CN103183845B - Fluorine-containing cobalt neocaprate and cobalt borate salt-mixture and preparation method thereof - Google Patents
Fluorine-containing cobalt neocaprate and cobalt borate salt-mixture and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a fluorine-containing cobalt neocaprate and cobalt borate salt-mixture. A method for preparing fluorine-containing cobalt borate comprises the following steps: (1) adding butyl borate into fluorine-containing cobalt neocaprate to conduct boracylate reaction; and (2) adding activated calcium carbonate to obtain a finished product of fluorine-containing cobalt borate salt-mixture. A method for preparing fluorine-containing cobalt neocaprate comprises the following steps: (1) placing pseudacetic acid, fluorine-containing pseudacetic acid, neodecanoic acid and cobalt hydroxide into a container, controlling the temperature and the reaction time, achieving temperature increment drainage and vacuum pressure relief, and discharging waste water; and (2) adding neopentanoic acid and fluorine-containing pentanoic acid into the reaction system, stirring, adjusting the temperature to control reaction, and discharging waste water and pseudacetic acid or acrylic acid to obtain the fluorine-containing cobalt neocaprate salt-mixture. The fluorine-containing cobalt neocaprate and cobalt borate salt-mixture has stronger rubber-metal interface binding force than a traditional cobalt decanoate and cobalt borate salt product. The cobalt salt product has the characteristics of higher cobalt content, strong reactivity, heat resistance, weather-proof property and the like, and is favorable for rubber ageing performance.
Description
Technical field
The present invention relates to a kind of rubber item and produce the fluorine-containing new cobalt decanoate of processing aid used and cobalt boracylate mixing salt and preparation method thereof, belong to field of chemical technology.
Background technology
Produce processing aid new cobalt decanoate used and cobalt boracylate mixing salt its role is to increase the bounding force between metal and rubber matrix as rubber item; it is mainly used as the adhesionpromoter of rubber and steel wire cord (comprising naked steel wire, copper-plated zinc etc.); can be used for the production of the rubber-metal composite products such as radial, rubber wire conveying belt, transition pipeline, also have part for coatings industry etc.Traditional new cobalt decanoate of preparing is all to adopt the raw materials such as cobaltous hydroxide and organic acid acid-base reaction under toluene, dimethylbenzene equal solvent exist, and then carries out boron acylation reaction and make organic cobalt salt finished product.Fluorine is the material that chemical property is the most active, oxidisability is the strongest.The characteristics such as fluorine atom radius is little, C-F bond energy height, can give organic fluorocompound special chemical performance.As the strong electrophilic of the C-F group of fluorine-containing propionic acid, fluorine-containing propionic acid is had compared with strongly-acid and activity etc.Therefore, fluorine atom is introduced to traditional new cobalt decanoate and cobalt boracylate, can strengthen new cobalt decanoate and cobalt boracylate activity, increase the bounding force between rubber-metal interface.And the more heat-resisting weathering resistance of fluorine-containing auxiliary agent, can improve ageing of rubber performance.
Summary of the invention
The invention provides a kind of fluorine-containing new cobalt decanoate and cobalt boracylate mixing salt and preparation method thereof, this fluorine-containing new cobalt decanoate and cobalt boracylate mixing salt have stronger rubber-metal interfacial adhesion power than traditional capric acid cobalt and cobalt boracylate salt product.Cobalt salt goods of the present invention have containing cobalt amount compared with high, reactive behavior is large, heat-resisting weather-proof, to features such as ageing of rubber performance are favourable.
The fluorine-containing new cobalt decanoate of the present invention and cobalt boracylate mixing salt are achieved in that
A kind of fluorine-containing cobalt boracylate mixing salt is provided, is prepared from by the raw material of following mass fraction:
60～80 parts of fluorine-containing new cobalt decanoate mixing salts;
10～30 parts of butyl borates;
5～15 parts of activated Calcium carbonates.
Further, in the fluorine-containing cobalt boracylate material of the present invention:
Described fluorine-containing new cobalt decanoate mixing salt is prepared from by the raw material of following mass fraction:
25～35 parts of cobaltous hydroxides;
40～55 parts of neodecanoic acids;
10～20 parts of propionic acid;
2～10 parts of fluorine-containing propionic acid;
3～6 parts of PIVALIC ACID CRUDE (25);
2～4 parts of fluorine-containing valeric acids.
Described fluorine-containing propionic acid is trifluoroacetic acid or perfluorinated acid.
Described fluorine-containing valeric acid is trifluoro valeric acid, five fluorine valeric acids or perfluor valeric acid.
Correspondingly, the present invention also provide a kind of fluorine-containing cobalt boracylate mixing salt preparation method, comprise following preparation process:
1) in mass fraction is 60～80 parts of fluorine-containing new cobalt decanoate mixing salts, adding mass fraction is 10～30 parts of butyl borates, distills out by product ester;
2) in above-mentioned reactant, add 5～15 parts of activated Calcium carbonates, stir, obtain fluorine-containing cobalt boracylate mixing salt.
Further, in the fluorine-containing cobalt boracylate method of above-mentioned preparation, described fluorine-containing new cobalt decanoate mixing salt is prepared by following method:
1. be that 10～20 parts of propionic acid, 2～10 parts of fluorine-containing propionic acid, 40～55 parts of neodecanoic acids and 25～35 parts of cobaltous hydroxides are placed in container by mass fraction, control reflux conditions heat up drainage, vacuum decompression, emit waste water;
2. in above-mentioned reaction system, add 3～6 parts of PIVALIC ACID CRUDE (25), 2～4 parts of fluorine-containing valeric acids to stir, control reaction conditions, emit waste water and propionic acid or vinylformic acid, obtain fluorine-containing new cobalt decanoate mixing salt.
Further, in the fluorine-containing new cobalt decanoate mixing salt of above-mentioned preparation method:
Described step 1. middle control reflux conditions temperature is 150～170 DEG C, 2～4 hours reaction times.
Described step is the middle reaction conditions of controlling 2., and temperature adjustment is controlled at 160～190 DEG C, reacts 2～4 hours.
After several fluorine-containing organic acids of the present invention and not fluorine-containing organic acid blend, carry out acid-base reaction and sour replacement(metathesis)reaction with cobaltous hydroxide, generate fluorine-containing new cobalt decanoate mixture, then carry out again boron acylation reaction.It is specific as follows:
(1) acid-base reaction
Taking the mixing acid of cobaltous hydroxide and propionic acid, fluorine-containing propionic acid, neodecanoic acid composition as raw material, in atmospheric pressure sealed container, 150～170 DEG C of back flow reaction >=2h of temperature, reaction generates fluorine-containing propionic acid-new cobalt decanoate mixing salt, and its total reaction formula is:
Wherein: R
2depending on the ratio of fluorine-containing propionic acid and propionic acid; X+y=5, x, y>=0;
(2) sour replacement(metathesis)reaction
In above-mentioned reaction system, fluorine-containing propionic acid-new cobalt decanoate mixing salt of generation, too much also defectiveness of propionic acid content, the especially fluorine-containing propionic acid of the acidity of propionic acid, what its acidity may corrosion metals steel wire.Consider this factor, need be by carbon number higher than propionic acid, displace propionic acid and the fluorine-containing propionic acid of part lower than the PIVALIC ACID CRUDE (25) of neodecanoic acid or fluorine-containing valeric acid.Specific experiment parameter: in above-mentioned reaction system, add PIVALIC ACID CRUDE (25) and fluorine-containing valeric acid, control 160～190 DEG C of temperature, time >=2h, back flow reaction displaces fluorine-containing propionic acid or propionic acid.Its reaction formula is:
Wherein: R
4depending on the ratio of PIVALIC ACID CRUDE (25) and fluorine-containing valeric acid; A+b=9, a, b>=0;
Above-mentioned sour replacement(metathesis)reaction is incomplete, only has part propionic acid and fluorine-containing propionic acid to be displaced by acid, and therefore prepared new cobalt decanoate is a kind of fluorine-containing mixture.
(3) boron acylation reaction
It is high that cobalt boracylate has reactive behavior than new cobalt decanoate when the vulcanization of rubber, containing cobalt amount high, therefore can in above-mentioned reaction system, add butyl borate, controls 180～200 DEG C of temperature, and time >=2 hour, carry out boron acylation reaction, and its reaction formula is as follows:
Subsequently, 180～190 DEG C of constant temperature, add activated Calcium carbonate, make fluorine-containing cobalt boracylate mixing salt goods.Calcium carbonate main purpose is the potential of hydrogen of equilibrium system, prevents that cobalt salt goods acidity is too strong.
In sum; the feature of this project is to replace propionic acid and PIVALIC ACID CRUDE (25) by fluorine-containing propionic acid and fluorine-containing valeric acid part; prepared fluorine-containing new cobalt decanoate and fluorine-containing cobalt boracylate have bonding force between stronger rubber and metal, and the introducing of fluorine simultaneously makes cobalt salt have heat-resisting, weather-proof, ageing-resistant performance.
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 DEG C) 0.99336g/cm
3.Fusing point-21.5 DEG C.141.1 DEG C of boiling points.Refractive index 1.3848.Viscosity (15 DEG C) 1.175mPas.58 DEG C of flash-points (opening cup).Inflammable, low toxicity.Be corrosive, Dermallly affixed upper after, used water rinse, operation is to wear face guard, equipment will seal.
Trifluoroacetic acid: molecular formula CF
3cH
2-COOH, molecular weight 128.05.
Basic physical and chemical: colourless liquid, has irritating smell, content >=99.5%.9.7 DEG C of fusing points, the density of water is 1.05g/cm relatively
3, 146 DEG C of boiling points, 92 DEG C of flash-points, refractive index 1.332.Can dissolve each other with water, alcohol, ether and chloroform.Be corrosive, Dermallly affixed upper after, rinse with large water gaging immediately, operation is to wear face guard, gloves and protective clothing, equipment will seal.
Five fluorine propionic acid: molecular formula C
2f
5-COOH, molecular weight 270.89.
Basic physical and chemical: colourless transparent liquid, irritant smell, content >=99.5%.96 DEG C of boiling points, relative density 1.561g/mL, specific refractory power 1.284.When operation, dress suitable protective clothing, gloves and use safety glasses or face shield.
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 DEG C of fusing points, 165 DEG C of boiling points, 86 DEG C 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 rinse, operation is to wear face guard, equipment will seal.
5,5,5-trifluoro valeric acid: molecular formula CF
3c
3h
6-COOH, molecular weight 156.10.
Basic physical and chemical: white solid, irritant smell, content >=99.6%.30 DEG C of fusing points, 170.2 DEG C of boiling points, relative density 1.278,170 DEG C of flash-points.Most organic solvents such as water-soluble, ethanol, ether.Skin and mucous membrane are had to stronger pungency and corrodibility, Dermallly affixed upper after, rinse with large water gaging immediately.When operation, dress suitable protective clothing, gloves and use safety glasses or face shield.
Perfluor valeric acid: molecular formula C
5f
11-COOH, molecular weight 246.06.
Basic physical and chemical: colourless liquid, irritant smell, content >=96%.140 DEG C of boiling points, relative density 1.731g/mL, 29.1 DEG C of flash-points, specific refractory power 1.294.Water soluble and organic solvent.Skin and mucous membrane are had to stronger pungency and corrodibility, Dermallly affixed upper after, rinse with large water gaging immediately.When operation, dress suitable protective clothing, gloves and use safety glasses or face shield.
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 dEG C) 0.915g/cm
3, 223～253 DEG C of boiling points, 120 DEG C of flash-points.Water-soluble and organic solvent.Have certain pungency, facility properly protects when operation.
Butyl borate: molecular formula (C
4h
9o)
3b, molecular weight 203.15.
Basic physical and chemical: colourless transparent liquid, irritant, content >=98%.231 DEG C of boiling points, 93 DEG C of flash-points, density 0.8550, refractive index 1.410.Meet water decompose rapidly, can with immiscible organic solvent.Irritant to eyes, respiratory system and skin.When operation, dress suitable protective clothing, gloves and use safety glasses or face shield.
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.
The fluorine-containing cobalt boracylate mixing salt of the present invention preparation method:
First, prepare fluorine-containing new cobalt decanoate mixing salt, comprise the steps:
1. be that 10～20 parts of propionic acid, 2～10 parts of fluorine-containing propionic acid, 40～55 parts of neodecanoic acids and 25～35 parts of cobaltous hydroxides are placed in container by mass fraction, controlling temperature is 150～170 DEG C, 2～4 hours reaction times; Heat up drainage, vacuum decompression, emit waste water;
2. in above-mentioned reaction system, add 3～6 parts of PIVALIC ACID CRUDE (25), 2～4 parts of fluorine-containing valeric acids to stir, temperature adjustment is controlled at 160～190 DEG C of reactions 2～4 hours, emits waste water and propionic acid or vinylformic acid, obtains fluorine-containing new cobalt decanoate mixing salt.
Then, utilize the fluorine-containing new cobalt decanoate of above-mentioned product to prepare fluorine-containing cobalt boracylate:
1) getting above-mentioned product quality umber is that in 60～80 parts of fluorine-containing new cobalt decanoates, to add mass fraction be 10～30 parts of butyl borates, distills out by product ester;
2) in above-mentioned reactant, add 5～15 parts of activated Calcium carbonates, stir 1 hour, obtain fluorine-containing cobalt boracylate mixing salt.
Below by specific embodiment, preparation method of the present invention is described in further details.
Embodiment 1
In the 250mL there-necked flask with moisture content collector, reflux condensing tube and vacuum pump, add respectively propionic acid 15g, trifluoroacetic acid 5g, neodecanoic acid 40g, cobaltous hydroxide 35g, controlling temperature is 160 DEG C, 3 hours reaction times, intensification drainage, vacuum decompression, emit waste water.Add PIVALIC ACID CRUDE (25) 3g and 5,5,5 trifluoro valeric acid 2g stir again, and temperature adjustment is controlled at 185 DEG C of reactions 2 hours, emits waste water and propionic acid or vinylformic acid, obtains fluorine-containing new cobalt decanoate.Subsequently, get the fluorine-containing new cobalt decanoate 80g of above-mentioned product, add butyl borate 10g, react 2 hours, distill out by product ester.Finally add activated Calcium carbonate 10g, as a child blowing of uniform stirring 1, obtains fluorine-containing cobalt boracylate finished product.Product cobalt contents 22.84%, 101 DEG C of fusing points, outward appearance is bluish voilet solid.
Embodiment 2
In the 250mL there-necked flask with moisture content collector, reflux condensing tube and vacuum pump, add respectively propionic acid 10g, perfluorinated acid 2g, neodecanoic acid 50g, cobaltous hydroxide 28g, controlling temperature is 150 DEG C, 4 hours reaction times, intensification drainage, vacuum decompression, emit waste water.Add PIVALIC ACID CRUDE (25) 6g and 5,5,5-, five fluorine valeric acid 4g to stir, temperature adjustment is controlled at 160 DEG C of reactions 4 hours, emits waste water and propionic acid or vinylformic acid, obtains fluorine-containing new cobalt decanoate again.Subsequently, get the fluorine-containing new cobalt decanoate 60g of above-mentioned product, add butyl borate 30g, react 2 hours, distill out by product ester.Finally add activated Calcium carbonate 10g, as a child blowing of uniform stirring 1, obtains fluorine-containing cobalt boracylate finished product.Product cobalt contents 22.52%, 104 DEG C of fusing points, outward appearance is bluish voilet solid.
Embodiment 3
In the 250mL there-necked flask with moisture content collector, reflux condensing tube and vacuum pump, add respectively propionic acid 20g, perfluorinated acid 10g, neodecanoic acid 40g, cobaltous hydroxide 25g, controlling temperature is 170 DEG C, 2 hours reaction times, intensification drainage, vacuum decompression, emit waste water.Add PIVALIC ACID CRUDE (25) 3g and perfluor valeric acid 2g to stir, temperature adjustment is controlled at 190 DEG C of reactions 2 hours, emits waste water and propionic acid or vinylformic acid, obtains fluorine-containing new cobalt decanoate again.Subsequently, get the fluorine-containing new cobalt decanoate 70g of above-mentioned product, add butyl borate 15g, react 2 hours, distill out by product ester.Finally add activated Calcium carbonate 15g, as a child blowing of uniform stirring 1, obtains fluorine-containing cobalt boracylate finished product.Product cobalt contents 22.34%, 108 DEG C 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 (6)
1. a fluorine-containing cobalt boracylate mixing salt, is characterized in that, is prepared from by the raw material of following mass fraction:
60～80 parts of fluorine-containing new cobalt decanoate mixing salts;
10～30 parts of butyl borates;
5～15 parts of activated Calcium carbonates;
Described fluorine-containing new cobalt decanoate mixing salt is prepared from by the raw material of following mass fraction:
2. fluorine-containing cobalt boracylate mixing salt according to claim 1, is characterized in that, described fluorine-containing propionic acid is trifluoroacetic acid or perfluorinated acid.
3. fluorine-containing cobalt boracylate mixing salt according to claim 1, is characterized in that, described fluorine-containing valeric acid is trifluoro valeric acid, five fluorine valeric acids or perfluor valeric acid.
Fluorine-containing cobalt boracylate mixing salt a preparation method, it is characterized in that, comprise following preparation process:
1) in mass fraction is 60～80 parts of fluorine-containing new cobalt decanoate mixing salts, adding mass fraction is 10～30 parts of butyl borates, distills out by product ester;
2) in above-mentioned reactant, add 5～15 parts of activated Calcium carbonates, stir, obtain fluorine-containing cobalt boracylate mixing salt;
Described fluorine-containing new cobalt decanoate mixing salt is prepared by following method:
1. be that 10～20 parts of propionic acid, 2～10 parts of fluorine-containing propionic acid, 40～55 parts of neodecanoic acids and 25～35 parts of cobaltous hydroxides are placed in container by mass fraction, control reflux conditions heat up drainage, vacuum decompression, emit waste water;
2. in above-mentioned reaction system, add 3～6 parts of PIVALIC ACID CRUDE (25), 2～4 parts of fluorine-containing valeric acids to stir, control reaction conditions, emit waste water and propionic acid or vinylformic acid, obtain fluorine-containing new cobalt decanoate mixing salt.
Fluorine-containing cobalt boracylate mixing salt according to claim 4 preparation method, it is characterized in that, it is 150～170 DEG C that described step is controlled reflux conditions temperature in 1., 2～4 hours reaction times.
Fluorine-containing cobalt boracylate mixing salt according to claim 4 preparation method, it is characterized in that, described step 2. in control reaction conditions, temperature adjustment is controlled at 160～190 DEG C, reacts 2～4 hours.
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