CN104629126A - Rubber composition, vulcanized rubber and application of vulcanized rubber - Google Patents
Rubber composition, vulcanized rubber and application of vulcanized rubber Download PDFInfo
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Abstract
The invention discloses a rubber composition, vulcanized rubber and application of vulcanized rubber. The rubber composition contains dialkene rubber, white carbon black, a hollow microbead filler and a coupling agent. Specifically, the hollow microbead filler is hollow glass microbeads, and has body density of 2.0-3.0g/cm<3> and bulk density of 1.0-1.8g/cm<3>. The hollow microbead filler contains 55-65wt% of SiO2 and 15-25wt% of Al2O3, and has an average particle size of 2-10 micrometers. The mineral phase of the hollow microbead filler is an amorphous vitreous body. The rubber composition can effectively improve the dispersion of white carbon black in a rubber matrix, and reduces the aggregation of white carbon black filler particles, so that mixed rubber can have good processing performance, the energy consumption of mixing is low, and the dynamic mechanical properties of the vulcanized rubber are also good.
Description
Technical field
The present invention relates to the application of a kind of rubber combination and vulcanized rubber and vulcanized rubber.
Background technology
China's Ethylene Development is rapid in recent years, and the ethylene industry of China's fast development can provide the C of a large amount of isoprene containing
5cut resource, makes the ternary integrated rubber (SIBR) of a large amount of excellent property of production become possibility.Along with the minimizing day by day of fossil oil and raw material resources, automobile industry is also more and more urgent to the requirement that tire is energy-conservation, and produce white carbon black without fossil feedstock, the focus that above factor will make SIBR/ white carbon black novel green tire tread glue become research and development application, market potential is huge.
EP863182B1 discloses a kind of rubber combination being mainly used in tread rubber, it mainly consists of: with 100 parts by weight of rubber for benchmark: or the coupling agent coupling of silicon stanniferous containing 40-75phr and the ternary integrated rubber (SIBR) of isoprene end-blocking, SIBR contains the vinylbenzene segment of 1-20 % by weight, the isoprene segment of 12-40 % by weight, the random distribution 1 of 40-87 % by weight, 3-butadiene segment, Tg scope is at-60 DEG C to-85 DEG C; The filler of 45-150phr, comprises the white carbon black of 30-90phr and the carbon black of 2-60phr; Also containing silane coupling agent and other activators, vulcanizing agent, vulcanization accelerator etc. in described composition.
US5489627A discloses a kind of rubber combination being mainly used in tread rubber, it mainly consists of: with 100 parts by weight of rubber for benchmark: the epoxy natural rubber containing 1.0-15phr, the carboxy nitrile rubber of 1.0-15phr, other rubber of 98-70phr, comprise the mixture of one or more be selected from medium vinyl polybutadiene, styrene-butadiene rubber(SBR), polyisoprene rubber, trans-isoprene, cis-1,4-polybutadiene rubber, styrene isoprene rubber, ternary integrated rubber, paracril; White carbon black containing 10-50phr; Silane coupling agent containing 0.5-8.5phr and other auxiliary agents, wherein, described silane coupling agent be Si69 two-[γ-(triethoxysilicane) propyl group]-tetrasulfide, two-[γ-(trimethoxy silicon) propyl group]-tetrasulfide and Si69 grafting white carbon black.
In the rubber combination of prior art, filler is generally white carbon black and carbon black and use, and the coupling agent of employing is generally silane coupling agent.Due to the filler in the rubber combination of prior art, dispersion as white carbon black and carbon black is uneven, thus cause the intensity of the rubber unvulcanizate obtained by this rubber combination and processing characteristics not satisfactory, the mechanical mechanics property of the vulcanized rubber thus obtained by described rubber unvulcanizate is not satisfactory.
Summary of the invention
The object of the invention is the above-mentioned defect of the rubber combination overcoming prior art, and a kind of can the improve rubber combination and vulcanized rubber and preparation method thereof of the dispersiveness of filler white carbon black and the application of vulcanized rubber are provided, make the rubber unvulcanizate obtained by rubber combination have higher intensity and processing characteristics, what make vulcanized rubber has preferably mechanical property.
The invention provides a kind of rubber combination, this rubber combination contains dience rubber, white carbon black, cenosphere filler and coupling agent; Wherein, described cenosphere filler is hollow glass microbead, and the bulk density of described cenosphere filler is 2.0-3.0g/cm
3and tap density is 1.0-1.8g/cm
3, the SiO containing 55-65 % by weight of described cenosphere filler
2with the Al of 15-25 % by weight
2o
3, and median size is 2-10 μm, the mineral facies of described cenosphere filler are amorphous glass body.
The present inventor finds, solution polymerized butadiene styrene rubber (or ternary integrated rubber)/white carbon black composite material is one of preferred material becoming following novel green tire tread glue with the wet-sliding resistant performance of its excellence and wear resisting property, but, due to white carbon black easy self aggregation and have impact on the performance of white carbon black filler in the effect of rubber MR medium reinforcing in the material, sizing material heat-dissipating also may be made to aggravate simultaneously.And rubber combination provided by the invention contains cenosphere filler, significantly can improve the dispersion of white carbon black in rubber matrix, thus improve intensity and the processing characteristics of the rubber unvulcanizate obtained, and the mechanical mechanics property of vulcanized rubber.
Present invention also offers the vulcanized rubber obtained in vulcanizing agent through mixing and sulfuration by rubber combination provided by the invention.
The vulcanized rubber adopting rubber combination provided by the invention to prepare has good mechanical mechanics property, and the rolling resistance of the tread rubber material made, wear resistance and wet-sliding resistant performance have good balance.
Present invention also offers vulcanized rubber provided by the invention and prepare the application in tire or tyre element.
In rubber combination provided by the invention, under preferable case, described dience rubber is ternary integrated rubber and/or solution polymerized butadiene styrene rubber, and filler is white carbon black and cenosphere filler, coupling agent is silane coupling agent, can improve the processing characteristics of rubber further; More preferably, in situation, also containing activator in described rubber combination, be preferably zinc oxide and stearic acid, described activator can significantly improve sulphidity and the thermotolerance of described rubber.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the speed versus time graph of rubber unvulcanizate H4 and DH1 when the process of Haake rheometer;
Fig. 2 is storage shear modulus-strain sweep curve that rubber unvulcanizate H4 and DH1 measures through rubber machining analyzer RPA;
Fig. 3 is loss shear modulus-strain sweep curve that rubber unvulcanizate H4 and DH1 measures through rubber machining analyzer RPA;
Fig. 4 is storage shear modulus-strain sweep curve that cross-linked rubber S4 and DS1 measures through rubber machining analyzer RPA;
Fig. 5 is the frequency sweeping curve of cross-linked rubber S4 and DS1 when rubber machining analyzer RP measures strain 2.51%;
Fig. 6 is the frequency sweeping curve of cross-linked rubber S45 and DS1 when rubber machining analyzer RPA measures strain 10.04%.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of rubber combination, this rubber combination contains dience rubber, white carbon black, cenosphere filler and coupling agent; Wherein, described cenosphere filler is hollow glass microbead, and the bulk density of described cenosphere filler is 2.0-3.0g/cm
3and tap density is 1.0-1.8g/cm
3, the SiO containing 55-65 % by weight of described cenosphere filler
2with the Al of 15-25 % by weight
2o
3, and median size is 2-10 μm, the mineral facies of described cenosphere filler are amorphous glass body.Preferably, the median size of described cenosphere filler is 2-4 μm.More preferably described tiny balloon filler is the manosil AS class inorganic powder material taken out by volcanic ash or coal ash lifting.
The filler of cenosphere described in the present invention can be that 325-5000 object hollow glass microbead is commercially available with specification.
In the present invention, described rubber combination contains cenosphere filler can reduce compound viscosity, improves processing characteristics, significantly reduces the mixing energy of sizing material, improves the physical and mechanical properties of cross-linked rubber.This may be because described cenosphere filler is dispersed in elastomer matrix with the form of the ultimate particle of microballoon shape, and the surface group of described cenosphere filler is inertia group, not easily produce physics and chemical action with rubber matrix or other filler, reduce the internal friction of rubber and the interaction between filler and filler.
According to the present invention, add described cenosphere filler and contribute to the intensity of rubber unvulcanizate that described rubber combination provided by the invention obtains and the raising of processing characteristics, and the raising of the dynamic mechanical properties of the vulcanized rubber obtained, the selectable range of the content range of each component of rubber combination described in the present invention is wider, but, in order to obtain the more excellent rubber combination of over-all properties, under preferable case, with the dience rubber of 100 weight parts for benchmark, the content of described cenosphere filler is 25-70 weight part, the content of described white carbon black is 20-45 weight part, the content of described coupling agent is 1.6-5.6 weight part, preferably, the content of described cenosphere filler is 25-35 weight part.
In the present invention, containing described cenosphere filler in described rubber combination, there is not active group comparatively stable (torpescence) in described cenosphere filling surface, but there is hydroxyl or free protons, this composition can with the polar group bonding of coupling agent, and coupling agent in cenosphere filler-coupling agent complex body after bonding can as non-polar group, crosslinked with rubber molecule or be wound around preferably, thus have better enhancement to rubber.
According to the present invention, described white carbon black can be the existing various white carbon black that can improve described rubber combination intensity, and it can be commercially available, and such as, can be the white carbon black of Z1165MP for the trade mark purchased from Qingdao Rhodia.
The present inventor finds, namely when described cenosphere filler and white carbon black of the present invention with weight ratio be 0.56-3.5:1 ratio with the use of time, processing characteristics and the use properties of the rubber obtained can be improved further.
According to the present invention, described dience rubber can be the dience rubber of various routine, and under preferable case, the weight-average molecular weight of described dience rubber is 150,000-80 ten thousand and molecular weight distribution is 1.0-5.0, and mooney viscosity is 45-60.It should be noted that, in the present invention, the mooney viscosity of described rubber all can measure according to method disclosed in GB/T1232.1-2000 and obtain, and wherein, warm up time is 1min, and rotation time is 4min, and test temperature is 100 DEG C.Described weight-average molecular weight can, according to gel permeation chromatography (GPC) method, use Waters company GPC515-2410 system type gel permeation chromatograph to measure.
According to the present invention, under preferable case, described dience rubber can contain solution polymerized butadiene styrene rubber and/or ternary integrated rubber.Preferably, in described solution polymerized butadiene styrene rubber, the content of vinylbenzene segment is 10-40 % by weight, and with the gross weight of the butadiene segment in described solution polymerized butadiene styrene rubber for benchmark, contents of ethylene is 10-50 % by weight, and described vinylbenzene segment is random arrangement or forms block; In described ternary integrated rubber, vinylbenzene segment content is 10-30 % by weight, and butadiene segment content is 40-45 % by weight, and isoprene segment content is 25-50 % by weight; And the arrangement of described vinylbenzene segment can be random arrangement or form block.
According to the present invention, under preferable case, described dience rubber is also containing extending oil, and with the dience rubber of 100 weight parts for benchmark, the content of described extending oil is 0.5-40 weight part.
According to the present invention, the functional group that described coupling agent has alkoxy grp and can react with organism, can make do not have the inorganics of consistency and organism combine and improve the interface cohesion of filler and rubber further, and improve the dispersiveness of filler; In addition, described coupling agent add the dynamic properties that can also improve described vulcanization of rubber glue.Under preferable case, described coupling agent for having the silane coupling agent of the structure shown in formula (I),
In formula (I), R can be vinyl, epoxy group(ing), amino, methacryloxy, sulfydryl or 3-propionyl sulfo--1-propyl group; X1, X2 and X3 are identical or different, are the functional group that can be hydrolyzed, and preferred X1, X2 and X3 are methoxyl group, oxyethyl group or chlorine independently of one another.Further preferably, described coupling agent is selected from least one in two-[γ-(triethoxysilicane) propyl group]-tetrasulfide, two (triethoxy propyl silane) disulphide and 3-propionyl sulfo--1-propyl-trimethoxysilane.
According to the present invention, under preferable case, described rubber combination is also containing activator.Described activator refers to the activity that can increase vulcanization accelerator, and then reduces the consumption of described vulcanization accelerator or shorten the material of curing time.Add sulphidity and thermotolerance that promoting agent can significantly improve described rubber.In the present invention, described activator can be existing various activator, such as, can be zinc oxide and/or stearic acid.With the dience rubber of 100 weight parts for benchmark, the content of described activator is 2-5 weight part, and preferably, described activator is zinc oxide and stearic acid, and described zinc oxide content is 2-4 weight part, and described stearic acid content is 1-3 weight part.
The present invention also provides the vulcanized rubber obtained through mixing and sulfuration by rubber combination provided by the invention and vulcanizing agent.
According to the present invention, described vulcanizing agent ensures that rubber combination tight cure is vulcanized rubber, and under preferable case, with the dience rubber of 100 weight parts in described rubber combination for benchmark, the consumption of described vulcanizing agent is 1.0-1.5 weight part.
According to the present invention, described vulcanizing agent can be the vulcanizing agent of various routine, such as, can be at least one in insoluble sulfur, dithio morpholine and four sulfuration two morpholines, is preferably insoluble sulfur.Described insoluble sulfur is the allotropic substance of sulphur, and it is insoluble to sulfurous gas and other solvent, is also insoluble to rubber, exists in rubber with dispersion state; After reaching curing temperature, these insoluble sulfurs be dispersed in rubber have one " activation stage ", i.e. chain type unzipping makes vulcanization rate accelerate, and reduce sulfur consumption, are conducive to the aging resistance improving rubber.
According to the present invention, under preferable case, described vulcanized rubber is also containing process oil, anti-aging agent and vulcanization accelerator; The content of described process oil is 8-12 weight part, and the content of described vulcanization accelerator is 2.00-3.00 weight part, and the content of described anti-aging agent is 1.3-2.2 weight part.
According to the present invention, the kind of described anti-aging agent is known to the skilled person.Anti-aging agent is divided into two kinds, physical antioxidant and chemical antiager.Physical antioxidant is mainly paraffin, and its main component is saturated straight chain alkane.And chemical antiager can be selected from 2,2,4-trimethylammonium-1, one or more in 2-dihyaroquinoline polymer, N-(1,3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine (commodity be called: antioxidant 4020), N-cumyl-N '-diphenyl-para-phenylene diamine (commodity are called: antioxidant 4010NA) and N-phenyl-2-naphthylamine (commodity are by name: antioxidant D).It should be noted that, 2,2,4-trimethylammonium-1,2-dihyaroquinoline polymers of the present invention refer to the dimer of 2,2,4-trimethylammonium-1,2-dihyaroquinoline, tripolymer or the tetramer (that is, n=2,3 or 4); And due to the dimeric anti-old performance of described 2,2,4-trimethylammonium-1,2-dihyaroquinolines very excellent, therefore, described 2,2,4-trimethylammonium-1,2-dihyaroquinoline polymers are preferably dimer, or dimer and tripolymer and/or tetrameric mixture.More preferably, when described 2,2,4-trimethylammonium-1,2-dihyaroquinoline dimer be dimer and tripolymer and/or tetrameric mixture time, with the gross weight of described mixture for benchmark, described dimeric content is 25-55 % by weight, and described dimer and trimerical total content are 45-75 % by weight.
According to the present invention, described vulcanization accelerator can be the existing various curing time that can shorten, reduce curing temperature, reduce vulcanizing agent consumption and improve the material of the physical and mechanical properties of rubber, such as, the N-tertiary butyl-2-[4-morpholinodithio base sulphenamide (commodity are called accelerator TBBS or NS) can be selected from, 2, 2 '-dibenzothiazyl disulfide (commodity are called: altax), the N-tertiary butyl-bis-(2-[4-morpholinodithio) sulfenamide (commodity are called: accelerator TBSI), (commodity are called N-cyclohexyl-bis-(2-mercaptobenzothiazole) sulphenamide: accelerant C BBS), at least one in N-cyclohexyl-2-[4-morpholinodithio base sulphenamide (commodity be called: accelerant CZ) and vulkacit D (commodity are by name: vulkacit D).
According to the present invention, described process oil refers to the petroleum oil product be added to when mixing in rubber for improving sizing material processing characteristics.In the present invention, described process oil can be existing various process oil, and under preferable case, described process oil can be aromatic hydrocarbon oil and/or naphthenic oil; Preferably, described process oil is aromatic hydrocarbon oil, and with the dience rubber of 100 weight parts in described rubber combination for benchmark, described aromatic hydrocarbon oil content is 9-11 weight part.
According to the present invention, described mixing method and condition are can be the compounding process of various routine and condition, as a rule, describedly mixingly can to carry out in mill or Banbury mixer.Wherein, mixing between each material can be carried out simultaneously, also can proceed step by step, is preferably proceed step by step.In addition, more even in order to enable each material be mixed to get, to obtain the more excellent rubber of performance, under preferable case, described mixing temperature is 30-150 DEG C, and mixing pressure is 0-0.8MPa, and the mixing time is 10-40 minute.
According to the present invention, as a rule, the method for sulfuration will be carried out through the above-mentioned mixing rubber unvulcanizate obtained and condition is conventionally known to one of skill in the art.Such as, described sulfuration can be carried out in vulcanization bed or vulcanizing press; Described cure conditions generally includes the temperature of sulfuration, pressure and time, wherein, as long as the temperature of described sulfuration, pressure and time can ensure described dience rubber and vulcanizing agent generation crosslinking reaction, such as, the temperature of described sulfuration can be 140-160 DEG C, the pressure of sulfuration can be 3.5-7MPa, and the time of sulfuration can be 0.15-1 hour.
In addition, present invention also offers and preparing the application in tire or tyre element by vulcanized rubber provided by the invention.Wherein, described tyre element can be the tread rubber of tire.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
In the present invention, the pressure related to all represents with gauge pressure.
To be further described in detail the present invention by specific embodiment below.
In embodiment and comparative example:
The solution polymerized butadiene styrene rubber trade mark: SSBR2305, Sinopec Yanshan Petrochemical synthetic rubber plant's industrialization finished product, weight-average molecular weight is 450,000 and molecular weight distribution is 1.5, and mooney viscosity is 58; Wherein the content of vinylbenzene segment is 25 % by weight, and contents of ethylene is 26 % by weight, and vinylbenzene segment is random arrangement;
The ternary integrated rubber trade mark is: SIBR2505, and Yanshan Mountain branch office of China Petrochemical Corp. produces, and weight-average molecular weight is 500,000 and molecular weight distribution is 1.9, and mooney viscosity is 55 ± 5; Wherein the content of vinylbenzene segment is 21.0 % by weight, and the content of butadiene segment is 41.8 % by weight, and the content of isoprene segment is 37.2 % by weight, and vinylbenzene segment is block arrangement;
White carbon black: purchased from Qingdao Rhodia, the trade mark is Z1165MP;
Anti-aging agent: purchased from Jiangsu Sheng'Ao Chemical Technology Co., Ltd, the trade mark is 4010NA;
Sulphur: contain Science and Technology Ltd. purchased from Jinchang, Guangzhou, S-80;
Accelerator CZ: purchased from Huangyan, Zhejiang chemical plant;
Accelerator D: purchased from Huangyan, Zhejiang chemical plant;
Activator: purchased from Liuzhou Xin Pin company limited;
Activator stearic acid: purchased from the polite Chemical Co., Ltd. in Hong Kong, the trade mark is SA1801;
Silane coupling agent: two-[γ-(triethoxysilicane) propyl group]-tetrasulfide: purchased from Nanjing dawn factory, the trade mark is Si69;
Cenosphere filler: purchased from Anji, Beijing Li An electronic engineering Technology Co., Ltd., the chemical composition of microballon and significant parameter are in table 1.
Table 1
Embodiment 1-5
Embodiment 1-5 is for illustration of the preparation of rubber unvulcanizate provided by the invention.
Each component of the embodiment 1-5 shown in table 2 is placed in mill, and roller temperature be 70 ± 5 DEG C, roller speed is 24 ± 1 revs/min, mix under the condition of roller speed ratio 1:1.4, obtain rubber unvulcanizate H1-H5.
Comparative example 1-4
This comparative example 1-4 is for illustration of the preparation of reference rubber unvulcanizate.
Rubber unvulcanizate is prepared according to the method for embodiment 1-5, unlike, by each component of the embodiment 1-5 shown in each component substitution tables 2 of the comparative example 1-4 shown in table 2, it is mixing to be placed in mill,
Obtain rubber unvulcanizate DH1-DH4.
Embodiment 6-10
Embodiment 6-10 is for illustration of the preparation of vulcanized rubber provided by the invention.
150 DEG C, under 5MPa, rubber unvulcanizate H1-H5 is carried out sulfidizing t90 at vulcanizing press (purchased from Shanghai first rubber machinery plant), and described t90 refers to that sizing material reaches the time of plateau cure; Obtain vulcanized rubber S1-S5.
Comparative example 5-8
This comparative example 5-8 is for illustration of the preparation of reference vulcanized rubber.
Vulcanized rubber is prepared according to the method for embodiment 6-10, unlike, substitute H1-H5 with DH1-DH4 respectively, obtain vulcanized rubber DS1-DS4.
Test case 1-5
Test case 1-5 is for illustration of the test of the performance of rubber unvulcanizate provided by the invention.
Carry out following performance test to H1-H5, acquired results is as shown in table 3.
(1) sign of rubber unvulcanizate heat treatment process and processing characteristics
Process rubber unvulcanizate with Haake (HAKKE) rheometer (Thermo Electron Corporation product), and study rubber unvulcanizate heat and shear field effect under moment and temperature variation, in order to characterize the processing characteristics of rubber unvulcanizate.
(2) dispersing property of filler and the sign of cross-linked rubber dynamic properties in rubber unvulcanizate
Adopt the test of RPA2000 rubber machining analyzer (U.S. alpha Products) strain sweep, condition is: temperature 100 DEG C, frequency 1Hz.
(3) vulcanization characteristics of rubber unvulcanizate
Adopt testing without the curability of rotor vulkameter to rubber unvulcanizate purchased from Taiwan height Inland Steel, test condition is: oscillation angle is 1 °, and frequency is 1.7Hz, and temperature is 150 DEG C.Acquired results is as shown in table 3, and wherein, ts1 represents the sulfuration security of rubber unvulcanizate, and t90 represents the sulfurizing time of rubber unvulcanizate.
Contrast test example 1-4
According to the performance of the method test DH1-DH4 of test case 1-5.Acquired results is as shown in table 3.
Test case 5-10
Test case 5-10 is for illustration of the test of vulcanized rubber performance provided by the invention.
Carry out following performance test to S1-S5, acquired results is as shown in table 4.
(1) tensile property of vulcanized rubber:
Rubber unvulcanizate H1-H5 rubber mixing mill (purchased from Shanghai Shuan Yi rubber and plastics machine factory, model is X (S) K-160) is made the thick mixed sheet of about 2mm; Then vulcanizing press (purchased from Shanghai first rubber machinery plant, model is XLB-400 × 400 × 2) is used to make the thick vulcanized rubber sheet of 2mm; Then according to the I type dumbbell shaped cut-off knife specified in GB/T528-1998, the vulcanized rubber sheet obtained is cut into dumbbell shaped standard film, (Japanese Shimadzu Corporation produces to adopt rubber puller system, model is AG-20KNG) carry out the test that described vulcanized rubber sheet carries out tensile property, it is 25 DEG C at probe temperature, pulling speed is under the condition of 500 mm/min, measures the stress at definite elongation of sample, tensile strength and elongation at break.
(2) tear resistance of vulcanized rubber:
Rubber unvulcanizate H1-H5 rubber mixing mill (purchased from Shanghai Shuan Yi rubber and plastics machine factory, model is X (S) K-160) is made the thick mixed sheet of 2mm; Then vulcanizing press (purchased from Shanghai first rubber machinery plant, model is XLB-400 × 400 × 2) is used to make the thick vulcanized rubber sheet of 2mm; And according to the square cut-off knife specified in GB/T529-1999, the vulcanized rubber sheet obtained is cut into square standard tearing sheet, (Japanese Shimadzu Corporation produces to adopt rubber puller system, model is AG-20KNG) carry out the test that described vulcanized rubber sheet carries out tear resistance, wherein, probe temperature is 25 DEG C, and pulling speed is 500 mm/min.
(3) dynamic properties of vulcanized rubber:
Adopt RPA2000 rubber machining analyzer (U.S. alpha Products) strain sweep and frequency sweeping test, test process is divided into two stages: 1) rubber unvulcanizate is in the sulfidation of RPA die cavity, cure conditions: 150 DEG C × t90, wherein t90 is sulfurizing time, and concrete numerical value is in table 3; 2), after sulfuration completes, generate strain sweep or the frequency sweeping of cross-linked rubber, strain sweep condition is: temperature 60 C, frequency 10Hz; Frequency sweeping condition is: temperature is 60 DEG C, and strain is set as 2.51% and 10.04% two kind.
(4) compression of vulcanized rubber deflects performance:
Temperature rise is subdued in the compression adopting Y3000E type compression heat generation trier (Beijing You Chen Electron equipment Co., Ltd product) to measure cross-linked rubber.
Contrast test example 5-8
Contrast test example 5-8 is for illustration of the test of reference vulcanized rubber performance.
According to the performance of the method test DS1-DS4 of test case 5-10.Acquired results is as shown in table 4.
Table 2
Note: above-mentioned numerical value is all with parts by weight.
Table 2
* note: mm:ss represents minute: second, as 8:46 in embodiment 1 represents 8 minutes 46 seconds.
Table 3
As can be seen from Table 3, be the rubber unvulcanizate of SSBR for basic glue, compared to the increase of white carbon black consumption, adding of glass microballon, do not make the mooney viscosity of rubber unvulcanizate increase a lot; And for rubber unvulcanizate H2 and DH3 of basis comparatively SIBR, Mooney Viscosity of Rubber Mix comparatively SSBR is low, this mainly contains two reasons, on the one hand, isoprene containing segment in SIBR, degrades time mixing, on the other hand, the lubrication of glass microballon, these two factors all make the processing characteristics of rubber unvulcanizate improve; In identical white carbon black number situation, ts1 and the t90 numerical value of rubber unvulcanizate is very close, illustrates that the vulcanization characteristics impact of glass microballon on rubber unvulcanizate is also very little.
As can be seen from Table 4, in identical white carbon black number situation, every mechanical property of cross-linked rubber is very close, in the sizing material adding more glass microballon, the performance of cross-linked rubber also slightly improves, illustrate glass microballon add can not reduce cross-linked rubber stretching, tear, the performance such as heat-dissipating, in certain amount ranges, slightly can increase the performance of cross-linked rubber.
Carry out in shearing and heat treated process with Haake torque rheometer to sizing material, melting temperature must be controlled, too low coupling agent and filling surface radical reaction speed lower and not exclusively, too high, easily cause sizing material incipient scorch (coupling agent contains sulphur, also can play the effect of vulcanizing agent) and rubber molecule to degrade.Therefore, if sizing material heat-dissipating is higher, cause sizing material temperature to raise, must mixing rotor speed be reduced; Otherwise, if sizing material temperature is lower, can rotating speed be improved.As can be seen from Figure 1, under identical processing temperature (150 DEG C), the sizing material H4 of hollow glass bead filler is added, its rotor speed is higher than DH1 rotating speed, when embodiment rubber compounding is described, heat-dissipating is lower, and embodiment rubber unvulcanizate has good processing characteristics, and rubber compounding energy is lower.
The effect that in filled rubber, dynamic viscoelastic depends on amplitude is called Payne effect, and dispersion and the filler-rubber interactions of this effect and filler are closely related.In the strain-storage shear modulus scanning curve of the strain-storage shear modulus scanning curve of Fig. 2 rubber unvulcanizate, the strain-loss shear modulus scanning curve of Fig. 3 rubber unvulcanizate and Fig. 4 cross-linked rubber, storage shear modulus G ' under small strain can characterize the power of Payne effect with the difference Δ G ' of the G ' under large sstrain, and namely the dispersion of the less explanation filler of Δ G ' in rubber matrix is better.As can be seen from Fig. 2, Fig. 3 and Fig. 4, the Δ G ' of H4 and S4 is all less than the Δ G ' of DH1, DS1, illustrates that adding of glass microballon improves the dispersion of filler in mixing rubber and cross-linked rubber matrix.
Fig. 5 and Fig. 6 is compared with small strain and the frequency sweeping compared with the cross-linked rubber under large sstrain, study of tire can be used in the process of moving, the change of loading material of rubber network: different strains represents the difference of vehicle loading weight, different frequencies then represents the different running velocity of vehicle, and dissipation factor Tan δ can represent the energy waste situation of sizing material.As can be seen from Fig. 5 and Fig. 6, under small strain (2.51%), the Tan δ of S4 is lower than the Tan δ of DS1; And under large sstrain (10.04%), the Tan δ of S4, also lower than the Tan δ of DS1, illustrates adding of glass microballon, in very large strain and range of frequency, alleviates the dynamic mechanical loss of cross-linked rubber.
Claims (13)
1. a rubber combination, this rubber combination contains dience rubber, white carbon black, cenosphere filler and coupling agent; Wherein, described cenosphere filler is hollow glass microbead, and the bulk density of described cenosphere filler is 2.0-3.0g/cm
3and tap density is 1.0-1.8g/cm
3, described cenosphere filler contains the SiO of 55-65 % by weight
2with the Al of 15-25 % by weight
2o
3, and median size is 2-10 μm, the mineral facies of described cenosphere filler are amorphous glass body.
2. rubber combination according to claim 1, wherein, the median size of described cenosphere filler is 2-4 μm.
3. rubber combination according to claim 1 and 2, wherein, described cenosphere filler is the manosil AS class inorganic powder material taken out by volcanic ash or coal ash lifting.
4. rubber combination according to claim 1, wherein, with the dience rubber of 100 weight parts for benchmark, the content of described cenosphere filler is 25-70 weight part, the content of described white carbon black is 20-45 weight part, and described coupling agent is 1.6-5.6 weight part; Preferably, the content of described cenosphere filler is 25-35 weight part.
5. according to the rubber combination in claim 1-4 described in any one, wherein, described coupling agent for having the silane coupling agent of the structure shown in formula (I),
In formula (I), R is vinyl, epoxy group(ing), amino, methacryloxy, sulfydryl or 3-propionyl sulfo--1-propyl group; X1, X2 and X3 are identical or different, are methoxyl group, oxyethyl group or chlorine independently of one another; Preferably, described coupling agent is selected from least one in two-[γ-(triethoxysilicane) propyl group]-tetrasulfide, two (triethoxy propyl silane) disulphide and 3-propionyl sulfo--1-propyl-trimethoxysilane.
6. rubber combination according to claim 1, wherein, described dience rubber contains solution polymerized butadiene styrene rubber and/or ternary integrated rubber; The weight-average molecular weight of dience rubber is 150,000-80 ten thousand and molecular weight distribution is 1.0-5.0, and mooney viscosity is 45-60.
7. rubber combination according to claim 6, wherein, in described solution polymerized butadiene styrene rubber, with the gross weight of described solution polymerized butadiene styrene rubber for benchmark, the content of vinylbenzene segment is 10-40 % by weight, and with the gross weight of the butadiene segment in described solution polymerized butadiene styrene rubber for benchmark, contents of ethylene is 10-50 % by weight, described vinylbenzene segment is random arrangement or forms block; In described ternary integrated rubber, with the gross weight of described ternary integrated rubber for benchmark, the content of vinylbenzene segment is 10-30 % by weight, the content of butadiene segment is 40-45 % by weight, the content of isoprene segment is 25-50 % by weight, and described vinylbenzene segment is random arrangement or forms block.
8. the rubber combination according to claim 6 or 7, wherein, described dience rubber is also containing extending oil, and with the dience rubber of 100 weight parts for benchmark, the content of described extending oil is 0.5-40 weight part.
9. rubber combination according to claim 1, wherein, described rubber combination is also containing activator, and described activator is zinc oxide and/or stearic acid, and with the dience rubber of 100 weight parts for benchmark, the content of described activator is 3-7 weight part; Preferably, described activator is zinc oxide and stearic acid, and with the dience rubber of 100 weight parts for benchmark, the content of zinc oxide is 2-4 weight part, and stearic content is 1-3 weight part.
10. the vulcanized rubber obtained through mixing and sulfuration by the rubber combination in claim 1-9 described in any one and vulcanizing agent.
11. vulcanized rubbers according to claim 10, wherein, with the dience rubber of 100 weight parts in described rubber combination for benchmark, the consumption of described vulcanizing agent is 1.0-1.5 weight part; Described vulcanizing agent is selected from least one in insoluble sulfur, dithio morpholine and four sulfuration two morpholines.
12. vulcanized rubbers according to claim 10 or 11, wherein, described vulcanized rubber is also containing process oil, anti-aging agent and vulcanization accelerator; With the dience rubber of 100 weight parts in described rubber combination for benchmark, the content of described process oil is 8-12 weight part, and the content of described vulcanization accelerator is 2.00-3.00 weight part, and the content of described anti-aging agent is 1.3-2.2 weight part; Described anti-aging agent is selected from least one in 2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer, N-(1,3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine, N-cumyl-N '-diphenyl-para-phenylene diamine and N-phenyl-2-naphthylamine; Described vulcanization accelerator is selected from the N-tertiary butyl-2-[4-morpholinodithio base sulphenamide, 2, at least one in 2 '-dibenzothiazyl disulfide, the N-tertiary butyl-bis-(2-[4-morpholinodithio) sulfenamide, N-cyclohexyl-2-[4-morpholinodithio base sulphenamide, N-cyclohexyl-2-[4-morpholinodithio base sulphenamide and vulkacit D; Described process oil is aromatic hydrocarbon oil and/or naphthenic oil; Preferably, described process oil is aromatic hydrocarbon oil, and with the dience rubber of 100 weight parts in described rubber combination for benchmark, the content of described aromatic hydrocarbon oil is 9-11 weight part.
The application in tire or tyre element prepared by vulcanized rubber in 13. claim 10-12 described in any one.
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| CN107141538A (en) * | 2017-07-11 | 2017-09-08 | 合肥康之恒机械科技有限公司 | A kind of wear-resisting tread rubber of bull dozer tire and preparation method thereof |
| CN109929149A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | For the rubber composition on tire sidewall and vulcanized rubber and its preparation method and application |
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| CN117844129A (en) * | 2024-01-08 | 2024-04-09 | 仙桃市聚兴橡胶有限公司 | Low-Mooney-viscosity butyl regenerated rubber and preparation method thereof |
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| CN107144502B (en) * | 2017-06-29 | 2019-12-20 | 中策橡胶集团有限公司 | Characterization method of dispersibility of white carbon black in sizing material |
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| CN109929149A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | For the rubber composition on tire sidewall and vulcanized rubber and its preparation method and application |
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| CN117844129A (en) * | 2024-01-08 | 2024-04-09 | 仙桃市聚兴橡胶有限公司 | Low-Mooney-viscosity butyl regenerated rubber and preparation method thereof |
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