were calibrated by adding butyl lithium in batches, when the end point was checked the start was made.

5 The polymerization of a polymer lane was started by adding the quantitative amount of 1.2816 mmol of (15 n-butyllithium: carried in cyclohexane) using a pump during 1 min 53 sec. °C within 23 minutes, the reaction was terminated after 133 minutes by adding methanol as a stopping agent, 1520 IRGANOX was introduced as an antioxidant.

13 Use a sampling tube with a stopcock stopper and a needle to determine the solids content. The TPMG shift ratio of 99.58: was measured. The resulting polymer was loaded with GPC: D = 1.346, 733763 = Mw, 557938 = Mn. The microstructure and styrene block content were measured by 1H-NMR. The following results were obtained: 54.5 = styrene 1,2-polybutadiene (vinyl, calculated on the basis of the ratio of 53 =)butadiene:, citrine

15th opaque styrene block bu more than 4 units = 86 styrene:, and opaque styrene block bu over 6 units = styrene:.

Example 18: (use 53) K-3,7-dimethyl-3-octylate: (in DOP/hexanes)

5244.72 g of dried cyclohexane was added to a 13 L nitrogen-purged, stainless steel reactor.

33 237.57 g of 18,431, 1,3-butadiene g of 3.1333, styrene mmol of

(53 K-3,7-dimethyl-3-octylate: in heptane), 2.521 mmol DOP was fed to the reactor (active butyl lithium /K mol/mol = 3.133, active butyl lithium /DOP mol/mol-3.948) The mixture was heated to 53 °C with stirring The impurities were titrated in the system by adding butyl lithium in batches When the end point was checked the polymerization of a polymer 35 was started by adding the quantitative amount of 1.1978 mmol of -n

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(15) butyllithium: carried in cyclohexane) using a pump during 1 min 46 sec, then a polymerization of a polymer lane process was started. The CC65 reactor was heated up within 23 min. The reaction was terminated after 333 min by adding methanol as a stopping agent. 1520 was introduced. IRGANOX as an antioxidant A sample was taken with 5 sampling tubes fitted with a stopcock stopper and a needle to determine the solids content.

Measurement of the TPMG shift ratio of 99.12:. The resulting polymer was loaded with GPC = 659395, D = 1.374, Mw = 859395. The microstructure and styrene block content were measured using 1H-NMR. The following results were obtained: vinyl,: 1,2-polybutadiene = 55.1 styrene, calculated on the basis of the ratio of 62.9 = (butadiene), styrene block 13 styrene block with more than 4 units styrene = 66, and styrene block: styrene block with more of 6 units 19 = styrene:.

Example 19: (use of 53 k-3,7-dimethyl-3-octylate: (in DOP/hexanes)

5417 g of dried cyclohexane was added to a 13 L nitrogen-purged, stainless steel reactor.

15th 233.38 g of 271, 1,3-butadiene g of 3.113, styrene mmol of 53 k-3,7-dimethyl-3-octylate: in heptane), and 1.14 mmol of DOP were fed to the reactor (butyl lithium/ Active K mol/mol = 3.135, active butyl lithium /DOP mol/mol-1.367). The mixture was heated to 73 °C with stirring. The impurities in the system were calibrated by adding butyl lithium in batches. When checking the end point the polymer corridor was started 33 polymerization of a polymer by adding the quantitative amount of 1.37 mmol of -n

(15) butyllithium: carried in cyclohexane) using a pump during 23 seconds. The polymerization of a polymer was then started. The temperature was kept constant in the reactor at 73 °C. The reaction was terminated after 133 minutes by adding methanol as a stopping agent. Introduced IRGANOX 1520 as an antioxidant A sample was taken with a 35 sampling tube fitted with a stopcock stopper and a needle to determine the solids content.

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Transformation of TPMG 98.88:. The resulting polymer was loaded with Mw, 672383-Mn: GPC = 883836, D = 1.238. The microstructure and styrene block content were measured using 1H-NMR. The following results were obtained: 1,2-(vinyl,: 55.6 = styrene polybutadiene, calculated on the basis of a ratio of 43.6 =) butadiene:, a 5-styrene block citrine with more than 4 units, 52 = styrene:, and a styrene block with more From 6 units 13 = styrene:.

Example 33: (use of 53 k-3,7-dimethyl-3-octylate: (in DOP/hexanes)

5287 g of dried cyclohexane was added to a 13 L nitrogen-purged, stainless steel reactor.

13 433.53 g of 368, 1,3-butadiene g of 3.111, styrene (53 mmol of 3.7-dimethyl-3-octylate: in heptane), and 1.117 mmol of DOP were fed to the reactor (butyl lithium). Active K mol/mol = 3.389, active butyl lithium /DOP mol/mol = 3.889). The mixture was heated to 73 °C with stirring, the impurities were titrated in the system by adding butyl lithium in batches. When checking the end point was started with a streak 15 polymerization of a polymer by adding the quantitative amount of 1.36 mmol of -n

(15) butyllithium: carried in cyclohexane) using a pump during about 23 seconds. The polymerization of a polymer was then started. The temperature was kept constant in the reactor at 73 °C. The reaction was terminated after 93 minutes by adding methanol

as a stopping agent. IRGANOX 1520 has been introduced as an antioxidant. Sample 33 was taken with a sampling tube fitted with a stopcock stopper and a needle to determine the solids content. TPMG conversion ratio: 99.95 was measured. The resulting polymer was loaded with GPC: D = 1.356, Mw = 761925, and Mn = 636718. The microstructure and styrene block content were measured using 1H-NMR. The following results were obtained: 43.7 = styrene 1,2-polybutadiene (vinyl, calculated on the basis of the ratio of 43 = (butadiene):, citrine

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mute styrene block whose bu is more than 4 units 42 = styrene:, and mute styrene block whose bu is more than 6 units = 7 styrene:.

Example 31: (Use of 53 k-3,7-dimethyl-3-octylate: (in DOP/hexanes)

Shipped 18,787 g of cyclohexane was dehydrated in an airless and washed reactor

<p>5 Nitrogen-purged 43 liter capacity, from stainless steel. 3242 g of 56,939, 1,3-butadiene was fed 1.692 mmol of styrene (53 mmol of K-3,7-dimethyl-3-octylate: in heptane), and 2.294 mmol of DOP to the reactor) butyl lithium /K active mol/mol = 3.396, butyl lithium /DOP active mol/mol = 3.193). The mixture was heated to 85 °C with stirring. The impurities were titrated in</p>

<p>13 The system was added by butyl lithium in batches. When the end point was checked, the polymerization of a polymer was started by adding the quantitative amount of 17.6 mmol of n-15 (butyllithium: carried in cyclohexane) by nitrogen pressure during 5 seconds. Then the polymerization of a polymerization process was started. The temperature was kept constant in the reactor at 65 ° C. The reaction was terminated after 63 minutes by adding methanol as an agent.</p>

<p>15th Discontinued, IRGANOX 1520 was introduced as an antioxidant. A sample was taken using a sampling tube fitted with a stopcock stopper and a needle to determine the solids content, a shift ratio of 99.67: The resulting polymer was loaded with GPC; 353673=Mn,</p>

D = 1.39, 375487 = Mw .

The microstructure and styrene block content were measured using 1H-NMR. 33 The following results were obtained, 1,2-polybutadiene (vinyl,: 38 = styrene, calculated on the basis of the ratio of 38.9 =) butadiene:, styrene block with more than 4 units, styrene = 45, and styrene block with more than 4 units. of 6 styrene units = 13:.

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The examples and comparative examples show that the current guidelines provide a butadiene-styrene copolymer with a targeted specific content of styrene that is more than 4 consecutive styrene units, in combination with a high quantitative content of styrene, the required vinyl content and a narrow molecular weight distribution. Using a process according to current guidelines, the polymeric pathway can be

5 The new and innovative features mentioned in the protections using standard pass-through technologies with high yield yield. All properties of polymers as disclosed herein are properties that precede any previous modifications, such as tip coverage, coupling, etc., as explained above. As a result of achieving the current guidelines for providing polymers with a narrow molecular weight distribution, a large amount of live cell ends can be obtained at the end of the polymerization of a polymer, so that a regular adjustment of the end of a polymer can be made.

13 Samsaha.

Invention No. 4

The present inventors surprisingly and unexpectedly discovered SSBR with a high percentage of styrene and a high percentage of vinyl with a narrow molecular weight distribution, embedding styrene in the form of blocks with more than 6 successive styrene units ranging between about 15 and about 25:

15th other as explained below. In some embodiments, SSBR which is high in styrene and high in vinyl also includes styrene in the form of successive masses of more than 4 styrene units ranging from about 63 to about 83 percent by weight.

Moreover, the present inventors have also discovered - surprisingly and unexpectedly - that it is possible to prepare the former SSBR explained with a high percentage of styrene and a high percentage of vinyl

2-(2-ethoxyethoxy)-2-like (dialkylethers and) butyl lithium 33 using a starter (such as

methylpropane) in combination with potassium alcoholate, in some embodiments under the following conditions: ≥25styrene content: by weight, molar ratio of potassium alcoholate/active initiator ≤3.4; polymerization of a polymerization temperature ≥ 93 °C.

In the context of the present invention, the following definitions must be taken into account:

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The term "polymer" refers in a broad sense to a substance prepared by passing polymerization of monomeric units. As used herein, the term “polymer” includes the terms “homopolymer” (a polymeric material prepared from one type of monomer), “copolymer” (a polymeric material prepared from two different types of monomers), and “interpolymer” (a polymeric material prepared from more than

Two different types of monomer (.

The term “alkyl group” refers to a straight, branched, or cyclic hydrocarbon chain, with or without substitution, preferably containing between 1 and 33 carbon atoms. Distinctive examples of alkyl groups that are not substituted for use according to the instructions

The current 13: methyl, ethyl, propyl, iso-propyl, includes the following, but is not limited to, and the like. , cyclopropyl, butyl, iso-butyl, tert-butyl, sec- butyl, cyclobutyl

The term "process" when used to refer to reactions in the polymerization of a polymer that include discontinuous, semi-continuous, and/or continuous processes. The term “non-continuous” or “semi-continuous” when used to refer to a by-pass process refers to a by-pass process

15th Charge of the solvent in the reactor along with the additional passive components before beginning the polymerization of a polymer with the initiator charge. The monomer may be charged immediately before initiator addition, partly before initiator addition, partly after initiator addition or continuously immediately after initiator addition over a period of time.

The term “continuous bypass” refers to a lane process in which the solvent, monomer(s), and any additional lane components are continuously pushed into a reactor in specified volume proportions. In some embodiments, two or more polymerization of a polymer lane reactors are used. polymers connected in series, in some embodiments, the reactor is driven into only one reactor,

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The term “vinyl content” refers to the percentage of muc (or weight) butadiene present at position 1, 3 in the polymerization, based on the butadiene fraction (the quantitative amount of butadiene polymerization) in the polymer.

The term “styrene content” refers to a percentage of the muted (or weighted) styrene in the polymer, based on the quantitative weight of the polymer.

The term “styrene block citrine content” refers to a weight ratio of styrene present in successive sequences of styrene units based on the quantitative amount of citrine that is incorporated into the polymerized styrene in the polymer.

The term "composition" refers to a mixture of materials including a polymer and, optionally, reaction products and/or 13 products bearing a component of the polymer material.

The term “active initiator” (nBL,pm) refers to the molar amount of an initiator (such as an organ lithium compound) that participates in a reaction in a polymerization reaction that has not been damped by impurities in the reaction medium. The term “initiator not excess” (nBL, exc) indicates the molar quantity of the initiator that is charged to dampen the impurities in the system.

15th the system, the expression “quantitative amount from the monomer feed stream” refers to the quantitative amount of styrene and butadiene, in g/min, driven into a continuous bypass reactor and, typically, in a first continuous polymerization of a polymer reactor,

The term “polymer quantitative transformation” refers to the final transformation of a polymer (such as the total final transformation of a polymer of styrene and butadiene) which is determined by the last reactor bypass and/or at the end of 33 reactions in a polymerization reaction.

As a general introduction, a polymer that embodies the properties of the present guidelines will have at least the following properties; (a) a styrene block styrene content containing more than 6 consecutive styrene units between about 15 and about 25 wt% of the total styrene content in the polymer; (b) a vinyl content of between about 35 and about 83 wt% of the qty

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of 1,3-butadiene; (c) a styrene content of between about 25 and about 75 percent by weight of the total weight of the polymer; and (d) a molecular weight distribution of 1.5 or less, in some embodiments, of the polymer in accordance with current guidelines also with at least the following additional properties: (e) (content of a styrene block containing more than 4 consecutive styrene units between about

5 83 and about 83 percent by weight of the quantitative content of styrene in the polymer.

In some embodiments, a polymer that embodies the properties of the present guidelines has a styrene block content of more than 6 styrene units in series between about 33 and about 23 percent by weight of the quantitative styrene content in the polymer.

In some embodiments, the polymer that embodies the properties of the present guidelines has a quantitative level of 13 for styrene ranging from about 43 to about 65 percent by weight, in some embodiments between about 53

and about 63 percent by weight.

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

15th In models, the molecular weight distribution is between about 1.1 and about 1.4. In some embodiments, the molecular weight distribution is between about 1.3 and about 1.25.

In some embodiments, the polymer is produced in a continuous process according to current guidelines.

In some embodiments, a polymer that embodies the properties of the present guidelines has an average molecular weight greater than or equal to and about 333333 g/mol. In some embodiments, the weight is

33 Molecular mean according to the number greater than or equal to and about 233,333 g/mol. In some embodiments, the mean molecular weight according to the polymorph is greater than or equal to and is about 533,333 g/mol.

In some embodiments, a polymer that embodies the properties of the present guidelines has an average molecular weight greater than or equal to and about 233,333 g/mol. In some embodiments, the weight is

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Molecular mean according to weight greater than or equal to about 433,333 g/mol. In some embodiments, the mean molecular weight according to weight is greater than or equal to and about 633,333 g/mol.

All previous models shall be explained in accordance with what has been disclosed in any combination, including combinations of the currently preferred models.

5 For a general introduction also, a process for the polymerization of a polymer includes

1,3-butadiene monomer and styrene monomer are derived from monomeric units

According to current guidelines, it contains monomeric units in the presence of a starter, potassium alcoholate and dialkylether.

In some embodiments, the molar ratio between dialkylethers and the active initiator is greater than

13 3.5. In some embodiments, the molar ratio between dialkylethers and the active initiator ranges between about

3.5 and about 13.

In some embodiments, the styrene content in the monomer mixture added in the polymerization of a polymer is greater than about 25 wt% of the quantitative weight of the added monomer.

15th In some embodiments, a bypass process is performed according to current guidelines at a temperature of less than about 93°C. In some embodiments, a bypass operation is performed according to current guidelines at a temperature between about 13°C and about 83°C,

Initiators currently preferred for use according to current guidelines include those suitable for anionic polymerizations, in some embodiments, the initiator according to

33 The current guidelines are an organ lithium compound (such as alkyl lithium). Examples of alkyl lithium-s for use according to current guidelines include, but are not limited to: -n n-pentyl lithium, butyl lithium -t, butyl lithium-s, butyllithium, and the like , and minea combinations, in some embodiments, include the initiator n-butyllithium

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In some embodiments, the shift quantum of the polymer is greater than about 96 wt% of the quantum amount of the monomer feed stream, in some embodiments, the shift quantum of the polymer is greater than about 98 wt% In some embodiments, the shift quantum of the polymer is greater than about 99 percent by weight.

5 In some embodiments, the polymer that embodies the properties of the present guidelines has a vinyl content of between about 35 and about 83 percent by weight of the quantitative amount of 1,3-butadiene. In some embodiments, the vinyl content ranges from about 23 to about 75 percent by weight.

In some embodiments of the process according to current guidelines, potassium alcoholate includes potassium-2, 7-di-2-methyl-octylate.

13 In some process models according to current guidelines, the molar ratio between dialkylethers and potassium alcoholate is between about 43:1 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 of a polymer processes according to current guidelines occur in solvents, with hydrocarbon solvents being preferred. Currently, in some embodiments, the polymerization solvent comprises an alkane. In some embodiments, the polymerization solvent includes cyclohexane. In some embodiments, . includes

Additional alkane with cyclohexane blinding mixture of polymerization solvent

one or more.

Also for general introduction, the polymer is formed according to current guidelines with a process of the type 33 described here.

In some embodiments, chemical modification of a live polymer can be made according to current guidelines using sesamoid tip modification and/or coupling reactions. Appropriate adjusting agents for the separating tip and/or coupling agents can be selected according to the intended use and the filler. Examples of coupling agents include, but are not limited to: tin tetrachloride,

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divinylbenzene, silicon tetrachloride, alkoxysilanes, etc., and mina combinations.

Examples of modifiers include, but are not limited to: amines, amides, silicon alkoxides, thioglycols, silane-sulfide modifiers.

5 sulfenyl halides, as described in European Application Document No. 1316674,

isocyanate, benzophenone, hydroxyl mercaptans as described in EO Document No. 3464478, acrylamide compounds as described in EO No. 3224343, etc., and combinations thereof. Additional modifiers include, but are not limited to, the following: amines, amides, amides, and modifiers.

13 Nitrile as described in EC No. 548799, EUR No.

513413, EC No. 451634, EC No. 183141, and US Patent No. 4413341. In some embodiments, silanes including but not limited to the following are used: epoxy-containing silanes to modify the polymer chain linkage for use in silica fillers as explained,

15th For example, in EC-A-399374, EC-A-133345, EC 3447366, and EC 3693492. Additional examples of Amendment Articles and/or references to opinions referring to these articles are in International Request Document No. 124665/3339.

Also for general presentation, the composition that embodies the properties of the present guidelines contains 33 polymers of the type described herein. In some embodiments, the composition contains according to current guidelines

Also containing additives, such as oil. In some embodiments, the composition according to current guidelines also contains oil in an amount ranging between about 5 and about 43 percent by weight of the total weight of the polymer. In some embodiments, the composition according to current guidelines does not contain oil.

In some embodiments, a composition according to the present guidelines contains a polymer of the type described herein 35 and at least one additive. In some embodiments, the polymer is incorporated and/or reacted with a material

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One or more fillers, a vulcanization agent, and/or optionally one or more other additives including, but not limited to: accelerators, coupling agents, uncrosslinked elastomeric polymers that are not It has crosslinks (i.e., conventional 5 elastomer elastomers that do not have crosslinks and that have not reacted with a modified material, but that 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. Distinctive examples of suitable fillers include, but are not limited to: carbon black, silica, dual-phase filler 13 carbon and silica, magnesium carbonate, calcium carbonate, clay,

What Shabu, and Minya combinations. In some embodiments, a combination of carbon black and silica, a dual-phase filler with carbon and silica or a dual-phase filler combination of carbon, silica, carbon black and/or silica is used.

15th In some embodiments, carbon black is manufactured by a furnace method, and if the surface area of ​​nitrogen adsorption is between about 53 and about 333 m 3 / g, and the DBP oil absorption is between about 83 and about 333 ml / 133 g (such as FEF). In some embodiments, “highly agglomerated” carbon black is used, in some embodiments, the addition of

33 carbon black or silica in an amount ranging from about 3 to about 133 parts by weight for every 133 parts by weight of the quantitative polymer. In some embodiments, carbon black or silica is added in an amount ranging from about 5 to about 133 parts by weight. In some embodiments, carbon black or silica is added in an amount ranging from about 13 to about 133 parts by weight, in some embodiments, carbon black or

35 silica in an amount ranging from about 13 to 95 parts by weight.

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Finally, also for general presentation, a product embodying the characteristics of the current guidelines contains at least one component of this composition, in some embodiments, the product being car tyres. In some embodiments, the product is an ingredient in the shoe.

5 The following examples and procedures illustrate the characteristics according to the current guidelines, and are provided only for the sake of illustration. This offense is not intended to limit the scope of the applicable elements of protection or their equivalent.

the sinners

The monomer shift was determined by measuring the solids concentration of the polymer solution at the end of the polymerization of a polymer, the maximum solids concentration at 133 was obtained: by weight the shift of charged butadiene (mBd) and styrene (mSt) to the final polymer 13 by the following relationship

TSC max- (mBd+ mSt)/(mBd + mSt + mpolar agent + mSL+

(mcyclohexane*100: A sample of a polymer cell ranging from about 1 g to about 13 g, according to the expected conversion of a monomer, was drawn from the reactor directly into a 333 mL Erlenmeyer flask filled with 53 mL ethanol). The weight of the filled Erlenmeyer flask was determined before

15th Sampling (“A”) and after sampling (“B”). Precipitated polymer was removed from ethanol by filtration on a weighted paper filter (Micro-glass, 93 mm diameter, MUNKTELL, weight “C”), and dried at 143 °C, using a moisture loader.

Mettier-Toledo (HR73 moisture analyzer) until a constant weight is reached. Criterion 5 was used.

33 Finally, a second drying period was carried out using 4 closing criteria to obtain the final mass “D”.

Dry sample on filter paper. The polymer content in the sample was calculated as follows:

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

The final transformation of the polymer was calculated as 100*TSC/TSC max:

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Both the molecular weight and molecular weight distribution of the polymer were measured using the Arvia size-exclusion chromatogram (SEC) based on standard levels of polystyrene. Each sample 9-11 (polymer) was dissolved in 13 ml (tetrahydrofuran) to make a carrier. The solution was filtered using a 3.45 µm filter. A 133 µm sample was fed.

5 Liters to GPC (1100) Hewlett Packard system column PO 3 3 µm PLgel columns (MiXED-B at 43 °C). Refraction Index direction was used.

detection as the detector for analyzing the molecular weight. The molecular weight was calculated as a polystyrene based on titration with

Polymer of polystyrene EasiCal PS1 Standard Levels (Easy A and B)

13 Laboratories. The values ​​of the mean molecular weight according to the polystyrene (Mn) and the values ​​of the mean molecular weight according to the weight (Mw) are given based on the standard levels of polystyrene. The molecular weight distribution is expressed as the degree of dispersion D = Mw/Mn dispersity.

Vinyl content and styrene content were quantified using 1H-NMR, by the ISO 21561-2005 method. Using a 433BRUKER Avance Mega . NMR Spectrophotometer

15th Hertz), and a 5 mm duplex probe. CDCl3/TMS was used as a solvent with a weight ratio of 3.35:: 99.95:. The styrene content of a styrene block consisting of more than 6 consecutive styrene units was determined according to the method by Y. Tanaka et al., in:

Using Rubber Chemistry and Technology, 1981, 54, No. 4, 685-691

The relative intensity of the ortho Ph-proton signal that gives a resonance at a blind of 6.7 ppm. The content of a styrene block consisting of 4 or more successive styrene units was determined according to the method described in German patent No. 69713963 using the relative intensities of the ortho Ph-proton signals that give a resonance ranging between 6.94 and 6 per million. The content of a styrene block consisting of between 4 and 6 successive units was calculated from the difference between each of the previous styrene block contents annotated.

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Comparative Example No. 13: (K-3,7-dimethyl-3-octylate) or K (KDMO usage hereinafter) (53: in hexanes)).

5276.55 g of cyclohexane was dried and dried to a 13 L nitrogen-purged nitrogen-washed reactor was added to a stainless 5 steel reactor. fed with 236.17 g of 432.72, 1,3-butadiene g of styrene,

and 3.382 mmol of (53 K-3,7-dimethyl-3-octylate: 53 K) in heptane (to the active butyl lithium /K reactor mol/mol = 3.376).

The mixture was heated to 53°C with stirring. The impurities in the system were titrated by adding butyl lithium in batches. When checking the end point, the polymerization of 13 a polymer was started by adding the quantitative amount of 1466 mmol of 15 (n-butyllithium: carried

in cyclohexane) using a pump over 1 minute 19 seconds.

Then a process of polymerization of a polymer began. The temperature in the reactor rose to 65°C within 23 minutes. The reaction was terminated after 333 minutes by adding methanol as a stopping agent. IRGANOX 1520 has been introduced as an antioxidant.

15th A sample was taken with a sampling tube fitted with a stopcock stopper and a needle to determine the solids content. The shift ratio of TPMG was measured as 99.57:.

The resulting polymer was loaded with GPC; D, 674699 = Mw, 522626 = Mn = 1.364. The microstructure and styrene block content were measured using 1H-NMR. The following results were obtained: 1,2-polybutadiene (vinyl) = 55.3 styrene, 33 calculated on the basis of the ratio of (butadiene = 13.2), styrene block &lt;6 (styrene block &lt;6 (styrene block) units = 42, and styrene block &lt;4) styrene block sequential units(= 86 : -

Comparative Example 12: (Using 3-(3-CMX) ethoxyethoxy)-2-methylpropane)

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5266.99 g of cyclohexane was dried and dried into a nitrogen-purged 13 L stainless steel reactor. 235.97 g of 432.23, 1,3-butadiene g of styrene, and 2.6713 mmol of CMX were fed to the reactor (active butyl lithium /CMX mol/5 mol=3.57).

The mixture was heated to 53°C with stirring. The impurities in the system were titrated by adding butyl lithium in batches. When the end point was verified the polymerization of a polymer was started by adding the quantitative amount of 1.439 mmol of (15 n-butyllithium: carried in cyclohexane) using a pump over 1 min 47 sec.

. polymerization of a polymer 13

The temperature in the reactor increased by 65°C within 23 minutes. The reaction was terminated after 333 minutes by adding methanol as a stopping agent. IRGANOX 1520 has been introduced as an antioxidant

. antioxidant

A sample was taken with a sampling tube fitted with a stopcock stopper and a needle to determine the content of

15th Solids, conversion ratio of 98.35 TPM: measured.

The resulting polymer was loaded with D, Mw = 731914, GPC = Mn = 587297: 1.339. The microstructure and styrene block content were measured using 1H-NMR. The following results were obtained: 1,2-polybutadiene (vinyl) = 55.3 styrene, calculated on the basis of the ratio of 43.3 = (butadiene:, styrene block &lt;6 (styrene block 33 units) = 56, and lump citrine &lt;4 (styrene). block sequential units(= 71 :.

Example 33: (Using 53 K-3,7-dimethyl-3-octylate: (in CMX/hexanes)

5243 g of dried cyclohexane was added to a nitrogen-purged 13 L stainless steel reactor. fed with 234.48 g of 431.33, 1,3-butadiene g of styrene,

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3.1338 mmol of (53 K-3,7-dimethyl-3-octylate: in heptane), and 2.5544 mmol CMX to the reactor (active butyl lithium /K mol/mol = 3.391, active butyl lithium /CMX 3.8). The mixture was heated to 53 °C with stirring The impurities in the system were calibrated by adding butyl lithium in batches When the end point was checked the start was started

5 The polymerization of a polymer lane was started by adding the quantitative amount of 1.2317 mmol of (15 n-butyllithium: carried in cyclohexane) using a pump during 1 min 43 sec. 65 °C during 23 minutes, the reaction was terminated after 153 minutes by adding methanol as a stopping agent, IRGANOX 1520 was introduced as an antioxidant, a sample was taken

13 Use a sampling tube with a stopcock stopper and a needle to determine the solids content. The TPMG shift ratio of 99.62: was measured. The resulting polymer was loaded with GPC: D = 1.2, Mw = 783217, Mn = 631932. The microstructure and styrene block content were measured using 1H-NMR. The following results were obtained: 55 = 1,2-polybutadiene (vinyl) styrene, calculated on the basis of the ratio of 42.2 = (butadiene:, citrine)

15th styrene block 6 &lt; styrene block (= 38 : , styrene block 4 &lt; styrene block (= 75 : .

Example 32: (Using 53 K-3,7-dimethyl-3-octylate: (in CMX/hexanes)

5636.74 g of cyclohexane was dried and dried to a 13 L nitrogen-purged nitrogen-washed reactor was added to a 13 L stainless steel reactor.

33 steel . fed 317.6 g of 367.8, 1,3-butadiene g of styrene,

3.116 mmol of 53 K-3,7-dimethyl-3-octylate: in heptane), and 2.467 mmol of CMX to the reactor (active butyl lithium /K mol/mol= 3.3837, active butyl /CMX lithium 2.467). The mixture was heated to 53 °C with stirring Impurities were titrated in the system by adding butyl lithium in batches When the end point was checked, the polymer cycle was started.

35 polymerization of a polymer by adding the quantitative amount of 3.7 mmol of -n

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(15) butyllithium: carried in cyclohexane) using a pump during 53 seconds. Then a polymerization of a polymer lane process was started. The temperature in the reactor was raised to 65 °C within 23 minutes. The reaction was terminated after 133 minutes by adding methanol as a stopping agent. Introduced IRGANOX 1520 as an antioxidant A sample was taken by 5 sampling tubes fitted with a stopcock stopper and a needle to determine the solids content A shift ratio of 99.47 TPMG was measured:

The resulting polymer was loaded with D = Mw = 892869, Mn = 636994: GPC = 1.47, the microstructure and styrene block content were measured using 1H-NMR. The following results were obtained: 1,2-polybutadiene (vinyl,: 52.9 = styrene, 13 calculated on the basis of the ratio of 25.5 = (butadiene):, styrene block &lt; 6 (styrene block sequential units) = 39, and styrene block &lt; 4 (styrene). block sequential units(=74 :.

Example 34: (Using: 53K-3,7-dimethyl-3-octylate (in CMX/hexanes)

2568.39 g of cyclohexane was dried and dehydrated to a nitrogen-purged 13 L stainless steel reactor was added. fed with 294.2 g of 365.56, 1,3-butadiene g of styrene,

3.1132 mmol of (53 K- 3,7-dimethyl-3-octylate: in heptane), and 2.2314 mmol of CMX to the reactor (active butyl lithium /K mol/mol = 3.397, active butyl lithium /CMX 3.917). The mixture was heated to 73°C with stirring The impurities were titrated in the system by adding butyl lithium in batches When the end point was checked the polymerization of a polymer was started by adding the quantitative amount of 1.1216 mmol of 15 (n-butyllithium: portable). in cyclohexane) using a pump over 1 minute 53 seconds. Then a polymerization of a polymer process was started, the temperature was kept constant in the reactor at 73°C during the reaction. The reaction was terminated after 143 minutes by adding methanol as a stopping agent, IRGANOX 1520 was introduced as an antioxidant 35. Sample was taken with a sampling tube fitted with a stopcock stopper and a needle

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To determine the solids content, the TPMG shift ratio of 99.71: was measured. The resulting polymer was loaded with D = 1.445, Mw = 912473, and GPC: Mn = 623355, and the microstructure and styrene block content were measured using 1H-NMR.

The following results were obtained: 1,2-polybutadiene (vinyl.: 29.6 = styrene,

5 Calculated on the basis of a ratio of 23.4 = (butadiene: styrene block &lt;6 consecutive units) = 33:, and styrene block &lt;4: sequential units = 64:.

Example 35: (Using 53 K-3,7-dimethyl-3-octylate: (in CMX/hexanes)

5874.42 g of dried cyclohexane was added to a nitrogen-purged 13 L stainless steel reactor. 294.4 g of 367.73, 1,3-butadiene g of styrene, 3.1391 mmol of (53 K-3,7-dimethyl-3-octylate: in heptane), and 2.2226 mmol of CMX were fed to the reactor (butyl lithium). Active /K mol/mol=3.383, active butyl /CMX lithium 3.516). The mixture was heated to 53°C with stirring, the impurities in the system were titrated by adding butyl lithium in batches, when checking the end point was started by the polymer passage.

15th polymerization of a polymer by adding the quantitative amount of 1.235 mmol of n-15 (butyllithium: carried in cyclohexane) using a pump during 1 min 13 sec. Then the process of polymerization of a polymer was started. The temperature was kept constant in the reactor at 53 °C during reaction The reaction was terminated after 313 minutes by adding methanol as a stopping agent IRGANOX 1520 was introduced as an antioxidant 33 Samples were taken with a stopcock stopper and a needle to determine the solids content. The 98.34 TPMG shift ratio was measured:. The resulting polymer was loaded with GPC: D = 1.3355, Mw = 676792, Mn = 561837. The microstructure and styrene block content were measured using 1H-NMR, and the following results were obtained: styrene = 29.9:, 1,2-polybutadiene (vinyl, calculated on the basis of the ratio of (butadiene = 44):,

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13

15

styrene block &lt;6 (sequentially units) = 31:, and styrene block (&gt;4: sequential units) = 65:.

Examples and comparative examples show that the current guidelines provide a styrene-diene copolymer with a targeted specific content of styrene with more than 4 styrene units in sequence, in combination with a high quantitative styrene content, a required vinyl content and a narrow molecular weight distribution. Using a process according to current guidelines, the new and innovative polymers mentioned in the Protections can be passed using standard pass-through techniques with high yield yield. All properties of polymers as disclosed herein are properties that precede any previous modifications, such as tip coverage, coupling, etc., as explained above. As a result of achieving the current guidelines to provide polymers with a narrow molecular weight distribution, it is possible to obtain a large amount of the ends of the live layer at the end of the polymerization of a polymer, so that a regular adjustment of the tip of a polymer can be made.

The entire contents of each of the inventions and patent documents mentioned above are included for reference by reference to them, except that in the event of any order or definition inconsistent with the current specifications, the current disclosure or definition shall be considered the approved.

The foregoing detailed description has been provided for explanation and illustration, and it is not intended to limit the scope of the applied elements of protection. Many of the changes in the currently preferred models described here will be within the ability of the person with ordinary skill in the art, and will remain within the scope of the attached protections and their equivalents.

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