JPS58162604A - Modificaton method of diene type polymeric rubber - Google Patents

Abstract

PURPOSE:To obtain a modified rubber having low rolling frictional resistance, high wet skid resistance and improved impact resilience, by reacting a diene type polymeric rubber containing an alkali metal with a specific aromatic ketonic compound. CONSTITUTION:A conjugated diene type polymeric rubber obtained by polymerizing or copolymerizing a conjugated diene monomer, e.g. 1,3-butadiene, is reacted with a catalyst based on an alkali metal, e.g. n-butyl lithium, and a polar compound such as an ethereal compound, e.g. dimethyl ether, in a hydrocarbon solvent to add the alkali metal thereto. The resultant diene type polymeric rubber containing the alkali metal is then reacted with 0.05-10mol, based on 1mol catalyst based on the alkali metal, aromatic ketonic compound, e.g. 4,4'-bis (dimethylamino)benzophenone, of the formula (R1 and R2 are H, alkyl or alkenyl; m and n are integers 1-5).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for modifying diene polymer rubber.
o), yo) The details are related to the Geno-based polymer rubber O modification method in which Alka 79 metal company di-engine polymer rubber and Tatami O aromatic ketonized food are reacted.In recent years, automobiles have been at-cost OI! Rolled as rubber for automobile tire treads due to demands for K and running safety) Fist III
There is a strong desire for rubber materials with low resistance and high wet skid resistance. However, these two properties are very important, and various weights are needed to achieve a balance between these two properties. Improved methods of coalescence have been proposed. For example, a method of adjusting the vinyl content and styrene content of a styrene-butadiene copolymer to a specific ratio (If II 1987-6224)
8), Method for achieving a specific styrene chain distribution (%
-145209), a method of creating a specific vinyl bond chain distribution (411 1987-149413), etc.However, the improvement effect of these polymers is slight, and
Further significant improvements are desired.

On the other hand, it has been proposed that impact resilience can be improved by reacting a specific aromatic thioketone compound with an active polymer having an alkali metal or alkaline earth metal end to introduce a KBH group at the end of the polymer. (U.S. m% permission No. 475
5.269). It is known that repulsion and rolling are inversely related to frictional resistance, and the higher the repulsion, the lower the frictional resistance (rolling), so the scissors method can also improve rolling without impairing wet skid resistance. This can be said to be a method of reducing frictional resistance. However, the 8H group in the polymer is extremely unstable to air, oxygen, or heat, and has the disadvantage of being degraded by these actions, so it should not be exposed to contact with air or high temperatures of 1,000 or more. There are problems that must be avoided, however, Filo
Depending on the type of rubber polymer drying method, it may be heated to a temperature of 1,500° C. Therefore, in the above method of introducing a BH group at the polymer end, The decomposition of the 08H group is unavoidable in one coagulation and drying machine, and with the occurrence of irritation in these 1 pieces, a homopolymer 0JEII is obtained.
The effect of improving elasticity is reduced. Thus, it is difficult to industrially implement the US patent method of introducing 8H groups at the terminals of polymer chains.

It is unclear why a polymer with an LBH group introduced at the end of the polymer chain exhibits high impact resilience, but it seems to be related to the monoactivity of the 811 group. The polymer separation and drying method carried out in the over-current O11 cold polymerization method, which does not include the disadvantages encountered in the above-mentioned process, can be carried out as is. After examining various modification methods, we surprisingly found that the polymer obtained by reacting an alkali metal-containing diene polymer rubber with a certain aromatic ketone compound contains 8H groups, which are presumed to be OH groups. Despite having a low-activity atomic group, this atomic group can be placed at the end of a polymer chain, even if it is introduced at a location other than the end of a nine-polymer chain. The present invention was achieved by discovering that the introduction of 8H groups has the effect of increasing the impact resilience equivalent to that of a good case.The purpose of the present invention is to introduce a diene system that improves the impact resilience while impairing wet skid resistance. Polymer rubber modification method (R15 in the formula
R1 is hydrogen, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, or an amino group.

This is achieved by reacting with an aromatic ketone compound represented by an alkylamino group, a sialyl ζ) group, a substituent different from /%O, and n is an integer from 1 to 5, respectively. By carrying out the method of the present invention, the rebound elasticity is improved without impairing the wet skid resistance, and the round plate is made of diene polymer rubber with low frictional resistance.No special measures are taken in the separation and drying process. It is possible to produce stable K11lt without at least decomposing the introduced atomic group. The alkali metal-containing polymer used in the present invention is obtained by polymerizing a conjugated diene monomer etc. using an aluminum-based catalyst. Alternatively, a polymer rubber in which an alkali metal is bonded to the end of a diene polymer chain obtained by copolymerization and a conjugated gene in one polymer rubber regardless of the polymerization method (melt polymerization, emulsion polymerization, etc.) This is a polymer rubber in which an alkali metal is added to a diene polymer rubber having units.

Diene polymer rubbers include ts-butadiene, isoprene,
ts-pentageno, 2. Polymers or copolymers of conjugated diene monomers, including s-dimethyl-1s-butadiene, ts-benzene, etc., methylene, α-methylstyrene, vinyltoluene, vinylnaphthalene, divinyl, which can be copolymerized with conjugated genomonomers. Contains benzene, trivinylbenzene, divinylnaphthalene, etc.
Examples include, but are not limited to, copolymer rubbers with aromatic vinyl compounds, unsaturated nitriles such as acrylonitrile, esters of (meth)acrylic acid, and vinylpyridine. ^ Physical Kd polybutadiene rubber,
Examples include polyisoprene rubber, butadiene-isoprene copolymer rubber, and butadiene-styrene copolymer rubber.

A diene polymer rubber in which an alkali metal is bonded to the end of the diene polymer rubber can be obtained by polymerizing the diene polymer rubber described above with an alkali metal base catalyst. Metals bond together and are good.

Commonly used alkali metal-based catalysts, polymerization solvents, randomization-1 conjugated diene unit microstructure modifiers, etc. can be used, and no alkali metals are added to the diene-based polymer rubber. 911 Katojukai using Kokonoe Shatai Rubber Alkali Metal Base Catalyst, 2011・r catalyst, etc.
It is obtained by polymerizing or copolymerizing the above-mentioned large conjugated diene monomer and a monomer copolymerizable with it by a conventional heavy metal method such as emulsion polymerization using a Redottas catalyst or the like. Geno-based copolymer Go typical ^
Physically, polybutadiene rubber, polyisoprene rubber, butadiene-styrene copolymer rubber, butadiene-isoprene copolymer rubber, polypentadieno rubber, butadiene/-biperile/copolymer rubber, butadieno-propyline cross-copolymer rubber, etc. For example, the method shown in solid line is usually used to add an alkali metal to diene copolymer rubber. In a medium, a common alkali metal a catalyst and an etherification compound, an a(ne) compound.

Of & sexual sex party-〇Presence K 50'
The addition reaction is carried out at a temperature of ~100C for several tens of minutes to several tens of hours. Amount of alkali metal catalyst used Diene polymer rubber 1oo)! AI usually (L may be in the range of 1 to 10 mmol; if α is less than 1 mmol, no improvement in impact resilience will be obtained; if it exceeds 10 mmol, side reactions such as crosslinking and cutting of the polymer will occur, reducing the improvement in impact resilience. .

The polar compound is usually α1 to 10 mol, preferably α5 to 2 mol per mol of the alkali metal-based catalyst. Examples of alkali metal-based catalysts and solvents used in polymerization and addition reactions are as follows. The alkali metal-based catalysts are lithium and sodium.

Potassium, rubidium, cesium metals are complexes with these metal hydrocarbons or polar compounds. ◎ Preferably, it is a lithium compound having 2 to 20 true atoms. For example, etel lithium.

Chicken-Probiluritiu A, i-Probiluriticum.

Calculation-butyl lithium, IO-butyl lithium, t-otacyllithium 2%-decyl lithium, phenyl wattium, 2-naphthyl lithium, 2-butyl lithium, 4-7 enyl lithium? I) Mu, cyclohexylsillithium, 4-7 clobentyllithium, t4-dilithio-butene-disodium naphthalene, sodium biphenyl.

These include a potassium-tetrahydrofuran complex, a potassium shedtane complex, and a salt of α-methylstyrene tetramer.

Polymerization reactions and alkali metal addition reactions are carried out using hydrocarbon-based bulk solvents such as tetrahydrofuran, tetrahydrofuran, diquaternary
It is carried out with an agent that does not destroy alkali metal-based catalysts such as 1a and #i, aliphatic hydrocarbons, aromatic hydrocarbons, and hydrocarbons. , propane with prime numbers 2 to 12 in 41, S-
Butane, 1-butane, S-pentane, i-pentane, S
- Hemunan.

Shitakuhennan, flopene, 1-butene, i-butene,
trans-2-butene, cis-2-butene.

1-pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene and the like are preferred. (9) These solvents can also be used in combination of two or more. The aromatic ketone compounds used in the present invention include general alkyl groups, cycloalkyl groups, alkenyl groups, alkoxy groups, aξ, and no groups. , alcoholic Lua Z
1m and n is an integer of 1 to 5), in which R1 and R1 represent one or more amino groups, dialkylamino groups, and halogens; The group is preferably a dialkylamino group. For example, 44'-bis(dimethylamino)-benzophenone, 44'-bis(diethylamino)
-benzophenone, 44'-bis(dibutylaζ))-
Benzophenone, 44'-diaminobenzopheno 7,
44'-dimethoxybenzophenone, 2.2/,
Preferred compounds include s/-tetramethylbenzophenone/, 4-dimethylaminobenzophenone, and the like.

The amount of aromatic ketone compound to be used is determined by the amount of the alkali metal-based catalyst used to produce diene polymer rubber with an alkali metal bonded to the end, or the alkali metal base catalyst used to introduce an alkali metal into diene polymer rubber. Metal-based catalyst 1
α is 05 to 10 moles], preferably α2 to 2 moles. The reaction between an aromatic ketone and an alkali metal-terminated activated polymer is important because the reaction between the alkali metal-added nine-conjugated geno-based polymer occurs quickly, so the reaction temperature and reaction time can be selected over a wide range, but in general The reaction, which is carried out at room temperature to 100C and takes from one second to several hours, is carried out by bringing an alkali metal-containing diene polymer rubber into contact with an aromatic ketone compound. A method of superimposing the rubber, stopping the heavy metal reaction, and adding a predetermined amount of C aromatic triton compound in the wrinkled polymer rubber i+n, after completing the alkali metal addition reaction in the geno-based superstructure rubber Sm, A method of subsequently adding an aromatic ketone compound and reacting can be exemplified as a preferred embodiment, but the method is not limited to this method @After the reaction is completed,
For the modified diene polymer rubber, the coagulation method used in the production of rubber by ordinary solution polymerization, such as addition of a coagulant from the reaction solution or steam coagulation, is used, and the coagulation temperature is not limited at all. The nine crumbs separated from the reaction system can be dried using band dryers, extrusion type dryers, etc. that are used in the production of ordinary metal rubber, and there are no restrictions on the drying temperature. Since the /Series 1 composite rubber has significantly improved rebound resilience, it is very useful as a rubber material for treads of fuel-efficient tires.

Example 1 Cleaning a stainless steel polymerization reactor with an internal volume of 2J.

After drying and purging with dry nitrogen, t3-butadiene 1
50), benzene 820), diethylene glycol dimethyl ether (diglyme) [L5 mmol, S-butyl lithium (I&-hexane solution @) t3t mmol were added, and the contents were polymerized at 40C for 1 hour without stirring.9 . After the polymerization reaction was completed, the compounds shown in Table 2 were added,
After stirring for 5 minutes, the polymer solution in the polymerization reactor was
- A small amount of monobutyl-r-cresol (BUT) was taken out in a 15% by weight methanol solution, and the resulting polymer was coagulated and dried under reduced pressure at 40 tll for 24 hours to maintain a constant Mooney viscosity.

In addition, in the same manner as above, a benzene solution of the nonapolymer i11kKg was reacted with the compounds listed in Table 2, and 100 parts by weight of the solid polymer was added. ) Add 1 part by weight of BUT to the mold, and then steam coagulate at 105C for 1 hour while stirring.9. After draining, dry with 80G hot air for 3 hours.9.

Vinyl content can be determined by conventional infrared spectroscopy. t
*, "Comparative Example O Experiment Book No. 14: After the polymerization reaction was completed, methanol was added, stirred for 5 minutes, and then 44'-bis(dimethylamino)benzophenone was added and stirred for 5 minutes. Coagulate and dry in the same manner.90 The nine polymer thus obtained is kneaded with each compounding agent on a roll according to the compounding recipe in Table 1 to obtain a compounded rubber.
Press vulcanized under the conditions of 60C x 25 minutes.The rebound elasticity of the vulcanized rubber was measured at 55C using a Dunlop trypsometer. Wet skid resistance was measured using a Stanley portable skid tester at 25C using a road surface (Mu8TM1505-74, 3M Arashi external type B, black, Safety Walk).

The results are shown in Table 2.

Iris Table 1 Compounding recipe Polymer 100 parts by weight■
M1 Carbon black 50 #Aromatic process oil 5 #Zinc l
1k5# Stearic acid 2 #Sulfur 1 #N-
Oxydiethylene-2-benzo 2 #thiazolesulfene ad a12 From the results in Table 12, it is clear that the modified polymer of the present invention maintains rebound resilience without decreasing wet skid resistance even if the coagulation method and IE drying method are changed. It can be seen that this has been significantly improved.

In the case of modification with aromatic thioketone as a comparative example, the effects of the present invention and Oka et al. can be obtained by slow coagulation and drying of the thermal track; If this occurs, the effect of improving rebound resilience will be reduced.

Example 2 Diethylene glycol dimethyl ether (diglyme) V A polymerization reaction was carried out under the same conductivity as in Example 1, except that the amount was varied as shown in Table 5.

Next, 5 mmol of ``t',44'-bis(dimethylamino)benzophenone or 50 mmol of methanol was added, and after pressing for 5 minutes, the mixture was coagulated with methanol and dried under reduced pressure in the same manner as in Example 1, and evaluated.

The results are shown in Table III.

It is clear that polybutadiene with a different amount of vinyl has the same effect of improving impact resilience.

Example 3 A stainless steel polymerization reactor with an internal volume of 21 cm was washed, dried,
Polybutadiene (Mooney viscosity 40°, vinyl content 70
mol 1k) 65f and dehydrated tethered heptane 650I were charged, stirred and WI eluted. Next, 33 milliliters of buty-butyllithium (Ill-hexane [)] and 2-5 millimoles of tetramethylethylenediamine are added, and 7
The reaction was carried out at 0C for 1 hour. Next, 44'-bis(dimethylai))benzophenone was added, stirred for 5 minutes, and then l! Methanol coagulation and drying under reduced pressure were carried out in the same manner as in Example 1, and evaluation was made. The results are shown in Table 4.

Table 4 Example 4 A stainless steel polymerization reactor with an internal volume of 2j was washed and dried,
After purging with dry nitrogen, 13-butadiene 112.5
#, styrene 57.51, tetrahydrofuran 0.7
5F, &-butyllithium (1-hexane i11[)2
．． 0 mmol was added, and polymerization was carried out at 45 U for 2 hours without stirring the contents. After the completion of the polymerization reaction, 44′-
Fifty millimoles of bis(dimethylamino)benzophenone was added, stirred for 5 minutes, and steam coagulated and hot air dried in the same manner as in Example 1.

After the completion of the polymerization reaction, 4,41-bis(dimethylamino)
A comparative sample was prepared in exactly the same manner except that 50 mmol of methanol was added instead of benzophenone.

The above two types of polymers were blended into Example 1 and rNJ*.

Vulcanized and evaluated. The results are shown in Table 5.

Example 5 The reaction was carried out in exactly the same manner as in Example 3, except that polybutadiene (Mooney viscosity [42.0, cis-14 content: 98 mol) was used. A vulcanizate was obtained and evaluated. The results are shown in Table 6.

Table 6 Procedures Amendment Book Commissioner of the Patent Office 1, Indication of Case Patent Application Sho 1f;'l -th3
'/71-/ No. 2, Title of the invention 3, Person who makes liquid stoppage 4, Number of inventions increased by liquid stoppage 5, Target of liquid stoppage (2)';'t; Page 12 T force) Uhi 6 Village 1 I Honjo J 3 'yr-7, g and T.

(2) Sai/IF page T power) Lao'J de 814 people with the desk and ltI Feng Yi shadow.

(Su No. 20 Ryoju to Take 1 Sren 37. Fushiyo no Tsurugi 8 Ben Jin>g20g, aE
H entrance 16°

Claims (1)

[Claims] Alkyl group, cycloalkyl group, alkenyl group. Alkoxy group, amino group, alkylamino group. A method for modifying a diene polymer rubber, which comprises reacting a substituent selected from a dialkylamino group and a halogen with an aromatic ketone compound represented by the following formula: and n represents an integer from 1 to 5. 0 2. Diene-based heavy rubber O described in Patent Claim 011111, item 1, which is reacted with an aromatic ketone compound represented by (same as alkali) obtained using an alkali metal-based catalyst.
Modification method. (In the formula, R1s “*s” and 11 companies are the same as above)
Patent for reacting with an aromatic ketone compound represented by - Kyo0
111@I Method for modifying O-die/based polymer rubber described in item 1.