Styrene-butadiene block copolymer

This invention relates to a styrene-butadiene block copolymer comprising two styrene-butadiene copolymer blocks different from each other in styrene content and in vinyl content in the butadiene portion, and optionally polybutadiene blocks.
Recently, owing to the increasing request for low fuel consumption and high running safety of automobiles, there has become strongly desired a rubber material having low rolling resistance and high wet skid resistance when used as rubber for tyre tread rubber of automobile. However, said two characteristics are antagonistic to each other, and, in addition, it is hardly possible to satisfy these characteristics and wear characteristics at the same time by use of a single rubber material. Therefore, in order to harmonize these characteristics, use has been made of blends of dissimilar rubber materials. For instance, a blend of styrene-butadiene copolymer rubber containing 10 to 30% by weight of bound styrene and not more than 20% of vinyl configuration which has relatively high wet-skid resistance with a polybutadiene rubber containing not more than 20% of vinyl configuration which has low rolling resistance and high wear resistance has been used as the rubber for tyre tread of automobile. This blend, however, is unsatisfactory in other characteristics, particularly in wet skid resistance.
More lately, for improving such wet skid resistance and rolling resistance, attempts have been made to modify butadiene rubber (BR) or styrene-butadiene rubber (SBR) which is obtained by using mainly an organolithium compound as polymerization initiator. For instance, a rubber composition containing BR rich in vinyl configuration has recently been proposed as a commercial product that can match said object (British Pat. No. 1,166,832). BR rich in vinyl configuration is indeed advantageous for giving a good balance between wet skid resistance and rolling resistance, but it is excessively poor in fracture and wear characteristics, so that such BR can hardly be used alone. For improving such fracture and wear characteristics, blends with other diene rubbers such as natural rubber (NR), high-cis BR, emulsion-polymerized SBR and the like have been proposed. The blends with NR or high-cis BR, however, are inferior in balance between the wet skid resistance and the fracture and wear characteristics, while the blends with SBR are inferior in rolling resistance.
In Japanese Patent Application Kokai (Laid-Open) No. 62248/79, there has been tried an improvement of both wet skid resistance and rolling resistance by use of a random SBR having a bound styrene content of 20 to 40% by weight and a relatively high vinyl content in the butadiene portion. Such a random SBR is certainly improved in balance of wet skid resistance, rolling resistance, wear resistance, etc., as compared with the conventional emulsion-polymerized SBR or SBR obtained by using an organolithium polymerization initiator. However, when it is used alone it is still unsatisfactory in balance between wet skid resistance and rolling resistance or in fracture characteristics. Therefore, it must rely on blends with other diene rubbers. However, when blended with other diene rubbers, for example, a blend with high-cis BR is improved in rolling resistance but inferior in wet skid resistance and fracture characteristics, and a blend with NR is inferior in wet skid resistance. A blend with emulsion-polymerized SBR is inferior in rolling resistance. Thus, in these blends, the individual features of the respective blend constituents are not fully utilized.
On the other hand, Japanese Patent Publication No. 37415/74 proposes an A-B type block BR comprising blocks different in vinyl content and an A-B type block SBR comprising blocks different in bound styrene content and in vinyl content in the butadiene portion for the improvement of wet skid resistance. However, said block BR is comparatively balanced in wet skid resistance and rolling resistance, but is remarkably inferior in fracture characteristics and is difficult to use alone.
Said block SBR is relatively well balanced in wet skid resistance, rolling resistance, wear resistance, and processability, as compared with conventional SBR obtained with organolithium initiators, but such an improvement is still unsatisfactory in view of high performance required in the tyre industry. Thus, the use of said block SBR alone for commercial purposes is difficult.
On the basis of these prior art proposals, the present inventors have made efforts for further improving the wet skid resistance and rolling resistance of SBR using an organolithium polymerization initiator, and have found that a styrene-butadiene block copolymer having a Mooney viscosity (ML.sub.1+4, 100.degree. C.) of 10 to 150 and comprising two styrene-butadiene random copolymer blocks different in average vinyl content in the butadiene portion and in bound styrene content, and optionally polybutadiene blocks, wherein the total vinyl content in the whole bound butadiene is 30 to 70% and the total bound styrene content is 10 to 40% by weight, is excellent in both wet skid resistance and rolling resistance, well balanced in fracture and wear characteristics and also satisfactory in processability and cold flow property.
According to this invention, there is provided a styrene-butadiene block copolymer (I) consisting essentially of (A) at least one styrene-butadiene random copolymer block having a bound styrene content of 10 to 50% by weight and a vinyl content of 25 to 50% in the butadiene portion and (B) at least one styrene-butadiene random copolymer block having a bound styrene content of 1 to 30% by weight and a vinyl content of at least 60% in the butadiene portion, wherein the fraction of said copolymer block (A) is 10 to 90% by weight, the total vinyl content in the whole bound butadiene is 30 to 70%, and the total bound styrene content is 10 to 40% by weight; a styrene-butadiene block copolymer (II) consisting essentially of (A') at least one styrene-butadiene random copolymer block having a bound styrene content of 20 to 50% by weight and a vinyl content of 40 to 75% in the butadiene portion and (B') at least one polymer block having a bound styrene content of not more than 10% by weight and a vinyl content of more than 20% but not more than 50% in the butadiene portion, wherein the total vinyl content in the whole bound butadiene is 30 to 70%, the total bound styrene content is 10 to 40% and the fraction of said copolymer block (A') is 10 to 90% by weight; or a styrene-butadiene block copolymer (III) consisting essentially of (A") at least one styrene-butadiene random copolymer block having a bound styrene content of 10 to 50% by weight and a vinyl content of 10 to 50% in the butadiene portion, (B") at least one styrene-butadiene random copolymer block having a bound styrene content of 1 to 30% by weight and a vinyl content of at least 60% in the butadiene portion, and (C) at least one polybutadiene back having a vinyl content of 10 to 50%, wherein each of the blocks (A"), (B") and (C) is contained in a proportion of at least 10% by weight, the total bound styrene content is 10 to 40% by weight and the total vinyl content in the whole bound butadiene is 30 to 70%.
The styrene-butadiene block copolymers obtained according to this invention are characterized by the excellent wet skid resistance, rolling resistance, fracture resistance and wear resistance and the improved processability as compared with the conventional SBR.
The excellent physical properties of the styrene-butadiene block copolymers of this invention result from the specific phenomenon that the two or three different blocks (A)-(B), (A')-(B') or (A")-(B")-(C) having the different characteristics and different solubility parameters are surprisingly rendered compatible through the vulcanization step.
The block copolymers according to this invention, when in a state of raw rubber, show different glass transition points corresponding to the respective blocks, but when vulcanized, they show a single glass transition point and also the temperature-tan .delta. distribution curve drawn up by a dynamic measuring method has a single peak and is very broad. It should be noted that the compositions formed by simply blending said respective blocks (A), (B), etc., are not rendered compatible to such a degree as to give a single glass transition point, so that such compositions are poor particularly in fracture characteristics and it is impossible to develop the physical properties of the above block copolymers.
The vinyl content in the respective blocks of the block copolymer (I) according to this invention is 25 to 50%, preferably 25 to 45% in the case of block (A) and at least 60%, preferably at least 70% in the case of block (B), and it is preferable that at least one of said blocks has a vinyl content distribution breadth of at least 20%. By allowing the blocks to have a vinyl content distribution breadth, the fracture characteristics are improved and the balance between wet skid resistance and rolling resistance becomes good as compared with the block copolymers having no such distribution breadth.
The term "vinyl content distribution breadth" is used herein to signify a change of vinyl content along one molecular chain. For example, when styrene and butadiene are copolymerized with a catalyst consisting of a combination of an organolithium compound and a Lewis base (such as an ether or an amine) as shown in, for example, Japanese Patent Application Kokai (Laid-Open) No. 149,413/81, the vinyl content can be varied by providing a difference between the temperature at the time of initiation of polymerization and that at the time of completion thereof. It is to be noted that if the vinyl content in the copolymer block (A) exceeds 50%, both fracture characteristics and rolling resistance are deteriorated, while if said vinyl content is less than 25%, it becomes difficult to favorably balance the fracture characteristics, wet skid resistance and rolling resistance. Also, if the vinyl content in the copolymer block (B) is less than 60%, it is hard to balance the wet skid resistance and other characteristics.
The bound styrene content in the respective blocks in the block copolymer (I) according to this invention is PG,9 within the range of 10 to 50% by weight, preferably 15 to 40% by weight, in the copolymer block (A) and 1 to 30% by weight, preferably 5 to 20% by weight, in the copolymer block (B). If the bound styrene content in the copolymer block (A) is less than 10% by weight, no satisfactory fracture characteristics are provided, while if said styrene content exceeds 50% by weight, the copolymer becomes inferior in rolling resistance. The same tendency as in the copolymer block (A) can be seen as to the bound styrene content in the copolymer block (B).
The weight ratio of the copolymer block (A) to the copolymer block (B) is within the range of 1:9 to 9:1. Even when the block copolymer (I) is composed of more than two blocks, such as (A)-(B)-(A) or (B)-(A)-(B), the excellent properties can be obtained if the total weight ratio of the copolymer block (A) to the copolymer block (B) defined above is satisfied.
The vinyl content in the respective blocks in the block copolymer (II) according to this invention is within the range of 40 to 75%, preferably 40 to 70%, in the copolymer block (A') and more than 20% but not more than 50%, preferably 25 to 50%, in the polymer block (B'). When at least one of the blocks (A') and (B') has a vinyl content distribution breadth of at least 20% the fracture characteristics can be improved without impairing the balance of other characteristics. The term "vinyl content distribution breadth" used herein has the same meaning as defined in connection with the block copolymer (I).
If the vinyl content in the copolymer block (A') is more than 75%, the fracture characteristics become inferior, and if said content is less than 40%, difficulties arise in providing a good balance between wet skid resistance and rolling resistance. Also, if the vinyl content in the polymer block (B') is more than 50%, low rolling resistance results, and if said vinyl content is not more than 20%, no good balance is provided between wet skid resistance and rolling resistance.
The bound styrene content in the respective blocks in the block copolymer (II) according to this invention is required to be 20 to 50% by weight, preferably 20 to 40% by weight, in the copolymer block (A') and not more than 10% by weight in the polymer block (B'). If the bound styrene content in the copolymer block (A') is less than 20% by weight, neither satisfactory wet skid resistance nor satisfactory fracture characteristics are provided, and if said content exceeds 50% by weight, the rolling resistance is excessively deteriorated. Also, if the bound styrene content in the block (B') exceeds 10% by weight, the block copolymer becomes unsatisfactory in rolling resistance.
The weight ratio of the copolymer block (A') to the polymer block (B') is within the range of 1:9 to 9:1, preferably 1:5 to 5:1. Even when the block copolymer (II) is composed of more than two blocks, such as (A')-(B')-(A') or (B')-(A')-(B'), excellent properties can be obtained as far as the above-defined total weight ratio is satisfied.
The vinyl content in the respective blocks in the block copolymer (III) according to this invention is 10 to 50%, preferably 20 to 50% in the copolymer block (A") and at least 60%, preferably at least 70%, in the copolymer block (B"), and 10 to 50%, preferably 20 to 40% in the polybutadiene block (C). Polymerization using an organolithium initiator can hardly give a block copolymer with a vinyl content of less than 10%. If the vinyl content in the copolymer block (A") is more than 50%, there results an unsatisfactory rolling resistance, and if the vinyl content in the copolymer block (B") is less than 60%, no good balance is provided between wet skid resistance and rolling resistance. If the vinyl content in the polymer block (C) is more than 50%, the fracture characteristics and wear characteristics become unsatisfactory.
The bound styrene content in the respective blocks in the block copolymers (III) according to this invention should be within the range of 10 to 50% by weight, preferably 20 to 40% by weight, in the copolymer block (A") and 1 to 30% by weight, preferably 5 to 20% by weight, in the copolymer block (B"). If the bound styrene content in the copolymer block (A") is less than 10% by weight, the resulting block copolymer is unsatisfactory in fracture characteristics, and if the bound styrene content is more than 50% by weight the rolling resistance becomes inferior. The same tendency is seen in the copolymer block (B").
Each of the polymer blocks is contained in an amount of at least 10% by weight in the block copolymer (III) according to this invention, and it is particularly desirable that the copolymer block (A") be contained in an amount of at least 40% by weight. A too low proportion of the copolymer block (A") results in poor fracture and wear characteristics, while a too low proportion of the polymer block (C) deteriorates the rolling resistance, and a too low proportion of the copolymer block (B") impairs the wet skid resistance.
In any of the block copolymers (I), (II) and (III) according to this invention, the total vinyl content in the whole bound butadiene should be 30 to 70%, and the total styrene content should be within the range of 10 to 40% by weight. If said contents are outside the above-defined ranges, it becomes impossible to secure a required balance among the fracture characteristics, the rolling resistance, the wear characteristics and the wet skid resistance.
For producing a styrene-butadiene block copolymer according to this invention, first the copolymer or polymer blocks (A), (A'), (A"), (B'), (B") or (C) are formed by polymerization and then the other copolymer blocks are formed by polymerization. The vinyl content in the copolymer blocks can be varied by changing the amount of the microstructure controlling agent or by changing the mean polymerization temperature without changing the amount of said microstructure controlling agent in the course of the polymerization of the respective copolymer blocks. Also, the bound styrene content can be changed by adjusting the styrene-butadiene monomer feed.
An organolithium compound may be used as polymerization initiator in the polymerization. Various types of ethers and amines may be used as controlling agent for vinyl content in the butadiene portion, and various types of ethers, amines and anionic surface active agents having a --SO.sub.3 M or --OSO.sub.3 M group (M representing Na, K, Rb or Cs) may be used as randomizing agent for styrene.
Examples of the organolithium compounds usable as polymerization initiator in this invention are methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium, tetramethylenedilithium, pentamethylenedilithium and decamethylenedilithium.
As the microstructure controlling agent, there may be used ether compounds and tertiary amines alone or in combination. Examples of such ether compounds and tertiary amines are diethyl ether or thioether, amyl ethyl ether, octyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, triethylamine, N,N,N',N'-tetramethylethylenediamine, triethylenediamine and N-methylmorpholine. These compounds can also serve as a styrene randomizing agent.
Beside said ethers and amines, there may be also used as randomizing agent an anionic surface active agent having an --SO.sub.3 M or --OSO.sub.3 M group (M representing Na, K, Rb or Cs). Examples of such surfactants are alkylarylsulfonates, amide-bonded sulfonates, ester-bonded sulfonates and ester-bonded sulfuric ester salts such as disclosed in Japanese Patent Publication No. 44315/79. Benzene, toluene, xylene, cyclohexane, hexane, heptane and the like may be used as polymerization solvent.
The polymerization temperature is important for deciding the vinyl content in the butadiene portion. In the polymerization using an organolithium compound and an ether or an amine, the vinyl content is influenced by the polymerization temperature, that is a low polymerization temperature leads to a high vinyl content and a high polymerization temperature leads to a low vinyl content. Usually the polymerization is carried out at a temperature within the range of 0.degree. to 150.degree. C. It is desirable to allow for a sufficient range of polymerization temperature for providing a required vinyl content distribution breadth in the blocks.
The styrene-butadiene block copolymers obtained according to this invention are markedly improved in wet skid resistance, rolling resistance, fracture and wear characteristics as well as in processability and cold flow characteristics as compared with the conventional SBR (obtained by using chiefly an organolithium compound as polymerization initiator), and thus, they can serve as a very excellent copolymer rubber.
By utilizing said characteristics, the block copolymers of this invention can be used, either alone or in blend with other rubbers, for the fabrication of tyres and other industrial products.

The present invention is described in further detail below referring to Examples and the accompanying drawings, but it is to be understood that this invention is by no way restricted to the Examples and the drawings.
In the drawings,
FIG. 1 is a graph showing a relation between polymerization temperature and vinyl content in the polymerization of the copolymer blocks (B) in Example 1, and
FIG. 2 is a graph showing a relation between polymerization temperature and microstructure in the polymerization of the copolymer blocks (A) in Example 11.

In the Examples, the wet skid resistance measured by a skid tester was adopted as an index of wet skid resistance of the products, and the impact resilience at 70.degree. C. and heat-build-up temperature as measured by a Goodrich flexometer were used as an index of rolling resistance.
EXAMPLES 1-10 AND COMPARATIVE EXAMPLES 1-10
A 2-liter reactor were charged with 2,500 g of a cyclohexane/n-hexane (90/10 by weight) mixture and predetermined quantities of styrene, butadiene, tetrahydrofuran and potassium dodecylbenzenesulfonate in a nitrogen atmosphere and polymerized isothermally or adiabatically within the temperature range shown in the column of "Copolymer block (A) polymerization conditions" in Table 1 by using n-butyllithium as polymerization initiator. (Comparative Examples 8-10 are the random SBR's which were not subjected to polymerization of the copolymer blocks (B)). After the polymerization conversion had reached 95 to 100%, predetermined quantities of butadiene, styrene and diethylene glycol dimethyl ether were further supplied and the mixture was polymerized within the temperature range shown in the column of "Copolymer block (B) polymerization conditions" in Table 1. Upon completion of the polymerization, 2,6-di-tert-butyl-p-cresol was added in an amount of 0.7 part by weight to 100 parts by weight of the polymer. After removing the solvent by steam stripping, the residue was dried on 100.degree. C. rolls to obtain a polymer. The properties of the thus obtained polymers are shown in Table 2. The microstructure of the butadiene portion in each polymer was determined according to D. Morero's method, and the styrene content in the copolymer was determined from the calibration curve using the absorbance at 699 cm.sup.-1. FIG. 1 shows the relation between polymerization temperature and microstructure under the copolymer block (B) polymerization conditions in Example 1. In the adiabatic polymerization of the copolymer blocks (B) at a polymerization temperature within the range of 35.degree.-80.degree. C., the vinyl content distribution breadth became about 25%.
The obtained polymers were mixed and compounded by an internal mixer and rolls with the recipe shown in Table 3 and then vulcanized at 145.degree. C. for 30 minutes.
The properties of the vulcanizates are shown in Table 4.
The styrene-butadiene block copolymer of Example 1 as higher in wet skid resistance, tensile strength, impact resilience and wear resistance than the random SBR of Comparative Example 8 which had almost the same vinyl contents and bound styrene contents as those of the copolymer of Example 1. The copolymer of Example 1 was also excellent in roll retention of compounded rubber. The copolymers of Examples 2-10 were also excellent in the above-said properties.
Comparative Examples 1, 3 and 5 were inferior to Example 1 in wet skid resistance; Comparative Examples 2, 4 and 6 were inferior in heat build-up and wear resistance; and Comparative Example 7 was inferior in impact resilience and heat build-up. Example 1 provided with said vinyl content distribution breadth was higher in tensile strength and wet skid resistance than Comparative Example 7 which had no vinyl content distribution breadth. Also, as appreciated from the results obtained from the Comparative Example 9/Comparative Example 10 (1/1) blend, the simple blends of copolymers cannot develop the excellent properties possessed by the block copolymers of this invention.
EXAMPLES 11-18 AND COMPARATIVE EXAMPLES 11-18
A 5-liter reactor was charged with 2,000 g of a cyclohexane/n-hexane (90/10 by weight) mixture and predetermined quantities of styrene, butadiene, tetrahydrofuran and potassium dodecylbenzenesulfonate in a nitrogen atmosphere and the mixture was subjected to isothermic or adiabatic polymerization under the polymerization conditions of the blocks (B') with a vinyl content as shown in Table 5 by using n-butyllithium as polymerization initiator. (In Comparative Examples 11 and 14, the polymerization was started with the block (A'), and in the others, the polymerization was started with the block (B'). Comparative Examples 16, 17 and 18 were random SBR's which were not subjected to the subsequent block polymerization.)
After the polymerization conversion had reached 95 to 100%, predetermined quantities of butadiene, styrene, tetrahydrofuran, diethylene glycol dimethyl ether and potassium dodecylbenzenesulfonate were supplied and the mixture was subjected to the remaining block (A') polymerization under the prescribed polymerization conditions. After completion of the polymerization, 2,6-di-tert-butyl-p-cresol was added in an amount of 0.7 part by weight to 100 parts by weight of the polymer, and after removing the solvent by steam stripping, the residue was dried on 100.degree. C. rolls to obtain a polymer. The properties of the thus obtained polymers are shown in Table 6.
The microstructure in the butadiene portion in the polymer was observed according to D. Morero's method, and the styrene content in the copolymer was determined from the calibration curve using the absorbance at 699 cm.sup.-1.
FIG. 2 shows the relation between polymerization temperature and microstructure under the polymerization conditions of the copolymer blocks (A') in Example 11.
In the adiabatic polymerization of the copolymer blocks (B') at a polymerization temperature within the range of 50.degree. to 90.degree. C., there was provided a vinyl content distribution breadth approximately 20%. The obtained polymers were mixed and compounded by an internal mixer and rolls according to the recipe shown in Table 3 and then vulcanized at 145.degree. C. for 30 minutes. The properties of the resulting vulcanizates are shown in Table 7.
Comparative Example 17/Comparative Example 18 blend is a simple 50/50 blend of the copolymers of Comparative Examples 17 and 18.
It will be seen that the block copolymers of Examples 11-18 according to this invention are better in processability (roll retention) than the random SBR of Comparative Example 16 which has the same levels of vinyl content and bound styrene content as said examples of this invention. Example 11 is superior to Comparative Example 16 in wet skid resistance, wear characteristics and heat build-up. Example 13 is inferior to Example 11 in fracture characteristics because the former has no specific vinyl content distribution breacth.
Comparative Example 11 is relatively well-balanced among such factors as wet skid resistance, impact resilience and wear resistance, but their values are still unsatisfactory in comparison with those of Example 11. Comparative Examples 12-15 are inferior to Examples 11-18 in balance of said factors.
Simple blends of the blocks A and the blocks B of this invention are poor in processability, wet skid resistance, wear resistance, impact resilience and fracture characteristics.
EXAMPLES 19-25 AND COMPARATIVE EXAMPLES 19-27
A 5-liter reactor were charged with 2,500 g of a cyclohexane/n-hexane (90/10 by weight) mixture and predetermined quantities of a monomer and an ether in a nitrogen atmosphere and polymerized under the block (C) polymerization conditions shown in Table 8. After the polymerization conversion had reached 95-100%, predetermined amounts of monomer, ether and potassium dodecylbenzenesulfonate were further supplied and the mixture was polymerized under the block (A") polymerization conditions. After reaching a polymerization conversion of 95-100%, to the polymerization mixture were further added predetermined amounts of a monomer and an ether, and then polymerized under the block (B") polymerization conditions. (The random SBR's of Comparative Examples 23-26 were polymerized with single feed of monomer and ether).
After completion of the polymerization, 2,6--di-tert-butyl-p-cresol was added in an amount of 0.7 part by weight to 100 parts by weight of the polymer, and after removing the solvent by steam stripping, the residue was dried on 100.degree. C. rolls to obtain a polymer. The properties of the thus obtained polymers are shown in Table 9. The microstructure of the butadiene portion in the polymer was determined according to D. Morero's method, and the styrene content in the copolymer was determined from the calibration curve using the absorbance at 699 cm.sup.-1.
The obtained polymers were mixed and compounded by an internal mixer and rolls with the recipe of Table 3 and vulcanized at 145.degree. C. for 30 minutes. The properties of the vulcanizates are shown in Table 10.
The block SBR's of Examples 19-25 showed a better roll retention than the random SBR of Comparative Example 23 and were also excellent in wet skid resistance, impact resilience, Lambourn wear and tensile strength. Comparative Example 19 was inferior to Examples 19-25 in tensile strength and wet skid resistance, and Comparative Examples 20, 21 and 22 were low in impact resilience and high in heat build-up.
A simple blend of the respective blocks (Blend 1) was unable to develop the properties of the block copolymers of this invention. Also, blending of the (A")-(C) or (A")-(B") block polymers with random SBR having the same amounts of bound styrene and vinyl configuration as (B") or (C) were incapable of acquiring the properties possessed by the (A")-(B")-(C) type block polymers.
TABLE 1__________________________________________________________________________ Copolymer block (A) polymerization Copolymer block (B) polymeri- conditions zation conditions Potassium Polymeri- Polymeriza- Tetra- dodecyl- zation tion Butadiene/ n- hydro- benzene- tempera- Butadiene/ Di- tempera- styrene BuLi*.sup.1 furan sulfonate ture styrene glyme*.sup.2 ture (A)/(B) (g) (g) (g) (g) (.degree.C.) (g) (g) (.degree.C) (wt. ratio) Remarks__________________________________________________________________________Example 1 188/62 0.35 2.0 0.1 35 225/25 220 35-80 1/1Example 2 " 0.31 " " " " 0.60 35-80 "Example 3 " 0.36 5.0 " " " 2.25 35-80 "Example 4 163/87 0.38 2.5 " " " 2.30 35-80 "Example 5 188/62 0.34 2.0 " " 237.5/12.5 2.15 35-80 "Example 6 " 0.31 2.0 0.1 20-50 " 1.91 50-90 "Example 7 " 0.33 " " 35 " 0.50 35 "Example 8 250/83 0.35 " " 20-60 150/17 4.30 60-75 2/1Example 9 94 322/108 0.38 1.8 " 10-60 64/7 2.30 60 6/1Example 10 125/42 0.30 " " 30 300/33 0.61 30-85 1/2ComparativeExample 1 225/25 0.29 -- 0.16 50 225/25 0.60 50-90 1/1ComparativeExample 2 188/62 0.32 2.0 -- 35 " 0.63 35-80 "ComparativeExample 3 237.5/12.5 0.31 1.5 -- " " 2.10 35-80 "ComparativeExample 4 100/150 0.37 5.0 0.1 " " 2.28 35-80 "ComparativeExample 5 188/62 0.35 2.0 " " " 0.30 35-80 "ComparativeExample 6 200/50 0.37 " " " 150/100 2.25 35-80 "ComparativeExample 7 213/37 0.28 -- 0.15 50 200/50 0.61 55 "ComparativeExample 8 410/90 0.28 -- 0.1 50 -- 0.29 50 -- Random SBRComparativeExample 9 450/40 0.25 -- -- " -- 0.60 50 -- "ComparativeExample 10 375/125 0.27 2.0 0.1 " -- -- 50 "__________________________________________________________________________ Note: Solvent: cyclohexane/nhexane (90/10 by weight), 2,500 g. *.sup.1 n-BuLi = nbutyllithium *.sup.2 Diglyme = diethylene glycol dimethyl ether
TABLE 2__________________________________________________________________________ Block (A) Block (B) Presence or Presence or Whole polymer Vinyl absence of Vinyl absence of Vinyl content in Bound vinyl content content in Bound vinyl content content in Bound butadiene styrene distribution butadiene styrene distribution butadiene styrene (A)/(B) portion (%) (%) breadth portion (%) (%) breadth portion (%) (%) ML .sub.1+4.sup.100.deg ree. C. (wt.__________________________________________________________________________ ratio)Example 1 32 25 Absent 81 11 Present 58 18 49 1/1Example 2 31 26 " 74 10 " 54 18 51 "Example 3 41 25 " 82 10 " 63 17 53 "Example 4 30 35 " 81 11 " 61 23 48 "Example 5 31 25 " 80 5 " 59 15 49 "Example 6 31 27 Present 75 10 " 55 19 50 "Example 7 31 28 Absent 81 11 Absent 58 20 47 "Example 8 30 25 Present 80 11 Present 49 20 53 2/1Example 9 29 26 " 80 10 Absent 38 24 51 6/1Example 10 31 27 Absent 74 10 Present 61 16 54 1/2Comparative 15 10 " 65 30 " 37 20 48 1/1Example 1Comparative 62 25 " 76 11 " 69 18 47 "Example 2Comparative 30 5 " 80 15 " 54 10 55 "Example 3Comparative 31 58 " 80 10 " 67 34 53 "Example 4Comparative 32 26 " 55 10 " 45 18 51 "Example 5Comparative 31 20 " 72 38 " 48 29 47 "Example 6Comparative 15 15 " 80 20 Absent 47 18 51 1/1Example 7Comparative 60 18 " -- -- -- 60 18 48 --Example 8Comparative 80 10 " -- -- -- 80 10 49 --Example 9Comparative 31 26 " -- -- -- 31 26 50 --Example 10__________________________________________________________________________
TABLE 3______________________________________ Parts by weight______________________________________Styrene-butadiene block copolymer 100Carbon black (ISAF) 50Aromatic process oil*.sup.3 10Zinc oxide 4Stearic acid 2AcceleratorMSA*.sup.1 0.54DM*.sup.2 0.86Sulfur 2.0______________________________________ Note: *.sup.1 N--oxydiethylene-2-benzothiazylsulfenamide (produced by Ouchi Shinko Kagaku Kogyo Co., Ltd., Japan) *.sup.2 Dibenzothiazyl disulfide (produced by Ouchi Shinko Kagaku Kogyo Co., Ltd., Japan) *.sup.3 High aromatic process oil (produced by Japan Synthetic Rubber Co. Ltd.)
TABLE 4__________________________________________________________________________ .sup.(2) .sup.(3) .sup.(4) .sup.(5) .sup.(6) .sup.(1) Tensile Elonga- Dunlop impact Heat-build Wet Lambourn Roll retention 300% modulus Strength tion Hardness resilience up tempera- skid wear of compounded (kg .multidot. f/cm.sup.2) (kg .multidot. f/cm.sup.2) (%) (JIS-A) at 70.degree. C. (%) ture .DELTA.T(.degree.C.) (Index) (Index) rubber__________________________________________________________________________Example 1 155 227 400 70 70 20 120 105 GoodExample 2 153 230 410 69 71 19 110 110 "Example 3 161 231 390 71 69 20 125 105 "Example 4 162 235 420 71 68 20 125 100 ExcellentExample 5 153 223 410 69 71 19 110 105 GoodExample 6 155 228 410 69 69 20 120 105 "Example 7 160 235 420 70 70 19 115 110 "Example 8 155 220 400 71 70 20 105 105 "Example 9 158 240 430 69 71 19 105 120 ExcellentExample 10 148 243 420 70 71 19 105 125 GoodExample 11 165 216 390 72 68 21 130 105 "Comparative 163 217 420 68 68 20 95 105 "Example 1Comparative 168 205 370 73 65 23 150 90 FairExample 2Comparative 140 200 380 70 72 19 90 105 "Example 3Comparative 165 240 390 72 63 25 150 100 ExcellentExample 4Comparative 155 235 410 70 71 19 95 120 GoodExample 5Comparative 160 225 400 72 64 24 140 95 "Example 6Comparative 158 210 400 69 67 22 105 100 "Example 7Comparative 160 212 400 69 68 21 100 100 FairExample 8Comp Ex. 9/ 150 205 400 70 67 21 105 95 Fair-BadComp Ex. 10blend (1/1)__________________________________________________________________________ Note: .sup.(1) Measured according to JISK-6301. .sup.(2) Measured according to B.S 903 Part 22 method. .sup.(3) Goodrich heat buildup, measured according to ASTMD-623/58 (Metho A). .sup.(4) Measured on the indoor wet asphalt road surface by using a skid tester made by Stanley Inc., of Britain. The value obtained from Comparative Example 8 was expressed as 100 by way of a reference index. The greater the figure, the better. .sup.(5) Measured by a Lambournwear tester at slip rate of 30% and at 25.degree. C. The value obtained from Comparative Example 8 was expressed as 100 by way of a reference index. The greater the figure, the better. .sup.(6) Roll retention of the compound mixed by an internal mixer was expressed by fourgrade rating (Excellent, Good, Fair and Bad).
TABLE 5__________________________________________________________________________ Block (A) polymeriza- tion conditions Block (B') polymeri- Potassium Polyme- zation conditions Tetra- dodecyl- rization Polymeriza- n- Butadiene/ hydro- benzene- tempera- Butadiene/ Tetrahydro- tion tem- BuLi*.sup.1 styrene furan sulfonate ture styrene furan perature (A')/(B') (g) (g) (g) (g) .degree.C.) (g) (g) (.degree.C.) (wt. Remarks__________________________________________________________________________Example 11 0.28 215/115 25 -- 50-92 170/0 1.25 50 2/1Example 12 0.26 " " -- 50-90 " 2.5 " "Example 13 0.27 " 7.5 -- 50 " 1.25 " "Example 14 0.29 " 25 -- 50-91 161/9 " " "Example 15 0.27 " " -- 30-72 170/0 " " "Example 16 0.25 230/100 " -- 20-60 " " " "Example 17 0.25 160/90 15 -- 50-80 250/0 " " 1/1Example 18 0.27 260/140 40 -- 50-105 100/0 " " 1/1Comparative 0.31 230/100 -- 0.18 60 170/0 15 60 2/1Example 11Comparative 0.29 " Dig- -- 50 " 1.25 50 "Example 12 lyme*.sup.2 1.95Comparative 0.28 130/200 25 -- 50 " " " "Example 13Comparative 0.26 215/115 " -- 50-90 " 25 30 "Example 14Comparative 0.27 " " -- 50-91 136/34 1.25 50 "Example 15Comparative 0.27 380/120 7.5 -- 50 -- -- -- -- UniformExample 16 polymerComparative 0.26 325/175 10 -- 50 -- -- -- -- UniformExample 17 polymerComparative 0.25 500/0 2.5 -- 70 -- -- -- -- UniformExample 18 polymer__________________________________________________________________________ Note: Solvent: cyclohexane/nhexane (90/10 by weight), 2,000 g *.sup.1 : nBuLi = normal butyllithium. *.sup.2 : Diglyme = diethylene glycol dimethyl ether.
TABLE 6__________________________________________________________________________ Block (A') Block (B') Vinyl Presence or Vinyl Presence or content absence of content absence of Whole polymer in buta- vinyl in buta- vinyl Vinyl con- Bound (A')/ diene Bound content diene Bound content tent in sty- (B') portion styrene distribution portion styrene distribution butadiene rene (wt. (%) (%) breadth (%) (%) breadth portion (%) (%) ML.sup.100.degree. C. .sub.+4 ratio) Remarks__________________________________________________________________________Example11 49 35 Present 29 0 Absent 40 23 51 2/112 50 34 " 40 0 " 45 22 50 "13 51 36 Absent 30 0 " 41 23 48 "14 50 35 Present 29 5 " 41 23 47 "15 58 35 " 31 0 " 46 23 52 "16 65 30 " 28 0 " 50 20 53 "17 44 35 " 29 0 " 35 18 51 1/118 50 35 " 30 0 " 44 28 53 4/1Comparativeexample 11 15 30 Absent 60 0 " 34 20 50 2/112 80 30 " 30 0 " 59 20 48 "13 50 60 " 30 0 " 39 40 47 "14 50 35 Present 70 0 " 57 23 51 "15 50 34 " 30 20 " 42 30 50 "16 41 22 Absent -- -- " 40 22 49 -- Uniform polymer17 51 35 " -- -- " 51 35 51 -- Uniform polymer18 30 0 " -- -- " 30 0 48 -- Uniform polymer__________________________________________________________________________
TABLE 7__________________________________________________________________________ (2) (3) (6) (1) Dunlop Heat-build (5) Roll reten- 300% Tensile Elonga- impact up tempera- (4) Lambourn tion of modulus strength tion Hardness resilience ture Wet skid wear compounded (kg .multidot. f/cm.sup.2) (kg .multidot. f/cm.sup.2) (%) (JIS-A) at 70.degree. C. (%) .DELTA.T. (.degree.C.) (Index) (Index) rubber__________________________________________________________________________Example11 155 223 430 68 71 18.5 115 110 Good12 157 220 400 68 69 19.0 115 115 "13 150 216 420 67 70 19.0 110 105 "14 147 227 410 69 70 19.5 120 120 "15 148 219 410 69 69 19.5 125 110 "16 152 220 420 68 69 19.5 120 110 "17 149 223 420 69 72 18.0 110 110 "18 155 231 430 69 67 20.5 125 125 "ComparativeExample11 147 217 400 69 68 20.5 105 105 "12 161 195 370 72 64 23 130 90 Fair13 149 210 380 72 62 25 140 95 Good14 160 215 390 70 66 22 125 100 "15 148 235 420 69 66 22 120 115 "16 151 223 410 68 68 20 100 100 Fair-BadComp. Ex. 17/ 145 210 390 67 67 21 100 95 Fair-BadComp. Ex. 18blend__________________________________________________________________________ Note: (1) Measured according to JISK-6301. (2) Measured according to B.S 903 Part 22 method. (3) Goodrich heat buildup, measured according to ASTM D623/58 (Method A). (4) Measured on the indoor wet asphalt road surface at 25.degree. C. by using a skid tester made by Stanley Inc., of Britain. The value of Comparative Example 6 was Expressed as 100 by way of a reference index. The greater the figure, the better. (5) Measured by Lambourn wear tester at a slip rate of 30% and at 25.degree. C. The value of Comparative Example 6 was expressed as 100 by way of a reference index. The greater the figure, the better. (6) Roll retention of the compound mixed by an internal mixer was expressed by fourgrade rating (Excellent, Good, Fair, and Bad).
TABLE 8__________________________________________________________________________ Block (C) polymerization conditions Block (A") polymerization conditions Polymerization Butadiene Tetrahydrofuran Polymerization n-BuLi*.sup.1 Butadiene Tetrahydrofuran temperature styrene DBS-K*.sup.3 temperature (g) (g) (g) (.degree.C.) (g) (g) (.degree.C.)__________________________________________________________________________Example19 0.33 125 1.5 40 188/62 2.5/0.1 4020 0.31 " " " 162/88 3.0/0.1 "21 0.30 " " " 175/75 5.0/0.1 "22 0.32 " " " " " "23 0.29 " " " " 5.0 "24 0.31 167 " " 117/50 6.0/0.1 "25 0.30 83 " " 234/100 " "ComparativeExample19 0.34 0 -- -- 212/38 --/0.2 "20 0.36 125 1.5 40 100/150 7.5/0.1 "21 0.29 " 1.5 40 175/75 5.0/0.1 4022 0.32 " 1.5 " 175/75 20/-- "23 0.31 415/85 -- -- -- 7.5/0.1 40-5024 0.28 500/0 1.5 40 -- 1.5 4025 0.32 350/150 -- -- -- 5/0.1 4026 0.31 450/50 -- -- -- --27 0.31 250 1.5 40 187/63 2.5/0.1 40__________________________________________________________________________ Block (B") polymerization conditions Butadiene/ Polymerization styrene Diglyme*.sup.2 temperature (C)/(A")/(B") (g) (g) (.degree.C.) (wt. ratio) Remarks__________________________________________________________________________ Example 19 113/12 1.4 40-60 1/3/1 20 " 1.3 " " 21 " 1.3 " " 22 " 3.3 " " 23 " 1.2 " " 24 150/17 1.3 " 1/1/1 25 75/8 1.3 50 1/4/1 Comparative Example 19 175/75 1.0 40-70 1/1((A")/(B")) 20 119/6 1.2 40-60 1/2/1 21 81/44 3.0 40-60 1/2/1 22 113/12 1.3 " " 23 -- -- -- -- 24 -- -- -- -- 25 -- -- -- -- 26 -- 0.7 50 -- 27 -- -- -- 1/1((C)/(A"))__________________________________________________________________________ Note: Solvent: cyclohexane/nhexane (90/10 by weight), 2,500 g. *.sup.1 n-BuLi = nbutyllithium. *.sup.2 Diglyme = diethylene glycol dimethyl ether. *.sup.3 Potassium dodecylbenzenesulfonate
TABLE 9__________________________________________________________________________ Block (C) Block (A") Block (B) Whole polymer Vinyl Vinyl Vinyl Vinyl content content content content in buta- in buta- in buta- in buta- diene Bound diene Bound diene Bound diene Bound portion styrene portion styrene portion styrene portion styrene (C)/(A")/(B") (%) (%) (%) (%) (%) (%) (%) (%) ML.sup.100.degree. C. .sub.1+4 (wt. ratio) Remarks__________________________________________________________________________Example19 30 0 31 25 77 10 43 15 51 1/2/120 31 0 30 36 78 11 44 20 50 "21 29 0 41 29 77 10 47 17 48 "22 30 0 40 30 85 10 49 18 52 "23 31 0 40 31 78 11 47 18 50 "24 30 0 40 30 79 10 49 13 51 1/1/125 29 0 39 31 77 11 44 22 52 1/4/1ComparativeExample19 -- -- 13 15 65 27 36 21 55 1/1((A")/(B"))20 30 0 40 60 77 5 49 31 51 1/2/121 32 0 40 31 78 35 45 24 49 1/2/122 29 0 60 30 77 10 55 17 50 "23 47 17 -- -- -- -- 47 17 58 -- Random SBR24 31 0 -- -- -- -- 31 0 49 -- "25 40 31 -- -- -- -- 40 31 52 -- "26 78 10 -- -- -- -- 78 10 51 -- "27 30 0 31 25 -- -- 30 17 50 1/2((C)/(A"))__________________________________________________________________________
TABLE 10__________________________________________________________________________ (1) (2) (3) (4) (5) (6) Roll 300% Tensile Elonga- Dunlop impact Heat-build up Wet Lambourn retention of modulus strength tion Hardness resilience temperature skid wear compounded -(kg .multidot. f/cm.sup.2) (kg .multidot. f/cm.sup.2) (%) (J IS-A) at 70.degree. C. (%) .DELTA.T (.degree.C.) (Inde x) (Index) rubber__________________________________________________________________________Example151 230 410 67 73 18 105 110 Good20 155 233 420 68 71 20 115 110 Excellent21 157 235 420 68 72 19 110 115 "22 158 229 400 69 71 20 115 110 "23 156 237 420 68 72 19 110 110 "24 148 225 420 69 73 18 105 110 Good25 153 240 410 67 71 20 110 120 ExcellentComparativeExample160 215 420 68 68 20.5 95 105 Good20 163 230 380 71 62 25 140 95 "21 160 220 390 71 63 24 140 95 "22 165 225 390 70 65 23 130 95 "23 145 215 410 67 68 20.5 100 100 Fair-BadBlend (7) 1 141 205 400 67 66 21.5 100 95 BadBlend (8) 2 156 205 410 68 69 20 90 100 Fair-BadBlend (9) 3 153 207 400 69 68 21 95 100 "__________________________________________________________________________ Note: (1) Measured according to JISK-6301. (2) Measured according to B.S 903 Part 22 method. (3) Goodrich heat buildup measured according to ASTM D623/58 (Method A). (4) Measured on the indoor wet asphalt road surface at 25.degree.C. by using a skid tester made by Stanley Inc., of Britain. The value of Comparative Example 24 was expressed as 100 by way of a reference index. The greater the figure, the better. (5) Measured by Lambourn wear tester at a slip rate of 30% and at 25.degree. C. The value of Comparative Example 7 was expressed as 100 by way of a reference index. The greater the figure, the better. (6) Roll retention of the compound mixed by an internal mixer was expressed by fourgrade rating (Excellent, Good, Fair and Bad). (7) Comp. Ex. 24, Comp. Ex. 25 and Comp. Ex. 26 were blended at a ratio o 1/2/1. (8) Comp. Ex. 19 and Comp. Ex. 24 were blended at a ratio of 2/1. (9) Comp. Ex. 26 and Comp. Ex. 27 were blended at a ratio of 1/2.

Number	Date	Country
55-178226	Dec 1980	JPX
55-186194	Dec 1980	JPX
55-186195	Dec 1980	JPX

Number	Name	Date
4089913	Miki	May 1978
4091051	Moczygemba	May 1978
4107236	Naylor	Aug 1978
4248982	Bi	Feb 1981

Styrene-butadiene block copolymer

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