CN102879489B - Analytical method for content of organic acid in organic acid cobalt salt of rubber and steel wire bonding agent - Google Patents
Analytical method for content of organic acid in organic acid cobalt salt of rubber and steel wire bonding agent Download PDFInfo
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Abstract
The invention aims at providing an analytical method for the total content of free organic acid and organic acid radical ions in a rubber and steel wire bonding agent, which is simple to operate, high in accuracy of analysis result and small in error. The chemical properties of the organic acid in the cobalt salt are greatly different due to the different lengths and branching degrees of the carbon chains, so that the organic acid is difficult to quantitatively test through a single process. The analytical method is realized by the following technical scheme: when the carbon number of the organic acid is C2-C8, selecting an organic acid with the carbon number of C2-C8 as an internal standard substance, and selecting monohydric alcohol with the carbon number of C3-C8 for esterification, preferably monohydric alcohol with the carbon number of C3-C5; when the organic acid is the organic acid with the carbon number of C8-C22, selecting monohydric alcohol with the carbon number of C8-C22 as an internal standard substance, and selecting monohydric alcohol with the carbon number of C1-C8 for esterification, preferably monohydric alcohol with the carbon number of C1-C4; and when the organic acid is isocaprylic acid and neodecanoic acid, selecting the organic acid with the carbon number of C6-C18 as an internal standard substance to realize the aim of using a gas chromatography to perform compartment analysis.
Description
Technical field
The invention belongs to rubber industry and use steel wire adhesive material field, be specifically related to the analytical approach of organic acid content in rubber wire bonding agent organic acid cobalt salt.
Background technology
Along with the development of rubber industry, the research of rubber ingredients is more and more subject to people's attention with production.Organic acid cobalt salt plays very important effect in radial tire steel wire and rubber adhesion process.Organic acid cobalt salt product is divided into capric acid cobalt, cobalt boracylate, cobaltous octadecanate, several classes of cobalt oleate, and basic structure formula is as follows:
In different manufacturers organic acid cobalt salt product, organic acid composition, content all have difference, and in the similar organic acid cobalt salt of accurate analysis product, the difference of various compositions is to the important meaning again such as the raw material contrast of tire plant, product purchasing, formulating, commercial production.In the world/national testing standard of organic acid cobalt salt, only stipulated cobalt content, ash content, softening point, a boron content test event at present, in organic acid cobalt salt, various organic acid analyses not yet have any document and method to announce, and still belong to blank.
Summary of the invention
The present invention aims to provide the analytical approach of organic acid content in a kind of rubber wire bonding agent organic acid cobalt salt, specifically comprises the following steps:
Step 1, accurately takes 1 part of cobalt salt powder, adds the internal standard compound matter of accurate weighing, then adds 10～100 parts of boron trifluoride-ol solution or strong acid solution, mixes;
Step 2 reacts above-mentioned mixed solution to 0.5-3.0 hour in the temperature range of regulation;
Step 3, adds normal heptane and saturated nacl aqueous solution to extract reaction product, and extraction product is analyzed, and by capillary column gas chromatography discrete testing, calculates organic acid content in cobalt salt.
Wherein, the internal standard compound matter in step 1 can be that carbon number is any in the organic acid of C2-C22, and alcohol can be that carbon number is any in the monohydroxy alcohol of C1-C8.Strong acid solution can be any one or more in hydrochloric acid, sulfuric acid, nitric acid.Temperature of reaction in step 2 is 70～100 ℃.
Described organic acid comprises that carbon number is straight chain/side chain of C2-C22, saturated/unsaturated fatty acid, includes but not limited to one or more in acetic acid, propionic acid, butyric acid, valeric acid, neopentanoic acid, isooctyl acid, neodecanoic acid, capric acid, dodecoic acid, tetradecylic acid, palmitic acid, stearic acid, oleic acid, linoleic acid.
Described organic acid is carbon number while being the organic acid of C2-C8, and internal standard compound matter is selected the organic acid that carbon number is C2-C8, and monohydroxy alcohol is selected the monohydroxy alcohol that carbon number is C3-C8; Described organic acid is carbon number while being the organic acid of C8-C22, and internal standard compound matter is selected the organic acid that carbon number is C8-C22, and monohydroxy alcohol is selected the monohydroxy alcohol that carbon number is C1-C8.This two classes acid is converted into after ester, through capillary column gas chromatography compartment analysis.
Wherein, organic acid massfraction (wt
i%) can be obtained by formula (1):
In formula:
Wt
i%---the massfraction of organic acid i, %;
A
i---corresponding to the peak area of the ester of organic acid i;
A
s---corresponding to the peak area of the ester of internal standard compound;
K '
i---the correction factor of-organic acid i;
K '
s---the correction factor of internal standard compound;
M---sample mass, the mg of unit;
M
s---internal standard compound quality, the mg of unit.
When described organic acid is one or both in isooctyl acid or neodecanoic acid, use strong acid treatment, it is the organic acid of C6-C18 that internal standard compound matter is selected a kind of carbon number, use strong acid solution replacement Treatment, after normal heptane extraction, directly enter capillary column gas chromatography compartment analysis, bring the test data of sample into typical curve quantitative organic acid to be measured.
Above method all needs first to do one without interior standard specimen, to determine in organic acid cobalt salt not containing the organic acid consistent with interior mark.
The invention has the advantages that:
(1) method pretreatment process is simple, and reagent routine is easily purchased, and analysis time is short.
(2) chemical property of different organic acids differs greatly, and is difficult to use single method compartment analysis, and it is divided three classes by chemical property, is processed respectively with distinct methods, uses different interior marks, reaches the object with chromatogram ration analysis.
(3) in, mark together carries out esterification (acidifying) processing with sample.Owing to selecting in interior mark and organic acid cobalt salt organic acid character close, esterification (acidifying) conversion ratio, the recovery of extraction in whole experimentation is all consistent with organic acid can to think interior mark, and the error effect factor in experimentation has been dropped to minimum.
(4) experimental repeatability, favorable reproducibility, analysis result accuracy rate is high, and error is little.
Embodiment
Embodiment 1: organic acid quantitative test in certain capric acid cobalt
1. the organic acid quantitative test that in capric acid cobalt, carbon number is C2-C8
1.1 interior mark liquid are prepared: take 191.5mg n-butyric acie in 25ml volumetric flask, normal heptane constant volume.
1.2 preparation of samples: get capric acid cobalt and fully grind, take respectively 15.2mg (without interior standard specimen), 14.2mg, 15.6mg, 15.4mg (Duplicate Samples) powdered sample is in four 10ml volumetric flasks, with liquid-transfering gun, accurately pipette in 500 μ l and mark liquid in three Duplicate Samples, add again 2ml boron trifluoride-n-amyl alcohol solution, be placed in 85 ℃ of water-baths 1h that lactonizes, add 3mL normal heptane firmly to shake at least 15s, continue to add 5mL saturated nacl aqueous solution fully to shake up, stratification, gets upper solution air inlet analysis of hplc.
1.3 results are calculated
According to formula (1), calculate, result of calculation is listed in the table below:
2. the quantitative test of isooctyl acid and neodecanoic acid in capric acid cobalt
2.1 standard items preparations:
A) mark liquid preparation in: take 111.3mg lauric acid in 25ml volumetric flask, normal heptane constant volume.
B) titer preparation: take 49.9mg isooctyl acid, 60.6mg neodecanoic acid in 10ml volumetric flask, normal heptane constant volume.Pipette respectively 0.5ml, 1.0ml, 1.5ml, the above-mentioned neodecanoic acid titer of 2ml, 2.5ml have added in the 10ml volumetric flask of marking liquid in 1ml lauric acid in 5, normal heptane constant volume, and after mixing, gas chromatographic analysis.
2.2 sample preparations: get capric acid cobalt and fully grind, take respectively 16.0mg (without interior standard specimen), 16.6mg, 16.0mg, 14.1mg (Duplicate Samples) capric acid cobalt dust is in four 10mL volumetric flasks, add the interior mark of 1ml lauric acid liquid in three Duplicate Samples, then add respectively the hydrochloric acid solution 3mL of 1: 1, in 60 ℃ of water-baths, be heated to entirely molten, add after 4mL normal heptane concussion extraction, with normal heptane, be settled to 10mL, shake up, gas phase analysis.
2.3 Specification Curve of Increasings:
2.4 mensuration that form
On the chromatogram of sample, find neodecanoic acid and lauric acid peak area, carry it into typical curve, calculate the quality of neodecanoic acid, according to following formula, calculate the massfraction (wt of isooctyl acid, neodecanoic acid
i%):
In formula: wt
i%---the massfraction of component i in organic acid cobalt salt, %;
M---sample mass, unit is mg.
3. by analysis, know the organic acid that this capric acid cobalt sample is not C8-C22 containing other carbon number, therefore the organic acid content of sample is:
| Component | Content % |
| Propionic acid | 18.60 |
| Neopentanoic acid | 17.90 |
| Neodecanoic acid | 39.44 |
Embodiment 2: organic acid quantitative test in certain cobaltous octadecanate
1. the organic acid quantitative test that in cobaltous octadecanate, carbon number is C8-C22
1.1 interior mark liquid are prepared: take 103.8mg capric acid in 25ml volumetric flask, normal heptane constant volume.
1.2 preparation of samples: get cobaltous octadecanate and fully grind, take respectively 15.3mg (without interior standard specimen), 17.3mg, 17.8mg, 15.0mg (Duplicate Samples) powdered sample is in four 10ml volumetric flasks.With liquid-transfering gun, accurately pipette in 500 μ l and mark liquid in three Duplicate Samples.Add after boron trifluoride-methanol solution 3mL, be placed in 75 ℃ of water-baths 1h that lactonizes, add 5mL normal heptane fully to rock extraction, continue to add 10ml saturated nacl aqueous solution, fully rock after stratification gas chromatographic analysis.
1.3 result of calculations are listed in the table below:
2. by analysis, know the organic acid, isooctyl acid or the neodecanoic acid that in this cobaltous octadecanate sample, containing any carbon number, are not C2-C8, therefore organic acid content is in this sample:
| Component | Content % |
| Palmitic acid | 31.58 |
| Stearic acid | 59.35 |
Embodiment 3: organic acid quantitative test in certain cobalt boracylate
1. carbon number C2-C8 organic acid quantitative test in cobalt boracylate
1.1 interior mark liquid are prepared: take 70.4mg n-butyric acie in 25ml volumetric flask, normal heptane constant volume.
1.2 preparation of samples: get cobalt boracylate and fully grind; take respectively 16.2mg (without interior standard specimen), 16.3mg, 17.3mg; 15.6mg (Duplicate Samples) powdered sample is in four 10ml volumetric flasks; with liquid-transfering gun, accurately pipette in 300 μ l and mark liquid in three Duplicate Samples; add again 2ml boron trifluoride-n-amyl alcohol solution; be placed in 85 ℃ of water-baths 1h that lactonizes; add 3mL normal heptane firmly to shake at least 15s; continue to add 5mL saturated nacl aqueous solution fully to shake up; stratification, gets upper solution air inlet analysis of hplc.
1.3 results are calculated
According to formula (1), calculate, result of calculation is listed in the table below:
2. the quantitative test of isooctyl acid, neodecanoic acid in cobalt boracylate
2.1 standard items preparations:
A) mark liquid preparation in: take 100.4mg lauric acid in 25ml volumetric flask, normal heptane constant volume.
B) titer preparation: take 69.59mg isooctyl acid, 211.2mg neodecanoic acid in 10ml volumetric flask, normal heptane constant volume.Pipette respectively 0.2ml, 0.5ml, 1.0ml, the above-mentioned neodecanoic acid titer of 2ml have added in the 10ml volumetric flask of marking liquid in 1.5ml lauric acid in 4, normal heptane constant volume, and after mixing, gas chromatographic analysis.
2.2 sample preparations: get cobalt boracylate and fully grind; take respectively 16.0mg (without interior standard specimen), 16.5mg, 17.1mg; 18.0mg (Duplicate Samples) cobalt boracylate powder is in four 10mL volumetric flasks; add the interior mark of 1ml lauric acid liquid in three Duplicate Samples, then add respectively the hydrochloric acid solution 3mL of 1: 1, in 60 ℃ of water-baths, be heated to entirely molten; add after 4mL normal heptane concussion extraction; with normal heptane, be settled to 10mL, shake up, gas phase analysis.
2.3 Specification Curve of Increasings:
2.4 mensuration that form
On the chromatogram of sample, find neodecanoic acid and lauric acid peak area, carry it into typical curve, calculate the quality of neodecanoic acid, according to following formula, calculate the massfraction (wt of isooctyl acid, neodecanoic acid
i%):
In formula: wt
i%---the massfraction of component i in organic acid cobalt salt, %;
M---sample mass, unit is mg.
3 know by analysis the organic acid that this cobalt boracylate sample is not C8-C22 containing any other carbon number, therefore the organic acid content of this sample is:
| Component | Content % |
| Propionic acid | 11.55 |
| Neopentanoic acid | 5.26 |
| Isooctyl acid | 27.49 |
| Neodecanoic acid | 20.02 |
Claims (2)
1. an analytical approach for organic acid content in rubber wire bonding agent organic acid cobalt salt, is characterized in that specifically comprising following steps:
Step 1, accurately takes 1 part of cobalt salt powder, adds the internal standard compound matter of accurate weighing, then adds 10-100 part boron trifluoride-ol solution or strong acid solution, mixes, and wherein strong acid is selected from one or more in hydrochloric acid, sulfuric acid, nitric acid;
Step 2 reacts above-mentioned mixed solution to 0.5-3.0 hour in the temperature range of regulation;
Step 3, adds normal heptane and saturated nacl aqueous solution to extract reaction product, and extraction product is analyzed, and by capillary column gas chromatography discrete testing, calculates organic acid content in cobalt salt;
Wherein, the organic acid content of analysis is the summation of free organic acid and organic acid anion-content in organic acid cobalt salt, comprises straight chain/side chain of C2-C22, saturated/unsaturated fatty acid; Described organic acid is selected from one or more in acetic acid, propionic acid, butyric acid, valeric acid, neopentanoic acid, isooctyl acid, neodecanoic acid, capric acid, dodecoic acid, tetradecylic acid, palmitic acid, stearic acid, oleic acid, linoleic acid;
(1) when described organic acid is carbon number while being the organic acid of C2-C8, internal standard compound matter is selected from a kind of in the organic acid that carbon number is C2-C8, and monohydroxy alcohol is selected from a kind of in the monohydroxy alcohol that carbon number is C3-C8;
(2) when described organic acid is carbon number while being the organic acid of C8-C22, internal standard compound matter is selected from a kind of in the organic acid that carbon number is C8-C22, and monohydroxy alcohol is selected from a kind of in the monohydroxy alcohol that carbon number is C1-C8;
(3) when described organic acid is one or both in isooctyl acid or neodecanoic acid, use strong acid treatment, wherein strong acid is selected from one or more in hydrochloric acid, sulfuric acid, nitric acid, and internal standard compound matter is selected from the organic acid that a kind of carbon number is C6-C18.
2. the analytical approach of organic acid content in a kind of rubber wire bonding agent organic acid cobalt salt as claimed in claim 1, is characterized in that, the temperature of reaction in described step 2 is 70～100 ℃.
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| CN103616446B (en) * | 2013-11-15 | 2015-09-02 | 北京彤程创展科技有限公司 | The resolution of fatty acid and quantitative analysis method in rubber |
| CN104198639A (en) * | 2014-09-09 | 2014-12-10 | 中国石油化工股份有限公司 | Quantitative analysis method for micromolecular organic acids in fluid extracted from oil field |
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| CN109490439B (en) * | 2018-11-21 | 2021-09-21 | 成都倍特药业股份有限公司 | Method for detecting pivalic acid in ampicillin and/or ampicillin sodium |
| CN109828065A (en) * | 2019-03-26 | 2019-05-31 | 江阴市三良橡塑新材料有限公司 | The measuring method of n-butyl propionate content in a kind of cobalt boracylate |
| 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 |
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