CN106032427B - A kind of rubber composition and vulcanized rubber and preparation method thereof - Google Patents
A kind of rubber composition and vulcanized rubber and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of rubber composition and vulcanized rubbers and preparation method thereof.The rubber composition contains main rubber, vulcanizing agent, vulcanization accelerator, activator and reinforcing agent, wherein, the main rubber contains polycyclic amylene rubber and solid butadiene-styrene rubber, on the basis of the total weight of the polycyclic amylene rubber, the content of transconfiguration is greater than 50 weight % in the polycyclic amylene rubber, and the rubber composition also contains liquid styrene butadiene rubber and/or liquid butadiene rubber.The Mooney viscosity of the rubber compound obtained by the rubber composition is suitable for, and obtained vulcanizate is while keeping preferable physical mechanical property, also have resistance to ag(e)ing, resilience and wearability good, permanent deformation and dynamic deformation are small, and heat is low, the very small advantage of rolling resistance, so as to improve rubber ageing-resistant performance, the durability for reducing tire heat, improving tire extends tyre life, it is energy-saving to be conducive to tire, great prospects for commercial application.
Description
Technical field
The present invention relates to a kind of rubber composition, using the rubber composition as the preparation method of the vulcanized rubber of raw material with
And the vulcanized rubber being prepared by this method.
Background technique
With the development increasingly of auto industry, the requirement to the rubber various aspects for being suitable for automobile tire is higher and higher,
Ensure that tire under the premise of safety, causes in the process of moving to extending Life of Tyre, reducing vehicle fuel consumption
Pay much attention to.This requires tires not only preferable physical mechanical property, also to there is excellent ageing-resistant performance, wearability
Energy, low permanent deformation, low-heat-generation, high wet-sliding resistant and low-rolling-resistance, and need to meet safety traffic and energy-efficient demand.
In addition also require rubber product larger in the raw rubber and strength of process, be more advantageous in this way the half of rubber product at
Product machine-shaping and dimensionally stable.
Although studies have shown that the physical mechanical property of butadiene-styrene rubber vulcanizate is preferable, strength is smaller, unfavorable
In the semi-finished product machine-shaping of rubber product and dimensionally stable, and due to its vulcanizate resistance to ag(e)ing, resilience and wearability
Generally, permanent deformation, heat are larger, and especially rolling resistance is larger, therefore are difficult to be used as High-performance green tire.And polycyclic penta
Although alkene rubber has, glass transition temperature is low, green strength is big, adherence is strong, air-tightness is high, resistance to ag(e)ing and shrinkage are good, resistance to
Flexibility is strong, carbon black and oily loading are big, processing performance is excellent and its vulcanized rubber can also present high rebound, low lag,
The advantages of low-heat-generation, low-rolling-resistance and excellent abrasion resistance, but its crude rubber Mooney viscosity is too big, is unfavorable for rubber
Processing, and vulcanizate tensile strength and tearing strength are smaller, are difficult to be used alone in rubber composition.
Summary of the invention
The purpose of the invention is to provide the new rubber composition of one kind, using the rubber composition as the vulcanization of raw material
The preparation method of rubber and the vulcanized rubber being prepared by this method.
Specifically, rubber composition provided by the invention contain main rubber, vulcanizing agent, vulcanization accelerator, activator and
Reinforcing agent, wherein the main rubber contains polycyclic amylene rubber and solid butadiene-styrene rubber, with the total of the polycyclic amylene rubber
On the basis of weight, the content of transconfiguration is greater than 50 weight % in the polycyclic amylene rubber, and the rubber composition also contains
There is liquid rubber, the liquid rubber is liquid styrene butadiene rubber and/or liquid butadiene rubber.
The present invention also provides a kind of preparation method of vulcanized rubber, this method includes will be each in the rubber composition
Component is kneaded, and rubber compound is obtained, and then vulcanizes the rubber compound.
In addition, the present invention also provides vulcanized rubbers prepared by the above method.
The present inventor has found after further investigation, although butadiene-styrene rubber and polycyclic amylene rubber are used alone
When there are some problems, but the two being used in mixed way, very perfect coordinated, obtained rubber can be played the role of
The Mooney Viscosity of Rubber Mix of glue composition is suitable for, to can not only obtain the biggish rubber compound of tensile strength and be conducive to rubber
The processing of product, and be conducive to the semi-finished dimensions stabilization and molding of rubber product；Obtained vulcanizate is keeping preferable
While physical mechanical property, also with resistance to ag(e)ing is good, resilience and wearability are good, permanent deformation and dynamic deformation are small, raw
Heat is low, the especially very small advantage of rolling resistance so as to improve rubber ageing-resistant performance reduces tire heat, improves
The durability of tire extends tyre life, and it is energy-saving to be conducive to tire, is highly suitable as green energy conservation tire material.This
Outside, the rubber composition also contains liquid styrene butadiene rubber and/or liquid butadiene rubber as liquid rubber, due to both
Specific liquid rubber acts not only as the softening agent or plasticizer of rubber processing process, and again can be with master in vulcanization
Body rubber participates in vulcanizing together, becomes reactive plasticizer, so as to further increase the ageing-resistant performance and object of vulcanizate
Mechanical performance is managed, reduces rubber heat, permanent deformation and rolling resistance, and the introducing of this reactive plasticizer can also subtract
It even is eliminated Conventional filler oil less and oozes out the defect polluted to human body and environment from rubber in use.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
Rubber composition provided by the invention contains main rubber, vulcanizing agent, vulcanization accelerator, activator and reinforcing agent,
Wherein, the main rubber contains polycyclic amylene rubber and solid butadiene-styrene rubber, and the total weight with the polycyclic amylene rubber is
Benchmark, the content of transconfiguration is greater than 50 weight % in the polycyclic amylene rubber, and the rubber composition also contains liquid
Rubber, the liquid rubber are liquid styrene butadiene rubber and/or liquid butadiene rubber.
In the present invention, the polycyclic amylene rubber refers to the polycyclic amylene being prepared by cyclopentene ring-opening polymerization
Rubber.Wherein, the polycyclic amylene rubber includes cis- polycyclic amylene rubber and trans- polycyclic amylene rubber, and specific structure is such as
Shown in lower:
As described above, in the rubber composition, on the basis of the total weight of the polycyclic amylene rubber, the polycyclic
The content of transconfiguration is greater than 50 weight % in amylene rubber, but in order to enable is prepared by the rubber composition
Vulcanized rubber has better processing performance and application performance, it is preferable that on the basis of the total weight of the polycyclic amylene rubber,
The content of transconfiguration is greater than 70 weight %, more preferably 75-95 weight %, most preferably 80- in the polycyclic amylene rubber
90 weight %.Usually, the number-average molecular weight of the polycyclic amylene rubber can be 60,000-60 ten thousand, preferably 100,000-35 ten thousand；
Molecular weight distribution can be 1-3, preferably 1.5-2.5.In addition, the Mooney viscosity of the polycyclic amylene rubber is typically
35-160, preferably 45-140.
The polycyclic amylene rubber can be prepared by cyclopentene ring-opening polymerization.Specifically, when using open loop
When polymerization reaction prepares polycyclic amylene rubber, the preparation method includes: in ring-opening polymerization catalyst and molecular weight regulator
In the presence of, cyclopentene is subjected to ring-opening polymerization in a solvent.
Wherein, the ring-opening polymerization catalyst can use the existing various catalysis that can make cyclopentene ring-opening polymerisation
Agent, such as tungsten or two component of molybdenum or three component catalysts can be used, in tantalum, niobium, rhenium catalyst and metallocene catalyst
It is at least one, it is preferred to use to be urged by what Tungstenic compound and/or molybdate compound, organo-aluminum compound and/or activator formed
Change system.Wherein, the Tungstenic compound can be tungsten hexachloride, and the molybdate compound can be molybdenum tetrachloride.It is described to have
Machine aluminium compound can be alkyl aluminum, preferably in triisobutyl aluminium, triethyl aluminum, aluminium diethyl monochloride, ethyl aluminum dichloride etc.
At least one.The activator can be oxygenatedchemicals and/or chlorine-containing compound, preferably tetrachlorophenol, trichlorophenol, 2,4,6,-T,
At least one of benzoyl peroxide, epoxychloropropane etc..In addition, the dosage and Tungstenic compound of the organo-aluminum compound
Molar ratio with total dosage of molybdate compound can be 0.5-8: 1, preferably 1-5: 1；The dosage and tungstenic of the activator
The molar ratio of total dosage of compound and molybdate compound can be 0.2-3.0: 1, preferably 0.5-1.5: 1.
Molecular weight regulator used in the cyclopentene ring-opening polymerization can be the alpha-olefin that carbon atom number is 2-10,
Preferably at least one of 1- butylene, 2- butylene, 1- octene etc..In addition, the dosage of the molecular weight regulator with contain tungsten
The molar ratio for closing total dosage of object and molybdate compound can be 0.1-10: 1, preferably 0.3-5: 1.
During the cyclopentene ring-opening polymerization, solvent used can be various nonpolarity commonly used in the art
Solvent, such as can be various hydrocarbon solvents, preferably C4-C8Linear chain or branched chain aliphatic saturated hydrocarbon or C6-C12Substitution or
Unsubstituted aromatic hydrocarbons.Specifically, the example of the solvent can include but is not limited to: benzene, toluene, hexamethylene, pentamethylene, just oneself
Alkane, normal heptane, is raffinated oil and one of hydrogasoline or a variety of at pentane.In addition, the dosage of the solvent can make list
The concentration of body is 5-60 weight %, preferably 10-40 weight %.
The present invention is not particularly limited the condition of the ring-opening polymerization, and generally including polymeric reaction temperature can
Think -20 DEG C to 50 DEG C, preferably -10 DEG C to 30 DEG C, polymerization pressure can be 0-1MPa, be preferably 0.05-0.5MPa,
Polymerization reaction time can be 0.5-10 hours, preferably 1-4 hours.In the present invention, the pressure refers both to gauge pressure.
The solid butadiene-styrene rubber can be existing various at room temperature in solid butadiene-styrene rubber.Usually, institute
The number-average molecular weight for stating solid butadiene-styrene rubber can be 100,000-50 ten thousand, preferably 120,000-40 ten thousand；Molecular weight distribution can be 1-
4, preferably 1.5-3.On the basis of the total weight of the solid butadiene-styrene rubber, styryl structures list in the solid butadiene-styrene rubber
The content of member can be 10-40 weight %, and the content of butadiene structural units can be 60-90 weight %；Preferably, with described
On the basis of the total weight of solid butadiene-styrene rubber, the content of styrol structural unit is 15-35 weight in the solid butadiene-styrene rubber
% is measured, the content of butadiene structural units is 65-85 weight %.With in the solid butadiene-styrene rubber butadiene structural units it is total
On the basis of weight, the content of 1,2- structure can be 8-75 weight %, preferably 10-65 weight in the butadiene structural units
Measure %, more preferably 10-30 weight %.In addition, the Mooney viscosity of the solid butadiene-styrene rubber can be 35-95, preferably 40-
70, more preferably 40-55.
The solid butadiene-styrene rubber can be commercially available, can also be according to well known to a person skilled in the art various sides
Method is prepared, for example, can be prepared using emulsion polymerization or the method for polymerisation in solution, i.e., the described solid butadiene-styrene rubber can
Think emulsion polymerized styrene butadiene rubber, or solution polymerized butadiene styrene rubber.Wherein, initiator used in the emulsion polymerization process can be with
Thermal decomposition initiating (such as persulfate), redox type initiator (such as mistake are used according to the difference for forming free radical mechanism
The mixture of hydrogen oxide and ferrous salt), organic peroxy class initiator (such as isopropyl benzene hydroperoxide, cumyl peroxide, mistake
At least one of hydrogen oxide isopropylbenzene, dibenzoyl peroxide, di-cyclohexylperoxy di-carbonate etc.).The polymerisation in solution
Used in the process of initiator can be at least one of organometallic lithium compounds, such as n-BuLi, s-butyl lithium etc..
In addition, other conditions in the solid butadiene-styrene rubber preparation process all can be this field conventional selection, to this ability
Field technique personnel can know that therefore not to repeat here.
The liquid styrene butadiene rubber various can be in a liquid state or the dynamic butadiene-styrene rubber of semi-fluid at room temperature to be existing.?
In the present invention, the number-average molecular weight of the liquid styrene butadiene rubber is less than the number-average molecular weight of the solid butadiene-styrene rubber.The liquid
The number-average molecular weight of body butadiene-styrene rubber can be 0.5 ten thousand-9.5 ten thousand, preferably 1.0 ten thousand-6.5 ten thousand, preferably 30,000-5 ten thousand；Molecule
Amount distribution can be 1-3, preferably 1.1-2.5, more preferably 1.2-2.0.In addition, with the total weight of the liquid styrene butadiene rubber
On the basis of, the content of styrol structural unit can be 10-40 weight %, preferably 15-35 weight in the liquid styrene butadiene rubber
% is measured, the content of butadiene structural units can be 60-90 weight %, preferably 65-85 weight %.
The liquid butadiene rubber various can be in a liquid state or the dynamic butadiene rubber of semi-fluid at normal temperature to be existing
Glue.Usually, the number-average molecular weight of the liquid butadiene rubber can be 10,000-9.5 ten thousand, preferably 1.0 ten thousand-6.5 ten thousand,
More preferably 40,000-6 ten thousand；Molecular weight distribution can be 1-3, preferably 1.1-2.5, more preferably 1.1-2.0.In addition, with described
On the basis of the total weight of liquid butadiene rubber, Isosorbide-5-Nitrae-structure content is preferably not less than 70 weights in the liquid butadiene rubber
Measure %, more desirably not less than 90 weight %.
The liquid styrene butadiene rubber and liquid butadiene rubber can be commercially available, can also be using existing each
Kind method is prepared, for example, can be prepared using anionic polymerization, radical polymerization or coordination polymerization method, it is excellent
It is first prepared using alkyl lithium initiator by anionic polymerisation process, specific preparation process and condition all can be abilities
The conventional selection in domain, therefore not to repeat here.
The rubber composition provided according to the present invention, although as long as containing polycyclic amylene rubber in the rubber composition simultaneously
Glue, solid butadiene-styrene rubber and liquid rubber can be effectively improved the comprehensive performance of rubber compound and vulcanizate, but in order to enable
The effect of performance improvement becomes apparent, it is preferable that relative to the main rubber of 100 parts by weight, the polycyclic amylene rubber contains
Amount is 5-70 parts by weight, and the content of the solid butadiene-styrene rubber is 30-95 parts by weight；It is highly preferred that relative to 100 parts by weight
Main rubber, the content of the polycyclic amylene rubber are 10-50 parts by weight, and the content of the solid butadiene-styrene rubber is 50-90 weight
Measure part.In addition, the main rubber relative to 100 parts by weight, the content of the liquid rubber is preferably 2-20 parts by weight, more preferably
For 4-10 parts by weight.
The present invention is not particularly limited the content of the vulcanizing agent, vulcanization accelerator, activator and reinforcing agent, example
Such as, the main rubber relative to 100 parts by weight, the content of the vulcanizing agent can be 1-3 parts by weight, the vulcanization accelerator
Content can be 1-5 parts by weight, and the content of the activator can be 0.5-8 parts by weight, and the content of the reinforcing agent can be
40-70 parts by weight.
The present invention is not particularly limited the type of the vulcanizing agent, vulcanization accelerator, activator and reinforcing agent,
Think the conventional selection of this field.For example, the vulcanizing agent can be selected from sulphur, insoluble sulfur, two thio morpholines and four
One or more of thio two morpholine.The vulcanization accelerator can be selected from N- tert-butyl -2-[4-morpholinodithio base time sulphonyl
Amine, 2,2 '-dibenzothiazyl disulfides, N- tert-butyl-bis- (2-[4-morpholinodithio) sulfenamide, N- cyclohexyl-bis- (2- sulfydryl
Benzothiazole) one of sulfenamide and diphenylguanidine or a variety of.The activator can be zinc oxide and/or stearic acid.Institute
Stating reinforcing agent can be carbon black and/or white carbon black.
In addition, the rubber composition can also contain anti-aging agent and/or antiscorching agent.Contain when in the rubber composition
When anti-aging agent, relative to the main rubber of 100 parts by weight, the content of the anti-aging agent can be 1-5 parts by weight.When the rubber
When containing antiscorching agent in composition, relative to the main rubber of 100 parts by weight, the content of the antiscorching agent can be 0.05-
0.35 parts by weight.
The present invention is not particularly limited the type of the anti-aging agent and antiscorching agent, all can be this field conventional choosing
It selects.Specifically, the anti-aging agent can be amines antioxidants and/or quinoline type antioxidant.Wherein, the amines antioxidants can be with
Selected from N- isopropyl-N '-diphenyl-para-phenylene diamine, N- (1,3- dimethylbutyl)-N '-diphenyl-para-phenylene diamine and the bis- (Isosorbide-5-Nitraes-of N, N '-
Dimethyl amyl group) one of p-phenylenediamine or a variety of, preferably N- (1,3- dimethylbutyl)-N '-diphenyl-para-phenylene diamine.Institute
Stating quinoline type antioxidant can be selected from 2,2,4- trimethyl -1,2- dihyaroquinoline condensates, 6- ethyoxyl -2,2,4- front three
Base -1,2- dihyaroquinoline and 6- dodecyl -2,2, one of 4- trimethyl -1,2- dihyaroquinoline or a variety of, preferably
It is 2,2,4- trimethyl -1,2- dihyaroquinoline condensates.The antiscorching agent can be selected from N- cyclohexyl thio phthalyl
One of imines, N nitrosodiphenyl amine, salicylic acid and phthalic anhydride are a variety of, preferably N- cyclohexyl thio neighbour benzene
Dicarboximide.
The preparation method of vulcanized rubber provided by the invention includes being kneaded each component in above-mentioned rubber composition,
Rubber compound is obtained, then vulcanizes the rubber compound.Wherein, each component in the rubber composition and its content be
It is described herein above, will not repeat herein.
The method and condition of the preparation method of the vulcanized rubber provided according to the present invention, the mixing can be this field
Conventional selection.Usually, the mixing can carry out in open mill or mixer, and the mixing between each substance can be with
It carries out, can also carry out step by step simultaneously, preferably substep carries out.A kind of specific embodiment according to the present invention, the mixing can
To be carried out as follows: in mixer, raw rubber (main rubber) is added and is kneaded 30-60s in 50-80 DEG C of pushing top,
It adds activator and other optional small powders (other small powders contain anti-aging agent and antiscorching agent) and top is pressed to be kneaded 60-90s, so
Reinforcing agent is added afterwards and liquid rubber pressure top is kneaded 2-4min, then mentions top and is kneaded 1-2min back glue, dump temperature 150-
170 DEG C, one section of rubber compound is obtained, obtain one section of rubber compound is cooled to room temperature placement overnight；By one section of rubber compound and vulcanization
Agent, vulcanization accelerator thin logical bottom sheet on a mill, obtain rubber compound.Wherein, the thin logical number can be according to rubber compound
Melting effect determine, the thin logical number is preferably greater than 2 times, more preferably 5-7 times.
The preparation method of the vulcanized rubber provided according to the present invention, the condition that rubber compound is vulcanized are art technology
Well known to personnel.For example, the vulcanization can carry out in vulcanization bed or vulcanizing press.The conditions of vulcanization generally includes sulphur
Temperature, pressure and the time of change, wherein if the temperature of the vulcanization, pressure and time can guarantee the main rubber and
Liquid rubber is crosslinked with vulcanizing agent to react, for example, the temperature that the condition of the vulcanization generally includes vulcanization can be
130-170 DEG C, the pressure of vulcanization can be 10-15MPa, and the time of vulcanization can be 10-50 minutes.
The present invention also provides vulcanized rubbers prepared by the above method.
It below will the present invention is further described in detail by specific embodiment.
Test method involved in following embodiment and comparative example is as follows:
(1) microstructure of molecular weight, molecular weight distribution and polymer:
The number-average molecular weight and molecular weight distribution of polycyclic amylene rubber, solid butadiene-styrene rubber and liquid rubber are using solidifying
Glue penetration chromatograph (GPC) is measured, wherein test condition includes: using tetrahydrofuran as mobile phase, and flow velocity is
1.0mL·min-1, temperature is 25 DEG C.
The structure of polycyclic amylene rubber, solid butadiene-styrene rubber and liquid rubber using infrared spectrometer (pressing potassium bromide troche) and
Nuclear Magnetic Resonance (solvent is tritium for chloroform, and test temperature is 25 DEG C, is calibrated with tetramethylsilane) is measured.
(2) Mooney viscosity:
Mooney viscosity uses the mooney's viscosimeter of the model SMV-300 of Shimadzu Corporation, according to GB/T1232.1-2000's
Method is measured, and test temperature is 100 DEG C, and preheating time is 1 minute, and rotation time is 4 minutes.
(3) Shao Er A type hardness tester:
Shao Er A type hardness tester is measured according to method specified in GB/T23651-2009.
(4) mechanical property:
Tensile strength, elongation at break, 100% stress at definite elongation, 300% stress at definite elongation and permanent deformation is pulled apart according to GB/
T528-1998 is tested；Tearing strength test is tested according to GB/T529-2008.
(5) test method:
Rubber test method is measured according to method specified in GB/T 3512-1983, experimental temperature
It is 100 DEG C, experimental period is 72 hours.
(6) rebound value:
Rebound value is measured by method specified in GB/T1691-1991.
(7) repeated compression test:
Repeated compression test is measured by method specified in GB/T7759-1996.
(8) Akron abrasion:
Akron abrasion by GBT/1689-1998 provide specified in method be measured.
(9) rolling resistance:
The rolling resistance of vulcanizate is measured using rolling resistance test instrument, test condition: load 15MPa, revolving speed
For 400rmin-1。
(10) dynamic temperature rise:
The dynamic temperature rise of vulcanizate uses rubber compression heat generation testing machine (RH-2000, the limited public affairs of Taiwan High Speed Rail Testing Instruments
Department) with 4.45 millimeters of stroke, load 1MPa, it tests 25 minutes and obtains at 55 DEG C.
(11) dynamic deformation:
The dynamic deformation of vulcanizate is measured by method specified in GB1683-81.
(12) fissipation factor:
The fissipation factor of vulcanizate is measured using dynamic mechanical analyzer (DMA), test condition: frequency 10HZ,
Heating rate is 2 DEG C of min-1, Range of measuring temp is -120 DEG C to 100 DEG C, sample size (mm) is about 20.00 × 5.00 ×
2.00 (length × width x thickness).
(13) vulcanization characteristics:
The vulcanization characteristics of vulcanizate is measured without rotor vulcameter by GB/T16584-1996 with MR-C3 type.
In the following Examples and Comparative Examples:
Solid butadiene-styrene rubber is emulsion polymerized styrene butadiene rubber SBR1502 and/or solution polymerized butadiene styrene rubber Tufprene2000R.Wherein,
Emulsion polymerized styrene butadiene rubber SBR1502 is purchased from Nanjing Yangzi petrochemical industry gold Pu rubber company, number-average molecular weight 30, and molecular weight distribution is
2.5, the content of styrol structural unit is 23.5 weight % (on the basis of the total weight of emulsion polymerized styrene butadiene rubber), butadiene structure
The content of 1,2- structure is 27 weight % (on the basis of the content of butadiene structural units in emulsion polymerized styrene butadiene rubber), door in unit
Buddhist nun's viscosity is 51.Solution polymerized butadiene styrene rubber Tufprene 2000R is purchased from Asahi company of Japan, and number-average molecular weight is 16.1 ten thousand, point
Son amount is distributed as 2.6, and the content of styrol structural unit is 25% (on the basis of the total weight of solution polymerized butadiene styrene rubber), butadiene
The content of 1,2- structure is 13 weight % (using the total weight of butadiene structural units in solution polymerized butadiene styrene rubber as base in structural unit
It is quasi-), Mooney viscosity 45.
Liquid styrene butadiene rubber is synthesized by Beijing Chemical Research Institute Yanshan Mountain branch, wherein number-average molecular weight is 4.2 ten thousand, molecule
Amount is distributed as 1.25, and the weight ratio of styrol structural unit and butadiene structural units is 30: 70,1,2- in liquid polyphenyl rubber
The content of structure is 35 weight % (on the basis of the total weight of butadiene structural units in liquid polyphenyl rubber).
Liquid polybutadiene rubber LIR-300 is purchased from Kuraray company, wherein and number-average molecular weight Mn is 4.7 ten thousand, point
Son amount is distributed as 1.2, and Isosorbide-5-Nitrae-structure content is 90 weight % (with liquid polybutadiene in liquid polybutadiene rubber LIR-300
On the basis of the total weight of alkene rubber).
Carbon black is high abrasion furnace black N330, is purchased from Guangzhou Li Ben rubber raw materials Co., Ltd.
Sulphur contains Science and Technology Ltd., trade mark S-80 purchased from Guangzhou Jinchang.
Vulcanization accelerator N- tert-butyl -2-[4-morpholinodithio base sulfenamide (NS) is purchased from Haiyang Chemical Plant, Qingdao.
Zinc oxide: it is purchased from Liuzhou Xin Pin Co., Ltd.
Stearic acid: the polite Chemical Co., Ltd. in Hong Kong, trade mark SA1801 are purchased from.
Anti-aging agent 2,2,4- trimethyl -1,2- dihyaroquinoline condensate (RD) are limited purchased from the holy chemistry science and technology difficult to understand in Jiangsu
Company.
Anti-aging agent N- (1,3- dimethylbutyl)-N '-diphenyl-para-phenylene diamine (4020) is purchased from the limited public affairs of Shanghai addition chemical industry
Department.
Antiscorching agent N- cyclohexylthiophthalimide (CTP) is purchased from Shandong Boxing section source new material Limited Liability
Company.
Aromatic naphtha is purchased from ten thousand Feng Yuan economy and trade Co., Ltd of Suifenhe City, trade mark TDAE.
Preparation example 1
The preparation example is for illustrating polycyclic amylene rubber provided by the invention and preparation method thereof.
In the 2L reactor replaced with purified nitrogen, it is separately added into cyclopentene 200g, n-hexane 800g, containing 0.05mol/
Toluene solution 20.0mL, the WCl containing 0.03mol/L of L trichlorophenol, 2,4,6,-T6Toluene solution 33.3mL and 1- containing 0.1mol/L butylene
Hexane solution 6.0mL, stir evenly and keep reaction mass temperature be 0 DEG C, then under stiring be added contain 0.3mol/L tri-
The toluene solution 13.3mL of aluminium isobutyl, filling purified nitrogen makes reactor pressure be maintained at 0.2MPa (gauge pressure), isothermal reaction 3.0
Hour, 2, the 6- di-tert-butyl-4-methy phenol second that 20mL concentration is 100g/L is added into reactor after terminating for polymerization reaction
Alcoholic solution terminates reaction, then releases glue and is agglomerated with ethyl alcohol, obtained polymer is dried in 50 DEG C of vacuum drying ovens to perseverance
Weight is stand-by, obtains the polycyclic amylene rubber of 155.5g.Through detecting, the content of transconfiguration is 86.3 weights in the polycyclic amylene rubber
% is measured, the number-average molecular weight of polymer is 289500, molecular weight distribution 1.75, Mooney viscosity 120.
Preparation example 2
The preparation example is for illustrating polycyclic amylene rubber provided by the invention and preparation method thereof.
Polycyclic amylene rubber is prepared according to the method for preparation example 1, unlike, by the first of the trichlorophenol, 2,4,6,-T containing 0.05mol/L
The toluene solution 16.0mL of benzole soln 20.0mL 0.05mol/L tetrachlorophenol is substituted, and the hexane of 0.1mol/L 1- butylene is molten
The additional amount of liquid is 7.2mL, and the additional amount of the toluene solution of the triisobutyl aluminium containing 0.3mol/L is 11.6mL, polymeric reaction temperature
It is -5 DEG C, reactor pressure is 0.5MPa (gauge pressure), and polymerization reaction time is 3.0 hours, obtains the polycyclic amylene rubber of 160.2g
Glue.Through detecting, the content of transconfiguration is 84.6 weight % in the polycyclic amylene, and the number-average molecular weight of polymer is 178500,
Molecular weight distribution is 1.87, Mooney viscosity 50.
Preparation example 3
The preparation example is for illustrating polycyclic amylene rubber provided by the invention and preparation method thereof.
Polycyclic amylene rubber is prepared according to the method for preparation example 1, unlike, the toluene of the trichlorophenol, 2,4,6,-T containing 0.05mol/L
The additional amount of solution is 24.0mL, and the additional amount of the hexane solution of the butylene of 1- containing 0.1mol/L is 20.0mL, contains 0.3mol/L tri-
The additional amount of the toluene solution of aluminium isobutyl is 16.6mL, and polymeric reaction temperature is 8 DEG C, polymerization pressure 0.3MPa
(gauge pressure), polymerization reaction time are 2.0 hours, obtain the polycyclic amylene rubber of 161.5g.It is trans- in the polycyclic amylene through detecting
The content of structure is 86.5 weight %, and the number-average molecular weight of polymer is 90200, molecular weight distribution 1.90, and Mooney viscosity is
35。
Embodiment 1-8
Embodiment 1-8 is for illustrating rubber composition and vulcanized rubber and preparation method thereof of the invention.
Each component and its dosage in the rubber composition of embodiment 1-8 is as shown in table 1 below, the specific preparation of vulcanized rubber
Process is as follows:
Each component shown in table 1 is performed the following operation: using two-stage process be kneaded, one section be kneaded in mixer into
Row, mixing room temperature are 60 DEG C, rotor speed 80rmin-1, calendering process are as follows: raw rubber (main rubber) is added and is kneaded afterwards
1min, is then added activator and other optional small powders (anti-aging agent and antiscorching agent) are kneaded 1.5min afterwards, adds reinforcing agent
With 3min is kneaded after liquid rubber, be kneaded 1.5min after pressure-raising top, dumping, dump temperature is not higher than 170 DEG C, obtains one section of mixing
Obtain one section of rubber compound is cooled to room temperature placement overnight by glue；Two-stage mixing carries out on a mill, calendering process are as follows: will
One section of rubber compound and vulcanizing agent and vulcanization accelerator are kneaded 8 minutes under the roller speed of 20rpm, thin to lead to 6 bottom sheet, obtain rubber compound
H1-H8.Then the rubber compound sizing material being vulcanized on vulcanizing press, curing temperature is 150 DEG C, sulfide stress 10MPa,
Vulcanization time 20min obtains vulcanized rubber S1-S8.Wherein, the performance of the rubber compound and vulcanizate is as shown in table 2.
Comparative example 1
The comparative example is for illustrating rubber composition and vulcanized rubber of reference and preparation method thereof.
Rubber compound and vulcanized rubber are prepared according to the method for embodiment 1, unlike, all solids of main rubber
Butadiene-styrene rubber, and liquid rubber is substituted with the aromatic naphtha of identical weight part, obtains rubber compound DH1 and vulcanized rubber DS1.Wherein,
The each component of the rubber composition is as shown in table 1, and the performance of the rubber compound and vulcanizate is as shown in table 2.
Comparative example 2
The comparative example is for illustrating rubber composition and vulcanized rubber of reference and preparation method thereof.
Rubber compound and vulcanized rubber are prepared according to the method for embodiment 1, unlike, all solids of main rubber
Butadiene-styrene rubber obtains rubber compound DH2 and vulcanized rubber DS2.Wherein, each component of the rubber composition is as shown in table 1, and institute
The performance for stating rubber compound and vulcanizate is as shown in table 2.
Comparative example 3
The comparative example is for illustrating rubber composition and vulcanized rubber of reference and preparation method thereof.
Rubber compound and vulcanized rubber are prepared according to the method for embodiment 1, unlike, the main rubber is all by making
The polycyclic amylene rubber that standby example 1 obtains, obtains rubber compound DH3 and vulcanized rubber DS3.Wherein, each group of the rubber composition
Divide as shown in table 1, and the performance of the rubber composition and vulcanizate is as shown in table 2.
Comparative example 4
The comparative example is for illustrating rubber composition and vulcanized rubber of reference and preparation method thereof.
Rubber compound and vulcanized rubber are prepared according to the method for embodiment 1, unlike, by the liquid rubber with identical heavy
The aromatic naphtha substitution for measuring part, obtains rubber compound DH4 and vulcanized rubber DS4.Wherein, each component of the rubber composition such as table 1
It is shown, and the performance of the rubber composition and vulcanizate is as shown in table 2.
As can be seen from the above results, when solid butadiene-styrene rubber is used alone in main rubber, the stretching of rubber compound is strong
Spend relatively small, vulcanizate is in addition to tensile strength and tearing strength are larger, and other physical mechanical properties are general, and vulcanizate
Tensile strength and elongation at break change rate before and after aging is larger, and permanent deformation, heat, abrasion and rolling resistance are larger, returns
Elasticity is smaller, and tan δ (60 DEG C) value is larger.When polycyclic amylene rubber is used alone in main rubber, Mooney Viscosity of Rubber Mix is too
Greatly, it is unfavorable for the machine-shaping of rubber compound, although the resistance to ag(e)ing of vulcanizate, wearability and resilience are good and heat is low,
The tensile strength and tearing strength of vulcanizate are smaller.It is strong except stretching after substituting liquid rubber with aromatic naphtha in rubber composition
Except degree, tearing strength, elongation at break and tan δ (0 DEG C) value are closer to, other performance is poor compared with using liquid rubber, especially
It is that volume worn is larger, temperature rise is higher, and tan δ (60 DEG C) value is larger.And in the main rubber of rubber composition provided by the invention
Contain polycyclic amylene rubber and solid butadiene-styrene rubber simultaneously, and the rubber composition also contains liquid styrene butadiene rubber and/or liquid
For body butadiene rubber as softening agent and reactive plasticizer, the Mooney viscosity and tensile strength of corresponding rubber compound are convenient,
The ageing-resistant front and back tensile strength of vulcanizate and elongation at break change rate are smaller and still maintain higher tensile strength, pull apart and stretch
Long rate and tearing strength illustrate that ageing-resistant performance is good, the service life of tire can be improved.In addition, vulcanization provided by the invention
The resilience of rubber is good, wearability is good, be permanently deformed and dynamic deformation is small, heat and rolling resistance are low, vulcanizate dynamic mechanical
It has excellent performance, the contradiction between high wet-sliding resistant, low-rolling-resistance and high-wearing feature can be balanced very well, than solid fourth is used alone
Benzene rubber and/or polycyclic amylene rubber and vulcanized rubber without liquid rubber in comprehensive performance compared to having obviously
Superiority.In addition, rubber composition provided by the invention and vulcanized rubber use liquid rubber substitution aromatic naphtha and naphthenic oil as
Filler, can not only obtain the better mixing rubber of comprehensive performance and vulcanized rubber, and to more environment-friendly, be very suitable to
As green energy conservation rubber material.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (17)
1. a kind of rubber composition, the rubber composition contains main rubber, vulcanizing agent, vulcanization accelerator, activator and increasing
Strong agent, which is characterized in that the main rubber contains polycyclic amylene rubber and solid butadiene-styrene rubber, with the polycyclic amylene rubber
Total weight on the basis of, the content of transconfiguration is greater than 50 weight %, and the rubber composition in the polycyclic amylene rubber
Also contain liquid rubber, the liquid rubber is liquid styrene butadiene rubber and/or liquid butadiene rubber, relative to 100 parts by weight
Main rubber, the content of the polycyclic amylene rubber is 10-50 parts by weight, and the content of the solid butadiene-styrene rubber is 50-90
Parts by weight, the content of the liquid rubber are 2-20 parts by weight.
2. rubber composition according to claim 1, wherein on the basis of the total weight of the polycyclic amylene rubber, institute
The content for stating transconfiguration in polycyclic amylene rubber is greater than 70 weight %.
3. rubber composition according to claim 2, wherein on the basis of the total weight of the polycyclic amylene rubber, institute
The content for stating transconfiguration in polycyclic amylene rubber is 75-95 weight %.
4. rubber composition according to claim 1, wherein the number-average molecular weight of the polycyclic amylene rubber is 60,000-60
Ten thousand, molecular weight distribution 1-3, Mooney viscosity 35-160.
5. rubber composition according to claim 4, wherein the number-average molecular weight of the polycyclic amylene rubber is 100,000-
350000, molecular weight distribution 1.5-2.5, Mooney viscosity 45-140.
6. rubber composition according to claim 1, wherein the number-average molecular weight of the solid butadiene-styrene rubber is 100,000-
500000, molecular weight distribution 1-4；The Mooney viscosity of the solid butadiene-styrene rubber is 35-95.
7. rubber composition described in any one of -6 according to claim 1, wherein with the gross weight of the solid butadiene-styrene rubber
On the basis of amount, the content of styrol structural unit is 10-40 weight % in the solid butadiene-styrene rubber, butadiene structural units
Content is 60-90 weight %；On the basis of the total weight of butadiene structural units in the solid butadiene-styrene rubber, the butadiene
The content of 1,2- structure is 8-75 weight % in structural unit.
8. rubber composition described in any one of -6 according to claim 1, wherein the number of the liquid styrene butadiene rubber is divided equally
Son amount is 0.5 ten thousand -9.5 ten thousand, molecular weight distribution 1-3；On the basis of the total weight of the liquid styrene butadiene rubber, the liquid fourth
The content of styrol structural unit is 10-40 weight % in benzene rubber, and the content of butadiene structural units is 60-90 weight %.
9. rubber composition described in any one of -6 according to claim 1, wherein the number of the liquid butadiene rubber is equal
Molecular weight is 10,000-9.5 ten thousand, molecular weight distribution 1-3；On the basis of the total weight of the liquid butadiene rubber, the liquid
The content of 1,4- structure is not less than 70 weight % in butadiene rubber.
10. rubber composition according to claim 9, wherein on the basis of the total weight of the liquid butadiene rubber,
The content of 1,4- structure is not less than 90 weight % in the liquid butadiene rubber.
11. rubber composition according to claim 1, wherein relative to the main rubber of 100 parts by weight, the liquid
The content of rubber is 4-10 parts by weight.
12. rubber composition according to claim 1, wherein relative to the main rubber of 100 parts by weight, the vulcanization
The content of agent is 1-3 parts by weight, and the content of the vulcanization accelerator is 1-5 parts by weight, and the content of the activator is 0.5-8 weight
Part is measured, the content of the reinforcing agent is 40-70 parts by weight.
13. rubber composition according to claim 1, wherein the rubber composition also contains anti-aging agent and/or anti-scorch
Agent.
14. rubber composition according to claim 13, wherein when the rubber composition also contains anti-aging agent, phase
For the main rubber of 100 parts by weight, the content of the anti-aging agent is 1-5 parts by weight；When the rubber composition also contain it is anti-
When burnt agent, relative to the main rubber of 100 parts by weight, the content of the antiscorching agent is 0.05-0.35 parts by weight.
15. a kind of preparation method of vulcanized rubber, this method includes by rubber group described in any one of claim 1-14
The each component closed in object is kneaded, and is obtained rubber compound, is then vulcanized the rubber compound.
16. according to the method for claim 15, wherein the condition of the vulcanization includes that curing temperature is 130-170 DEG C, sulphur
Change pressure is 10-15MPa, and vulcanization time is 10-50 minutes.
17. the vulcanized rubber that the method as described in claim 15 or 16 is prepared.
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| CN109388042B (en) * | 2017-08-02 | 2021-06-22 | 纳思达股份有限公司 | Conductive elastomer roller, method for producing same and use thereof |
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