CN103183843B - 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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- CN103183843B CN103183843B CN201310084830.2A CN201310084830A CN103183843B CN 103183843 B CN103183843 B CN 103183843B CN 201310084830 A CN201310084830 A CN 201310084830A CN 103183843 B CN103183843 B CN 103183843B
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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 containing undersaturated new cobalt decanoate mixing salt and corresponding Technology.
Background technology
New cobalt decanoate is a kind of of main adhesionpromoter bonding between steel wire and rubber, be mainly used in the initial adhesion of radial tyre, conveying belt, steel band steel metal and rubber in the rubber-metal matrix materials such as sebific duct, it has guaranteed use properties and the work-ing life of tire, guarantee again still can there is higher viscosity conservation rate after later stage ageing of rubber and corrosion, thereby new cobalt decanoate has become indispensable component in the production of rubber-metal matrix material simultaneously.Its theoretical molecular formula of new cobalt decanoate is: [CH
3(CH
2)
8cO
2]
2co, theoretical only have 14.7% containing cobalt amount, do not reach the service requirements of rubber production.Therefore, the new cobalt decanoate of domestic and foreign literature and patent report is all a kind of mixtures at present, be a kind of carboxylic acid that carbochain length is different in three to four react with cobalt salt produce by the mazarine vitreum fixedly forming, its synthetic method is all the production technique of the raw materials such as employing cobaltous hydroxide and three to four kinds of unsaturated organic acids under solvent existence.Yet, the method synthetic containing saturated acidic group new cobalt decanoate and rubber matrix itself bonding be only the model ylid bloom action power of physics, the relative chemical interactions 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 containing unsaturated acid and preparation method thereof, through retrieval professional technique data, has no relevant report and patent application both at home and abroad.
Summary of the invention
The object of the invention is to be to provide and contain a kind of new cobalt decanoate mixing salt and preparation technology containing unsaturated acid, this neodecanoic acid cobalt salt containing unsaturated acid had both kept binding cobalt salt power, when the vulcanization of rubber, the two keys of the C=C of unsaturated acid participate in sulfuration and form new chemical bond simultaneously, make the bonding force between this metal to rubber stronger.The capric acid cobalt that the present invention prepares, high containing cobalt amount, fusing point is high, and particularly bounding force is strong.
The object of the present invention is achieved like this:
Containing a new cobalt decanoate mixing salt for unsaturated acid, comprise 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, 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 containing unsaturated acid preparation method, the method comprises the steps:
1) by mass fraction, 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 are placed in atmospheric pressure sealed container, reflux, reaction generates acrylic or methacrylic acid-propionic acid-new cobalt decanoate mixing salt;
2) then in above-mentioned reaction system, adding mass fraction is 3～6 parts of PIVALIC ACID CRUDE (25) and 2～4 parts of 4-pentenoic acids, controls back flow reaction condition, displaces propionic acid or vinylformic acid;
3) control temperature condition, interpolation mass fraction is the activated Calcium carbonate of 3～6 parts, under constantly stirring, makes the new cobalt decanoate mixing salt containing unsaturated acid.
Further, in described method:
In described step 1) at 140～180 ℃ of back flow reaction 3～5h of temperature.
Described step 2) in, reflux temperature is 160～200 ℃, and the reaction times is 2～4h.
In described step 3), controlling temperature is 170～200 ℃, 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, finally generates the new cobalt decanoate mixture containing unsaturated acid, comprising:
(1) acid-base reaction
The mixing acid that cobaltous hydroxide and propionic acid, vinylformic acid (or methacrylic acid), neodecanoic acid form of take is raw material, in atmospheric pressure sealed container, 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, depending 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 generating, 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 of rubber product and metal steel wire after vulcanization of rubber dissociation.Consider this factor, need be by carbon number higher than propionic acid, lower than the PIVALIC ACID CRUDE (25) of neodecanoic acid or 4-pentenoic acid, displace propionic acid and the vinylformic acid (or methacrylic acid) of part.Specific experiment parameter: in above-mentioned reaction system, add PIVALIC ACID CRUDE (25) and 4-pentenoic acid, control 160～200 ℃ of 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, depending 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, controlling temperature is 170～200 ℃, adds active calcium carbonate, makes and take new cobalt decanoate as main organic cobalt salt mixture finished product.
In sum, feature of the present invention is 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 metal, participate in again the vulcanization of rubber 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)
2for 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.In air or under high temperature, be easily oxidized to henna hydrous oxide.
Propionic acid: molecular formula CH
3cH
2cOOH, molecular weight 74.08.
Basic physical and chemical: achromaticity and clarification oily liquids, slightly pungent foul odour.Content >=99.5%.Can be miscible with water, be dissolved in ethanol, chloroform and ether.Relative density (d
20 ℃) 0.99336g/cm
3.Fusing 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, Dermallly affixed upper after, used water is rinsed, operation is to wear 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, Dermallly affixed upper after, used water is rinsed, operation is to wear 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, irritant 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, Dermallly affixed upper after, used water is rinsed, operation is to wear 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, gently poison.Dermallly affixed upper after, used water is rinsed, operation is to wear 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.There is corrodibility, can cause and burn, irritant to eyes and respiratory system.Dermallly affixed upper after, used water is rinsed, operation is to wear 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, other for carbon containing number be 9,11 and above acid, content >=99.6%.Density (d
20 ℃) 0.915g/cm
3, 223～253 ℃ of boiling points, 120 ℃ of flash-points.Water-soluble and organic solvent.Have certain pungency, 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
3.Almost insoluble in water, insoluble in ethanol, slightly soluble in the water containing quaternary ammonium salt or carbonic acid gas.Process silane coupling agent surface treatment before using.
Embodiment
Below by embodiment, the present invention is described in further details.But described example is not construed as limiting the invention.
Preparation the present invention containing the new cobalt decanoate mixing salt of unsaturated acid method, comprise the steps:
1) by mass fraction, 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 are placed in atmospheric pressure sealed container, 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) then in above-mentioned reaction system, adding mass fraction is 3～6 parts of PIVALIC ACID CRUDE (25) and 2～4 parts of 4-pentenoic acids, and controlling reflux temperature is 160～200 ℃, and the reaction times is 2～4h, displaces propionic acid or vinylformic acid;
3) controlling temperature is 170～200 ℃, 1～2 hour temperature condition of churning time, and interpolation mass fraction is the activated Calcium carbonate of 3～6 parts, under constantly stirring, makes the new cobalt decanoate mixing salt containing 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 with reflux condensing tube and vacuum pump successively, and controlling temperature is 150 ℃, and in 3 hours reaction times, intensification drainage, vacuum decompression, emit waste water.Add PIVALIC ACID CRUDE (25) 3g and 4-pentenoic acid 2g to stir, temperature adjustment is controlled at 190 ℃ of reactions 2 hours, emits waste water and propionic acid or vinylformic acid again.Turn down temperature to 180 ℃, add activated Calcium carbonate 3g, uniform stirring is blowing after 1 hour, obtains new cobalt decanoate mixing salt product.Product cobalt contents 20.74%, 90 ℃ of fusing points, outward appearance is 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 with reflux condensing tube and vacuum pump successively, and controlling temperature is 180 ℃, and in 3.5 hours reaction times, intensification drainage, vacuum decompression, emit waste water.Add PIVALIC ACID CRUDE (25) 4g and 4-pentenoic acid 2g to stir, temperature adjustment is controlled at 200 ℃ of reactions 3 hours, emits waste water and propionic acid or vinylformic acid again.Turn down temperature to 170 ℃, add activated Calcium carbonate 4g, uniform stirring is blowing after 2 hours, obtains new cobalt decanoate mixing salt product.Product cobalt contents 20.57%, 91 ℃ of fusing points, outward appearance is 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 with reflux condensing tube and vacuum pump successively, and controlling temperature is 140 ℃, and in 5 hours reaction times, intensification drainage, vacuum decompression, emit waste water.Add PIVALIC ACID CRUDE (25) 5g and 4-pentenoic acid 2g to stir, temperature adjustment is controlled at 160 ℃ of reactions 4 hours, emits waste water and propionic acid or vinylformic acid again.Heighten temperature to 200 ℃, add activated Calcium carbonate 3g, uniform stirring is blowing after 1 hour, obtains new cobalt decanoate mixing salt product.Product cobalt contents 20.55%, 93 ℃ of fusing points, outward appearance is bluish voilet solid.
Above content is in conjunction with concrete preferred implementation further description made for the present invention; can not assert that the specific embodiment of the present invention only limits to this; for 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 submitted to claims.
Claims (3)
1. containing a new cobalt decanoate mixing salt for unsaturated acid, it is characterized in that, comprise the raw material of following mass fraction:
Described activated Calcium carbonate is through silane coupling agent surface-treated activated Calcium carbonate before using.
2. a kind of new cobalt decanoate mixing salt containing unsaturated acid according to claim 1, is characterized in that, described vinylformic acid or alternative with methacrylic acid.
Containing the new cobalt decanoate mixing salt of unsaturated acid a preparation method, it is characterized in that, the method comprises the steps:
1) by mass fraction, 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 are placed in atmospheric pressure sealed container, 140～180 ℃ of 3～5h that reflux, reaction generates acrylic or methacrylic acid-propionic acid-new cobalt decanoate mixing salt;
2) then in above-mentioned reaction system, adding mass fraction is 3～6 parts of PIVALIC ACID CRUDE (25) and 2～4 parts of 4-pentenoic acids, controls 160～200 ℃ of reflux temperatures, and the 2～4h that refluxes, displaces propionic acid or vinylformic acid;
3) control 170～200 ℃ of temperature, interpolation mass fraction is the activated Calcium carbonate of 3～6 parts, and churning time 1～2h, makes the new cobalt decanoate mixing salt containing unsaturated acid.
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| CN106832401B (en) * | 2017-02-20 | 2018-10-19 | 江苏麒祥高新材料有限公司 | 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 |
| 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 |
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2013
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| 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 |
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