CN103788432B - The application of rubber combination and vulcanized rubber and preparation method thereof and vulcanized rubber - Google Patents
The application of rubber combination and vulcanized rubber and preparation method thereof and vulcanized rubber Download PDFInfo
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Abstract
The invention discloses the application of a kind of rubber combination and vulcanized rubber and preparation method thereof and vulcanized rubber.Described rubber combination contains dience rubber, white carbon black, coupling agent, anti-aging agent, vulcanizing agent and vulcanization accelerator, it is characterized in that, described coupling agent contains oligopolymer coupling agent, containing there is the group of condensation reaction with Si-OH in described oligopolymer coupling agent molecule structure, the number-average molecular weight of described oligopolymer coupling agent is 2000-5000.The present invention can improve the dispersion of white carbon black in rubber matrix effectively, improves filler-rubber interface and combines, thus makes that strength is high, good processability, and the mechanical mechanics property of cross-linked rubber is also very good.
Description
Technical field
The present invention relates to the application of a kind of rubber combination and vulcanized rubber and preparation method thereof 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, described rubber combination contains dience rubber, white carbon black, coupling agent, anti-aging agent, vulcanizing agent and vulcanization accelerator, wherein, described coupling agent contains oligopolymer coupling agent, containing there is the group of condensation reaction with Si-OH in described oligopolymer coupling agent molecule structure, the number-average molecular weight of described oligopolymer coupling agent is 2000-5000.
The present inventor finds, ternary integrated rubber/white carbon black composite material becomes one of preferred material of novel green tire tread glue in the future 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 containing described oligopolymer coupling agent in the coupling agent of rubber combination provided by the invention, significantly can improve the dispersion of white carbon black in rubber matrix, improve the interface cohesion of filler-rubber, thus improve intensity and the processing characteristics of the rubber unvulcanizate obtained, and the mechanical mechanics property of vulcanized rubber.
Another object of the present invention is to provide a kind of preparation method of vulcanized rubber, and the method comprises and being mixed by rubber combination of the present invention, obtains rubber unvulcanizate, and by described rubber unvulcanizate sulfuration, obtains vulcanized rubber.
Another object of the present invention is to provide a kind of vulcanized rubber obtained by preparation method of the present 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.
Another object of the present invention is to provide a kind of tire adopting vulcanized rubber of the present invention to prepare.
In rubber combination provided by the invention, under preferable case, described dience rubber is ternary integrated rubber and/or solution polymerized butadiene styrene rubber, filler is all white carbon black, coupling agent contains described oligopolymer coupling agent, or in certain proportion with the silane coupling agents such as the Si69 of routine with the use of time, the processing characteristics of rubber can be improved 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; Again under preferable case, also containing the dispersion to promote filler further such as dispersion agent in described rubber combination, to improve processing characteristics and the use properties of rubber further.
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 frequency sweeping curve of the rubber unvulcanizate H1-H5 obtained by method of the present invention;
Fig. 2 is the stress strain curve of the rubber unvulcanizate H1-H5 obtained by method of the present invention;
Fig. 3 is the equilibrium relationship figure of the wet-sliding resistant performance of the vulcanized rubber S1-S5 obtained by method of the present invention, wear resistance, rolling resistance;
Fig. 4 is the infrared spectra spectrogram of the oligopolymer coupling agent Ci800 that the present invention adopts.
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.
According to the present invention, described rubber combination contains dience rubber, white carbon black, coupling agent, anti-aging agent, vulcanizing agent and vulcanization accelerator, wherein, described coupling agent contains oligopolymer coupling agent, containing with Si-OH, the group of condensation reaction occurring in described oligopolymer coupling agent molecule structure, the number-average molecular weight of described oligopolymer coupling agent is 2000-5000, is preferably 3000-4000.
In rubber plastic processing, the key problem in technology that two kinds of inconsistent materials are combined into one is the surface treatment of material, and to apply maximum be at present coupling agent activation.Because organic segment of conventional coupling agents is shorter, little with matrix effect, limited to the improvement of the raising of material mechanical performance, product properties.Therefore, people wish the coupling agent that can adopt a kind of novel texture, except keeping the amphiphilic structure of traditional coupling agent, can also be wound around with stronger bonding force and base resin, bonding, association or the physical action of other form occurs.
According to the present invention, described oligopolymer coupling agent can strengthen the interface interaction power between dience rubber and white carbon black, improves the consistency of white carbon black in dience rubber; That is, can reach and significantly improve the dispersion of white carbon black in rubber matrix, improve the effect of the interface cohesion of filler-rubber.Because the molecular weight ratio of described oligopolymer coupling agent is larger, and be by adding polar group in nonpolar segment, copolymerization forms amphipathic (oleophylic, hydrophilic) material, such structures shape it there is excellent coupled action, by means of intermolecular linkage force, impel two kinds of inconsistent materials to be combined in one, and then obtain stable blend.
Such as can at least one functional group in carboxyl (-COOH), hydroxyl (-OH), ester group (-COO-), anhydride group (-O-CO-O-) and aldehyde radical (-CO-) containing the group that with Si-OH condensation reaction can occur in described oligopolymer coupling agent molecule structure, the end group of described oligopolymer coupling agent molecule can be carboxyl, hydroxyl, ester group, anhydride group or aldehyde radical, and/or containing at least one functional group be selected from carboxyl, hydroxyl, ester group, anhydride group and aldehyde radical in molecule segment.According to the present invention, as long as goal of the invention of the present invention can be reached containing the group that with Si-OH condensation reaction can occur in described oligopolymer coupling agent molecule structure, but in order to realize goal of the invention of the present invention better, under preferable case, with 1mol oligopolymer coupling agent molecule for benchmark, the group that with Si-OH condensation reaction can occur contained in described oligopolymer coupling agent molecule structure is at least 1mol.
Due in the end group of described oligopolymer coupling agent molecule and/or molecule segment containing a certain amount of polar functional group, to filler, pigment, polar resin, the wetting action of non-polar resin tool, thus facilitate the dispersed of inorganic particulate, the combination between inorganic particulate and polymkeric substance can be improved, there is excellent coupling, splendid dissemination, also there is inside and outside portion lubricating property simultaneously.
According to the present invention, more preferably in situation, described oligopolymer coupling agent contains by divinyl 1, the structural unit that 2-polymerization is formed, by divinyl 1, the structural unit that 4-polymerization is formed and the structural unit formed by maleic anhydride, be polymerized the structural unit formed and be at least more than 1:1 with the mol ratio of the structural unit formed by maleic anhydride by divinyl 1,2-; By divinyl 1, the structural unit that 4-polymerization is formed is at least more than 4:1 with the mol ratio of the structural unit formed by maleic anhydride, further preferably, in order to suitably improve the mechanical property of rubber, described oligopolymer coupling agent also contains by monovinylarene, as vinylbenzene, the structural unit of formation, the structural unit formed by single vinyl aromatics is 0.1-1:1 with the mol ratio of the structural unit formed by maleic anhydride.Wherein, the described structural unit formed by maleic anhydride has following structure:
Described oligopolymer coupling agent can for be obtained by divinyl and maleic anhydride, is preferably by divinyl, maleic anhydride and styrene copolymerizedly obtains, and also above-mentioned polymer water solution can be obtained above-mentionedly with Si-OH, the group of condensation reaction can occurring.Specifically, the polybutadiene oligomer coupling agent of described oligopolymer coupling agent to be the trade mark be Ci800.
According to the present invention, as long as goal of the invention of the present invention can be realized containing described oligopolymer coupling agent in described rubber combination, in order to realize goal of the invention of the present invention better, under preferable case, the content of described oligopolymer coupling agent is the 25-100 % by weight of coupling agent total mass, more preferably 25-50 % by weight.
According to the present invention, described coupling agent can be all above-mentioned oligopolymer coupling agent.Described silane coupling agent has and the alkoxyl group of the hydroxyl reaction being present in mineral surfaces and the functional group can reacted with organism, therefore, 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 silane coupling agent add the dynamic properties that can also improve described vulcanization of rubber glue.Therefore, described coupling agent is also preferably containing silane coupling agent, the silane coupling agent of the various routines in rubber combination that what described silane coupling agent was known to the skilled person may be used for, under preferable case, described silane coupling agent has the structure shown in formula I:
In formula, R can be vinyl, epoxy group(ing), amino, methacryloxy, sulfydryl or 3-propionyl sulfo--1-propyl group; X
1, X
2and X
3identical or different, be the functional group that can be hydrolyzed, under preferable case, X
1, X
2and X
3be methoxyl group, oxyethyl group or chlorine separately.Further preferably, described silane coupling agent is selected from one or more in two-[γ-(triethoxysilicane) propyl group]-tetrasulfide, two (triethoxy propyl silane) disulphide and 3-propionyl sulfo--1-propyl-trimethoxysilane.
According to the present invention, as mentioned above, as long as goal of the invention of the present invention can be realized containing described oligopolymer coupling agent in described rubber combination, therefore, the selectable range of the consumption of described silane coupling agent is wider, such as, with the dience rubber of 100 weight parts for benchmark, the content of described silane coupling agent is 0-5 weight part.
The present inventor finds, when described silane coupling agent and oligopolymer coupling agent of the present invention with weight ratio be 0.5-3:1 ratio with the use of time can improve processing characteristics and the use properties of the rubber obtained further.
According to the present invention, inventive point of the present invention is the raising adding the mechanical property to the intensity of the rubber unvulcanizate obtained by rubber combination of the present invention and the raising of processing characteristics and vulcanized rubber of oligopolymer coupling agent in coupling agent, therefore, 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 anti-aging agent is 1-3 weight part, the content of described vulcanizing agent is 1.5-2.5 weight part, the content of described vulcanization accelerator is 1-4 weight part, the content of described white carbon black is 20-80 weight part, usually, with the dience rubber of 100 weight parts for benchmark, the content of coupling agent is 4-15 weight part.
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 add-on of the present invention to described white carbon black is not particularly limited, as long as intensity and the processing characteristics of described rubber can be improved, and makes it have better reinforcing effect and do not affect other performances, such as, the total mass of described coupling agent and the mass ratio of white carbon black are preferably 0.05-0.3:1, are more preferably 0.1-0.3:1.
According to the present invention, described dience rubber can be the dience rubber of various routine, such as, and solution polymerized butadiene styrene rubber and/or ternary integrated rubber.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; Wherein, the arrangement of described isoprene segment, butadiene segment both can random arrangement, also can form block.Under preferable case, the molecular weight distribution of described dience rubber 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 measures according to method disclosed in GB/T1232.1-2000 and obtains, and wherein, warm up time is 1min, and rotation time is 4min, and test temperature is 100 DEG C.
According to the present invention, described dience rubber can also contain extending oil, and with the dience rubber of 100 weight parts for benchmark, the content of described extending oil is 0-40 weight part.
According to the present invention, the kind of described anti-aging agent is known to the skilled person.Such as, described anti-aging agent can be selected from 2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer, N-(1,3-dimethylbutyl) one or more in-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 vulcanizing agent can be the vulcanizing agent of various routine, such as, can be one or more in insoluble sulfur, dithio morpholine and four sulfuration two morpholines, be 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, 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: one or more accelerant C BBS) and in vulkacit D (commodity by name: vulkacit D).
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 2-3 weight part, and described stearic acid content is 0.5-1.5 weight part.
According to the present invention, under preferable case, also containing dispersion agent in described rubber combination.The short mix between dience rubber and additive that the adding of described dispersion agent can not only promote different viscosity, polarity and solubility parameter, improve different sorts rubber and the mixed performance between rubber and additive; The processing characteristics of rubber unvulcanizate can also be improved, improve melting efficiency, reduce energy consumption.
The present invention is not particularly limited the kind of described dispersion agent and content, such as, described dispersion agent can be selected from saturated fatty acid zinc salt, unsaturated fatty acid zinc salt and high fatty alcohol one or more.The kind of described saturated fatty acid zinc salt, unsaturated fatty acid zinc salt, high fatty alcohol and organic ester is known to the skilled person, such as, described saturated fatty acid zinc salt can be carbonatoms is the saturated fatty acid zinc salt of 14-18, described unsaturated fatty acid zinc salt can be carbonatoms be the unsaturated fatty acid zinc salt of 14-18, described high fatty alcohol can be carbonatoms be 14-18, hydroxyl quantity is the high fatty alcohol of 1-3, the organic ester of described organic ester can be carbonatoms be 16-25.Described saturated fatty acid zinc salt, unsaturated fatty acid zinc salt, high fatty alcohol and organic ester are all by being commercially available.With the dience rubber of 100 weight parts for benchmark, the content of described dispersion agent can be 1-3 weight part usually.
According to the present invention, under preferable case, also containing releasing agent in described rubber combination.Described releasing agent add the performance that not only can not affect rubber combination, the defect of easy roll banding in Rubber processing process can also be overcome, improve its processing characteristics, can also overcome silica compound open refining and internal mixing pass in viscosity become the roll banding phenomenon caused greatly.The kind of described releasing agent and content are conventionally known to one of skill in the art, and such as, described releasing agent can be selected from amine hydroxybenzene, erucicamide, stearylamide and N, N ' one or more in-ethylenebisstearamide.With the dience rubber of 100 weight parts for benchmark, the content of described releasing agent can be 0.5-2 weight part usually.
According to the present invention, the preparation method of described vulcanized rubber comprises and being mixed by above-mentioned rubber combination, obtains rubber unvulcanizate, and by described rubber unvulcanizate sulfuration, obtains vulcanized rubber.In described rubber combination, the kind of each component and content according to carrying out choose reasonable above, will can repeat at this no longer one by one.
According to the present invention, the method for described mixing and condition are to be the blending means of various routine and condition, and as a rule, described mixing can be carried out in mill or Banbury mixer.Wherein, the mixing between each material can be carried out simultaneously, also can proceed step by step, is preferably distribution and carries out.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, the temperature of described mixing is 30-150 DEG C, and the pressure of mixing is 0-0.8MPa, and the time of mixing is 10-40 minute.
According to the present invention, as a rule, method and the condition of rubber unvulcanizate being carried out sulfuration are 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 a kind of vulcanized rubber prepared by method of the present invention.
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.
To be further described in detail the present invention by specific embodiment below.
In embodiment and comparative example:
The oil-filled number of ternary integrated rubber two trade mark: SIBR2535(25 parts), SIBR2505(is non-oil-filled), Yanshan Petrochemical synthetic rubber plant industrialization finished product, mooney viscosity is 53;
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 4020;
Vulcanizing agent insoluble sulfur: contain Science and Technology Ltd. purchased from Jinchang, Guangzhou, S-80;
Vulcanization accelerator NS: purchased from Haiyang Chemical Plant, Qingdao;
Accelerator D: purchased from upper sea blue source bio tech ltd;
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;
Oligopolymer coupling agent Ci800: be butadiene-styrene oligopolymer (vinylbenzene segment is less)-modified by maleic acid anhydride graft product, thick liquid, number-average molecular weight is 3000, purchased from the wise and farsighted Chemical Co., Ltd. in Shanghai.Fig. 4 is the infrared spectra spectrogram of this oligopolymer coupling agent, as seen from Figure 4, this oligopolymer coupling agent is polybutadiene oligomer, containing vinylbenzene segment, side base or end group contain carboxyl, hydroxyl, ester group (with 1mol oligopolymer coupling agent molecule for benchmark simultaneously, carboxyl, hydroxyl, ester group are 1mol, and styrene chain hop count is 3-30); The mechanism of described oligopolymer coupling agent Ci800 and white carbon black coupling is: maleic anhydride functional groups is hydrolyzed and produces acid, can react (organo-tin compound is the catalyzer reacted) with the Si-OH on white carbon black surface, and after crosslinked, Ci800 becomes a rubber matrix part;
Releasing agent amine hydroxybenzene: large purchased from CRODA(Britain standing grain) company, the trade mark is CrodamideVRX;
Dispersion agent organic ester: carbonatoms is the mixing organic ester of 16-25, purchased from the Sino-German company in Hangzhou, the trade mark is ZD-6.
Embodiment 1-7
Embodiment 1-7 is for illustration of the preparation of rubber unvulcanizate provided by the invention.
Each component shown in table 1 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-H7.
Comparative example 1-3
This comparative example 1-3 is for illustration of the preparation of reference rubber unvulcanizate.
Rubber unvulcanizate is prepared according to the method for embodiment 1-7, unlike, described formula is mixing according to comparative example 1-3 respectively, obtains rubber unvulcanizate DH1-DH3.
Embodiment 8-14
Embodiment 8-14 is for illustration of the preparation of vulcanized rubber provided by the invention.
150 DEG C, under 5MPa, rubber unvulcanizate H1-H7 is carried out sulfuration place 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-S7.
Comparative example 4-6
This comparative example 4-6 is for illustration of the preparation of reference vulcanized rubber.
Vulcanized rubber is prepared according to the method for embodiment 8-14, unlike, described rubber unvulcanizate replaces with the rubber unvulcanizate DH1-DH3 that comparative example 1-3 prepares respectively, obtains vulcanized rubber DS1-DS3.
Test case 1-7
Test case 1-7 is for illustration of the test of the performance of rubber unvulcanizate provided by the invention.
(1) rubber unvulcanizate in conjunction with glue content:
The filling rubber unvulcanizate placed at least one week under mixing rear room temperature (25 DEG C) is cut into the length of side by rubber unvulcanizate H1-H7 and is about 1mm
3fine grained chippings, take about 2g(accurate weight W
1) package in line style rubber macromolecule can through and (weight W in the impervious clean stainless (steel) wire of gel or in filter screen
2), be dipped in room temperature (25 DEG C) immersion 72h, every 24h in 100ml solvent (for raffinating oil, main component is hexane and hexanaphthene to described test solvent) and change a solvent, take out filter screen vacuum-drying to constant (weight W
3).
In conjunction with glue calculation formula:
Bound rubber=[W
3-W
2-(W
1packing quality mark in × rubber unvulcanizate)/(W
1rubber quality mark in × rubber unvulcanizate)] × 100%
Interface cohesion in conjunction with the higher explanation filler of glue content and rubber is better, or the dispersion of filler is better.
(2) rheometer performance test:
Adopt U.S. TA company SR5 type rheometer measurement, carry out the frequency sweeping of rubber unvulcanizate H1-H5, frequency sweeping curve is (strain 0.25%, temperature 60 C) as shown in Figure 1.
(3) intensity (Green strength) of rubber unvulcanizate:
Rubber unvulcanizate H1-H7 is placed 8 hours-72 hours under room temperature (25 DEG C), with rubber mixing mill (purchased from Shanghai Shuan Yi rubber and plastics machine factory, model is X (S) K-160) cross roller slice, thickness is about 2.5mm, put into the mould that 2mm is thick, last layer polyfluortetraethylene plate (0.3mm is thick) is padded between rubber unvulcanizate and mould, 2.5MPa on vulcanizing press, mold pressing 5min at 100 DEG C, take out the sample in mould, in order to test strength, take off from rubber unvulcanizate again when polyfluortetraethylene plate is to be tested, be cut into dumb bell sample (GB/T 528-1998 I type cut-off knife), rate of extension 100mm/min.The maximum stress σ of test rubber unvulcanizate
max, strain stress (σ that maximum stress is corresponding
max) and fracture (maximum) strain stress of rubber unvulcanizate
max, wherein:
σ
max=maximum pull/(specimen width × sample thickness);
Acquired results is as table 2.The stress strain curve of H1-H5 as shown in Figure 2.Wherein, maximum stress σ
max, strain stress (σ that maximum stress is corresponding
max) and fracture (maximum) strain stress of rubber unvulcanizate
maxwherein one or a few Xiang Yue great illustrate that processing characteristics is better.
(3) vulcanization characteristics of rubber unvulcanizate:
Adopt testing without the curability of rotor vulkameter to rubber unvulcanizate purchased from Taiwan height Inland Steel, wherein, 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 2, and wherein, ts1 represents the sulfuration security of rubber unvulcanizate, and tc90 represents the sulfurizing time of rubber unvulcanizate.
Contrast test example 1-3
According to the method for test case 1-7, the processing characteristics of rubber unvulcanizate, curability and intensity are tested, unlike, the described rubber unvulcanizate rubber unvulcanizate DH1-DH3 prepared by comparative example 1-3 respectively replaces.Acquired results is as shown in table 2.
Test case 8-14
Test case 8-14 is for illustration of the test of vulcanized rubber performance provided by the invention.
(1) tensile property of vulcanized rubber:
Rubber unvulcanizate H1-H7 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, 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.Acquired results is as shown in table 3.
(2) tear resistance of vulcanized rubber:
Rubber unvulcanizate H1-H7 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.Acquired results is as shown in table 3.
(3) dynamic properties of vulcanized rubber:
Adopt U.S. TA company DMA-2980 type viscoelastic spectrometer to measure, wherein, frequency is 2Hz, and temperature rise rate is 5 DEG C/min, and sample size is 40mm × 5mm × 1mm.Acquired results is as shown in table 3, and wherein, characterize the wet-sliding resistant performance of vulcanized rubber with tan δ (0 DEG C), tan δ (0 DEG C) is larger, represents that vulcanized rubber wet-sliding resistant performance is better; Characterize the rolling resistance of vulcanized rubber with tan δ (60 DEG C), tan δ (60 DEG C) is less, represents that vulcanized rubber rolling resistance is less; Characterize the wear resisting property of vulcanized rubber with glass transition temperature Tg, Tg is less, represents that vulcanized rubber wear resisting property is better.Acquired results is as shown in table 3.
The equilibrium relationship figure of the wet-sliding resistant performance of vulcanized rubber S1-S5, wear resistance, rolling resistance as shown in Figure 3.
Contrast test example 4-6
Contrast test example 4-6 is for illustration of the test of reference vulcanized rubber performance.
According to the method for test case 8-14, the tear resistance of vulcanized rubber and mechanical property are tested, unlike, the described vulcanized rubber vulcanized rubber DS1-DS3 prepared by comparative example 4-6 respectively replaces.Acquired results is as shown in table 3.
Table 1 embodiment and comparative example formula table
Note: above-mentioned numerical value is all with parts by weight.
The processing characteristics of table 2 rubber unvulcanizate and vulcanization characteristics table
* note: H4 and DH2 system is due to the existence of extending oil, and loosely, a part of gel particle is less in the combination of white carbon black and rubber molecule, departs from filter screen, causes in conjunction with cementing fruit test not for actual in glue value, therefore is negative value in conjunction with glue numerical value.
* note: mm:ss represents minute: second, as 3:47 in embodiment 1 represents 3 minutes 47 seconds.
The mechanical mechanics property table of table 3 cross-linked rubber
* note: because specific elongation is less than 300%, therefore there is no 300% stress at definite elongation numerical value.
As can be seen from the result of table 2, table 3 and Fig. 1, Fig. 2 and Fig. 3, because rubber combination of the present invention have employed described oligopolymer coupling agent, thus facilitate the dispersion of filler and the interface cohesion with matrix, therefore, the processing characteristics of the rubber unvulcanizate obtained is (maximum stress σ in embodiment better
max, strain stress (σ that maximum stress is corresponding
max) and fracture (maximum) strain stress of rubber unvulcanizate
maxwherein one or several are higher than comparative example), the mechanical mechanics property of the vulcanized rubber obtained is relatively good (in embodiment in the performance such as tensile strength, tear strength one or several higher than comparative example) also, also has good balance between wet-sliding resistant performance, abrasion performance and rolling resistance 3 performances.
Claims (22)
1. a rubber combination, described rubber combination contains dience rubber, white carbon black, coupling agent, anti-aging agent, vulcanizing agent and vulcanization accelerator, it is characterized in that, described coupling agent contains oligopolymer coupling agent, containing with Si-OH, the group of condensation reaction occurring in described oligopolymer coupling agent molecule structure, described oligopolymer coupling agent contains by divinyl 1, the structural unit that 2-polymerization is formed, by divinyl 1, the structural unit that 4-polymerization is formed and the structural unit formed by maleic anhydride, by divinyl 1, the structural unit that 2-polymerization is formed is at least more than 1:1 with the mol ratio of the structural unit formed by maleic anhydride, the structural unit formed by divinyl Isosorbide-5-Nitrae-polymerization is at least more than 4:1 with the mol ratio of the structural unit formed by maleic anhydride, and the number-average molecular weight of described oligopolymer coupling agent is 2000-5000.
2. rubber combination according to claim 1, wherein, with 1mol oligopolymer coupling agent molecule for benchmark, the group that with Si-OH condensation reaction can occur contained in described oligopolymer coupling agent molecule structure is at least 1mol; The number-average molecular weight of described oligopolymer coupling agent is 3000-4000.
3. rubber combination according to claim 1 and 2, wherein, described oligopolymer coupling agent is also containing the structural unit formed by monovinylarene, and the structural unit formed by monovinylarene is 0.1-1:1 with the mol ratio of the structural unit formed by maleic anhydride.
4. rubber combination according to claim 1, wherein, the content of described oligopolymer coupling agent is the 25-100 % by weight of coupling agent total mass.
5. rubber combination according to claim 1, wherein, described coupling agent is also containing silane coupling agent, described silane coupling agent has the structure shown in formula I, in formula, R is vinyl, epoxy group(ing), amino, methacryloxy, sulfydryl or 3-propionyl sulfo--1-propyl group; X
1, X
2and X
3identical or different, be the functional group that can be hydrolyzed;
6. rubber combination according to claim 5, wherein, described coupling agent is also containing silane coupling agent, described silane coupling agent has the structure shown in formula I, in formula, R is vinyl, epoxy group(ing), amino, methacryloxy, sulfydryl or 3-propionyl sulfo--1-propyl group; X
1, X
2and X
3identical or different, be methoxyl group, oxyethyl group or chlorine separately;
7. rubber combination according to claim 6; wherein, described silane coupling agent is selected from one or more in two-[γ-(triethoxysilicane) propyl group]-tetrasulfide, two (triethoxy propyl silane) disulphide and 3-propionyl sulfo--1-propyl-trimethoxysilane.
8. the rubber combination according to claim 4 or 5, wherein, the mass ratio of described silane coupling agent and oligopolymer coupling agent is 0.5-3:1.
9. according to the rubber combination in claim 1 and 5-7 described in any one, wherein, with the dience rubber of 100 weight parts for benchmark, the content of described white carbon black is 20-80 weight part, described coupling agent is 4-15 weight part, the content of described vulcanizing agent is 1.5-2.5 weight part, and the content of described vulcanization accelerator is 1-4 weight part, and the content of described anti-aging agent is 1-3 weight part.
10. rubber combination according to claim 9, wherein, the total mass of described coupling agent and the mass ratio of white carbon black are 0.05-0.3:1.
11. rubber combinations according to claim 1, wherein, described dience rubber contains solution polymerized butadiene styrene rubber and/or ternary integrated rubber; The molecular weight distribution of dience rubber is 1.0-5.0, and mooney viscosity is 45-60.
12. rubber combinations according to claim 11, wherein, in described ternary integrated rubber, the content of vinylbenzene segment is 10-30 % by weight, and the content of butadiene segment is 40-45 % by weight, and the content of isoprene segment is 25-50 % by weight; Wherein, described isoprene segment, butadiene segment are random arrangement or form block.
13. rubber combinations according to claim 11, 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.
14. rubber combinations according to claim 1, wherein, described anti-aging agent is selected from 2,2,4-trimethylammonium-1, one or more in 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 vulcanizing agent be selected from insoluble sulfur, dithio morpholine and four sulfuration two morpholines one or more; Described vulcanization accelerator is selected from the N-tertiary butyl-2-[4-morpholinodithio base sulphenamide, 2, one or more in 2 '-dibenzothiazyl disulfide, the N-tertiary butyl-bis-(2-[4-morpholinodithio) sulfenamide, N-cyclohexyl-bis-(2-mercaptobenzothiazole) sulphenamide and vulkacit D.
15. rubber combinations 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 2-5 weight part.
16. rubber combinations according to claim 15, wherein, 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 2-3 weight part, and stearic content is 0.5-1.5 weight part.
17. rubber combinations according to claim 1, wherein, described rubber combination is also containing dispersion agent; Described dispersion agent be selected from saturated fatty acid zinc salt, unsaturated fatty acid zinc salt, high fatty alcohol and organic ester one or more; With the dience rubber of 100 weight parts for benchmark, the content of described dispersion agent is 1-3 weight part.
18. rubber combinations according to claim 1, wherein, also containing releasing agent in described rubber combination, described releasing agent is selected from amine hydroxybenzene, erucicamide, stearylamide and N, N ' one or more in-ethylenebisstearamide; With the dience rubber of 100 weight parts for benchmark, the content of described releasing agent is 0.5-2 weight part.
The preparation method of 19. 1 kinds of vulcanized rubbers, the method comprises and being mixed by the rubber combination in claim 1-18 described in any one, obtains rubber unvulcanizate, and by described rubber unvulcanizate sulfuration, obtains vulcanized rubber.
20. methods according to claim 19, wherein, the temperature that the condition of described sulfuration comprises sulfuration is 140-160 DEG C, and the pressure of sulfuration is 3.5-7MPa, and the time of sulfuration is 0.15-1 hour.
21. 1 kinds of vulcanized rubbers, is characterized in that, this vulcanized rubber is prepared by the method described in claim 19 or 20.
22. 1 kinds of tires adopting vulcanized rubber according to claim 21 to prepare.
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| CN104558975B (en) * | 2014-12-12 | 2018-10-30 | 东莞东阳光科研发有限公司 | A kind of modified fluororubber compounded rubber and preparation method thereof |
| CN104530837B (en) * | 2014-12-23 | 2016-09-14 | 兰州理工大学 | The preparation method of epoxidation solution polymerized butadiene styrene rubber coating |
| CN106589491B (en) * | 2016-11-29 | 2019-02-26 | 茂泰(福建)鞋材有限公司 | A kind of anti-slip rubber outsole and its manufacture craft |
| CN109929159B (en) * | 2017-12-15 | 2021-08-03 | 中国石油化工股份有限公司 | Rubber composition and vulcanized rubber for tire tread as well as preparation method and application of rubber composition and vulcanized rubber |
| CN109096557A (en) * | 2018-05-29 | 2018-12-28 | 陶玲 | The preparation method of abrasive rubber material |
| CN113956376B (en) * | 2021-10-29 | 2023-06-13 | 北京化工大学 | Coupling agent for modifying liquid rubber, preparation method, application and modified white carbon black |
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