CN101875730A - Rubber-metal bonding enhancer for steel wire radial tyre and preparation method thereof - Google Patents
Rubber-metal bonding enhancer for steel wire radial tyre and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of rubber chemicals and discloses a rubber-metal bonding enhancer for a steel wire radial tyre. The enhancer is prepared from four kinds of metal salts of cobalt, nickel, copper and zinc; and the proportion of the metal salts by metal molar mass: cobalt: nickel: copper: zinc is (50% to 70%): (20% to 40%): (6% to 10%): (2% to 4%). The preparation method of the bonding enhancer comprises the steps of: using the four kinds of metal salts as starting materials to sequentially prepare alkali carbonate metal composite salt by a temperature gradient method and a concentration step method, prepare an intermediate by a continuous dehydration method and prepare low cobalt boroacylate metal composite salt by a boroacylate replacement reaction to obtain the bonding enhancer. In the invention, the proportion of the cobalt is regulated to 50% to 70% from 100% in a traditional technology; and the consumption of precious metal cobalt is reduced; the cost is reduced by 10% to 20%. The physical and chemical indexes and utilization property of the product of the invention are equivalent to those of a boroacylate cobalt product; and the drawing force and retention rate of an aged product are better than those of the boroacylate cobalt product.
Description
Technical field
The invention belongs to the rubber ingredients field, relate to a kind of rubber-metal bonding enhancer for steel wire radial tyre of low cobalt content specifically.
Background technology
In producing the radial wire cord tire process, the rubber that contacts with steel wire endless belt and steel wire band, in the rubber unvulcanizate process, need to add cobalt salt adhesive, to improve the bounding force between steel wire and the rubber, and the lasting bonding effect of maintenance, to reduce the possibility that tire is blown out under the load-carrying and the state that runs up, security, use properties and the life-span of improving radial wire cord tire.
The prescription of existing cobalt salt adhesive and production method are:
1. metal proportioning: 100% cobalt metal (embodying) with rose vitriol or cobalt chloride form;
2. cobaltous dihydroxycarbonate production: rose vitriol or cobalt chloride are dissolved as the solution of 30% concentration in reactor (or reactive tank), continuing under the evenly stirring, the sodium carbonate solution that will be stored in 40% concentration in the header tank under 80～85 ℃ of temperature utilizes action of gravity to add reaction in the reactor (or reactive tank), and reaction end pH value is controlled at 9.0～9.5.To obtain cobaltous dihydroxycarbonate behind material precipitation, cleaning, press filtration, the drying and dewatering;
Reaction equation is as follows:
3. synthetic intermediate: adding reactor according to quantitative various organic acids of formula calculation and solvent below 50 ℃, add cobaltous dihydroxycarbonate then, and stir temperature reaction, and total reflux occur behind the cut, 90～110 ℃ of temperature ranges through 1 hour.Total reflux finishes, and heats up solvent and water are deviate from simultaneously, and 110～190 ℃ of temperature ranges vacuumize to 190 ℃ and to get rid of residual water-content and solvent, obtain intermediate;
Reaction equation is as follows:
Used organic acid is C
3～C
18Saturated carboxylic acid.
4. boron acidylate replacement(metathesis)reaction process: intermediate cools to 170 ℃; in intermediate, add quantitative tributyl borate, carry out boron acidylate replacement(metathesis)reaction, progressively be warming up to 220 ℃; vacuum is taken off most byproduct, and reaction product obtains particulate state cobalt boracylate product after the melting granulator granulation.
Reaction equation is as follows:
The prescription of above-mentioned prior art and production method existing problems have:
1. the problem of filling a prescription: cobalt is a kind of scarce resource, costs an arm and a leg, and prior art adopts the production of inorganic of 100% cobalt, and the cost of inorganic cobalt salt accounts for 70% in one ton of cobalt boracylate product material cost, and product cost is very high;
2. problem during cobaltous dihydroxycarbonate is produced: the dispersity of alkali lye is not enough, the concentration of lye height, this moment, concentration of metal ions was also very high, the alkali lye and the metal inorganic salt that add sharply react, easily moment generates the carbonate (that is we usual alleged partial over-alkali) of standard construction, though the relatively thick precipitation easily of the carbonate crystallization of standard construction, the reactive behavior of itself and weak organic acid is not enough.Just can obtain our required subcarbonate so must carry out Structure Conversion.The carbonate of the standard construction that generates in order to make is converted to subcarbonate, and the enough reaction times must be arranged, and simultaneously the later stage more will be controlled the adding speed of alkali lye well.This has just prolonged reaction times and reduced production efficiency, and has at least 3% above divalent cobalt ion to be oxidized to can not to participate in building-up reactions trivalent cobalt ion, cause the decline of metal yield, influence product structure, raise the cost;
3. intermediate building-up reactions problem:
The a total reflux time is not enough, and the organic acid that causes being partially soluble in water causes environmental pollution and influences product structure along with steaming with the solvent azeotropic and running off, and further influences physical and chemical performance and use properties;
B solvent and water are together deviate from, and are unfavorable for the effective elimination of water generation reaction, make reaction process difficult to reach terminal point, have reduced efficient.And material viscosity increases, and is unfavorable for reacting the carrying out of uniform and complete, influences product structure;
C need consider cobalt ion oxidation ratio problem, adopts the excessive required various organic acid quality of computation schemes of cobalt.Because of cobalt ion oxidation ratio difference, it is unbalance to cause filling a prescription, and influences the physical and chemical performance and the use properties of product.
4. cobalt boracylate product very easily moisture absorption oxidation in storage influences the bond properties of product.General preservation period is no more than 1 year.
Present improvement for the cobalt boracylate product also is confined to the improvement to its technology basically; as publication number is the Chinese patent application of CN101643480A, and publication number is that Chinese patent application and the publication number of CN101003544A is Chinese patent application of CN101348505A or the like.
Summary of the invention
The objective of the invention is to by a kind of new prescription and novel process; produce the substitute products of cobalt boracylate-low cobalt boron acidylate bimetallic salt complex, reach effectively reduce cost, improve the metal yield, reduce environmental pollution, stable prod structure, extending the shelf life guarantees and improves the physical and chemical indexes of product and the purpose of use properties.
Specifically, technical scheme of the present invention is as follows:
A kind of rubber-metal bonding enhancer for steel wire radial tyre, it is to adopt four kinds of metal-salts of cobalt, nickel, copper and zinc to prepare, and described metal-salt in the proportioning of metal molar quality is: cobalt: nickel: copper: zinc=50～70%:20 ~ 40%:6 ~ 10%:2 ~ 4%.
As preferred version, according to rubber-metal bonding enhancer for steel wire radial tyre of the present invention, wherein, wherein said metal molar quality proportioning is a cobalt: nickel: copper: zinc=50:40:7.5:2.5, the product that adopts this proportioning to obtain can reach service requirements, and substitutes the cobalt metal to greatest extent.
As preferred version, according to rubber-metal bonding enhancer for steel wire radial tyre of the present invention, wherein, described metal-salt embodies with vitriol or chlorate form.Reason is that employing chlorate and sulfate process process are fairly simple, and the work in-process of the subcarbonate structure of the metal active that can be maintained.
As preferred version, according to rubber-metal bonding enhancer for steel wire radial tyre of the present invention, wherein, described adhesiving reinforcing agent also contains the paraffin of its weight 2-5%.Discover; adopt the boron acidylate bimetallic salt complex of four kinds of metal-salt preparations of the present invention; its fusing point is higher than boron acidylate cobalt product a little; for further optimizing product performance, the contriver filters out a kind of processing aid of polyolefine-paraffin through a large amount of research trials; the adding of test card alum wax; improve the physical and chemical indexes of product, also further improved dispersiveness and the mutual solubility of product in rubber unvulcanizate, improved the bounding force of product.Formed layer protecting film at product surface during granulation simultaneously, slowed down the speed of the product moisture absorption and oxidation, the quality guaranteed period of product can prolong more than half a year.
Cobalt is a kind of scarce resource, costs an arm and a leg, and prior art adopts the production of inorganic of 100% cobalt, and the cost of inorganic cobalt salt accounts for 70% in one ton of cobalt boracylate product material cost, and product cost is very high.The theoretical foundation of products material prescription of the present invention is cobalt adhesive effect mechanism and has the metal of same electrical sublayer distribution to have similar characteristic.
The mechanism of action of cobalt salt adhesive in radial is as follows:
(1) steel wire adopts brass coating in the radial, and brass is the alloy of copper and zinc, and in tire vulcanization process, the inner complex of copper, zinc and sulphur (vulcanization accelerator) generates Cu
xS and ZnS, Cu
xS has very strong chemical bond; ZnS and Cu
xThe formation of S makes cupric ion and zine ion carry out scattering and permeating subsequently; Since dendroid (dentation) structure, Cu
xThe S layer can produce very strong bonding force with vulcanized rubber by strong physical linkage power.(2) because ion produces transport phenomena (dezincify), the product ratio is easier to aging and causes: Cu
xMore and more thicker (if the Cu of S layer
xIt is very thick that the S layer becomes, so Cu
xThe S layer will come off with brass), form and thickeied ZnO/Zn (OH)
2Very weak border, ZnS(does not have chemical bond) in the limit, form, its position is nearest from rubber components, and the dezincify process is considered to the topmost factor that causes the bonding failure.(3) if in prescription, introduce cobalt salt adhesion promotion agent, then situation changes: cobalt is introduced into zone of oxidation and has greatly entered to ratio the metal sulphide layer on upper strata, along with metallic sulfide ground increases, cobalt has been considered to replace relative brass and zinc mixing zone to guarantee preferentially to form Cu
xS, relative inhibition the generation of ZnS.Cobalt is considered to be retained in blank dot matrix zone of oxidation of nonstoichiometry sulfuric horizon and the slit owing to the generation of metal fused layer with the CoS form.Dezincify process in this way, gradual slow has been set up ZnO and has correspondingly been set up cohesive strength (key is strong) subsequently.
From cobalt adhesive effect mechanism, in conjunction with steel wire coating is the characteristic of brass (brass is copper zinc alloy), the contriver has studied the characteristic of various metals, have the characteristics of similar characteristics from metal with similar electronic shell distribution, copper, zinc, class copper metals such as nickel and cobalt have proximate electron structure, metal with approximate electron structure has some identical physicochemical characteristic usually, as variable valency, magnetic, ductility, oxidation-reduction quality etc., in the periodic table of chemical element, cobalt nickel is adjacent, copper zinc is adjacent, and also exist with the mineral intergrowth form at occurring in nature cobalt nickel, we draw in view of the above, copper, zinc, nickel is the same with cobalt, also has certain bond properties.The scheme that nickel, copper, zinc three kind copper metals replace part cobalt metal is selected in proposition from metal family.And nickel, copper, zinc will be higher than cobalt far away at natural reserves, are easy to get, and price is also relatively cheap, adopts composition of raw materials of the present invention, has reduced the consumption of cobalt resource, significantly reduces production costs.
In composite metal, cobalt has extremely similar characteristic with nickel, outermost layer also has two electronics, quite (cobalt is 58.93 to molecular weight, nickel is 58.69), and cobalt and nickel are present in nature with symbiotic form usually, have highly similar metal active, therefore infer that nickel necessarily has the adhesive effect similar with cobalt.The texture ratio of B-O-Ni-R a little less than, Ni in the sulfidation
2+Can rupture from molecular chain rapidly, with rubber highly " transportation " following and sulphur formation NiS of the hydroxy-acid group of mutual solubility is being arranged, can enter each layer metallic compound interface by replaced C oS, also can suppress the formation of ZnS in the interface, and NiS also has very strong chemical bond, therefore, though the content of cobalt has descended in the new prescription, but nickel has played substituting effect, can't cause the decline of bounding force.
And copper zinc also is the metal that constitutes steel wire coating except having similar electronic shell distributes with cobalt.Consider Cu
xS has very strong chemical combination key, if can form more Cu
xS then can improve Cu
xThe bounding force of S layer and rubber.And zinc is a kind of framework material in the rubber compounding, can improve rubber intensity, and the adding of zinc can make the zinc on the coating be slowed down, and under the inhibition of cobalt and nickel, can not form ZnS with reaction of Salmon-Saxl, has the very ZnO of strong chemical bond and slowly generate.Because the coating of steel wire is extremely thin, if the formation compound of copper in the coating and zinc overdose, then coating easily and steel wire itself come off, cause adhesion failure.Therefore, an amount of adding copper and zinc in prescription, the persistence that helps to prolong bounding force.
After having drafted alternative metals, single kind copper metal and the test of cobalt metal under different ratios have at first been carried out, the feasibility of checking replacement scheme.Test shows that the single replacement scheme of various metals is feasible, and this direction that has proved imagination is correct.If but the ratio that replaces cobalt is very low, then can not significantly reduce cost,, cause quality product to go wrong again easily if the replacement amount is too high or arrange in pairs or groups unreasonablely.Can either make product reach technical requirements in order to find out, the preferred plan that can reduce cost to greatest extent again, the present inventor has designed staggered testing program, has carried out a large amount of basic tests.According to the result who the lab scale sample has been carried out test and test, final determining that composition of raw materials of the present invention prepares the rubber-metal bonding enhancer for steel wire radial tyre product for four kinds of metal-salts that adopt cobalt, nickel, copper and zinc, is cobalt in the proportioning of metal molar quality: nickel: copper: zinc=50 ~ 70%:20 ~ 40%:6 ~ 10%:2 ~ 4%.Be cobalt with metal molar quality proportioning wherein: nickel: copper: zinc=50:40:7.5:2.5 is as preferred version, and product can reach service requirements, and substitutes the cobalt metal to greatest extent.Described metal-salt embodies with vitriol or chlorate form.
The present invention also provides the preparation method of above-mentioned rubber-metal bonding enhancer for steel wire radial tyre, and it comprises the steps:
(1) temperature gradient method and concentration staircase method prepare the basic carbonate bimetallic salt complex, and detailed process is (referring to an accompanying drawing 1):
A. prepare mass concentration and be three kinds of sodium carbonate solutions of 15%, 25% and 35%, standby;
B. four kinds of metal-salts are mixed with the solution that mass concentration is 25-35%, be warming up to after 55 ℃ that slowly to add concentration be 25% sodium carbonate solution, and be warming up to 70 ℃ gradually, when the pH value reaches 7, slow adding concentration is 35% sodium carbonate solution in reaction mass, and be warming up to 80 ℃ gradually, when the pH value reaches 9.5, slow adding concentration is 15% sodium carbonate solution in reaction mass, and be warming up to 85 ℃ gradually, and reaching reaction in 10 o'clock to the pH value and finish, whole process need constantly stirs, the material that obtains is through precipitation, clean, obtain the basic carbonate bimetallic salt complex after press filtration and the drying, enter next step;
Reaction equation is as follows:
In the formula, Me represents a kind of metal in cobalt, nickel, copper, the zinc.
Add the vaporific yellow soda ash alkali lye of 25% concentration 55～70 ℃ temperature ranges, and control its pH value in 7, make each metal ion species evenly generate transitional period product of subcarbonate earlier, also guarantee that the reaction of each metal ion species carries out synchronously simultaneously; After the pH value reached 7, initial reaction was finished, and heated up gradually, and added the vaporific yellow soda ash alkali lye of 35% concentration, and the transitional period product that impels subcarbonate is to the subcarbonate structural transformation, and produced compound (because of subcarbonate comprises two metal ions); When temperature reaches 80 ℃, the pH value reaches at 9.5 o'clock, structural transformation is finished substantially, but in order to impel each metal ion species better compound, also must go into the vaporific yellow soda ash alkali lye of 15% concentration, be warming up to 85 ℃, adjust pH value to 10, impel the carbonate structure all to convert basic carbonate bimetallic salt complex structure to.
Because of various metal reaction speed differences, tradition need produce subcarbonate separately, mixes then, causes production efficiency low, the energy consumption height; Quality is synthesized in mechanically mixing product homogeneity and active bad influence.Use explained hereafter of the present invention, having prevented to cross the alkali phenomenon takes place, the disposable basic carbonate bimetallic salt complex structure that obtains standard (can judge below 0.3% that from the heptane insolubles of producing the gained finished product with these work in-process what obtain is basic carbonate bimetallic salt complex structure), reactive behavior and homogeneity have been guaranteed, reduced the oxidation ratio of metal ion, in preferred version of the present invention, adopt the de-oiling dried compressed air to blow the oxidation that the filter dehydration can further prevent metal ion simultaneously, improve the metal yield, enhance productivity, cut down the consumption of energy, reduce cost.
(2) the continuously dehydrating legal system is equipped with intermediate, and detailed process is (referring to an accompanying drawing 2):
The organic acid of long-chain and the solvent of weight of solvent 65 ~ 75% in adding in the reactor, add the basic carbonate bimetallic salt complex then, stir 30 ~ 40min, divide the organic acid that adds short chain for several times again, each 15 ~ 20min at interval, add remaining solvent at last, heat up gradually after stirring 50 ~ 60min, temperature keeps refluxing 2 hours between 90-110 ℃, between 105-170 ℃, carry out continuously dehydrating then and make the solvent internal reflux, between 170-190 ℃, vacuumize at last and take off most solvent, obtain intermediate, enter next step
Described organic acid is C
3-C
18Saturated carboxylic acid; Solvent is a dimethylbenzene; Wherein said organic acid: solvent: the weight proportion of basic carbonate bimetallic salt complex is 33 ~ 36%:21 ~ 24%:41 ~ 44%.
Reaction equation is as follows:
Me represents any one in cobalt, nickel, copper, four kinds of metallic elements of zinc in the formula, and R-COOH represents organic acid.
Because the organic acid of short chain is easier and basic carbonate metal composite reactant salt, reactant will increase material viscosity, be unfavorable for that blocky basic carbonate bimetallic salt complex dissolving disperses, can influence the synthetic thoroughness, so organic acid and most of solvent of long-chain in adding earlier, one is the organic acid and the reaction earlier of basic carbonate bimetallic salt complex of long-chain in promoting, another makes block basic carbonate bimetallic salt complex be dissolved in material by stirring to form tiny particle, guarantee that reaction can be abundant, prevent that the later stage from producing half-cooked material; Simultaneously, try to be the first and basic carbonate metal composite reactant salt for the organic acid of controlling short chain, form a large amount of short chain organic salt, control by the mode that minute minor tick adds, make the various reaction product can be even, this feed way can prevent effectively that also " dashing material " phenomenon from taking place; Prolong the total reflux process, water-soluble organic acid can be returned in the reactor react fully, prevent that the acid loss from causing environmental pollution, guaranteed that also metal can all participate in reaction, improves yield, the stable prod structure with material; Continuously dehydrating technology assurance water can constantly be deviate from, and (latent heat of vaporization of water is very high, utilize water and solvent azeotropic characteristics to quicken dehydration at this) and take off to the greatest extent, make reaction quicken to carry out also reaching terminal point towards positive dirction, the solvent that refluxes can reduce the viscosity of product, the contact surface of organic acid and solid salt is increased greatly, improve the condition of reaction, reaction is carried out uniformly, also further accelerated to react the speed that reaches terminal point, can prevent also that simultaneously " dashing material " phenomenon from taking place; In the end deviate from the process of solvent,, also can guarantee to take off to the greatest extent in this stage even contain a spot of water; Have benefited from extremely low oxidation ratio of basic carbonate bimetallic salt complex and good activity, in calculating synthesizing formula, need not the problem of considering that metal is excessive, keeping the mole proportion balance to calculate required material with organic acid and salt gets final product, guarantee that product structure is stable, this also is the better major reason of aged properties during product uses.
The work in-process that adopt this explained hereafter to go out, reaction is thorough, Stability Analysis of Structures.This novel process has effectively solved the problem that the sour water dissolubility runs off, reduced environmental pollution, also make metal ion fully participate in reaction, improve yield, fine basic carbonate bimetallic salt complex has guaranteed the balance of prescription, make the structure of product normally stable, provide assurance for obtaining the fine the finished product.Effectively dewatering process guarantees that reaction reaches terminal point fast, has improved efficient, has reduced energy consumption.
(3) the low cobalt boron acidylate bimetallic salt complex of boron acidylate replacement(metathesis)reaction preparation, detailed process is (referring to an accompanying drawing 3):
The tributyl borate that in the time of 170 ℃, in intermediate, slowly adds metal molar quality/3 * 230 weight; be warming up to 215 ℃ and be incubated 50 ~ 60min gradually; fully carry out boron acidylate replacement(metathesis)reaction; vacuum is taken off most byproduct then; be cooled to 190 ℃ of processing aid of polyolefine paraffin that add product theoretical weight 2-5% again; the back granulation that stirs obtains the low cobalt boron acidylate bimetallic salt complex of particulate state, promptly described rubber-metal bonding enhancer for steel wire radial tyre.
Reaction equation is as follows:
Me represents any one in cobalt, nickel, copper, four kinds of metallic elements of zinc in the formula.
Adopt the low cobalt boron acidylate bimetallic salt complex that the present invention newly fills a prescription, the novel process scheme is produced, the purer cobalt product of its fusing point height (fusing point of pure cobalt product cobalt boracylate is 90 ~ 110 ℃, and fusing point of the present invention is 100 ~ 125 ℃).Fusing point is high can to influence solvability and the dispersiveness of product in rubber; thereby influence use properties; in order to address this problem; cause problems such as quality guaranteed period weak point in conjunction with the easy moisture absorption of boron acidylate metal composite product salt and oxidation; the contriver has filtered out a kind of processing aid of polyolefine-paraffin; be the effect that improves boron acidylate bimetallic salt complex fusing point index of realizing ideal, the add-on of paraffin is a most suitable proportional range at 2～5% of theoretical product weight.Add paraffin, also improved the mutual solubility of boron acidylate bimetallic salt complex and rubber simultaneously, impel more effective being dispersed in the rubber of product energy, improve bounding force; After adding paraffin, it forms layer protecting film at product surface, can effectively prevent the product oxidation and the moisture absorption, makes shelf life of products extend to a year and a half from 1 year.
As preferred version, preparation method according to rubber-metal bonding enhancer for steel wire radial tyre of the present invention, wherein, sodium carbonate solution is prepared and is incubated standby under 75 ~ 80 ℃ among the A of described step (1), and the temperature of sodium carbonate solution remains between 60-80 ℃ in the reaction process; Slowly add among the B and operate as follows: sodium carbonate solution adopts topping-up pump, adds in the mode of spraying, and with the speed of reverse flow valve control liquid feeding, speed control is at 3.4 ~ 4.5kg/min; The mode that drying among the B adopts dried compressed air to blow filter is dewatered; Temperature rise rate is controlled at 5 ℃/h among the B.
Temperature to sodium carbonate solution is controlled, and guarantees to form microcrystallization because of the alkali liquid temperature back that descends, and is mixed in the product, and another prevents that alkali liquid temperature from crossing low delayed response, and forms a false pH value, and the degree of reacting is judged in influence.The pump supercharging of yellow soda ash alkali lye adds in the mode of spraying, with the speed of reverse flow valve control liquid feeding, the alkali lye of Jia Ruing is vaporific like this, can evenly react slowly with salts solution, prevent that the part inorganic salt from producing carbonate rapidly, also just say to prevent partial over-alkali.Cleaned basic carbonate bimetallic salt complex, blow filter with dried compressed air, the moisture that rests in the pressure filter is further discharged, reduce water content, reduced the process of oven dry, prevent that divalent-metal ion is because of the oven dry oxidation, improve the yield of metal, and the water content minimizing, also reduced the time of dewatering for the back step is synthetic, cut down the consumption of energy, raise the efficiency.
As preferred version, according to the preparation method of rubber-metal bonding enhancer for steel wire radial tyre of the present invention, wherein, the rate-controlling that heats up gradually in the described step (2) is at 15 ~ 20 ℃/h; The vacuum tightness that vacuumizes is-0.07 ~-0.08Mpa, moisture and solvent are all taken off to the greatest extent guaranteeing.
As preferred version, according to the preparation method of rubber-metal bonding enhancer for steel wire radial tyre of the present invention, wherein, the speed that heats up gradually in the described step (3) is 5 ~ 10 ℃/h; The vacuum tightness of vacuum is-0.07 ~-0.08Mpa, by product is all taken off to the greatest extent guaranteeing.
Compared with prior art, advantage of the present invention has:
1, metal proportioning: the ratio of cobalt metal is adjusted into 50～70% from 100%, has reduced the consumption of noble metal cobalt, reduces cost 15～20%, and its usage quantity as rubber to metal adhesive is the same with cobalt boracylate.
2, developed the technology that temperature gradient method and concentration staircase method are once produced the basic carbonate bimetallic salt complex.The basic carbonate bimetallic salt complex that adopts this explained hereafter to go out has the active and homogeneity highly of same reaction, and energy and organic acid carry out synchronous reaction, the disposable basic carbonate bimetallic salt complex (Me that obtains
2(OH)
2CO
3), prevent to produce standard construction carbonate (MeCO
3), raise the efficiency more than 50%, cut down the consumption of energy about 15%.Also effectively solved the problem that is oxidized to trivalent metal cation in the traditional technology production process because of the drying and dewatering divalent metal by the dehydration of de-oiling dried compressed air, since in the process that generates the basic carbonate composite salt also better controlled the bivalent ions oxidation of cobalt, adopt the bivalent ions oxidation ratio of cobalt of this technology to be controlled at below 0.3%, and the oxidation ratio of traditional technology is generally greater than 3%; Efficiently solve the building-up reactions instability problem that mechanically mixing is brought simultaneously, improved production efficiency, the metal yield has improved more than 2.5%, has reduced energy consumption and production cost.
3, developed continuously dehydrating technology.This novel process has effectively solved the problem that the sour water dissolubility runs off, reduced environmental pollution, also make metal ion fully participate in reaction, improve yield, fine basic carbonate bimetallic salt complex has guaranteed the balance of prescription, make the structure of product normally stable, help improving the physical and chemical indexes and the use properties of product, provide assurance for obtaining the fine the finished product; Effectively dewatering process guarantees that reaction reaches terminal point fast, has improved efficient, has reduced energy consumption.
4, the adding of processing aid of polyolefine-paraffin has improved the physical and chemical indexes of product, has also further improved dispersiveness and the mutual solubility of product in rubber unvulcanizate, has improved the bounding force of product.Formed layer protecting film at product surface during granulation simultaneously, slowed down the speed of the product moisture absorption and oxidation, the quality guaranteed period of product can prolong more than half a year.
5, adopt the product of prescription of the present invention and explained hereafter, physical and chemical indexes reaches the company standard requirement fully, and it is suitable with cobalt boracylate product effect that use properties reaches client's requirement fully, and extraction power and conservation rate after wearing out are better than the cobalt boracylate product slightly.
Description of drawings
Fig. 1 is the present invention produces the basic carbonate bimetallic salt complex with temperature gradient method and concentration staircase method a process flow sheet.
Fig. 2 is the process flow sheet of the present invention with continuously dehydrating explained hereafter intermediate.
Fig. 3 is a boron acidylate replacement(metathesis)reaction process flow sheet of the present invention.
Embodiment
Below in conjunction with embodiment, be described more specifically content of the present invention.Should be appreciated that enforcement of the present invention is not limited to the following examples, all will fall into protection domain of the present invention any pro forma accommodation and/or the change that the present invention made.
In the present invention, the per-cent of metal proportioning is molar mass per-cent, and other all parts, per-cents that do not refer in particular to are weight unit, and all equipment and raw material etc. all can be buied from market or the industry is commonly used.
Embodiment 1
Get the raw materials ready according to the proportioning under 1 of the embodiment in the table 1, low cobalt boron acidylate bimetallic salt complex prepares as follows:
(1) temperature gradient method and concentration staircase method are produced the basic carbonate bimetallic salt complex
A. yellow soda ash is dissolved as concentration respectively and is 15%, 25%, 35% solution under 80 ℃ of temperature, respectively
The different storage tanks of putting into insulation are standby, and the temperature of sodium carbonate solution remains between 60-80 ℃ in the reaction process;
B. rose vitriol, single nickel salt, copper sulfate and zinc sulfate water are dissolved into the solution of 35% concentration, place reactor, under lasting the stirring, heat up with 5 ℃/h speed, in the time of 55 ℃, begin to add concentration with the topping-up pump atomizing and be 25% sodium carbonate solution, and be warming up to 70 ℃ with 5 ℃/h speed gradually, control pH to 7.0.When the pH value reached 7.0, the concentration that adding atomizes with topping-up pump in reaction mass was 35% sodium carbonate solution again, and is warming up to 80 ℃ with 5 ℃/h speed gradually, control pH value to 9.5.When the pH value reached 9.5, the concentration that adding atomizes with topping-up pump in reaction mass was 15% sodium carbonate solution again, and is warming up to 85 ℃ with 5 ℃/h speed gradually, control pH value to 10.0, and reaction finishes.When the basic non-foam of material liquid surface, putting into washing trough is cooled to below 50 ℃ and is pressed into the pressure filter continuous wash, after below the rinse water pH value to 6, further dewater, anhydrously draw off the basic carbonate bimetallic salt complex that obtains standby after deviating from the de-oiling dried compressed air
(2) continuously dehydrating explained hereafter intermediate
The acid (being neodecanoic acid, PIVALIC ACID CRUDE (25) and rosin) of long-chain and the solvent xylene of solvent total amount 75% in reactor, adding earlier under 50 ℃, add the basic carbonate bimetallic salt complex again, stir 30min, divide 3 times by the speed of each interval 15min again and add short chain organic acid (being propionic acid), add residual solvent at last, slowly heat up with 15 ℃/h speed behind the stirring 60min.Begin to occur cut when temperature is raised to more than 90 ℃, opens the total reflux valve, cut all is back in the reactor, the internal reflux time kept 2 hours, and this phase temperature is 90～110 ℃.Internal reflux finishes, beginning continuously dehydrating process, solvent refluxing is to reactor simultaneously, this phase temperature remains on 105-115 ℃, until substantially anhydrous deviate from after, heating up steams solvent, this phase temperature scope is 115～170 ℃.Beginning to be evacuated to 190 ℃ to 170 ℃ and take off most solvent, vacuum tightness is-0.07 ~-0.08Mpa, obtain intermediate, enter next step,
(3) the boron acidylate generates low cobalt boron acidylate bimetallic salt complex
When 170 ℃ of temperature, in intermediate, slowly add tributyl borate; heat up gradually; temperature rise rate increases progressively gradually along with temperature raises, and temperature rise rate changes between 5-10 ℃, is warming up to 215 ℃; be incubated 1 hour; fully carry out boron acidylate replacement(metathesis)reaction, vacuum is taken off most byproduct then, and vacuum tightness is-0.07 ~-0.08Mpa; in reaction product, add paraffin after being cooled to 190 ℃, stir after obtain the low cobalt boron acidylate metal composite product salt of particulate state after the melting granulator granulation.
Its physical and chemical index detected result of the product that present embodiment obtains sees Table 2, the service index detected result see Table 3 and cost analysis see Table 4.
Embodiment 2
Get the raw materials ready according to the proportioning under 2 of the embodiment in the table 1, metal adopts vitriol, low cobalt boron acidylate bimetallic salt complex
Preparation as follows:
(1) temperature gradient method and concentration staircase method are produced the basic carbonate bimetallic salt complex
A. yellow soda ash is dissolved as concentration respectively and is 15%, 25%, 35% solution under 75 ℃ of temperature, respectively
The different storage tanks of putting into insulation are standby, and the temperature of sodium carbonate solution remains between 60-80 ℃ in the reaction process;
B. rose vitriol, single nickel salt, copper sulfate and zinc sulfate water are dissolved into the solution of 25% concentration, place reactor, under lasting the stirring, heat up with 5 ℃/h speed, in the time of 55 ℃, begin to add concentration with the topping-up pump atomizing and be 25% sodium carbonate solution, and be warming up to 70 ℃ with 5 ℃/h speed gradually, control pH to 7.0.When the pH value reached 7.0, the concentration that adding atomizes with topping-up pump in reaction mass was 35% sodium carbonate solution again, and is warming up to 80 ℃ with 5 ℃/h speed gradually, control pH value to 9.5.When the pH value reached 9.5, the concentration that adding atomizes with topping-up pump in reaction mass was 15% sodium carbonate solution again, and is warming up to 85 ℃ with 5 ℃/h speed gradually, control pH value to 10.0, and reaction finishes.When the basic non-foam of material liquid surface, putting into washing trough is cooled to below 50 ℃ and is pressed into the pressure filter continuous wash, after below the rinse water pH value to 6, further dewater, anhydrously draw off the basic carbonate bimetallic salt complex that obtains standby after deviating from the de-oiling dried compressed air
(2) continuously dehydrating explained hereafter intermediate
The acid (being neodecanoic acid, PIVALIC ACID CRUDE (25) and rosin) of long-chain and the solvent xylene of solvent total amount 65% in reactor, adding earlier under 50 ℃, add the basic carbonate bimetallic salt complex again, stir 40min, divide 3 times by the speed of each interval 20min again and add short chain organic acid (being propionic acid), add residual solvent at last, slowly heat up with 20 ℃/h speed behind the stirring 50min.Begin to occur cut when temperature is raised to more than 90 ℃, opens the total reflux valve, cut all is back in the reactor, the internal reflux time kept 2 hours, and this phase temperature is 90～110 ℃.Internal reflux finishes, beginning continuously dehydrating process, solvent refluxing is to reactor simultaneously, this phase temperature remains on 105-115 ℃, until substantially anhydrous deviate from after, heating up steams solvent, this phase temperature scope is 115～170 ℃.Beginning to be evacuated to 190 ℃ to 170 ℃ and take off most solvent, vacuum tightness is-0.07 ~-0.08Mpa, obtain intermediate, enter next step,
(3) the boron acidylate generates low cobalt boron acidylate bimetallic salt complex
When 170 ℃ of temperature, in intermediate, slowly add tributyl borate; heat up gradually; temperature rise rate increases progressively gradually along with temperature raises, and temperature rise rate changes between 5-10 ℃, is warming up to 215 ℃; insulation 50min; fully carry out boron acidylate replacement(metathesis)reaction, vacuum is taken off most byproduct then, and vacuum tightness is-0.07 ~-0.08Mpa; in reaction product, add paraffin after being cooled to 190 ℃, stir after obtain the low cobalt boron acidylate metal composite product salt of particulate state after the melting granulator granulation.
Its physical and chemical index detected result of the product that present embodiment obtains sees Table 2, the service index detected result see Table 3 and cost analysis see Table 4.
Embodiment 3
Get the raw materials ready according to the proportioning under 3 of the embodiment in the table 1, metal adopts chlorate, low cobalt boron acidylate bimetallic salt complex
The preparation method is with embodiment 1.
Its physical and chemical index detected result of the product that present embodiment obtains sees Table 2, the service index detected result see Table 3 and cost analysis see Table 4.
Comparative example
The cobalt boracylate product of existing prepared.
Table 1 embodiment 1-3 and comparative example proportioning raw materials
Table 2 embodiment and comparative example physical and chemical index test result
Table 3 embodiment 1-3 and comparative example performance test results
The cost analysis following (average price in April, 2010) of table 4 couple embodiment 1-3 and comparative example prescription:
Can find out that from table 4 the cobalt amount of being substituted is 30～50%, the material cost of boron acidylate bimetallic salt complex per ton descends 14～20%.Its physical and chemical index of embodiment 1 product is best, and the basic components of judging embodiment 1 is maximum replacement cobalt metal formulations, and replacing the cobalt amount is 50%, and manufacturing cost descends 20%.
Although the contriver has done comparatively detailed elaboration to technical scheme of the present invention and has enumerated, be to be understood that, for the those skilled in the art in this area, the foregoing description is modified and/or flexible or to adopt the replacement scheme that is equal to be obvious, the essence that all can not break away from spirit of the present invention, the term that occurs among the present invention is used for can not being construed as limiting the invention the elaboration of technical solution of the present invention and understanding.
Claims (8)
1. rubber-metal bonding enhancer for steel wire radial tyre, it is characterized in that, it is to adopt four kinds of metal-salts of cobalt, nickel, copper and zinc to prepare, and is cobalt in the proportioning of metal molar quality: nickel: copper: zinc=50 ~ 70%:20 ~ 40%:6 ~ 10%:2 ~ 4%.
2. rubber-metal bonding enhancer for steel wire radial tyre according to claim 1 is characterized in that, described metal molar quality proportioning is a cobalt: nickel: copper: zinc=50:40:7.5:2.5.
3. rubber-metal bonding enhancer for steel wire radial tyre according to claim 1 is characterized in that, described metal-salt embodies with vitriol or chlorate form.
4. rubber-metal bonding enhancer for steel wire radial tyre according to claim 1 is characterized in that described adhesiving reinforcing agent also contains the paraffin of its weight 2-5%.
5. the preparation method of the described rubber-metal bonding enhancer for steel wire radial tyre of one of claim 1-4 is characterized in that, described preparation method comprises the steps:
(1) temperature gradient method and concentration staircase method prepare the basic carbonate bimetallic salt complex, and detailed process is:
A. prepare mass concentration and be three kinds of sodium carbonate solutions of 15%, 25% and 35%, standby;
B. four kinds of metal-salts are mixed with the solution that mass concentration is 25-35%, be warming up to after 55 ℃ that slowly to add concentration be 25% sodium carbonate solution, and be warming up to 70 ℃ gradually, when the pH value reaches 7, slow adding concentration is 35% sodium carbonate solution in reaction mass, and be warming up to 80 ℃ gradually, when the pH value reaches 9.5, slow adding concentration is 15% sodium carbonate solution in reaction mass, and be warming up to 85 ℃ gradually, and reaching reaction in 10 o'clock to the pH value and finish, whole process need constantly stirs, the material that obtains is through precipitation, clean, obtain the basic carbonate bimetallic salt complex after press filtration and the drying, enter next step;
(2) the continuously dehydrating legal system is equipped with intermediate, and detailed process is:
The organic acid of long-chain and the solvent of solvent total amount 65 ~ 75% in adding in the reactor, add the basic carbonate bimetallic salt complex then, stir 30 ~ 40min, divide the organic acid that adds short chain for several times again, each 15 ~ 20min at interval, the solvent that adds surplus at last, heat up gradually after stirring 50 ~ 60min, temperature kept internal reflux 2 hours between 90-110 ℃, between 105-170 ℃, carry out continuously dehydrating then and make the solvent internal reflux, between 170-190 ℃, vacuumize at last and take off most solvent, obtain intermediate, enter next step
Described organic acid is C
3-C
18Saturated carboxylic acid; Solvent is a dimethylbenzene; Wherein said organic acid: solvent: the weight proportion of basic carbonate bimetallic salt complex is 33 ~ 36%:21 ~ 24%:41 ~ 44%,
(3) the low cobalt boron acidylate bimetallic salt complex of boron acidylate replacement(metathesis)reaction preparation, detailed process is:
The tributyl borate that in the time of 170 ℃, in intermediate, slowly adds metal molar quality/3 * 230 weight; be warming up to 215 ℃ and be incubated 50 ~ 60min gradually; vacuum is taken off most byproduct then; be cooled to 190 ℃ of paraffin that add product theoretical weight 2-5% again; the back granulation that stirs obtains the low cobalt boron acidylate bimetallic salt complex of particulate state, promptly described rubber-metal bonding enhancer for steel wire radial tyre.
6. preparation method according to claim 5 is characterized in that, sodium carbonate solution is prepared and be incubated standby under 75 ~ 80 ℃ among the A of described step (1), and the temperature of sodium carbonate solution remains between 60-80 ℃ in the reaction process; Slowly add among the B and operate as follows: sodium carbonate solution adopts topping-up pump, adds in the mode of spraying, and with the speed of reverse flow valve control liquid feeding, speed control is at 3.4 ~ 4.5kg/min; The mode that drying among the B adopts the de-oiling dried compressed air to blow filter is dewatered; Temperature rise rate is controlled at 5 ℃/h among the B.
7. preparation method according to claim 5 is characterized in that, the rate-controlling that heats up gradually in the described step (2) is at 15 ~ 20 ℃/h; The vacuum tightness that vacuumizes is-0.07 ~-0.08Mpa.
8. preparation method according to claim 5 is characterized in that, the speed that heats up gradually in the described step (3) is 5 ~ 10 ℃/h; The vacuum tightness of vacuum is-0.07 ~-0.08Mpa.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106460318A (en) * | 2014-04-30 | 2017-02-22 | 株式会社普利司通 | Brass-plated steel wire for reinforcement of rubber articles |
| CN110330424A (en) * | 2019-07-24 | 2019-10-15 | 浙江巍翔科技集团有限公司 | A kind of preparation method and application of neodecanoic acid nickel |
| CN111717942A (en) * | 2020-07-01 | 2020-09-29 | 江西核工业兴中新材料有限公司 | Preparation method of spheroidal high-density basic nickel carbonate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5679813A (en) * | 1994-06-20 | 1997-10-21 | Rhone-Poulenc Chemicals Limited | Metal organic compounds and their use |
| CN1912040A (en) * | 2006-08-24 | 2007-02-14 | 朝阳市征和化工有限公司 | Composite metal salt adhesion improver and its preparation method |
| WO2007144609A1 (en) * | 2006-06-12 | 2007-12-21 | Omg Uk Limited | Adhesion promoters for improved rubber to metal bonding |
-
2010
- 2010-06-09 CN CN 201010195263 patent/CN101875730A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5679813A (en) * | 1994-06-20 | 1997-10-21 | Rhone-Poulenc Chemicals Limited | Metal organic compounds and their use |
| WO2007144609A1 (en) * | 2006-06-12 | 2007-12-21 | Omg Uk Limited | Adhesion promoters for improved rubber to metal bonding |
| CN1912040A (en) * | 2006-08-24 | 2007-02-14 | 朝阳市征和化工有限公司 | Composite metal salt adhesion improver and its preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 《地质科技情报》 19930930 马亭等 油田卤水中短链有机酸的来源、分布及其地球化学意义 73-77，81 1-5 第12卷, 第3期 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106460318A (en) * | 2014-04-30 | 2017-02-22 | 株式会社普利司通 | Brass-plated steel wire for reinforcement of rubber articles |
| CN106460318B (en) * | 2014-04-30 | 2019-11-22 | 株式会社普利司通 | Brass-plated steel wire is used in rubber product reinforcement |
| CN110330424A (en) * | 2019-07-24 | 2019-10-15 | 浙江巍翔科技集团有限公司 | A kind of preparation method and application of neodecanoic acid nickel |
| CN110330424B (en) * | 2019-07-24 | 2022-04-15 | 浙江巍翔科技集团有限公司 | Preparation method and application of nickel neodecanoate |
| CN111717942A (en) * | 2020-07-01 | 2020-09-29 | 江西核工业兴中新材料有限公司 | Preparation method of spheroidal high-density basic nickel carbonate |
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