JPS5945338A - Butadiene polymer rubber composition - Google Patents

Abstract

PURPOSE:A rubber composition useful as tire tread, rubber vibration insulator, having low heat generating properties, improved failure characteristics, rolling resistance characteristics, containing a long-chain branched structure linked by a butadienyl-tin bond and a coupling agent except tin in the molecular chain. CONSTITUTION:A rubber composition comprising a butadiene polymer containing >=20wt%, preferably 30-80wt% branched butadiene polymer, wherein the butadiene polymer has 0-40wt% (especially 3-30wt%) bonded aromatic vinyl compound 30-80wt%, preferably 40-70wt% of the branched polymer is bonded by a tin-butadienyl bond, and the remaining 20-70wt%, preferably 30-60wt% of it is linked by a coupling agent containing no tin. A straight-chain butadiene polymer having the desired molecular weight is obtained in a hydrocarbon solvent using an organolithium compound as an initiator, and a tin coupling agent and the coupling agent containing no tin are added to it, to give the above-mentioned butadiene polymer.

Description

[Detailed description of the invention]

The present invention relates to a rubber composition containing a novel butadiene-based polymer containing a long chain branched structure in the molecular chain, which is bonded by a butadiene-loose bond and a coupling agent other than tin. The present invention provides an excellent rubber composition suitable for rubber applications, particularly for tire treads and anti-vibration rubber applications. Among butadiene alone and copolymers of butadiene and styrene, those containing a metal-carbon bond or a conventional coupling agent in the molecular chain are known. The main focus of these first studies was on improving the low-temperature flow of the produced polymer. Generally, a polymer with a branched structure of Keyaki has a shorter chain length than a linear polymer with the same molecular weight. For example, if we consider a trifunctional branched polymer as a branched polymer, compared to a linear polymer with the same number of molecules, the length of the fully extended chain is 2/3. There are also a large number of molecular ends that do not react, and therefore heat generation (hysteresis loss) also increases. However, polymers with a monobranched structure having a sugetagenyl compound have a 1'-(exotherm of 7) (exotherm of 7) (which is clearly small). Recently, in order to improve the fuel efficiency of automobiles, the 1V friction resistance has been reduced, the wet skid resistance has been increased, and the fracture properties have been improved. A highly vinyl-bonded nophtadiene system-vehicle combination has been proposed (for example, Japanese Patent Application Laid-Open No. 57-55912). In 111 minutes after the unexploded town (name of the unexploded town), the butanhoun spinning wheel frame structure was further investigated, and as a result, the result was +j1. :
By introducing a branched structure using a coupling agent other than a tin compound into the polymer molecule of the publication [a], a tl-i composite rubber with improved heat generation properties and low F and fracture properties can be obtained. In just one process, the processability and unvulcanized degree of 7-lend of this car body rubber and other diene thread rubber were significantly improved, and the physical properties after processing were also excellent. . According to the present invention, (1) lithiation in a hydrocarbon bath medium 4)'
With the proboscis as an initiator] 11 concatenates 17 bifurcated Butaje 7
(1) The content of the bonded aromatic vinyl compound in the chassis body is 0 to 40. (11) 3 of the branched butadiene-based intermediate coalesce (1 to 80 folds are bonded with a tin compound), and the remaining 20 to 70 J (i,
'r, a coupling agent that does not contain tin': A rubber compound having a branched J thousand I, containing a butadiene yarn JI tip coalescence -1) that is a tin-free coupling agent, is provided. Sa J-L. Butagene yarn East combined com i+i formation of the present invention! l
L2, low heat generation, workability, unvulcanized strength and vulcanized ipf
The physical properties are good, and even when blended with different types of tf, it does not have a tropism or low F ('
I0 "Unexploded" Butadiene A

[The content of the combined aromatic vinyl compound is 0 to 40%, preferably 3 to 0.
↓1 I am sorry. If you exceed 40 vehicles, you will get a fever! Characteristic VL
jt; It's inferior. The dispersion of the branched butadiene-based polymer in the butadiene-based polymer of the present invention is 20 tons or more, preferably 3 to 80 times. 207, Beat: Chimi-Wui is not inferior in terms of tensile strength. In addition, branched butadiene yarn (1, E, σ) 311-8
0 car) Yi-person, good 1, or 40~7 () phantom 1] is susu-butadienyl 4.+'j or I->'f! ＜Conformation;
111, remaining 20-70 turtles; set chi, preferably 3 ()
~60% and 1% have Jli derivatives branched with tin-free coupling agents. Me, zoobutadienyl binding table included: 30-car, 屓φ木 (full in addition i ・i4i
, unvulcanized rubber strength, ex-heated beef F 1', 'i, transfer resistance custom made: 16 and inferior,)i L), jl,
If it exceeds i1i, the strength of the unvulcanized rubber will be poor. The soot-butadienyl bond in the branched polymer can be balanced by changing the B content of the branched polymer from 30 to 80 V-)n. . The amount of vinyl bond in the butadiene moiety of the butadiene polymer of the present invention is not limited to 1:00, but from the viewpoint of improving wet skid resistance characteristics, it is preferably 30% or more. The butadiene-based offshore compound of the present invention uses an organolithium compound as an initiator in a hydrocarbon medium, for example,
15.Create a desired amount of straight-chain pucdiene complex by the method shown in No. 38fi, etc., and then add a tin-based coupling agent and a tin-free coupling agent in a predetermined ratio. I am more talented than ever. The camping agent reacts almost quantitatively with the terminal living polymer formed by the anion j (1).Therefore, in the case of a coupling agent having n couplingable groups, the camping agent additive solution reacts with the terminal living polymer 1 formed by the anion j (1). x0 by adding [for moles], /n moles tit
04 coupling is performed. The tin-compounded power nogling agent in the entire coupling fI is defined by the present invention as a polymer and 1. C) First, use l, c molar ratio (・. ?/f), secondly,
For example, when using a coupling agent and (2) 41 tin crystallized silicon, the 4 cutoff ring arches lf groups in the first chair are effectively used as an initiator. For every 1 mole of tin chloride per month, the combination of tin tetrachloride and silicon tetrachloride 41-: M and t7 and 1/4 mol hi per month, 4j tin and 41 The molar ratio of silicon oxide is approximately 30:7 (1 to 1 to 0:2 (1 to 2) or separately added to conduct the coupling reaction/, r
That's fine. Moreover, the butadiene spinning wheel itself of the present invention consists of +m': l self-chain butadiene-based Oki ear body mixed with a tin thread coupling agent and r re-cutting, and one coupled with a coupling agent that does not contain tin yarn. Separately, prepared in No. 2, 17.
The branch structure for J is 30 to 80 cars, and also includes tin.
, (branched structure bonded with a coupling agent is 2()~
It can also be obtained by blending at a mixing ratio of 70% by weight. Examples of hydrocarbon solvents used in the incorporation of the butadiene polymer of the present invention include aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as butane, pentane, hexane, heptane, and octane, cyclohexane, C. Which alicyclic hydrocarbons can be used alone or in combination of two or more? Particularly preferred are cyclohexane, hexane, and heptane. Examples of organic lithium compounds include n-butyllithium, Kasa-butyllithium, and Shi-butyllithium 1.1.4.
-Alkyl lithium such as dilithiobutane, alkylene dilithium, fl, 02~(
1,2rM Used in provincial praise. In addition, as a microstructure modifier, Lewis bases such as ethers, amines, etc., specifically diethyl needle, tetrahydrofuran, propyl ether, butyl ether,
Higher ethers, Shobuko, -T, 'f-ref/Glygol dimethyl ether, Ethyl/N glycol dimethyl ether, Diethylene glycol dibutyl ether, Triethylene glycol dimethyl ether, Ether derivatives of polyethylene glycol such as narenol, amines include tertiary amines such as tetramethylethylenediamine, pyridine, and tributylamine, and are used with butylene 1) and 11. Ru. Of the butadiene-based polymer of the present invention! Used for 11 go 1.) Rero Nanatsuma - and 12 teha

[1,3-phytaziconin alone or 19,3-butadiene and an aromatic vinyl compound are used I-) Oscilloscope. 19,3-butadiene may contain a portion of pentazine and isofuran-49-phytannine derivatives. Aromatic vinyl compounds and shear (styrene, p-methylstyrene, vinyltoluene, a-methylstyrene, etc.) are preferred. Among these, styrene is preferred. Branched getadiene-based polymers with tin-butadienyl bonds include tin compounds. It can be obtained by using 7f'C as a coupling agent and adding a small amount of 1.;3 butadiene (0.5 to 100 mol per 1 lithium ly atom of the organolithium compound) before the coupling reaction. As the above-mentioned tin compounds, tetrachlorotin, trichloromethyltin, tetrachlorotin, tin, bistrichlorostannylethane; halogenated tin compounds are preferably used. halides such as silicon, germanium, lead, and boron; and phosphorus pentachloride, phosphorus trivalent; polyepoxides, such as epoxidized soybean oil, triglycidylaminophenol, tetraglycidylaminodine enylmethane; polyisocyanates, such as toluenediyl Son Anate,
Hexamethylene diisocyanate; polyhalogenated carbon, eg cc4. (2-,,)(Hα −- <-: −C” (Atofuchloroethane) 1.C which (7!/ \L'1 Trihalogenated carbon such as tetrahalogenated carbon, chloroorm, trichlene, etc.; Polyester For example, adipic acid diester, terephthalic acid diester, etc.; polyvinyl aromatic compounds such as divinylbenzene 1 etc. can be used. In particular, if we consider the Callan ring reaction, l
J OC is Ilf (2 years old, the weight is ＞
t-: Controlled to +i degrees and actually h...shi2゛(also,
Alternatively, it may be carried out by removing heat and applying 1 vorticity FK. If the coupling agent containing tin does not react with the tin compound, the two will mix and cave in. It's okay, it's soil.
They may be added separately. The proportion of the branched structure of the polymer is determined by gel permeation chromatography (GPC).
It can be calculated from the area of the HII heater, and in some cases, it may be calculated from the difference between the GPC pattern of the polymer before the coupling reaction and the GPC pattern after the coupling reaction. The amount of tin-butadienyl bond in the branched polymer was determined by determining the tin content in the branched polymer using an atomic absorption spectrometer. The Mooney viscosity of the butadiene-based polymer of the present invention is ML++
4.100c, 30 to 150; if it is less than 30, the tensile properties and impact resilience will deteriorate (2 is not preferred; if it exceeds 150, the processability will be poor and it is not desirable). The butadiene polymer of the present invention is Can it be used alone?
Diene thread rubber, such as natural rubber, polyisoprene rubber, polybutadiene rubber, emulsified 11-styrene-butadiene rubber, etc., can be blended in any proportion and used as a rubber composition. In this case, from the viewpoint of the effects of the present invention, it is more preferable that the content of the butadiene-based polymer of the present invention is 30% or less. If necessary, the product is oil-extended, a conventional compounding agent for vulcanized rubber is added, and the product is vulcanized and used for tire tires, flood control rubber, belts, hoses, and 11 other industrial products. Hereinafter, the present invention will be described in detail by way of example embodiments, and the present invention is not limited thereto. The forgetfulness was measured using Method V in F. Tensile strength is JIS K 6:3 +11
K-i asked if he was busy. The microstructure was determined by the infrared method (Morello method). In addition, the bonded styrene concentration was determined from a phenyl infrared method based on the absorption of the phenyl group. The exothermic properties were determined by △1゛ using a Goodlinch flexometer: ILI+IIi l-b, 2. Workability was evaluated by visually inspecting the appearance of the lumps and gloss after kneading. The transfer resistance time was measured using a mechanical spectrometer manufactured by RMS.
One song was rated by andδ. Regarding raw rubber strength, tensile strength is 5 (1 (l ar
The stress-strain curve of π-rate elongation at m/min was determined. Example 1゜Drying 1st. In a 5t autoclave under a sugar water atmosphere, 2.5Kg of cyclohexane, 375g of 3-butadiene,
? , styrene 7 (10y, tetofhydrofuran 257
was added and adjusted to 2 (lC). Next, n-butyllithium ibis (1,3259 liters) was taken off the ship, and the reaction heat was reduced to 1>4
-I left the car without leaving it. The reaction was completed in 30 minutes. Add 252 more 1,3-butadiene to this reaction system,
After the reaction is completed, i.e., tin tetrachloride (S n r: +4) and tin tetrachloride (S
tα4) was added to Table 1 at a ratio of 7J
minute reaction, 2,6-di-t-p-cresol 31
Add i+ to 5 ml of methanol! The polymer (A-G) was obtained by adding it to the system, stopping the reaction, and drying it using a conventional method to obtain the polymer (A-G).
σ) Miri ro material report, conclusion a) Methi 1/n included 1r1
111j of the shell de, (bro. Butadiene part micro, 11 made mistake I, 411Isub heat: le l, /I (j 2φ transformer 24-coupled steel: /contains I jl' rule 70 section J -, 2'A1.-: Hori Ma -(A-G
1 jX4'4'l IFyy3)
I got 111+f1 for 145 C31) minutes. The gender of the saturated substance < eJ4--1 female to 1 child 8 ratio example A&
11 In addition, in terms of sex, Dump Rubber's 1 and 10 are likely to be worse, and 4 (゛Rubber strength + 1 + 1 is also small. Also, the appearance is large. Comparison / Examples F and G are cow stingray insects +6-1 Tensile strength Tel) C poor-') "Ci4..・1
31% 11j1! Example Noll ~ I (is D-to 1'-, raw Ko゛ l-?) main +14,
ノJll 1Illj 'i り 1、! Ii
：Heat σ) point, 11 years old and well balanced). Table-2 Compounding recipe (parts by weight) Polymer I()0 carbon black (HAF) 50 lead powder
; stearic acid
] Anti-aging agent (810N A)"' ■ Vulcanization accelerator (DPG)"" 0.8 (DM) *3 (1, (i sulfur 1.5*I)N
-Phenyl-N'-isopropyl-p-phenylenediamine *2) Diphenylguanidine *3) Benzothiazyl disulfide Example 2゜The 11th reaction was carried out in the same manner as in Example 1, and the molecular terminal was formed into polybutadienyl lithium. Then, 5ncz4 and each bright coupling agent were added and reacted in order to form a polymer (H to K
) was obtained. The Snα4/tin-free coupling agent was added at a ratio of 1/l (1th) to carry out the J-tubbling reaction. Clothing the scabbard -: (VLL 7.1
＼-4゜Example 3゜Actual hm In Example 1, n~glylithium added stitching was 0.2
Polymerization was performed in place of 7f. The reaction was completed in 45 minutes. Add 252 more 1.3 butadiene to this thread,
After reacting for 30 minutes, a coupling reaction consisting of Snα and 5LCI+ was added at a ratio of 0.2 moles (Table 4, VcyB-e addition amount) per mole of n-butyllithium. Microstructure and bound snalene content of the obtained polymer
:'P, the result was similar to Example coloring 1. The obtained polymer and natural rubber are 50:50 (ratio to Megumi)
The blended product was evaluated in the same manner as in Example 1 in 11 rows. The results are summarized in Table 4. It can be seen that this example shows a 4-superior effect in blending processability and also satisfies the other effects of the invention. Example 4 In Example 1, instead of (Snα4+, S′ is also C14), 5nC140,l tl was used as the coupling agent, and δ"c(,'l!* (
After blending with the polymer bath liquid obtained using +- (167
Nelko. Same as Example 1/, c method, +1 pun f-te/f1]
lko. Zhao Guo? :Not listed in Table-4. Thing 7. Cru Coupling Qi 11 [Yo 4] Holimurf. Even though the blended product is still younger than Example I, the effect of the present invention is 1-).

Claims (1)

[Scope of Claims] (1) In a butadiene-based copolymer containing at least 20 M of a branched butadiene copolymer prepared by using an organolithium compound as an initiator in a hydrocarbon solvent. , (1) the content of the bonded aromatic vinyl compound in the polymer is 0 to 40%; (11) the content of the branched butadiene-based intermediate polymer is 3() to 801%;
A rubber composition characterized by containing a butadiene copolymer in which the eyes are linked by tin-butadienyl bonds, and the remaining 20 to 7 ON@ groups are branched by a soot-free coupling agent. (2) Particularly #i of Claim 1, characterized in that the vinyl bond content of the butadiene moiety of the butadiene-based hybrid is at least 3()! The rubber composition according to item (1).