CN101481591B - Preparation of organic cobalt salt adhesion promotion agent - Google Patents
Preparation of organic cobalt salt adhesion promotion agent Download PDFInfo
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- CN101481591B CN101481591B CN2009100255334A CN200910025533A CN101481591B CN 101481591 B CN101481591 B CN 101481591B CN 2009100255334 A CN2009100255334 A CN 2009100255334A CN 200910025533 A CN200910025533 A CN 200910025533A CN 101481591 B CN101481591 B CN 101481591B
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Abstract
The invention discloses a method for preparing an organic cobalt salt adhesion promoter. The method comprises the following steps: cobalt solution, sodium hydroxide solution and sodium carbonate solution, which respectively have certain concentration, are respectively prepared; after the cobalt solution is heated, the sodium hydroxide solution is slowly added till the pH value of the reactant liquid reaches 7, and then the sodium carbonate solution is slowly added till the pH value of the reactant liquid reaches 9.5; the reaction liquid undergoes standing, and precipitates are rinsed with water; and the rinsed precipitate inorganic cobalt salt undergoes twice dehydration and then the reaction with weak organic acid in an organic solution so as to obtain the organic cobalt salt adhesion promoter product. The highly-active basic cobaltous carbonate powder produced according to the method has requirement-meeting indexes such as appearance, cobalt content, water content, trivalent cobalt content, impurity content, grain size, stacking density, and the like; and more importantly, the basic cobaltous carbonate powder has good reactive behavior. After the basic cobaltous carbonate powder undergoes neutralization reaction with the weak organic acid, the organic cobalt salt adhesion promoter product with high quality can be obtained.
Description
Technical field
The invention belongs to field of material engineering technology, be specifically related to the preparation method of organic cobalt salt adhesion promotion agent.
Background technology
Strengthen rubber item industries such as travelling belt, Rubber Hose Braided With Steel Wire at radial wire cord tire, steel wire, need elastomerics such as rubber and metallic framework material high-tenacity bonding.For effectively guaranteeing the high-tenacity bond properties of rubber and metallic framework; and performance such as higher anti-aging, heat-resisting oxygen, moisture-proof heat, salt water resistance corrosion; prior art adopts direct addition type organic cobalt salt adhesion promotion agent (mainly comprising cobalt stearate, cobalt naphthenate, capric acid cobalt and cobalt boracylate four big classes) usually; and the manufacture method of this type of cobalt salt adhesion promotion agent product is: inorganic solubility cobalt salt transforms into the inorganic precipitation cobalt salt; make fine powder by the removal of impurities after drying again; last and corresponding organic acid carries out replacement(metathesis)reaction, obtains desired product.And the precipitate cobalt of above-mentioned indication is nothing but cobaltous hydroxide or cobaltous dihydroxycarbonate (hereinafter to be referred as cobalt powder), as everyone knows, cobaltous hydroxide and cobaltous dihydroxycarbonate all are a kind of weak base, and when producing cobalt salt adhesion promotion agent, the organic acid that reacts with these weak base all is weak acid (as the organic acid of a plurality of carbon atoms such as stearic acid, naphthenic acid, capric acid), weak acid and weakly alkaline reaction require stronger reaction conditions, and speed of response is slow and be difficult to carry through to the end.The organic cobalt salt that adds organic acid and generation all has toughness, therefore, the reactive behavior of cobalt powder and the dispersiveness particularly important that just seems, it is the key factor that can reaction be carried out smoothly, controlledly carry through to the end.
Because the singularity of cobalt, be that the cobaltous hydroxide colloidality is very strong, adsorptivity is also very strong, in pulverizing process the sodium salt that generates and excessive alkali be difficult for cleaning, not only need a large amount of water also to prolong the rinsing time simultaneously, thereby make the cobalt ion of divalence longer, and divalent cobalt ion is very easy to the oxidation by airborne oxygen institute under alkaline condition in the following time of alkaline condition, become stable high price cobalt, be the undissolvable high price cobalt of acid of irreducibility.Its quality product is not easy control, and the patent No. is 200610039605.7,200710019326.9 all to be to adopt this manufactured.For this reason, present some cobalt salt manufacturing firm at home adopts cobaltous dihydroxycarbonate as the main raw material(s) of producing organic cobalt salt adhesion promotion agent more.But adopt the cobaltous dihydroxycarbonate method, though reduced the cobaltic possibility of divalence cobalt conversion arranged, if but in the dry pulverizing process in later stage, control bad, still can exist above-mentioned divalence cobalt to be oxidized to cobaltic possibility, therefore indivedual producers adopt wet method synthetic, wet method is synthetic to be to utilize the direct and organic acid reaction of wet cobaltous dihydroxycarbonate, the organic acid cobalt that obtains.Though the synthetic problem of having avoided the trivalent cobalt oxidation of wet method, but throwing the cobalt amount from it is that rule of thumb numerical value calculates prescription, not only data are not accurate enough, and bad dispersion, long reaction time, when dropping into organic acid, not only also to control feed temperature, speed etc. well by acid strong and weak order, the requirement condition harshness, operation easier is big etc., and quality product can't guarantee.As the patent No. is 200310105264.5.The producer that also has adopts dry production, but it adopts the drying room class static dry, trivalent cobalt composition is higher, active relatively poor in this type of cobalt powder, be not better than wet method synthetic product qualitatively, we can say that domestic present cobalt salt quality product is very different, can't contend with external product at all, this just the cobalt salt product still have the basic reason of the dependence on import more than 60% so far.
Summary of the invention
Technical problem to be solved by this invention provides the improved preparation method of organic cobalt salt adhesion promotion agent, makes the problem of difficulty to overcome above-mentioned cobalt powder.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of preparation method of organic cobalt salt adhesion promotion agent comprises the steps:
(1) inorganic solubility cobalt salt is dissolved in water, the configuration cobalt concentration reaches the cobalt liquor (to contain pure cobalt amount) of 15～45g/L, configuration concentration is that sodium hydroxide solution and the concentration of 100～300g/L is the sodium carbonate solution of 150～300g/L respectively again, and above-mentioned three kinds of solution are standby after filtering respectively;
(2) cobalt liquor is heated to 85 ± 5 ℃, under the agitation condition, slowly the adding temperature is 40～50 ℃ a sodium hydroxide solution, when the pH of reaction solution value is 7, under the agitation condition, slowly add temperature again and be 40～50 ℃ sodium carbonate solution, when the pH of reaction solution value is 9.5, stop to add sodium carbonate solution, holding temperature continues to be stirred to the pH value and does not change at 50～60 ℃;
(3) reaction solution that step (2) is obtained leaves standstill, and gets precipitation and uses water rinse, reaches 7 until the pH of rinsing liquid value;
(4) rinsing is the good inorganic cobalt salt of precipitation carries out the dehydration first time, and its water content is reached below 50%;
(5) will adopt the rotary flashing drying system to carry out the dehydration second time through the inorganic cobalt salt of precipitation after the dehydration for the first time;
(6) will through the inorganic cobalt salt of the precipitation of twice dehydration in organic solvent with weak organic acid reaction 10～24 hours, temperature of reaction slowly rises to 160 ℃ by room temperature;
(7) after the reaction of step (6) finishes, steam remaining organic solvent, carry out granulation, obtain the organic cobalt salt adhesion promotion agent product.
In the step (1), described inorganic solubility cobalt salt is rose vitriol, cobalt chloride or Xiao Suangu.
In the step (2), the agitation condition when adding sodium hydroxide solution is 50～60rpm; Agitation condition when adding sodium carbonate solution is 20～40rpm.
In the step (4), the mode of centrifugal or press filtration is adopted in the described dehydration first time.
In the step (5), the time of adopting the rotary flashing drying system to carry out dehydration for the second time is no more than 5 seconds, promptly easily oxidized divalent cobalt ion is in the moment dehydration, hightail oxidized environment, avoid the divalence cobalt to be oxidized to the trivalent cobalt, in dehumidification system, cut simultaneously with air-flow, so the cobalt powder particle is a primary particle, not only particle is little, and loose, and tap density has only 0.4～0.5g/cm
3, water content is less than 3%, and the trivalent cobalt contents is less than 0.1%, has higher chemical reactivity, examine under a microscope this type of cobalt powder, find that each small-particle surface all has numerous aperture, cobalt powder that this present invention just produces and the conventional cobalt powder difference of making.
In the step (6), described organic solvent is dimethylbenzene or industrial naptha.
In the step (6), described organic acid is any one or a few the combination from the organic acid of the straight chain hydrocarbon of ten carbon atoms of two carbon atoms to three or cross isomery or ring texture.The combination of any one or a few in preferred stearic acid, compound fat acid, sylvic acid, naphthenic acid, neodecanoic acid, isocaprylic acid, 910 acid, PIVALIC ACID CRUDE (25), propionic acid and the acetate.
Temperature of reaction described in the step (6) slowly rises to 160 ℃ by room temperature and carries out as follows: temperature of reaction heats up with the speed of 10～20 ℃/h below 100 ℃ the time; Temperature of reaction is in the time of 100～140 ℃, with the speed intensification of 5～10 ℃/h; Temperature of reaction is in the time of 140～160 ℃, and the control heating-up time, reaction finished when temperature reaches 160 ℃ at 4～5 hours.
In the step (6), precipitate inorganic cobalt salt and weak organic acid reaction, its reacting material ratio is followed routine techniques.
Beneficial effect: the inventive method is utilized special process to produce to have highly active basic carbonate cobalt powder, not only outward appearance, cobalt contents, moisture content, trivalent cobalt contents, foreign matter content with and the indexs such as size of particulate size, tap density on meet the requirements, the more important thing is to have good reaction activity.Carry out neutralization reaction with weak organic acid again, obtain high-quality organic cobalt salt adhesion agent product, its quality product meets or exceeds external product fully.
The highly active cobaltous dihydroxycarbonate that the present invention is prepared, with weak organic acid reaction process in, not only carry out on cobalt powder particulate surface, also be penetrated into cobalt powder small-particle inside by aperture, carry out simultaneously inside and outside the reaction, make the cobalt powder thorough " disintegration " of fine granularity, avoided the parcel problem that in reaction process, occurs and reacted halfway problem, solved high-quality organic cobalt salt and made the big problem of difficulty.Therefore the products obtained therefrom index is all in the standard-required scope, and constant product quality.
The organic cobalt salt adhesion promotion agent that the present invention manufactures is not only chemical index and can be reached standard-required fully, and aspect some physical indexs, also gives prominence to the high-performance of its product.As in the product of cobalt salt adhesion promotion agent, the trivalent cobalt that does not have the halfway divalence cobalt of reaction and can not participate in reacting, the cobalt contents of being analyzed in analytic process all is effective cobalt, can both form-O-Co-or-chemical bond of B-O-Co-, in vulcanization of rubber process the metallic surface promote metallic copper and sulphur formation CuxS again with rubber in the combining of sulphur, form stable chemical bond (Cux-S-Sy-Rub), have very strong bounding force between rubber and the intermetallic thereby make.And adopt the organic cobalt salt adhesion promotion agent of active imperfect cobalt powder manufacturing, wherein to have be the divalence cobalt that has neither part nor lot in reaction to the cobalt contents of being analyzed on a small quantity, therefore it can not form above-mentioned chemical bond, just effectively cobalt contents is low, on prescription, will take higher limit or more thus, the divalence cobalt that has neither part nor lot in reaction is simultaneously brought in the rubber item with the impurity form again, easily forms galvanic cell in the metallic surface, has reduced the anti-steam aging of salt water resistance burn into and the ageing resistance of rubber.
Embodiment:
According to following embodiment, the present invention may be better understood.Yet, those skilled in the art will readily understand that the described concrete material proportion of embodiment, processing condition and result thereof only are used to illustrate the present invention, and should also can not limit the present invention described in detail in claims.
The employed rotary flashing drying of following examples system is the DCS full automatic control rotary flashing drying system that Nanjing three general companies produce, and the significant parameter in the drying process is: 210 ℃ of inlet temperature, 80 ℃ of air outlet temperatures; Blower current 16～17A; The induced draft fan electric current will reach more than the 25A; Charging (referring to that water content is at 40～50% wet cobalt cakes) speed is at 100～120kg/h.Dewatering time is no more than 5 seconds.
Embodiment 1:
Rose vitriol is dissolved in water, and the configuration cobalt concentration reaches the cobalt liquor of 15g/L, and configuration concentration is that sodium hydroxide solution and the concentration of 300g/L is the sodium carbonate solution of 150g/L respectively again, and above-mentioned three kinds of solution are standby after filtering respectively;
Cobalt liquor is heated to 85 ± 5 ℃, under the 50rpm agitation condition, slowly the adding temperature is 40～50 ℃ a sodium hydroxide solution, when the pH of reaction solution value is 7, under the 30rpm agitation condition, slowly add temperature again and be 40～50 ℃ sodium carbonate solution, when the pH of reaction solution value is 9.5, stop to add sodium carbonate solution, holding temperature continues to be stirred to the pH value and does not change at 50～60 ℃;
Reaction solution is left standstill, get precipitation and use water rinse, reach 7 until the pH of rinsing liquid value;
The inorganic cobalt salt of the precipitation that rinsing is good carries out the dehydration first time through press filtration, and its water content is reached below 50%;
To adopt the rotary flashing drying system to carry out the dehydration second time through the inorganic cobalt salt of precipitation after the dehydration for the first time;
To in the xylene solvent environment, react through the inorganic cobalt salt of the precipitation of twice dehydration (17.3KG) with stearic acid (91KG), when temperature of reaction below 100 ℃ the time, heat up with the speed of 20 ℃/h,, heat up with the speed of 5 ℃/h when temperature of reaction during at 100～140 ℃; When temperature of reaction during at 140～160 ℃, the control heating-up time, reaction finished when temperature reaches 160 ℃ at 4 hours;
After reaction finishes, steam remaining dimethylbenzene, carry out granulation, obtain organic cobalt salt adhesion promotion agent product (cobalt stearate), its physicochemical property parameter sees Table 1.
The physicochemical property parameter of the cobalt stearate that table 1 embodiment 1 makes
| Project | Standard index | Analysis indexes |
| Outward appearance | Hyacinthine or red-purple are granular | Red-purple is granular |
| The cobalt mass percent, % | 9.6±0.6 | 9.4 |
| Softening temperature, ℃ | 80～100 | 91 |
| Ash content mass percent (550 ℃), %≤ | 13.4 | 13.01 |
| Weight loss on heating (105 ℃, 2h), %≤ | 2.0 | 0.45 |
| Density, g/cm 3 | 1.09±0.03 | 1.10 |
| Infrared spectra (reference standard collection of illustrative plates) | Comparable | Comparable |
Embodiment 2:
Cobalt chloride is dissolved in water, and the configuration cobalt concentration reaches the cobalt liquor of 30g/L, and configuration concentration is that sodium hydroxide solution and the concentration of 200g/L is the sodium carbonate solution of 150g/L respectively again, and above-mentioned three kinds of solution are standby after filtering respectively;
Cobalt liquor is heated to 85 ± 5 ℃, under the 60rpm agitation condition, slowly the adding temperature is 40～50 ℃ a sodium hydroxide solution, when the pH of reaction solution value is 7, under the 40rpm agitation condition, slowly add temperature again and be 40～50 ℃ sodium carbonate solution, when the pH of reaction solution value is 9.5, stop to add sodium carbonate solution, holding temperature continues to be stirred to the pH value and does not change at 50～60 ℃;
Reaction solution is left standstill, get precipitation and use water rinse, reach 7 until the pH of rinsing liquid value;
The inorganic cobalt salt of the precipitation that rinsing is good carries out the dehydration first time through press filtration, and its water content is reached below 50%;
To adopt the rotary flashing drying system to carry out the dehydration second time through the inorganic cobalt salt of precipitation after the dehydration for the first time;
To in the industrial naptha environment, react through the inorganic cobalt salt of the precipitation of twice dehydration (39KG) with acetate (13KG), PIVALIC ACID CRUDE (25) (25KG) and neodecanoic acid (42KG), when temperature of reaction below 100 ℃ the time, speed with 15 ℃/h heats up, when temperature of reaction during, heat up with the speed of 10 ℃/h at 100～140 ℃; When temperature of reaction during at 140～160 ℃, the control heating-up time, reaction finished when temperature reaches 160 ℃ at 5 hours;
After reaction finishes, steam remaining dimethylbenzene, carry out granulation, obtain organic cobalt salt adhesion promotion agent product (new cobalt decanoate), its physicochemical property parameter sees Table 2.
The physicochemical property parameter of the new cobalt decanoate that table 2 embodiment 2 makes
| Project | Standard index | Analysis indexes |
| Outward appearance | Bluish voilet is granular | Bluish voilet is granular |
| The cobalt mass percent, % | 20.5±0.5 | 20.5 |
| Weight loss on heating (105 ℃, 2h), %≤ | 1.0 | 0.34 |
| Softening temperature, ℃ | 80--100 | 87 |
| Density, g/cm 3 | 1.2±0.1 | 1.2 |
| Infrared spectra (reference standard collection of illustrative plates) | Comparable | Comparable |
Embodiment 3:
Method with embodiment 2, different is that Xiao Suangu is dissolved in water, the configuration cobalt concentration reaches the cobalt liquor of 45g/L, and configuration concentration is that sodium hydroxide solution and the concentration of 100g/L is the sodium carbonate solution of 300g/L respectively again, and above-mentioned three kinds of solution are standby after filtering respectively.
Claims (7)
1. the preparation method of an organic cobalt salt adhesion promotion agent is characterized in that this method comprises the steps:
(1) inorganic solubility cobalt salt is dissolved in water, the configuration cobalt concentration reaches the cobalt liquor of 15～45g/L, configuration concentration is that sodium hydroxide solution and the concentration of 100～300g/L is the sodium carbonate solution of 150～300g/L respectively again, and above-mentioned three kinds of solution are standby after filtering respectively;
(2) cobalt liquor is heated to 85 ± 5 ℃, under the agitation condition, slowly the adding temperature is 40～50 ℃ a sodium hydroxide solution, when the pH of reaction solution value is 7, under the agitation condition, slowly add temperature again and be 40～50 ℃ sodium carbonate solution, when the pH of reaction solution value is 9.5, stop to add sodium carbonate solution, holding temperature continues to be stirred to the pH value and does not change at 50～60 ℃;
(3) reaction solution that step (2) is obtained leaves standstill, and gets precipitation and uses water rinse, reaches 7 until the pH of rinsing liquid value;
(4) rinsing is the good inorganic cobalt salt of precipitation carries out the dehydration first time, and its water content is reached below 50%;
(5) will adopt the rotary flashing drying system to carry out the dehydration second time through the inorganic cobalt salt of precipitation after the dehydration for the first time;
(6) will through the inorganic cobalt salt of the precipitation of twice dehydration in organic solvent with weak organic acid reaction 10～24 hours, temperature of reaction slowly rises to 160 ℃ by room temperature;
(7) after the reaction of step (6) finishes, steam remaining organic solvent, carry out granulation, obtain the organic cobalt salt adhesion promotion agent product;
Agitation condition when wherein, adding sodium hydroxide solution in the step (2) is 50～60rpm; Agitation condition when adding sodium carbonate solution is 20～40rpm;
Wherein, the temperature of reaction described in the step (6) slowly rises to 160 ℃ by room temperature and carries out as follows: temperature of reaction heats up with the speed of 10～20 ℃/h below 100 ℃ the time; Temperature of reaction is in the time of 100～140 ℃, with the speed intensification of 5～10 ℃/h; Temperature of reaction is in the time of 140～160 ℃, and the control heating-up time, reaction finished when temperature reaches 160 ℃ at 4～5 hours.
2. the preparation method of organic cobalt salt adhesion promotion agent according to claim 1 is characterized in that the inorganic solubility cobalt salt described in the step (1) is rose vitriol, cobalt chloride or Xiao Suangu.
3. the preparation method of organic cobalt salt adhesion promotion agent according to claim 1 is characterized in that the described dehydration first time of step (4) adopts the mode of centrifugal or press filtration.
4. the preparation method of organic cobalt salt adhesion promotion agent according to claim 1 is characterized in that the time of adopting the rotary flashing drying system to carry out dehydration for the second time in the step (5) is no more than 5 seconds.
5. the preparation method of organic cobalt salt adhesion promotion agent according to claim 1 is characterized in that the organic solvent described in the step (6) is dimethylbenzene or industrial naptha.
6. the preparation method of organic cobalt salt adhesion promotion agent according to claim 1 is characterized in that the organic acid described in the step (6) is any one or a few the combination from the organic acid of the straight chain hydrocarbon of ten carbon atoms of two carbon atoms to three or cross isomery or ring texture.
7. the preparation method of organic cobalt salt adhesion promotion agent according to claim 6 is characterized in that the organic acid described in the step (6) is any one or a few combination in stearic acid, sylvic acid, naphthenic acid, neodecanoic acid, isocaprylic acid, 910 acid, PIVALIC ACID CRUDE (25), propionic acid and the acetate.
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864088B (en) * | 2010-06-13 | 2012-03-28 | 宜兴市卡欧化工有限公司 | Preparation method of compound type cobalt stearate adhesion promoter |
| CN102702573B (en) * | 2012-06-01 | 2013-09-04 | 江苏卡欧化工有限公司 | Preparation method of environment-friendly compound adhesion promoter |
| CN103113206A (en) * | 2012-12-31 | 2013-05-22 | 大连爱柏斯化工有限公司 | Preparation method of neodecanoic acid cobalt |
| CN103086869A (en) * | 2012-12-31 | 2013-05-08 | 大连爱柏斯化工有限公司 | Preparation method of cobalt stearate |
| CN103275356B (en) * | 2013-05-30 | 2014-07-16 | 江苏卡欧化工有限公司 | Method for preparing high-performance low-cobalt borate acylated cobalt adhesion promoter |
| CN103265727B (en) * | 2013-06-14 | 2014-08-27 | 江苏卡欧化工有限公司 | Preparation method of cobalt stearate adhesion promoter with high performance and low cobalt content |
| CN103265726B (en) * | 2013-06-14 | 2014-07-16 | 江苏卡欧化工有限公司 | Preparation method of solid cobalt naphthenate adhesion promoter with high performance and low cobalt content |
| CN103265728B (en) * | 2013-06-14 | 2014-07-16 | 江苏卡欧化工有限公司 | Preparation method of cobalt decanoate adhesion promoter with high performance and low cobalt content |
| CN110092942A (en) * | 2019-05-08 | 2019-08-06 | 国运科技（大连）有限公司 | A kind of novel cobaltous octadecanate adhesion promotor and preparation method improving cobalt content |
| CN110358145B (en) * | 2019-07-09 | 2021-02-09 | 江阴市三良橡塑新材料有限公司 | Cobalt salt adhesion promoter mainly based on cobalt palmitate and preparation method thereof |
| CN110759825A (en) * | 2019-11-11 | 2020-02-07 | 山东阳谷华泰化工股份有限公司 | Synthesis method of cobalt stearate |
| CN111974331B (en) * | 2020-08-17 | 2022-07-05 | 江苏全邦材料科技有限公司 | Green and environment-friendly water-based cobalt salt rubber accelerator preparation system and use method thereof |
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