CN104356407A - Method for preventing packing in rubber blend from migration - Google Patents
Method for preventing packing in rubber blend from migration Download PDFInfo
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- CN104356407A CN104356407A CN201410608342.1A CN201410608342A CN104356407A CN 104356407 A CN104356407 A CN 104356407A CN 201410608342 A CN201410608342 A CN 201410608342A CN 104356407 A CN104356407 A CN 104356407A
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Abstract
The invention relates to a method for improving the interaction of packing rubber, preventing packing in rubber blend from migration and maintaining the good initial dispersion state of packing. The method comprises the following steps: for rubber blend consisting of two-component or multi-component rubber, a reinforcing filling agent and other ingredients, firstly, mixing each rubber component with the reinforcing filling agent and any irradiation sensitizing agent respectively so as to prepare rubber master batch; subsequently mixing the rubber master batch of different rubber components with ingredients such as an anti-aging agent, a vulcanizing agent and oil so as to prepare a rubber compound; performing electronic irradiation treatment on the rubber compound; vulcanizing the rubber compound, so as to obtain the rubber.
Description
Technical field
The present invention relates to rubber stock production field, the interphase interaction of a kind of reinforcing filler rubber is particularly provided, hinder filler migration, maintain filler initial good distribution status method in rubber matrix, improve the production technique of rubber mix physical performance.
Background technology
Along with going deep into filler and rubber phase study on interaction, particularly M.-J.Wang, Rubber chem.Techno delivers, for the application of electron irradiation pre-curing technology in rubber materials provides enough theories integration filler and polymkeric substance, filler and filler interaction theory.
Patent CN101318384 mono-radial tyre inner lining air barrier component and preparation technology thereof, by carrying out electron irradiation process to air barrier component, improve the performances such as the Green strength of air barrier component, bond strength, scantlings of the structure stability; Patent CN20120126133 discloses a kind of method of the thinning air barrier component for radial, utilizes electron irradiation preconditioning technique, can thinning air barrier component, and its foothold is to improve sizing material Green strength, structural stability aspect equally; The cross-linking radiation pre-treatment of a kind of radial tyre structured material of patent 200610140583 open class is convenient, and its result is the tensile strength improving tire construction material, reduces thickness, reduces natural gum consumption, improves the advantages such as the stability of tire composition material; These patents all lay particular emphasis on raising to elastomeric material Green strength and dimensional stability aspect, really do not recognize that electron irradiation is when to filled rubber pre-treatment, to the effect that the effect of filler in rubber plays.
According to M.-J.Wang, the interaction of Rubber chem.Techno to solid matter surface and storeroom describes, only identical with the energy response of polymer surfaces at filler, namely polymkeric substance and filling surface are enough to compensate the impact of difference between polymkeric substance and the surface energy of filler alkali and the internal cohesive energy of filler and polymkeric substance itself due to hydrogen bond, acid-alkali interacts or other polar interaction produce energy of adhesion, and the filler disperseed in polymeric matrix could be stablized.Simultaneously, filler has the trend of assembling and forming aggregate in rubber, this is the buildup effect of filler in rubber, filler is assembled will cause the various degradation of sizing material, and wherein diffusion is one of factor affecting filler gathering, diffusion constant △=KT/6 π η r, K-Boltzmann's constant, T-temperature, η-compound viscosity, r-radius filler.
Carbon black is in the rubber stock be made up of different rubber, because they are different from the interaction power of each component rubber, in rubber unvulcanizate parking period, always there is the trend of moving to the strong rubber phase that interacts from the weak rubber phase that interacts in it, TEM test result display in Yi Weiyi rubber research institute internal report Inner Liner Compound, in the rubber stock that halogenated butyl rubber and natural gum form, in rubber unvulcanizate parking period, carbon black always can to natural gum middle migration mutually from halogenated butyl rubber, and finally natural gum mutually in settle out, this is disadvantageous to the performance of air retaining wall.
First this patent adjusts the rubber mixing technique of rubber unvulcanizate, improve the interaction ability of each component rubber and filler to greatest extent, and then by each component rubber rubber master batch and other Synergist S-421 95s are mixing obtains rubber unvulcanizate, then electron irradiation pre-treatment is carried out to the rubber unvulcanizate that this method obtains, to the three-dimensional net structure by precrosslink, the filler in rubber matrix is fixed and grappling, make it not move, farthest keep the initial good distribution state of filler in rubber matrix.
The brief introduction of electron irradiation pre-curing technology:
Electron irradiation prevulcanized refers at normal temperatures and pressures, through the free radical that high-power electron beam excites rubber molecule to produce, in conjunction with generation covalent linkage, occurs crosslinked, form tridimensional network between rubber molecule.Irradiation pre-curing technology is a kind of new type rubber modification and processing means, its fast, flexibly, the feature such as energy saving standard, make it improving the dispersion of filler in rubber matrix, improve rubber item over-all properties and have congenital advantage.
Summary of the invention
The object of this invention is to provide the interphase interaction of a kind of reinforcing filler rubber, hinder the migration of filler in rubber stock, maintain the method that the initial dispersion state of filler in rubber stock improves rubber over-all properties.
Method of the present invention is: to the rubber stock be made up of two components or polycomponent rubber, reinforcing filler, other Synergist S-421 95, first by each component rubber respectively with reinforcing filler, optional irradiation sensitizing agent is mixing prepares rubber rubber master batch; After by each component rubber rubber master batch and anti-aging agent, vulcanizing agent and/or oily mixing formation rubber unvulcanizate; Rubber unvulcanizate is carried out electron irradiation process; Then sulfuration is carried out to rubber unvulcanizate, obtain rubber.
Described rubber components is two or more rubber in natural rubber, synthetic rubber, and wherein synthetic rubber comprises: one or more in polyisoprene rubber, cis-butadiene cement, terpolymer EP rubber, butyl rubber, styrene-butadiene rubber(SBR), halogenated butyl rubber, chloroprene rubber, paracril, chlorosulfonated polyethylene rubber.
Described irradiation sensitizing agent is two functional groups, trifunctional, four-functional group crosslinking coagent one or more arbitrarily and use.Wherein, two functional group's crosslinking coagents, comprise neopentyl glycol double methacrylate, tripropylene glycol double methacrylate, ethoxylated neopentylglycol double methacrylate or polyethyleneglycol diacrylate; Trifunctional crosslinking coagent, comprises triallyl cyanurate or triallyl isocyanurate or pentaerythritol triacrylate; Four-functional group crosslinking coagent, comprises tetramethylol methane tetraacrylate or ethoxylation tetramethylol methane tetraacrylate or dimethacrylate Tetraglycol 99 ester.
Described reinforcing filler is carbon black, white carbon black, modified filler or other there is the functional filler (as: carbon nanotube, Graphene, polynite, potter's clay, kaolin, talcum powder) of reinforcing effect, comprise wherein one or more and use filler.Loading level is 10-150 weight part, preferred 20-100 weight part.
Described anti-aging agent is the rubber anti-aging agent such as quinoline, amine, phenols, protection wax.The consumption of anti-aging agent is 1-10 weight part.
Described vulcanizing agent is Sulfur and vulcanization accelerator, peroxide vulcanizing agent, metal oxide.For Sulfur and vulcanization accelerator.The consumption 0.3-10 weight part of Sulfur; The consumption 0.3-10 weight part of promotor.
Described oil is aromatic hydrocarbon oil, naphthenic oil, paraffin wet goods rubber-like oil.The consumption of oil is 1-50 weight part, preferred 1-30 weight part, more preferably 5-25 weight part.
Described rubber combination also comprises the rubber-like Synergist S-421 95s such as other promoting agent, coupling agent, tackiness agent, Hardening agent, anti-recovery agent.Synergist S-421 95 consumption is 0.1-10 weight part.
Described mixing be two-stage mixing method or three-stage mixing method.
Wherein two sections are mixingly specially:
First paragraph is mixing, and adopt Banbury mixer to be undertaken mixing by each component rubber, reinforcing filler, radiosensitizer respectively by above-mentioned formula, melting temperature scope is 60-200 DEG C, mixing time is 2-10 minute, Banbury mixer rotating speed is that 20-100 turns, and mixing evenly rear binder removal, parks more than 4 hours.Obtained each component rubber rubber master batch respectively.
Second segment is mixing, to park rear each component rubber rubber master batch and anti-aging agent, oil and other Synergist S-421 95, vulcanization system to add in Banbury mixer and carry out refining operation end, melting temperature scope is 60-120 DEG C, and mixing time is 1-8 minute, Banbury mixer rotating speed is that 20-80 turns, and completes rubber unvulcanizate preparation.
Wherein three-stage mixing is specially:
First paragraph is mixing, and adopt Banbury mixer to be undertaken mixing by each component rubber, reinforcing filler, radiosensitizer respectively by above-mentioned formula, melting temperature scope is 60-200 DEG C, mixing time is 2-10 minute, Banbury mixer rotating speed is that 20-100 turns, and mixing evenly rear binder removal, parks more than 4 hours.Obtained each component rubber rubber master batch respectively.
Second segment is mixing, and undertaken mixing by each component rubber rubber master batch after parking and anti-aging agent, oil and other Synergist S-421 95, melting temperature scope is 60-200 DEG C, mixing time is 2-10 minute, and Banbury mixer rotating speed is that 20-100 turns, mixing evenly rear binder removal, park more than 4 hours, obtained two-stage mixing glue.
Three-stage mixing, the two-stage mixing glue after parking and vulcanization system are added in Banbury mixer and carry out refining operation end, melting temperature scope is 60-180 DEG C, and mixing time is 1-5 minute, and Banbury mixer rotating speed is that 20-80 turns, and completes rubber unvulcanizate preparation.
The multistage of more than three sections is mixing just increases one or many back mixing before refining section eventually, other content is identical with three segment process, back mixing technique is: added in Banbury mixer by upper two-stage mixing glue and carry out back mixing operation, melting temperature is 60-150 DEG C, mixing time is 0.5-5 minute, Banbury mixer rotating speed is that 10-80 turns, and mixing evenly rear binder removal, parks more than 4 hours.
Carry out high-energy electron irradiation prevulcanized operation by rubber mixed, operate on the irradiation line having accelerator installation by offline mode, also can increase Accelerating electron apparatus to realize continuously online irradiation on rubber mixed production line.
The operational condition of electron irradiation is as follows:
1, accelerator voltage: 0.1-10MeV
2, energy instability :≤± 2%
3, the acceleration voltage rise time: 50 ± 5 seconds
4, the speed that fixes stream: 100 ± 10mA
5, Beam breakup unstability degree :≤± 2%
6, the line rise time: within 300 seconds
7, unevenness is scanned: < ± 5%
8, sweep length :≤200cm
9, corresponding sweep length maximum beam density: 1mA
10, by exposed material width maximum beam density: 200cm
11, by exposed material thickness: 0-100cm
12, irradiation dose: 0-200kGy
Wherein said rubber stock is formed by two kinds of rubber combinations, wherein a kind of rubber combination is polar rubber or low-pole rubber and reinforcing filler, optional irradiation sensitizing agent is mixing is prepared from, and another kind of rubber combination is non-polar rubber and reinforcing filler, optional irradiation sensitizing agent is mixing is prepared from.Wherein said polarity, low-pole and non-polar rubber are in certain rubber blend, the power relatively of the polarity between different components rubber.
Wherein said polar rubber or low-pole rubber are one or more of chloroprene rubber, paracril, chlorosulfonated polyethylene rubber, vinyl chloride rubber, halogenated butyl rubber, styrene-butadiene rubber(SBR) etc.; Described non-polar rubber is one or more of natural gum, polyisoprene rubber, cis-butadiene cement, terpolymer EP rubber, isoprene-isobutylene rubber etc.
Technique effect:
Rubber stock is through high-energy electron irradiation process, mainly contain some advantage following: one, in irradiation pre-vulcanization process, some polarity or low-pole rubber such as the halogen element in halogenated butyl rubber can under the impacts of high-power electron beam, rapid scission of link, distribute with the form of hydrogen halide or gas, the polarity of rubber reduces, filler and its Interaction enhanced; Two, the interfacial effect of Reinforced Rubber, two component rubber that relative consistency is bad, under high-energy electron irradiation effect, the free radical that two-phase interface produces can bonding again, forms covalent linkage, strengthens interfacial interaction; Three, high-energy electron irradiation technology, can induce the rubber macromolecule chain generating portion in rubber stock to be cross-linked, improve sizing material viscosity.According to M.-J.Wang filler diffusion theory, the diffusion constant △ of filler diminishes, and can restrained effectively the travelling speed of filler in rubber stock, and meanwhile, the three-dimensional network be cross-linked to form can fixing filler grain to a certain degree, limits its migration; Four, partial cross-linked sizing material network structure, can significantly improve the intensity of rubber, keeps dimensional stability, reduces heat-vulcanized scrap rate.
Accompanying drawing explanation
Fig. 1 is rubber unvulcanizate 1 in the embodiment of the present invention, contrasts the photo of rubber unvulcanizate 1 in conjunction with four kinds of rubber unvulcanizate phenomenons in glue test process;
Fig. 2 is rubber unvulcanizate 1F in the embodiment of the present invention, the contrast rubber unvulcanizate 1F photo in conjunction with four kinds of rubber unvulcanizate phenomenons in glue test process.
Embodiment
Filling a prescription by reality is below that embodiment further describes the present invention, but scope of the present invention is by the restriction of these embodiments.
(1) embodiment uses following plant and instrument and measuring method:
Plant and instrument prepared by table 1 rubber sample
| Sequence number | Device name | Specifications and models | Manufacturer |
| 1 | Banbury mixer | XSM-1/10-120 | Shanghai Kechuang rubber and plastics machine equipment company limited |
| 2 | Mill | 152.5*320 | Zhanjiang Machine Factory, Guangdong Prov. |
| 3 | Vulcanizing press | XLB-D600*600 | Zhejiang Huzhou east Machinery Co., Ltd. |
Table 2 cross-linked rubber test event and method
(2) embodiment and comparative example
Raw material:
Brominated butyl rubber, BIIR2222, ExxonMobil Chemical Asia Pacific
Natural rubber, STR20, Thailand's product
SBR1500, Qilu Petrochemical Company's product
BR9000, Qilu Petrochemical Company's product
Carbon black N660, Cabot (China) Investment Co., Ltd
Carbon black N339, Cabot (China) Investment Co., Ltd
Zinc oxide, Dalian zinc oxide factory
Stearic acid, PF1808, Malaysian Li Cheng company limited
Calcium carbonate, Jiangsu Sheng Ao Chemical Co., Ltd.
Hydrocarbon resin blend, 40MSF, STRUKTOR company of the U.S.
C5 petroleum resin, Linyi Tian Yuan Chemical Co., Ltd.
Octyl group phenolic tackifying resins, Wuhan Jinghe Chemical Co., Ltd
Sulfur flour, Lin Yiluo Zhuan Xin Anhua factory
Accelerator NS, Shandong Sunsine Chemical Co., Ltd.
Altax, Shandong Sunsine Chemical Co., Ltd.
Vulcanization accelerator TMTD, Shandong Sunsine Chemical Co., Ltd.
Alleged number is weight part below.
Embodiment 1
Polarity, low-pole and non-polar rubber are only in certain rubber blend, and the power relatively of the polarity between different components rubber, for BIIR2222 and STR20, STR20 is non-polar rubber, and BIIR2222 is low-pole rubber.
100 parts of BIIR2222,60 parts of N660 are added in Banbury mixer carry out one section mixing, melting temperature 160 DEG C, mixing time is 5 minutes, 100 parts of STR20,60 parts of N660 are added in Banbury mixer carry out one section mixing, melting temperature 160 DEG C, mixing time is 5 minutes, and Banbury mixer rotating speed is 60 turns, mixing evenly after binder removal, after parking 4 hours, by the BIIR2222 rubber master batch of 120 parts a section and 40 parts of one section of STR20 rubber master batch, 18 parts of calcium carbonate, 0.8 part of stearic acid, 6 parts of naphthenic oils, 12 parts of hydrocarbon resin blend, 4 parts of C5 petroleum resin, 2 parts of octyl group phenolic tackifying resins add in Banbury mixer and carry out two-stage mixing, melting temperature 160 DEG C, mixing time is 5 minutes, Banbury mixer rotating speed is 60 turns, mixing evenly rear binder removal, after parking 4 hours, by two sections of master batchs, 0.63 part of sulfur flour, 1.3 parts of altaxs, 0.7 part of NS, 6.25 parts of zinc oxide add Banbury mixer, carry out refining operation end, melting temperature is 100 DEG C, mixing time is 3 minutes, Banbury mixer rotating speed is 30 turns, mixing evenly rear binder removal.By processing condition bottom sheet on a mill until, obtain rubber unvulcanizate 1.
After rubber unvulcanizate 1 is parked 8 hours, to plateau cure, obtain cross-linked rubber 1 with vulcanizing press sulfuration under 165 DEG C of conditions.
Or, offline mode is adopted to carry out electron irradiation prevulcanized operation to rubber unvulcanizate 1, electron accelerator irradiation voltage 2.5MeV, beam intensity 60mA, electron beam scanning width 1600mm, radiation absorber amount selects 20kGy, irradiation line speed 30m/min, radiation environment is anoxybiotic environment, completes the preparation to rubber unvulcanizate 1F.After rubber unvulcanizate 1F is parked 8 hours, to plateau cure, obtain cross-linked rubber 1F with vulcanizing press sulfuration under 165 DEG C of conditions.
Comparative example 1:
By 25 parts of STR20, 75 parts of BIIR2222, 60 parts of N660 carbon blacks add in Banbury mixer carry out one section mixing, melting temperature is 160 DEG C, mixing time is 5 minutes, Banbury mixer rotating speed is 60 turns, mixing evenly rear binder removal, 18 parts of calcium carbonate are added at Banbury mixer after parking 4 hours, 0.8 part of stearic acid, 6 parts of naphthenic oils, 12 parts of hydrocarbon resin blend, 4 parts of C5 petroleum resin, 2 parts of octyl group phenolic tackifying resins carry out two-stage mixing, melting temperature is 160 DEG C, mixing time is 5 minutes, Banbury mixer rotating speed is 60 turns, mixing evenly rear binder removal, in Banbury mixer, two sections of master batchs are added after parking 4 hours, 0.63 part of sulfur flour, 1.3 parts of altaxs, 0.7 part of NS, 6.25 part zinc oxide, carry out refining operation end, melting temperature is 100 DEG C, mixing time is 3 minutes, Banbury mixer rotating speed is 30 turns, mixing evenly rear binder removal.By processing condition bottom sheet on a mill until, obtain contrasting rubber unvulcanizate 1.
After contrast rubber unvulcanizate 1 is parked 8 hours, to plateau cure, obtain control cure glue 1 with vulcanizing press sulfuration under 165 DEG C of conditions.
Or, offline mode is adopted to carry out electron irradiation prevulcanized operation to contrast rubber unvulcanizate 1, electron accelerator irradiation voltage 2.5MeV, beam intensity 60mA, electron beam scanning width 1600mm, radiation absorber amount selects 20kGy, irradiation line speed 30m/min, radiation environment is anoxybiotic environment, the preparation of complete paired comparison rubber unvulcanizate 1F.After contrast rubber unvulcanizate 1F is parked 8 hours, to plateau cure, obtain control cure glue 1F with vulcanizing press sulfuration under 165 DEG C of conditions.
Test-results
According to the discussion of M.-J.Wang filled polymers interaction correlation theory, show: be characterize the most effective means of filler-polymer interaction power in conjunction with glue.
The rubber that can not be extracted by rubber good solvent in unvulcanized filling glue is referred in conjunction with glue; Higher in conjunction with glue content, illustrate that the reactive force between rubber and filler is stronger, the various physicalies of rubber item as intensity, elasticity, tear, wear hardness etc. is better;
The described measuring method in conjunction with glue is:
The filling rubber unvulcanizate that mixing rear ambient temperatare is put at least one day is cut into about 1mm
3fine grained chippings, take about 0.5g (W) package in linear rubber macromole can through and in the impervious clean stainless (steel) wire of gel or in filter paper, then be dipped in 100mL toluene, at room temperature soak 48h, then again change solvent and soak 48h again, take out final vacuum and be dried to constant weight (W
fg), then with following formulae discovery in conjunction with glue content:
W-example weight
W
fg-filler and the weight in conjunction with glue
M
fthe weight of filler in-rubber unvulcanizate
M
pthe weight of rubber in-rubber unvulcanizate
Finally get the arithmetical av of twice measured value as measurement result.
Table 3 rubber unvulcanizate 1, contrast rubber unvulcanizate 1, rubber unvulcanizate 1F and contrast rubber unvulcanizate 1F are in conjunction with glue content balance table
| Test event | Rubber unvulcanizate 1 | Contrast rubber unvulcanizate 1 | Rubber unvulcanizate 1F | Contrast rubber unvulcanizate 1F |
| In conjunction with glue content, % | 34.2 | / | 65.8 | 52.1 |
Fig. 1 and Fig. 2 is that rubber unvulcanizate 1, contrast rubber unvulcanizate 1, rubber unvulcanizate 1F and the contrast rubber unvulcanizate 1F put by mixing rear ambient temperatare at least one day is cut into about 1mm respectively
3fine grained chippings, take respectively about 0.5g package in linear rubber macromole can through and in the impervious clean stainless (steel) wire of gel, be dipped in 100mL toluene, at room temperature soak the digital photograph figure after 48h.
As can be seen from Fig. 1 and Fig. 2: rubber unvulcanizate 1 only has a small amount of carbon black to be dissolved in toluene solution, solution is still settled solution, and it is completely muddy to contrast rubber unvulcanizate 1, rubber unvulcanizate 1F to move out phenomenon without carbon black, solution is clarified, contrast rubber unvulcanizate 1F also comparatively clarifies, but can see the carbon black moved out on a small quantity on copper mesh.This phenomenon shows: the interaction between the improvement energy reinforcing filler rubber of calendering process, rubber unvulcanizate after high-energy electron beam irradiation, carbon black can be fixing and coated by the three-dimensional net structure of partial cross-linked rubber macromolecule chain formation, table 3 rubber unvulcanizate 1, contrast rubber unvulcanizate 1, rubber unvulcanizate 1F and contrast rubber unvulcanizate 1F are in conjunction with glue content balance table, and what obtain demonstrates this point equally in conjunction with glue data.
Table 4 cross-linked rubber 1, control cure glue 1, cross-linked rubber 1F and control cure glue 1F performance comparison table
Table 4 is cross-linked rubber 1, control cure glue 1, cross-linked rubber 1F and control cure glue 1F performance comparison table, cross-linked rubber 1F is the cross-linked rubber that after rubber mixing technique adjustment, irradiation obtains, control cure glue 1F is the cross-linked rubber that conditional electronic irradiation technique obtains, the cross-linked rubber of cross-linked rubber 1 for obtaining after rubber mixing technique adjustment, the cross-linked rubber that control cure glue 1 obtains for traditional technology, find after contrast: the cross-linked rubber 1F performance that after rubber mixing technique adjustment, irradiation obtains all is better than other three kinds of cured propertiess obtained, cross-linked rubber 1 performance only obtained rubber mixing technique adjustment is also better than control cure glue 1. and rubber mixing technique adjustment and radiation treatment is described, sizing material can be made to show more excellent over-all properties.
Embodiment 2
Polarity, low-pole and non-polar rubber are only in certain rubber blend, and the power relatively of the polarity between different components rubber, for BR9000 and SBR1500, BR9000 is non-polar rubber, and SBR1500 is low-pole rubber.
100 parts of BR9000,60 parts of N339 carbon blacks, 3 parts of irradiation sensitizing agent pentaerythritol triacrylates are joined in Banbury mixer carry out one section mixing, melting temperature 160 DEG C, mixing time is 5 minutes, and Banbury mixer rotating speed is 60 turns, mixing evenly after binder removal, 100 parts of SBR1500,60 parts of N339 carbon blacks, 3 parts of irradiation sensitizing agent pentaerythritol triacrylates are joined in Banbury mixer carry out one section mixing, melting temperature 160 DEG C, mixing time is 5 minutes, Banbury mixer rotating speed is 60 turns, mixing evenly rear binder removal, after parking 4 hours, respectively by one section 32 parts of BR9000 rubber master batch, 128 parts of SBR1500 rubber master batch, 3 parts of zinc oxide, 2 parts of stearic acid, 1.5 parts of anti-aging agent RDs, 2 parts of antioxidant 4020s, 10 parts of naphthenic oils join in Banbury mixer and carry out two-stage mixing, melting temperature is 160 DEG C, mixing time is 5 minutes, Banbury mixer rotating speed is 60 turns, mixing evenly rear binder removal, after parking 8 hours, by two sections of master batchs, 2.5 parts of Sulfurs, 1.2 parts of NS join in Banbury mixer and carry out refining operation end, melting temperature is 100 DEG C, mixing time is 3 minutes, Banbury mixer rotating speed is 30 turns, mixing evenly rear binder removal, by processing condition bottom sheet on a mill until, obtain rubber unvulcanizate 2.
After rubber unvulcanizate 2 is parked 8 hours, to plateau cure, obtain cross-linked rubber 2 with vulcanizing press sulfuration under 165 DEG C of conditions.
Or, offline mode is adopted to carry out electron irradiation prevulcanized operation to rubber unvulcanizate 2, electron accelerator irradiation voltage 2.5MeV, beam intensity 60mA, electron beam scanning width 1600mm, radiation absorber amount selects 20kGy, irradiation line speed 30m/min, radiation environment is anoxybiotic environment, completes the preparation to rubber unvulcanizate 2F.After rubber unvulcanizate 2F is parked 8 hours, to plateau cure, obtain cross-linked rubber 2F with vulcanizing press sulfuration under 165 DEG C of conditions.
Comparative example 2
By 20 parts of cis-1,4-polybutadiene rubbers, 80 parts of styrene butadiene rubber sbrs 1500, 60 parts of N339 carbon blacks, 3 parts of irradiation sensitizing agent pentaerythritol triacrylates, 3 parts of zinc oxide, 2 parts of stearic acid, 1.5 parts of anti-aging agent RDs, 2 parts of antioxidant 4020s, 10 parts of naphthenic oils add in Banbury mixer carry out one section mixing, melting temperature is 160 DEG C, mixing time is 5 minutes, Banbury mixer rotating speed is 60 turns, mixing evenly rear binder removal, after parking 8 hours, by one section of master batch, 2.5 parts of Sulfurs, 1.2 parts of NS join in Banbury mixer and carry out refining operation end, melting temperature is 100 DEG C, mixing time is 3 minutes, Banbury mixer rotating speed is 30 turns, mixing evenly rear binder removal, by processing condition bottom sheet on a mill until, obtain contrasting rubber unvulcanizate 2.
After contrast rubber unvulcanizate 2 is parked 8 hours, to plateau cure, obtain control cure glue 2 with vulcanizing press sulfuration under 165 DEG C of conditions.
Or, offline mode is adopted to carry out electron irradiation prevulcanized operation to contrast rubber unvulcanizate 2, electron accelerator irradiation voltage 2.5MeV, beam intensity 60mA, electron beam scanning width 1600mm, radiation absorber amount selects 20kGy, irradiation line speed 30m/min, radiation environment is anoxybiotic environment, the preparation of complete paired comparison rubber unvulcanizate 2F.After contrast rubber unvulcanizate 2F is parked 8 hours, to plateau cure, obtain control cure glue 2F with vulcanizing press sulfuration under 165 DEG C of conditions.
Test-results
Table 5 rubber unvulcanizate 2, contrast rubber unvulcanizate 2, rubber unvulcanizate 2F and contrast rubber unvulcanizate 2F are in conjunction with glue content balance table
| Test event | Rubber unvulcanizate 2 | Contrast rubber unvulcanizate 2 | Rubber unvulcanizate 2F | Contrast rubber unvulcanizate 2F |
| In conjunction with glue content, % | 42 | 38 | 73 | 59 |
Table 5 is rubber unvulcanizate 2, contrasts rubber unvulcanizate 2, rubber unvulcanizate 2F with contrast rubber unvulcanizate 2F in conjunction with glue content balance table, and can see, cross-linked rubber 2F is the highest in conjunction with glue content
Rebound performance when 60 DEG C, tan δ value are relevant to the rolling resistance performance of tire, and wherein, rebound value is high, then rolling resistance is low for tan δ value; DIN abrasion reflect the abrasion resistance of sizing material, and wear index is higher, and abrasion resistance is better.Table 6 is cross-linked rubber 2, control cure glue 2, cross-linked rubber 2F and control cure glue 2F performance comparison table, can find out: cross-linked rubber 2F properties is all optimum.
Table 6 cross-linked rubber 2, control cure glue 2, cross-linked rubber 2F and control cure glue 2F performance comparison table
Claims (13)
1. the method for reinforcing filler rubber interphase interaction, the filler migration hindered in rubber blend, the initial good distribution state of maintenance filler, it is characterized in that: to the rubber stock be made up of two components or polycomponent rubber, reinforcing filler, other Synergist S-421 95, first by each component rubber respectively with reinforcing filler, optional irradiation sensitizing agent is mixing prepares rubber rubber master batch; After by each component rubber rubber master batch and anti-aging agent, vulcanizing agent and/or oily mixing formation rubber unvulcanizate; Rubber unvulcanizate is carried out electron irradiation process; Then sulfuration is carried out to rubber unvulcanizate, obtain rubber.
2. method according to claim 1, wherein said irradiation sensitizing agent is two functional groups, trifunctional, four-functional group crosslinking coagent one or more also use, wherein, two functional group's crosslinking coagents, comprise at least one of neopentyl glycol double methacrylate, tripropylene glycol double methacrylate, ethoxylated neopentylglycol double methacrylate or polyethyleneglycol diacrylate; Trifunctional crosslinking coagent, comprises at least one of triallyl cyanurate or triallyl isocyanurate or pentaerythritol triacrylate; Four-functional group crosslinking coagent, comprises at least one of tetramethylol methane tetraacrylate or ethoxylation tetramethylol methane tetraacrylate or dimethacrylate Tetraglycol 99 ester.
3. method according to claim 1, wherein said rubber components is natural rubber, two or more rubber elastomeric.
4. method according to claim 3, wherein said synthetic rubber comprises: one or more in polyisoprene rubber, cis-butadiene cement, terpolymer EP rubber, butyl rubber, styrene-butadiene rubber(SBR), halogenated butyl rubber, chloroprene rubber, paracril, chlorosulfonated polyethylene rubber.
5. method according to claim 1, wherein said reinforcing filler comprise in carbon black, white carbon black, modified filler, carbon nanotube, Graphene, polynite, potter's clay, kaolin, talcum powder one or more, the consumption of reinforcing filler is 10-150 weight part relative to the rubber of 100 weight parts, preferred 20-100 weight part.
6. method according to claim 1, wherein said anti-aging agent is at least one of quinoline, amine, phenols, protection wax class rubber anti-aging agent.
7. method according to claim 1, wherein said vulcanizing agent comprises at least one of Sulfur and vulcanization accelerator, peroxide vulcanizing agent, metal oxide.
8. method according to claim 1, wherein said oil is rubber filling treated oil, and the consumption of oil is 1-50 weight part, preferred 1-30 weight part.
9. method according to claim 1, wherein said rubber unvulcanizate also comprises at least one of promoting agent, coupling agent, tackiness agent, Hardening agent, anti-recovery agent.
10. method according to claim 1, wherein said mixing be two-stage mixing or three-stage mixing.
11. methods according to claim 1, wherein said rubber stock is formed by two kinds of rubber combinations, wherein a kind of rubber combination is polar rubber or low-pole rubber and reinforcing filler, optional irradiation sensitizing agent is mixing is prepared from, and another kind of rubber combination is non-polar rubber and reinforcing filler, optional irradiation sensitizing agent is mixing is prepared from.
12. methods according to claim 11, wherein said polar rubber or low-pole rubber are one or more of chloroprene rubber, paracril, chlorosulfonated polyethylene rubber, vinyl chloride rubber, halogenated butyl rubber, styrene-butadiene rubber(SBR) etc.; Described non-polar rubber is one or more of natural gum, polyisoprene rubber, cis-butadiene cement, terpolymer EP rubber, isoprene-isobutylene rubber etc.
Rubber unvulcanizate prepared by 13. 1 kinds of methods according to any one of claim 1-12.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106978016A (en) * | 2017-04-06 | 2017-07-25 | 天长市润达金属防锈助剂有限公司 | A kind of metal antirusting agent with excellent damping performance |
| CN109796641A (en) * | 2017-11-16 | 2019-05-24 | 三橡股份有限公司 | It is a kind of by nitrile rubber and butadiene-styrene rubber and with the mixing method for preparing blended rubber |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1896123A (en) * | 2005-07-12 | 2007-01-17 | 北京化工大学 | Improvement of rubber compression elasticity at low-temperature |
| CN102532626A (en) * | 2012-01-12 | 2012-07-04 | 山东大学 | High strength rubber with radiation resistance and thermal aging resistance and preparation method thereof |
| CN102604243A (en) * | 2012-01-13 | 2012-07-25 | 河南省科学院同位素研究所有限责任公司 | Radial truck tire air-tight layer component and preparation process thereof |
| CN103788388A (en) * | 2014-01-23 | 2014-05-14 | 怡维怡橡胶研究院有限公司 | Method for improving elasticity and themogenesis performance of rubber product |
-
2014
- 2014-11-03 CN CN201410608342.1A patent/CN104356407A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1896123A (en) * | 2005-07-12 | 2007-01-17 | 北京化工大学 | Improvement of rubber compression elasticity at low-temperature |
| CN102532626A (en) * | 2012-01-12 | 2012-07-04 | 山东大学 | High strength rubber with radiation resistance and thermal aging resistance and preparation method thereof |
| CN102604243A (en) * | 2012-01-13 | 2012-07-25 | 河南省科学院同位素研究所有限责任公司 | Radial truck tire air-tight layer component and preparation process thereof |
| CN103788388A (en) * | 2014-01-23 | 2014-05-14 | 怡维怡橡胶研究院有限公司 | Method for improving elasticity and themogenesis performance of rubber product |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106978016A (en) * | 2017-04-06 | 2017-07-25 | 天长市润达金属防锈助剂有限公司 | A kind of metal antirusting agent with excellent damping performance |
| CN109796641A (en) * | 2017-11-16 | 2019-05-24 | 三橡股份有限公司 | It is a kind of by nitrile rubber and butadiene-styrene rubber and with the mixing method for preparing blended rubber |
| CN110204747A (en) * | 2019-06-21 | 2019-09-06 | 江南大学 | A method of improving rubber roller cushion rubber performance |
| CN110294850A (en) * | 2019-06-21 | 2019-10-01 | 江南大学 | A method of improving rubber roller cushion rubber cross-linking efficiency |
| CN110305342A (en) * | 2019-06-21 | 2019-10-08 | 江南大学 | A method of improving rubber roller cushion rubber performance |
| CN110818992A (en) * | 2019-11-05 | 2020-02-21 | 湖北洋田塑料制品有限公司 | Conductive polymer material and preparation method thereof |
| CN114149621A (en) * | 2021-11-17 | 2022-03-08 | 中国核电工程有限公司 | Blended rubber of natural rubber and ethylene propylene diene monomer |
| CN115534368A (en) * | 2022-09-21 | 2022-12-30 | 湖北航天化学技术研究所 | Preparation method of graphene-based anti-migration layer |
| CN115534368B (en) * | 2022-09-21 | 2024-04-05 | 湖北航天化学技术研究所 | Preparation method of graphene-based migration-preventing layer |
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