RU2794941C2 - Two-component block copolymers - Google Patents

Abstract

FIELD: copolymers.

SUBSTANCE: invention relates to a group of inventions: a composition of a two-component block copolymer, especially useful in microporous rubber compounds and adhesive compositions; options for obtaining a composition of a two-component block copolymer; composition for a cross-linked porous rubber product; composition for hot melt adhesive. The composition of the two-component block copolymer contains C and U. C includes: [D-(D/A)-A₁] _n -X; [B-(B/A)-A₁] _n -X; [(B/A)-A₁] _n -X; or [B-A₁] _n -X. U includes: D-(D/A)-A₂ or D-(D/A)-A₂ and D-(D/A)-A₁; B-(B/A)-A₂ or B-(B/A)-A₂ and B-(B/A)-A₁; (B/A)-A₂ or (B/A)-A₂ and (B/A)-A₁; or B-A₂ or В-А₂ and В-А₁. B is a polymer block derived only from the conjugated diene monomer. (B/A) is a random polymer block made from at least a conjugated diene monomer and at least a monovinyl aromatic monomer. D is a polymer block derived from at least a conjugated diene monomer and at least a monovinyl aromatic monomer, wherein the conjugated diene repeating units are in a greater molar amount than the monovinyl aromatic repeating units, along the entire length of the polymer block. (D/A) is a polymer block derived from at least a conjugated diene monomer and at least a monovinyl aromatic monomer, where the end of the polymer block opposite A₁ or A₂ predominantly consists of conjugated diene repeating units, where the composition of the polymer block gradually varies along the length of the block until it is essentially composed of monovinyl aromatic repeating units at the end adjacent to A₁ or A₂. A₁ and A₂ are polymer blocks derived from monovinyl aromatic monomer only, where the A₂ polymer block has a higher molecular weight than the A₁ polymer block. X is the remainder of the binding agent. n is an integer from 2 to 30. The invention also provides methods for producing new two-component block copolymers in a batch reactor. The composition for a product made of cross-linked microporous rubber contains a composition of a two-component block copolymer, a foaming agent and a crosslinking agent. The pressure-sensitive hot melt adhesive composition contains a two-component block copolymer composition; tackifying resin; filler oil and antioxidant. Development of a block copolymer of a conjugated diene and vinylaromatic repeating units, which can be mixed with additional ingredients to obtain microporous cross-linked rubber compounds without premature blistering and without premature crosslinking. This two-component block copolymer composition provides cross-linked microporous rubber compounds without shrinkage during their manufacture.

EFFECT: Obtaining moulded articles with excellent appearance, free from bubble defects, with improved softness and high resilience.

23 cl, 9 dwg, 10 tbl, 41 ex

Description

Cross-reference to related applications

This application claims priority of U.S. Patent Application No. 16/595,913, filed October 8, 2019, and U.S. Provisional Application No. 62/782,668, filed December 20, 2018, each of which is incorporated herein by reference.

Background of the invention

1. Scope of invention

The present invention is directed to bicomponent block copolymers of conjugated diene monomers and monovinyl aromatic monomers, and in particular to microporous crosslinked rubber compounds and hot melt pressure sensitive adhesives containing bicomponent block copolymers. The novel two-component block copolymers of the invention can be used to produce microporous, cross-linked, closed-cell rubber compounds of uniform size, free from blistering defects, with improved softness and higher resilience. Hot melt pressure sensitive adhesives based on new two-component block copolymers show improved tack and operating temperature.

2. Description of the prior art

Microporous rubber compounds are widely used in the manufacture of various products such as shoe soles, sandals, cushion pads, floatation products, sound absorbing sheets, vibration damping materials, shock absorbing treads, sealing materials, and the like. In addition, these materials have gained wide acceptance in the market due to their lightness and cost-effectiveness.

When foaming these mixtures, closed cells are formed as a result of chemical or physical expansion of the blowing agent under the action of heat, or a combination of heat and decompression at typical temperature and pressure to cure the mixture. Cross-linking of microporous rubber compounds provides improved and durable mechanical characteristics. The elasticity of the rubber during foaming, which in most processes is enhanced by partial crosslinking prior to or simultaneously with the foaming step, is important for maintaining a closed cell structure. During the time elapsed between the end of the expansion and the achievement of optimal crosslinking, foamed rubber compounds tend to shrink. To avoid this shrinkage defect, block copolymers of conjugated diene monomers and monovinyl aromatic monomers have been used in crosslinked microporous rubber compositions.

GB 1249220 discloses non-crosslinked elastic foams based on block copolymers of the form (BS) _n or (BS) _n B or (SB) _m where B is actually a 1-3 butadiene polymer, S is actually styrene polymer, n is an integer from 2 to 10 and m is an integer from 1 to 10. These compositions also include polystyrene homopolymer. However, these compositions have drawbacks because they include chlorohydrofluorocarbons as blowing agents, which are harmful to the environment and have a rather large pore size of 0.6 to 1.1 mm.

EP 0323653 A1 discloses crosslinked foamed rubber compositions containing block copolymers of monovinyl aromatic and conjugated diene monomers with the general formula (A-E) _n A, (A-E) _n or ((AE) _n ) _m X, where n is in 1 to 4, m is 2 to 8, A is a monovinyl aromatic polymer block, Ε is a conjugated diene polymer block and/or a selectively hydrogenated product thereof, and X is a binder residue. These compositions also include other rubbers such as natural rubber, diene-type synthetic rubber and non-diene synthetic rubber.

EP 2546291 discloses crosslinked foamed rubber compositions comprising a block copolymer containing vinyl aromatic monomer units and conjugated diene monomer units and/or a block copolymer containing vinyl aromatic monomer units, conjugated diene monomer units and alkylene monomer units. This composition also includes an olefin-based copolymer (such as polyethylene, ethylene-1-butene copolymers, ethylene-octene copolymers, etc.) and optionally an ethylene-based copolymer having an unsaturated group, such as EPDM. Among the many sequence structures disclosed for block copolymers, preferred block configurations have end blocks rich in vinyl aromatic repeat units and middle blocks of elastomeric repeat units.

WO 2008/083451 A1 discloses vulcanized foam rubber compositions containing block copolymers with a molecular configuration consisting of polystyrene end blocks and elastomeric middle blocks, where the elastomeric middle blocks are based on butadiene, isoprene, ethylene, butylene or propylene. These blends further include styrene-butadiene random copolymers with high and/or medium bound styrene content, as well as ethylene-propylene copolymer (EPR) or ethylene-propylene-diene terpolymer (EPDM).

The compositions disclosed in EP 0233653 A1, EP 2546291 and WO 2008/083451 A1 contain block copolymers with end blocks rich in vinyl aromatic repeat units surrounding mid blocks rich in repeat units of the conjugated diene (or their hydrogenated products). Consequently, they all have the disadvantage of requiring high mixing temperatures. This is because the end blocks, rich in vinylaromatic repeating units of the block copolymers described therein, form an intermolecular physical network that softens sufficiently and flows only at temperatures above 120°C. Such a high mixing operating temperature can cause premature decomposition of the chemical blowing agent and/or premature initiation of crosslinking. This is particularly restrictive when mixing is done in batch mixers such as the Banbury.

GB 1111250 describes crosslinked microporous foam rubber compositions containing gradient diblock copolymers of a conjugated diene and vinylaromatic monomers. The disclosed gradient diblock copolymers are produced by batchwise anionic solution polymerization. The compositions also include random copolymers of a conjugated diene and vinylaromatic monomers, obtained either by anionic solution polymerization or by free radical emulsion polymerization.

US Pat. No. 4,003,860 describes crosslinked microporous foam rubber compositions containing gradient diblock copolymers of a conjugated diene and monovinyl aromatic monomers. The disclosed gradient diblock copolymers are prepared by a batch anionic polymerization process. The compositions also include an ethylene-vinyl acetate copolymer.

The main advantage of the compositions disclosed in GB 1111250 and US 4003860 is adequate processability in a batch mixer and minimization of shrinkage of foamed mixtures. However, the crosslinked microporous rubber compositions containing the block copolymers described therein have disadvantages of non-uniform pore size, blistering defects, low softness and low resilience.

BRPI 0601080-6 A discloses formulations for vulcanized microporous rubber compounds containing a styrene-butadiene block copolymer as the main component. To give hardness, a small amount of polymer with a styrene content of 40 to 80% is added to the formulation. Such a formulation is said to be preferred for molding microporous or microcellular sandal soles. This patent lacks a description of the molecular configuration of the block copolymer and information on its range of composition.

EP 0674578 B1, US 8,772,414 B2 and US 2015/0259491 A1 show various polymer foam compositions in which the polymers used have preferred values of the tangent of the angle δ (eng. Tan delta - The ratio of mechanical loss modulus to shear modulus, also known as the coefficient scattering) slightly below 1 in the molten state for adequate closed-cell foaming.

Microporous crosslinked rubber compounds comprising gradient block copolymers of butadiene and styrene, obtained by anionic solution polymerization in a continuous reactor process, are known to have a good balance of shrinkage and surface aesthetics, as well as adequate processability in batch mixing equipment. However, they still impart hardness and low resilience to microporous crosslinked rubber compounds. Moreover, a continuous anionic polymerization process lacks the flexibility of a batch process to change polymerization formulations to produce different grades of rubber without the cost of producing sub-standard products when switching to other formulations.

As discussed above, there is a need for block copolymers of a conjugated diene and vinyl aromatic repeat units that can be adequately blended with additional ingredients to produce microporous crosslinked rubber compounds without the problems of premature blistering or premature crosslinking. There is also a need for compositions based on conjugated diene block copolymers and vinyl aromatic repeat units that provide crosslinked microporous rubber compounds without shrinkage problems during their manufacture. There is also a need for crosslinked foam rubber compounds containing block copolymers of a conjugated diene and vinyl aromatic repeat units that can be molded into products with excellent appearance, no blistering defects, improved softness and high resilience. There is a further need for batch polymerization processes to produce block copolymers of conjugated diene and vinyl aromatic repeat units with excellent foaming characteristics.

The essence of the invention

The present invention provides novel two-component block copolymers prepared from monovinyl aromatic and conjugated diene monomers by alkyl lithium initiated solution polymerization. The terms "two-component block copolymer" or "two-component block copolymers", as used in the description and claims of the present invention, refer to polymer compositions that contain two types of block copolymer molecules that differ from each other in molecular weight, block structure and content monovinyl aromatic repeating units.

Each type of block copolymer molecules in a two-component block copolymer can be characterized as a peak in the molecular weight distribution of the entire two-component block copolymer. The fraction with the highest molecular weight peak in the molecular weight distribution corresponds to the bound block copolymer molecules. In these linked block copolymer molecules, the linking agent moiety is covalently bonded to only two or more internal blocks of the monovinyl aromatic homopolymer. The remainder of each bonded block copolymer molecule consists of polymeric blocks consisting of a conjugated diene with inserts of monovinyl aromatic repeating units or containing only conjugated diene repeating units. Near the peak of the bound block copolymer in the molecular weight distribution of the two-component block copolymer in the range of lower molecular weights, an additional peak or pair of peaks related to molecules of the unbound block copolymer can be distinguished. These unbound block copolymer molecules have one monovinyl aromatic homopolymer end block per molecule, and the remainder of each unbound block copolymer molecule is built from polymer blocks containing either conjugated diene repeat units with inserts of monovinyl aromatic monomer repeat units, or only conjugated diene repeat units. The average content of monovinyl aromatic repeating units in the molecules of the bound block copolymer is lower than in the molecules of the unbound block copolymer. Moreover, the average molecular weight of the individual monovinyl aromatic homopolymer internal blocks in the bound block copolymer molecules is lower than that of the monovinyl aromatic homopolymer end blocks present in the unbound block copolymer molecules. In addition, the average molecular weight of the outer blocks containing the conjugated diene repeating units in the bound block copolymer is about the same as the molecular weight of the blocks containing the conjugated diene repeating units found in the unbound block copolymer.

The invention also provides methods for producing new two-component block copolymers in a batch reactor.

The invention also relates to compositions for the preparation of crosslinked microporous rubber compounds containing a new two-component block copolymer, among other typical ingredients for this class of compounds.

The compositions of the invention allow the compounding step in the production of crosslinked microporous rubber in internal batch mixers such as the Banbury to be carried out at a reduced temperature, thus avoiding premature expansion of the chemical blowing agent and avoiding problems of premature crosslinking. The blending step also runs at a lower torque than with prior art block copolymers of the same Mooney viscosity, so incorporating two-component block copolymers in this kind of formulation is beneficial as energy savings are achieved during blending. The compositions of the invention also provide the advantage of negligible shrinkage of the microporous polymer during the crosslinking step. Molded articles obtained using the compositions of the present invention exhibit excellent surface appearance, no bubbles, high softness and high resilience.

The invention also provides hot-melt pressure-sensitive adhesive compositions containing a novel two-component block copolymer, among other typical ingredients for this class of adhesives. Surprisingly, the hot melt pressure sensitive adhesive containing these new two-component block copolymers has been found to have improved tack and operating temperature range.

Brief description of graphic materials

In FIG. 1 schematically shows a two-component block copolymer, consisting of approximately 38 wt. % bound block copolymer With the formula [D-(D/A)-A ₁ ] ₄ -X (left) and approximately 62 wt. %. unbound block copolymer U of formula D-(D/A)-A ₂ (right).

In FIG. 2 schematically shows a two-component block copolymer, consisting of approximately 34 wt. % bound block copolymer With the formula [D-(D/Α)-Α ₁ ] ₄ -Χ (left) and approximately 66 wt. %. unbound block copolymer U of formulas D-(D/A)-A ₂ (4 molecules top right) and D-(D/A)-A ₁ (bottom right).

In FIG. 3 schematically shows a two-component block copolymer consisting of approximately 38 wt. % bound block copolymer C of the formula [B-(B/A)-A ₁ ] ₄ -X (left) and approximately 62 wt. %. unbound block copolymer U of formula B-(B/A)-A ₂ (right).

In FIG. 4 schematically shows a two-component block copolymer consisting of approximately 34 wt. % bound block copolymer With the formula [Β-(Β/Α)-Α ₁ ] ₄ -Χ (left) and approximately 66 wt. %. unbound block copolymer U of formulas B-(B/A)-A ₂ (4 molecules, top right) and B-(B/A)-A ₁ (bottom right). A _t is approximately 39 wt. %.

In FIG. 5 schematically shows a two-component block copolymer consisting of approximately 38 wt. % bound block copolymer With the formula [(B/A)-A ₁ -X (left) and approximately 62 wt. % unbound block copolymer U of formula (B/A)-A ₂ (right).

In FIG. 6 schematically shows a two-component block copolymer consisting of approximately 34 wt. % bound block copolymer C of the formula [(B/A)-A1] ₄ -X (left) and approximately 66 wt. % unbound block copolymer U of formulas (B/A)-A ₂ (4 molecules, top right) and (B/A)-A ₁ (bottom right).

In FIG. 7 schematically shows a two-component block copolymer, consisting of approximately 38 wt. % of the associated block copolymer With the formula [B-A ₁ ] ₄ -X (left) and approximately 62 wt. % unbound block copolymer U of formula B-A ₂ (right).

In FIG. 8 schematically shows a two-component block copolymer, consisting of approximately 34 wt. % bound block copolymer With the formula [B-A ₁ ] ₄ -X (left) and approximately 66 wt. % unbound block copolymer U of formulas B-A ₂ 4 molecules from top right) and B-A ₁ (bottom right).

In FIG. 1-8, the black bars represent the monovinyl aromatic repeat unit sequences, the gray bars represent the conjugated diene repeat unit sequences, and X represents the residue of the tetrafunctional coupling agent. In FIG. 1-6, the black lines among the conjugated diene repeat sequences represent various structures in which the monovinyl aromatic repeat units are copolymerized with the conjugated diene repeat units; their locations and spacings are not specific positions of individual monovinyl aromatic repeat units, rather they show a concentration trend of monovinyl aromatic repeat units embedded along blocks also containing conjugated diene repeat units. Thus, a small gradient followed by a steep concentration gradient profile characteristic of damped copolymerization is shown in FIG. 1 and 2; randomization with only a portion of the conjugated diene repeat units is depicted in FIG. 3 and FIG. 4; and a fully randomized arrangement with all repeat units of conjugated dienes shown in FIG. 5 and FIG. 6.

In FIG. 9 shows the molecular weight distribution of the two component block copolymers of Examples 4 and 13 compared to the prior art block copolymers of Comparative Example C-2 and Buna® BL 30-4548.

Detailed description of illustrative embodiments of the invention

The present invention provides novel two-component block copolymers derived from monovinyl aromatic and conjugated diene monomers containing two types of block copolymer molecules C and U.

In one embodiment, the two-component block copolymers have a molecular weight distribution with at least two distinguishable fractions, each with a peak in the molecular weight distribution, as determined by gel permeation chromatography using a set of 3 columns and a differential refractive index detector. using a universal molecular weight calibration curve based on polystyrene standards (GPC-RI). Neighboring fractions are separated from each other at local minima of the molecular weight distribution curve. Block copolymer C consists of the fraction with the highest molecular weight peak in the molecular weight distribution, and block copolymer U makes up the remainder of the molecular weight distribution.

In one embodiment, the bicomponent block copolymers of the invention comprise an amount of block copolymer C, quantified by integrating the fraction with the highest molecular weight peak relative to the overall molecular weight distribution of the bicomponent block copolymer obtained by GPC-RI, from 20% to 80%, more preferably 30% to 60% and most preferably 35% to 45%. In addition, the bicomponent block copolymers of the invention contain an amount of block copolymer U quantified by integrating the remainder of the molecular weight distribution obtained by GPC-RI relative to the entire molecular weight distribution of the bicomponent block copolymer, ranging from 80% to 20%, more preferably 70% to 40% and most preferably 65 to 55%. In one embodiment, the two-component block copolymers of the present invention have a total content of monovinyl aromatic repeating units, % A _t , from 20% to 50 wt. % as determined by proton NMR analysis.

The two-component block copolymers of the invention have a characteristic degree of blockiness of the monovinyl aromatic repeating units, as determined by proton NMR analysis. The degree of blockiness of monovinyl aromatic repeating units is quantified as the molar percentage of monovinyl aromatic repeating units in the block copolymer that are not covalently bonded to the repeating units of conjugated dienes, based on the total number of monovinyl aromatic repeating units. In one embodiment, the bicomponent block copolymers of the invention have a monovinyl aromatic repeat unit blockiness of from about 76 mol% to about 100 mol%, more preferably from about 81 mol% to about 100 mol%, and most preferably from about 85 mole % to about 100 mole % of total monovinyl aromatic repeating units.

A distinctive feature of the two-component block copolymers of the invention is that the content of monovinyl aromatic repeating units in block copolymer U is higher than the content of monovinyl aromatic repeating units in block copolymer _C. the percentage of monovinyl aromatic repeating units in block copolymer C, %A _C , and the weight percent difference of monovinyl aromatic repeating units between fractions U and C of block copolymers, % CD, are calculated as follows:

where %C _uv is the percentage of the fraction with the highest molecular weight peak, which corresponds to block copolymer C, relative to the total molecular weight distribution of the double block copolymer of the invention, obtained by GPC with a set of 3 columns using a UV absorbance detector on wavelength of 261 nm and using a universal molecular weight calibration curve based on polystyrene standards (GPC-UV);

%A _t is the total content of monovinyl aromatic compounds of the entire two-component block copolymer of the present invention, calculated on a weight basis, obtained by proton NMR analysis; And

%C _ri is the percentage of the fraction with the highest molecular weight peak, which corresponds to block copolymer C, relative to the total molecular weight distribution of the double block copolymer of the invention, obtained by gel permeation chromatography using a set of 3 columns, a differential refractive index detector and using a universal molecular weight calibration curve based on polystyrene standards (GPC-RI).

In one embodiment, the two-component block copolymers of the invention exhibit a weight percent difference of monovinyl aromatic repeating units between the U and C fractions of the block copolymer, % CD, of at least 10 wt. %, preferably at least 15 wt. % and most preferably at least 20 wt. %.

The tangent δ (Tan delta), which is defined as the ratio of mechanical loss modulus to shear modulus, is well known in the art as a very suitable indicator of the balance between flowability and melt strength and hence foamability for various polymeric materials. Without wishing to be bound by any particular theory, it is believed that polymeric materials with tan delta values below 1.0 may have sufficient melt strength to maintain a closed cell structure during blowing agent expansion, which would be useful in narrowing the pore size distribution, providing improved foam appearance. In contrast, polymeric materials with tan delta values greater than 1.0 under processing conditions will therefore be prone to rupture of the porous membrane and coalescence of pores during foaming, which can widen the pore size distribution to the point of blistering on the surface in foamed castings.

After extensive research, it has been confirmed that prior art copolymers obtained by batch solution copolymerization of monovinyl aromatic and conjugated diene monomers with alkyl lithium cannot have an appropriate tan delta profile, and it has also been found that their viscoelastic properties lead to poor foaming characteristics. Several structures of prior art block copolymers have been tested (gradient linear block copolymers, partially bonded gradient block copolymers, different block levels of monovinyl aromatic repeat units, different levels of monovinyl aromatic compounds, different molecular weights, oil-filled block copolymers, and even mixtures of gradient linear block copolymers with varying amounts of monovinyl aromatic repeating units) and all had tan delta profiles with values slightly above 1.0 over a much broader range of vibrational shear frequencies. These prior art alternatives, when incorporated into crosslinked microporous foam compositions, produced molded articles that lacked a neat appearance as blister defects were evident. However, it has surprisingly been found that the two-component block copolymers of the present invention have characteristic viscoelastic characteristics that make them useful for foaming because they exhibit tan delta values of only below 1.00 over a wide range of shear and processing temperatures before having place any stitching. Accordingly, it has been found that cross-linked microporous compositions based on two-component block copolymers have a very uniform pore size, and their castings have excellent surface aesthetics and are free from blistering defects.

In one embodiment, the two-component block copolymers of the invention exhibit maximum tan delta values in a dynamic shear vibration test over a vibration frequency range of 0.25 rad/s to 200 rad/s, at 100° C. and a strain of 13.95 %, from 0.74 to 0.95, more preferably from 0.74 to 0.88 and most preferably from 0.74 to 0.81. Typically, in a dynamic shear vibration test, the two-component block copolymer of the present invention has a tan delta of less than 1.00 when the vibration frequency changes from 0.25 to 200 rad/s, at a temperature of 100°C and a strain of 13.95 %. At a higher temperature, it was also found that in a dynamic shear vibration test, the two-component block copolymer of the present invention has tan delta values of less than 1.00, 0.95, 0.90, or 0.85 at a vibration frequency of 0.25 up to 200 rad/s, at a temperature of 140°C and a deformation of 13.95%.

In one embodiment, the two-component block copolymer of the invention has a Mooney viscosity (ML 1+4 at 100° C.) of 25 to 90, preferably 30 to 60, and more preferably 35 to 55.

In one embodiment, the two-component block copolymer of the invention has a complex dynamic shear viscosity, determined at a strain of 13.95%, at an oscillation frequency of 0.99 rad/s and a temperature of 100°C, from 50,000 Pa*s to 360,000 Pa*s. In one embodiment, the two-component block copolymer of the invention has a complex dynamic shear viscosity, determined at 100 rad/s at 100° C., from 3000 Pa*s to 12000 Pa*s.

Periodic copolymerization of conjugated diene monomers and monovinyl aromatic monomers, initiated by alkyllithium, in bulk or in solution of a non-polar hydrocarbon solvent, in the absence of polar modifying compounds or randomizers, gives the so-called gradient or "conical" diblock copolymers of the D-(D/A)-A type where D is a polymer block rich in conjugated diene repeat units; where (D/A) is a polymeric block richer in conjugated diene repeat units towards its end adjacent to the D block and which gradually changes its composition until it becomes substantially richer in monovinyl aromatic repeat units towards its opposite end; and where A is a polymer block consisting only of monovinyl aromatic repeating units. The manufacture and use of such graded or "conical" diblock copolymers of conjugated diene and monovinyl aromatic monomers is well known to those skilled in the art, defined and described in H.L. Hsie, R.P. Quirk, Anionic Polymerization: Principles and Practical Applications, Marcel Dekker, Inc., pp. 239-251 and 448-454.

In a preferred embodiment of the invention, the two-component block copolymer of the invention comprises a block copolymer C and a block copolymer U, where the block copolymer C has the general formula: [D-(D/A)-A ₁ ] _n -X; And

block copolymer U has the general formula:

D-(D/A)-A ₂ ; or

D-(D/A)-A ₂ and D-(D/A)-A ₁ where

D is a polymer block derived from at least a conjugated diene monomer and at least a monovinyl aromatic monomer, wherein the conjugated diene repeating units are in a greater molar amount than the monovinyl aromatic repeating units along the length of the polymer block;

(D/A) is a polymer block consisting of at least a conjugated diene monomer and at least a monovinyl aromatic monomer, where the end of the polymer block opposite Α ₁ or A ₂ is predominantly composed of repeating units of the conjugated diene and which gradually changes its the composition along its length until it becomes essentially consisting of monovinyl aromatic repeating units towards the end adjacent to Α ₁ or A ₂ ;

Α ₁ and A ₂ are polymer blocks derived from monovinyl aromatic monomer only;

polymer block A ₂ has a higher molecular weight than polymer block A ₁

X is the remainder of the binding agent;

n is an integer from 2 to 30;

molecules of the associated block copolymer of the formula [D-(D/A)-A ₁ ] _n -X are from about 20 to about 80 wt. % molecular weight distribution of the two-component block copolymer, as determined by GPC-RI;

molecules of unbound block copolymer of the formula D-(D/A)-A ₂ are from about 20 to about 80 wt. % molecular weight distribution of the two-component block copolymer, as determined by GPC-RI; And

molecules of unbound block copolymer of the formula D-(D/A)-A ₁ are from about 0 to about 20 wt. % molecular weight distribution of the two-component block copolymer, as determined by GPC-RI.

In another embodiment, the bicomponent block copolymer of the invention comprises a C block copolymer and a U block copolymer, wherein

block copolymer C has the general formula:

[B-(B/A)-A ₁ ] _n -X; And

block copolymer U has the general formula:

B-(B / A) -A ₂ ; or

B-(B/A)-A ₂ and B-(B/A)-A ₁ , where:

B is a polymer block consisting of only one or more conjugated diene monomers;

(B/A) is a polymer block consisting of at least a conjugated diene monomer and at least a monovinyl aromatic monomer, wherein the conjugated diene repeat units and the monovinyl aromatic repeat units are arranged randomly along the polymer block;

Α ₁ and A ₂ are polymer blocks derived only from monovinyl aromatic monomer, where the polymer block A ₂ has a higher molecular weight than the polymer block A ₁ ;

X is the remainder of the binding agent;

n is an integer from 2 to 30;

molecules of the associated block copolymer of formula [B-(B/A)-A ₁ ] _n -X are from about 20 to about 80 wt. % molecular weight distribution of the two-component block copolymer, as determined by GPC-RI;

molecules of unbound block copolymer of formula B-(B/A)-A ₂ are from about 20 to about 80 wt. % molecular weight distribution of the two-component block copolymer, as determined by GPC-RI; And

molecules of unbound block copolymer of formula B-(B/A)-A ₁ are from about 0 to about 20 wt. % molecular weight distribution of the two-component block copolymer, as determined by GPC-RI.

In another embodiment, the bicomponent block copolymer of the invention comprises a C block copolymer and a U block copolymer, wherein

block copolymer C has the general formula: [BA ₁ ] _n -X; And

block copolymer U has the general formula

B-A ₂ ; or

B-A ₂ and BA ₁ , where:

B is a polymer block consisting of only one or more conjugated diene monomers;

Α ₁ and A ₂ are polymer blocks obtained only from monovinyl aromatic monomer,

polymer block A ₂ has a higher molecular weight than polymer block A ₁ ;

X is the remainder of the binding agent;

n is an integer from 2 to 30;

molecules of the associated block copolymer of the formula [Β-Α ₁ ] _n -Χ are from about 20 to about 80 wt. % molecular weight distribution of the two-component block copolymer, as determined by GPC-RI;

molecules of unbound block copolymer of the formula B-A ₂ are from about 20 to about 80 wt. % molecular weight distribution of the two-component block copolymer, as determined by GPC-RI; And

molecules of unbound block copolymer of the formula Β-Α ₁ are from about 0 to about 20 wt. % molecular weight distribution of the two-component block copolymer, as determined by GPC-RI.

In another embodiment, the bicomponent block copolymer of the invention comprises a C block copolymer and a U block copolymer, wherein

block copolymer C has the general formula:

[(B/A)-A ₁ ] _n -X; And

block copolymer U has the general formula:

(B/A)-A ₂ ; or

(B / A) -A ₂ and (B / A) -A ₁ where:

(B/A) is a polymer block consisting of at least a conjugated diene monomer and at least a monovinyl aromatic monomer, wherein the conjugated diene repeat units and the monovinyl aromatic repeat units are arranged randomly along the polymer block;

A ₁ and A ₂ are polymer blocks derived only from a monovinyl aromatic monomer, where the A ₂ polymer block has a higher molecular weight than the A ₁ polymer block;

X is the remainder of the binding agent;

n is an integer from 2 to 30;

molecules of the associated block copolymer of formula [(B/A)-A ₁ ] _n -X are from about 20 to about 80 wt. % molecular weight distribution of the two-component block copolymer, as determined by GPC-RI;

molecules of unbound block copolymer of formula (B/A)-A ₂ are from about 20 to about 80 wt. % molecular weight distribution of the two-component block copolymer, as determined by GPC-RI; And

molecules of unbound block copolymer of the formula (Β/Α)-Α ₁ are from about 0 to about 20 wt. % molecular weight distribution of the two-component block copolymer, as determined by GPC-RI.

Another aspect of the invention relates to methods for producing new two-component block copolymers in a batch reactor, including: the interaction of at least one monomer of a conjugated diene and one monovinyl aromatic monomer under anionic polymerization conditions and the formation of a two-component block copolymer containing two types of molecules C and U block -copolymer.

A preferred embodiment of the present invention is a method for producing a new two-component block copolymer in a batch reactor, comprising:

adding to the reactor a hydrocarbon solvent, at least a monovinyl aromatic monomer, and at least a conjugated diene monomer in any order;

adding a monofunctional organolithium initiator to the reactor and carrying out anionic polymerization of the mixture of monomers until complete conversion with the formation of block copolymer anions of the formula D-(D/A)-A ₁ ^(-) ;

adding a binding agent to the reactor in a limited amount to bind only a part of the D-(D/A)-A ₁ ^(-) anions of the copolymer, thus obtaining a mixture of D-(D/A)-A ₁ ^(-) anions of an unbound block copolymer and molecules of the associated block copolymer of the formula [D-(D/A)-A ₁ ] _n -X;

adding a monovinyl aromatic monomer to the reactor and carrying out the anionic polymerization of this monomer, which is added to the remaining block copolymer anions D-(D/A)-A ₁ ^(-) , thus obtaining a mixture of anions of the formula D-(D/A)-A ₂ ^(-) an extended chain gradient block copolymer and linked block copolymer molecules of the formula [D-(D/A)-A ₁ ] _n -X; And

adding to the reactor a proton-donor compound or an electrophilic monofunctional additive in an amount sufficient to deactivate all remaining block copolymer anions D-(D/A)-A ₂ ^(-) .

Thus, a two-component block copolymer containing two types of C and U block copolymer molecules is produced in-situ in a batch reactor where:

C is a block copolymer of the general formula [D-(D/A)-A ₁ ] _n -X;

U is a block copolymer of the general formula D-(D/A)-A ₂ ;

D is a polymer block derived from conjugated diene monomers and from monovinyl aromatic monomers where the conjugated diene repeating units are in the predominant molar amount;

(D/A) is a polymer block that is richer in conjugated diene repeat units towards its end adjacent to the D block and which gradually changes its composition until it becomes substantially richer in monovinyl aromatic repeat units towards its opposite end;

A ₁ and A ₂ are polymeric blocks containing only monovinyl aromatic repeating units;

polymer block A ₂ has a higher molecular weight than polymer block A ₁ ;

X is the remainder of the binding agent;

n is an integer that varies from 2 to about 30, depending on the binding agent used;

block copolymer C has a higher molecular weight and lower content of monovinyl aromatic repeating units than block copolymer U.

A further embodiment of the present invention is a process for producing a novel two-component block copolymer in a batch reactor, comprising: adding to the reactor a hydrocarbon solvent, at least a monovinyl aromatic monomer, and at least a conjugated diene monomer in any order; adding a monofunctional organolithium initiator to the reactor and carrying out anionic polymerization of the mixture of monomers until complete conversion with the formation of an anion of the formula D-(D/A)-A ₁ ^(-) block copolymer; adding a binding agent to the reactor to bind only a part of the D-(D/A)-A ₁ ^(-) block copolymer anions to obtain a mixture of D-(D/A)-A ₁ ^(-) block copolymer anions and molecules of the associated gradient block copolymer of the formula [D-(D/A)-A ₁ ] _n -X; adding a limited amount of a proton-donor compound or an electrophilic monofunctional compound to the reactor to deactivate only a part of the block copolymer anions, thus obtaining a mixture of block copolymer anions with the formula D-(D/A)-A ₁ ^(-) , molecules of the associated block copolymer formulas [D-(D/A)-A ₁ ] _n X and block copolymers D-(D/A)-A ₁ ; adding a monovinyl aromatic monomer to the reactor and carrying out the anionic polymerization of this monomer, which is added to the remaining block copolymer anions D-(D/A)-A ₁ ^(-) , thus forming a mixture of block copolymer anions of the formula D-(D/A) -A ₂ ^(-) chain extended, molecules of the associated block copolymer of the formula [D-(D/A)-A ₁ ] _n -X and molecules of the block copolymer of the formula D-(D/A)-A ₁ ; adding to the reactor a proton-donor compound or an electrophilic monofunctional compound, or mixtures thereof, in an amount sufficient to deactivate any remaining D-(D/A)-A ₂ ^(-) block copolymer anions.

Thus, a two-component block copolymer containing two types of block copolymer molecules C and U is produced in situ in a batch reactor, where C is a block copolymer of the general formula [D-(D/A)-A ₁ ] _n - X and U is a block copolymer of the general formula D-(D/A)-A ₂ and D-(D/A)-A ₁ ; and where D is a polymer block derived from conjugated diene monomers and from monovinyl aromatic monomers, where the conjugated diene repeating units are in the predominant molar amount; and where (D/A) is a polymer block that is richer in conjugated diene repeat units towards its end adjacent to the D block and which progressively changes its composition until it becomes substantially richer in monovinyl aromatic repeat units towards its opposite end; and where Α ₁ and A ₂ are polymer blocks containing only monovinyl aromatic repeating units; and where the polymer block A ₂ has a higher molecular weight than the polymer block A ₁ and where X represents the remainder of the binding agent; and where n is an integer from 2 to about 30, depending on the binding agent used; and wherein block copolymer C has a higher molecular weight and lower content of monovinyl aromatic repeating units than block copolymer U.

Another embodiment of the present invention is a method for producing a new two-component block copolymer, including: adding to the reactor a hydrocarbon solvent, a randomizer or a polar modifier and at least a conjugated diene monomer in any order; adding a monofunctional organolithium initiator to the reactor and anionically polymerizing the conjugated diene monomer to achieve a conversion level of from about 80% to about 95% to form a polymeric anion of formula B ^(-) ; adding a monovinyl aromatic monomer to the reactor, which first randomly copolymerizes with the remaining conjugated butadiene monomer to form the B-(B/A) ^(-) block copolymer anion until the conjugated diene is completely converted, after which only the monovinyl aromatic monomer is included in the block copolymer anions up to until complete conversion of monovinyl aromatic monomer with the formation of polymeric anions of the formula B-(B/A)-A ₁ ^(-) ; adding a binding agent to the reactor in a limited amount to bind only a part of the anions of the copolymer Β-(Β/Α)-Α ₁ ^(-) thus obtaining a mixture of block copolymer anions Β-(Β/Α)-Α ₁ ^(-) and molecules of the associated block copolymer of the formula [B-(B/A)-A ₁ ] _n -X; adding a monovinyl aromatic monomer to the reactor and carrying out the anionic polymerization of this monomer, which is added to the block copolymer anions Β-(Β/Α)-Α ₁ ^(-) thus forming a mixture of block copolymer anions of the formula B-(B/A)- A ₂ ^(-) with an extended monovinyl aromatic chain and molecules of the associated block copolymer of the formula [B-(B/A)-A ₁ ] _n -X; adding to the reactor a proton donor compound or an electrophilic monofunctional additive in an amount sufficient to deactivate all remaining block copolymer anions B-(B/A)-A ₂ ^(-) .

Thus, a two-component block copolymer containing two types of block copolymer molecules C and U is produced in situ in a batch reactor, where C is a block copolymer of the general formula [B-(B/A)-A ₁ ] _n - X and U is a block copolymer of the general formula B-(B/A)-A ₂ ; and where B is a polymer block containing only repeating units of the conjugated diene; and where (B/A) is a polymer block containing repeating monovinyl aromatic and conjugated diene units, which are randomly located along the polymer block; and where A ₁ and A ₂ are polymer blocks containing only monovinyl aromatic repeating units; and where the polymer block A ₂ has a higher molecular weight than the polymer block A ₁ ; and where X is the remainder of the binding agent; and where n is an integer from 2 to about 30, depending on the binding agent used; and wherein block copolymer C has a higher molecular weight and lower content of monovinyl aromatic repeating units than block copolymer U.

Another embodiment of the present invention is a method for producing a new two-component block copolymer, including: adding to the reactor a hydrocarbon solvent, a randomizer or a polar modifier, and at least a conjugated diene monomer in any order; adding a monofunctional organolithium initiator to the reactor and anionically polymerizing the conjugated diene monomer to achieve a conversion level of about 80% to about 95% to form a polymeric anion of formula B ^(-) ; adding a monovinyl aromatic monomer to the reactor, which first randomly copolymerizes with the remaining conjugated butadiene monomer to form the block copolymer anion В-(В/А) ^(-) until the conjugated diene is completely converted, after which only the monovinyl aromatic monomer is included in the block copolymer anions up to until the monovinyl aromatic monomer is completely converted to form polymeric anions of the formula B-(B/A)-A ₁ ^(-) ; adding a binding agent to the reactor in a limited amount to bind only a part of the copolymer anions B-(B/A)-A ₁ ^(-) thus obtaining a mixture of block copolymer anions Β-(Β/Α)-Α ₁ ^(-) and molecules of the associated block copolymer of the formula [B-(B/A)-A ₁ ] _n -X; adding to the reactor a proton-donor compound or an electrophilic monofunctional additive in a limited amount to deactivate only a part of the block copolymer anions, thus obtaining a mixture of block copolymer anions B-(B/A)-A ₁ ^(-) and molecules of the associated block copolymer of the formula [ B-(B/A)-A ₁ ] _n -X and block copolymers of the formula B-(B/A)-A ₁ ; adding a monovinyl aromatic monomer to the reactor and carrying out the anionic polymerization of this monomer, which is added to the block copolymer anions B-(B/A)-A ₁ ^(-) , thus forming a mixture of block copolymer anions of the formula B-(B/A)- And ₂ ^(-) with an extended chain, the molecules of the associated block copolymer of the formula [B-(B/A)-A ₁ ] _n -X and the molecules of the block copolymer of the formula B-(B/A)-A ₁ ; adding to the reactor a proton-donor compound or an electrophilic monofunctional additive in an amount sufficient to deactivate all remaining block copolymer anions B-(B/A)-A ₂ ^(-) .

Thus, a two-component block copolymer containing two types of block copolymer molecules C and U is produced in situ in a batch reactor, where C is a block copolymer of the general formula [Β-(Β/Α)-Α ₁ ] _n - X and U is a block copolymer of the general formula B-(B/A)-A ₂ and B-(B/A)-A ₁ ; and where B is a polymer block containing only repeating units of the conjugated diene; and where (B/A) is a polymer block containing repeating monovinyl aromatic and conjugated diene units, which are randomly located along the polymer block; and where A ₁ and A ₂ are polymer blocks containing only monovinyl aromatic repeating units; and where the polymer block A ₂ has a higher molecular weight than the polymer block A ₁ ; and where X is the remainder of the binding agent; and where n is an integer from 2 to about 30, depending on the binding agent used; and wherein block copolymer C has a higher molecular weight and lower content of monovinyl aromatic repeating units than block copolymer U.

Another embodiment of the present invention is a method for producing a new two-component block copolymer, including: adding to the reactor a hydrocarbon solvent, a randomizer or a polar modifier, at least a monovinyl aromatic monomer and at least a conjugated diene monomer in any order; adding a monofunctional organolithium initiator to the reactor and carrying out anionic polymerization of monovinyl aromatic monomers and conjugated diene monomers until complete conversion with the formation of an anion of a random copolymer of formula (B/A) ^(-) ; adding a monovinyl aromatic monomer to the reactor and carrying out anionic polymerization of this monomer, which is added to the anions of the random copolymer (B/A) ^(-) , thus forming the anions of the block copolymer of the formula (B/A)-A ₁ ^(-) ; adding a binding agent to the reactor in a limited amount to bind only a part of the anions of the block copolymer (Β/Α)-Α ₁ ^(-) thus forming a mixture of anions of the block copolymer (Β/Α)-Α ₁ ^(-) and molecules of the bound a block copolymer of the formula [(B/A)-A ₁ ] _n -X; adding a monovinyl aromatic monomer to the reactor and carrying out anionic polymerization of this monomer, which is added to the anions of the block copolymer (B/A)-A ₁ ^(-) , thus forming a mixture of block copolymer anions with an extended chain of the formula (B/A)-A ₂ ^(-) and the molecules of the associated block copolymer of the formula [(Β/Α)-Α ₁ ] _n -Χ; adding to the reactor a proton-donor compound or an electrophilic monofunctional additive in an amount sufficient to deactivate all remaining block copolymer anions (B/A)-A ₂ ^(-) .

Thus, a two-component block copolymer containing two types of block copolymer molecules C and U is produced in situ in a batch reactor, where C is a block copolymer of the general formula [(B/A)-A ₁ ] _n -X and U is a block copolymer of general formula (B/A)-A ₂ ; and where (B/A) is a polymer block containing randomly arranged repeating monovinyl aromatic and conjugated diene units; and where A ₁ and A ₂ are polymer blocks containing only monovinyl aromatic repeating units; and where the polymer block A ₂ has a higher molecular weight than the polymer block A ₁ ; and where X is the remainder of the binding agent; and where n is an integer from 2 to about 30, depending on the binding agent used; and wherein block copolymer C has a higher molecular weight and lower content of monovinyl aromatic repeating units than block copolymer U.

Another embodiment of the present invention is a method for producing a new two-component block copolymer, including: adding to the reactor a hydrocarbon solvent, a randomizer or a polar modifier, at least a monovinyl aromatic monomer and at least a conjugated diene monomer in any order; adding a monofunctional organolithium initiator to the reactor and carrying out anionic copolymerization of monovinyl aromatic monomers and conjugated diene monomers until complete conversion with the formation of anions of a random copolymer of formula (B/A) ^(-) ; adding a monovinyl aromatic monomer to the reactor and carrying out anionic polymerization of this monomer, which is added to the anions of the random copolymer (B/A) ^(-) to thereby form the anions of the block copolymer of the formula (B/A)-A ₁ ^(-); adding a binding agent to the reactor in a limited amount to bind only a part of the anions of the block copolymer (B/A)-A ₁ ^(-) thus obtaining a mixture of anions of the block copolymer (B/A)-A ₁ ^(-) and molecules of the bound block copolymer of formula [(B/A)-A ₁ ] _n -X; adding to the reactor a proton-donor compound or an electrophilic monofunctional compound in a limited amount to deactivate only a part of the anions of the block copolymer, thus obtaining a mixture of block copolymer anions of the formula (Β/Α)-Α ₁ ^(-) , molecules of the associated block copolymer of the formula [( Β/Α)-Α ₁ ] _n -Χ and block copolymers of the formula (Β/Α)-Α ₁ ; adding a monovinyl aromatic monomer to the reactor and carrying out the anionic polymerization of this monomer, which is added to the remaining anions of the block copolymer (B/A)-A ₁ ^(-) , thus obtaining a mixture of anions of the formula (B/A)-A ₂ ^(-) block a chain-extended copolymer, linked block copolymer molecules of the formula [(B/A)-A ₁ ] _n -X, and block copolymer molecules of the formula (B/A)-A ₁ ; adding to the reactor a proton-donor compound or an electrophilic monofunctional compound or mixtures thereof in an amount sufficient to deactivate all remaining anions of the (B/A)-A ₂ ^(-) block copolymer.

Thus, a two-component block copolymer containing two types of block copolymer molecules C and U is produced in situ in a batch reactor, where C is a block copolymer of the general formula [(B/A)-A ₁ ] _n -X and U is a block copolymer of the general formula (B/A)-A ₂ and (B/A)-A ₁ ; and where (B/A) is a random polymer block containing repeating monovinyl aromatic and conjugated diene units; and where Α ₁ and A ₂ are polymer blocks containing only monovinyl aromatic repeating units; and where the polymer block A ₂ has a higher molecular weight than the polymer block A ₁ ; and where X is the remainder of the binding agent; and where n is an integer from 2 to about 30, depending on the binding agent used; and wherein block copolymer C has a higher molecular weight and lower content of monovinyl aromatic repeating units than block copolymer U.

Another embodiment of the present invention is a method for producing a new two-component block copolymer, including: adding to the reactor a hydrocarbon solvent, a randomizer or a polar modifier, and at least a conjugated diene monomer in any order; adding a monofunctional organolithium initiator to the reactor and carrying out anionic polymerization of the conjugated diene monomer until complete conversion with the formation of a polymer anion of the formula B ^(-) ; adding a monovinyl aromatic monomer to the reactor and carrying out the anionic polymerization of this monomer, which is added to the polymer anions B ^(-) to thereby form the anions of the block copolymer of the formula B-A ₁ ^(-) ; adding a binding agent in a limited amount to the reactor to bind only a part of the anions of the copolymer B-A ₁ ^(-) thus obtaining a mixture of anions of the block copolymer B-A ₁ ^(-) and molecules of the associated block copolymer of the formula [Β-Α ₁ ] _n -X; adding a monovinyl aromatic monomer to the reactor and carrying out anionic polymerization of this monomer, which is added to the anions of the block copolymer B-A ₁ ^(-) thus forming a mixture of anions of the formula B-A ₂ ^(-) of the extended chain block copolymer and molecules of the associated block -copolymer of the formula [B-A ₁ ] _n -X; adding to the reactor a proton-donor compound or an electrophilic monofunctional additive in an amount sufficient to deactivate all remaining anions of the BA ₂ ^(-) block copolymer.

Thus, a two-component block copolymer containing two types of block copolymer molecules C and U is produced in situ in a batch reactor, where C is a block copolymer of the general formula [Β-Α ₁ ] _n -X and U is a block -copolymer of general formula B-A ₂ ; and where B is a polymer block containing only repeating units of the conjugated diene; and where Α ₁ A ₂ are polymer blocks containing only monovinyl aromatic repeating units; and where the polymer block A ₂ has a higher molecular weight than the polymer block A ₁ ; and where X is the remainder of the binding agent; and where n is an integer from 2 to about 30, depending on the binding agent used; and wherein block copolymer C has a higher molecular weight and lower content of monovinyl aromatic repeating units than block copolymer U.

Another embodiment of the present invention is a method for producing a new two-component block copolymer, including: adding to the reactor a hydrocarbon solvent, a randomizer or a polar modifier and at least a conjugated diene monomer in any order; adding a monofunctional organolithium initiator to the reactor and carrying out anionic polymerization of the conjugated diene monomer until complete conversion with the formation of a polymer anion of formula B ^(-) ; adding a monovinyl aromatic monomer to the reactor and carrying out anionic polymerization of this monomer, which is added to polymer anions B ^(-) to thereby form anions of a block copolymer of the formula Β-Α ₁ ^(-) ; adding a binding agent to the reactor in a limited amount to bind only a part of the anions of the copolymer B-A ₁ ^(-) thus forming a mixture of anions of the block copolymer Β-A ₁ ^(-) and molecules of the associated block copolymer of the formula [BA ₁ ] _n -X; adding to the reactor a proton-donor compound or an electrophilic monofunctional compound in a limited amount to deactivate only a part of the anions of the block copolymer to obtain a mixture of anions of the block copolymer of the formula Β-Α ₁ ^(-) , molecules of the associated block copolymer of the formula [Β-Α ₁ ] _n - Χ and block copolymers of the formula B-A ₁ ; adding a monovinyl aromatic monomer to the reactor and carrying out the anionic polymerization of this monomer, which is added to the remaining anions of the block copolymer B-A ₁ ^(-) , thus forming a mixture of anions B-A ₂ ^(-) of the extended chain block copolymer, molecules of the associated block -copolymer of the formula [BA ₁ ] _n -X and block copolymer molecules of the formula Β-A ₁ ; adding to the reactor a proton-donor compound or an electrophilic monofunctional compound, or mixtures thereof, in an amount sufficient to deactivate all remaining anions of the BA ₂ ^(-) block copolymer.

Thus, a two-component block copolymer containing two types of block copolymer molecules C and U is produced in situ in a batch reactor, where C is a block copolymer of the general formula [Β-Α ₁ ] _n -X and U is a block -copolymer of general formula B-A ₂ and B-A ₁ ; and where B is a polymer block containing only repeating units of the conjugated diene; and where Α ₁ and A ₂ are polymer blocks enriched with monovinyl aromatic repeating units; and where the polymer block A ₂ has a higher molecular weight than the polymer block A ₁ ; and where X is the remainder of the binding agent; and where n is an integer from 2 to about 30, depending on the binding agent used; and wherein block copolymer C has a higher molecular weight and lower content of monovinyl aromatic repeating units than block copolymer U.

In some embodiments of the methods for preparing two-component block copolymers of the invention, proton donors and/or monofunctional electrophilic terminators are added to partially deactivate the anions of the block copolymer prior to block copolymerization of the last batch of monovinyl aromatic monomer. Such terminators may be added to the reactor before the last charge of monovinyl aromatic monomer or simultaneously with the last charge of monovinyl aromatic monomer. Examples of such terminators are water, polymerization inhibitors such as tert-butylcatechol, phenolic antioxidants, alcohols, organic acids, inorganic acids, chlorotrimethylsilane, and the like.

Block copolymerization is usually carried out in inert hydrocarbon solvents in an inert atmosphere with highly purified reagents to prevent premature termination of the polymerization reaction. Suitable solvents for the practice of this invention include, but are not limited to, pentane, hexane, heptane, octane, decane, cyclopentane, cyclohexane, cycloheptane, methylcyclohexane, methyl cycloheptane, benzene, naphthalene, toluene, ethylbenzene, o-xylene, m-xylene , p-xylene, n-propylbenzene, isopropylbenzene, n-butylbenzene, and the like. or mixtures thereof. Cyclohexane is the preferred solvent for the present invention.

In some embodiments, randomizers, also known as polar modifiers, are used to promote the random copolymerization of monovinyl aromatic and conjugated diene monomers to form (B/A) random polymer blocks, as well as to promote the addition of monovinyl aromatic monomers to polymer anions that terminate in conjugated dienyllithium units. Randomizers also increase the 1,2- and 3,4-addition of anionically polymerized conjugated dienes. However, 1,2-vinyl and 3,4-vinyl conjugated diene repeat units are more reactive towards crosslinking/vulcanization reactions. Therefore, the optimum amount of polar modifying compound should be selected to balance the rate of copolymerization in the preparation of the two-component block copolymer of the present invention and the crosslinking kinetics of the microporous rubber composition of the present invention. The acceleration of block polymerization kinetics and the enhancement of 1,2-vinyl and 3,4-vinyl addition during conjugated diene polymerization varies with the chosen polar modifier, a behavior that is well known to those skilled in the art. Polar modifiers that can be used to prepare the two-component block copolymer of the present invention include Lewis bases such as ethers, tertiary amines, amine esters, and ΙA alkali metal alkoxides, as well as combinations thereof. Specific examples of these suitable polar ether modifiers include, but are not limited to, monofunctional, multifunctional, and oligomeric alkyl and cyclic ethers such as dimethyl ether, diethyl ether, ethyl methyl ether, ethyl propyl ether, di-n-propyl ether, methyl- tert-butyl ether, tetramethylene oxide (tetrahydrofuran), 1,2-dimethoxyethane, bis-tetrahydrofuran, ditetrahydrofurylpropane (DTHFP), ethyltetrahydrofurfuryl ether. Specific examples of suitable tertiary amine polar modifiers include, but are not limited to, monofunctional, multifunctional or oligomeric alkyl and cyclic tertiary amines such as dimethylethylamine, trimethylamine, triethylamine, Ν,Ν,Ν',Ν'-tetramethylethylenediamine (TMEDA), Ν ,N,N',N'',N''-pentamethyldiethylenetriamine, 1,3,5-trimethylhexahydro-1,3,5-triazine, combinations thereof, and the like. Specific examples of suitable polar amino ether modifiers include, but are not limited to, tetrahydrofurfuryl-N,N-dimethylamine, bis(2-(dimethylamino)ethyl) ether, 2,2-dimorpholinoethyl ether, and the like, as well as mixtures thereof. . Specific examples of suitable ΙΑ group alkali metal alkoxides (salts of lithium, sodium, potassium, rubidium and cesium) include, but are not limited to, monofunctional, multifunctional and oligomeric alkyl and cyclic metal alkoxides such as sodium t-butoxide, sodium t-amylate , sodium mentholate, potassium t-butoxide, potassium t-amylate, potassium mentholate, potassium 3,7-dimethyl-3-octanolate, and the like, and mixtures thereof. Polar modifiers may be loaded directly into the reactor or may be pre-dissolved in a solvent for use in the process. The concentration of the polar modifier in the reaction system of the invention is 5 to 5000 ppm solvent, more preferably 10 to 1000 ppm solvent, most preferably 20 to 100 ppm solvent.

Suitable conjugated diene monomers for use in preparing the two-component block copolymers of the present invention include, but are not limited to, 1,3-butadiene, isoprene, 1,3-pentadiene, methylpentadiene, phenylbutadiene, 2,3-dimethyl-1,3- butadiene, 2,4-hexadiene, 1,3-hexadiene, 1,3-cyclohexadiene, 3,4-dimethyl-1,3-hexadiene, 1,3-octadiene, 4,5-diethyl-1,3-octadiene and their combinations.

Suitable monovinyl aromatic monomers for use in preparing the two-component block copolymers of the present invention include, but are not limited to, styrene, 3-methylstyrene, α-methylstyrene, p-methylstyrene, α,4-dimethylstyrene, t-butylstyrene, o-chlorostyrene, 2 -butenylnaphthalene, 4-t-butoxystyrene, 3-isopropenylbiphenyl, 4-vinylpyridine, 2-vinylpyridine, isopropenylnaphthalene, 4-n-propylstyrene, and combinations thereof.

The two-component block copolymer of the invention is prepared by anionic polymerization by contacting anionically polymerizable monomers with a monofunctional organolithium compound as an initiator. A preferred class of these compounds may be represented by the formula RLi, where R is a hydrocarbon radical selected from the group consisting of aliphatic, cycloaliphatic and aromatic radicals containing from 1 to 20 carbon atoms, although higher molecular weight initiators may be used. Many anionic polymerization initiators are well known and commercially available. Monofunctional organolithium compounds such as butyllithium are examples of commonly used initiators. Specific examples of these initiators include methyllithium, ethyllithium, t-butyllithium, sec-butyllithium, n-butyllithium, n-decyllithium, isopropyllithium, eicosyllithium, cycloalkyllithium compounds such as cyclohexyllithium, and aryllithium compounds such as phenyllithium, naphthyllithium, p-tolllithium, 1,1-diphenylhexyllithium and the like. Monofunctional organolithium compounds substituted with protected polar functional groups can also be used as anionic polymerization initiators.

In embodiments relating to the process for preparing the two-component block copolymer of the present invention, the amount of monofunctional organolithium initiator varies depending on the desired viscosity of the two-component block copolymer and the purity levels of the solvent and monomers used in the process for their preparation. Preferably, the amount of the monofunctional organolithium initiator in the process for producing a two-component block copolymer of the present invention is from about 2 millimoles to about 30 millimoles per kilogram of total conjugated diene monomer plus the amount of monovinyl aromatic monomer loaded into the reactor, more preferably from about 12 millimoles to about 26 millimoles per kilogram of total conjugated diene monomer plus the amount of monovinyl aromatic monomer loaded into the reactor, most preferably from about 16 millimoles to about 22 millimoles per kilogram of total conjugated diene monomer plus the amount of monovinyl aromatic monomer loaded into the reactor.

Anionic polymerization is usually carried out at temperatures in the range from -100°C to 150°C, preferably from 25°C to 120°C. Typically, 50 to 90% by weight of the reaction solvent is used to control the viscosity within the reaction zone, preferably 70 to 85%. A typical residence time for anionic polymerization varies depending on reaction temperature, monomer concentration and initiator level from 0.1 to 5 hours, preferably from 0.2 to 1 hour.

In embodiments of the methods provided by the present invention, the block copolymer anions obtained by anionic polymerization undergo partial binding. Partial bonding means that a portion of all living chain ends of the anionically polymerized polymer undergoes binding with coupling agents. Reaction of the live chain ends of the anionically polymerized block copolymer with suitable coupling agents results in linked block copolymers without active anionic sites for further polymerization. It is desirable that the coupling agents bind from 2 to 30 anionically polymerized polymer chains, although coupling agents capable of coupling more chains can also be used. Suitable coupling agents for use in the partial coupling step include, but are not limited to, epoxidized soybean oil, silicon halides, a functionalized silicon compound such as a silane compound, and functionalized oligomeric compounds such as those listed in US Pat. No. 7,517,934. The full disclosure of US Pat. No. 7,517,934 is incorporated herein by reference. Silicon tetrachloride, methyl silicon trichloride and dimethyl silicon dichloride are specific examples of suitable coupling agents, silicon tetrachloride being particularly well suited for this application. Partial binding is achieved by controlling the stoichiometric ratio of binding agent to living polymer. Partial bonding provides a mixture of block copolymers with the desired properties.

Upon completion of the polymerization reaction, the entire reaction mixture is then processed to stop the formation of block copolymer anions and recover the two-component block copolymer of the present invention. This termination is achieved by introducing a proton donor compound such as water, alcohol, or an organic or inorganic acid into the reactor. The amount of terminator added should be at least a stoichiometric amount corresponding to the amount of block copolymer anions remaining in the reactor.

The next step in all embodiments of the method for producing a two-component block copolymer of the present invention is the addition of an antioxidant system while the two-component block copolymer is still in hydrocarbon solution. The antioxidant system protects the two-component block copolymer from degradation in later processing steps to separate it from the solvent and extend the shelf life of the final product. A wide variety of antioxidant systems are well known in the art, and any system can be used without limiting the scope of the present invention. Preferred antioxidant systems consist of a synergistic mixture of hindered phenolic and phosphite type antioxidants. Examples of suitable hindered phenolic type antioxidants include, but are not limited to, octadecyl-3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3, 5-ditert-butyl-4-hydroxybenzyl)benzene, pentierythritol-tetrakis(3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate, 2,4-bim(octylmercapto)-6-(4-hydroxy-3 ,5-ditert-butylanilino)-1,3,5-triazine, 2,4-bis(octylthiomethyl)-6-methylphenol, 2,4-bis(dodecylthiomethyl)-6-methylphenol, 2-(1-(2- hydroxy-3,5-ditert-pentylphenyl)ethyl)-4,6-ditert-pentylphenylacrylate, alphatocopherol, etc., and mixtures thereof Examples of suitable phosphite-type antioxidants include, but are not limited to, tris(nonylphenyl)phosphite, tris(2,4-ditert-butylphenyl)phosphite, butylidenebis[2-tert-butyl-5-methyl-p-phenylene]-P,P,P',P'-tetratridecylbis(phosphine), 3,9-bis( 2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, mixed triesters of 2,4-bis(1,1-dimethylpropyl)-phenyl and 4-(1 ,1-dimethylpropyl)phenyl phosphoric acid, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(isodecyloxy)-2,4 ,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 2-(1,1-dimethylethyl)-6-methyl-4-[3-[[2,4,8,10-tetrakis(1, 1-dimethylethyl)-dibenzo-[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]propyl]phenol and the like, and mixtures thereof. The preferred dosage of the antioxidant system is 0.1 to 1.5 parts per hundred parts by weight of the two-component block copolymer of the present invention.

An additional step in all embodiments of the method for producing a two-component block copolymer of the present invention is the separation of the two-component block copolymer from the solvent using any of the finishing methods well known in the art, such as rolling, vacuum evaporation, precipitation and drying, stripping steam followed by dehydration and drying, etc.

An optional step in all embodiments of the method for producing a two-component block copolymer of the present invention is the introduction of a filler oil into the two-component block copolymer. The oil can be added while the two-component block copolymer is still in the hydrocarbon solvent solution, or thereafter at any stage of the finishing process. Suitable carrier oils include, but are not limited to: mineral oil, paraffin oil, naphthenic oils, moderate naphthenic oil, moderate aromatic oil, aromatic oil, high aromatic oil, extremely high aromatic oil, and the like. or mixtures thereof. The preferred oil content is from 0 to 12 parts per hundred by weight of the two-component block copolymer, more preferably from 0 to 10 parts per hundred by weight of the two-component block copolymer, and most preferably from 0 to 8 parts per hundred by weight of the two-component block copolymer. copolymer.

Another aspect of the invention provides compositions for making cross-linked microporous rubber compounds comprising:

two-component block copolymer;

blowing agent or mixture of blowing agents; And

a cross-linking agent; or a mixture of cross-linking agents.

Optionally, the composition includes other additives such as styrene-butadiene random copolymers, styrene-isoprene-butadiene random copolymers, natural rubbers, polybutadienes, polyisoprene rubbers, ethylene/a-olefin/non-conjugated diene terpolymers, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, ground crosslinked microporous rubber compounds, fillers, plasticizers, blowing agent activators, crosslinking activators, crosslinking accelerators, vulcanization retardants, antioxidants, antiozonants, UV stabilizers, light stabilizers, fragrances or odorants, antitermite agents, antimicrobial agents, metal deactivators, dyes, pigments , mold release agents, etc. or mixtures thereof.

Another aspect of the invention provides a composition for obtaining a cross-linked microporous mixture, containing:

(1) a two-component block copolymer containing two types of C and U block copolymer molecules, where:

C is a block copolymer of the general formula [D-(D/A)-A ₁ ] _n -X and U is a block copolymer of the general formula D-(D/A)-A ₂ or D-(D/A) -A ₂ and D-(D/A)-A ₁ ,

D is a polymer block derived from at least a conjugated diene monomer and at least a monovinyl aromatic monomer, wherein the conjugated diene repeating units are in a greater molar amount than the monovinyl aromatic repeating units along the length of the polymer block;

(D/A) is a polymer block consisting of at least a conjugated diene monomer and at least a monovinyl aromatic monomer, wherein the end of the polymer block opposite A ₁ or A ₂ predominantly consists of conjugated diene repeating units and which gradually changes its the composition along its length until it becomes essentially consisting of monovinyl aromatic repeating units towards the end adjacent to Α ₁ or A ₂ ;

Α ₁ and A ₂ are polymer blocks derived from monovinyl aromatic monomer only; polymer block A ₂ has a higher molecular weight than polymer block A ₁ ;

X is the remainder of the binding agent;

n is an integer from 2 to 30; And

the amount of two-component block copolymer is from 50 to 100 parts per hundred mass parts of the original polymeric materials included in the composition to obtain a cross-linked microporous rubber mixture;

(2) a blowing agent or a mixture of chemical blowing agents in an amount of from 1 to 10 parts per hundred mass parts of the original polymeric materials included in the composition to obtain a cross-linked microporous rubber composition; And

(3) a cross-linking agent or a mixture of cross-linking agents in an amount of from 0.5 to 5 parts per hundred mass parts of the initial polymeric materials included in the composition to obtain a cross-linked microporous rubber composition.

The composition may include one or more optional additives such as:

other polymers, including styrene-butadiene random copolymers, styrene-isoprene-butadiene random copolymers, natural rubbers, polybutadienes, polyisoprene rubbers, ethylene/α-olefin/non-conjugated diene terpolymers, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, any mixture thereof, where such polymers preferably include from 0 to about 50 parts per hundred mass parts of the original polymeric materials in the composition to obtain a crosslinked microporous rubber composition;

a filler or a mixture of fillers or a powder of a rubber vulcanized composition, preferably in an amount of from 0 to about 200 parts per hundred mass parts of the starting polymeric materials contained in the composition for obtaining a crosslinked microporous rubber composition;

a plasticizer or a mixture of plasticizers in an amount of from 0 to 40 parts per hundred mass parts of the original polymeric materials contained in the composition for obtaining a crosslinked microporous rubber mixture;

an antioxidant or a mixture of antioxidants, preferably in an amount of 0 to 2 parts per hundred mass parts of the original polymeric materials contained in the composition for obtaining a crosslinked microporous rubber composition;

a blowing agent activator or a mixture of chemical blowing agent accelerators, preferably in an amount of from 0 to about 5 parts per hundred mass parts of the initial polymeric materials contained in the composition for obtaining a cross-linked microporous rubber composition;

a crosslinker activator or a mixture of crosslinker activators, preferably in an amount of 0 to 5 parts per hundred mass parts of the starting polymeric materials contained in the composition for obtaining a crosslinked microporous rubber composition;

a crosslinking accelerator or a mixture of crosslinking accelerators, preferably in an amount of 0 to 5 parts per hundred mass parts of the starting polymeric materials contained in the composition for obtaining a crosslinked microporous rubber composition; And

other additives such as vulcanization retardants, antiozonants, UV stabilizers, light stabilizers, fragrances or odorants, anti-termite agents, antimicrobial agents, metal deactivators, dyes, pigments, mold release agents, and the like, and mixtures thereof.

Another embodiment of the present invention provides a composition for making a crosslinked microporous rubber compound comprising:

(1) a two-component block copolymer containing two types of C and U block copolymer molecules, where the C block copolymer has the general formula [B-(B/A)-A ₁ ] _n Χ and the U block copolymer has the general formula B-(B/A)-A ₂ or B-(B/A)-A ₂ and B-(B/A)-A ₁ ; where B is a polymer block consisting of only one or more conjugated diene monomers, where (B/A) is a polymer block consisting of at least a conjugated diene monomer and at least a monovinyl aromatic monomer, where the repeating units of the conjugated diene and monovinyl aromatic repeating units are randomly distributed along the polymer block, where Α ₁ and A ₂ are polymer blocks derived only from monovinyl aromatic monomer, where the A ₂ polymer block has a higher molecular weight than the A ₁ polymer block, where X is the remainder of the binding agent, where n is an integer from 2 to 30, where the amount of two-component block copolymer is from 50 to 100 parts per hundred mass parts of the original polymeric materials contained in the composition to obtain a crosslinked microporous rubber composition;

(2) a blowing agent or a mixture of chemical blowing agents, preferably in an amount of from 1 to 10 parts per hundred mass parts of the starting polymeric materials contained in the composition for obtaining a crosslinked microporous rubber composition; And

(3) a cross-linking agent or a mixture of cross-linking agents, preferably in an amount of 0.5 to 5 parts per hundred mass parts of raw polymer materials contained in the composition for obtaining a cross-linked microporous rubber composition.

The composition may include one or more optional additives such as:

other polymers, including styrene-butadiene random copolymers, styrene-isoprene-butadiene random copolymers, natural rubbers, polybutadienes, polyisoprene rubbers, ethylene/α-olefin/non-conjugated diene terpolymers, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, any mixture thereof, where such polymers preferably include from 0 to about 50 parts per hundred mass parts of the original polymeric materials in the composition to obtain a crosslinked microporous rubber composition;

filler or mixture of fillers or powder vulcanized rubber composition, preferably in an amount of from 0 to about 200 parts per hundred mass parts of the original polymeric materials contained in the composition to obtain a crosslinked microporous rubber composition;

a plasticizer or a mixture of plasticizers in an amount of from 0 to 40 parts per hundred mass parts of the original polymeric materials contained in the composition for obtaining a crosslinked microporous rubber mixture;

an antioxidant or a mixture of antioxidants, preferably in an amount of 0 to 2 parts per hundred mass parts of the original polymeric materials contained in the composition for obtaining a crosslinked microporous rubber composition;

a blowing agent activator or a mixture of chemical blowing agent accelerators, preferably in an amount of from 0 to about 5 parts per hundred mass parts of the initial polymeric materials contained in the composition for obtaining a cross-linked microporous rubber composition;

a crosslinker activator or a mixture of crosslinker activators, preferably in an amount of 0 to 5 parts per hundred mass parts of the starting polymeric materials contained in the composition for obtaining a crosslinked microporous rubber composition;

a crosslinking accelerator or a mixture of crosslinking accelerators, preferably in an amount of 0 to 5 parts per hundred mass parts of the starting polymeric materials contained in the composition for obtaining a crosslinked microporous rubber composition; And

other additives such as vulcanization retardants, antiozonants, UV stabilizers, light stabilizers, fragrances or odorants, anti-termite agents, antimicrobial agents, metal deactivators, dyes, pigments, mold release agents, and the like, and mixtures thereof.

Another embodiment of the present invention provides a crosslinked microporous blend composition comprising:

(1) a two-component block copolymer containing two types of molecules C and U of the block copolymer, where the block copolymer C has the general formula [B-A ₁ ] _n -X and the block copolymer U has the general formula B-A ₂ or B -A ₂ and Β-Α ₁ ; where B is a polymer block consisting of one or more conjugated diene monomers, Α ₁ and A ₂ are polymer blocks derived from a monovinyl aromatic monomer, polymer block A ₂ has a higher molecular weight than polymer block Α ₁ , X is the remainder of the binding agent, n is an integer from 2 to 30, preferably where the amount of two-component block copolymer is from 50 to 100 parts per hundred mass parts of the original polymeric materials contained in the composition to obtain a crosslinked microporous rubber mixture;

(2) a blowing agent or a mixture of chemical blowing agents, preferably in an amount of 1 to 10 parts per hundred parts by weight of the starting polymeric materials in the composition; And

(3) a cross-linking agent or a mixture of cross-linking agents, preferably in an amount of 0.5 to 5 parts per hundred mass parts of the original polymeric materials in the composition.

Other polymers can be added to the composition, such as: styrene-butadiene random copolymers, styrene-isoprene-butadiene random copolymers, natural rubbers, polybutadienes, polyisoprene rubbers, ethylene/α-olefin/non-conjugated diene terpolymers, ethylene-propylene copolymers, copolymers ethylene and vinyl acetate; and any mixtures thereof, preferably, wherein such polymers comprise from 0 to about 50 parts per hundred parts by weight of the starting polymer materials in the composition to form the crosslinked microporous rubber compound.

The composition may include one or more optional additives such as:

filler or mixture of fillers or powder of the rubber vulcanized mixture, preferably in an amount of from 0 to about 200 parts per hundred mass parts;

a plasticizer or a mixture of plasticizers, preferably in an amount of from 0 to 40 parts per hundred mass parts;

an antioxidant or a mixture of antioxidants, preferably in an amount of 0 to 2 parts per hundred mass parts;

a blowing agent activator or mixture of chemical blowing agent accelerators, preferably in an amount of from 0 to about 5 parts per hundred mass parts;

a crosslinker activator or a mixture of crosslinker activators, preferably in an amount of 0 to 5 parts per hundred mass parts;

a crosslinking accelerator or a mixture of crosslinking accelerators, preferably in an amount of 0 to 5 parts per hundred mass parts; And

other additives such as vulcanization retardants, antiozonants, UV stabilizers, light stabilizers, fragrances or odorants, anti-termite agents, antimicrobial agents, metal deactivators, dyes, pigments, mold release agents, and the like, and mixtures thereof.

Another embodiment of the present invention provides a crosslinked microporous blend composition comprising: a two-component block copolymer, a blowing agent and a crosslinking agent. The two-component block copolymer includes C and U molecules of the block copolymer, where:

block copolymer C has the general formula [(B/A)-A ₁ ] _n -X and block copolymer U has the general formula (B/A)-A ₂ or (B/A)-A ₂ and (B/A )-A ₁ ;

(B/A) is a polymer block consisting of at least a conjugated diene monomer and at least a monovinyl aromatic monomer, preferably wherein the conjugated diene repeat units and the monovinyl aromatic repeat units are randomly distributed along the polymer block;

Α ₁ and Α ₂ are polymer blocks derived from monovinyl aromatic monomer, polymer block A ₂ has a higher molecular weight than polymer block A ₁ ;

X is the remainder of the binding agent; And

n is an integer from 2 to 30, preferably where the amount of two-component block copolymer is from 50 to 100 parts per hundred mass parts of the starting polymer materials contained in the composition for obtaining a crosslinked microporous rubber composition. The blowing agent is preferably added in an amount of 1 to 10 parts per hundred mass parts, and the crosslinking agent is preferably added in an amount of 0.5 to 5 parts per hundred mass parts.

Optional ingredients in the composition, in parts per hundred parts by weight of polymeric starting materials contained in the composition to form a crosslinked microporous rubber compound, include:

other polymers, including styrene-butadiene random copolymers, styrene-isoprene-butadiene random copolymers, natural rubbers, polybutadienes, polyisoprene rubbers, ethylene/α-olefin/non-conjugated diene terpolymers, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, any mixture thereof, preferably in an amount from 0 to about 50;

a filler or a mixture of fillers or a powder of a rubber vulcanized mixture, preferably in an amount of from 0 to about 200 parts;

a plasticizer or a mixture of plasticizers, preferably in an amount of 0 to 40 parts;

an antioxidant or a mixture of antioxidants, preferably in an amount of 0 to 2 parts;

a blowing agent activator or mixture of chemical blowing agent accelerators, preferably in an amount of 0 to about 5 parts;

a crosslinker activator or a mixture of crosslinker activators, preferably in an amount of 0 to 5 parts per hundred mass parts;

a crosslinking accelerator or a mixture of crosslinking accelerators, preferably in an amount of 0 to 5 parts; And

other additives such as vulcanization retardants, antiozonants, UV stabilizers, light stabilizers, fragrances or odorants, antitermite agents, biocidal agents, antifungal agents, antimicrobial agents, antibacterial agents, metal deactivators, dyes, pigments, mold release agents, and the like. , as well as their mixtures.

Suitable fillers for use in the crosslinked microporous foam rubber composition of the present invention include, but are not limited to, carbon black, silica, calcium silicate, aluminum silicate, magnesium silicate, sodium silicate, potassium silicate, chalk, dolomite, kaolin clay, calcined clay , hard clay, activated clay, halloysite, sericite, wollastonite, bentonite, light calcium carbonate, heavy calcium carbonate, magnesium carbonate, talc, diatomaceous earth, titanium oxide, zinc oxide, calcium oxide, aluminum hydroxide, magnesium hydroxide, gypsum, mica, barium sulfate, calcium sulfate, alumina trihydrate, natural fibers, synthetic fibers, and combinations thereof.

Suitable plasticizers for use in the crosslinked microporous foamable rubber composition of the present invention include, but are not limited to, mineral oils such as paraffin oil, naphthenic oil, moderate naphthenic oil, moderate aromatic oil, aromatic oil, highly aromatic oil, extremely highly aromatic oil; paraffins such as straight paraffins, isoparaffins, ceresins, isoceresins, paraffin wax and other mineral waxes; VAT residues of hydrocarbons such as mountain waxes, ozocerite, asphalt, bitumen and pitch; fatty acids such as stearic acid or palmitic acid; fatty acid metal salts such as unsaturated fatty acid zinc soap, saturated fatty acid zinc soap, unsaturated fatty acid calcium soap, zinc stearate and calcium stearate; organic acid monoesters such as alkyl or alkoxyalkyl oleates and stearates; organic acid diesters such as dialkyl, dialkoxyalkyl and alkylaryl phthalates, terephthalates, sebacates, adipates and glutarates; coumarone and indene resins; trialkyl, trialkoxyalkyl, alkyldiaryl and triaryl phosphates; esters of polyhydric alcohols and fatty acids, such as pentaerythritol-tetrastearate; castor oil, linseed oil, rapeseed oil, coconut oil, palm oil, soybean oil, epoxidized soybean oil, tall oil, pine resin, beeswax, carnauba wax, lanolin, factis, and combinations thereof.

Suitable antioxidants for use in the crosslinked microporous foam rubber composition of the present invention include, but are not limited to, hindered phenols such as 2,6-di-tert-butyl-para-cresol (BHT), 2,4-dimethyl-6- t-butylphenol, 2,4-dimethyl-6-(α-methylcyclohexyl)-phenol, 4-methoxymethyl-2,6-di-tert-butylphenol, butylated reaction product of p-cresol and dicyclopentadiene, alkylated phenol, styrolyzed and alkylated phenol , styrolyzed phenol (SPH), pentaerythritol-tetrakis(3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate), 2-(1,1-dimethylethyl)-6-[[3-(1,1- dimethylethyl)-2-hydroxy-5-methylphenyl]methyl]-4-methylphenylacrylate; bisphenols such as 2,2'-methylene-bis-(4-methyl-6-tert-butyl-phenol) (BPH), 2,2'-methylene-bis(4-methyl-6-cyclohexylphenol) (CPH) , 2,2'-isobutylidene-bis-(4,6-dimethylphenol) (ΙΒΡΗ), 2,2'-dicyclopentyl-bis(4-methyl-6-tert-butylphenol) (DBPH), 2,2'-methylene -bis(4-ethyl-6-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol); benzimidazole derivatives such as 2-mercapto-benzimidazole (MΜΒΙ), 4-methyl-2-mercaptobenzimidazole and 5-methyl-2-mercaptobenzimidazole (MΜΒΙ), zinc-2-mercaptobenzimidazole (ΖΜΒΙ), zinc-4-methyl-2- mercaptobenzimidazole and zinc-5-methyl-2-mercaptobenzimidazole (ΖΜΜΒΙ).

Suitable blowing agents for use in the crosslinked microporous foam rubber composition of the present invention include, but are not limited to, organic chemical blowing agents such as azodicarbonamide (ADC), N,N'-dinitrosopentamethylenetetramine (DNPT), benzenesulfohydrazide (BSH), benzene- 1,3-disulfohydrazide, 4,4'-oxybis-(benzenesulfonylhydrazide), p-toluenesulfonic acid hydrazide, toluenesulfonylsemicarbazide, 5-phenyltetrazole, trihydrazinetriazine; inorganic chemical blowing agents such as sodium hydrogen carbonate, sodium carbonate, ammonium hydrogen carbonate, ammonium carbonate, potassium hydrogen carbonate, potassium carbonate; physical blowing agents such as nitrogen or high pressure supercritical carbon dioxide, and combinations thereof.

Suitable chemical blowing agent activators for use in the crosslinked microporous foam rubber composition of the present invention include, but are not limited to, zinc oxide, zinc benzenesulfinate, zinc stearate, zinc 2-ethylhexanoate, zinc carbonate, zinc ditolylsulfonate, calcium carbonate, calcium oxide, oxide magnesium, silicon dioxide, urea, stearic acid, adipic acid, triethanolamine, diphenylamine derivatives, and combinations thereof.

Suitable crosslinking agents for use in the crosslinked microporous foam rubber composition of the present invention include, but are not limited to, sulfur; sulfur donors such as dithiodimorpholine (DTDM), caprolactam disulfide, N,N'-dithio-bis-(hexahydro-2H-azepinone) (CLD), 2-morpholinodithio-benzothiazole (MBSS), dipentamethylenethiuram tetrasulfide (DPTT), N- oxydiethylene-dithiocarbamyl-N'-oxydiethylene-sulfonamide (OTOS), and tetramethyl-thiuramsulfide (TMTD); and organic peroxides such as dicumyl peroxide, t-butylperbenzoate, t-butylcymyl peroxide, di-t-butyl peroxide, lauroyl peroxide, 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane, α,α'-bis( tert-butylperoxy)-1,3-diisopropylbenzene, α,α'-bis(tert-butylperoxy)-1,4-diisopropylbenzene, n-butyl-4,4-bis(tert-butylperoxy)valerate, tert-butylperoxyisopropyl carbonate, 1 ,4-bis-(t-butylperoxyisopropyl)benzene, di-t-amyl peroxide, t-butylperoxybenzoate, t-amylperoxybenzoate, 1,1-bis-(t-butylperoxy)-3,3,5-trimethylcyclohexane, and the like. or mixtures thereof.

Suitable crosslinking accelerators for use in the crosslinked microporous foam rubber composition of the present invention include, but are not limited to, mercapto accelerators such as 2-mercapto-benzothiazole (MBT), dibenzothiazyl disulfide (MBTS), zinc-2-mercaptobenzothiazole (ZMBT); sulfonamide accelerators such as N-cyclohexyl-2-benzothiazylsulfenamide (CBS), N-tert-butyl-2-benzothiazylsulfenamide (TBBS) and 2-benzothiazyl-N-sulfenmorpholide (MBS); thiuram accelerators such as tetramethylthiuram disulfide (TMTD), tetramethylthiuram monosulfide (TMTM), and tetraethylthiuram disulfide (TETD); dithiocarbamate accelerators such as zinc dimethyldithiocarbamate (ZDMC), zinc diethyldithiocarbamate (ZDEC), and zinc dibutyldithiocarbamate (ZDBC); dithiocarbamylsulfenamide accelerators such as N-oxydiethylenedithiocarbamyl-N'-oxydiethylenesulfonamide (OTOS); guanidine accelerators such as diphenylguanidine (DPG), di-o-tolylguanidine (DOTG) and o-tolylbiguanidine (OTBG), triazine accelerators, xanthate accelerators, aldehyde-amine accelerators, amine accelerators, thiourea accelerators, dithiophosphate accelerators, and mixtures thereof.

Suitable crosslinker activators for use in the crosslinked microporous foam rubber composition of the present invention include, but are not limited to, zinc oxide, magnesium oxide, Ca(OH) ₂ , stearic acid, zinc stearate, zinc laureate, dibutylaminooleate, 1,3-diphenylguanidine phthalate , monoethanolamine, diethanolamine, triethanolamine, dibutylamine, dibenzylamine and mixtures thereof.

Another aspect of the invention provides compositions for making hot melt pressure sensitive adhesives comprising:

two-component block copolymer;

tackifying resin; And

filler oil or plasticizer; And

antioxidant.

The pressure-sensitive hot melt adhesive composition optionally includes other additives such as: fillers, waxes, photoinitiators, cross-linking agents, cross-linking co-agents, cross-linking retarders, adhesion promoters or coupling agents, UV stabilizers, light stabilizers, ozone stabilizers, epoxy resins, asphalt , reinforcing resins, fragrances or odorants, anti-termite agents, biocidal agents, antifungal agents, antibacterial agents, metal deactivators, dyes, pigments, colorants, flame retardants, blowing agents, blowing agent activators or refractive index adjusting agents.

A preferred embodiment of the present invention is a pressure sensitive hot melt adhesive composition comprising:

(a) from about 20 wt. % to about 50 wt. % of a two-component block copolymer with a molecular weight distribution having at least two fully or partially resolved peaks, and containing C and U, where

C is encompassed by the higher molecular weight peak in the molecular weight distribution of the two-component block copolymer and contains the molecules of the linked block copolymer of the formula:

[D-(D/A)-A ₁ ] _n -X; or

[B-(B/A)-A ₁ ] _n -X; or

[(Β / Α) -Α ₁ ] _n -Χ; or

[Β-Α ₁ ] _n -Χ, or mixtures of the above, and where

U is encompassed by the remaining lower molecular weight peak, or peaks, in the molecular weight distribution of the two-component block copolymer and contains unbound block copolymer molecules of the formula:

D-(D/A)-A ₂ or D-(D/A)-A ₂ and D-(D/A)-A ₁ ; or

B-(B/A)-A ₂ or B-(B/A)-A ₂ and B-(B/A)-A ₁ ; or

(B/A)-A ₂ or (B/A)-A ₂ and (B/A)-A ₁ ; or

V-A ₂ or V-A ₂ and V-A ₁ or mixtures of the above, where

B is a polymer block derived only from a conjugated diene monomer, where

(B/A) is a random polymer block made from at least a conjugated diene monomer and at least a monovinyl aromatic monomer, where

D is a polymer block consisting of at least a conjugated diene monomer and at least a monovinyl aromatic monomer, where the conjugated diene repeat units are in a greater molar amount than the monovinyl aromatic repeat units along the length of the polymer block, where

(D/A) is a polymer block consisting of at least a conjugated diene monomer and at least a monovinyl aromatic monomer, where the end of the polymer block opposite A ₁ or A ₂ predominantly consists of repeating units of the conjugated diene, where the composition of the polymer block gradually changes along the length of the block until it is essentially composed of monovinyl aromatic repeat units at the end adjacent to A ₁ or A ₂ , where

Α ₁ and A ₂ are polymer blocks derived from monovinyl aromatic monomer only, where the A ₂ polymer block has a higher molecular weight than the Α ₁ polymer block, where

X is the remainder of the binding agent, and where

n is an integer from 2 to 30;

(b) from about 30 wt. % to about 70 wt. % tackifying resin;

(c) from about 10 wt. % to about 30 wt. % filler oil or plasticizer;

(d) from about 0.05 wt. % to about 3.0 wt. % antioxidant;

(e) optionally, other additives such as: fillers, waxes, photoinitiators, cross-linking agents, cross-linking co-agents, cross-linking retarders, adhesion promoters or coupling agents, UV stabilizers, light stabilizers, ozone stabilizers, epoxy resins, asphalt, reinforcing resins, fragrances or odorants, anti-termite agents, biocidal agents, antifungal agents, antibacterial agents, metal deactivators, dyes, pigments, colorants, flame retardants, blowing agents, blowing agent activators or refractive index adjusting agents.

Suitable tackifying resins for use in the hot melt pressure sensitive adhesive composition of the present invention include, but are not limited to: rosin esters such as Sylvalite® RE100L, Sylvalite® RE115, Sylvalite® RE85L, Foral® 85, Foral® 105, Pentalyn® H, and Permalyn® 3100; styrolyzed terpenes such as Sylvares® ZT5100, Sylvares® ZT105LT, and Sylvares® ZT115LT; polyterpene resins such as Sylvares® TR1100, and Sylvares® TR7115; terpene phenols such as Sylvares® TP2040 and Sylvares® TP115; aliphatic hydrocarbon resins such as Piccotac® 1100, Piccotac® 115, and Wingtack® 95; hydrogenated hydrocarbon resins such as Regalrez® 1094, Eastotac® Η100, and Eastotac® Η130. Sylvalite® and Sylvares®; terpenephenol resins; synthetic C5 resins; alkyl-aryl resins; phenol-formaldehyde resins and the like, and mixtures thereof. Tackifying resins are commercially available from Kraton Corporation. Tackifier resins Foral®, Pentalyn®, Permalyn®, Piccotac®, Regalrez®, and Eastotac® are commercially available from Eastman Chemical Company. Tackifying resins Wingtack® are commercially available from Total CrayValley.

Suitable extender oils for use in the pressure sensitive hot melt adhesive of the present invention include, but are not limited to: mineral oils; naphthenic oils; paraffin oils; aroma oils; vegetable oils; oils of animal origin and the like, and mixtures thereof.

Suitable plasticizers for use in the hot melt pressure sensitive adhesive of the present invention include, but are not limited to: olefin oligomers; epoxy oils; phthalates such as dioctyl phthalates, diisoundecyl phthalate, diisononyl phthalate; dialkyl esters of aliphatic dicarboxylic acids; polybutene or polyisobutylene with a molecular weight below 3000 and the like, and mixtures thereof.

Suitable antioxidants for use in the hot melt pressure sensitive adhesive of the present invention include, but are not limited to: phenolic antioxidants such as Irganox® 1010, Irganox® 1076, Irganox® 565, Irganox® 1520, Irganox® 1098, Anox® 20 or Ultranox® 276; phosphite antioxidants such as: Alkanox® TNPP, Alkanox® 240, Ultranox® 626 or Weston® 618F; thioether antioxidants such as Naugard® DSTDP; and mixtures thereof, such as Ultranox® 877A. Irganox® antioxidants are commercially available from BASF; Anox®, Ultranox®, Alkanox®, Weston® and Naugard® antioxidants are commercially available from Addivant.

Examples

The following examples are intended to show the features of the present invention and are not intended to limit its scope. Comparative examples using prior technologies are included for comparison. The two-component block copolymers, as well as the prior art copolymers synthesized in the ^following examples and comparative examples, were characterized by the following methods: the content of repeating units of styrene, as well as the content of styrene in the blocks. The total content of repeating units of styrene in block copolymers is measured in accordance with the international standard ISO 21561-1. In the following examples, the total content of repeating units of styrene is indicated in mass percent of the total mass of the block copolymer. The measurement of styrene content in blocks takes into account repeating styrene units included as homopolymer blocks; that is, the number of styrene repeating units forming part of a given block copolymer that do not have covalent bonds with the conjugated diene monomer. The styrene content of the blocks is measured by proton NMR as described in US Pat. No. 9,771,473 B2. In the following examples, the styrene content of the blocks is given as a percentage by weight of the total block copolymer. Since styrene is the only monovinyl aromatic monomer used in these examples, the total monovinyl aromatic repeating units (%A _t ) quantitatively corresponds to the total styrene content measured in the examples. Likewise, the degree of blockiness of the monovinyl aromatic repeating units in these examples is calculated as the ratio of the styrene content of the blocks to the total styrene content, and is expressed as mole percent based on the monovinyl aromatic repeating units.

Gel permeation chromatography (GPC) using Waters Alliance e2695 HPLC in combination with a set of three columns to cover the molecular weight measurement range from 1000 to 4,000,000 g/mol, related to the narrow standards of polystyrene MWD , worked with a differential refractive index detector and a diode array detector in series. In GPC-RI mode (RI - refractive index from English, refractive index) to measure molecular weight distribution, weight average molecular weight (M _w ) and polydispersity index of molecular weight distribution (MWD, ratio of weight average molecular weight and number average molecular weight, M _w /M _p ) of the various block copolymers analyzed used a differential refractive index detector signal and a universal calibration curve of molecular weight versus elution time based on narrow MWD (molecular weight distribution) polystyrene standards. GPC-RI was also used to estimate the amount of bound block copolymer (%C _ri ) by integrating the highest molecular weight peak and reported as a percentage of the total molecular weight distribution according to the GPC-RI of the analyzed block copolymer when in molecular weight distribution many peaks appeared. In GPC-UV mode, to measure the weighted number of monovinyl aromatic repeating units of the associated block copolymer (% C _uv ), a diode array detector signal at a wavelength of 261 nm, which responds only to the number of monovinyl aromatic repeating units in the block copolymer, as well as a universal calibration a molecular weight curve derived from narrow MWD polystyrene standards; % C _uv was obtained by integrating the highest molecular weight peak in the weighted molecular weight distribution of monovinyl aromatic repeating units, and reported as a percentage of the total weighted molecular weight distribution of monovinyl aromatic repeating units according to GPC-UV when multiple peaks appeared in the molecular weight distribution.

%A _t (i.e., total styrene repeating units) derived from proton NMR, %C _ri derived from GPC-RI, and %C _uv derived from GPC-UV are then used to calculate the weight percent the content of monovinyl aromatic repeating units in the unbound fraction of the block copolymer, %A _U , and is also used to calculate the weight percentage of monovinyl aromatic repeating units in the bound fraction of the block copolymer, %A _C . Finally, they are used to calculate the difference in monovinyl aromatic repeating units between unbound and bound fractions of block copolymers, % CD, as follows:

The viscoelastic properties of the block copolymers obtained in the examples were evaluated on the RPA 2000 equipment from Alpha Technologies. Vibrational shear measurements are carried out at 100° C. or 140° C. with a maximum strain of 13.95%. The complex dynamic shear viscosity (η*) is recorded at vibration frequencies of 0.99 and 100 rad/s, and the tangent of the delta angle is recorded at several vibration frequencies covering the frequency range from 0.25 to 200 rad/s. Mooney Viscosity (ML 1+4) is determined at 100°C using Monsanto Mooney MV 2000 equipment in accordance with ASTM D1646.

Example 1 according to the invention:

Synthesis of a two-component block copolymer; a prototype prepared using silicon tetrachloride as a coupling agent, 0.896 kg of cyclohexane, 0.042 kg of styrene and 0.105 kg of butadiene were charged into a 2-liter reactor under nitrogen atmosphere with stirring. The initial loading of the reactor was heated to a temperature of 74.0°C, after which 2.845 mmol of n-butyllithium was fed into the reactor. The polymerization of the first batch of monomer reached a maximum temperature of 110.8°C. After a 1 minute wait, 0.188 mmol of a coupling agent based on silicon tetrachloride was loaded into the reactor. After a 5-minute wait, 0.028 kg of styrene was loaded into the reactor, during this loading the temperature of the reactor momentarily dropped to 91.6°C. As a result of the heat of polymerization of the second load of styrene, the reaction reached a maximum temperature of 94.7°C. After a 1 minute wait, 1.782 millimoles of a monofunctional alcohol were fed into the reactor to stop the formation of polymer anions. The specific composition and polymerization process conditions for this two-component block copolymer synthesis example are shown in Table 1. Then, 0.5 wt.h. phenolic antioxidant and 0.6 wt.h. phosphite antioxidant. The block copolymer was isolated by rolling. The weight average molecular weight (M _w ) of the synthesized two-component block copolymer was 169.8 kg/mol. The molecular weight distribution shows a polydispersity index of 1.26. The molecular weight distribution of the block copolymer has two peaks: a low molecular weight peak corresponding to the unbound linear gradient block copolymer of formula D-(D/A)-A ₂ and a high molecular weight peak corresponding to the bound gradient styrene-butadiene block -copolymer [D-(D/A)-A ₁ ] _n=2-4 -Si. The content of bound gradient block copolymer (%C _ri ) was 27.4% of the total molecular weight distribution of the block copolymer as determined by GPC-RI. The weighted level of binding of monovinyl aromatic repeating units according to GPC-UV (% C _uv ) was 22.0%. The total content of repeating units of styrene in the two-component block copolymer was 40.0 wt. %, and the content of block styrene was 31.8 wt. %. Therefore, the degree of blockiness of the monovinyl aromatic repeating units in the two-component block copolymer was 79.5 mol%. The content of monovinyl aromatic repeating units in the fraction of the associated gradient block copolymer (% _AS ) was 32.2 wt. %, and in the fraction of unbound gradient block copolymer (% A _U ) - 42.9 wt. % as determined by calculation using binding levels measured by GPC-RI and GPC-UV and total styrene measured by proton NMR. The difference in the content of monovinyl aromatic repeating units between unbound and bound fractions of the gradient block copolymer (%CD) was 10.7%. The specific characteristics of this two-component block copolymer, determined by GPC and NMR, are shown in Table 2. The complex dynamic shear viscosity of the two-component block copolymer at 0.99 rad/s was 76198 Pa-s and decreased to 4744 Pa-s at an oscillation frequency of 100 rad/s. The tan delta of the two-component block copolymer showed predominantly elastic behavior (tan delta less than 1.00) over the entire frequency range from 0.25 to 200 rad/s with a maximum value of 0.81 at 2.51 rad/s (Tan delta _max ). Details of the rheological characteristics of this two-component block copolymer are shown in Table 3.

Embodiments of the invention

As used herein, the terms two-component block copolymer or two-component block copolymers (DCBC) refer to polymer blends that contain two types of block copolymer molecules that differ in molecular weight, block structure, and monovinyl aromatic repeating unit content. A molecular weight distribution with two peaks, such as shown for Comparative Example C-2 in FIG. 9 does not by itself meet the characteristics required for DCBC. Various other characteristics are also required for DCBC according to the present invention. Aspects to consider for DCBC include: higher content of monovinyl aromatic repeating units in the unbound fraction; a binding agent that connects the internal blocks of the monovinyl aromatic homopolymer; a certain range of binding; a certain range of total content of monovinyl aromatic repeating units; certain structures of conjugated diene blocks; Mooney viscosity range; complex viscosity range and tan delta profile, although not all of these aspects are required to characterize the two-component block copolymer of the present invention. Some embodiments of methods for obtaining DCBC are presented below. The claims submitted to grant a patent for this invention are incorporated into this specification by reference to provide direct, verbatim support for the claims in the specification.

1. A method for producing a two-component block copolymer, including the following steps:

loading the batch reactor with a solvent such as cyclohexane, a monovinyl aromatic monomer such as styrene, and a conjugated diene monomer such as butadiene to provide initial content [with or without a randomizer or polar modifier for alternatives];

[in alternative embodiments, only the conjugated diene is initially charged, without the monovinyl aromatic monomer, and is either fully or partially converted]

mixing and heating the original content;

adding n-butyllithium or a similar lithium initiator to the reactor;

polymerization of the original content and the formation of polymeric anions;

partial binding of the polymer anions by adding a coupling agent such as silicon tetrachloride or methyl silicon trichloride to the reactor, and preferably waiting less than 10 minutes, more preferably less than about 1 minute;

[in another embodiment, the polymer anions are partially deactivated at this stage]

adding additional monovinyl aromatic monomer, such as styrene, to the reactor;

[you can use the same or a different monovinyl aromatic monomer]

addition of a chain terminating agent, such as a monofunctional alcohol, to the reactor, resulting in deactivation of the polymer anions.

adding to the reactor, preferably an antioxidant, such as a phenolic antioxidant and/or a phosphite antioxidant; And

isolation of the block copolymer by any of the methods well known in the art, such as stripping - dehydration - steam drying, direct desolventization, vacuum removal of the solvent, and the like.

2. The method according to embodiment 1, wherein the weight average molecular weight ( _Mw ) of the synthesized two-component block copolymer is in the range of 70 to 500, preferably 120 to 230, and more preferably 150 to 180 kg/mol, wherein one example is is the value of 169.8 kg/mol.

3. The method according to embodiment 1 or 2, wherein the two-component block copolymer has a molecular weight distribution with two peaks and a polydispersity index between 1.00 and 1.90, preferably between 1.10 and 1.40, more preferably - between 1.20 and 1.33, where 1.26 is a particular example.

4. The method according to embodiment 3 wherein one of the two peaks is a lower molecular weight peak and the other peak is a higher molecular weight peak, wherein the lower molecular weight peak corresponds to an unbound linear gradient block copolymer having formula D -(D/A)-A ₂ where the higher molecular weight peak corresponds to the associated gradient, preferably styrene-butadiene block copolymer having the formula [D-(D/A)-A ₁ ] _n=2-4 -Si .

5. The method according to embodiment 4, wherein the content of bound gradient block copolymer (%C _ri ]) in the total molecular weight distribution of the block copolymer, as determined by the GPC-RI method, is between 20 and 80%, preferably between 25 and 50%, more preferably between 30 and 45% with typical values between 35 and 42%, with 38.6% being a particular example.

6. Process according to embodiment 1 or 5 wherein the difference in monovinyl aromatic repeating units between unbound and bound fractions of the %CD bicomponent block copolymers is between 10% and 35%, preferably between 15% and 30%, more preferably between 17% and 28% with typical values between 20 and 26%, where 25.6% is a particular example.

7. The method according to embodiment 1, 5 or 6, wherein the blockiness of the monovinyl aromatic repeating units is between 76 and 88 mol%, preferably between 78 and 86 mol%, more preferably between 80 and 83 mol%, where the value 82.3 mol.% is a particular example.

8. The method according to option implementation 1, 5, 6 or 7, where the total content of monovinyl aromatic repeating units, %A _t , two-component block copolymer is between 20 and 50 wt. %, preferably between 30 and 50 wt. %, more preferably between 38 and 48 wt. %, where the value is 40.1 wt. % is a particular example.

9. The method according to embodiment 1, 7 or 8, where the total content of monovinyl aromatic repeating units of the fraction of the associated gradient block copolymer (% A _C ) is between 5 and 35 wt. %, preferably between 15 and 30 wt. %, more preferably between 20 and 25 wt. %, where the value is 24.8 wt. % is a particular example.

10. The method according to embodiment 1, 7, 8 or 9, wherein the complex dynamic shear viscosity of the two-component block copolymer at 0.99 rad/s is between 50,000 and 360,000 Pa-s, preferably between 60,000 and 90,000 Pa-s or more preferably between 70.000 and 82.000, where 76.198 Pa-s is one example.

11. The method of Embodiment 10 wherein the complex dynamic shear viscosity of the two-component block copolymer at 100 rad/s is between 3,000 and 12,000 Pa-s, preferably between 4,200 and 5,200 Pa-s, and more preferably between 4,500 and 4,900 Pa-s, where the value 4.744 Pa-s is one example.

12. The method according to any one of embodiments 1-11, wherein the coupling agent is silicon tetrachloride.

13. The method according to any one of embodiments 1-11, wherein the coupling agent is methyl silicon trichloride.

14. The method according to embodiment 1 or 2, wherein the two-component block copolymer has a molecular weight distribution with three peaks.

15. The method of Embodiment 14 wherein the weight average molecular weight (M _w ) of the synthesized two-component block copolymer is in the range of 70 to 500, preferably 140 to 190, and more preferably 150 to 180 kg/mol, where the value is 159 .6 kg/mol is one example.

16. The method according to embodiment 15, wherein the two-component block copolymer has a polydispersity index between 1.00 and 1.90, preferably between 1.10 and 1.40, more preferably between 1.15 and 1.30, where the value 1.22 is a particular example.

Example 2 according to the invention:

Synthesis of a two-component block copolymer; the prototype was obtained using silicon trichloride as a coupling agent. To obtain a two-component block copolymer, the same procedure was used as in Example 1, but instead of silicon tetrachloride, 0.230 mmol of methyl silicon trichloride was used as a coupling agent. The specific composition and polymerization process conditions for this two-component block copolymer synthesis example are shown in Table 1. Then, 0.5 wt.h. phenolic antioxidant and 0.6 wt.h. phosphite antioxidant. The block copolymer was isolated by rolling. The weight average molecular weight (Mw) of the synthesized two-component block copolymer was 171.8 kg/mol. The molecular weight distribution shows a polydispersity index of 1.19. The molecular weight distribution of the block copolymer showed two peaks: a low molecular weight peak corresponding to the unbound linear gradient block copolymer of formula D-(D/A)-A ₂ and a high molecular weight peak corresponding to the bound gradient styrene-butadiene block -copolymer [D-(D/A)-A ₁ ] _n=2-3 -Si-CH ₃ . The content of bound gradient block copolymer (%C _ri ) was 25.5% of the total molecular weight distribution of the block copolymer as determined by GPC-RI. The total content of repeating units of styrene in two-component block copolymers was 40.2 wt. %, and the content of block styrene was 32.1 wt. %. Therefore, the degree of blockiness of the monovinyl aromatic repeating units in the two-component block copolymer was 79.9 mol%. The specific characteristics of this two-component block copolymer, determined by GPC and NMR, are shown in Table 2. The complex dynamic shear viscosity of the two-component block copolymer at 0.99 rad/s was 72962 Pa-s and decreased to 4833 Pa-s at an oscillation frequency of 100 rad/s. The tan delta of the two-component block copolymer exhibited predominantly elastic behavior (tan delta less than 1.00) over the entire frequency range from 0.25 to 200 rad/s with a maximum value of 0.86 at 0.99 rad/s. Details of the rheological characteristics of this two-component block copolymer are shown in Table 3.

Examples 3-12 according to the invention:

Synthesis of two-component block copolymers; prototypes with wide differences in levels of viscosity, binding and composition. A 189 liter reactor was charged with 71.50 plus/minus 0.14 kg of cyclohexane, about 1.58 or about 2.56 kg of styrene, and 6.64 plus/minus 0.02 kg of butadiene under nitrogen with stirring. The initial temperature of the reactor was set from about 56.0 to about 66.0°C, and then from about 273.0 to about 321.0 millimoles of n-butyllithium was fed into the reactor. The polymerization of the first batch of monomer reached a maximum temperature of about 99.7 to about 104.8°C. After a 1 minute wait, about 13.88 to about 31.42 millimoles of silicon tetrachloride coupler were loaded into the reactor. After a 5 minute wait, approximately 2.78 or approximately 1.82 kg of styrene was charged to the reactor. When loading the last monomer, the temperature of the reactor dropped to about 98.1 plus/minus 2.4°C. Due to the heat of the polymerization reaction of the second batch of styrene, the reaction temperature increased to about 102.0 plus/minus 1.5°C. After a 1 minute wait, 143.3 plus/minus 23.3 millimoles of a monofunctional alcohol were fed into the reactor to deactivate the polymer anions. The specific composition and polymerization process conditions for each example of the synthesis of a two-component block copolymer are shown in Table 1. Then, 0.5 wt.h. phenolic antioxidant and 0.6 wt.h. phosphite antioxidant. The block copolymer was isolated by steam stripping and drying in an oven. The weight average molecular weight (M _w ) of the synthesized block copolymers ranged from 147.4 to 225.5 kg/mol. The molecular weight distribution showed a polydispersity index of 1.24 to 1.40. The molecular weight distribution of the block copolymer showed two peaks: a low molecular weight peak corresponding to the unbound linear gradient block copolymer of formula D-(D/A)-A ₂ and a high molecular weight peak corresponding to the bound gradient styrene-butadiene block -copolymer of the formula [D-(D/A)-A ₁ ] _n=2-4 -Si. The content of the associated gradient block copolymer (%C _n ) ranged from 23.0 to 38.6% of the total molecular weight distribution of the block copolymer, as determined by GPC-RI. The weighted binding level of monovinyl aromatic compounds as measured by GPC-UV (%C _ri ) ranged from about 14.6% to about 24.6%. The total content of styrene repeating units in two-component block copolymers ranged from 39.9 to 40.8 wt. %, and the content of styrene blocks ranged from 30.5 to 35.6%. Therefore, the degree of blockiness of monovinyl aromatic repeating units of two-component block copolymers varied from 76.5 mol. % up to 87.5 mol. %. The content of repeating vinylaromatic units in the associated fraction of the gradient block copolymer (%A _C ) ranged from about 24.8 to about 32.6 wt. %, and in the unbound fraction of the gradient block copolymer (% Au) was from about 43.6 to about 50.5 wt. % as determined by calculation using binding levels measured by GPC-RI and GPC-UV and total styrene measured by proton NMR. The difference in the content of monovinyl aromatic repeating units between unbound and bound fractions of the gradient block copolymer (% CD) ranged from about 11.1 wt. % to 25.6%. The molecular weight distribution from Example 4 according to the invention is shown in FIG. 9. The specific GPC and NMR characteristics of these two-component block copolymers are shown in Table 2. The complex dynamic shear viscosity of the block copolymers at 0.99 rad/s ranged from 52210 to 142236 Pa-s and decreased to values from 3571 up to 6241 Pa-s at an oscillation frequency of 100 rad/s. The Mooney block copolymer viscosities (ML 1+4 at 100° C.) ranged from 28.6 to 66.0. Tan delta of the two-component block copolymer reflects predominantly elastic behavior (tan delta less than 1.00) over the entire frequency range from 0.25 to 200 rad/s, showing maximum values in the range from 0.75 to 0.93 at different frequencies . Details of the rheological characteristics of these two-component block copolymers are shown in Table 3.

Example 13 according to the invention:

Synthesis of a two-component block copolymer; a prototype with partial deactivation of block copolymer anions before elongation of the monovinyl aromatic chain. The formulation used in Example 4 was scaled up 272.7 times to a commercial reactor. However, some of the block copolymer anions remaining alive after binding were deactivated prior to the polymerization of the second styrene charge. The weight average molecular weight (M _w ) of the two-component block copolymer was 159.6 kg/mol. The molecular weight distribution shows a polydispersity index of 1.22. The molecular weight distribution of the block copolymer showed three peaks: a low molecular weight peak corresponding to an unbound linear gradient block copolymer of the formula D-(D/A)-A ₁ , a product of the partial deactivation of the anions of the block copolymer prior to polymerization of the second batch of styrene, a peak with a high molecular weight, corresponding to the associated gradient block copolymer of styrene and butadiene of the formula [D-(D/A)-A ₁ ] _n=2-4 -Si, and an intermediate molecular weight peak corresponding to the unbound linear gradient block copolymer of the formula D -(D/A)-A ₂ obtained after the polymerization of the second load of styrene. The GPC-RI molecular weight distribution of the two-component block copolymer prepared in Example 13 is shown in FIG. 9. The content of bound gradient block copolymer (%C _ri ) was 37.4% of the total molecular weight distribution of the block copolymer as determined by GPC-RI. The weighted level of binding of monovinyl aromatic compounds according to GPC-UV (% C _uv ) was 24.8%. The content of unbound linear gradient block copolymer D-(D/A)-A ₁ was 15.6% of the total molecular weight distribution of the block copolymer, as determined by GPC-RI. The total content of repeating styrene units of the two-component block copolymer was 39.8 wt. %, and the content of block styrene was 34.2 wt. %. Therefore, the degree of blockiness of the monovinyl aromatic repeating units was 86.0 mol. %. The content of vinylaromatic repeating units in the bound fraction of the gradient block copolymer (% _AC ) was 26.4 wt. %, and in the unbound fraction of the gradient block copolymer, taking into account two peaks with a lower molecular weight, was 47.7 wt. % as determined by calculation using binding levels measured by GPC-RI and GPC-UV and total styrene measured by proton NMR. The difference in the content of monovinyl aromatic repeating units between unbound and bound fractions of the gradient block copolymer (%CD) was 21.3%. The specific GPC and NMR characteristics of this two-component block copolymer are shown in Table 2. The complex dynamic shear viscosity of the block copolymers at 0.99 rad/s was 71321 Pa-s and decreased to 4709 Pa-s at an oscillation frequency of 100 rad/s. The Mooney viscosity of the block copolymers (ML 1+4 at 100° C.) was 39.0. The tan delta of the two-component block copolymer reflects predominantly elastic behavior (tan delta less than 1.00) over the entire frequency range from 0.25 to 200 rad/s, showing a maximum value of 0.85, at 2.51 rad/s. Details the rheological characteristics of this two-component block copolymer are shown in Table 3.

Comparative Example C-1:

Synthesis of a linear gradient block copolymer; low viscosity prototype. 71.56 g of cyclohexane, 4.32 kg of styrene and 6.64 kg of butadiene were charged into a 189 liter reactor under nitrogen with stirring. The reactor charge temperature was adjusted to 50.5° C. and then 286.6 millimoles of n-butyllithium were charged to the reactor. The polymerization of the first batch of monomer reached a maximum temperature of 106.3°C. After a 1 minute wait, 347.4 millimoles of a monofunctional alcohol were fed into the reactor to deactivate the polymer anions. The specific composition and polymerization process conditions for this example of the synthesis of an unbound gradient block copolymer are shown in Table 1. Then, 0.5 wt.h. phenolic antioxidant and 0.6 wt. hours of phosphite antioxidant. The unbound gradient block copolymer was isolated by steam stripping and drying in an oven. The weight average molecular weight (M _w ) of the synthesized unbound gradient block copolymer was 93.2 kg/mol. The molecular weight distribution showed a polydispersity index of 1.03, with a single narrow peak corresponding to an unbound linear gradient block copolymer of the formula D-(D/A)-A. The total content of repeating units of styrene in the unbound gradient block copolymer was 40.5 wt. %, and the content of styrene blocks was 30.0 wt. %. Therefore, the degree of blockiness of the monovinyl aromatic repeating units was 73.9 mol. %. The specific GPC and NMR characteristics of this unbound gradient block copolymer are shown in Table 2. The complex dynamic shear viscosity of this unbound gradient block copolymer at 0.99 rad/s was 49951 Pa-s and decreased to 4927 Pa-s at an oscillation frequency of 100 rad/s. The viscosity of this unbound Mooney gradient block copolymer (ML 1+4 at 100° C.) was 32.4. The tan delta of the two-component block copolymer reflects predominantly elastic behavior (tan delta less than 1.00) over the entire frequency range from 0.84 to 25 rad/s, showing a maximum value of 1.36 at 5.0 rad/s. Details of the rheological characteristics of this unbound gradient block copolymer are shown in Table 3.

Comparative Example C-2:

Synthesis of a linked gradient block copolymer; prototype with an average level of viscosity. 71.41 kg of cyclohexane, 4.36 kg of styrene and 6.63 kg of butadiene were charged into a 189 liter reactor under nitrogen with stirring. The initial load of the reactor was heated to a temperature of 51.5°C, after which 285.5 millimoles of n-butyllithium were fed into the reactor. The peak polymerization temperature was 108.6°C. After a 1 minute wait, 19.9 millimoles of a coupling agent based on silicon tetrachloride was loaded into the reactor. After a 5 minute wait, 178.1 millimoles of a monofunctional alcohol were fed into the reactor to deactivate the block copolymer anions. The specific composition and polymerization process conditions for the synthesis example of this partially bonded gradient block copolymer are shown in Table 1. Then, 0.5 wt. hours of phenolic antioxidant and 0.6 wt. including phosphite antioxidant. The block copolymer was isolated by steam stripping and drying in an oven. The weight average molecular weight (M _w ) of the block copolymer was 160.1 kg/mol. The molecular weight distribution showed a polydispersity index of 1.39. The molecular weight distribution of the block copolymer showed two peaks: a low molecular weight peak corresponding to the unbound linear gradient block copolymer of formula D-(D/A)-A and a high molecular weight peak corresponding to the bound gradient styrene-butadiene block copolymer. a copolymer of formula [D-(D/A)-A] _n=2-4 -Si. The content of the bound gradient block copolymer (% Cri) was 34.5% of the total molecular weight distribution of the partially bound gradient block copolymer, as determined by GPC-RI. The weighted binding level of monovinyl aromatic repeat units obtained with GPC-UV (%C _uv ) was 35.5%, which corresponded very well with the level of binding obtained with GPC-RI as a result of the same content of monovinyl aromatic repeat units in unbound and related factions. The total content of repeating styrene units in the partially bound gradient block copolymer was 42.2 wt. %, and the content of block styrene in it was 31.6 wt. %. Therefore, the degree of blockiness of monovinyl aromatic repeating units was 74.7 mol. %. The specific GPC and NMR characteristics of this partially bonded gradient block copolymer are shown in Table 2. The complex dynamic shear viscosity of the partially bonded gradient block copolymer at 0.99 rad/s was 75924 Pa-s and decreased to s at an oscillation frequency of 100 rad/s. The viscosity of the partially bonded Mooney gradient block copolymer (ML 1+4 at 100° C.) was 40.6. The tan delta of the two-component block copolymer reflects predominantly elastic behavior (tan delta less than 1.00) in the frequency range from 0.84 to 25 rad/s, showing a maximum value of 1.27 at 5.0 rad/s. Details of the rheological characteristics of this two-component block copolymer are shown in Table 3. The molecular weight distribution of Comparative Example C-2 is shown in FIG. 9.

Comparative Example C-3:

Synthesis of a high-viscosity linear gradient block copolymer in a pilot plant reactor. The same procedure was followed as in Comparative Example C-1, but the dosage of n-butyllithium was reduced to 264.4 mmol to increase the molecular weight. The specific composition and polymerization process conditions for each synthesis example of the unbound gradient block copolymer are shown in Table 1. The weight average molecular weight (M _w ) of the synthesized unbound gradient block copolymer was 107.8 kg/mol. The molecular weight distribution shows a polydispersity index of 1.03, with a single narrow peak corresponding to an unbound linear gradient block copolymer of formula D-(D/A)-A. The total content of repeating units of styrene in the unbound gradient block copolymer was 38.9 wt. %, and the content of block styrene was 28.8%. Therefore, the degree of blockiness of the monovinyl aromatic repeating units was 74.0 mol. %. The specific GPC and NMR characteristics of this unbound gradient block copolymer are shown in Table 2. The complex dynamic shear viscosity of the unbound gradient block copolymer at 0.99 rad/s was 96249 Pa-s and decreased to 6269 Pa-s at oscillation frequency 100 rad/s. The viscosity of the unbound gradient block copolymer according to Mooney (ML 1+4 at 100°C) was 53.1. The tan delta of the two-component block copolymer reflects predominantly elastic behavior (tan delta less than 1.00) in the frequency range from 0.25 to 5 rad/s, showing a maximum value of 1.17 at 0.99 rad/s. Details of the rheological characteristics of this unbound gradient block copolymer are shown in Table 3.

It can be seen that the batch synthesis process carried out in Inventive Examples 1 to 13 produces two-component block copolymers, each of

which has at least two distinguishable fractions with different molecular weights and the number of monovinyl aromatic repeating units, and the lower molecular weight fraction has more monovinyl aromatic repeating units than the higher molecular weight fraction.

It can also be seen that all of the bicomponent block copolymers prepared in Inventive Examples 1 to 13 have a higher degree of blockiness of monovinyl aromatic repeating units than the prior art gradient block copolymers, linear or linked, prepared in Comparative Examples 1 to 3. This is a result of the monovinyl aromatic chain elongation that occurs on the remaining polymeric anions after the coupling step.

The polydispersity index of all two-component block copolymers prepared in Examples 1 to 13, which reached 1.40 at its highest, is in the typical low range expected for an organolithium-initiated batch polymerization process followed by bonding. It is worth mentioning that such low levels of polydispersity cannot be achieved with organolithium initiated continuous polymerization processes in alternative prior technologies that are commonly used to produce block copolymers intended for the production of crosslinked microporous rubber products. Comparison of the molecular weight distributions of the two-component block copolymers prepared in Invention Examples 4 and 13 and Comparative Example 2 prepared in a batch reactor and the commercial reference Buna® BL 30-4548 (from ARLANXEO) which has a unimodal but The very broad molecular weight distribution typical of prior art block copolymers produced in a continuous polymerization reactor is shown in FIG. 9.

All of the two-component block copolymers prepared in Examples 1 to 13 exhibit tan delta values only below 1.0 over the entire frequency range examined, regardless of their levels of complex dynamic shear and Mooney viscosity, or regardless of the type of coupling agent used. . When considering examples 1 and 11 of the invention, it can be seen that the difference in the composition of monovinyl aromatic repeating units between unbound and bound fractions of two-component block copolymers (% CD) of only 11% is still enough to contribute to this behavior of the tan delta angle. In contrast, prior art linear gradient block copolymers prepared in Comparative Example 1 at a low viscosity level and Comparative Example 3 at a high viscosity level show predominantly viscous behavior over a large portion of the frequency spectrum examined, as indicated by tan delta values above 1 ,0. Similarly, the partially bonded gradient block copolymer from Comparative Example 2 with a homogeneous composition of monovinyl aromatic repeat units between bound and unbound fractions and an average level of viscosity prepared according to the prior art procedure also exhibited tan delta values greater than 1.0 over a broad range. frequency range. As previously stated, it is well known in the art that polymeric materials with predominantly elastic characteristics, i.e. tan delta values below 1.0, are better suited for foaming due to their higher melt strength during blowing agent expansion. By comparing these tan delta profiles, it can be concluded that the two-component block copolymers of the invention are more suitable for foaming than prior art linear gradient block copolymers or homogenous partially bonded gradient block copolymers.

In example 13 according to the invention and in FIG. 9 shows that two-component block copolymers can have a trimodal molecular weight distribution. In particular, in example 13 according to the invention, the unbound fraction U of the block copolymer consists of molecules of a gradient linear block copolymer of the formula D-(D/A)-A ₁ , which is approximately 15.6% of the molecular weight distribution, and molecules of a gradient linear block copolymer formula D-(D/A)-A ₂ that is approximately 47.0 wt. % molecular weight distribution, where the monovinyl aromatic blocks A ₂ have a higher molecular weight than the monovinyl aromatic blocks A ₁ . Despite this trimodal molecular weight distribution, the two-component block copolymer obtained in example 13 according to the invention shows tan delta values only below 1.0 over the entire frequency range examined.

Example 14 according to the invention:

Synthesis of a two-component block copolymer with a high content of monovinyl aromatic repeating units. Approximately 65.98 kg of cyclohexane, approximately 1.88 kg of styrene and approximately 5.75 kg of butadiene were charged into a 189 liter reactor under nitrogen with stirring. The reactor temperature was set to 55.7° C., after which 322.9 millimoles of n-butyllithium were fed into the reactor. The polymerization of the first batch of monomer reached a maximum temperature of 98.8°C. Then, 31.42 millimoles of a coupling agent based on silicon tetrachloride was loaded into the reactor. After a 3 minute wait, about 3.08 kg of styrene was charged to the reactor. Due to the heat of polymerization reaction of the second load of styrene, the reaction temperature increased to about 101.2°C. After a 1 minute wait, all polymeric anions were deactivated by adding a monofunctional alcohol. The composition and conditions of the polymerization process are shown in Table 4. Then, 0.5 wt.h. phenolic antioxidant and 0.6 wt. hours of phosphite antioxidant. A sample of the two-component block copolymer was isolated by rolling at 125° C. and characterized. The weight average molecular weight (M _w ) of the two-component block copolymer was 181.0 kg/mol, with a polydispersity M _w /M _n of 1.23; molecular weight distribution according to GPC-RI showed three peaks: 11.0% of the low molecular weight peak corresponding to the unbound linear gradient block copolymer of formula D-(D/A)-A ₁ , 51.6% of the medium molecular weight peak , corresponding to the unbound linear gradient block copolymer of formula D-(D/A)-A ₂ , and 37.4% of the high molecular weight peak (% Cn) corresponding to the bound gradient styrene-butadiene block copolymer [D-(D /A)-A ₁ ] _n=2-4 -Si. The total content of repeating units of styrene in the two-component block copolymer was 47.8 wt. %, and the content of styrene blocks was 39.9%. Therefore, the degree of blockiness of the monovinyl aromatic repeating units of the two-component block copolymer was 83.4 mol. %. Specific characteristics of the two-component block copolymer according to GPC and NMR are shown in Table 5. The complex dynamic shear viscosity of the two-component block copolymer at 0.99 rad/s was 105345 Pa-s, and when determined at an oscillation frequency of 100 rad/s, it decreased to 5649 Pa. -With. The Mooney viscosity (ML 1+4 at 100°C) was 48. The tan delta of the two-component block copolymer characterizes predominantly elastic behavior (tan delta less than 1.00) over the entire frequency range from 0.25 to 200 rad/s, demonstrating a maximum value of 0.76 at a frequency of 2.51 rad/s when tested at 100°C and a strain of 13.95%. The same oscillatory shear test, but at a temperature of 140°C, revealed a maximum value of tan delta equal to 0.70 at a frequency of 25.12 rad/s. The rheological characteristics of this two-component block copolymer are shown in Table 6.

Example 15 according to the invention.

Synthesis of a two-component block copolymer with a high content of monovinyl aromatic repeating units and a high molecular weight. Approximately 48.02 kg of cyclohexane, approximately 1.40 kg of styrene and approximately 4.19 kg of butadiene were charged into a 189 liter reactor under nitrogen with stirring. The reactor temperature was set to 54.1°C, after which 219.7 millimoles of n-butyllithium were fed into the reactor. The polymerization of the first batch of monomer reached a maximum temperature of 96.8°C. Then, 18.33 millimoles of a coupling agent based on silicon tetrachloride was loaded into the reactor. After a 3 minute wait, about 2.35 kg of styrene was charged to the reactor. Due to the heat of polymerization reaction of the second charge of styrene, the reaction temperature was raised to about 99.0°C. After a 1-minute wait, monofunctional alcohol was fed into the reactor to deactivate all polymeric anions. The composition and conditions of the polymerization method are shown in Table 4. Then, 0.5 wt. hours of phenolic antioxidant and 0.6 wt. including phosphite antioxidant. A sample of the two-component block copolymer was isolated by rolling at 125° C. and characterized. The weight average molecular weight (M _w ) of the two-component block copolymer was 233.7 kg/mol, with a polydispersity M _w /M _n of 1.17; molecular weight distribution according to GPC-RI showed three peaks: 4.0% of the low molecular weight peak corresponding to the unbound linear gradient block copolymer of the formula D-(D/A)-A ₁ , 54.3% of the medium molecular weight peak , corresponding to the unbound linear gradient block copolymer of formula D-(D/A)-A ₂ , and 41.7% of the high molecular weight peak (%C _ri ) corresponding to the bound gradient styrene-butadiene block copolymer [D-(D /A)-A ₁ ] _n=2-4 -Si. The total content of repeating units of styrene in the two-component block copolymer was 48.4 wt. %, and the content of styrene blocks was 39.7%. Therefore, the degree of blockiness of the monovinyl aromatic repeating units of the two-component block copolymer was 82.0 mol. %. Characteristics according to GPC and NMR of the two-component block copolymer are presented in Table 5. The complex dynamic shear viscosity of the two-component block copolymer at 0.99 rad/s was 155221 Pa-s, and when determined at an oscillation frequency of 100 rad/s, it decreased to 6467 Pa-s. With. The Mooney viscosity (ML 1+4 at 100° C.) was 66. The tan delta of the two-component block copolymer exhibits predominantly elastic behavior (tan delta less than 1.00) over the entire frequency range from 0.25 to 200 rad/s, demonstrating a maximum value of 0.68 at a frequency of 0.50 rad/s, when determined at 100° C. and a strain of 13.95%. The same test for oscillatory shift, but at a temperature of 140°C, showed the maximum value of the tangent of the delta angle of 0.62 at 2.51 rad/s. The rheological characteristics of this two-component block copolymer are shown in Table 6.

Example 16 according to the invention.

Two-component block copolymer containing paraffin oil. To the rubber solution prepared in example 15 of the invention was added 4 parts of PRIMOL® 352 paraffin oil from ExxonMobil per 100 parts of the solution. A sample of the oil-filled two-component block copolymer was isolated by rolling at 125° C. and characterized. The complex dynamic shear viscosity of the two-component block copolymer at 0.99 rad/s was 101760 Pa-s, and decreased to 4968 Pa-s when measured at an oscillation frequency of 100 rad/s. The Mooney viscosity (ML 1+4 at 100°C) was 50. The tan delta of the two-component block copolymer characterizes predominantly elastic behavior (tan delta less than 1.00) over the entire frequency range from 0.25 to 200 rad/s, demonstrating a maximum value of 0.72 at a frequency of 0.99 rad/s, when determined at 100° C. and a strain of 13.95%. The same test for oscillatory shift, but at a temperature of 140°C, showed the maximum value of the tangent of the delta angle of 0.65 at 5.00 rad/s. The rheological characteristics of this two-component block copolymer are shown in Table 6.

Example 17 according to the invention.

Synthesis of a two-component block copolymer with a high content of vinylaromatic repeating units and a low degree of binding. Monomer loadings, reaction sequence and reaction temperatures were used as in Example 15 of the invention, but loaded with 174.5 millimoles of n-butyllithium and 6.55 millimoles of silicon tetrachloride. The detailed formulation and reaction temperatures are shown in Table 4. A sample of the rubber solution was taken from the batch and the two-component block copolymer was isolated from the solvent by rolling at 125°C. The weight average molecular weight (M _w ) of the two-component block copolymer was 190.5 kg/mol with a polydispersity M _w /M _n of 1.18; molecular weight distribution according to GPC-RI showed two peaks: 80.0% of the low molecular weight peak corresponding to the unbound linear gradient block copolymer of formula D-(D/A)-A ₂ , and 20.0% of the high molecular weight peak weight (%Cri), corresponding to the associated gradient styrene-butadiene block copolymer [D-(D/A)-A ₁ ] _n=2-4 -Si. The total content of repeating styrene units of the two-component block copolymer was 48.7 wt. %, and the content of styrene blocks was 39.6%. Therefore, the degree of blockiness of the monovinyl aromatic repeating units of the two-component block copolymer was 81.3 mol. %. The GPC and NMR characteristics of the two-component block copolymer are presented in Table 5. The complex dynamic shear viscosity of the two-component block copolymer at 0.99 rad/s was 248560 Pa-s, and decreased to 8761 Pa-s when measured at an oscillation frequency of 100 rad/s. With. The Mooney viscosity (ML 1+4 at 100° C.) was 83. The tan delta of the two-component block copolymer characterizes predominantly elastic behavior (tan delta less than 1.00) over the entire frequency range from 0.25 to 200 rad/s, demonstrating a maximum value of 0.69 at a frequency of 0.25 rad/s, when determined at 100° C. and a strain of 13.95%. The same test for oscillatory shift, but at a temperature of 140°C, showed the maximum value of the tangent of the delta angle of 0.70 at 0.25 rad/s. The rheological characteristics of this two-component block copolymer are shown in Table 6.

Example 18 according to the invention.

Two-component block copolymer containing naphthenic oil. To the rubber solution prepared in Example 15 of the invention was added 9 parts of NYNAS NYFLEX® 223 Naphthenic Oil per 100 parts of the solution. A sample of the oil-filled two-component block copolymer was isolated by rolling at 125° C. and characterized. The complex dynamic shear viscosity of the two-component block copolymer at 0.99 rad/s was 124840 Pa-s, and decreased to 6594 Pa-s when measured at an oscillation frequency of 100 rad/s. The Mooney viscosity (ML 1+4 at 100°C) was 49. The tan delta of the two-component block copolymer characterizes predominantly elastic behavior (tan delta less than 1.00) over the entire frequency range from 0.25 to 200 rad/s, demonstrating a maximum value of 0.87 at a frequency of 0.99 rad/s, when determined at 100° C. and a strain of 13.95%. The same test for oscillatory shift, but at a temperature of 140°C, showed the maximum value of the tangent of the delta angle equal to 0.80 at 0.84 rad/s. The rheological characteristics of this two-component block copolymer are shown in Table 6.

Example 18 according to the invention.

Two-component block copolymer containing naphthenic oil. To the rubber solution prepared in Example 15 of the invention was added 9 parts of NYNAS NYFLEX® 223 Naphthenic Oil per 100 parts of the solution. A sample of the oil-filled two-component block copolymer was isolated by rolling at 125° C. and characterized. The complex dynamic shear viscosity of the two-component block copolymer at 0.99 rad/s was 124840 Pa-s, and decreased to 6594 Pa-s when measured at an oscillation frequency of 100 rad/s. The Mooney viscosity (ML 1+4 at 100° C.) was 49. The tan delta of the two-component block copolymer exhibited predominantly elastic behavior (tan delta less than 1.00) over the entire frequency range from 0.25 to 200 rad/s, demonstrating a maximum value of 0.87 at a frequency of 0.99 rad/s, when determined at 100° C. and a strain of 13.95%. The same test for oscillatory shift, but at a temperature of 140°C, showed the maximum value of the tangent of the delta angle equal to 0.80 at 0.84 rad/s. The rheological characteristics of this two-component block copolymer are shown in Table 6.

Inventive Examples 14 to 18 show that the rheological properties of oil-free bicomponent block copolymers, such as the block copolymers of Invention Example 14, can be comparable to those of oil-filled, two-component block copolymers, such as the block copolymers of Examples 16 and 18 of the invention, simply by increasing the molecular weight by the required amount depending on the oil content. Regardless of the type of oil or level of binding, oil-filled two-component block copolymers remain predominantly elastic, as evidenced by tan delta values below 1.0 over the entire vibrational shear frequency spectrum tested. These examples of the invention also demonstrate that the predominant elastic behavior of two-component block copolymers prevails even at temperatures up to 140°C.

Hypothetical examples

The structure of the bicomponent block copolymers of the present invention is illustrated in FIG. 1-8.

In FIG. 1 shows a schematic representation of a two-component block copolymer containing approximately 38 wt. % bound block copolymer With the formula [D-(D/A)-A ₁ ] ₄ -X (left) and approximately 62 wt. % unbound block copolymer U of formula D-(D/A)-A ₂ (right). The total content of monovinyl aromatic repeating units, A _t , is approximately 41 wt. %. The degree of blockiness of monovinyl aromatic repeating units is 87.5 mol. %. The mass percentage of monovinyl aromatic repeating units in the block copolymer C, %A _C is approximately 21 wt. %. The weight percentage of monovinyl aromatic repeating units in the U block copolymer, %A _U , is approximately 52 wt. %; therefore, the difference in composition, in weight percent, of monovinyl aromatic repeating units between the U and C fractions of the block copolymer, % CD, is approximately 31 wt. %.

In FIG. 2 schematically shows a two-component block copolymer containing approximately 34 wt. % bound block copolymer With the formula [D-(D/A)-A ₁ ] ₄ -X (left) and approximately 66 wt. % unbound block copolymer U of formulas D-(D/A)-A ₂ (4 molecules on top right, equivalent to about 57 wt.%) and D-(D/A)-A ₁ (bottom right, equivalent to about 9 wt. %). A _t is approximately 39 wt. %. The degree of blockiness of monovinyl aromatic repeating units is approximately 86.5 mol. %. A _C - approximately 21 wt. %, A _U - approximately 48 wt. %; therefore, %CD is approximately 27 wt. %.

In FIG. 3 schematically shows a two-component block copolymer containing approximately 38 wt. % bound block copolymer C of the formula [B-(B/A)-A ₁ ] ₄ -X (left) and approximately 62 wt. % unbound block copolymer U of formula B-(B/A)-A ₂ (right). A _t is approximately 41 wt. %. The degree of blockiness of monovinyl aromatic repeating units is 87.5 mol. %. A _C is approximately 21 wt. %, and A _U is approximately 52 wt. %; therefore, %CD is approximately 31 wt. %.

In FIG. 4 schematically shows a two-component block copolymer containing approximately 34 wt. % bound block copolymer With the formula [B-(B/A)-A ₁ ] ₄ -X (left) and approximately 66 wt. % unbound block copolymer U of formulas B-(B/A)-A ₂ (4 molecules on the top right, equivalent to about 57 wt.%) and B-(B/A)-A ₁ (bottom right, equivalent to about 9 wt. %). A _t is approximately 39 wt. %. The degree of blockiness of monovinyl aromatic repeating units is approximately 86.5 mol. %. A _C is approximately 21 wt. %, and A _U is approximately 48 wt. %; therefore, %CD is approximately 27 wt. %.

In FIG. 5 schematically shows a two-component block copolymer containing approximately 38 wt. % bound block copolymer With the formula [(B/A)-A ₁ ] ₄ -X (left) and approximately 62 wt. % unbound block copolymer U of formula (B/A)-A ₂ (right). A _t is approximately 41 wt. %. The degree of blockiness of monovinyl aromatic repeating units is approximately 87.5 mol. %. A _C is approximately 21 wt. %, and A _U is approximately 52 wt. %; therefore, %CD is approximately 31 wt. %.

Fig. 6 schematically shows a two-component block copolymer containing approximately 34 wt. % bound block copolymer C of the formula [(B/A)-A₁]₄-X (left) and approximately 66 wt. % unbound block copolymer U of formulas (B/A)-A₂ (4 molecules from top right, equivalent to approximately 57 wt%) and (B/A)-A₁ (bottom right, equivalent to approximately 9 wt. %). At is approximately 39 wt. %. The degree of blockiness of monovinyl aromatic repeating units is approximately 86.5 mol. %. A_C is approximately 21 wt. %, and A_U is approximately 48 wt. %; therefore, %CD is approximately 27 wt. %.

Fig. 7 schematically shows a two-component block copolymer containing approximately 38 wt. % of the associated block copolymer With the formula [B-A ₁ ] ₄ -X (left) and approximately 62 wt. % unbound block copolymer U of formula B-A ₂ (right). A _t is approximately 41 wt. %. The degree of blockiness of monovinyl aromatic repeating units is approximately 100 mol. %. A _C is approximately 21 wt. %, and A _U is approximately 52 wt. %; therefore, %CD is approximately 31 wt. %.

Fig. 8 schematically shows a two-component block copolymer containing approximately 34 wt. % bound block copolymer With the formula [BA ₁ ] ₄ -X (left) and approximately 66 wt. % unbound block copolymer U of formulas B-A ₂ (4 molecules on top right, equivalent to about 57 wt. %) and B-A ₁ (bottom right, equivalent to about 9 wt. %). A _t is approximately 39 wt. %. The degree of blockiness of monovinyl aromatic repeating units is approximately 100 mol. %. A _C is approximately 21 wt. % and A _U is approximately 48 wt. %; therefore, %CD is approximately 27 wt. %.

In FIG. 1-8, the black bars denote the monovinyl aromatic repeat unit sequences, the gray bands denote the conjugated diene repeat unit sequences, and X is the tetrafunctional coupling agent residue. In FIG. 1-6, the black lines among the sequences of conjugated diene repeat units represent various patterns in which monovinyl aromatic repeat units are copolymerized with conjugated diene repeat units; their locations and spacings are not specific locations of individual monovinyl aromatic repeat units, rather they show a trend towards concentration of monovinyl aromatic repeat units embedded along blocks also containing conjugated diene repeat units. Thus, a small gradient followed by a steep concentration gradient characteristic of gradient copolymerization is shown in FIG. 1 and FIG. 2; randomization with only a portion of the conjugated diene repeat units is depicted in FIG. 3 and FIG. 4; and a fully randomized arrangement with all repeat units of conjugated dienes shown in FIG. 5 and FIG. 6.

Examples for end use

The following examples of the invention show the composition of rubber compounds containing two-component block copolymers, a chemical blowing agent and a crosslinking agent. The rubber compounds are pre-crosslinked in a sealed and heated mold, then a sharp pressure reduction and mold opening are performed to achieve expansion of the microporous rubber compound; thereafter, the crosslinking step of the microporous rubber samples is completed in a forced convection oven. The same composition and method for preparing crosslinked microporous rubber samples is used in comparative examples, but using the prior art block copolymers obtained in comparative examples 1-3, as well as using a commercial block copolymer comparison sample showing unimodal and very broad molecular weight distribution (Buna® BL 30-4548).

Samples of the crosslinked microporous rubber compound were visually inspected to determine the appearance of the surface, they were also measured before and after the crosslinking step to determine the volumetric shrinkage. In addition, the samples were analyzed for the following aspects:

Density was measured with a MUVER electronic densimeter, model 5085-2, according to ISO 2781 standard method. Number average pore size and pore size standard deviation were measured by epifluorescence microscopy using a Carl Zeiss AXIOTECH 100HD microscope and digital image analysis. Hardness was measured using a Bareiss Shore A hardness tester conforming to DIN 53505 and ISO 868, mounted on a MUVER 5019 holder. Elasticity was measured using a Zwick 5109 Rebound elasticity tester.

Example 19 according to the invention:

A rubber compound was prepared by mixing 100 phr (parts per 100 parts of solution) of the two-component block copolymer obtained in example 3 of the invention, 6 phr of azodicarbonamide as a blowing agent (Celogen® AZ-130 from CelChem, LLC) and 1.1 phr of dicumyl peroxide in as a crosslinking agent in a roller mixer. The rubber compound was pressure molded with an excess of 3% added to provide a leak-tight mold. The mold was clamped with heated plates at 150° C. and a clamping pressure of 92.8 kgf/cm ² for 3 minutes. Thereafter, the mold was cooled to 120° C. while maintaining the pressure. The clamp pressure on the mold was then released and the press plates were opened. There was immediate foaming, which could be seen by lifting the top plate of the mold. The pre-crosslinked foam sample was cooled in water at 23°C. Crosslinking was completed by placing the pre-crosslinked foam sample in a forced convection oven at 100° C. for 6 hours. The foam rubber sample was then held for 24 hours at 23°C. The crosslinked microporous foam rubber samples thus obtained had a smooth surface without bubble defects. Volumetric shrinkage when comparing the volumes of pre-crosslinked and fully crosslinked samples was 3.9%. The crosslinked microporous foam rubber sample had a density of 0.446 g/cm ³ , a number average pore size of 6.74 µm, a standard deviation of pore size of 2.09 µm, a Shore A hardness of 28.0, and a resilience of 37.9%. The composition and characteristics of the crosslinked foam rubber sample are compared with the rest of the invention and comparative examples in Table 7.

Example 20 according to the invention:

A rubber compound and a crosslinked foam rubber sample were prepared as in Invention Example 19, but containing the two-component block copolymer obtained in Invention Example 4. The thus obtained sample of cross-linked microporous rubber had a smooth surface without blistering defects. The volume shrinkage when comparing the volume of the pre-crosslinked and fully crosslinked sample was 3.9%. The crosslinked microporous sample had a density of 0.464 g/cm ³ , number average pore size of 8.08 µm, a standard deviation of pore size of 2.40 µm, a 38 Shore A hardness, and an elasticity of 37.9%. The composition and characteristics of the crosslinked foam rubber sample are compared with the rest of the invention and comparative examples in Table 7.

Example 21 according to the invention:

A rubber compound and a crosslinked foam rubber sample were prepared as in Invention Example 19, but containing the two-component block copolymer obtained in Invention Example 5. The crosslinked foam rubber sample thus obtained had a smooth surface without blistering defects. The volume shrinkage when comparing the volume of the pre-crosslinked and fully crosslinked sample was 4.0%. The density of the cross-linked microporous sample is 0.662 g/cm ³ , Shore A hardness is 38.0, and elasticity is 37.0%. The composition and characteristics of the crosslinked foam rubber sample are compared with the rest of the invention and comparative examples in Table 7.

Comparative Example C-4:

A rubber compound and a crosslinked foam rubber sample were prepared as in Invention Example 19, but containing the unbound gradient block copolymer of the prior art prepared in Comparative Example C-1. The crosslinked microporous foam rubber sample thus made had an uneven surface with blistering defects. The volume shrinkage when comparing the volume of the pre-cross-linked and fully cross-linked sample was 3.9%. The crosslinked foam rubber sample had a density of 0.526 g/cm ³ , number average pore size of 13.1 µm, a standard deviation of pore size of 8.79 µm, a Shore A hardness of 55.0, and a resilience of 28.2%. The composition and characteristics of the crosslinked foam rubber sample are compared with the rest of the invention and comparative examples in Table 7.

Comparative Example C-5:

A rubber compound and a crosslinked foam rubber sample were prepared as in Invention Example 19, but containing the prior art bonded gradient block copolymer prepared in Comparative Example C-2. The crosslinked microporous rubber sample thus produced had an uneven surface with blistering defects. The volume shrinkage when comparing the volume of the pre-crosslinked and fully crosslinked sample was 4.0%. Cross-linked foam rubber sample density 0.790 g/cm ³ , number average pore size 9.50 µm, pore size standard deviation 3.38 µm, Shore A hardness 76.0 and elasticity 31.0%. The composition and characteristics of the crosslinked foam rubber sample are compared with the rest of the invention and comparative examples in Table 7.

Comparative Example C-6:

A rubber compound and a crosslinked foam rubber sample were prepared as in Invention Example 19, but containing the prior art unbound gradient block copolymer prepared in Comparative Example C-3. The crosslinked microporous rubber sample thus produced had an uneven surface with blistering defects. The volume shrinkage when comparing the volume of the pre-cross-linked and fully cross-linked sample was 3.9%. The crosslinked foam rubber sample had a density of 0.694 g/cm ³ , number average pore size of 6.40 µm, a standard deviation of pore size of 2.00 µm, a 53 Shore A hardness, and a resiliency of 32.8%. The composition and characteristics of the crosslinked foam rubber sample are compared with the rest of the invention and comparative examples in Table 7.

Comparative Example C-7:

A rubber compound and a crosslinked foam rubber sample were attempted to be prepared as in Example 19, but containing prior art Buna® BL 30-4548 block copolymer (unimodal and very broad molecular weight distribution block copolymer shown in Fig. 9 , a commercial reference for foam rubber applications), instead of a two-component block copolymer. Although the pressing, mold cooling, pressure release, and mold opening conditions were the same as in Invention Example 19, when the hot mold load pressure was released and the press plates were opened, the expansion of the rubber compound occurred to a very limited extent, since the rise of the top plate of the mold was not noticeable. The crosslinked rubber sample thus produced had a smooth surface without blistering defects. Volumetric shrinkage when comparing the volume of pre-crosslinked and fully crosslinked sample was 0%. The crosslinked rubber sample had a very high density of 1.042 g/cm ³ , indicating poor foamability of the rubber compound. Optical microscopy analysis revealed very few pores with a number average pore size of 14.25 µm with a pore size standard deviation of 5.04 µm. The crosslinked rubber sample had a Shore A hardness of 43 and a resilience of 37.5%. The composition and characteristics of the crosslinked foam rubber sample are compared with the rest of the invention and comparative examples in Table 7.

In Inventive Example 19 and Comparative Example C-4, the block copolymers used in the formulation had very similar Mooney viscosities of 32.0 and 32.4, respectively, and very similar complex shear viscosity profiles at 100°C as and can be viewed in Table 3 (see Invention Example 3 and Comparative Example C-1). It can be seen that the use of the two-component block copolymer according to the invention in the formulation of the rubber compound in the example 19 of the invention results in a cross-linked microporous rubber sample with a smoother surface, lower density, smaller and more uniform pores, lower hardness and higher resiliency than using the prior art unbound graded block copolymer in Comparative Example C-4. Low volume shrinkage was obtained for both Invention Example 19 and Comparative Example C-4.

In Inventive Example 20 and Comparative Example C-5, the block copolymers used in the formulation had very similar Mooney viscosities of 39.2 and 40.6, respectively, and very similar complex shear viscosity profiles at 100°C as can be seen in Table 3 (see Invention Example 4 and Comparative Example C-2). It can be seen that the use of the two-component block copolymer according to the invention in the formulation of the rubber compound in example 20 of the invention results in a cross-linked microporous rubber sample with a smoother surface, lower density, smaller and more uniform pores, lower hardness and higher resiliency than using the prior art bonded graded block copolymer in Comparative Example C-4. Low volume shrinkage was obtained for both Invention Example 20 and Comparative Example C-5.

In Invention Example 21 and Comparative Example C-6, the block copolymers used in the formulation had very similar complex shear viscosity profiles at 100°C, as can be seen in Table 3 (see Invention Example 3 and Comparative Example C-1) . It can be seen that the use of the inventive two-component block copolymer in the formulation of the rubber compound in Invention Example 21 results in a crosslinked microporous rubber sample with a smoother surface, lower density, lower hardness, and higher resilience than using an unbonded gradient prior art block copolymer in Comparative Example C-6. Low volume shrinkage was obtained for both Invention Example 21 and Comparative Example C-6.

Example 22 according to the invention:

A foamable rubber compound was prepared by mixing 100 phr of the two-component block copolymer from Example 13, 6 phr of azodicarbonamide and 1.1 phr of dicumyl peroxide in a roller mill. The foamable rubber compound was pressure-molded with a 3% excess of rubber compound added to ensure the mold was sealed. The mold was clamped with heated plates at 170° C., at a clamping pressure of 92.8 kgf/cm2, for 3 minutes. The pressure on the mold was then released and the press plates were opened. There was an immediate expansion of the foam, which could be seen by lifting the top plate of the mold. Then the mold and sample of crosslinked microporous rubber were quenched in water at 23°C. The crosslinked microporous rubber sample was removed from the mold and dried with absorbent paper. The crosslinked foam rubber sample was then conditioned in a controlled atmosphere room at 23° C. and 50% relative humidity for 7 days.

The thus obtained sample of cross-linked microporous rubber had a smooth surface without blistering defects. It had a density of 0.624 g/cm ³ and showed 0% shrinkage after 7 days of conditioning in a controlled atmosphere; the composition and properties of the crosslinked microporous rubber compound are shown in Table 8.

Comparative Example 7:

A foamable rubber compound and a crosslinked foam rubber sample were prepared as in Invention Example 22, but containing Buna® BL 30-4548 instead of the two-component block copolymer. Although the compression molding conditions were exactly the same as in Invention Example 22, when the load pressure on the hot mold was released and the compression press plates were opened, the foamed rubber compound expanded to a very limited extent because the lifting of the upper mold plate was not noticeable. The crosslinked microporous foam rubber sample thus obtained had a smooth surface without bubble defects; its density of 0.986 g/cm ³ reflects the low foamability of this mixture. The composition and properties of the crosslinked microporous rubber compound are shown in Table 8.

In general, in every case where the two-component block copolymer of the present invention was used to make cross-linked microporous rubber samples, the resulting surface appearance was smooth, while when using a gradient block copolymer of the prior art, either unbound or bonded, the resulting microporous the rubber samples had bubble defects on their surface. Better foamability has also been demonstrated using the inventive two-component block copolymers as evidenced by lower sample densities and greater uniformity in pore size than prior art alternatives. Moreover, higher softness (lower Shore A hardness) and higher resilience have been obtained in crosslinked rubber compounds when the inventive two-component block copolymer is included. It should be noted that under the same pre-crosslinking/shaping, decompression, and crosslinking conditions, formulations containing two-component block copolymers made it possible to obtain crosslinked microporous rubber samples, while no microporous foaming occurred when using the commercial Buna® BL 30-4548 reference sample.

In the following examples, the evaluation of the preparation of the mixture was performed in a laboratory internal mixer. The compositions contained either the bicomponent block copolymers of the invention or prior art gradient block copolymers. Torque and temperature readings were collected to evaluate blending efficiency. Mixture evaluation was performed in a Brabender Intelli-Torque Plasti-Corder equipped with a Prep-Mixer measuring head, with CAM blades and a net chamber volume of 420 ml. The standard formulation used also included SBR (styrene butadiene rubber) emulsion, fillers, plasticizers, antioxidant, chemical blowing agent, blowing agent activator, crosslinking agent, crosslinking accelerator, crosslinking activator.

Example 23 according to the invention

Evaluation of the preparation of the mixture was carried out in a laboratory internal mixer. The initial charge included 80 phr of the two-component block copolymer prepared in Example 3 and 20 phr of Emulprene 1502 (cold emulsion 23.5% styrene repeating styrene butadnene random copolymer from Dynasol Group), mixing started with the chamber temperature stabilized at 45 °C. With a stirring time of 1 minute, 2.5 phr of naphthenic oil and 1.7 phr of paraffin wax were added. At a mixing time of 4 minutes, 70 phr of hard clay, 35 phr of aluminum silicate, 4.5 phr of azodicarbonamide (Celogen® AZ-130) and 1.0 phr of Wingstay® L antioxidant (from OMNOVA Solutions Inc.) were added. At a stirring time of 8 minutes, 3.0 phr of sulfur, 3.5 phr of stearic acid and 3.5 phr of zinc oxide were added. With a stirring time of 10 minutes, 1 phr of diphenylguanidine (DPG) and 2.3 phr of 2-benzothiazyl-N-sulfenemorpholide (MBS) were added. With a total mixing time of 12 minutes, the torque reading was 106.2 Nm and the internal temperature of the mixing chamber was 87°C. The results of the evaluation of the preparation of the mixture are shown in Table 9.

Example 24 according to the invention:

The blending evaluation was carried out as in Invention Example 23, but using the two-component block copolymer of Example 4. With a total mixing time of 12 minutes, the torque reading was 110.2 Nm and the internal temperature of the mixing chamber was 87°C. The results of the evaluation of the preparation of the mixture are shown in Table 9.

Example 25 according to the invention:

The blending evaluation was carried out as in Invention Example 23, but using the two-component block copolymer of Example 13. With a total mixing time of 12 minutes, the torque reading was 110.0 Nm and the internal temperature of the mixing chamber was 87°C. The results of the evaluation of the preparation of the mixture are shown in Table 9.

Example 26 according to the invention:

The blending evaluation was carried out as in Invention Example 23, but using the two-component block copolymer of Example 5. With a total mixing time of 12 minutes, the torque reading was 115.6 Nm and the internal temperature of the mixing chamber was 88°C. The results of the evaluation of the preparation of the mixture are shown in Table 9.

Comparative Example C-9:

The blending evaluation was carried out as in Invention Example 23, but using the gradient linear block copolymer from Comparative Example 1. With a total blending time of 12 minutes, the torque reading was 109.9 Nm and the mixing chamber internal temperature was 88°C. The results of the evaluation of the preparation of the mixture are shown in Table 9.

Comparative Example C-10:

The blending evaluation was carried out as in Invention Example 23, but using the gradient bonded block copolymer from Comparative Example 2. With a total mixing time of 12 minutes, the torque reading was 112.2 Nm and the internal temperature of the mixing chamber was 87°C. The results of the evaluation of the preparation of the mixture are shown in Table 9.

Comparative Example C-11:

The blending evaluation was carried out as in Invention Example 23, but using the gradient block copolymer from Comparative Example 3. With a total mixing time of 12 minutes, the torque reading was 119.6 Nm and the internal temperature of the mixing chamber was 90°C. The results of the evaluation of the preparation of the mixture are shown in Table 9.

Comparative Example C-12:

The evaluation of the preparation of the mixture was carried out as in example 23 of the invention, but using Buna® BL 30-4548. With a total mixing time of 12 minutes, the torque reading was 114.3 Nm and the internal temperature of the mixing chamber was 90°C. The results of the evaluation of the preparation of the mixture are shown in Table 9.

In Invention Example 23 and Comparative Example 9, the block copolymers used in the formulation had very similar Mooney viscosities of 32.0 and 32.4, respectively, and very similar complex shear viscosity profiles at 100° C., as can be seen in Table 3 (see example 3 of the invention and comparative example 1). It can be seen that at the end of the blend cycle, slightly lower torque and lower chamber temperatures were obtained when the formulation contained the two-component block copolymer than when it contained the prior art unbound gradient block copolymer.

In Inventive Examples 24 and 25 and Comparative Example 10, the block copolymers used in the composition had very similar Mooney viscosities of 39.2, 39.0 and 40.6 respectively, and very similar complex shear viscosity profiles at 100° C, as can be seen in Table 3 (see Invention Example 4, Invention Example 13 and Comparative Example 2). Again, it can be seen that at the end of the blend cycle, slightly lower torque and lower chamber temperatures were obtained when the composition contained the two-component block copolymer than when it contained the prior art unbound gradient block copolymer.

In Invention Example 26 and Comparative Example 11, the block copolymers used in the composition had very similar complex shear viscosity profiles at 100° C., higher than in the previous examples, as can be seen in Table 3 (see Invention Example 3 and Comparative Example 1). Again, it can be seen that at the end of the blend run, slightly lower torque and lower chamber temperatures were obtained when the composition contained the two-component block copolymer than when it contained the prior art unbound gradient block copolymer.

Moreover, when comparing the preparation of the mixtures in Invention Examples 23-26 with the preparation of a mixture containing prior art commercial reference Buna® BL 30-4548, in Comparative Example 12, it can be seen that the two-component block copolymers of the invention show a slightly lower temperature at the end of the mixture cycle and in most cases slightly lower final torque.

The slightly lower torque when preparing blends containing the two-component block copolymers of the present invention provide an advantage as less power is required for the blending operation. The slightly lower end temperature of the inner chamber when preparing blends containing the two-component block copolymers of the present invention provides an advantage in that the problems of pre-crosslinking and pre-foaming during the blending operation are better prevented; this is particularly advantageous when using crosslinking systems and/or blowing agent systems with low activation temperatures.

The following examples show the compositions and characteristics of pressure sensitive hot melt adhesives containing a two-component block copolymer of the present invention or a block copolymer of the prior art. The formulation used has been adapted for labeling purposes. Adhesive properties were evaluated using the following test methods: Brookfield viscosity at 150, 160 and 177°C according to ASTM D1084/D2556; ring and ball softening temperature according to ASTM D36; loop stickiness tests at 23° C. were performed in accordance with PSTC-16; the stickiness of the rolling ball was evaluated at 23°C in accordance with the standards PSTC-6; peel strength at an angle of 180° and 23°C - according to PSTC-1; and shear strength at 23°C according to ASTM D3654.

Example 27 according to the invention:

A pressure sensitive hot melt adhesive for labels was prepared using the following composition: 100 mass parts of a two-component block copolymer with characteristics similar to those of example 13 of the invention (M _w = 174.0 kg/mol, content of unbound block copolymer D-( D/A)-A ₁ =15.16%, content of unbound block copolymer D-(D/A)-A ₂ =46.01%, content of bound block copolymer [D-(D/A)-A ₁ ] _n=2-4 -Si=38.83%, %D=40.08, blockiness=83.06%, Mooney viscosity ML 1+4 at 100°C=4 0.7, Tan deltamax in the range vibration frequencies from 0.25 to 200 rad/s at 100°C and a strain of 13.95%=0.81), 178 parts by weight hydrogenated rosin for tackifying Foral® 85 from Eastman Chemical Company, 50 parts by weight Nyflex® naphthenic oil 223 from NYNAS, and 4 parts by weight of Irganox® 1010 antioxidant from BASF. The mixture was prepared in a 500 ml cylindrical metal container equipped with an adjustable heating mantle and adjustable stirring speed with a three-bladed screw. The tackifier, naphthenic oil, and antioxidant were first heated at 135° C. under nitrogen atmosphere with gentle stirring to melt the components. After melting, the stirring speed was set to 300 rpm and the temperature was raised to 155° C. over a 30 minute period. The two-component block copolymer was then gradually added and the stirring speed was increased to 750 rpm. The temperature was then maintained at 170 plus/minus 5°C for the next 2 hours with stirring at 750 rpm to ensure homogenization of the mixture. This adhesive showed a Brookfield viscosity of 66300 cP at 150°C, 46380 cP at 160°C and 19680 cP at 177°C; ring and ball softening point 90.9°C; loop tack at 23°C 8.853 lbf-in (1.000256205 J), rolling ball tack at 23°C 0.28 inch (0.7112 cm); peel strength at 180° and 23°C 4.04 lbf (17.97 Newton); and shear strength at 23°C of 9.58 minutes with a load of 1000 g. The composition and characteristics of the adhesive are shown in Table 10.

Comparative Example C-13:

A pressure sensitive hot melt adhesive for labels was prepared as in Invention Example 27, but with the two component block copolymer replaced with Solprene® 1205 from Dynasol Group. wt. %, the content of block styrene 17.5 wt. % and a Mooney Viscosity ML 1+4 at 100° C. of 47, which is a well-established reference for formulating pressure-sensitive hot melt adhesives. This adhesive had a Brookfield viscosity of 14000 cP at 150°C, 10750 cP at 160°C and 7050 cP at 177°C; ring and ball softening point 69.95°C; loop initial tack at 23° C. 6.132 lbf/inch (0.69282402 J); roll stickiness at 23°C - 0.44 inches (1.1176 cm); peel strength at an angle of 180 ° and 23 ° C - 3.275 pounds of force (14.57 Newton); and shear strength at 23°C - 1.55 minutes at a load of 1000 g. The composition and characteristics of this adhesive are shown in Table 10.

Comparative Example C-14:

A pressure sensitive hot melt adhesive for labels was prepared as in Invention Example 27, but with the two component block copolymer replaced with Calprene® 540 from the Dynasol Group. Calprene® 540 is a linear styrene-butadiene-styrene triblock copolymer with a total styrene 40 wt. % and the content of block styrene 38 wt. %, which is also sold for the preparation of pressure sensitive hot melt adhesives. This adhesive had a Brookfield viscosity of 13260 cP at 150°C, 9300 cP at 160°C and 5470 cP at 177°C; ring and ball softening point of 85.3°C; initial loop tack at 23°C of 5.05 pound-force per inch (0.57057425 J); 23°C rolling ball tack 0.98 in. (2.4892 cm); peel strength at 180° and 23°C 4.09 lbf ( 18.19 Newton); and shear strength at 23°C - 713.5 minutes at a load of 1000 g. The characteristics of this adhesive are presented in Table 10.

Evaluation of the performance of hot melt pressure sensitive adhesives for labels indicates that the two-component block copolymer imparts excellent tack, which may be due to the higher wetting and adhesion properties of blocks rich in conjugated diene of its bound fraction. On the other hand, a higher softening temperature of a two-component block copolymer adhesive may be useful for widening the operating temperature range of the adhesive, as it may be useful for product labels exposed to high temperatures during shipping. The Brookfield viscosity of the hot melt adhesive according to the present invention is at the upper limit of suitability for its processing, however, it can be easily reduced by proper control of molecular parameters, such as molecular weight, level of binding and/or functionality of the applied coupling agent.

End use

Summarizing the above, in one embodiment, the invention provides a two-component block copolymer containing C and U, where C includes: [D-(D/A)-A1]nX; [B-(B/A)-A1]n-X; [(B/A)-A1]n-X; or [B-A1]n-X, or a mixture of the above, and where U includes: D-(D/A)-A2 or D-(D/A)-A2 and D-(D/A)-A1; B-(B/A)-A2 or B-(B/A)-A2 and B-(B/A)-A1; (B/A)-A2 or (B/A)-A2 and (B/A)-A1; or B-A2 or B-A2 and B-A1, or a mixture of the above, where B is a polymer block derived from a conjugated diene monomer only, (B/A) is a random polymer block derived from at least a conjugated diene monomer and at least a monovinyl aromatic monomer, D is a polymer block consisting of at least a conjugated diene monomer and at least a monovinyl aromatic monomer, wherein the conjugated diene repeat units are in a greater molar amount than the monovinyl aromatic repeat units along the entire length of the polymer block , (D/A) is a polymer block consisting of at least a conjugated diene monomer and at least a monovinyl aromatic monomer, where the end of the polymer block opposite A ₁ or A ₂ predominantly consists of repeating units of the conjugated diene and which gradually changes its composition along its length until it becomes essentially consisting of monovinyl aromatic repeating units towards the end adjacent to A ₁ or A ₂ ; A ₁ and A ₂ are polymer blocks obtained only from a monovinyl aromatic monomer, where the A ₂ polymer block has a higher molecular weight than the A ₁ polymer block, X is the remainder of the binding agent, n is an integer from 2 to 30.

Preferably, the molecular weight distribution of the two-component block copolymer has at least two partially or completely resolved peaks; and/or block copolymer C constitutes the fraction with the highest molecular weight peak in the molecular weight distribution and block copolymer U constitutes the remainder of the molecular weight distribution, and/or block copolymer C constitutes from about 20 to about 80% by molecular weight distribution. Perhaps the total content of monovinyl aromatic repeating units of the two-component block copolymer is from about 20 to about 50 wt. %; and/or the content of monovinyl aromatic repeating units in the U block copolymer by at least 10 wt. % higher than the content of monovinyl aromatic repeating units in block copolymer C.

The main intended end use of the two-component block copolymers of the present invention is the manufacture of the crosslinked microporous rubber products described herein. However, the two-component block copolymers of the present invention may also be useful in asphalt reinforcement, adhesives, sealants, coatings, insulation and plastic compositions. The end use of block copolymers is described in US Patent Application No. 15/417193, filed January 26, 2107 and published July 27, 2017 under the number US 2017/0210841 A1, which is incorporated herein by reference. One application is in a bituminous composition which may include bitumen, one or more additives selected from the group consisting of plasticizers, fillers, crosslinkers, flow resins, tackifiers, processing aids, antiozonants and antioxidants, and a two component block of the copolymer described and claimed herein, wherein the bituminous composition comprises from about 0.5 to about 25 weight percent, preferably from about 0.5 to about 8 weight percent for road surfaces and from 3 to about 25 weight percent for roofing, tiles and waterproofing membranes. The bituminous composition can also be emulsified in water using an emulsifier.

One application is a sealant composition that may include at least one additive selected from the group consisting of tackifier resin, plasticizers, solvents, binders, crosslinkers, photoinitiators, and antioxidants, and a two-component block copolymer composition as described. and stated herein, where the sealant composition comprises from about 0.5 to about 50 weight percent of the composition of the two-component block copolymer. Another use is in a sealant composition that may include at least one additive selected from the group consisting of tackifier resin, plasticizers, fillers, binders, processing aids, and antioxidants, and a two-component block copolymer composition as described and claimed in herein, where the sealant composition comprises from about 0.5 to about 50 weight percent of the two-component block copolymer composition. Another suitable application of the invention is the production of high impact styrenic resins such as HIPS and ABS, obtained by bulk polymerization of styrene or bulk copolymerization of styrene and acrylonitrile in the presence of a two-component block copolymer for the specific purpose of improving gloss with minimal compromise on toughness, which may include a mixture of polymer compositions and composition of a two-component block copolymer, as described and claimed in this document.

After the foregoing description of the invention above, various modifications of technologies, techniques, materials and equipment will be apparent to those skilled in the art. All such variations within the scope and spirit of the invention are intended to be included within the scope of the appended claims.

Claims (158)

1. A two-component block copolymer composition particularly useful in microporous rubber compounds and adhesive formulations, where the composition contains C and U, where C includes: [D-(D/A)-A ₁ ] _n -X; [B-(B/A)-A ₁ ] _n -X; [(B/A)-A ₁ ] _n -X; or [BA ₁ ] _n -X; And U includes: D-(D/A)-A ₂ or D-(D/A)-A ₂ and D-(D/A)-A ₁ ; B-(B/A)-A ₂ or B-(B/A)-A ₂ and B-(B/A)-A ₁ ; (B/A)-A ₂ or (B/A)-A ₂ and (B/A)-A ₁ ; or BA ₂ or B-A ₂ and B-A ₁ , where B is a polymer block derived only from a conjugated diene monomer, where (B/A) is a random polymer block made from at least a conjugated diene monomer and at least a monovinyl aromatic monomer; Where D is a polymer block derived from at least a conjugated diene monomer and at least a monovinyl aromatic monomer, where the conjugated diene repeat units are in a higher molar amount than the monovinyl aromatic repeat units, along the entire length of the polymer block, where (D/A) is a polymer block derived from at least a conjugated diene monomer and at least a monovinyl aromatic monomer, where the end of the polymer block opposite A ₁ or A ₂ predominantly consists of conjugated diene repeating units, where the composition of the polymer block is gradually varies along the length of the block until it is essentially composed of monovinyl aromatic repeat units at the end adjacent to A ₁ or A ₂ , where A ₁ and A ₂ are polymer blocks derived only from a monovinyl aromatic monomer, where the A ₂ polymer block has a higher molecular weight than the A ₁ polymer block, where X is the remainder of the binding agent, where n is an integer from 2 to 30; and where: the molecular weight distribution of the two-component block copolymer has at least two peaks; And block copolymer C constitutes the fraction with the highest molecular weight peak in the molecular weight distribution and block copolymer U constitutes the remainder of the molecular weight distribution; And block copolymer C is from 20 to 80% of the molecular weight distribution; And the total content of monovinyl aromatic repeating units of a two-component block copolymer is from 20 to 50 wt.%; And the content of monovinyl aromatic repeating units in the block copolymer U is at least 10 wt.% higher than the content of monovinyl aromatic repeating units in the block copolymer C; And possibly a two-component block copolymer additionally contains a filler oil. 2. The composition of the two-component block copolymer according to claim 1, where C includes: [D-(D/A)-A ₁ ] _n -X and where U includes: D-(D/A)-A ₂ or D-(D/A)-A ₂ and D-(D/A)-A ₁ where: molecules of the unbound block copolymer of the formula D-(D/A)-A ₂ constitute from 20 to 80 wt.% of the molecular weight distribution of the two-component block copolymer, molecules of the unbound block copolymer of the formula D-(D/A)-A ₁ constitute from 0 to 20 wt.% of the molecular weight distribution of the two-component block copolymer, the degree of blockiness of the monovinyl aromatic repeating units of the two-component block copolymer is equal to or greater than 76 mol.% of the total content of monovinyl aromatic repeating units and optionally, the two-component block copolymer additionally contains from 0 to 12 wt.% of the filler oil. 3. The composition of the two-component block copolymer according to claim 1, where C includes: [B-(B/A)-A ₁ ] _n -X and where U includes: B-(B/A)-A ₂ or B-(B/A)-A ₂ and B-(B/A)-A ₁ where: molecules of the unbound block copolymer of the formula B-(B/A)-A ₂ constitute from 20 to 80 wt.% of the molecular weight distribution of the two-component block copolymer, molecules of the unbound block copolymer of the formula B-(B/A)-A ₁ constitute from 0 to 20 wt.% of the molecular weight distribution of the two-component block copolymer and optionally, the two-component block copolymer additionally contains from 0 to 12 wt.% of the filler oil. 4. The composition of the two-component block copolymer according to claim 1, where C includes: [(B/A)-A ₁ ] _n -X, and where U includes: (B/A)-A ₂ or (B/A)-A ₂ and (B/A)-A ₁ where: molecules of the unbound block copolymer of formula (B/A)-A ₂ constitute from 20 to 80 wt.% of the molecular weight distribution of the two-component block copolymer, molecules of the unbound block copolymer of formula (B/A)-A ₁ constitute from 0 to 20 wt.% of the molecular weight distribution of the two-component block copolymer, and optionally, the two-component block copolymer additionally contains from 0 to 12 wt.% of the filler oil. 5. The composition of the two-component block copolymer according to claim 1, where C includes: [BA ₁ ] _n -X and where U includes: BA ₂ or BA ₂ and BA ₁ where: molecules of the unbound block copolymer of formula BA ₂ constitute from 20 to 80 wt.% of the molecular weight distribution of the two-component block copolymer, molecules of the unbound block copolymer of formula BA ₁ constitute from 0 to 20 wt.% of the molecular weight distribution of the two-component block copolymer, the degree of blockiness of the monovinyl aromatic repeating units of the two-component block copolymer is equal to or greater than 90 mol.% of the total content of monovinyl aromatic repeating units and optionally, the two-component block copolymer additionally contains from 0 to 12 wt.% of the filler oil. 6. The bicomponent block copolymer composition of claim 2, wherein the degree of blockiness of the monovinyl aromatic repeating units of the bicomponent block copolymer is at least 80 mole % of the total content of monovinyl aromatic repeating units. 7. The composition of the two-component block copolymer according to any one of paragraphs. 1-5, where the content of monovinyl aromatic repeating units in U is at least 20 wt.% higher than in C. 8. The composition of the two-component block copolymer according to any one of paragraphs. 1-5, where the ratio of polydispersity M _w /M _n two-component block copolymer is from 1.00 to 1.90. 9. The composition of the two-component block copolymer according to any one of paragraphs. 1-5, where, when performing a dynamic shear vibration test, the Tan delta values are less than 0.95 at an oscillation frequency of 0.25 to 200 rad/s, at a temperature of 100 °C and a strain of 13, 95% possible where, when performing a dynamic shear vibration test, tan delta values are less than 0.95 at a vibration frequency of 0.25 to 200 rad/s, at a temperature of 140 °C and a strain of 13.95%. 10. The composition of the two-component block copolymer according to any one of paragraphs. 1-5, where, when performing a dynamic shear vibration test, the tan delta values are less than 0.90 at an oscillation frequency of 0.25 to 200 rad/s, at a temperature of 100 °C and a deformation of 13.95%, possible where, when performing a dynamic shear vibration test, the tan delta values are less than 0.90 at a vibration frequency of 0.25 to 200 rad/s, at a temperature of 140 °C and a strain of 13.95%. 11. The composition of the two-component block copolymer according to any one of paragraphs. 1-5, where, when performing a dynamic shear vibration test, the tan delta values are less than 0.85 at an oscillation frequency of 0.25 to 200 rad/s, at a temperature of 100 °C and a deformation of 13.95%, possible where, when performing a dynamic shear vibration test, tan delta values are less than 0.85 at a vibration frequency of 0.25 to 200 rad/s, at a temperature of 140 °C and a strain of 13.95%. 12. The composition of the two-component block copolymer according to any one of paragraphs. 1-5, where the Mooney viscosity (ML 1+4 at 100°C) of the two-component block copolymer is 25 to 90; And the complex dynamic shear viscosity of the two-component block copolymer, measured at a frequency of 0.99 rad/s, a temperature of 100°C and a strain of 13.95%, is between 50,000 Pa⋅s and 360,000 Pa⋅s; And the complex dynamic shear viscosity of the two-component block copolymer, measured at a frequency of 100 rad/s, a temperature of 100°C and a strain of 13.95%, is between 3000 Pa⋅s and 12000 Pa⋅s. 13. A two-component block copolymer composition derived from conjugated diene monomers and monovinyl aromatic monomers, which is particularly useful in microporous rubber compounds and in adhesive formulations, where the composition contains a block copolymer C and a block copolymer U, where C is a bonded block copolymer containing repeating units from a conjugated diene and monovinyl aromatic monomers, where C has only conjugated diene rich ends and only monovinyl aromatic internal blocks, where in C, each inner monovinyl aromatic unit is bonded at one end to a coupling agent moiety and bonded at its opposite end to one diene-rich conjugated end, where C has one coupling agent moiety per molecule, where the coupling agent moiety is bonded only to the monovinyl aromatic inner blocks, where U is an unbound block copolymer containing repeating units from a conjugated diene and monovinylaromatic monomers, where U has only one monovinyl aromatic end block and one conjugated diene rich end, where U has a lower molecular weight than C, where U has a higher content of monovinyl aromatic repeating units than C, where U has a higher average molecular weight monovinyl aromatic block than the individual monovinyl aromatic internal blocks in C, where U and C have conjugated diene-rich ends of the same molecular weight, where the conjugated diene-rich ends contain conjugated diene monomer repeat units with inserts of monovinyl aromatic monomer repeat units or only conjugated diene monomer repeat units, where (a) the molecular weight distribution of the two-component block copolymer has at least two peaks; (b) block copolymer C constitutes the fraction with the highest molecular weight peak in the molecular weight distribution and block copolymer U constitutes the remainder of the molecular weight distribution; (c) block copolymer C comprises 20 to 80% of the molecular weight distribution; (d) the total content of monovinyl aromatic repeating units of the two-component block copolymer is from 20 to 50 wt.%; (e) the content of monovinyl aromatic repeating units in block copolymer U is at least 10 wt.% higher than the content of monovinyl aromatic repeating units in block copolymer C; (f) the degree of blockiness of the monovinyl aromatic repeating units of the two-component block copolymer is equal to or greater than 77 mol.% of the total content of monovinyl aromatic repeating units; (g) the Mooney viscosity (ML 1+4 at 100°C) of the two-component block copolymer is from 25 to 70; (h) the complex dynamic shear viscosity of the two-component block copolymer, measured at a frequency of 0.99 rad/s, at a temperature of 100 °C and a strain of 13.95%, is greater than 50,000 Pa⋅s and less than 150,000 Pa⋅s; (i) the complex dynamic shear viscosity of the two-component block copolymer, measured at a frequency of 100 rad/s, at a temperature of 100 °C and a strain of 13.95%, is greater than 3000 Pa⋅s and less than 7000 Pa⋅s; And (j) in a dynamic shear vibration test, the tan delta values of the two-component block copolymer are less than 0.95 at a vibration frequency of 0.25 to 200 rad/s, at a temperature of 100°C, and at a strain of 13.95%. 14. The two-component block copolymer composition according to claim 13, where the block copolymer C has the general formula: [D-(D/A)-A ₁ ] _n -X and the block copolymer U has the general formula: D-(D/A)-A ₂ or D-(D/A)-A ₂ and D-(D/A)-A ₁ , Where: (a) D is a polymer block made from at least a conjugated diene monomer and at least a monovinyl aromatic monomer, wherein the conjugated diene repeating units are in a greater molar amount than the monovinyl aromatic repeating units along the entire length of the polymer block; (b) (D/A) is a polymer block derived from at least a conjugated diene monomer and at least a monovinyl aromatic monomer, wherein the end of the polymer block opposite A ₁ or A ₂ is predominantly composed of conjugated diene repeating units, where the composition polymer block gradually changes until it becomes essentially consisting of monovinyl aromatic repeating units at the end adjacent to A ₁ or A ₂ , (c) A ₁ and A ₂ are polymer blocks derived from monovinyl aromatic monomer only; (d) polymer block A ₂ has a higher molecular weight than polymer block A ₁ ; (e) X is a binder residue and n is an integer from 2 to 30; And (f) the molecules of the associated block copolymer of the formula [D-(D/A)-A ₁ ] _n -X constitute from 20 to 80% of the molecular weight distribution of the two-component block copolymer; (g) molecules of the unbound block copolymer of formula D-(D/A)-A ₂ constitute from 20 to 80 wt.% of the molecular weight distribution of the two-component block copolymer; (h) the molecules of the unbound block copolymer of formula D-(D/A)-A ₁ constitute from 0 to 20 wt.% of the molecular weight distribution of the two-component block copolymer. 15. A method for producing a composition of a two-component block copolymer described in paragraph 2, including the following stages: loading into the batch reactor a hydrocarbon solvent, a conjugated diene monomer and a monovinyl aromatic monomer, loading into a batch reactor of an organolithium initiator; the implementation of complete copolymerization of monomers and the formation of polymer anions; loading a batch reactor with a binding agent to bind only a portion of the polymer anions; loading into the batch reactor an additional amount of monovinyl aromatic monomer; carrying out a complete block copolymerization of the monovinyl aromatic monomer; deactivation of any remaining polymeric anions in the batch reactor; And isolation of the two-component block copolymer. 16. A method for producing a two-component block copolymer composition according to claim 3, including the following steps: loading into the batch reactor a hydrocarbon solvent, a randomizer and a conjugated diene monomer; loading into a batch reactor of an organolithium initiator; polymerization of the conjugated diene monomer loaded into the batch reactor to a conversion level of 80 to 95%; loading monovinyl aromatic monomers into the batch reactor; the implementation of complete copolymerization of the remaining monomers of the conjugated diene and monovinyl aromatic monomers loaded into the reactor, where polymer anions are formed; loading into the batch reactor a binding agent for partial binding of polymer anions; loading into the batch reactor an additional amount and/or other monovinyl aromatic monomer; carrying out a complete block copolymerization of the monovinyl aromatic monomer; deactivation of any remaining polymeric anions; And isolation of the two-component block copolymer. 17. A method for producing a two-component block copolymer composition according to claim 4, including the following steps: loading into the batch reactor a hydrocarbon solvent, a randomizer, a conjugated diene monomer and a monovinyl aromatic monomer, loading into a batch reactor of an organolithium initiator; carrying out the complete copolymerization of the conjugated diene monomer and the monovinyl aromatic monomer; loading into the batch reactor an additional amount and/or other monovinyl aromatic monomer; the implementation of a complete block copolymerization of monovinyl aromatic monomer loaded into a batch reactor, where polymer anions are formed; loading a binding agent to bind only a part of the polymer anions, loading into the batch reactor an additional amount and/or other monovinyl aromatic monomer; carrying out a complete block copolymerization of the monovinyl aromatic monomer; deactivation of the remaining polymeric anions; And isolation of the two-component block copolymer. 18. A method for producing a two-component block copolymer composition according to claim 5, including the following steps: loading into the batch reactor a hydrocarbon solvent, a randomizer and a conjugated diene monomer, loading into a batch reactor of an organolithium initiator; carrying out complete polymerization of the conjugated diene monomer; loading monovinyl aromatic monomer into the batch reactor, the implementation of a complete block copolymerization of monovinyl aromatic monomer loaded into a batch reactor, where polymer anions are formed; loading a binding agent for partial binding of polymer anions, loading into the batch reactor an additional amount and/or other monovinyl aromatic monomer; carrying out a complete block copolymerization of the monovinyl aromatic monomer; deactivation of the remaining polymeric anions; And isolation of the two-component block copolymer. 19. The method according to any one of paragraphs. 15-18, further comprising the following steps: loading the batch reactor with a proton donor or electrophilic monofunctional compound to deactivate only a portion of the polymeric anions before the step of loading additional and/or other monovinyl aromatic monomer; or loading into the batch reactor a proton donor or electrophilic monofunctional compound to deactivate only a portion of the polymeric anions simultaneously with the step of loading an additional amount and/or another monovinyl aromatic monomer. 20. Composition for products made of cross-linked microporous rubber, containing: the composition of the two-component block copolymer according to any one of paragraphs. 1-5; a blowing agent; and a crosslinking agent. 21. The composition of claim 20, further comprising at least one additive selected from the group consisting of styrene-butadiene random copolymers, styrene-isoprene-butadiene random copolymers, natural rubbers, polybutadienes, polyisoprene rubbers, ethylene/alpha-olefin terpolymers / non-conjugated diene, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, ground crosslinked microporous rubber compounds, fillers, plasticizers, blowing agent activators, crosslinking activators, crosslinking accelerators, vulcanization retardants, antioxidants, antiozonants, UV stabilizers, light stabilizers, fragrances or odorants, antitermite agents, biocidal agents, antifungal agents, antimicrobial agents, antibacterial agents, metal deactivators, dyes, pigments, mold release agents, or mixtures thereof. 22. Composition for pressure-sensitive hot melt adhesive, containing: the composition of the two-component block copolymer according to any one of paragraphs. 1-5; tackifying resin, extender oil and antioxidant. 23. The composition of claim 22, further comprising at least one additive selected from the group consisting of fillers, waxes, photoinitiators, crosslinkers, crosslinkers, crosslinking retarders, adhesion promoters or coupling agents, UV stabilizers, light stabilizers, ozone stabilizers, epoxy resins, asphalt, reinforcing resins, fragrances or odorants, anti-termite agents, biocidal agents, antifungal agents, antibacterial agents, metal deactivators, dyes, pigments or colorants, flame retardants, blowing agents, blowing agent activators, refractive index adjusting agents or their mixtures.

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