High styrene high vinyl styrene-butadiene rubber with narrow molecular weight distribution and methods for preparation thereof.

(54) Title: STYRENE-BUTADIENE RUBBER WITH HIGH STYRENE CONTENT AND HIGH VINYL CONTENT WITH A NARROW DISTRIBUTION OF MOLECULAR WEIGHT AND METHODS FOR THE PREPARATION OF THE SAME.

(54) Title: HIGH STYRENE HIGH VINYL STYRENE-BUTADIENE RUBBER WITH NARROW MOLECULAR WEIGHT DISTRIBUTION AND METHODS FOR PREPARATION THEREOF.

(57) Summary

A polymer having at least the following characteristics: (a) a block styrene content with more than 6 consecutive styrene units of from about 15 to about 35 weight percent based on the total styrene content in the polymer; (b) a vinyl content of from about 25 to about 80 percent by weight based on the total amount of polymerized 1,3-diene; and (c) a styrene content of from about 35 to about 75 percent by weight based on the total weight of the polymer; and (d) a molecular weight distribution (Mw / Mn) of 1.5 or less.

(57) Abstract

A polymer having at least the following characteristics: (a) a block styrene content with more than 6 consecutive styrene units from about 15 to about 35 weight percent based on total styrene content in the polymer; (b) a vinyl content from about 25 to about 80 weight percent based on total amount of polymerized 1,3-diene; and (c) a styrene content from about 35 to about 75 weight percent based on total weight of polymer; and (d) a molecular weight distribution (Mw / Mn) of 1.5 or less.

Mexican Institute of Industrial Property

<img file="MX345472B_D0001.tif" />

PATENT TITLE NO. 345472

<td>Headlines):</td><td>TRINSEO EUROPEGMBH</td>

<td>Home:</td><td>Zugerstrasse 231, CH-8810, Horgen, SWITZERLAND</td>

Denomination:

STYRENE-BUTADIENE RUBBER WITH A HIGH STYRENE CONTENT AND HIGH VINYL CONTENT WITH A NARROW DISTRIBUTION OF MOLECULAR WEIGHT AND METHODS FOR THE PREPARATION OF THE SAME.

Classification:

lnt.CI.8: C08F212 / 08; C08F236 / 10; C08L25 / 10; C08L9 / 06

Inventor (s):

EVEMARIE HAMANN, SILVIA VALENTI, G ABRI ELE HCLTZ

REQUEST

Number:

L MX / a / 2013/014879

International filing date of June 2012 -S

PRIORITY

Country:.

Date:

Number:.

June 2011 EP

11170966.3

Validity: Twenty years

Date of Vei | cimicMito: June 22, 2032

The reference patent is granted based on articles 1, 2, section V, and 6, section III. and 58 of the Industrial Property Law.

In accordance with Article 23 of the Industrial Property Law, this patent is valid for twenty years, renewable, starting from the date of presentation of the international application and will be subject to payment 0 * the tBffti to keep the "rights." g '_r

Whoever subscribes the owner does so based on the provisions of uM art chooses β ° HMKm&gt; s lll and 7 ° bis 2 of the Industrial Property Law (t * rio Oficial de la Federacion (D.o.F.) 27 / 0 &amp; 1W1 reform the 02λΜΠ9Μ 10/25/1996, 12/26/1987, 05/17/1999, ^ 01/26/2004, 06/16 / 200® 01/25/2006, 05/06/2009,06 / 01/2010, 1W98 / 20T0, 3k06faMA 27 «5í» O12 and 04/09/2012); articles J ·. 3 »section V Jnciso a), 4th and 12th sections I and III of the Regulations of the Industrial Property Institute (DOF 12/14/1999, amended on 07/1/2002, 07/15/2002) 07/2 ^ 4 and 7/09/2007); items 1^or, 3«, 4°, 5^or fraction V, subsection aj, 16 fractions I and III and 30 of the Organic E &amp; rtuto la PropfedaJtMus »tat (DOF 2W12fí8W, refWffíBte tí íOrtWl» 04/08/2004 and 1WO9 / 2007); one^or, 3rd and 5th subsection a) of the Agreement that delegates powers to the Deputy General Directors, Coordinator, Divisional Directors, Heads of Regional Offices, Divisional Deputy Directors, Departmental Coordinators and other subordinates of the Mexican Institute of Industrial Property. (DOF 12/15/1999, amended on 02/04/2000, 07/29/2004, 08/04/2004 and 09/13/2007).

Issue Date: February 1, 2017

<img file="MX345472B_D0002.tif" />

<img file="MX345472B_D0003.tif" />

IMPI ^{, nst}'i57'? - *^Ixican

OF INDUSTRIAL NOFI

<img file="MX345472B_D0004.tif" />

<img file="MX345472B_D0005.tif" />

HIGH STYRENE-BUTADIENE RUBBER

STYRENE AND HIGH VINYL CONTENT WITH DISTRIBUTION

NARROW MOLECULAR WEIGHT AND METHODS FOR THE PREPARATION OF THE SAME

Technical field

The present teachings generally refer to styrene-butadiene rubber based on a high-styrene-high-vinyl (SSBR) solution - particularly to high-styrene-high-vinyl SSBR with a narrow molecular weight distribution - and the methods for their preparation.

Background

High styrene, high vinyl SSBR is difficult to produce due to copolymerization kinetics. Typically, polar agents known as randomizers are added to the polymerization system to achieve random incorporation of styrene.

The use of certain randomization generators can result in a high vinyl SSBR with a lower block styrene content (&gt; 6 successive styrene units) below 10%. Long block styrene can worsen hysteresis as reported, for example, by S. Futamura and G, Day who observed a decline of approximately 18% from tangent.

IMPI

MEXICAN INSTITUTE OF THE ΝΟΕΙ INDUSTRIAL AGE

<img file="MX345472B_D0006.tif" />

delta at 60 ° C when the block styrene content increases from 2 to about 7% (Kautschuk Gummi Kunststoffe, 1987, 40, no. 1,

39-43) in a carbon black filled compound. In contrast, the incorporation of small blocks of styrene can result in improved abrasion and tensile strength, particularly in silica compounds, as reported by I. Hattori et al. (143^toMeeting of the ACS Rubbers Division, Spring 1993, page 22).

Potassium 3,7-dimethyl-3-octylate is described in US Patent No. 6,521,712 for the preparation of low-vinyl random soft blocks in block copolymers. Likewise, United States Patent No. 6,197,889 describes the use of potassium 3,7-dimethyl-3-octylate as a randomizer, in the two patents, the molecular weight of the resulting polymer is very low (range 3000-200,000 g / mol).

In United States Patent No. 3,294,768, the use of sodium and potassium alcoholates as randomness generators for low-vinyl SSBRs is reported. In United States Patent No. 3787,377, sodium potassium tert-amylate and mentholate are described in the context of continuous anionic polymerization, at a temperature of 110 to 125 ° C. United States Patent No. 5,916,962 describes a rubber compound conjugate, showing a broad molecular weight distribution of 1.7 or more after coupling with silicon tetrachloride. International Patent Publication No. WO 2004/016666 describes a method for producing polymers using conjugated dienes and vinyl compounds

OF INDUSTRIAL FIOriBTY aromatics. United States Patent —Dilm — _ 7 034 08.1 _______ Ja______ Publication of United States Patent Application No. 2003/0125476, and US Patent No. 6,841,648 describe the preparation of low styrene highly branched SSBR polymers.

In certain applications, it would be desirable to achieve a high vinyl high styrene SSBR with a defined incorporation of styrene as blocks of more than 6 consecutive styrene units with a narrow molecular weight distribution.

Brief description of the invention

The scope of the present invention is defined only by the appended claims and is not affected in any degree by the statements within this summary.

By way of introduction, a polymer incorporating the elements of the present teachings has at least the following characteristics: (a) a block styrene content containing more than 6 consecutive styrene units of from about 15 to about 35 percent by weight based on the total styrene content in the polymer; (b) a vinyl content of from about 25 to about 80 percent by weight based on the total amount of 1,3-butadiene polymerized; (c) a styrene content of from about 35 to about 75 percent by weight based on the total weight of the polymer; and (d) a molecular weight distribution D (Mw / Mn) of 1.5 or less.

A process for the polymerization of a polymer that comprises

IMPI

MEXICAN INSTITUTE DE LA PROrilDAD INDUSTRIAL monomeric units derived from a styrene monomer and a 1,3-butadiene monomer that embodies the characteristics of the present teachings includes polymerizing the monomeric units in the presence of an initiator, a potassium alcoholate and an ether compound organic selected from diakyl ethers of formula R¹-O-CH₂CH (R³) -OR², where R¹ and R² independently represent alkyl groups with 1 to 10 carbon atoms, R³ represents hydrogen, methyl or ethyl, and wherein the molar ratio of potassium alcoholate to active initiator is 0.4 mol / mol or less. In some modalities, R¹ is methyl or ethyl and R² it is a branched alkyl group which, in some embodiments, is t-butyl.

Detailed description

The present inventors discovered - surprisingly and unexpectedly - a high vinyl high styrene SSBR with a narrow molecular weight distribution, a block incorporation of styrene of more than 6 consecutive styrene units in the range of about 15 to about 35%, and with additional elements as described below. In some embodiments, the high styrene, high vinyl SSBR has additional styrene incorporation in blocks of more than 4 consecutive styrene units in the range of about 60 to about 80 weight percent.

Furthermore, the present inventors discovered - surprisingly and unexpectedly - that it is possible to prepare the above-described high styrene high vinyl SSBR using an initiator (eg butyl lithium) and a dialkyl ether (eg 2- ^ 2ethoxyethoxy ) -2-methylpropane) in combination with a potassium alcoholate. In some embodiments under the following conditions: styrene content s 35% w; molar ratio of potassium alcoholate / active initiator 0.4; and polymerization temperature &lt;90 'C.

Throughout this description and the appended claims, the following definitions are to be understood:

The term "polymer" broadly refers to a material prepared through the polymerization of monomer units. As used herein, the term polymer includes the terms homopolymer (polymeric material prepared from a single type of monomer), copolymer (polymeric material prepared from two different types of monomers), and interpolymer (polymeric material prepared from starting from more than two different types of monomers).

The phrase "alkyl group" refers to a linear, branched or cyclic, substituted or unsubstituted hydrocarbon chain containing preferably 1 to 20 carbon atoms. Representative examples of unsubstituted alkyl groups for use in accordance with the present teachings include but are not limited to methyl, ethyl, propyl, isopropyl, cyclopropyl butyl, iso-butyl, tert-butyl, sec-butyl, cyclobutyl, and the like.

The term process used in reference to polymerization reactions includes batch, semi-batch and / or

<img file="MX345472B_D0007.tif" />

IMPI

MEXICAN INSTITUTE

LF THE INDUSTRIAL PSOMIDAO CONTINUOUS.

The phrase discontinuous or semi-discontinuous used in reference to polymerization refers to a polymerization in which more than 80% of the solvent is charged into the reactor along with additional polymerization ingredients prior to initiating charge polymerization. The monomer can be charged all at once before the initiator addition, partially before the initiator addition, partially after the initiator addition, or simultaneously continuously after the initiator addition for a certain period of time.

The phrase "continuous polymerization" refers to a polymerization process in which the solvent, monomer (s), and any additional polymerization ingredients are continuously fed into a reactor at specific volumetric ratios. In some embodiments, two or more polymerization reactors connected in series are used. In some embodiments, the reactants are fed to only one reactor.

The phrase "vinyl content" refers to a percent by mass (or weight) of butadiene incorporated at the 1,2 position in the polymer chain, and is based on the portion of butadiene (total amount of polymerized butadiene) in the polymer.

The phrase "styrene content" refers to a percent by mass (or weight) of styrene in the polymer, and is based on the total weight of the polymer.

The phrase block styrene content refers to a

<img file="MX345472B_D0008.tif" />

weight fraction of styrene incorporated as consecutive sequences of styrene units based on the total amount of styrene polymerized in the polymer.

The term "composition" refers to a mixture of materials that include a polymeric material and, optionally, reaction products and / or decomposition products formed from the polymeric material.

The term active initiator (nBL.pm) refers to the molar amount of initiator (eg, organolithium) that takes part in a polymerization reaction and that is not deactivated by impurities in the reaction medium. The term "excess initiator" (nBL.exc) refers to the molar amount of initiator that is charged to deactivate impurities in the system.

The phrase "total amount of monomer fed" refers to the total amount of styrene and butadiene, in g / min, fed into a continuous polymerization reactor and, typically, the first continuous polymerization reactor.

The phrase "total monomer conversion" refers to the final monomer conversion (eg, the final sum of the styrene and butadiene conversion) determined by the last polymerization reactor and / or at the end of the polymerization reaction.

By way of general introduction, a polymer according to the present teachings has at least the following characteristics: (a) a block styrene content containing more than 6 consecutive styrene units from about 15 to about 35

Mexican ΜΡΙ r percent by weight based on to4ak content of styrene in the ..... polymer; (b) a vinyl content of from about 25 to about 80 percent by weight based on the total amount of

Polymerized 1,3-butadiene; (c) a styrene content of from about 35 to about 75 percent by weight based on the total weight of the polymer; and (d) a molecular weight distribution of 1.5 or less. In some embodiments, a polymer in accordance with the present teachings further has at least the following additional feature: (e) a block styrene content containing more than 4 consecutive styrene units of from about 60 to about 80 percent by weight based on the total styrene content in the polymer.

In some embodiments, a polymer in accordance with the present teachings has a block styrene content with more than 6 units of between about 20 and about 30 percent by weight based on the total styrene content in the polymer.

In some embodiments, a polymer in accordance with the present teachings has a total styrene content of between about 40 and about 65 percent by weight, in some embodiments between about 50 and about 60 percent by weight.

In some embodiments, the polymer is produced in a batch process, and in some embodiments, it is produced continuously. Currently, however, a batch process is preferred. The polymer according to the present teachings has a

<img file="MX345472B_D0009.tif" />

IMPI

MEXICAN INSTITUTE

FROM INDUSTRIAL PROPERTY molecular weight distribution (Mw / Mn) of 1.5 or less, such as from about 1.05 to about 1.45. In some embodiments, the molecular weight distribution is from about 1.1 to about 1.4. In some embodiments, the molecular weight distribution is from about 1.2 to about 1.35.

In some embodiments, a polymer is produced in a continuous process in accordance with the present teachings.

In some embodiments, a polymer in accordance with the present teachings has a number average molecular weight greater than or equal to about 200,000 g / mol. In some embodiments, the number average molecular weight is greater than or equal to about 300,000 g / mol. In some embodiments, the number average molecular weight is greater than or equal to about 500,000 g / mol.

In some embodiments, a polymer in accordance with the present teachings has a weight average molecular weight greater than or equal to about 300,000 g / mole. In some embodiments, the weight average molecular weight is greater than or equal to about 400,000 g / mol. In some embodiments, the weight average molecular weight is greater than or equal to about 600,000 g / mol.

All of the modalities described above are understood to be described in any combination, including combinations of the presently preferred modalities.

As a further general introduction, a process for

<img file="MX345472B_D0010.tif" />

<img file="MX345472B_D0011.tif" />

Polymerizing a polymer comprising monomeric units derived from a styrene monomer and a 1,3-butadiene monomer in accordance with the present teachings includes polymerizing the monomeric units in the presence of an initiator, a potassium alcoholate, and a dialkyl ether.

In some embodiments, a molar ratio of the first dialkyl ether to the active initiator is greater than about 0.5. In some embodiments, a molar ratio of dialkyl ether to active initiator is between about 0.5 and about 10.

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

In some embodiments, a polymerization in accordance with the present teachings is carried out at a temperature of less than about 90 ° C. In some embodiments, in accordance with the present teachings, a polymerization is conducted at a temperature of between about 10 ° C and about 80 ° C.

Initiators currently preferred for use in accordance with the present teachings include those suitable for anionic polymerizations. In some embodiments, an initiator for use in accordance with the present teachings is an organolithium (eg, alkyl lithium). Representative lithium alkyl agents for use in accordance with the present teachings include but are not limited to

<img file="MX345472B_D0012.tif" />

IMPI ^WrTVTOMfXI_DOG, '' • UJar to n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-pentyl lithium, and the like, and combinations thereof. In some embodiments, the initiator comprises n-butyl lithium.

In some embodiments, the total monomer conversion is greater than about 96 percent by weight based on the total amount of monomer fed. In some embodiments, the total monomer conversion is greater than about 98 percent by weight. In some embodiments, the total monomer conversion is greater than about 99 percent by weight.

In some embodiments, the polymer according to the present teachings has a vinyl content of from about 25 to about 80 percent by weight based on the total amount of 1,3-butadiene polymerized. In some embodiments, the vinyl content is from about 30 to about 75 percent by weight.

In some embodiments of a process according to the present teachings, the potassium alcoholate comprises potassium 3,7-dimethyl3-octylate

In some embodiments of a process in accordance with the present teachings, the molar ratio of dialkyl ether to potassium alcoholate is from about 40: 1 to about 5: 1.

The process according to the present teachings allows the preparation of the polymer as described in the present description.

Polymerizations in accordance with the present teachings are preferred herein to take place in solvents, hydrocarbon solvents are preferred herein. In some embodiments, the polymerization solvent comprises an alkane. In some embodiments, the polymerization solvent comprises a cyclohexane. In some embodiments, the polymerization solvent comprises a mixture of cyclohexane with one or more additional alkanes.

By way of a further general introduction, a polymer in accordance with the present teachings is formed by a process of a type described herein.

In some embodiments, a living polymer in accordance with the present teachings can be chemically modified by chain end modification and / or coupling reactions. Suitable chain end modifiers and / or coupling agents can be selected according to the target application and filler. Representative coupling agents include but are not limited to tin tetrachloride, silicon tetrachloride, divinylbenzene, alkoxysilanes, and the like, and combinations thereof.

Representative modifiers include but are not limited to amines, amides, thioglycols, silicon alkoxides, silanesulfide modifiers, sulfenyl halides as described in European Patent Document No. EP1016674, benzophenone isocyanate, hydroxyl mercaptans as described in European patent document no. EP0464478, acrylamide compounds as described in European patent document no. EP0334042, and the like, and combinations thereof. Additional modifiers include

IMPI

MEXICAN INSTITUTE

OS THE FROMSDAO

WUSTRIAL

<img file="MX345472B_D0013.tif" />

but not limited to modifiers of amines, amides, imides, and nitriles as described in European patent documents nos.

EP548799, EP510410, EP451604 and EP180141, and in the patent of

United States No. 4,412,041. In some embodiments, silanes including, but not limited to, epoxy-containing silanes are used to modify the end of the polymer chain for use in silica fillers as described, for example, in European Patent Nos. EP-A-299074, EP-A-102045, EP0447066, and EP0692493. Additional representative modifiers and / or patent references referring to these are provided in International Patent Document No. WO 2009/34665.

By way of a further general introduction, a composition incorporating the elements of the present teachings includes a polymer of a type described herein. In some embodiments, a composition in accordance with the present teachings further includes additives, such as an oil. In some embodiments, a composition in accordance with the present teachings further includes an oil in an amount of from about 5 to about 40 percent by weight based on the weight of the polymer. In some embodiments, a composition in accordance with the present teachings does not include an oil.

In some embodiments, a composition in accordance with the present teachings includes a polymer of a type described in the present disclosure and at least one additive. In some embodiments, the polymer combines and / or reacts with one or more fillers, an agent

<img file="MX345472B_D0014.tif" />

MEXICAN INSTITUTE Dt LA IROTilOAL IHDUTOUAL

<img file="MX345472B_D0015.tif" />

vulcanization, and / or optionally one or more additional additives including but not limited to accelerators, coupling agents, unmodified elastomeric polymers, (i.e., conventional non-crosslinked elastomeric polymers that have not reacted with a modifier, but that were prepared and finished), and the like, and combinations thereof.

In some embodiments, a composition in accordance with the present teachings includes one or more fillers, which serve as reinforcing agents. Representative examples of suitable fillers include but are not limited to carbon black, silica, carbon-silica dual phase fillers, clay, calcium carbonate, magnesium carbonate, and the like, and combinations thereof. In some embodiments, a combination of carbon black and silica, carbon-silica dual phase fillers, or a carbon-silica dual phase filler combination and carbon black and / or silica are used.

In some embodiments, carbon black is manufactured by a furnace method, and has a nitrogen adsorption specific surface area of ​​about 50 to about 200 µm.²/ g, and a DBP oil absorption of about 80 to about 200 ml / 100 grams (for example, carbon black class FEF, HAF, ISAF or SAF). In some embodiments, a high agglomeration type carbon black is used. In some embodiments, carbon black or silica is added in an amount of from about 2 to about 100 parts by weight per 100 parts by weight of the total polymer. In some embodiments, carbon black or

<img file="MX345472B_D0016.tif" />

<img file="MX345472B_D0017.tif" />

INSTITUTE MiXiCANC DE LA PROPERTY INDUSTRIAL silica in an amount of approximately 5 to approximately 100 parts by weight. In some embodiments, carbon black or silica is added in an amount of about 10 to about 100 parts by weight. In some embodiments, carbon black or silica 5 is added in an amount of about 10 to 95 parts by weight.

Finally, by way of a further general introduction, an article incorporating the elements of the present teachings includes at least one component formed from said composition. In some embodiments, the article is a tire. In some embodiments, the article is a shoe component.

The following representative examples and procedures illustrate features in accordance with the present teachings, and are provided by way of illustration only. These are not intended to limit the scope of the appended claims or their equivalents.

Examples

The monomer conversion was determined by measuring the solids concentration of the polymer solution at the end of the polymerization. The maximum solids content is obtained at a conversion of 100% by weight of the butadiene (mBd) and styrene (mSt) loaded for the final polymer by TSC max = (mBd + mSt) / (mBd + mSt + mpolar agent + mBL + mcyclohexane) * 100%. A sample of the polymer solution in the range of about 1 g to about 10 g, depending on the expected monomer conversion, was drawn from the reactor directly into an Erlenmeyer flask.

<img file="MX345472B_D0018.tif" />

200-ml bottle loaded with ethanol (50 ml). The weight of the loaded Erlenmeyer flask was determined before sampling (A) / after sampling (B). The precipitated polymer was removed from the ethanol by filtration on a heavy paper filter (microfiber glass paper, Π 90 mm, MUNKTELL, weight C), dried at 140 ° C, using a moisture analyzer HR73 (Mettler-Toledo) until a constant mass was achieved. Criterion 5 was used. Finally, a second drying period was carried out using cut-off criterion 4 to obtain the final mass D of the dry sample on the filter paper. The content of the polymer in the sample was calculated as TSC = (DC) / (BA) '100%. The final monomer conversion was calculated as TSC / TSC max '100%.

The molecular weight and molecular weight distribution of the polymer were each measured using size exclusion chromatography (SEC) based on polystyrene standards. Each polymer sample (9-11 mg) was dissolved in tetrahydrofuran (10 ml) to form a solution. The solution was filtered using a 0.45-pm filter. A 100-µΙ sample was fed onto a GPC column (Hewlett Packard 1100 system with 3 PLgel 10pm MIXED-B columns, temperature 40 ° C). Detection of refractive index was used as a detector for molecular weight analysis. Molecular weight was calculated as polystyrene based on calibration with Polymer Laboratories EasiCal PS1 (Easy A and B) polystyrene standards. Figures of number average molecular weight (Mn) and figures of weight average molecular weight (Mw) are given based on polystyrene standards. The molecular weight distribution is expressed as the · ί^D industrial

<img file="MX345472B_D0019.tif" />

dispersity D = Mw / Mn. _

The total styrene and vinyl content was measured using ¹H-NMR, followed by ISO 21561-2005, using an NMR spectrometer

BRUKER Avance 400MHz), and a dual 5-mm probe. CDCI₃/ TMS was used as solvent in a weight ratio of 0.05%: 99.95%. The content of block styrene having more than 6 consecutive styrene units was determined according to the method reported by Y. Tanaka et al. In Rubber Chemistry and Technology, 1981, 54, no. 4., 685-691 using the relative signal intensity of the resonant ortho Ph proton higher than 6.7 ppm. The content of block styrene having 4 and more consecutive styrene units was determined according to the method described in German patent document no. DE69712962 using the relative intensity of resonant ortho Ph proton signals in the range between 6.94 and 6 ppm. The content of block styrene having 4 to 6 consecutive units was calculated from the difference between the two contents of block styrene described above.

Comparative Example 1 (Use of K-3,7-dimethyl-3-octylate (KDMO or K hereinafter) (50% in hexanes))

5376.55 g of dry cyclohexane was charged into a 10-liter stainless steel reactor purged with nitrogen and free of air. 326.17 g of 1,3-Butadiene, 403.73 g of styrene, and 0.083 mmol of K-3,7-dimethyl-3-octylate (50% in heptane) were fed into the reactor (K / active butyl lithium mol / mol = 0.076) .

MEXICAN INSTITUTE DF LA MOHEDA D INDUSTRIAL

The mixture was heated to 50 ° C with stirring. The impurities Rn. The system were titled by gradually adding butyllithium. Recognizing the end point, the polymerization was initiated by adding the total amount of 1,466 mmol of n-butyl lithium (15% solution in cyclohexane) through a pump within 1 minute 19 seconds. Then the polymerization started. The temperature in the reactor rose to 65 ° C in 30 minutes. The reaction was terminated after 200 minutes by the addition of methanol as a capping agent. Irganox 1520 was introduced as an antioxidant.

A sample was taken through a sampling tube with a stopcock and a needle to determine the solids content. A conversion of 99.57% was measured.

The resulting polymer was analyzed by GPC: Mn = 533636, Mw = 674699, D = 1.264. The microstructure and content of block styrene were measured by¹H-NMR. The following results were obtained: styrene = 55.2%, vinyl (1,2-polybutadiene, calculated on the butadiene fraction) = 12.3%, block styrene (&gt; 6 consecutive units) = 43%, and block styrene (&gt; 4 consecutive units) = 86%.

Comparative Example 2 (Use of 2- (2-ethoxyethoxy) -2-methylpropane (CMX)) 5366.99 g of dry cyclohexane was charged into an air-free, nitrogen purged 10-liter stainless steel reactor. 325.97 g of 1,3-butadiene, 403.32 g of styrene, and 3.6712 mmol of CMX were fed into the reactor (CMX / active butyl lithium mol / mol = 2.57).

s impurities

The mixture was heated up to 50 ° C with agfttatro in the system and titrated gradually adding butyllithium. Recognizing the end point the polymerization was started by adding the total amount of 1,429 mmol of n-butyl lithium (15% solution in cyclohexane) through a pump within 1 minute 47 seconds. Then the polymerization started. The temperature in the reactor rose to 65 ° C in 30 minutes. The reaction was terminated after 200 minutes by the addition of methanol as a capping agent. Irganox 1520 was introduced as an antioxidant.

A sample was taken through a sampling tube with a stopcock and a needle to determine the solids content. A conversion of 98.25% was measured.

The resulting polymer was analyzed by GPC: Mn = 587397, Mw = 72 914, D = 1229. The microstructure and content of the styrene block were measured by 'H-NMR. The following results were obtained: styrene = 55.2%, vinyl (1,2-polybutadiene, calculated on the butadiene fraction) = 42.2%, block styrene (&gt; 6 consecutive units) = 56%, and block styrene (&gt; 4 consecutive units) = 71%.

Example 1 (Use of K-3,7-dimethyl-3-octylate (50% in hexanes) / CMX)

5342 g of dry cyclohexane was charged into a 10-liter stainless steel reactor purged with nitrogen and free of air. 324.48 g of 1,3-butadiene, 401.02 g of styrene, 0.1208 mmol of K-3,7-dimethyl-3octylate (50% in heptane), and 3.6644 mmol CMX were fed into the

<img file="MX345472B_D0020.tif" />

U * £&gt; y8T «UAL reactor (K / active butyl lithium mol / mol = 0.091, CMX / active butyl lithium 2.8). The mixture was heated to 50 ° C with stirring. Impurities in the system were titrated by gradual addition of butyl lithium. Recognizing the end point, the polymerization was started by adding the total amount of

1.3217 mmol n-butyl lithium (15% solution in cyclohexane) through a pump within 1 minute 40 seconds. Then the polymerization started. The temperature in the reactor rose to 65 ° C in 30 minutes. The reaction was terminated after 150 minutes by the addition of methanol as a capping agent. Irganox 1520 was introduced as an antioxidant. A sample was taken through a sampling tube with a stopcock and a needle to determine the solids content. A conversion of 99.63% was measured. The resulting polymer was analyzed by GPC: Mn = 601903. Mw = 782317, D = 1.3. The microstructure and content of block styrene were measured by¹H-NMR. The following results were obtained: styrene = 55%, vinyl (1,2-polybutadiene, calculated on the butadiene fraction) = 43.3%, block styrene (&gt; 6 consecutive units) = 28%, and block styrene (&gt; 4 consecutive units) = 75%.

Example 2 (Use of K-3,7-dimethyl-3-octylate (50% in hexanes) / CMX)

5606.74 g of dry cyclohexane was charged into a 10-liter stainless steel reactor purged with nitrogen and free of air. 217.6 g of 1,3-butadiene, 267.8 g of styrene, 0.116 mmol of K-3,7-dimethyl-3octylate (50% in heptane), and 3,467 mmol CMX were fed into the reactor (K / mol / active butyl lithium mol = 0.0807, CMX / active butyllithium 3.467).

O £ ΙΛ eWrtMÍAC 0Xi -.- # LBS iMtWSTWAt Xaa,

The mixture was heated to 50 ° C with stirring. Impurities in the system were titrated by gradually adding butyllithium. Recognizing the end point, the polymerization was started by adding the total amount of 0.7 mmol of n-butyllithium (15% solution in cyclohexane) through a pump within 50 seconds. Then the polymerization started. The temperature in the reactor rose to 65 ° C in 30 minutes. The reaction was terminated after 120 minutes by the addition of methanol as a capping agent. Irganox 1520 was introduced as an antioxidant. A sample was taken through a sampling tube with a stopcock and a needle to determine the solids content. A conversion of 99.47% was measured. The resulting polymer was analyzed by GPC: Mn = 606994, Mw = 893869, D = 1.47. The microstructure and content of the styrene block were measured by¹H-NMR. The following results were obtained: styrene = 53.9%, vinyl (1,2-polybutadiene, calculated on the butadiene fraction) = 35.5%, block styrene (&gt; 6 consecutive units) = 29%, and block styrene (&gt; 4 consecutive units) = 74%.

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

3568.29 g of dry cyclohexane was charged into a 10-liter stainless steel reactor purged with nitrogen and free of air. 394.3 g of 1,3-butadiene, 265.56 g of styrene, 0.1103 mmol of K-3,7-dimethyl3-octylate (50 in heptane), and 3.3014 mmol CMX were fed into the reactor (K / active butyl lithium mol / mol = 0.097, CMX / active butyllithium 2.917). The mixture was heated to 70 ° C with stirring. Impurities in the

<img file="MX345472B_D0021.tif" />

iHtrm / ro Muicano. C € LA r «o» »r» * o system were titrated by gradually adding butillition ^^ Cbnoil at the end point the polymerization was started by adding the total amount¹¹1.1316 mmol of n-butyl lithium (15% solution in cyclohexane) through a pump within 1 minute 50 seconds. Then the polymerization started. The temperature in the reactor was kept constant at 70 ° C during the reaction. The reaction was terminated after 140 minutes by the addition of methanol as a capping agent. Irganox 1520 was introduced as an antioxidant. A sample was taken through a sampling tube with a stopcock and a needle to determine the solids content. A conversion of 99.71% was measured. The resulting polymer was analyzed by GPC: Mn = 632055, Mw = 93472, D = 1.445. The microstructure and content of the styrene block were measured by¹HNMR. The following results were obtained: styrene = 39.6%, vinyl (1,2-polybutadiene, calculated on the butadiene fraction) = 30.4%, block styrene (&gt; 6 consecutive units) = 20%, and block styrene (&gt; 4 consecutive units) = 64%.

Example 4 (Use of K-3,7-dimethyl-3-octylate (50% in hexanes) / CMX)

5874.43 g of dry cyclohexane was charged into a 10-liter stainless steel reactor purged with nitrogen and free of air. 394.4 g of 1,3-butadiene. 267.72 g of styrene, 0.1091 mmol of K-3,7-dimethyl3-octylate (50% in heptane), and 3.3336 mmol CMX were fed into the reactor (K / active butyl lithium mol / mol = 0.082, CMX / active butyllithium 2.516 ). The mixture was heated to 50 ° C with stirring. Impurities in the system were titrated by gradual addition of butyl lithium. Recognizing the

IMPI

MEXICAN INSTITUTE

OF INDUSTRIAL PROPERTY

<img file="MX345472B_D0022.tif" />

End-point polymerization was initiated by adding the total caiillUaU of 1,325 mmol of n-butyl lithium (15% solution in cyclohexane) through a pump within 1 minute 10 seconds. Then the polymerization started. The temperature in the reactor was kept constant at 50 ° C during the reaction. The reaction was terminated after 210 minutes by the addition of methanol as a capping agent. Irganox 1520 was introduced as an antioxidant. A sample was taken through a sampling tube with a stopcock and a needle to determine the solids content. A conversion of 98.24% was measured. The resulting polymer was analyzed by GPC: Mn = 561807, Mw = 676793, D = 1.2055. The microstructure and content of the styrene block were measured by¹HNMR. The following results were obtained: styrene = 39.9%, vinyl (1,2-polybutadiene, calculated on the butadiene fraction) = 44%, block styrene (&gt; 6 consecutive units) = 21%, and block styrene (&gt; 4 consecutive units) = 65%.

The examples and comparative examples demonstrate that the present teachings provide a styrene-diene copolymer with a defined target styrene content with more than 4 consecutive styrene units, in combination with a high total styrene content, a desired vinyl content and a narrow molecular weight distribution. Using a process in accordance with the present teachings, the novel and inventive polymers as claimed in the present disclosure can be polymerized using standard high throughput polymerization techniques. All properties of polymers as described in the present description are properties before any subsequent modification, such as terminal coating, coupling etc. as described above. Due to the performance of the present teachings to provide polymers with a narrow molecular weight distribution, it is possible to obtain a large number of living chain ends at the end of the polymerization, so that uniform chain end modification becomes possible. .

The entire content of each of the aforementioned patent and non-patent documents is hereby incorporated by reference, except in the case of any definition or description inconsistent with the present description, the definition and description herein shall prevail.

The detailed description above is provided by way of illustration and explanation, and is not intended to limit the scope of the appended claims. Many variations on the present preferred embodiments illustrated herein will be apparent to one of ordinary skill in the art, and will be within the scope of the appended claims and their equivalents.