CN103183843A - Cobalt neodecanoate salt mixture containing unsaturated acid and preparation method thereof - Google Patents
Cobalt neodecanoate salt mixture containing unsaturated acid and preparation method thereof Download PDFInfo
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- CN103183843A CN103183843A CN2013100848302A CN201310084830A CN103183843A CN 103183843 A CN103183843 A CN 103183843A CN 2013100848302 A CN2013100848302 A CN 2013100848302A CN 201310084830 A CN201310084830 A CN 201310084830A CN 103183843 A CN103183843 A CN 103183843A
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Abstract
The invention discloses a cobalt neodecanoate salt mixture containing unsaturated acid and a preparation method thereof. The preparation method comprises the following steps: (1) placing cobalt hydroxide, and propionic acid, crylic acid or methacrylic acid and neodecanoic acid in a normal-pressure seal container, and refluxing to generate crylic acid or methacrylic acid-propionic acid-cobalt neodecanoate salt mixture; (2) adding neopentanoic acid and 4-pentenoicacid, controlling the reflux reaction condition, and replacing propionic acid or crylic acid; and (3) controlling the temperature condition, adding activated Calcium carbonate, and ceaselessly stirring to prepare the cobalt neodecanoate salt mixture containing unsaturated acid. Part of crylic acid (or methacrylic acid) and 4-pentenoicacid replace propionic acid and neopentanoic acid, the prepared cobalt neodecanoate salt mixture remains the adhesion between rubber and metal, and participates in the vulcanization to form a new chemical bond, and the adhesion is higher than that of cobalt neodecanoate in a traditional process.
Description
Technical field
The invention belongs to technical field of organic synthesis, be specifically related to a kind of undersaturated new cobalt decanoate mixing salt and corresponding Technology of containing.
Background technology
New cobalt decanoate is a kind of of main adhesionpromoter bonding between steel wire and the rubber, be mainly used in the initial adhesion of radial tyre, conveying belt, steel band steel metal and rubber in rubber-metal matrix materials such as sebific duct, it has guaranteed use properties and the work-ing life of tire, guarantee simultaneously after later stage ageing of rubber and corrosion, still can have higher viscosity conservation rate again, thereby new cobalt decanoate has become indispensable component in the production of rubber-metal matrix material.Its theoretical molecular formula of new cobalt decanoate is: [CH
3(CH
2)
8CO
2]
2Co, theory contains the cobalt amount and has only 14.7%, does not reach the service requirements of rubber production.Therefore, the new cobalt decanoate of domestic and foreign literature and patent report all is a kind of mixtures at present, be a kind of by the different carboxylic acid of carbochain length in three to four and cobalt salt reaction produce by the mazarine vitreum of fixedly forming, its synthetic method all is employing cobaltous hydroxide and three to four kinds of raw material production technique in the presence of solvent such as unsaturated organic acid.Yet this method is synthetic, and to contain saturated acidic group new cobalt decanoate and rubber matrix itself bonding only be the model ylid bloom action power of physics, the chemical relatively reactive force of this physical force a little less than.Based on above-mentioned technical background and product requirement, this patent has been invented a kind of new cobalt decanoate mixing salt that contains unsaturated acid and preparation method thereof, and the professional technique data are not seen relevant report and patent application both at home and abroad by retrieval.
Summary of the invention
The objective of the invention is to provide and contain a kind of new cobalt decanoate mixing salt and preparation technology who contains unsaturated acid, this neodecanoic acid cobalt salt that contains unsaturated acid had both kept binding cobalt salt power, the two keys of the C=C of unsaturated acid participate in sulfuration and form new chemical bond when the vulcanization of rubber simultaneously, make that the bonding force between this metal-rubber is stronger.The capric acid cobalt that the present invention prepares contains cobalt amount height, the fusing point height, and particularly bounding force is strong.
The object of the present invention is achieved like this:
A kind of new cobalt decanoate mixing salt that contains unsaturated acid comprises the raw material of following mass fraction:
25～35 parts of cobaltous hydroxides;
40～50 parts of neodecanoic acids;
10～15 parts of propionic acid;
2～10 parts in vinylformic acid;
3～6 parts of PIVALIC ACID CRUDE (25);
2～4 parts of 4-pentenoic acids;
3～6 parts of activated Calcium carbonates.
Further, described vinylformic acid or alternative with methacrylic acid.
Correspondingly, the present invention also provide a kind of new cobalt decanoate mixing salt that contains unsaturated acid the preparation method, this method comprises the steps:
1) be that cobaltous hydroxide and 10～15 parts of propionic acid, 2～10 parts of acrylic or methacrylic acid and 40～50 parts of neodecanoic acids of 25～35 parts place the normal pressure sealed vessel with mass fraction, reflux, reaction generates acrylic or methacrylic acid-propionic acid-new cobalt decanoate mixing salt;
2) adding mass fraction then in above-mentioned reaction system is 3～6 parts of PIVALIC ACID CRUDE (25) and 2～4 parts of 4-pentenoic acids, and control back flow reaction condition displaces propionic acid or vinylformic acid;
3) control temperature condition, the interpolation mass fraction is 3～6 parts activated Calcium carbonate, constantly stirs down, makes the new cobalt decanoate mixing salt that contains unsaturated acid.
Further, in the described method:
In the described step 1) at 140～180 ℃ of back flow reaction 3～5h of temperature.
Described step 2) reflux temperature is 160～200 ℃ in, and the reaction times is 2～4h.
The control temperature is 170～200 ℃ in the described step 3), churning time 1～2 hour.
The present invention carries out acid-base reaction and sour replacement(metathesis)reaction with cobaltous hydroxide after by unsaturated acid and unsaturated organic acid blend, generates the new cobalt decanoate mixture that contains unsaturated acid at last, comprising:
(1) acid-base reaction
The mixing acid of forming with cobaltous hydroxide and propionic acid, vinylformic acid (or methacrylic acid), neodecanoic acid is raw material, in the normal pressure sealed vessel, 140～180 ℃ of back flow reaction 3～5h of temperature, reaction generates vinylformic acid (or methacrylic acid)-propionic acid-new cobalt decanoate mixing salt, and its total reaction formula is:
Wherein: the scope of n is 3～5, decides on the ratio of vinylformic acid and propionic acid.
(2) sour replacement(metathesis)reaction
In above-mentioned reaction system, vinylformic acid (or methacrylic acid)-propionic acid-new cobalt decanoate mixing salt that generates, low carbon acid cobalt salt content is also defectiveness too much, and the acidity of low carbon acid cobalt salt may add the corrosion of the aging and metal steel wire of rubber product after vulcanization of rubber disassociation.Consider this factor, need to be higher than propionic acid, to be lower than the PIVALIC ACID CRUDE (25) of neodecanoic acid or propionic acid and the vinylformic acid (or methacrylic acid) that the 4-pentenoic acid displaces part with the carbon number.Concrete experiment parameter: in above-mentioned reaction system, add PIVALIC ACID CRUDE (25) and 4-pentenoic acid, 160～200 ℃ of control temperature, time 2～4h, back flow reaction displaces propionic acid or vinylformic acid.Its reaction formula is:
Wherein: the scope of m is 7～9, decides on the ratio of PIVALIC ACID CRUDE (25) and 4-pentenoic acid; The scope of n is 3～5.
(3) preparation of finished product
In above-mentioned reaction system, the control temperature is 170～200 ℃, adds active calcium carbonate, makes the organic cobalt salt mixture finished product based on new cobalt decanoate.
In sum, characteristics of the present invention are partly to replace propionic acid and PIVALIC ACID CRUDE (25) with vinylformic acid (or methacrylic acid) and 4-pentenoic acid, prepared new cobalt decanoate mixing salt has kept bonding force between rubber and the metal, participate in the vulcanization of rubber again and form new chemical bond, bounding force is better than the new cobalt decanoate of traditional technology.
Prepare various material performance of the present invention and require as follows:
Cobaltous hydroxide: molecular formula Co (OH)
2, molecular weight 93.95.
Basic physical and chemical: Co (OH)
2Be rose monocline or tetragonal system xln, density 3.6g/cm
3, water content＜2%.Water insoluble and alkali is dissolved in acid and ammonium salt solution.Be oxidized to henna hydrous oxide in air or under the high temperature easily.
Propionic acid: molecular formula CH
3CH
2COOH, molecular weight 74.08.
Basic physical and chemical: the achromaticity and clarification oily liquids has pungent foul odour slightly.Content 〉=99.5%.Can be miscible with water, be dissolved in ethanol, chloroform and ether.Relative density (d
20 ℃) 0.99336g/cm
3Fusing point-21.5 ℃.141.1 ℃ of boiling points.Refractive index 1.3848.Viscosity (15 ℃) 1.175mPas.58 ℃ of flash-points (opening cup).Inflammable, low toxicity.Be corrosive, after Dermallly affixed the going up, the used water flushing, operation is to have worn face guard, equipment will seal.
Vinylformic acid: molecular formula CH
2=CH-COOH, molecular weight 72.06.
Basic physical and chemical: colourless liquid has irritating smell, content 〉=99.5%.13.5 ℃ of fusing points, the density of water is 1.05g/cm relatively
3, 141 ℃ of boiling points, 68.3 ℃ of flash-points.Can dissolve each other with water, alcohol, ether and chloroform.Be corrosive, after Dermallly affixed the going up, the used water flushing, operation is to have worn face guard, equipment will seal.
Methacrylic acid: molecular formula CH
2=C (CH
3)-COOH, molecular weight 86.09.
Basic physical and chemical: colourless crystallization or transparent liquid have irritating smell, content 〉=99.6%.15 ℃ of fusing points, relative density 1.01,161 ℃ of boiling points, 68 ℃ of flash-points.Most organic solvents such as water-soluble, ethanol, ether.Moderate toxicity has stronger pungency and corrodibility to skin and mucous membrane, after Dermallly affixed the going up, and the used water flushing, operation is to have worn face guard, equipment will seal.
PIVALIC ACID CRUDE (25): molecular formula is C
5H
10O
2, molecular weight 102.14.
Basic physical and chemical: white water absorbability crystalline solid, sharp aroma, content 99.7%.35 ℃ of fusing points, 165 ℃ of boiling points, 86 ℃ of flash-points, density is 0.905g/cm
3, refractive index 1.3931.Water soluble has corrodibility, light poison.After Dermallly affixed the going up, the used water flushing, operation is to have worn face guard, equipment will seal.
4-pentenoic acid: molecular formula CH
2=CH-(CH
2)
3-COOH, molecular weight 100.12.
Basic physical and chemical: colourless liquid, sharp aroma.Content 〉=99.5%.Fusing point-22.5 ℃, 89 ℃ of flash-points, density 0.981g/cm
3, specific refractory power 1.4281.Be slightly soluble in water, be soluble in ethanol and ether.Have corrodibility, can cause and burn that eyes and respiratory system are had pungency.After Dermallly affixed the going up, the used water flushing, operation is to have worn face guard, equipment will seal.
Neodecanoic acid: molecular formula C
10H
20O
2, molecular-weight average 172.26.
Basic physical and chemical: light yellow liquid or colourless is a kind of mixed organic acid with branched structure, and principal constituent is neodecanoic acid, and other are 9,11 and above acid for the carbon containing number, content 〉=99.6%.Density (d
20 ℃) 0.915g/cm
3, 223～253 ℃ of boiling points, 120 ℃ of flash-points.Water-soluble and organic solvent.Certain pungency is arranged, and facility properly protects during operation.
Activated Calcium carbonate: molecular formula CaCO
3, molecular weight 100.09.
Basic physical and chemical: white powder solid.Density 2.83g/cm
3Almost insoluble in water, insoluble in ethanol, slightly soluble in the water that contains quaternary ammonium salt or carbonic acid gas.Process silane coupling agent surface treatment before using.
Embodiment
Be described in further details below by the present invention of embodiment.But described example is not construed as limiting the invention.
The preparation the present invention contain unsaturated acid the new cobalt decanoate mixing salt method, comprise the steps:
1) be that cobaltous hydroxide and 10～15 parts of propionic acid, 2～10 parts of acrylic or methacrylic acid and 40～50 parts of neodecanoic acids of 25～35 parts place the normal pressure sealed vessel with mass fraction, at 140～180 ℃ of back flow reaction 3～5h of temperature, reaction generates acrylic or methacrylic acid-propionic acid-new cobalt decanoate mixing salt;
2) adding mass fraction then in above-mentioned reaction system is 3～6 parts of PIVALIC ACID CRUDE (25) and 2～4 parts of 4-pentenoic acids, and the control reflux temperature is 160～200 ℃, and the reaction times is 2～4h, displaces propionic acid or vinylformic acid;
3) the control temperature is 170～200 ℃, 1～2 hour temperature condition of churning time, and the interpolation mass fraction is 3～6 parts activated Calcium carbonate, constantly stirs down, makes the new cobalt decanoate mixing salt that contains unsaturated acid.
Below by specific embodiment enforcement of the present invention is further described.
Embodiment 1
Propionic acid 10g, vinylformic acid 2g, neodecanoic acid 50g, cobaltous hydroxide 30g are joined in the 250mL there-necked flask that has reflux condensing tube and vacuum pump successively, and the control temperature is 150 ℃, and in 3 hours reaction times, intensification current drainage, vacuum decompression are emitted waste water.Add PIVALIC ACID CRUDE (25) 3g and 4-pentenoic acid 2g again and stir, temperature adjustment control is emitted waste water and propionic acid or vinylformic acid 190 ℃ of reactions 2 hours.Turn down temperature to 180 ℃, add activated Calcium carbonate 3g, evenly stir blowing after 1 hour, get new cobalt decanoate mixing salt product.Product cobalt contents 20.74%, 90 ℃ of fusing points, outward appearance is the bluish voilet solid.
Embodiment 2
Propionic acid 10g, methacrylic acid 5g, neodecanoic acid 40g, cobaltous hydroxide 35g are joined in the 250mL there-necked flask that has reflux condensing tube and vacuum pump successively, and the control temperature is 180 ℃, and in 3.5 hours reaction times, intensification current drainage, vacuum decompression are emitted waste water.Add PIVALIC ACID CRUDE (25) 4g and 4-pentenoic acid 2g again and stir, temperature adjustment control is emitted waste water and propionic acid or vinylformic acid 200 ℃ of reactions 3 hours.Turn down temperature to 170 ℃, add activated Calcium carbonate 4g, evenly stir blowing after 2 hours, get new cobalt decanoate mixing salt product.Product cobalt contents 20.57%, 91 ℃ of fusing points, outward appearance is the bluish voilet solid.
Embodiment 3
Propionic acid 15g, vinylformic acid 10g, neodecanoic acid 40g, cobaltous hydroxide 25g are joined in the 250mL there-necked flask that has reflux condensing tube and vacuum pump successively, and the control temperature is 140 ℃, and in 5 hours reaction times, intensification current drainage, vacuum decompression are emitted waste water.Add PIVALIC ACID CRUDE (25) 5g and 4-pentenoic acid 2g again and stir, temperature adjustment control is emitted waste water and propionic acid or vinylformic acid 160 ℃ of reactions 4 hours.Heighten temperature to 200 ℃, add activated Calcium carbonate 3g, evenly stir blowing after 1 hour, get new cobalt decanoate mixing salt product.Product cobalt contents 20.55%, 93 ℃ of fusing points, outward appearance is the bluish voilet solid.
Above content is to further describing that the present invention does in conjunction with concrete preferred implementation; can not assert that the specific embodiment of the present invention only limits to this; for the general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; can also make some simple deduction or replace, all should be considered as belonging to the present invention and determine scope of patent protection by claims of submitting to.
Claims (6)
1. a new cobalt decanoate mixing salt that contains unsaturated acid is characterized in that, comprises the raw material of following mass fraction:
25～35 parts of cobaltous hydroxides;
40～50 parts of neodecanoic acids;
10～15 parts of propionic acid;
2～10 parts in vinylformic acid;
3～6 parts of PIVALIC ACID CRUDE (25);
2～4 parts of 4-pentenoic acids;
3～6 parts of activated Calcium carbonates.
2. a kind of new cobalt decanoate mixing salt that contains unsaturated acid according to claim 1 is characterized in that, described vinylformic acid or alternative with methacrylic acid.
A new cobalt decanoate mixing salt that contains unsaturated acid the preparation method, it is characterized in that this method comprises the steps:
1) be that cobaltous hydroxide and 10～15 parts of propionic acid, 2～10 parts of acrylic or methacrylic acid and 40～50 parts of neodecanoic acids of 25～35 parts place the normal pressure sealed vessel with mass fraction, reflux, reaction generates acrylic or methacrylic acid-propionic acid-new cobalt decanoate mixing salt;
2) adding mass fraction then in above-mentioned reaction system is 3～6 parts of PIVALIC ACID CRUDE (25) and 2～4 parts of 4-pentenoic acids, and control back flow reaction condition displaces propionic acid or vinylformic acid;
3) control temperature condition, the interpolation mass fraction is 3～6 parts activated Calcium carbonate, constantly stirs down, makes the new cobalt decanoate mixing salt that contains unsaturated acid.
The new cobalt decanoate mixing salt that contains unsaturated acid according to claim 3 the preparation method, it is characterized in that, in the described step 1) at 140～180 ℃ of back flow reaction 3～5h of temperature.
The new cobalt decanoate mixing salt that contains unsaturated acid according to claim 3 the preparation method, it is characterized in that described step 2) in reflux temperature be 160～200 ℃, the reaction times is 2～4h.
The new cobalt decanoate mixing salt that contains unsaturated acid according to claim 3 the preparation method, it is characterized in that the control temperature is 170～200 ℃ in the described step 3), churning time 1～2 hour.
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Cited By (3)
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| CN106832401A (en) * | 2017-02-20 | 2017-06-13 | 镇江泛华新材料科技发展有限公司 | Direct addition type high-performance cobalt salt adhesion promoter and preparation method thereof |
| CN107986955A (en) * | 2017-11-22 | 2018-05-04 | 浙江三晟化工有限公司 | A kind of preparation method of new cobalt decanoate |
| 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 |
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Cited By (4)
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| CN106832401A (en) * | 2017-02-20 | 2017-06-13 | 镇江泛华新材料科技发展有限公司 | Direct addition type high-performance cobalt salt adhesion promoter and preparation method thereof |
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