JPH0715027B2 - Improved rubbery polymer composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a rubber-like polymer composition which gives a vulcanized rubber having improved tensile strength, impact resilience, and abrasion resistance. More specifically, the present invention relates to an improved rubber-like polymer composition containing a rubber-like polymer obtained by reacting carbodiimides with a polymerized living polymer as a rubber component and adding an amino compound. Further, the composition is used by adding a compounding agent and then forming a vulcanized rubber.

[Problems to be Solved by Prior Art and Invention]

In recent years, due to the soaring price of crude oil, energy conservation has been advocated in various fields of industry, and many attempts have been made to reduce gasoline consumption in automobiles as well, improvements in engines, weight reduction of car bodies and tires, Air resistance of vehicle bodies and rolling resistance of tires have been reduced.

Among the energy-saving efforts associated with these cars,
Various attempts have been made to reduce rolling resistance of automobile tires, and various methods of introducing functional groups into the ends of living polymers have been proposed as methods of improving raw material rubber. For example, there is a method in which a living polymer is produced using a bifunctional anion initiator, and then organic sulfenyl chloride is allowed to act to introduce active groups into both ends of the molecule (Japanese Patent Publication No. 44-855).

However, in this method, there is a problem in industrial use that a polymer having a high molecular weight and living ends at both ends is difficult to obtain, and organic sulfenyl chloride is difficult to handle, and the obtained polymer also has tensile strength and modulus. It was inadequate. There is also a method of introducing an amino group at the terminal (Japanese Patent Laid-Open Nos. 59-38209 and 58-1626).
04, JP-A-60-137913, JP-A-60-137914) In addition to the drawback that the Mooney viscosity of the compound significantly increases and the workability is impaired, impact resilience, low heat buildup, abrasion resistance, wet skid resistance, etc. Was insufficiently improved.

The present inventor has also made a vulcanized rubber containing a functional group-containing rubber-like polybutadiene-based polymer as a rubber component, which is obtained by reacting carbodiimides at the ends of the polymer, with a compound of the same rubber-like polymer. It was found that the wet skid resistance did not change, the high-temperature impact resilience was remarkably improved, and the tensile strength was also improved as compared with the case where no reaction was performed (Japanese Patent Application No. 61-2279).

However, it has been found that this method has the following problems. That is, the functional group-containing rubbery polybutadiene-based polymer obtained by reacting a carbodiimide with a living polymer has a remarkable increase in Mooney viscosity when left to stand at room temperature for a long time, and a compounding agent using the polymer is used. The Mooney viscosity of the added compound also remarkably rises, making it difficult to process, and in addition, important performances such as impact resilience of the vulcanized rubber at high temperatures are deteriorated. Therefore,
There is a demand for an improvement in which the original Mooney viscosity of the unsaturated rubber-like polymer is maintained for a long period of time, the processability is not lowered, and important properties such as high-temperature impact resilience are maintained.

[Means and Actions for Solving Problems]

The inventors of the present invention have conducted extensive studies to solve the above-mentioned drawbacks, and at least 30% by weight of a functional group-containing rubbery polybutadiene polymer obtained by reacting a carbodiimide with a living polymer is contained in a rubber component, and an amino compound The functional group 1
It has been found that not only the above-mentioned drawbacks are ameliorated but also abrasion resistance is improved by providing a rubber-like polymer composition characterized by containing 0.1 to 40 times mol of amino groups per mol. Came to complete.

That is, the present invention is a rubber-like polybutadiene polymer polymerized in a hydrocarbon solvent using an organolithium catalyst, a living polymer having a vinyl bond in the butadiene portion of 10 to 80% is reacted with carbodiimides. At least 30 parts of the polymer modified by polymer end modification in the rubber component
%, And an amino compound is contained in an amount of 0.1 to 40 moles per amino group added to the rubber-like polymer as an amino group.

Hereinafter, the present invention will be described in detail.

The organolithium catalyst used in the present invention is a hydrocarbon having at least one or more lithium atoms bonded thereto, such as ethyllithium, propyllithium and n-.
There are butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium, propenyllithium, hexyllithium, etc., and particularly preferable are n-butyllithium and sec-butyllithium. This organolithium catalyst can be used not only as one kind but also as a mixture of two or more kinds. The amount of the organolithium catalyst used depends on the Mooney viscosity of the polymer produced, but is usually 0.3 to 3 mmol, preferably 0.5 to 1.5 mmol, per 100 g of the monomer.

As the hydrocarbon solvent used in the present invention, n-butane, n-pentane, iso-pentane, n-hexane,
It is n-heptane, iso-octane, cyclohexane, methylcyclopentane, benzene, toluene and the like, and particularly preferable solvents are n-hexane, n-heptane and cyclohexane. This hydrocarbon solvent may be used alone or in combination of two or more kinds, and it is usually used in an amount of 1 to 20 parts by weight per 1 part by weight of the monomer.

The rubber-like polybutadiene-based polymer of the present invention is polybutadiene rubber or styrene-butadiene copolymer rubber, and the bound styrene content of the styrene-butadiene copolymer rubber is 45% by weight or less. If it exceeds 45% by weight, heat generation increases and impact resilience also decreases, resulting in poor performance. on the other hand,
When the amount of bound styrene is low, the tensile strength decreases, and it is preferably 5% by weight or more. From the viewpoint of the balance among wet skid, tensile strength, impact resilience and heat generation, a particularly preferred range is 10 to 35% by weight.

The vinyl bond in the butadiene portion of the rubbery polybutadiene-based polymer of the present invention is 10 to 80%, preferably 15 to 50%. Small vinyl bonds have low wet skid resistance, whereas high vinyl bonds reduce wear resistance. Particularly preferably, it is in the range of 20 to 45%.

The carbodiimides used in the present invention are disubstituted carbodiimide compounds having a general formula —N═C═N- bond or disubstituted carbamide imides having a general formula N—C≡N bond, such as dialkylcarbodiimide and alkylarylcarbodiimide. , Diarylcarbodiimide,
Dialkyl cyanamide, alkylaryl cyanamide,
It is a compound containing diaryl cyanamide and is used as one kind or as a mixture of two or more kinds.

For example, dimethylcarbodiimide, diethylcarbodiimide, dipropylcarbodiimide, dibutylcarbodiimide, dihexylcarbodiimide, dicyclohexylcarbodiimide, dibenzylcarbodiimide, diphenylcarbodiimide, methylpropylcarbodiimide, butylcyclohexylcarbodiimide, ethylbenzylcarbodiimide, propylphenylcarbodiimide, phenylbenzylcarbodiimide, dimethylcyanamide. , Diethylcyanamide, dipropylcyanamide, dibutylcyanamide, dihexylcyanamide, dicyclohexylcyanamide, dibenzylcyanamide, diphenylcyanamide,
Examples include methylpropyl cyanamide, butylcyclohexyl cyanamide, ethylbenzyl cyanamide, propylphenyl cyanamide, and phenylbenzyl cyanamide.
Of these, particularly preferred are dicyclohexylcarbodiimide, diphenylcarbodiimide and diphenylcyanamide.

These compounds are based on 1 mol of the living polymer,
It is fed at a rate of 0.2 to 5 mol, preferably 0.3 to 3
It is a molar ratio. The ratio is more preferably 0.5 to 2 mol. In the reaction of living lithium with carbodiimides in the present invention, there is almost no increase in Mooney viscosity after the reaction, and the processability does not decrease. When the amount of feed is small, the effect of improving the physical properties is small. On the other hand, when the amount of feed is large, it is unreacted and the vulcanization time is shortened and the tensile strength is lowered. The reaction between the living polymer and these compounds is extremely rapid, and the reaction temperature is generally room temperature to 120 ° C. and the reaction time is several seconds to several hours.

Further, more preferably, the living polymer is added in an amount of 0.1 to 0.7 equivalents, more preferably 0.1 to 0.7 equivalent, per mol of the living active sites.
A carbodiimide is introduced into all the remaining living active sites by branching it using 0.5 equivalent of a trifunctional or higher functional coupling agent. In that case, the cold flow of the rubber-like polymer is prevented, the processability is excellent, the performance of the vulcanizate is also extremely excellent, and a well-balanced rubber-like polymer is obtained. In this case, when the amount of the functional groups of the trifunctional or higher-functional coupling agent used is less than 0.1 equivalent to 1 equivalent of the living active site, the cold flow preventing effect is small and the processability is deteriorated. Is inferior in the performance of the vulcanizate in which the amount of carbodiimides introduced is less than 0.3 mol.

Examples of trifunctional or higher-functional coupling agents include trichloromethylsilane, tetrachlorosilane, hexachlorodisilane, tetrachlorotin, trichlorobutyltin, tetraiodotin, polyhalogen compounds such as carbon tetrachloride, diethyl adipate, and diphenyl carbonate. Compounds having two or more diglycidylamino groups in the molecule such as diesters, tetraglycidyl-1,3-bisaminomethylcyclohexane, polyepoxy compounds such as epoxidized liquid polybutadiene, polyisocyanates, polyimines, polyaldehydes , Polyketone, polyanhydride, etc.
No. 36957, and particularly preferably polyhalogenated tin such as tetrachlorotin.

The Mooney viscosity ML (1 + 4,100 ° C.) of the polybutadiene or styrene-butadiene copolymer rubber used in the present invention, which is obtained by reacting carbodiimides and introducing terminal modifying groups.
Is 20 to 150, preferably 25 to 130. If the Mooney viscosity is lower than this, the vulcanized rubber will be inferior in tensile strength, abrasion resistance, impact resilience, and low heat buildup, and excessive torque will be applied during kneading with a roll or Banbury, or carbon dispersion will be poor. As a result, the performance of vulcanized rubber is inferior.

The polymerization reaction, the reaction with carbodiimides, and the coupling reaction may be carried out batchwise or continuously without any limitation.

The amino compound used in the present invention has the general formula Rn-
NHm (wherein R is an alkyl, cycloalkyl, alkylcycloalkyl, aryl, alkylaryl, arylalkyl group having 1 to 20 carbon atoms, n is 1 to 1)
An integer of 3, m is 0, 1, 2 and satisfies n + m = 3), an organic amino compound of the general formula Rp-NHq-R'-
(NH-R ') u-NHr-Rs (wherein R is an alkyl, cycloalkyl, alkylcycloalkyl, aryl, alkylaryl, arylalkyl group having 1 to 20 carbon atoms, and R'is 2 to 20). Is an alkylene, cycloalkylene, alkylcycloalkylene, cycloalkylalkylene, arylene, alkylarylene, arylalkylene, arylcycloalkylene group having a carbon atom of, p is 0,1,2, q is 0,1,2 p + q = 2 is satisfied, r is 0,1,2, s is 0,1,2, and r + s
= 2 and u is 0 or an integer of 1 to 9), a polyvalent amine or polyamine compound of the general formula (Wherein R is an alkyl, cycloalkyl, alkylcycloalkyl, aryl, alkylaryl, arylalkyl group having 1 to 20 carbon atoms, and R'is 2 to 20.
Alkylene having a carbon atom of, cycloalkylene, alkylcycloalkylene, cycloalkylalkylene,
It is an arylalkylene or arylcycloalkylene group, and M is an O atom or an S atom. ) And other imine compounds, and nitrogen-containing heterocyclic compounds.

Examples of specific compounds include ethylamine, propylamine, butylamine, hexylamine, decylamine,
Octadecylamine, cyclohexylamine, aniline, naphthylamine, toluidine, benzylamine, diethylamine, dibutylamine, dihexylamine, didecylamine, ethylhexylamine, methylpentylamine, dicyclohexylamine, ethylcyclohexylamine, diphenylamine, methylaniline, phenylnaphthylamine, butylbenzylamine , N-methyltoluidine, triethylamine, tributylamine, trihexylamine, tridecylamine, methylethylbutylamine, dimethyloctadecylamine, dimethylcyclohexylamine, N, N-dimethylaniline, methylethylbenzylamine, N, N-dimethyltoluidine, Ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylene Diamine, 1,12-diaminododecane, 1,4-diaminocyclohexane, m-phenylenediamine, p-phenylenediamine, 3,6-dimethyl-1,4-diaminobenzene, p-aminomethylbenzylamine, N-butylethylenediamine , N-methylpropylenediamine, N-methyl-p-phenylenediamine, N, N'-diethylethylenediamine, N-methyl-
N'-butylethylenediamine, N, N'-dimethylhexamethylenediamine, N, N'-dimethyl-p-phenylenediamine, N, N'-dioctyl-p-phenylenediamine, N-ethyl-N'-cyclohexyl-p -Phenylenediamine, N-propyl-N'-phenyl-p-phenylenediamine, N, N-diethylethylenediamine, N, N
-Dibutylethylenediamine, N, N-dimethylhexamethylenediamine, N, N-dimethyl-p-phenylenediamine, 4-N, N-dimethylaminomethylbenzylamine, ethylenediamine, N, N, N'-tributylhexamethylenediamine, N, N, N ', N'-tetrabutylethylenediamine, N, N, N', N'-tetramethylhexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, bis (3-amino Ethyl) amine, 1,3-bis (3′-aminopropylamino) propane, ethyleneimine, trimethyleneimine, 2-ethylethyleneimine, cyclohexeneimine, pyrrolidine, piperidine,
Examples include nonamethyleneimine, piperazine, cyclodi (trimethylene) diimine, N-methylethyleneimine, morpholine, thiomorpholine, pyridine, pyrrole, pyrimidine, triazine, indole, quinoline and purine.

Of these, compounds having a primary or secondary amino group are preferred, and among these, tetraethylenepentamine, diethylenetriamine, N, N'-dibutylethylenediamine, N, N'-dioctyl-p-phenylenediamine. Particularly preferred are polyvalent amines or polyamine compounds such as, imine compounds such as morpholine and thiomorpholine, and aromatic amine compounds such as toluidine and N-methylaniline.

As a method of adding an amino compound in the present invention,
A method of batchwise or continuously adding to a solution of a functional group-containing rubbery polymer obtained by reacting a living polymer with carbodiimides, and a solvent from a solution of the functional group-containing rubbery polymer by a usual finishing method. After removal, it is possible to use any method such as a method of adding by mechanical kneading. In particular, a method of reacting a living rubber-like polymer and carbodiimides in a solution, subsequently adding an amino compound to the reaction solution, further adding an antioxidant such as BHT, and then removing the solvent is a method. preferable. In that case, as compared with other methods, the effect of preventing the Mooney viscosity from increasing in the obtained rubber-like polymer composition is particularly remarkable, and in other post-addition methods, the Mooney viscosity increases during the removal of the solvent. In some cases, it may be recognized.

In the present invention, the amount of the organic amino compound added is 0.1 per mol of the functional group added to the rubber-like polymer.
To 40 times mol, preferably 0.5 to 20 times mol, more preferably 1.0 to 15 times mol. If it is less than 0.1 times the molar amount, there is no effect of preventing the Mooney viscosity of the rubber-like polymer composition from increasing.
If the amount exceeds 40 times by mole, the amino compound may cause bleeding, and the vulcanization speed may be increased when the compounding agent is added and vulcanized to cause a problem.

The rubbery polymer composition of the present invention can be made into an oil-extended rubber by the Mooney viscosity of the rubber component. At that time, aromatic oil, naphthene oil, paraffin oil, etc. can be used as the process oil depending on the purpose, and usually 5 to 50 parts by weight are used per 100 parts by weight of the rubber component, and Mooney as a rubber-like polymer composition is used. Viscosity (ML _{1 + 4} , 100 ℃) is preferably 20
It is in the range of ~ 80. If the Mooney viscosity is less than 20, cold flow tends to occur, while if it exceeds 80, torque is applied during compounding and processing is difficult.

The process oil used has a total acid number [mg KOH / g]
It is preferably 0.4 or less, particularly preferably 0.1 or less. If a process oil having a high total acid value is used, it is not possible to sufficiently prevent the Mooney viscosity of the rubbery polymer composition of the present invention from increasing.

The rubbery polymer composition of the present invention is used alone or in combination with another rubber as a rubber component. When used in combination with other rubber, the other rubber includes emulsion-polymerized styrene-butadiene copolymer rubber, solution-polymerized polybutadiene rubber, styrene-butadiene copolymer rubber, polyisoprene rubber, butadiene-isoprene copolymer rubber, Natural rubber etc. are included, and one or two of these are included depending on the purpose.
More than one species are selectively used. In that case, the rubber-like polymer composition of the present invention must be contained in the rubber component at least 30% by weight. If it is less than 30% by weight, the effect of improving impact resilience cannot be obtained.

The rubbery polymer composition of the present invention is used by mixing it with other rubbers, if necessary, using a mixing machine such as a roll or Banbury, and various mixing agents. The various compounding agents used are not particularly limited as long as they can be selected from those commonly used in the rubber industry, and those suitable for the purpose of use of the rubber composition can be selected.

Normally, sulfur, stearic acid, zinc white, various vulcanization accelerators (thiazole-based, thiuram-based, sulfenamide-based, etc.) or organic peroxides are used as the vulcanization type, and HAF, ISAF, etc. are used as the reinforcing agents. Various grades of carbon black,
Calcium carbonate, talc, etc. are used as a filler such as silica, and process oils, processing aids, vulcanization retarders, antiaging agents, etc. are used as other compounding agents. The type and amount of these compounding agents are selected according to the purpose of use of the rubber composition, and are not particularly limited in the present invention.

The functional group-containing polymer composition containing the amino compound according to the present invention is effectively prevented from increasing the Mooney viscosity after long-term storage, and the compound Mooney viscosity after compounding is increased as compared with the system containing no amino compound. Is suppressed and workability is improved. Further, the performance of the vulcanizate in the present invention is also excellent in impact resilience, low exothermicity, tensile strength and abrasion resistance.

〔Example〕

The present invention will be specifically described below with reference to some examples, but the present invention is not limited to these examples.

In the following Examples and Comparative Examples, "parts" means "parts by weight" unless otherwise specified. Further, "phm" means "parts by weight per 100 parts of monomer".

Examples 1 and 2 and Comparative Example 1 Cyclohexane 4598 was placed in a reactor equipped with a stirrer and having an internal volume of 10.
g, 780 g of purified 1,3-butadiene, 162 g of purified styrene and 38 g of tetrahydrofuran, were maintained at a temperature of 40 ° C., 0.52 g of n-butyllithium was injected to initiate polymerization, and thereafter adiabatically. The polymerization temperature was raised. Inner temperature is 75
From the point when the temperature reached ° C, a mixture of 138 g of butadiene and 322 g of cyclohexane was added using a metering pump over 15 minutes. The maximum temperature in the reaction was 100 ° C.
1 minute after the addition was completed, 0.132 g of tin tetrachloride (0.25 to Li was added)
(Equivalent amount), and after 1 minute, 1.26 g of dicyclohexylcarbodiimide (0.75 mol relative to Li) was added and reacted for 20 minutes. Then, the amino compound shown in Table 1 was added and stirring was continued for 10 minutes. Then, as an antioxidant in the polymer solution
After adding 8 g of BHT, the solvent was removed by heating to obtain a polymer composition. The polymer obtained has a Mooney viscosity [ML _{1 + 4} , 100 ° C] of 5
0, styrene content 15% by weight, microstructure of butadiene part was 1,4 trans bond 34%, cis 1,4 bond 23%, 1,2 vinyl bond 43%. The Mooney viscosity [ML _{1 + 4} , 100 ° C.] of the polymer immediately before the addition of tin tetrachloride was 30 (Examples 1 and 2). Further, Comparative Example 1 was prepared by the same method except that no amino compound was added after polymerization, addition of tin tetrachloride and terminal modification with dicyclohexylcarbodiimide.

Examples 3, 4, 5 and Comparative Examples 2, 3 In a reactor equipped with a stirrer with an internal capacity of 10, cyclohexane 4598
g, 780 g of purified 1,3-butadiene, 162 g of purified styrene and 38 g of tetrahydrofuran, were maintained at a temperature of 40 ° C., 0.52 g of n-butyllithium was injected to initiate polymerization, and thereafter adiabatically. The polymerization temperature was raised. Inner temperature is 75
From the point when the temperature reached ° C, a mixture of 138 g of butadiene and 322 g of cyclohexane was added using a metering pump over 15 minutes. The maximum temperature in the reaction was 100 ° C.
One minute after the end of the addition, 0.132 g of tin tetrachloride (0.25 for Li
(Equivalent amount) was added, and 1 minute later, 1.19 g of diphenylcarbodiimide (0.75 mol with respect to Li) was added and reacted for 20 minutes. Then, the amino compound shown in Table 1 was added and stirring was continued for 10 minutes. Then add 8 g of BHT as an antioxidant to the polymer solution.
After adding, the solvent was removed by heating to obtain a polymer composition. The polymer obtained has a Mooney viscosity [ML _{1 + 4} , 100 ° C] of 51, a styrene content of 15% by weight, and a microstructure of the butadiene portion of 1,
4 trans bond 34%, cis 1,4 bond 23%, 1,2 vinyl bond 4
It was 3%. The Mooney viscosity [ML _{1 + 4} , 100 ° C.] of the polymer immediately before the addition of tin tetrachloride was 31 (Example 3)
And 4).

Further, Comparative Example 2 was prepared in the same manner, except that no amino compound was added after polymerization, addition of tin tetrachloride and terminal modification with diphenylcarbodiimide.

In the same manner, after polymerization, addition of tin tetrachloride and terminal modification with diphenylcarbodiimide, 8 g of antioxidant was added.
After adding BHT and removing the solvent by heating,
Example 5 was a polymer composition obtained by mixing the amino compounds shown in the table with a roll. In Comparative Example 3, the terminal modification and the addition of the amino compound were not performed.

Examples 6, 7, 8 and Comparative Examples 4, 5 Two stainless steel stirrers having an internal volume of 10 and jacketed reactors were connected in series, 1,3-butadiene as a monomer and n-hexane as a solvent. , N-butyllithium as catalyst at a ratio of 0.050 g per 100 g of monomer (phm), and tetramethylethylenediamine as vinylating agent at 0.25 ph
m, 1,2-butadiene was used as the allene compound in an amount of 0.03 mol per mol of the catalyst to carry out continuous polymerization. The internal temperature of the first unit was controlled so as to be 100 ° C., and the monomers and the like were supplied by a metering pump so that the average residence time was 45 minutes.

Further, the polymer solution was continuously introduced into the second group, and the carbodiimides (1 equivalent to Li) shown in Table 1 were continuously added to the living polymer in the second group, and the internal temperature became 100 ° C. Controlled. After continuously adding the amino compound shown in Table 1 at the outlet of the second unit and introducing it into the in-line mixer to add BHT as an antioxidant,
The solvent was removed with a drum dryer at 30 ° C. to obtain a polymer composition.

The microstructure of polybutadiene has a 1,4-trans bond 33
%, Cis-1,4 bond was 12%, and 1,2-vinyl bond was 65%.
Mooney viscosity of polymer composition immediately after production [ML _{1 +} 4,100
C] was 54 (Examples 6, 7, and 8).

Further, a polymer not added with an amino compound by the same method was set as Comparative Example 4, and a polymer not end-modified or added with an amino compound was set as Comparative Example 5. The styrene content and the microstructure of the butadiene portion of the polymer compositions of Examples 1 to 5 were determined by measuring the infrared absorption spectrum and calculating by the method of Hampton.

After Examples 1 to 8 and a Mooney viscosity immediately after preparation of the polymer composition of Comparative Example _{1~5 [ML 1 + 4, 100} ℃] and 2 weeks, 1 month, the Mooney viscosity after 3 months [ML _{1 + 4} , 100 ° C.] was measured. The results are shown in Table 1.

Also, using the polymer composition after the lapse of 3 months and using the Banbury mixer for testing having the compounding recipe shown in Table 2 and the internal content of 1.7, the standard compounding procedure of ASTM-D-3403-75 is used. Compounds were obtained by B, vulcanized, and measured for each physical property. The measurement was performed by the method shown below.

(1) Hardness and tensile strength: In accordance with JIS-K-6301.

(2) Impact resilience: Lupke method according to JIS-K-6301, after preheating the sample in an oven at 70 ° C for 1 hour, then quickly taking it out and measuring.

(3) Goodrich heat generation Using a Goodrich flexometer, a test was conducted under the conditions of a load of 48 lbs, a displacement of 0.225 inch, a start of 50 ° C and a rotation speed of 1800 rpm, and the difference in temperature rise after 20 minutes was expressed.

(4) Wet skid resistance Stanley London portable skid tester was used, and the safety walk (made by 3M) was used as the road surface, and the resistance was measured according to the method of ASTM-E-808-74.
It is indicated by an index with the measured value of Comparative Example 3 or 4 as 100.

(5) Abrasion resistance The measured value of Comparative Example 3 or 4 was 10 using a Pico abrasion tester.
The index was set to 0.

Table 2 Rubber-like polymer composition 100 parts by weight Aromatic oil ^{* 1} 10 parts by weight Carbon black N339 50 parts by weight Stearic acid 2 parts by weight Zinc white 3.5 parts by weight Accelerator CZ ^{* 2} 1.3 parts by weight Sulfur 2 parts by weight * 1 Kyodo Petroleum X-140 * 2 N-cyclohexyl-2-benzothiazylsulfenamide Vulcanization condition: 160 ° C. × 20 minutes The carbon gel of the compound polymer after blending sulfur in Example 1 and Comparative Example 1 was measured. Results, Comparative Example 1
Is 25% and Example 1 is 35%, and the present invention using the amino compound has more carbon gel than the comparative example not using this. The measurement of carbon gel is based on the method described below.

Ft: Weight ratio of benzene insoluble compounding agent Fr: Weight ratio of rubber component Wo: Weight of compound polymer before test (approx. 0.1g divided into 10) WG: Benzene immersion 24 hours after removal 2 at 70 ° C vacuum dryer
Weight after drying for 4 hours Harris basket used: 100 mesh brass Amount of benzene used 100 cc The results of the measurement of the physical properties of the compounds of Examples 1 to 8 and Comparative Examples 1 to 3 were performed.
The results are shown in Table 4 and Table 4.

As described above, the examples of the present invention are effectively prevented from increasing the Mooney viscosity after long-term storage as compared with Comparative Examples in which an amino compound is not added, and also suppress the increase in compound Mooney viscosity after blending. Processability is improved.
Further, the performance of vulcanized physical properties, impact resilience in the examples of the present invention,
It is clear that heat generation, tensile strength, and abrasion resistance are all excellent.

〔The invention's effect〕

The rubber-like polymer composition according to the present invention is an improvement in the drawbacks of conventionally known functional group-containing rubber-like polymers,
It shows outstanding performance and processability that have never been seen before. Therefore,
It is suitable for use in the rubber industry including tires, and its significance is great.

Claims (1)

[Claims] 1. A rubbery polybutadiene-based polymer polymerized in a hydrocarbon solvent using an organolithium catalyst,
At least 30% of a polymer obtained by reacting a carbodiimide with a living polymer having a vinyl bond in the butadiene portion of 10 to 80% is modified in the rubber component, and an amino compound is added to the rubber-like polymer. Functional group 1
A rubber-like polymer composition containing 0.1 to 40 moles of amino groups per mole.