CN101747527A - High-activity vulcanized rubber powder and preparation method thereof - Google Patents
High-activity vulcanized rubber powder and preparation method thereof Download PDFInfo
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Abstract
The invention provides high-activity vulcanized rubber powder. The rubber powder with the fineness between 60 and 100 meshes is obtained by uniformly mixing non-desulfurized rubber particles with the average grain diameter between 5 and 10 mm and 2 to 5 percent active modifier, performing room-temperature shearing, grinding and instant extrusion, raising temperature to between 140 and 170 DEG C, raising pressure to between 8 and 12 MPa and then performing low-temperature pressure release. The appearance of the rubber powder is like fluffy bobbles, and the specific surface area of the rubber powder is more than or equal to 0.4 m<2>/g. The rubber powder is mixed with various rubber materials, can be in full contact with the rubber materials, and chemical bonding is produced between the interfaces of the rubber powder and the rubber materials so as to form strong interface bonding strength to ensure that the mechanical strength and properties of rubber products basically remain unchanged. The rubber powder can replace 30 or more percent of original rubber to process the rubber products of which all properties basically remain the same.
Description
One, technical field
The present invention relates to the comprehensive utilization of waste old, specifically a kind of high-activity vulcanized rubber powder and preparation method thereof.
Two, background technology
21 century, the mankind enter kownledge economy and recycling economy epoch, all developing a circular economy and setting up conservation-minded society as the important channel of realizing sustainable development, the comprehensive utilization of waste or used vulcanized rubber enjoys the concern of national governments and society always as the important component part of recycling economy in countries in the world.Waste or used vulcanized rubber belongs to thermoset copolymer material, is difficult to degraded under field conditions (factors), if abandon in the face of land or be embedded in the underground more than ten years also imputrescibility is rotten.The accumulation land occupation of waste old, contaminate environment is not only damaged residents ' health, and fire hazardous, and people claim that it is " black pollution ".Therefore, although waste old proportion in the solid waste total amount is less, be one of subject matter of solid waste processing.It is a kind of renewable resources that waste old has been handled well, and handling bad then is to the deleterious rubbish of environment for human survival.
China is rubber consumption big country, ranks first in the world in continuous 6 years, and the consumption of virgin rubber has surpassed 1/5th of global rubber industry consumption glue amount at present.But China is again the very deficient country of rubber sources, only accounts for about 10% of world's virgin rubber total resources.In recent years, China all needs about 1,330,000 tons of import natural rubber more than 1,600,000 tons, synthetic rubber every year.Annual about 1,800,000 tons of the waste old that produces in the whole nation, wherein 65～70%, damaged tire, and also damaged tire every year is also with 10% speed increase.Meanwhile, statistic data shows that the utilization ratio of the present waste old of China is about 60%, also has bigger gap apart from the recovery utilization rate level of industrially developed country 80%.In the face of resource, environment two big bottlenecks, make full use of waste rubber resources, walk the road of recycling economy, alleviate the rubber sources shortage, preserve the ecological environment conscientiously, promote that china natural resources saving type and friendly environment society's construction are imperative.At present, the waste old of China comprehensive utilization processing mode mainly contains: the dynamic desulfurization of (1) High Temperature High Pressure, produce desulfurization regeneration glue; (2) grinding and processing becomes rubber powder; (3) tyre rebuilding; (4) cracking recovery etc.But at present, because the recycling of the waste rubber cracking of China still all is being in the starting stage in technological development aspect the fundamental research, technical problems such as many chemical processes and equipment temporarily also can't resolve, the severe contamination that brings of environment was also once given in " indigenous oil refining " of once overflowing on the contrary, and country proscribes by formal decree.Add the shortage of rubber sources, the man government of China temporarily is the recycling of restriction waste rubber cracking, thus main still in first three kind mode, now plant grinding and processing and become the method for rubber powder to be summarized as down (2):
It is a physical mechanical process that the waste old processing powder is broken into rubber powder.Producing the technical process of rubber powder simplifies, the operations such as High Temperature High Pressure desulfurization, washing, kneading and refining in the desulfurization regeneration glue production technique have been saved, and complicated component, the color depth that must add, multiple auxiliary agents such as the bigger mineral oil softener of irritating smell, contaminative and promotor, tackifier, oxidation inhibitor are arranged, not only eliminated of the pollution of the waste water,waste gas and industrial residue of desulfurization, washing, also saved investment and reduced production cost environment.Rubber powder adds in the sizing material that sulfuration back performance is good, cost is low in addition, and the performance of the various rubber items of production is better than reclaimed rubber, and range of application is more extensive than reclaimed rubber.The rough and careless estimation of a tree name is produced rubber powder than the desulfurization regeneration glue energy-conservation about 40% of producing equal quality.Therefore the waste old processing powder is broken into rubber powder, should be best suited for one of mode that reduces discharging the cycles, economized utilization, so external high-quality rubber powder output increases year by year.
Rubber powder is meant waste old under the effect of machinery, is processed into the powdered granule of various different fineness according to different purposes, and particle diameter is less than the rubber powder of the meaning of 1.5mm.External rubber powder is classified by different-grain diameter.See Table 1.
The classification of table 1. rubber powder and purposes
Late 1990s, China mainly is that the exploitation of tyre crusher, fine glue powder pulverizer has obtained success aspect the equipment of the common rubber powder of waste old normal temperature pulverizing manufacturing new breakthrough having been arranged, and this tooling relatively is fit to China's national situation.At present the rubber powder production capacity of China has reached 1,000,000 tons/year, but only 500,000 tons of actual outputs, and mainly be to be used for the higher reclaimed rubber of High Temperature High Pressure dynamic desulfurization production quality.Directly or indirectly the rubber powder of using only is mainly used in pave the way modifying asphalt and athletic ground.But because of price is low excessively, and all do not push (if after popularization is opened, year needs more than 600,000 tons) open, every year is also with regard to tens0000 tons.
In all kinds of rubber powders, meticulous, micro glue powder enjoys the attention of various countries, except because its production process is simple, compares with producing reclaimed rubber, has saved a large amount of specific equipments, factory building, power and manpower; Chemical raw materials such as tenderizer, activator have been saved; Do not have secondary pollution, production environment has clear improvement; The more important thing is thin rubber powder of particle diameter and new sizing material blend, performance is more superior than reclaimed rubber.Therefore, abroad when producing meticulous, micro glue powder, be devoted to use important function for of research, thus for enlarge meticulous, little rubber powder industrial scale, for product cost is improved the quality of products, reduced to application industry, raising business economic benefit has been created favourable condition.
Production method meticulous at present, micro glue powder mainly contains 3 kinds: normal temperature crushing up, pulverize at low temperature method and wet pulverization method.In addition, many new breaking methods are still among constantly researching and developing.As ozone comminuting method, high pressure blasting procedure, high temperature hypervelocity pulverize, auxiliary agent soaks to mix and pulverizes and the high pressure shooting is pulverized etc.
Table 2. is meticulous, the production method of micro glue powder
(1) normal temperature crushing up
Normal temperature crushing up is meant that generally processing temperature is at 50 ± 5 or slightly make a kind of comminuting method of rubber powder under the high-temperature by the mechanical effect crushing rubber.Its pulverization principle is rubber is cut off and to crush by the effect of mechanical shear stress.This rubber powder is compared with freezing pulverize at low temperature rubber powder, has large surface area, so help carrying out activation modification, it is also bigger simultaneously it to be engaged in the new sizing material bonding force with base rubber.Normal temperature crushing up the earliest is to adopt the pulley type comminuting method, mainly contains coarse crushing and 2 operations in small, broken bits, and the equipment that coarse crushing is adopted is the fluted two roller primary crushers in surface, the not two roller fine crushers of with groove of surface that then adopt in small, broken bits.Waste old by coarse crushing and in small, broken bits after, then carry out iron removal by magnetic separation and fiber separation, and then sieve out the rubber powder of different-grain diameter, the meal that surpasses particle size range returns again to be pulverized.Roller speed surpasses 50m/s, then is called normal temperature high speed pulverization method, simultaneously crushing rubber and filamentary material.Occurred non-pulley type normal temperature crushing up in recent years, wherein Germany, Japan use a kind of fluted disc crusher, coarse crushing and one in small, broken bits; Germany CONDVX company also has a kind of peg type mill freezing crusher, and the rubber powder granularity is thinner, and production efficiency is higher; The domestic normal temperature fine pulverizer of also having developed belongs to abrasive disk type, and the temperature of supporting at normal temperatures and pressures water cycle cooling control crushiing chamber has made the rubber powder (can reach 80 orders～more than 120 orders) of high fineness.
(2) pulverize at low temperature method
The pulverize at low temperature method is to adopt liquid nitrogen or the cooling of air turbo expanding type, makes rubber freezing below second-order transition temperature, then the method for pulverizing with hammer or dry pan at low temperatures.Pulverize at low temperature can be divided into 3 kinds of modes by the treatment process difference before pulverizing: waste old is pulverized at low temperatures through directly freezing after the pre-treatment; Broken and 2 operations of pulverizing are all carried out at low temperatures; Be ground into thick rubber powder under normal temperature condition earlier, it is broken to carry out fine powder then under cold condition.In these 3 kinds of modes, more suitable with the method for normal temperature and pulverize at low temperature and usefulness, its production line can be produced normal temperature method rubber powder or low temperature process rubber powder flexibly according to market demand.The liquid nitrogen cryogenics comminuting method all has industrial production line in developed country, can produce the serial rubber powder of rubber powder 0.2mm (about 65 orders), 0.1mm (about 150 orders), 0.05mm (about 300 orders) as U.S. connection carbon (UCC) company low temperature process.The a tree name SmitherLabortkries Inc. of Rubber processing institute that carries weight most studies show that, adds below 50 parts in sizing material, 70 order UCC rubber powders, and its cured properties reduces hardly.But its liquid nitrogen consumes height (the 1kg rubber powder consumes the 1kg liquid nitrogen), production cost height; Japan Northwest environment exploitation Co., Ltd. adopts normal temperature pulverizing and pulverize at low temperature and usefulness, reduces the liquid nitrogen consumption of knowing clearly, the thinnest 90 orders that reach of rubber powder; The achievement that the Hogerd company of Germany and INTEC company reduce liquid nitrogen consumption is the most remarkable, produces 1kg rubber powder liquid nitrogen and drops to respectively below the 0.5kg and near 0.5kg; China has seven, eight companies to introduce low temperature process production rubber powder equipment last century end, and none can survive so far, and it has various reasons, but still is that scientific and technological quality is not as the people after all.But it is reported 609 institutes of Industry Corporation of China Air China, once used ten thousand tons of air freezing waste old fuel pulverizing plants of aviation air turbo circularly cooling technology development, promoted the research work that the low temperature process rubber powder is made.
(3) wet method or solution comminuting method
This method is the patent of RAPRA (abbreviation RAPRA), so this method abbreviates the RAPRA method again as.U.S. Gould company obtains the right to use of this patent, has set up pilot plant in the Ohio.This method divided for three steps carried out, and the first step is to adopt general method with the waste old coarse reduction; Second step was to carry out the pre-treatment of thick rubber powder with chemical or big water gaging; It is broken that the 3rd step application disk colloidal mill carries out fine powder.Carry out liquid-solid separation, washing, drying after the pulverizing and obtain RAPRA method rubber powder, can obtain the above ultra tiny rubber powder of 200 orders, and the vulcanized rubber powder structure made from colloidal mill twist, surface-area is bigger, and during with rubber mass compounding, the physical strength of cross-linked rubber is good.But the technical process of this method is longer, and also there is the handling problem of waste liquid or waste water in the cost height.
Rubber powder has limited the application of rubber powder in rubber if the unprocessed physical and mechanical properties that can make sizing material in the sizing material that is incorporated into descends, and therefore, necessary activation treatment is to improve the surfactivity of rubber powder.In addition, the fineness of homemade rubber powder mostly not enough (even not reaching 40 orders), this is that China does not still have the suitability for industrialized production of low temperature process micro glue powder so far because be subjected to the restriction of crushing technology, disintegrating apparatus and refrigerant cost, thereby lay particular emphasis on activation modification by rubber powder, to remedy the deficiency of fineness.Table 3 shows, after fineness is brought up to a certain degree, though reinforcing effect further improves along with fineness, but it is and not obvious, this explanation is not reasonable economically desirable road merely by improving fineness yet, thus suitable fineness add the surface active modification can the higher rubber powder of acquired price ratio.
Table 3. different-grain diameter rubber powder is to the influence of sizing material tensile strength
The simplest method of rubber powder activation modification is a mechanochemical method, is about to chemical reaction properties-correcting agent and makes an addition in the rubber powder, and the tool effect that takes this opportunity under certain condition makes rubber powder produce chemical reaction and a kind of method of modified glue powder.This method is simple, practical, effective, is widely used.For the preparation of activated rubber powder, US5425904 is reported in and adds 1～4% latex, 0.5～3% sulphur (as vulcanizing agent) in the waste rubber powder, fully stirs 5～10 minutes under 70～90 ℃ of temperature, makes a kind of activated rubber powder; Chinese patent 96115406.3 was adding in the Hot mixer thorough mixing 7～9 minutes with the activator of 60～80 purpose rubber powders and 6～7%, 6～8% rubber cracking agent under 105～108 ℃ of temperature, obtain a kind of activated rubber powder; Chinese patent 200510022107.7 joins tetramethyl alkynediols in the waste tyre rubber powder according to 3～10% ratio, mixes and stirs wettingly under the normal temperature, obtains a kind of activating rubber powder.The technology of preparing of mentioning in the above patent all is traditional " pulverizing earlier, postactivated " production technique.Chinese patent 01113692.8 also discloses and has a kind ofly relied on the temperature in the crushing process to promote the activatory method.
Three, summary of the invention
The present invention aims to provide a kind of highly active vulcanized rubber powder, technical problem to be solved is to increase specific surface area by the irregular roughness of particle surface, mix the physical and chemical activity of rubber powder when rubber unvulcanizate vulcanizes thereby improve, strengthen rubber powder and combine, reach alternative part rubber but the constant purpose of over-all properties with the interface of cross-linked rubber.
The high-activity vulcanized rubber powder that the present invention is alleged, be that the micelle of pulverizing the median size 5～10mm that obtains with undesulfured waste old is a raw material, mixing fineness 60～100 order rubber powders that post-treatment obtains with active modification agent (can be by the rubber powder of 60～100 mesh sieves, about 0.15～the 0.25mm of median size is equivalent to fine glue powder by table 1 classification).This rubber powder is observed down the pattern of single powder in scanning electron microscope (SEM), similar expansible " puffed rice " or like fluffy " bobbles ", its surface tissue has countless concavo-convex, many tiny cracks, sees Fig. 1～Fig. 6; Specific surface area measuring instrument (BET method) is measured the specific area 〉=0.4m of this active colloidal powder
2/ g.
Described active modification agent is selected from: fluorine silanol oligomer thing, the tetrafluoroethylene oligopolymer, thiofide is (as N-oxygen diethylene-2-[4-morpholinodithio sulphenamide, the 2-benzothiazolyl mercaptan, dibenzothiazyl disulfide etc.), rubber anti-chark agent is (as the N-cyclohexylthiophthalimide, N-morpholine sulfo-phthalic imidine etc.), organic acid is (as oleic acid, citric acid etc.), softening agent is (as clorafin, polyester etc.) one or more mixed active modification agents in, addition is 2～5% of a micelle weight, when using two or more mixed active modification agent, relative proportion is any.
This rubber powder is like this preparation, at first micelle and active modification agent is mixed in proportion and obtains compound, processes with improved cold feed rubber machine then.Expect that from mixing rubber powder is successively through shearing, grind, push, heat up, boost and the release of pressure process, shear, grind under room temperature (≤30 ℃) and finish, by the extruding, (3～5sec) heat up, boost to 140～170 ℃ and 8～12MPa in moment, release of pressure obtains rubber powder under ℃ condition of temperature≤10 at last, rubber powder screens classification through sieve apparatus, crossing 60～80 purposes is high-activity vulcanized rubber powders, and the following person of 60 orders returns feed bin and waits for processing next time.
The effect of release of pressure is the high pressure gas abrupt release that makes in the sizing material internal void of high temperature, high volumetric stress rapidly, produce " puffed rice " effect, form " bobbles " shape particle, " bobbles " pattern " curing " is kept, prevent distortion and inter-adhesive simultaneously by cooling.High temperature, high pressure are moments, and active modification agent can not decompose.
This preparation method comprises batch mixing, shears, grinds, extruding, release of pressure and screening, difference with the prior art is ℃ condition down cut in temperature≤30, grinds, heat up, boost to 140～170 ℃ and 8～12MPa, release of pressure under ℃ condition of temperature≤10 at last by being squeezed in 3～5 seconds.
For this carries out following improvement to existing cold feed rubber machine:
(1) machine barrel, screw rod are selected high strength, high abrasion, scleroid steel alloy processing and manufacturing for use, and handle through brinelling on the surface again;
(2) machine barrel at the scissors of correspondence, grind the zone and be processed with the but chuck of usefulness of cooling, its exit end diameter amplifies and forms release of pressure district, also is processed with the but chuck of usefulness of cooling in the release of pressure district;
(3) with the supporting screw rod of machine barrel in corresponding shearing, grind region surface and be processed with fine and closely wovenly than shallow trench, be beneficial to shear and grind, its inside is processed into hollow and is beneficial to cooling, cooling.At crush zone, screw rod is transited into the screw channel of certain depth, is beneficial to extruding;
(4) gap between machine barrel and the screw rod along the material working direction by diminishing greatly gradually, promptly, less relatively at crush-zone in that to shear, grind difference relatively large, heat up, boost in order to moment.
This rubber powder adds to and carries out mixingly in the various rubber mass, can fully contact with sizing material, and contact area is more much bigger than other rubber powders.At the initial stage of sulfidation, the sizing material that is in the viscous state rubber unvulcanizate can be invaded in the tiny crack of this vulcanized rubber powder under sulfide stress, infiltrate its inside, continue to enlarge contact surface, and under the effect of its surfactivity modification agent, participate in the vulcanization reaction of sizing material, between the interface of rubber powder and sizing material, produce chemical bonding, thereby form strong interface binding power, make blending active colloidal powder of the present invention up to 30% vulcanized rubber material, still keeping original physical strength and performance constant substantially.This just makes this rubber powder alternative 30% even more virgin rubber, and its physical strength of the rubber item of being processed and performance are constant substantially.
Add the cost rubber powder and use universal machine, only need to improve a little, cost is low, energy consumption is little, pollution-free.
Four, description of drawings
Fig. 1～Fig. 6 is the SEM photo that 60～100 order NBR and active its surface topography of vulcanized rubber powder of EPDM of the present invention preparation is characterized with the Sirion of U.S. FEI Co. 200 type scanning electron microscope.Wherein Fig. 1～Fig. 3 is that the active vulcanized rubber powder of NBR amplifies 1000,10000,20000 times SEM photo successively; Fig. 4～Fig. 6 is that the active vulcanized rubber powder of EPDM amplifies 1000,10000,20000 times SEM photo successively.
From photo, can significantly find out the similar expansible of active colloidal powder " puffed rice " or like fluffy " bobbles " shape, its surface tissue is that countless concavo-convex, many tiny cracks are arranged.
Fig. 7, Fig. 8 have carried out the figure as a result that measures with the U.S. ASAP2020M+C of Micromeritics company type hole and specific surface absorption instrument to active its surface-area of vulcanized rubber powder of 60～100 order NBR, the EPDM of the present invention's preparation.Test philosophy is: adopt five-spot to make 1/Q (P
0/ P-1) to P/P
0Fitting a straight line, testing software calculates the specific surface area of sample automatically.As seen from the figure, the data point discreteness of test is less, and linear relationship is better, and test data is reliable.
Five, embodiment
1, active vulcanized rubber powder production
(1) with 100 parts through the median size 5～10mmNBR of twice magnetic separation purification scrap rubber grain and 1 part of fluorine silanol oligomer thing, a dibenzothiazyl disulfide and 1 part of N-cyclohexylthiophthalimide mix, add then in the hopper of improved cold feed rubber machine, starter motor and reflux cooling system, compound at first enters shearing, grind the district, under the effect of 25 ℃ and high shear force, torn and ground, then enter extruding, heating zone, temperature rises to 160 ℃ in 3～5sec, pressure rises to more than the 11MPa. under the dual function of high temperature and volumetric stress, lower boiling small-molecule substance in the rubber powder (b.p.＜160 ℃) is vaporized rapidly and is compressed, then enter release of pressure district (under the normal pressure) release of pressure immediately, at this moment the gas in the rubber powder microporosity sharply expands, produce " puffed rice " effect, and cooling rapidly under 5 ℃ of conditions, make " bobbles " pattern " curing ".
The active colloidal powder of preparation is decomposed through the sieve apparatus screening; after delivering to feed bin less than the thick rubber powder of 60 purposes; mix with micelle by a certain percentage again and return grinding machine and regrind, greater than 60 purpose rubber powders active colloidal powder product then for producing, can also be as required further sieve classification again.
(2) 100 parts are mixed through the median size 5～10mmEPDM of twice magnetic separation purification scrap rubber grain and 1 part of tetrafluoroethylene oligopolymer, 0.5 part of 2-benzothiazolyl mercaptan, 0.5 part of oleic acid and 0.5 part of clorafin.Later operation is with (1).20 ℃ of shearing, ground temperature, the control extruding is warming up to 150 ℃ and the above release of pressure of 10MPa, and release of pressure district cooling jacket temperature is controlled at 5 ℃.
2, adopt scanning electron microscope and specific surface area measuring instrument (BET method) to observe the pattern and the measurement the specific area of active colloidal powder respectively.See accompanying drawing 1～Fig. 8.The active vulcanized rubber powder specific surface area of NBR 0.42m in accompanying drawing 7
2/ g, the specific surface area 0.41m of the active vulcanized rubber powder of EPDM in accompanying drawing 8
2/ g.
3, active colloidal powder application testing
(1) application of the active vulcanized rubber powder of NBR butadiene-acrylonitrile rubber
See Table 5.
Table 5. adds the N7307 cross-linked rubber prototype test result of the active vulcanized rubber powder of NBR
| The N7307 cured properties | Technical requirements | Do not add rubber powder | Add 100 |
Add 100 order rubber powders 30% | |
| ??1 | Outward appearance and sectional layer | ??- | Indifference | Only section has been compared Light Difference with virgin rubber | |
| ??2 | Hardness, Shao A | ??70±5 | ??71 | ??71 | ??71 |
| ??3 | Tensile strength at yield/MPa | ??≥10 | ??11.1 | ??11.2 | ??11.0 |
| ??4 | Tensile yield/% | ??≥350 | ??423 | ??420 | ??414 |
| ??5 | Hot air aging (100 ℃ * 70h) |
| The N7307 cured properties | Technical requirements | Do not add rubber powder | Add 100 |
Add 100 order rubber powders 30% | |
| ??5.1 | Changes in hardness/Shao Er A/ degree | ??≤+15 | ??+6 | ??+6 | ??+7 |
| ??5.2 | Tensile strength at yield changes % | ??≤-20 | ??-2.9 | ??-3.0 | ??-3.1- |
| ??5.3 | Tensile yield variation/% | ??≤-30 | ??-19.1 | ??-20 | ??--19.6 |
| ??6 | The oil of anti-No.1 (100 ℃ * 70h) | ||||
| ??6.1 | Changes in hardness (Shao A)/degree | ??0～+10 | ??+6 | ??+7 | ??+7 |
| ??6.2 | Tensile strength at yield variation/% | ??≤-20 | ??+2.8 | ??+3.0 | ??+3.1 |
| ??6.3 | Tensile yield variation/% | ??≤-30 | ??-21.1 | ??-22 | ??-22 |
| ??6.4 | Volume change % | ??-10～+5 | ??-9.4 | ??-9.0 | ??-9.2 |
| ??7 | 100 ℃ * 70h of oil resistant, IRM903 oil | ||||
| ??7.1 | Changes in hardness/degree | ??0～-25 | ??-8 | ??-8 | ??-9 |
| ??7.2 | Tensile strength at yield variation/MPa | ??≤-35 | ??+0.8 | ??-2.7 | ??-3.2 |
| ??7.3 | Tensile yield variation/% | ??≤-35 | ??-9.1 | ??-9.9 | ??-10.2 |
| ??7.4 | Volume change/% | ??0～+30 | ??+10.1 | ??+10.1 | ??+10.6 |
| ??8 | Density/g/cm 3 | Sample ± 0.03 | ??1.270 | ??1.269 | ??1.270 |
*N7307 is enterprise's numbering of butyronitrile rubber unvulcanizate
Above testing data shows, mixes 20%, 30% the active vulcanized rubber powder of 100 order NBR, and the rerum natura of sulfuration NBR glue is not had influence substantially. grope to improve the incorporation of active colloidal powder by certain prescription, reduce cost better.
N7307 is enterprise's numbering of butyronitrile rubber unvulcanizate.
(2) application of the active vulcanized rubber powder of EPDM terpolymer EP rubber
See Table 6.
Table 6. adds the E6203K sulfuration prototype test result of the active vulcanized rubber powder of EPDM
| The E6203K cured properties | Technical requirements | Do not add rubber powder | Add 60 order rubber powders 20% | Add 80 order rubber powders 30% | |
| ??1 | Outward appearance and sectional layer | ??- | Equal indifference | Equal indifference | |
| ??2 | Hardness, Shao A/ degree | ??45～65 | ??57 | ??57 | ??57 |
| ??3 | Tensile strength at yield/MPa | ??≥10 | ??16.7 | ??16.2 | ??16.4 |
| ??4 | 100% tensile modulus/MPa | ??1.2～5 | ??2.0 | ??2.0 | ??2.1 |
| ??5 | Tensile yield/% | ??≥300 | ??476 | ??470 | ??475 |
| ??6 | Tear strength/KN/m | ??≥4 | ??4.8 | ??4.4 | ??4.7 |
| ??7 | 150 ℃ * 96h of hot air aging | ||||
| ??7.1 | Changes in hardness/Shao A/ degree | ??0～+10 | ??0 | ??+1 | ??+1 |
| ??7.2 | Tensile strength at yield/MPa | ??≥10 | ??17.4 | ??16.9 | ??16.8 |
| ??7.3 | Tensile yield/% | ??≥270 | ??447 | ??441 | ??442 |
| ??7.4 | 100% tensile modulus/MPa | ??≥1.2 | ??2.7 | ??2.8 | ??2.6 |
| ??7.5 | Tear strength/KN/m | ??≥4 | ??5.8 | ??5.6 | ??5.6 |
| ??8 | 150 ℃ * 96h of anti-cooling fluid (water/ethylene glycol=50/50) | ||||
| ??8.1 | Changes in hardness/Shao A/ degree | ??-4～+6 | ??-2 | ??-2 | ??-2 |
| ??8.2 | Tensile strength at yield/MPa | ??≥10 | ??15.7 | ??14.8 | ??15.0 |
| ??8.3 | Tensile yield/% | ??≥300 | ??421 | ??416 | ??418 |
| ??8.4 | 100% tensile modulus/MPa | ??≥1 | ??2.0 | ??1.9 | ??2.0 |
| ??8.5 | Tear strength/KN/m | ??≥4 | ??4.7 | ??4.5 | ??4.6 |
| The E6203K cured properties | Technical requirements | Do not add rubber powder | Add 60 order rubber powders 20% | Add 80 order rubber powders 30% | |
| ??8.6 | Quality change/% | ??0～+6 | ??+2.0 | ??+2.2 | ??+2.1 |
| Density/g/cm 3 | ??1.049 | ??1.05 | ??1.05 |
*E6203K is enterprise's numbering of Ethylene Propylene Terpolymer rubber unvulcanizate
Above data presentation, add 30%80 order rubber powders after, the basic no change of cross-linked rubber rerum natura; Add 20%60 order rubber powders, because of particle diameter is bigger, cross-linked rubber intensity slightly changes.
E6203K is enterprise's numbering of Ethylene Propylene Terpolymer rubber unvulcanizate.
Claims (2)
1. high-activity vulcanized rubber powder, micelle with undesulfured median size 5～10mm is a raw material, it is characterized in that: the micelle of median size 5～10mm and 2～5% active modification agent mix fineness 60～100 purpose rubber powders that post-treatment obtains, exterior appearance such as fluffy " bobbles ", specific surface area 〉=0.4m
2/ g.
2. by the preparation method of the described high-activity vulcanized rubber powder of claim 1, comprise batch mixing, shear, grind, extruding, release of pressure and screening, it is characterized in that: shear during in temperature≤30 ℃, grind, grind the back and be warming up to 140～170 ℃ and 8～12MPa in 3～5 seconds, at last ℃ following release of pressure in temperature≤10 by being squeezed in.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008102438299A CN101747527B (en) | 2008-12-16 | 2008-12-16 | High-activity vulcanized rubber powder and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102438299A CN101747527B (en) | 2008-12-16 | 2008-12-16 | High-activity vulcanized rubber powder and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101747527A true CN101747527A (en) | 2010-06-23 |
| CN101747527B CN101747527B (en) | 2011-12-28 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2008102438299A Expired - Fee Related CN101747527B (en) | 2008-12-16 | 2008-12-16 | High-activity vulcanized rubber powder and preparation method thereof |
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| CN (1) | CN101747527B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010531A (en) * | 2010-11-17 | 2011-04-13 | 安徽安大中鼎橡胶技术开发有限公司 | Modified-surface activated waste vulcanizate powder |
| CN102888019A (en) * | 2012-09-28 | 2013-01-23 | 郭光� | Technology for modifying vulcanized rubber powder |
| CN109503865A (en) * | 2018-12-18 | 2019-03-22 | 广西远景资源再生有限公司 | A kind of technique that rubber powder surface is modified |
| CN109942923A (en) * | 2018-12-28 | 2019-06-28 | 宿迁绿金人橡塑机械有限公司 | A kind of formula for preparing Mooney viscosity and stablizing reclaimed rubber |
| CN110003677A (en) * | 2019-04-24 | 2019-07-12 | 安徽大学 | A kind of halogen-free polypropylene flame redardant wood plastic composite and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL9002673A (en) * | 1990-12-05 | 1992-07-01 | Vredestein Icopro Bv | METHOD FOR ACTIVATING VULLCANIZED WASTE RUBBER PARTICLES AND METHOD FOR MANUFACTURING A RUBBER-ARTICLE USING THE ACTIVATED WASTE RUBBER PARTICLES |
| CN1169661C (en) * | 2001-06-14 | 2004-10-06 | 刘扬生 | Process for directly producing active rubber powder with waste rubber |
| CN1308084C (en) * | 2004-07-19 | 2007-04-04 | 四川大学 | Method of preparation high surface activity rubber powder by waste tyre |
-
2008
- 2008-12-16 CN CN2008102438299A patent/CN101747527B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010531A (en) * | 2010-11-17 | 2011-04-13 | 安徽安大中鼎橡胶技术开发有限公司 | Modified-surface activated waste vulcanizate powder |
| CN102888019A (en) * | 2012-09-28 | 2013-01-23 | 郭光� | Technology for modifying vulcanized rubber powder |
| CN109503865A (en) * | 2018-12-18 | 2019-03-22 | 广西远景资源再生有限公司 | A kind of technique that rubber powder surface is modified |
| CN109942923A (en) * | 2018-12-28 | 2019-06-28 | 宿迁绿金人橡塑机械有限公司 | A kind of formula for preparing Mooney viscosity and stablizing reclaimed rubber |
| CN110003677A (en) * | 2019-04-24 | 2019-07-12 | 安徽大学 | A kind of halogen-free polypropylene flame redardant wood plastic composite and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101747527B (en) | 2011-12-28 |
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