CN101348505B - Process for preparing cobalt boracylate by hybrid reaction of cobaltous carbonate and organic carboxyl acid - Google Patents
Process for preparing cobalt boracylate by hybrid reaction of cobaltous carbonate and organic carboxyl acid Download PDFInfo
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- CN101348505B CN101348505B CN2008101383458A CN200810138345A CN101348505B CN 101348505 B CN101348505 B CN 101348505B CN 2008101383458 A CN2008101383458 A CN 2008101383458A CN 200810138345 A CN200810138345 A CN 200810138345A CN 101348505 B CN101348505 B CN 101348505B
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Abstract
The invention provides a process for preparing a carboxyl cobalt-boron complex by the mixing reaction of cobalt carbonate and an organic carboxylic acid, belonging to the organic synthesis technical field. Cobalt carbonate is taken as a material, and the invention is characterized in that the preparation process comprises the following steps that: (1) cobalt carbonate, glacial acetic acid, neodecanoic acid and isooctanoic acid are taken as materials and put in a normal pressure sealing reactor, the reaction temperature is controlled to be between 100 and 110 DEG C, and the reaction time is no less than 3h; (2) tributyl borate is added in the reaction system, the reaction temperature is controlled to be between 160 and 180 DEG C, the reaction time is no less than 2h, and the carboxyl cobalt-boron complex and the side product of butyl acetate are generated; (3) the temperature is controlled to be between 175 and 185 DEG C, and active carbon and resin acid are added to obtain the refined product. In the invention, cobalt carbonate is used to replace cobaltous hydroxide, the carboxyl cobalt-boron complex is added with adhesion agent and activated calcium carbonate with amphoteric compound, thereby effective balancing ph in the system, making the product effectively prevent corrosion of metal, enhancing adhesion level and improving thermal oxygen resistant, heat resistant and steam ageing resistant performances.
Description
Technical field
The invention belongs to technical field of organic synthesis, be specifically related to a kind of Technology for preparing the carboxyl cobalt boracylate.
Background technology
Cobalt boracylate, its theoretical molecular formula is B (O-C
0-O-R
n)
3Cobalt boracylate is the higher adhesion promotor of a kind of activity, be mainly used in natural rubber, synthetic rubber or with the adhesion promotion of the steel wire cord of brass, zinc naked copper and brass-plating, zinc, hawser, metal sheet.It is to be raw material with cobaltous hydroxide with propionic acid and relevant organic acid, carries out acid-base reaction earlier, then carries out sour replacement(metathesis)reaction again and makes.It is higher to contain the cobalt amount by the cobalt boracylate of this method preparation.They are when the vulcanization of rubber, and reactive behavior is big, and the bonding enhancing of rubber and steel wire is played a major role, but the free fatty acids total acidity that reaction generates is higher, reduced rubber and steel wire adherent stability, be unfavorable for that rubber and steel wire are persistent bonding, and the metallic surface is corrosive.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides and a kind ofly make the preparation technology of carboxyl cobalt boracylate with cobaltous carbonate and organic carboxyl acid hybrid reaction, the cobalt boracylate of preparing, its degree of adhesion lasting stability has heat-resisting oxygen, heatproof, the aged of anti-steam performance.
The present invention solves the technical scheme that its technical problem adopts: designing and a kind ofly make the preparation technology of carboxyl cobalt boracylate with cobaltous carbonate and organic carboxyl acid hybrid reaction, is raw material with the cobaltous carbonate, it is characterized in that preparation technology carries out as follows successively:
(1) saponification reaction: with in the cobaltous carbonate, Glacial acetic acid, neodecanoic acid and isocaprylic acid be raw material, in the normal pressure sealed reactor, control reaction temperature 100-110 ℃, reaction times were not less than 3 hours, and the reaction back generates the cobalt salt mixture that neodecanoic acid-isocaprylic acid-Glacial acetic acid cobalt is formed; Its reaction formula is:
Wherein, n is 7 or 9.
This operation is participated in reaction with cobaltous carbonate instead of hydrogen cobalt oxide and Glacial acetic acid, and product is after the vulcanization of rubber is used, and total acidity reduces,
To the bonding of rubber and steel wire with prevent that corrosion of metal is favourable, it is stable that the degree of adhesion of physicals keeps.
(2) acylation reaction: add tributyl borate in above-mentioned reaction system, control reaction temperature 160-180 ℃, the reaction times was not less than 2 hours, generated carboxyl cobalt boracylate and byproduct N-BUTYL ACETATE; Its reaction formula is:
Wherein, n is 7 or 9.
This reaction key is a control acidylate temperature, and the acidylate temperature is too high, and then fusing point is too high, and the acidylate temperature is low excessively, and acylation reaction is bad, and insolubles is too much, and corrosion-resistant unfavorable with ageing-resistant performance to the glue based article, influence is used.
(3) make finished product: controlled temperature 175-185 ℃, add treated carbonates and resinous acid then, make finished product.
Wherein control reaction temperature is 105 ℃ in saponification reaction; Control reaction temperature is 170 ℃ in the acylation reaction; Make that temperature is 180 ℃ in the finished product technology.
The performance and the requirement that prepare consumption raw material of the present invention:
Cobaltous carbonate: molecular formula CoCO
3, molecular weight 118.94.
Proterties: cobaltous carbonate is red monoclinic crystal or blue powder.Water insoluble, pure, in air, be oxidized to the high cobalt of carbonic acid (trivalent cobalt), not with cold nitric acid and hydrochloric acid reaction.
Glacial acetic acid: molecular formula C
2H
4O
2, molecular weight 60.05.
Proterties: colourless transparent liquid has strong impulse acid smelly, content 〉=98%, proportion 1.0492g/cm 3,16.6 ℃ of fusing points, 117.9 ℃ of boiling points, 42.78 ℃ of flash-points, 465 ℃ of spontaneous ignition temperatures, acid number 935.35mgKOH/g.Water-soluble, ether, glycerine are insoluble to dithiocarbonic anhydride.Play esterification with alcohol and generate ester, generate salt with metal and oxide compound effect.Chance naked light, high temperature, oxygenant have danger of combustion, meet Mars when its vapor concentration reaches limits of explosion and can blast limits of explosion 5.4-16%.Stronger corrodibility is arranged, and after Dermallly affixed the going up, the used water flushing during operation, has been dressed safety appliance, and equipment will seal.
Neodecanoic acid: general structure is
Molecular formula is C
10H
2O
3, molecular-weight average is 172.26.
Proterties: colourless or light yellow liquid, chemical ingredients carboxylic acid, eo-acid, acid value 305-335, content 100%, zero pour-39 ℃, the boiling point amplitude is between 243 and 253 ℃, 122 ℃ of flash-points, 440 ℃ of spontaneous ignition temperatures, density (20 ℃) 0.911, viscosity (20 ℃) 40est, deliquescence does not have pungency to eyes and skin.
Isocaprylic acid: molecular formula C
8H
16O
2, molecular weight 144.22.
Proterties: colourless liquid odorous slightly, zero pour-83 ℃, 226.9 ℃ of boiling points, 127 ℃ of flash-points, density 0.9077, specific refractory power 1.4252, acid number 389.04mgKOH/g is slightly soluble in water.Flammable.Low toxicity has stimulation to skin.
Resinous acid: molecular formula C
20H
30O
2, molecular weight 302.44.
Proterties: yellowish to brown red amorphous solid, transparent and matter is crisp under the normal temperature, gloss is had on the surface slightly, band rosin fragrance.Density 1.05-1.10g/cm
3, fusing point 110-135 ℃, softening temperature (ring and ball method) is greater than 72 ℃, and acid number 164mgKOH/g meets heat and is deliquescing and glues 300 ℃ of boiling points (65Pa), 216 ℃ of flash-points, point of ignition 480-500 ℃, 30 ℃ of second-order transition temperatures, specific refractory power 1.5453.Water insoluble, be slightly soluble in hot water, can be dissolved in ethanol, ether, acetone, benzene, dithiocarbonic anhydride, ethylene dichloride, sherwood oil, gasoline and turpentine wet goods organic solvent.Easily oxidation in the air, color and luster deepen, inflammable.Steam is poisonous.Add rubber item and reclaimed rubber, can improve the viscous force and the elasticity of product.
Tributyl borate: molecular formula C
12H
27BO
3, molecular weight 203.16.
Proterties: colourless transparent liquid, fusing point-70 ℃, 232 ℃ of boiling points, 93 ℃ of flash-points, density 0.85 (28/11 ℃), can with common solvent such as methyl alcohol to miscible, meet water decomposition.
Treated carbonates: molecular formula CaCO
3, molecular weight 100.087.
Proterties: be the powder product of realizing improving particle surface through surface treatment.The surface treatment agent that uses has lipid acid, coupling agent and tensio-active agent.Particle is fusiform, major diameter 1-3 μ m.Have dispersed preferably for organic polymer.
Preparing various raw material consumption amounts of the present invention (mass parts) is:
Cobaltous carbonate (45%) 48-50 part
Glacial acetic acid (98%) 30-32 part
Neodecanoic acid (100%) 35-37 part
Isocaprylic acid (98%) 17-19 part
Tributyl borate (〉=98%) 30-32 part
Treated carbonates (〉=95%) 8-10 part
Resinous acid 10-12 part
The present invention utilizes cobaltous carbonate instead of hydrogen cobalt oxide; tackifier and treated carbonates in the carboxyl cobalt boracylate, have been added with amphoteric substance; potential of hydrogen in the effective equilibrium system; thereby make product effectively prevent corrosion of metal; strengthened level of adhesion; improved heat-resisting oxygen, heatproof, the aged of anti-steam performance, further made carboxyl cobalt boracylate physicals keep secular stability.
Embodiment one
Embodiment:
Glacial acetic acid 60g, neodecanoic acid 70g, isocaprylic acid 34g, cobaltous carbonate 100g are added in the 1000ml four-hole boiling flask that has reflux exchanger, temperature adjustable electrically heated cover and vacuum pump successively, 105 ℃ of control reaction temperature, in 3 hours reaction times, the water that reaction generates is got rid of in the intensification current drainage.Under 170 ℃ temperature, add 60g tributyl borate, 2 hours reaction times, intensification current drainage, vacuum decompression current drainage; discharge N-BUTYL ACETATE; under 180 ℃ temperature, add treated carbonates 16g, resinous acid 20g, evenly stir blowing after 1 hour, obtain the cobalt boracylate product.The cobalt boracylate that makes, its cobalt contents 22.7%, outward appearance is bluish voilet.
Embodiment two
With Glacial acetic acid 64g; neodecanoic acid 74g; isocaprylic acid 36g; cobaltous carbonate 98g adds successively and has reflux exchanger; in the 1000ml four-hole boiling flask of temperature adjustable electrically heated cover and vacuum pump; 100 ℃ of control reaction temperature; 4 hours reaction times; the intensification current drainage; get rid of the water that reaction generates; under 160 ℃ temperature; add the 64g tributyl borate, 2.5 hours reaction times, intensification current drainage; the vacuum decompression current drainage; discharge N-BUTYL ACETATE; add treated carbonates 18g at 175 ℃; resinous acid 24g evenly stirs blowing after 1 hour, gets the cobalt boracylate product; cobalt contents 22.5%, outward appearance is bluish voilet.
Embodiment three
With Glacial acetic acid 62g; neodecanoic acid 73g; isocaprylic acid 38g; cobaltous carbonate 96g adds successively and has reflux exchanger; in the 1000ml four-hole boiling flask of temperature adjustable electrically heated cover and vacuum pump; 110 ℃ of control reaction temperature; 4 hours reaction times; the intensification current drainage; get rid of the water that reaction generates; under 180 ℃ temperature; add the 62g tributyl borate, 3 hours reaction times, intensification current drainage; the vacuum decompression current drainage; discharge N-BUTYL ACETATE; add treated carbonates 20g at 185 ℃; resinous acid 22g evenly stirs blowing after 1 hour, gets the cobalt boracylate product; cobalt contents 22.1%, outward appearance is bluish voilet.
Claims (4)
1. making the preparation technology of carboxyl cobalt boracylate with cobaltous carbonate and organic carboxyl acid hybrid reaction for one kind, is raw material with the cobaltous carbonate, it is characterized in that preparation technology carries out as follows successively:
(1) saponification reaction: with cobaltous carbonate, Glacial acetic acid, neodecanoic acid and isocaprylic acid is raw material, in the normal pressure sealed reactor, 100 ℃-110 ℃ of control reaction temperature, the reaction times was not less than 3 hours, and the reaction back generates the cobalt salt mixture that neodecanoic acid-isocaprylic acid-Glacial acetic acid cobalt is formed;
(2) acylation reaction: add tributyl borate in above-mentioned reaction system, control reaction temperature 160-180 ℃, the reaction times was not less than 2 hours, generated carboxyl cobalt boracylate and byproduct N-BUTYL ACETATE;
(3) make finished product: controlled temperature 175-185 ℃, add treated carbonates and resinous acid then, make finished product.
2. a kind of carboxyl cobalt boracylate preparation technology who makes with cobaltous carbonate and organic carboxyl acid reaction according to claim 1 is characterized in that control reaction temperature is 105 ℃ in the saponification reaction.
3. a kind of carboxyl cobalt boracylate preparation technology who makes with cobaltous carbonate and organic carboxyl acid reaction according to claim 1 is characterized in that control reaction temperature is 170 ℃ in the acylation reaction.
4. a kind of carboxyl cobalt boracylate preparation technology who makes with the reaction of cobaltous carbonate and organic carboxyl acid according to claim 1 is characterized in that making that temperature is 180 ℃ in the finished product technology.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101383458A CN101348505B (en) | 2008-07-18 | 2008-07-18 | Process for preparing cobalt boracylate by hybrid reaction of cobaltous carbonate and organic carboxyl acid |
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|---|---|---|---|
| CN2008101383458A CN101348505B (en) | 2008-07-18 | 2008-07-18 | Process for preparing cobalt boracylate by hybrid reaction of cobaltous carbonate and organic carboxyl acid |
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| CN101348505A CN101348505A (en) | 2009-01-21 |
| CN101348505B true CN101348505B (en) | 2011-07-20 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102363A (en) * | 2012-12-31 | 2013-05-15 | 大连爱柏斯化工有限公司 | Preparation method of low insoluble substance cobalt boroacylate |
| CN107955028A (en) * | 2017-11-22 | 2018-04-24 | 浙江三晟化工有限公司 | A kind of preparation method of cobalt boracylate |
| CN114507489A (en) * | 2022-01-26 | 2022-05-17 | 江苏卡欧化工股份有限公司 | Cobalt boracylate adhesive and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4340515A (en) * | 1981-06-16 | 1982-07-20 | Akzo Nv | Solid rubber adhesion promoter and a method for improving the adhesion of rubber to metal reinforcing elements embedded therein |
| EP0137986A1 (en) * | 1983-09-19 | 1985-04-24 | The Firestone Tire & Rubber Company | Method for improving rubber-to-metal adhesion and adhesion retention |
| CN1242976C (en) * | 2003-12-02 | 2006-02-22 | 颜秉舟 | Technology process for synthetic oragnocobalt solt |
-
2008
- 2008-07-18 CN CN2008101383458A patent/CN101348505B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4340515A (en) * | 1981-06-16 | 1982-07-20 | Akzo Nv | Solid rubber adhesion promoter and a method for improving the adhesion of rubber to metal reinforcing elements embedded therein |
| EP0137986A1 (en) * | 1983-09-19 | 1985-04-24 | The Firestone Tire & Rubber Company | Method for improving rubber-to-metal adhesion and adhesion retention |
| CN1242976C (en) * | 2003-12-02 | 2006-02-22 | 颜秉舟 | Technology process for synthetic oragnocobalt solt |
Non-Patent Citations (2)
| Title |
|---|
| 李晓如等.硼酰化镍的合成及性能.《中南工业大学学报(自然科学版)》.2000,第31卷(第04期),第321-323页. * |
| 王军.金属――橡胶粘合的钴盐类促进剂.《当代化工》.1988,(第06期),第45-48页. * |
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